Handbuch der analytischen Chemie

John W. Price · R. Smith

Tin
 HANDBUCH DER
ANALYTISCH EN
CHEMIE
HERAUSGEGEBEN
VON

W. FRESENIUS
WIESBADEN

DRITTER TEIL
 HANDBOOK OF

ANALYTICAL
CHEMISTRY
EDITED
BY

W. FRESENIUS
WIESBADEN

PARTIII

VOLUME 4ay

TIN

SPRINGER-VERLAG
BERLIN HEIDELBERG GMBH
1978
 TIN
BY

J. W. PRICE AND R. SMITH

WITH 31 FIGURES

SPRINGER-VERLAG
BERLIN HEIDELBERG GMBH
1978
 ]. W. PRICE and R. SMITH
51 Tudor Gardens London W3 ODU, Great Britain

ISBN 978-3-662-10561-0 ISBN 978-3-662-10559-7 (eBook)

DOI 10.1007/978-3-662-10559-7

Library of Congress Cataloging in Publicarion Daca (Revised). Main entry und~ eitle: Handbuch der analytischen Chemie. Bach volume has also
speciaJ t p. 195o- ed. by Wilhdm Fresenius and Gerhart Jande. Indudc:s bibliographics. CONTENTS: 2. T. Qualitative Nachweisverf.thren. Bd. 1 a.
Elemente der asten Hauptgruppe (einschl. Ammonium) Wasserstoff, Lithium, Natrium, Kalium, Ammonium, Rubidium, Eacsium, bc:ub. von H.
Schilling, H. Spandau und 0. Tomkok. 1944. Bd. I b. Elemente der ecsten Nebengruppe, Kupfer, Silber, Gold, bearb. von H. Bode. 1955 (etc.]. I.
O,emisrry, An•lyric. I. Fresenius, Remigius, 187S- ed. I!. J•nder, Gerhan, 1892- 1961, ed. III. Fresenius, Wilhelm, 1913- ed.
QD75.H25 543 41-36317 '""·

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PREFACE

Tin, one of the very few metals known in antiquity, owed its importance in early
times to its ability to harden copper, the usefulness of the resulting alloy for the pro-
duction of weapons and tools being so great that historians now refer to a 'Bronze
Age'. Since those times, tin has continued tobe in demand, mainly in the metallic
form for the production of alloys or as a coating on steel.
In the early stages of tin production, small parcels of ore would be smel ted and
the product retumed to the miner for sale. As the scale of refming became larger, the
smelting of single parcels became impracticable and the smelter developed assaying
methods, usually based on a miniature smelting operation on a representative sample,
carried out in a crucible with carbon or, later, cyanide as reducing agent. Today rapid
and accurate methods of analysis have been developed and tin analysis is no longer
the sole province of the tin miner and smelter but is an essential service in many of
today's industries.
It is mainly to industrial analysts concemed with tin in one form or another that
this book is directed. In addition to the metallurgical uses of tin, accounts have been·
included of the analysis of electroplating solutions and of organotin compounds and
it is hoped that the latter will be of help to those working in this new field.
No attempt has been made to catalogue all published work but rather to reflect as
far as possible current methods. lt is inevitable in any work of this nature that the
authors' own experience must influence and perhaps bias the selection of material.
This is particularly so in those areas where there are few relevant publications, and
here the authors have relied on previously unpublished work.
An aspect of analysis in general that has hitherto been somewhat neglected is that
of sampling and sample preparation, and there is little doubt that, with many of the
materialsdealt with here, sampling requires more attention than does the analysis
itself. The authors have therefore included sampling methods as part of the work.
The sampling methods given here have in large part been drawn from accepted prac-
tice within the authors' experience.
ACKNOWLEDGEMENT

The Authors wish to express their thanks to all those who have assisted in the pre-
paration of this book.
One ofus (J.W.P.) would like to thank Dr. D.A. Robins, Director of the Tin
Research Institute, for library facilities at the Institute and also Miss A.H. Chapman,
who has carried out the experimental work in the Analytical Dept. of the Institute
over a period years, for helpful discussions.
One ofus (R.S.) wishes to thank the Directors of Capper Pass Ltd. for permission
to publish some of the work referred to in the text and for their personal interest dur-
ing the preparation of the manuscript. In addition, he thanks his colleagues past and
present at Capper Pass whose experience has been a steady foundation upon which
to write, and especially Messrs. P. Fishand J. Harding for their helpful comrnents.
Finally, the authors offer their grateful thanks to their wives Doris Price and Beryl
Smith for typing the manuscript, and for their help and encouragement during the
course of this work.

J.W. Price
R.Smith
CONTENTS

Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chapter 2 Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 3
2. Ores and Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 3
3. Slags and Residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 4
4. Aqueous Salutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 4
5. Metals and Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 5
5 .1. Chernical Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 5
5.2. Tin-base and Lead-base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 6
5.3. Iron and Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 6
5.4. Aluminium and Magnesium Alloys. . . . . . . . . . . . . . . . . . . . . . . . . .. 6
6. Surface Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 6
7. Organic Matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 7
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . _. 7

Chapter 3 Gravimetrie Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1. Precipitation of Hydrous tin(IV) Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2. Precipitation of Metastarrnie Acid . -. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Precipitation as Sulphide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4. Reducing Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4 .1. Precipitation of Hg 2 Cl 2 , . • . • • . • • . • • . • • • • • • • • • • • . • • • • • • • • . 9
4.2. Preeipitation of Se . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.3. Precipitation ofTin(IV) Selenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Precipitation with Organic Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.1. Cupferron and Neo-cupferron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5 .2. N-benzylphenylhydroxylarnine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.3. Ammonium Benzoate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.4. Arsonic Acid Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.5. Tannin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
5.6. 8-Hydroxyquinoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Chapter 4 Volumetrie Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

1. Iodometrie Titrati:ons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.1. Introduction and Basic Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.2. Removal of Impurities with Iron Powder . . . . . . . . . . . . . . . . . . . . . . 14
1.3. Wet Reduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.4. Effect of Air on Stannous Salutions. . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.5. Iodirre and Iodate Titrants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
X

1.6. End-Point Delection .................................... 23

1. 7. Standardisation ....................................... 24
1.8. Interferences ......................................... 26
2. Other Redox Titrants ....................................... 31
2.1. Potassium Bromate and Related Compounds .................... 31
2.2. Potassium Ferricyanide .................................. 32
2.3. Ferric Chloride ....................................... 32
2.4. Other Titrants ........................................ 33
2.5. Iodine Monochloride Titrations ............................. 34
3. Complexometric Titrations .................................... 35
3.1. Direct Titrations ...................................... 35
3 .2. Back Titrations .................................. - .... 37
3.3. Indirect Titrations ..................................... 38
3.4. Displacement Titrations ............•..................... 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Chapter 5 Photometrie Methods . . . . . . . : . . . . . . . . . . . . . . . . . . . . . . . . . . 43
1. Introduction ............................................. 43
2. Methods of Separation of Small Amounts of Tin ..................... 44
2.1. Distillation .......................................... 44
2.2. Extraction into an Organic Solvent .......................... 45
2.3. Precipitation, Classical Methods ............................ 45
2.4. Ion-exchange ......................................... 46
3 . Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.1. Introduction ......................................... 46
3.2. Dithiol ............................................. 48
3.3. Phenylfluorone ....................................... 49
3.4. Catechol Violet ....................................... 51
3.5. Gallein ............................................. 53
3.6. Quercetin ........................................... 54
3.7. Haematoxylin and Haematin .............................. 54
3.8. 4-Hydroxy-3-nitrophenyl Arsonic Acid ........................ 55
4. Fluorimetric Methods ....................................... 56
References .............................................. .. 57
Chapter 6 Electrochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
1. Introduction ............................................. 61
2. E1ectrodeposition .......................................... 61
3. Controlled Potential Electrolysis;Cou1ometric Analysis ................. 61
4. Po1arography ............................................. 62
5. Amperometry ............................................ 63
6. Anodic Stripping Voltammetry ................................. 64
References .............................................. .. 65
Chapter 7 Solvent Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
1 . Ion Association Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
1.1. Fluoride Extractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
1.2. Chloride Extractions .................................... 67
1.3. Bromide Extractions .................................... 67
1.4. Iodide Extractions ..................................... 69
1.5. Thiocyanate Extractions ................................. 70
1.6. High Molecular Weight Amines ............................. 71
 XI

2. Phosphorus Containing Extractants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7I

2.1. Alkylphosphoric Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7I
2.2. Alkylthiophosphoric Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3. Alkyldithiophosphoric Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.4. Trialkylphosphine Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3. Chelate Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3 .1. Acetylacetone and Related Compounds . . . . . . . . . . . . . . . . . . . . . . . 73
3.2. 8 Hydroxyquinoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.3. Cupferron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.4. Hydroxamic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.5. Dithizone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3 .6. Dithiocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76.
3.7. Xanthates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.8. Toluene 3, 4 Dithiol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.9. Other Extractants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Chapter 8 Atomic Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 80
I. Atomic Absorption Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
1.1. Absorption Wavelengths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
I.2. Choice of Flarnes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
1.3. Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2. Atomic Flame Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.1. Molecular Emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.2. Chemiluminescence Atomic Emission . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.3. Thermally Excited Atomic Emission . . . . . . . . . . . . . . . . . . . . . . . . . 85
3. Atomic Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4. Electrotherrnal Atomisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5. Separation Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.1. Solvent Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5 .2. Coprecipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.3. Sublimation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5 .4. Other Separations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9I
6. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Chapter 9 Emission Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
I. Spectral Characteristics of Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
I .I. Molecular Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
I.2. Atomic Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
1.3. Atomic Line Interferences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2. Types of Discharge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I 03
3. Behaviour of Tin in Are Discharges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I 04
3.1. Ionisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I04
3 .2. Volatilisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
3 .3. Interna! Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4. Metallurgical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4 .1. Aluminium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
4.2. Antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
4 .3. Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I 08
4.4. Bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
XII

4.5. Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

4.6. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
4.7. Gallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.8. Hafnium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.9. Irons, Steels, Ferroalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.10. Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113'
4.11. Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.12. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.13. Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.14. Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.15. Silver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.16. Tantalum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.17. Titanium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.18. Thallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.19. Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.20. Yttrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.21. Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5. Geochernical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
6. Miscellaneous Inorganic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7. Organic Materials, Foodstuffs, Biological Specimens . . . . . . . . . . . . . . . . . . 121
8. Environmental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

Chapter 10 X-Ray Fluorescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

1. General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
1.1. Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
1.2. Spectral Characteristics of Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
2. Ores and Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.1. Direct Analysis of Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.2. Fusion Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
2.3. Non-Dispersive Instruments . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . 132
3. Solders and Whitemetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3.1. Structure ofSolders, Segregation, Ageing . . . . . . . . . . . . . . . . . . . . . 134
3.2. SampiePreparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
3 .3. Standards Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 7
3 .4. Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4. Copper Base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
5. Other Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ' . . . . . . . . . . 142
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

Chapter ll Radiochemical and Mössbauer Methods . . . . . . . . . . . . . . . . . . . . . 145

1. Radiochernical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
2. Mössbauer Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . · . · · · 148

Chapter 12 Analysis of Tin Ores and Concentrates . . . . . . . . . . . . . . . . . . . . . -149

1. Tin Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2. Sampling ofTirr Ores and Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.1. Size of Bat eh or Consignment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 0
2.2. Prirnary Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
 XIII

Crushing and Dividing

2.30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 • 0 0 0 0 0 0 0 0 0 0 0 0 0 150

Practical Aspects
2.40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 153

Maisture Determination
2050 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 154

30 Pretreatment of Sampie 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

Roasting
301. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

Nitric Acid Treatment

3 020 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

Hydrofluoric Acid Treatment

303 .. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

40 Decomposition Procedures 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

Fusion Methods
401. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 156

Reduction Methods
4020 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 159

Sublimation with Ammonium Iodide

4030 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 160

Decomposition by Acids
4.40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 161

50 Analytical Methods 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 161

DeterminationofTin
501. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0161

Determination of Impurity Elements

5020 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 166

References 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 170

Chapter 13 Analysis of Secondary Materialsand Intermediates 0 0 0 0 0 0 0 0 0 0 0 0 0 173

10 Drosses and Ashes 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 173

20 Slags 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 175

30 Fume, Flue Dusts 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 o, 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 176

40 Turnings, Borings 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 176

50 Muds, Slimes, Detinning Residues 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 178

60 Hardhead and Irony Intermediates 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 178

Chapter 14 Analysis of Tin Alloys and Solders 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 180

Sampling
10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 , 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 180

Standard Methods
1.1. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 181

Solders 1.20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 183

Antimonial Alloys
1.30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 183

Chemical Analysis
20 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 184

Tin 201. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 184

Lead 2020 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 185

Antimony 2.30 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 186

Copper 2.40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 187

Other Elements
2050 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 187

Density Methods
2060 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 188

References 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 190

Chapter 15 Analysis of Ingot Tin 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 192

Sampling
1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 192

20Analysis 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 193

Determination of Tin
201. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 193

Photometrie Methods for Impurities

2 020 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 194

Emission Spectroscopic Methods for lmpurities

2030 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 196

References 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 198

Chapter 16 Tin in Copper -Base Alloys 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 199

1.Sampling 0 0 0 0 0 o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 199

20Volumetrie Methods 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 202

3 Instrumental Methods
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 203

References 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 • 0 0 0 0 0 0 0 0 0 0 0 0 0 0 204
XIV

Chapter 17 Tin in F errous Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
2. Volumetrie Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
2.1. General Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
2.2. Rapid Method for Cast Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
3. Photometrie Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
3.1. Phenylfluoraue Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
3 .2. Pyrocatechol Violet Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
3 .3. 4-Hydroxy-3-nitro-phenylarsonic Acid Method ................. 207
4. Atomic Absorption Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.1. Cast Iran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
4.2. Sintered Iran Compacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208

Chapter 18 Tinplate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
2. Determination of Tin Coating Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
2 .1. Coulometric Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
2.2. X-ray Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
2.3. BendixMethod . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
2.4. 'Strip and Weigh' Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
2.5. Volumetrie Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
3. Determination ofOil Film Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
4. DeterminationofOxideFilm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
5. Performance Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213

Chapter 19 Organotin Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
2. Eiemental Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
2 .1. Determination of Tin . . . . . . . . . . . . . . . . . . . ·. . . . . . . . . . . . . . . 215
2.2. Determination ofCarbon and Hydrogen . . . . . . . . . . . . . . . . . . . . . . 216
2.3. Determination of Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
2.4. Determination of Sulphur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
2.5. Determination of Halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3. Determination of Functional Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.1. Carboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3 .2. Hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
3.3. Oxidesand Hydroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4. Determination of Organatin Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4.1. Volumetrie Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
4.2. Photometrie Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
4.3. Electrochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.3 .1. Polarography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
4.3.2. Amperometry and Voltarnmetry . . . . . . . . . . . . . . . . . . . . . . . 224
4.3.3. Anodic Stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
4.4. Fluorimetric Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
4.5. Atomic Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
4.6. Miscellaneous Physical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
5. Separations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
 XV

5 .1.Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
5.1.1. Gas-Liquid Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . 227
5.1.2. Paper Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
5.1.3. Thin Layer Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . 230
5.2. Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
5.3. Solvent Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
5.4. Steam Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
6. Radiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7. Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
8. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
8.1. PVC Stabilisers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
8.1.1. Determination of Stabilisers . . . . . . . . . . . . . . . . . . . . . . . . . . 235
8.1.2. Migration From PVC into Foods and Food Simulants ......... 236
8.2. Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
8.2.1. Crop Residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
8.2.2. Residues in Solls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
8.3. Wood and Anti-fouling Paints . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
8.4. Environmental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
8.4.1. Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
8.4.2. Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
Chapter 20 Tin and Tin-Alloy Electroplating Solutions . . . . . . . . . . . . . . . . . . 248
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2. Tin Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
3. Tin-Lead Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
4. Tin-Copper Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
5. Tin-Nickel Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
6. Tin-Zinc Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
7. Other Tin Alloy Plating Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
8. Atomic Absorption Methods of Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 251
9. Coating Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
9 .1. Destructive Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
9.1.1. Strip and Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
9.1.2. Jet Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
9.1.3. Coulometric Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
9.2. Non-destructive Methods ........... _ .................... 252
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Chapter 21 Tin Chemieals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
2. Tin(II) Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3. Tin(IV) Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4. Tin(II) Sulphate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254 ·
5. Sodium and Potassium Stannates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
6. Tin(II) Fluoroborate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
7. Tin(II) Octoate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256

CHAPTER 1

INTRODUCTION

By J.W. Price

Tin does not occur naturally as metal, but is found associated with granitic rock as
the mineral cassiterite, Sn0 2 , most of the tin now being found in unconsolidated de-
posits censisting of gravels, sands and clay resulting from the denudation of tin-bear-
ing rocks. Mining of these deposite is carried out by dredging or hydraulically with
high-pressure water jets. Hard rock deposits occur in Bolivia, Australia, South Africa
and Cornwall, the cassiterite being present as lodes or veins in the rock and these are
worked by sinking vertical shafts and driving tunnels at different levels; in mountain-
ous terrain vertical shafts may be unnecessary, tunnels being driven·in from the hill-
sides.
Cassiterite having a high density of about 7 g/cm 3 can be concentrated from the
mined ore by gravity methods, usually on shaking tables or jigs, and separation from
other accompanying heavy minerals is effected by froth flotation and magnetic Sepa-
ration. The resulting concentrates are smelted into metal by heating with carbon,
usually in the form of anthracite, in reverberatory furnaces; in the case of high grade
material the resulting metal is of high purity, while that produced from lower grade
concentrates is likely to contain a high level of impurities which are usually removed
by electrolysis. Tin in slags and in 10\v-grade material is increasingly being recovered
in volatilisation plants. Details of these processes are given in the publications cited in
References [1, 2, 3].
Aceurate analysis of ores, concentrates, mill products etc. presents the analyst with
some difficulty because of the insolubility of cassiterite in acid and the sample must
be brought into solution by e.g. alkaline fusion or hydrogen reduction. Tin, except in
small amounts, is traditionally determined volumetrically and this method is still the
most accurate and most widely used in the industry; though now well understood it
still presents pitfalls to the inexperienced.
Tin metal is marketed in the form of ingots, typically weighing 1OOlb., each ingot
being stamped with the producers brand name; these brand names are almost univer-
sally accepted as a guarantee of purity so that analysis of such ingots is rarely, if ever,
necessary. National standard specifi.cations exist for ingot tin and examples of these
are given in Chapter 15. The principal standard on the continent of Europe and in the
U.S.A. for pure tin is now 99.9 %, while in the U.K. 'standard tin' T.2, 99.75% is ac-
cepted for many uses. In general, the impurity contents of commercial tin metal are
weil within acceptable lirnits and it is only for special uses that very high purity metal
is essential. For example, a case where impurity levels are important is the manufac-
ture of tin oxide for ceramic use, where as little as 0.05% of antimony or lead can
produce as slightly yellow instead of a pure white product.
Annual world consumption of metallic tin is of the order of 200,000 tonnes. This
amount is seen in perspective when compared with 30 times as much copper and 20
times as much lead or zinc, but the relatively high price of tin makes its total value
2 Introduction [Ref.p. 2

comparable with that of the other 'base' metals. Ofthis total consumption figure of
200,000 tonnes nearly half is used in the production of tinplate - tin-coated steel
sheet- with 25% being used for solders and 15% for white meta! alloys including
pewter and for copper-base alloys such as bronze. The remaining 10% is taken up by
a variety of uses, among which tin chemicals, both inorganic and organic, occupy an
increasing share.
Annual world production of tinplate is of the order of 12 - 15 x 106 tonnes, more
than 90% of it being produced by electrodeposition of the tin in a continuous strip
process. A wide range of tin coating thicknesses is available and the general analyst
may be called upon to check that the thickness of the coating is suitable for the par-
ticular purpose for which the tinplate is to be used. Detailed testing of tinplate is
somewhat specialised and is usually carried out only by the !arge users, the can mak-
ers and their customers, traditionally the food and beverage industries, accounting
for perhaps 80% of the tinplate used. F ood in cans, if stored for long periods at ele-
vated temperatures, may dissolve some of the tin coating from the interior of the
cans, and although this dissolved tin is harmless if ingested, regulationsexist in many
countries which'specify maximum permitted Ievels, typically 100ppm in solid foods.
Tin at these Ievels is best determined photometrically or by atomic absorption after
wet-oxidation of the organic matter.
Solder composition is the subject of numerous national standards for a wide vari-
ety of uses e.g. B.S.219; A.S.T .M. B.32; D.l.N. 1707, tin content being the most im-
portant consideration, though impurities which affect fluidity and wetting during the
soldering operation have become of increasing significance, particularly because of
the growth of high-speed mass soldering in the electronics industries, and the analyst
must also be prepared to determine such impurities as aluminium, zinc and cadmium
at very low concentrations in solder baths.
The metallurgical uses of tin date from ancient times, bronze and pewter having
both been in use for more than 3,000 years. Both tin-base and copper-base alloys are
today of considerable commercial importance - world production of copper-tin al-
loys is about 600,000 tonnes annually - and in addition tin is fmding increasing use
in zirconium and titanium alloys, in powder metallurgy and, in small amounts, as an
additive to cast iron. National and international specifications exist for many alloys
containing tin and referee methods for their analysis have been published. The met-
allurgical analyst must use rapid methods for production control and here in partic-
ular automated instrumental methods are important; strictly chemical methods of
analysis are less used except for standardisation purposes.
lt is, however, in the new field of organotin compounds that the analyst is likely
to meet the most challenging problems. These compounds are used, broadly speaking,
in two separate fields - as plastics stabilisers, particularly for PVC, and as biocides in
a variety of applications such as crop protection, timher preservation, anti-fouling
paints etc. In these uses the organotin compounds can come into contact with foods
and residues from agricultural applications can pose ecological questions. Much work
has been published during the last few years and satisfactory analytical methods are
beginning to emerge, particulary for the determination of very low concentrations of
these compounds.
References
1. Mantell, C.L.: Tin, A.C.S. Monograph 51. Reinhold (1949)
2. Wright, ·P.A.: The Extractive Metallurgy of Tin, Elsevier (1967)
3. Mackey, T.S.: The Electrolytic Tin Refining Plantat Texas City, J. Metals, 22, 32 (1969)
CHAPTER 2

DETECTION

By J .W. Price

1. Introduction

With the establishment of instrumental methods, classical qualitative analysis has

become of less importance, particularly as such methods as e.g. spectrochemical,
X-ray fluorescence (for the examination of solid samples) and atomic absorption (for
samples in solution) are generally specific for the element concemed, thus avoiding
the need for Separations. Accordingly group separations and general reactions of tin
compounds in solution are dealt with here only briefly, as they are covered in most
analytical texts. In particular, a very full account of methods for the detection of tin
published before 1956 is given in the book edited by Fresenius andJander [1).

Tin, a group IV element, can form compounds in both the IV+ and II+ oxidation
states. Both tin(II) and tin(IV) compounds are amphoteric, in the latter the acidic
properties being more prominent than the basic, so that tin(IV) compounds in aque-
ous solution exist almost exclusively as complex anions, this being much less marked
in tin(II) compounds. Both types of compound are very readily hydrolised in solution,
with precipitation of basic salts or hydrated oxides, no true tin hydroxides being
known. Tin(II) compounds are strong reducing agents, both the solid compounds and
their aqueous solutions being readily oxidised in the air, and most of the reactions
used for the detection of tin depend on the reducing properties of tin(II) on both or-
ganic and inorganic compounds. Classical group separations are based on the insolu-
bility of tin sulphides in dilute acid (0.5 M hydrochloric acid) and their solubility in
alkali sulphide or hydroxide; in this procedure tin is accompanied by arsenic and an-
timony and also by Au, Pt, Ir, Mo, Ge, Se, Te andRe, if present. Numerous schemes
have been put forward for the separation oftin from these elements [1], some exam-
ples of which are given in Table 1. In addition, separations are possible by paper- and
column-chromatography, details of which are also given i~ Reference [ 1).

2. Ores and minerals

Tin concentrations down to 0.001% have been detected by direct spectrographic
examination of powdered samples, while higher detection Iimits have been reported
for the use of Mössbauer spectrometry in geological surveying (Chapter 11). Portable
X-ray fluorescence equipment is also available for use in surveying. Chernical tests based
on acid attack on the sample are of doubtful value owing to the insolubility of cassite-
rite and alkaline fusion should be used whenever possible, the melt being dissolved in
acid and tin looked for in the solution. By the reaction of Sn0 2 with hydriadie acid
to form red Snl 4 it has been found possible to detect as little as 0.1 mg Sn. This test
4 Detection [Ref.p. 7

is better carried out by heating the sample with ammonium iodide; mix 0.2g of the
powdered sample with 2g ammonium iodide and heat to 450 - 500° in a test tube. A
yellow to red Sublimate condenses on the wall of the tube if tin is present. This can be
confirmed by dissolving in 2M hydrochloric acid and testing with dithiol. In a sirnilar
test [2] the sample is heated with arnmonium chloride and a little granulated magne-
sium meta!. The colourless sublimate in this case contains some tin(II) chloride, which
can be detected by placing in contact with cotton wool moistened with a solution of
arnmonium phosphomolybdate. A blue colour is produced with a minirnum of 1mg
Sn0 2 .

Chemical Separations of the Sulphides of the Tin Group

Elements
Present
Sb, As 1. Add excess oxalic acid to a solution of the sulphides in HCI and pass H 2 S. Sb and
(Se, Te, Mo) As (also Se, Te and Mo if present) are precipitated, Sn remains in solution.
2. Dissalve sulphides in conc. H 2 S0 4 , dilute, add HF and pass H 2 S. Sb and As are
precipitated, Sn remains in solution. To the solution add excess boric acid,
neutralise free acid with ammonia. Sn precipitated as sulphide.
Sb 1. Dissalve sulphides in HCl, reduce with metallic Fe or Ni. Sb metal precipitated, Sn
remains in solution.
2. Pass H 2 S into a solution which is 2 N in HCI. Sb is precipitated, Sn remains in
solution.
As Heat sulphide precipitate in 5 M HCI. As is insoluble, Sn (+ Sb) goes into solu-
tion.
Mo, Se, Te, Heat sulphide precipitate in conc. HCI. Only Sb and Sn are dissolved.
Au, Pt

3. Slags and residues

These should be separated into 'meta!' and 'fines' by grinding and sieving and the
two fractions examined separately. The metallic portion is dissolved in hydrochloric
acid with the addition of a few drops of hydrogen peroxide and tin looked for in the
solution. The 'fines' are fused with sodium hydroxide/peroxide, the cooled melt dis-
solved in water, the solution acidified with hydrochloric acid and tested in the same
way.

4. Aqueous solutions

Dilute acid solutions containing Sn(II) or Sn(IV) are unstable, precipitating hy-
drated oxides at pH values above 2.5; alkaline solutions of Sn(IV) e.g. sodium stan-
nate, are stable in the presence of excess alkali but alkaline stannites decompose, es-
pecially on heating, with disproportionation to metallic tin and stannate.
For the detection of Sn(II) in the presence of Sn(IV) there arenot many suitable
tests available. The classical formation of 'purple of Cassius' by the reducing action of
Sn(II) on solutions of gold chloride is very sensitive; other reducing agents, particular-
ly Fe 2 •, must be absent. Salts of the platinum metals give similar colour reactions,
the formation of a deep red with a platinaus salt being clairned [3] tobe specific for
 Ref.p. 7] 5.1 Chemical Reactions 5

Sn(II). Addition of oxalic acid to a solution of a tin salt in ethanol gives a precipitate
ofthe Sn(II) oxalate, the Sn(IV) compound being soluble [4], but the test is not very
sensitive. Other reactions stated to be specific for Sn(II) in the presence of Sn(IV) are
the decolorisation of solutions of methylene blue [5], Bordeaux Red and Brilliant
Vialet [6] in hydrochloric acid solution, but other reducing agents must be absent.
In alkaline solution stannite can be detected in the presence of a !arge excess of
stannate as follows: precipitate bismuth hydroxide from an acid solution of a bismuth
salt by makingjust alkaline with sodium hydroxide, fllter, and pour the hat alkaline
solution to be tested over the precipitate on the filter paper. A black deposit of bis-
muth meta! is obtained if stannite is present, the surface of the bismuth hydroxide
being coloured brown if only traces of Sn(II) are present.
Mixtures of the two tin oxides can be separated by heating to boiling in a solution
containing 4% oxalic acid and 4% ammonium oxalate. The tin(II) oxide dissolves but
Sn0 2 is insoluble. Metallic tin, if also present, is removed by first dissolving in neutral
5% ferric sulphate solution [7].
As already stated, tin(II) compounds are strong reducing agents and almost any
compound that produces a colour change or a precipitate with a reducing agent can be
used as a test for tin. Tin(IV) compounds are readily reduced to tin(II) in hydrochloric
acid solution by metals such as iron, Iead, nicke!, aluminium or zinc and the resulting
solution can be used for the test. Very few of the reagents that have been proposed
are specific for tin and most of them are of historical interest only; details of more
than 100 of them are given in Reference [ 1].
The reagents that have been found satisfactory for the photometric determination
of tin (Chapter 5) can of course be used for qualitative tests and the elimination of
possible interferences can be carried out as described there. Perhaps the most useful
test for tin in solution is the production of a red colour with dithiol (zinc derivative),
while the equally sensitive test with cacothelene - the formation of a violet colour -
is not interfered with by bismuth as is dithiol.
Cacothelene test: to the hydrochloric acid solution add hydroxylammonium chloride, dilute
with water so that the acid concentration is 1 - 2 M, and add a few drops of a saturated aqueous
solution of the reagent. A red-violet colour is produced with as little as 10 jJ.g/ml Sn(II).
Dithiol test: to the hydrochloric acid solution ('"'2N) add a few drops of thioglycollic acid
and a little solid zinc dithiol and warm gently. A red colour is produced by 1 jJ.g/ml Sn and a
red precipitate by !arge amounts. Many other metals react to give coloured precipitates but in
the presence of an excess of the reagent on!y bismuth gives a red colour.
Both these reagents can be used as 'spot' tests: a drop of the test solution is placed on filter
paper followed by a drop of the reagent solution.

5. Metals and alloys

Spectrographic methods of test are given in Chapter 9 and arenot referred to here.

5 .1 Chemical Reactions
Chemically a reaction that is specific in the absence of Ti and Zr depends on the
formation of a turbidity with 4-hydroxy-3-nitrophenyl arsonic acid (Chapter 5.3.8).
The sample is dissolved in nitric acid, the solution evaporated to dryness and the resi-
due dissolved in hydrochloric acid. On addition of an aqueous solution of the re-
agent (0.8%) !arge amounts of tin give an immediate white precipitate while as little
as 50jJ.g in a volume of 30m! give a visible turbidity on warming or allowing to stand.
6 Detection [Ref.p. 7

The same test has been used to detect down to 0.2% Sn in lead-antimony alloys. With
these the hydrochloric acid solution is diluted with an equal volume of water and
cooled, the solution decanted from the precipitated Iead chloride and heated to
boiling after addition of the reagent.

5.2 Tin-base and Lead-base alloys

Tin-rich samples can be dissolved in hydrochloric acid with formation of Sn(II)
chloride which can be tested for directly with cacothelene or dithiol. Lead-rich ma-
terial should be dissolved in nitric acid and the solution evaporated to dryness. Large
amounts of tin are precipitated as metastaunie acid, which can be isolated by flltra-
tion and dissolved in hydrochloric acid; with small amounts the whole residue should
be heated with hydrochloric acid, the solution diluted with an equal volume of water
and the precipitated Iead chloride separated by decantation. Tin is then present in
the clear solution as Sn(IV) and must be reduced to Sn(II) before testing with these
reagents.

5.3 Iron and Steel

Direct chemical methods of test are not very satisfactory and it is usually neces-
sary to dissolve a sample in dilute sulphuric acid and to precipitate the tin as sulphide,
adding a copper salt as collector. The sulphide precipitate is then dissolved in acid and
the solution tested with dithiol as above.

5.4 Aluminium and magnesium alloys

A simple chemical test has been described [8] in which the sample is dissolved in
5 M hydrochloric acid and a drop of the solution treated with a drop of dilute starch-
iodine (1 rnl of 0.1 N iodine + 5 ml of 5% starch solution diluted to 100ml). Immediate
decolorisation indicates the presence of tin.
A test proposed for the detection of down to 0.02% Sn in a number of alloys [9]
relies on the green fluorescence of a tin-morin complex under UV light. The sample
is heated with a few drops of concentrated sulphuric acid and, after diluting with wa-
ter, solid potassium iodide is added and the tin extracted into a 5% solution of iodine
in benzene. A drop ofthe benzene solution is placed on fllter paper and treated succes-
sively with arnmonia vapour, a drop of sodium sulphite solution to remove iodine, and
a drop of a 0.05% solution of morin in acetone. Excess reagent is removed by dipping
the paper in acetic acid and the spot viewed under UV light. A green fluorescence can
be seen with as little as 0.05J.tg Sn.

6. Surface coatings
Tin coatings, both electroplated and hot-dipped, are readily identified by placing a
drop of 5 M hydrochloric acid on the degreased surface and after 2 - 3 min transferring
the drop to fllter paper and testing with dithiol or cacothelene. This procedure can
also be used for the testing of tin-lead and tin-zinc coatings but is not suitable for tin-
copper or tin-nicke! alloys, which may be identified as follows: place 1 - 2 drops of
bromine water on the degreased surface and allow to react for 5 min. Transfer the drop
to fllter paper, add 1 drop of 10% thioglycollic acid and 1 drop of a methanolic solu-
tion of zinc dithiol. A red colour indicates the presence of tin. Copper and nicke! may
 Ref.p. 7] 7. Organic matter 7

be detected in a similar way, a blue colour produced on making the spot on the fllter
paper alkaline with ammonia indicating copper and a red colour formed on adding di-
methylglyoxime to the alkaline spot indicating. nicke I.

7. Organic matter
Methods of test involving preliminary ignition of the sample to remove organic
matter are to be avoided if possible as there is in some cases a danger of loss of tin by
volatilisation and generally the tin in the ash is more or less insoluble in acid, requiring
an alkaline fusion to take it into solution. Wet oxidation with sulphuric acid and an
oxidising agent, usually nitric acid, can be carried out rapidly provided that the nitric
acid is added in small amounts and the water forrned in the reaction evaporated before
the addition of more acid. Canned foods should be wet-oxidised with the exception
of some fruits and vegetables, from which tin can be extracted by heating with 5 M
hydrochloric acid. Tin is separated from the sulphuric acid solution obtained after
wet-ashing by precipitation as sulphide, adding a coppersalt as collector, or as hydra-
ted oxide by making alkaline with arnmonia after the addition of a ferric or an alumi-
nium salt. The resulting precipitate is ftltered, dissolved in acid, and tested with dithiol
as above.

Re[erences

1. Fresenius, W., Jander, G.: Handbuch der analytischen Chemie Part li, Vol. 4(1I) Springer-
Verlag 1956
2. Ben-Dor, L., Markovitz, G.: Mikrochim.Acta, 1967, 957
3. Chotulew, Y.P.: Chem. Abstr., 32, 8978 (1938)
4. Meyer, E.G., Kahn,M.: J. Amer. Chem. Soc., 73,4950 (1951)
5. Wohlmann, E.: Z.Anal.Chem., 122, 161 (1941)
6. Smith, J. W., Rogers, H.E.: J.Chem.Educat., 16, 143 (1939)
7. Gauzzi, R.: Ann.Chim.Ital., 47, 1316 (1957); (C.A., 52,7017 (1958))
8. Clark, J., Stross, W.: Metallurgia, 46,212 (1952)
9. Feig!, F., Gentil, V.: Mikrochim. Acta, 93 (1954)
CHAPTER 3

GRA VIMETRIC METHODS

By J.W. Price

Classical gravimetric procedures for the determination of tin are based mainly on
the dehydration of hydrous tin(IV) oxide at 800°C and the thermal stability of the
oxide Sn0 2 on heating in air at temperature up to 950°C [1 ]. The hydrous oxide can
be obtained by neutralising an acid solution of a tin(IV) salt, usually the chloride, or
a complex with an organic reagent can be precipitated from acid solution and ignited
to destroy organic matter and leave a residue of Sn0 2 , but the most important method
is that of nitric acid attack on a tin-containing alloy with formation of 'metastannic
acid'.

1. Precipitation of Hydrous Tin(IV) Oxide

Precipitation of hydrous tin(IV) oxide is not much used except as a means of Sepa-
ration from e.g. Cu, Ni and Mo, as the precipitate is difficult to filter and wash. Pre-
cipitation is carried out (i) by making the solution alkaline with arnmonia (ii) by
boiling the faintly acid solution with excess of arnmonium nitrate:

(iii) by adding a 20% aqueous solution of pyridine to the hot solution containing
5 - 10% NH4 Cl until it is alkaline to methyl orange. In all cases the precipitate is
washed with 1% NH 4 N0 3 solution to remove chlorides which may cause loss of tin
during ignition.

2. Precipitation of Metastannic Acid

Precipitation by nitric acid attack on a metal sample:

3Sn + 4HN0 3 + H 2 0 -+ 3Sn0 2 .H 2 0 + 4NO

has long been used for control purposes, particularly for copper alloys. It is important
to bear in mind the limitations of this method: (i) if the sarnple is dissolved in dilute
(5 - 10 %) acid it is necessary to evaparate the solution to dryness to ensure complete
precipitation of the tin. This evaporation can be avoided by dissolving in SO% acid,
boiling to expel oxides ofnitrogen, diluting with an equal volume of water and di-
gesting for 30 min near the boiling point before filtering. (ii) Copper alloys con-
taining large amounts of phosphorus (1 - 2 %) dissolve very slowly in nitric acid and
for these the method is not suitable. Both phosphorus and antimony are precipitated
with the tin, quantitatively if there is a ten-fold excess of tin present. (iii) Iron in
 Ref.p. 11] 4.2 Precipitation of Se 9

!arge amounts (> 0.5 %) can peptise some of the hydrated tin mtide causing low re-
sults: smaller amounts are partly adsorbed on the precipitate, causing high results.
(iv) Cantamination of the precipitate is tobe expected by silica, tungsten, tantalum
and niobium and, to a lesser extent, by copper and zinc. Correction for this can be
made by heating the ignited and weighed precipitate with ammonium iodide at 450°C,
volatilising the tin as Snl 4 . The residue is treated with nitric acid and again ignited and
its weight deducted from the original. (v) Precipitation of small amounts (< 0.1 %) of.
tin is incomplete, and for these the use of Mn0 2 as a 'collector' by boiling the nitric
acid solution of the sample with permanganate/manganous nitrate allows complete
recovery but of course involves a further step in the determination [ 13].

3. Precipitation as Sulphide
While forming the basis of a number of classical methods of separation [ 14] precip-
itation as sulphide is not much used as a method of determination owing to the diffi-
culty of flltering a somewhat slimy precipitate. The sulphide is obtained by the pas-
sage of H 2 S into dilute acid solutions or by formation of the soluble thiostannate in
alkaline solution and then acidifying with acetic acid. Tin(IV) sulphide may also be
precipitated with thioacetamide from homogenaus solution which is 0.8 M in HCl,
[ 15] with thioformamide [ 16] or with thiourea dioximide (17]. The addition of a
small amount of HgCl 2 has been recommended in order to obtain complete precip-
itation of the tin; any mercury in the precipitate is removed during ignition of the
precipitate to Sn0 2 .

4. Reducing Reactions
Methods based on the reducing power of Sn(II) solutions suffer from the disadvan-
tages of the difficulty of ensuring complete reduction of tin-containing solutions and
of the relative ease with which reoxidation can take place.

4.1 Precipitation of Hg 2 Cl 2
In one such method, which is stated to give good results in the ana1ysis of tin-base
alloys [ 18], tin is first reduced to the meta! in hydrochloric acid solution by means
of metallic zinc, the tin re-dissolved by heating the solution with the exclusion of air,
and the cooled solution quickly poured into an excess of mercuric chloride solution.
The precipitated Hg 2 Cl 2 is filtered ar,d dried at 105°C before weighing; it has a favour-
able conversion facter of 0.2514.

4.2 Precipitation of Se
A sirnilar procedure involves the addition of selenous acid to the reduced tin solu-
tion, with precipitation of elementary Se, which can be dried at 110° C and weighed.

H 2 Se0 3 + 2 SnC1 2 + 4 HCl--+ 2 SnCl4 + 3 H 2 0 +Se

10 Gravimetrie Methods [Ref.p. 11

4.3 Precipitation of Tin(IV) Selenite

An alternative procedure [ 19] which does not require prior reduction of the tin,
precipitates Sn(IV) selenite by the addition of H 2 Se0 3 to the oxidised· solution can-
tairring 2% v/v of hydrochloric acid. In this case the precipitate is ignited and weigh-
ed as Sn0 2 .

5. Precipitation with Organic Reagents

5.1 Cupferron and neo cupferron

Cupferron and neo cupferron ( the ammonium salts of nitrosophenyl- and nitro-
sonaphthyl-hydroxylarnine) form bulky white precipitates by replacement of the hy-
drogen of the oxime group, giving complexes with Sn(II) and Sn(IV). Precipitation is
carried out in acid solution (-6% HCl) in the cold ( < 10°); the precipitate filters well
but the reagents are not specific, so that prior separation from e.g. Cu and Pb is nec-
essary. Antimony does not interfere if oxidised to Sb(V) with permanganate, while
Cu and Pb may be eliminated by precipitation with H2 S from a solution cantairring
3- 5% HF, the tin in the filtrate being precipitated with cupferron after the addition
of boric acid and boiling to expel H2 S. Cupferron has been recommended for the pre-
cipitation of tin after it has been isolated by distillation as the brornide (2]. In all
cases the precipitate is dried and ignited to Sn0 2 at 800- 850°C.

5.2 N-benzoylphenylhydroxylamine
A related compound N-benzoylphenylhydroxylamine behaves rather differently in
that in acid solution it frrst reduces Sn(IV) to Sn(II) and then forms an addition com-
pound which is stable up to 170°C and so can be dried at ll0°C and weighed, or can
be ignited to Sn0 2 . No interference is caused in 6% HCl solution by Cu or Pb, so that
a direct determination of tin in copper alloys is possible by dissolving the sample in
HCl (3).

5.3 Ammonium benzoate

Ammonium benzoate added to an acid solution (pH3) precipitates tin(IV)
benzoate which can be ignited to Sn0 2 [ 4] .The reagent is not specific, but some
interferences can be avoided by adding suitable complexing agents.

5.4 Arsonic Acid Derivatives

Several arsonic acid derivatives give precipitates in acid solution which can be ignited
to Sn0 2 e.g. phenylarsonic acid in 5% HCl allows separation from Cu, Pb, Sb and Ni,
but Zr and Th interfere. A micromethod using this reagent has been described [5].
Similar precipitates are abtairred with anthraquinone-arsonic acid [6], tetraphenylar-
sonium chloride [7] and 4-hydroxyl-3-nitrophenyl arsonic acid [8], the last of these
being a useful reagent for the turbidimetric determination of small amounts of tin
[9). Benzene arsonic acid has recently been used for the precipitation of tin from
dilute acid solutions containing Pb. A saturated aqueous solution of the reagent is
added to the hot sample solution, the precipitate fJ.ltered, washed with 4% NH4N0 3
solution and ignited to Sn0 2 [10].
 Ref.p. 11] 5.6 8-Hydroxyquinoline 11

5.5Tannin
Tannin added in slightly acid solution ( -Q.OS N) produces a bulky white precip-
itate by flocculation of the disperse positively charged hydrous tin(N) mtide by the
negative tannin sol, and in chloride solutions this affords a separation of tin from Cu,
Pb, Fe, Al, Be, As and V, but Sb is co-precipitated [ 11]. The interference of Zr can
be prevented by the addition of oxalate. The precipitate is ignited to Sn0 2 •

5.6 8-Hydroxyquinoline
8-Hydroxyquinoline added to a solution of Sn(IV) in 0.2 M HO forms the complex
SnC1 2 -(C 9 H 6 NOh which may be dried at 110° C and weighed as such. Citrate, phosphate
and tartrate as weil as Bi, Sb and Mo interfere [12].

References

1. Dupuis, T., Duval, C.: Anal. Chim. Acta, 4, 201 (1950)

2. Mogerman, W.D.: J.Res.Nat.Bureau Stds., 33, 307 (1944)
3. Ryan, D.E., Lutwick, G.D.: Canad.J.Chem., 31, 9 (1953)
4. Jewsbury, A., Osborn, C.H.: Anal. Chim. Acta, 3, 642 (1949)
5. von Mach, N., Hecht, F.: Mikrochim. Acta, 2, 227 (1937)
6. Kuznetsov, V.!.: Zavod. Lab., 11, 263 (1945)
7. Willard, H.H., Smith, G.M.: Ind. Eng. Chem. (Anal. Ed.), 11, 186, 269 (1939)
8. Tougarinoff, B.: Bull. Soc. Chim. Beige, 45,542 (1936)
9. Karsten, P., Kiess, H.L., Walraven, J.: Anal. Chim. Acta, 7, 355 (1952)
9a. Dozinel, C.M., Gill, H.: Chemist. Analyst., 45, 105 (1956)
9b. Pohl, H.: Metall, 12, 103 (1958)
10. Fano, V., Zanotti, L.: Microchem. J, 18, (1973), (A.A., 26, 2606) (1974)
11. Holness, H., Schoeller, W.R.: Analyst 71,217 (1946)
12. Hamaguchi, H., Jkeda, N., Ogawa, K.: Buli. Chem. Soc. Japan, 32, 656 (1959)
13. Luke, C.L.: Ind. Eng. Chem. (Anal. Ed.), 15,626 (1943)
14. Hillebrand, W.F., Lundell, G.E.F., Bright, HA., Hoffmann, J.I.: Applied Inorganic Analysis 1953
New York, Wiley and Sons
15. Martinez Lope, M.J., Maccira Vidan, A., Vidan, Marti-Burriel, F.: An Quim. 71, 84 (Anal. Abstr.,
29, 313100) (1975)
16. Musil, A., Gagliardi, H., Reischl, K.: z. Anal. Chem., 140, 342 (1953)
17. Nieuwenburg, C.J., van Lighten, J. W. .L.: Chem. Anal., 36,41 (1954)
18. Fairchild, J.G.: Ind. Eng. Chem. (Anal., Ed.), 15,625 (1943)
19. De Carvalho, R.G.: Rev. Quim. Pura e appl., 1, 24 (1950)
CHAPTER 4

VOLUMETRIC ANALYSIS

By R. Smith

The early development of volumetrie methods was largely a result of the need of
rnining assayers during the nineteenth eentury to irnprove their unseleetive and vari-
able dry assay proeedures. Lenssen [ 1] in 1859 titrated stannous solutions against
iodine in an alkaline tartrate solution, Benas [2] found that aeeurate results with the
iodirnetrie titration eould only be obtained in the absenee of air, while Borgmann [3]
claimed that iodides present in the assay solution eatalysed the oxidation of stannous
ehloride by dissolved oxygen. The aeeeptanee of the wet assay was by no means uni-
versal. Crookes [4] in his 'Seleet Methods in Chemical Analysis' published in 1871
offers no volumetrie methods for tin, whereas Parry [5] writing in 1906 reeommended
the wet assay as being more reliable than dry methods for the valuation of tin ores.
Pa"y gave six titrants for the tin assay: FeC1 3 , Acid I 2 , alkaline I 2 , KMn0 4 ,
K2 Cr 2 0 7 and ~Fe(CN)6.
Potassium iodate eame into use as a titrant following the work of Andrews [6].and
was applied to the determination of tin by Jamieson [7]. During the first half of the
twentieth eentury there were many investigations into the ehoiee of titrant, redueing
agent and deeomposition proeedure, as weil as into the effeets of other elements. As
the tin determination is now known to be a very eomplex system, many of the eonclu-
sions made during this period should be eritieally examined.
In more reeent years, Wright [8] has rationalised many of the apparently eontradie-
tory results of earlier authors. He has treated the redox equilibria involved on a quan-
titative theoretical basis. Despite this, the iodometrie tin assay remains a topie of eon-
tinual investigation and speeulation. The determination is based on an empirieal stan-
dardisation which beeomes inereasingly justified as the eomplexity of the method
beeomes understood.
Complexometrie titrations involving EDTA ( ethylenediarnine tetra aeetie aeid) have
been restrieted, hitherto, to the determination of tin in alloys and simple matriees.

1. Iodometrie Titrations

1.1 Introduetion and Basie Method

Iodometrie titration is the most widely used teehnique for the deterrnination of tin
in amounts greater than 1 %, and may easily be extended down to 0.1 %. The assay has
a number of irnportant variations, all eapable of giving poor results if applied without
eonsideration of the nature of the sample. Thesevariations in proeedure are embodied
in the main stages of the determination: (i) Prelirninary treatment-In the ease of
some ores and minerals it may be neeessary to remove irnpurities by a prelirninary
 Ref.p. 40] 1.1 Introduction and Basic Method 13

acid leach or by roasting. (ii) Decomposition and complete dissolution of the sample.
(iii) Separation of major quantities of interfering elements. (iv) Separation of minor
and trace impurities by cementation on iron powder. (v) Reduction of tin to the
stannous form, in acid solution and usually by means of a dissolving metal. (vi) Titra-
tion of tin (II) against a solution of iodine or potassium iodate, usually with a large
excess of potassium iodide in the absence of air.
Items (i) - (iii) will be treated in conjunction with specific applications in later
chapters. As a practical introduction we give below a method suitable for the deter-
mination of tin above 1 % following a sodium peroxide fusion.

C0 2 INLET

SOOml FLASK

Fig. 1 Flask (500 ml) for Nickel Reduction

Nickel Reduction Method

Fuse 1 g of sample with 1.5 g of sodium Carbonate and 5 g of sodium peroxide in a zirconium cru-
cible under a cover of 1 g of sodium peroxide. Cool, and leach with 100m! water in a 400ml beaker.
Wash out the crucible and acidify carefully with 70ml of concentrated hydrochloric acid. Finally
wash the crucible with water and inspect for complete dissolution. Add a few crystals of potassium
iodide and 3g of iron powder, heat at approximately 70°C to dissolve the iron powder but do not
boil. When the iron has almost dissolved, filter into a 500ml round flask through a small cotton
wool plug. Wash twice with hot 2% hydrochloric acid and reserve the filtrate. Transfer the plug to
the original beaker and dissolve the residue with 30 ml of concentrated hydrochloric acid and
0.5 g potassium chlorate. Heat until the precipitate is dissolved and excess chlorine has been re-
moved. Cool, add 3 g of iron powder and heat at 70°C until the iron is nearly dissolved. Filter
through a cotton wool plug into the 500ml flask containing the first filtrate. Wash six times with
hot 2% hydrochloric acid and dilute to 300m! with water. Insert a bung carrying a tube and glass
rod with a nicke! coil as shown in Fig. 1. (The coil is made from 30 cm of 2 mm diameter nicke!
rod). Boil for 60 min, and connect irnmediately to a supply of carbon dioxide and p lace in a
cooling tank. When cold remove the coil, wash with the minimum of water, add two or three mar-
ble chips and starch indicator. Titrate with N/6 potassium iodate solution to a permanent blue
colour.
Standardise by dissolving 0.4g of pure tin foil in 30m! of warm concentrated hydrochloric acid
and 2m! of 0.1% antimony trichloride solution. Add a fusionblank obtained by carrying out the
14 Volumetrie Analysis [Ref.p. 40

fusion of sodium carbonate and peroxide above in a zirconium crucible. Leach the blank with
100 ml of water then with 70ml of concentrated hydrochloric acid, and proceed through the meth-
od above.
Iodate factor (g. of Sn/rn!) Weight of Tin Standard
Titre on Standard

Tin% Titre x Factor x 100

Weight of Sampie
N/6 Potassium Iodate: Dissolve 5.998 g of dried potassium iodate and 100 g of potassiurn iodidein
water. Add 2 g of sodiurn hydroxide and dilute to 1 litre. (1 g of tin is equivalent to approxirnately
100 ml of titrant).

1.2 Removal of Impurities With Iron Powder

Iron powder removes certain impurities by cementation as metals. These include
Ag, As, Bi,Cu, Hg, Se, Sb and Te. The Separation is carried out in acid solution using
1 - 5 g of iron powder and filtering before the iron is completely dissolved. Failure to
do this results in dissolution of impurities. Heavy deposits of cementate occlude
tin and complete dissolution in hydrochloric acid and potassium chlorate, followed by
re-precipitation with more iron is necessary. Iron treatment is usually carried out after
the removal of major impurities and before the reduction stage.
It is common practice to use a mixture of equal weights of hydrogen reduced
(ferrum reductum) and electrolytic iron powders. The object of mixing is to give a
wide range of particle sizes, allowing high initial activity followed by a more pro-
longed action. The rate of dissolution depends on the level of impurities present; cop-
per coats the iron surface and slows the reaction, antimony accelerates the rate of
solution. Other authors have reported the use ofiron wire [5] and iron nails [20].
This author has encountered several poor batches of iron powder, these were contami-
nated with traces of grease which caused severe foaming and also had a high carbon
content. Surprisingly, the assays were not affected and this has led us to the conclu-
sion that the choice of iron powder is not a critical feature of the determination. Sul-
phur is often present as an impurity in iron powder and under extreme circurnstances
may precipitate tin as sulphide.
Coprecipitation of tin with cementates of copper and antimony is well-known
[ 15, 26, 33, 64] and several studies have been carried out. Traces of tinarealso pre-
cipitated by iron as Table 1 shows [61]. The results of Table 1 were obtained using
the Nickel Reduction procedure given earlier. The solution from the second iron
powder treatmentwas assayed separately; titrations were carried out using N/ 12
potassium iodate with 50g/l potassium iodide. It can be seen that appreciable
coprecipitation occurs with Ag, As, Bi, Cu and Sb. The amounts of copper tested
were small yet had a marked effect. Evans and Higgs [ 15 J showed that up to one
tenth of the tin content of an assay could be removed by coprecipitation with an
equal weight of copper during reduction with iron.
The behaviour of mi;x.tures of impurity elements during cementation is complex;
copper is removed by iron only with difficulty in "clean" solutions. This has been
attributed [61] to masking of iron by smooth deposits of copper. When antimony and
copper are present together, cementation is improved and a non-adherent deposit is
produced. Furthermore, in the presence of both elements, the occlusion of tin is very
much reduced [35]. This behaviour has been attributed to the precipitation of the
compound Cu 2 Sb and for this reason, several procedures call for the addition of an an-
timony solution before cementation.
Attempts to calculate the concentration of impurities remaining in solution using
the oxidationpotential of iron in contact with a ferrous solution have been un-
successful. The Fe 2 +/Fe couple generates a potential of- 0.46v relative to the stan-
 Ref.p. 40] 1.3 Wet Reduction 15

Table 1. Precipitation of Tin During Iron Cementation [61]

lmpurity lmpurity% Sn
added 0.5 g sample Retained
(mg) (mg)
Nil Nil 1.07
0.53
0.80
0.80
Ag 7.5 1.5 1.60
15 3 1.60
As 25 5 1.07
75 15 1.60
Bi 100 20 1.34
200 40 1.60
Cu 5 1 1.07
10 2 1.27
15 3 1.67
Sb 50 10 1.01
100 20 2.27
200 40 4.54
300 60 6.38

Table 1 showing amount of tin precipitated in first cementation with iron powder, results were
obtained by dissolving the cementate as described in the Ni reduction method, treating with
more iron powder and analysing the second flltrate for tin (0.2g tin used)

dard hydrogen electrode when dissolution of 3 g·of iron powder in 200 · 250ml of
solution is nearly complete. This potential would be sufficient to remove nearly all
the tin from the assay solution and it is more reasonable to suppose that under the
conditions of the reaction, the iron surface is occluded with cementate and gaseous
hydrogen. As a result the activity of the iron surface is considerably less than unity.

1.3 Wet Reduction

The most commonly used reductants for the tin assay are aluminium and nicke!.
Other reducing agents include: antimony, cadmium, cobalt, hypophosphite, iron, Iead
and zinc. The ideal choice should be capable of quantitatively reducing tin only to the
stannous form; stronger reducing agents affect the selectivity of the procedure by con-
verting foreign elements to interfering lower valence states. Very powerful reductants,
such as sodium borohydride [63] cause Iosses of tin by volatilisation [10] as the gaseous
hydride, stannane.
In a survey of metallic reducing agents (Table 2). Evans and Higgs [ 15] found that
only nicke! did not precipitate tin as the metal. In the case of zinc and aluminium
reductions, the precipitation of tin is an accepted feature of the method. Tin is
redissolved after addition of more acid.
(i)Aluminumis widely used as a reducing agent, although it is not mentioned in the
earlier classical works on tin assaying [5, 11, 12] presumably because of its very high
cost. Aluminium reduces tin to spongy metal; should the acid strength be too great the
solution froths and tin is easily lost by 'creeping'. The spongy tin is then dissolved be-
fore titration by boiling with more acid. Tin precipitated in the cold is reported [13,
14] to di~solve rhore rapidly than if precipitated from hot solution. Aluminium reduc-
tion has the advantages of leaving a colourless solution for titration; there is no pas-
16 Volumetrie Analysis [Ref.p. 40

Table 2. Precipitation of Tin by Common Reductants [15]

Reductant HCl Added Elements (mg) Coprecipitated

(% of conc.acid) Sn Sb Cu Sn(mg)

Lead 10 200 200 2

10 200 200 2
20 200 200 27
50 200 200 13
Iran 20 100 100 3
20 200 200 7
20 200 200 2
Nickel 20 100 100 nil
20 200 200 nil
50 200 200 nil
Zinc 10 200 100 141
10 200 200 21
Aluminium 10 200 100 125
10 200 200 162

sivation (as with iron) and the deposit does not adhere to the reductant causing erratic
action (as with zinc). Complete reduction is easily achieved and vigoraus prolonged
boiling (as with nicke!) is unnecessary. Aluminium is a powerful reducing agent, how-
ever, and many common elements which could interfere in the subsequent titration
are precipitated as metals (eg Sb, Cu) or are reduced to lower valence states. Losses by
coprecipitation are, therefore, easily possible. Under suitable conditions, aluminium
will return assays which are comparable with those obtained using nicke! [16, 17, 18]
or iron [16, 17] reduction. For the reasons given above, aluminium is preferable to
nicke! for the determination of tin in concentrations greater than 50% andin the
presence of few impurities.
Aluminium Reduction Method
Carry out the sodium peroxide fusion on 0.5 g of sample as outlined in the Nickel Reduction
method. Carry out double iron powder treatmentalso and filter into a SOOml round flask. Add
20 ml of concentrated hydrochloric add and 3 g of alumini um meta!. Fit a Göckel trap containing
saturated sodium bicarbonate solution. When the reaction ceases, add 0.5 g of aluminium and
40 ml of concentrated hydrochloric acid. When no further reaction takes place, boil to dissolve
precipitated tin. Cool, ensuring some bicarbonate is drawn into the flask, remove the trap and
titrate immediately using a starch indicator as described in the Nickel Reduction procedure.

(ii) Nickel is recommended as a reducing agent in the early literature, [5, 11, 12,31]
and is the author's personal preference for low grade or complex materia1s. The ad-
vantages of nicke! are its mild reducing action, and consistent performance. The dis-
advantages are the prolonged and vigoraus boiling required to achieve reduction, the
green colour of the resultant solution and the diminished activity of the meta! if it is
not properly cleaned and etched between assays. Nickel has been used as sheet [ 17,
19, 20, 23, 24], shot [ 15], coiled wire [ 16] or powder [21, 25] although the last men-
tioned is not recommended (see below).
Before use nicke! must be activated by etching. This is done by boiling the coil or
sheet in 1 :3 hydrochloric acid: water containing 5% sodium chloride until the lustre
of the surface is dulled. Coils or strips of nicke! sheet should be cleaned by boiling
in the above solution.
Because of its mild reducing action, nicke! would be expected to give rise to fewer
interferences than stronger reducing agents. Although nicke! does not normally reduce
 Ref.p. 40] 1.3 Wet Reduction 17

stannous solutions to metallic tin, workers in Bolivia [16, 22] have noted the precip-
itation of small quantities of tin under rather special conditions. At the high altitudes
encountered in that country, the boiling point of the assay solution is considerably
lowered. To achieve complete reduction, of stannic tin, therefore, unusually prolon-
ged boiling times must be used [22]. Any metallic tin precipitated must be redissolved
by boiling the solution with the nickel coil removed before titration.

Table 3. Reduction of 0.1g Tin on Boiling with Nickel [61]

Tin Found (rng)

Time (rnin) Ni Sheet NiCoil
5 75 79
10 91 89
15 96 93
20 99 99
25 97 99
30 101 101

Evans andHiggs [15] recommended nickel reduction in that no deposition ofme-

tallic tinwas encountered. Holness [26] found that with the greater surface area of
nickel powder amounts of 0.1 - 0.2mg tin were lost from solutions containing 10-20mg
tin. In the presence of 0.1 -.I g antimony, the loss increased to 1 - 1.5mg tin. Only
very slight retention of tinwas found [26] when nickel sheet was used. This may ex-
plain the fmdings ofSteger[157] who obtained assays of 2.44, 2.42, 2.40and 2.39% Sn
on Canadian Mineral Seiences MP-1 Zn/Sn/Cu ore using Al foil, Fe granules, Ni powder
or Pb shot respectively. The differences were said tobe statistically significant.
The time required for complete reduction using a nickel coil is recommended, in
the method given, as 60 min after boiling commences. Some laboratories prefer to
count the boiling time from the disappearance of yellow ferric ions. Results on solu-
tions containing tin only, suggest that the recommended boiling time of 60 rnin is ex-
cessive (Table 3). In practice, we have found [61] this tobe necessary.
(iii) Zinc is somewhat sirnilar to aluminium in its reducing action and deposits metallic
tin from solution. Beringerand Stephens [27] assayed tin ores by a preliminary decom-
position procedure involving reduction of cassiterite by zinc dust at red heat [5, 11].
The excess zinc remaining after fusion was used as the reducing agent during acid at-
tack of the residue. Other groups have used: 20 mesh zinc [28], zinc rods [14], zinc
amalgam [29] and zinc tumings [30].
Zinc appears to suffer from the disadvantage that the surface becomes covered with
tin sponge which prevents further reduction [14, 30].
In modern practice, aluminium has largely replaced zinc as a reducing agent, except
in those instance where a dry reduction of cassiterite is frrst carried out using zinc pow-
der.
(iv) Lead was used by Powell [32] as a reductant and has proved popular with other
writers [18, 33- 36]. Theoretically, lead is the mildest of the common effective agents.
18 Volumetrie Analysis [Ref.p. 40

The standard oxidation potentials [37] of several metals in contact with normal solu-
tions are:
Eo volts
- 0.126
-0.250
-0.440
-0.763
- 1.66
Lead causes no reduction to spongy tin, nevertheless in the presence of antimony
or copper severe coprecitipation of tin is said to occur [15]. Soviet workers [36] have sug-
gested that tin is volatilised as the chloride during reduction with lead and recommend
the use of alumini um. The precipitation of lead chloride on cooling has not been men-
tioned by the advocates ofthe method.Evans [34] and Clarke [35] found that the
theoretical factor could be obtained if air was excluded from both the reduction and
the titrant. Usually the theoretical factor (i.e. that obtained by standardisation against
a titrant such as arsenious oxide) is not obtained and tin is used as a standard; granu-
lar or strip (30 cm x 2.5 cm) lead may be used.
Lead Reduction Method
Carry out the sodium peroxide fusion on 0.5 - 1 g of sample as outlined in the Nickel Reduction.
Cool the crucible, leach with 20m! of water, then wash out with 125 ml of concentrated hydro-
chloric acid. Carry out the iron powder treatment as described previously, fJ.lter into a 500ml
round flask and dilute to approxirnately 250m!. Add 15 g of granulated Iead or a strip of foil
(30cm x 2.5cm), heat to boiling and continue for a period of 45 min after the disappearance of
the yellow chloroferrate ion. Cool under an atmosphere of carbon dioxide. When cold, add starch
indicator solution and titrate immediately and rapidly as described before.
( v)Iron is reported to give quantitative reduction oftin, quiet liberation ofhydrogen
and does not precipitate tin from solution [38 - 40]. In practice, small quantities of
tin can be precipitated by iron powder [61], and appreciable quantities are coprecipi-
tated in the presence of copper [ 15]. lron is easily passivated and is not easily cleaned.
( vi)Antimony is not commonly used as a reductant despite the many accounts in the
literatme [15, 25, 41 - 44, 72]. lt is a milder reducing agent than lead as the oxidation
potentials [37] show:
Sn 2+/Sn4 + E =+ 0.151 + 0.0295log (Sn4 +/Sn 2 +)
Pb/Pb 2 + E =- 0.126 + 0.295log (Pb 2 +)
Sb/SbO+ E =+ 0.212- 0.0394pH + 0.0197log (SbO+)
From these equations it can be seen that antimony will act as a reducing agent for
tin only under suitable conditions. Millerand Currie [42] found that sticks of antimony
were satisfactory but required cleaning and recasting between determinations. Evans
and Higgs [ 15] found that the reducing power of antimony varied with particle size
and that accurate results could only be obtained with particles of 0.02- 0.04mm di-
ameter. Sieving gave incorrect particle sizing and water elutriation was used to sepa-
rate size fractions.
( vii) Cobalt has also been suggested [ 15] as a metallic reductant, but appears to offer no
advantages. Bismuth amalgam [78] reduction requires a temperature of 45°C in 5 - 12M
hydrochloric acid with shaking. Under these conditions, reduction is complete in .only
10 min.
( viii)Evans [45,46] found Sodium Hypophosphitetobe a convenient reducing agent
for tin. Complete reduction is obtained on boiling a 50% hydrochloric acid solution
in the presence of a mercuric chloride catalyst. When the solution is diluted with five
times its own volume of air-free water, the acid strength diminishes to a point where
 Ref.p. 40] 1.4 Effect of Air on Stannous Salutions 19

the excess hypophosphite does not interfere with the titration. Iron and copper have
tobe separated and nitric acid must be absent. The interference of antimony is
eliminated by addition of potassium iodide just before titration. Interference from
fluoride [47] could be avoided by. the addition of either sodium tetraborate or boric
acid. Tungstate and iodide were also reported [47] as interfering anions. Applications
of the hypophosphite reduction have been published for the analysis of non-ferrous
alloys [48, 51, 52, 55]; steels, irons and iron ore [54] and tin ores [49, 50]. Deter-
minations have been carried out [55] of as little as 0.002% Sn, titrating against
0.005N KI0 3 . Hypophosphite reduction has been suggested [56] as a satisfactory way
of overcoming copper interference in the conventional tin assay. In all the procedures
·mentioned mercuric chloride has been used as a catalyst; the titration is usually car-
ried out after the addition of both potassium iodide and pcitassium thiocyanate.
Pourbaix [37] claims that Cu, Ni, Pd and powdered graphite also act as catalysts for
the oxidation of hypophosphite. The use of orthophosphite as a reducing agent has
also been reported [57].

Hypophosphite Reduction Method

Carry out a fusion on 0.5 g of sample as described in the Nickel Reduction method. Leach the
sample with 50ml of water and wash the crucible with 70ml of concentrated hydrochloric acid
and carry out the iron powder treatment described. To the round flask containing the flltrate add
1 ml of saturated mercuric chloride solution, 5 g of sodium hypophosphite and 2 g of tartaric acid.
Boi!, then simmer gently for 5-6 min, fit a Gockeltrap and cool. Add lg of potassium iodide,
starch indicator and titrate with 0.1 N iodine solution. The end-point is quite clear but the blue
colour of the starch solution may fade after a few seconds.

(ix) The necessity for wet reduction may be avoided if a metal sample is being analysed
Hourigan [57] andNechamkin [128] dissolved tin/lead alloys in boiling concentrated
hydi:ochloric acid under carbon dioxide and titrated directly with potassium iodate.

1.4 Effect of Air on Stannous Solutions

In 1884, Benas [2] discovered that dissolved air oxidises stannous solutions and
seriously affects the accuracy of the tin titration. lt is now accepted practice, that
immediately after reduction with a metal, the assay solution should be allowed to
cool under an inert atmosphere (usually carbon dioxide). The inert atmosphere may
be maintained during the titration by the addition of marble chips:

Rubber -"
\ I
NaHC0 3
Seal
Soln.

Fig. 2 Göckel-Contat traps

The atmosphere of carbon dioxide is provided in a nurober ofways. A cylinder,

reduction valve and lute allowing about 30cm water pressure is convenient for a batch
of up to 40 assays. The gas may be used to occupy the headspace of the reduction
20 Volumetrie Analysis (Ref.p. 40

flask (see Fig. 1) or can be bubbled through the solution. Solid carbon dioxide (9]
(approximately 8cm3) is a suitable alternative to gaseaus co2.
Provision of an inert atmosphere during cooling by the addition of sodium bicar-
bonate or marble chips is cautioned as these reduce the acid strength and may allow
tin to precipitate. The presence of ferric iron impurities in marble chips may cause
significant errors, particularly if added to a hot solution. A popular and convenient
alternative to gaseaus carbon dioxide is the Göckel trap [76] shown in Fig. 2. This is
filled with saturated sodium bicarbonate solution. During reduction, steam is expelled
through the trapo On cooling, bicarbonate solution is drawn into the reduction flask,
co2 is generated and maintains a positive pressureo
Okell and Lumsden [59] have contributed the mostdefinitive work on the subject
of air interference and Iist the following measures as being effective in overcoming
this:
(i) Reduction of the acid concentrations [28]0 (ii) Reduction of the iodide concentration as iodide
was thought to catalyse the reaction between oxygen and stannous chloride [3]0 (iii) Addition of
a catalytic inhibitor, usually antimony [60] o(iv) Prevention of air ingress to the titration flasko
(v) Addition of excess titrant and back-titrationo
Most of these measures advocated in the early Iiterature are undesirableo Acid con-
centrations should be kept at 2 - 4 M hydrochloric acid for nickel and aluminium reduc-
tions to prevent tin hydrolysis and to maintain an active reductiono Low iodide con-
centrations are to be avoided at all costs as under these conditions iodate and iodine
titrants are strongly oxidising and may titrate impurity elementso Backtitration is also
undesirable in that traces of precipitated metals such as arsenic or antimony may dis-
solve in the excess titrant and score as tin, alternatively thesemetals can be slowly
oxidised by stannic salts and will again give high results [57] 0

3SnC14 + 2Sb ~ 3SnC12 + 2SbC1 3

A rapid conventional titration is, therefore, commonly used to minimise the dissolu-
tion of precipitated metals.

Table 40 Nickel Reduction Method-Showing Effect of Air on Stannous Solutions [61]

Theoreticala Cooled Cooled Cooled in b

Titre inair inC02 co2 +CaC03
(ml) (ml) (ml) (ml)

0.4 g tin meta!

standard 39090 38o90 39079 39o91
a Obtained by calculation
b CaC0 3 added as Marble Chips before titration
All results are the average of three titrations

The only successful way to eliminate the effect of air on the tin assay is by cooling
and titrating under an atmosphere of carbon dioxideo Same analysts obtain good re-
sults by cooling under air, however, this approach relies on proportionate oxidation of
both standards and unknownso Titrations obtained on pure tin Standards, reduced by
nickel, are listed above (Table 4) and indicate the importance of a C0 2 purge [61] 0
 Ref.p. 40] 1.5 lodine and Iodate Titrants 21

Okell and Lumsden [59] took note of the oxygen dissolved in the titrant. Titrating
0.1 g of tin against iodirre of different strengths they found appreciable differences
from the theoretical titre with dilute iodirre solutions. When dissolved oxygen was
removed from the most dilute titrant, theoretical titres were found. (see Table 5)

Table 5. Effect of Dissolved Air in Titrant Solution [59]

lodine Theoretical Actual Error

Titrant Titre (ml) Titre (ml) %

N/5 8.42 8.41 -0.1

N/10 16.85 16.81 -0.2
N/20 33.70 33.28 - 1.3
N/40 67.40 65.04 - 3.6

1.5 Iodirre and Iodate Titrants

Both iodine and potassium iodate are widely used as titrants for the oxidation of
stannous solutions:

3SnC1 2 + K10 3 + 6HC1 3SnC14 + K1 + 3H 2 0 (i)

+ 2HC1 SnC1 4 + 2HI (ii)

and at the end point:

K10 3 + SKI + 6HC1 = 31 2 + 6KC1 + 3H 2 0 (iii)

With both titrants the end-point is the appearance of free iodine and is easily de-
tected with a starch indicator. The use of iodine is traditional and dates from the nine-
teenth century [1 - 3, 5, 11] whereas the use of ioda te has followed from the later
work of Andrews [6] and Jamieson [7]. It is very important that the titrant or assay
solution should contain a !arge excess of iodide. If this precaution is not taken, the
oxidising power of the titrant becomes so great that interfering substances are ti-
trated.
Formost work, iodirre or iodate strengths of N/5 or N/10 are commonly used. Rou-
tine assay laboratories frequently use N/6 titrants for which 1 gram of tin is approx-
imately equivalent to 100m!. Successful titrations with N/100 iodirre or iodate have
been reported [45, 59]; this author has found N/60 iodatetobe satisfactory for the
determination of 1 - 20mg of tin.
Fig. 3 shows the stability domains of iodine in aqueous solution at 25°C, calculated
[37] from electrochemical oxidation potentials. The solid lines indicate the potential
of equimolar solutions, the broken lines indicate the potentials for decomposition of
water to hydrogen or oxygen. For example, a solution of O.SM K1 and O.SM K.l0 3 at
pH 12 will be represented by point a in Fig. 3 and will have a potential of approxima-
tely + 0.4 volt (relative to the standardhydrogen electrode). lt can be seen from Fig. 3
that in alkaline solutions, iodate and iodide ions are stable in the presence of one an-
22 Volumetrie Analysis (Ref.p. 40

E
(volts) HI04

1.0

0 1-

-1.0

-2 0 2 4 6 8 10 12
pH

Fig. 3 Potential - pH equilibrium diagram for the system iodine waterat 25° C for solutions
containing 1 g atom 1/litre. Dotted Jines show potentials for evolution of gaseaus oxygen and
hydrogen. (FromM. Pourbaix, Ref. (37] p. 621)

other. Alkaline iodine solutions are unstable and disproportionate to iodate and iodide
ions:

31 2 + 6KOH =KI0 3 + SKI + 3H 2 0 (iv)

Conversely, in acid solutions, Fig. 3 shows that the reaction in equation (iii) takes
place and that iodine is the stable species. Titrants based on iodine are, therefore,
equivalent to standard iodate solutions provided both contain a large excess of iodide.
The two titrants differ only in their acidity.
The advantage of iodate titrants is their superior stability. Kolb [80] found that
potassium iodate solutions could be stored for periods of over one year without a
change in normality. Our experience [61] is that iodate/iodide solutions in constant
use decrease steadily in normality and must be standardised daily.
Other iodine species are present in the acid assay solution particularly the tri-iodide
ion 13. The equilibria involved in the titration are:

E = + 0.621 + 0.0295log {hl_ (v)

(02
E = + 0.536 + 0.0295log (13) (vi)
(03
Under the conditions of the tin titration, the reaction with both titrants may be looked
upon as:
(vii)
 Ref.p. 40] 1.6 End-Point Detection 23

1.6 End-Point Detection

The use of starch as an indicator is almost universal for the tin(II) titration. Kalthoff
and Beleher [67] state that concentrations of iodine of 2-10 x 10-s N are sufficient to
give a blue colour with starch in 0.002N potassiurn iodide. In a 200rnl solution this
is equivalent to an end-point error of 0.04rnl with a 0.1 N iodine titrant. The indicator
sensitivity is reduced with iodide contents lower than 0.002N but is not increased
substantially on increasing the arnount of iodide. Sirnilarly, ions which form strong
cornplexes or insoluble cornpounds with iodide ( e.g. rnercury or copper) reduce the
sensitivity of the indicator. The sensitivity of the end-point is further decreased if
warm solutions are used [67] and with solutions of over 70°C the end-point is a
dirty green. Under these conditions the end-point error with 0.1 N iodirre solution
is greater than 1rnl. In acid solutions, starch will detect [67] 2 x 10-s N free iodine.
This, therefore, allows us to calculate the potential of the I 2 Jr couple for the end-
poirrt conditions [8] using equation (v) and hence calculate the equilibriurn con-
centrations of stannic and stannous ions. Furthermore, it is also possible to rnake
calculations of the equilibriurn concentrations of interfering species (see Table 6).
This clearly shows the irnportance of iodide in determining the selectivity of the
titration. Iron is present in rnany assays frorn the crucible, sarnple and frorn the iron
powder cernentation. In the exarnple given in Table 6, in 0.01 M iodide solution,
log 10 (Fe 3 •;Fe 2 ) = · 2.89 or Fe 3 •;Fe 2 • = 1.3 x 10- 3 . Therefore, if lOg of iron are
present, 13rng Fe will be titrated to Fe 3 • and will score as tin. This calculation is ap-
proxirnate in that no allowance is made for stabilisation of the ferric state by complex
formation of the type FeC1 4 -,Fe CI~-. The stabilisation of the upper valence state in-
creases the iron interference beyond that calculated in Table 6.
Where very low titres are involved, it is obviously not sufficient, to incorporate an
excess of iodide in the titrant. Potassiurn iodide should be added to the assay solution
before reduction.
Starch has sorne disadvantages as an indicator for iodornetric titrations; its insol-
ubility in cold water, the instability of aqueous dispersions, and the insolubility of
the starch iodine cornplex. The last necessitates the addition of starch solutions irn-
rnediately before the end-point. Kalthoffand Beleher [67] have authoritatively re-
viewed the use of starch as an indicator and recornrnend the following preparation:
Prepare a paste by rubbing 2g of starch with lOmg of mercuric iodidein 30m! of water. Add the
paste to 1 litre of boiling water and continue heating until a clear solution is obtained. The mer-
curic iodide acts as a preservative, and should remain stable for long periods if stored in a stop-
pered bottle. The production of a reddish colour with iodine is an indication that the starch solu-
tion has deteriorated and needs replacing.

Table 6. Equilibrium Concentrations of Va!ence States at End Point of the Tin Titration

Iodide Concentration I- 1M O.lM O.OlM O.OOlM O.OOOlM

Redox Potential E volts +0.482 +0.541 +0.600 +0.659 +0.715
Jogi o(Sn4+/Sn2+) 11.22 13.22 15.22 17.22 19.22
log 1 o<Fe*/Fe2+) -4.89 . 3.89 -2.89 . 1.89 -0.89

Dry preparations of starch which rnay be sprinkled into the titrated solution are popu-
lar and are soldunder various trade narnes. This author uses such an indicator, which
is a reaction product of urea and starch. This is very convenient in use and is added at
24 Volumetrie Analysis [Ref.p.40

the beginning of the titration. Starch/urea indicators may be made by the method of
Clarke [ 126] who refluxed starch and urea (1 : 19) with xylene; the urea melts but
does not decompose. On cooling the residue is ground. On adding to titration solu-
tions, the urea dissolves leaving a finely powdered suspension of starch.
Immiscible organic liquids, such as chloroform or carbon tetrachloride are coloured
violet by traces of free iodine produced at the end-point and have long been used as
indicators. Organic liquids are said [67] tobemoresensitive than starch as indicators
and are preferable for strong acid solutions. Practically, however, immiscible solvents
are inconvenient in use and must be shaken vigorously after each addition of titrant.
This outweighs any marginal advantages gained by better sensitivity. Stoppered titra-
tion flasks must be used to eliminate the introduction of air during shaking.
Electrometric end-point indication has not been widely used. Swinehart [ 127] re-
ported an amperometric titration using two polarised platinum electrodes with an
applied potential of 50mV. Before the end-point, the applied potential is insufficient
to cause any electrode reaction. At the end-point free iodine is present in solution,
depolarisation of the cathode occurs and a current passes as a result of the electrode
processes:
I 2 + 2e--+ 2r (cathode)
21" -+ I2 + 2e- (anode)
The end-point is, therefore, signalled by a sharp rise in current.
Sandved [14] used a potentiometric titration for the determination oftin with po-
tassium bromate. The indicator electrode was a 19 sq cm piece of platinum foil with a
N calomel reference. The presence of !arge amounts of ferrous iron in solution serious-
ly decreased the sensitivity in the region of the point of inflection in the plotted titra-
tion curve. Basinka and Rychcik [96] used a similar potentiometric system for the
titration of tin with potassium ferricyanide.

1. 7 Standardisation
The tin assay is unusual in that the "theoretical" normality for the titrant should
not be used. The "theoretical" normality isthat obtained by standardisation against
arsenious oxide. Oxygen dissolved in the titrant is the main reason for differences
in normality when standardising against tin as opposed to arsenious oxide. lf the
titrant is purged with carbon dioxide or if a back·titration is employed, theoretical
normalities may be approached. In addition to the problern of dissolved oxygen
there is also the probability of slight Iosses of tin during cementation with iron pow-
der, particularly if the recommended procedure is abbreviated and the cementate is
not dissolved and re-precipitated. Furthermore, if insufficient iodide is present, a
small overtitration will arise from the oxidation of ferrous iron.
In view of these uncertainities, it is particularly important that standardisation
should be as closely controlled as possible. The following observations [61] were made
made with standards of pure tin taken through the nicke! reduction method given
earlier ( see Table 7).
a) Weight of Tin Standard. When different weights of tin are used for standardisa-
tion, quite different iodate factors are obtained. A plot of titre against weight of
standard gives a straight line which does not pass through the origin. In other words,
there is a titration blank of approximately 0.3 ml in the absence of tin. The blank
arises partly from the amount of titrant required to change the indicator (0.03 -
 Ref.p .40] 1. 7 Standardisation 25

0.05 ml) and also from the titration of ferrous iron as predicted in Table 6. The blank
is insignificantly small when !arge amounts of iron are absent.
For example, if we were to assay three samples and obtained titres of 30,50 and
70ml it would be possible to obtain wide differences of tin content depending on the
standard used (Table 8). The factors obtained experimentally in Table 7 were used to
calculate Table 8. The "correct" results in Table 8 are obviously 30.40%, 50.27% and
70.55%. In practice, titres of standard and unknown are matched fairly closely by
selecting appropriate sample weights. Other analysts prefer to deduct a small blank
from the titres of standards and unknowns before carrying out calculations. If a blank
of 0.3 ml were deducted from both the standardisation titrations of Table 7 and the
titratious of Table 8, then the determined tin contents would all be within 0.05% Sn
of the "correct" results. The result would then be independant of the weight of
"standard used.

Table 7. Effect of Weight of Tin Standard on Standardisation of Iodate Solution [61]

Tin Standard Titre a Factor Mean

Weight (g) (ml) (g/lOOml) Factor
""

0.2924 29.20 1.0014 1.0014

0.3034 30.30 1.0013
0.4900 48.80 1.0041 1.0054
0.5023 49.90 1.0066
0.7095 70.37 1.0082 1.0083
0.7144 70.85 1.0083

aApproximately N/6 iodate used

Table 8. Effect of Weight of Tin Standard on Assay Results

Assay %Tin Found
Titre
ml 0.3g Standard 0"5 g Standard 0.7g Standard
30"0 30.04 30.16 30.23
50.0 50.07 50.27 50.40
70.0 70"10 70.38 70.55

The factors obtained in Table 7 on 0.3g, 0.5g and 0.7g standards were used in this Table to
calculate the results of three titrations" Approximately N/6 iodate used

b) Effect of Iran Powder in Standards. The small titration blank discussed above is
practically absent when iron is omitted from the determination [61 ]. Needless to say,
the iron used in the study was proved spectrographically to be free from tin. When
varying additions of iron were made to a 0.4 g pure tin standard the following iodate
factors were obtained (Table 9). The effect on a 30.0ml titre of an unlc'l.own with no
iron is shown in the third column. Serious errors are unlikely if standards and unknowns
have approximately the same iron content (i.e. to within 2g).
26 Volumetrie Analysis [Ref.p. 40

Table 9. Effect of Iron Additions to Tin Standards [61]

Added Factor % TinPound

Iron g/100ml 30.0 ml.titre
0 1.0122 30.37
2.0 1.0091 30.27
4.0 1.0086 30.26
6.0 1.0062 30.18
8.0 1.0040 30.12
(Approximately N/6 iodate used)

c) Choice of Standard. Tin metal is almost universally used as a standard. Donald-

son et al [68) recommend the use of tin(II) acetate purified by vacuum sublimation.
This may be dissolved in acid in the absence of air and titrated directly. As can be seen
from the foregoing discussion, this would successfully standardise the titrant but is
unlikely to standardise the whole procedure. Kallmann [20] advocates the use of a
standard tin concentrate available from the National Bureau of Standards. This has the
advantage that standardisation follows exactly the same procedure as is used for the
unknown.

1.8 lnterferences
The rationalisation of Observations on interfering substances is a difficult task.
Studies reported in the Iiterature refer to different experimental conditions and for
this reason an element which interferes in one determination may not interfere with
another. The main factors goveming the magnitude of interference effects in the iodo-
rrietric tin assay with either iodine or iodate titrants are:
(i) The choice of reducing agent; which determines the degree of reduction of the foreign element
and the valence state to which it is reduced. (ü) The oxidising power of the titrant; determined by
the iodide content of the final solution. (üi) The rate of titration; slow titrations encourage in-
terference by dissolution of precipitated metals. It is common practice to titrate very rapidly until
the last few drops. This also minimises the ingress of atmospheric oxygen. (iv) The acid strength
of the solution; this is known to affect the magnitude of the iron interference for example. (v)
Multi-element effects; interferences are not additive. For example, copper precipitates tin seriously
during the iron cementation; this can be minimised by the addition of antimony.
(i) Antimony
Antimony is likely to be present in tin-bearing secondary materials up to about 30%
and is a constituent of some minerals such as frankeite. Additions of antimony are
made in many methods to aid dissolution oftin standards, to encourage cementation
of copper with iron powder and to reduce tin to the stannous form.
High concentrations of antimony ( over 1OOmg) will occlude tin during the cemen-
tation with iron powder (see Table 1), and a second iron treatment on a solution of
the deposit is neccessary [ 15, 64) (See Nickel Reduction Method). Jarvinen [64] has
carried out a definitive study of cementation with iron and has found that precipitated
antimony redissolves in the absence of iron powder. Care should, therefore, be taken
to maintain an excess of undissolved iron during flltration.
The usual reductants: iron [15, 64), nickel [15, 21], aluminium [15, 57, 64), zinc
[15] and Iead [15, 35) precipitate antimony metal if this escapes removal by iron pow-
der. In the case of nickel coil reduction, small amounts of antimony blacken the coil
and may reduce its activity. Larger amounts of antimony may break off the coil and
be carried through to the titration. Under these conditions, high results will be
obtained by the reaction [57]:

2Sb + 3SnC14 =3SnCl 2 + 2SbCh (viii)

 Ref.p. 40] 1.8 lnterferences 27

Antimony interference in this way may be avoided by rapid titration. With aluminium
or zinc reduction, antimony is precipitated and traces are volatilised as highly toxic
stibine.
Provided proper care is taken With the iron cementation, antimony contents of l 0%
or less cause no problems [74, 61].
(ii) Arsenic
Arsenic is quantitatively removed by iron powder or is lost as the volatile trichloride
on gently boiling the assay solution. With zinc or aluminium reduction, gaseous arsine
will be generated. Needless to say, all work with hot hydrochloric acid solutions should
be carried out in fume cupboards. Losses of tin may occur if strong HCl solutions are
boiled vigorously to remove arsenic.
With ores having arsenic contents of over a few percent, removal by roasting at
500 - 700°C for 30 min has been recommended [73]. The author's experience is that
quantities of arsenic up to 15%, either with tin or in admixture with other metals
such as copper, present no problems.
(iii) Bismuth
Bismuthis similar to arsenic and antimony in that it is reduced to metal by iron pow-
der and removed by this treatment. Occlusion of tin in the cementate isslight [61, 74].
Bismuth which escapes the iron powder treatment is reduced to meta! and may be
titrated to give high results. In the case of nicke! coils, the deposit is adherent and is
removed with the coil; some deactivation of the coil may take place. Bismuth deposit-
ed by aluminium or zinc is unlikely to be redissolved with tin and will tend to give
erratic results.
(iv) Chromium
Chromium has been the subject of conflicting reports and it would appear that its in-
terference depends on the method of reduction. No interference has been found in the
reductions with nicke! [61], Iead [12], iron [72) or hypophosphite [54]. Amounts of
less than 0.5% chromium present with 2- 20% tin required removal when aluminium
reduction was used [62, 67]. This was carried out by precipitation ofthe tin as sulphi-
de.
It is worth noting that a standard preparation of chromium(II) solutions involves
reduction of chromic salts by zinc or zinc amalgam [71] under an inert atmosphere.
The reduction is carried out in acid solution to give blue chromaus solutions which
are easily oxidised by air.
(v) Cobalt
No reports can be found of cobalt interference in any variation of the iodometric titra-
tion. Cobalt(II) solutions are stable at all oxidation potentials likely tobe encountered
in the tin assay provided strongly complexing species are absent. Cobalt chloride is
sometimes added [28] in the alumini um reduction method to speed the dissolution of
precipitated tin sponge. Cobalt metal has been studied [15] as a reductant for tin.
(vi) Copper
Copper interferes with many stages of the determination and should be removed by
precipitation of tin with a ferric hydroxide carrier in ammoniacal solution. The blue
filtrate is rejected. This should be carried out if the copper content of the sample ex-
ceeds 2- 3% with a lg assay and is normally done if the hydrochloric acid solution of
the sample is very pale blue. With copper contents greater than 10%, the precipitate
of tin and iron hydroxides should be dissolved in acid and reprecipitated with arnmo-
nia.
28 Volumetrie Analysis [Ref.p. 40

Smaller amounts of copper are removed by cementation with iron powder but even
this is not always straightforward. When copper only is present as an impurity, an
adherent deposit is produced which slows or almost stops the iron dissolution [61 ].
Under these conditions, copper may be carried through to the titration. Coprecipi·
tation of tin is also more serious with copper than with any other meta! during the
iron cementation. To overcome both effects, antimony is added to the assay solution
before treatment with iron powder.
Copper, which is carried through to the reduction and titration may behave erratic-
ally. In the nicke! reduction, no interference occurs unless the copper forms a protec-
tive layer round the nicke! coil and reduces its activity. Occlusion of tin does not take
place with a nicke! coil [ 15]. With the Iead, zinc or aluminium reductions, occlusion
of tin by precipitated copper is appreciable [ 15]. Cupric ions which escape reduction
precipitate cuprous iodide on titration. This liberates iodine which in turn is consumed
by tin leading to low results [12].
Copper may be removed from most samples by the following separation: Dissalve 1 g of sample
by fusion as described in the Nickel Reduction method. Add 10m! of 10% ferric ammonium
sulphate and 1 g of potassium chlorate. Boi! for 10 min, cool and add ammonium hydroxide until
cupric hydroxide dissolves to the deep blue cuprammonium ion. Heat to boiling, filter hot and
wash twice with hot 2% ammonium hydroxide. Dissolve the precipitate in 90ml of concentrated
hydrochloric acid and continue with the method by adding potassium iodide and iron powder.

(vii) Fluorine
Fluorides form complexes with tin but do not interfere even up to 40%F in the deter-
mination described [61]. When an ammonia precipitation is carried out to remove
copper, no interference is encountered from fluoride, provided a !arge excess of ferric
iron is present to preferentially mask fluoride. Fluoride retards the reduction with
hypophosphite [47] but may be masked by the addition of sodium tetraborate or
boric acid.
( viii) Germanium
Germanium does not interfere if Iead is used as a reductant as it is precipitated as an
insoluble compound [67]. However, the precipitation is not quantitative with iron
reduction and a positive interference may be obtained [12].
(ix)Iron
Iron does not interfere in any quantity when present in a 1 g sample provided a suffi-
cient excess of iodide is present for the titration. Large amounts of iron introduced as
carriers in the copper removal, as iron powder or as impurities from fusion in an iron
pot may cause a slight positive interference. The subject of iron interference is dealt
with in detail in the section dealing with standardisation. Ferric impurities added to
the reduced tin solution with marble chips oxidise tin(II) quantitatively and Iead to
low results for both standards and unknowns. The errors need not necessarily be com-
pensating.
(x)Lead
Lead does not interfere with the tin determination when present up to 90% of a 1g
sample. Greene [ 19i claims that Iead interferes in the presence of high quantities of
sulphur in low grade ores - this is not the experience of this author [61].
(xi) Manganese
As many workers [75] have used coprecipitation of tin with a manganese dioxide car-
rier, which is later dissolved and taken through the assay procedure, it is unlikely that
manganese will interfere.
 Ref.p. 40] 1.8 Interferences 29

(xii) Mercury
No reports can be found of mercury interference, however, it is likely tobe lost in
fusion or will be removed in the iron separation.
(xüi) Molybdenum
Molybdenum has been the subject of several contradictory reports. Provided Mo is
first oxidised with H 2 0 2 , interference was found only in the presence of very large
Mo excesses. In this case (72] iron was used as the reductant. In ore analysis, the levels
of Mo normally present caused no interference after iron, nickel or aluminium reduc-
tion [74]. Nevertheless, Greene (19] found that with the nickel reduction, 25mgMo0 3
and 22mgSn gave a titration equvalent to 6I mgSn. Kalimann (20] noted the contra-
dictions of published work and clairned that Mo gave high results.
De Carvalho [70] carried out a detailed study of the interference of Mo with the
aluminium reduction and found a positive interference, with Mo0 3 less than one
third of the tin content, but at greater Mo0 3 concentrations the interference became
negative. The interference ranged from + I% to- 30% of the tin content. When the
same experiment was carried out with a single iron cementation (using I. 7 g of "fer-
rum reductum") before reduction with alurninium no interference was encountered.
The author [70] concluded that the interference was suppressed by ferrous ions pres-
ent in the solution and it is worth noting that other authors carrying out assays in the
presence of iron have found no interference from molybdenum [ I9, 20, 75].
(xiv) Nickel
Nickel does not interfere in the tin assay in any way.
(xv) Nitrates, Nitrites
Nitratesandnitrites interfere seriously by oxidising iodide to iodirre [67]. They are
removed by carrying out a precipitation of tin with ammonia and ferric hydroxide
(see Interferences - Copper).
(xvi) Niobium
De Carvalho (69] studied the interference ofniobium on the aluminium reduction fol-
lowing a report by van Tongeren (77] that niobium caused some interference. He (69]
concluded that some reduction of Nb(V) to Nb(IV) took place; with 0.5 g Sn0 2 and
0.2g Nb 2 0'5 an error equivalent to +2mg Sn was found. With very high niobium con-
centrations a pale blue colour is sometimes obtained [69 J. Niobium may be separated
by the same procedure as that recommended for tantalum.

(xvii) Phosphates
Phosphorus does not normally cause interference as hypophosphite has been advocated
as a reducing agent for tin. However in the assay of low grade ores containing both
phosphorus and sulphur, Greene (19] encountered a positive interference. The inter-
ference only occurred with high sulphide ores following a fusion with sodium peroxide.
No other reports can be found of this remarkable observation.
(xviii) Selenium
Selenium is removed as the metal in the treatment with iron powder.

(xix) Silver
Silver has been found to interfere [6I] only insofar as it coprecipitates tin during the
iron cementation (I5 mg Ag will precipitate approximately I mg Sn from an assay can-
tairring I50mg Sn). Silver also retards the dissoiution of iron powder. Filtration of
the AgCl precipitate is usually advisable before cementation.
30 Volumetrie Analysis (Ref.p. 40

(xx) Sulphur
Sulphide present in tin ores has been found (61] to give rise to an undesirably vigoraus
reaction with sodium permöde during fusion. This can easily be overcome by fusing
first with sodium hydroxide, then adding sodium peroxide. Altematively sulphur may
be oxidised by roasting before analysis [19] at a low temperature. High temperature
roasting to remove sulphur may encourage Iosses of tin by volatilisation.
(xxi) Tantalum
De Carvalho [69] has investigated the interference oftantalum with the aluminium
reduction method in some detail. After reduction a milky precipitate of tantalic acid
was observed which absorbed some tin from solution. With 0.5 g Sn0 2 · and 0.2g Ta 2 0 5
the loss was only 0.3mg Sn and isnegligible for most purposes. A removal can be car-
ried out by the method [69] below for high grade cassiterite ores.
Fuse 0.5- l.Og oftin ore with 5- 8g ofpotassium pyrosulphate (K2S20 7 ). Cool then warm with 25 ml
of 25% tartaric acid and wash with 80 ml of hot water containing 5 ml of concentrated sulphuric acid.
Precipitate tin present in the flltrate by addition of saturated hydrogen sulphide solution. Filter, ignite
the residue in an iron or zirconium crucible then fuse with 5 g of sodium p eroxide and confmue with
the Aluminium Reduction method.

(xxii) Tellurium
Tellurium is removed as the metal by cementation with iron powder.
(xxiü) Titanium
Titanium is one of the most thoroughly studied interferences in the tin assay. With
aluminium reduction titanium, added asTiCh, was found [59] to react with air in the
titrant leading to slightly high results. This was overcome using an air-free titrant or
by adding a small amount of TiC1 3 solution to standards and unknowns. This latter
practice has been advocated [62, 63] in the analysis ofzirconium alloys with aluminium
reduction.
No interference has been found with nickel [61 ], iron [72] or sodium hypophosphi-
te [55] reductions.
The use of an insufficient excess of KI in the titrant will result in titration of tita-
nium and the addition of 2g KI to the assay after reduction has been recomrnended
[55].
(xxiv) Thallium
No reports are available on the effects of thallium. Examination of oxidation poten-
tials [37] suggests that vigoraus reductants (such as zinc or aluminium) would precip-
itate thallium metal and that this could react with the titrant giving high results.
(xxv) Tungsten
Tungsten is reduced by most of the comrnon reductants to blue tungsten oxide. This
appears as an intense coloration which may obscure the starch end-point. Our expe-
rience [61] isthat with a nickel reduction in approximately 3M HCI, approximately
5% wo3 may be tolerated with a 1g assay and that with 10% wo3 the end-point can
be detected only with great difficulty. Tungsten does not otherwise interfere with the
nickel reduction assay [12, 20, 24, 61, 67, 74]. However, Greene [19] found ~at when
W0 3 was present at several times greater than the tin concentration, very high errors
were obtained.
Tungsten is traditionally removed from high grade tin ores by an evaporation with
HN0 3 followed by leaching with dilute ammonia. Alternatively, precipitation of tin
with ferric hydroxide and amrnonia, leaves tungsten in the flltrate tobe discarded.
The interferences of heteropolytungstates e.g. arsenotungstates or phosphotungstates
have not been reported in the Iiterature reviewed.
 Ref.p. 40] 2.1 Potassium Bromate and Related Compounds 31

(xxvi) Uranium
No references can be found on the effects of uranium in the tin assay.
(xxvii) Vanadium
Vanadium gives a positive interference in the tin assay [12, 20, 24, 72, 74], and is not
removed by cementation with iron. Most metallic reductants will reduce vanadate or
vanadyl ions in acid solution to vanadous (III) ions which consume iodine during the
titration. Vanadium may be successfully removed as soluble ammonium vanadate when
tin is precipitated with ammonia and ferric hydroxide.
(xxviii) Zinc
Zinc does not interfere and is used as a reductant.

2. Other Redox Titrants

Titrants other than iodine or potassium iodate are only rarely used for the determi-
nation of tin and as a result, interferences are less weil understood.

2.1 Potassium Bromate and Related Compounds

(i) Potassium bromate is reduced by stannous chloride according to the reactions
[67]:
Br03 + 6H+ + 6e--+ Br·+ 3H2 0 (ix)

and at the end-point:

(x)

As with iodate, the titrant incorporates an excess of potassium bromide or this may
be added to the solution to be titrated. The action of a bromate/bromide mixture is
sirnilar to that of an iodate/iodide solution: in strongly alkaline solutions the titrant
is stable but in acid solutions it reacts as a standard bromine solution. This succesfully
overcomes the problems of storing unstable solutions.
Experimental details are very sirnilar to those for iodate or iodine assays.Tin is
reduced to the stannous form, cooled under carbon dioxide and titrated in an inert
atmosphere. Standardisation is carried out using metallic tin.
Indicators rely on the irreversihle bleaching action of free bromine and include:
methylorange [81], indigo carmine [82] and Rhodamine B [84]. Starch-potassium
iodide [30, 83] appears to be the most popular indicator, turning blue at the end-point
because of the oxidation of iodide to iodine by free brornine. Sandved [14] has studied
the potentiometric titration of tin with potassium bromate using both a Pt/normal
calomel electrode pair and a Pt/Pt system polarised by a current of 8p.A.
Bromate titrations have been applied to the determination of tin in the presence of
bismuth [86], antirnony [87], in rninerals and alloys [88], white metal bearing alloys
[89] and other tin alloys [30].
Potassium bromate appears to offer no advantage over potassium iodate as a titrant.
1t is considerably more oxidising and, therefore, would be expected to show poorer
selectivity.
32 Vo lumetric Analysis [Ref.p. 40

(ii) Potassium chiorale [90, 91] has been used as a titrant for tin(II). In the former
study, the titrationwas conducted in 5 - 7 M HCl with methylene blue or phenosa-
franine as indicator.
(iii) Potassium periodate has been suggested [92, 93] as a possible titrant for tin(Il).

2.2 Potassium Ferncyanide

Potassium ferricyanide reacts with tin(II) according to the reactions:

SnCl 2 + 2K 3 Fe(CN) 6 + 2KCl = SnCl4 + 2K4 Fe(CN) 6 (xi)

Mugnier and Raa [94] titrated tin(II) with potassium ferricyanide keeping the solution
under carbon dioxide. Safranine T and Neutral Red were suitable indicators but could
not be used for the reverse titration. Rasinka and Rychcik [95] used 3,3' dimethyl-
naphthidine or o-dianisidine as indicators for titration in 6 - 9 M hydrochloric acid. A
very sharp end-pointwas found under these conditions giving an error ofless than
0.1 %. No interference was found from Ag, Al, Pb or Zn and the method was applied
to the analysis of tin/lead alloys. In a later paper [96] the same workers used poten-
tiometric end-point detection using a platinum/saturated calomel electrode pair. No
interference was noted from Al, Cd, Co, Ni, Pb, Sb or Zn but Cu, Fe and nitrate in-
terfered.
Titrations have also been carried out in alkaline solutions. In the presence of sodium
pyrophosphate, tin(II) was determined [97] by direct titration with 0.1 potassium fer-
ricyanide at pH 11 - 12.5 using cacotheline as indicator. Titrations carried out [98] un-
der nitrogen in 2.5 -SM potassium hydroxide solution used Alizarin Yellow R (C.I.
Mordant Yellow I) as indicator. The colour changewas from yellow to violet. Inter-
ference from Cu, Co, Fe(II), Fe(III), Mn and Ni was encountered, Aland Zn did not
interfere. Potassium tartrate was added to prevent the interference of lead.

2.3 Ferric Chloride

Ferric chloridewas highly recommended as a titrant for the tin assay by Parry [5].
The determination is carried out in at least SM hot concentrated hydrochloric acid
after reduction with zinc. Precipitated As, Cu, Sb dissolve at an appreciable rate and
must be removed by decanting or by a prior cementation with iron wire. Unfortunate-
ly the presence of ferrous iron retards the end-poirrt and interferes with the colour in-
dication. In Parry's method the end-point was detected by the yellow colour imparted
by an excess of ferric chloride.
Schlüttig [99] used at least SM hydrochloric acid with indigo carmine as indicator.
The colour change is very sharp, from yellow to indigo blue, and is signalled by a bot-
tle-green colour.
More recently tin has been determined [100] by addition of excess ferric chloride
in 6M hydrochloric acid followed by titration of the ferrous iron produced agairrst
potassium dichromate with potentiometric end-point detection. Fluoride was found
to interfere giving low results. Donaldson and Maser [ 106] determined the ferrous
chloride produced in the oxidation first by decolorising with phosphoric acid,then
titrating with 0.1M ceric sulphate using 1 : 10 phenanthroline/ferrous sulphate as the
indicator. Alternatively [ 101] the excess of ferric chloride can be titrated against a
reducing agent; in this instance hypovanadous solutions i.e. V(II) were advocated;
chromaus sulphate solutions, CrS0 4 have [ 114] also been used.
 Ref.p. 40] 2.4 Other Oxidising Titrants 33

2.4 Other Oxidising Titrants

Some other oxidising agents which have been used for the estimation of tin are
described below. In view of the very few studies actually carried, out, the Iist is of
academic rather than practical value.
(i) Potassium dichromate as a titrant for tin(II) was mentioned by Parry [5] al-
though no directions were given for its use. Saz [102] determined tin in cassiterite
by reduction with zinc and sodium hydroxide. He then acidified, added sodium bicar-
bonate to maintain an inert atmosphere and titrated using diphenylamine as an indica-
tor. Other indicators [103] are promethazine, fluoropromazine, trifluoroperazine and
promazine, all of which give blue to red colour changes. Perazine changes from blue to
violet and methotrimeprazine changes from blue to orange. Gottlieb [ 104] in a rather
interesting series of papers, titrated tin(II) with 0.1 N potassium dichromate in 3M
sulphuric acid with the addition of 5 ml of 0.1 M hydrazine sulphate per 5 ml of solu-
tion as indicator. At the end-point, excess dichromate reacts with the hydrazine sul-
phate giving an evolution of nitrogen gas. A plot of titrant against volume of gas
evolved must be drawn to determine the end-point.
(ii) Sodium orthovanadate Na 3 V0 4 can be used [ 1OS] to titrate tin(II) in a carbon
dioxide atmosphere in the presence of a mixed indicator of 3,3-diphenylbenzidene
and methylene blue.
(iii) Cerium(IV) was used [107] to titrate tin(II) with cacotheline as an indicator.
The presence of large excesses of Iead interferes.
(iv) Copper diaryl or dialkyl thiosemicarbazides have been found [ 108] to oxidise stan-
nous solutions. Colourless cuprous complexes are produced at the end-point. Reagents
used were cupric compo.unds with 1-phenylthiosemicarbazide and also the 1,4-diphenyl-
1-phenyl-4-o-tolyl and 4-p methoxyphenyl-1-phenyl-thiosemicarbazides.
(v) Potassium permanganate has been mentioned as a titrant which will oxidise tin(II)
solutions quantitatively [5, 67] but iodometric titration is recommended in both ref-
erences.
(vi) Cobalt{Ill} solutions produced by anodic oxidation of cobalt(II) acetatein glacial
acetic acid have been used [ 109] as titrants for tin(II) with potentiometric end-poirrt
detection. The method appears to offer little advantage for either conventional or
coulometric titrations.

(vii) Beck [ 11 0] found that 0.1 M titanium(IV) sulphate solution can be used to sta-
bilise hydrogen peroxide. The intersely coloured orange solution acts as its own indicator
and has been applied to the determination of tin in hot (80- 90°C) 10% hydrochloric
acid solution. A O.lM hydrogen peroxidesolutionwill not change its normality over
a period of 8 hours if stored in the dark [ 112].

y~13 +H 2 0

SO,NC!Na

( viii) Chloramine T is the sodium salt of p-toluene sulphochloramide and behaves like
sodium hypochloritein its reactions with stannous solutions [67]. The reagent solution
should be stored in brown-glassware and gives a constant titre even after several months.
34 Volumetrie Analysis [Ref.p. 40

Chloramine B, C6 H 5 S0 2 NC1 Na.3H 2 0 is sirnilar. Titrationsare carried out [113] in

3 - 5% hydrochloric acid in the presence of an inert gas using lead [67] or zinc [ 113]
reductions. For practical determinations the oxidising power of the titrant is too great
and the addition of 50 g/1 potassium iodide in 0.1 M titrant is suggested. Chloramine
compounds have been used as oxidants in the Andrews iodine monochloride titration
(see Section 2.5). ·
(ix) An unusual titrant for stannous tin is methylene blue [122] which is reduced to
the colourless leuco dye by stannous salts. The end-point is the appearance of a blue
colour.
(x) A number of interhalogen compounds have been proposed as alternatives to
iodine although they have not been seriously applied to practical analysis. Iodine
monochloride [117] prepared by addition of equivalent amounts of potassium iodate
and iodide in hydrochloric acid solutionwas used for the semirnicro determination of
tin. Chemically, the titration is similar to a conventional iodine determination and is
rather different from the so-called iodine monochloride procedures described later.
Iodine monobromide [123] prepared by mixing iodine and bromine has been used sirn-
ilarly. Cyanogen bromide [ 124] could not be used as a titrant for tin(II) in the pre-
sence of copper or lead. N-Bromosuccinimide [ 125] in a solution of hydrochloric and
hydrobromic acids has also been suggested.

2.5 Iodine Monochloride Titrations

In strong hydrochloric acid solutions (i.e. greater than 4M HCl), iodides may be
converted to iodine monochloride by very strong oxidising agents. Potassium iodate,
chloramine T, permanganate, dichromate and ceric sulphate have all been used as
oxidants, following the initial use of chlorine water [ 115]. In the determination of
tin with potassium iodate (containing no potassium iodide) for example:

KI0 3 + 3SnC12 + 6HC1 = 3SnC1 4 + K1 + 3H 2 0 (xii)

After the oxidation of tin, the iodide produced is oxidised:

KI0 3 + SKI + 6 HCl = 3I 2 + 6KC1 + 3H2 0 (xiii)

Finally in strong hydrochloric acid and with very strong oxidants:

KI0 3 + 2I 2 + 6HC1 = SI Cl+ 3H2 0 + KCl (xiv)

In the second reaction, free iodine is liberated until all the iodide has been oxidised.
Further oxidation to iodine monochloride removes iodine from solution. The end-
poirrt is detected by adding an immiscible solvent such as chloroform or carbon tetra-
chloride. If the titration is carried out in a glass-stoppered flask, which is shaken be-
tween additions, the organic solvent will change from violet to colourless as the last
traces of iodine are converted to iodine monochloride. Starch may also be used as an
indicator.
It is important to recognise that in the iodate procedure recommended earlier in
this chapter, the titrant contains a large excess of potassium iodide and that this is
irnportant in regulating the selectivity of the titrant. With the strong oxidants em-
ployed in the so-called "iodine monochloride procedures", interference from elements
such as As, Fe, Sb and V will occur if they arenot completely removed.
 Ref.p. 40] 3.1 Direct Titration 35

Procedures for several elements using iodine monochloride have been given by
Andrews [6] andJamieson [7]. The procedure given below is an example:
Dissalve 0.2g of tin in 100m! of hydrochloric acid and a few drops of nitric acid. Add 3g of tar-
taric acid, add 200 ml of water and transfer to a 500 ml boiling flask fitted with a rubber bung.
The bung should have an exit tube to allow the escape of water vapour and a glass rod holding a
nicke! coil prepared from 30 cm of 3 mm diameter nicke!. Heat at boiling for 45 min and cool
under a current of carbon dioxide. Remove the coil, washing with the minimum amount of water
and add potassium iodate (0.1 N KIQ3with no iodide) from aburette until the solution becomes
brown due to the formation of iodine. Continue adding the iodate and the solution willlighten as
the iodine becomes oxidised to iodine monochloride. Just before the iodine colour disappears add
starch solution and titrate from blue to yellow.
Published applications of the method include the determination of tin in solder, type
metals and bronzes [7, 116].
A number of procedures have been published where tin(II) is first oxidised with an
excess of iodine monochloride solution (prepared by mixing potassium iodate with
potassium iodide in strong hydrochloric acid). The iodine produced is then titrated
with a powerful oxidant to give iodine monochloride. The end-point is the disappear-
ance of iodine from solution and is detected by starch or organic solvents such as
chloroform or carbon tetrachloride. Oxidants used have included ceric ethylene
diamine sulphate [118 ], chloramine T [ 119] and chloramine B [120, 121 ].

3. Complexometric Titrations
Ethylenediaminetetracetic acid disodiumsalt (EDTA) has found some limited use
as a titrant for the determination of tin. The main advantages are the rapidity of the
determination, the stability of the reagent and the simpler technique and apparatus
compared with the iodometric method. The use of EDT A has been fairly well devel-
oped for the analysis of simple matrices such as white meta! and copper base alloys,
but is not suitable at the present time for routine tin determinations on minerals and
complex residues.
The Solution chemistry of tin/EDTA complexes has been studied hardly at all. The
main reason for this has been the ease of precipitation of tin hydroxides and hydrated
oxides, even in acid solutions. Tin(IV) shares with uranium(VI), antimony(III) and
beryllium the property of being precipitated by arnmonia in the presence of EDTA.
As a result, the normal techniques for the determination of stability constants can not
be applied.
Table 10 [ 129] gives the stability constants of selected elements and includes a val-
ue for the tin(IV)/EDTA complex obtained by Kragten [130]. Tab1e 10 also shows
the minimum pH values [ 131] for effective titration; these parallel the stability
constants and tend to confirm the very high stability found by Kragten.

3.1 Direct Titration

The direct titration of tin with EDTA is at its most selective in solutions of very low
pH; under these condition~, few ionsform stable EDTA complexes. However, masking
of interferences by simple reactions is correspondingly more difficult and there is also
the problern of finding a suitable indicator. As a result, direct complexometric titra-
tions are carried out at pH 2 - 5, usually in the presence of weak complexing agents
which maintain tin in solution.
36 Volumetrie Analysis [Ref.p. 40

Yurist [ 132] determined tin in solders by adding a substoichiometric volume of

0.01 M EDTA to the sample solution in 50-60% hydrochloric acid. The solutionwas
boiled to complete the reaction and a small quantity of 0.01 M bismuth nitrate solu-
tion added. After adjusting to pH 1.8 with ammonium acetate and buffering, tin and
bismuth were titrated with 0.01 M EDT A using xylenol orange indicator which changes

Table 10. Stability Constants K [129, 130] and Minimum pH for Titration [131] of Metal/EDTA
Complexes

Cation LogloK pH Min. Cation Log 10 K pHMin.

Na• 1.7 a Cu 2 • 17.8 3
Lt 2.8 a vo 2• 18.4 b
Ag• 7.2 a Ga 3 • 19.9 2.5
Ba 2• 7.8 10 Hg2• 20.4 2
Sr 2• 8.6 9 Th4• 23.2 2
Mg2• 8.7 9 Cr 3 • 24.0 b
Ca 2• 10.6 7.5 Fe 3 • 25.1 2
Mn 2• 13.5 5.5 y3• 25.9 b
Fe 2• 14.3 5 In 3 • 26.0 b
Cct 2• 15.0 4 Sn 4 • 34.5 <I
Zn 2+ 15.3 4 Co 3 • 36 b
Co 2 • 15.4 4
Al 3 • 15.5 4
Pb 2 + 16.8 3.5
Ni 2• 17.5 3

a Not listed but titrations normally impracticable because of weak complex formation.
b Not listed.

from purple to yellow. The EDTA required to complex the added bismuth solution
must be de.ducted from the titre. Bismuth and iron interfere with the titration. A sim-
ilar method was used by Dixon et al. [ 140].
A later paper by Yurist [ 133] for tin in solders, describes the use of copper/EDT A/
1-(2-pyridylazo)-2-naphthol (PAN) as indicator. The reaction is carried out in hot
tartrate solution at pH 1.8. Because of the greater stability of the tin/EDTA complex,
copper is displaced from the indicator and the solution has the red-violet colour of
the copper/PAN complex. At the end-point, copper is titrated with EDTA and the
yellow colour of free PANis observed. It is advisable to boil the solution immediately
before the end-point to obtain a clear change. No interference from Cd, Mn, Ni, Pb or
Zn was encountered but Bi, Fe, In and Zr gave trouble.
Dubsky [134] titrated tin directly at pH 5.5-6 in a pyridine acetate buffer solution
using methylthymol blue as indicator which changes to yellow at the end-point. Tar-
taric acidwas added to mask antimony.
Shakhova [ 135] dissolved In/Pb/Sn/ Ag ;llloys in sulphuric acid, removed insoluble
Iead sulphate by filtration and titrated tin at 70°C in 0.5% tartaric acid at pH3 - 4.
Xylenol orange was used as an indicator. The pH was then adjusted to pH 4.5 - 5 for
titration of indium with EDT A using the same indicator.
Using a similar approach to Yurist [ 133], Krleza and Vuletic [136] used a Zn/EDTA/
xylenol orange indicator for the titration of tin in the presence of chromium. To the
 Ref.p. 40] 3.2 Back Tiration 37

sample in O.SM hydrochloric acid, they added sufficient glycerol to mask trivalent
chromium. Then 2ml ofO.lM Zn/EDTA were added and the solution diluted to 11.
Xylenol orange (50 -100mg) andhexamine were added to an aliquot and the red-
violet solution, now at pH 5-6 was titrated with 0.02M EDTA to a yellow/green end-
point.
EDTA Method-Direct Titration [133]
Dissalve 0.2- 0.4g of solder sawings by boiling with 20ml of concentrated hydrochloric acid and
a few drops of 30% hydrogen peroxide, sufficient to give a slight yellow colour to the solution.
Dilute to 100ml with 1 : 1 hydrochloric acid : water. Treat an aliquot with 10ml of 20% tartaric
acid solution (use 1.5 ml for every lOmg of tin), dilute with 80ml of water and boil for 1 - 2 min.
Add 1 ml of 0.01 M copper/EDTA complex, 5 - 7 drops of PAN indicator solution and sufficient
aqueous ammonia to give a reddish-violet colour. Add 5ml of pH 1.8 buffer, and titrate the hot
solution with 0.02M EDTA. Just before the end-point heat the solution to boiling. The end-point
isapure yellow colour.
0.01 M copper/EDTA complex-Titrate 50ml of boiling 0.02M copper sulphate with 0.02M EDTA
in the presence of 5-7 drops of 0.1% ethanolic PAN (1-(2-pyridylazo)-2 naphthol) at pH 3 to a
green end-point.
pH 1.8 Buffer - Add 50 ml of M sodium acetate to 54 ml of M hydrochloric acid and dilute to
250ml.

3.2 Back Titration

Determinations of tin by addition of excess EDTA and back titration against a stan-
dard metal solution have been reported by several authors. In general the procedures
are unselective but convenient. They are well suited to simple Situations such as in the
analysis of organo-tin products, where other metals are unlikely to be present in major
quantities. In back titration procedures the initial reaction of tin and EDTA usually
takes place at about pH 2. The actual titration is normally carried out after adjustment
to approximately pH 5. It is very important that this adjustment of pH be carried out
carefully, with stirring and with a dilute alkali. High local concentrations of basic solu-
tion have been known to induce precipitation of tin hydroxide which does not com-
pletely re-dissolve.
One of the most popular back titrants is a standard thorium solution [130, 137-
139]. The very high stability constant ofthe thorium/EDTA complex is an advantage
in that weakly complexing metal ions are displaced from their EDTA complexes by
thorium and hence do not interfere with the determination. Furthermore, the back-
titration can be carried out at pH 2 - 3 which eliminates many interfering complex-for-
rning reactions.
a
In theoretical paper, Kragten [ 130] determined tin by back titration with tliorium
nitrate solution at pH 1.8 - 2.0 using xylenol orange as indicator. The method was ap-
plied to the determination of tin in organotin compounds down to 3 J,Lg/ml Sn. At
trace levels, xylenol orange was not suitable as an indicator and semixylenol orange
was recommended. As this indicator is commercially unobtainable at present the ori-
ginal paper should be consulted. A rather similar procedure for the deterrnination of
tin in organic materialsandin tinsaltswas reported by Hoyme et al. [139].
Kinnunen and Wennerstrand [137] published the method given below for the ana-
lysis of tin bronzes and gunmetals. Iron is a very common interfering element in most
EDTA procedures. Wakamatsu [138] deterrnined small quantities of tin (approxima-
tely 0.01% Sn) in iron and steels by coprecipitation at pH 8 - 9 with beryllium in the
presence of EDTA. Uranium and antimony arealso precipitated under these condi-
tions but no other elements. The precipitate was then oxidised with sulphuric acid and
potassium chlorate to destroy any accompanying EDTA; ascorbic acid, ammonium
38 Volumetrie Analysis [Ref.p. 40

acetate buffer and excess standard EDTA were added and a back titration carried out
with 0.001 M thorium nitrate solution at pH2 - 3 with xylenol orange irrdicator. The
irrfluence of iron and tungsten is completely elirnirrated.
EDTA Method -Back Titration [137]
Dissolve 0.25 g of gurunetat or tin bronze with 3 rnl of concentrated hydrochloric acid and a few
drops of 30% hydrogen peroxide. Add 0.01 M EDTA solution in excess (lOrng Sn= 8.5rnl) and
20ml ofsaturated thiourea solution. Adjust to pH2 by addition of 2- 5g of arnmonium acetate.
Add 3 drops ofxylenol orange solution and back titrate the excess EDTA with O.OlM thorium
nitrate solution until the colour changes from yellow to red.

In a rather similar method tothat given above [141- 142] excess EDTA was titrated
agairrst standard zinc chloride solution at pH 5 ± 0.2. The procedure was applied to
phosphor bronzes using hexamine as buffer and xylenol orange as irrdicator. Interferen-
ce from copper was prevented by the addition of thiourea (25 ml of a 10% solution).
Phosphorus should be oxidised to phosphate before titration. Pastukhova and
Kuryakova [143] determirred tirr in silicon/copper alloys by dissolving0.2- 0.3g of
alloy in hydrofluoric and nitric acids, evaporating to fumes with 3ml of concentrated
sulphuric acid to remove silicon and dissolving the residue in 20- 25m! of0.01M EDTA
with 25 ml of water. Copper was masked by adding 2.5 ml of saturated thiourea solution,
3 ml of 4% ascorbic acid and 9 g of glycirre ( to give a pH 2 - 2.5). The solu tion was di-
luted to 150rnl and titrated agairrst standard bismuth nitrate solution using xylenol
orange as indicator.
Organotin compounds have been analysed for tin after wet ashirrg with concentrated
H2 S0 4 /fuming HN0 3 /60% HC10 4 [144], or with 2:5 concentrated HN0 3 /30% HC10 4
[ 145], or with 10:10:2 concentrated H2 S0 4 /concentrated HN0 3 /Na 2 S0 4 [ 146 ]. Ex-
cess EDTA is added and is tritrated with standard copper solution [144, 146] at pH3 or
with standard zirrc Solution [145] at pH6. Catechol violet may be used as indicator for
the titration with zinc. Naphthyl azoxine S [8-hydroxyquirroline, 7-(6-sulphonic acid,
2-naphthylazo) quirrolirre 5 -sulphonic acid] was used [144] as the indicator for the titra-
tion with copper.
Other back titrations include the use of Iead nitrate solution [ 14 7] in a hexamine
buffered solution at pH 5 - 6 with a catechol violet indicator. The colour change is
from yellow to blue-green. Cobaltaus chloride has been suggested as a titrant for the
back-titration ofEDTA in the tin determination [149]. The determination is carried
out in 0.6M arnmonium acetate solution, and after the initial complexation reaction a
mixture of saturated potassium thiocyanate solution and acetone (4 : 20 by volume)
is added. The excess of EDTA is then titrated agairrst standard cobalt chloride to a
colour change from pale rose to purple then to blue with a !arge excess of titrant. The
author clairns that under the conditions of the titration the stability of the cobalt/
EDTA complex is so great that several metals (eg, Pb, Zn, Cd) are displaced from
their complexes and do not interfere.
A novel approachisthat of Weisz andKiss [148] who added excess 0.02M EDTA,
0.5 rnl of M ammonium carbonate solution and 1 rnl of 5% resorcinol in hydrogen
peroxide. Unconsumed EDTA was titrated with 0.02M manganese chloride solution,
the end-point being detected thermometrically by plotting temperature agairrst vol-
ume of titrant.

3.3 Indirect Titration

F ew reports of indirect titratiöns have been recorded. Yurist and Korotkova [ 150]
analysed alloys containing Sn, Pb, Ni, Zn and Cd. Total complexing ions were deter-
 Ref.p. 40] 3.4 Displacement Titrations 39

mined by the addition of excess standard EDTA to an acetate solutionbuffered at

pH5 followed by back-titration ot the excess with ferric chloride solution using sulpho-
salicylic acid as indicator. The total ions other than tin were determined by carrying
out the titration in the presence of tartaric acid at pH 10.
Other indirect determinations can be devised using the displacement reactions given
below.

3.4 Displacement Titrations

Displacement titrations are carried out by complexing the reactive meta! ions pre-
sent. Tin is then displaced from its EDTA complex using a selective masking agent,
and the EDTA liberated is titrated against a standardised meta! solution.
Fluoride is the most common masking agent used in displacement reactions and
has been applied to the determination oftin in white metals [151], solders [152] and
canned foodstuffs [153).

EDTA Method- Displacement Titration [ 151]

Dissalve 0.5g of white meta! sawings in 10m! of concentrated hydrochloric acid and 2ml of con-
centrated nitric acid; avoid unnecessary heating. Add 25m! of 4% potassium chloride and 25m!
of 0.2M EDTA. Boil gently for 1 min, cool and dilute to 250m!. To a 25m! aliquot add saturated
thiourea solution until the blue colour due to any copper is discharged, add 0.5 ml in excess then
15m! of 30% hexamine solution. Dilute to 150m! and titrate the excess EDTA with 0.05M Iead
nitrate to a red end-point with xylenol orange. Add 2g of sodium fluoride to release tin from its
EDTA complex then titrate the liberated EDTA with Iead nitrate solution to a red end-point which
is stable for 1 min.

Zohm [153) ashed foodstuffs with sulphuric and the minimum of nitric acid before
diluting with aqueous arnmonium oxalate solution and excess 0.005M EDTA. The
acidity was adjusted to pH 5.6 with hexamine before titration of excess EDTA with
Iead nitrate solution to xylenol orange. Ammonium bifluoride was added to complex
tin and the displaced EDTA was titrated against Iead nitrate solution.
Jankovsky [ 154] used triethanolamine as the masking agent for tin but found it
necessary to add it with the excess of EDTA. This necessitated two titrations, with
and without triethanolamine.
A procedure [155) for tin in alloys containing Bi, Cd, Co, Cu, Ni, Pb and Zn used
lactic acid as the displacing agent: To an acid solution containing more than 200mg of
tin, add 0.025M EDTA. Adjust to pH 2 with dilute arnmonia avoiding high local con-
centration and titrate with 0.25M Iead nitrate solution using xylenol orange indicator
to a red end-point. Add 10ml of 20% lactic acid solution and titrate the liberated EDTA
with Iead nitrate.
Solvent extraction may be used to increase the selectivity of the determination; an
example [156) uses the separation oftin into chloroform from a solution containing
0.5 - 1M sulphuric acid, 8 g of potassium iodide and 0.1 g of ascorbic acid. The extrac-
tant was 15ml of chloroform containing 0.7g of diantipyrinylmethane. Tin was strip-
ped from the organic extract after Separation ofthe phases by shaking with EDTA in
very strong alkali (2- 3% potassium hydroxide). Under these conditions tin forms a
complex with EDTA and excess EDTA can be back-titrated with bismuth nitrate solu-
tion at pH 1.5 - 2 using the disappearance of the orange bismuth iodide complex as
the indicator.
40 Volumetrie Analysis

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34. Evans, B.S.: Analyst 52, 590 (1927)
35. Clarke, S.G.: Analyst 56,82 (1931)
36. Bayula, A.G., Losinskaya, V.S.: Soobshch.Dal'nevost.Fil.Sibirsk.Otd., Akad.Nauk SSSR
45 (1960). Anal.Abstr. 9, 1848 (1962)
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Pergarnon 1966
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45. Evans, B.S.: Analyst 56, 171 (1931)
46. Evans, B.S., Higgs, D.G.: Analyst 69, 201 (1944)
47. Popov, M.A., Bershadskaya, NM., Matukhno, S.E., Dovyat, A.D.: Uchern.Zap.Tsent.
nauchno- issled.Inst. olovyan.Prorn. 9 (1965): Anal.Abstr. 14, 2503 (1967)
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49. Popov, M.A., Shashkova, A.M.: Uchen.Zap.Tsent.Nauchno- issled. Inst. olovyan.Prorn.
18 (1965); Anal.Abstr. 14, 2504 (1967)
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54. Ikegami, T., Suematsu, K., Kammori, 0.: Japan Analyst 5, 379 (1956)
55. Challis, H.J.G., Jones, J.T.: Analyst 82,658 (1957)
56. Farnsworth, M., Pekola, J.: AnaL Chern., 31,410 (1959)
57. Hourigan, HF.: Analyst 61, 328 (1936)
 References 41

58. Rapport, R.: Foundry 81, 115 (1953)

59. Okell, F.L., Lumsden, J.: Analyst 60, 803 (1935)
60. Kolthoff, J.M.: Z.Anal.Chem. 60,448 (1927)
61. Unpublished work and Standard Methods- Capper Pass Ltd.
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63. Kawahatta, M., Mochizuki, H., Kajiyama, R., Ishii, M.: Japan Analyst. 11, 963 (1962)
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65. Evans, D.H.: Anal.Chem. 36,2435 (1964)
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88. Deutsch; L.: Ann.Chim.Anal. 18, 10 (1936)
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90.Murty, C.R., Rao, G.G.: Talanta 19,45 (1972)
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95. Basinska, H., Rychcik, W.: Talanta 10, 1299 (1963)
96. Basinska, H., Rychcik, W.: Chemia Analit. 12, 949 (1967)
97. Kiboku, M.: Japan Analyst 10,19 (1961)
98. Basinska, H., Wisniewski, W.: Anal. Abstr. 14, 2502 (1967)
99. Schlüttig, W.: Z. Anal. Chem. 70, 55 (1927)
100. Collins, R. W., Nebergall, W.H.: Anal. Chem. 34, 1511 (1962)
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103.Puzanowska-Tarasiewicz, H.: Chemia Analit. 15,939 (1970)
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105. Wawrzyczek, W., Wisniewska, K.: Chemia Analit. 10, 1287 (1965)
106. Donaldson, J.D., Moser, W.: Analyst 84, 10 (1959)
107. Wawrzyczek, W., Wisniewska, K.: Z.Anal.Chem. 207, 182 (1965)
108. Koshkin, N. V.: Izv.Vyssh.Ucheb.Zavedenii,Khim.Tekhnol. 3, 56 (1960); Anal.Abstr. 8,
3653 (1961)
109. Minczewski, J., Pszonicka, M.: Chemia Analit. 10, 1357 (1965)
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111. Ceausescu, D., Sitbu, A.: Revta Chim. 20, 700 (1969)
112. Vulterin, J., Zyka, J.: Chem. Listy SO, 311 (1956)
113. Rupp, E.: Z. Anal. Chem. 51, 73 (1928)
114. Tandon, J.P., Mehrotra, R.C.: Z.Anal.Chem. 164, 314 (1958)
115. Dupre, A., Dupre, F.: Liebigs Ann. Chem. 94, 365 (1855)
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117. Cihalik,J.: Chem. Listy 49,1167 (1955)
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119. Singlr, B., Sood, K.C.: Anal.Chim.Acta 13, 301 (1955)
42 Volumetrie Analysis

120. Singh, B., Sood, K.C.: Anal.Chim.Acta 11, 313 (1954)

121. Singh, B.: J.Indian Chem.Soc. 31, 647 (1954)
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123. Nazrullaaev, S.N., Gengrinovich, A.J., Murtazaev, A.M.: Anal.Abstr. 11, 854 (1964)
124.Paul, R.C., Chauhan, R.K.,Parkash, R.: Indian J.Chem. 9, 879 (1971)
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128. Nechamkin, H.: Analyst 49, 20 (1960)
129. West, T.S., Sykes, A.S.: Analytical Applications of Diamino-Ethane-Tetra-Acetic Acid,
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130. Kragten, J.: Talanta 22, 505 (1975)
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132. Yurist, I.M.: Zavod.Lab.30, 805 (1964), Anal.Abstr. 12,5643 (1965)
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136. Krleza, F., Vuletic, N., Croat. Chem. Acta 42, 75 (1970); Anal. Abstr. 20, 139 (1971)
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CHAPTER 5

PHOTOMETRie METHODS

By J .W. Price

1 Introduction
Values of molar extinction, E, given in this section, refer to the ratio:

Optical density
=e
Cell depth ( cm) x molar concentration

In the earlier stages of the developmen t of colorimetric methods of analysis, selec-

tivity was the main requirement in the search for suitable reagents, and in the case of
tin this meant that dithiol, first suggested in 1936, remained for years practically the
only compound in use, the magenta-red colour of the precipitate formed with Sn(II)
being quite specific and serving weil as a qualitative 'spot test' for tin, as weil as being
useful in quantitative work.
A number of reagents were proposed during the 1950s in an attempt to improve on
the sensitivity of dithiol, but they are all now mainly of historical interest. They
included:
a) Formation of molybdenum blue by reduction of various heteropoly molybdic
acids such as silicomolybdic [ 1] and phosphomolybdic acids. This reaction is of course,
non-specific, the tin must be in the reduced form and the coloured products are unstable
in air.
b) Formation of a violet colour (A. max. = 560 nm) with cacotheline (Nitrobruciqui-
none) with Sn(II) in acid solution. The system is unstable but good results were ob-
tained by Goto and Kakita [4] for the determination of tin in iron and steel and by
Lopez '[5] for small amounts of tin in Iead. (See also Fritz and Scheer[6]). The reagent
has been suggested for the qualitative detection of Sn(II) in solutions of Sn(IV).
c) Extraction of the tin(IV)-8-hydroxyquinoline complex into chloroforrn solutions
of pH 2.5 - 5.5 and photometric measurement of the resulting yellow solution at
390nm [7]. The method has been used for the determination of tin in iron and steel
[8], in nuclear reactor materials [9] andin Zircaloy [10]. The 5,7-dibromo derivative
has also been used [11, 12].
d) Extraction of the tin(II)-diethylarnmonium diethyldithiocarbamate complex
into ch!oroform and photometric measurement of the yellow extract at 385 nm [ 13,
14]. The method is irrsensitive and the colour of the extract fades rapidly. Improved
results are obtained by using sodium pyrrolidine dithiocarbamate [ 15] and Eberius
[16], by taking a lOg sample and employing a preliminary extraction with cupferron
was able to determine tin in the range 0.0001 - 0.1% in zinc and Iead alloys with this
reagent, measuring the absorption of the yellow extract in carbon tetrachloride at 405
44 Photometrie methods [Ref.p. 57

nm.The reagent was also used successfully by Kovacs and Guyer [17] to determine tin
and other metals in zinc and antimony and tin in iron and steel.
e) Formation oftin(IV) halide complexes
1. Bromides. In 48% HBr solution tin produces a yellow colour which can be measu-
red at 366 nm [ 18 ]. The poor sensitivity is somewhat improved by adding thiourea
[ 19].
2. Chlorides. In 6M HCl solution the tin complexes absorb in the ultraviolet and, by
measuring at 215nm, tin up to 10ppm can be determined [20].
3. Iodides. In 1.2M HCl + 4M KI solution the yellow species formed can be extracted
into ethyl iodide and the colour measured at 420nm [21]. Tanaka [22] considered
this extraction tobe non-quantitative, but obtained good results by extraction from
H2 S0 4 solutions into cyclohexane and measuring absorbance at 364nm.In this way
he determined tin in orange juice (5- 88ppm) after wet-ashing andin iron and steel in
the range 0.02 - 0.03 %. Arsenic(III) and germanium(IV) are also quantitatively extrac-
ted.
However, Sandeli [23], was able to state with some justification in 1959 that more
specific and sensitive reagents were needed, thinking none of these methods entirely
satisfactory. Since then the situation has changed considerably, with the emphasis
shifting to a search for increased sensitivity rather than specificity, interference by
other elements being avoided by irnproved and more convenient methods of isolation
of small amounts of tin.

2 Methods of Separation of Small Amounts of Tin

2.1 Distillation

The volatility of the halides of Ge, As, Sb and Sn was made use of in the classical
distillation procedure of Scherrer for their serial separation. Scherrer 's procedure [24]
was modified by Onishi and Sandeli [25] for the isolation of tin (5- 50J1g) by distilla-
tion from an all-ghss apparatus consisting of a 200m! round-bottom flask fitted with
a separating funnel, thermometer weil and an outlet tube connected to a vertical
condenser. Germanium, arsenic ~nd antirnony were first removed by distillation as
the chlorides and the only element found to accompany the tin was selenium, which
had tobe removed from the distillate by precipitation with so2. This method of Sepa-
ration was used prior to the photometric determination of tin in silicate rocks, sulphi-
des and iron and steel with dithiol. The distillation procedure given by Sandeli is as
follows:
Transfer the sample solution (5-50 Jlg Sn for the dithiol method) freed from nitric acid if neces-
sary by evaporation with sulphuric acid, to the distillation flask with 25m! of 1 : 1 H 2Sü 4 , 3m!
of H 3 P0 4 , 20 ml of 6 M HCl and 1 g hydrazine sulphate. Pass a current of C0 2 through the solu-
tion and heat to boiling. When the temperature of the solution reaches 160°C add 20m! HCl
dropwise, maintaining the temperature at 155 -165°C and catching the distillate in 30m! of water.
This distillate, containing any Ge, As and Sb present, is discarded. Place a receiver containing 15 ml
of water under the condenser and add a mixture of 15 ml 6 M HCl and 7 ml HBr dropwise to the
distillation flask, maintaining a temperature of 145- 160°C. To the distillate add O.Sml H2S04
and 5 ml HN0 3 and evaparate to fuming to remove halides. Cool and dilute to a known volume.
The distillation method gives good results but is rather time-consuming and is tending to be re-
placed by the iodide extraction method (see page 69).
 Ref.p. 57) 2.3.1 Precipitation, Classical Methods 45

2.2 Extraction into an Organic Solvent

2.2.1 Dithizone forms a red complex with tin(II) which can be extracted into carbon
tetrachloride at pH 6- 9, but the extract is unstable. Tin(IV) cannot readily be extrac-
ted and this reagent is used mainly to separate other metals from tin. The red complex
formed with dialkyl tin compounds has been used in the analysis of organotin com-
pounds. (See Chapter 19).

2.2.2 The tin(IV)-Cupfe"an complex (Chapter 3, section 1) can be extracted into

chloroformfromM acid solutions, affording a separation from Pb, Zn, Cd, Ni, Mn,
As and Sb. The main use of this reagent is however, as a precipitant for tin.

2.2.3 The Tin(IV)-8-Hydroxyquinoline complex can be extracted into chloroform at

pH 2.5- 5.5 (see page 43).

2.2.4 Diethylammonium diethyldithiocarbamates can be used to extract tin(II) but

not tin(IV) from acid solution (see page 76). The reagent has been used by Luke for
the separation of metals which interfere in the determination of tin with phenylfluo-
rone (see page 49). Copper, bismuth, arsenic and antimony are first extracted from
a solution in which the tin is present as Sn(IV), then tin(II) is extracted in the presence
of thioglycollic acid and the chloroform extract wet-ashed. It was found that only
molybdenum was not separated by this double extraction procedure.

2.2.5 Tris (2-ethylhexyl) phosphine oxide (0.01M in cyclohexane) extracts tin(IV)

(10- 100 J.Lg) from solutions that are 1M in HCl and 2-3M in H2 S0 4 . Only Ga, Sb,
Fe and Moare partly coextracted, and these can be removed by back-washing with
1M HCl- 2M H 2 S0 4 . Back-extraction of the tin into aqueous solution is difficult
owing to hydrolysis and so far the method has been used only for the determination
of tin with catechol violet in the organic solvent (see page 51).

2.2.6 Tin( IV) iodide is soluble in organic solvents and the conditions for the selective
and quantitative extractions of small amounts of tin as the iodide have been investiga-
ted in detail by several workers. Gilbert and Sandeli [21] found that microgram amounts
of tin were quantitatively separated from a solution (20m!) that was 1.5 M in perchlo-
ric acid, 0.5M in sodium iodide and 3M in sodium perchlorate by a single extraction
with benzene (5ml). Chloride and fluoride interfered and were removed by prior evapo-
ration with H2 S0 4 ; arsenic(III) and germanium(IV) were partly extracted but could
be removed by washing the benzene layer once with a 5 ml portion of solu tion of the
same composition as the original aqueous phase. Tin was removed from the benzene
by shaking with 5 ml of 0.25 M H2 S0 4 . Tanaka [27] found that complete extraction
of tin into benzerre took place from solutions that were 3.5 - 4.5 M in H2 S0 4 with 0.5 M
iodide and that the tin could be back-extracted with 1-2M HCl, whileNewman and
Iones (28] preferred extraction into toluene from a solution which was 4.5M in H2 S0 4
and 0.5M in iodide (see page 52 Catechol vio1et method).

2.3 Precipitation, Classical Methods

2.3.1 Precipitation of metastannic acid by nitric acid attack on a meta! sample has
already been discussed ( Chapter 3, Section 1). Precipitation of small amounts of tin
46 Photometrie rnethods (Ref.p. 57

in this is incomplete but complete recovery is possible by co-precipitation with Mn0 2

and this is of value in the analysis of alloys [29]. The sample is dissolved in nitric acid,
the solution diluted and heated to boiling with the addition of 1ml of KMn0 4 solution
(1 %) and 1ml of manganous nitrate solution (5%). The coagulated precipitate is fll-
tered on paper and afterwashing the paper and contents are wet-ashed with H2 S0 4 /-
HN03.

2.3.2 Precipitation oftin(II) and tin(N) sulphides from dilute acid solution as in the
standard 'group separation' is sometimes of value. A collector is necessary for small
amounts, and for this copper is generally used, though cadmium and molybdenum
have also been suggested.

2.3.3 Precipitation of hydrated Sn0 2 with ammonia serves toseparate tin from e.g.
copper and nickel. Here also a collector- usually Fe(III) - is necessary for small
amounts. The use of an aluminiumsalt instead of iron for this purpose is sometimes an
advantage, as described by Godar and Alexander [30].

2.4 Ion-Exchange

This method has so far seldom been used, though complete recoveries have been
obtained by absorption of the tin as the chloro-complex from acid solution by anion-
exchange resins, such as 'Dowex 1 - X8'. This resin was used by Kojima [31] toseparate
tin from !arge amounts oflead in 8M hydrochloric acid, and 'Jy Shimizu [32] to recover
small amounts of tin from common salt, the resirr being washed with dilute hydrochlo-
ric acid to remove Ge, Ti, Zr, Sb, Se and Fe, and the tin eluted with M NaOH. Hafer and
Land/ [33] determined 0.001 - 0.2% of tin in Iead by dissolving a 1 g sample in a mix-
ture of nitric and tartaric acids and after the addition of hydrochloric acid, extracting
the tin with the liquid resirr 'Anberlite LA-2' in xylene and back-extracting the tin
from the organic phase with 0.5 N HN0 3 . Khalizova et a/. [34] separated tin (0.5 mg)
from excess of a number of other metals in 2M HCl and Kodama and Tsubota [35]
separated tin (~ 2Jlg/l) from sea-water (SOOml) after addition ofhydrochloric acid,
the tin being eluted with 2M HN0 3 .

3. Reagents

3.1 Introduction

During the last twenty-years more than 50 reagents have been put forward for the
photometric determination of tin (Table 1) though the majority of these would seem
tobe of theoretical rather than analytical interest. A few comparative studies of some
of the reagents have been reported, the most detailed being by Babko and Karnokhova
[36] who, after examining twelve reagents, concluded that haematoxylin, quercetin
and catechol violet were the best. Tataev and Shakhadbudinov [37] made a spectro-
photometric study of the coloured compounds produced w!th tin by methylene blue,
xylenol orange, pyrogallol red, Stilbazo and p-dimethylaminofluorone, while recentlv
 Ref.p. 57] 47

Table 1 Photometrie Reagents

Reagent References
Alizarin Blue [131 J
Antipyrine dyes [132]
Azo Rubine [133 J
N-Benzoylphenylhydroxylamine derivatives [134 J
2,2' -Biquinoxalinyl [135]
Bismuthiols [136]
Brilliant Green [137]
Bromopyrogallol Red [138]
Butylrhodamine S [139]
Crystal Violet [140]
Diantipyrinylmethane Iodide [141 J
[4-(dimethylamino )phenyl J
[4-(benzy!methylamino )phenyl J
antipyrinyl carbinol [142]
Dimecapththiop yrone derivs. [143]
p-Dimethylaminobenzylidene Rhodamine [144]
Dimethylglyoxime-Fe(II) complex [145]
3 ,5-Dinitropyrocatechol [146]
1,5-Diphenylcarbazide [147]
Fast Sulphon Black [148]
Flavonalsulphonic acid [149 J
G!yoxal-bis (2-hydroxyanil) [150]
2 Hydroxyperinaphthiden-1-one [151]
9-(2-hydroxyphenyl)-2, 3, 7 -trihydroxy-6-
fluorone-antipyrine system [152]
3-(o-hydroxyphenyl) benzthiazoline [153]
Janus Green [154]
Lumogallion . [155 J
Malachite Green [156]
4-methoxybenzo (thio-hydroxamic acid) [157 J
Methylene Blue Tetraiodoiodate [158]
Methylthymol blue [159]
Methyl violet [160 J
Nitrose-R salt [161 J
1,1 0-Phenanthroline-F e(Il) [162]
Picrolonic acid [163]
4-(2-pyridylazo) resorcinol [164]
Quinalizarin [165]
s-chloro-8-(2,4- dihydroxypheny lazo )-2-
hydroxybenzen e arsonic acid (Rezarson) [166]
(Salicylideneamino) 2-thiophenol [167]
Stilbazo [168]
3 ,4,5 ,6-tetrachloro-3 ',4 ',5 ',6 '-tetrahydroxy fluoran [169 J
3,5, 7,4 '-tetrahydroxyflavone [170]
4-(2-thiazolylazo) pyrocatechol [171]
Triphenyltetrazolium chloride [172]
Triphenylmethane dyes [173]
48 Photometrie methods [Ref.p. 57

Ackermann andHeegn [38] made a detailed study ofthe complexes of Sn(IV) with
o-diphenols and o-hydroxyquinones, from which they concluded that Gallein and
oxyhydroquinone phthalein are highly sensitive, the latter compound serving for the
determination of tin in the range 0 - 6 f,Lg/20ml and the complex having an extinction
coefficient of 108,000, this making it the mostsensitive reagent so far described.
The choice of reagents, other things being equal, will inevitably contain an element
of personal preference and in selecting six reagents for more detailed discussion, consi-
deration has been given to the number of publications on each reagent since 1959 (in
all cases more than I 0) and to experience gained in their use in the analyticallabora-
tories of the Tin Research Institute. Those discussed are dithiol, phenylfluorone, pyro-
catechol violet, gallein, quercetin and haematoxylin. They are not arranged in any 'order
of merit as the choice of reagent will depend on the material being analysed (interferences
to be avoided) and the amount of tin likely to be present (sensitivities vary from e =
-6,000 for dithiol to -90,000 for phenylfluorone).
In addition to the above, details are given of a turbidirnetric method using 4-hydro-
xy-3-nitrophenyl arsonic acid. This method, though of only moderate sensitivity, can
often by used without the need for prior separation of the tin, and is particularly suit-
able for the analysis of organic matter such as foods, after wet-ashing.

3.2 Dithiol
Toluene 3,4-dithiol forms a magenta-red precipitate in dilute acid solution with
Sn(II), the reaction product having the composition SnR 2 • Tin(IV) is slowly reduced
by the reagent to form the same product, but it is standard practice to add thioglycol-
lic acid, ensuring reduction to Sn(II) without interference. The reagent produces colou-
red precipitates with most of the heavy metals, e.g. Mo(VI) and W(VI) form greenish
complexes which are useful analytically, bu t the- only red dithiolate apart from Sn is
formed by Bi. Halides of the alkali and alkaline earth metals and of Al, Zn, Mg do not
interfere, but phosphate reduces the colour intensity. Tartrate can be tolerated as well
as Fe(II) up to 0.5% so that it is often possible to use dithiol for the direct determina-
tion of Sn in biological materials, particularly foods. The reagent itself is unstable in
air and a more convenient source is the solid zinc dithiolate [39), which is air-stable
and can be used as a solution in dilute alkali.
When first described by Clark in 1936 [40) dithiol was practically the only known
reagent producing a coloured complex with Sn and the suggested procedure involved
visual comparison of suspensions of the dithiolate~ A ttempts were made to obtain
stable colloidal solutions of the Sn dithiolate by adding a dispersing agent. The frrst
of these suggested [41] was Teepol X, a proprietory Iong-ehain aliphatic sulphonate,
but it was found that the concentration of the dispersing agent was of critical irnpor-
tance and that comrnercial materials were unsatisfactory owing to variations in con-
centration of the active material from batch to batch. Although satisfactory results
were reported for the use of Santomerse S [42, 43) it is now considered preferable
to employ a single compound such as sodium lauryl sulphate which is available in a
pure form [44). However, good results continue tobe reported using comrnercial
dispersing agents [45], presumably under carefully controlled conditions. A procedure
for the determination of 30- 150f,Lg of Sn in organic matter has been published [46]
details of which are as follows:
After destruction of the organic matter by wet-ashing with H2 S0 4 /HN03 dilute the clear solution
so that it contains not more than 4ml H2 S0 4 /100ml. Transfer a lOml aliquot containing between
 Ref.p. 57] 3.3 Phenylfluorone 49

30 and 150 j.J.g Sn to a separating funnel and if Cu is present extract with successive portions of
5 ml dithizone solution (0.02% in CCI 4 ) until the extract remains green. Transfer the aqueous layer
to a 20m! flask and add 20% H2 S0 4 so that the final solution contains between 0.7 and 1 ml
H2 S0 4 . Add 1 ml sodium lauryl sulphate solution (1% aq.) and 1 ml zinc dithiol solution (dissolve
0.2g in 1% NaOH containing a few drops of ethanol, add 1 ml thioglycollic acid and dilute to
100m! with 1% NaOH) dilute to the mark and immersein a boiling water bath for 1 min. Cool,
allow to stand at room temperature for 20 - 30 min and measure the extinction of the solution in
a lern cell at 535nm. Prepare a calibration graph to cover the range 30 -lSOjJ.g Sn by dissolving
O.lg of tin meta! in 20m! H 2S0 4 , diluting to 500ml after the addition of a further 65 ml H2S04
and diluting a 10m! aliquot ofthis solution to 100m! so that lml ofthisfinal solution contains
20j.J.g Sn. To aliquots of this solution add Sm! of 20% H2S0 4 and continue as in the procedure.

The dithiol method has been extensively used for the determination of tin in
canned fcrods where it is particularly suitable in that the tin can often be determined
directly after wet-ashing ofthe sample [47], though it is sometimes preferred to effect
a preliminary separation of the tin by precipitation as the sulphide [48] or by distilla-
tion of the bromide [49]. The method is not especially sensitive (E = - 6,000) and at-
tempts have been made to improve sensitivity though without great success. Thus
Jantsch and co-workers [50] determined 3JJ.g Sn by collecting the dithiolate precipi-
tate on a small fllter paper disc and matehing the colour with standards. Recently
Gagliardi and Durst [51] extracted the precipitate into an organic solvent (methyl
ethyl ketone or 2-heptanone) and measured the absorbance of the resulting yellow
solution. Detailed procedures have been given for the determination with dithiol of
up to 0.1% Sn in silicate rock after separation of the tin by distillation of the bromide
[42, 52]. Lovibond discs are available for measurement with this reagent.

3.3 Phenylfluorone
This is the trivial name for 2,3,7-trihydroxy-9-phenyl-6-fluorone, which is well-
known as a sensitive reagent for germanium. It forms red sparingly soluble complexes
with many metals, which by use of a suitable protective colloid, e.g. gum arabic, can
be kept in colloidal suspension and used for photometric measurement. The commer-
cial reagent is of variable quality, impurities reducing its stability in solution to both
storage and light. It should have a molar extinction coefficient E of about 40.000 at
4 70 nm. It can be purified by re-crystallisation by dissolving in warm ethanol acidified
with HCI and adding ammonia, or by extraction of the impurities into ethanol [53].
Phenylfluorone forms an SnR 2 complex with Sn(IV) and was first suggested for
the determination of tin by Luke in 1956 [54]. In spite of its Iack of selectivity, in-
volving in many cases tedious separations, it has attracted more attention than any
other reagent, and since that time more than 50 papers have been published describing
its use for the determination of tin in metals and alloys, slags, rocks and various organic
materials.
Luke's original procedure involved reaction in sulphuric acid solution at pH 3 at
25°C, under which conditions colour development is rapid but unfortunately inter-
ferences are at a maximum and the acidity is very critical. Copper, Bi, As(III) and
Sb(III) were separated by extraction with diethyldithiocarbamate in chloroform, the tin
then reduced with mercaptoacetic acid/ascorbic acid and the Sn(II) extracted into
chloroform. The chloroform was evaporated, organic matter destroyed by heating
with sulphuric/perchloric acids and all acid removed by careful evaporation to dryness.
Then 5.0ml of 1 :4 sulphuric acid were added and evaporatedjust to fuming, avoiding
any loss of acid. After the addition of 9 ml of water, 1ml of 3% hydrogen peroxide,
1Oml of acetate buffer and 1 ml of 1% gum arabic solution, 1Oml of the reagent solu-
tion (0.05 g dissolved in 1ml hydrochloric acid and a little methanol and diluted to
50 Photometrie methods [Ref.p. 57

500ml with methanol) were added and the solution allowed to stand for 5 min. After
diluting to 50ml with 1 : 9 hydrochloric acid the absorbance of the solution was mea-
sured in a 1 cm cell at 51 Onm. A reagent blank was deducted and a calibration curve
prepared using a solution of tin metal in sulphuric acid and covering the range 0- 80
f.lg Sn/50rnl.
Luke has since published a modified procedure [55] in which interferences due to
other metal ions are minimised by colour development in solutions of higher acidity
(pH 1.2). Under these conditions both the rate of colour development and the fmal
colour intensity are reduced, so that it is still necessary to control both the acid con-
centration and the time of colour development rather closely in order to obtain repro-
ducible results. Good values were reported by Luke [56] in the determination of
tin (1 - 10%) in both copper- and lead-base alloys without Separations of any kind. In
most case, however, a preliminary separation of the tin is preferable, and this can be
done as above or by precipitation as the hydrated mdde using e .g. Be as collector, by
ion-exchange, by extraction of the iodide into an organic solvent, or by distillation of
the bromide. Improvements to the Luke procedure include the use of tartaric acid
instead of acetate buffer [57], eliminating several interferences and allowing colour
development at a higher pH (2- 3), the use of poly(vinyl) alcohol [58] instead of gum
arabic as a dispersing agent, and, perhaps most important, extraction into organic sol-
vents. It has recently been found [59] that colour development can be enhanced by
the catalytic action of oxalate ion in the presence of cetylpyridinium chloride, the
sensitivity being improved as a result to 0.003f.1g Sn/cm 2 • A disadvantage in the use of
phenylfluorone at the lower end of the tin concentration range has been that the re-
agent itself absorbs appreciably at 510nm, the reagent blank in a 4cm cell having an
absorbance of about 0.2. It was found by Kanna and Ogura [60] that excess reagent in the
final solution can be extracted into chloreform without loss of the tin complex, thus
reducing the extinction ofthe reagent blank to below 0.1 when measured at 480nm,
and this procedure was applied by these authors to the determination of tin in canned
fruit and fruit juices.
An attractive alternative is the extraction of the tin complex itself into an organic
solvent, leaving the excess reagent in the aqueous phase. This would have the advan-
tage of reducing the volume of the final solution e.g. from 50 to 1Oml, at the same
time providing a solutionrather than a suspension for measurement, both factors
extending considerably the lower end of the concentration range. Although this prin-
cip1e has not as yet been much used analytically an indication of its possibilities can be
seen in the increase of E from 40,000- 50,000 for aqueous suspension to 96,000 for
solutions of the tin complex in cyclohexanone [61]. Another approach [62] is toseparate
the coagulated comp1ex, dissolve it in HCl and measure the extinction of the liberated
reagent, but the resulting colour intensity is less than that of the disso1ved complex. The
working range for aqueous suspensions in a final vo1ume of 50rnl is about 10- 70f.1g Sn
when measured in a 1 cm cell at 510 nm.

Derivatives of Phenylfluorone
Increased sensitivity has been found by Nazarenko at al. for the 9-(2,4-disulphopheny1)-
[63] and the p-nitrophenyl- [64] derivatives, the latter having an E value of 60,000 in
20% ethanol at 530nm, while Asmus and co-workers have published a series of papers
on the use of 9-(3-pyridyl) fluorone, which is stated to have an E value of 100,000
at 546nm and a working range of 0.01 - 0.2f.1g Sn/rnl. This reagent has been used for
the determination of tin ( ~ 0.001 %) in zinc and brass [65], in steels [66], hydrogen
peroxide [67] and in organotin compounds [68].
 Ref.p. 57] 3.4 Cateehol Violet 51

Applications
In addition to the references quoted above, many papers have appeared recently on
the determination of small amounts of tin with phenylfluorone. In almost all cases a
preliminary separation of the tin is carried out, the method of separation being chosen
according to the material being analysed. The Luke diethyldithiocarbamate procedure
is widely used though extraction of the iodide Snl 4 into an organic solvent seems to
offer advantages in several cases.

Ores and Minerals

Nazarenko, V.A., Lebedeva, N. V.: Zavod. Lab. 28, 268 (1962)
Baumgaertel, E., Gaertner, P.: Z. Anal. Chem. 208,416 (1965)
Pollack, E.N., Zopatti, L.P.: Anal. Chem. 37, 290 (1965)
Kizyk, A.: Repub. Soc. Rom., Com. Geol. 1964/5,52, 229 (1964)
Smith, DJ: Anal. Chim. Acta 57, 371 (1971)

Steels and Fe"o-Alloys

Picasso, G., Pizzimenti, A.: Met. Ital. 55, 361 (1963)
Luke, C.L.: Anal. Chim. Acta 37, 97 (1967)
Leblond, A.M., Boulin, R.: Chim. Anal. (Paris) 50, 171 (1968)
Amsheev, A.A.: Zavod. Lab. 34, 789 (1968)
Dymov, A.M., et al.: Zh. Analit. Khim. 26, 2360 (1971)
Ashken, A., et al.: Z. Anal. Chem. 264, 133 (1973)
Romantseva, T.I., /vanov, I.G.: Chem. Abstr. 80, 22323 (1974)
Silaeva, E. V., Kurbatova, V./.: Zavod. Lab. 27, 1462 (Fe/Mo) (1961)
Jankovsky, J.: Hutn. Listy 18, 276 (1963)
Hata, A., Hasegawa, M.: Japan Analyst 17, 1118 (Fe/We) (1968)

Non-Fe"ous Metals and Alloys

Yakovlev, P. Ya., et al.: Chem. Abstr. 59,4537 (Nickel) (1963)
Hafer, A.: Z. Anal. Chem. 240, 229 (Nickel) (1968)
Hafer, A., Land!, B.: Z. Anal. Chem. 244, 103 (Lead) (1969)
Gur'ev, S.D., Saraeva, N.F.: Zavod. Lab. 24, 1195 (Lead) (1958)
Gur'ev, S.D., et al.: Chem.Abstr. 59, 12173 (Pb/Sb) (1963)
Zaichikova, L.B., Lutchenko, N.N.: Chem. Abstr. 60, 2324 (Mo) (1964)
/shihara, Y., Kemuro, H.: Japan Analyst 12, 380 (Tellurium) (1963)
Raczka, E., Suchy, H.: Rudy Met. Niezelazne 6, 274 (Zinc) (1961)
Raykovic, D.: Z. Anal. Chem. 263, 324 (Zircalloy) (1973)

Foods
Thompson, M.H., McClellan, G.: J. Assoc. Offic. Agr. Chemists 45,979 (1962)
Glathe, M.: Chem. Mikrobiol. Technol. Lebensm. 3, 125 (1974)
Fruit & vegetable products - determination of tin: I.S.O. 244 7; 1974

3.4 Catechol Violet

Pyrocatechol violet, 3,3', 4'-trihydroxyfuchsone-2"-sulphonic acid, or, more
simply, catechol violet, forms a water-soluble red complex with tin(IV) which was
first suggested as a reagent for the determination of tin by Sagakova and Lyubivaya
[69], though Suk and Malat [70] had previously suggested that the colour of the com-
plex could be used as an indicator in the titrimetric determination of tin with EDT A.
52 Photometrie methods [Ref.p. 57

The nature of the tin-catechol violet system is not fully understood. Ross and White
[71] reported the existence of two coloured species at pH 2.S, the predominant one
SnR 2 being formed in the presence of excess reagent and having an absorption max-
imum at 55Snm and an extinction coefficient of about 6S,OOO, a second coloured
species Sn 2 R being formed when the mole fraction of tin exceeds 0.5, and having an
absorption maximum at 620nm and extinction coefficient of about halfthat of the
SnR 2 complex. More recently in a computer analysis of the absorption spectra of so-
lutions at pH 3, Wakeley and Varga [72] have found evidence for the existence of
three complexes, two of them, SnR and SnR 2 , having absorption maxirna at the same
wavelength, 550nm, with the third, Sn 2 R, showing a small peak at 610nm. However,
the SnR 2 complex is the only one of analytical importance. Ross and White [71]
determined tin successfully at pH 2.5 in phthalate buffer by measuring at the 55S nm
peak, but encountered interference by a nurober of other metals, which could not be
prevented by the usual masking agents such as tartrate or EDT A. They therefore pro-
posed prior extraction of the tin from solutions of M HCl with tris(2-ethylhexyl)-
phosphine oxide (O.OlM in cyclohexane) and fmal photometry in the organic phase,
a procedure claimed to be almost specific. However, extraction of the iodide Snl 4
into benzene or toluene seems more convenient and most of the recent work with
catechol violet makes use of this method of Separation. Tanaka [73] separated tin
from interfering elements by extraction of the iodide into benzene and then back·
extracted it with 1 - 2 M.HCl and determined the tin by photometry in the aqueous
solution at pH 3.S in acetate buffer. This procedure he used for the determination
of tin in iron and steel [74]. The Tanaka method was modified by Newman and
Jones [7S] and their procedure has been recommended [76] for the determination of
small amounts of tin up to 30J,Lg in organic matter such as foodstuffs, after destruction
of the organic matter by wet-oxidation with nitric and sulphuric acids.

A suitable aliquot of the sulphuric acid solution containing not more than 30J,Lg Sn
is diluted to approximately 4 - SM, and for each 2S ml of the solution 2.5 ml of SM potas-
sium iodide solution (dissolve 83g of KI in water to produce lOOml) and 10m! of
toluene are added. After shaking in a separating funnel for 2 min the layers are allowed
to separate and the aqueous layer is discarded. The toluene layer is washed without shaking
with 5 ml of a solution prepared by mixing 2S ml of 4 - 5 M sulphuric acid with 2.S ml of
the potassium iodide solution and the washings discarded. Five ml of water are added
to the toluene layer and then 5 M sodium hydroxide dropwise until the pink colour of
the iodine is discharged and then two drops in excess. After shaking for 30 sec and
allowing the layers to separate the aqueous layer is transferred to a beaker, the toluene
shaken with 3 ml of 0.1 M sodium hydroxide and the aqueous layer combined with
the first extract. This solution is acidified with 2.S ml of SM hydrochloric acid, the
liberated iodine decolourised by dropwise addition of a S% ascorbic acid solution and
2ml of catechol violet (O.OS% aq.) added. The toluene layer is washed with Sml of
sodium acetate solution (20%), the washings added to the aqueous solution, and after
adjusting the pH to 3.8 with SM ammonia solution by means of a pH meter, it is di-
luted to 2Sml and its optical density measured after 30 min in a 1 cm cell at 5S2 nm.
Increased sensitivity, together with a shift in the absorption maxirnum to a higher
wavelength in the presence of gelatine was reported by Malat [77], while the addition
of cetyltrimethylammonium bromide results in the formation of a ternary complex
with an absorption maximum at 662nm and an extinction coefficient of 95,000
[78]. This increased sensitivity enabled Corbin [79], using lOcm cells, to determine
tin in the range 0.5- 8J,Lg/50ml, with a detection limit of about O.OSJ,Lg.
 Ref.p. 57] 3.5 GaUein 53

Catechol violet has been used for the determination of tin in bronzes [80] in vine-
gar, orange drinks and cooking oil in the range 0.2 - 1.6~g [81], in seawater (0.6 - 2
~g/1) [82] andin effluents [83 ], after separation and concentration of the tin by
ion-exchange, andin fats [84] (5-20~g/g) by direct extraction with a solution of the
reagent in ethyl acetate.

3.5 Gallein

HO
HO OH

Gallein, pyrogallolpthalein, or 4,5,6-trihydroxy-3-oxo-9 (phenyl o-carboxylic acid)

xanthene, forms with Sn(IV) a red SnR 2 complex which is only slightly soluble in
dilute acid.lt was first used by Wood [85] and by Stanton andMcDonald [86] as a
field test for tin in geochemical prospecting, in which the tinwas sublimed as Snl 4 by
heating the sample (1 g) with an equal weight of ammonium iodide, and the sublimate
leached in 10% hydrochloric acid. After flltration a suitable aliquot (1 - 2~g Sn) was
decolorised with hydrazine and diluted to 100rnl after the addition of 10rnl of Chlor-
acetate buffer (378g chloracetic acid + 80g sodium hydroxidein 1litre of water) to
bring the pH to 2- 2.5. After the addition of 0.5 rnl of the reagent (0.1 %in ethanol)
the complex was extracted into 1Ornl of iso-amyl alcohol and its absorption measured
at 500nm in a 1 cm cell. lnterferences have been investigated by a number of workers
andin particular Mah and Tupper [87] pointed out that high results can be obtained
if the iodide fusion is prolonged, owing to volatilisation of iron and titanium. The
above procedure was used successfully by Hutehin and Fiander [88] for the determina-
tion of tin'(O.Ol - 2%) in a variety of mine samples. These workers fused a 0.1 g sample
with 0.5 g ammonium iodide and measured the absorption of the complex in the
aqueous solution without extraction into an organic solvent, and it is interesting to
note that Heegn [89], who studied the tin-gallein system in detail, found no great
difference between extinction coefficients in aqueous solution and in cyclohexanone
(e aq. = 29; e ext. =42 x 103 ). Forthedetermination of tin (0.1 - 1 %) in ores and ore
dressing products, Heegn fused a 1 g sample with sodium peroxide, extracted the melt
with water, and after the addition of tartaric and asorbic acids, acidified with hydro-
chloric acid and diluted to a known volume, so that the final concentrations of reagents
were 5g/1 tartaric acid, 2.5g/1 ascorbic acid and acidity 0.5M. A suitable aliquot
containing up to 3 ~g Sn was neutralised to phenolphthalein, its pH adjusted to 1.9 by
the addition of 5 rnl of chloracetate buffer and after the addition of 1rnl of the reagent
solution and dilution to 25rnl the complex was extracted into 10rnl of cyclohexanone
and its extinction measured at 496 nm in a 1 cm cell.
The Gallein method has been used for the determination of tin in iron and steel
and in non-ferrous metals and alloys [90, 91] and in a number of food products [92,
93, 94].
54 Photometrie methods [Ref.p. 57

3.6 Quercetin
Quercetin, 3,5,7,3',4'-pentahydroxyflavone, forms an SnR 2 complex with Sn(IV)
in acid solutions; the complex is a bright yellow-orange colour, having an absorption
maximum at 437 nm and is soluble in 50% aqueous ethanol. The reagent is moderately
sensitive (E = 26,000) and Beer's Law is obeyed over the range of 0- 50 J.J.g Sn in 50ml
using a 4 cm cell. lt was fust used by Liska [95] for the determination of small amounts
of tin in copper alloys and by Janousek and Studlar [96] for the determination of
0.001- 0.1% Sn in steels after separation by ion-exchange or by distillation. It appears
to be suitable for the direct determination of tin in organic materials such as canned
foods, as the products of wet-ashing do not interfere, apart from large amounts of
phosphate which above 0.5% cause some fading of colour. Lyaskovskaya and
Krasil'nikova [97] determined tin in canned meat by this method, finding good
agreement with results obtained by using dithiol. Tin has been determined in canned
foods by other workers [98, 99, 100, 101, 112] and also in wines and spirits [ 102, 103].
A procedure described by Kirk and Packfington [99] is as follows:
Wet-ash a food sample containing not more than 1,000J.J.g Sn with HN0 3 /H 2 S0 4 using Sm! of
the latter. Dilute to 50ml, take a 2m! aliquot and to this add 2,4-dinitrophenol indicator and
10% sodium carbonate dropwise until the appearance of a yellow colour. Discharge the colour by
dropwise addition of 2.5 M HCI and then a further 5 ml of the acid. Add 3ml of a saturated solu-
tion of thiourea to mask any iron present, and 5 ml of a 0.2% solution of the reagent in ethanol,
followed by 25 ml of ethanol. Dilute to 50ml with water and after 30 min measure the extinction
of the solution at 437nm in a 4cm cell. Prepare a calibration graph by dissolving 0.0500g of pure
tin in 50ml of H2 S0 4, adding 120m! ofwater and diluting to 200m! with 25% H2 S04. Add
aliquots of 1,2,3 and 4ml to a series of flasks containing 10m! HN0 3 and Sm! H2 S0 4, evaparate
to fuming and continue as in the procedure.
Quercetin has also been used for the determination of small amounts (0.001 - 0.1 %)
of tin in steels after Separation by distillation of the bromide [ 104], extraction of the
iodide or precipitation of the hydroxide [ 105], in ferrotitanium after separation by
ion-exchange [106], and at concentration of about 1 ppm in samples oflead, indium
and bismuth after separation by precipitation as hydroxide or by ion-exchange [107].
An interesting modification described in the last of these papers is the increased sen-
sitivity obtained by extraction of the tin-quercetin complex into an organic solvent
(15 ml of methyl iso-butylketone) allowing the detection of 0.1 ppm Sn using a lOg
sample and making the fmal measurement in a 1 cm cell.
Marin
The 3,5, 7 ,2' ,4' -isomer of quercetin reacts with many metals including tin in acid or
neutral solution to give strongly fluorescent products [108]. The reaction is very
sensitive and has been used for the fluorimetric determination of tin [ 109]. Photome-
trie procedures are less sensitive;Patrovsky [110] and Stolyarov et al. [ 111] reported
procedures in which a 1 : 1 complex is formed at pH 2, having an absorption maxi-
mum at 420nm (E = 27,000), Beer's Law being obeyed over the range 0.04- 3.6J.J.g
Sn/ml, but the reagent appears to offer no particular advantage.

3.7 Haematoxylin and Haematin

Haematoxylin forms a red lake with Sn(IV) in acid solution,the colour intensity
being pH-dependent and the absorption maximum varying between 510 and 590nm
according to the conditions. Teicherand Gordon [113] developed the colour at pH 0.8
and measured absorption at 515 nm, covering the range 0.1 - 14J.J.g Sn/ml. Norwitz
[114] in a detailed study found that colour development at pH 5.4 in the presence of
sodium acetate gave higher sensitivity and that more rapid development took place
on heating in the presence of gelatin. In this way he was able to determine 1% Sn in
 Ref.p. 57] 3.8 4-Hydroxy-3-nitrophenyla.rsonic acid 55

nitroce!lulose propellants after wet-ashing and without a preliminary separation of

the tin, the only other meta! present - Iead - having no harmful effect. In general,
however, many other metals cause serious interference, the most important being
Fe(III), Sb(III) and Ti(IV) and isolation of the tin is a prerequisite when using this
reagent. In addition, the reagent itself is unstable and all the more recent work has
been concentrated on the use of oxidised haematoxylin or haematin. The use of hae-
matin was investigated by Asmus and co-workers in 1966 [ 115] who found that the
1 : 2 complex ( € = 70 x 10 3 ) could be used for the determination of Sn(II) or Sn(IV)
with little or no interference from the small amount of the 1 : 1 complex formed at
the same time. The interference of Fe(III) was eliminated by reduction with ascorbic
acid and of Sb(III) by oxidation to Sb(V). Since then this reagent has been used for
the determination of tin in steels after separation of the iodide into benzerre [ 116]
and, at low concentrations ( ~ 1o-4 %) in Iead alloys [ 117]. In addition, Genda and
Marikawa [ 118] determined tin (> 10%) in organotin compounds after wet-ashing
a 5 mg sample.

3.8 4-Hydroxy -3-nitrophenylarsonic acid

~As0(0H) 2
Ho-y
N0 1

Arsonic acidderivatives form insoluble precipitates with Sn(IV) in acid solution

(Chapter 3, Section 4) and of these the 4-hydroxy-3-nitrophenyl derivative was first
suggested by Karsten, Kies and Walraven [ 119] for the turbidimetric determination of
small amounts (0.1 - 0.2mg) of tin in antimony sulphide. They found that !arge
amounts of chloride prevented precipitation, but that, apart from titanium and zir-
conium, there was little interference from other metals. Iran in up to 100-fold excess
could be tolerated but delayed complete precipitation for several hours, so that it was
preferable to allow the solution to stand overnight, the precipitate which settled out
being readily and reproduciby re-dispersed by shaking. In the presence of a large
excess of iron some contamination of the precipitate takes place and in such cases
it was suggested that the precipitate should be filtered off, wet-ashed and re-precipi-
tated. These authors measured the turbidity at 424nm, but there is no sharp absorp-
tion maximum and measurement can be made at any point between 420 and 470nm.
The absence of interferences makes it possible to determine tin directly by this
method in a number of metals and alloys. Thus Dozinell and Gill [120] determined
tin in refmed copper, and Challis andJones [121] determined 0.001-0.4% tin in a
series of copper-base alloys, while Pohl [122] determined 0.0001 - 0.1% tin in zinc-
base alloys, and a standard procedure has been published [ 123] for the determination
of the same range of tin content in aluminium alloys.
The reagent is suitable for the determination of tin in organic matter such as foods
after wet-ashing. To an aliquot of the resulting sulphuric acid solution containing 0.1-
0.2mg Sn in 5 ml H2 S0 4 are added 1Oml of 30% tartaric acid solution and after
mixing, 4ml of reagent solution (2g dissolved in 50ml of methanol and diluted to
lOOml with water) and the solution diluted to 20ml. After standing for two to three
hours or preferably overnight to allow complete precipitation the solution is shaken
and its turbidity measured in a 2cm cellatabout 450nm.
56 Photometrie methods [Ref.p. 57

4. Fluorimetric Methods

Compounds which are reduced to fluorescent products by Sn(II), particularly vari-

ous naphthol sulphonic acids have been used for the detection and determination of
tin as described in a series of publications by Anderson et al [ 124], but it is only
since the fairly recent availability of commercial spectrofluorimeters that the increased
sensitivity of fluorimetric methods as compared with photometric procedures has be-
come of interest for the determination of trace amounts of tin.
Although Anderson ( 1956) was able to determine 0.1 J.(g/ml of tin by its reaction
with 6-nitro-2-naphthylamine-8-sulphonic acid, the reacting species is Sn(II) and as
already mentioned in the case of the molybdenum blue method, one is then faced with
the problems of oxidation of the tin and of positive interferences by other reducing
ions present, so that it is essential when possible to use reactions based on tin(IV). It
was found by Coyle and White [125] that flavonal (3-hydroxyflavone) produces a
bright blue fluorescence with tin(IV) in dilute acid solution, with a sensitivity of about
0.1 J.(g Sn/mi. Quantitative results were obtained in a 33% dimethylformamide solution
that was 0.06M with sulphuric acid and fluorescence was measured at 405/450nm.
with a calibration range of 0.2- 0.6J.(g Sn/25 ml. It was found that zirconium, chloride,
fluoride and phosphate interfered and that close control of the dimethylformamide
concentration was necessary. This reagent has recently been used for the fluorimetric
determination of triphenyltin compounds (see Chapter 9).
8-Hydroxyquinoline has been suggested [ 126] as a fluorescent reagent for tin, but
produces only a weak fluorescence (2 J.Lg/ml Sn) but Pa! and Ryan [ 127] found that
the 5-sulphonic acid derivative is much more sensitive and that fluorescence intensi-
ties are independent of the valence state of the meta!. Although F e(III), Cu( II) and
Hg(II) quench the fluorescence, 300ppm ofFe(III), 75J.Lg/ml ofCu(II) and 100ppm
of Hg(II) do not interfere in the determination of 0.1 ppm of tin in the presence of
hydroxylamine or thioglycollic acid (iron), thiosulphate (copper) or chloride (mer-
cury). Small amounts of fluoride and EDTA quench the fluorescence, large amounts
of organic acids (citrate, tartrate, oxalate) reduce the intensity by 50% while traces
of Al, Zn and Zr increase it considerably and nicke! reduces it. The neutral sample
solution (0.05- 2.5J.Lg Sn) (1 ml) is treated with 3ml of acetic acid/acetate buffer
(pH 4.0- 5.2) and with a 250 molar excess of reagent solution (10" 3 M in water)
diluted to 1Omland the fluorescence measured at 360/512nm.
Improved sensitivity and good tolerance to other elements have been reported by
Filer [128] for 3,4,7-trihydroxyflavone. Here alse a nurober of elements interfere in
the direct determination of the tin and a preliminary separation by extraction of the
iodide into toluene is suggested. Any iron present must be reduced to Fe(II) and com-
plexed with sulphamic acid in sulphate buffer to prevent serious interference. Fluo-
rescence is measured at 427/473nm and calibration curves arelinear up to 6J.(g Sn/
25 ml and the detection Iimit is stated to be 0.007 J.(g Sn.

Other reagents that have been put forward are Rhodamine B (range up to lOJ.(g
Sn/Sml;measurement at 555/580nm) and morin [130] (range 0.1- SOJ.(g Sn;measure-
ment at 420/SOOnm).
Although all these reagents have some disadvantages the high sensitivity of fluori-
metric methods and the increasing need for methods of determining smaller and
smaller amounts of tin make this an interesting field for further study.
 References 57

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89. Heegn, H.: Freiberg Forsch. A, 455, 47 (1969)
89a. Ackermann, G., Heegn, H.: Talanta 21,431 (1974)
90. Murano, M., Mijazaki, S.: Bunseki Kagaku 15, 657 (1966)
90a. Murano, M., Mijazaki, S.: Kanagawa-Ken Kogyo Shikensho Kenyo Hokuku 21,51 (1968);
Chem.Abstr. 70, 73986 (1969)
91. Jones, J.C.H.: Analyst 93, 214 (1968)
92. Timofeeva, O.A., Podolenko, A.A.: Sadovod. Vinograd. Vinodel. Mold. 24, 27 (1969)
93. Stanton, R.E.: Food Tech. Australia 22, 236 (1970)
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98. Karvanek, M., Curda, D., Mi/er, V.: Prumysl Potravin 16, 369 (1965)
99. Kirk, R.S., Pocklington, W.D .. : Analyst 94,71 (1969)
100. Eyrich, W.: Deut. Lebensm. Rundsch. 68, 280 (1972)
101. Fitak, F.,Pilkowska, B.: Rocz. Panstw. Zakl. Hig. 24,331 (1973)
102. Raik, Y.S., Timopeeva, O.A.: Isobret Prom. Obraztsy Tovarnye Znaki 45, 10 (1969)
103. Bondarev, M. V., Gandel'man, Kh.K.: Vinodel Vinograd SSSR, 29, 28 (1969)
104. Chetkowski, W.: Prace Inst. Hutn. 18, 109 (1966)
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106. Ponosov, V.!., et al.: Anal. Abstr. 23, 280 (1972)
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110. Patrovsky, V.: Chem. Listy, 48, 1694 (1954)
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23, 133 (1969)
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 References 59

115. Asmus, E., Altman, H.J., Thomasz, E.: Z. Anal. Chem. 216, 3 (1966)
116. Spelker, H., Graffmann, G.: Z. Anal. Chern. 228, 401 (1967)
117. Shirodker, R., Schibilla, E.: Z. Anal. Chern. 248, 173 (1969)
118. Genda, S., Morikawa, T.: Kagaku.To Kogyo (Osaka) 43, 265 (1969); Chern. Abstr. 71,
108908 (1969)
119. Karsten, P., Kies, H.L., Walraven, J.J.: Anal. Chim. Acta 7, 355 (1952)
121. Challis, H.J.G., Jones, J.T.: Anal. Chirn. Acta, 21,58 (1959)
122. Pohl, H.: Metall, 12, 103 (1958)
123. Association Francaise de Normalisation: N.F.A. 06-578 (1956)
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17,453 (1957); 19,257 (1958); 22,1 (1960)
125. Coyle, C.F., White, C.E.: Anal. Chern. 29, 1486 (1957)
126. Shkrobot, E.P., Ginzberg, L.B.: Zavod. Lab. 23,527 (1957)
127. Pa/, B.K., Ryan, E.D.: Anal. Chim. Acta 48, 227 (1969)
128. Filer, T.D.: Anal. Chern. 43,1753 (1971)
129. Nishikawa, Y., eta/.: Japan Analyst 19,1224 (1970)
130. Shcherbov, D.P., et a/.: Zavod. Lab. 39,546 (1973); Chern. Abstr. 79,73291 (1973)
131. Hirokawa, K.: Sei. Rep. Tokio Univ. A, 13,426 (1961)
132. Zhivopistesev, V.P., etal.: Zhur. Anal. Khim. 26,761 (1971);Anal. Abstr. 23,1368 (1972)
133. Bosch Sessat, F.: Inform. Quirn. Anal. 22, 227 (1968); Chern. Abstr. 70, 111308 (1969)
134. Alimarin, I.P., et al.: Zhur. Anal. Khim. 25, 2287 (1970)
135. Barinowski, R., etal.: Chernia Anal. (Poland) 19,997 (1974)
136. Busev,A.I., etal.: Tr. Korn. Anal. Khirn. Akad. Nauk. SSSR 17,218 (1969);
Chern. Abstr. 72, 128316 (1970)
137. Busev, A.l., et al.. : Zhur. Khim. 26, 1517 (1971)
138. Thierig, D., Umland, F.: Z. Anal. Chern. 221, 229 (1966)
139. Shumova, T.l., Blyum, I.A.: Zavod. Lab. 34, 659 (1968)
140. Köthe, J.: Chernia Anal. (Poland) 17,445 (1972); Anal. Abstr. 24, 2765 (1973)
141. Zhivopistev, V.P., Minima, U.S.: Vch. Zap. Rerrn. Gas. Univ. 178,196 (1968);
Chern. Abstr. 73, 136996 (1970)
142. Zhivopister, V.P., Minima, U.S.: Vch. Zap. Rerrn. Gas. Univ. 141, 213 (1966);
Chern .. Abstr. 69, 15909 (1968)
143. Usatenko, Yu. I., et al.: Zhur. Anal. Khirn. 22, 1823 (1967);
Chern. Abstr. 68, 65430 (1968)
144. Dey, Arun K.: Chirn. Anal. 40, 202 (1958); Anal. Abstr. 6, 1180 (1959)
145. Elinson, V.A., Tsvetkova, V.T.: Zavod Lab. 37, 662 (1971)
146. Nazarenko, V.A., et al.: Zhur. Anal. Khim. 28, 1100; Chern. Abstr. 79, 87158 (1973)
147. Zaidi, S.A.A., et al.: Ind. J. Chern. 9, 374 (1971); Chern .. Abstr. 74, 146969 (1971)
148. Be/eher, R., et al.: Anales Real. Soc. Espan. Fis. Quim. 59, 281 (1963)
149. Yoshinga Oka etal.: Japan Analyst 83,699 (1962);Chern. Abstr. 59,10761 (1963)
150. Okac, A., Urchlabsky, M.: Z. Anal. Chern. 182,425 (1961);Anal. Abstr. 9,1406 (1962)
151. Bagdasarov, K.N., et al.: Elektrochirn. Optichn. Metody Analiza Sb. 176 (1963);
Chern. Abstr. 61, 3 (1964)
152. Tataev, O.A., Shakhabudinov, A.Sh.: Chern. Abstr. 80, 10343 (1974)
153. Uhlemann, E., Pohl, V.: Anal. Chirn. Acta 65,319 (1973);Chern. Abstr. 79,100116 (1973)
154. Ting, H.H., Ch'en, K. Y.: K'o Hsueh T'ung Pao, 3, 93 (1959)
155. Obolonchik, N. V.: Trudy Korn. Analyt. Khim. 16, 41 (1968); Anal. Abstr. 16, 2388 (1969)
156. Ackermann, G., Köthe, J.: Chernia Analit. (Poland) 17, 445 (1972); Chern. Abstr. 78, 37533
(1973)
157. Skakov-Trybula, Z., Polanska, J.: Chernia Analyt. (Poland) 15,635 (1970);
Anal. Abstr. 20, 3712 (1971)
158. Meditsch, J. de 0.: Rev. Qzirn. lnd. (Rio de Janeiro) 39, 14 (1970)
Chern. Abstr. 74, 150703 (1971)
159. Tataev, O.A., Shakhabudinov, A. Sh.: Novey Metody Khirn. Anal. Mater 1, 49 (1971)
Chern. Abstr. 77,121755 (1972)
160. Popov, M.A.: Anal. Abstr. 12, 602 (1965)
161. Lopez, Ramon, A., Lachica, M.: An. Quim. 67, 751; Chern. Abstr. 76, 121170 (1972)
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Anal. Abstr. 18, 3871 (1970)
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60 Photometrie methods

168. Kobayashi, T., Yado, M.: Shokulin Eiseigaku Zasshi 9, 465 (1968)
Chem. Abstr. 70, 76506 (1969)
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CHAPTER 6

ELECTROCHEMICAL METHODS

By JoWo Price

1. lntroduction
Electrochemical methods have been relatively little used in the analysis of tin,
apart from the use of controlled potential electrolysis for the analysis of some alloy
systems and the use of conventional polarography for the determination of moderate
amounts of tin in eogo organic matter. However, improved instrumentration, giving
increased sensitivity, particularly in aoco polarography, has made it possible to deter-
mine tin at very low concentrations; the work so far donein this field seems highly
promising, though difficulties with eogo reagent blanks, may prove a limiting factor.

20 Electrodeposition
Tin, present either as Sn(II) or Sn(IV) can be electrodeposited from acid chloride
solutions [ 1] Low results can be caused by partial re-dissolution of the tin by elec-
0

trolytic action during washing; this error is reduced by using a copper-plated platinum
cathode and by neutralisation of the electrolyte just before termination of the electro-
lysiso A depolariser such as hydroxylammonium chloride must be presento Other met-
als present are co-deposited so that preliminary Separation of eogo copper and antimony
is necessaryo Lead and tin, co-deposited from chloride solution, can be separated by
dissolution of the deposit in a mixture of nitric and hydrofluoric acids, followed by
deposition of the lead as Pb0 2 Oxalate solutions were once used for the electrodepo-
0

sition of tin following Separation of copper and antimony as sulphides, whiie slightly
acid tartrate solutions can be used to separate copper and lead from tin by electrolysis,
the tin being subsequently deposited after the addition ofhydrochloric acid [2]0
Phosphoric acid can be used instead of tartaric acid to complex the tin, the same Sepa-
rations being possible, tin again being deposited after the addition of hydrochloric acid
[3] 0

30 Controlled potential electrolysis; coulometric analysis

Electrodeposition of tin without voltage control is now of little importance but the
use of controlled potential electrolysis is of value in the analysis of a number of alloys
containing tino Thus, in the analysis of copper-base alloys copper, bismuth and anti-
mony can be deposited from chloride solution by maintaining the cathode potential
at about- 0.35Vo vso Socoeo, leaving tin, lead, nicke!, and zinc in solution [4]0 lf desired
tin and lead can be removed with the copper by increasing the potential to- Oo7Vo
62 Electrochemical methods [Ref.p. 65

after deposition of the copper. The separation of copper, Iead, tin and antirnony by
this method has been studied by Al[onsi [5] and used by him for the analysis of
copper-base [6], Iead [7] and tin- [8] base alloys. However, perhaps the most im-
portant form of controlled potential electrolysis is the mercury pool cathode, flrst des-
cribed by Lingane [9 ], particularly for the separation of the copper group elements. Thus
in weakly acid tartrate solution (pH 4.5) copper can be removed by electrolysis at a
potential of- 0.15V. vs. s.c.e., copperplus bismuthat- 0.4 V. and copperplus bismuth
plus most of the Iead at- O.SSV., leaving cadmiurn in solution. Lead and tin cannot
be separated in this way but the method has been used for the determination of im-
purities such as zinc and aluminiurn in tin-base alloys.

In electrolysis with a mercury cathode, the weight of meta! deposited cannot be

determined directly but coulometric methods can be used and, with modern instru-
mentation, using current integrators etc., are capable ofhigh accuracy. The work
done by Bard and Lingane [ 10] showed that the electrolytic reduction of tin can be
carried out in acid chloride solutions at constant current and constant potential. When
using a mercury pool electrode in constant potential electrolysis it was shown by
Meites [ 11] that reduction of an ion to the meta! proceeds rather slowly, while during
oxidation, fewer side reactions exist, resulting in lower background currents and bet-
ter accuracy and precision. These findings were applied by Wise and Williams [ 12] to
the determination of tin by coulometric oxidation in glasses, copper alloys and tin
concentrates. Using a supporting electrolyte of 3M KBr + 0.2M HBr and a mercury
pool cathode, they carried out the reduction step at- 0.7V. vs. Ag/AgCl until only a
small constant background current (< 0.01 ma) persisted. The polarity of the electro-
des was then reversed and the tin oxidised at- 0.3V. until the background current was
again less than 0.01 ma. Interference due to cadmium can be avoided by carrying out
the tin reduction at- O.SSV. and antimony can be removed by flrst electrolysing at
- 0.3V. and then reducing the tin at- 0.7V. using a fresh portion ofmercury. Thein-
terference of Iead cannot be avoided in this way but, tagether with cadmium, it can
be removed by reduction at- 0.9V. from an ammoniacal tartrate solution, the solu-
tion then neutralised with hydrobromic acid and the tin determined as above after
addition of the same supporting electrolyte [ 13].

4. Polarography

The conventional d.c. polarography of tin solutions was described in detail in a se-
ries of papers by Lingane et al. and the earlier work in this fleld has been summarised
by KolthoffandLingane [14]. In most media Sn(II) gives two waves, an anodic step,
Sn(II) ""' Sn(IV) + 2e,
and a cathodic step
Sn(II) ""' Sn( o),
which is usually reversible and well-defmed and which has been used in a number of
cases for analytical purposes. Unfortunately there are difflculties in being certain of
obtaining all the tin in a solution in the Sn(II) form and further uncertainty exists in
maintaining the sample in this state in view of the ease with which air-oxidation can
take place. For these reasons it is generally preferable to work with solutions in which
the tin is present as the stable Sn(IV), which in a base electrolyte consisting of 1M hy-
 Ref.p. 65] 5. Amperometry 63

drochloric acid cantairring 4M ammonium chloride gives two steps, the first resulting
from the reduction of the SnCWcomplex to the SnClfcomplex and the second from
the reduction of SnCl~-to the metal. The second of these steps was used successfully
by Lingane [15] to determine tin in copper-base alloys and by Godar andAlexander
[ 16] for the determination of tin in foods; it was subsequently found [ 17] that better-
defined steps are obtained in SM hydrochloric acid solution and linear calibration
curves are obtained in this medium over the concentration range 10" 3 - 10" 5 M
(E 112 ~ 0.5V). A serious disadvantage of this method lies in the interference caused
by copper, antimony, bismuth and Iead, all of which have E 1; 2 values morepositive
than- 0.6V in acid chloride solutions. The interference oflead is likely tobe the most
important as it frequently accompanies tin and various methods of separation have
been put forward: no step is given by Sn(II) in sodium hydroxide or arnmonical
tartrate solution, while Iead gives well-defmed steps in both media, so that a correc-
tion can be made to the combined tin-lead wave found in acid solution. Alternatively
tin may be removed from the sample solution by volatilisation as the bromide after
measurement of the combined wave, the residual step being due to Iead alone. None
of these methods is entirely satisfactory and they are now largely of historical interest.

The development of more sensitive polarographic methods such as square-wave

[ 18] or cathode ray oscillography [ 19], while allowing the direct determination of
small amounts oftin in e.g. iron and steel, did not altogether solve the problern of
Iead in terference and many workers prefer to make a preliminary separation of the
tin before polarography e.g. by distillation of the bromide [20] or by co-precipitation
with manganese dioxide [21, 22].
More recently a.c. methods of polarography have been found in general to offer
advantages in increased sensitivity and freedom from interferences and application
of these methods to the determination of tin has confirmed their superiority over
d.c. methods. A comparison of available methods has been made by Bond [23] who
concluded that for tin concentrations within the range 10-3 - 10-6 M in hydrochloric
acid supporting electrolytes, conventional a.c. polarography with a dropping mercury
electrode of natural drop frequency is superior to other methods of conventional and
inverse d.c. polarography and to both a.c. and d.c. rapid polarography. For lower
concentrations of tin, down to 1o-s M, anodic stripping polarography ( see Section
6) is recommended. A.c. polarography has been used successfully for the direct
determination of tin down to 0.005% in a variety of geochemical materials, using a
1 g sample, no interference from overlapping waves of other elements being observed
[24]. The peak potential of the a.c. Sn(II) wave vs. Ag/ AgCl was observed between
- 0.4 and- 0.7V, depending on the nature of the supporting electrolyte. Sampies were
taken into solution by fusion with peroxide or with a mixture of 2 g boric acid and
3 g sodium fluoride, the latter being preferred for most rock samples. For the polaro-
graphy of organotin compounds see Chapter 19.

5. Amperometry
The first amperometric titration of tin using the dropping mercury electrode was
suggested by Lingane [25] who determined Sn(II) in amounts up to 10mg/50ml by
titration with Cu(II) solutions in an acidtartratemedium of pH 4.3, using an applied
potential of- 0.2V vs. s.c.e. In this way the anodic diffusion current due to the tin
is compensated by the cathodic current of the copper tartrate complex, the end-point
64 Electrochernical methods [Ref.p. 65

of the titration being where the net current becomes zero after correcting for the re-
sidual current. The more usual from of amperometric titration in which the element to
be determined is precipitated by addition of a suitable reagent is exemplified by the
work of Kalthoffand Johnson on the determination of Sn(IV) with m-nitrophenyl-
arsonic acid [26] and tetraphenylarsonium chloride [27]. The former was used to
determine 60 - 120mg Sn/ lOOml in 0.2M hydrochloric acid, but equilibrium condi-
tions are reached only slowly and better results were obtained with the second rea-
gent, working in 2-4M hydrochloric acid and 3 - 4M chloride, with an applied valtage
of- 0.3 V vs. s. c. e. Methods of this kind are subject to numerous interferences, both by
elements producing steps at the applied valtage and by those forming precipitates with
the titrating reagent, the need for Separations thus making them less attractive. Other
examples of precipitation reagents that have been used in this way are tannin [28] and
cupferron [29], the latter being made interference-free in the analysis of Zircaloy
samples by a preliminary distillation of the tin as the bromide. The solubility of the
tin-cupferron complex is kept low by addition of 3M ammonium sulphate and the
titration carried out with 0.05 M cupferron at - 0.84 V vs. Ag/ Agf:_l.
Amperometric methods for the determination of tin(II) suffer from the uncertainty
of complete reduction of small amounts of tin and ease of oxidation by air. Satisfactory
results have been reported by the use of bromate [30], dichromate in formate solution
at pH 3 (31] and permanganate [32]. For the application of amperometry to the deter-
mination of organotin compounds see Chapter 19.

6. Anodic Stripping Voltammetry

In this method a sufficiently negative potential is applied to a hanging mercury
drop electrode system to reduce Sn(IV) to Sn(o) and by controlled electrolysis at this
potential the tin can be concentrated into the mercury drop. The amalgam can then
be stripped of its tin by changing the potential of the drop in a positive direction so
that the tindiffuses back into the solution, the peak height of the current-voltage
curve being proportional to the tin concentration. The method was used by DeMars
[33] for the analysis of binary tin-indium alloys (0.0 1 - 20% In) and was investigated
by Phillips and Shain [34] for the direct determination of tin (~ 0.001 %) in steel,
using a 0.1g sample. Interference by molybdenum, tungsten and copperwas mitigated
by the use of a standard addition technique.
Detailed studies by Bond et al. [35, 36] have shown that while the inverse method
is not generally as accurate, rapid or reproducible as conventional a.c. polarography,
in the tin concentration range of 1o- 3 - 10-6M it is superior in sensitivity and is re-
commended by them for analysis of tin in the range 1o-6 - 1o-s M. These workers
used a supporting electrolyte of SM hydrochloric acid and electrolysed for 3 min at
a potential of- l.OV vs. Ag/AgCI. The strippingwas then carried out by scanning over
the range of- 1.0- OV at a scan rate of 1 V per minute.
Anodic Stripping has recently been used [37] for the determination of traces
(0.3ppb) oftin in copper, the tin being first isolated from a 2g sample by distillation
of the bromide, while traces of tin, down to 1o-6 % have been determined without
separation in 0.1 g samples of galliumarsenidein hydrochloric acid solution [38].
 Ref.p. 65] 6. Anodic Stripping Voltammetry 65

Tin and lead have been determined in the presence of each other by means of a car-
bon paste electrode (39].
For the application of anodic stripping to the deterrnination of organotin com-
pounds see Chapter 19.

References

1. Lindsey, A.J.: Analyst 75, 104 (1950)

2. Lingane, J.J., Jones, S.L.: Anal. Chem. 23, 1798 (1951)
3. Aylward, G.H., Brison, A.: Analyst 78, 651 (1953)
4. Lingqne, J.J.: Ind. Eng. Chem. (Anal. Ed.) 18,429 (1946)
5. Alfonsi, B.: Anal. Chim. Acta 19, 276, 289, 569 (1958)
6. Alfonsi, B.: Anal. Chim. Acta 20, 277 (1958)
7. Alfonsi, B.: Anal. Chim. Acta 25, 374 (1961)
8. Alfonsi, B.: Anal. Chim. Acta 26, 316 (1962)
9. Lingane, J.J.: lnd. Eng. Chem. (Anal. Ed.) 16, 147 (1944)
10. Bard, A.J., Lingane, J.J.: Anal. Chim. Acta 20,463 (1959); 22, 577 (1960)
11. Meites, L.: Anal. Chim. Acta 18,364 (1958)
12. Wise, W.M., Williams,J.P.: Anal. Chem. 37, 1292 (1965)
13. Wise, W.M., Campbell, D.E.: Anal. Chem. 38, 1079 (1966)
14. Kolthoff, I.M., Lingane, J.J.: 'Polarography' Vol. II Interscience 1952
15. Lingane, J.J.: lnd. Eng. Chem. (Anal. Ed.) 18,429 (1946)
16. Godar, E.M., Alexander, O.R.: Ind. Eng. Chem. (Anal. Ed.) 18,681 (1946)
17. Fe"ett, D.J., Milner, G. V.C.: Analyst 81, 193 (1956)
18. Barker, G.C., Jenkins, l.L.: Analyst 77, 685 (1952)
19. Rooney, R.C.: Analyst 88,959 (1963)
20. Kai/mann, S., Liu, R., Oberthin, H.: Anal. Chem. 30, 485 (1958)
21. Goto, H., Ikeda, S., Watanabe, S.: Japan Analyst 3, 320 (1954)
22. Schofes, P..H.: Analyst 86, 392 (1961)
23. Bond, A.M.: Anal. Chem. 42, 1165 (1970)
24. Bond, A.M., O'Donell, T.A., Waugh, A.B.: Anal. Chem. 42, 1168 (1970)
25. Lingane, J.J.: J. Amer. Chem. Soc. 65, 866 (1943)
26. Kolthoff, I.M., Johnson, R.A.: J. Electrochem. Soc. 98, 138 (1951)
27. Kolthoff, I.M., Johnson, R.A.: J. Electrochem. Soc. 98, 231 (1951)
28. Subramanian, N.: J. Sei. lnd. Res. 16, 518 (1957)
29. Yamamura, S.S., Rein, J.E., Booman, G.L.: Anal. Chem. 31, 1868 (1959)
30. Subramanian,N.: J. Sei. Ind. Res.16, 516 (1957)
31. Deshmukh, G.S., Murty, S. V.S.S.: Z. Anal. Chem. 198, 328 (1963)
32. Singh, D., Sharma, S.: Indian J. Chem. 8, 192 (1970)
33. DeMars, R.D.: Anal. Chem. 34, 259 (1962)
34. Phillips, S.L., Shain, /.:Anal. Chem. 34, 262 (1962)
35. Bond,A.M.: Anal. Chem. 42,1165 (1970)
36. Bond,A.M., O'Donnell, T.A.: Anal. Chem. 42,1168 (1970)
37. Van Dyck, C., Verbeek, F.: Anal. Chim. Acta 66, 251 (1973)
38. Troshima, G.M.: Tr. Tomsk. Gos. Univ. 237,69 (1973); Chem. Abstr. 80,90828 (1974)
39. Monien, H., Zinke, K.: Z. Anal. Chem. 250, 178 (1970)
CHAPTER 7

SOLVENT EXTRACTION

By R. Smith

Salutions of stannous and stannic salts precipitate hydroxides of tin at pH 1 - 2

and therefore solvent extraction procedures are best carried out in strong acid solu-
tions to avoid this complication. Solvent extraction processes and associated theory
aredealt with in detail in books on the subject (1 - 4), furthermore recent develop-
ments are reviewed biannually in the journal, Analytical Chemistry. Several conve-
nient and quantitative extraction procedures are available for tin and in view of the
universal application of such procedures in all branches of analytical chemistry it is
quite impossible to review them completely here. Forthis reason, the authors have
included here only those solvent extraction prodedures which have been used either
as concentration or separation techniques. Extractive reagents which are likely to be
used only in colorimetric analysis have been included in the relevant chapter.

1. Ion Association Systems

In acid solutions containing halide or thiocyanate tin exists as complex ions of the
type Sn X ~-; where the associated cation may be the hydrogen ion H+ or a protonated
solvent molecule, suchasthat formed by diethyl ether, H(OEt 2 f. Strongly basic, high
molecular weight aminessuch as the so-called liquid anion exchangers (e.g. tri-octyl-
arnine) exist as the protonated form in acid solutions and may also serve as the counter
ion.
In addition to the extraction of anionic complexes, tin may also be extracted as
simple molecules of the type SnX 4 . Tin has a maxirnum Co-ordination nurober of six
and the remaining co-ordination sites are occupied by electron donor molecules such
as dibutylphosphoric acid, diethylether or trioctylphosphine oxide.

1.1 Fluoride Extractions

Both Sn(II) and Sn(IV) are quantitatively extracted (99.9%) by diethylether from
aqueous solution containing 4.6M HF [5]. No extraction was noted for Ag, Bi, Cd,
Co, Cr, Ga, K, Mn, Ni, Os, Te, Ti, U or Zr. Partial extraction was noted for As(III),
Mo(IV), Sb(III) and Se(IV), while other elements extracting appreciably with Sn were
Ta(V) and Nb(V). Other workers [6] have found the fluoride system for tintobe
less satisfactory and give only partial extraction (5%) when working with 20M HF
solutions and diethylether.
Tin is not extracted from either 6M HC1/0.4M HF or 6M H2 S0 4 /0.4M HF into
di-isopropyl ketone (7). In the former system, appreciable extraction of As(III),
Fe(III), Ga, Nb, Sb(V), Se(VI), Ta and Te(VI) occurs, whilst in the latter system only
 Ref. p. 78] 1.3 Bromide Extractions 67

Se, Ta and Te extract. Similarly, no extraction of tin takes place into methyl isobutyl
ketone from 6M H 2 S04 /10M HF/2.2 M NH 4 F [8].

1.2 Chloride Extraction

Fig. 1 shows the extractability of Sn(IV) into diethylether from HCl solutions [ 1).
At best this approaches 30% extraction with 4.5M HCL Similar observations have
been made by Swift [9], who found 15% extraction from Sn(II) solutions of 6M HCl,
and by Mylius and Huttner {10] who reported 17% extraction of Sn(IV) from 6M
HCL

~or-----~r-------r-------r-------r-------~------r-----~

2 3 4 5 6
Fig.l HCI MOLARITY

Methyl isobutyl ketone (MIBK), however, is a better extractant [ 11] and with
greater than 5.5M HCl both Sn(II) and Sn(N) are quantitatively extracted. The pres-
ence of other acids (H 2 S0 4 or HC10 4 ) facilitates the extraction. F e(II) is not extract-
ed under these conditions, but Sb(III), Sb(V), Se(IV) and Fe(III) are extracted if
acid strengths greater than 8M HCl are used. In 8M HCI other ions extracted are:
As(III) 90%, As(V) 25%, Ge(IV) 98% and Te(IV) 96%. Other elements extracting
[12] from 8M HCI into MIBK were Cr(III) 82%, Mo(VI) 95%, V(V) 10%. Similar
results were obtained by Waidich and P[annhauser [13].
Extraction of Sn(IV) from 7M HCI into iso amyl acetate [ 14] or ethyl acetate is
said to be negligible and may be used to separate tin from antimony as extraction of
Sb(V) is quantitative.

1.3 Bromide Extractions

Both tin(II) and (IV) are extracted (Table 1) from 4M HBr into diethylether [15].
The extraction is not quantitative (84%) but is nevertheless significantly better than
68 Solvent Extraction [Ref. p. 78

that obtained from a chloride solution. Other elements extracting weil under these
conditions include: Au, Fe(III), Ga, In, Sb{IV) and Te{III). Less than 25% extraction
was encountered with: As{III), Hg{II), Mo(VI) and Sb(III).

O(o

100

z
0
;:
~
<!
1-
X
UJ
so

2 3 4 5 6
Fig. 2 HBr MOLARITY

The use of methyl isobutyl ketone, MIBK, improves the extraction of tin(II) and
{IV) from both chloride [12] and bromide [16] media. The extraction is quantitative
for both species from 4M HBr and is particularly useful when one considers the wide-
spread use of HBr/Br 2 as acid for the dissolution of solders and whitemetal alloys.

Table 1. Extraction of Elements from Hydrobromic Acid Salutions into Ether. Table shows
percentage extractionfrom solutions of 0.1M with 1, 2, 3, 4, 5 or 6M HBr into an equal volume
of diethyl ether.

Element Hydrobromic Acid Molarity

1 2 3 4 5 6

As(III) 3.0 6.7 22.8 63.1 72.9

Au(III) 99.5 99.9
Cd (li) 0.4 0.9
Co (II) 0.01 0.08
Cu(II) 0.5 1.5 4.2 6.2
Fe(III) 0.1 1.4 55.0 97.1 97.1 94.6
Ga(III) 0.9 1.5 54.8 96.7 95
Hg(II) 3.4 2.3 1.5
Mo (VI) 0.16 28 25.0 54.1
Ni(II) 0.03 0.03
Sb(III) 37.9 22.3 14.9 9.0 6.1
Sb(V) 95.4 79.6
Se(IV) 0.3 3.5 18.3 31
Sn (li) 32 64 79 84 78 36
Sn (IV) 11.5 45.2 73.6 85.4 77.4 45.1
Te(IV) 0.7 2.2
Tl(III) 99.9 99.9 99.9 99.9 99.0
V(IV) 0.001 0.001
Zn(II) 1.3 5.0 4.9 3.6
 Ref. p. 78] 1.4 Iodide Extractions 69

Elements not extracting from 4M HBr into MIBK include: Ag, Al, Be, Co, Fe(II),
Hg(II), Mn and Ni. Elements extracting weil (80%) are: As(III), Au, Cd, Cu, Fe(III),
Ga, Ge, In, Mo(VI), Sb(V), Te(III), Zn. The extractability of some of these elements
( e.g. Cu and Zn) is similar to that of tin in that incomplete extraction is obtained with
diethylether, but is significantly better with MIBK.

1.4 Iodide Extractions

Tin(II) extracts quantitatively from 7M HI into diethylether [ 17], tagether with
Au, Cd, Hg(II), Sb(III) and Te(IV). No extraction occurs with: Al, Ba, Be, Ca, Co, Cr,
Cs, Fe(II), Ga, K, Mn, Ni, Os, Pb, Pd, Pt, Ru, Th, Ti, U, V and Zr. Rather improved
selectivity can be obtained by the use of 1.5 M KI/ 1.5 N H 2 S0 4 [ 18] as the aqueous
phase (Table 2); there is the additional advantage that the inconvenience of using
unstable hydriadie acid is avoided.
Benzene and toluene are more widely used for the extraction of tin from iodide
media than diethylether. Tin(IV) is extracted into benzene quantitatively [ 19] from
greater than 2M HI or from 2M, 3M or 4M H 2 S0 4 with l.OM, 0.5M or O.lM KI
respectively. Extractions are inhibited by the presence of chloride and with 1 - 10M
HC!, the iodide content must exceed 4M for quantitative separation. Toluene and
benzene appear to be of equal value as organic phases but the former is favoured from
the point of view of its lower toxicity. Other e!ements extracting into toluene are:
As(III), Ge, Hg(II) and Sb(III), whereas Au, Be, Cd, Cu, Ga, Mo, Wand Zn do not
extract (20]. Bi, In and Pb extract partially; Se(IV) is reduced to finely divided meta!
which is soluble in toluene.

Table 2. Extraction of Elements from Hydriadie Acid Salutions into Ether

% Extraction
Element
6.9 M HI 1.5 M KI/1.5 M H2S04
AS(III) 62
Au(III) 100
Bi(III) 34 < 10
Cd(II) 100 100
Hg(II) 100 33
ln(III) 8 100
Mo(VI) 6 < 1
Sb(III) 100 50
Sn(II) 100 100
Te(IV) 5
Zn(II) 11 33

Improved selectivity may be obtained by the use of masking agents. Although

Fe(II) is difficult to stabilise under the conditions of the extraction, small amounts
of iron may be reduced tagether with Cr(VI) using aqueous Ti 2 (S0 4 h; tungsten is
masked by a trace of phosphoric acid (21]. This method is suitable for the determi-
nation of tin in iron and steel if the extraction into benzene or toluene is carried out
from 3.5- 4.5M H2 S0 4 /0.5M Nal. EDTA may be added to mask Mo, V and Zr.
70 Solvent Extraction [Ref. p. 78

Perchlorate/iodide media have also been used for the extraction of tin(IV) into
toluene or benzene using 1.5M HC10 4 /3M NaC10 4 /0.5M KI(22) or M H2 S0 4 /4.6M
NaC10 4 /M KI [23]. In the former instance the concentration of sulphuric acid should
be less than 0.5M.
For colorimetric and atomic absorption determination, it is sometimes convenient
to re-extract the tin into a clean aqueous phase. As benzene and toluene are less
dense than water the stripping process may be carried out in the same separating fun-
nel after rejecting the original aqueous phase. N ewman and Jones [24] found in-
complete back extraction with dilute hydrochloric, sulphuric and perchloric acids
and recommended Stripping with 0.1M sodium hydroxide. Other authors removed
tin from the organic phase by shaking with M HCl [21] or 0.25 M H2 S0 4 [22, 23, 25].
Additions of ascorbic acid can be made to reduce any free iodine which might inter-
fere with subsequent colorimetric reagents. The extraction procedure developed by
Newman and Jones has been applied to the determination of tin in steel [26], organic
matter [27] and foodstuffs [28]. The complete extraction and stripping procedure is
given in the Chapter on Atomic Absorption Spectroscopy, the use of at least 1.5M
KI inecommended [28] to inhibit the co-extraction of antimony.
Other solvents used for the extraction of tin(IV) iodide include cyclohexane [29],
hexane [30], aliphatic alcohols [31], carbon tetrachloride [32] or carbon disulphide
[32]. Partial extraction occurs with MIBK and other ketones [33].

1.5 Thiocyanate Extraction

Tin(IV) is almost quantitatively extracted (99.3%) from 1-7M NH 4 SCN/0.5M
HCl solutions into diethylether [34]. The system is useful in that some elements

Table 3. Extraction of Elements from Ammonium Thiocyanate into Ether. 0.1 M Element
extracted into an equal volume of diethyl ether from 0.5 M HCl

Molarity of Thiocyanate
Element 0.5 1 2 3 4 5 6 7

Al(III) 1.1 9.0 19.4

As(III) 0.4 0.4
As(V) 0.1 0.03
Be(II) 3.8 24.3 49.7 84.1 92.2
Bi(III) 0.3 0.1
Cd(II) 0.1 0.2
Co(ll) 3.6 37.7 58.2 74.9 75.2
Cr(III) 0.06 3.4
Cu(l) 2.9 0.4
Fe(III) 88.9 83.7 75.5 53.3
Ga(III) 18.3 65.4 90.5 99.3
Ge(IV)
Hg(II)
< 0.3 < 0.5
0.15 0.15
ln(III) 26.0 51.5 75.1 75.3 68.3 47.6
Mo(V) 99.3 97.2 97.3
Ni(II) 0.01 0.003
Sb(III) ppt ppt ppt ppt ppt ppt 2.2
Sc(III) 12.7 55.4 79.8 84.6 89.0
Sn (IV) 99.3 99.9 99.9 99.9 99.9 99.9
Ti(III) 14.7 58.8 80.5 84.0 79.8 76.3
Ti(IV) 13.0
U(VI) 45.1 41.4 29.4 13.8 6.7
V(IV) 10.7 15.0 13.1 8.7 2.2
Zn(II) 96.0 97.4 94.8 92.8
 Ref. p. 78] 2.1 Alkylphosphoric Acids 71

which extract with tin from iodide solutions arenot extracted with thiocyanate e.g.
As(III), As(V), Sb(III). However, several elements are extractable as coloured com-
plexes which may interfere with subsequent colorimetry e.g. Fe(III) red, Co(II)
blue, Ru(III) pink, W purple, Mo orange and U yellow.
Tin has been determined in antimony metal [35] by evaporation of a O.Sg sample
to fumes with 20ml H2 S0 4 • After removal of most of the acid, the residue was cooled,
taken up in 15ml of 50% tartaric acid solution in water, 15ml of (1 : 1) H 2 S0 4 and
10ml of 50% NH 4 SCN solution added. The solutionwas diluted to 70ml and extract-
ed with 20ml of ethyl acetate. Under these conditions As, Bi, Ge, Sb and Ti remain in
the aqueous phase and Sn is extracted.

1.6 High Molecular Weight Amines

Tin(IV) is extracted from 5 - 6M HCl into xylene with N-dodecyl trimethylamine
(Amberlite LA- 1) and may be separated from lead by this system [42]. The amine
provides a hydrophobic counter ion for the tin chloro-complex and thereby improves
the extractability in chloride solutions from about 15% in the absence of amines to
nearly 100%. Incomplete extraction of tin occurs at acidities as low as O.SM HCl and
it is, therefore, not usually possible to carry out a prior extraction to remove other
elements. Back extraction using 0.5 - 1M HN0 3 is claimed to be quantitative but is
incomplete with either HCl or H2 S0 4 [42]. This extraction procedure has been ap-
plied to the determination of tin and lead in copper base alloys [46]: up to 10mg of
tin was extracted with 10% Amberlite LA - 1 in xylene from 5 - 6M HCI and back
extracted by three treatments with 30ml of O.SM HN0 3 . Lead remains in the original
aqueous solution and any which extracts may be removed if required by shaking with
20ml of 8M HCI before back extracting tin.
Rather similar extractions using tetrahexylammonium chloride and dichlorometha-
ne have been reported [44] for SM HCl but the extractability oftin falls sharply with
greater than 6M HCl.

2. Phosphorus Containing Extractants

Phosphorus extractants form ion-association complexes with tin and other metals,
However, it is convenient to deal with these systems separately.

2.1 Alkylphosphoric Acids

Scadden and Ballou [36] studied extractions of several elements with a mixture of
di- and mono- n-butylphosphoric acids (4.5 : 1)

Di-n-butylphosphoric acid (DBP).

When the extraction was carried out in M HN0 3 , with di-n-butylether as the organ-
ic phase, approximately 50% extraction of Sn(IV) was obtained with 0.06M DBP and
over 95% with 0.6M DBP. Other elements extracting quantitatively with 0.6M DBP
were: In, Nb,Y and Zr. Partial extractions were obtained with Mo (23%) and Ta
72 Solvent Extraction [Ref. p. 78

(85%) and less than 5% extraction with: Ag, As(V), Cd, Cs, Ge, La, Pd, Th, Ru, Sb(III),
Sb(V), Se, Sr and Te(IV).
Somewhat inferior extraction of tin(IV) was found with 1 g/1 Sn from an aqueous
phase containing 1M H 2 S0 4 /2.5M (NH4 h S0 4 /0.004M oxalic acid/6% H 2 0 2 • With
0.6M DBP, 50% extraction of tin into di-n-butylether occurred and with 0.06M DBP
only 15% extraction took place [36].
DBP suffers from the disadvantage that it forms emulsions quite readily and some
improvement in ease of extractability can be made by the use of octylphosphoric
acids. Di-2-ethylhexyl-phosphoric acid has a lower solubility in water than DBP but
only 50% extraction of tin into toluene occurs with 0.01 - 1M HCl and 1.5M di-2-
ethylhexylphosphoric acid [37].

2.2 Alkylthiophosphoric Acids

Di-n-butylthiophosphoric acid (DBTP) has been studied by Handley [38] as an

extractant for tin(II) and other metals from acid solutions into carbon tetrachloride.
With 0.22M DBTP extractions of greater than 90% were obtained with: Ag(0.02-
SM HCl), As(III) (9M HCl), Au (9M HCl), Bi (2M HCl), Cd (2.5M HCl), Cu (9M HCI),
Fe(III) (0.2M HCl), Ga (0.03M HCl), Hg(II) (0.5 - 9M HCl), In (0.1 N HCI), Mo(VI)
(O.OSM HCI), Pb (2M HCl), Pd(II) (0.1 - 9M HCl), Se(IV) (9M HCl), Sn(II) (0.8M
HCI), Tl(I) (0.2M HCI) Zn (0.1 M HCl).

Di-n-butylthiophosphoric acid (DBTP)

2.3 Alkyldithiophosphoric Acids

Handley andDean [39] made an analogaus study of dibutyldithiophosphoric acid
(DBDTP), using 0.2M and carbon tetrachloride as the organic phase.

Di-n-butyldithiophosphoric acid (DBDTP)

Free DBDTP is easily oxidised and the sodium, ammonium or mercury salts are
used for extractions. Metals extracting more than 90% include: Ag (0.2- 9M HCl),
As(III) (0.1- 8M HCl), Au (0.5- 9M HCl), Bi (0.5- 8M HCl), Cd (0.02- 2M HCI),
Co (0.01 M HCl), Cu (0.5 - 9M HCl) Hg(II) (0.5 - 8M HCl), In (8M HCl), Mo(VI)
(0.01 - 9M HCl), Ni (0.01 -2M HCl) Pb (M HCI), Pd(II) (0.2- 9M HCl), Sb(III)
(0.5- SM HCI), Se(IV) (9M HCl) Sn(II) (0.7MHC1), Tl(I) (IM HCl), Zn (0.3M HCl).
Diethyldithiophosphoric acid (DEDTP) is analogaus to DBDTP and behaves simi-
larly in extracting metals into carbon tetrachloride [40]. Using a 0.1 % solution of
the sodium salt of DEDTP greater than 90% extraction was obtained with: Ag(4M
HCl), As(III) (0.1 - 6M HCI), Au (3M HCI), Bi (0.1- 4M HCI), Cd (pH 2- 9), Cu
(SM HCI), Fe(III) (pH 2- 3), Hg(II) (pH 10 or SM HCI), In (0.1M HCI), Mo(VI)
(SM HCl after hydrazine reduction), Pb (pH 1 - 7), Pd(II) (0.1 -10M HCI), Sb(III)
(0.1 - 4M HCI), Se(IV) (0.1- SM HCI), Sn(II) (0.1M HCI), Te(IV) (1 -10M HCI).
 Ref. p. 78] 3.1 Acetylacetone and Related Compounds 73

2.4 Trialkylphosphine Oxides

Only two alkylphosphine oxides are irnportant in the extraction of tin(IV) from
aqueous solution, these are tri-n-octylphosphine oxide (TOPO) and the branched
chain analogue tri-ethylhexylphosphine oxide (TEHPO).

Tri-n-octylphosphine oxide (TOPO)

or
Tri-ethylhexylphosphine oxide (TEHPO)

TOPO is by far the more widely used of the two compounds and can be used in
the commercially available form; a detailed extraction procedure for the determina-
tion of tin in aluminium, iron and nickel base alloys [41] is given in the Chapter deal-
ing with Atomic Absorption Spectroscopy. Tinexhibits the greatest extractability
with TOPO of all elements and is irrespective of the initial oxidation state of the metal
as the extracted species is always SnC14 .2TOPO. No extraction occurs from HN0 3 or
H 2 S0 4 in the absence of chloride [3] or iodide [41].
Complete extraction into cyclohexane using O.lM TOPO occurs with;Au (IM
HCl), Bi (2M HCl), Cr(VI) (1 - 4M HCl), Fe(III) (1 - 7M HCl), Ga (7M HCl), Hf(IV)
(1-7M HCl), Mo(VI) (4- SM HCl), Nb(V) (4M HCl), Sb(III) (2-4M HCl), Sb(V)
(8 -10M HCl or O.SM HC1/H 2 S0 4 ), Sn(IV) (1- SM HCl), Th(S -7M HCl), U (2-10M
HCI), Zn (1M HCl), Zr(IV) (5 M HCl). Partial extraction occurs with.Cd, In, Hg and Pr.
Some irnprovement in selectivity can be brought about by the use of 7M HCI as
the aqueous phase [ 1]. Under these conditions complete extraction occurs only with:
Au, Cr(VI), Fe(III), Ga, Hf, Mo, Sb(III), Sn(IV), Ti, U, V and Zr.
TEHPO is interesting in th~t the ethyl group is in a position to exert steric hin-
drance and will, therefore, extract fewer metals than TOPO. Despite this advantage,
the reagent has not been developed further and in view of the commercial availability
of TOPO it is unlikely that TEHPO will be widely used in analysis. Ross and White
[43] extracted 10- 100 11g Sn fromM HCl/2- 3M H2 S0 4 into 0.01M TEHPO in cy-
clohexane. Coextraction of Fe, Ga, Mo and Sb was overcome by stripping into M HCl/
2M H2 S04.

3. Chelate Systems

3.1 Acetylacetone and Related Compounds

Divalent tin is partially (75 %) extracted by 0.1 M acetylacetone in benzerre at pH 6.
No significant extraction occurs below pH 3 or above pH 10 [2]. Sirnilar behaviour
is found with benzoylacetone [2] and for this reason diketone extractants arenot
generally used in the determination of tin or in the analysis of tin compounds. De-
spite this, multiple extractions with methylisobutylketone solutions of thenoyltriflu-
oroacetone have been reported [4 7] for the determination of tin in rocks by neutron
activation analysis. After extraction, tinwas stripped into aqueous tartaric acid solu-
tion.

H3C CH 2 CH 3
'c/"-c/
11 II Acetylacetone
0 0
74 Solvent Extraction [Ref. p. 78

Stokeley and Moore [87] claimed a highly selective extraction of tin(lV) using
1-2M HCl/0.5 -IM H2 S0 4 /l %H 2 0 2 with O.SM thenoyltrifluoroacetone inMIBK.
The organic phasewas scrubbed with 0.6M H2 S0 4 /2M NH 4 Cl/ I% H2 0 2 . Tin could
be back-extracted with IM tartaric acid after shaking for I 0 min.

3.2 8-Hydroxyquinoline

Initial studies on the extraction of tin(IV) into ch!oroform using 0.07M 8-hydro-
xyquinoline [48] claimed quantitative separation after two minutes shaking. Later
work [49] failed to reproduce these early claims and showed that extraction was
possible only in the presence of halide ions at pH 0.85.
Separations using 8-hydroxyquinoline have been used in the photometric determina-
tionoftirr in nuclear reactor material [50], silicate rocks [51], copper alloys [52] and
steels [53]. The last application is interesting in that tin(II) was first extracted into
methylisobutyl ketone from 6M HCI. The organic layer was shaken with a 1% solu-
tion of 8-hydroxyquinoline in 20% acetic acid and the absorbance of the tin complex
in methylisobutyl ketone measured at 390nm.

rl(1 8-Hydroxyquinoline
~N~
OH

Procedure [50]- Ta 50ml ofsarnple solution in sulphuric acid, adjusted to pH = 0.85 ±0.10
and containing less than 50 mg of tin add a few drops of 10% hydrogen peroxide to oxidise
tin(II), 5 ml of 20% ammonium chloride and 25 ml of 4% 8-hydroxyquinoline in dilute sul-
phuric acid at pH 0.85. Shake for 2 min with exactly 20m! of chloroform. Filter the organic
phase and measure the absorbance of tin at 385 nm. Only Mo, Nb, V and Ware reputed to inter-
fere. Molybdenum may be removed by a prior extraction at pH 0.85 in the absence of halide ions.

5,7 Dibromo-8-hydroxyquinoline is ·easily prepared by the bromination of 8-hydro-

xyquinoline in acid solution with dilute bromirre water. The product may be precipi-
tated by neutralising the solution. Ruf [54] used this reagent for the extraction of
tin(IV) from dilute HCl at pH 1 using isobutanol as the organic phase.
8-Mercaptoquinoline forms a strong complex with tin(II) which is readily extracted
into chloroform, benzerre and toluene [66, 67]. The extraction may be prevented by
strong hydrochloric acid or sodium fluoride. The reagent is somewhat inconvenient in
use because of its easy oxidation and is very unselective. Other metals extracting in-
clude: Bi, Co, Cu, Fe(III), Ga, In, Mo, Os, Pb, Pd, Pt, Re, Sb, V(V) and Zn.

3.3 Cupferron

Cupferron is widely used as a precipitant for tin. The complex is soluble in ethyl
acetate, diethylether, benzene, isoamyl alcohol and chloroform and solvent extraction
separations are practicable. The reagent is normally used as a I - 5% aqueous or chlo-
roform solution. For best results solutions should be made daily, although it is possible
to store them in a refrigerator with the addi tion of 5Omg of acetophenetide per 15 Oml
as a stabilizer [55]. The decomposition product is nitrobenzerre and a c!oudy appearance
indicates deterioration.
 Ref. p. 78] 3.5 Dithizone 75

Both Sn(II) and Sn(IV) cupferrates are completely extracted from 1 - 2M HCl by
ethyl acetate, benzene or chloroform [56- 58]. Elements extracting into chloroform
from aqueous solutions of less than pH 1 include: Bi, Cu, Fe, Ga, Hg, Mo, Nb, Sb-
(III), Ta, Ti, V, Wand Zr. Elemen~s not extracting into chloroform below pH 1 include:
Ag, Al, Ba, Be, Ca, Cd, Co, In, La, Mn, Ni, Pb, Sb(V), Se, Y and Zn.

Ammonium N-Nitrosophenylhydroxylamine
(Cupferron)

Shumova and Blyum [59] reported an extraction of tin from sulphuric acid solutions
of antimony and copper ores and of ores with high tellurium contents. The acid solu-
tion contained 1% cupferron and the tin cupferron complex was extracted into butyl-
acetate.
lf copper cupferronate is used as the extractant from dilute sulphuric acid solutions
[60], only Mo, Nb, Sb, Sn, Ta, Ni, V and Zr are extracted into chloroform or carbon
tetrachloride. Iron cupferronate will extract only Zn.
In 0.3 - 0.6M HN0 3 containing tartaric acid, tin forms a cupferron complex which
is extractable into chloreform [82].

3.4 Hydroxamic Acids

N-Benzoylphenylhydroxylamine is almostinsoluble in water (0.002M solution) but
is readily soluble in chloroform (0.74M), benzene, ethylacetate and other organic sol-
vents. lt is stable towards sulphuric and hydrochloric acids up to 8N but is decom-
posed by alkalis and strong nitric acid solutions. It is stable towards heat, light and air
[2] and is used as a 1% solution in the organic solvent.

N-Benzoyl-N-phenylhydroxylamine

Tin(II) was shown [61 - 63] tobe oxidised by N-benzoylphenylhydroxylamine to

tin(N) before reacting to form a complex. Tin is extracted into chloroform tagether
with Sb(III) from SM sulphuric acid [64 ].Extraction from perchloric acid solutions is
also complete [63] but is only 92% from 2M HCl and is less with strenger acid. The
maximum extraction was obtained [65] with 0.2- O.SM HCl and the extraction was
further improved by the addition of ethanol, acetic acid or chloroacetic acid. Ce(N),
Cr(VI), Hf, Mo(VI), Nb, Sb(V), Ta, Ti, V, Wand Zr were also extracted but could be
masked by the addition of tartaric acid or hydrogen peroxide. The latter reduces chro-
mate to Cr(III) which does not extract.

3.5 Dithizone
Divalent tin reacts with dithizone at pH 5 - 9 to form a red complex which is extract-
able into carbon tetrachloride [2]. However, Oxidation by atmospheric oxygen is rapid
and the complex decomposes. For all practical purposes, therefore, extraction of tin
with dithizone is of no analytical importance.
76 Solvent Extraction [Ref. p. 78

The use of dithizone to remove other metals from tin(IV) is of some value and un-
der appropriate conditions [see references 1,2 or 3] the following elements can be ex-
tracted: Ag, Au, Bi, Cd, Co, Cu, Fe, Ga, Hg, In, Ni, Pb, Pd, Pt, Se, Te and Zn.

NH-NH-o
S=C/ - Diphenylthiocarbazone (Dithizone)
~NH-NH-o
Diethyltin, but not triethyltin, is extracted from 10% trichloracetic acid solution
into achloreform solution of dithizone [86]. If a pH 8.4 borate buffer is used, both
alkyltins are extracted; EDTA can be used to prevent co-extraction of Ca, Cu, Pb, Zn
etc.

3.6 Dithiocarbama tes

Dialkyldithiocarbamates react with all metals which form insoluble sulphides to
give complexes which are generally insoluble in water and extractable into a wide range
of solvents. Organic phases commonly used are: chloroform, carbon tetrachloride
and ethyl acetate. Elements not extracting include: Al, Cr(III), Ca, Ge, Ir, La, Mo, Nb,
Os, Rh, Ru, Sc, Th, Ti, V(IV), W, Y, Zr tagether with the alkali and alkaline earth met-
als.
Sodium diethyldithiocarbamate
(NaDDC)

D N-C
<""s
'---s-
Ammonium pyrrolidinedithiocarbamate
(APDC)

Diethyldithiocarbamates are very unstable towards oxidation in acid or weakly

acid solutions and the sodium salt (NaDDC) has a half-life at pH 4 of approximately
30 sec. Other commonly used dithiocarbamates are ammonium pyrrolidine dithio-
carbamate (APDC) and diethylammonium diethyldithiocarbamate (DDDC). APDC
and DDDC arerather more stable than NaDDC towards oxidation in acid solutions.
All three are extracted into chloroform or carbon tetrachloride as free acids below
pH4.
Bode [69 - 71] has carried out a thorough study of the extractability of metal
dithiocarbamate complexes into carbon tetrachloride. Tin is extracted quantitatively
at pH 4- 6.2 [68] with NaDDC into carbon tetrachloride or ethyl acetate and may be
extracted with APDC into MIBK over a similar range. In all cases, tin is only extracted
as the starrnie complex at pH 4- 6.2. At pH values higher than 7.5, tin is not extracted
[69 - 71]. Masking agents, such as citrate, tartrate or EDT A do not interfere with the
extraction. An extraction procedure for Sn(IV) by APDC into MIBK is given in the
Chapter on Atomic Absorption Spectroscopy. In this method tin is converted to the
starrnie state by evaporation to fumes with sulphuric acid. Other suitable oxidations
include dissolution of tin/lead alloys with hydrochloric acid and bromine, potassium
chlorate or a few drops ofhydrogen peroxide. Avoid !arge excesses or oxidising agents
as these will destroy the extractant.
In dilute mineral acid solutions (e.g. 1-4M HCI or 0.5- SM H 2 S0 4 ) tin is extract-
ed into carbon tetrachloride or chloroform only as the Sn(II) dithiocarbamate complex
[72, 74- 77]. The procedure below illustrates this and uses a preliminary "clean-up"
extraction with tin present as Sn(IV).
 Ref. p. 78] 3.8 Tolune-3 ,4-Dithiol 77

Extraction of Sn(IJ) with Diethylammonium Dithiocarbamate [74]

To a hydrochloric acid solution of the sample, add 10m! of sulphuric acid and 1 ml of perchloric
acid. Evaparate to 7 ml, cool, add 0.3 g hydrazine sulphate and heat until foaming subsides in order
to reduce Sb (V) to Sb(III). Cool, add Sm! of water, heat to boiling and digest for a few minutes
to dissolve precipitated sulphates. Co_ol, add 30 ml of water, and fllter into a separating funnel to
remove Iead. Wash with 1 Oml of water, add 25 ml of 1 % diethylammonium dithiocarbamate in
chloroform, shake for 30 sec and discard the chiaraform layer. Repeat the extraction if the organic
extract is strongly coloured.
Run the aqueous layer into a beaker, heat to 50°C, add 2m! of 10% thiog!ycollic acid, lml of
6% potassium iodide add 1 ml of 3% ascorbic acid. Cool and return to the separating funne!. Ex-
tract the solution with 10m! of 1% diethylammonium dithiocarbamate in chloroform and separate
the organic layer: wash the aqueous layer with 5 ml of chloroform and add the washings to the
organic extract which contains the tin.
The tin(Il) complex may be destroyed either by evaporating the organic layer to fumes with
2ml of sulphuric acid and 0.5 ml of perchloric acid or by shaking with 0.1 M NaOH.

3.7 Xanthates
Xanthates are chemically similar to dithiocarbamates and are normally used as
freshly preparared 0.1% aqueous solution. They are decomposed by light and alkalis
and offer no advantages over dithiocarbamates. Their extraction properties have been
incompletely studied from the viewpoint of analytical chemistry.

Potassium ethyl xanthate

Potassium ethyl xanthate and potassium benzyl xanthate are the most important
of this class of compounds. Tin is extracted as either Sn(II) or Sn(IV) from dilute acid
media [78]; other elements extracting include: As(III), Bi, Cd, Co (pH 4), Fe(III), Mo,
Ni (pH 4), Sb (III), Tc(VII), V and Zn.

3.8 Toluene-3 ,4-Dithiol

In acid solution, toluene·3,4-dithiol reacts with Sn(II) and Sn(IV) to give colloidal
red precipitates which are of importance in colorimetric analysis. The precipitates are
extractable into butyl acetate or chloreform but the solutions are yellow. Dithiol is
extremely unstable towards air oxidation and is generally stored as the zinc complex
which is used to prepare I% solutions in sodium hydroxide within a few hours of use.
The reagent has not been thoroughly studied and other elements extracting with
tin include: Mo, Se, Tc and W. The tin complex is formed only on warming, the reac-
tion being more rapid with Sn(II). Thioglycollic acid may be used as a reducing agent
for Sn(IV). Tin dithiolate is not extracted into petroleum ether [80].

~HSH
Toluene-3,4-dithiol

Diacetyltoluene-3 ,4-dithiol ( diacetyldithiol) is hydrolysed by alkalis to dithiol but

is stable towards acids. lt has been proposed [81] as a convenient alternative to dithiol
as its solutions in ethyl acetate or ethyl cellosolve are stable for long periods.
78 Solvent Extraction

3.9 Other Extractants

1-(2 Pyridylazo)-2-naphthol (PAN) forms extractable complexes with Sn(II) [83]
and with alkyl tin compounds [84] of the type R 2 Sn(OH)(PAN). The former are ex-
tractable into amyl acetate, the latter into chloroform.
1,1 Diantipyrinyl-3-methylbutane [85] was used to extract tin prior to a subsequent
determination by EDTA titration. If a large excess of zinc is present, Bi, Cd, Co, Cr,
Fe, Mo, Ni, Pb, Sb, Th, Ti, U, V, W, Zr and rare earths are prevented from extracting.
Tin was then back extracted into sodium hydroxide solution.

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CHAPTER 8

ATOMIC ABSORPTION SPECTROSCOPY

By R. Smith

1. Atomic Absorption Characteristics

1.1 Absorption Wavelengths

Table 1 shows the main absorption wavelengths for tin [ 1 - 3] and their sensitivity
(concentration of tin in f..Lg/ml required to give 1% absorption).It will be seen from
Table 1 that some of the secondary absorption lines do not originate in the 3 P 0

Table 1. Characteristic. Wavelengths for the Atomic Absorption of Tin [f is the absorption
oscillator strength]

Wavelength [ 1] Energy Levels Spectral f [2] Sensitivity [2, 3]

(nm) [2,3](eV) Terms [1] (j.Jg/ ml/%)
224.61 0 - 5.518 3Po-3DI 0.41 1.1
233.48 0.210-5.518 3 P1- 3 DI 1.7
235.48 0.210-5.473 3 P1-3 D2 0.27 2.2
266.12 0.210-4.867 3pl_Ipl 46
286.33 0 -4.329 3Po-3PI 0.23 1.8

ground state but in the thermally-populated 3 P ~> 2 Ievels. This is shown with the aid
of a Grotrian diagram in Fig. 1. On increasing flame temperature, for example by
using a N2 0/acetylene flame, it should be possib1e to deplete the 3 P0 ground state
population and increase the 3 P 1 , 3 P2 populations. As a result, the variation of tin ab-
sorbance with flame type is a rather complex relationship depending on the particular
flame and on the wavelength of observation. This effect has been studied in detail by
Rubeska [4] and Capacho-Delgado and Manning [5], and to some extent explains the
unusually !arge enhancement of resonance line absorption when lower temperature
flames are used (Table 2).

1.2 Choice of Flame

The behaviour of tin in different flames has been the subject of considerable study
[4- 7] andin Section 1.1 the effects of flame temperature on the population of the
several atomic states of tin were mentioned. In addition to the effect of temperature,
there is evidence to suggest that the free atom concentration of tin is greatest in hy-
drogen based flames and that the tin free atom concentration is related to the hydrogen
radical concentration of the flame [4]. This was demonstrated clearly by Ha"ison and
 Ref. p. 94] 1.2 Choice of Flame 81

v.V
_,_
-·-
'p, 'o." lp. 1p •p 3D, 'o 3

--' ~ 6

[sd
[6s ~TT 5

Fig. 1. Grotrian diagram for tin showing electronic transitions of importance in atomic
absorption spectroscopy [4]

Juliano [6] who showed that addition of very small amounts of an organic solvent
drastically reduced the absorbance of tin in an air/H 2 flame. For example, 5% of ace-
tone reduced the absorbance of 50!1g/ml Sn solution by a factor of ten. Similar effects
may be obtained by including small quantities of hydrocarbons in the flame gas mix-
ture. If direct nebulisation of organic solvents is necessary, hydrogen flames give in-
ferior performance to fuel-lean N2 0/acetylene [9]. With entirely aqueous solutions,
however, the Ar/H 2 diffusion flame gives the best sensitivity but is prone to solute
volatilisation interference effects and as a practical proposition, air/H 2 is preferred.
Care should be taken, however, to use a fuel-lean air/H 2 flarne to minimise interference,
at the expense of sensitivity. Where sensitivity is notaproblern the fuel-lean N 2 0/ace-

Table 2. Absorbance of Tin Lines in Three Flames [4]

Absorbance
Wavelength Lower State Ratio
(nm) (Term) Air/C2H2 Air/H2 Ar/H2 Ar/H2 :Air/C2H2
286.33 3p 0.115 0.169 0.553 4.8
3 0
270.65 PI 0.081 0.075 0.120 1.5
284.00 3p2 0.069 0.045 0.035 0.5
82 Atomic Absorption Spectroscopy [Ref. p. 94

Table 3. Atomic Absorption Parameters for Tin in Different Flames

Ar/H2 Air/H 2 Air/C 2H2 N20/C2H2 Ref.

Max. Temperature (°K) 800 2160 2548 3050 [22]

Max. Buming Velocity (ern/sec) 310 158 160 [2]
Free Atom Fraction, Sn 0.38 0.1 0.35 [2]
% Ionisation, Sn 0.1 0.1 0.1 3.0 [23]
Absorbance for 200 pg/ml Sn
at 224.6 nm 0.821 0.320 0.298 [5,8]
at 286.3 nm 0.492 0.182 0.166 [5,8]
at 235.4 nm 0.398 0.227 0.240 [5,8]
Detection Iimit 224.6 nm, pg/ml Sn 0.02 0.1 0.4 [5,8]

tylene flame should be used. lnvariably the air/acetylene flame offers poor sensitivities
and detection limits and has no advantages over air/H 2 or N2 0/acetylene. (See Table 3).

1.3 Interferences
The remarkable interference caused by the presence of organic compounds on the
determination of tin in hydrogen flames has already been mentioned [6]. When or-
ganics are present at above 0.5% in the solutiontobe nebulised, a N2 0/acetylene
flame is recommended. If the solution contain a very large proportion of organic ma-
terials the N2 0/acetylene flamealso offers better sensitivities and detection limits [9].
In air/H 2 flames, Capacho-Delgado andManning [5, 10] found that variations of
hydrochloric acid (0- 20%) or fluoboric acid (0 - 10 %) caused no change in absorp-
tion of 20t.tg/rnl Sn at 224.6nm. Nitric, phosphoric and su1phuric acids interfered
seriously and must be matched with Standards (Fig. 2). These interference effects were
reduced considerably by the use of the hotter air/acetylene flame attended by a deter-
ioration in sensitivity. No change in absorptionsignalwas noted with 1000t.tg/ml Cu,
Ni, Pb or Zn. Grison [ 11], however, confirmed the depression of signal with phospho-

Ofo
30

~ HN01

'
20
-.......;:

-
~""--

10
--...... r-.. H3P04

H.S04

0
0 10 20
ACID CONCEN TRATION 0/ov/v

Fig. 2 Influence of nitric, phosphoric and sulphuric acids an atomic absorption of tin in an
air/H2 f\ame [5]
 Ref. p. 94] 2.1 Molecu!ar Emission 83

ric and sulphuric acids in air/Hz flames but found that Cu and Ni gave rise to an
enhancement. Johns [ 14] has also reported an enhancement by Cu although Perry
[13], working on the analysis oflead-based alloys found 1000J..Lg/ml quantities ofCu,
Fe, Ni, or Zn tobe without effect. Similar amounts of As or Sb gave rise to a slight
enhancement. Other work [ 12] suggests that 100-fold excess of Ca, Mg, Mo, Sr and
U could depress the absorption signal of 5 J..Lg/ml Sn by 5 - 10% in air/Hz flames
although similar amounts of the following elements could be tolerated: Al, Ba, Cd,
Co, Cs, Cu, Fe, Hg, K, Li, Mn, Na, Ni, NH;, Pb, Rb, Ti, Tl, Zn, Zr, Br-, citrate,
er, HPO~-, r, Mn04,, N03, PO~-, SO~-. It was claimed [12] that with fuel-rich
air/Hz flames even volatile elements such K, Tl and Zn interfere.
In cool Ar/Hz or Nz/Hz diffusion flames interferences are considerably more
serious than with air/Hz(8, 15, 16). Enhancements were observed with HCI, HC10 4 ,
HF or ammonium halides. Nitric, phosphoric and sulphuric acids depressed the signal
seriously, as did the presence of alcohols. Ferric chloridewas added [15] as an enhan-
cing and releasing agent to standards and samples in the analysis of copper-base alloys
and steel.
The Observations listed above almost certainly involve a chemical interference af-
fecting the volatilisation or atornisation of tin in the flame. Spurious absorption sig-
nals caused by scattering of incident light by !arge concentrations of solid analyte par-
ticles in the flame are well-known [ 18]. As scattering is always more pronounced at
low wavelengths there is some advantage in using the Sn 286.33 nm line in preference
to the Sn 224.61 nm wavelength.
The ionisationpotential of tin is comparatively high (7 .34eV). The calculated ion-
isation [23] is ab out 3% in Nz 0/acetylene flames and is negligible in air/Hz, Ar/Hz or
air/acetylene. It is advisable, therefore, to incorporate an ionisation buffer of 1OOOJ..Lg/
ml of an alkali meta! in standards and samples when working with the Nz 0/acetylene
flame.

2. Flame Emission Spectroscopy

The flame emission spectroscopy of tin has three distinct fields of interest depending
on the flame conditions employed:

(i) Molecular ernission- from SnO or SnH in Ar/Hz or Nz/Hz diffusion flames.

(ü) Atornic ernission- excited by conventional thermal processes in prernixed N2 0/

acetylene flames

(üi) Chemiluminescence atomic ernission - atornic lines of high excitation energy stimu-
lated by chernical reactions in air/Hz or air/acetylene flames.

2.1 Molecular Emission

SnO. The band spectrum of SnO may be observed at very high concentrations in
the outer cone of the turbulent air/acetylene flame supported on a total consumption
burner [1]. The spectrum is weak, diffuse and of no analytical utility, although a blue
flame test for tin suggested by Meissner [20] and studied by Tamura and Kawahara
84 Atornic Absorption Spectroscopy [Ref. p. 94

[21] is alrnost certainly due to the SnO band emission. lt may also be observed in hy-
drogen diffusion flames [19] and allows a visuallimit of detection of about 5J.Lg/rnl Sn.
Fig. 3 shows the emission spectrum of SnO in a N2 /H 2 diffusion flame.

Na

>- SnO SnH

1-
üi
z
L1J
1-
z
z
0
IJ)
IJ)

:::E
L1J

400 450 500 550 600 650

WAVELENGTH nm
Fig. 3 Emission spectrum ofthe SnO and SnH molecules in a N 2 /H 2 diffusion flame. 0.03M Sn in
0.5M HCI[l9]

SnH. In cantrast to the SnO spectrum, the SnH band (Fig. 3) is sharp and has a
line-like appearance at 609.5 nm [19]. Introduction of oxygen into the support gas
extinguishes the SnH emission and gives rise to the blue SnO bands. A didymium glass
fllter between the flame and monochromator reduces the Na 589.0/589.6nm emission
signal by 99.5% but transmits 60% ofthe SnH radiation at 609.5nm [19]. Calibrations
arelinear up to 3000 J.Lg/rnl Sn. Salutions of tin(IV) chloride give 60% more intense
emission than tin(II) chloride because of the higher volatility of the former. lt is like-
ly that chemical interferences from concomitant elements will be serious in cool flames
such as these and that future analytical applications should incorporate a separation
techniq~e.

SnCl. SnBr. In O.lM hydrochloric or hydrobromic acids, spectra attributed to SnCl

and Snßr were observed [ 19] as thin dark blue or green cones respectively about 1 cm
above the burner head in the coolest part of the flame used for excitation of SnH.
These spectra have not been used for analytical purposes.

2.2 Atomic Emission

The premixed N2 0/acetylene fla:me has been exarnined in detail as a source for
atomic emission by Pickert and Koirtyohann [28] anq the emission characteristics of
tin, in particular, have been studied by the same au thors [ 17]. The flame was support-
ed on a Semslot burner and was viewed "end-on" in the conventional atomic absorp-
tion mode of operation. If a monochromator ofmedium dispersion is used (e.g. 1.6
nm/mm first order) a Iimit of detection of 0.3 J.Lg/rnl Sn can be obtained at 284.0nm.
 Ref. p. 94] 2.3 Chemiluminescence Atomic Emission 85

This wavelength corresponds to the transition from the 4.789eV 3 P 2 state to the
0.425eV 3 P 2 state and is also the strongest line in the d.c. arc emission spectrum. In
fuel-lean flames, some emission from the OH band occurs at 284.0nm, this can be
almost completely suppressed by increasing the acetylene flow to give a fuel-rich fla-
me with a red reaction zone about 9mm high; this is considerably richer than the
corresponding flame used for atomic absorption. No serious chemical interferences
were encountered [17] in this flame, but because the technique appears to offer few
advantages over atomic absorption it has received little further attention.

2.3 Chemiluminescence Atomic Emission

All the important atomic emission lines for tin have relatively high excitation ener-
gies. The lowest isthat of the 286.33 nm line ( 4.33 eV) and even this is not excited to
any useful extent in an air/H 2 flame by purely thermal means. However, certain exo-
therrnie reactions taking place in the flame may be exploited such that the energy
liberated in the reaction is used for excitation and hence to stimulate atomic emission.
Buell [24] has observed strong emission of tin down to 207.3 nm, involving excita-
tion potentials of 6.4eV under suitable conditions. Limits of detection of the order
of lJ.Lg/ml Sn were obtained by Buell using a turbulent 0 2 /H 2 flame supported on a
total-consumption burner and using naphtha as the solvent. In addition, a great deal
of work on chemiluminescence has been carried out by Gilbert [26] and it is a great
pity that much of it is unpublished or available only as conference reports. Fig. 4
shows the chemiluminescence emission spectrum of tin [26] in a turbulent
air/H 2 flame using iso-propanol as the solvent.

Cl)

"'"'
N

>-
.....
Ui
z
....UJ
~
z
0
Ui
"'
~
UJ
"'
..;
N
N
"'~ ..,
Cl) r-
-
."' "'
;:::
"'
..;
..,
N ..,
Cl)

"'"'
N
"'
N N
N

"'

225 230 235 240 245 250 255

WAVELENGTH nm

Fig. 4 Chemiluminescence atomic emission spectrum of 100J..Ig/ml Sn in a turbulent air/H 2 flame

using iso-propanol as solvent [26]
86 Atomic Absorption Spectroscopy [Ref. p. 94

Alkemade and Zeegers [27] have summarised excitation processes involved in chemi-
luminescence flame spectroscopy and suggest the reactions below as being responsible
for excitation:
CH+O -)-
CO* + H 6H = -7.6eV
CH+OH -)-
CO* + H2 6H =- 7.7eV
C2 + o -)-
CO* + CO 6H =- 8.85 eV
CO*+ Sn -)-
Sn* + CO
CO*+ SnO -)-
Sn*+ C02
Most of the interest in chemiluminescence flame spectroscopy was shown before
atomic absorption developed as an accepted analytical technique. Recent studies [25]
have received little further support and it is unlikely that research of practical value to
the analyst will be carried out in the near future.

3. Atomic Fluorescence Spectroscopy

Initial studies [80] of the atomic fluorescence of tin using an air/H 2 flame and high-
intensity hollow cathode lamps as excitation sources were rather disappointing and a
detection lirnit of 1OOpg/ml Sn was reported. This au thor [81] abtairred similar results
with organotin compounds in air/hydrogen and argon/hydrogen flames using a micro-
wave-excited electrodeless discharge tube as the exci tation source. Subsequently,
Browner, Dagnall and West [12], using electronically modulated electrodeless,dis-
charge tubes were able to observe atomic fluorescence at several wavelengths from tin
in Ar/02/H2, Ar/H2 and air/acetylene flames. The relative fluorescence intensities
abtairred from 1OOpg/ml Sn in these flames is given in Table 4. As in atomic absorp-
tion, the best Iimits of detection were found in a very fuel-rich Ar/0 2/H 2 flame
(0.11 pg/ml Sn). Under these conditions interferences were found tobe prohibitive and
a lean air/H2 or Ar/02/H 2 flame was recommended ( detection limit 0.3 pg/ml Sn in
Ar/02/H2 and 2pg/ml Sn in air/H 2). In atomic fluorescence, the presence of Ar in
place of N 2reduces collisional quenching of excited atoms and usually results in con-
siderably enhanced fluorescence intensities. Calibration curves were linear up to 250pg/
m1 Sn.

Table 4. Atomic Fluorescence Relative Intensities for Tin in Different Flames [12]

Relative Fluorescence Intensity

Wavelength Re!. Source
(nm) Intensity Ar/02 /H2 Ar/H2 Air/C2 H2
224.61 1.00 3.70 2.15
235.48 32.1 3.61 3.00
242.95 54.3 7.42 6.30 3.54
254.66 46.0 5.92 4.75 2.55
326.23 570 8.14 35.5 17.0
270.65 380 81.5 58.5 27.0
284.00 500 215.0 58.5 72.0
333.06 725 37.0 4.74 8.06
286.33 330 237 122 36.5
300.91 420 200 94.0 31.4
. 303.41 620 519 130 91.2
317.51 780 482 213 64.4
380.10 718 66.7 39.6 12.1
 Ref. p. 94] 5.1 Solvent Exttaction 87

4. Electrothermal Atomisation
Replacement of the atomic absorption flame by an electrically heated carbon tube
or filament is now part of accepted analytical practice and a number of authoritative
articles on this aspect of atomic absorption have been published [2, 83 · 87, 97]. The
technique is finding applications where extreme sensitivity is required and where
relatively poor precision ( coefficients of variation of 10 - 20%) is acceptable.
In some very early work, L 'vov [86] obtained 1% absorption at 286.3nm with 2 x
10-1 2 g Sn using a heated tube atomizer with arc volatilisation. Fora 1OOt-tl sample
this corresponds to a concentration of 2 x 1o-s ,ug/ml Sn and is by far the lowest con-
centration of tin measured using electrothermal atomisers. Everett, West and Williams
[58] obtained a 1% absorption signal with 9 x 10- 11 g Sn at 286.3nm and 7 x 1o-ll g
Sn at 224.6nm, using a carbon filament. Pub1ications [88, 89] from the University of
Floridareport detection limits of the order of 1o-ll g Sn or 0.02,ug/ml Sn with gra-
phite filaments and atomic fluorescence detection. A detection limit of 10- 10 g Sn was
reported [90] using a heated tantalum filament atomizer. The use of an Ar/H 2 or H 2
sheathing gas in conjunction with graphite filament and rod atomisers gives improved
detection limits, precision and freedom from interference for a number of elements.
Tin is one element where this practice is almostessential [58, 88, 89, 91, 92, 93] to
achieve complete reduction and gives enhancemen ts of ten-fold over a nitrogen
sheathed fJJ.ament [58]. Typical flow rates are 2.81/min N2 and 1.31/min H 2 ; with
open fllaments the glowing carbon automatically ignites the hydrogen sheathing gas
and the resultant flame must be extinguished before the next sample can be introduced.
Electrothermal atomisers have been used mainly for the analysis of oils, where the
presence of tin may indicate impending bearing failures [58, 92, 93]. There appear
tobe many interfering elements [58] at least with fllament atomisers, although the
consequences of interference may be unimportant at the low levels for which the
technique is used. Tin has also been determined in steel samples [55] using an induc-
tion heated graphite furnace of a rather unique design. The determination is of interest
in that direct analysis of solid drillings samples was carried out in this particular in-
stance.

5. Separation Procedures
Separation procedures are used in atomic absorption either to increase the concen-
tration of an elementtobe determined or toseparate the element from !arge quanti-
ties of matrix constituents which might interfere or cause burner blockage. Because of
the inherent selectivity of atomic absorption, many more concomitants may be toler-
ated than would be the case in solution spectrophotometry, for example. Many of the
concentration procedures used for other techniques would be applicable to atomic ab-
sorption, however, only the siruplest are usually necessary.

5.1 Solvent Extraction

Solvent extractions used in the determination of tin by atomic absorption usually
employ either a sulphur ligandsuch as ammonium pyrrolidine dithiocarbamate or an
ion-association systemsuch as the extraction from acidic solutions. In both instances,
the organic extract may be nebulised directly (preferably into a nitrous oxide/ acetyl-
ene flame) or tin may be stripped into an aqueous phase which is then nebulised.
88 Atomic Absorption Spectroscopy [Ref. p. 94

The most suitable solvents for atornic absorption include methyl isobutyl ketone,
ethyl acetate and saturated hydrocarbons. Solvents such as benzene or toluene produce
excessively fuel-rich flames; carbon tetrachloride or chloroform produce large quanti-
ties of hydrochloric acid and other noxious products which may even extinguish the
flame with some types of instrument. Extremely volatile solvents, such as diethyl
ether, should be avoided on the grounds of safety; viscous solvents interfere with phase
separation during extraction and have low uptake rates on nebulisation.
Although organic and aqueous phases should be allowed to settle out after shaking,
it is rarely necessary to remove the unwanted phase; the nebuliser capillary may be
dipHed directly into the appropriate phase.
Ammonium pyrrolidine dithiocarbamate (APDC) - This has been used extensively
as a non selective extractant for many metals for atomic absorption [29], and has
found some applications in the deterrnination of tin. lt may be used almost interchange-
ably with sodium diethyl-dithiocarbamate (NaDDC), both being storedas 1% aqueous
solutions. Atmospheric oxidation of both reagents is rapid, particularly in acid solutions
and stocks should be made up daily. APDC is more resistant to oxidation in acid solu-
tion than NaDDC. Extractions may be carried out into either ethyl acetate or methyl
isobutyl ketone.
The rnain disadvantage with APDC or NaDDC is that they are stable only above
pH 4, under which conditions tin is readily precipitated as the hydroxide. Tin is
extracted quantitatively with NaDDC only as Sn(IV) [31] at pH 5.6.
Table 5 gives a summary of the pH ranges over which several elements may be ex-
tracted into MIBK using APDC [30].

Table 5. Ranges of pH for Complete Extraction of Meta!/ APDC complexes [30]

pH Elements Extracted
2 -14 Ag, Au, Cu, Ir, Rh, Tl(III)
2 -10 Bi, Co, Fe, Hg, In, Ni, Os, Pb, Pd, Pt, Re, Ru, Zn
3- 8 Ga
3- 7 Cr(VI) not Cr(III)
2- 6 Se, Sn(IV)
4- 6 Mn, Th, V
3- 5 .Sb, Te
2- 4" As(III), Nb, U
2- 3 Mo,W

APDC Extraction Procedure for Tin in Lead Alloys [32]

Heat 0.5 g of Iead alloy sawings with 20 ml concentrated sulphuric acid and 4 g of potassium sul-
phate until no further reaction occurs and strong fumes are evolved. Cool and treat with 250 ml
of water, fllter and dilute to 500ml with 10% hydrochloric acid. To a 50ml aliquot add 5ml of
2% aqueous APDC and extract immediately with lOml of MIBK. Nebulise the organic extract
into a nitrous oxide/acetylene flame and measure the tin absorbance at 286.3nm.

Ion association systems are widely used for the extraction of tin and success-
fully overcome the disadvantages of chelating extractions. The extraction is carried
out in strong acid solutions using simpleandinexpensive reagents. Excellent selec-
tivity may be obtain~d for tin and, if necessary, comparatively large amounts may be
 Ref. p. 94] 5.2 Coprecipitation 89

extracted. The various extraction systems used rely on the formation of complexes
such as Snl~- or Sn(SCN)~-: The positive ion accompanying the tin complex into the
organic phase may be the hydrogen ion or a Iong-ehain amine.
The solvent used for extraction is important and quantitative separations which are
successful with toluene or benzerre are often unsuccessful with MIBK. Two procedures
given below have been used for the atomic absorption determination of tin in food-
stuffs [33] and antimony, bismuth, Iead and tin in aluminium, iron and nicke! base
alloys [34]. Details of the chemistry of solvent extraction systems will be found in
the chapter on Solvent Extraction.

Solvent Extraction for Tin in Foodstuffs [33]

lOg of eanned food were ashed with 10m! of eoneentrated sulphuric acidplus suffieient 30%
hydrogen peroxide to give eomplete ashing. Vegetables and materials eontaining organotin com-
pounds should be wet ashed with nitrie acid instead of hydrogen peroxide. Transfer the digest to
a 50 ml volumetrie flask, add suffieient sulphurie aeid to give 12 ml in all, then dilute to volume
with water. Transfer a 25 ml aliquot (or less) into a separating funnel and add 2.5 ml of 83% po-
tassium iodide solution (or 2g of solid potassium iodide). Add 10m! of toluene and shake vigor-
ously for 2 min, separate the phases and diseard the aqueous phase. Clean the toluene layer by
shaking with 5 rnl of 1 : 4 sulphurie aeid and 0.4g potassium iodide, diseard the aqueous layer.
Add 5 ml of water and 0.5 ml of 5 M potassium hydroxide solution and shake for 30 sec. Col-
leet the aqueous layer in a 25 ml volumetrie flask, aeidify with 5 ml of 1 : 1 hydrochloric aeid and
1ml of 5% aseorbic aeid so!ution to reduce free iodine.
Dilute to volume and nebulise into an air/hydrogen flame measuring at 224.6nm. Aqueous
standards eontaining the same amounts of potassium hydroxide, hydrochlorie acid and aseorbic
aeid should be used and should be in the range 0.2- 100,Ug/rnl Sn. Alternatively an air/aeetylene
flame may be used with standards in the range of 2 - 360 pg/rnl Sn.

Solvent Extraction Procedure for Tin in Metals [34]

Dissalve 1- 5g of alloy in 60ml of eoneentrated hydrochloric acid with 60ml of water (nicke!
base alloys), or with 20m! of eoneentrated nitrie aeid (iron base and Fe-Ni-er alloys), and dropwise
addition of 30% hydrogen peroxide (Al alloys). Evaparate to 5 ml, add 10m! of hydrochloric acid
and add formic aeid dropwise to remove nitrie acid. Add 5 ml of hydrochlorie acid, wash down
with 5ml of water and add 4g of aseorbie acid to samples eontaining iron. Add 15m! of 30%
potassium iodide solution and transfer to a 150m! separating funnel, rinsing with water to give a
final volume of about 50ml. Pipette 10m! of 5% trioetylphosphine oxidein MIBK, shake for
30 sec and separate the phases. Discard the aqueous layer. If an emulsion forms it may be broken
by centrifuging or flltration. Some phase separation papers contain tin eompounds soluble in
MIBK, so take eare.
Nebulise the extraet into a nitrous oxidefacetylene flame measuring at 286.3 nm. Prepare stan-
dards in the range 1 - 50 ,Ug/ml Sn by taking aqueous standards through the same proeedure. An-
tirnony, bismuth and Iead may be ineorporated in the standards; the use of organo metallic stan-
dards is not recommended [94].

5.2 Coprecipitation
Coprecipitation is a relatively easy technique for the removal of traces of tin from
solutions containing !arge amounts of matrix elements. The few reported applications of
coprecipitation have been modifications of standard procedures used with other tech-
niques.

Kono [35] separated tin by coprecipitated with manganese dioxide from solutions
of zinc base alloys and with beryllium hydroxide from solutions of ferrous alloys. The
precipitates were then dissolved in hydrochloric acid and the solutions sprayed into a
nitrous oxide/acetylene flame, measuring at 286.3nrn. Another application ofmangane-
se dioxide as a carrier has been in the determination of antimony, bismuth lead and tin
in nicke! [36]. Manganese dioxide is formed by the reaction of manganaus sulphate
and potassium permanganate in a solution of the sample at 70 - 100°C in the presence
of 0.001 - 0.1 M nitric or perchloric acid. The precipitate is dissolved in concentrated
90 Atomic Absorption Spectroscopy (Ref. p. 94

hydrochloric acid with addition of 30% hydrogen peroxide. The manganese concen-
tration in the final solution is less than 0.3% and very little nickel is coprecipitated.
Tin in the range 1 - lOO~g/g can be determined using an argon/hydrogen diffusion
flame in the presence of up to 1 g of nickel, iron or copper.
Traces of antirnony, arsenic, bismuth, iron, Iead, selenium, tellurium and tin may
be recovered from up to 20g of copper by coprecipitation with lanthanum hydroxide
(37]. This also acts as a releasing agent for subsequent atomic absorption.
Coprecipitation of Tin from Copper by Lanthanum Hydroxide (37]
Dissalve 20g of copper in nitric acid and boil to expel nitrous fumes. Add water to dissolve the
residue and add 20 ml of 5 % lanthanum nitrate solution. Add slowly 200 ml of concentrated
ammonia solution, [Jlter and wash with 1 : 10 ammonia solution then with water to remove cop-
per. Dissalve the precipitate in 10m! of concentrated hydrochloric acid and 40ml of 1 : 1 nitric
acid and dilute to 200m! for atomic absorption. Standards should incorporate 10ml of a "matrix"
solution containing 1g/l copper, 50g/llanthanum nitrate (La(N0 3 h.6H 2 0) and 1: 10 nitric acid.
Other elements: As, Bi, Fe, Pb, Se, Sb and Te may be incorporated in the standards and deter-
mined. The rangeswill depend on the source of the copper.

Coprecipitation of Tin from Copper. Zinc or Aluminium with Manganese Dioxide

Dissalve 5g of alloy or meta! in 35m! of 1 : 1 nitric acid, dilute to approximately 200m! and add
Sm! of 10% manganese nitrate solution and 5ml of 1% potassium permanganate solution. Boil for
a few minutes, filter, rejecting the filtrate then dissolve the manganese dioxidein 20rnlof 1: 3
hydrochloric acid and 30% hydrogen peroxide added as required to complete the dissolution. Di-
lute to 100m! for atomic absorption using an air/hydrogen flame at 286.3 nm comparing against
standards of 2- 200~g/ml containing 5g/l manganese nitrate and 5% hydrochloric acid.

5.3 Sublimation
The classical distillation procedures for separating tin as the volatile bromide or
chloride have not been employed in atomic absorption analysis as they are relatively
time consuming and do not permit the treatment of large of numbers of samples.
Bromide volatilisation can be used for the removal of Iarge amounts of antirnony, ar-
senic and tin if these are matrix elements and must be removed for the determination
of other constituents.
Sublimation oftin iodide, however, has been used by Bowman [38] for the separa-
tion of down to 0.02% Sn from ores and concentrates for atomic absorption. The
procedure is simple and can be carried out in a test tube according to the procedure
below. Furthermore, an automatic sublirnation apparatus has been devised (39] to
treat up to 30 samples at any one time. The apparatus consists of two concentric
rings, slotted to carry 30 test tubes radially. The tubes are inclined at .20° to the hor-
izontal, their ends extending 4 cm beyond the outer ring and 2 cm beyond the inner
one. They are rotated at 22 revs/min for 12 min then at 8 revs/min for 8 min. Heat is
supplied by two bumers beneath the bottoms of the tubes and a flXed arm with a rubber
shoe causes the tubes to rotate about their axes for a quarter turn as they pass the arm.
Guimont (95] described an apparatus in which a rack containing forty 25 rnl test
tubes was placed in a fumace so that the lower ends of the tubes were at 550°C while
the upper ends were kept cool in a water-bath. A combination of iodide sublimation and
solvent extraction has recently been used by Welsch and Chao (96] for the analysis of
tin ores.

Sublimation Method for Ores and Concentrates [38]

Mix 0.2 g of fi!lely ground ore with 1 g of ammonium iodide in a test tube. Heat gently so that the
sublimate condenses on the walls gradually and does not escape from the tube. Dissalve the subli-
matein 10 ml of 2M hydrochloric acid at 75°C and dilute to 50ml with 2M hydrochloric acid
 Ref. p. 94] 5.4 Other Separations 91

after filtering. Determine tin by atomic absorption in an air/hydrogen or nitrogenfhydrogen dif-

fusion flame at 224.6nm against Standards of 2- 200pg/ml containing 2% ammoniumiodidein
2M hydrochloric acid.

5.4 Other Separations

Few other practicable separation techniques have been reported in conjunction with
the atomic absorption determination of tin. Direct extractions of feedstuffs with chlo-
roform [40] have been carried out to determine organotin compounds, such as dibu-
tyltin dilaurate. The extract was evaporated to low bulk then diluted with methanol
before spraying. Similar exploitations of the solubility of organotin compounds in
non-aqueous solvents have been made for the determination of tin in organametallic
biocides on woollen fabrics [41] andin paint and vinyladditives [42].
Tin in tinplate has been determined by anodic dissolution of the sample between
two carbon cathodes in 1 : 8 hydrochloric acid [43]. The nebuliser capillary tubewas
dipped into the electrolyte and tinwas determined in an air/acetylene flame. The ef-
fects of iron were overcome by addition of 1000 - 2000,ug/ml iron to both electrolyte
and standards. Forthedetermination of down to 2,ug/g tin in geological materials
[44] a peroxidefusionwas carried out followed by electrolysis at 60- 80°C, 1.5- 2V
and 0.7 - 1.0amp in the presence of a hydrochloric acid solution containing copper
and lead with hydroxylammonium chloride added as a depolariser. Copper-coated
electrodes were used and the deposit was dissolved in hydrochloric acid for the deter-
mination of tininan air/hydrogen flame at 224.6nm.
Tin may be volatilised from 0.5M hydrochloric acid solutions as the hydride
stannane: Thompson and Thomerson [82] found that addition of 2ml of 1% sodium
borohydride solution to 1ml ofthe sample in 0.5M hydrochloric acid generated volat-
ile SnH 4 as a single pulse. This was taken up in a stream of nitrogen or argon carrier
gas and passed into a heated silica tube aligned with the optical axis of the atomic ab-
sorption spectrophotometer. The silica tube was mounted above the grid of a wide-
path air/acetylene burner and was heated in the air/acetylene flame. An auxiliary ni-
tragen stream was used to cool the carrier gas input and was also injected into trans-
verse tubes near the ends of the silica tubein order to prevent ignition of hydrogen
produced during the vigoraus decomposition of sodium borohydride. A schematic
diagram of the generator cell an silica atomisation tube is given (Fig. 5). Because of

- N in
2

path

Fig. 5. Schematic of (a) hydride generator cell and (b) silica atomisation tube for the separation
of tin as stannane
 Table 6. Determination of Tin by Atomic Absorption Spectroscopy - Applications
Matrix Concen tration Sampie Treatment Ref.
Al Alloys 0.0002-0.1% Diss. Al alloys in HN03/HCI/H 2 S04 and [35]
extract with MIBK from 3.5M H2S0 4 /3.5 M
HCJ:N20/C2H 2 flame 286.3nm
Al Alloys 0.0002-0.1% See extraction with HCI/KI/TOPO - [34]
MIBK, this Chapter
Cu Metal J.lg/g Ievels See coprec. with La(OHh, this Chapter [37]
Cu Alloys 0.1 -10% Diss. in 1:1:2 HCI/HN03!H 2 0, add HCJ [14]
for Sn and dilute. Add Cu to standards
N2 O/C2H2 flame
Cu Alloys 0.1 -10% Diss. in 1:1 HCI/H 2 0 with min HN0 3 [69]
Air/H 2 flame 2 24 .6 nm
Cu Alloys 0.6-4.5% Diss. in HCI with min HN03. Ar/H 2 or [15]
N 2/H 2 flame. Add FeCJ 3 releasing agent
Cu Alloys 0.1 -10% ... [56,70]
Iron 0.0002-0.1% Coprec. with Be(OH) 2 and redissolve [35]
Ferrosilicon ... Diss. in HF in PTFE bomb [76]
Ferro- >0.002% Diss. in 1:1 HCl, air/C 2H2 [71]
manganese
Steel ... Several methods for wide range of mild, [75]
low alloy, high alloy steels and iron
Steel ... Diss. in HCI/HN03/HCJ04, N20/C2H2 [77]
flame, add Fe to standards
Steel Traces See extraction with HCl/KI/TOPO - [34]
MIBK, this Chapter
Steel 0.001-0.25% Diss. in HCI/HN0 3 , extract from 0.5M [48]
HCI/0.5 M KSCN/ascorbic acid into MIBK.
N20/C 2 H2 flame, 224.6nm
Steel 0.33% Diss. in HCI/HN03 [15]
Steel ... Induction heated graphite furnace [55]
Ni Alloys 0.0002 - 0.1% See extraction with HCl/KI/TOPO - MIBK, [34]
this Chapter
Pb Alloys 0.001 -0.005% Diss. lOg in 15 ml conc. HN0 3/15 ml 2% [13]
NH 4 F. Air/H 2 flame, 224.6nm, match
standards for Pb/HN0 3 /NH4F
Pb Alloys 3-7% Diss. in 1:2:10 HBF 4 /HN0 3/H 20, add. 0.2g [49]
tartaric acid. Air/C 2 H2 flame 235.8nm
Standards from type metals
Pb Alloys <1% See APDC Extraction Method, this Chapter [32]

Pb Alloys 0.35-0.45 Diss. in 5 ml HBF 4 /4 ml30% H 20 2 , dil. to [52]

100 ml. Match Standards for Pb/HBF 4 /H 20 2 .
N20/C 2 H2 flame, 286.3 nm
Pb Alloys Alllevels Diss. in 15 ml 1:1:1 HBF 4 /30 % H20 2/0.2 M [54]
EDTA, Air/C 2H 2 flame
Pb Alloys >o.l% Diss. under reflux with 8:2:3:5 50% tartaric [72]
acid/HF/15M HN03/H 2 0
Pb Alloys ... Rapid diss. in 2:3:5 HBF 4/HN0 3 /H 20 with [62]
ultrasonic agitation in cold. Sn not deter-
mined
Zn Alloys Traces Coprec. with Mn0 2 , redissolve, N 20/C 2 H2 [35]
flame, 286.3 nm
Zr Alloys ... Diss. in HF/HN03, add sat. H3B03, air/ [46]
C2H2 flame
Tinplate 0.1 - 1 % Diss. by anodic electrolysis. Det. Sn in [43]
electrolyte with air/C 2H2 flame. Add 0.1-
0.2% Fe to standards and unknown
Matrix Concentra tion Sampie Treatment Ref
U Fission ... . .. [11]
Products
Cr Plating .. . ... [51]
Soln.
Sn Plating ... Dilute, air/C2H2 flame [74]
Soln.
H202 >0.05JJ.g/ml Direct, 0 2 /H2 flame, 286.3nm [63]
Slag, Soots, 0.2-10% Diss. in HN03/HF, fuse residue with [73]
ZnConcen- Na2C03/Na2B40 7 and leach with HCI
trates Air/C2H2 flame, 286.3nm
Ores, Con- 200 - 1500 JJ.g/ml Grind and disperse in water, nebulise [4 7]
centrat es suspension, air/H 2 flame, 224.6nm
Ores,Con 0.02-80% See Sublimation Separation- this Chapter [38]
centrates
Ores, Con- 0.005-80% FuselSublime with NH4I as ref. [38]. Add [60]
centrates ascorbic acid/HCI/KI and extract with
Trioctylphosphine oxide/MIBK. N20/C2H2
flame, 286.3 nm
Sphalerite 0.08% N2/H2 or Ar/H2 flame, 224.6nm [50]
Sulphide >0.0002% Fuse with Na2 0 2 , diss. and electrolyse· [44]
Ores, with HCI/hydroxylamine/Cu/Pb. Diss.
Silicates residue. Air/H 2 flame, 224.6nm
T.Jsed Oils >0.5JJ.g/ml Dilute 1:2 with MIBK, N20/C2H2 flame [9]
286.3 nrn
Used Oils 0.2 - 2.5 JJ.g/ml Dry at 250°C, ash to 440°C, atomise (57]
2000°C with graphite rod, 224.6 nrn 0.5 jJ.I
sample, aqueous standards
Oils, 0- 20ng/ml Direct, carbon filament with H2 flame (58]
Xylenes 224.6 or 286.3 nm
Organa Sn 0.5 -lOOJJ.g/ml Sensitivity study on MIBK solutions, (59]
air/C2H2 and N20/C2H2, 224.6 nm,
286.3nm
Organa Sn 300JJ.g/g Ash, convert Sn to acetate, air/C2H2 flame [65]
in PVC 224.6nm
Organa Sn Either decompose with 1:1 HN03/H20 or (42]
in Paints ... dilute with MIBK, Air/C 2H2 flame
Organa Sn ... > l2jJ.g Sn required. Diss. in ethanol [41]
in Fabrics
Organa Sn 0.03% Extract with CHCI 3 , evaparate add methanol [40]
in Feeds and spray, air/C2 H2 flame, 286.3 nrn Dibutyl-
Sn-Dilaurate additives
Organa Sn ... Extract with HCI/Ethanol, separate by ion- (53]
inWood exchange, add 0.1% Li to all solutions.
N20/C 2H2 flame, 224.4nrn
Polymers, ... Wet ash with H2S04/H202 [78]
Wool, Cotton
Cellulose, >ltJ.g/g ... [66]
Nylon,
Polyester
Juices 1 - lOOOjJ.g/ml Centrifuge, dilute, air/C2H2 [45]
Juices, 1 -lOOOJJ.g/ml Centrifuge, dilute, heat to remove C02 [68]
Drinks from carbonated drinks
Juices >3JJ.g/ml To 20ml add lOml HCI, dil. to lOOml, [67]
centrifuge. N2 0/C 2 H2 flame, 286.3nrn
Foods ... Ash with H2 S04/HN0 3 , extract Sn into [64]
MIBK
Foods 10 -lOOOJJ.g/g See Extraction Method for Foods- this [33]
Chapter
Food ... ... [61]
94 Atomic Absorption Spectroscopy

the pulse-like nature of the absorption signal a detection lirnit of 0.0005 J.J.g/ml Sn at
224.6nm was recorded in this work [82]. At the time of writing, the work has not
been applied to practical analytical problems and the effects of oxidation state and
interferences are as yet unknown. Nevertheless, the technique could provide an extre-
mely sensitive method for tin using inexpensive accessories with a conventional AAS
spectrometer and is already under active investigation for the determination of ele-
mentssuch as As, Bi,Ge, Pb, Sb, Se, Te which also form volatile hydrides.

6. Applications
Practical applications of atomic absorption to the deterrnination of tin are given in
Table 6. Abrief reference is given to the sample treatment adopted and will suffice
for most purposes. In most cases the determinations are carried out directly after dis-
solution of the sample.
The applications listed cover the range of tin technology from alloying components,
tin plating, organo tin additives, to tin catalyst residues in fibres. Tin determinations in
used lubricating oils are a valuable pointer in diagnosing bearing wear and impendings
failure. As a contaminant, tin is present in foods and drink, and is very harmful contam-
inant in the manufacture of steel.

References
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 References 95

35. Kono, T.: Japan Analyst 20, 552 {1971)

36. Burke, K.E.: Anal. Chem., 42, 1536 {1970)
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CHAPTER 9

EMISSION SPECTROSCOPY

By R. Smith

A nurober of authoritative textbooks are available on the subject of emission spec-

troscopy and deal thoroughly with the fundamental principles of the technique. Some
of the more recent books are those of Moenke [ 1], Mika and Torok [2], Grove [3],
Addink [4] and Slavin [5]. In addition, a nurober of excellent reviews [6, 7) or abstracts
[8] are published at regular intervals. Other useful publications are the ASTM book
[9], the IUPAC recommendations on terminology [10] and several compilations of
atomic wavelengths [ 11 - 14].
This chapter deals with the emission spectroscopy of tin using conventional arc/
spark emission source units. A nurober of other emission sources are available at the
time of writing, including inductively-coupled plasma torches, glow discharge lamps,
hollow cathode lamps, Iaser microprobes, etc. These techniques are for the most part
undergoing development and evaluation, and as they are not widely used at present
for strictly routine use, the authors have omitted them from this chapter. Further-
more, the emission spectroscopy of tin using a flame as the excitation source has
found only limited applications and is described in the chapter on Atomic Absorption
Spectroscopy. The analysis of tin meta! or alloys by emission spectroscopy is describ-
ed in the appropriate chapters.

1. Spectral Characteristics of Tin

1.1 Molecular Spectra

Molecular spectra, such as those emitted by SnH or SnO, may be excited in flames
[ 15 J but are unimportant in arc/spark emission spectroscopy.

1.2 Atomic Spectra

The emission spectroscopic determination of tin, present as minor or trace quanti-
ties, is convenient in that there are several atomic lines of varying intensity covering
a wide range of wavelengths. The characteristic wavelengths [ 12, 13] are given in Table 1
together with their approximate relative intensities. Tin resonance transitions (i.e.
emissions terrninating in the 3 P 0 ground state) occur at 207.31, 224.61, 254.66 and
286.33nm. In addition, a nurober of transitionsexist which terrninate in the low en-
ergy 3 P1 (0.21 e V) state: 197.08, 209.16, 211.39, 214.87, 219.93, 233.48, 235.48,
238.07, 266.12, 270.65,300.91 and 303.14nm. Both types oftransition will be
subject to self-absorption and self-reversal. This will Iimit the linearity of calibrations
on certain instruments and, where possible, these lines should be avoided.
 Ref. p. 122] 1.3 Atomie Line Interferenees 97

Table 1. Atomie Emission Speetrum of Tin [ 12, 13]

Wavelength Are Energy Levels Wavelength Are Energy Levels

nm Intensity K nm Intensity K

197.080 2600 1692-52416 248.34 110 3428-43683

198.355 1500 3428-53826 249.57 110 8613-48670
204.066 800 3428-52416 252.39 15
207.308 480 0-48222 254.66 240 0-39257
209.158 550 1692-49487 257.16 100 8613-47488
259.44 55 8613-47146
209.639 140 8613-56299
210.093 150 3428-51010 266.12 140 1692c39257
211.393 550 1692-48982 270.65 700 1692-38629
214.873 60 1692-48216 276.18 11 3428-39626
215.143 140 3428-49894 277.98 100 8613-44576
278.50 32 8613-44509
219.449 160 3428-48982 281.26 12 17163-52707
219.934 220 1692-47146
220.965 320 3428-48670 281.36 60 8613-44145
221.105 30 8613-53826 284.00 1400 3428-38629
223.172 48 3428-48222 285.06 170 8613-43683
286.33 1000 0-34914
224.605 420 0-44509 291.35 24 17163-514 75
225.117 19 8613-53021 300.91 700 1692-34914
226.719 48 8613-52707
226.891 320 3428-4 7488 303.28 40 17163-50126
228.668 65 3428-4 7146 303.41 850 1692-34641
314.18 4 17163-48982
231.723 220 8613-51754 317.51 550 3428-34914
233.480 140 1692-44509 326.23 550 8613-39257
235.484 550 1692-44145 333.06 110 8613-38629
235.790 6 8613-51010
238.072 20 1692-43683 365.58 40 17163-44509
380.10 280 8613-34914
240.815 26 8613-50126 452.47 40 17163-39257
242.170 360 8613-49894 563.17 4 17163-34914
242.949 550 3428-44576 855.26 1 34914-46603
243.34 7 4 3428-44509
245.52 5 3428-44145

1.3 Atomic Line Interferences

A more important criterion for line selection, however, is a consideration of line
overlap with the spectrallines of other elements. Table 2lists some of the more useful
tin lines tagether with potentially interfering lines from other elements [ 14]. The data
of Table 2 were obtained by mixing a synthetic sample containing the elements of
interest with a matrix of Li 2 C0 3 and graphitein the ratio (1 : 4 : 20). A graphite
crater electrode was fllled with 35 mg of the mixture and completely burned in a d.c.
arc for 150 sec. The spectrum was recorded photographically. From Table 2, it is
possible to assess the importance of line overlap in a particular application. F or exam-
ple, in the range 0.04 - 0.4% Sn, there will be a pronounced interference from Cr
303.42 nm on the Sn 303.41 nm line. The limit of detection of the former is 0.03%
Cr and that of the latter 0.003% Sn. However, at the Sn 283.99 nm wavelength,
Cr 284.00nm is also coincident, but the detection limits are 0.003% Sn and 1% Cr;
hence interference occurs only at much higher chromium concentrations. At Sn
326.23nm there are no neighbouring chromium lines and this wavelength would be
chosen if the interference from other elements permitted.
98 Emission Spectroscopy [Ref. p. 122

Table 2. Line Overlap Interference with Tin Spectral Lines [14]

Analytical Sensitivity Concentration Range Interfering !:J./1. Sensitivity

Line (%) (%) LineA A (%)
1:4:20 1:4:20 1:4:20

Th 3174.460 - 0.559 30
Mn3174.651 - 0.368 10
Mo3174.672 - 0.347 20
Ti 3174.80 - 0.219 10
Pt 3174.824 - 0.195 15
Co 3174.905 - 0.114 2
Fe 3174.96 - 0.059}
Fe 3175.035 +0.016 50
Sn I 3175.019 0.002 0.025-0.3 Fe 3175.0 - 0.019 -
Mo3175.049 +0.030 2
Mn3175.2 +0.181 25
u 3175.358 +0.339 2
Fe 3175.447 +0.428 1
Mo3175.53 +0.511}
Mo3175.587 +0.568 0.5
Cr 3175.6 +0.581 20

Zr 2839.330 - 0.650} 0.5

Zr 2839.4 - 0.589
V 2839.437 - 0.552 2
Mo2839.585 - 0.404 1
u 2839.651 - 0.338 15
Ta 2839.778 - 0.211 10
Nb 2839.80 - 0.189 5
Ti 2839.80 - 0.189 5
u 2839.890 - 0.099 1
Sn I 2839.989 0.0025 0.035-0.4 Mn2840.001 +0.012 10
Cr 2840.021 +0.032 1
Al 2840.05 +0.061 30
w 2840.097 +0.108} 20
w 2840.220 +0.231
w 2840.1 +0.111
V 2840.106 +0.117 10
Th 2840.156 +0.167 5
Ti 2840.2 +0.211 5
Ta 2840.39 +0.401 5
Fe 2840.423 +0.434 1
Cr 2840.438 +0.449 5
u 2840.466 +0.477 5
V 2840.599 +0.610 10
u 2840.623 +0.634 2

Mn3033.563 - 0.558 50
w 3033.575 - 0.546 5
V 3033.822 - 0.299 0.1
Nb 3034.0 - 0.121 1.5
u 3034.049 - 0.072 20
Th 3034.069 - 0.052 } 0.7
Sn I 3034.121 0.003 0.04-0.45 Th 3034.1 - 0.021
Cr 3034.190 +0.069 0.03
w 3034.195 +0.074 5
Mo3034.2 +0.079 5
Co 3034.433 +0.312 0.6
Ni 3034.5 +0.379 2
Fe 3034.538 +0.417 1
Ref. p. 122] Atomic Line Interferences 99

Table 2 (continued)

Analytical Sensitivity Concentration Interfering !:::.">..

Sensitivity
Line (%) Range(%) LineA A (%)
1:4:20 1:4:20 1:4:20
Pt 3261.692 - 0.636 10
Nb 3261.695 - 0.633 5
u 3261.718 - 0.610 0.5
Mn3261.8 - 0.528 30
Zr 3261.8 - 0.528 3
Mo3261.84 - 0.488 3
Nb 3261.879 - 0.449 0.2
Ba 3261.96 - 0.368 20
Fe 3262.013 - 0.315 15
V 3262.062 - 0.266 1
Mo3262.188 - 0.140 30
Ba 3262.275 - 0.053 5
Fe 3262.280 - 0.048 10
Ta 3262.3 - 0.028 10
V 3262.3 - 0.028 1
Sn I 3262.328 0.003 0.04-0.45 Mo3262.353 + 0.025 1
Pb 3262.353 + 0.025} 10
Pb 3262.4 + 0.072
Mo3262.628 + 0.300 0.1
Th 3262.671 + 0.343 0.1
u 3262.7 + 0.372 15
Mn3262.9 + 0.572} 25
Mn 3262.9 + 0.572
V 3008.505 - 0.642} 0.5
V 3008.614 - 0.533
Ni 3008.8 - 0.347 1
Mn3008.822 - 0.325 30
u 3008.922 - 0.225 2.5
Nb 3008.964 - 0.183} 10
Nb 3009.0 - 0.147
w 3009.076 - 0.071 3
Sn I 3009.147 0.005 0.07-0.8 Fe 3009.092 - 0.005 5
Ca 3009.205 + 0.058 0.5
Mn3009.4 + 0.253 20
u 3009.42 + 0.273 0.7
Fe 3009.570 + 0.423 0.1
V 3009.6 + 0.453 2
Th 3009.725 + 0.578 1
Sr 3329.988 - 0.606 } 0.3
Sr 3330.1 - 0.494
Fe 3330.313 - 0.281 50
u 3330.399 - 0.195 1.5
Th 3330.475 - 0.119 0.1
Sn I 3330.594 0.015 0.25- 3 Co 3330.6 + 0.006 7
Cr 3330.60 + 0.006 5
Mo3330.663 + 0.069 10
Mn3330.668 + 0.074 0.7
Ta 3331.007 + 0.413 } 1
Ta 3331.2 + 0.606
Fe 2445.979 - 0.573 0.025
V 2545.983 - 0.569 } 0.5
V 2546.0 - 0.552
Cr 2546.456 - 0.096 40
Sn I 2546.552 0.04 0.6 -7 Mn2546.607 + 0.055 20
Fe 2546.661 + 0.109 50
Co 2546.737 + 0.185 } 7
Co 2546.8 + 0.248
Ta 2546.803 + 0.251 5
Fe 2546.874 + 0.322 2
V 2547.075 +0.523 10
w 2547.136 + 0.584 1
100 Emission Spectroscopy [Ref. p. 122

Table 2 (continued)

Analytical Sensitivity Concentration Interfering I::::.'I\ Sensitivity

Line (%) Range(%) LineA A (%)
1:4:20 1:4:20 1:4:20
u 2849.983 - 0.635 2
Co 2850.043 - 0.575 3
u 2850.487 - 0.131 1
Ta 2850.491 - 0.127 0.1
Cr 2850.5 - 0.118 5
Sn I 2850.618 0.04 0.6 -7 V 2850.686 + 0.068} 2
V 2850.768 + 0.150
Mo2850.787 + 0.169} 2
Mo2850.898 + 0.280
w 2850.800 + 0.182 10
u 2850.820 + 0.202 2
Co 2850.951 + 0.333 10
Ta 2850.985 + 0.367 0.03
Ti 2851.102 + 0.484 0.5
Sb 2851.112 + 0.494 3
Mo2851.179 + 0.561 3
V 2851.254 + 0.636 30
Th 2851.261 + 0.643 0.5
Mg2852.129 +1.511 1

Co 2660.6 - 0.648 25
Mn2660.619 - 0.629 50
Ti 2660.640 - 0.608 3
u 2661.1 - 0.148 10
Sn I 2661.248 0.07 1 -11 Fe 2661.196 - 0.052 5
Fe 2661.312 + 0.064 5
Ta 2661.336 + 0.088 0.05
Th 2661.38 + 0.132 10
V 2661.423 + 0.175 0.1
w 2661.557 + 0.309 15
Co 2661.715 + 0.467 15
Cr 2661.728 + 0.480 1
Nb 2661.856 + 0.608 2.5
Ta 2661.886 + 0.638 1

Fe 2779.299 - 0.518 10
Zr 2779.3 - 0.517 5
w 2779.317 - 0.500 40
Nb 2779.361 - 0.456 0.5
u 2779.406 - 0.411 1.5
Mo2779.476 - 0.341 1
Fe 2779.70 - 0.117 30
Ta 2779.704 - 0.113 10
Nb 2779.719 - 0.098 0.5
w 2779.724 - 0.093 15
Sn I 2779.817 0.1 1.5 -16 Mg2779.834 + 0.017 0.008
Mn2779.998 + 0.181 } 1
Mn278Q.Q. + 0.183
Mo2780.036 + 0.219 0.08
u 2780.040 + 0.223 1
V 2780.097 + 0.280 30
As 2780.197 + 0.380 0.7
Ta 2780.208 + 0.391 5
Nb2780.245 + 0.428 0.25
w 2780.283 + 0.466 25
Cr 2780.703 + 0.886 5
Ref. p. 122] Atomic Line Interfetences 101

Table 2 (continued)

Analytical Sensitivity Concentration Interfering /Sl\ Sensitivity

Line (%) Range(%) Line Ä Ä (%)
1:4:20 1:4:20 1:4:20
V 2483.070 - 0.333 20
Fe 2483.270 - 0.133 0.005
Pt 2483.367 - 0.036 2
Ta 2483.4 - 0.003 5
Fe 2483.535 + 0.132 3
Co 2483.612 + 0.209 1
V 2483.648 + 0.245 15
Sn I 2483.403 0.1 1.5-20 Mn2483.7 + 0.297 60
Nb2483.717 + 0.314 25
Nb2483.882 + 0.479 25
Ta 2484.0 + 0.597 2
u 2484.008 + 0.605 5
Ni 2484.034 + 0.631 3

Ti 2571.034 - 0.558 0.5

V 2571.057 - 0.535 20
Ta 2571.192 - 0.400 1
Nb 2571.326 - 0.266 2
Zr 2571.391 - 0.201 } 0.02
Zr 2571.4 - 0.192
Sn I 2571.592 0.1 1.5- 18 w 2571.445 - 0.147 5
Cr 2571.741 + 0.149} 0.5
Cr 2572.1 + 0.508
Nb 2572.102 + 0.510 5
Cr 2572.146 + 0.554 2
Co 2572.237 + 0.645 2

Ti 2812.982 - 0.600 2
u 2813.042 - 0.540 2
Fe 2813.288 - 0.294 0.05
Cr 2813.41 - 0.172}
Cr 2813.552 - 0.030 15
Cr 2813.685 + 0.103
Mn2813.473 - 0.109 0.5
Sn I 2813.582 0.2 2.5- 30 u 2813.549 - 0.033 8
u 2813.795 + 0.213 10
u 2813.982 + 0.400 10
Mn2813.992 + 0.410 2
V 2814.0 +0.418 10
Mo2814.046 + 0.464 5

w 2495.264 - 0.455 2
Zr 2495.274 - 0.445 30
u 2495.291 - 0.428 25
Th 2495.353 - 0.366 8
Co 2495.551 - 0.168 1
Sn I 2495.719 0.2 2.5-35 Cr 2495.7 - 0.019 25
u 2495.77 + 0.051 25
V 2495.788 + 0.069 10
Ni 2495.8 + 0.081 15
Pt 2495.817 + 0.098 1
Fe 2495.863 + 0.144 3
Ni 2496.0 + 0.281 15
B 2496.1 + 0.381 3
Ta 2496.237 + 0.518 15
Cr 2496.309 + 0.590 0.3
102 Emission Spectroscopy [Ref. p. 122

Table 2 (continued)

Analytical Sensitivity Concentration Interfering ISJ\ Sensitivity

Line (%) Range(%) LineA A (%)
1:4:20 1:4:20 1:4:20
Mn3032.3 - 0.475 50
Mo3032.545 - 0.230 30
Sn I 3032.775 0.25 3-35 Nb3032.768 - 0.007 0.1
As 3032.84 + 0.065 15
Cr 3032.927 + 0.152 3
u 3032.979 + 0.204 5
Sb 3033.0 + 0.225 15
Fe 3033.101 + 0.326 10
u 3033.193 + 0.418 0.5
Mo3033.234 + 0.459} 3
Mo3033.33 + 0.555
Mo3033.3 + 0.525
Ta 3033.392 + 0.617 10
Nb 3033.393 + 0.618 1
Cr 3033.4 + 0.625 5

Ni 2593.9 - 0.523 2
Cr 2594.02 - 0.403 5
Fe 2594.Q38 - 0.385} 3
Fe 2594.150 - 0.273
Co 2594.158 - 0.265 2
Ta 2594.247 - 0.176 0.5
u 2594.275 - 0.148 25
Sn I 2594.423 0.3 3.5 -40 Nb2594.338 - 0.085 3
Ta 2594.536 + 0.113 15
Ti 2594.629 + 0.206 10
Nb2594.740 + 0.317 1
u 2594.989 + 0.566 15
Th 2595.033 + 0.610 10

u 2784.450 - 0.581 0.5

Ti 2784.643 - 0.388 3
u 2784.669 - 0.362 3
Ta 2784.967 - 0.064 1.5
Th 2784.978 - 0.053 3
Mo2784.992 - 0.039} 0.3
Sn I 2785.031 0.4 4.5-50 Mo2785.0 - 0.031
u 2785.17 + 0.139 10
Fe 2785.213 + 0.182 10
Ba 2785.264 + 0.233 10
V 2785.543 + 0.512 3
Th 2785.613 + 0.582 5

Ta 3141.380 - 0.429 10
Mo3141.415 - 0.394 3
w 3141.424 - 0.385 5
V 3141.485 - 0.324 1.5
Ti 3141.537 - 0.272 0.05
u 3141.538 - 0.271 5
Pt 3141.658 - 0.151 15
Ti 3141.670 - 0.139 0.5
Mo3141.730 - 0.079 3
Sn I 3141.809 0.8 > 10 Cr 3141.82 + 0.011 5
Th 3141.849 + 0.040} 1
Th 3141.0 + 0.091
u 3141.953 + 0.144 0.8
w 3142.145 + 0.336 10
V 3142.186 + 0.377 20
Cu 3142.444 + 0.635 5
Fe 3142.453 + 0.644 5
 Ref. p. 122] 2. Types of Discharge 103

Table 2 (continued)

Analytical Sensitivi ty Concentration Range Interfering 6A. Sensitivi ty

Line (%) (%) LineA A (%)
1:4:20 1:4:20 1:4:20

V 2811.980 - 0.586 10
Cr 2812.006 - 0.560 3
Fe 2812.049 - 0.517} 3
Fe 2812.1 - 0.466
Mo2812.147 - 0.419 3
V 2812.169 - 0.397 10
Sn 1 2812.566 2 > 20 u 2812.235 - 0.331 15
Ni 2812.3 - 0.266 10
Mo 2812.585 +0.019} 3
Mo2812.6 +0.034
V 2812.694 +0.128 20
Mn2812.845 +0.279 0.5
Ti 2812.982 +0.416 2
u 2813.042 +0.4 76 2

2 Types of Discharge

A comprehensive classification of discharge types has been given by Mika and

Torok [2]. A less comprehensive, but convenient classification [9] describes the
commercially available source units in current use:
a) Continuous d.c. arc - a self-maintaining d.c. discharge.
b) Intermittent d.c. arc- a non-capacitative discharge having a series of pu1ses of the same
polarity and usually Iasting for less than 0.1 sec.
c) A.C. arc - a non-capacitative discharge consisting of a series of pulses of alternating
polarity. The pulses are extinguished in each half cycle when the potential across the analytical
gap falls to a value that is insufficient to maintain the discharge.
d) Triggered Capacitor Discharge - A series of electrical discharges from capacitors which may
be oscillatory, critically damped or over damped. It is initiated by separate means and is extin-
guished on each half cycle.
e) Spark - A series of electrical discharges from capacitors, each of which is self-initiated and
oscillatory and is extinguished on each half cycle.

The spark source is differentiated from the triggered capacitor discharge in that the
latter needs aseparate means for initiating the discharge. In general, a spark source
produces potentials of the order of 10 - 40 kV using capacitances of 0.001 - 0.02 pF.
A triggered capacitor discharge produces potentials of 0.2 - 2 kV using capacitances
of 1 - 25 0 pF. Both discharges may be unidirectional ( successive discharges have
similar polarity) or bipolar (successive discharges have opposite polarity). Schreiber
and Joseph [ 16] have compared three of the more comrnon source units for the
determination of Sn in Iead alloys.
The conventional, high-valtage spark or triggered capacitor discharge source pro-
duces typically 50 sparks/sec. Comparatively recently, so-called "high-repetition rate"
sources producing up to 1000 sparks/sec have become commercially available and offer
considerable advantages in shorter analysis times for a given precision and better repro-
ducibility overall.
104 Emission Spectroscopy [Ref. p. 122

3. Behaviour of Tin in Are Discharges

3.1 Ionisation
Semenova [17] demonstrated the relationship between the absolute temperature of
a d.c. arc and the ionisation potential of the arc constituents. Easily ionised elements
reduce the arc temperature whereas elements such as carbon (ionisation potential
11.3 eV) allow temperatures of up to 8000°K. This relationship is illustrated in Fig. 1.
Elements oflow ionisation potential have a disproportionately pronounced effect on
temperature [ 18] and alkali metal salts are often deliberately added to the sample
to buffer the effects of the matrix constituents present.

TEMP. (OK)

8000

6000

Copper arc 1163)

2000L----L----~---L----4---~----~--~~--~--~
5 6 7 8 9 10 II 12

IONISATION POTENTIAL (cV)

Fig. 1 Effect of arc constituent on temperature [17]

Fig. 2 shows the degree of ionisation of tin at various temperatures from calcula-
tions based on the Saha equation [ 19]. In the carbon arc at 8000°K tin is ionised by
about 18%, but this becomes negligible on adding alkali metal salts. The atornic line
emission intensity is, however, exponentially related to temperature and reductions
in the arc temperature caused by excessive additions of alkali metal salts, may decrease
sensitivity unacceptably. Forthis reason, particularly in qualitative analysis, carbon
powder is often mixed with the sample to increase the arc temperature. Frequently
the sample is mixed with alkali metal salts and carbon. The choice of additive is also
important in that it must volatilise throughout the whole duration of the burn; from
this point of view calcium salts are usually preferable to alkali metal salts.
 Ref. p. 122) 3.2 Volatilisation 105

IONISATION
0 /o

10.0

1.0

O.IL-----L--....U.--'---.....1.---'--___.JL...-_--l
0 4000 8000 12000

TEMPERATURE (°K)

Fig. 2 Ionisation of tin at various temperatures [18]

3.2 Volatilisation
Selective volatilisation of elements in the arc can be of considerable value; the most
celebrated example is the "carrier distillation" technique of Scribner and Mullin [20].
In the d.c. arc analysis ofuranium mdde, 2% Ga 2 0 3 was added to the sample. This
encouraged the volatilisation of trace elements relative to that of uranium. As a re-
sult, the spectra of tin and several other elements were observed with very little in-
terference from the complex uranium spectrum. Gallium may be used, in this partic-
ular instance, as an internal standard.
Table 3 gives the order of volatilisation of elements, oxides and sulphides in an arc
[ 18]. The high vapour pressures of the sulphides and halides of tin may be exploited
to reduce exposure time and, therefore, reduce background spectra. Zavorotnova
[21] found alkali meta! fluorides were particularly effective as carriers for tin using
carbon electrodes and [22] that NaF must be present in at least one hundredfold

Table 3. Order ofVolatilisation of Elements in the Are [18]

As Elements
Hg, As, Cd, Zn, Sb, Bi, TI, Mn, Ag, Sn, Cu, In, Ga, Ge, Au, Fe, Co, Ni, Pt, Zr, Mo, Re, Ta, W
As Sulphides
As, Hg, Sn, Ge, Cd, Sb, Pb, Bi, Zn, TI, In, Cu, Fe, Co, Ni, Mn, Ag, Mo, Re.
As Oxides
As, Hg, Cd, Pb, Bi, Tl, In, Ag, Zn, Cu, Ga, Sn, Li, Na, K, Rb, Cs, Mn, Cr, Mo, W, Si, Fe, Co,
Ni, Mg, Al, Ca, Ba, Sr, V, Ti, Be, Ta, Nb, Sc, La, Y, Zr, Hf.
106 Emission Spectroscopy [Ref. p. 122

excess over the tin content. Smaller additions of NaF caused systematic errors in the
determination of tin in mineral specimens. Additions of 1 - 2% carbon powder with the
NaF were also recommended [22]. Hanna andAbdella [23] determined tin in sand
after adding BaF 2 and graphite powder and found that anodic excitation of the sam-
ple was preferable to cathode layer excitation, particularly for tin. Other fluoride car-
riers used for tin determinations include: AgF [25, 29] and polytetrafluoroethylene
(PTFE) [26- 29].
Chloride salts are also effective carriers for tin and have found wide application.
Kawaguchi, Shigematsu andMizuike [30], for example, determined 0.01- 0.02~-tg Sn
by adding 20~-tl of a test solution containing 0.1% NaCl on to a graphite electrode
impregnated with a solution of 1% paraffm in benzene to prevent absorption of the
aqueous test solution. Excitation was in a 30 amp. d.c. arc with argon atmosphere for
0.7 sec. with a 6 mm gap. Cobalt ( 4~-tg/rnl) was used as the internal standard.
Another approach is to design the lower electrode as a graphite crucible fitted with
a smalllid with a hole in the centre ("boiler cap" electrode). During the burn, the
crucible remains relatively cool and only the very volatile elements escape into the
discharge. This technique has been used to determine tin and As, Au, Bi, Cd, Ga, Ge,
In, Pb, Sb, Tl in minerals using NH 4 Cl/K 2 C0 3 as carrier [33] and in Nb 2 0 5 with an
AgCl/ AgF carrier [24] .
Tennant [31] controlled the rate of evaporation of very volatile elements (As, Hg
and Sn) by adding Al 2 0 3 /CaC0 3 /K 2 C0 3 . In this instance, the additive acted as a
matrix buffer rather than a carrier. Sirnilarly, Yokohama [32] recommended calcium
nitrate as a buffer for 0.3~-tg Sn added as a solution in M HN0 3 to a carbon electrode.
The solution contained 3mg/ml Ca(N0 3 h and 0.2mg/ml Cd(N0 3 ) 2 internal standard
and was evaporated to dryness before excitation in a 6 amp d.c. arc for 30 sec.
Finally, it must be emphasised that in mineral specimens, tin is present as discrete
particles of the sulphide or oxide widely dispersed in the base matrix. Poor precision
is often encountered as a result. Care should be taken to grind these samples as fmely
as possible and to use a buffer which will fuse the sample during the burn or to carry
out a fusion before spectroscopic analysis.

3.3 Interna! Standards

Another consequence of volatilisation and matrix effects lies in the choice of a
suitable internal standard. The Standard should be pure with respect to the elements
sought, it should volatilise at a similar rate, it should have atomic lines of similar ex-
citation potential and wavelength to those of interest, and the lines should be free
from self-absorption. Table 4 shows data obtained by Scott [34] using cathode layer
excitation with a d.c. arc. The effects of matrix variations on line intensity are clearly
demonstrated. Gallium is used frequently as an internal standard for tin, although
Table 4 suggests that major changes in matrix composition would affect the two
elements in rather different ways. Similarly, it is particularly important when using a
carrier, that both tin and the internal standardundergo similar reactions in the arc
electrode. A more detailed discussion of internal standardswill be found in the sec-
tians dealing with specific applications.
 Ref. p. 122] 4.1 Aluminium 107

Table 4. Variation of Line Intensity with Matrix for Several Elements

Element % Changes in Intensity Relative to Al203 Matrix
Al203 Si02 CaC03 Ca3(P04)2 N~P207 NaCl Na2C03
Co 345.3 Nil - 10 - 7 - 9 - 64 - 8 -57
Fe 345.1 Nil - 34 - 24 - 15 - 66 - 20 -72
Ni 341.4 Nil + 174 - 9 - 7 - 60 - 9 -56
V 318.5 Nil - 99 + 230 + 185 - 40 + 16 -53
Mo 317.0 Nil - 49 + 7 + 10 +50 - 3 -55
Zr 339.1 Nil - 32 + 54 + 50 - 52 + 22 -41
Fe 330.5 Nil - 31 - 6 - 21 - 73 - 36 -76
Ag 328.0 Nil - 5 - 5 - 44 - 53 - 75 -55
Cu 327.3 Nil - 16 - 39 - 34 - 63 -72
Ga 294.3 Nil - 52 + 63 + 6 + 4 - 43 -36
Sn 283.9 Nil - 4 + 21 - 17 - 54 - 36 -41
- -- -- -- -- -- --
Fe 283.8 Nil - 32 - 21 - 19 - 62 - 9 -62
Pb 283.3 Nil - 36 - 9 - 45 - 66 - 44 -49

4. Metallurgical Analysis
This section is devoted specifically to the determination of tin in metals. The deter-
mination of tin in other items of metallurgical interest such as slags, mattes and refrac-
tories has more in common with the techniques used in geochemical analysis and will
be found in that section.
In general, when standards of an appropriate range and metallurgical state are
available, metals are analysed in a sparkor tiggered capacitor discharge. The surface
to be examined is usually machined to a clean finish and is supplied to the instrument
as a rod or flat sample for mounting in a Petrey stand. When the sample is available
only as drillings or filings it may be prepared by melting (in which case the analysis is
similar tothat foramassive metal specimen), compacted into a briquette, analysed by
a molten-globule technique or dissolved and analysed by arc discharge methods nor-
mally reserved for non-metals. The particular type of discharge will reflect the need
for precision (spark discharges used) or sensitivity (arc discharges used).

4.1 Aluminium
The spectrographic analysis of aluminium is described in ASTM E101 (photographic)
and ASTM E227 (direct-reader) methods for tin and 14 or 22 elements respectively
(9]. Samples for both methods are prepared as chill-cast discs finished on a lathe by
removing 1.3 mm off the chilled face. Turnings and sheet should be pressed into a bri-
quette, melted and cast into a disc. Thick sheets may be analysed directly after ma-
chining 0.8 mm from the surface to be exarnined. Samples are inserted in a Petrey
stand with an ASTM C5a graphite counter electrode (6.15mm diameter with 20°
rounded tip). The Sn 326.233 or 317.502nm lines are used.
Results are obtained by plotting log Intensity vs log Concentration and a coefficient
of variation of 2-4% should be expected for 0.05% Sn.
The line Sn 317 .502nm is used for ASTM E227 in the first order (0.1 - 1.0% Sn) and
in the second order (1.0- 8.0% Sn). The calibration is linear with a detection lirnit of
0.001% Sn (Spark) or 0.0002% Sn (Capacitor Discharge ). At 0.04% Sn the coefficient
of Variation with the triggered capacitor discharge is 2.4 %.
108 Emission Spectroscopy [Ref. p. 122

Conditions for Photographie Spectrography (ASTM E101) are:

Fuessner Arc-Interrupted Rectified Spark HVSpark

Spark Spark Rotary Interrupter
Capacitance, !J.F 0.021 0.009 - 0.017 0.007 0.005 - 0.025
Inductance, iJ.H 400- 1400 300-500 300-800 200- 1500
Potential, V 75 250 230-250
Discharges, sec-I 120 240 240 60-240
Gap,mm 3 3 3 3
Preburn, sec 5- 10 5- 10 5- 10 5 -10
Exposure, sec 10-30 10-30 10- 30 10-30

Conditions for Direct-Reading Spectrography (ASTM E277) are:

HV Spark Triggered
Capacitor Discharge
Capacitance, !J.F 0.007 60
Inductance, iJ.H 360 300
Voltage, kV _1 20 0.94
Discharges, sec 240 60
Preburn, sec 3-5 3
Exposure, sec 10- 15 10-15

Redfield and Wagoizer [35] have studied the mould-casting of aluminium for spec-
trography whilst Stickers, Wild and Hofmann [36] have discussed elimination of mtide
band spectra using an argon and/or hydrogen atmosphere.

4.2 Antimony
Tin and fifteen elements were determined in antimony (37] by grinding to a pow-
der, mixing with one tenth of its weight of graphite and exciting 50mg in a graphite
cup electrode using a 10 amp d.c. arc in an atmosphere of oxygen. A detection Iimit
of 0.4!J.g/g Sn was obtained at the Sn 284.0nm line. Standards were made from spec-
troscopically pure antimony and oxides of the impurities.
Zone refining [38] may be used to concentrate tin and fourteen impurities. More
than 90% of the impurity content passes to the concentrate and offers a novel ap-
proach for the analysis of low-melting metals and alloys.

4.3 Arsenic
Tin may be determined [39] in arsenic metal by heating 1 g of sample in air at
190°C to volatilise As 2 0 3 • Dissolve the residue in nitric acid, evaparate and redissolve
in hydrochloric acid. Add 2!lg Pd as internal standard and add an aliquot to a 9 : 1
sodium chloride: graphite powder mixture for excitation in a 13 amp d.c. arc with
graphite electrodes. The Iimit of detection is 0.005!J.g Sn.
Alternatively [40], I g of sample may be dissolved in 3 : 1 HCI : HN0 3 , diluted
with water and very carefully evaporated with Hßr to remove arsenic but not tin.
After dilution, 6- 20mg Bi(N0 3 ) 3 is added, then KOH. The bismuth hydroxide pre-
cipitate is fllt.ered, washed, mixed with powdered graphite and examined in an 8 amp
d.c. arc to give a detection Iimit of 0.02!J.g/g Sn.
Ref.p.122] 4.6 Copper 109

4.4 Bismuth
Standards may be made by melting the meta! and impurities in air or under pahn
oil [41] and casting into 1Omm diameter rods which are sawn in two and flled flat
with a coarse file. Care should be taken not to break the rods which are very brittle.
Excite in a triggered capacitor discharge using a pointed graphite counter electrode.
The Bi 303.49nm line has been found tobe of similar intensity to the Sn 303.41 nm
line for pure Bi and 0.14% Sn [42].

4.5 Cadmium
Standards may be prepared [44] by melting cadmium and tin in a graphite crucible
at 500°C in a muffle, which is purged continuously with carbon dioxide. Alternati-
vely the metals may be melted in a 6mm diameter glass tube attached to a vacuum
pump, the glass being broken away after cooling. The sticks are machined to give a
flat surface for excitation in a 3.5 amp a.c. arc with 4 mm gap, 10 sec preburn and
30 sec exposure. Controlled cooling of a 250g sample of cadmium effectively concen-
trated impurities in the liquid phase and allowed determinations of down to 0.2ng/g
Sn[45].
Impurities may also be concentrated [46] by removal of cadmium at 380°C, 0.1
torr by vacuum sublimation of a SOg sample. Sublimation is continued until a residue
of 0.2 - 0.5 g is obtained, this is dissolved in HN0 3 , evaporated and heated at 500-
600°C. The residue is mixed with one fifth of its weight of graphite powder and ex-
cited in a 10amp d.c. arc for 30sec. A Iimit of detection of lOng/g Sn was claimed with
similar Ievels for sixteen other elements. Synthetic standards based on CdO were used.
Tin may be concentrated by partial precipitation of Cd(OH) 2 by arnmonia from a
nitric acid solution. The washed, dried precipitate is redissolved in 4- 5 drops of HN03,
added to graphite powder and examined in an 8 amp a.c. arc. Manganese dioxide
[48] or aluminium hydroxide [48] have also been used as coprecipitants and give
a detection Iimit of O.lt.tg/g Sn.
Yusupov and Shavrin [49] studied the spectrographic analysis of binary alloys of
Cd with Sn, Pb and Zn. The intensity of impurity lines (Bi, Cu, Pb, Sb and Sn) cor-
responded to the degree of arc or spark erosiqn and was closely related to the thermal
conductivity of the alloy.

4.6 Copper
ASTM E486 describes [9] the determination of 0.9- 1.2% Sn in admiralty meta!
using a chill-cast disc or 30mm x 8mm diameterrod sample. Approximately 2 mm
should be machined from the chill-cast face. Excite using a 6mm diameter pointed
graphite rod counter electrode (ASTM CS) and the conditions given on page 110:
In all cases with direct metals analysis, samples and Standards should be in similar
metallurgical states. The segregation of Iead and to a lesser extent, tin in ]arge castings
is well-known. Coldworked copper and brasses are said [50] to give more intense im-
purity spectra than annealed metals.
Brownsdon and Van Sameren [51] analysed brasses as 6mm diameter rods, cubic
ingots or thick strips in a 5 amp d.c. arc with sample as cathode and a pure copper
rod anode. Cathode excitation was used [51, 52] for Cu/Ni, Cu/Zn, copper and bras-
ses. Cast discs of tin bronz es were analysed for tin [53] using a high-voltage spark and
mask of insulating resin on the disc surface leaving an area for excitation of 15mm
diameter. Schatz [57] used an interrupted d.c. arc for tin in copper alloys.
110 Emission Spectroscopy [Ref. p. 122

Conditions for analysis of Admiralty Meta! (ASTM E486)

AC Spark Triggered
Capacitor
Discharge
lnductance, pH 40 400
Capacitance, pF 0.015 60
Current, A 5-8 0.6
Voltage, V 230 940
Preburn, sec 3- 20 3-20
Exposure, sec 15- 17 15- 17
Gap,mm 3 3
Coefficient of Variation,% 3.0 2.5
Analytical Lines: Sn Cub
266.125a 302.156a
317.505 306.342
286.333 299.736
238.999 299.736

a Triggered capacitor discharge

b 50% transmittance fJlter

The "globule-arc" method has been traditionally used for the determination of
impurities in copper (54, 55]. A 0.2- 0.5 g sample of drilling is placed in a notch in
the end of a graphite rod acting as the lower negative electrode. A copperrod is used
as anode. When the arc is ignited the sample melts to give a globule; the electrodes
should be manipulated to keep a steady arc incident on the globule. A copper anode
is said to give considerably less CN band background than a graphite counter electrode.
The "globule-arc" method gives fewer ion lines than an solid electrode arc and gives a
detection Iimit (44] of Spg/g Sn in a 7 amp d.c. arc. An oxygen atmosphere may be
used (56] to further reduce CN background.
Leichtle (58] analysed copper base alloys compacted into pellets using a 14 amp d.c.
arc with an upper graphite cathode and the sample supported in a graphite crater elec-
trode. A similar briquetting technique was recommended in ASTM E414 for 1 - 30
pg/g Sn and eight other elements present in copper. The sample was excited as cathode
in a d.c. arc with a copper counter electrode. The Sn 284.00nm and Cu 284.65nm lines
were measured photographically to give a coefficient of variation of 6- 13% in the
range 2- 10pg/g Sn.
When suitable standards are not available or if a !arge sample must be taken (for
reasons of representative sampling), it may be preferable to dissolve the material in
nitric acid. Jaycox [59] diluted the resultant solutions of copper-based alloys with ni-
neteen parts of copper nitrate solution. The diluted solution was absorbed on to porous
graphite electrodes, dried and excited in a d.c. arc. A more recent study by Elwell
andPeake (60] examined the determination of 0.005- 0.2% Sn insmall samples of
copper-base alloys. They found briquetting procedures introduced excessive iron con-
tamination from the press and that the samples frequently disintegrated during excit-
ation. They dissolved 0.3g ofsample in Sm! of 1 : 1 HN0 3 , evaporated and ignited
at 400°C. The oxidewas ground in an agate mortar, transferred to a graphite cup elec-
trode (9mm height, 12mm o.d., lOmm i.d., Smm base thickness) which was supported
on a 25mm diameter graphite pillar. A 15 sec exposure was used with sample as cathode
(60pH, 250pF, 10!2). Twelve other elements were determined with tin.
A manganese dioxide coprecipitation was used by Park (61] to determine 0.4- 15
pg/g Sn in high purity copper, using a 100 g sample, dissolved in 11itre of 2 : 3 HN0 3 /
 Ref. p. 122] 4.9 Irons, Steels, Ferroalloys 111

water. Trace elements were precipitated by adding 10m! of 20% KBr and 10ml of 3%
KMn0 4 and boiling. Two precipitations were carried out, the residues were dissolved
in 50m1 of hydrochloric acid, neutralised with ammonia and 1ml of concentrated hy-
drochloric acid added. Tin and other elements were precipitated with hydrogen sul-
phide, fütered, dissolved in nitric and hydrochloric acids and evaporated to 5ml. Ali-
quots were absorbed on graphite electrodes for excitation in the d.c. arc.

4.7 Gallium
The method of reference [40] for tin in arsenic has been used for the analysis of
gallium and gallium arsenide.

4.8 Hafnium
Tin and twenty other elements were determined [62] by direct analysis of metal
fllings or oxide powders using a graphite crater electrode and d.c. or a.c. arc. The same
method was used for zirconium.

4.9 Irons, Steels, Ferroalloys

Tin occurs in iron and steel as a contaminant from metal scrap where it is present
as tinplate or soldered joint residues. Tin is added to some cast irons.
Plain carbon and low alloys steels- may be analysed for Sn (0.005 - 0.02%) and eight
other elements by ASTM E403 [9] which is applicable to chill-cast or rolled and for-
ged specimens, 25- 64mm diameter and 10- 38mm thick. Steels with total alloy
contents of less than 3% are claimed to show no metallurgical state matrix effects.
Standards can be obtained commercially [63, 64] or may be chemically analysed
[65].
Sampiesare prepared (ASTM E403) by machining 2mm from a flat surface, pol-
ishing wet or dry with 80 grit alumina or silicon carbide cloth and finishing with 120
grit. Mount in a Petrey stand with 6.15 mm diameter graphite counter electrode with
either 120° sharp (ASTM C2) or 20° rounded (ASTM C5) points. Excite in a trig-
gered capacitor or discharge using conditions A or B. (A: 7 - 10pF, 50pH, 2.5 - 5 n.,
0.94 - l.OkV, 0.3 - 0.8amp r.f., 5 - 35 discharges/sec, 3 mm gap) (B: 40 - 60pF, 360pH,
25- 30rl., 0.94- 1.0kV, 2- 3amp r.f., 60 discharges/sec). Both methods use a 25 sec
exposure and measure Sn 317.502, Sn 326.33 and Fe 271.441 nm lines with a direct-
reading spectrograph. Note that the iron reference line is ionic whereas the tin lines
originate in the atomic spectrum. Sn 317 .502nm is subject to line interference from
Mo, Co, Ti and Cr; Sn 326.233nm coincides with weak lines from Fe and Mo. The
coefficient of variation for 0.012% Sn is 4.8%.
The mostsensitive tin lines, however, lie in the vacuum ultraviolet and may be ob-
served with a vacuum spectrograph and argon-flushed spark chamber. Tin (0.003 -
0.040%) may be determined tagether with twelve other elements including carbon
(193.09nm), sulphur (180.73nm) and phosphorus (178.29nm) by ASTM E415 [9].
The method is intended for control analysis of preliminary and !adle tests from basic
oxygen, open hearth or electric furnaces and for finished metal. Sampies are prepared
as for ASTME E403 above and are mounted in a Petrey stand with a counter electrode
of 6.4 mm diameter hard-drawn silver rod or a 1.5 mm diameter thoriated tungsten rod.
The rods are machined to a 90° or 120° cone and are polished with fine abrasive cloth.
Replace counter electrodes after 40- 50 bums when a black deposit accumulates and
intensity diminishes. Thoriated tungsten may allow over one hundred bums before
replacement. Both types of counter electrode should be conditioned by 2- 6 spark-
112 Emission Spectroscopy [Ref. p. 122

ings before use. Dischargeparameters are: 10- lSJ.tF, 50 -70Jili, 3- sn, 0.94-1.0
kV, 0.3- 0.8amp r.f., 60 discharges/sec, preburn 6- 20 sec, exposure 8- 25 sec,
3- 5 mm gap, Sn 189.99nm, Fe 271.44nm. In this procedure both Sn 189.99 and
Fe 271.44 nm lines are ion spectra. The coefficient ofvariation ranges from 16% at
0.005% Sn to 4% at 0.25% Sn.
Maekawa and Suzuki [66] using a 0.94kV condensed arc discharge and a direct
reading spectrometer studied the line overlap of Mo 317.505 and Sn 317 .502nm in
the range 0.005 - 0.15% Sn. lnterference with tin determinations was noted with
molybdenum contents greater than 0.15% Mo. An empirical diagram was used to
correct for 0.15- 1.2% Mo. Coefficients ofvariation were 18% (0.003% Sn) and 3.4%
(0.042% Sn).
Plain carbon and low alloy steels have also been analysed [67] for tin using a low-
wattage intermittent arc with graphite or silver counter electrodes. An a.c. arc or
condensed spark discharge gave better sensitivity for tin than a purespark [68].
Vacuum spectrographs have been used for tin in low alloy steels by Tunney [69] and
Goto [70] who used an oscillatory discharge (lOJ.tF, SOJ.Lf:l, 3Q, 0.9kV) for the
carbon 193.09, 165.70, 156.14 and 172.01 nm lines but preferred an overdamped
discharge (30J.LF, SOJ.Lf:l, 25n, 0.9kV) for Sn 181.13nm and As 197.26nm with
Fe 210.91 nm as reference.
Direct analysis of steels is only possible when standards of a sirnilar metallurgical
state are available. ASTM E403 claims that steels with total alloying contents ofless
than 3% do not show this type of matrix effect for tin and the particular elements
examined. Nevertheless with steels which have been rolled, annealed or otherwise
worked it is unlikely that suitable standards could be obtained for accurate determi-
nations of the elements of interest. A nurober of recasting techniques have been stud-
ied to overcome this problern [71 -73]. Stamp [72] pressed drillings into a pellet af-
ter mixing with aluminium which was used as a deoxidant. The pellets were melted
in a d.c.arc under a reduced pressure of 50 torr of argon. Tunney and Hughes [73]
melted their samples in an argon arc before casting into moulds (38mm diameter by
3mm deep). The cast samples were lapped or linished and could be used for x-ray
fluorescence or atomic emission spectroscopy. The Iosses of some elements during
melting were corrected for (eg C, Mn, P, Sand Si).
Chemical treatments may be employed to overcome matrix effects and to facilitate
standardisation. Weisberger, Pristera and Reese [74] determined tin and thirteen other
elements in iron and steels by heating 0.01 g with HN0 3 to convert to oxide, mixing
the residue with graphite and exciting in a high-valtage a.c. arc. Up to 0.2% Sn could
be determined with ± 10% accuracy. Iron powders were analysed [75] for tin and
sixteen elements by treatment with HN0 3 and NH4 N0 3 followed by ignition at
250°C. The residue was mixed with PTFE (polytetrafluoroethylene) powder and
graphite (100 : 10 : 25).The PTFE acted as a carrier for excitation in a IOamp d.c.
arc using iron as an internal standard. The dissolution of ferrous alloys in nitric acid
followed by ignition is typical of several reported procedures.
In a study on the effects of various buffers on volatilisation curves, arc temperature
and line intensities [76] a mixture of potassium nitrate and silica (1 : I) was recom-
mended for tin and other volatile elements e.g. Ag, As, Bi, In, Sb and Te. On applying
the method to iron and steels [77], the buffer incorporated 0.5% Sb 2 0 3 as internal
standard. Volatilisation of the above elements in a 9 amp d.c. arc was complete in
60 sec although the buffer reduced the volatility of iron and minirnised its inter-
ference. The Iimit of detection was 3J.tg/g for Sn. A somewhat sirnilar chemical
 Ref. p. 122) 4.10 Lead 113

treatment but without the addition of buffer or standardwas used [78) with a 9amp
d.c. arc operating in a magnetic field.
Tin has been coprecipitated (80] as the sulphide using cadmium as the collector
fromM H 2 S0 4 containing 1% sodium acetate and 10% acetic acid. The precipitate
was carefully ignited to avoid Iosses of tin sulphide, mixed with an equal weight of
graphite powder and excited in a 4amp d.c. arc for 30 sec. The Sn 317 .5nm and Cd
308.3nm lines were used and the method was employed down to 0.0015% Sn.
Other approaches involve solvent extraction of tin (81] into ether from 6.5M HCl.
Afterevaporation and extraction of the residue into etherfromM HCl/2% arnmonium
thiocya"hate, the organic extract was again evaporated and tin determined in a Feuss-
ner arc. Anion-exchange procedure (82] was used to concentrate traces (1 - lOOJ.Lg/g)
of tin in highly alloyed steels. After dissolution of 1.5 g of sample in an appropriate
acid mixture and evaporating almost to dryness, a solution of the residue in SOml of
2M HCl was passed down a column of a strong anion exchange resin (250 mm x 10
mm diameter) in the chloride form, previously equilibrated with 2M hydrochloric
acid. After wet ashing of the resin with H2 S0 4 /HN0 3 , 7.5 mg of copper was added
(as a copper sulphate solution) as internal standard. The mixturewas ignited at 400°C
mixed with carbon powder (1 : 3) and excited in a 10amp d.c. arc between carbon
electrodes. Cast irons were analysed directly [44] by chill-casting in a sand mould
(50~ 25 x 25 mm). The sample was broken in half and the fractured surface polished
then excited in a Samp d.c. arc for 10 sec with a 4mm gap. The Sn 335.23 and Fe
335.33nm lines were used. A 150 I.M.M.mesh gauze filterwas used as an attenuator,
estimated errors were: 0.01-0.15% ± 0.01% Sn and 0.15-0.02% ± 0.02% Sn.
Ferro alloys: binary alloy,s of iron, are most conveniently analysed by solution techni-
ques in view of the difficulty of obtaining a range of suitable standards. Some alloys
such as ferrosilicon may be ground in a ring mill. Svehla and Kvopkova (83] deter-
mined tin in ferrotungsten with an error of ± 12% at the 0.1% Sn Ievel using powdered
samples placed in a nicke! electrode and excited in a d.c. arc. Up to 0.07% Sn in ferro-
manganese has been determined [79] by spark excitation of 6M HCl solutions in a
porous cup electrode. Limits of detection for tin (0.02 %) and five other elements
were generally poor and repeatability was of the order of 10 - 25%. The method was
claimed to be superior to atomic absorption only for tin.

4.10 Lead
The determination of tin in Iead alloys is relatively easy in that synthetic standards
may be easily prepared. Master alloys are frrst made [41] by melting tin, Iead and any
other low melting metals under palm oil, stirring with a graphiterod and burning off
the oil before casting the metal into thin strips for subsequent dilution with lead. Rods
(lOOmm x lOmm diameter) may be cast after melting the master alloy with more Iead
in a silica crucible - oil is unnecessary at this stage. High melting elements such as iron
and copperwill not be lost as a dross ifpresent in amounts less than 0.2%. The rods
are cut in two and the cut surfaces flled and excited as the cathode in a triggered ca-
pacitor discharge with graphite rod anode and photographic recording. The detection
Iimit is 1 - 2J.Lg/g Sn with a 3 min exposure. This method [41] is similar to ASTM
E-117 [9] which use a disc sample instead of a rod. Discharge conditions [9] are for a
high valtagespark (0.14J.LF, 330J.LH, 30 sec exposure) or triggered capacitor discharge
(20J.LF, 200J.LH, 0.94kV, 10D, 1.2amp, 30 sec exposure). Line pairs Sn 303.41 and
Pb 322.05 nm were used.
114 Emission Spectroscopy [Ref. p. 122

Other excitation sources have been studied [84] for Iead analysis but no single
source is outstandingly superior. A Iimit of detection of 2/J.g Sn was obtained [85]
with an interrupted a.c. arc and 9 mm x 6 mm diameter rods. An interrupted d.c. arc
(0.01 sec pulses) was used by Janda and Sehroll [118] todeterminedown to 1.2/J.g/g Sn
with a Iead cathode and graphite anode. Brownsdon and Van Sameren [51] determined
0.002- 9.0% Sn in Iead and its alloys. Breckpot [86] described a method for tin and
eight other elements in binary alloys of Iead and conducted a study of the Sn/Pb/Sb
system [87] with Sb and Sn in the range 0.1 - 3%. Breckpot showed that a 1 amp d.c.
arc could be sustained between Iead electrodes if they are sufficiently massive to avoid
melting and if the opposing surfaces exceed 2 - 3 cm 2 •
Tin was determined in the range 0.13- 1.8% in antimoniallead alloys [88] using a
low voltage spark (4/J.F, 8 amp, 150 sparks/min). Sampies were 6 mm diameter rods
with wedge shaped ends; Sn 317.5nm and Pb 322.0nm lines were measured. Stan-
dards for antimonial alloys should be prepared by first melting pure Iead and anti-
mony without covering in an iron !adle or !arge crucible. After casting, a weighed
amount of the alloy is melted with tin and other low-melting metals to give standards
or master alloys. With rod electrodes, undue segregation takes place if the antimony
content exceeds 20% (41) and dilution of samples with Iead is recommended before
analysis. Lazebruk and Yatsenko [89] vaporised the sample and allowed the vapour
to condense on a copper electrode which was excited in a 2.5 amp a.c. arc. Nausester
[90] determined up to 20% Sn in type metals (containing up to 28% Sb) and also up
to 60% Sn in solders using a point-to-plane spark excitation method. The importance
of a chill cast sample was emphasised.
Downarowicz and Zagorski [91] effected a 200-fold concentration of tin and anti-
mony in high-purity Iead by coprecipitation with manganese dioxide. The precipitate
was excited in an a.c. arc between carbon electrodes using the Sn 235.5 and Mn 247.3
nm lines. Alternatively, 1 g of Iead may be dissolved in HN0 3 , evaporated to dryness,
taken up in 60- 80ml concentrated HCI and passed down a column of 100- 200
mesh Dowex 1 -X 10 strongly basic anion exchange resin equilibrated with 9M HCI.
The colurnn is washed with 25 ml of 9 M HCI and Sn tagether with Bi, Cu and Fe elu-
ted with 6M HN0 3 . Afterevaporation to dryness, 20mg of residue was excited be-
tween graphite electrodes in an 18 amp a.c. spark for 40 sec. The Iimit of detection
was 38ng Sn.

4.11 Manganese
Muzgin and Gladysheva [93] dissolved the sample in HN0 3 , evaporated to dryness
and ignited the residue at 250°C. Volatile elements (Bi, Cd, Cu, Pb and Sn) were vola-
tilised at 1400°C from 40mg of residue and condensed on a carbon electrode which
was excited in a 6 amp a.c. arc. Further enhancements could be achieved by volatil-
ising in the presence of 3% NaN0 3 .

4.12 Nickel
ASTM E483 [9] describes the determination ofvolatile elements: Bi, Pb and Sn in
nickel-base alloys using a carrier distillation technique. About 200mg of drillings are
dissolved in 2m! of HF and 1Ornl of HN0 3 by warming in a PTFE beaker. An inter-
nal standard of 1rnl of 40/).g/ml indium solution is added and the solution evaporated
to dryness in a platinum crucible. The residue is ignited for 20 min at 800°C, ground,
weighed and 10% of AgCI:LiF mixture (11 : 1) added. Charges of SOmg are weighed
into ASTM S2 graphite cup electrodes, mounted on an Sl pedestal with a 3.05 mm
 Ref.p. 122] 4.16 Tantalum 115

flat-ended rod as the counter electrode. The charges are vented by pressing a conical
tool into the centre to give a hole 4.57mm deep by 1.25mm diameter. The tool also
acts as a ram to compact the charge. Excite in a 12amp d.c. arc with 33 sec exposure
and a 50% transmission frlter. Measure the Sn 286.33 andIn 275.39nm lines photo-
graphically. Other tin lines must be used ifthe Fe 286.'25 and Fe 286.34nm interfere.
Coefficients of variation are 5 - 25%. The method is described in detail by Atwell and
Golden [94].
High purity nicke! has been analysed [95] for Bi, Co, Cu, Sn and Zn by dissolution
in HN0 3/H 2S0 4 , evaporating to dryness, oxidising with one drop of permanganate
and extracting with 4% ammonium thiocyanate and 0.3% diantipyrinylmethane into
chloroform. Afterevaporation to dryness the residue is excited in a d.c. arc.
Monel has been analysed by Barker [96] andArnott [97].

4.13 Phosphorus
Tin has been determined [98] by dissolving 5 g of phosphorus in 20ml of HN0 3 in
a PTFE beaker. After boiling to remove HN0 3 , 8ml of HCl and cobalt chloride (40
J,Lg/ml) is added then diluted to 50ml. A 1ml aliquot is applied to a rotating graphite
electrode and excited in a 10kV spark. Tin may be determined below 10pg/g.

4.14 Selenium
Tin and twenty two other elements were determined [99] by dissolving 1g in 10
ml of HN03 and 2.5 ml of H2 so4 with addition of 2J,Lg of Pd internal Standard. After
evaporation to dryness at 300°C to remove Se02 , the residue was dissolved in 6M HCl
and transferred with 1Omg of NaCl :graphite (1 :9) to a graphite crater electrode and
excited in a d.c. arc.

4.15 Silver
Tin is deterrnined in silver by ASTM E378 [9] in the range 0.0001 - 0.005% Sn.
1g is dissolved in 5 ml of 1 : 3 HN0 3 :H 20, evaporated to dryness, ground and packed
into an ASTM S4 graphite electrode (6.15 mm diameter with very shallow cavity and
undercut). Excite in a 12 amp d.c. arc for 30 sec with a 40% transrnission frlter, measure
Sn 284.0 or Sn 286.33 mm line.

4.16 Tantalum
Tantalum has a complex spectrum which hinders the determination of impurities.
Ifthe metal is converted to oxide [100] by heating at 600- 700°C for 2 hours, impu-
rities may be evaporated at 1400°C and condensed on copper electrodes as in refer-
ence [93] (see analysis of manganese). An internal standard of 0.01% thallium was
added before volatilisation of impurities and the line pairs Sn 259.85 and Tl 258.01
nm were measured. The detection Iimit was 3 x 10-s% Sn.
Similarly 1g of tantalum or niobiumwas converted to oxide [101] as above, fused
with potassium persulphate (25g for Nb, 60g for Ta) for 15 min, leached with 60ml
of 10% citric acid (tartaric for Nb) and 0.15ml of copper nitrate solution (lOOmg/ml
Cu) added. Insoluble sulphides were precipitated with H 2S; were frltered, washed and
dried at 500°C. 20 mg of residue was placed in a graphite crater electrode (3.5 mm
diameter, Smm deep) as anode and excited in a 6amp d.c. for 60 sec. Standards were
prepared similarly and a detection Iimit of 0.1 pg/g Sn was obtained at Sn 317.50 nm.
116 Emission Spectroscopy [Ref. p. 122

4.17 Titanium
Titanium was analysed for tin and twenty other elements [102] by converting to
oxide and subjecting the residue to d.c. arc spectrography. Synthetic standards were
made by hydrolysis of TiCI 4 with addition of impurities.

4.18 Thallium
Thallium may be separated from impurities by distillation under vacuum as TICI
or TIN0 3 and the residue analysed by d.c. arc for tin and fifteen other elements
[103].

4.19 Tungsten
Tin may be determined in tungsten or molybdenum powder by direct d.c. arc
spectrography of 50mg ofmetal powder in a 7 amp arc using a 4.5 mm diameter,
5 mm deep graphite crater electrode. A detection Iimit of 10~g/g Sn at Sn 283.99
can be obtained with a 2 min burn. Lower Ievels of tin [ 101] may be determined by
calcination of the meta! to oxide at 600°C for 45 min followed by dissolution of the
residue by heating with 4rnl of 30% NaOH and then addition of 30% tartaric acid to
pH2. After addition of 15 mg of copper as a solution of the nitrate, proceed as in
reference [101] for the analysis oftantalum.

4.20 Yttrium
Tin (0.3 - 1OO~g/g) was determined [ 104] by dissolving in HN0 3 , heating at 800°C
to convert to oxide, adding 4% of arnmonium hydrogen fluoride and exciting a 50
mg portion in a d.c. arc. A graphite anode (6mm diameter, with crater 4.8mm dia-
meter, 4.5 mm deep with 1.5 mm diameter central post) was used. The technique of
converting metals with rich spectra to involatile oxides has been reported elsewhere
[62, 100, 101, 105].

4.21 Zinc
Zinc may be analysed directly in a d.c. arc [106] or may be dissolved in HCI and
impurities (i.e. As, Bi, Cd, Pb, Sb and Sn) extracted from 0.5- l.SM HCI with diethyl-
dithiophosphate [1 07]. The extract is evaporated on to carbon powder in a porcelain
crucible and a portion of residue examined in a 6 amp a.c. arc. Alternatively [ 108 ],
tin may be coprecipitated at pH 8- 10 with 0.14 mM aluminium nitrate and 0.7 mM
ammonium nitrate solution. The precipitate is mixed with carbon powder and sodium
chloride for analysis in a 9 amp a.c. arc with graphite electrodes.
In ASTM E27 [9] tin may be determined in zinc or zinc alloys by dissolution of
drillings or sawings in equal volumes of 1 : 4 HCl : H 2 0 and 1 : 4 HN0 3 : H 2 0 to
give a final 0.33 g/ml of the meta! sample. Approximately 0.1 ml is added to an ASTM
S6 graphite cup electrode (6.16 mm diameterrod with 4.1 mm diameter, 6.4 mm
deep cavity). After drying for 1 hour at 75°C the sample is examined in a 7 amp d.c.
arc in a 60 sec burn using a 20- 80% transmission fii.ter. The counter electrode is an
ASTM C6, 3.05 mm diameter flat-ended grapliite rod. Synthetic standards incorporate
tin, zinc and major matrix elements. The method is suitable for 0.001 - 0.05% Sn. Zinc
is used as internal standard; the Sn 284.00, 317.50 and Zn 267.05 nm lines are used.
Ref. p. 122] 5. Geochemical Analysis 117

5. Geochemical Analysis
The determination of tin in rocks, ores and minerals is restricted exclusively to arc
methods and in particular to those involving the d.c. arc. The general behaviour of
tin in the arc has already been discussed in Section 3; the relevant factors insofar as
geochemical analysis is concerned are:
a) Addition of a flux - in the majority of methods an alkali metal salt is added in order
to bring about fusion of the sample in the electrode crater; this also serves as an ionisa-
tion buffer. Compounds used include: borates, carbonates, chlorides, phosphates and
sulphates of the alkali metals.
b) Addition of a matrix buffer- several methods include addition of a relatively in-
volatile compound which controls the rates of volatilisation of the elements under
examination. Alumina [125], quartz [115], calcium carbonate [122, 125] and barium
su1phate [119] have been used in this way.
c) Addition of a ca"ier- the sulphides and halides of tin are relatively volatile and it
is sometimes convenient to use a carrier of this type to give a cleaner spectrum. Invol-
atile impurities with fairly complex spectra are not excited, but elements such as As,
Bi, Cd, Cu, Sb and Sn can be effectively isolated. Carriers employed include: sodium
chloride [115, 123], PTFE [26, 117],cupric chloride [26, 117], sulphur [ 119] and
ammonium chloride [33].
d) Addition of carbon powder - to raise the arc temperature and to act as a matrix
buffer. Its use is of more benefit in the determination of other impurity elements than
in the determination of tin, which is easily excited and relatively volatile.
e)Addition ofintemal Standards-these include antimony [113, 121, 126], beryllium
[116], bismuth [123, 125], cadmium [115, 120], gallium [119], germanium [114, 128],
indium [ 112, 124] and palladium [ 127]. Care should be taken with internal standards
as complex and low grade ores may contain the above elements, particularly Bi, In
and Sb.
The determination of tin in specimens of geochemical interest is summarised in Table 5.

Table 5. Geochemical Analysis by Emission Spectroscopy

Matrix Range Details Ref.

Ores > 0.02% Mix 1:1 with flux and excite in d.c. arc with [112]
graphite electrodes. Flux: 0.2 · 5% Jn 2 0 3
in K2S04. Sn 317.51, Sn 326.23, In 325.86
nm.
Ores 0.004. 0.5% For ores with !arge amounts of Al, Fe, Si [113]
and Be, Cu, Ga, In, Pb, Ti, Zn. Mix 1 :1 with
flux: carbon powder/Na 2 C0 3 /Sb 2 0 5 (90:
10:1 ), a.c. arc with carbon electrodes. Sn
303.41, Sn 284.00, Sb 287.79 nm.
Ores 0.03-10% Mix with ZnS containing Ge0 2 internal [114]
standard. 9 amp d.c. arc with carbon elec-
trodes in Stallwood jet assembly.
Ores ... Grind to 200 mesh with buffer. Sample/NaCI [115]
CdS04/Si02(5:1 :1 :46), 16 amp a.c. arc with
powder introduced in air stream. Sn 303,41,
Cd 298.06 nm
118 Emission Spectroscopy [Ref. p. 122

Tab!e 5 (continued)
Matrix Range Details Ref.
Rocks, > 10 p.g Fume Si0 2 with HF/H 2S04 in Pt crucible. [116]
soils Remove Fe by extraction with HCI/NH 4 SCN
from 6.5 M HCI/H 2 0 2 . Extract Sn into
CHCI 3 with ammonium tetramethy!ene
dithiocarbamate, evaparate to dryness, add
Be internal standard
Rocks ... Mix sample/PTFE/CuCI 2 carrier (1 :1 :1) [26,117]
(granites)
Rocks ... Mix sample/Li2C03/(NH4hS04 (15:3:1) [118]
(carbona- ... Excite 0.4 g in 7- 10 amp d.c. arc in micro-
ceous) graphite crucible
Rocks ... As Ref. 109, incorporating 5% S, 7.5% BaS0 4 [119]
(carbona- 7.5% Ga203 in rock matrix
ceous)
Rocks ... Precipitate with 8 - hydroxyquinoline at [120]
(gypsum) pH 5.9 in presence of tannic acid and
thionalide with Al collector. lgnite at 600°C.
Mix with graphite, Na 2P03 containing Lu 2 03
and CdO internal standards. Burn for 80 sec in
20 amp. d.c. arc
Rocks 0.01-2% Mix sample/potassium antimony tartrate [121]
(1 :1), 12 amp. a.c. arc with carbon electrodes.
Sn 242.95, Sb 242.64 nm. Same calibration
for silicate, Fe silicate or sulphide minerals.
Rocks ... Mix 0.5 g sample/flux (3 :1). Flux: NH 4 CI/ [33]
minerals K2C03 (1 :1). Place in graphite crucible (11
mm diameter, 28 mm deep) fitted with Iid
with hole (3 mm diameter) a.c. arc.
Rocks ... Mix sample/CuC03/C/NaH 2P0 4 (3 :1:1 :1), [122]
(silicates) d.c. carbon arc
Rocks 0.003-0.1% Mix sample/NaCI (2:1). NaCI contains 2.92% [123]
(silicates) Bi 20 3 internal standard, 7 amp d.c, arc for
45 sec. Standards from basalt matrix
Rocks > 10p.g/g Grind to 150 mesh and mix sample/K 2 S0 4 [124]
(silicates) (3 :1). K2S04 contains 0.1% In 2 0 3 intemal
standard. Excite 130 mg twice in superimposed
bums in d.c. arc with 0 2 atmosphere.
Sn 317.51, In 325.86 nm
Silicates >1 p.g/g Mix 20 mg sample with 20 mg buffer. Buffer: [125]
AI203/CaC03/K2C03 (7:3:1) containing

I
0.1% Bi203. d.c. carbon arc.
Silicates ... Mix sample with C powder containing 0.8% [126]
Sb 2 0 3 internal standard (for Sn, Pb, Ga) and
0.04% Pd black (for Ni, Cr, Co, V, Sc)
Silicates ... Mix 6 mg sample/buffer (1 :4) Buffer: [127]
synthetic silicate/graphite (1 :3). Counter
electrode rod made from graphite powder
containing 0.2% Pd internal standard. 5 amp
d.c. arc to smooth burn then 15 amp for 70 sec.
With direct reader gives ± 5 % at 1 p.g/ g Sn.
Silicates ... Mix sample/Na 2 C0 3/Ge0 2 /graphite (2:2:3 :4) [128]
and excite in 8 amp d.c. are with graphite
electrodes using Ge as internal standard
 Ref. p. 122] 6. Miscel!aneous Inorganic Materials 119

6. Miscellaneous Inorganic Materials

The analysis of inorganic solid materials follows the general principles discussed un-
der Geochemical Analysis. The use of fluorinated carriers is apparently fairly wide-
spread particularly where an involatile matrix is being examined. Sodium fluoride
[130, 143], silver fluoride [24, 25) and PTFE powder [27, 29] have all been used
with success.
An interesting concentration technique is that of Krasilshchik et al. [ 134] who re-
moved tin and other elements from solution by electrolysis on to a carbon cathode.
The carbon rod was tightly wrapped with PTFE so that only the end was exposed to
the solution. After 30 min electrolysis in a pH 2.5 citrate buffer, the rod was removed,
dried, the PTFE taken off and the rod excited as an anode in a 12 amp d.c. arc dis-
charge.

Table 6. Analysis of Miscellaneous Inorganic Materials by Emission Spectroscopy

Matrix Range Details Ref
Arsenic > 1 pg/g Extract AsC1 3 from HCl into benzene and [129]
trichloride evaparate aqueous solutionon to carbon
powder for excitation in 14 amp d.c. arc
Boron nitride 2. 50J1g Mix 30 mg with graphite (1 :1). Graphite [130]
contain 4% NaF and 2% La 2 0 3 (internal
std) Sn 284.0 nm
Copper sme1· 0.001 . 1% Applied to concentrates, smelting charges, [131]
ting products residues, slags and flue dusts. Standards
prepared on same base as unknown. Mix
with MgO (1 :2) and arc for 1 min for Sn
and 6 other volatile elements. Sn 284.0 nm
Cesium sal ts ... In graphite cavity (4 mm dia, 10 mm deep) [27]
place 60 mg PTFE powder then sample mixed
with carbon powder (5 :1). Excite with 15 amp
a.c. arc. PTFE allows wide range of Cs con-
tents
Cadmium ... See Ref. [ 13 9] und er Zinc electrolytes [139]
e1ectro1ytes
Gallium ... Remave epitaxial GaAs layer with methanoll [28]
arsenide bromine and remove gallium by applying the
soln.to a column of PTFE/decanol. Wash
with 5 M HCl to remove. Fe, In, Sn; evaparate
to dryness and excite residue in arc
Gallium ... Mix 50 mg with graphite and PTFE powder [29]
arsenide (5: 1:1 ). Excite in graphite cavity electrode
with 15 amp d.c. arc
Gallium 5 - 200 Jlgfg Ball mill 5 mg with carbon powder (1 :3) [132]
arsenide Excite in cavity electrode. Sn 317.5, As
311.9, 243.7 nm
Gold p1ating ... Evaparate to dryness, mix with graphite [133]
solutions containing 1 % In 2 0 3 (internal standard)
and sufficient potassium salts to give 30% K
Magnesium ... Magnesium salt electro1ysed in 0.1 M Na citrate [134]
salts and 6 M citric acid at pH 2.5 for 30 min
at 10 V, 0.4 amp with 1 mm dia. Pt wire
anode and 6 mm dia. carbon rod cathode. Are
carbon rod in 12 amp d.c. arc as anode with
carbon cathode.
120 Emission Spectroscopy [Ref. p. 122

Table 6 (continued)

Matrix Range Details Ref.

Niobium ... Pack30mgof AgCl/AgF (1:1) into carbon [24]
oxide cup electrode followed by 20 mg graphite
powder then 100 mg of a mixture of
Nb 2 0 5 and graphite (7 :3 ). Place cap with
hole over cup and excite in d.c. arc
Niobium 0.001-3% Sn and Nb vaporised at sarne rate during [135]
oxide mid portion of arc. PbO added as internal
standard (0.1 %). Sn 286.33. Pb 287.33.
Rare earth ... Mix 86 mg with 14 g carbon powder and [136]
Molybdates 9 mg Ga 2 0 3 (internal Standard) and 1 mg
sodium iodide. Excite in graphite cavity
electrode in 12 arnp d.c. arc for 55 sec after
a 5 sec preburn
Sodium ... Dissolve in ethanol, add conc. HCl, evaporate [13 7]
meta! or at 60°C and dry at 200°C. Mix residue (or
sodium NaCI) with graphite and an internal standard.
chloride Excite in d.c. arc
Sodium ... Mix with Si0 2 and carbon powder (20:7:1) [138]
potassium excite in 14 amp d.c. arc
Iithium
mixed
carbonates
Sodium ... See reference [ 136] under Rare Earth [136]
molybdate Molybdates
Tantal um ... Direct in d.c. arc using Ta as internal [139]
oxide standard
Telluric acid <40J1g/g Dehydrate at 160°C for 24 hr, mix with [140]
graphite, NaCl/KCl and Ge0 2 (30:10:1 :0.1 %).
Excite in 12 amp d.c. arc
Titanium ... Mix with carbon powder and K 2 C0 3 [141]
diboride (10:1 :1) incorporating 100J1g/g Co and
Ga internal standards. Excite in 10 amp
d.c. arc with carbon cavity e!ectrode and
carbon disc counter electrode
Uranium 1-100J1g/g Mix with Ga 2 0 3 (100:2) and excite in 14 [9]
oxide amp d.c. arc for 35 sec with 5 sec preburn. Sn
317.50,326.23 nm.ASTME402
Yttrium ... Mix 10 mg with graphite powder (1 :1) and [142]
oxide excite in 10 amp d.c. arc in Ar/0 2 (4:1)
Yttrium Mix with NaF/AgCI/_graphite (10:1 :4 :5) and [143]
...
oxide excite in d.c. arc
Yttrium ... Mix with AgF /Ga 2 0 3 (3: 1 :2) and excite in [25]
oxide d.c. arc
Zinc elec- 0.01 -0.1 Jlg/ml Evaparate 10 ml to dryness on 1/8 its weight [144]
trolytes of carbon powder. Are 150 mg in 8 amp
d.c. arc

In the determination of tin in mixed alka1i carbonates [ 138], silica was added to
render the matrix 1ess vo1atile and to act as a buffer. Similarly, it was claimed [136]
that additions of carbon to a matrix of sodium mo1ybdate suppressed the Mo spec-
trum by formation of the refractory carbide.
Ref. p. 122] 7. Organic Materials, Foods, Biological Specimens 121

7. Organic Materials, Foods, Biological Specimens

These applications are surnrnarised in Table 7, the main areas of study are:
a) Oil analysis - tin is an important bearing metal and its determination in used air-
craft engine oils [146] often gives warning ofimpending failures. From the determi-
nation of several wear metals it is often possible to locate the type of component about
to fail.
b) Foodstuffs- these studies [148- 150] are concerned with the dissolution oftin
from cans and subsequent contamination of foods.
c) Biological fluids- tin is generally regarded as being non-toxic to human and advan-
ced life forms. The metabolism of tin in the body has not yet been studied in depth,

Table 7. Analysis of Organic Materials by Emission Spectroscopy

Matrix Range Details Ref.

Organic ... Evaparate to dryness with 50 mg carbon powder [145]

Solvents and 1 mg aqueous oxalic acid. lgnite for 5 min at
350°- 400°C and excite in a.c. arc
...
Oils Direct analysis of tin wear meta! in jet and piston [146]
engine oils by rotating graphite electrode
Be er ... Add BiCI3, TiC14 and Pb(NO;h solutions and [147]
octanol to prevent foaming. Adjust to pH 8.5 - 9
with ammonia, boil, cool. Centrifuge precipitate,
dry and excite 8 mg in carbon e!ectrode in d.c.
arc. Calibrate by adding Sn to tin-free beer.
Sn 317.50, Bi 299.33 nm
Beer, malt, ... Freeze dry, then ash 200m! beer, lOg malt or 2g [148]
hops hops. Fuse with 2g K2 C03 + Na 2 C03 dissolve and
precipitate on A1 2 (OHh + 5% Fe(OHh by addition
of ammonia. Excite in d.c. carbon arc
Canned milk 10- 300~/g Dry 5 g milk in silica crucible, ash at 400°C overnight [149]
and mix 40 mg residue with 260 mg of graphite/CdO/
NiO/KCl/CaC0 3 (20:1:1:2:2). Excite in d.c. arc
Sn 284.0, Cd 326.1 nm
Fish > 0.05jJg/g Dry 2- 5g at 100° and ash at 400- 450°C. Excite [150]
(canned/fresh) 20mg ash in carbon electrode in 14 amp a.c. arc.
Mixture of NaCI, KCI, Ca3 (P0 4 h and MgO used
as matrix for Standards. Sn 284.0 nm
Biological ... Ash 2m! serum with lml HN0 3 + 0.25ml HC10 4 [151]
fluids at 130°C for 5-6 hr. Evaparate residue with lml
HCl and dissolve in 1ml1% NH 4 C! and excite a
0.2ml aliquot in carbon crater electrode with 10
amp d.c. arc.
Biological Ash 125 mg sample in activated 0 2 stream. Mix with [152]
sarnples ... Ga 2 03 and excite in graphite cup electrode
Plants, soils ... lg Soil or lOg plant ash fused with Na 2 C03 and [153]
dissolved in 150m! water. Add sodium citrate and
adjust to pH 8.3 with ammonia. Extract with 0.1%
dithizone in CHC1 3. Evaparate to dryness on 100 mg
graphite. lgnite at 450°C, mix with lOmg Li 2 C0 3
(internal standard) and excite in d.c. arc
Plants ... Camparisan of anodic and cathodic excitation for [154]
ashed residues
122 Emission Spectroscopy [Ref. p. 122

8. Environmental Analysis
Tin is of some considerable interest as an enviromental contaminant, although its
toxic properties have yet to be studied in detail. The main source of tin in the envi-
ronment is in the widespread use of organo-tin chemicals, which have attractive prop-
erties as plastics stabilizers, pesticides, fungicides, etc. Although these compounds
range from highly toxic to edible, they degrade to hydrated tin oxide after a relatively
short period and have no Iasting effects as pollutants. A selection of environmental
applications is listed in Table 8 and, in addition, there are some analyses of relevant
interest in Table 7.

Table 8. Environmental Analysis by Emission Spectroscopy

Matrix Details Ref.

Airborne Collect on filter paper disc, fold and roll disc. Insert into a hollow (155]
Particulates cylindrical graphite electrode. A tungstenrod operated by a motordriven
cam pushes the paper into the gap of an a.c. spark during a 30 sec
exposure
Airborne Place 4 mm dia. portion of filter in a graphite crater electrode previously (156]
Particulates treated with liquid paraffin and packed with NaF /graphite powder (1 :4 ).
Add 50pl of 30pg/g In solution in 2M HN0 3 and excite in d.c. arc.
Sn 317.50, In 325.6lnm
Soils See Ref. (153] Table 7 [15 3]
Soils Dry at 105°C and ignite at 550°C for 1 hour. Grind, mix with Li2 C0 3 / [157]
K2 S0 4 /graphite powder and excite in d.c. arc. Detection Iimit 1 pg/g Sn.
Improved reproducibility and precision are obtained by LiB02 fusion.
Waters Evaparate to dryness at 180°C, add NaCl/Si~ /CaC0 3 . Detection Iimit (158]
8pg/g Sn in residue.
Waters Evaparate to dryness on to Na2 S0 4 /MgS0 4 /CaS04 (52:22:26) and [159]
exci te in arc discharge
Waters Extract 0.5- lOOpg Sn from 1-20 l. water from hot springs by
extraction at pH 5 - 6 with dithizone/CCI 4 from tartrate solution. Evapo-
rate extract to dryness and treat with HN0 3 . Add lümg NaN0 3 and heat
residue to fuse. Excite residue in d.c. arc
Waters Pass 50 litres through 200g of cation exchange resin in the H+ form. [161]
Elute with 2M HCI and extract Sn with sodium diethyldithiocarbamate
at pH 4-5 into CHCJ 3 or CCI 4 . Excite aliquot in 13 amp. a.c. arc for
2min.
Waters Shake llitre with 500mg of activated sugar carbon, thioacetamide, [162]
dithizone and diethyldithiocarbamate at pH 5-8 and settle for 15 min.
Ash at 550°C, mix residue with carbon powder/K 2 S0 4 (2:1) and excite
in 16 amp. d.c. arc

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98. Osumi, Y., Higashi, K., Mikaye, Y.: Japan Analyst 18, 1219 (1969)
99. Joshi, B.D., Banga, T.R., Dalvi, A.G./.: Z. Anal. Chem. 260, 107 (1972)
100. Zakharov, E.l., Lipis, L. V., Petrov, K.l.: Zhur. Analit. Khim. 14, 135 (1959)
101. Ryabchikov, D.l., Vainshtein, E.E., Bonsova, L. V., Volynets, M.P., Korolev, V. V.,
Kutsenko, Y.I.: Trudy Komiss. Anal. Khim. Akad. Nauk. SSSR 12, 82 (1960)
102. Melamed, S.G.: Zavod. Lab. 21, 1066 (1955)
103. Chalkov, N. Y., Yudelevich, l.G., Ustimov, A.M.: Izv. Sib. Otdel. Akad. Nauk. SSSR
Ser. Khim. Nauk. 161 (1972)
104. Kaneko, K.. Goseki. S.: Japan Analyst 18, 220 (1969)
105. Vainshtein, E.E., Belyaev, Y.l., Akhmanova, M. V.: Trudy Komiss. Anal. Khim. Akad. Nauk.
SSSR 12, 236 (1960)
106. Alvarez-Herrero, C., Burriel-Marti, F.: Revta Meta!. 8, 200 (1972)
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 References 125

115. Gruzdeva, N.I: Obogaschchenie Rud. 1, (1960). Anal. Abstr. 9, 611 (1962)
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126. Hamaguchi, H., Kuroda, R., Negishi, R.: Bull. Chem. Soc. Japan 33, 901 (1960)
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129. Kuz'min, N.M., Popova, G.D., Kuzovlev, l.A., Solomatin, V.S.: Zhur. Analit. Khim. 24,
899 (1969)
130. Vengsarkar, B.R., Machado, I.J., Malhotra, S.K.: Talanta 22, 903 (1975)
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Anal. Abstr. 20,3071 (1971)
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CHAPTER 10

X-RA Y FLUORESCENCE

By R. Smith

1. General

1.1 Instrumentation
A number of different X-ray fluorescence instruments are in routine use:
(i) Crystal dispersion, tube excitation, sequential counting. (ii) Crystal dispersion, tt!be excita-
tion, simultaneaus counting. (iii) Crystal dispersion, electron excitation. (iv) Non-dispersive,
Ross filter, radio isotope excitation. (v) Non-dispersive, semi-conductor detector.

Types (i) and (ii) are used in laboratories throughout the world and unless otherwise
stated, any reference in this chapter will assume instruments of type (i). Instruments
of type (iv) arealso widely used but arerather more limited in their scope and tend
to be used for well-defmed applications. Type (iv) instruments may also be obtained
as portable monitors and are used in prospecting, mining and on-line mineral dressing
applications. Instruments of types (üi) and (v) are available cornmercially but have
found few applications in the analysis of materials containing tin.
A more complete description of X-ray instrumentation will be found in standard
texts [ 1, 2] or in manufacturers' literature. Biennial reviews are published in the jour-
nal, Analytical Chemistry and comprehensive bibliographies are produced by Philips
N.V. [5).

1.2 Spectral Characteristics of Tin

Tin absorbs X-radiation at wavelengths of 0.4247 A and less (K absorption edge)
and at wavelengths of 2. 777 A or less (LI absorption edge ). In addition, weaker Ln
and Lm absorption edges occur at 2.982 A and 3.156 A. The MI absorption edge
occurs at 13.8 A and is unlikely tobe of irnportance other than in the determination
of elements lighter than Mg. The other M absorption edges are outside the usual
working range of current spectrometers.
The principal fluorescence emission lines for tin are the SnKa 1 and Sn Ka 2 at
0.4906 A and 0.4951 A respectively. Resolution of these two lines is not normally
attempted and a convoluted peak at 0.4921 Ais usually measured. The Sn Kß lines
are usually about one third of the intensity of the Ka 1 2 line and are found at: Kß 1
0.4352, Kß 2 0.4258, Kß 3 0.4359, Kß4 0.4252 and Kß: 0.4318 A. Antimony with
Sb Ka 1 2 0.4 719 A may overlap the Sn K a line at the short wavelength wing and may
require 'careful resolution. The presence of Sb, however, does not hinder the deter-
mination of tin other than in limiting the coice of wavelengths for counting back-
ground radiation. The Ag Kß spectrum at 0.487 - 0.498 A also overlaps the Sn K a
line. Under some circumstances ( eg the examination of photographic residues) it may
be possible to confuse the Sn Ka and Sn Kß lines with the Ag Kß and I Ka lines respec-
tively.
 Ref.p. 143] 1.2 Spectral Characteristics of Tin 127

In the analysis of light matrices, such as organic materials, the magnitude of scat-
tered background radiation is likely to be fairly high at the Sn Ka wavelength, parti-
cularly if trace analysis is being undertaken. Under these circumstances, measurement
of the Sn La 1 3 .600, Sn La 2 3.609, Sn l.ß 1 3 385 or Sn Lß 2 3.175 A may be prefer-
able. These wavelengths may also be of use if Sn Ka/Sn La ratios are to be measured
in examining effects caused by particle size in the sample [3].
The most suitable crystal for the Sn L spectrum is LiF (200) (2d spacing 4.027 A);
the choice for Sn Kais rather more varied; LiF (200) is by far the most popular crystal
for resolving Sn Ka radiation, unfortunately the angle of diffraction (20 = 14.0°) is
extremely low and although high count rates may be obtained, dispersion is poor.
Considerable improvement in dispersion at the Sn Ka wavelength may be obtained
using LiF (220), LiF (420) or LiF (422) crystals. This is expressed in Table 1. The im-
provements in resolution are accompanied by a decrease in diffracted intensity and for
most purposes the LiF (220) crystal represents a reasonable compromise. Use of the
LiF (420) or LiF (422) crystals may be attended with other disadvantages: both are

Table 1. Crystals Used for Dispersion of Sn Ka Radiation

Crystal 2d (Ä) 2fJO d%x

LiF (200) 4.028 14.03 0.52
LiF (220) 2.850 19.89 0.75
LiF (420) 1.802 31.69 1.21
LiF (422) 1.645 34.81 1.30
Topaz (303) 2.712 20.91 0.79

d is the interplanar spacing of the crystallattice

(J is the angle of diffraction
~~ is a measure of dispersion with respect to wavelength
dfJ 1
dA.= d cos2fJ

capable of resolving the Sn Ka 1 and Sn K.a 2 !ines, almost completely. In most in-
stances it is more convenient to measure the two lines as an unresolved single peak.
The topaz (303) crystal, although important historically, is rarely used in modern X-ray
practice. Topaz, ho.wever, gives good dispersion at the Sn Ka wavelength, slightly bet-
ter than LiF (220); the temperature coefficient has been found [4, 5) tobe less than
that of LiF (220). LiF (220) exhibits "forbidden" reflections from the 110,330 and
550 planes giving rise to spurious spectrallines at the 3/2, 5/2 orders; topaz also gives
rise to series of spurious reflections which differ in intensity from crystal to crystal
(Fig. I). The LiF (220) crystal gives intensities which are markedly superior to those
0f the topaz (303) crystal and for this reason alone is generally favoured. The scintil-
lation counter is always used for measurements of Sn K radiation and the proportional
flow counter for Sn. L.
128 X-Ray-Fluorescence [Ref.p. 143

COUNTS/SEC
X 100 SnK ..

20

10

2nd ORDER
SIV<o<

40 30 20

ANGLE 0 29

Fig. 1 Spurious reflections from 99.999% pure tin with topaz (303) crystal, scintillation counter,
tungsten target tube 50 k V, 40 mA

2. Ores and Concentrates

X-ray fluorescence is used for most of the routine analysis in modern mining and
mineral dressing. lt is rapid and reliable in dealing with ores obtained from a single
source with relatively limited ranges of matrices. Although possibly accurate to ±
0.2% Sn, X-ray fluorescence has not been adopted for the assay of concentrates for
commercial exchanges. lt is almost universal practice to carry out these assays using
the iodometric titration. Unfortunately, most of the work on concentrates is either
unpublished or has been presented at unrecorded conferences.

2.1 Direct Analysis of Powders

Sweatman, Wong and Toong [6] and later Wong and Seevaratnam [7] described
methods for tin in Malaysian ores and concentrates from 1 - 8% Sn [7] and 57- 77%
Sn [6]. In both papers the sample was ground to less than 300 mesh (53 J.Lm) in a Sieb-
technik vibratory ring mill. F or the analysis of high-grade tin concentrates [6], the
sample was mixed with twenty times its weight of ferric oxide; a 1Og charge was
mixed for 2 min in the same mill. Sn Ka was measured with a LiF (200) crystal and
scintillation counter using a tungsten-target tube Operating at 40 kV, 6 mA. Back-
ground count rates were negligible and constant and were, therefore, disregarded. The
plot of count rate vs Sn% was linear over the range 55%- 77% Sn, the method was
not recommended for low-grade Malaysian concentrates. Ferric oxide was preferred
to quarz as a diluent because of the similarity in density and mass absorption coeffi-
cient for Sn Ka of ferric oxide and cassiterite.
The use of ferric oxide as a diluent was extended [7] to columbite and tantalite
ores containing minor portions of cassiterite, ilmenite, rutile, monazite, xenotirne,
 Ref.p. 143] 2.1 Direct Analysis of Powders 129

wolframite and zircon. Sampies were ground to 300 mesh (53MID) as above then
0.5000g of sample and 1.5000g of ferric oxide were ground together for 5 min. The
diluted sample was made into a boric acid backed and edged disc; a similar disc was
made from 2g of original sample and these were counted with a reference disc at Sn
Ka (LiF (200), 40 kV, 20 mA, scintillation counter) and at background angles approxi-
mately ± 1° 28 from the Ka peak. After correction for background the result was eva-
luated from:

Sn%= (i)

where: Je, Id, ! 5 are net count rates for concentrate, diluted concentrates and reference sample.
].{ is the proportionality constant.

The method was applied to 1 - 5% Sn0 2 in concentrates containing 20- 60% Nb 2 Os,
10- 45% Ta 2 Os and 1 - 4% Ti0 2 . This approach is an application of the "double
dilution" method [8]; the coefficient of variation was 0.12% for tin; Nb, Ta and Ti
could also be determined on the same set of discs.
A rather more complex method of determining tin in the range 0.06- 77% Sn, in
a wide range of matrices, is also covered in the paper by Sweatman et al. [6]. In this
work, matrix absorption effects were overcome by actually measuring the mass ab-
sorption coefficient of a thin disc of the sample, using a simple instrumental modifi-
cation. A discoflOg of concentrate, in a windowless holder is counted at Sn Ka (LiF
(200), 40 kV, 6 mA). For measurement of the mass absorption coefficient, 0.2g of
sample is pressed into a 12mm hole in a Perspex holder. This thin disc is then placed
immediately in front of the short collimator which is normally attached to the detec-
tor [9] head. The mass absorption coefficient is measured with any sample ofhigh tin
content in the counting position. After correcting for dead-time, results are calcula-
ted from:

(ii)

and
(iii)

where: a is the cross-section area of the thin disc, cm 2 .

m is the mass of concentrate in the thin disc, g.
Io is the corrected count rate on the high-tin sample.
It is the corrected count rate on the high-tin sample with the thin disc of concentrate
in front of the detector
is the count rate for the concentrate sample.
are constants.

k and K are evaluated by analysing at least two concentrates of known tin content.
Twenty three samples were assayeJ for tin by this method and were compared with
chemical analyses carried out by three competent organisations. A standard deviation
was computed by subtracting individual X-ray results from the mean of the chemical
analyses for the particular sample. This was 0.16% Sn in the range 0.06 - 77% Sn. It
will be noted that this method only corrects for matrix absorption effects; enhance-
ments are not affected.
130 X-Ray-Fluorescence [Ref.p. 143

A rather similar approach, requiring no instrumental modifications was proposed by

Ca"-Brion [ 10] for zinc concentrates and later applied to tin concentrates [ 11 ]. A thin-
fllm of concentrate, 0.5 mm ± 0.05 mm is placed in the sample holder and a count rate
I~ measured. A thick disc of tin is placed over the film and the total count rate
(I~+ It measured. The film is removed, replaced by a steel spacer of the same thick-
ness and Io, the count rate of the tin disc alone is measured. After correcting for dead-
time losses, the factor (A/a) is calculated from equation (ii). A, in this instance, applies
to both excitation and fluorescence radiation. As the fllmis neither theoretically "thick"
nor "thin", the countrate Itmust be corrected tothat for a infinitely "thick" disc
I~:

I""
c (iv)

One calibration graph is required. This plots the countrate per 1% Sn for an infi-
nitely thick standard R~ against (A/a) and is obtained by measuring I;, and hence cal-
culating R~and (A/a), for a range of standards of known tin content. This graph cor-
rects for the effects of matrix (measured by A/a) on countrate and gives a value
R~: the countrate per 1% Sn for the concentrate sample. The tin content is calcula-
ted from I~/R~. Thin discs are made by grinding samples to pass 300 mesh (53
pm);mixing 0.333g with 0.667 g ofparaffln wax powder and Sml oflight petroleum
60° - 80°C) in an agate mortar until a powder is obtained, and then pressing the powder
in a 0.5 ± 0.05 mm steel spacer between a double layer of 6J.lffi Melinex under a Ioad of
10 tonnes. After removing the steel plates and Melinex f!lms, a disc of 31 mm diameter
was cut in the film, weighed and counted. Agreement with chemical analyses was nor-
mally ± 2% relative in the range 10- 80% Sn [ 11 ], but errors as !arge as -10% could
be encountered with very fine powders. Corrections for matrix enhancement effects
must be applied separately after calculation of I~.
Machacek [ 12] determined tin and thirteen other elements in rocks and minerals,
using internal standards and a polyvinyl alcohol binder. Interna! standardisation was
also used by Lavrentev [ 13]. These and even simpler techniques are often quite ade-
quate for determinations of tin at Ievels where an error of 5% relative or more is
acceptable. At very low concentrations, as with ores, the sampling errors are usually
greater than analytical errors.
Impurities in cassiterite concentrates (Sn 35 - 78 %) have been analysed by a gene-
ral method [ 14] developed by the Lempriere Company of Australia. Concentrates
are counted for impurity elements, background contents are determined using a
sample of cassiterite concentrate which is free from impurities. Once concentrations
have been established, these are corrected for inter-element effects using a set of em-
pirically determined factors. For iron and tin a count ratio method is used with a ma-
ster standard; for other elements net counts are used. Corrections are applied flrst to
iron, then to tin and the corrected values used for subsequent elements (see Table 2).
As is well-known the Pb La and As Ka lines are coincident as are the Pb Lß and Sn
Ka 2nd order. Lead is measured at the weak Pb L-y line. Arsenic is measured at As
Kß. A LiF (200) crystal is used for all elements except Si and S. (PE crystal). A scin-
tillation counter is used for all elements except Si, S, Ti (flow counter) and a fme
collimator for a11 but Si and S. A 2 kW tungsten tube at 60 kV, 24 mA is recommen-
ded. About 20g of concentrate (-1 00 mesh, 152J.lffi) is ground for 2 minutes in a
Siebtechnik vibratory ring mill, a measured volume of approximately 3 g weight is
mixed with 2-3 dropsofaliquid bonding agent- Tensol 7- until dry. The concentra-
 Ref.p. 143] 2.2 Fusion Methods 131

te is pressed into a disc with a boric acid backing. Table 2 sumrnarises conditions not
mentioned in the text. This approach is probably similar to many now in use throug-
hout the world and is typical of the practical and unsophisticated techniques prefer-
red by the metallurgical and mining industries.

Table 2. Determination of Impurities in a LimitedRange of Cassiterite Concentrates [14]

Element/ Time Background Correct Range%

Line (secs) (counts) for
S Ka 20 1,060 Y,Nb 0.01- 10
Fe Ka 10 - Si, S 0.1 - 10
NiKa 10 200 y 0.01 - 1
CuKa 10 430 0.01- 2
ZnKa 10 460 0.01 - 2
As Kß 20 2,760 Sn, W,Si 0.01- 2
Sb Ka 20 13,490 Sn, Si, Nb, Ta 0.01- 2
W L'Y 20 6,600 Ta, Fe 0.5 - 10
Pb L'Y 40 5,587 Sn, Si, Y, Zr, Bi 0.01- 2
Pb La 20 1,360 Sn, Si, As 0.01 - 2
Bi La 20 1,540 Sn, Si, Ta 0.01- 2
Sn Kß 10 - Si, Zr, Nb, Ta 50 - 78
SiKa 20 2,700
YKa 10 1,500
ZrKß 10 2,720
NbKß 10 3,700
Ta La 20 790
TiKa 10 600

2.2 Fusion Methods

Because of the additional effort involved, fusion techniques are used only for the
analysis of a small range of mining products. Fusion methods are particularly valuable
for multi-element analysis of a wide ·range of rocks and many schemes are available
( 15 - 17]. Although fusions successfully overcome particle size and mineralogical
effects, incorporation of an internal standard is not always straightforward, as it is of-
ten difficult to find a standard which is not present in the actual sample.
Cassiterite is not attacked by the fluxes, such as borates and pyrosulphates, common-
ly used in X-ray fluorescence spectrometry. Sodium peroxide is hygroscopic and cor-
rosive; mixtures of peroxide and borax, invariably possess the undesirable qualities of
one or both constituents. Oxidising borate fluxes, incorporating potassium nitrate, have
been recommended for low-grade cassiterite concentrates (18). A typical flux would
require: 0.3 g of sample, 0.1 g of Sb 2 0 3 internal standard, 0.5 gor l.Og of KN0 3 and
lOgofeither Na 2 B4 0 7 or LiB0 2 • Fusionsare carried out over ablast burner, or in a
muffle, using Pt/Rh or Au-lined Pt crucibles, which arenot wetted by the fusion mix-
ture. Glass beads are cast directly from the crucible into a Iead ring supported on a
thick, warm aluminium plate; the Iead ring is removed as soon as the bead solidifies.
Although the use of oxidising fluxes appears to be comparatively rare, reducing
fluxes for x-ray fluorescence have been described by several authors. Invariably the fu-
132 X-Ray-Fluorescence [Ref.p. 143

sion is carried out in a graphite or vitreous carbon crucible which acts as the reductant.
Carr-Brion [ 11] fused 0.1 g of sample with 0.1 g Sb2 0 3 and 9.8 g borax glass in a gra-
phite or carbon crucible and cast into an aluminiumring on a 6 mm thick, cold alumi-
nium plate [19]. The ring was left on the disc producing an extensively cracked but
coherent bead. Payne [20, 21] used a rather similar fusion mixture but worked with
detachable glass beads - fusions were carried out in vitreous carbon crucibles which
had a very limited life. Lueschow and Schaefer [22] used a fusion mixture of: 0.5 g of
sample, 0.1 g In 2 0 3 internal standard, 9 g Li 2 B4 0 7 , 0.5 g Si0 2 and 0.5 g LiOH. The
melt was cast into a cold graphite crucible; on cooling the bead was detached and po-
lished. The standard deviation of six deterrninations at 27.5% Sn was 0.09% Sn.
Borax fusions may be used for the analysis of slags [23] without the necessity for
including an oxidising or reducing agent. Alternatively, as slags are fused products any-
way, powdered samples may be analysed equally weil. In the range 0 - 12% Sn, matrix
effects were overcome [23] by using scattered background radiation as an internal
standard. A plot of (Sn Ka counts 7 Background) against Sn% is used as a calibration:
both peak and background counts are inversely proportional to matrix density over a
limited range of composition. Sanner and Ehrhardt [23] used a borax fusion for 0.1 -
15% Sn in mixed Nb 2 Os /Ta 2 Os samples and the same matrix correction approach.

2.3 Non-Dispersive Instruments

Simple non-dispersive instruments, having balanced filters, are used regularly at
mine working surfaces for following the tin values of a vein. Such instruments norrnal-
ly have a hand-held excitation source and detector which may be placed on the rock
surface (Fig. 2). Labaratory instruments having a rotating sample turret, similar to
crystal dispersive instruments, are also available where limited numbers of elements
are to be deterrnined in fairly well-defined matrices. Instrumentsare usually tailored
by the manufacturer to suit a particular application.
A schematic diagram of the sampling head of a non-dispersive detector [25] is gi-
ven in Fig. 2 - excitation is provided by a radioisotope source of about 1 Ci. In
Bowie's design, a 147 Pm/ Al source was used, but other sources (Table 3) are available.
The 241 Am source is rather too energetic for excitation of Sn Ka and sensitivity
is poor. The 1 s 3 Gd source has a short half-life, whilst the 147 Pm/Al and 147 Pm/Ba
bremsstral!lung sources have a wide energy range but usually give higher background
counts.
The filter is based on a principle credited to Ross [24] and comprises circles of Ag
and Pd foils, or salts of these elements incorporated in a silicone rubber membrane.
Reference to Fig. 3 shows that the Ag foil absorbs X-rays which are more energetic
than Sn Ka; the Pd foil absorbs X-rays more energetic than InKa. With a well-balanced
filter pair, the difference in counts is due to Sn Ka only. In practice, two sets ofmea-
surements are made, one with the Ag filter, the other with the Pd filter.
The scintillation counter is almost always used as a detector for Sn Ka radiation,
but suffers from the disadvantage of having poor resolution. Fig. 3 shows that the ba-
lanced Ross filters transmit radiation at all wavelengths. Hence background radiation
may score as Sn Ka if the filtersarenot perfectly balanced. Recently, the development of
rugged, sealed proportional counters has improved the situation. Proportional coun-
ters have a comparatively high resolution and may be tuned to the Sn Ka energy by
adjustment of the electrode voltage. This author [4] has used sealed proportional
counters in a works enviroment for over a year with no problems. The commercially
available instrument in which they are fitted uses a split Rossfilter pair consisting of
 Ref.p. 143] 2.3 Non-Dispersive Instruments 133

TEST MATERIAL

SEALED ISOTOPE
SOURCE 141 Pm/AI
WINDOW

DETECTOR

Fig. 2 Sampling head of portable, non-dispersive, isotope source X-ray fluorescence instrument [25]

Table 3. Characteristics of Radioisotope Sources Used for Excitation of Sn Ka

Source Emission Energy (ke V) Half-Life

241Am "Y 60 480 years

153Gd X-rays 43 236 days
147 Pm/Al Bremsstrahlung 10- 100 2.6 years
147 Pm/Ba Bremsstrahlung 10- 100 2.6 years

PdK Absorption Edgc 0.509

0~--------~------~L-~~---------L----------~
0.3 0.4 0.5 0.6 0.7
WA VELENGTH til

Fig. 3 Absorption spectra ofbalanced Ag and Pd fllters used in non-dispersive X-ray fluorescence
instruments. Also shown are Sn Ka, Sb Ka, InKa, wavelengths
134 X-Ray-Fluorescence [Ref.p. 143

two half-circles, arranged in such a way that simultaneaus measurements may be made
with two counters. Despite their inferior resolution, non-dispersive instruments are
often more stable than crystal-dispersive spectrometers and very much poorer peak-
to-background count ratios may be tolerated.
Tin is particularly suited to determination by non-dispersive X-ray fluorescence
because of the relatively high energy of Sn Ko: and the fortuitous fact that neigh-
bouring elements having X-rays of similar energy are not usually present in !arge
amounts in tin minerals.
In addition to Bowie's thorough paper [25], a number of other reports [26 - 31]
deal with the use of non-dispersive instruments for tin determinations in ores and
concentrates. The same instruments may also be used for on-line analysis of pulp
streams [31] and drilling muds. Rules for sample preparation are similar to those for
conventional X-ray fluorescence in that Standards should be of a similar form and ma-
trix composition to the unknown and that high precision can only be obtained if
samples are finely ground. Calibrations are usually made with a plot of direct count
agairrst concentration. The graphs are updated regularly to compensate for decay in
source activity.

3. Soldersand Whitemetals
As is common in X-ray spectrometry, published work gives very little indication
of typical industrial practice. The most important feature of tin alloy analysis is the
tendency for intermetallic phases to segregate and to exist in a wide range of sizes de-
pending on the cooling conditions of the melt. These effects are accentuated by the
relatively low critical depth of Sn Ko: radiation in Sn/Pb alloys (Sn Ko: critical depth
is about 50prn in Iead). Furthermore, segregation is not arrested by solidification and
metallic phases "grow" in size on standing for periods of several days.

3.1 Structure of Solders, Segregation and Ageing

Fig. 4 shows the phasediagram for the Pb/Sn binary system. If an alloy containing
30% Sn/70% Pb is melted and slowly cooled, solidification will occur at about 255°C.
At this point, a solid phase having a composition given by the line AD at 255°C will
begin to separate. As solidification proceeds, the composition ot the solidphasewill
progress down the line AD while that of the liquid will be given by AC. During slow
solidification the lead-rich o:-phase "grows" to form !arge particles which tend to settle
because of their greater density. On complete solidification at 183°C, the solid con-
sists of large particles of o:-phase (Sn 8 - 19%) in a fine matrix of o:-(Sn 19%) and
ß-(Pb 3 %) phases.
Once the melt has cooled to room temperature, it will be seen from Fig. 4 that the
composition of the o:- and ß-phases (given by lines DF and EG respectively) is very
different from ihat at 183°C. In fact, Sn is soluble to about 2% in the o:-phase;Pb
is virtually insoluble in the ß-phase at room temperature. Therefore, there is a tenden-
cy for almest pure Pb and Sn phases to form on standing. This effect is hindered be-
cause the alloys are solid and takes place over a period of several days. Its influence
is to increase the apparent count rate for Sn Ko: in both Sn- and Pb-rich alloys. The
ageing of solders has been appreciated since the early part of the twentieth century
[4] and its importance in X-ray analysis investigated from ab out 1965 onwards [4,
 Ref.p. 143] 3.1 Structure of Solders, Segregation an Ageing 135

32, 33]. Ageing is only slightlyretarded by storing alloys in a refrigerator but is acce-
lerated considerably by storing in an oven at 100°C (Table 4). Metallographie exami-
nations [4, 33] clearly show that both o:- and ß-phase particles grow on ageing. The
phenomenon of ageing may be simply reversed by remelting and it is usual practice
[4] to retain a stock of about 1 kg of master standard which is remelted twice per
week. Allcountsare expressedas a ratio to those obtained on this standard.

The formation of !arge o:- or ß-phase particles and their subsequent segregation on
settling may be overcome by chill-casting samples in a massive steel mould (Fig. 5).
Moulds should be allowed to cool after casting a maximum of three discs. Discs are

300

•c Liquid

B
<><• Liquid
200

G
O(~f

0
0 20 40 60 80 100
WEIGHT Ofo~n

Fig. 4 Phase diagram of Pb/Sn binary system

Table 4. Effect of Ageing of Chili-cast Solder Standards Intensity of Sn Ko: [33]

Alloy Time Sn% at Storage Temperature

(days) 0°C 20°C 100°C
63 Sn/37 Pb 0 63.8 64.0 64.3
28 64.2 64.1 65.3
91 64.5 64.3 66.0
182 64.4 64.5 66.5
243 - 64.6 66.6
259 64.6 64.9 66.8
Remelt 63.8 63.7 63.8
10 Sn/90 Pb 0 11.2 10.9 11.1
28 11.1 10.9 11.0
101 11.4 11.5 11.5
171 11.5 11.7 12.0
255 11.6 11.8 -
Remelt 10.9 11.0 10.8
136 X-Ray-Fluorescence [Ref.p. 143

finished by turning on a lathe, having a tool with a 60° point mounted at right angles
to the face (i.e. cutting angle of 60°). A cut of about 0.5 - 1.5 mm should be taken
from the disc; more than this exposes a surface which is not truly chill-cast. Although
slight dragging of the machined surface is unavoidable with 2 Sn/98 Pb solders, this
has been shown to have no effect on the Sn intensity when a tungsten X-ray tube is
used.
Antimonial alloys are normally analysed by the chill-cast disc method only up to
a maximum of 20% Sb. Above this level the alloys are excessively segregated and must
be melted with sufficient leadtobring the al1oy to about 15% Sb. In general, antimo-
nial solders show the same properties as Sn/Pb alloys but with a greater tendency to-
wards segregation. Alloys containing Sb/Pb with 5% Sn and Sn/Sb alloys such as 95 A
solders (5% Sb/95% Sn) show little or no ageing effects.

3.2 SampiePreparation

The chill-cast sample technique is the simplest and is suitable for all Sb/Sn/Pb
alloys containing less than 20% Sb. Metals outside this range should be melted with
lead as described in Section 3.1. Chili-caststandardsare also subject to the effects of
ageing. The following procedure is typical [4]:

Melt 0.2 · 1 kg of sarnple in an iron !adle cleaned with tallow or wax. Stir with a carbon rod
and pour into a rnoilld (Fig. 5). It is good practice to pour whilst stirring. Alloys containing rnore
than 15% Sb should be rnelted under wax, tallow, palrn oil or glycerine and poured just as the
oil has nearly burned off. Discs are finished by turning on a lathe as described under Section 3.1,
taking a cut of 0.5 - 1.5 rnrn. There is no need to polish sarnples on abrasive cloth.

Lumb [34, 35] uses a similar casting procedure tothat above but finishes on a
lathe using a fly-cutting process. Two carbide-tip tools are mounted on a rotating
spindie diametrically opposed to one another. The 'roughing' cutter takes a cut of
about 0.2 mm and the 'finishing' cutter describes a circle of 1 mm less in diameter
and takes a further 0.05 mm cut. The sample disc is held in a fixed, three-jawed chuck
and is traversed across the rotating cutters. This is rather different from the scheme in
the previous paragraph where the cutting tool is traversed and the sample rotated.
Roussow [36] used a chill-casting technique without any subsequent surface fmishing
for the analysis of stereotype, linotype and monotype alloys.
Zannin and Hooser [37] chill-cast solders containing Ag, Au and Cu contaminants
by melting under rosin and splashing the metal on an aluminium plate. The metal
splashes were cut into small pieces of about 0.5 g rnixed and pressed into a disc at
3 tonnes/sq. cm. The disc was polished on wet silicon carbide papers of 220, 320,
400 and 600 grit. Sampies containing up to 3% Cu were melted in a sealed tube un-
der vacuum to prevent oxidation. Fillmore, Eckert and Scholle [38] prepared chill-
cast specimens by pouring molten metal into water. The resulting granules were pres-
sed into a disc which was analysed without further fmishing. This last approach,
however, was applied only to Sn (0.15- 0.75%) in antimoniallead (Sb 2- 7%).
Lueschow and Steil [39] cooled their samples ofPb/Sb/Sn alloys in liquid nitrogen
before taking turnings for pressing into a pellet.
 Ref.p. 143] 3.3 Standards Preparation 137

MILD STEEL - ALL DIMENSIONS IN MM.

1 - - - - - 80 ----~

T I
100

1
Fig. 5 Steel mould for chill-casting meta! discs for X-ray fluorescence [4]

3.3 Standards Preparation

The X-ray analysis of Pb/Sb/Sn alloys is unusual in that synthetic standards may
be easily produced from pur~ metals. In view of the high precision obtainable with
X-ray fluorescence, the technique rivals the iodometric method as a primary method
for determining tin in this type of material.
Primary standards are prepared by placing pieces of suitably pure antirnony, lead
and tin to give 2 kg total weight in a 600 rnl glass beaker, covering with palm oil and
leaving on a hotplate for about 8 hours. When all the metals have melted, as much
oil as possible is removed by decanting. The beitker is heated over a gauze on a gas-
burner and excess oil burned off. When only carbon remains, the melt is thoroughly
stirred and cast into strips ab out 3 -~-~-~m thick. After wiping clean, the strips should
show a weight loss ofless than 0.02%. Sampie discs are prepared by remelting the
strips and chill-casting the required number of discs. The remaining metal is cast
into strips and reserved for future use. At all points in the process the melt should
be stirred with a carbon rod. The sarne metals may be used to calibrate the density
assay (see Chapter on Tin Alloys and Solders p. 188).
Impurity standards containing Ag, Au and Bi are prepared by incorporating these
metals in the above procedure. Other metals are dissolved only with some difficulty.
Copper may be dissolved by stirring fme drillings or clippings in molten tin at over
350°C ,under an oil for several hours. The required arnount of lead should then be
added slowly with stirring to avoid separation of the copper. lt is almostimpossible
to dissolve more than about 1 %Cu in lead homogeneously under any conditions and
difficult to produce a 3% Cu in 60% Sn/Pb solder without loss of copper by oxidation.
Alternatively, copper may be dissolved in tin at 900°C under molten borax very rapid-
ly and with little loss. The resulting master alloy can be assayed chemically and added
to a base Pb/Sb/Sn matrix. Iron and arsenic may be dissolved in tin or lead by heating
under a thin borax cover at 900°C. The resulting master alloy should be assayed chemi-
138 X-Ray-F1uorescence [Ref.p. 143

cally. Because of the tendency for iron to segregate from low-melting metals, the
chill-cast disc technique cannot be used above 1% Fe in Sn or above 0.5% Fe in sol-
ders. Impurity elements do not show significant ageing effects and once standards are
made they need not be remelted.
Lumb [40), successfully prepared stable master Standards which did not age by
mixing the appropriate proportions of 400 mesh (37pm) metal powders with lOOg
of Araldite epoxy resin and hardener. The metal powder content was 1.5 g for 10 -
65% Sn. For 4% Sb the very stable background of the epoxy disc was used as a ratio
standard. After several months, the epoxy resin degrades under the influence of the
X-ray beam and the standard may require replacing with a duplicate prepared at the
same time. Duplicate standards were trimmed with a lathe to give sirnilar count rates
and were always used with a backing disc of Iead.

3.4 Calibration
Short Range Calibrations are normally used for specification analysis where a stan-
dard metal is under inspection; these calibrations have been described in detail by
Lumb [34, 35, 40]. Inter-element corrections are minimised because of the narrow
range. Over a range of about 15% Sn or Sb, calibrations approximate to straight lines.
Foreach range, at least three Sn/Pb standards are required to establish the line; one of
these is used as the ratio standard. Inter-element corrections are determined from sets
of at least two standards containing the impurity element and appropriate Sn/Pb con-
tents. If antimonial metals are usually assayed, it is normal to use a calibration and
ratio standard containing 5- 10% Sb. Backgroundcountsare small and may be igno-
red. Dead-time Iosses are appreciable above 35% Sn; corrections need not be made.
Wide Range Calibrations require considerably more calibration effort and checking
but make the analysis of metals of intermediate compositions more convenient. The
scheme below [4] gives results correct to ± 0.2% Sn and ± 0.1% Sb over most of the
range but with rather better accuracy below 5% Sn and 3% Sb. Standardsaremade by
the synthetic method of Section 3.3 and are divided into three ranges. Lead is the
base matrix and is not measured.

Low Tin Calibration Range: 0- 20% Sn at intervals of 5% Sn for 0% Sb

0 - 20% Sn at intervals of 5 % Sn for 5% Sb
0-20% Sn at interva1s of 5% Sn for 10% Sb
0- 20% Sn at intervals of 5% Sn for 15% Sb
Ratio Standard: 10Sn/5Sb

Solder Calibration Range 20-70% Sn at intervals of 5% Sn for 0% Sb

20 - 70% Sn at intervals of 5% Sn for 5 % Sb
20-70% Sn at intervals of 5% Sn for 10% Sb
Ratio Standard: 50Sn/5Sb

High Tin Calibration Range : 70-100% Sn at intervals of 5% Sn for 0% Sb

: 70 - 100% Sn at intervals of 5 % Sn for 5% Sb
: 70- 100% Sn at intervals of 5% Sn for 10% Sb
Ratio Standard: 85Sn/5Sb or 100Sn (for common tin assay).

Counting conditions: scintillation counter, fine collimator, topaz crystal, 10 sec count, SnKa 20.86"
28, SbKa 19.96"28, 80 kV, 25mA (20 mA on high tin range). Background not counted.
 Ref.p. 143] 3.4 Calibration 139

10°/o5b
COUNT 5°/o Sb
RATIO 00/o 5 b

OL---~-----L----~----~----~--~
20 40 60 80
0 fo Sn

Fig. 6 Calibration for Sn in Solders: topaz crystal, scintillation counter, fine collimator, 10 sec count,
80kV/25mA, standard 50Sn/5Sb, SnKa

A plot of Sn ratio against Sn% (Fig. 6) is made on very !arge scale graph paper (ma-
de by sticking several sheets together) and a set of tables is drawn from this. The tab-
les !ist Sn% in steps of 0.1% Sn against count ratio and for Sb concentrations at 1%
Sb intervals. A second plot of Sb ratio against Sb% (Fig. 7) is made on !arge scale graph
paper similarly.

Unknowns are evaluated by an iterative method: the Sn count ratio is converted to

Sn% using the calibration tables and an estimated value of Sb%. The Sb count ratio
is converted to Sb% from the graph using the derived Sn%. Finally, the Sn% is obtai-
ned from the tables using the original Sn count ratio and the measured Sb %. This
procedure is satisfactory for solders eontaining Sn, Sb, Pb only.
Impurity eorreetions are applied for Ag, As, Cu, Fe, Ni and Zn when these are
present at 0.1 - 1%. lmpurities enhance SnKa by replacing the denser Pb matrix. Bi
has a mass absorption eoefficient for SnKa similar to that of Pb and has no effeet.
Cerreetion factors are obtained from standards containing 0.2, 0.5 and 0.7% impurity
in 10 Sn/5 Sb, 30 Sn/5 Sb, 60 Sn/5 Sb and tin-base matriees. Cerreetions for up
to 8% Cu are available for eertain whitemetal alloys and unrefined materials. Cerree-
tion factors are plotted against impurity eoneentration; they are all subtraeted from
the Sn %. Unlike ratio standards which are melted twiee per week, impurity stan-
dards are only lightly polished on fine grit with oil when the ealibration is checked.
If impurity standards are remelted they are re-assayed and invariably show a loss of
Fe (if present above 0.3% Fe) or Cu (if present above 1% Cu).
140 X-Ray-Fluorescence [Ref.p. 143

COUNT
RATIO
700/cSn

0 5 10 15

0 /o Sb

Fig. 7 Calibration for Sb in Solders: counting parameters as in Fig. 6, SbKa

Mathematical Matrix Correction . The rather !arge amount of calibration data accu-
mulated historically has allowed mathematical corrections based on empirical factors
to be made for the Sn/Sb/Pb ternary system [4].
For Pb/Sn binaries the Lachance-Traill method [70] gives corrections accurate to
± 0.1% Sn. The form of the correction is:

(v)

Where: C refers to mass fraction ofthe element concerned

R is the measured count ratio
ß , is the slope proportionality factor
a is the matrix correction factor

Csn + CPb = 1 (vi)

therefore from equations (v) and (vi):

(vii)

A plot of Csn/Rsn against Csn gives a straight line having a slope -apt/ßsn and inter-
cept (1 + apb)/ßSn·

The Lachance-Traill method failed to give adequate correction for the effect of
antimony when a correction ofthe type below was used:
 Ref.p. 143] 4. Copper-Base Alloys 141

(vüi)

However, a modified form of this equation similar to that of Rasberry and Hein-
rich [72] gave a good correction to ± 0.2% Sn.

(ix)

IfCsn is calculated from equation (ix) assuming aSb = 0, then D.Csn is the differ-
ence between the corrected and uncorrected values. A plot of D.Csn/Rsn agairrst 1/CPb
gives two straight lines for Sb= 5% and Sb= 10% with slopes equal to Rsna'sbCsb/ßsn
Values found were <Xpb = 0.611, a·Sb = 0.13, ßsn = 2.545, for the solder calibration.
For the low tin calibration, values were: apb = 1.538, ßsn = 22.79,a' Sb= 0. As CPb
is not normally measured in this scheme, both CPb and Csb must first be estimated
and iterative corrections carried out preferably using a computer. Cerreetions for dead-
time count Iosses were not applied as they offered no improvement.

Impurity corrections based on the existing data can then be applied in the same
way as before.

4. Copper-Base Alloys

The determination of tin in copper-base alloys is one of the most important appli-
cations of X-ray fluorescence. Table 1 of the Chapter on Copper-Base Alloys shows
that these contain 1 - 13% Sn and that tin must be less than 0.1 - 1.5% in other alloys.
In all cases, copper exists in quantities greater than 55%. A number of general schemes
[41 - 43] exist for the determination of several elements in a fairly wide range of cop-
per-base materials. In the analysis of brasses using the Sn La line and a Cr target tube,
slight matrix effects were found tobe caused by Pb absorption for 0.02- 2.0% Sn. A
correction based on the equation below was used:

Csn = Isn [0.4785 + 0.0664IPb] + 0.09765-0.1289 Icr (x)

Where: C refers to concentration.

I refers to intensity.

Icr is the intensity of the scattered Cr Ka tube line and was used as a general correction
[43]. Pb was present in the range 0- 3.5%.
Thiele [44] examined similar brasses: Sn 0.1 - 1.5 %, Pb 0.1 - 3% and recommended
an empirical correction:

Csn = C'sn [I+ 0.015 CPb] (xi)

Where: C'sn is the uncorrected Sn%.

142 X-Ray-Fluorescence [Ref.p. 143

For leaded gunmetals, corrections are only required when one of the matrix ele-
mentsfalls weil outside the specification range [34, 35]. For Sn Ka the mass absorp-
tion coefficients are: Ni 16.8, Cu 17.8, Zn 19.8, Sn 11.7 and Pb 48.6. At Sn La the
mass absorption coefficients are: Ni 495, Cu 528, Zn 582, Sn 467 and Pb 1700. Only
lead is likely to have an effect requiring correction. Surface finishin copper-base
alloys is critically important when lead is present. Lathe fmishing with a blunt tool
tends to smear lead (but not tin) giving higher lead counts and reducing the counts
for other elements. This effect is very noticeable where lead exists as discrete partic-
les in a hard matrix but is comparatively unimportant in chill-cast solder or lead al-
loys.
Copper-base alloys can only be analysed directly when standards and samples are
in the same metallurgical state, usually as chill-cast discs. When this is not possible,
determinations must involve a fusion or dissolution procedure. Cullen [45] fused
lOOmg of sample with 5 g of K 2 S2 0 7 at 300- 700°C in a silica crucible. The melts
were ground and pelletised. Synthetic Standards were prepared from stock solutions;
the method was applied to Sn, Cu, Ni, Pb and Zn in brasses and bronzes. Brill and
Faust [46] dissolved 5g ofsample in 150m! ofHN0 3 , 5ml ofHF and 20rnl ofwater.
Afterdilution to lOOrnl the solutionwas analysed for Sn, Cu, Pb, and Zn. Alloys te-
sted were phosphor bronze, high-leaded bronze, high-leaded tin-bronze (DIN 1716)
and leaded gunmetal (DIN 1705).

5. Other Applications
Tin is an important harmful impurity in low-alloy steels and offers no problems in
its determination. Several published reports discuss the determination of Sn and other
minor elements [47- 52], no matrix corrections were found necessary. Griffiths and
Whitehead [53] determined Sn and eight other elements in cast irons after wet polis-
hing on a 600 grit.
Tin has been determined [54] in leaddown to 0.03% at Sn Ka using an energy dis-
persive instrument with Ge (Li) detector and 45 mCi 241 Am source. Ag and Sb were
also determined. Similar detectors and multi-channel analysers were used to determine
Sn in gallium arsenide [55], steels [56] and copper-base alloys [56].
Aluminium alloys have been analysed for Sn and Zr [57] and Sn and ten other
elements [58]. The mass absorption coefficients for Ni,Cu and Zn are ten timesthat
of Al at Sn Ka and that for Zr is twenty times. After applying corrections for Ni, Cu
and Zn absorption, linear plots were obtained for (Sn Ka .;- background) against Sn%
when Sn< 0.3% [57].
Titanium alloys were analysed using standardinstrumental conditions [59]. Sn Ka
was affected by Zr and empirical corrections involving mass absorption coefficients
were employed. Alternatively [60] 1 g of alloy may be dissolved in HC1/HN0 3 /HF
(1: 1 :2) and Sb incorporated as an internal standard for 3 - 10% Sn.
Other alloy systems which have been analysed for Sn include Sn/Sm [61], Cd/Sn
[62], Sn/Zn [62],Nb/Sn [63].
Organatin PVC stabilisers were assayed [64] by dissolving the stabiliser in 2-ethyl
hexanol to give a concentration of 0.9 -'1. 7% Sn and counting Sn Ka excited by a
241 Am source in a non-dispersive instrument with a scintillation counter. Tin and
 5. Other Applications 143

copper wood preservatives were determined (65] in railway sleepers by grinding and
pelleting the sarnple.
Wlotzka [66] determined 0.1- 500t.Lg ofSn in 0.4M HCl solutions by adding 100
t.Lg of Cu as a carrier, precipitating with H 2 S and fi.ltering on a 15 rnrn diarneter rnern-
brane. Sirnilarly (67] colour pigrnents were ashed with oxygen activated by a radio-
frequency discharge at reduced pressure, dissolved in M H 2 S0 4 and heavy metals
precipitated with sodiurn diethyldithiocarbarnate. Tin and twenty elernents were de-
termined down to about 5t.Lg. Chamberlain and Leech (68] determined 1 - 20t.Lg of
Sn in glass sarnples by an ion-exchange technique.
Irnpurities in crude tin have been determined (69] by pelleting the sarnple sheet
or powder at 25 tonnes pressure before counting Sn Ko: (40 kV, 6 rnA), Pb La: (20
kV, 10 rnA) and Cu Ko: (20 kV, 10 rnA). X-ray fluorescence is ideally suited for de-
terrnining irnpurities in cornrnon tin (Sn> 99.0 %) down to ab out 0.02% [4]. This in-
cludes As, Cu, Fe, Pb, Sn and Zn. As rnust be determined at the As Kß wavelength
and Pb at the Pb La after subtracting a correction for As. The technique is not ade-
quate for assaying Sn % to lirnits required by the specification. Electrolytic tin is not
normally assayed by X-ray fluorescence unless the particular brand contains only a
few rnajor irnpurities at relatively high levels.

References
1. Jenkins, R., De Vries, J.L.: Practical X-Ray Spectrometry, 2nd ed., London: McMillan 1969
2. Liebhafsky, H.A., Pfeiffer, H.G., Winslow, E.H., Zemany, P.D.: X-Ray Absorption and
Emission in Analytical Chemistry New York: Wiley 1960
3. Jenkins, R.: Bulletin 79. 177/FS 29, Eindhoven: Philips (1970)
4. Unpublished Work and Standard Methods, Capper Pass, Ltd.
5. De Vries,J.L.: X-Ray Fluorescence Spectrometry- Review of Literature 7th ed., Eindhoven:
Philips 1976
6. Sweatman, T.R., Wong, Y.C., Toong, K.S.: Trans. Inst. Min. Metall. 76B, 149 (1967)
7. Wong, Y.C., Seevaratnam, S.: Analyst 96, 562 (1971)
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9. Sweatman, T.R., Norrish, K., Durie, R.: C.S.I.R.O. Div. Coal Res. Mise. Rept. 177 (1963)
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11. Carr-Brion, K.G.: Analyst 90,9 (1965)
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17. Ingamells, C.O.: Anal. Chim. Acta 52, 323 (1970)
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19. Carr-Brion, K.G.: Analyst 89, 556 (1964)
20. Payne, K. W.: Proc. 7th Phiiips X-Ray Conference, Durharn (1970)
21. Payne, K. W.: 8th Philips X-Ray Conference, Birmingharn (1972)
22. Lueschow, H.M., Schaefer, H.P.: Z. Anal. Chem. 250, 317 (1970)
23. Sanner, G., Ehrhardt, H.: Neue Hütte 13, 751 (1968)
24. Ross, P.A.: 1. Opt. Soc. Amer., Rev. Sei. Instrum. 16,433 (1928)
25. Bowie, S.H.U., Darnley, A.G., Rhodes, J.R.: Trans. Inst. Min. Metall. 74, 361 (1965)
26. Garson, M.S., Bateson, J.H.: Trans. lnst. Min. Metall. 76B, 165 (1967)
27. Cox, R.: Trans. lnst. Min. Metall. 77B, 109 (1968)
28. Gallagher, M.J.: Proc. 9th Commonwealth Min. Metall. Congr. 2, 691 (1969)
29. Nikitin, F. V., Kats, l.E.: Zavod. Lab. 36, 159 (1970)
30. Brunner, G., Dahn, E.: Isotopenpraxis 8, 300 (1972)
31. Nikitin, F.V.: Zavod. Lab. 31,966 (1965)
32. Glade, G.H., Post, H.R.: Appl. Spectros. 22, 123 (1968)
33. Glade, G.H., Post, H.R.: Appi. Spectros. 24,193 (1970)
34. Lumb, P.G.,: Proc. 7th Philips X-Ray Conference, Durharn (1970)
144 X-Ray-Fluorescence

35. Lumb, P.G.: Bulletin 7000.38.1700.11, Eindhoven: Philips (1971)

36. Roussow, A.J.: S.Afr.lnd.Chem. 14,44 (1960)
37. Zanin, S.J., Hooser, G.E.: Appl. Spectros. 22, 105 (1968)
38. Fillmoore, C.L., Eckert, A.C., Scholle, J. V.: Appl. Spectros. 23, 502 (1969)
39. Lueschow, H.M., Steil, H.U.: Z. Anal. Chem. 245, 304 (1969)
40. Lumb, P.G.: Metallurgia 80, 127 (1969)
41. Bareham, R.F., Fox, J.G.M.: J.lnst.Metals 88, 344 (1960)
42. Manners, V.J., Craig, J. V., Scott, F.H.: J.Inst.Metals 95, 173 (1967)
43. Jenkins, R., De Klerck, J., Van Gelder, S.: Bulletin 7000.38.0310.11 Eindhoven:
Philips (1971)
44. Thiele, B.: Siemens Z. 44, 707 (1970)
45. Cullen, T.J.: Dev.Appl.Spectros. 1, 25 (1962)
46. Brill, M., Faust, W.: Z. Anal. Chem. 258, 349 (1972)
47. Barbier, M., Rondeau, J.M.: Chim. Anal. 53,470 (1971)
48. Tunney, A.A., Hughes, H.: Brit. Steel Corp. Open Rept. GS/TECH/240/1/71/C (1971)
49. Griffiths, JM., Whitehead, H.R.: N.P.L. Rept. Chem. 16 (1972)
50. Tunney, A.A.: Brit. Steel Corp.Open Rept. GS/EX/22/73/C (1973)
51. Tunney, A.A.: Brit. Steel Corp.Open Rept. GS/EX/4/73/C (1973)
52. Campbell, W.J., Neylan, D.L.: Rept. Invest. U.S.Bur. Mines RI 7773 (1973)
53. Griffiths, JM., Whitehead, H.R.: N.P.L.Rept.Chem. 17, (1972)
54. De Neef,J., Adams, F., Haste, J.: Anal. Chim. Acta 62, 71 (1972)
55. Porter, D.E., Woldseth, R.: Anal. Chem., 45, 60A (1973)
56. Hol/stein, M., De Voe, J.R.: J. Radioanalyt. Chem. 6, 139 (1970)
57. Suzuki, S., Matsumoto, S., Itoh, J.: Japan Analyst 19, 1523 (1970)
58. Dick, J.G., Fraser,A.R.: Can.J.Spectros.l7,135 (1972)
59. Matsumura, T., Kotani, N., Goto, T.: Japan Analyst 19, 1393 (1970)
60. Vassilaros, G.L., McKaveney, J.P.: Talanta 16, 195 (1969)
61. Percheron, A., Pinta, M.: Anal. Chim. Acta 42, 489 (1968)
62. Sarian, S., Weart, H. W.: Anal. Chem. 35, 115 (1963)
63. Bertin, E.P.: Anal. Chem. 38, 826 (1964)
64. Havranek, E., Bumbalova, A., Kapinska, V.: Chemicky Prum. 20, 536 (1970); Anal.Abstr.
21,1902 (1971)
65. Ishii, Y., Kawamura, H., Yagi, S.: Japan Analyst 17, 3 (1968)
66. Wlotzka, F.: Z.Anal.Chem. 215, 81 (1966)
67. Kobliska, J.J., Kodama, S.P., Eckhart, C. G., Gaydosh, R.J., McMeekin, L.J., Santacana, F.,
Prescott, W.B> Paint Varn.Prod. 62, 27 (1972); Anal. Abstr. 24, 2269 (1973)
68. Chamberlain, B.R., Leech, R.J.: Talanta 14, 597 (1967)
69. Nakanishi, H., Yoshimura, M., Yoshisako, K., Itsuki, K.: Japan Analyst 13, 1131 (1964)
70. Lachance, G.R., Traill, R.J.: Can.J. Spectros. 11,43 (1966)
71. Rasberry, S.D., Heinrich, K.F.J.: Anal. Chem. 46, 81 (1974)
CHAPTER 11

RADIOCHEMICAL & MOSSBAUER METHODS

By J.W. Price

1 . Radiochemical methods
Irradiation of tin with thermal neutrons produces several radioactive isotopes, and
of these 113 Sn which is a -y-emitter with a half-life of 119 days, has been used for
labeHing organotin compounds in studies of animal metabolism and of agricultural
residues (see Chapter 19.6). The other important use ofradiochemical methods is in
the determination of trace amounts of tin by neutron activation analysis and for
this the most suitable isotope is 121 Sn, which is a pure ß-emitter with a half-life of
27 hours. Irradiation is carried out in a flux of about 10 12 n.cm -2 s- 1 for periods of
6-24 hours, Cle sample being allowed to decay for 24 hours before processing. A
disadvantage in the use of 121 Sn is the need to obtain a radiochemically pure com-
pound for ß-counting, the main contaminants being arsenic, antimony, molybdenum
and tellurium, and a series of Separations, usually involving one or more solvent ex-
tractions, must be carried out. The radiochemistry of tin and suggested schemes of
chemical Separation, particularly from fission products, are given in detail in a mono-
graph by Nervik [1).
The determination of tindown to 0.0001% in iron and alloy steels by neutron
activation has been described by Williams [2]. The irradiated sample (1 g) tagether
with 20mg tincarrierwas dissolved in hydrochloric acid, the solution oxidised with
bromine and sulphides precipitated after neutralisation of most of the free acid with
ammonia. The precipitate was dissolved in hydrochloric acid, oxidised and sulphides
re-precipitated and re-dissolved in 1ml of the acid. After addition of copper, antimo-
ny and molybdenum carriers and 0.5 ml each of sulphuric and hydrofluoric acids and
dilution to 10 ml, sulphides were again precipitated, leaving the tin in solution. Tra-
ces of sulphide in suspension were removed by scavenging with lanthanum fluoride,
and tin precipitated as sulphide after addition of 10m! of saturated boric acid solu-
tion. Traces of iron were removed as hydroxide by adding iron carrier to a solution
of the sulphide precipitate in 1 ml of hydrochloric acid after oxidising with bromine,
by making strongly alkaline with 10M sodium hydroxide. The ftltrate was acidified
with hydrochloric acid and tin again precipitated as sulphide, ignited to oxide and
counted. (It is preferable to ignite the sulphide precipitate to oxide before counting
in order to reduce self-absorption of the low-energy ß-particles). Counting was con-
tinued at 24 hour intervals for 10 days in order to obtain the slope of the decay cur-
ve; this was extrapolated to zerotime to give the uncorrected count for 121 Sn and
the tail of the decay curve was also extrapolated to determine the activity caused by
long-lived tin isotopes and radiochemical impurities. Finally the corrected activity
was converted to weight of tin by comparison with a standard sample of tin meta!
(2 mg) irradiated and processed in the same way as the sample.
A different radiochemical Separation procedure was used by Hamaguchi et al
[3) to determine 50 - 300 pgj g of tin in ferro alloys. The sample, tagether with 20mg
of tin carrier, was dissolved in 20ml of 6M hydrochloric acid, 4ml of 9M. sulphuric
146 Radiochemical & Mossbauer Methods [Ref.p. 148

acid and 2ml of nitric acid, flltered, diluted to 150rnl and sulphides precipitated with
H2 S after addition of 2 g of tartaric acid. The sulphide percipitate was dissolved in
5ml ofhydrochloric acid and, after addition of 2mg of iron(III), 5ml of 2.5M hydro-
fluoric acid and 5 ml of water, extracted with 15 rnl of methyl isopropyl ketone. Tin
in the aqueous phasewas then precipitated as sulphide after addition of 10rnl of sat-
urated boric acid solution and the precipitate dissolved in 4ml of sulphuric acid can-
tairring 0.2 g of hydrazine sulphate and 2mg each of Sb 3 +, As 3 • and Cu 2 • carriers. Af-
ter addition of 22rnl of water, foreign activities were extracted with 20ml portians of
diethylarnmonium diethyldithiocarbarnate (10gll chloroform) until no more colour
was produced in the extract. Tin was then extracted as the iodide from the aqueous
phase with 20rnl of methyl isopropyl ketone after addition of 5 g of potassium iodide,
the organlc phase washed with 1.5M potassium iodidein l.SM sulphuric acid and the
tin stripped by shaking with lOrnl of 2.5 M hydrofluoric acid. Finally tin sulphide
was precipitated after adding 15 ml of saturated boric acid solution, flltered, dissol-
ved in a mixture of 1 ml of nitric acid and 2ml of perchloric acid and the solution
evaporated to fuming to precipitate Sn0 2 • After diluting with water the precipitate
was filtered, ignited, weighed to determine the chemical yield and mounted for coun-
ting.
The same scheme of Separation was used successfully by these workers for the
determination of tin in sea-water andin biological materials, while Byme [4] deter-
mined down to 0.1 Jlglg Sn in kale, human hair and fruit juices, after irradiating and
ashing, by dissolving the ash in 4.5M sulphuric acid- 0.5M potassium iodide and ex-
tracting Snl 4 into toluene. The extract was washed with 1.5M sulphuric acid IM po-
tassium iodide to remove arsenic and antirnony and the tin back-extracted into 1.5M
sulphuric acid for measurement of the 1-activity of 123 m Sn (half-life 40 min). This
procedure was considered by Bowen [5] to give inadequate decontarnination from
arsenic and antirnony and he included a further step involving a thiocyanate extrac-
tion ofthe tin as follows; the toluene solution cantairring the tinwas stripped with
10ml of 1M hydrochloric acid and the aqueous layer after the addition of arsenic
and antirnony carriers and 5ml of 3M potassium thiocyanate was extracted with
15 ml of diethylether. Tin was back-extracted from the ethereallayer into 10ml of
2M sodium hydroxide and, after the neutralisation of the solution with hydrochloric
acid, precipitated as the sulphide, filtered, weighed for chemical yield and the activi-
ty of the 121 Sn counted. No corrections were found necessary for dead time or self-
absorptio.n and a precision of ± 10% in the range 50 - 300nglg was found, with a sen-
sitivity of 10- 20ng.
A further radiochemical procedure suitable for the determination of tin in nicke!
alloys has been described [6]. After precipitation of the tin as metastarrnie acid the
precipitate is heated with arnmonium iodide to sublime Snl 4 which is dissolved in a
mixture of 1.5M perchloric acid I 2.5M I sodium iodide and extracted into benzene.
After back-extraction into 0.5M hydrochloric acid tin is precipitated with N-benzoyl-
phenylhydroxylarnine, the precipitate dried and weighed, the activity of 121 Sn then
being counted as above. Substantially the sarne procedure has been used by Tejinus
and Haidar [7] for the analysis of biological and geological sarnples.
F or the determination of tin ( 10-1 ,OOOppm) in geological material Johansen and
Steines [8] preferred a method based on 113 Sn, the sarnples being irradiated for 14
days at a neutron flux of 10 12 n.cm- 2 s- 1 and stored for 14 days before processing.
They were then fused with 2g of sodium hydroxide after addition of tin carrier and
zinc holdback carrier, the melt dissolved in water, the solution acidified with sulphu-
ric acid and the tin precipitated as sulphide by the addition of thioacetarnide. The
 Ref.p. 148] 2. Mössbauer Spectroscopy 147

precipitate was dissolved in 5 ml of hydrochloric acid and 0.5 ml of nitric acid, 20ml
of 5 M ammonium thiocyanate added and tin extracted by shaking three times with
30m! of diethyl ether. The combined extracts were evaporated over 50ml of 3M sul-
phuric acid and tin again precipitated from the filtered solution with thioacetamide,
the sulphide filtered, ignited to Sn0 2 and weighed. After allowing 24 hours for the
transient equilibrium 113 Sn - 113 m In to be established the 1-activity based on the
392ke V photopeak of 113 m In was recorded.
A similar method was used by Obrusnik [9] for the determination of indium and
tin in granite. Chemical separation of the tinwas avoided by extraction of indium
into dithizone from alkahne cyanide solution, followed by substoichiometric replace-
ment by mercury, the dithizone extract being shaken with a solution of 400ttg of
mercury in tartrate buffer (pH 7 .5). The 1-activity of the 113 m In in the aqueous pha-
se was then measured as above.
Of other methods of separation that can be used in radiochemistry (see Ref. ( 1])
the most important are chromatography and ion-exchange.
Chromatography. The separation of arsenic, antimony and tin by thin-layer chroma-
tography has been described by Seiler [ 10 ], who used as developing solvent a mixture
of methanol-ammonia-water-polysulphide (35: 10:5:1) and detected arsenic and an-
timony as their sulphides and tin with diphenylcarbazide, while Stronski [ 11] separa-
ted In-Sn-Te and Sb-Sn by extraction chromatography with Amberlite LA-2 for the
production of carrier-free radioisotopes from irradiated targets.
Ion-exchange. A complete separation of tin and antimony activities can be obtai-
ned by using cation-exchange resin (Dowex 50) and solutions which are 12M in hy-
drochloric acid, the SnC!~ -complex not being absorbed while the antimony is strong-
ly held [ 12].
Mixtures of tellurium, antimony and tin tracer in 0.1 M oxalic acid solution have
been separated on Dowex-1 columns [ 13]; using 0.1 M oxalic acid neutralised to pH
4.8 as eluent, antimony is removed from the column while tin can be eluted with 0.1
M sulphuric acid.
Mixtures of Sn 4 + and Sb 5 + can be separated on Amberlite IRA-400 using ammonium
malonate as eluent (14]; the tin complex is strongly held by the resin but can be strip-
ped with 4.5M sulphuric acid.
Neutron activation analysis has been used for the determination of trace impuri-
ties in samples of high-purity tin metal, and detailed separation schemes have been
put forward for the simultaneaus determination of up to 15 impurities in the sub-
microgram range using a 1g sample [ 15, 16].

2. Mössbauer Spectroscopy
The Mössbauer effect has been of considerable value in the study of the structure
of tin compounds, particularly of the organotins [ 17] but its application to quantita-
tive measurements has so far been less important. The possibility of using a relatively
simple non-destructive method for the determination of Sn0 2 has led to its investiga-
tion for the analysis of ores and minerals [ 18] and in geological surveying ( 19]. A por-
table field apparatus has been described (20], which uses a source of 1-quanta in the
form of Sn0 2 enriched in 119 Sn and a scintillation counter detector for 1-quanta of
24keV. When the source is stationary some of the quanta passing through the sample
are resonance-absorbed by the 119 Sn nuclei present, while if the source is moving the
148 Radiochernical & Mossbauer Methods

energy of the quanta changes owing to the Doppler effect and no resonance-absorp-
tion takes place, the difference between the number of pulses registered being propor-
tional to the amount of tin in the sample .. A sensitivity of about 0.1% Sn is obtained
with an accuracy at the 1% level of about ± 10%.
The problems involved in using Mössbauer spectroscopy for the accurate determi-
nation of tin have been examined in detail by Pe/la et aL [21] using synthetic mixtures
of Sn0 2 and Al 2 0 3 with Pd 3 - 119 rn Sn as a source, and their fmdings applied to the
determination of tin in copper-base alloys [22). The source used in this case was
lOmCi of 119 m Sn as BaSn0 3 , a 0.05mm Pd foil being placed over the source to fiJ.ter
the 25keV Sn X-rays, and using a sample thickness of O.Smm. An intemal standard
was prepared by grinding a mixture of tin metal powder with Al 2 0 3 and casting the
mixturein resin to form a disc O.Smm thick and 3cm 2 in area, with a tin content of
8mg/cm 2 • The alloy samples (I - 8% Sn) were dissolved in nitric acid and the precip-
itated metastannic acid fiJ.tered, ignited and mixed with enough Al 2 0 3 to give a total
weight of 165mg. The mixturewas transferred to a cell holder and spectra accumula-
ted until 7 x 10 5 counts per charmel were obtained. Calibration curves were obtained
by dissolving known weights of tin metal in nitric acid and continuing as above, the
areas of the Sn0 2 and ß-tin absorption peaks being evaluated and C1eir ratio plotted
against the tin concentration.
Sn0 2 is particularly suitable in Mössbauer studies because of its sensitive analytical
response in terms of the change in absorption intensity per unit change in concentra-
tion, so that determination of naturally occurring cassiterite and determination of tin
in alloys soluble in nitric acid would appear the most suitable applications for Möss-
bauer spectrometry in quantitative work.

References

1. Nervik, W.E.: The Radiochemistry of tin NAS-NS 3023 U.S. Atomic Energy Commission 1960
2. Williams, A.I.: Analyst 84,433, 1959
3. Hamaguchi, H., Kawabuchi, N., Oniama, R., KurociJI, R.: Anal.Chirn.Acta 30, 335, 1964
4. Byrne,A.R.: Radiochern. Radioanalyt. Lett. 7, 287,1971
5. Bowen, H.JM.: Analyst 97,1003, 1972
6. Morris, D.F.C., Denny, JA.: Radiochem. Radioanalyt. Lett. 8, 219, 1971
7. Tejinus, B.M., Ha/dar, B.S.: Radiochem.Radioanalyt. Lett. 13, 25, 1973
8. Johansen, 0., Steines, E.: Analyst 94,976, 1969
9. Obrusnik, /.: Talanta 16,563, 1969
10. Seiler, H.: Helv.Chirn.Acta 54,533, 1971
11. Stronski, I.: Radiochem. Radioanalyt. Lett. 5,"113, 1970
12. Kraus, KA., Michelson, C.D., Nelson, F.: J.Amer.Chem.Soc. 81, 3204, 1959
13. Smith, G. W., Reynolds, SA.: Anal.Chim.Acta 12, 151, 1955
14. Dawson, J., Magee, R.J.: Mikrochim.Acta 3, 325, 1958
15. Lanfranco, G.: Metallurg.Ital. 63, 225, 1971
16. Maenhaut, W., Adams, F., Hoste, J.: J.Radioanalyt.Chem. 6, 83, 1970; 9, 27, 1971; 14,
295,1973
17. ~mith, P.J.: Organomet.Chem.Rev.Sect.A. 5, 373, 1970
18. Kalmakov. AA., Salakhutdinov, N.: Izv. Vysshikh Uchebn.Zaved, Tsvetn. Met. 8, 158 (1965).
Chem. Abstr. 64, 3107 (1966) Salakhutdinov, N.: Teor. Sredstva Avtomat., 396 (1968)
Chem.Abstr. 71, 27232 (1969) Salakhutdinov, N., Kalrnakov A.A.: Izv. Vyssh. Ucheb.
Zaved.Tsvet.Met. 13, 17 (1970) Chern. Abstr. 73, 105200 (1970) Stuart, R.A., Donohoe,
A.J., Boyle, A.J.F.: Proc.Austral.Inst.Min.Metall., 230, 69 (1969) Chem. Abstr. 71,
56356 (1969)
19. Dolenko et al., A. V.: Vses.Nauk-Tekh.Konf, 467, 1968, Atomizdat USSR 1971 (Chem.
Abstr. 77, 121696, 1972)
20. Goldanskii, V./., et al.: Tr.Vses.Nauk.-Issled.lnst.Yad.Geoflz.Geokhim. 3, 220, 1968 (Chern.
Ab~r. 72,139362) 1970
21. Pella, P.A., Devoe, J.R., Snediker, D.K.: Anal. Chem. 41, 46, 1969
22. Pe/la, PA., DeVoe,J.R.: Anal. Chem. 42, 1833, 1970
CHAPTER 12

ANALYSIS OF TIN ORES & CONCENTRATES

By R. Smith

1. Tin Minerals
The principal tin minerals are given in Table 1, tagether with their formulae and
areas of occurrence. In addition to the elements listed in Table 1, other elements asso-
ciated with tin include:
As, Bi, Cd, F, In, Mo, Nb, Ta, Ti, Wand Zn.

Table 1. Principal Tin Minerals [ 1]

Native Tin Sn Nesbitt LaBine Mine

Saskatchewan
Niggliite (PtTe)x(PtSnly Insizwa, S.Africa
Stannopalladinite Pd3Sn2 USSR
Cassiterite Sn02 Widespread occurrence
Souxite (wood tin) Sn02,xH20 Mexico; Bolivia
Cuprocassiterite Sn02 ,2Cu(0Hh ,Sn(OHh
Hochschildite PbSn03,4H20
Montesite, herzenbergite SnS Bolivia
Stannite Cu2FeSnS4 Widespread occurrence
Hexastannite Cu 6FeSnSs Bolivia
Mawsonite Cu7Fe2SnS10 Bolivia
Sakuraite (CuZnF eAg)J (lnSn)S4 Ikurno Mine, Japan
Teallite PbSnS2 Bolivia
Cyiindrite Pb6Sn6Sb2S1s or Pb3Sn4Sb2S10 Bolivia
Franckeite PbsSn3Sb2S14 Bolivia;Yukon, Canda
Canfieldite,argyrodite Ag 8 (SnGe)S6 Bolivia;Gerrnany;Tasmania
Nordenskioldinite CaSn(B03h
Stockesite CaSnSi(OH)407

Tin concentrates range from almostpure cassiterite with 78% Sn found in Central
Africa to low-grade Bolivian materials with as little as 10% tin and containing !arge
quantities of sulphur, lead and zinc.
150 Analysis of Tin Ores & Concentrates [Ref.p. 170

2. Sampling of Tin Ores and Concentrates

The principles of bulk sampling statistics and geochemical value assessment have
recently been reviewed by Ingamells [2]; guidelines for sampling bulk materials are
given in a Japanese Standard [3] and a publication by the Institute ofMining and Me-
tallurgy [4] contains a number of articles on all aspects of the sampling of solids. The
following guidelines for sampling tin concentrates refer particularly to consignments
or batches of material and are based on practical experience in the European smelting
industry.

2.1 Size of Batchor Consignment- the consignment may be of any size but should
be subdivided into "lots" to minimise the effects of random errors. For purchasing
transactions a convenient Iimit to the size of lots is 20 tonnes Sn in concentrate with
a maximum of 100 tonnes of material in the Iot. A combined error of ± 0.2% Sn for
assaying and sampling is, therefore, ± 200kg Sn on the largest Iot.

2.2 Primary Sampling - it is impossible to give a scheme for the drawing of a prima-
ry sample as the consigment will vary. Where possible trucks, containers, railwagons,
etc., should be sampled during unloading. Tipping trucks or containers should be
sampled immediately after the Ioad has been tipped - samples should be taken from
all over the heap which should then be thoroughly turned over, preferably with a me-
chanical digger and sampled again Bags and drums should be sampled during emptying.
With drums and !arge bags the sample should include increments from top, middle and
bottom. Spear sampling from intact bags tends to reject material from the bottarn of
the bag and also !arge lumps [82]
At all stages in sampling, care should be taken to avoid loss of moisture by keeping
the bulk sample in a covered container. Heaps of material should not be allowed to dry
out or become wetted between weighing and sampling.
Care should be taken to avoid loss of fine material in windy conditions or rejection
of !arge particles which tend to roll off sampling shovels.
It is common practice to draw a primary sample equal to 5% or 10% of the weight
of the Iot, giving a maximum of 5 or 10 tonnes of sample.lf 1000 shovelfuls (n) of
concentrate are taken for the bulk sample and the standard deviation (s) of the tin con-
tents of individual shovelfuls is 5% Sn then:

+~ t is Student's 't'
9 5% confidence Iimit -..rn
± 1.95 X 5 = ± 0.31% Sn
J 1000
Table 2 illustrates the errors which may be obtained in taking 5% primary samples.
If a 10% sample were taken using twice the number of increments, the errors would
be reduced by a factor of 1.41.

2.3 Crnshing and Dividing- primary samples are usually divided by coning and quarter-
ing or by a mechanical device to give a sample of 50- 150kg having a maximum particle
diameter of about 15mm. This should be crushed to pass a 2 mm (1 /16 inch) sieve and
then further divided for final sample preparation. The concentrate should be dried and
250- 1000g milled to pass a 76pm sieve (B.S. 200). The sample should be dried again
before assay and at least 0.3g taken by the assayer.
 Ref.p. 170] 2. Sampling of Tin Ores and Concentrates 151

Table 2. Errors (95% Confidence Limits) of Primary Sampling with 2kg Increments to
give a 5% Sampie - if Standard Deviation of Increments is 5% Sn

LotSize Primary Sampie Sampling Sampling

tonnes Increments Error Error
±%Sn ±kg Sn

100 2500 0.195 195

50 1250 0.275 138
20 500 0.435 87
10 250 0.613 61

A number of sampling models exist which enable calculations to be made of errors

for varying particle sizes and sample weights. All theories assume that the sample is
well mixed and that the only error is the so-called "fundamental error". This error is
committed when sampling is perfect and is analagous to the error involved in estima-
ting the number of black and white balls in a collection of a hundred by taking a ran-
dom sample of ten balls.

The fundamental sampling error may be calculated by the 'size/weight ratio' theory
of Bailey [6, 7]. This assumes that only the largest particles contribute to the error,
that the mineral is completely liberated from the gangue and that the particles are
cubic. A more sophisticated theory by Gy [4, 8] overcomes these objections at the
expense of introducing more variables.

(i)

Where: a 2 (FE) is fundamental error expressedas a relative variance.

Ms is the sample weight.
M is the lot weight.
a is the mineral (Sn0 2 ) content of the lot, expressedas a decimal
p A ; PG are densities of the mineral and gangue respectively.
f is a 'shape' factor (for ores and concentrates f =0.5).
g is a 'size distribution' factor (g = 0.50 for products graded between two
screens and g = 0.25 for products graded through only one screen).
is the 'liberation' factor given by Table 3
d is the diameter of largest particles. (Screen opening to retain 5% oversize).
d0 is the particle diameter at which the mineral is effectively liberated from the
gangue

Table 3. Calculation of Liberation Factor '1' in Gy Sampling Theory

Liberation F actor 1 1 0.8 0.4 0.2 0.1 0.05 0.02

d/d 0 1 1 4 10 40 100 400

152 Analysis of Tin Ores & Concentrates [Ref.p. 170

Equation (i) may be simplified to:

a2 (FE)= Cd3 (ii)
Where: Cis a constant. Ms

Figs 1, 2, 3 and 4 show the standard deviations involved when concentrates

of Sn 75%, 63%, 30% and 10% are subdivided to sarnples of different weights and
having different sizes of the largest particles. These calculations refer to the 'fundamen-
tal error' on a thoroughly mixed sarnple.
Figs 1, 2, 3 and 4 also suggest that the recomrnendations of the practical sarnpling
scheme given in this paragraph are probably over cautious and that the major sarnp-
ling errors will be associated with drawing the primary sarnple.

109~--------~~~--~--L-~~----------~
0.01 0.1 1.0 10

d (cml

Fig. 1 Fundamental sampling errors (Standard deviation) for concentrates with 75% Sn (95%
SnQz ) and Iiberation slze 10 mm
 Ref.p. 170] 2.4 Practical Aspects 153

2.4 Practical Aspects

Some practical points in the sampling of tin ores are:
(i) Concentrates may increase or decrease in tin content with particle size. (ii) Sampling tools or
techniques which reject particular size fractions are almost certain tobe biased. Size analysis is
generally a more sensitive indication of bias than tin assay. (iii) Where a few !arge trucks or con-
tainers are to be sampled as one Iot, it is good practice to treat each truckload as a separate samp-
le and combine the dried fmes in proportion to the weight of the Ioad at the sample preparation
stage. Separate moisture determinations should be carried out and a proportioned moisture calcu-
lated for the combination. (iv) Care should be taken when milling to pass a given mesh size that
oversize material is not lost on returning to the mill. Because this is more difficult to mill, it is
almost certain to be of a different composition from the fines. (v) When milling high grade ores
in particular, take care not to lose the less dense gangue minerals as dust. (vi) In sample prepara-
tion, avoid the use of mild steel mills or bucking boards which may wear and contaminate the
sample. Introduction of one gram or more of steel into a 250g sampie in this way has been en-

IOOOkgr-------------r-------------r---------~-,

0.01 0.1 1.0 10

d (cm)
Fig. 2 Fundamental sampling enors for concentrates with 63% Sn (80% Sn0 2 ) and Iiberation
size 1 mm
154 Analysis of Tin Ores & Concentrates [Ref.p.170

countered in some exceptional instances by the author. (vii) Critical comparisons of mills, mi-
xers and sample dividers are available in the Iiterature [4, 9, 10]. Large mills should be easily
cleaned and enable complete recovery of the sample; for sample preparation ring mills of the
'Tema' type are satisfactory, although for samples smaller than 50g agate mortars are preferred.
Spinning riffles are the most accurate means of sample division [4, 9 ], but almost all other means
are acceptable for tin concentrates. Sampie mixers should be thoroughly tested before use, as so-
me may actually induce Segregation. Rolling the sample on a plastic sheet, followed by quartering
is a reliable means of dividing 5 kg of concentrate or Jess. Care should be taken to avoid loss of f"mes
by vigorous mixing.

2.5 Determination of Moisture

This should be carried out on 10 - 20kg of material obtained from the primary
sample. If this is not available immediatelyaseparate moisture sample of about

IOgL------L--~~-L---L--~--~~----------~
0.01 0.1 1.0

d (cm)
Fig. 3 Fundamental sampling errors for concentrates with 30% Sn (38% Sn02) and Iiberation
size 0.1 mm
 Ref.p.170] 2.5 Determination of Maisture 155

1% of the Iot weight should be taken and reduced to 10- 20kg. Moisture is deterrnin-
ed as a weight loss on heating in an oven at 105°C ± 0.5°C.
Some low grade concentrates may releaseeiemental sulphur which sublimes inside
the oven. This can be detected by smell and by yellow deposits of sulphur in the oven
flues. In such cases the only solution is to make sure that the sample is heated to con-
stant weight and that the dried material for the assay sample is heated to constant
weight at the same temperature.
It is good practice to check the moisture deterrnination by recording the weight
loss on drying fines for the assay sample. Agreements to within 0.3% moisture are ob-
tained fairly easily; the moisture content of the assay sample will always be lower as
a result of milling, dividing etc.

~9~~~~--~~~~~----~----------~
0.01 0.1 1.0 10

d (cm)

Fig. 4 Fundamental sampling errors for concentrates with 10% Sn (12.6% Sn0 2 ) and Iiberation
size 0.01 mm
156 Analysis of Tin Ores & Concentrates [Ref.p.l70

3. Pretreatment of Sampie
Removal of impurities by preliminary treatment of tin concentrates before dissolu-
tion is traditional practice which is not usually followed at present. The following
treatments are of value in special circumstances, usually for the determination ofless
than 5%Sn.

3 .I Roasting
Arsenic may be removed by roasting at 500 - 700°C for 30 min [ 11] although this
should not be necessary for volumetric assays involving a peroxide fusion. Sulphur
may give rise to undesirably vigorous fusion with sodium peroxide when present in
stannite concentrates or flue dusts and may be removed by roasting although this is
not absolutely necessary (see below). In the author's opinion, roasting of concentra-
tes should be avoided as tin is easily lost at red heat as the volatile sulphide.

3.2 Nitric Acid Treatment

Concentrates may be moistened with nitric acid and evaporated to dryness to oxi-
dise sulphur prior to sodium peroxide fusion or reduction with hydrogen or ammonia.
This overcomes the objections of vigorous oxidations with peroxide fusions and pre-
vents Iosses of volatile sulphides with reductive decompositions. Nitric acid oxidation
is invariably preferable to roasting for overcoming the effects of sulphur, even so, it
is very rarely necessary even with concentrates containing 30% sulphur.
Preliminary treatment of concentrates with nitric and hydrochloric acids followed
by flltration and fusion of the residue has been traditionally used to remove Bi, Cu, Ge,
Mo, S and V. In practice, 0.3 - 5 g of sample are evaporated to dryness with 1Oml HN0 3 ;
the residue issimmered for 10 min with 100m! of 5% HN0 3 and filtered on a Whatman
42 paper. The residue and filter are removed, dried, ashed and subjected to the decom-
position proper. This approach suffers from the objections that eiemental sulphur
should be picked out of the 5% HN0 3 solution and that tin Iosses to the filtrate are
probable.

3.3 Hydrofluoric Acid Treatment

Removal of silica by fuming 0.2 - 5 g of concentrate with 1Oml of HF and a few
drops of conc. H2 S0 4 may be necessary with siliceous ores where serious precipitation
of silica in acid solution creates a problern [36, 37]. Slight precipitation may be over-
come by addition of a few drops of HF to the acid solution obtained after fusion.

4. Decomposition Procedures

4.1 Fusion Methods

Cassiterite is incompletely attacked by alkali carbonates, hydroxides or borates
and if present as !arge particles may be almost unaffected.
(i) Sodium peroxide fusion is widely used for the decomposition of allgrades of tin
concentrate and is particularly useful for medium and low-grade ores (below 50% Sn),
for which reductive attacks are less suitable. Fusions are carried out in iron, nicke! or
 Ref.p. 170] 4.1 Fusion Methods 157

zirconium crucibles of approximately 40ml capacity over a Meker burner; a single

Bunsen burner is not usually adequate. In 1951 Petretic [12] reported the superior
resistance of zirconium metal to attack by malten sodium peroxide. Systematic stu-
dies on crucible materials have been carried out by Blake andHolbrook [13] and
Beleher [ 14] with the conclusion that zirconium is an outstanding first choice. This
author finds the service life of zirconium crucibles to be of the order of several thou-
sand fusions compared with about five fusions for iron or nickel. Where zirconium is
not available, iron crucibles are preferable to nickel.

WEIGHT
LOSS
(mg)
ISOOr---------------~--------------~------------~

600 700 800

TEMPERATURE (°C I

Fig. 5 Weight loss (rng/5g of sodiurn peroxide) against ternperature for crucibles of various
rnaterials [ 13]

Fusion with sodium peroxide alone is very effective with cassiterite ores but is excep-
tionally corrosive towards iron or nicke! crucibles. It is recommended that 0.3 - 2g of
ore be weighed on to 1.5g of sodium carbonate, lOg of sodium peroxide added and the
solids mixed throughly with a knife or wire. After brushing any adhering solids from the
knife into the crucible, lg of sodium peroxide is added as a cover and the mixture heated
over a low flame. Just before the melting point the peroxide darkens in colour; at this
point the crucible should be moved about to avoid 'hot spots'. As melting takes place
the crucible should be moved and finally swirled when the mass is completely malten.
The burner should be turned up until the melt is a dull cherry-red; continue heating and
swirling for a full 5 rnin. Before cooling, the melt should be exarnined for complete fusion.
Incomplete fusion should always be looked for after the melt has been leached
first with water then dissolved in hydrochloric acid. Clean, high-grade ores are often
resistant to fusion and may require prolonged fusion with up to 25 g of sodium pero-
xide. Cassiterite concentrates of particle size greater then B.S. 150 mesh (104p.rn
sieve aperture) require careful, prolonged fusion.
158 Analysis ofTin Ores & Concentrates [Ref.p. 170

Sulphide ores of up to 25% sulphur may be decomposed by the above fusion

method if care is taken avoid 'hot spots' at the melting point and to swirl the crucible
thoroughly. lf this is still ineffective, the sample should be weighed out on to 1.5 g
sodium carbonate as before, lOg of sodium hydroxide pellets added and the mixture
fused. Sodium peroxide (5 g) should be added cautiously to the melt insmall portians
and the fusion completed as usual. Alternatively fusions with Na 2 C0 3 /Na 2 0 2 mixtures
(2: 1) are much less vigoraus than peroxide alone.
Marvin and Schumb [ 15] mixed a 1 g sample with 15 g of sodium peroxide and 1 g
of sugar charcoal in a 40ml nicke! crucible. The crucible was surrounded in cold,
flowing water whilst the contents were ignited.
(ii) Freibergian Jusion - using mixtures of alkali carbonates and sulphur has been
described by Kaliman [ 16] as leaving a residue of insoluble carbonates and hydroxides.
Tin is converted to soluble thiostannate SnS~-:
The sample is mixed with six to eight times its weight of powdered sulphur and
Na 2 C0 3 or K 2 C0 3 (3 :5). The mixture is covered with 2g of the flux and heated in
a covered porcelain crucible over a low flame for 15 - 20 min during which time an al-
kali polysulphide is formed in the flux. The temperature is then raised for a further
10 - 15 min to form meta! sulphides. The crucible is cooled slowly to avoid cracking.
When the contents are leached with hot water and flltered, As, Ge, Mo, Sb, Sn, V and
Ware present in solution. The residue should be washed with 1% Na 2 S solution then
with hot water. To remove sulphur, the solution may be treated with sodium sulphite,
potassium cyanide or hydrogen peroxide [38, 39]. Acidification precipitates the me-
tals as insoluble sulphides although tin may be retained in solution in the presence of
fluoride or tartrate [40].
Freibergian fusion has been used [40] for ores containing canfieldite, cassiterite and
stannite. Difficulties are associated with high iron contents [ 16] where colloidal iron
sulphide may form. If the solution is greenish rather than golden-yellow, it should be
treated with 1 g KCl or NH 4 Cl and warmed until it clears completely [40].

(iii) Fluoride Jusion - complete attack of cassiterite is possible using a three to five-
fold excess of potassium hydrogen fluoride [ 17, 18, 19] or a threefold excess of so-
dium fluoride with a twelvefold excess of potassium hydrogen sulphate [20]. Platinum
crucibles are used and excess fluoride may be removed by heating with H 2 S0 4 [ 18]
or hot H 3 B0 3 [ 19]. In a11 cases, fumes of HF are evolved in copious amounts and
extreme care should be taken even if an efficient fume cupboard is used. In the early
stages of fusion it is advisable to heat at a low temperature after melting- KHF 2 will
decompose to KF and HF; the melt will gradually solidify. Then raise the temperature
to 700- 800°C and heat strongly until the melt is clear.
(iv) Reductive Jusions - alkali hydroxides used alone give incomplete attack on cassi-
terite [40]. Complete decomposition has been claimed for small particles ofless than
30,um diameter [25] or if an iron crucible is used [ 17].
Fusion of 0.5 - lg of tin concentrate with I 0- ISg NaOH and 0.05g carbon at
red heat gives complete attack in a nicke! or silver crucible [21, 22]. Similarly, addi-
tions of other reducing agents to alkali fusions have been advocated and include:
50- IOOmg ofNaCN (23], 0.2- O.Sg zinc [40] and sodium meta!. This author's ex-
perience has been that low or high-grade tin concentrates (20 - 78% Sn) of less than
76,um partide diameter are incompletely attacked by alkali fusion. Additions of 0.2 -
1 g of zinc allow complete attack, however, the melt spits continuously as hydrogen
 Ref.p. 170] 4.2 Reduction Methods 159

is evolved; great care must be taken to avoid losses and as a clear melt is never obtain-
ed it is impossible to ascertain if fusion is complete. Sodium peroxide fusion is by far
superior.
Fusion with sodium or lithium tetraborates or metaborates in carbon crucibles has
been used for tin concentrates in conjunction with X-ray fluorescence spectroscopy
[24 ].
Potassium cyanide fusions are descended from the dry assay procedures of antiqui-
ty when 20g or so of concentrate was fused in a fireclay pot with 40 - lOOg of sodium
or potassium cyanide [17]. For volumetric assay it is sufficient to fuse 0.5 g of concen-
trate with 3 g of potassium cyanide in a porcelain crucible [26, 27]. Flux is removed
by boiling with water and metallic tin is filtered off. It is usual to carry out an acid
cleaning procedure beforehand with HCl and HN0 3 ; sulphide ores are oxidised first
by evaporation to dryness with HN0 3 • Corrections must be established and applied
for tin losses in the acid cleaning Solution, the cyanide flux, the crucible and Iid. A
volumetric assay is carried out on the metallic tin obtained and although this may be
a simplified procedure, omitting separations and possibly reduction steps, there appe-
ars to be little advantage over the conventional peroxide fusion approach. As an al-
ternative, the tin button may be weighed and impurities determined spectrographically.

4.2 Reduction Methods

Some methods which use reductive fusions have been described already in Sec-
tion 4.1; this section describes the so-called "dry" reductions.
(i) Reduction with Hydrogen or Ammonia- 0.3- O.Sg sample is weighed into the crucible
shown in Fig. 6, containing approximately 3g of lime (CaO). The charge is mixed thoroughly
using a knife or wire and is covered with a further 2g of lime. Alternatively, the mixed charge
may be placed on a bed of lime in the crucible then covered as before. The crucible is supported

~H 2 orNH 3

LI ME MIXED CHARGE

Fig. 6 Crucible for hydrogen/ammonia reduction of tin concentrates

on a triangle and is heated over a Meker burner to about 600°C (temperature of the charge) for
5 min, then hydrogen or ammonia is led in at 1 - 2 cu.ft/hr/assay. The temperature is raised to
800 - 900°C for a further 30 min and allowed to cool with gas flowing. When cool, the residue is
knocked out into a 250m! beaker, moistened with water and 40ml concentrated HCI added. The
beaker is warmed on a hotplate for 1 hr or preferably left overnight. The crucible is washed out
with concentrated HCI into the beaker and a little saturated potassium chlorate solution added
to oxidise and dissolve metals present. The solution should be at 40 - 55°C at this stage. Add 1 g of
iron powder and c_ontinue with the assay as detailed under the Ni or Al reduction methods in sec-
tion 5.1 of this chapter.
160 Analysis of Tin Ores & Concentrates [Ref.p. 170

With very pure concentrates it may be acceptable to eliminate the use of iron powder
completely and proceed directly with the reduction after adding 20ml HCI.
Standardsaremade from 0.3g tin dissolved in 30ml HCI and KC10 3 with reduced
lime blanks added. Hydrogen or ammonia are interchangeable for this procedure, alt-
hough a fume cupboard must be used with the latter. Gas flows of 0.8 - 2.0 cu.ft/hr/
assay give complete recoveries. It is important to cool with a flow of reducing gas as
reoxidation occurs easily. Instead of lime, it is possible to use either calcium hydroxide
or calcium carbonate - ignition before use is unnecessary but these must be free from
sulphur impurities which tend to give slightly lower results; presumably by loss of
volatile stannous sulphide. A small quantity of HF may be added to assay solutions
before treatment with iron to dissolve silica if this appears in suspension.
(ii) Reduction with Metals- the Beringer assay is based on reduction of a tin concen-
trate with zinc powder at 950°C. This has been modified by Beringerand Stephens
[28).
Afteracid cleaning with HCl and HN0 3 (if necessary), the residue or 0.5g of concentrate is
mixed with 0.25g Na 2 C0 3 and 6g zinc dust. This is placed in a fireclay crucible lined with zinc
oxide and is covered with zinc oxide. A mica sheet covers the charge and is weighed down with
an iron washer or a small cupel. Alternatively, an inverted crucible Iid may be used instead of a
mica sheet. The crucible is heated in a muffle furnace to red heat (600- 750°C) and then for a
further 10 min. When the crucible has been removed and cooled, the Iid may be removed and
the contents added to a 250 ml flask containing 20 ml of water. The crucible and Iid are washed
out with 70ml of concentrated HCI which is added to the flask. A bung and delivery tube are
fitted and the flask heated to boiling. When all the meta! has dissolved, the flask is cooled under
co2 and titrated as usual.
The use of sodium carbonate is claimed [28] to aceeierate the reduction process such
that it may be carried out at red heat rather than 950°C. In the above procedure there
are no provisions for removal of impurities, other than by acid washing. Gangue ele-
ments remain in the assay solution as an insoluble residue, and complete attack cannot
be inspected easily.
More recently Mischenko and Kiparisova [30] decomposed tin concentrates by
sirrtering 0.3 g with 3 - 4 g of zinc dust and ammonium chloride (1 :2 v/v) in a sealed
tube at 600°C. Sulphide samples were ignited before sintering.
Hempel [29] used reduction by either metallic sodium or magnesium to reduce
starrnie oxide but no applications have been developed.

4.3 Sublimation with Ammonium Iodide

Sublimation with ammonium iodide is a very convenient method of separating
small quantities of tin from large quantities of gangue. Forthis reason it is particular-
ly suited to the analysis of ores before concentrating and tailings [31 - 35].
In most reported procedures 0.2- 0.5g of sample is mixed with 0.5 - 2g of NH 4 I and heated
at 450- 550"C for ab out 20 min. Stannic iodide condenses on the cooler parts of the glass tube.
The sublimate and residue is leached with 50 ml of warm 2M HCI, flltered and tin determined on
the filtrate.

This separation has been used in conjunction with several finishes including: spec-
trophotometric [31], volumetric [32) and atomic absorption [34, 50). Details of auto-
matic apparatus [50] for the fusion are given in the Atomic Absorption Spectroscopy
chapter tagether with the method of Bowman [34 J. With the volumetric finish [32),
it is recommended that the residue and sublimate are washed with 20ml of water,
8 ml of 10 ,ug/ml ferric solution and aqueous ammonia until strongly alkaline to remo-
ve copper and other impurities. The residue is then leached with 50ml concentrated
 Ref.p. 170] 5.1 Determination ofTin 161

HCI; the solution is diluted with 150ml of water, reduced with nicke! and titrated
against 12 or KI/KI0 3 .
Cassiterite is completely decomposed by heating with NH 4 1, however, tin present
in a silicate lattice is unaffected. For this reason a prior decomposition by heating to
dryness with HF/HN0 3 (2: 1) has been recommended (31].

4.4 Decomposition by Acids

The most successful means of decomposing tin concentrates with mineral acids is
by treatment with HF in a PTFE (polytetrafluoroethylene) bomb:
A 0.5- lg sample is weighed into a PTFE vessel and 20m! of concentrated HF added, leaving
a headspace of at least 20 ml. The PTFE Iid is put into place and the vessel is heated in a stain-
less steel pressure vessel at 200°C for 12 hours. The vessel should be cooled for several hours be-
fore opening.
The use of a PTFE bomb is necessitated by the high temperature required for de-
composition and the volatility of tin fluorides. Acid attack has an advantage over fu-
sion methods in that !arge amounts of dissolved solids are absent from the assay solu-
tion. The extent of decomposition will vary according to the type of rock exarnined.
The technique has been used in the author's laboratory for the determination of alkali
metals in low and medium grade concentrates by atomic absorption spectroscopy [5].
A wider range of minerals may be decomposed by using mixtures of equal volumes
of HF with either H2 S04 or HCI04.
Wood tin (hydrated tin oxide) and stannite (Cu 2 FeSnS 4 ) have been [41] selecti-
vely dissolved from ores and concentrates by heating 0.5 - 1g of sample with 1OOml
of concentrated sulphuric acid for 1 hour at just under the boiling point of the acid.
Stannite may be dissolved [41] by refluxing 0.5 - l.Og of sample with 2ml ethanol
saturated with bromine and 5 ml of carbon tetrachloride. The residue is washed with
lOml of ethanol and the ftltrate evaporated at low temperature to remove most of
the bromine. Tinhydroxideis precipitated by addition of ammonia. Zverev and
Petrova [42] reacted 0.5- 2g of sample for 2 1/ 2 hours with 25m! of carbon tetrachlo-
ride, 1Oml of bromine and 1g of sulphur to dissolve stannite. Tin was extracted from
the organic layer by shaking with an equal volume of 1M H 2 S0 4 •
Stannite has also been selectively dissolved by the action of potassium chlorate in
concentrated HCI (43] or by evaporation nearly to dryness with 1 g ofNaN0 3 and
70ml of glacial acetic [44]. In the latter procedure the beaker is washed down with
5 ml of concentrated hydrochloric acid and 50ml of water. If a volumetric assay is to
be undertaken tin must be first separated from nitrate by precipitation with ammonia.

5. Analytical Methods

5.1 Determination of Tin

Lister and Ga/lacher [45] conducted a comparative survey of the analysis of four
tin ores by twenty laboratories using a variety of techniques. The ores consisted of a
75.7% Sn comniercial concentrate, and mixtures of this concentrate with quartz to
give 6.4% Sn, 0.63% Sn and 0.08% Sn. Their results are summarised in Table 4. The
laboratories involved included government geological surveys, mining companies, me-
162 Analysis of Tin Ores & Concentrates [Ref.p. 170

tallurgical companies and commercial assay laboratories. Techniques included volume-

tric, gravimetric and X-ray fluorescence for all samples with colorimetric, polarographic
and ernission spectrochernical methods for the 0.63% Sn and 0.08% Sn samples. Volu-
metrieanalysis was the most popular method and was fairly reliable. Polarography and
colorimetry gave fairly good agreements at low levels with volumetric methods. Gra-
vimetrie and X-ray methods gave widely scattered results.
A survey by Faye, Bowman and Sutarno [46] included 237 results on a complex
CuPbSnZn ore MP - 1 issued by the Canadian Mineral Seiences Division (Mines
Branch) Ottawa. This work suggested that the metal used as reductant in the volume-
tric determination influenced the assay; Steger [48] obtained results of 2.44% Sn,
2.42% Sn, 2.40% Sn and 2.39% Sn using aluminium foil, iron granules, nickel powder
and Iead shot respectively on MP - 1. The differences were said to be significant alt-
hough the reasons for this were not clear.
The survey conducted by the Warren Spring Labaratory [4 7] involved volumetric
methods used by European tin smelters (Table 4). The rather better standard deviat-
ions obtained in this survey probably resulted from the restricted range of technique
and the fact that the laboratories concemed used the methods routinely under close
supervision. Good agreement was obtained with clean, high-grade concentrates and
"dirty", low-grade concentrates. Rather wider scatter was obtained with concentrates
containing more than 1 % tungsten or with 1% niobium. The latter was particularly
difficult to fuse with sodium peroxide.
The following procedures have been used routinely for the assay of a wider variety
of tin ores, particularly where the impurities present are known only approximately.
It is probable that for weil characterised ores, more abbreviated methods could be
employed.
(i) Peroxide Fusion and Nickel Reduction Method.
Suitable for Sn 5 · 40% (1 g sample) and Sn 40 · 78% (0.5 g sample) in concentrates
containing Cu 2% and W0 3 5%.

Table 4. Interlaboratory Surveys of Analysis of Tin in Ores and Concentrates

No.of No. of Mean Median Std.Dev. a Coeff.Var. Ref.

Labs Assays %Sn %Sn %Sn %

19 45 0.081 0.077 0.022 26.8 45

18 46 0.629 0.63 0.040 6.4 45
19 49 6.40 6.43 0.262 4.1 45
18 47 75.70 76.0 0.85 1.1 45
5 19 49.05 0.332 0.67 47
5 22 43.83 0.245 0.56 47
5 18 57.61 0.118 0.20 47
5 19 75.55 0.047 0.06 47
5 20 45.47 0.098 0.22 47
5 23 21.37 0.082 0.38 47
5 24 30.59 0.029 0.10 47
5 20 16.42 0.035 0.21 47
5 19 24.29 0.105 0.43 47
5 19 73.97 0.237 0.32 47

~tandard deviations of Ref 4 7 are calculated from the mean values obtained by each of the five
laboratories
 Ref.p. 170] 5.1 Determination ofTin 163

Mix 0.5g or l.Og of sample with 1.5g of Na2 C03 and lOg of Na2 0 2 in a zirconium (prefer-
able) or iron crucible. Cover with 1 g of Na 2 0 2 and fuse as described in section 4.1 of this chap-
ter until decomposition is complete. Cool and place the crucible in a covered 400ml beaker con-
taining 100m! of water. Leach the melt carefully then wash the crucible out with 100m! of con-
centrated HCI. Finally wash the crucible with water and inspect for complete dissolution. Add
a few crystals of KI and 3g of iron powder, heat at approxirnately 70°C to dissolve the iron pow-
der but do not boil. When the iron has almost dissolved, filter into a 500 ml round flask through
a small cotton wool plug. Wash with two 20m! portians of hat 2% HCI and reserve the filtrate.
Transfer the plug back to the original beaker and dissolve the residue with 30m! of concentrated
HCI and 0.5g KC10 3 . Heat to remove excess chlorine, add 3g of iron powder and heat at 70°C
until the iron has nearly dissolved. Filter through a cotton wool plug into the 500ml flask con-
taining the first filtrate. Wash with six lOml portians ofhot 2% HCI and dilute to 300m! with
water. Insert a bung carrying an activated nicke! coil, boil gently for 60 min and cool under a
supply of carbon dioxidein a water bath. When cold, remove the coil, wash with the minimum of
water, add two or three marble chips and starch indicator. Titrate rapidly with N/6 potassium
iodate to a permanent blue colour.
Standardise by dissolving 0.3 or 0.4g of pure tin foil in 30m! of warm concentrated HCI and
2ml of 0.1% SbCl 3 solution. Add a blank fusion leached with 100m! of water and 70ml of con-
centrated HCI and proceed as above.
N/6 Potassium iodate. Dissalve 6.0g of KI0 3 and lOOg of KI in water. Add 2g of NaOH and
dilu te to 1 litre.
Notes
1. The nicke! coil should be activated by boiling in 1:1 HCI containing 5% N aCl.
2. Dissolution of the first cementate and reprecipitation by a second treatment with iron pow-
der is unnecessary with low grade ores containing less than about 2% total base metal irnpurities.
3. The method may be applied in the range 0.1-5% Sn by using a 5g sample fused with 20g
of Na 2 0 2 and titrated with N/50 iodate.
4. The assay may be left after dissolution of the fusion product, or just before insertion of the
nicke! coil.

(ü) Peroxide Fusion and Aluminium Reduction Method

Suitable for Sn 5-40% (1 g sample) and Sn 40- 78% (0.5 g sample) in concentrates
containing Cu < 2 % and W0 3 < 2 %.
Foilow the method for nicke! reduction up to the point where the nicke! coil is inserted into
the flask. Add 20m! of concentrated HCI and 3g of aluminium instead. Warm until the reaction
starts and shake continuously. When the reaction ceases, add 40ml of concentrated HCI, 0.5 g_
of aluminium and fit a Göckel trap containing saturated NaHC0 3 solution. Allow to react, boil
to dissolve tin sponge, cool, rinse down the inside of the flask with the minirnum of water, add
two or three marble chips and starch indicator. Titrate rapidly with N/6 potassium iodate to a
permanent blue coiour.
Not es 2, 3 and 4 of the previous method also apply.

(iii) Hydrogen or ammonia decomposition

Described in section 4.2 of this chapter, reductive decomposition is valuable for
the analysis of clean, high-grade ores where complete fusion using sodium peroxide
may sometimes be difficult. This is particularly true ifNb or Ta are present at the
level of a few percent. Reductive decomposition is likely to give low results with
lew-grade, complex ores of Sn 35% or less.

(iv) Copper/Silver Concentrates

If Cu> 3% or Ag> 0.5 %, these elements should be removed or low results are likely:
Dissalve 1 g of sample by fusion with 1.5 g sodium carbonate and 11 g sodium peroxide. Be
particularly careful as copper/tin ores contain !arge amounts of sulphur and either slow heating
or fusion with 3g Na 2 C03 and 3g Na 2 0 2 with a 1g cover of Na 2 0 2 may be necessary. Dissalve
the cooled melt in 100m! water and 100m! of concentrated HCI, add 10m! of 10% ferric ammo-
nium sulphate and 1g of potassium chlorate. Boi! for 10 min, cool and add ammonium hydroxide
until the solution is deep blue. Heat to boiling, filter hat through a Whatman 40 paper and wash
twice with 20m! of hat 2% ammonium hydroxide. Dissalve the precipitate in 90ml of concen-
164 Analysis of Tin Ores & Concentrates [Ref.p. 170

trated HCl. If the solution is more than slightly blue repeat the addition of potassium chlorate
and ammonia. lf not, continue with the nicke! or aluminium reduction methods by adding pot-
assium iodide and iron powder.
Not es
1. Hydrofluoric acid should not be added to dissolve silica when the fusion products are dis-
solved in HCJ. This may render tin soluble and hence give low results. Fluorides in the sample
are masked by the use of iron as the coprecipitant.

(v) Concentrates containing Nb, Ta or W.

The errors caused by relatively large amounts of Nb or Ta present in the sample are
unlikely to compensate for the Iosses which are almost unavoidable in the following
procedure given by De Carvalho [49]. This may also be used for the removal of tungsten
which will obscure the end-point if present in large amounts.
Fuse 0.5 -LOg of sample with 5- 8g potassium pyrosulphate (K 2 S2 0 7 ) in a silica crucible.
Cool, then warm with 25 ml of 25% tartaric acid and wash with 80 ml of hat water containing
5ml of concentrated H 2 S0 4 . Add saturated H 2 S solution until precipitation is complete or bubb-
le the gas for 20 min. Allow to settle for 1 - 2 hours and filter on a Whatman No. 3 paperwashing
with 2% H 2 S04. lgnite the residue in an iron or zirconium crucible then fuse with sodium perox-
ide and continue with either the nicke! or aluminium reduction method.

( vi) Ores containing Sn < I%

Volumetrie methods -the direct classical tin assays already given may be applied down
to about 0.1% Sn by fusing 5g samples with 20g ofNa 2 0 2 and titrating with N/60
iodate. Precipitation of silica can offer problems and a preliminary separation may be
required. Fuming with HF/H 2 S0 4 [36, 37], sublimation with NH 4 I [32], distillation
from HBr/H 2 S0 4 /H 3 P0 4 [53], co-precipitation with Mn0 2 [51, 52] or Be(OHh
[32] may be used. At low Ievels, the interference ofiron becomes significant and,
therefore, iron crucibles should be avoided. Where possible, the amount of iron used
for cementation should be reduced to 1 gor eliminated entirely. A 'double iron' ce-
mentation is usually unnecessary. Determinations of 0.002% Sn in iron ores [51, 52]
using precipitation with an Mn0 2 collector probably represent a limit to the volume-
tric technique at present. Sublimation with NH 4 I (section 4.3 this chapter) followed
by cementation, nickel reduction and titration is probably the most convenient and
reliable approach.
Photometrie methods - Procedures for the determination of tin in geological
materials have been outlined in Chapter 5 -Photometrie Methods. Phenylfluorone
(2, 3, 7-trihydroxy-9-phenyl-6-fluorone) has been used [32] following treatment with
HF to remove silica and Na 2 0 2 fusion. The melt was leached toseparate ferric hydro-
xide before acidifying. Tin was then precipitated by addition of ammonia solution
in the presence of EDTA and a beryllium coprecipitant. After dissolution in H 2 S0 4 ,
Sn(IV) was determined using phenylfluorone. With a 1 - 2g sample a precision of
± 0.006% Sn was claimed for up to 0.5% Sn. Agterdenbos and Vlogtman [31] decom-
posed silicate rocks with a mixture of HF /HN0 3 (2: 1) then heated with NH 4 I. After
dissolution, tinwas extracted into benzene from a iodide solution, stripped into 0.25M
H 2 S0 4 and determined with phenylfluorone. Pollock and Zopatti [54] and Smith[55]
used phenylfluorone methods for tin in complex silicates, whi1st Nazarenko and Lebe-
deva [56] used p-nitrophenylfluorone for amounts greater than 0.0001% Sn in low
grade ores. GaUein ( 4'5' dihydroxyfluorescein) has been investigated by a number of
groups [57- 61] for the determination of tin in minerals and mining products- details
of some of these methods are given in Chapter 5 -Photometrie Analysis. Varand [37]
treated 0.2 - 2 g sample (0.001 - 0.5% Sn) with 25 ml HF and IOml H2 S0 4 (I: 1) in a
platinum dish and heated to fumes twice to remove silica. The residue was dissolved
in water and ammonia solution added to precipitate tin. The residue after flltration
 Ref.p. 170] 5.1 Determination of Tin 165

was ignited at 500- 600°C, fused with 0.5 g Na 20 2 and 5 g NaOH, extracted with
hot water, acidified with H 2 S0 4 (1: 1) and filtered. The filtrate was treated with
2m! of 10% MnS0 4 and 1 rnl of 4% KMn0 4 solutions and boiled for 10- 15 min. The
precipitate ofMn0 2 was flltered off, dissolved in 1Oml of HCI (1: 1) and diluted to
25m!. An aliquot of 1- Sm! was neutralised with ammonia solution; lml of 2.5M
H2 so4 and 2m! of saturated thiourea Solution added to reduce Fe(III) and after
15 - 20 min, 1Ornl of ethanol and 2m! of ethanolic quercetin (I mg/ml) added. The
solutionwas diluted to 25m! and measured photometrically at 420- 450nm after 15
min. Toluene-3, 4-dithiol forms a magentared precipitate with stannous salts on war-
ming and has been used for the determination of tin in geological materials [62]; a de-
tailed procedure is given by Sandeli [63]. Salicylidene aminobenzene [64] and butyl-
rhodamine S [65] have also been used but may be difficult to obtain commercially.
Scherbov et al. [66] decomposed 0.1 - 0.5 g of sample with HF /H 2S04, fused the
residue with Na 2B4 0 7 /Na 2C0 3 , leached the melt with H2S04 (1: 10) and diluted
to Süml with the same acid. An aliquot containing 0.05 - 5Jlg Sn was extracted into
benzene after addition of 4mfof 10% KI solution and water. Antimony may be strip-
ped from the extract by washing with 10m! of 0.2M HCI and tin by washing with
10m! of O.OSM HCI. To each extract was added 1ml of 0.05%morin and the two me-
tals determined fluorimetrically.
Polarography- In 6M HCI at 25°C the half wave potential of tin(IV) at the drop-
ping mercury electrode occurs at- 0.52V vs S.C.E. For simple silicate matrices the
direct method of Love and Sun [67] may be applied : a 1g sample is fused with Sg
of Na 20 2 , leached with 150m! of boiling water and diluted to 200m! with water.
After allowing any residue to settle, 25 ml is pipetted into a SOml volumetric flask
and diluted to volume with concentrated HCI. Sampies containing more than 2% tin
require the addition of 0.1 ml of 2% gelatin solution before dilution. Iron hydroxide
remairring in the leach residue after fusion is said to retain Iead, but not tin which is
present as soluble stannate.
Bond et al. [68, 69] polarograph tin in SM HCI after fusion with NaF and H 3 B0 3 •
Limits of detection were 0.0005% Sn (and 0.00005% Sn by anodic stripping voltam-
metry). Interfering elements [70] include Tl, W, Pb and to a lesser extent Ti and As:
V and Ge distort the wave. Tin may be separated after evaporation with HN0 3 and
fusion with Na 20 2 , then by precipitating with ammonia from a solution containing
excess EDTA. Blyum and Zyryanova [71] fused with Na 20 2 , dissolved in HCI, preci-
pitated tin with ammonia and dissolved this in H 2S0 4 /HCI/H 3 P0 4 before distilling
tin as the bromide. The distillate was treated with FeCI 3 and ammonia. The precip-
itate was dissolved in 1:1 HCI, reduced with 0.2g of iron powder, deaerated with hy-
drogen and polarographed after addition of gelatin. This time-consuming method was
recommended [71] for 0.005- 0.1% Sn in ores of any kind. A rather similar method
[72] for 0.025 - 1.5% Sn uses separation by distillation as the bromide, coprecipitation
with aluminium hydroxide and polarography in 2M HCI/15% NH4 Cl solution. Weiss
[39] fused 0.5 - 2.5 g of sample with a sevenfold excess of KNaC0 3 /S (2: I) in a cov-
ered porcelain crucible for 20 min at low heat then strongly for 15 min. The melt was
then boiled with 150m! of water and lüg NaOH added. The solutionwas oxidised
with 30% H 20 2 and 5 ml added in excess. After boiling to remove H 20 2 , 30m! HCI
were added and 5% KMn0 4 until pink. The solutionwas treated with 100m! ofhot
6M HCI and 0.5 g of iron powder. When the iron had dissolved O.Srnl of saturated
HgCI 2 and 15m! of 50% NaH 2 P0 2 were added and the solution boiled. A small
amount ofNaHC0 3 was added to generate a C0 2 atmosphere, 3m! of 5% gelatin
added and the solution diluted with 6 M HCI to 250m!. A portion of the solution was
166 Analysis of Tin Ores & Concentrates [Ref.p. 170

polarographed after bubbling nitrogen and the method was said to be suitable for the
determination of 0.01 - 10% Sn in ores containing Iead.
Atomic Absorption Spectroscopy - the rather poor sensitivity of atomic absorp-
tion for tin invariably demands the use of a separation precedure to remove the bulk
of the sample matrix. Sublimation with NH 4 I [34, 35, 50, 73] is convenient and al-
lows determinations in the range 0.02% Sn upwards. Separation by electrolysis [74]
of an HCl/hydroxylamine solution containing copper and Iead following a Na 2 0 2 fu-
sion gives a Iimit of detection of 0.0002% Sn. (See Chapter 8, Table 6).
D.C. Are Spectrography- Table 5 of the Chapter on Emission Spectrography sum-
marises eleven methods for tin in ores and silicate samples. Under suitable conditions
as little as 111g/ g Sn may be detected directly. Precision is usually poor ( coefficient of
variation typically 20%) andin the correlation programme of Listerand Ga/lacher
[45] low results were generally obtained by arc spectrographic methods.
X-Ray Fluorescence - This is used widely throughout the world by mines and geo-
logical institutions and the reader is referred to the Chapter on X-Ray Fluorescence
Spectroscopy.

Other methods -Neutron activation of 1OOmg samples has been used for the
determination of traces of tin in granites and ores [75- 78]. Irradiation times varied
from 10 min with a flux of 10 16 neutrons/m 2 /sec [75] to 14 days at 10 18 neutrons/
m 2 /sec [76]. All methods required a decay period of a further 24- 28 hours. Amounts
of tin down to 0.1 11g were reported. Mössbauer spectroscopy has been used to deter-
mine tin in the range 0.1 - 1% with a coefficient of variation of 10% for 30 sec counting
times [79, 80]. Mass spectroscopy has been used for traces of tin in granites and ba-
salts after fusion with Na 2 B4 0 7 at 1000°C in the presence of graphite.
No account of the assay of tin in ores and concentrates would be complete with-
out mentioning the Vanning Assay. The account below is tak:en from Beringer's
'Textbook of Assaying' of 1912 and is one ofthe few printed descriptions ofthe
technique.
About one ounce (28g) of crushed calcined ore is weighed on to a vanning shovel having a con-
cave blade. The vanner stands in front of a tub of water and allows 30 - 40ml of water to flow on
to the ore. He raises the shovel and with an elliptical swirling motion causes the gangue mud to
become suspended in the liquid, which is run off into the tub. This is repeated until the water is
almost clear. About half as much wateras before is added but ajerk is introduced into the swirling
motion to create a wave which draws with it the lighter gangue and carries it to the front of the
shovel. The best of the "black tin" is then thrown weil up on one side of the shovel to form a cresent
(the "head ") leaving room to work with the "tailings". The tailings are crushed with a 2 lb hammer to
separate iron oxide and worked up with rather less water and a more vigorous, rapid motion. The
whole of the black tin is finally brought to the centre of the shovel and washed two or three tirnes
to remove traces of waste. The residue is dried, iron removed with a magnet and weighed to give
the yield of concentrate. The amount of tin is determined by running down the concentrate in a
fire und er potassium cyanide.

The vanning testnot only gave an estimate of the yield of tin after dressing and
smelting, but was a necessary part of the cyanide reduction assay which gives very poor
results with material containing 1ess than 50% Sn.

5.2 Determination of Impurity Elements

Kaliman [16] describes methods for the determination of Al, As, Bi, Ca, Cu, Fe,
Mg, Pb, S, Sb, Si, Ti, Wand Zn in Bolivian concentrates. It is this author's opinion
that the most satisfactory general technique for impurity and gangue elements is ato-
 Ref.p. 170] 5.2 Determination of Impurity Elements 167

mic absorption spectroscopy. This combines ease of operation with speed and free-
dom from interference.
Determination of Al, Bi, Cd, Cu, Fe, In, Mg, Pb, Sb, Si and Zn [5]
Weigh 1g of powdered concentrate on to 1.5g ofNa 2C0 3 in a zirconium crucible. Add lOg
of Na 2 0 2 , stir well and cover with 1 g of Na 2 0 2 . Fuse gently at dull red heat. Cool and place
crucible on its side in a 400ml beaker containing 100m! of water. When the reaction stops, remo-
ve the crucible and wash clean with water then with 100m! of HCI, finally rinse with water. Add
a few drops of HF to dissolve silica (using up to Sm! if necessary), add 2- 3g of potassium hydro-
gentartrate and dilute to 200m! in a volumetric flask. Dilute a further five times for atomic ab-
sorption.
Standards should contain 0.5 g of potassium hydrogen tartrate and a blank fusion solution car-
ried out as above. Conditions for the determination are given in Table 5.
Not es
1. The ranges in Table 5 may be exceeded at both ends, although precision is inadequate for the
higher Ievels of Cu, Fe and Pb.
2. Iron crucibles arenot recommended for the fusion as Bi, Cu and Sb are removed from solu-
tion by cementation.
3. Background correction for scatter is recommended for the detennination of Bi, Cd, Cu, Pb
and Sb.
4. Rotation of the burner may be required to reduce sensitivity.

Table 5. Conditions for Determination of lmpurities in Tin Concentrates by Atomic Absorption

Spectroscopy [5]

Element Range(%) Wavelength (nm) Standards (pg/ml) Flame

Al (0.2 - 2%) 309.3 2 20 N20/C2H2

Bi (0.05 - 0.5%) 223.1 0.5 - 5 air/C2H2
Cd (0.005- 0.1%) 228.8 0.05- 1 air/C2H2
Cu (1 - 10%) 327.4 10 -100 air/C2H2
(0.1 - 1%) 324.8 1.0 - 10 air/C2H2
(0.01 - 0.1%) 324.8 0.1 - 1.0 air/C2H 2
In (0.05 0.5%) 303.9 0.5 - 5 air/C2H2
Fe (1 -10%) 372.0 10 - 100 air/C 2H2
(0.1 1%) 248.3 1 - 10 air/C2H 2
Mg (0.1 - 1%) 285.2 1 - 10 N20/C2H2
Pb (1 - 10%) 261.4 10 - 100 air/C2H2
(0.1 - 1%) 283.3 1.0 - 10 air/C2H2
(0.01 1%) 283.3 0.1 - 1.0 air/C2H2
Sb (0.05 - 0.5%) 217.6 0.5 - 5 air/C2H2
Si (1 - 15%) 251.6 10 - 150 N20/C2H2
Zn (0.1 - 1%) 213.9 1.0 - 10 air/C2H2

Determination of Arsenic (above 0.5%) [16]

Weigh lg of concentrate into a 250m! beaker, add 20m! of HN0 3, 15m! of H 2S0 4 and evaparate
to strong fumes of S03. Cool, add 15 ml of saturated S0 2 water, evaparate to fumes, add 10m!
of water and evaparate to fumes once more.
Transfer to a distillation flask with a small amount of water. Add 45 ml of hydrazine sulphate
solution (10 g/1 hydrazine sulphate, 20 g/1 KBr) and 70ml of HCI. Immerse the outlet of the con-
denser beneath the surface of 250 ml of cold water in a 500 ml conical flask cooled in water. Di-
stil until the volume has been reduced to 75ml, add 40ml of HCI and distil again to 75ml.
Rinse the condenser into the conical flask, make alkaline with ammonia to methyl orange
then acid with HCI. Cool to below l5°C, add 8g of NaHC0 3 and titrate with 0.02N iodine solu-
tion using a starch indicator.
168 Analysis of Tin Ores & Concentrates [Ref.p. 170

Standardise against 0.05g As 2 0 3 dissolved in 10m! of 10% NaOH, then diluted to 250 ml, 100m!
of HC! added, neutralised with ammonia and acidified with HCI. Cool then and proceed as above.
1ml0.02N I2 = 0.00075g As
Determination of Arsenic (below 0.5%)
Weigh 0.2g of sample into a 250m! beaker, add 10m! of HN0 3 , 20m! of 1 : 1 H 2S04 and eva-
parate to fumes of S0 3 • Cool, add 20m! of water and 1g of ammonium oxalate and evaporate
again to fumes. Add 20m! water, break up solids thoroughly, transfer to a 200m! volumetric
flask and di!ute. Pipette an aliquot of this solution into a 250m! Quickfit conical flask (Fig. 7)
(use 10m! for 0.01-0.1% As, Sm! for 0.1-0.5% As). Add 50ml ofwater, 20m! of 1 : 1 H2S04,
2m! of 15% KI solution and 1 ml of 40% SnCI 2 solution. Stand for 10- 15 min then add 5g of
granulated zinc and assemble the apparatus immediately. The side arm should contain 8.0ml of
0.5% silver diethyldithiocarbamate in pyridine and should be shielded from direct sunlight. Leave
for at least 1 1/ 2 hours and measure the absorbance of the solution at 540 nm. Calibrate using
so!utions from 5- 50J.J.g As. Carry out a blank with each set of determinations. This is not appli-
cable to copper/tin concentrates.
Determination o[Calcium
Fuse 0.5g of sample with 1.5g of Na 2C0 3 and llg Na 20 2 in a zirconium crucible. Leach with
100 ml of water in a 400ml beaker and acidify with HC!. Remove crucible, rinse and add 1 g po-

/ 0 5°/o SILVER DIETHYL-

/ DITHIOCAP.BAMATE
IN PYRIDINE

COTTON WOOL SOAKED

IN SAT'D LEAD ACETATE
AND DRIED

Fig. 7 Apparatus for the determination of arsenic

tassium chlorate, boil for 10 rnin. Make alkaline with arnmonia, heat to boiling and filter hot
through a Whatman 541 paper reserving the flltrate. Wash thoroughly with hot water. Open the
paper and wash the precipitate into the original beaker with hot water. Dissolve the precipitate
in HCI and reprecipitate with ammonia. Filterhot into the original filtrate and wash with water.
Add 3.5g of ammonium oxalate to the filtrate, warm and boil for 1 min. Filter through a pulp
pad, wash eight times with hot water then wash pad and residue into a beaker with 150m! of wa-
ter. Add 10m! of 1 : 1 H2S0 4 , warm to 80°C for 5 min and titrate hot against 0.1N KMn04 SO-
lution to a permanent pink.
 Ref.p. 170] 5.2 Determination of lmpurity Elements 169

1 ml of 0.1 N KMn04 = 0.002804g CaO = 0.002004g Ca. Calcium may also be deterrnined in
an N 2 0/C 2 H2 flame by atomic absorption spectroscopy following Na 2 0 2 fusion and addition of
10g/llanthanum. In silicate samples the use of an air/C 2 H 2 flame is not recommended even in
the presence of lanthanum.

Determination of Fluorine
Fuse 0.2g of sample with a weighed 2.0g of Na 2 C0 3 and a weighed 4.0g Na 2 0 2 in a zirconium
crucible. (The use of zirconium does not affect the result). Knack the cooled melt into a plastic
beaker and wash the crucible out with 50ml of water and lml of HCI. Warmgentlyon a water
bath to dissolve soluble components and dilute to 200 ml in a volumetric flask. Filter a little of
this solution and pipette 10m! of filtrate into a 100m! Volumetrie flask. Acidify with HC! to
bromothymol blue, add 50ml of Complexing Buffer Solution and dilute to volume. (CBS con-
tains: 18g/11,2 diaminocyclohexane tetracetic acid CDTA; 20g/l NaOH; 300g/l sodium citrate;
30g/l NaÖ;adjusted to pH 6.0 with HCI).
Determine fluorine using a fluoride ion-selective electrode and standards in the range 10-s -
10- 3 M F. Standardsaremade from blankfusionstaken through the determination and with ad-
ditions of stock fluoride so!ution before the last dilution. Plastic volumetric ware and beakers
should be used throughout although glass Volumetrie flasks are permissible provided solutions are
immediately transferred to plastic bottles after dilution.

Determination of Iran
Take the precipitate produced by addition of ammonia in the calcium determination and dissol-
ve in 25 ml of HCJ. Wash the paper with 2% HCJ and heat to boiling. Add 150g/l stannous
chloride solution until the solution is colourless; add 3 - 4 drops in excess. Fit the flask with a
bunsen valve, cool in a water bath to 1s•c and add 15 ml saturated mercuric chloride solution.
Stand for 5 minutes. A silky white precipitate should be obtained. Dilute to 250m!, add 10m!
1: 1 H 2 S0 4 , Sm! of H 3 P0 4 and 8 drops of0.2% diphenylamine sulphonic acid. Titrate with
0.1 N K 2 Cr 2 0 7 from green to purple.
lml O.lN K2 Cr 2 0 7 = 0.005585g Fe
Alternatively Fe may be deten;üned by atomic absorption (see Table 5 ].

Determination of Silica
Fuse 0.5 - 1 g of sample in a nicke! crucible with 1.5 g of Na 2 C0 3 and 6g Na 2 0 2 . Cool and
leach with 50ml water. Acidify, and wash out the crucible with 25m! of HCI. Evaparate to dry-
ness and bake on a hotplate for 15 min. Cool, add 50 ml of HC!, 100 ml of water and boil. Filter
through a small pulp pad, wash with hot 2% HCI. Transfer the precipitate and pad to a porcelain
crucible and ignite at 900°C to constant weight. lf the precipitate is contaminated, transfer to
a platinum crucible and weigh. Add 3 drops of H 2 S0 4 and 5 ml of HF, evaparate to dryness, cool
and weigh. The loss is entirely due to silica.

Determination of Silver
Mix 5 - lOg of sample with 50 g of PbO, 20g of Na 2 C0 3 , 26g of borax glass and 6g of potassium
hydrogen tartrate. Transfer to a fireclay pot and cover the surface with borax glass. Heat in a
crucible fire until the action has completely ceased (approximately 900°C). Remave the pot,
pour off the slag into a mould and the meta! into a button mould. Return the slag to the pot
tagether with any slag adhering to the meta! add 30 g of PbO, 10 g of Na 2 C0 3 and 3 g of potas-
sium hydrogen tartrate and repeat the fusion. Prepare standards containing the same weight of
silver asthat expected in the assay. Wrap in Iead foil equal in weight to the two assay buttons.
Heat a number of 1 inch or 1 1/ 2 inch (25 or 36 mm) bone ash cupels to 950°C in a muffle and
on each place the standards or the two assay buttons. Close the muffle door. When the black
ernst of Iead oxide melts and Iead oxide flows from the meta! bead into the cupel, open the muff-
le door slightly and continue cupellation at 850°C (cupel temperature). Towards the end of cupel-
lation, close the muffle door. Remave cupels, cover !arge prills with an asbestos mat and cool.
Detach the prill from the cupel and weigh. Add to this weight the weight lass an the standard and
subtract the weight of silver in the litharge.

Notes
1. Gold and other precious metals are not usually present in significant quantities. Partingof the
prill in nitric acid and cupellation ofthe residue is unnecessary.
2. Formation of a white crust on the cupel indicates tin interference. This may be removed by eva-
poration to dryness twice of the sample with 20m! of HCI, 20m! of HBr and 10m! of Br 2 before
170 Analysis of Tin Ores & Concentrates

carrying out the pot fusion. Clean up the evaporated residue with 3g of moist Na 2 C0 3 and fii-
ter paper. Use only 5g ofpotassium hydrogentartratein the frrst fusion to allow [or the reducing
action of the filter paper.
Determination of Sulphur
Weigh 0.5 g of sample and grind in an agate mortar with 3 g of sintering mixture (100 g ZnO, 50 g
Na 2 C0 3 , 50g KN0 3). Transfer to a small procelain crucible, cover with lg of sintering mixture
and heat for 1 - 1 1h hours at 700°C in a muffle. Cool, damp slightly with water and priseout
the cake with a knife. Wash the crucible with hot water, and 10m! of H 2 0 2 (20 vols.). Add to
the cake in a beaker, wash the crucible with hot water and boil the cake with the washings for
3 min. Decant the Iiquor through a pulp pad, add 75ml of water and 10m! of H 2 0 2 , boil for 3
min and filter through the pad. Wash the pad with hot water six tinles. To the filtrate and was-
hings add methylorange and neutralise with concentrated HCI. Add 4ml of HCI in excess, dilute
to 400ml and bring to the boil. Add slowly 25m! of 100 g/1 BaCI 2 solution and leave overnight.
Filter through a pulp pad, washing eight tinles with hot water. Ignite the pad at 700°C in a silica
crucible, cool in a desiccator and weigh as BaS04.
Notes
1. The use of a fusion with Na 2 0t gives a satisfactory attack, but coprecipitation of sodium, iron
and tin sulphates gives low results [16].
Determination o[Tungsten
>
Weigh sample (lg for 0- 2% W0 3 : 0.5g for 2- 10% W0 3 ; 0.25g for 10% W03) into a zirconium
crucible and fuse with 5 g of Na 2 0 2 . Extract the cooled melt in a 400ml beaker with 100 ml of
water, add 1 ml of 20 vol. H 2 0 2 and bring just to boiling. Cool, transfer to a 200 ml Volumetrie
flask, wash the beaker with a few drops of HCI and dilute to volume. Allow the residue to settle.
Decant 50ml of solution through a dry Whatman 541 filter and pipette an aliquot into a 100m!
>
graduated flask (10m! for 0-5% W0 3 ; 5ml for 5% W0 3 ). Add, whilst mixing, 10m! of H2 S0 4 ,
20m! of HCI, !Oml of 2M stannous chloride Solution, 1 ml of 1% titanaus chloride. Heat on a
boiling water bath for 5 min then cool in a water bath. Cool in running water for 15 min then add
10m! of IM sodium thiocyanate, mixweiland dilute to volume. Replace in cold waterandstand
for lSmin. Measure absorbance using 2cm cells at 400nm. Standardise using aliquots of a solu-
tion containing 0.1 mg/ml W0 3 (0.14227g/l sodium tungstate). Vanadium and, to a much lesser
extent, molybdenum interfere. There is no interference from niobium, tantalum or titanium.
Other impurities
The other elements of interest in the analysis of tin ores and concentrates include:
Ge, Mo, Nb, Ti and Ta. Classical procedures for these elements are fairly complex
[81] and wherever possible X-ray fluorescence methods are recommended.
Sodium and potassium may be determined by dissolution of 0.1 - 0.5 g of sample
in 15 rnl of HF in a closed PTFE pressure vessel at 200° C. On cooling add 20m! of
saturated boric acid solution and dilute for atomic absorption spectroscopy in an
air/C 2 H2 flame for both elements.

References
1. Ramdohr, P.: The Ore Mineralsand their Intergrowths, Oxford: Pergarnon (1969)
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Bulk Materials, 1972
4. Sampling in the Mineral and Metallurgical Processing Industries. Spec. Pub!. Inst. Min.
Metall. 1974
5. Unpublished Work and Standard Methods- Capper Pass, Ltd.
6. Davies, O.L.: Statistical Methods in Research and Production, 3rd Edn., London:
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17. Parry, L.: The Assay ofTin and Antirnony, London: Mining Journal Office, 1906
18. Gibbs, W.: J. Arner. Chern. Soc. 37, 358 (1864)
19. Lurje, J.J., Troitzkaja, M.l.: Zavod. Lab. 6, 153 (1937)
20. C/arke, F. W.: Arner.J.Sci. 45, 173 (1868)
21. Burghardt, C.Z.: Chern. Newsbl. 61, 260 (1890)
22. Gilbert, A.: Z. OffentaL Chem. 16,441 (1910)
23. Brunck, 0., Höltje, R.: Angew. Chern. 45, 331 (1932)
24. Payne, K. W., Philips: X-Ray Conference, Durharn, England (1970)
25. Tamaru, S., Ando, N.: Z. Anal. Chern. 84, 89 (1931)
26. Liebig, J.: Ann. 41, 285 (1845)
27. Rose, H.: Pogg. Ann. 91,112 (1854); 75, 1 (1848); 9, 45 (1827)
28. Beringer, H.R., Stephens, A.F.H.: Mining Mag. 360 (1928)
29. Hempel, W.: Pharrn. Zentralhalle Deutschland 38, 84 7 (1897)
30. Mischenko, L. V., Kiparisova, L.S.: Zavod. Lab. 36, 1048 (1970)
31. Agterdenbos, J., Vlogtman, J.: Talanta 19, 1295 (1972)
32. Schweinsberg, D.P., Hefferman, B.J.: Talanta 17, 332 (1970)
33. Ward, F.N., Lakin, H.W., Canney, F.C.: U.S.Geol. Surv. Bull. 1155,74 (1963)
34. Bowman, J.A.: Anal. Chirn. Acta 42, 285 (1968)
.35. Sierra, J., Leon, J.M.: Trans.Inst.Min.Metall. 76B, 210 (1967)
36. Baumgärtel, E., Gärtner, P.: Z. Anal. Chern. 208, 416 (1965)
37. Varand, V.L.: Nauch. Trudy lrkutsk. Nauch-Jssled. Jnst. Redk. Met. 11,56 (1963). Anal.
Abstr. 12, 1673 (1965)
38. Dolezal, J., Beran, P.: Coll. Czech. Chern. Cornrn. 22, 727 (1957)
39. Weiss, D.: Chern. Listy 52, 1817 (1958). Anal. Abstr. 6, 2083 (1959)
40. Dolezal, J., Povondra, P., Sulcek, Z.: Decornposition Techniques in lnorganic Analysis,
London: Jliffe, 1968
41. Karapetyan, E.T., Sharko, E.D.: Obogasch. Rud. 102 (1970). Anal. Abstr. 20,2980 (1971)
42. Zverev, L. V., Petrova, N. V.: Zavod. Lab. 23, 1403 (1957)
43. Vlasova, GM.: Uck. Zap. Tsentr. Nauchn.-lssled.Jnst.Olovyan. Prorn. 14 (1965)
44. Steger, H.F.: Talanta 22, 543 (1975)
45. Lister, B., Ga/lacher, M.J.: Trans. Jnst. Min. Metall. 79, 213 (1970)
46. Faye, G.H., Bowman, W.S., Sutarno, R.: Anal. Chirn. Acta 67, 202 (1973)
4 7. Gregory, G.R.E.C.: Warren Spring Labaratory, Report CR 488 (PC), Departrnent of
Trade and lndustry, February (1971)
48. Steger, H.F.: Anal. Chirn. Acta 77, 337 (1975)
49. De Carvalho, R.A.G.: Rev. Port. Quirn. 5, 55 (1963)
50. Guimont, J., Bouchard, A., Pichette, M.: Talanta 23, 62 (1976)
51. Tan, H.B., Thng, S.T.: Overseas Geol. Miner. Resource 10, 231 (1969)
52. Jkegami, T., Suematsu, K., Kammori, 0.: Japan Analyst 5, 379 (1956)
53. Scherrer, J.A.: J. Res. Nat. Bur. Stds. 16,253 (1936) and 21,95 (1938)
54. Po/lock, E.N., Zopatti, L.P.: Anal. Chern. 37, 290 (1965)
55. Smith, D.J.: Anal. Chirn. Acta 57, 371 (1971)
56. Nazarenko, V.A., Lebedeva, N. V.: Zavod. Lab. 28, 268 (1962)
57. Wood, G.A.: Geochern. Res. Centre, imperial College, London, Tech. Cornrn. No. 11.(1957)
58. Stanton, R.E., McDonald, A.J.: Trans. Inst. Min. Metall. 71, 27 (1961)
59. O'Keefe, J.O.: Carnbourne School of Mines Mag. 61, 18 (1961)
60. Heegn, H.: Freiherger Forsch. A 455,47 (1969)
61. Hutchin, F., Fiander, S.J.: Trans. lnst. Min. Metall. 76,69 (1967)
62. Famsworth, M., Pekola, J.: Anal. Chern. 26,735 (1954)
63. Sande//, E.B.: Colornetric Determination of Traces of Metals, p. 856, New York: Wiley
Interscience 1959
64. Gregory, G.R.E.C., Jeffery, P.G.: Analyst 92, 293 (1967)
65. Shumova, T.J., Blyum, I.A.: Zavod. Lab. 34,659 (1968)
66. Scherbov, D.P., Astaf'eva, I.N.: Plotnokova, R.N., Zavod.Lab. 39, 546 (1973)
67. Love, D.L., Sun, S.C.: Anal. Chern. 27, 1557 (1955)
68. Bond, A.M., O'Donnell, T.A., Waugh, A.B., McLauchlin, R.J. W.: Anal. Chem. 42, 1168
(1970)
69. Bond, AM.: Anal. Chern. 42,1165 (1970)
70. Bouber/ova-Kosinova, L.: Vest. Ustred. Ustavu Geol. 29, 13 (1954)
71. Blyum, I.A., Zyranova, N.G.: Zavod. Lab. 22,46 (1956)
172 Analysis of Tin Ores & Concentrates

72. Richardson, J., Alvin, J.F.: Proc. Austr. Inst. Min. Metall. 203, 95 (1962)
73. Mensik, J.D., Seidemann, J.: Perkin Eimer A.A. Newsletter 13, 8 (1974)
74. Mo/dan, B., Rubeska, /., Mikovsky, M., Huka, M.: Anal. Chim. Acta 52, 91 (1970)
75. Bowen, H.J.M.: Radiochem. Radioanalyt. Lett. 7, 75 (1971)
76. Johansen, 0., Steinnes, E.: Analyst 94,976 (1969)
77. Schmidt, D., Starke, K.: Radiochim. Acta 11, 197 (1969)
78. Das, H.A., Van Raaphorst, J.G., Umans, H.J.L.M.: J. Radioanalyt. Chem. 4, 21 (1979)
79. Stuart, R.A., Donahoe, A.J., Boy/e, A.J.F.: Proc. Austr. Inst. Min. Metall, 230, 69 (1969)
80. Shumilovski, N.N., Salakhutdinov, N., Jalmakov, A.A.: Izv. Akad. Nauk. Uzbek SSR, Ser.
Tekh. Nauk. 5, 29 (1964). Anal. Abstr. 13, 1223 (1966)
81. Schoeller, W.R., Powell, A.R.: The Analysis of Mineralsand Ores of the Rarer Elements,
London: Griffin 1940
82. Progress Rept., West Malaysia: Malaysia Geol. Surv. Ann. Rept. 156 (1969)
CHAPTER 13

ANALYSIS OF SECONDARY MATERIALSAND INTERMEDIATES

By R. Smith

It is impossible to Iist the wide range of valued intermediates and secondary ma-
terials which contain tin. In all cases, the actual sampling of these items is more de-
manding than their analysis. Because of the many ways in which they are transported
it is impossible to give recommended sampling methods for primary sampling. Almost
always, quantities of up to a few tonnes will have tobe manipulated and large-scale
machinery such as mechanical diggers, jawcrushers and hydraulic breakers must be
either hired or purchased.
The guidelines given here are empirical and where they have been tested, the samp-
ling error has been found to be less than ± 0.5% Sn. Whenever possible, dissimilar ma-
terials should be separated. Where this is not practicable, thorough mixing should be
carried out.

1 . Drosses and Ashes

Drosses cover a wide range of materials from completely nonmetallic to metallic.
They are all products from the top of baths of malten metals and usually consist of oxi-
dation products, liquation residues or products of chemical treatment to remove im-
purities. Great care should be taken in sampling as drosses are usually very valuable
but also heterogeneous.
Drosses containing acidic flux residues of zinc chloride (so-called "chloriney dros-
ses") should be treated with sodium carbonate otherwise a stable sample will not be
obtained. If the dross is very hygroscopic and is not treated it will become physically
wet during milling. Similarly, caustic drosses should be stabilised by milling with so-
dium bicarbonate.
Aluminium or calcium is used in some meta! refineries to remove antimony. The
greatest care should be taken with these drosses as exposure to moist air or water is
likely to generate arsine or stibine. This type of material should be isolated and neu-
tralised at the works where it is made and not transported in its active form.
As the first stage of primary sampling, the consignment should be sorted into dif-
ferent types according to appearance and apparent metallics content before emptying.
Each type should be weighed and sampled separately. Sampling can only be carried
out during unloading- a 10% by weight sample should be taken from each drum
from fines and small metallics. Large non-metallic lumps should be broken and samp-
lied- if this is not possible, all the !arge lumps should be pulled out for separate tre-
atment. Alllarge pieces of meta! should be pulled out and treated separately. The pri-
mary bulk samples should be mixed separately and reduced to 100 or 200 kg for treat-
ment in a pot or by milling. The first stage of treatment should aim to separate meta!
174 Analysis of Secondary Materialsand Intermediates

from non-metallic and to stabilise the sample. The example below serves to illustrate
the sampling of an acidic solder dross with metallics.
With samples of dry tin or solder ashes it is usually preferable to separate metallics
by milling and/or screening before treating in a pot.
Consignments of high grade material ( 40% Sn or greater) should be divided into
lots of 20 tonnes or less for sampling and assay.

Example
The consignment consists of 15,030 kg of acidic solder dross in 200 litre (45 gallon) drums.
The drums are emptied and treated as one sub-sample. Large metallic pieces are removed, cleaned
off and weighed. The weight of the remainder is obtained by difference. The finesandsmall
metallics are sampled, mixed and reduced.
Weight Sample Reduced Sample %
kg kg kg
Fines etc. 14045 1400 179 93.45
Large Metallics 985 985 985 6.55
100.00

The large metallics are melted in a pot, a dip sample of metal is taken and the dross is reduc-
ed to 20kg.
To Pot kg %
Metallics 985 6.55
From Pot
Metal A 893 5.94
Dross A 79 0.52
Loss A 13 0.09
985 6.55

The fines etc. are treated in apotat very low heat. Na 2C0 3 is added to prevent lasses of tin
by fuming and to neutralise the "chloriney" flux residues.
To Pot kg %
Fines 179 9 3.45
Na2C03 14 7.31
193 100.76

From Pot
Meta] B 105 54.82
Dross B 42 21.93
Loss B 46 24.01
193 100.76

The meta] is dip sampled, the dross because of its ]arge volume contains some occluded me-
tal. It is mixed after cooling and reduced to 21.93 kg then milled with 0.52 kg of dross from the
!arge metallics. The millings are graded on sieves, the coarse fractions are metallic. Fractions frorn
the rnill are weighed, the fines determined by difference.
To Mill kg %
Dross A 0.52 0.52
Dross B 21.93 21.93
22.45 22.45

From Mill
Fines- 2mm 16.38 16.38
+2mm -4mm 2.45 2.45
+4mm- 8mm 1.89 1.89
+8mm 1.73 1.73
22.45 22.45
 2. Slags 175

The metals are cornbined by rnelting tagether portians of the dip sarnples and the + 4 rnrn and
+ 8rnrn rnill fractions. Note that at this stage, proportionate weights give a 2000g sarnple.
Metal Sampies g %
Metal A 118.8 5.94
Meta! B 1096.4 54.82
+ 4rnrn- 8rnrn 37.8 1.89
+ 8rnrn 34.6 1.73

Cornbined Metals 1287.6 64.38

The dry fines (- 2rnrn; 327.6g) and oversize (+ 2rnrn;49.0g) are rnilled through a BS 60 rnesh
(250 J.lm) sieve and any rnetallics granulated with fines through the sieve. (See Chapter on Tin
Alloys- section 1.3). The fines are graded on a B.S. 85 rnesh sieve (178J.1rn) to give fmes and
roughs fractions. Final proportians are:
%
Fines - 85 rnesh 12.23
Roughs+ 85 rnesh 6.60
Metallics 64.38
Loss 24.10
107.31 (Na 2 C0 3 added 7.31 %)

If the above portians are assayed separately, multiplication by the appropriate

fraction will give a correct retum of metal values in the original sample. Because
Na 2 C0 3 has been added, some of the loss is due to the neutralisation reaction. It is
impossible in this case to give an accurate loss and a sample which is stable. Because
of the uncertainty in the loss, assays or weights expressed on a 'dry state' basis will
be meaningless. Assays and weights expressedas 'natural or original state' will be cor-
rect.
The metal fractions are assayed using sawings and the methods given in the Chap-
ter on Tin Alloys and Solders. Fines may be assayed according to the methods in the
Chapter on Ores and Concentrates. Roughs may be assayed by a combination of these
methods - usually the methods for fmes are adequate.

2. Slags

Furnace slags should be sampled by selection of a 10% bulk sample. Unless the
slag is of very low grade ( 10% Sn or less) the bulk sample should be:
(i) Crushed to- 25mm, then reduced to 300kg. (ii) Crushed to- 6mm, then redu-
ced to lOOkg. (iii) Milled to- 2mm, then reduced to 2kg. (iv) Milled to- 124J.lffi
(B.S. 120 mesh) for the assay sample.
If during crushing, metallic pieces should separate, these should all be reserved and
treated as aseparate portion. Even if they can be reduced to a powder during sample
preparation it is wiser to keep them separate as they are usually of very different com-
position from the slag itself.
The sampling ofslags by the above procedure is not entirely satisfactory in that
it applies to materials of less than 150mm particle size and of low grade (Sn 30% or
less). Outside this range it may be necessary to crush or break up the whole consign-
ment before sampling or to crush the bulk sample to- 5mm.
Slags may be assayed by methods appropriate to low grade tin concentrates using
separations for interfering elements if these are present.
176 Analysis of Secondary Materialsand Intermediates

Themaisture determination should be carried out on 20kg of- Smm material.

Assay as a tin concentrate.

Slags in fumaces may be sarnpled by inserting a cold steel rod into the melt or
by sampling with a hand !adle at intervals during slag tapping.

3. Fume, Flue Dusts

These are often high grade materials (Sn greater than 50%) but this depends on
their origin. The main difficulty is the hygiene problern associated with sampling dry
dusts. If the consignment arrives in paper bags it is satisfactory to sample by spearing
the bags, using a 10mm wide open spear which samples the length of one whole bag,
provided the contents are homogeneous. Material packed in other ways should be
treated as a concentrate and a 10% sample taken. Once sampled the dusts may be
treated as concentrates.
(i) Mix and reduce bulk sample to 100kg. (ii) Mill to- 2mm, reduce to 2kg. (iii)
Mill to- 250J,Ull (B.S. 60 mesh) for the assay sample.
It will be almost impossible to screen many flue dusts through a finer sieve because
of their tendency to aggregate during screening. Formostdusts it is unlikely that
milling will be necessary at any stage.
The maisture determination should be carried out on reject from the bulk sample.
Assay as a tin concentrate but beware of carbonaceous or sulphur-containing flue
dusts which require fusion with NaOH before small additions ofNa 2 0 2 are made.

4. Turnings, Borings
Small turnings and chippings are relatively easy to sample; a primary sample of 10%
should be taken, reduced to about 100 kg and treated as below. Large tumings and
borings are difficult to separate but the same approach should be followed. Consign-
ment sizes should be limited to 5 tonnes because of the !arge bulk of turnings and
their relative inhomogeneity.
The reduced sample should be heated in a pot to determine maisture plus oil and
to separate white metal if this is possible. It often suffices to set fire to the sample
in an open metal tray using kerosene. Cool and mill the residue, grade on a series of
sieves; separate magnetic materials. Depending on the material and the facilities avai-
lable it is possible to treat the sieve fractions in two ways.lf a melting crucible is avai-
lable, at least 2kg of screenings may be melted or converted to a sulphide (or alumi-
nium) matte as described in the sampling of copper-based alloys. If this is not avai-
lable, the Screenings may be combined in proportion to give a 2 kg total sample and
rnilled in a ring-mill of the Tema type, through a 178J,Ull (B.S. 85 mesh) sieve, then
graded on a 124~m (B.S. 120 mesh) sieve for the assay sample.
Aluminium-based borings will contain an apparently higher maisture content becau-
se of their low density. Losses of 30% or so are often found with wet borings. Alumi-
nium may be reduced to a crushable alloy by heating at 900°C with an equal weight
of iron powder.
Titanium alloy turnings are almost impossible to grind in a ring mill but may be
reduced to a crushable alloy by heating at 900°C with an equal weight of aluminium.
 4. Turnings, Borings 177

Large Iosses of tin may be encountered during matting with sulphur and for this
reason it should be restricted to the treatment of materials where tin is present in in-
significant amounts. Aluminium treatments may result in the production of an alloy
which may produce arsine or stibine on exposure to water or moist air. lf this hap-
pens the sample will be unacceptable.
Assay as a solder or copper-base alloy, depending on material.

Example
A consignment consists of 3,583 kg of oily whitemetal turnings contaminated with !arge
amounts of steel and coppery turnings. A bulk sample of 350kg is taken, this is reduced to 100
kg approximately and treated in a pot.
To Pot kg %
Oily Turnings 98.32 100.00
From Pot
Turnings 68.53 69.70
Whitemetal 12.08 12.29
Loss 17.71 18.01
98.32 100.00

Whitemetal is dip sampled during stirring, remelted into thin strips and sawings taken. The tur-
nings are milled and graded. Magnetics are separated, fractions weighed - the fines fraction being
obtained by difference.
To Mill kg %
Turnings 68.53 69.70
From Mill
Fines - 2mm 42.01 42.72
+ 2mm,- 4mm 7.02 7.14
+ 2 mm,- 4 mm (iron) 4.32 4.39
+ 4mm,- 8mm 5.18 5.28
+ 4mm,- 8mm (iron) 2.84 2.89
+ 8mm, -12mm 2.95 3.00
+ 8mm,-12mm (iron) 1.96 1.99
+ 12mm 0.87 0.89
+ 12 mm (iron) 1.38 1.40
68.53 69.70

Mill 854.4g of fines (- 2mm) with 142.8g of + 2mm/-4mm and 87.8g of + 2mm/-4mm iron,
through a 178J.l.m sieve (B.S. 85 mesh). Call this: Fines A.
To a plumbago crucible add proportians of + 4mm fractions and greater. Add an equal weight
of pure lump aluminium and heat at 900- 1200°C in a frre, stir frequently with caution until the
sample has decomposed. Lift out the pot, cool in an isolated position, invert and knock out the
product which willberather like a piece of metallic clinker. Clean out the pot and weigh the pro-
duct. Mill through a 178J.l.m sieve (B.S. 85 mesh) to give:Fines B.
To Pot g %
+ 4mm,- 8mm 264.0 5.28
+ 4mm,- 8mm iron 144.5 2.89
+ 8mm, -12mm 150.0 3.00
+ 8mm,- 12mm iron 99.5 1.99
+ 12mm 44.5 0.89
+ 12mm iron 70.0 1.40
772.5 15.45

Aluminium 800.0
From Pot g %
Matte 1634.3 32.71
178 Analysis of Secondary Materialsand Intennediates

Note the apparent weight gain due to oxidation. Finalproportions for assay are:
%
Fines A 54.25
Fines B 32.71
, Whitemetal 12.29
Loss on burning 18.01
117.26

If the assay results are multiplied by the appropriate fraction and added together, a correct
'original state' assay will be obtained.

5. Muds, Slimes, Detinning Residues

During unloading any supernatant liquor should be decanted off and sampled. The
consignrnent should then be reweighed. -As with other secondaries, a 10% prirnary
sample should be taken. This is then reduced to about 50- 150kg. Muds arriving loose
in 20 tonne containers or trucks should be sampled and reduced separately then
combined in proportion to the container weights to give a total sample of about
150kg. If the sample isahomogeneaus paste it may be mixed in a pan or mulling
mill, and a sample of 10- 20kg taken for maisture determination and subsequent
sample preparation. Heterogeneaus samples i.e. containing lumps of hard material,
should be heated gently in a pot (150kg) with constant stirring to give analmostdry
product. This should be cooled, weighed and milled. Any oversize should be graded
and magnetic constituents separated. A maisture determination should be carried
out on 10- 20kg ofmixed fme material and this added to the loss found at the pot.
A final sample of I or 2kg should be prepared from the milled, dried, fmes and any
oversize material by milling through a B.S. 60 mesh (250,um) sieve.
Caustic residues should fust be milled with sodium bicarbonate to give a stable
sample. The amount required is usually but not always 5 - 25% by weight.
Supernatant Iiquors should be evaporated to dryness and any residue mixed in
proportion with sample fines för final milling. The evaporation loss should be added
to any moisture· determined on the sample.
Assay as a low-grade tin concentrate.

6. Hardhead and Irony Intermediates

Hardhead is a tin-iron alloy produced by exhaustive smelting of tin slags, usually
to remove the last traces of tin before the slag is discarded.
These are normally encountered in very large pieces often up to 1 m in length. If
the consignrnent consists of very large pieces these should all be broken up with a
hydraulic breaker or pneumatic drill. If the consignrnent is very large and there are
many such pieces it is permissible to select a primary sample by breaking up 20% of
the large pieces. Usually it is sufficient to take a 10% primary sample. If the Ioad is
very valuable a 20% sample should be selected. The whole of the bulk sample should
be crushed to less than 25mm then treated as a slag as in Section B of this Chapter.
 6. Hardhead and Iron Intermedials 179

Irony intermediates containing tungsten crush with difficulty and resist milling to
the point where they may darnage the mill. They may sometimes be attacked by
heating at 900°C in a crucible with no additives. The cooled, oxidised product may
then be milled. Smaller quantities may be attacked by heating with aluminium at
900- 1200°C but the almost certain presence ofphosphorus, arsenic or antimony in
these materials gives a product which will generate toxic hydrides on exposure to
moist air. Treatment with aluminium is unlikely tobe practicable for this reason.
CHAPTER 14

ANALYSIS OF TIN ALLOYS AND SOLDERS

By R. Smith

Tin alloys cover a wide range of composition and uses, the most irnportant being:
a) Solders. b) Printing alloys. c) Bearing alloys. d) Pewter and casting alloys.
Tables 1 - 3 give the compositions of several important solders and whitemetals.

Table 1. Chemical Composition of British Standard Solders [ 1]

Tin% Antimony%
B.S. Solder min. max. max. min. Melting Range °C

A 64 65 0.6 183-185
K 59 60 0.5 183-188
F 49 50 0.5 183-212
R 44 45 0.4 183-224
c 39
34
40
35
0.4
0.3
183-234
183- 244
H
J 29 30 0.3 183-255
V 19 29 0.2 183-276
w 14 15 0.2 227- 288
B 49 50 3.0 2.5 185-204
M 44 45 2.7 2.2 185-215
c 39 40 2.4 2.0 185- 227
L 31 32 1.9 1.6 185-243
D 29 30 1.8 1.5 185 - 248
N 18 18.5 1.1 0.9 185-275
95A 94.5 95.5 5.25 4.75 236- 243
5Sa 4.75 5.25 0.10 296- 301
!Sa 1.0 1.5 0.10 309- 310
62Sb 61.5 62.5 0.2 178
9asc 96.3 96.5 0.1 221
T 49 50 0.1 145

In addition: As <0.05%, Fe <0.02%, Cu <0.3% oftin content except for 95A, 5S and IS
where Cu <0.05 %. Al, Zn, Cd etc. should not affect the properties of the solder. AP and KP
solders are similar to A and K but with 0.2% Sb max.
alS and 5S also contain 1.4- 1.6% Ag c96S contains 3.5 - 3.7% Ag
b62S contains 1.8-2.2% Ag dT contains 17.5-18.5% Cd

1. Sampling
The method of sampling depends very much on the circumstances of the buyer or
seller. lf a consignment of standard solder or bearing alloy ingots is bought from a
reputable supplier, the recomrnendations for sampling of the relevant standards
should be followed.
 Ref.p. 190] 1. Standard Methods 181

Table 2. Chemical Composition ofWhitemetal Hearing Alloysa [5]

ASTM Sn% Pb% Sb% Cu% As% Melting

Alloy Range°C

1 90 -92 0 .. 35 4 - 5 4 -5 0.1 223-371

2 88 -90 0.35 7 - 8 3 -4 0.1 241 - 354
3 86- 89 0.35 7.5 - 8.5 7.5-8.5 0.1 240-422
7 9.3- 10.7 rem. 14 - 16 0.5 0.3 - 0.6 240- 268
8 4.5- 5.5 rem. 14 - 16 0.5 0.3-0.6 237- 272
11 86 -89 0.5 6 - 7.5 5.0-6.5 0.1 244- 262
13 5.5- 6.5 rem. 9.5 - 10.5 0.5 0.25 -
15 0.8- 1.2 rem. 14.5-17.5 0.6 0.8 - 1.4 248- 281

aAll values are maximum allowable unless range is given

Table 3. Nominal Chemical Composition of Type Meta! Alloysa [2]

DIN 16512 Alloys Sn Sb As Pb

Stereotype 6 15 0.3 rem.

Monotype 11 19 0.3 rem.
Linotype 5 12 0.3 rem.
Backing meta! 3 4 0.3 rem.
Type meta! 5.5 28 0.3 rem.

aln addition to this composition Cu +Ni of 0.3% max. is allowed

1.1 Standard Methods

For standard solders, B.S. 3338 [3] recommends that, for ingots or bars, at least
10 per cent of the ingots or bars shall be taken at random and melted in a clean iron
pot to at least 50° C above the liquidus of the alloy [ 1]. Dip samples should be taken
and chi!l-cast in a cold shallow iron mould. Sawings or filings from the cast strips
should be used for analysis. With solder wire or small sticks of a form suitable for di-
rect soldering, a 1 per cent sample containing not less than ten pieces per batch
should be taken. Cut pieces from the sample and melt these under rosin to 50 -
100°C above the liquidus temperature [1] and pour the melt into a cold, shallow, iron
mould. Clean the surface of the strip with ethanol to remove rosin, clean with a wire-
brush and take an assay sample by sawing or flling.
For standard whitemetal ingots, B.S.3338 (4] recommends selection of a prirnary
sample consisting of the numbers of ingots given in Table 4. Reetangularingots should
be placed side by side and a line drawn diagonally from the top of the first to the bot-
tom of the last. A saw cut should be made at a point opposite the intersection of the
diagonal and the centre line of the ingot. Sawings should be made from edge to centre
line and the sawings collected for the sample. A fine saw with 7 teeth per cm (18 teeth
perinch) isrecommended.
182 Analysis of Tin Alloys and Solders [Ref.p. 190

Table 4. Selection of Primary Sampie of Standard Whiterneta! Ingots - B.S. 3338 [4]

Number of Ingots in Ingots for

Consigment Sampie

1- 4 All
5- 6 4
7- 9 5
10-13 6
14 -18 7
19-27 8
28-43 9
44-89 10
90 or over 11

Corresponding ASTM sampling schemes are given for solders [5] and whitemetal
or habbitt alloys [6]. In both instances, three ingots are recommended as the sample
for 450kg of metal, five ingots for 450 - 4500kg and ten ingots for over 4500kg. The
bulk samples are treated by melting (solders) or sawing (whitemetal) as above.
The sampling schemes recommended by the B.S. or ASTM are designed as a basis
for testing metals to the appropriate specification. They are not necessarily a basis
for commercial valuation of a consignment of solder in terrns of tin, Iead etc. con-
tents. They are defmitely not recommended for the sampling of scrap or recovered
metals, where the values are likely to be quite different in individual ingots. Further-
more, there is likely tobe considerable segregation in Sn/Pb solder ingots (Fig. 1)
[41] and even more in alloys containing Sb or Cu. Because of the wide variety of
scrap whitemetals available, it is not possible to give clear sampling schemes for all
instances. The following paragraphs are guidelines illustrating current practice.

A B c

\
D E F

~ ~
II
~ ~ ~
f
\ 61.6 62.05 62.1 61.5 ;
LENGTH 60cm
WIDTH(TOP) 12 cm \60.3 62.3 62.0 60.6}
DEPTH 9 cm
\55.3 54.8 54.8 56.2/

\56b 56.1 55. 3 5-,J

Fig. 1 Segregation ofTin and Iead in simple Sn/Pb solder. Solder ingot, 59.0% Sn, air-coo!ed in cast
iron mould. Average of drillings A- F was 62.0% Sn. Lugdrilling A was 58.8% Sn. A 20 mm cross-
section was sawn out giving assays shown
 Ref.p. 190] 1.3 Antimonial Alloys 183

1.2 Solders
Antimonial or non-antimonial solders should be samp1ed by melting the whole of
the consignment in an iron pot, usually capable of holding up to 20 tonnes. The melt
should be stirred mechanically for 15 - 20 min and a dip sample taken during stirring.
The sample should be chill-cast in a thin, strip mould and sawings taken for analysis.
Where considerable dross or iron scrap is present, stirring should be interrupted and
the dross or iron removed, weighed and treated as a separate portion. Metal should
be weighed before and after melting to determine a melting loss, which is usually zero
with clean ingots. If the consignment is very !arge and individual ingots can be shown
to have similar composition it may be adequate to select a 10% primary sample for
melting. If this is done, it should be remernbered that the final error expressed in cash
terms could be high; it is usually preferable to divide the consignment into smaller
batches or 'lots' for sampling, assay and settlement. Where solder contaminated with
gold or silver is tobe sampled, the whole consignment should be melted.

1.3 Antimonial Alloys

Alloys containing in excess of 10% Sb can provide formidable sampling problems
particularly when tin is present. The melting points of antimony, Iead and tin are
630°, 327° and 232°C respectively and there is a great tendency for an antimony-
rich dross toseparate at the cool surface of the melt. This dross, unlike a non-metal-
lic dross, is impossible to separate from the metal completely but may sometimes be
dissolved by the use of a high pot temperature ( 400 - 450°C). The presence of im-
purities such as arsenic, copper, iron or nicke! increase the tendency to form a metal-
lic dross. A fairly good test is to heat a sample of metal in a !adle at abou t 360°C -
if a homogeneaus melt is obtained, it is likely that sampling may be carried out by
large-scale melting in an open pot at 450°C. If the cooling meta! shows signs of hav-
ing a wide plastic range, bulk melting is likely to be difficult. Alloys exhibiting a
visible crystal structure on newly fractured surfaces will almost certainly give trouble on
melting, as will alloys which fracture easily. If melting is impossible it is often practica-
ble to sample by crushing, in which case the whole of the consignment should be bro-
ken and crushed before sampling. It is not sufficient to breakpiecesoff ingots as white-
metal alloys are always grossly segregated and a biased sample will result. It may be
necessary to use pneumatic drills or hydraulic breakers to treat the material before
processing in a jaw-crusher. If the metal cannot be sampled by melting or crushing,
then drilling or sawing is usually the last resort. Drilling is not satisfactory because of
the tendency for Segregation in whitemetals and should be avoided.
Sampie preparation of antimonial metals is also difficulf. In some instances the
metal may be melted in a !adle, cast into a thin strip and sawings taken for analysis.
Where there is greater than 20% Sb, Segregation is likely to occur even with small
quantities of metal and other methods of preparation must be used. These include:
(i) Melting with an equal portion of Iead ( or more if necessary). Sampiestrips may be
sawn or the alloy analysed by X-ray fluorescence.
(ii) Milling - metal drillings may be milled with cross-beater mills, provided meta!
does not smear on the inside of the mill and bias the sample.
(iii) Granulation - high antimonial alloys, particularly those containing As, Cu, Ni
etc., may be melted in a !adle and gradually cooled. During cooling the melt is stir-
red until solidification sets in. If the pasty metal is stirred and tossed about with a
carbon rod a powder can be obtained. This should be sieved on a B.S. 60 mesh
184 Analysis of Tin Alloys and Solders (Ref.p. 190

{0.251 mm) screen and the process repeated with the oversize material until it a1l passes
the sieve. The product should then be sieved on a B.S. 85 mesh {0.178 mm) or B.S. 120
mesh {0.124mm) to give 'rough' and 'fme' fractions.
{iv) Sweating- drillings or crushed metal may be heated in a ladle and stirred con-
tinuously with a carbon rod. Low melting components may be removed by pouring
offfluid metal which contains mainly Sn, Pb with some Sb. This may be remelted to give
a metal strip which is then sawn for the sample. The remaining metal in the ladle
contains most of the higher melting irnpurities and may be treated by granulation.
Removal of Sn and Pb by sweating always makes subsequent granulation easier.

Example
50 Ingots of whitemetal alloy of approxirnate composition Sn 60%, Sb 15 %, Cu 3% and Pb rem.
are sarnpled by drilling three holes through each ingot such that 12 different sites are covered in
all. The drillings are graded on sieves:
kg %
+ 10mm 0.75 10.49
+ 5 mm,- 10mm 1.82 25.45
+ 2mm,- Srnrn 3.25 45.46
-2mm 1.33 18.60

7.15 100.00

Each fraction is mixed, then reduced by coning and quartering. The following weights are com-
bined in a ladle: 209.8g of + 10mm, 509.0g of + 5 rnrn, 909.2g of + 2mm, 372g of- 2mm. The
ladle is heated gently and meta! removed by sweating. The remaining meta! is granulated through
a 0.25mm screen and sieved on a 0.18mm screen. Final proportians obtained are:
g %
Rough(+ 0.18mm) 274.1 13.70
Fine(- 0.18mm) 893.5 44.68
Meta! 832.4 41.62

2000.0 100.00

2. Chemical Analysis
2.1 Tin
Standard methods for the determination of tin in solders are given by ASTM [7],
BS [8] and the Tin Research Institute [9] and for whitemetals by ASTM [10] and BS
[ 11]. Sriveeraraghavan and Parthasaradhy [ 12] have reviewed methods for the analy-
sis of alloys of tin and lead and give a number of tin assays including titrations with
Kl0 3 , EDTA, K3 Fe{CN)6 and Na3 V0 4 •
Methods for the dissolution of 0.3- 2g of alloy include:
{i) heating with 20ml of H2 S0 4 [9, 13, 4 ]. {ii) heating with 20ml of H2 S0 4 and
5- 15gofKHS04 to fumes [7, 10]. (iii) heating with 25ml ofHN0 3 or 40ml of 1:1
HN0 3 [17]. (iv) gentle heating with 5 ml of HBr and 5 ml of Br 2 [ 18]. (v) gentle
heatingwith SOml ofHCl and O.Sml ofBr 2 [11]. (vi) gentle heating with 50ml of
HCl and 1g ofKCI0 3 . (vii) gentle heating with IOml ofHCl and 2ml ofHN0 3 [15,
16]. (viii) gentle heating with 20ml ofHCl and 5ml of 30% H 2 0 2 [20].
 Ref.p.190] 2.2 Lead 185

The method given below is the B.S. procedure for tin in whitemetal bearing alloys
[11]:
Dissolve 0.5g of meta! sawings in 50ml of wann HCl containing 0.5ml Br 2 • Add 50ml of wa-
ter and 4g of iron powder. Heat until the iron has dissolved, add 1g of iron powder and filter
through a paper pulp pad into a 500ml conical flask. Wash the residue three tirnes with 10% HCL
Return the residue to the original beaker and dissolve in 20m! of HCl with 0.2 ml of Br 2 . Add 4 g
of iron powder and filter into the first filtrate through a small pulp pad before the iron has dis-
solved completely. Wash three tirnes with 10% HCL Introduce a nicke! coil and boil gently for
30 min. Cool in running water under an atmosphere of C0 2 or with a Göckel trap fitted. Remave
the coil, rinse with water, add starch indicator and titrate rapidly with N/6 iodate (6 g/1 KI0 3,
30g/l KI, 1g/1 NaOH).
Standardise with 0.4g of pure tin foil and 50mg of antirnony added as a solution of the chlo-
ride.
Notes
1. The nicke! coil should be etched in boiling 1:1 HCl containing 5% NaCl before use.
2. The method is suitable for 5 - 90% Sn and is reproducible to ± 0.2% Sn.
3. For tin contents 1ess than 50% use a lg sarnple and for less than 10% use N/30 iodate with a O.lg
standard.
Photometrie methods for tin are used mainly for the analysis of antimoniallead
alloys, where tin is present as a minor or trace constituent. Reagents used include
dithiol [22), galleirr [23), phenylfluorone [24, 25), xylenol orange [26) and haematin
[27). A turbidimetric method for tin in antimoniallead uses 4-hydroxy-3-nitrobenzene
arsonic acid [28].
Complexometric methods for the determination of Sn in tin-base alloys have been
developed [15, 16, 21) and are discussed in Chapter 4.
The chapter on X-ray fluorescence gives a detailed discussion of the application of
the technique to solders and antimonial tin/lead alloys.
Atomic absorption spectroscopy is insufficiently accurate for most valuation and
specification analyses where Sn exceeds 10%. A number of references are given in
Table 6 of Chapter 8 and include tin in lead cable sheathing [29) and type metals
[30). In most of the recent applications, the alloy has been dissolved in aqueous
HBF 4 (10- 50%) containing an oxidising agentsuch as HN0 3 (30%) or 100 vol
H2 0 2 (30- 50%). In some work, the presence of a complexing agent is recommended
e.g. 0.2M EDTA [30).

2.2 Lead
The B.S. determinations of lead in solders [31] and whitemetal alloys [32) are
based on dithizone photometric and electrodeposition methods respectively. These
methods are really only applicable for < 5% Pb. The ASTM method [10] uses a remo-
val of antimony and tin by volatilising with HBr/Br 2 /HC10 4 (18 :2:1 0). Lead is pre-
cipitated as sulphate and determined gravimetrically.
This author finds that EDT A titration gives the most satisfactory method for lead
and a suitable referee method is given below. For simple matrices this procedure may
be abbreviated by the elimination of one or more Separations.
Evaparate lg of sample sawings to dryness gently in a tall beaker with 40ml of HCI/HBr/Br 2
mixture (10:9 :1). Repeat twice with 25 m1 portions. Add 50ml of 1:2 HN03, boil for five min
and filter into a 650ml beaker through a small pu1p pad, washing with hot 2% HN03. To the
filtrate add 20 ml of 1:1 H2 S04, evaparate to fumes and fume strongly for 5 min. Cool, add
100m1 of water, boil gent1y and cool in a water bath for 1 hour or preferably overnight. Filter
through a small, well-compacted pulp pad, wash twice with 10% H 2 S04 and six tirnes with cold
2% H 2 S0 4 . Transfer the pad and residue back to the 650ml beaker, washing with lOOml of hot
200g/l arnmonium acetate solution. Bring to the boiland sirnmer for 2 min. Filter through a
186 Analysis of Tin Alloys and Solders [Ref.p. 190

small pulp pad, wash three times with hot 1% ammonium acetate and once with hot water.
Dilute the filtrate to 300m!. Cool, add 0.5g of ascorbic acid, and 4 drops of xylenol orange in-
dicator and titrate with 0.1 M EDT A from purple to clear yellow.
Standardise 0.1M EDTA against 0.7g of lead foil dissolved in 20m! of 1:3 HN0 3 . Add 100m!
of 200g/l ammonium acetate, 0.5g of ascorbic acid and xylenol orange before diluting to 300m!
for titration.
The presence of an orange or muddy coloured indicator shows that iron or tin have been in-
completely removed. The addition of 0.5g of ammoniurn hydrogen fluoride may help although
excessive additions precipitate Iead fluoride.
If the reaction with HCI/HBr/Br 2 is excessively violent, evaparate !rrst to dryness with 40ml
of 1:4 HN0 3 or add an equal volume of water to the acid mixture.

Bismuth/lead alloys containing small amounts of tin may be dissolved [33] by

treating 0.2g with 25ml of 4% NaF and IOml ofHN0 3 . Afterdilution with 20- 30
ml of hot water and 50ml of cold water, titrate bismuthat pH 1.5- 2 with 0.05M
EDTA from red to yellow. Add ammonia until red or violet, buffer to pH4 with
lOml of sodium acetate buffer (500g sodium acetate, 10ml acetic acid) and titrate
from violet topaleorange with 0.05M EDTA.
Another rapid method [20] is to dissolve 0.5 g in 20ml ofHCl with 5rnl of 100
vols. H2 0 2 , evaparate to 5 rnl, cool, add 20ml of 20% tartaric acid and dilute to I OOrnl
with water. Neutralise with ammonia to methyl red, add 5ml of 0.025M magnesium
EDTA and titrate with 0.05M EDTA to a blue end-point with Eriochrome Black T
or methyl thymol blue. Shakhova and KaratZeova [34] dissolved in I: I HN0 3 and
removed tin by filtration as metastaunie acid after dilution to 200ml. They claimed
the leadwas not adsorbed on the precipitate as did Luzina [35] who used a similar
method with additions of NaCN for lead in cadmium containing solders.

2.3 Antimony
The determination of antimony in solders and whitemetals is Straightforward and
most authorities [7, 9, 10, I6, 36] recommend dissolution and evaporation to fumes
with H2 S0 4 , reduction with S0 2 or sodium sulphite and titration with potassium bro-
mate using methyl orange as indicator. Arsenic interferes and may be removed by boil-
ing with HCl; excessive evaporation results in loss of antimony -the temperature should
be kept below I05°C. The method below isthat of ASTME-57 [10].
Heat 0.5- 2.0g of meta! sawings in a 500ml conical flask with 15m! of H 2 S04 and 7g of
KHS0 4 or K2 S2 0 7 . Heat gently to avoid melting the meta! then heat vigorously for 3 min over
an open flame to expel sulphur. Cool and cautiously add 10 ml of water then 75 ml of HCI and
1g of Na 2 S0 3 . Evaparate to 60 ± 5 ml, di!ute to 300m! with boiling water and bubble air vigor-
ously for 1 min to oxidise cuprous compounds. This should be done ifCu >0.3% [36]. Titrate
at 80- 90°C with O.OSN KBr0 3 with methylorange indicator from red to colourless. This author
finds that continuous replenishment of methyl orange is necessary throughout the titration.
Antimony may also be determined photometrically after reduction to Sb(III) and
extraction into iso-propyl ether [37] or xylene [38] or toluene [38] from I - 4M HCJ
with rhodamine B [37] or methyl violet [38]. Antimony has also been extracted
from 6M HCl [39] into methyl iso-butyl ketone - the organic extract was then intro-
duced into an air/C 2 H2 flame for atomic absorption at 2I7.59nm. As little as 0.002%
Sb in tin was determined by this method which is equally applicable to solders and
whitemetals.
The most convenient method for antimony is by direct X-ray fluorescence of
metal samples; this is discussed in Chapter I 0.
 Ref.p. 190] 2.5 Other Elements 187

2.4 Copper
Photometriedetermination using HBr/H 3 P0 4 [9, 40] is a reliable convenient
method for 0.01- 2% Cu in solders or whitemetals. Great care must be taken in mel-
ting samples to avoid removal of copper preferentially as a dross when present in
amounts greater than 0.5%.
Dissolve l.Og of sample in 9 ml of HBr and 1 ml of Br 2 . Evaparate to dryness, add 25 ml of
HBr/H3P0 4 mixture (1000rnl of HBr: 1ml of Br2: lOOOml of H3P04), transfer to a 50ml graduated
flask, dilute to volume with HBr/H3P04 . Allow any so Iids to settle and measure the absorbance
at 600nm in 1 or 4 cm cells. Carry out a blank determination. Calibrate using 0.2- 0.8mg Cu
taken through the procedure. The standardstock solution is made from copper dissolved in 5ml
of HBr ap.d 0.5ml of Br2.
Higher Ievels of copper (above 2%) may be determined by electrodeposition after
removal of As, Sb and Sn by evaporation with HCl/HBr/Br 2 , removal of Pb as sul-
phate and electrodeposition of copper in the presence of a suitable depolariser [ 10,
32]. It is unlikely that methods based on precipitation of cuprous iodide and titra-
tion of liberated iodine with thiosulphate would give an accuracy of better than ±
0.3% Cu at the 8% Cu level. Photometrie determinations based on the blue cupram-
monium complex are fraught with difficulty as it is almost impossible to add sufficient
ammonia to reach a stable equilibrium of ammine species [41].

2.5 Other Elements

Arsenic may be determined by heating 1 - 5 g of sample with 15 g of KHS0 4 and
20ml of H 2 S0 4 gently, and then fuming for 2- 3 min over an open burner. Add 15ml
of water, cool, add 50ml ofHCl, 1 g of FeS0 4 .7H 2 0 and lOg ofNaCL Transfer to a
distillation apparatus and collect the distillate in 200ml of water. Distil until the
temperature of the vapour reaches 105°C. If the antimony content is greater than
5% add 1Oml of HN0 3 and 1Oml of H 2 S0 4 , evaporate to fumes and repeat the di-
stillation. Heat the distillate to 80 - 90°C and titrate with 0.01 N K.Br0 3 with methyl
orange indicator [7, 10). Altematively arsenic may be determined photometrically
in the distillate as the blue reduced arsenomolybdate [43).
Iron [9, 44] may be determined by a double evaporation with 9ml of HBr and
lml ofBr 2 to remove tin and antimony. Take up in 5ml ofHN0 3 , boil out bromine,
add 1 ml of H2 S0 4 and evaporate to fumes. Cool, take up in 25 m1 of water, pass
H2 S for 10 min, filter, remove H 2 S from the flltrate by boiling and evaporate to 20ml.
Neutralise with ammonia then acidify to litmus with acetic acid. Add 2ml of 10% hy-
droxylammonium chloride solution, 15ml ofbuffer solution (270g/l anhydrous sod-
ium acetate, 240ml/l acetic acid) and heat just to boiling. Transfer to a 50ml volum-
etric flask, add 1Oml of 2.5 g/1 1,10 phenanthroline and dilute to volume. Measure at
510nm in a 1 cm cell. The method is suitable for 0.005-0.06% Fe in solders and
whitemetals. This method is similar tothat published earlier by Ota [45]. In a later
paper [46], the sample is treated directly, interfering elementssuch as Bi, Cu, Sb, Sn,
Zn etc. being masked with EDTA.
Bismuth [1, 10, 4 7] is easily determined as the thiourea complex at 440nm after
removal of As, Sb and Sn with HBr/Br 2 (see Chapter 15).
The B.S. methodsfor Al [48], Zn [49] and Cd [50) are fairly complex procedures
based on photometry with chrome-azurol S [48] and dithizone [49, 50]. Ota [51]
determined Al with aluminon after removal of tin with HBr/H2 S0 4 and other metals
by mercury cathode electrolysis.
188 Analysis of Tin Alloys and Soiders [Ref.p.l90

Si/ver [52] may be determined up to 3% by dissolving lOg of sample in lOOml of

HN0 3 ,boiling to expel nitrous fumes, dilu tion to 200ml and titrating with 0.1 N am-
monium thiocyanate using 5ml of 10% ferric sulphate as indicator.
Nickel may be determined [53] with dimethylglyoxime in citrate solution after tin
removaL
Gold may be determined [54] afterremoval of antimony and arsenic with HBr/Br 2
and coprecipitation with tellurium from tartrate solution using stannous chloride as
the reductant. Afterdissolution in aqua regia and evaporation almost to dryness, the
solution is taken up in HCI and the absorbance of the AuC14 complex measured at
312 nm. Alternatively [54] gold may be extracted into dichloromethane as the AuBr,j
polyoxyethylene glycol complex for spectrophotometry at 394nm. Determinations
based on fire assay should include a double tinremoval with HCl/HBr/Br 2 (41].
By far the most satisfactory technique for trace elements in solders and whiteme-
tals and is emission spectroscopy [42]. To avoid undue segregation, alloys with over
15% Sb should first be melted with a suitable quantity of pure Iead. Rod or disc
specimens should be excited as the upper electrode [42] against a 120° graphite coun-
terelectrode (ASTM C-2) and spectra recorded photographically in the range 243.0-
350.0nm (0.0063t.tF, 300t.tH, l.OD, 6.0 amps RF, 7 Bks per 1/ 2 cycle, 50 sec burn,
3 mm gap). The Sn 314.18nm line should be approximately 45% transmission. Lines
used are: Ag 328.07, Al309,28, As 286,05, Au 312,28, Bi 306,77 Cd 340,36 or Cd
346.62, Cu 327.40 or Cu 324.75, Fe 302.06, In 303.94, Ni 341.48 and Zn 334.40
nm. Differentranges were covered using 60% and 0.6% transmission filters. Stan-
dards are made from analysed master alloys diluted with tin and Iead to give a 60 Sn/
40 Pb matrix. Corrections must be applied for solders of different composition. Prin-
ciples for the preparation of tin/lead master alloys are given in Chapter 10.

2.6 Density Methods

Davis, Easton and Freezer [55] described a density method for the analysis of sol-
der alloys accurate to within ± 0.5% Sn. The determinationwas carried out on a 4g
sample using a density bottle, filled with air-free waterat 20°C. The absence of a
resirr core from parts of the same reel could be easily detected.
After the publication of this work, it was found [41] that the method could be
irnproved considerably by weighing a 200g sample in air and then in air-free water
at l8°C (65°F). The sample is melted in an iron ladle or glass beaker and cast into
the copper mould shown in Fig. 2 The mould is placed on an iron block. After cooling,
the triplicate samples are removed, any surface irnperfections are removed with a clean
file and a saw cut is made at the base of the stem. The stem is cut off leaving a large
blob of solder with a small stem; a length of 2_1 cm of 0.35mm diameter nylonfishing
line is tied through the saw cut and is used to hang the inverted bob on the arm of a
four-place balance. After weighing in air, a bridge is positioned over the balance pan
and the bob is weighed in boiled waterat 18° ± 1°C. The use of boiled water elirn-
inates the formation of air bubbles. The immersed length of nylon line is about 2 cm
and is equivalent to 0.002g.
Weight in Air
S.G. =
Weight in Air- Weight in Water
 Ref.p.190] 2.6 Density Methods 189

B
ISS
I
39 40
·I
40
I 32
dia.

79 1 $

51
dia
9
.. ·., . ~.
····-··-: ::···--··
--- ·-- · · -~ ~------ ·

I· 2s .1• 2s ·I
HOLE FOR 9mm dia. BOL T SECTION 88 dia.
WITH WING NUT S
MOULD TO ~
SPLIT ON>t_

Fig. 2 Meta! mould for casting density buttons. Made from copper all dimensions in millimetres.
Before use the long stem is cutdown to 10 mm and a notch cut in the stub. The remaining bob
is inverted and weighed in air and water

Table 5. SJ>ecific Gravity of Sn/Pb Solders as Determined by the Water Displacement Method
[41]at18C

Sn% S.G. Sn% S.G. Sn% S.G. Sn% S.G. Sn% S.G.

1 11.3145 16 10.4235 31 9.6790 46 9.0510 61 8.4890

2 11.2505 17 10.3705 32 9.6320 47 9.0115 62 8.4535
3 11.1890 18 10.3210 33 9.5880 48 8.9725 63 8.4185
4 11.1285 19 10.2720 34 9.5440 49 8.9330 64 8.3845
5 11.0690 20 10.2230 35 9.5000 50 8.8945 65 8.3505
6 11.0065 21 10.1750 36 9.4575 51 8.8560 66 8.3170
7 10.9430 22 10.1250 37 9.4145 52 8.8175 67 8.2835
8 10.8820 23 10.0730 38 9.3715 53 8.7810 68 8.2495
9 10.8240 24 10.0240 39 9.3290 54 8.7430 69 8.2155
10 10.7670 25 9.9720 40 9.2880 55 8.7055 70 8.1820
11 10.7120 26 9.9220 41 9.2480 56 8.6680 71 8.1490
12 10.6500 27 9.8710 41 9.2075 57 8.6310 72 8.1165
13 10.5890 28 9.8220 43 9.1675 58 8.5955 73 8.0830
14 10.5320 29 9.7730 44 9.1295 59 8.5595 74 8.0520
15 10.4770 30 9.7250 45 9.0900 60 8.5240 75 8.0205

Intermediate values may be determined by linear interpolation to 0.01% Sn.

Calibrations are given in Tables 5 - 6 and are based on synthetic standards made
by dissolving tin, Iead and antimony under palm oil, burning off the palm oil and
casting into thin strips. The strips are remelted and treated as a sample.
Antimony must be assayed chemically and corrected for (Table 6).
On 24 replicates of the samesolder a range of 58.88%- 58.93% Sn was obtained
with a standard deviation of 0.02% Sn [41].
Some ageing of solders occurs on standing and shows as an increase in specific
gravity. Forthis reason, weighings should be made within 5 hours of casting.
190 Analysis of Tin Alloys and Solders

Table 6. Specific Gravity of Sn/Pb/Sb Solders - Antirnony Cerreetion [41]

Sb% Uncorrected Sn %
22.5 27.6 32.6 37.6 42.6 47.5
to to to to to to
27.5 32.5 37.5 42.5 47.5 55.0

0.2 0.10 0.10 0.10 0.10 0.15 0.15

0.4 0.30 0.30 0.30 0.30 0.35 0.35
0.6 0.55 0.45 0.50 0.45 0.55 0.55
0.8 0.75 0.65 0.70 0.65 0.75 0.75
1.0 0.95 0.85 0.85 0.85 0.95 0.95
1.2 1.20 1.05 1.10 1.05 1.15 1.15
1.4 1.45 1.30 1.30 1.25 1.35 1.35
1.6 1.70 1.50 1.50 1.45 1.60 1.55
1.8 1.95 1.75 1.75 1.70 1.80 1.80
2.0 2.20 2.00 2.00 1.95 2.05 2.00
2.2 2.50 2.25 2.25 2.20 2.25 2.25
2.4 2.75 2.50 2.50 2.45 2.50 2.45
2.6 3.05 2.85 2.80 2.75 2.80 2.70
2.8 3.35 3.15 3.10 3.05 3.00 2.95

In all cases the correction should be su btracted frorn the uncorrected Sn %.

References
1. Soft Solders, British Standard, 219 (1977)
2. German Standard, DIN 16512
3. Metbads for the Sampling and Analysis of Tin and Tin Alloys, British Standard, 3338, Part
12 (1961)
4. Reference 3, B.S. 3338, Part 14 (1961)
5. 1975 ASTM Annual Book of Standards, Part 8, B 23 (1973)
6. Reference 5, B 32 (1970)
7. 1975 ASTM Annual Book of Standards Part 12, E 46 (1972)
8. Reference 3, B.S. 3338, Part 11 (1961)
9. Price, J. W., Coppins, W.C.: The Analysis ofTin-Base Bearing Metals, London: Tin Research
Institute Publication, 1954
10. Reference 7, ASTM, E 57 (1972)
11. Reference 3, B.S.3338, Part 16 (1965)
12. Sriveeraraghavan, S., Parthasaradhy, N. V.: Met. Finishing 105 (1971)
13. Pinkston,J.L., Kenner, C.: Anal. Chern. 27,447 (1955)
14. Cinnerman, C.H., Arie/, M.: Anal. Chirn. Acta 12, 13 (1955)
15. Onuki, S., Utigak, K.: Japan Analyst 11, 1313 (1962)
16. Ottendorfer, L.J.: ehernist Analyst 47,96 (1958)
17. Pribil, R., Kopanica, M.: Chernist Analyst 48, 87 (1959)
18. Frederick, K., Kurtz, R.B.: Anal. Chern. 28, 1206 (1956)
19. Not Used
20. Studlar, K., Janousek, I.: Hutn. Listy 13, 805 (1958)
21. Yurist, IM., Korotkova, 0.1.: Zavod. Lab. 28,660 (1962)
22. Kawabuchi, K., Kaya, M., Duchi, Y.: Japan Analyst 15,543 (1966)
23. Iones, J.C.H.: Analyst 93, 214 (1968)
24. Luke, C.L.: Anal. Chern. 28, 1276 (1956)
25. Tanaka, M., Morikawa, H.: Japan Analyst 10, 396 (1961)
26. Danilova, V.N.: Zavod. Lab. 29,407 (1963)
27. Shirodker, R., Schibilkz, E.: Z. Anal. Chern. 248, 173 (1969)
28. Vasadi, K.: Magy. Kern. Lap. 23,344 (1968). Anal. Abstr. 17, 2052 (1969)
29. Quamll; T.M., Powell, R.J.W., Cluley, H.J.: Analyst 98,443 (1973)
30. Gouin, J.U., Holt, J.L., Miller, R.E.: Anal. Chem. 44, 1042 (1972)
 References 191

31. Reference 3, B.S. 3338, Part 5 (1961)

32. Reference 3, B.S. 3338, Part 15 (1965)
33. Shteiman, EA., Dobrynina, Z.G., Mordovskaya, E.E.: Zavod .. Lab. 30, 1200 (1964)
34. Shakhova, P.G., Korotkova, 0.1.: Zavod. Lab. 31, 295 (1965)
35. Luzina, L.N.: Zavod. Lab. 31,808 (1965)
36. Reference 3, B.S. 3338 part 13 (1965)
37. Coppins, W.C., Price, J. W.: Metallurgia 53, 183 (1956)
38. Ishutchenko, E.I., Eliseeva, V.M.: Zavod. Lab. 21, 791 (1955)
39. Yanagisawa, M., Suzuki, M., Takeuchi, T.: Anal. Chim. Acta 47, 121 (1969)
40. Reference 3, B.S. 3338, Part 4 (1961)
41. Unpublished Work and Standard Methods- Capper Pass, Ltd.
42. Pickup, W.F., Townley, C. W.: Tin Research Institute Publication 378
43. Reference 3, B.S. 3338, Part 9 (1965)
44. Reference 3, B.S. 3338, Part 10 (1961)
45. Ota, K.: Japan Analyst 5, 3 (1956)
46. Onuki, S., Watanuki, K., Yoshino, Y.: Japan Analyst 13, 23 (1964)
47. Reference 3, B.S. 3338, Part 8 (1961)
48. Reference 3, B.S. 3338, Part 18 (1966)
49. Reference 3, B.S. 3338, Part 19 (1966)
50. Reference 3, B.S. 3338, Part 17 (1965)
51. Ota, K.: Japan Analyst 7, 162 (1958)
52. Reference 3, B.S. 3338, Part 7 (1961)
53. Reference 3, B.S. 3338 Part 20 (1970)
54. Chapman, A.H.,Price,J. W.: Metallurgia 78, 217 (1968)
55. Davis J., Easton, A.J., Freezer, J.: Sheet Meta! Ind. 32, 208 (1955)
CHAPTER 15

ANALYSIS OF INGOT TIN

By R. Smith

In general, methods for the analysis of tin/lead solders apply equally weil to ingot
tin. Specifications for ingot tin are covered by 'B.S. 3252: Ingot Tin',DIN 1704,
UNI 3271 (ltaly) and 'ASTM B 339.72 PigTin'. Table 1 gives the specifications for these
Standards. In addition to standard grades of tin, high purity metals of 99.99% Sn and
99.999% Sn are produced in industrial quantities by Capper Pass Ltd.; smaller quan·
tities of higher purity metal are available from Iabaratory supply houses. In most cases,
ingot tin is soldunder brand names with consistent and defined impurity Ievels.

Table 1. Specification for Ingot Tin

Specification Min. Max. Max. Max. Max. Max. Max. Max. Max. Max. Max. Max. Max.
Sn Pb Sb Bi Cu Fe As s Ni+Ce Zn Cd Al Zn+Cd+Al

USA
ASTM
Grade AAA 99.98 0.01 0.008 0.001 0.002 0.005 0.0005 0.002 0.005 0.001 0.001
GradeAA 99.95 0.02 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.005 0.001
Grade A 99.8 0.05 0.04 0.015 0.04 0.015 0.005 0.01 0.01 0.005 0.001
UK
BS 3252 TI 99.90 0.04 0.04 0.04 0.04 0.01 0.04 0.04 0.04
Pb +Sb +Bi +Cu +Fe +As ::1>0.1
T2 99.75 0.08 0.08 0.08 0.05 0.01 0.05 Total other impurities :I> 0.05
Pb +Sb +Bi +Cu +Fe +As ::1>0.20
T3 99.00 Pb +Sb +Bi +Cu +Fe +As ::1>0.90 Total other impurities ::1>0.10
W.GER-
MANY
DIN 1704 99.95 0.02 0.02 0.002 0.01 0.01 0.01 0.002 0.001 0.002 0.002
99.90 0.04 0.03 0.01 0.03 0.01 0.03 0.002 0.001 0.002 0.002
99.75 0.08 0.08 0.02 0.05 0.01 0.05 0.002 0.001 0.002 0.005
99.50 0.40 0.10 0.03 0.05 0.01 0.08 0.002 0.001 0.002 0.005
99.00 1.0 0.20 0.03 0.10 0.05 0.10 0.002 0.001 0.002 0.005
ITALY
UNI 3271 99.9 0.03 0.02 0.03 0.015 0.07 Total other impurities :I> 0.03
99.75 0.05 0.10 0.05 0.015 0.07 Total other impurities )> 0.05

1. Sampling

Ingots [1] shall be selected from a consignment according to Table 2. The ingots
shou1d be placed side by side in rows of five and a line drawn diagonally across the
row from the top of the first to the bottarn of the fifth, ignoring any Iug on the in-
 Ref.p 198] 2.1 Determination of Tin 193

gots. A saw cut shall be made, with a coarse, widely set saw at the side of each ingot
at a point opposite the intersection of the diagonal and the centre line. Saw halfway
through each ingot and collect the sawings. The sawings should be mixed and any
iron removed with a magnet and rejected; if any oil is present the sawings should be
cleaned in petroleum ether and dried. Sufficient sawings should be taken to provide
a final sample of 1 kg.

Table 2. Selection of Sampie from a Consignment of Tin Ingots [1]

Number of Ingots Number of Ingots

in Consignrnent in Sampie

1- 4 All
5-44 4
45-54 5
55-64 6
N 4+ (N-4)/10

The above British Standard method of sampling is generally acceptable in that a

10% sample is taken and impurities are unlikely tobe introduced or lost in sampling.
If sawings aretobe melted for emission spectroscopy, this should be donein an acid-
cleaned silica crucible over a Bunsen burner. The melt should be stirred with a thin
rod of spectroscopic graphite. The mould and sample file should be specially reserved
for this purpose.

2. Analysis
2.1 Determination of Tin
lt is almost universal practice to express the puri ty of metals as 100% minus the
total sum of impurities. Few metals are usually assayed as such for the principal
component, exceptions being electrolytic copper, silver and gold.
B.S. 3338 gives a method for the determination of tin in ingot tin having a range
from 99.0 - 99.8% Sn and a reproducibility of ± 0.05% Sn. The method requires con-
siderable skill and practice but is capable of the performance claimed.
Weigh accurately to 0.0001g, six portians of dried KI0 3 (-60 mesh) and transfertosmall
beakers. To each add 1 g of NaHC0 3 and 50 ml of boiled, cooled water; cover, warm to dissolve
and reserve.
Weigh accurately to 0.0001 g (at the same time as the iodate) triplicate portians of 2.5 g of
sample or pure tin and transfer each to a 250m! tall beaker. To each add 50ml of HCI and 1 drop
of 0.1% antimony chloride solution. Cover and heat at 45°C on a hotplate until only a small
black residue of impurities remains. Add 4.0ml of 200g/l sodium chlorate slowly with stirring
and cool to 30°C in running water.
At 5 min intervals (timed with a clock) remove three beakers at a time and to each add 1 g ±
0.25 g of iron powder. Allow to stand for 5 min then replace in running water. During the 5 min
standing period of the second and subsequent sets, filter the contents of the previous set of be-
akers through a pad of asbestos pulp on a fritted funnel into 500ml flat bottomed flasks contain-
ing 180m! of 1 : 1 HCI and 0.25g of iron powder. Wash with warm (30- 35°C) 1: 10 HCI and
combine the washings with the filtrate. The volume in each flask should be 300 to 350 ml.
194 Analysis of Ingot Tin [Ref.p. 198

Add Sg of aluminium strip, connect to a supply of C0 2 and warm if necessary to start the
reaction then immerse in a cold water bath. When the aluminium has almest dissolved, loosen
the Stopper hoiding the CÜ2 inlet and rinse down the neck of the flask and bung with warm 1; 10
HCL Replace the bung and heat the flask to boiling on a hotplate slowly to dissolve the deposited
tin. Boi! gently to dissolve tin, close the exit tube with a rubber cap and cooi in running water
under C0 2 .
Remave each flask from the water-bath, wash the stopper with water. Cap the neck with the
palm of the hand and add one of the previously prepared iodate solutions, rinsing this into the
flask with boiled, cooled water. Add 1-2m! of starch indicator and titrate with 3g/l KI0 3, 3g/l
KI and O.S g/1 NaHC03, which has been purged with C0 2 ; swirl gently during titration. The ti-
trant should be kept in a 10 ml burette graduated in 0.02ml.

Tin% = (A + B) F x 100
w
where: A weight of KI0 3 added (g).
B weight of KI0 3 added in titrant (g).
w weight of sample (g).
Ws
F where subscript, s, refers to standard.
A +B
s s
Note For pure tin weigh 1.493g of solid KI0 3 (Sn 99.9%).
For refined tin weigh 1.490g of solid KI03 (Sn 99.8%).
For common tin weigh 1.478g of solid KI0 3 (Sn 99.0%).

2.2 Photometrie Methods for Impurities

Standard methods are given below; other published work is summarised.

Antirnony [3]
Dissalve 0.2Sg of sample in 10m! of H 2S0 4 , cool, add 30m! of water then SOml of HCI,
transfer to a 100m! volumetric flask and dilute to volume. To a separating funnel add 10m! of
this solution (for O.OS- 0.1% Sb use Sm! and for 0.01- 0.2S% Sb use 2m!- dilute to 10m! with
1 : 1 HCI) and O.Sml of lOg/! sodium metabisulphite solution. Cool to below 2S°C, add 3m! of
ceric sulphate (3.3g in 100m! H 2 S04 ) and O.Sml of lOg/1 hydroxylammonium chloride solu-
tion. Stand until the ceric sulphate is reduced then dilute to 60ml.
Add lO.Oml of isopropyl ether and shakefor 30 sec. Runoff the aqueous layer, wash twice with
2ml of 1:10 HCI and finally add 2m! of 0.2g/l Rhodamine Bin 1 : 10 HCI and shake for 10 sec.
Discard the aqueous layer tagether with a few drops of the organic layer, dry the stem of the
funnel with a roll of paper and run off into a stoppered bettle. Measure the absorbance in a 2 cm
(0.004- 0.024% Sb) or 1 cm (0.024- O.OS% Sb), cell at SSOnm.
Calibrate with 1- Sm! aliquots of 2.4mg/l Sb in HCI solution diluted to Sm! with HCL Add
5 ml of water and carry through the procedure from the addition of sodium metabisulphite.

Arsenic
B.S. 3338 [4] recommends a procedure involving separation of arsenic by distilla-
tion as AsCI 3 followed by reaction with arnmonium rnolybdate and reduction with
hydrazine sulphate to molybdenum blue. A more rapid alternative is to dissolve 0.1 g
of tin in 20m! of 1:1 H 2 S0 4 in an arsine generation apparatus filled with 0.05% sil-
ver diethyldithiocarbamate in pyridine ( see Chapter 12). When the tin has dissolved,
except for a few black specks, add 2ml of 15% Kl, 50ml of water and 5 g of granu-
lated zinc. Reassemble the apparatus quickly and shield frorn direct sunlight. Leave
for at least 1 1I 2 hours and measure the absorbance at 540nrn. Calibrate using solu-
tions from 5 - 50J.,Lg As.
 Ref.p. 198] 2.2 Photometrie Methods for Impurities 195

Bismuth [5]
Dissalve 2g of sample in 18 ml of HBr, 2m! of Br2 and Sml of HCl04 and evaparate to fuming
(in a perchloric acid compatible fume cupboard). lf the solution is cloudy add more HBr. Cool,
dilute and transfer to a 50ml volumetric flask. Pipette 25m! of 8% w/v thiourea solution and dil-
ute to volume. Measure the absorbance with a 1 cm cell at 465 nm for Bi 0.07% or with a 4cm
cell for Bi 0.001 -0.015%. Calibrate with standards in the range 0.05- 1.4mg Bi taken through
the full procedure. Carry out all measurements at 20° ± 1°C.
The ASTM method for bismuthin solders [6] is very sirnilar. The colour formed is
extremely sensitive to temperature.

Copper
B.S. 3338 [7] gives a method for 0.001 - 0.04% Cu using a photometric deterrnina-
tion in gum arabic solution with rubeanic acid, after removal of tin with HBr/Br 2 • The
photometric method [8, 9] using HBr/H 3 P0 4 afterremoval of tin with HBr/Br 2 is
suitable for 0.01- 2% Cu on a 1 g sarnple with 4crn cells. (See Chapter 14, Section
2.4). Considerable increases in sensitivity may be obtained by the use of a lOg sarnple.

Iron
This may be deterrnined by the photometric 1,10 phenanthroline method given in
Section 2.5 ofChapter 14 [8, 10].

Lead
The B.S. method for lead in ingot tin [11] involves tinremoval with HBr/Br 2 fol-
lowed by extraction with dithizone into chloroforrn from a solution containing sodium
tartrate, hydroxylarnmonium chloride and potassium cyanide.
Other References of Interest:
Ag General scherne for 13 irnpurities after precipitation on La(OHh [12]
Atornic absorption, graphite tube [44]
Al Eriochrorne cyanine R, colorirnetric [13]
Chrome Azurol S (C.I. Mordant Blue 29), colorirnetric [14]
As Neutron activation [15]
B Extraction of BF 4/rnethylene blue cornplex into CH 2CI 2 colorirnetric [16]
Benzoin, fluorirnetric [17]
Bi See Ag [12, 44]
Anodic stripping voltamrnetry [18]
Thionalide extraction colorirnetric [19]
Cd See Ag [12, 44]
Co See Ag [12, 44]
Cr Diphenylcarbazide colorirnetric [20]
Cu See Ag [12,44]
Neutron activation [21]
Anodic stripping voltamrnetry [18]
Polarography [22]
Diethyldithiocarbamate extraction colorirnetric [23]
Ion exchange separation [24]
Arnrnonia colorirnetric [25]
Dithio-oxamide extraction colorirnetric [25]
196 Analysis of lngot Tin [Ref.p.198

Cu Square wave polarography [261

Fe See Ag [121
Bipyridyl extraction colorimetric [27,291
Thiocyanate colorimetric [281
H Coulometric [301
Hg See Ag [121
In See Ag [121
5, 7 Dichloro-8-hydroxyquinoline extraction colorimetric [31 1
Neutron activation [321
Mn See Ag [12 1
Neutron activation [321
Ni See Ag [12,441
0 'Y·Activation [331
Fusion gravimetric [34 1
p Reduced phosphomolybdate extraction colorimetric [35, 361
Pb See Ag [12,441
Anodic stripping voltammetry [181
Ion exchange separation [241
s Combustion conductimetric [37, 381
Sb Anodic stripping voltammetry [39, 401
Neutron activation [15 1
Se Neutron activation [15 1
Si Reduced silicomolybdate colorimetric [41 1
Tl See Ag [121
Zn See Ag [121
Potassium ferricyanide titration, crude tin [421

2.3 Emission Spectroscopic Methods for Impurities

A wide range of impurities may be deterrnined in tin by direct photographic emis-

sion spectroscopy on metal samples down to 1p.g/g with comparative ease [431. Whe-
never possible, tin should be sampled from a well-stirred melt and chill-cast into
spectrographic rods or discs. Remelting, if necessary, shou1d be carried out in a clean
porcelain or glass vessel; the melt should be stirred with a rod of spectrographic carbon.
Standardsaremade from master alloys, diluted by melting with 99.999% or
99.9999% tin. Formost purposes the forrner is adequate as the 10p.g/g of impurity is
usually much less than the specification lirnit and is distributed between several ele-
ments. Master alloys may be made in a number of different ways:
(i) Melting under glycerol or palm oil - absolute standards may be made by separate-
ly melting Al, As, Bi, Cd, In, Pb, Sb and Zn to give a 1% alloy of each. With some me-
tals it may be neccessary to melt at a rather higher temperature (500°C) in the absence
of an oil. Losses by Vaporisation or oxidation should be less than 10%.
(ii) Melting under borax or potassium cyanide - the standards produced are usually
absolute but it is wise to check by chemical assay. Elements such as Ag, Au, Cu and
 Ref.p. 198] 2.3 Emission Spectroscopic Methods for Impurities 197

Fe require heating at 900°C to obtain a 1% solution in a reasonably short time. Cop-

perand silver may be dissolved by prolonged heating at temperatures as low as 400°C.
Iranstandardsare best obtained from works intermediates if these are available.
Spectrographic conditions are:
(i) High Purity Tin (99.999%).
(0.5mH, 120pF, 4mm gap, 60° carbon electrode, 3 min burn)
Standards (J.Lg/g): Ag Bi Cu Fe In Pb Sb
5 5 5 10 5 10 10
2 2 2 52 55
111 21 2 2
Wavelengths (nm) 328.1, 306.8, 327.4, 259.84, 325.9, 262.4, 259.8

(ü) Electrolytic Tin (99.95 %)

(0.5mH, 120J.lF, 4mm gap, 60° carbon electrode, 30 sec burn)
Standards (J.Lg/g): Ag As Bi Cu Fe Ge In Pb Sb
100 100 100 100 100 20 20 100 300
30 30 30 30 30 10 10 30 100
10 10 10 10 10 0 0 10 50
Wavelength (nm) 328.1 234.9 306.8 327.4 259.8 265.1 235.9 288.3 259.8
Sn Ref. (nm) 322.4 278.8 314.1 322.4 278.8 278.8 322.4 276.2 278.8

(iii) Common Tin (99.0%)

(0.5mH, 120J.lF, 4mmgap, 60° carbon electrode, 30 sec burn)
Standards(%): As Cu Fe Pb Sb
0.30 0.10 0.5 1.0 0.5
0.10 0.05 0.2 0.4 0.25
0.05 0.02 0.08 0.2 0.1
0.03 0.005 0.01 0.1 0.05
0.003 0.05 0.025
0.01
Wavelength (nm): 234.9 296.1 259.8 282.3 259.8
Sn Ref: 278.8 327.4 278.8 283.3 278.8
314.1

For the analysis oftraces of impurities present at less than 1J.lg/g a number of So-
viet researches are of interest. Yudelevich [45] used an 80mg powdered sample pla-
ced in a carbon anode in a 15 amp d.c. arc to obtain Iimits of detection of 0.2J.lg/g Cd,
4/lg/g Te and 0.4 J.lg/g Zn. At the end of the burn, 99% of the sample remained alt-
hough the impurities had volatilised. Enhanced sensitivities were obtained for Co, Fe,
Ni etc. by mixing the sample with an equal weight of sulphur to volatilise tin before
the impurities. Traces of Al, Ca, Cu, Fe, Mg and Si were determined [46] down to
lJ.lg/g or less by igniting the sample, then mixing 20mg of oxide with lOmg of car-
bon for excitation in a 1Oamp. d.c. arc with 2.5 mm electrode gap. Limits of detec-
tion ofthe order ofng/g were obtained [47] for many elements by treating 1- 5g of
tin in a silica dish with 50mg of carbon, 2mg of NaC!, 2ml of CC14 and 2- 8ml of
Br 2 (added in 0.5 ml portions). After decomposition was complete, the dish was hea-
ted to 180- 200°C to remove Sn as the bromide. The residue was packed in a carbon
anode of 4mm diameter, 3mm depth for excitation in a d.c. arc. Synthetic standards
were easily prepared for nineteen elements by adding aqueous solutions to carbon and
NaC! and taking through the procedure.
198 Analysis of lngot Tin

References
1. Methods for the Sampling and Analysis of Tin and Tin A!loys British Standard, B.S. 3338,
Part 1 (1961)
2. Reference 1, B.S. 3338, Part 2 (1961)
3. Reference !, B.S. 3338, Part 3 (1961)
4. Reference 1, B.S. 3338, Part 9 (1965)
5. Reference 1, B.S. 3338, Part 8 (1961)
6. 1975 ASTM Book of Standards Part 12, E46 (1972)
7. Reference 1, B.S. 3338, Part 6 (1961)
8. Price, J. W., Cappins, W.C.: The Analysis ofTin-Bearing Base Metals: Tin Research Institute
Publication 161, London, 1954
9. Reference 1, B.S. 3338, Part 4 (1961)
10. Reference !, B.S. 3338, Part 10 (1961)
11. Reference 1, B.S. 3338, Part 5 (1961)
12. Marczenko, Z., Kasiura, K.: Chemia Analit. 10, 449 (1965)
13. Lel'chuk, Y.L., Sokalovich, V.B., Drelina, O.A.: Izv. Tomsk. Politekh. Inst.128, 101 (1964).
Anal. Abstr. 13,5477 (1966)
14. Shvaiger, M.l., Rudenka, E.I.: Zavod. Lab. 26, 939 (1960). Anal. Abstr. 8, 1448 (1961)
15. Maenhaut, W.,Adams, F., Haste, J.: J. Radioanalyt. Chem. 6, 83 (1970)
16. Lel,chuk, Y.L., Jvashina, V.A.: lzv. Tomsk. Politekh. Inst. 148, 157 (1967)
17. Le/'chuk, Y.L., Jvashina, V.A.: lzv. Tomsk. Politekh. lnst. 148,152 (1967). Anal. Abstr.
17,115 (1969)
18. Brainina, K.Z., Neiman, E. Y., Trukhacheva, L.N.: Zavod. Lab. 38, 12 (1972). Anal. Abstr.
23, 130 (1972)
19. Lilie, H.: Z. Anal. Chem. 159,196 (1958)
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20, 2389 (1971)
21. Wölfe, R., Herpers, U., Herr, W.: Z. Anal. Chem. 233, 241 (1968)
22. Stromberg, A.G., Zakharav, M.S., Garadavykh, V.E.: Zavod. Lab. 27, 517 (1961)
23. Jkeda, S., Nagai, H.: Japan Analyst 7, 76 (1958)
24. Kataev, G.A., Slezko, N.J.: Trudy. Tomsk. Gos. Univ. 170, 76 (1964). Anal. Abstr. 13,
1727 (1966)
25. Zhivopistev, V.P., Selezneva, E.A.: Uch. Zap. Permsk. Univ. 25, 84 (1963)
26. Jtsuki, K., Kaji, T.: Japan Analyst 8, 703 (1959)
27. Le/'chuk, Y.L., Kristalev, P. V., Skripava, L.L., Kristaleva, L.B.: Izv. Tomsk. Politekh. lnst.
128,96 (1964)
28. Bradshaw, G., Rands, J.: Analyst 85, 76 (1960)
29. Kristalev, P. V., Kristaleva, L.B.: Sb. Nauch. Trudy. Permsk. Politekh. Inst. 14, 65 (1963).
Anal. Abstr. 12, 2737 (1965)
30. Yashimari, T.,lshiwari, S.: Talanta 17, 349 (1970)
31. Raby, R.A., Banks, C. V.: Anal. Chim. Acta 29,532 (1963)
32. Maenhut, W., Adams, F., Haste, J.: J. Radioanalyt. Chem. 9, 27 (1971)
33. Kapitza, S.P., Samasyuk, V.N., Tsipenyuk, Y.M., Kunin, L.L., Chapyzhnikov, B.A.,
Wasserman, A.M., Yakovlev, Y. V.: Radiochem. Radioanalyt. Lett. 5, 217 (1970)
34. Gumilevskaya, G.P., Chekanava, V.D., Guseva, K.S., Tashkava, Z.l., Murilina, A.J.:
Trudy. Vses. Nauch. lssled. Proektno. Teknol. Inst. Elektrougol'n. Jzdelii. 1, 119 (1970).
Anal. Abstr. 21, 129 (1971)
35. Sokolavich, V.B., Lel'chuk, Y.L., Drelina, D.A.: lzv. Tomsk. Politekh. Inst. 148, 162 (1967).
Anal. Abstr. 17,117 (1969)
36. Lel'chuk, Y.L., Sakalovich, V.B., Detkava, G.A.: lzv. Tomsk. Politekh .. lnst. 148, 144
(1967). Anal. Abstr. 17, 116 (1969)
37. Pell, E., Malissa, H., Murphy, N.A., Chamberlain, B.R.: Anal. Chim. Acta 43,423 (1968)
38. Chamberlain, B.R., Murphy, N.A.: Anal. Chim. Acta 59, 151 (1972)
39. Zaichko, L.F., Zakharov, M.S., Mardvinava, V.D.: lzv. Tomsk. Politekh. lnst. 128,50 (1964)
40. Zaichka, L.F., Yankauskas, V.F., Zakharav, M.S.: Zavod. Lab. 31, 265 (1965). Anal. Abstr.
13, 3504 (1966)
41. Pilipenka, A.T., Nabivanets, B./., Shainskaya, L.G.: Zavod. Lab. 22,2214 (1972)
42. Papov, M.A., Repkina, A.E.: Uchen. Zap. Tsent. Nauch. Issled. Inst. Olovyan. Prom. 90
(1965). Anal. Absü. 14, 1364 (1967)
43. Unpublished Work and Standard Methods, Capper Pass, Ltd.
44. Medina, R.: z. Anal. Chem. 271, 346 (1974)
45. Yudelevich, J.G., Shelpakava, I.R., Sukankina, T.A., Prakharava, S.A.: Zavod. Lab. 34,
1074 (1968). Anal. Abstr. 8, 124 (1970)
46. Usenko, L.E., Kalinchuk, S. V.: Zavod. Lab. 34, 686 (1968). Anal. Abstr. 17, 2053 (1969)
47. Malakhav, V. V., Protapopava, N.P., Trukhacheva, V.A., Yudelevich, J.G.: Trudy. Korn. Analit.
Khim. 16, 89 (1968)
CHAPTER 16

TIN IN COPPER-BASE ALLOYS

By R. Smith

Table 1 gives an illustrative selection of copper-based alloys where tin is an impor·

tant element in the specification [ 1].

1. Sampling
The sampling of copper-based materials (particularly scrap) is complex and becau-
se of the many situations which may arise, only guidelines can be given here. Meta!
used for casting should be dip sampled and poured into a chill-cast mould.
In any sampling scheme for assorted materials, it must be decided if the material
can reasonably be sorted into different types or if a single primary sample is to be
drawn.In the secondary copper industry, experienced samplers can grade articles such
as castings, ingots, etc., into alloy types by examination of the meta! and its drilling
characteristics. Wherever possible, consignments should be sorted into sub-samples
and weighed. With small consignments, this exercise alone may be acceptable for val-
uation purposes. Where samples for assay are required the following guidelines illu-
strate current practice.
Large castings, ingots - sampled by drilling completely through, bearing in mind
that considerable segregation of Iead is probable in !arge castings. The weight of drill-
ings taken should reflect the size of the casting. Whitemetal bearings, iron or steel
items, etc., should be separated and treated separately. Whitemetal may be melted and
sawings taken, iron or steel can usually be rejected after weighing. Drillings should be
milled through a 5 mm screen and graded on a 2 mm screen to give oversize and under-
size which are weighed. Assay samples may be prepared by milling 1 kg of the drillings,
combined in proportion, through a B.S. 30 mesh screen. An example is given on p 201.
The final assay results should be multiplied by the % to give the concentration in the
original consignment.

Small mixed castings - where drilling would be excessively time consuming and
castings are small, a sarnple may be prepared by melting SOkg of castings in a crucib-
le furnace usually without a flux. Copper-based alloy may then be poured off into
an ingot mould leaving behind a residue of nicke! or irony material with small amounts
of the alloy: whitemetals usually reside with the copper portion. The irony residue
may be treated at red heat with rock sulphur and stirred to form a fluid matte of iron
sulphide which may be cast and crushed on cooling. Iranpyrites (free from copper)
or aluminium meta! may also be used for attacking irony residues. Losses of tin as
the volatile sulphide during matte preparation may be considerable and this should
only be considered when a good Separation from the bulk of the copper alloy has al-
ready been achieved. Direct treatment of copper alloys by heating with aluminium
is possible to give a crushable aluminium/copper alloy (usually equal portians by
 N
0
0

Table 1. Composition of Same British Standard Copper Alloy Castings Containing Tin
..,
s·
s·
British Standard Casting Cu Sn Zn Pb p Ni Fe Al Si Other (')
0
'0
Phosphor Bronze PB! REM > 10.0 <o.o5 <0.25 > 0.50 < 0.10 < 0.10 <O.Ol < 0.02 '0
Phosphor Bronze PB2 REM 11.0- 13.0 <o.3 <o.5 > 0.15 < 0.5 < 0.15 <0.01 < 0.02
Phosphor Bronze PB4 REM > 9.5 <o.s <0.75 > 0.4 < 0.5 ~
~
Leaded Phosphor Bronze LPB1 REM 6.5-8.5 <2.0 2.0-5.0 > 0.3 < 1.0 (I)

Copper Tin CTI REM 9.0 - 11.0 <o.os <0.25 < 0.15 < 0.25
Leaded Bronze LBl REM 8.0- 10.0 <Lo 13.0-17.0 < 0.1 < 2.0 < 0.02 Sb <o.s ~
Leaded Bronze LB2 REM 9.0- 11.0 <1.0 8.5 - 11.0 < 0.1 < 2.0 < 0.15 <o.o1 < 0.02 Sb <o.s 'a
Leaded Bronze LBS REM 4.0-6.0 <Lo 18.0- 23.0 < 0.1 < 2.0 < 0.01 Sb <o.s I
Gunmetal GI REM 9.5- 10.5 1.75-2.75 <1.5 < 1.0 < 0.15 <O.Ol < 0.02
Nickel Gunmetal G3 or G3-TF REM 6.5- 7.5 1.5 - 3.0 0.1-0.5 < 0.02 5.25-5.75 <o.o1 < 0.01 Bi <0.03
Leaded Gunmeta I LG1 REM 2.0- 3.5 7.0- 0.5 4.0-6.0 < 2.0 <o.o1 < 0.02 ni<O.l
Leaded Gunmetal LG2 REM 4.0-6.0 4.0 -6.0 4.0-6.0 < 2.0 <o.o1 < 0.02
Leaded Gunmetal LG4 REM 6.0- 8.0 1.5 - 3.0 2.5-3.5 < 2.0 < 0.2 <O.Ol < 0.01 Sb <0.25
Brass (Sand Casting) SCBl 70.0- 80.0 1.0- 3.0 REM 2.0-5.0 < 1.0 < 0.75 <o.o1
Brass (Sand Casting) SCB3 63.0- 70.0 <u REM 1.0-3.0 < 1.0 < 0.75 <o.l
Naval Brass SCB4 60.0-63.0 1.0 - 1.5 REM <o.s <O.Ol
Brass (Die Casting) DCB3 58.0- 63.0 < 1.0 REM 0.5-2.5 < 1.0 < 0.8 0.2-0.8 < 0.05 Mn <o.s
Brass (Die Casting) PCBl 57.0- 60.0 <o.s REM 0.5-2.5 < 0.3 <o.s
Brass (High Tensile) HTBl >ss.o <Lo REM <o.s < 1.0 0.7-2.0 0.5-2.5 < 0.10 Mn <3.0
Brass (High Tensile) HTB3 >55.0 <o.2 REM <o.2 < 1.0 1.5 - 3.25 3.0-6.0 < 0.10 Mn <4.0
Cu/Mn/Al CMAl REM <1.0 <o.s <o.os 1.5 - 4.5 2.0-4.0 7.5-8.5 < 0.15 Mn 11-15
Cu/Mn/Al CMA2 REM <J.o <o.s <o.os 1.5 -4.5 2.0-4.0 8.5-9.0 < 0.15 Mn 11 - 15
Aluminium Bronze AB1 REM <o.1 <o.s <o.os < 1.0 1.5- 3.5 8.5- 10.5 < 0.25 Mn <1.0
Aluminium Bronze AB2 REM <o.1 <o.s <o.o5 4.0-5.5 4.0-5.5 8 .. 8- 10.0 < 0.1 Mn<l.S
- - - - - -- ---- --

';t;'
(I)
!"'>
'>'
N
0
-""
 Ref.p. 204] 1. Sampling 201

Example
Sampling of gunmetal castings with steel studs and whitemetal inserts. Castings range from ap-
proximately 30- 100 cm.
kg %
Consignment weight 3,522 100.0
Primary sample 108 100.0
Deterrnine burning loss on whole sample, then remove whitemetal by melting. Remove suffi-
cient steel studs to assess the total weight of steel in the primary sample. Sampiecastings by
drilling.
kg %
Loss 0.9 0.83
Whitemetal 5.1 4.72
Iron 2.5 2.31
Copper (difference) 99.5 _211.±._
108.0 100.00

Reduce the whitemetal by melting in a !adle and casting a series ofthin strips. Do not treat the
iron portion further. Mill the copper drillings through a 5 mm screen and grade on a 2 mm screen.
kg %
Copper + 2 mm 3.6 51.83
Copper · 2 mm ~ 40.31
6.4 92.14

Combine 518.3g of + 2 mm and 403.1g of- 2 mm drillings in a ring mill and mill through a 0.25
mm screen (B.S. 60 mesh). Further grading of the sample is unnecessary.
%
Final proportions:
Copper (-0.25 mm) 92.14
Whitemetal sawings 4.72
Iron (rejected) 2.31
Loss ~
100.00

weight are used). Care should be taken to stir weil throughout the procedure as failure
to do this may result in a minor explosion of malten meta!. Forthis reason and because
of the risk of generating arsine or stibine when the crushed alloy comes into contact
with moist air, aluminium treatment is usually regarded as a last resort, tobe used
when other treatments fail.
Drillings, turnings, swarf, etc. - usually these contain a mixture of elements in
cluding ferrous metals. A burning lass should be carried out on lOkg as soon as pos-
sible. Melting mixed drillings is a convenient way of preparing a sample; the presence
offenaus metals, however, may give a meta! strip which is difficult to drill or saw.
In this instance the drillings should be coarsely milled through a 5mm screen, iron
separated by magnet and the remaining copper alloy melted under a flux. The iron
portion will almost certainly contain some copper and may be converted to an assay
portion either by milling in a ring mill through a B.S. 60 mesh sieve or by matte for-
mation with sulphur. An example is given on p 202.
Iran castings with gunmetal inserts - the iron and gunmetal portians must be
separated on a11 of the primary sample if practicable to obtain the proportians of
casting and insert. These can then be sampled and processed separately.
Slaggy metal- gunmetal skimmings, for example, occur with slag adhering to
meta!. The whole of the primary bulk sample should be treated to separate the two
202 Tin in Copper-Base Alloys [Ref.p. 204

Example
Sampling of coppery borings.
kg %
Consignment weight 4,503 100.00
Prirnary sample 25 100.00
A small primary sample is necessary because of the bulky nature of borings. Determine burning
loss,mill through a 5 mm screen and grade on 2mm screen. No iron found on testing with mag-
net.
kg %
Meta!+ 2mm 13.5 54.00
Meta!- 2mm 10.3 41.20
Loss 1.2 4.80
25.0 100.00

Combine 540g + 2mm and 412g- 2mm meta! in a crucible with 50g ofborax glass. Melt, cast
meta! strip, clean off flux and weigh.
g %
Meta! 943.1 94.31
Flux 42.0 4.20
985.1 98.51

Note that some of the flux is always lost in glazing the crucible. All the meta! should be reco-
vered but a small amount will be taken into the flux which should also be assayed. The assays
on the meta! should be multiplied by 0.9431, those on the flux by 0.0420, the two should be ad-
ded to give the concentration in the original consignment.

components. This is usually done by breaking the slag with a hammer or jaw crusher
and removing the metal by hand or by screening. Drilling of slaggy metal always gives
a biased sample, usually deficient in metal.
Moisture, buming loss - The determination of moisture or burning loss should be
carried out on as large a sample as possible soon after weighing. Sampies of up to
50kg may be accomodated in relatively small ovens if the shelves are removed.
Burning Iosses may be easily carried out by weighing, pouring kerosene or diesei oll
over 5 - 50kg sample, igniting, cooling and reweighing.

2. Volumetrie Methods

British Standard Method [2]- based on an acid dissolution, ammonia precipita-

tion with iron hydroxide collector, nickel reduction and iodate titration. The stan-
dard deviation is 0.04% Sn (at 1% Sn) and 0.1% Sn (at 14% Sn).
Dissolve 1 - 5 g of sample in 30 ml of HCI and 30 ml of HN03 and allow to stand on a hotplate
to expel nitrous fumes. Dilute to 125 ml with warm water add 2 - 3 ml of 10% FeCI3 solution in
1% HCI and add concentrated ammonia solution until the precipitate of copper hydroxide has
completely dissolved. Add a further 5ml of amrnonia and bring to the boil with stirring. Keep
hot for 30 min on the edge of a hotplate. Filter through a Whatman 541 paper, wash with hot
1% (NH4hS04 solution discarding the washings. Dissolve the precipitate off the paper with hot
50% HCI and wash the paper with hot water. Reprecipitate by adding amrnonia to the filtrate
with 5 ml in excess as before. Filter through the original paper and wash with hot 1% (NH4hS04.
Place the funnel in the neck of a 500ml conical flask marked at 150m!; openout the paper and
support in the funnel. Wash the precipitate into the flask with a jet of hot water (about 25 ml)
 Ref.p. 204] 3. Instrumental Methods 203

and wash the paper with hot 50% HO until the volume in the flask is 150m!. Add 25 ml of con-
centrated HC!. Add two drops of 2% Sb03 so!ution in 50% HC! and insert a nicke! coil. Boil
for 45 min, cool under C0 2 or with a Göckel trap. Add 2 or 3 marble chips, starch indicator and
titrate with N/20 potassium iodate (1.784g/l KI03, 20g/l Kl, 0.01 M NaOH).
To standardise take a weight of pure copper equal to the sample weight tagether with a weight
of tin approxirnate!y equal to the weight of tin in the sample and carry through the procedure
above.
A rapid method developed by the British Non-Perraus Metals Research Association
[3] requires the use of sodium hypophosphite as a reductant for tin. Under the con-
ditions employed no copper removal is necessary. The method is similar to that of
Wiedmann [4] andDozinel [5].
Dissalve lg (1.0- 7.5% Sn) or O.Sg (7.5 -14%) of sample in 30m! of 50% HCI and Sm! of
30% H2 0 2 (100 vol). Warm to initiate the reaction and allow to stand to complete dissolution.
Boi! to remove peroxide, add 1 ml of saturated HgCI2 solution and lOml of hypophosphoraus
acid (approx. 31 %). Simmer for 15-20 min but do not boil. Fit a Göckel trap or supply of C02
and cool to below l5°C. Add 2gofNaHC0 3 , 10mlof20% NH4SCN and 1-2mlofoleic acid
and shake thoroughly. Add 70 ml of water and starch indicator. Titrate with 0.02N potassium
iodate (Sn< 2.5 %) or 0.5 N potassium iodate (Sn 2.5 - 15 %). Add 5 g of KI just before the end-
point.
Standardise by taking 0.5 or LOgcopper with 50mg of tin (0.5 N iodate) or 20mg tin (0.2 N
iodate) through the procedure. The end-point is somewhat transitory but is irnproved by addi-
tion of oleic acid and KI just before the fmish.
An EDT A method for tin in copper-based alloys has been developed by Kimumen
and Wennerstrand [6] and is given in detailinChaper 4. In mixed meta! systems it is
recommended that excess sodium fluoride is added after titration to complex tin. The
displaced EDT A is then titrated with thorium as before. Other methods include that of
Furuya and Tajiri [7] for phosphor bronzes.

3. Instrumental Methods

Tin may be determined in copper-based materials by a variety of instrumental

methods of which the most commonly used are X-ray fluorescence and emission
spectroscopy. Details of these methods are included in the appropriate chapters and
will not be repeated here.
Photometrie determinations include the use of catechol violet [8], quercetin [9],
phenylfluorone [10, Il], 9- (3-pyridyl) fluorone [ I2], 8-hydroxyquinoline [15] and
oxidised haematoxylin. In nearly all these methods separation of tin by extraction as
the iodide, distillation as brornide, precipitation with Mn0 2 or Fe(OH) 3 , or iron-
exchange Separations [11] are required. 4-Hydroxy-3-nitrophenyl arsonic acid [I3,
14] has been used as the basis of a turbidimetric method.
Atomic absorption spectroscopy is a reliable alternative to titrimetry [I7- 20].
In the BNFMRA method [3], I - 5 g of alloy is dissolved in 50ml of 10% HCl : 30%
HN0 3 ; on cooling 50ml of 30% tartaric acid is added and the solution diluted to 1
litre. Copper (I - 5 g) is added to standards and the use of composite Standards con-
taining several elements is recommended. Standards also contain similar amounts of
acid to the sample solution. The Sn 224.6 nm line is used with an air/H 2 flame; the
method is suitable for 0.1- I3% Sn with calibrations in the range 20- IOO,ug/ml Sn.
Other methods do not usually include tartaric acid or composite standards. Scott
and Wallen [I8] used an air/H 2 flame supported on a three-slot burner and an elec-
trodeless discharge lamp. Johns and Price [I7] preferred the N2 O/C 2 H 2 flame.
204 Tin in Copper-Base A!loys

References
1. Copper Alloy Ingotsand Copper Alloy Castings, British Standard, 1400 (1973)
2. Methods for the Analysis of Copper Alloys, British Standard, 1748, Part 6 (1960)
3. Chernical Analysis of Copper Alloys for Castings, Brit. Non-Perraus Met. Res. Assoc. (1972)
4. Wiedmann, H.: Z. Metallkunde 12, 1005 (1958)
5. Dozinel, C.M.: Z. Metallkunde 18, 1193 (1964)
6. Kinnunen, J., Wennerstrand, B.: ehernist Analyst 46, 34 (1957)
7. Furuya, M., Tajiri, M.: Japan Analyst 12,59 (1963)
8. Kamaukhova, N.N.: Zavod. Lab. 36, 1047 (1970)
9. Liska, K.: Chern. Listy 49, 1656 (1955)
10. Luke, C.L.: Anal. Chern. 31,1803 (1959)
11. Kurbatova, V.!., Stepin, V. V.: Trudy Vses. Nauchno-issled. Inst. Standartn. Obraztsov.
Spektr. Etalnov.1, 14 (1964). Anal. Abstr. 13,6802 (1966)
12. Asmus, E., Zraetch, J.: Z. Anal. Chern. 223,401 (1966)
13. Dozinel, CM., Gill, H.: Chernist Analyst 45, 105 (1956)
14. Challis, H.J.G., Jones, J.T.: Anal. Chirn. Acta 21, 58 (1959)
15. Tsukahara, I., Yamamoto, T., Tonomura, T.:·Japan Analyst 18, 1229 (1969)
16. Tanaka, R.: Japan Analyst 10, 336 (1961)
17. Johns, P., Price, W.J.: Metallurgia 81, 75 (1970)
18. Scott, C.C., Wallen,M.A.: Spectros. Lett. 4, 353 (1971)
19. Bamett, W.B., Kerber,J.D.: Perkin Eimer A.A. Newsletter 13,56 (1974)
20. Nakahara, T., Munemori, M., Musha, S.: Anal. Chirn. Acta 62, 267 (1972)
CHAPTER 17

TIN IN FERROUS ALLOYS

By J.W. Price

1. Introduction

Small amounts of tin, introduced in the remelting of scrap, have a deleterious ef-
fect on the physical properties of low-carbon steels and the tin content of such ma-
terial is generally kept to below 0.25% by removal in the blast furnace. On the other
hand, the deliberate addition of about 0.1% tin to flake graphite or spheroidal graphi-
te iron produces a pearlitic structure giving high hardness and good wear resistance.
More recently, the addition of 2% tinplus 3% copper instead ofup to 10% copper
alone as a sintering aid in the manufacture of components from iron powder compacts
has been found beneficial in reducing sintering temperatures and allowing closer dimen-
sional control.
Direct determination of tin at these Ievels by emission spectrography and by X-
ray fluorescence is dealt with in Chapters 9 and 10 and is not further considered here.
Of the chemical methods in use, the classical procedure involves dissolution of a large
sample ( 5 - 10 g) in acid, separation of the tin as sulphide and volumetric determination
with iodate. Photometrie methods, which are becoming more generally used, have the
advantage of requiring only small samples, down to as little as 0.1 g. There are con-
flicting views in the Iiterature on methods of sample dissolution, the use of non-oxidi-
sing acids being thought in some cases to involve loss of tin in the insoluble residue, or
by volatilisation or even by formation of organic tin compounds which are not precip-
itated by H 2 S. Consequently the standard ASTM method [ 1] uses nitric acid to dis-
solve the sample whenever possible and further treats any insoluble residue by heating
to fuming with nitric/sulphuric acids. On the other hand, dissolution of the sample in
hydrochloric acid has been investigated in detail [2] with a series of plain carbon as
well as high-speed and niobium steels and no loss of tin was found in the carbide resi-
dues, while with suitable precautions, other Iosses could be prevented. This work has
led to the publication of a standard method suitable for the determination of tin in
most samples of iron and steel [3]. The only materials for which these general proce-
dures are not applicable are tungsten meta! and ferrotungsten, for which the sample
is dissolved in a mixture of sulphuric, hydrofluoric and nitric acids [3).

In view of the great variety of composition of ferrous alloys in general it may be

possible to encounter occasional samples which cannot be analysed by dissolution
in non-oxidising acids, but the procedure is more rapid than that using nitric acid in
that no treatrnent of the insoluble residue is needed and so is tobe preferred when
possible.
Methods of sampling of iron, steel and ferro-alloys are given in Ref. [3) and are not
discussed here.
206 Tin in Ferrous Alloys [Ref.p. 208

2. Volumetrie Methods

2.1 General Method

Dissolve a 5g sample in 60ml of hydrochloric acid, adding 10m! of a saturated aqueous solu-
tion of sulphur dioxide and keeping the temperature of the solution below 65°. Add 100m! of
water and a further 25 ml of the sulphurous acid solution, add a little ashless fiiter pulp and boil
for 5min, Filter through a pulp pad, washing with hot 5% hydrochloric acid and discard the
residue. Add 5 ml of bromine water to the filtrate and boil for a few min, then neutralise with
ammonia to the appearance of a faint permanent precipitate, acidify with hydrochloric acid and
add 10m! excess. Dilute to about 450ml, add 2m! of a 1% ammonium molybdate solution to
act as collector, and pass H 2 S through the solution for 1 hour. Allow the precipitate to settle and
filter through a pulp pad, washing with 1% sulphuric acid saturated with H 2 S. Return the pad and
precipitate to the beaker and destroy organic matter by heating with 10m! of sulphuric acid and
evaporating to fuming. Cool, add 100 ml of water and 15 ml of hydrochloric acid and Sm! of 1%
ferric chloride solution and make alkaline with ammonia. Filter and wash with hot water, then
dissolve the precipitate through the paper with 140m! of 5 M hydrochloric acid into a 500ml
conical flask, washing the paper with hot 5% hydrochloric acid. (At this stagein the published
procedure [3] addition is made of 2m! of a 1% antimony trichloride solution so that fincly-divi-
ded metallic antimony is precipitated along with the tin on subsequent treatment with aluminium.
This is claimed to cause a more rapid reduction of the tin, but is subject to a negative error by
loss of tin in the antimony precipitate and a positive error due to some dissolution of antimony by
iodine during the titration. The fact that correct results may be obtained by a balancing of these
errors does not justify the addition of antimony particularly as reduction with aluminium alone is
entirely satisfactory, as is shown in Chapter 4). Heat nearly to boiling, add 1g oftin-free aluminium
in small portions, stopper the flask with a bung carrying a bent delivery tube and boil gently for
30 min. Place the end of the delivery tubein a beaker containing 200m! of 10% sodium hydrogen
carbonate solution, remove the flask from the heat and cool to room temperature, allowing the
carbonate solutiontobe drawn into the flask to evolve C0 2 • Add 10m! of 10% potassium iodide
solution and 5 ml of 0.5% starch solution and titrate immediately with 0.01 N potassium iodate
solution to a permanent blue end-point.
T" t _ ml of iodate X 0.05935
m per cen - weight of sample
Modification of attack for samples of ferrotungsten or tungsten meta!: dissolve a 2g sample in
a platinum dish in a mixture of 5 ml of 50% sulphuric acid and 5 ml of hydrofluoric acid, adding
nitric acid dropwise until dissolution is complete. Add 10m! of 50% sulphuric acid and evaporate
to fuming to remove fluoride and nitrate. Add 100 ml of 20% citric acid, neutralise with ammonia,
add 10 ml excess and heat to dissolve tungstic acid. Acidify with 50% sulphuric acid, add 5 ml in
excess, dilute to 450 ml and continue as above.

2.2 Rapid method for cast iron

Dissolve a 2g sample in 20m! of 5 M hydrochloric acid without heating, add 20m! of 50% sul-
phuric acid and 40ml of water and bring to boiling to cornplete solution. Filter through a pulp
pad into a 500 ml flask, washing with hot water, add 50 ml ot" hydrochloric acid and a nicke! coil,
dilute to 200m!, stopper the flask with a bung carrying a bent delivery tube and boil gently for
30 min. Cool in an atmosphere of C0 2 as described above, add 1 - 2g of potassium iodi~e and
5 ml of starch solution and titrate with 0.01 N potassium iodate solution to a permanent blue end-
point.
This method is suitable for the determination of tin at the Ievel of about 0.1% in simple cast
iron; it may not be accurate for highly-alloyed material containing laige amounts of e.g. tungsten.

3. Photometrie Methods

Most of the reagents mentioned in Chapter 5 have been used for the determination
of tin in ferrous materials but tedious preliminary Separations are often necessary and
the methods described here are those in which Separations can be kept to a minimum.
 Ref.p. 208] 3 .3 4-Hydroxy-3-nitro-phenylarsonic acid Method 207

3.1 Phenylfluorone Method

As many metals react with phenylfluorone it is difficult to evolve a procedure to
eliminate all possible interferences. If it is known that the sample to be analysed con-
tains less than 0.3% As, Ge or Sb a direct photometric method is possible [4 ].
Dissalve a 1g sample in 7S ml of 20% sulphuric acid, adding a few drops of hydrogen peroxide
if necessary to complete solution. Dilute to 100m! and take a 10m! aliquot (if the tin content is
above 0.03% take a Sml aliquot and add S ml of 2.7M sulphuric acid). Add in order 10m! of S%
ascorbic acid solution, 10m! of acetate buffer pHS, Sm! of 1% gum arabic solution and 10m! of
a 0.01% methanolic solution of the reagent. Dilute to SOml and after 10min measure the optical
density of the solution at S10 nm. Prepare a calibration curve by adding known amounts of tin (10-
40pg) in 1S% sulphuric acid to 0.1g portions of iron in the samemedium and continue as above.
A more general method for the determination of 0.001 - 0.1% of tin in 0.1 - 0.01 g
samples of low-alloy steels has been developed by Luke [5]. This involves dissolution
of the sample in a 4:1 hydrochloric acid-nitric acid mixture, precipitation of the tin
as sulphide, adding 1mg of copper as carrier, followed by a double carbamate-chloro-
form extraction. To the final solutionhydrogen peroxide and ammonium oxalate are
added. lncreased sensitivity can be obtained by extraction of the coloured tin complex
into MIBK. This method requires modification in the presence of Mo (> 5 %), Ta, Nb
andW.

3.2 Pyrocatechol Violet Method

A procedure based on the extraction of tin(IV) iodide into benzene from sulphuric
acid solutions of concentration greater than 4M has been used by Tanaka [6] to deter-
mine small amounts, down to 0.002%, of tin in iron and steel as follows.
Dissolve 0.1- O.Sg of sample (tin up to 100pg) in nitric acid or a mixture of nitric and hydro-
chloric acids, add 1 -2m! of perchloric acid and evaparate to fuming. Add 20m! of 30% sulphuric
acid and reduce Fe(III) and Cr(IV) with titanous sulphate solution. Add 1ml of SM sodium iodide
solution for each 10m! of the solution and extract the tin(IV) iodide into 10m! of benzene. Back-
extract tin from a S ml aliquot of the benzene into 1 - 2M hydrochloric acid, add acetate buffer
pH 3.S - 4, 1 ml of a O.OS% solution of the reagent, dilute to 2S ml and measure extinction in a
1 cm cell at 552nm.
This procedure was modified by Newman and Iones (7], who found it preferable
to extract into toluene rather than benzene and to back-extract into sodium hydroxide
solution instead of acid.

3.3 4-Hydroxy-3-nitro-phenylarsonic acid Method

This method has been used successfully at the Tin Research Institute for the ana-
lysis of cast iron.
Dissolve the sample (1 g for up to 0.04% Sn; 0.25 g for 0.05 - 0.15% Sn; 0.1 g for 0.15 - 0.4%
Sn) in 20m! of SM hydrochloric acid, add 30m! of water and neutralise with ammonia to the for-
mation of a faint permanent precipitate. Acidify with 5 M hydrochloric acid and add 1 ml in ex-
cess. Add 3ml of 0.5% copper sulphate solution and precipitate tin and copper sulphides with
H2S. Filter the precipitate and wash free from chloride with hot water. Return the precipitate and
paper to the original beaker, add 5 ml of sulphuric acid and sufficient nitric acid to destroy organic
matter. Evaporate to fuming and add nitric acid dropwise until all carbides are decomposed and the
residue is white. Fina!ly add 10m! of water and evaparate to fuming. Cool, add Sm! ofwater, 10
m1 of 30% tartaric acid solution and filter into a SOml graduated flask,washing with lS ml of the
tartaric acid solution. Add 10m! of the reagent solution (2g dissolved in 100m! of 0.5% sodium
hydroxide sol_ution), di~ute to the mark, mix throughly and a!low to stand for several hours, pre-
fera~l~ overmght. R~-d1sperse the precipitate by shaking and measure the optical density of the
turbidlty at 4SO nm m a 2 cm cell. Prepare a calibration curve with a standard tin solution (0.1 -
0.4 mg Sn) and the same amounts of reagents as above.
208 Tin in Ferrous Alloys

4. Atomic Absorption Methods

Brief details are given in Chapter 8 of published methods for the determination of
tin in steels. Methods that have been found satisfactory for the analysis of cast iron
and iron compacts are given below.

4.1 Cast Iron

Dissalve a 1 g sample in 10 ml of 30% sulphuric acid, adding water as required to keep the
iron salts in solution. After dissolution is complete, oxidise by dropwise addition of nitric acid
(about lml is necessary) and boil for 1- 2min. Cool, add 1g of ammonium chloride and dilute to
50ml in a graduated flask. Filter through a dry paper and nebulise into an air-acetylene flame
(for details see Chapter 8).

4.2 Sintered Iron Compacts

Dissalve a 1g sample in 20ml ofmixed acid (3 HCl: 1HN0 3 : 3H 2 0), bring to the boil for
1 - 2 min, cool and dilute to 100ml in a graduated flask, Filteroff traces of carbon through a
dry paper and continue as above.
Prepare standards using 1 g portians of iron powder or tin-free cast iron to which are added
standard amounts of tin and continuing as above.

References
1. Chemical Analysis of Ferrous Metals (E.30). Book of A.S.T.M. Standards Part 32 (1975)
2. B.I.S.R.A. Methods of Analysis Committee. J. Iron and Steel Inst. 165, 190 (1950).
176, 156 (1954)
3. Methods for the Sampling and Analysis of Iron, Steel and other Ferrous Metals. B.S. Handbook
No. 19, 1970
4. Picasso G., Pizzimenti, A.: Metallurg. Ital. 55,361 (1963)
5. Luke, C.L.: Anal. Chim. Acta 37, 97 (1967)
6. Tanaka, K.: Japan Amtiyst 13, 725 (1964)
7. Newman, E.J., Jones, P.D.: Analyst 91,406 (1966)
CHAPTER 18

TINPLATE

By J.W. Price

1. Introduction

Owing to its non-toxic nature and its resistance to atrnospheric corrosion tin has been
used for rnany years as a coating on other rnetals, particularly for cooking vessels and
other articles used in contact with food. Tinplate is mild steel sheet which has been co-
ated on both faces with tin, and it is this material which is today used on a very !arge
scale for the production of a great variety of containers for foodstuffs and other pro-
ducts. Current annual world production of tinplate is of the order of 14 rnillion ton-
nes, accounting for ncarly half of the tin consurned, and while this material was origi-
nally produced by 'hot dipping', i.e. by irnrnersing steel sheets in rnolten tin, rnore than
90% is now rnade by electrodepostition in a continuous process. The thickness of the
tin coating is usually less than 0.0025 rnrn but the properties of the tinplate depend
very largely on the amont of tin present, so that the rnain analytical requirernent in
the examination of tinplate is a deterrnination of the tin coating thickness.
This thickness can be expressed in several different ways. For rnany years the tin-
plate industry has used a unit of area known as the 'basis box', consisting of 112
sheets of tinplate, each 20 x 14 ins. and having an area of 31 ,360in 2 (20.3435 rn 2 );
the weight of the tin coating is then calculated in 'pounds per basis box'. (It is irnpor-
tant to remernher that because both faces of the steel sheet are tin-coated, the area of
tinned surface in a basisbox is twice that given above, i.e. 62,720in 2 (40.465rn 2 ).
Code letters and nurnbers are used to designate the various available cornrnercial
grades of tinplate, e.g. 'H100' or 'E1 00' indicate a tin coating of 1lb/basis box produced
respectively by hot-dipping or by electrodepostion, while 'E25' is an electrolytic coating
of 0.25 lb./basis box.
The recent developrnent of thinner steel base for tinplate, and the very general use
of thinner electrolytic tin coatings for packaging rnaterials, together with the change
to the rnetric systern in the U.K. have led to the developrnent of !arger and rnore con-
venient units such as the French unit of 100 sheets of tinplate, each 1rn 2 in area. Ho-
wever, the concept of 'coating thickness' is tending to be replaced by 'tin coating
weight' expressed in g/rn 2 , and cornrnercial grades of tinplate are increasingly being
specified in these units. Taking the density of tin as 7.28, a tin coating weight of 11b/
basisbox is equivalent to a tin thickness of 0.001544rnrn on each face and to a weight
of 22.4 g/rn 2 of tinplate (i.e. half of this amount on each face). Under this systern code
figures for cornrnercial grades of tinplate are derived frorn the nominal coating weight
on each surface of the tinplate and a grade such as E25 under the older systern, beco-
rnes E2.8/2.8. The need for specifying the thickness of coating on each surface arises
frorn the existence of differentially coated electrolytic tinplate which is used rnainly
for containers needing high internal corrosion resistance. The rnost cornrnonly used
210 Tinplate [Ref.p. 213

differential tinplate, codedas Dl00/25 under the 'basis box' system, becomes Dll.
2/2.8, having 11.2g/m 2 oftin on one surface and 2.8g/m 2 on the other. As men-
tioned above, the corrosion resistance of tinplate increases with the tin coating weight
and so the choice of a particular grade of tinplate will depend on the conditions it
will be expected to meet. Thus the thicker tin coatings will be needed for such things
as kitchen and dairy equipment or for canning some kinds of fruit, sauces or vegetab-
les that are very corrosive in themselves, while the thinnest coatings are suitable for
canning mildly corrosive materials such as meat and fish, or for some dry packs and
for vacuum packed goods. It should be stated that other factors enter into the selec-
tion of a suitable grade of tinplate, and further information is given in Tin Research
Institute's publication No. 181 [12].

2. Determination of Tin Coating Weight

For control purposes rapid instrumental methods have been developed for the de-
termination of tin coating weight and of these the most important are (i) the coulo-
metric, (ii) the X-ray, and (iii) the Bendi:x procedures.

2.1 Coulometric Method

The Francis coulometric method [ 1] measures the time taken to dissolve the free
(unalloyed) tin coating anodically in 10% sodium hydroxide at constant current den-
sity, while theKunze and Willey procedure [2] uses 1M HCI as electrolyte and the
apparatus is arranged to produce on a recorder a plot of a potential-time curve against
a reference electrode. The advantage of this latter method is that the two steps produced
in the potential-time curve correspond to the dissolution of first the free tin and then
the alloy layer of the coating. (The alloy layer, consisting of the compound FeSn 2
( ~ 19% Fe) is formed at the steel-tin interface in the flow-melting stage of tinplate
manufacture and is now recognised as being important for the assessment of the pro-
perties of tinplate ).

2.2 X-Ray Method

The X-ray fluorescence method [3] measures either the attenuation of the seconda-
ry fluorescent radiation from the steel base on passage through the tin coating or the
tin fluorescent radiation, the intensity of which is proportional to the coating thick-
ness. Both these methods are in use for the on-line control of tinplate production, a
radioisotope such as hydrogen- 3 being used instead of an X-ray generator to excite the
fluorescent radiation. It is non-destructive and is particularly suitable for continuous
monitoring of the tin thickness during manufacture on an electrolytic line.

2.3 Bendix Method

In the Bendix method [4] the tin coating is dissolved anodically in HCI containing
an excess of a standard iodate solution, the carbon rod cathodes enclosed in porous
pots. Afterdissolution of the tin is complete the excess iodine is back-titrated with
standard thiosulphate. Some care is needed in judging the termination of the dissolu-
tion process: it can be stopped when only the free tin is removed, but the point at
which the alloy layer is dissolved is not easily detected visually, and continued electro-
lysis Ieads to erroneous results owing to dissolution of iron.
 Ref.p. 213] 2.5 Volumetrie Method 211

2.4 'Strip and Weigh' Method

Probably the siruplest procedure for use when only occasional samples of tinplate
are examined is the 'strip and weigh' method, originally put forward by Clarke [5].
A sample of convenient size, say 50- 100 crn 2 , is degreased, dried and weighed. It is then
immersed in 100m! of HCI containing 2g Sb 2 0 3 and allowed to remain in the stripping solution
for about 1 min. after gas evolution has ceased. It is then washed, the black deposit of antimony
removed by swabbing with cotton wool, dried and re-weighed. The weight loss represents the
sum of the free tin and the alloy layer, so that a correction is needed for the amount of iron in
the alloy layer, though for electrolytic tinplate this correction may usually be neglected. For hot-
dipped plate the correction is about 1.4g/m 2 and for electrolytic plate about 0.4g/m 2 . If consi-
dered necessary the correction may be found from a determination of the alloy layer as in 2.1
above. Differential plate may be evaluated by this method by coating one surface of the specimen
with a suitable cellulose lacquer, allowing to dry and applying a second coat of lacquer. After
this is dry the exposed tin surface is removed as above and the lacquer removed by dissolving in
acetone before re-weighing. The sample is again immersed in the stripping solution and a second
weight lass obtained.

2.5 Volumetrie Method

For referee purposes tin coating weights are generally determined chemically and a
number of national standard specifications give details of approved methods [6]. The
ISO recommendation [7] setsout a typical volumetric method, in which the tin
coating is dissolved in acid, the tin in solution is reduced to Sn(II) with metallic Aland
tin determined by titration with standard iodate solution.
Procedure.
From each bulk package of 1000 sheets of tinplate two sheets of hot-dipped or one
sheet of electrolytic plate are taken for checking the tin coating. From each of the
selected sheets three specimens each of an area of not less than 25 cm 2 and preferably
in the form of discs, are punched, one from the centre of the sheet and the other two
from diagonally opposed corners.
(i) Hot·dipped tinplate. Degrease with ether the specimens (24) from eight sheets taken as
above. Form a flat spiral of two turns and approx. 12.5 cm diameter from a length of about
75 cm of platinum wire of 0.6 mm diameter and place the spiral centrally in a shallow dish. Place
six of the discs in a circle on the platinum wire and pour 150m! of hydrochloric acid (750g/1,
prepared by diluting 750ml of the ooncentrated acid (d. 1.16) to 1 litre with water) into the
dish. When the tin coating is dissolved (3 - 15 min acoording to its thickness) transfer the acid to
a 1 litre volumetric flask, wash twice with 25 ml of water, transferring the washings to the flask.
Repeat the procedure with three successive lots of six discs, combining the acid and washings in
the same flask and finally diluting to the rnark with water. Transfer a 100m! aliquot of the solu-
tion to a 750ml conical flask, add 30ml ofhydrochloric acid (d. 1.16), dilute to 250m! and heat
to nearly boiling. Add 2g of aluminium (99.5%, tin free andin the form of heavy foil, coarse
millings or drillings) in small amounts, and before complete dissolution of the last addition of
aluminium, close the flask with a Contat-Göckel trap filled with a saturated solution of sodium
hydrogen carbonate (Fig. 2, Chapter 4 ). Boi! gently for 30min to redissolve the precipitated tin me·
tal, cool slightly and close the outler tube with a rubber cap. Cool in running water to room tempe-
rature (<20°) remove the trap, add 5 ml of a 1% starch solution and 10m! of a 10% potassium -
iodide solution and titrate with standard 0.1 N potassium iodate solution (3.567 g/1; 1 ml =
0.005935g Sn) to a permanent blue colour.
(iia) Electrolytic tinplate. Degrease the 12 specimens from four sheets, strip in two batches
of six discs as above, and dilute the combined acid and washings to 1 litre. Transfer a 100 ml ali-
quot to a 750ml flask and reduce with aluminiurn as above. Cool and titrate as above with stan-
dard 0.05 N potassium iodate solution. (1.7835g/l; 1ml =0.002967 5 g Sn).
(iib) Differential tinp/ate. Degrease the 12 specimes from four sheet and coat the faces
carrying the heavier tin coating with a cellulose lacquer. Allow to dry, apply a second coat of
lacquer and again allow to dry. Treat two batches of six discs as above, placing the discs with
the unlacquered faces in contact with the platinum wire, and dilute the combined acid and was-
hings to 1 litre. Dry the discs and retain them. Reduce and titrate a 100m] aliquot as above, using
a more dilute standard iodate solution (0.025N: 0.8918g/l; 1ml =o.00148375g Sn) for the final
212 Tinplate [Ref.p. 213

titration. Remave the lacquer from the retained specimens with acetone, place six of them with
their unstripped surface uppermost on the platinum wire and continue as above.
In all cases the average coating weight value is given by the expression.

Tin coating weight (g/m 2 ) = 5 · 935 ~103 VN

where V volume of potassium iodate in ml
N normality of the potassium iodate solution
A total specimen area in cm 2

3. Determination of Oil Film Weight

The oil film on the surface of hot dipped tinplate consists of residual palm oil from
the tinning process and is relatively tll.ick. Electrolytic tinplate, however, carries a very
thin film of dioctyl or dibutyl sebacate or cottonseed oil, which is applied at the last
stage of production in order to allow easier handling, to prevent to some extent, the
growth of the air-formed oxidefilm on the tin surface, and possibly to improve the
lacquering and printing quality of the plate. The weight ofthisfilm is of the order of
2- 1Omg/m 2 of surface, though film weights of one-tenth of this arenot unusual. Hea-
vier oil films are sometimes encountered but if the amount of oil is substantially in-
creased it may have a deleterious effect on any subsequent lacquering process. The
determination can be carried out (i) by using a 'hydrophil balance' [8], the oil film
being transferred to distilled water in a Langmuir trough by passing the tinplate sam-
ple through the water surface a number of times. A sliding barrier is then moved
along the trough towards a flxed floating strip connected to a torque head by a tor-
sion wire and previously set to a reading of 3° of torque. The position of the sliding
barrier is noted when the torque indicator returns to zero. The apparatus is calibrated
by addition of known amounts of oil to the water surface in the trough. (ii) by dis-
solving the oil in an organic solvent e.g. benzene, in a Soxhlet extractor, evaporating
the benzene solution to low volume (~Sm!) and then continuing as in(l) or by adding
the concentrated solution by micrometer syringe to a water surface of known area and
observing the point at which a permanent lens of oil appears on the surface. (iii) by
an optical method using an ellipsometer [9]. This method involves examination in
polarised light of the tinplate surface before and after removal of the oil ft!m.

4. Determination of Oxide Film

On exposure to air the tin surface on tinplate acquires an oxide film, consisting
mainly of SnO. The majority of electrolytic tinplate is subjected to a chemical or
electro-chemical treatment in chromate solutions to produce a complex surface film
containing both oxides of chromium and a mixture of SnO and Sn0 2 . The composi-
tion of the oxide film has an important effect on the adhesion of lacquers to the
tinplate surface and on its resistance to staining, particularly by sulphur-containing
products. The tin oxide content of the film is best determined by coulometric reduc-
tion [10] either in dilute HBr solution or in potassium chloride solution containing
phosphate buffer (pH 7.3). The time taken to reduce the oxidefilm at constant current
as indicated by a sharp rise in potential between the specimen and a reference electrode .
is used to calculate the number of millicoulombs/cm 2 for film reduction and the re-
 5. Performance Tests 213

sult is reported in these terms, owing to uncertainties in its actual chemical compo-
sition.
The chromium content of the oxide film can be derived (i) by isolation of the
fllm by coating the sample with a clear lacquer and immersing it in mercury to amal-
gamate the tin under the oxide film. The lacquer-coated oxide film is then peeled
away and its chromium content determined chemically by dissolution in acid fol-
lowed by photochemical determination with diphenylcarbazide or by X-ray fluores-
cence. (ü) by dissolution of the film from the tinplate specimen by boiling in a solu-
tion containing sodium hydroxide ( 40g/l) and sodium phosphate (SOg/1). Chromium
in the Strippingsolution is determined photometrically as above after oxidation with
persulphäte. (iii) electrochemically by anodic polarisation in neutral phosphate solu-
tion. The potential/time curve shows an arrest, the duration of which is an indication
of the Cr0 presen t in the passivation film [ 11 ] .
The chromium content of the surface film on commercial tinplate is of the order
of 0.1 - l.Opg/cm 2 •

5. Performance Tests

In addition to the above, several performance tests are used industrially to assess
the suitability of a sample of tinplate for particular purposes. These include tests for
porosity or continuity of the tin coating and general corrosion-resistance, as well as
Solderability and lacquering quality, the 'Pickle lag test'. the 'alloy-tin couple' (ATC)
test and the 'iron solution' test. Thesetests have been developed to indicate the
behaviour of samples of tinplate under service conditions and do not, strictly speaking,
involve analysis as generally understood. Consequently detailsarenot given here, but
a useful summary of all these tests is given in a publication 'Tinplate testing' available
from the Tin Research Institute [ 12].

References
1. Francis, H.T.: J. Electrochem. Soc. 93, 79 (1948)
2. Kunze, C.T., Willey, A.R.: J. Electrochem. Soc. 99, 354 (1952)
3. Smuts, J., Plug, C., can Niekerk, J.N.: J.S. Afr. Mining and Met. 67,462 (1967); Chem. Abstr.
67,75624 (1967)
4. Bendix, G.H., Stammer, W.C., Car/e, A.H.: Ind. Eng. Chem. (Anal. Ed.) 15,501 (1943)
5. C/arke, S.G.: Analyst 59, 525 (1934)
6. British Standards Institution: Cold-reduced tinplate and cold-reduced blackplate. B.S. 2920:
1969
6a. Amer. Soc. Test. Mat.: Single-reduced electrolytic tinplate A 624-68; Double-reduced electrolytic
tinplate A 626-68 (1968)
6b. Deutsche Normenausschuss: Blackplate and tinplate in sheets DIN. 1616 (1967)
7. International Standards Organisation: Cold-reduced tinplate and cold-reduced blackplate.
ISO 1111 (1969)
8. Dane/san, J.G., Neish, R.A.: Analyt. Chem. 21, 1102 (1949)
9. Murray, T.P.: Rev. Sei. Instruments 33, 172(1962)
9a. Richard, M.J.: Nature 200, 768 (1963)
10. Frankentha/, R.P., Butler, T.J., Davis, R.T.: Analyt. Chem. 30,441 (1958)
lOa. Willey, A.R., Kelsey, D.F.: Analyt. Chem. 30, 1804 (1958)
lOb. Brittan, S.C., Bright, K.: Metallurgia 56, 163 (1957)
11. Brittan, S.C.: Brit. Corros. J. 10,85 (1975)
12. Haare, W.E., Brittan, S.C.: Tinplate Testing, Publication No. 313; Tin Research Inst. (1964)
13. Haare, W.E.: Tinplate Handbook, Publication No. 181, Tin Research Inst. (1964)
CHAPTER 19

ORGANOTIN COMPOUNDS

By J.W. Price

1. Introduction

The organic compounds of tin dealt with in this section are those in which there is
at least one direct bond between tin and a carbon atom. As stable organotin com-
pounds based on bivalent tin are virtually unknown, this means that four types of
compound based on tetravalent tin, can be formed - R 4 Sn, R 3 SnX, R 2 SnX2 and RSnX 3 ,
where R is an alkyl or aryl group attached to tinvia carbon and Xis any substituent group
attached to tin through an electronegative atom such as halogen, oxygen, nitrogen or
sulphur. The chemistry of these compounds is discussed in detail in specialist text-
books [ 1] and is not considered here. Their industrial importance is due primarily to
a) the biocidal properties of the R 3 SnX compounds
b) the stabilising action of R 2 SnX 2 compounds in PVC, particularly in rigid
non-plasticised material.

The analyst, as well as determining the individual compounds, may be called upon
to identify and measure the amounts of e.g. the more toxic R 3 Sn compounds, pre-
sent not only in R 1 - and R 2 Sn materials, but also in residues and extracts, and also
to identify breakdown products, bearing in mind that R groups can be serially remov-
ed by oxidative processes, leaving inorganic tin, usually as Sn0 2 , as the final product.
A considerable amount of work has been reported during the last decade on the
separation and determination of the various organotin compounds; lately emphasis
has shifted to their determination in trace amounts in the environment, and although
good progress has been made, the problems that arise when examining e.g. soil, air
and effluents have not yet been completely solved. Work is continuing, however, and
the methods so far developed will no doubt be improved or superseded in due course.
The main compounds at present of industrial importance are;
1. Mono- and di-methyltin, and the dibutyl- and dioctyltin compounds, used as PVC
stabilisers.
2. Tributyltin oxide (TBTO) and other tributyltin compounds used as industrial
biocides and surface disinfectants, in wood preservation andin antifouling paints.
3. Triphenyltin hydroxide and acetate, used as agricultural fungicides, particularly
on potatoes.
4. Tricyclohexyltin hydroxide used as a miticide.
 Ref.p. 243] 2.1 Determination of tin 215

2. Eiemental Analysis

2.1 Determination of tin

It is important to realise that a determination of the tin content of an unknown
sample may not provide sufficient information unless other tests such as e.g. TLC
have shown that the sample being examined contains in fact only one compound.
For example, mixtures of R 3 Sn- and RSn- compounds can have the sametotal tin
content as the corresponding R 2 Sn compound, and in such cases a preliminary sepa-
ration is neccessary before determination of tin (see Section 5).

The first step in the determination of tin is conversion to the inorganic form,
usually by wet oxidation, after which any of the conventional methods may be fol-
lowed. Details of these are not given here as they have been covered in earlier chap-
ters, but examples are cited of the methods that have been found most useful when
dealing with the organotins.
Possibly the simplest method of tin determination is that first used by Kocheshkov
[2] in which the sample (0.1 - 0.2g) is placed in a tared silica test tube and 30 drops
of a mixture of equal volumes of fuming nitric and sulphuric acids carefully added.
The vessel is heated with a very small flame to expel brown fumes and then more
strongly to remove sulphuric acid; after expulsion of allliquid the tube is ignited to
constant weight at 850°C, the increase in weight giving the tin content as Sn0 2 •

Weight of Sn0 2 x 0.7877

%Sn= x 100
Weight of sample

A modification of this procedure was put forward by Kohama [3], who dissolved
the sample in 2- 3rnl of concentrated sulphuric acid in a tared platinum crucible and
added 1 g of solid arnmonium nitrate in small portions with warming, the final colour-
less solution being evaporated and the residue ignited as above.
Several procedures have been suggested to prevent Iosses of tin if very volatile
compounds are being analysed, e.g. the lower tin tetra-alkyls and hydrides. Gi/man
and King [4] first brominated the sample in carbon tetrachloride forming the less
volatile alkyltin bromide and then oxidised with nitric/sulphuric acid as above. The
hydrides can be brominated directly by carrying out the reaction in a vessel immer-
sed in a freezing mixture [13]. Brown and Fowles [5] described an apparatus in which
the sample is carried in a current of oxygen into a weighed silica tube where it is ig-
nited to Sn0 2 • A better alternative is to carry the vaporised sample in a current of
nitrogen into a nitric/sulphuric acid mixture, continuing as in the Kocheshkov pro-
cedure.
Wet oxidation can be carried out by any of the standard procedures, using sul-
phuric acid with either nitric or nitric/perchloric acids or hydrogen peroxide. If the
fmal determination of the tin is volumetric it is important to remove a11 traces of
nitric acid before carrying out the tin reduction. A typical procedure is given below
for wet oxidation with nitric/sulphuric acid followed by volumetric determination
of the tin after nickel coil reduction:
Ta a weighed sample containing 50 -100mg Sn add lOml of concentrated nitric acid and
allow to stand for a few minutes. Add 5 ml of concentrated sulphuric acid, warm to expel brown
fumes and heat slowly to evaparate nitric acid. lf the solution chars or is coloured yellow, add
nitric acid dropwise until it clears and then evaparate to fuming. Cool, add 5 ml of water and
216 Organatin Compounds [Ref.p. 243

evaparate again to fuming to decompose nitrosylsulphuric acid, repeat the addition of water and
fume to remove all traces of nitric acid. Cool, add 10m! of water and 75 ml of hydrochloric acid,
dilute with water and transfer to a 500ml conical flask, making up the final volume with water
to 250m!. lntroduce a nicke! coil, simmer gently for 40 min in absence of air (see Chapter 4)
cool to room temperature under C0 2 , add 1 g of potassium iodide and starch solution and
titrate with 0.1 N potassium iodate without shaking.

This procedure has been used successfully by Farnsworth and Pekola [6] for the
determination of tin in a number of organic compounds and in mixtures.
Wet oxidation with chloric acid, HC10 3 , and hydrochloric acid has been used by
Geyer and Seidlitz [7] for the determination of tin in butyltin compounds. Oxidation
of a small sample ( ~60mg) is very rapid by this method and the whole determina-
tion can be carried out in 20 min, concluding with a complexometric EDTA titra-
tion of Sn(IV). These authors added excess EDTA and back-titrated the excess
with 0.05M zinc acetate solution using catechol violet as indicator. A simi!ar com-
plexometric titrationwas used by Chromy and Vrestal [8] for the analysis of butyl-
tin compounds after wet oxidation, with nitric/sulphuric acids. The excess EDTA
was titrated with 0.05M copper sulphate, using TAN (1-(2-thiazolylazo)-2-naphthol)
as indicator.
Oxidation of organotin compounds by Schöniger flask combustion [9] or by Parr
bomb peroxide fusion [ 10 J has also been suggested.

Photometrie determination of tin after wet-ashing, often preceded by separation

from other organotin compounds, has been extensively used, particularly in inves-
tigations dealing with trace amounts in extracts and biological materials, but is not
particularly suitable for the analysis of the compounds themselves. Farnsworth and
Pekola [ 11] however, were able to determine tin photometrically in the range 10 -
70% in organotin compounds by the dithiol method after peroxide fusion. Trace
determinations are dealt with in Section 8.

2.2 Determination of carbon and hydrogen

The standard micro-method using a Pregl combustion tube requires modification
for the determination of these elements in organotin compounds. The procedure first
put forward by Silbert and Kirner [ 12] in which part of the copper oxide-lead chrom-
ate filling is replaced by a cylinder of platinum gauze filled with granulated red lead,
has been used successfully by Van der Kerk et al. [ 13] for the examination of a !arge
number of organotin compounds, whi1e Colaitis and Lesbre [ 14] have reported a semi-
micro method using silver vanadate as catalyst in the combustion.

2.3 Determination of nitrogen

The original Pregl-Dumas combustion method as modified by Zimmermann [15]
has proved satisfactory, while the Kjeldahl digestion method has also been used
[16], though it is of less general applicability.

2.4 Determination of sulphur

Gravimetrie [16] or combustion methods can be used but are somewhat time-
consuming. If the sulphur is directly attached to the tin atom advantage can be
taken of the fact that the Sn-S bond undergoes quantitative oxidation with iodine,
a simple titration with standard iodate being all that is required [17], e.g.
3Bu 2 Sn(SR) 2 + Kl0 3 + 6H+ ~ 2Kl + 3RSSR +3Bu 2 SnO + 3H 2 0
 Ref.p. 243) 3.1 Carboxylates 217

The end-point can be detected visually or potentiometrically. A typical procedure

for the determination of sulphur in dibutyltin bis(iso-octylthioglycollate) is as fol-
lows: Dissalve 0.5 - 1 g of the compound in 80rnl of glacial acetic and titrate with
0.1 N KI0 3 to a colour change from colourless to pale yellow. The end-point is
characterised potentiometrically by a sharp increase in EMF, using a couple of plati-
num (input) and silver (reference) electrodes. The sarne titration can be carried out
coulometrically [18). A similar procedure was reported by Abel andBrady [19] for
the determination of Sn-S bonds in some trialkyltin compounds.
The only disadvantage of these procedures is that any other mercaptide present
e.g. sodium iso-octylthioglycollate, is titrated at the sarne time.
A mercurimetric procedure in which the sarnple is titrated with o-hydroxymercu-
ribenzoic acid using thiofluorescein as indicator after hydrolysis with alkali has been
described by Chromy and Srp [20].

2.5 Determination of halogen

a) Halogen attached to carbon.
Combustion in oxygen over a platinum catalyst and adsorption of the halogen by
silver gauze [21] is not completely satisfactory owing to inactivation of the catalyst
by tin and the classical Carius method is tobe preferred.
b) Halogen attached to tin.
Halogen directly attached to tin is ionised in aqueous solution and so can be deter-
mined in aqueous ethanol or acetone by reaction with silver nitrate. The silver halide
produced can be collected and weighed or the solution can be titrated potentiometri-
cally with a solution ofO.lM silver nitrate (see Reference [16]). High frequency ti-
tration with the samesolutionwas used by Matsuda andMatsuda [22] for the analysis
of di- and tri- alkyltin halides, and an amperometric method has also been described
[23].
A turbidimetric procedure is specified in B.S. 4630 [24] for the determination of
up to 1% of ionizable chloride calculated as Bu 3 SnCl in technical tributyltin oxide:
a 1 g sample is dissolved in 45ml of glacial acetic acid in a Nessler cylinder and, after
the addition of 5 ml of concentrated nitric acid and 1 rnl of silver nitrate (1 0%), the
turbidity produced is compared with standard turbidities obtained by using known
amounts of 0.01 M hydrochloric acid and equal quantities of the test reagents.

3. Determination of Functional Groups

Apart from the general methods of organic chemistry, published work has so far
been confined to the determination of carboxylates, hydrides, oxides and hydroxides.

3.1 Carboxylates
The more volatile acids such as acetic acid have been determined by distillation
from phosphoric acid solutions [25) and, more generally, RCoo-groups can be
analysed by titration in non-aqueous solution [26]. The sarnple (~0.3g) is dissolved
in pyridine and titrated with 0.1 M sodium methoxide in pyridine, the end point
being determined potentiometrically or by using thymolphthalein as indicator.
An oscillographic study has been made by Geyer and Rotermund [27] of a series
of organotin acetates.
218 Organotin Compounds [Ref.p. 243

3 .2 Hydrides
Two photometric procedures have been put forward [28] for the determination of
di- and tri- alkyl and -aryltin hydrides. In the first, which is stated to be specific in
the presence of other organotin compounds, ninhydrin in ethanol solution is reduced
to a 2-hydroxyindanedione tin salt, with formation of a blue colour. Air must be
rigorously excluded to prevent fading of the colour and other reducing agents must
be absent. In the second, isatin in the presence of azo-bis(isobutyronitrile) is reduced
to colourless dioxindole, the reduction in colour being measured at 425nm.
Neuman et al. [29] have determined organotin hydrides by measurement of the
I.R. adsorption of the Sn-H band at about 1850cm-1 .

3.3 Oxidesandhydroxides
Trialkyl and -aryltin oxides and hydroxides can be determined separately or in
mixtures by a Karl Fischertitration [30]
(R3Sn) 2 0 + 12 + S0 2 + CH 30H ~ 2R 3Sni + CH 3HS04
R 3SnOH + I 2 + S0 2 + CH 30H ~ R 3Sni + CH 3HS04 + HI
From these equations it can be seen that oxides consume 1 mol of iodine for 2
tin atons, while hydroxides require 1 mol for a single tin atom, and from this the
amounts of the two types of compound present can be calculated by comparison of
the 'apparent' water found in the titration with the theoretical values.
Forthedetermination of the oxide content of technical tributyltin oxide a pH
titration with acid is specified in B.S.4630 [31]: a sample of 4 - 5 g is dissolved in
200m! of iso-propanol, the glass and calomel electrodes of a pH meter inserted, and
the solution titrated with stirring with 0.5M hydrochloric acid. The pH obtained for
each addition is plotted against the volume of acid, the end-point occurring between
pH 4 and 5.
14.9 x ml of acid used
% oxide content, expressed as tributyltin oxide = - - - - - - - -
Mass of sample taken

4. Determination of Organotin Compounds

4.1 Volumetrie methods

lt was shown by Bürger [32] that mono- and di- alkyl and -aryltin compounds in
alcoholic solution form deep blue coloured complexes with catechol violet, while
the tetra- und tri-compounds do not react. The blue colour of the complexes in
solution is destroyed by EDTA, with a sharp change at the equivalence point from
blue through green to yellow, the colour of the catechol violet. Bürger determined
small amounts of di-alkyl and -aryl compounds and particularly diphenyltin in tech-
nical triphenyltin acetate by a simple titration; the sample containing 1 - 1Omg of the
diphenyltin compound was dissolved in 20ml of methanol in the cold and, after addi-
tion of 4 drops of catechol violet solution (0.1% in ethanol) the solutionwas titrated
with 0.02M EDTA to a colour change from blue to yellow. Inorganic tinalso forms a
blue complex with catechol violet which is not destroyed by EDTA and so must be
absent.
lml 0.02M EDTA =7.814mg diphenyltin acetate
 Ref.p. 243] 4.2 Photometrie methods 219

The stability of the catechol violet complexes of the mono- and di- butyltin chlo-
rides at different pH values was investigated by Efer et al. [33] who found that the
blue mono- complex was formed over a pH range 1.2-2.2, while the di- complex was
stable at pH 2.3- 5 but gave a red colour below pH 2.3. From this they developed a
procedure for the determination of monobutyltin down to 0.1% in technical dibu-
tyltin chloride or oxide. The chloride sample (1 g) was dissolved in 20ml of methanol,
5- 10 drops of catechol violet added and the solution titrated with 0.05M EDTA to a
colour change from blue-green through red-violet to red. The oxide sample was dis-
solved in 7 ml of methanolic hydrochloric acid ( d 0.82) by warming on a water bath,
20ml of methanol and 5 - 10 drops of indicator added and the red colour changed to
blue by dropwise addition of 1M methanolic potassium hydroxide. The solution was
then titrated with EDTA as for the chloride.
In using this procedure for the analysis of commercial dialkyltin stabilisers Herold
and Droege [34] found that thioglycollates which are frequently used in organotin
stabilisers interfere unless first oxidised as follows: dissolve 1 g of sample in 25 m1 of
methanol and 5ml of chloroform, add 2m! ofmethanolic hydrochloric acid and a
concentrated methanolic iodirre solution until a pale brown colour is obtained.
Remave the excess iodirre with thiosulphate, add 5 - 8 drops of catechol violet solu-
tion and add 1M methanolic potassium hydroxide dropwise until a blue colour is
obtained, then titrate with 0.05 M EDT A as above to a colour change to red-violet.
This procedure has recently been used by Koch and Figge [35] for the determi-
nation of monomethyltin iso-octylthioglycollate ( ~20%) in a commercial methyltin
stabiliser, using a 0.5 g sample.

Weight of sample (mg)

4.2 Photometrie methods

Of the dozen or so compounds found so far to form coloured complexes with or-
ganotin compounds (Table 1) only dithizone, diphenylcarbazone, PAR and quercetin
have been investigated in any detail. Most of the cornpounds suggested react only
with mono- and di- alkyl and -aryltin, but dithizone can form coloured complexes
with all four types of organotin compounds and so has been the most used, particular-
ly br the determination of small amounts of tri- alkyl and -aryltin compounds.
Dithizone
Aldridge and Cremer [36] found that mixtures of di- and tri- ethyltin compounds
can be separated by shaking with chloroform and borate/EDTA buffer of pH 8.4, the
tri- compound passing into the organic layer while the di- compound remains in the
aqueous phase. On the addition of dithizone (0.004% in chloroform) to the aqueous
portion an orange-colaured complex is formed, showing maxirnum difference in ab-
sorption compared with the original dithizone solution at 485 nm, while treatment of
the original chloreform phase with the reagent gives a yellow colour due to the trie-
thyltin complex and having an absorption maximum at 440nm. Greater sensitivity
can be obtained by measuring the reduction of absorption at the reagent maxirnum of
610nm rather than that due to the complex at 440nm. It is irnportant that all handling
and measurements of the tri-compound complex should be carried out in subdued light,
as bright light causes rapid degradation to diethyltin. The diethyl-dithizone complex
on the other hand shows reasonable light stability, the absorption remairring constant
220 Organetin Compounds [Ref.p.243

Table 1. Suggested Reagents for the Photometrie Determination of Organetin Compounds

Reagent References

36. Dithizone Aldridge, W.N., Cremer, J.E. Analyst, 82, 37 (1957)

37. Diphenylcarbazone
38. 2,2'Dipyridyl
39. 8-Hydroxyquinoline
40. o-Phenanthroline
41. Catechol Violet
42. Acetylacetone
4 3. Picolinie acid
44. Alizarin Red S
45. PAR
46. PAN
4 7. Quercetin
Skeel, R.T., Bricker, C.E.
Blake, D., Coates, G.E.
Blake, D., Coates, G.E.,
Tate, J.M.
Alleston, D.L., Davies, A.G.
Adamson, JJ!.
Yasuda, M., Tobias, R.S.
Yasuda, M., Tobias, R.S.
Cassa!, A., Magon, L.
Pilloni, G., Plazzogna, G.
Pilloni, G.
Waggon, H., Koehler, U.,
Uhde, W.-J.
Anal. Chem., 33,428 (1961)
J. Chem. Soc., 756 (1961)
J. Chem. Soc., 756 (1961)
J. Chem. Soc., 2050 (1962)
Analyst, 87,597 (1962)
Inorg.Chem., 2, 207 (1963)
Inorg.Chem., 2, 207 (1963)
J. lnorg. Nucl. Chem.
27' 1297 (1965)
Anal. Chim. Acta, 35, 325 (1966)
Anal. Chim. Acta, 37, 497 (1967)
Nahrung, 11, 809 (1967)

Further References
48. Helberg, D.
49. Herold, B., Droege, KJ!.
50. Vrestal, J., Havir, J.
51. Kahara, T., Takei, S.
52. Selivokhin, P.I.
53. Wieczorek, H.
54. Sawyer, R.
55. Freitag, K.D., Bock, R.
Dt. Lebensmitt. Rundsch., 63, 69 (1967)
Z. Anal. Chem., 245, 295 (1969)
Chem. Prum., 23, 135 (1973), Chem. Abstr., 79, 26934 (1973)
J. Inorg. Nucl. Chem., 33,4129 (1971)
Chem. Abstr., 63, 17155 (1965)
Dt. Lebensmitt. Rdsch., 65, 74 (1969)
Analyst, 92,569 (1967)
Z. Anal. Chem., 270, 337 (1974)

in subdued light for several hours. It was found that other alkyltin compounds as
weil as the phenyltins behave in the same way as the ethyl compounds, the di-com-
plexes all having absorption maxima at ab out 485 nm and the tri-complexes at around
450nm. Beer's Law is obeyed up to ab out 20JJg of diethyltin, 30JJg of triethyltin and
60J.lg of triphenyltin compound, using 1 cm cells and a final volume of 5 ml.
Later work has shown that tetraalkyltins behave like trialkyl compounds in that
they give a yellow solution in chloroform with dithizone on shaking with borate
buffer, the solution having an absorption maximum at ab out the same wavelength
as the tri- compounds. However, any mono-compounds present are precipitated at
pH 8.4 and so do not interfere, but do react with dithizone in the presence of acid
e .g. 10% trichloracetic acid to give a red colour._ This latter reaction has not so far
been used for analytical purposes.
A variation of the above procedure was used by Helberg [48] for the determina-
tion of dibutyl- and dioctylin stabilisers, after separation by TLC. After development
of the chromatogram, the position of the 'spot' was located by spraying with dithi-
zone, the orange zone scraped off the plate and the compound (20- 100JJg) extracted
into 0.5 ml of a propanol/hydrochloric acid solution (10:1). After the addition of
15 ml of carbon tetrachloride the solution was shaken for 1 min. with 5 ml of bor-
ate bufferas used by Aldridge and Cremer (19g sodium tetraborate + 12g boric acid
+ 2.5g EDTA in llitre; pH8.4), 4ml of dithizone solution (0.012% in carbon tetra-
chloride) added and the mixture again shaken for 1 min. The lower layer was separat-
ed and the excess dithizone removed from it by shaking with 5 ml of 0.5% arnmonia
solution. Finally the volume of the solution was made up to 20m! with carbon tetra-
chlroride and absorption measured at 490nm in a 2cm cell.
 Ref.p. 243] 4.2 Photometrie methods 221

A similar method was used by Herold and Droege [49] to determine tetra-, tri- and
dialkyltin compounds. After separation by TLC the developed chromatogram was ex-
posed to bromine vapour for lOmin., thus oxidising tetra- and tri- compounds to the
corresponding dialkyltin. The 'spots' were then seraperl off the TLC plate and the
compounds extracted and determined as above. In this way it was found possible to
use a single calibration curve for all compounds, not only butyl and octyl but tetra-,
tri- and di- as weil.

Vrestal andHavir [50] determined trialkyltin compounds with dithizone by photo-

metric titration in chlorobenzene solution, dialkyl compounds being removed by
extraction with O.lM sodium hydroxide/EDTA, and Kahara and Takei [51] have in-
vestigated the nature of the complexes formed between dithizone and the dialkyltin
compounds.

Tri- and diphenyltin compounds can be determined with dithizone in chloroform

solution by measurement of the reduction of absorption at 610nm [55]. The calibra-
tion curve is linear over the range 0- I8t.tg/rnl for the tri- compound and 0- I Ot.tg/rnl
for the di- compound. The colours are stated tobe stable for at least Ihr.

Diphenylcarbazone
Skeel and Bricker [37] used this reagent to determine dibutyltin dichloridein the
presence of the corresponding mono-, tri- and tetra-<:ompounds. At pH 1.8 a 3: 1 red
complex is formed in chloroform solution having an absorption maximum at 5IOnm.
The mono-<:ompound interferes and is removed by prior extraction with EDT A at
pH 2.05. The working range is 3 - 150t.tg and a correction is necessary for the absor-
bance of the excess reagent:
This reagent has been used by Selivokhin [52] to determine small amounts of
diethyl- and dibutyltin compounds in air (see section 8.4.I).
Diphenyltin compounds can be extracted from aqueous citrate/phosphate/EDTA
buffer solution (pH8.5) with a chloroform solution ofthe reagent [55] and the ex-
tinction measured at 546nm. The calibration range is 0- 8t.tg/rnl with a detection
Iimit of 0.2t.tg/rnl.

Quercetin
In the course of a study of the migration of organotin stabilisers from PVC
Woggon et al. [4 7] found that dibutyl- and dioctyltin compounds in acid solution
form stable yellow-orange complexes with quercetin which have absorption maxima
at 437 nm, the same wavelength asthat of the complex with inorganic tin(IV) and,
using this reagent, were able to determine these compounds in sunflower oil in the
range 15 -150t.tg/rnl.
A more detailed study of the quercetin complexes was made by Wieczorek [53]
who developed methods for the determination of mono-, di-, tri- and tetra-octyltin
after separation from mixtures by TLC, the two latter being converted to the di-
compound by bromination before reacting with quercetin. The silica gel 'spot' was
scraped off the plate after development of the chromatogram, 0.1 rnl of 25% sulphuric
acid, 4rnl of n-butanol and 1 rnl of 0.1% quercetin in methanol added and, after
shaking, the solution was filtered into a I cm cell and the extinction measured at
443nm (mono-octyl) or 428nm (di-octyl). Detection Iimits were about 2pg Sn and
calibration curves were linear up to about 15mg Sn/5rnl.
222 Organatin Compounds [Ref.p. 243

Diphenyltin compounds can be extracted from aqueous citrate/phosphate/EDTA

buffer solution (pH 8.5) with an iso-amyl alcohol solution of the reagentand the extinc-
tion measured at 442 nm [55]. Range 0- 20Mg/rnl; detection limit 0.5,ug/rnl.

PAR
Pilloni andPlazzogna [45] found that this compound- 4-(2-pyridylazo)-resorcin-
ol - forms 1:1 pink-colaured complexes with dialk:yltins but not with the mono-,
tri- or tetra- compounds, andSawyer [54] used it to determine dibutyl and dioctyl-
tin compounds in aqueous extracts from PVC. A suitable volume of extract was
shaken with lOml of chloroform and 30ml of reagent solution (100ml of O.lM EDTA
+ 50rnl PAR Solution, 2 X 10-3 M, adjusted to pH 10- 11), the Chloroform layer run
into a 1 cm cell and the extinction measured at 518 nm. Calibration curves cover the
range 1 x 10-<> - 1 x w-s M. The results obtained agreed with those found by the
dithizone method, but reagent stability and ease ofhandling were considered superior.
Diphenyltin compounds can be extracted from citrate/phosphate/EDTA buffer with
an iso-amyl alcohol solution of the reagent and the extinction measured at 518nm.
Range 0- 15,ug/rnl; detection Iimit 0.13,ug/ml. PAN can also be used in the same way
for the range 0 - 30mg/ml but is rather less sensitive.

4.3 Electrochemical Methods

4.3 .1 Polarography
Following the early work of Costa [56] and of Torapova and Saikina [57] who
described the polarographic behaviour of some alk:yltin compounds, many publica-
tions have appeared, dealing in the main with electrode processes and mechanisms
rather with quantitative determination, and much of this work has been summarised
in recent papers by Fleet and Fouzder [58]. In spite oflimitations involving the exis-
tence of multiple waves and the rather narrow concentration ranges over which wave
height is proportional to concentration, the high sensitivity of the polarographic met-
hod makes it useful for the determination of small amounts of organotins in residues,
extracts etc., rather than for the analysis of individual compounds. The compounds
of main interest have been the butyl- and octyltins and the phenyltins, though Devaud
et al. [59] in a series of papers have investigated the polarography of mono-, di- and
tri- ethyltin compounds and Bark and Selivokhin [60] have described methods for
their deterrnination in mixtures in 0.5 - 1.0M hydrochloric acid in aqueous methanol.
In this medium half-wave potentials were -0.55V (mono-), -0.7 to -0.8V (di-) and
-0.9 to -1.1 V (tri-), the minimum amounts determined beingabout lOOppm Sn.
Butyltin compounds have been investigated by a nurober of workers, the main
problems being the determination of small amounts of the more toxic tri-compound
in the presence of mono- and di- butyltin and the determination of mixtures of all
these in extracts. Jehring et al. in a series of papers (61] studied mixtures of di- and
tri-butyltin chlorides. They found that by d.c. polarography in buffered solutions
of pH 10 and containing 30% iso-propanol and 0.5M potassium chloride, down to 1%
of the tri-compound could be determined by measurement of the first wave in the
concentration range 10-6 - 10- 7 M. Sensitivity could be improved by the use of
a.c. polarography, down to 0.1% ot the tri- compound being determined in the same
medium by measurement ofthe first wave at about -l.OV. They later investigated the
possibilities of phase selective and square wave polarography as well as anodic strip-
 Ref.p.243] 4.3.1 Polargraphy 223

ping in the same supporting electrolyte and found sensitivities of 1o-6 , 1o- 7 and 1o-s M
respectively.
In determining both di- and tri- butyltin by d.c. polarography Williams f641 found
that in a supporting electrolyte containing l.OM hydrochloric acid and 2.5% ethanol
in 1M potassium chloride the di-compound gave two waves at -0.64 and -0.75 V, the
tri- compound giving a single wave at -0.85 V which overlapped the secend dibutyl
wave, preventing determination of the tri- compound, although the first dibutyl wave
could be used. In this work the two compounds were first separated by column chrom-
atography before being determined polarographically as above.
In the presence of appreciable amounts of a monobutyltin compound the waves
of di- and tri- butyltin are both overlapped by maxima produced by the mono- com-
pound, so that separation of the waves is not possible. Issleibet al. [65] have found
that in a supporting electrolyte containing 5% sodium acetate trihydratein methanol
the addition of sodium diphenyldithiocarbamate moves the reduction wave of the
mono-compound to more negative potentials, thus allowing determination of both
di- and tri- compounds. On the basis of this finding the authors proposed a scheme
for the determination of mixtures of the four butyltin compounds as follows:
·Monobutyltin: determine volumetrically with EDTA.
Di- and tri- butyltin: add carbamate and determine by d.c. polarography. If the
di- compound is present in !arge amounts, precipitate it as the thioglycollate from pe-
troleum ether solution, fi.lter and re-dissolve in a mixture of ether and methanol and
polarograph.

Tetrabutyltin: Determine total tin by wet-oxidation, and find by difference. The

determination of this compound by polarography is not possible, Bu 4 Sn not being
reduced at the dropping mercury electrode.
By using oscillopolarography Geyer and Rotermund [66] reported the determina·
tion of mixtures of the butyltin compounds without the need for previous Separations
and using supporting electrolytes of hydrochloric acid-ethanol in various concentra·
tions. The di- compound was determined in the presence of mono- and tri- butyltin
and the tri- compound (10-4M) in the presence of an excess of the di- cömpound
(10- 2 M).
The electrochemistry of triphenyltin compminds has been studied by Dessy et aL
[67] and by Boothand Fleet [68]. For determination by d.c. polarography the best·
defined waves were obtained in 50% aqueous ethanol containing 0.1 M acetate buffer
(pH 7.3) and 0.002% Triton X 100 as maximum supressor. Both the adsorption pre·
wave at - 0.65 V ( concentration dependent over the range w·s - 10-4 M) and the
first reduction step at - 0.9 V ( concentration dependent between 10-4 and 10-3 M)
can be used. A.c. polarography under the same conditions shows two peaks at - 0.68
and- 0.98 V, the first being useful in the concentration range 10-4 to 10- 5 M, the
second between 1o- 3 and 1o-4 M, below which it disappears.
Several other supporting electrolytes have been used for the determination of di-
and mono-phenyltin chlorides [69] but no work has appeared on their determination
in mixtures, and if preliminary separations are necessary the polarographic method
for these compounds does not appear to offer much advantage.
224 Organetin Cornpounds [Ref.p. 243

4.3.2 Amperometry and Voltammetry

Tagliavini and Pilloni and their co-workers have been active in this field over a nuro-
ber of years. It was found [70] that halogenation of hexaalkylditins by electrolytically
generated bromine or iodine
R 3 Sn-SnR3 + Br 2 -+ 2R 3 SnBr

at a platinum anode at constant current could be followed coulometrically by using a

pair of indicator e!ectrodes, the end-point of the reaction being found from a plot of
indicator current vs. time. Selective determination of e.g. Me 3 Ph 3 Sn 2 (-10- 3 M) in
the presence of an excess of Ph 6 Sn 2 was found possible [71] by using electrolytically
generated silver ions, adding a complexing agent such as quinoline to slow down the
reaction rate of the hexaphenyl compound.
A potentiometric procedure has been described [72] for the determination of di-
and tri- alkyl tin chloride (-10- 2 M) in acetonitrile solution by titration with tetra-
phenylarsonium chloride or tetraethyl ammonium bromide, while Plazzogna and
Pilloni [73] determined the sum of di- and tri- methyl- or ethyltins (-10- 3 M) by
potentiometric titration with alkali. The di-compound was then determined in a sepa-
rate sample by amperometric titration with 8-hydroxyquinoline in ammonium nitrate
buffer (pH9.2) [74]. A coulometric procedure has also been described [75]. Kreshkov
et al. [76] have · described the amperometric titration of alkyltin halides in iso-propanol
solution using a pair of copper indicator electrodes, while Haasova and Pribyl [77]
determined dibutyl- and dioctyl- tins by amperometric titration in dilute acetic acid
solution with oxalic acid. It was found that the tri- compounds did not interfere and
that the interference of mono -compounds could be masked by adding EDT A.

4.3.3 Anodic Stripping and Voltammetry

Woggon et al. [78] examined the possibility of the determination of monobutyl

and mono-octyltin chlorides by anodic stripping and found that 12% hydrochloric
acid was a suitable supporting electrolyte. Pre-electrolysis times were 5 - 1Omin at a
potential 200- 400mV morenegative than the peak potentials and the working range
was 0- 0.4pg Sn/mi, with a detection Iimit of 0.025pg Sn/mi. Di- and tri- alkyltin
compounds could not be determined in this way, but schemes were put forward for
their separation from the mono- compounds and subsequent determination as inorga-
nic tin after wet-oxidation.
Woggon et al. [79] have also investigated the separation and determination of
trace am::mnts of di- and tri- alkyltins in foods and food simulants andin surface
waters and have used anodic stripping to increase the sensitivity of the final determi-
nation. Afer separation the individual compounds were broken down to inorganic tin
by UV irradiation, so that the method, strictly speaking, does not involve determina-
tion of the organotin compounds as such; however, the high sensitivity found ( work-
ing range 1.25 - 1Opg Sn in 25 ml; detection Iimit 0,05 pg Sn/ml) makes it very useful
for the determination of these small amounts.
The determination of triphenyltin compounds by anodic stripping has been inve-
stigated by Booth and Fleet [80] using a rotating mercury-coated platinum e!ectrode
with a platinum wire counter-electrode and a SCE reference. The pre-electrolysis
step was carried out by electrolysing for 2min at a potential of- l.OV in an electro-
lyte ( 15 ml) sontaining 50% ethanol, acetate buffer (pH 7 .3) and a maximum suppres-
sor (Triton X-100). Peak height vs. concentration was linear over the range 10- 7 -
 Ref.p. 243] 4.5 Atomic Absorption 225

w-s M and amounts of triphenyltin acetatedown to 0.001J.Lg/g in potatoes were

determined in this way (see Section 8.2.1). A fully automatic apparatus has been des-
cribed [81] in which the various operations of sample addition, pre-electrolysis and
stripping are controlled by a cycle-timer, allowing determination of sub-microgram
amounts of the triphenyltin compounds.

4.4 Fluorimetric Methods

It has recently been reported [82] that triphenyltin acetatein benzene reacts with
3-hydroxyflavone to form a 1: 1 complex showing a green fluorescence which can be
measured at 415/497nm. The sensitivity is high, the calibration curve (final volume
5 ml; 1 cm cell) covering the range 0- 7 J.Lg Sn. Of greater importance is the absence
of interference from inorganic tin, mono- or di- phenyltin; excitation and emission
maxima of the complexes of these species with the reagent and of the reagent itself,
tagether with intensities at the triphenyltin wavelengths were found tobe as follows:
Species Wavelengths(nm) Relative intensities at triphenyltin
wavelengths

Triphenyltin 415/497 100

Diphenyltin 465/495 0
Monophenyltin 470/496 1.4
Tin( IV) 470/496 3.1
Reagent 382/525 0

Using this method with a 500g sample the author was able to determine 0.001 J.Lg/g
Sn present as triphenyltin in potato crops that had been sprayed with a formulated
triphenyltin fungicide during growth (see Section 8.2.1).
The high sensitivity coupled with high selectivity rriakes the fluorimetric procedure
very attractive for the determination of trace amounts of organotin compounds and,
though as yet no further work has been reported, it is reasonable to expect the devel-
opment of analogaus procedures for the determination of other, particularly alkyl-
tin compounds.

4.5 Atomic Absorption

As would be expected from earlier attempts to determine Iead tetraalkyls in petrol
by atomic absorption, the direct evaluation of organotin compounds in organic sol-
vents by this method suffers from serious difficulties. In the first place sensitivities
vary with the size and character of the groups attached to the tin atom, decreasing
with e.g. increasing size of alkyl group [83]. This makes it necessary to prepare cali-
bration Standards from the same organotin compound as in the solution to be ana-
lysed. Further, the sensitivity of a single compound in the flame varies considerably
with the matrix solution e.g. a relatively small change in the composition of a mixed
hydrocarbon solvent has been found to produce errors in the tin determination, thus
involving fresh calibration with new batches of solvent. It therefore seems preferable
to convert the organotin compound to the inorganic form by wet-oxidation before
using this method, except when the compound and the solvent are of known compo-
sition. This can arise in e.g. the determination of TBTO for control purposes in an
organic solvent used as a wood preservative.
However, atomic absorption has been used successfully in a few cases. Jeltes [84]
determined TBTO in air ( ~0.1 mg/m 3 ) by collection on glass fibre filters and extrac-
226 Organatin Compounds [Ref.p. 243

tion into methyl isobutyl ketone, using standards ofTBTO in the same medium.
Freeland andHoskinson [85] studied the absorption of tributyltin chloride on
wool, by extracting the compound into ethanol; they found the absorbance of the
ethanolle solutions was linear over the concentration range of 100- 1000~g/ml Sn.
Williams [86] deterrnined TBTO in wood by extraction into acid-ethanol mixtures
(see Section 8.3).

4.6 Miscellaneous Physical Methods

1. Spectrochemical
Chromy et al. [87] in experiments on leaching rates of antifouling paints (see Sec-
tion 8.3) deterrnined TBTO (-3ppm) in aqueous solution by comparing the inten-
sity of the Sn line at 283.9989nm with that of a copper standard at 282.437nm,
while Rautschke and Heinrich [88] studied solutions of organotin compounds in
ethanol by this method.
2. Radioactivation
Byrne [89] deterrnined tin in biological samples after activation in a neutron flux of
4 x 106 n m-2. s-\ by wet-ashing with a tin carrier, extracting as the iodide and deter-
rnining123 m Sn by scintillation counting, but was unable to detect less than 0.1~g/g
Sn; Bowen, however, by using a langer time of irradiation, was able to detect down
to 60ng Sn/g by measuring the activity of 121 Sn. Van der Maas et al. [91] used this
method in investigating the toxicity of triphenyltin compounds to pond snails, while
Owaki et al. [92] deterrnined residual tin in this way in sanitised nylon cloth as a
function of washing time.
3. X-Ray Fluorescence
Ishii et al. [93] deterrnined tributyltin terephthalate in wood by this method, while
Havranek and Bumbalova [94] used it to deterrnine tin in stabilisers and in PVC
foils. Figge and Zeman [95] studied the surface structure of organotin-stabilised PVC
by means of X-ray photoelectron spectroscopy (ESCA).
4. Biological
Rivett [96] has assessed the leaching rate of tributyltin compounds from antifouling
compositions by observing their effect on the growth of green algae.

5. Separation Techniques
5.1 Chromatography
The chromatography of organotin compounds is discussed below under the three
headings of gas-, paper-, and thin-layer.
The first of these was studied in detail some ten - fifteen years ago, and while
it has proved useful in, for example, the routinemonitaring of the product in the
manufacture of butyltin compounds, it has been found to suffer from the disadvan-
tage of the thermal instability of the organotins, resulting not only in decomposition
but disproportionation on the column during the process of chromatography. This
can be prevented by alkylation to tetra-compounds with a Grignard reagent and this
procedure has been found satisfactory for the separation of the various alkyltins using
quite small samples.
 Ref.p. 243] 5.1.1 Gas Chromatography 227

Paper chromatography is of value for rapid qualitative Separations of simple mix-

tures, e.g. the detection of a tri- alkyl compound in a di-compound, or the differen-
tation between a dioctyl and a dibutyl tin stabiliser. Quantitative results can be ob-
tained by cutting out appropriate areas of paper after development of the chromato-
gram and wet-ashing, converting the organotin compound to inorganic tin, which can
be determined by any suitable method. The limiting factor here is the size of sample
that can be handled; not more than about 100J.Lg of compound can be used without
overloading with the production of !arge diffuse spots.
Thin-layer chromatography using silica gel or sometimes kieselguhr plates has
proved of great value as a means of separating the different organotin compounds,
and quantitative results have been obtained by scraping offseparate areas of the
plate surface and wet-ashing to inorganic tin as is done with paper chromatography.
Recent work, however, is tending to avoid this wet-ashing step and instead to extract
the organotin compound from the si!ica gel with a suitable solvent and to determine
the compound itself, usually photometrically. This technique has been used for the
analysis of organotin PVC stabi!isers and also for the study of the extraction of the
stabiliser from PVC into a variety of solids and liquids. This is discussed in greater
detail in Section 8.

5.1.1 Gas Chromatography

A quantitative study was made in 1960 by Matsuda and Matsuda [97] of the separa-
tion of the halides of the lower alkyltin compounds from each other and from the tetra-
alkyls, using a 3m column at 170°C with a si!icone oil as the stationary phase.
They reported some success but noticed new peaks in their chromatograms which
they attributed to redistribution reactions. The possibility of disproportionation was
confirmed by Franc et al. [98] using a 145 cm column and temperatures of 180 -
2l0°C and it was concluded by them that the method was suitable only for qualitative
work. In a series of papers Pollard et al. [99] investigated means of overcoming break-
down of the alkyltins on the column and found that trans-esterification could be
prevented by suitable pre-treatment of the supporting phase and were able to separa-
te organotin hydrides and a series of methyl-ethyl tins. Geissler and Kriegsmann
[ 102] using a 3m column at temperatures between 160 - 190°C and a variety of sta-
tionary phases for the separation of the butyltin chlorides found that tetrabutyltin
reacted with the mono-compound under all conditions to form a mixture of the di-
and tri- compounds and also with the di-butyl compound in al! the liquid phases
examined except Carbowax.. However, Gerrard et al. [ 103] found that by using a
short column (16cm) at a lower temperature (90°C) it was possible toseparate tetra-
butyltin and the three chloro-compounds without decomposition or disproportiona-
tion. The short column was used successfully by Tange [ 104] for the analysis of
butyl-, octyl- and phenyl- tin halides under the following conditions:

Column: 16 cm stainless steel, 4mm intemal diameter

Column Temperature: l10°C (butyl), 180°C (phenyl), 210°C (octyl)
Injection temperature: 380 - 400°C (butyl), 400- 425°C (phenyl and octyl)
Stationary phase: 5% silicone oil MS 200 on Celite 545
Sampie size: O.l5J.ll
Detector: Flame ionisation
Flow rate: 120m! nitrogen per min.
Retention time~ of the butyltin bromides on the short column were of the order of: mono-
3min; di- 6min; tri- 9min.
228 Organatin Compounds [Ref.p. 243

The problems of interference by tetra-alkyl compounds and of decomposition on

the column led to a new approach by Steinemyer et al. [ 105] to the analysis of mix-
tures of the butyltin bromides. In their procedure, the bromides are first quantitatively
converted to their butylmethyltin analogues by means of a methyl Grignard reagent,
the resulting products being more volatile and also stable in the presence of one another
even at elevated temperatures. A rather !arge sample size (4g) was used for the Grig-
nard reaction, the final mixture of butylmethyl tins being obtained in 1OOml of ethyl
ether. Good recoveries were obtained but inorganic tin, present as SnBr 4 , could not
be tolerated, as it reacted with any tetrabutyltin present before reaction with the
Gignard reagent. This method was used by Jitsu et al. [106] to analyse mixtures of
the halides of butyl-, octyl- and phenyl- tins after conversion to e.g. BunSnPr 4 .n or
OctnSn(Cs Hu )4 -n·
This principle of converstion of all the constituents of a mixture to tetraalkyltins
before determination by GLC has recently been used by Neubert and Wirth [107]
for the analysis of commercial samples of methyl-, butyl- and octyl-tin PVC stabilis-
ers. These workers found that alkylation could be carried out quantitatively not only
with the alkyltin oxides and chlorides, but also with the alkyltin thioglycollates. In
the latter case it was necessary to absorb the tin-free by-products on silica gel before
proceeding with the determination. In analysing methyltin compounds it was found
preferable to octylate rather than to butylate them, as Iosses occurred when butyl-
ating trimethyltin compounds, presumably owing to the high volatility of the Me 3 -
BuSn formed. This finding may weil explain the low results sometimes obtained in
the determination of monobutyltin compounds in mixtures by methylation to the
same compound. Instrument conditions used by these authors were
MeBu compounds MeOctyl compounds
1. Column Perkin Eimer F7 and F20H
2. Column temperature 150°C 230°C
3. Injection temperature 260°C 350°C
4. Stationary phase 5% polyglycol 20,000 30% Carbowax on
on Sterchamol R Chromosorb W
5. Detector Thermal conductivity and hot wire
6. Flow rate 36m! helium per min.
The tetraalkyltins were obtained in ether solution after carrying out the Grignard
reaction and the residue after removal of the ether by distillation was applied to the
column. A sample weight was not required as relative proportians were calculated from
chromatogram peak areas, but a sample containing 0.5 - 1 g Sn was generally used.

5 .1.2 Paper Chromatography

Following the publication in 1958 of the first of a series of papers by Barbieri et
al. [ 108], in which was reported a separation of di-and tri-ethyltin and of di-, tri- and
tetraphenyltin from Sn(II) by means of paper chromatography, a detailed study was
made by Williams and Price [1 09] of the possibilities of this technique for the separa-
tion of a !arge nurober of organotin compounds. In this work descending-solvent
chromatograms were developed on Chromatographie paper, solutions of the organotin
compounds in ethanol being applied by means of a microlitre syringe, and Rf values
were obtained using a nurober of developing solvents. The positions of the various
'spots' were located by spraying the paper with a 0.1% solution of Catechol Violet
in 95% ethanol. This compound does not react with tetra-alkyl or tetra-aryl tin com-
pounds and gives a reddish-mauve colour with tri- compounds but is not particularly
sensitive to them, while di- and mono-compounds show the blue colour given by in-
 Ref.p. 243] 5.1.2 Paper Chrornatography 229

Table 2. Rf values obtained with different developing solvents

Developing solvent
Cornpound Pyridine Butanol Butanol Butanol
60% pyridine- arnrnonia- ethanol-
water water water
Me2SnCI2 0.36c 0.55b 0.03 0.67b
Me3SnCI 0.35 0.25 0.32
EtSnCb Streaks to Streaks Streaks Streaks
0.8 length of length of length of
paper paper paper
Et2SnCI2 0.36c o.8ob 0.16c 0.98b
Et 2Sn0Ac 0.40 o.85b 0.95b
Et3SnOH 0.88 0.94 0.94 0.95
Pr2SnCI2 o.oob 0.9b Streaks to 0.98
0.52
(Pr3SnhO 0.85 0.94
(isoPr3SnhO 0.87 0.94
Pr3SnCH2CH2COONa 0.82 0.90 0.83
BuSnCI3 Streaks to 0.99b Streaks Streaks
0.8 length of length of
paper paper
Bu2SnCI2 o.ooa 0.93 o.oob 0.98a
Bu 2Sn dilaurate o.ooa 0.95 0.96
Bu3SnCI 0.85 0.92 0.95 0.94
Bu 3Sn Iaurate 0.82 0.92 0.94
(Bu3SnhO 0.82 0.97 0.96
Bu3 Sn abietate 0.84 0.97 0.94
Hexabutyl distannane 0.94 0.95
o.8d o.8d
0.3d 0.3d
Bu4Sn 0.00 0.93 0.94 0.92
n-Hexyl 2Sn dilaurate 0.00 0.95 0.95
n-Octyl 2Sn dilaurate 0.00 0.94
n-Octy!3SnCI 0.00 0.94 0.93 0.95
n-Octy4Sn 0.00 0.90 0.94 0.83
PhSnCb Streaks to 0.99b Streaks Streaks
0.85 length of length of
paper paper
Ph2SnCI2 0.00 0.00 0.00 0.95b
Ph3SnCI 0.85 0.95 0.97 0.97
Ph3SnOAc 0.85 0.95 0.97 0.97
Ph4Sn 0.00 0.00 0.00 0.00
SnC4 0.00 0.00 0.00 o.ooa

a-sligh t tail. b-severe tailing c-elongated spot. d-probably irnpurity

organic tin and this reaction is adequately sensitive. However, it was found that ir-
radiation of chromatograms of tetra- or tri- compounds for 5 - lOmin with an ultra-
violet lamp before spraying caused sufficient oxidation to di- and mono- compounds
for them to be readily detected by the reagent. (The same result is obtained by ex-
posing the chromatogram to bromine vapour for a few minutes). The detection Iimit
with Catechol Violet is of the order of 0.5 Jlg Sn per spot.
Quantitative results were obtained for the separation of mixtures of di- and tri-
phenyltin chlorfdes by applying known volumes of solutions across the width of the
paper and, after development, irradiation and spraying, cutting out the blue bands
obtained, wet-ashing with sulphuric/nitric acids and determining the inorganic tin in
the resulting solutions turbidirnetrically with 4-hydroxy-3-nitro-phenylarsonic acid.
230 Organotin Compounds [Ref.p. 243

The developing solvents used and the Rf values obtained are given in Table 2.
Reversed-phase systems were also investigated using dinonyl phthalate (1) tritolyl
phosphate (2) or 2-phenoxyethanol (3) as the stationary phase, andin this way im-
proved separations become possible, particularly with mixtures of di- and tri- methyl
and -ethyltins. Results are given in Table 3.

Table 3. Rf Values Obtained with Different Reversed-Phase Systems

Stationary Phase 1 2 3
Deve!oping Solvent
Compound MeOH-M HCI MeOH-M HCI 2,24-Trimethylpentane-
(1 +3) (1 +1) acetic acid (92.5+7 .5)
Me2SnCI2 0.96 0.96 0.02
Me3SnC! 0.80
EtSnCI3 0.91 0.00
Et2SnCI2 0.88 0.64 0.13
Et 3 SnOH 0.29 0.29 0.44
Pr 2SnCI 2 0.32 0.20 0.38
(Pr3SnhO 0.00 0.03 0.76
BuSnCI3 0.88 0.00
Bu 2SnCI2 0.06 0.49
Bu3SnCI 0.00 0.06 0.84
Bu4Sn 0.00 0.96
Hex 2Sn(laurateh 0.00 0.69
Oct2SnCI2 0.00 0.85
Oct3SnCI 0.00 0.95
Oct4Sn 0.00 0.96
Et2laury!SnOAc 0.00
PhSnC! 3 0.84 0.00
Ph 2SnCI2 0.14 0.10
Ph3SnCI 0.00 0.27
Ph4Sn 0.00 Streaks

During the course of this work it was found that rapid separations of simple mix-
tures were possible using pieces of paper 15 x 15 cm carrying 2-phenoxy-ethanol as
the stationary phase and developing by the ascending-solvent technique with 2,2,4-
trimethylpentane-acetic acid (92.5 :7 .5). In this way it is possible to detect 1% of
tributyltin in dibutyltin dichloride and to differentiate between dibutyl- and dioctyl-
tin stabilisers in PVC in 20- 30min by extraction with petroleum spirit under reflux
and applying 10- 20J.L1 of the extract to a square of paper.
Reversed-phase system were investigated at about the same time by other groups
and their work is summarised in Table 4.

5 .1.3 Thin Layer Chromatography (TLC)

The first applications of TLC to organotin compounds were by TürZer and Högl
[114] and by van der Heide [ 115] for the identification of stabilisers in PVC (see
Section 8.1.1). Dibutyl, dioctyl and dibenzyl compounds were separated and mixtures
of di- and tri- butyl salts detected. Amounts of 1 - 10J.Lg of the compounds were ap-
plied to silica gel plates, chromatograms developed with n-butanol-acetic acid (50-
100: 1) saturated with water, or preferably, with butanol-acetic acid-ethanol-water
(5:0.15:5:10) and spots located by spraying the plates with dithizone.Bürger [116]
 Ref.p. 243] 5.1.3 Thin Layer Chromatography (TLC) 231

Table 4. Separations Obtained with Other Reverse-Phase Systems

Stationary Phase Developing Solvent Spot Detection Compounds Ref.

Separated

Petroleum (220- 260°C) Ethanol-acetic acid Dithizone Et1-4, Pr2,4 [1!0]

water (100:5:70) Bul-4• Octl,3,4
Olive Oil Methanol in M HCl Diphenyl Di-aryltins [1!1]
carbazone
1-Bromonaptha!ene 70 % Acetic acid Dithizone AlkylnSn~-n [1!2]
sa tura ted wi th Ca teehol
stationary phase Violet
Liquid paraffin Acetone-water-acetic Dithizone Bu 1-4, Oct2 ,Sn(IV) [113]
acid (100:50:5) Diphenyl
Butanol saturated carbazone
with 2M HCI
Acetone-water-
lutidine (1 00:50:50)

and also Neubert [ 117] made more detailed studies, using respectively iso-propanol-
10% ammonium carbonate-5M ammonia (6:2:1) or iso-propanol-M acetic acid-M
sodium acetate (4:1 : 1) and iso-propyl ether containing 1.5% acetic acid and 1ocating
spots with Ca teehol Violet. The latter author reported a detection limit of 1p.g of
the organotin compound. Helberg [ 116] used ring chromatography on silica gel pla-
tes to separate organotin stabilisers, with iso-octane-iso-propyl ether-acetic acid
(80:3:8) as developing solution and locating spots by spraying with a mixture of
Rhodamine B and Catechol Violet after treatment with bromine vapour. Quantita-
tive results were obtained [ 119] for the determination of 5 - 1OOp.g of dioctyl com-
pounds by extracting them from the developed chromatogram with propanol-hydro-
chloric acid (10:1), treating the e1uate with dithizone in borate buffer (pH8.4) and
measuring photometrically. (See Section 4.2).
Phenyltin compounds were separated successfully by Jitsu et al. [ 120] using iso-
propanol-acetic acid-sodium acetate (2: 1: 1) and by Braun and Heimes [121] using
hexane-benzene (80:20). Figge [ 122] found that silanised silica ge1 gave better separa-
tions and more clearly-defined spots in the separation of octyltin compounds prior to
their determination radiometrically (see Section 6). Good separations of the four oc-
tyltin compounds and inorganic tin were obtained using 2M HC1-tetrahydrofuran-iso-
amyl alcohol-2-chloroethanol (5:3:2:5).Herold andDroege [123] separated mix-
tures of the four octylin compounds and dibutyltin, all present as chlorides or as thio-
glycollates, using butanol-acetic acid (60:1) saturated with water, and determined al1
but the mono-compounds with dithizone as described above [119], while mono-oc-
tyltin was determined volumetrically on aseparate sample with EDTA (see Section
4.1).
Wieczorek [124] separated the four octyltin compounds tagether with dimethyl-
diethyl- and dibutyl-compounds with various acidified rnixtures of benzene and hex-
ane with ethyl ether, and determined all compounds photometrically with quercetin,
first converting tetra- and tri- compounds to the corresponding di-alkyls by exposure
to bromine vapour.
232 Organotin Compounds [Ref.p. 243

Separation of the four methyltin compounds by TLC was achieved by Koch and
Figge [ 125] who used mixtures of chloroform and formic acid with acetylacetone or
dimethylsulphoxide as developing solvent and a mixture of Rhodamine B and Cate-
chol Violet (3 mg + 30mg in 1OOml of acetone) as spray reagent. Spots of the tetra-
and tri- compounds were first neutralised in triethylamine vapour and then oxidised
in bromine vapour before spraying. Mono-methyl compounds were determined photo-
metrically with quercetin, the di- and tri- polarographically or photometrically with
Catechol Violet after conversion to inorganic tin by wet-oxidation. It was found that
tetra-methyltin in PVC stabilisers was best determined by GLC on aseparate sample.

5.2 Ion-Exchange
The adsorption of mixtures of di- and tri- butyltin chlorides on Amberlite CG-120
cation-exchange resin was studied by Williams [ 126], who used ion-exchange to sep-
arate the compounds from wood extractives in a solution of 0.05% hydrochloric acid
in ethanol (see Section 8.3). Complete retention ofthe organotin compounds was ob-
tained on diluting this leached solution with half of its volume of water. Elution tests
showed that the tri-compound could be recovered from the resin with a solution of
10% of water and 0.3% of hydrochloric acid in ethanol, while the di- compound could
be subsequently eluted with 5% of the acid in ethanol.
Little other work has been reported, but silica gel columns have been used to ad-
sorb dialkyltin compounds from such materials as liquid paraffin, sunflower seed oil
etc., the adsorbed compound being eluted with a solution of 2% formic acid in ether
[127]. Separations of e.g. mono- and di-alkyltins by this method have not been stud-
ied but it seems probable that any mono-compound present would be adsorbed on
the column but may not readily be eluted.

5.3 Solvent Extraction

Detailed studies have been made by Bocket al. on the separation of the tri-, di-
and mono- phenyltin compounds from each other and from inorganic tin by solvent
extraction and this work is summarised in a paper by Freitag and Bock [ 128]. They
found that
a) in the absence of other anions and of complex-forming reagents, triphenyltin chlo-
ride can be separated from the di- and mono- compounds by extraction with an organ-
ic solvent such as chloroform or methylene chloride;
b) addition of a suitable complexing reagent allows extraction of the diphenyltin
chloride;
c) afterremoval of the tri- and di- compounds the monophenyltin can be extracted as
its complex with tropolone or diethyldithiocarbamate. A typical scheme for separa-
tion and determination is given below:
Solutions containing 2 - 1OO,ug of the chlorides of the three phenyltin compounds
and of stannic ch.loride in 25m! were treated with an equal volume of citrate-phos-
phate-EDTA buffer solution (pH 8.5) (42.3 g Na 2 HP0 4 .12H 2 0 + 7.7 g citric acid + 2g
EDTA disodiumsalt in llitre) and extracted twice with IOml ofmethylene chloride
The triphenyltin in the organic layer was determined photometrically with dithizone.
The aqueous layer was then extracted with an equal volume of a 1o- 3 M solution of
either dithizone in chloroform, PAR in iso-amyl alcohol, a benzoinoxime in chloro-
form or acetylacetonein chloroform and the diphenyltin in the organic layer deter-
mined photometrically with dithizone. The mono-compound remairring in the aque-
 Ref.p. 243] 6. Radiometry 233

ous layer was then extracted with either tropolone or diethyldithiocarbamate in

chlotoforrn and deterrnined photometrically with dithiol after wet-oxidation to inor-
ganic tin.

Woggon and fehle [ 129] have investigated the solvent extraction of small amounts
of tributy1 and triphenyltin chlorides and their breakdown products from aqueous
solutions, but their approach differed in that they co-extracted all the organotin com-
pounds present and then separated them by TLC of the organic solvent. For isolation
of the triphenyltin compound a 1 litre sample was evaporated to 200m! after the ad-
dition of 5 ml of a 5% EDT A solution and extracted with 5 ml of cyclohexane after
adding 5 rnl of M hydrochloric acid. Separations from other compounds followed by
TLC.
Recovery of trace amounts of di- and tri-alkyltins by solvent extraction does not
so far appear to be quite as successful as that of the phenyltins, but is seems probable
that methods similar to those discussed above will be found suitable.

5.4 Distillation
In the deterrnination of trace amounts of organotin compounds in water any loss
by volatilisation during a concentration step can usually be prevented by the addi-
tion ofEDTA but this has been found to fail with TBTO. In such cases the TBTO can
be separated from di- and mono-butyltin compounds as well as from triphenyltin by
steam distillation of the chloride as follows: (130]
Add 30m! of 1M hydrochloric acid to a filtered llitre water sample containing up to lOpg Sn
and steam-distil 200m!. The TBTO in the distillate can then be extracted into 5 ml of an organic
solvent such as cyclohexane and determined by any preferred method.

6. Radiometry

The high sensitivity of radiometric methods makes them of interest in the study of
animal metabolism, fungicide residues and the migration of stabilisers from PVC. The
tin isotope 113 Sn with a half-life of 119 days has been used successfully for these
purposes. It is formed in an n, -y-reaction from the naturally occuring 112 Sn and chan-
ges via 113 m In to 113 In by electron capture; the "Y and X-rays emitted can be measured
readily with a scintillation counter. Measurement is made of the 260keV -y-emission
of 113 Sn and the 390keV emission of 113 m In (ha1f-life 1.73hrs.), radioactive equili-
brium being reached in about 19hrs and detection Iimits (one-tenth background) are
reported to be of order of 0.0001 ppm 113 Sn.
e
Herok and Götte [ 131], using 13 Sn] triphenyltin acetate with a specific activity
of 8mCi/g, investigated its distribution and excretion when fed to sheep and cows,
the deterrnination of 113 Sn being carried out with a scintillation counter with weil
crystal, the measuring volume being 5ml. Milk, urine and various organs were wet-
oxidised with sulphuric acid/peroxide, the final volume being made up to 5 rnl with
concentrated acid, while blood samples were measured directly after the addition
of citrate. The results obtained represented 'total tin' rather than a particular phenyl-
tin compound, though evidence for the presence of some inorganic tin was adduced
from a graphical analysis of rates of elimination.
A similar method was used by Heath [132] in a distribution study on rats given
[ 113 Sn]
triphenyltin chloride. Here again the results did not show that the compound
234 Organotin Compounds [Ref.p.243

recorded was triphenyltin but isotope dilution analysis and some separation procedu-
res indicated that excretion and breakdown of triphenyltin to inorganic tin was not
as rapid as was at f!rst thought.
A somewhat different approach was made by Barnes et al [ 133] who used 4 C] e
triphenyltin acetatein an investigation of the persistence of the compound in the
soil. (See Section 8.2.2). The specif!c activity of the compound was 0.25 mCi/g and
liquid scintillation counting was carried out using butyl PBD in toluene as phosphor.

The chemistry of PVC stabilisation by organotin compounds, R 2 SnX 2 , has been

studied radiometrically by Frye et al. [ 134] using 113 Sn, 14 C and 35 S, while SeidZer
et al. used both 14 C- and 35 S- Iabelied dioctyltin compounds in studies on their di-
stribution in rats after feeding single doses [ 135 ], and also to investigate the migration
into sunflower oil of the compounds from PVC containing 2% of the stabiliser [ 136].
Figge et al. in a series of papers have described the use of 113 Sn in dibutyl and
dioctyltin stabilisers to follow the migration of the stabiliser into edible oils [137]
and beer [ 138], and also to assess the loss of stabiliser due to volatilisation during
milling.

7. Spectroscopy

Although many publications have appeared in recent years on the spectroscopy of

organotin compounds, these have been concerned preponderantly with investigations
of their structural chemistry and their possible modes of action as e.g. stabilisers or
fungicides rather than with their quantitative determination. Of the very few examp-
les of quantitative studies may be mentioned that of Domange and Guy [ 140] who
examined the IR spectra of solutions of the di- and tri- ethyltin iodides in carbon
disulphide solution with the object of determining the tri- compound in mixtures.
They found, however, that the transmission of a mixture at 8 .12J.L was distinguishab-
le from that of the di- compound alone only if the mixture contained more than 10%
triethyltin. Later Friebe andKelker [141] studied the IR spectra ofthe triphenyltin
hydroxide-bis(triphenyltin)oxide system and found that the components could be
determined in a solid phase suspension in liquid paraff!n.
The IR spectra of a series of ethyltin compounds in the region 2- 45J.L have been
reported by Lohmann [142] and assignments have been made for many stretching
frequencies (Sn-C, Sn-halogen, Sn-0) most of which have been summarised by Poller
[143], while Cummins and Dunn have published a useful set of spectra of the organo-
tin stabilisers and related compounds [ 144].
Detailed studies have been made of the UV spectra of the phenyltin chlorides
[ 145] and the existence of absorption bands in other compounds has been discussed
by Poller [143].
PMR studies involving the hydrogen atoms of the organic groups attached to tin
have proved of value in determining conf!gurations, particularly of alkenyltin com-
pounds and many of these have been reviewed by Poller [143]. More recently 119 Sn
PMR studies involving the hydrogen atoms of the organic groups attached to tin
in structural investigation and a useful review has been published [ 146].
119 rn Sn Mössbauer spectroscopy has also in recent years contributed to a know-

ledge of the structure of organotin compounds and a compilation of the values so

 Ref.p. 243] 8 .1.1 Determination of Stabilisers 235

far obtained for isomer shifts and quadrupole splitting has been made by Smith
[ 14 7], who has also published a bibliography of the organotin crystal structures that
have been evaluated up to mid-1974.

8. Applications

8.1 PVC Stabilisers

The main commercial organotin stabilisers in present use are mercaptans, mercapto-
esters and -carboxylates or sulphur-free carboxylates and esters of mono- and dimethyl,
-butyl and -octyltin. Formulated plastics may contain stabilisers, plasticisers, optical
brighteners, antoxidants, UV absorbers, lubricants or odorant as weil as flller. It has
been found that !arge amounts of plasticiser and/or lubricants in formulated PVC can
cause considerable migration of the organotin stabiliser and for this reason the use of
plasticisers in PVC for food-contact use is undesirable. For the unplasticised ('rigid')
materials used in food packaging, lists of approved organotin stabilisers have been
issued in several countries and regulations are in force in the U.S.A., West Germany
etc. covering permitted amounts (usually not more than 2%) as well as the purity of
the compounds used. Schemes have been put forward for the identification of stabi-
lisers as such [ 149] andin plastics formulations after Soxhlet extraction into ether
[ISO]. The alkyl groups attached to tin were identified by infra-red spectrometry or
by TLC and the acid groups present by NMR or mass spectrometric examination.
Analytical methods for the general examination of plastics are available in the books
given in Reference [1S1, 1S2].

8.1.1 Determination of Stabilisers

In this section consideration is given to the identification and determination of
organotin stabilisers present in processed PVC.
If the organotin compound present is known its amount may be found by wet-
oxidation to inorganic tin which can then be determined volumetrically after reduc-
tion to the stannous form. Precautions are necessary to prevent loss of tin during the
rapid evolution of hydrochloric acid in the early stages of the decomposition of the
PVC; the fitting of a short air condenser to the vessel containing the sample is usually
sufficient. To detect and identify the stabiliser in unknown material a O.S g sample,
cut into small pieces, is extracted under reflux with petro1eum spirit or 1,2-dichloro-
ethane, the solvent decanted and tested with dithizone as follows: to a S ml aliquot
add Sm! of borate/EDTA buffer pH 8.4, (19g Na 2 B4 0 7 .10H 2 0, 12g H 3 B0 3 , 2.S g
EDTA in 1litre) and 1m! of dithizone solution (0.008% in dichloroethane). Shake and
allow the two layers to separate. An orange-red colour indicates the presence of a dial-
kyltin compound. If another S ml aliquotisshaken with S ml of M sodium hydrox-
ide, dimethyl-and dibutyltin compounds pass into the aqueous layer but dioctyltins
remain in the organic layer and may be detected by shaking this layer with Sm! of
10% trichloracetic acid and 1ml of the dithizone solution, when a red colour is prod-
uced. Alternatively the original extract may be examined by TLC or paper chromato-
graphy; a rapid procedure using the latter method is described in Section S .1.2.
236 Organatin Compounds (Ref.p. 243

The dithizone method above can be madequantitative as follows [153]:

Heat under reflux a finely divided sample of PVC containing not more than 700pg Sn (0.1 -
0.2g is usually sufficient) with 25 ml of 1 ,2-<iichloroethane until the PVC has dissolved. Add 25 ml
of hydrochloric acid and heat until the solvent has refluxed for 5 min; this step in necessary in
order to extract into the acid any inorganic tin or other meta! salts which can react with dithi-
zone. Cool, allow the layers to separate and transfer the organic layer to a 50ml flask, wash the
acid layer with two successive portians of 10m! of solvent, add these to the flask and make up
the volume to 50ml. Transfer an aliquot of this solution containing about 10pg Sn to a separat-
ing funnel and add solvent to give a total volume of 5 ml. Add 5 ml of borate buffer and 1 ml of
dithizone solution and shake for 1 min. Run the dithizone layer into a 10m! flask, make up to
volume and measure the adsorption of the solution at 490nm. Prepare a calibration curve by
dissolving O.lg of dibutyltin dichloridein 100m! of 1,2-<iichloroethane and from this prepare a
solution containing 10pg/ml of the compound, equivalent to 3.9pg Sn. Treat aliquots of from
1 - 4 ml with borate buffer and dithizone as above. This curve can be used for all the dialkyltins
but not for diaryltin compounds.
An EDTA titration has been used by Bergner et al. [154] for the direct determina-
tion of mono- and di- alkyltin compounds in PVC as follows.
A 200mg sample of the PVC is dissolved in 20m! of tetrahydrofuran by warming on a water
bath, the polymer precipitated by the addition of 50ml of ethanol, filtered off and washed with
ethanol (2 x 10m!). The filtrate is heated to boiling on a water bath, catechol violet added, giving
a blue or blue/green colour and the solution titrated hot with 0.001 M EDTA to a colour change
through green to yellow. (This titrationwas considered to give the sum of mono- and di- com-
pounds if both were present, but this point was not investigated in detail as at that time mono-
compounds were likely tobe present only at low Ievels).
Cornrnercial samples ofPVC may contain in addition to organotin compounds,
salts of other metals such as magnesium, zinc or cadmium, and these, if present, would
be included in the above titration. A correction can be applied as follows.
Dissolve a 200mg sample as above, precipitate the polymer with ethanol and filter; to the
filtrate add Eriochrome Black T and 1 ml of ammonia solution (d 0.88). The organotin com-
pounds produce a blue colour with the indicator, which is not affected by EDT A but the other
metals give a red colour which can be titrated. The solution is accordingly titrated hot with the
same EDTA solution to a colour change from red-violet to a pure blue, the difference between
the two titrations giving the amount due to the organotin compounds.

Recently Koch and Figge [15 5] have published methods for the determination of
mono-, di-, tri- and tetra- methyltin compounds in cornrnercial methyltin stabilisers.
Mono-compounds are determined volumetrically with EDTA (see Section 4.1) and, in
the absence of significant amounts of tri- and tetra-tins, total tin may be determined by
wet oxidation and the di- compound found by difference. If the other compounds are
tobe determined, the tetra- compound down to 0.1% can be found by gas chromato-
graphy, using a 1 metre column of 'Porapak Q' and injecting a solution ofthe sample
in n-octane, or the compounds can be separated by TLC on silica gel as described in
Section 5.1.3.

8.1.2 Migration from PVC into Foods and Food Simulants

In view of the extensive use of tin-stabilised PVC for food packaging much work
has been done on the migration of organotin compounds from PVC into foods and
food sirnulants and regulations have been published in a number of countries lirniting
the amounts extracted into foods and also specifying methods of carrying out extrac-
tion tests. Typical extracting solutions are water, dilute acid (usually 2% acetic or
citric) ethanol-water mixtures (typically 5 or 15% ethanol) and a fatty food sirnulant
such as medicinal paraffin or olive oil containing 2% oleic acid. Although methods
of test and maxirnum permitted amounts extracted have been specified in some de-
tail, no methods of analysis have so far been laid down.
 Ref.p. 243] 8.2.1 Crop Residues 237

Earlier work was concerned with the deterrnination of dibutyl- or dioctyltin com-
pounds, no need arising for their separation from other organotins, but current stabi-
lisers now include the methyltin compounds and may contain up to 20% of a mono-
compound, so that separations are generally necessary.
The analysis of aqueous extracts centairring dibutyl- or dioctyltins presents no
special difficulties and satisfactory photometric procedures have been described
[ 156] (see Section 4.2). Adamsan [157] determined dibutyltin compounds in fats and
olive oil by shaking with a solution of catechol violet in ethanol, the blue colour of
the dibutyltin-catechol violet complex being measured at 550nm. Repeated extrac-
tion with ethanol is necessary in order to remove all of the complex and separation
into twci layers is in some cases slow and incomplete.
The photometric determination of dioctyltin compounds in vinegar and orange
drinks after solvent extraction with petroleuro spirit has been described by Adcock
andHope [158]. For their determination in sunflower seed oil the authors first ad-
sorbed the organotin compounds on a column of silica gel and eluted them with a
2% solution of formic acid in ether; after separation by paper chromatography, final
determination was with catechol violet after wet-oxidation. Franzke et a/. [ 159] in
studying the migration of a dioctyltin compound into olive oil have used quercetin
instead of catechol violet as the chromogenic agent (see Section 4.2). This paper is
one of a series published by these workers [160] who in addition to photometric
methods have used radiometry and TLC to determine these compounds.
The migration of the organotin stabilisers has also been studied in detail by Figge
et al. [ 165] and recently they have published the results of extraction tests of a se-
ries of methyltin compounds, followed radiometrically using 14 C, into edible fats
and fat simulants [168].

8.2 Agriculture

8.2.1 Crop Residues

a) Triphenyltin Compounds
Triphenyltin acetate ('Brestan') and hydroxide ('Duter') have been used extensi-
vely as agricultural fungicides, particularly on potatoes and sugar beet, and tolerances
for residues of these compounds on crops varying from 0.001 to 0.1 p.g/g have been
proposed. A considerable number of analytical investigations have been made, mainly
on triphenyltin Ievels on treated potato crops and also on the possible metabolic path
of trace amounts consumed by cattle fed with treated fodder. These latter have been
carried out mainly by radiometric methods and are discussed in Section 6. Chemical
methods for the determination of crop residues involve solvent extraction of the veg-
etable material, followed by separation of triphenyltin from its degradation products,
di- and mono- phenyltin, and more or less standard 'clean-up' procedures, ending with
determination by any preferred method. An excellent summary of the various meth-
ods of determination that have proved useful is given by Freitag and Bock [ 169].
A typical procedure for the deterrnination of triphenyltin compounds on the
surface of the leaves of a treated crop of e.g. sugar beet is as follows [ 170]: extract
lOg of fresh leaves with 50ml chloroform, adding 3m! of O.IM sodium hydroxide,
and repeat the extraction with two further 50rnl portians of the solvent. Shake the
combined extracts with a mixture of 20m! of 0.1 M sodium hydroxide and lOrnl of
0.5 M sodium tartrate; this leaves only the triphenyltin in the organic layer. Evaparate
238 Organatin Compounds [Ref.p. 243

the chloroform on a water bath after the addition of 3 drops of sulphuric acid, wet-
ash by the addition of nitric acid, and remove the sulphuric acid completely by heating
to dryness. Re-dissolve the residue in 5 ml of 5 M hydrochloric acid and determine tin
by polarography over the range - 0.4 to - 0.9 vs s.c.e. The smallest amount of triphen-
yltin acetate determined in this way was 6J..Lg in a lOg sample, i.e. 0.6J..Lg/g, and it was
found by Nangniot andMartens [171] that a 100-fold increase in sensitivity could be
obtained by pre-electrolysis at a hanging drop mercury electrode at - 0.7v vs.
Ag/AgCl/KCl and measurement of the anodic dissolution peak between - 0. 7 and
· 0.1 V.
The same method of extraction followed by polarographic determination of inor-
ganic tin was used by Wit and van Lier [ 172] to measure the rate of decomposition
with time of triphenyltin on celery while Hardon et al. [ 173] used a photometric
method when studying the same crop. They extracted 150g of celery with 300ml
of methylene chloride, evaporated an aliquot of the extract to dryness, dissolved the
residue in 6ml of chloroform and removed interfering plant material, which is co-
extracted, by adsorption on an alurnina/infusorial earth column. Triphenyltin was
then determined with dithizone, using the standard borate buffer (pH 8.4) procedure.
The method was sensitive to about 0.1 J..Lg/g of the compound.

It is sometimes considered preferable that a direct determination of the organotin

compound itself should be made rather than converting it to the inorganic form,
though in the extraction procedures described it appears probable that, in the absence
of any complexing agents, little if any of the di- and mono-phenyltin that may be
present as breakdown products, is likely to be co-extracted with the triphenyltin.
The technique of anodic stripping was applied by Booth and Fleet [ 174] to the di-
rect determination of residues of the triphenyltin compound on potatoes after extrac-
tion with acetonitrile as follows:
A 100g sarriple was dried at 90°C for one hour to remove most of the water and then macerat-
ed for 5 mins with 200m! of the solvent, followed after decantation by a secend extraction with
100m!. The combined extracts were passed down a column containing anhydrous sodium sulphate
to remove water, followed by alumina to remove oils and starchy material, and then evaporated
to low volume (<10m!). After the addition of acetate buffer and Triton X-100 the solutionwas
diluted to 15 ml to contain 50% ethanol and the triphenvltin determined by anodic stripping
(see Section 4.3). The Iimit of detection was found tobe 10"8 M and amounts down to 0.001J..Lg/g
were determined.

Similar methods were used by Bruggemann et al. [175] who studied in detail the
fate of triphenyltin acetate on sugar beet leaves, soon after spraying and also after
ensilage for cattle fodder. They used the photometric dithiol method after solvent
extraction followed by wet-oxidation to inorganic tin. The compound was also deter-
mined in the range 5 - 40J..Lg/l in milk from cows fed with treated sugar beet leaves
[ 176]. A 5 I sample was spray-dried and extracted with chloroform.
In determining residual triphenyltin compounds on potatoes sprayed during
growth with an organotin fungicide the low Ievel to be expected - of the order of
O.OOlf!g/g- necessitates the use of a large sample - 100- 500g according to the
method of determination used - with corresponding large volumes of extracting
solvent. An extraction and 'clean-up' procedure followed by wet oxidation to inor-
ganic tin of the isolated triphenyltin has been reported by Thomas and Tann [ 177],
while improved sensitivity was found by Vernon [178] who, using substantially the
same extraction method, determined triphenyltin as such by fluorimetry. The Thomas
and Tann procedure is a follows:
 Ref.p. 243] 8.2.1 Crop Residues 239

Macerate a 250g sample of potatoes with 250m! of acetone and 20ml M sulphuric acid.
Filter andre-macerate the residue with 200m! of dichloromethane, again filter and repeat with
a further 200m!. Combine all the filtrates, adjust the pH of the upper aqueous phase to 7 - 8
with 2M potassium hydroxide, add 2g EDTA and shake for 1 min, re-adjusting the pH if necessary,
Filter the organic layer through lOg of anhydrous sodium sulphate and wash the aqueous phase
with two 100m! portians of dichloromethane. Evaparate the solvent to 10- 15 ml on a rotary
evaporator under reduced pressure and heating to about 60 6 C and concentrate to about 1 ml
with a current of air. Add 5 ml concentrated sulphuric acid, heat at 65°C for 30 min, add 25 ml
of water and filter through 1g of Celite on a sintered disc, washing with 25 ml 3M sulphuric acid.
Extract the combined filtrates with two 50ml portians of chloroform, followed by 50ml of
carbon tetrachloride. Add 3 ml of perchloric acid to the remaining aqueous phase followed by
15 ml of saturated sodium iodide solution and extract the stannic iodide with two lOml portians
of carbon tetrachloride. Add 2ml hydrogen peroxide to the combined extracts and evaparate
with a current of air, heating in a water bath to about 90°C. Add 5 drops of sulphuric acid and
evaparate to fuming; add 2 ml o f nitric acid and again heat strongly to fuming. Add 5 ml 0 .1M
sulphuric acid, 5 ml 0.5 M sodium acetate solution, 1 ml of 0.003% catechol violet solution.
Dilute to 25mland measure absorbance in a 4 cm cell at 665 nm. The Iimit of detection of inor-
ganic tin by this method is 0.5 )lg and after correction forablank an apparent Iimit of detection
for triphenyltin was stated tobe O.OOl,Ug/g.

Vernon found a detection Iimit of 0.16,ug Sn with a fluorimetric method in which

he extracted a 500g sample with dichloromethane as above and continued with the
procedure until the volume of the solvent was reduced to lOml in a rotary evaporator.
Then, instead of wet-ashing, he added 1OOml of benzene, again evaporated nearly to
dryness, added 5 ml of 0.01% 3-hydroxyflavone in benzene followed by 1ml of sat-
urated sodium acetate solution. After shaking mechanically for 30min the benzene
layer was transferred to a 1 cm fluorimeter cell and the fluorescence intensity measur-
ed at 415/497nm. In this method separation of the triphenyltin is not necessary as
both di- and mono- phenyltin and inorganic tin show no appreciable interference,
after shaking with sodium acetate. The reason for this is at present somewhat obscure,
but it appears that in this treatment both the mono- and di- complexes are transfer-
red to the aqueous layer.
b) Tricyclohexyltin compounds
Tricyclohexyltin hydroxide is in commercial use under the name 'Plictran' as a
miticide, principally on apples, pears and citrus fruits, and regulations are in force in
e.g. the U .S.A. [ 179]limiting the combined residues of the miticide and its two or-
ganotin metabolites in or on apples and pears to a miximum of 2,ug/g. Corbin [180]
determined tin in the range 0.1 - 4,ug/g on apples and pears treated with Plictran by
wet oxidation of a 1OOg sample with nitric/sulphuric acids, followed by separation
of the tin either by distillation of the bromide or by extraction of the iodide into
hexane and finally determining photometrically with dithiol. Trombetti and Maini
[181] also examined apples and pears sprayed with Plictran but differentiated bet-
ween 'surface organic tin', 'surface inorganic tin' and 'total interior tin'. Surface
organic tin was dissolved from 4 · 5 whole fruits with three successive 30ml portions
of hexane-acetic acid (99: 1) and a suitable aliquot of the solution evaporated nearly
to dryness and wet-ashed as above. From the sample already treated 'surface inorgan-
ic tin' was recovered by extracting with three successive 30m! portions of hydrochlo-
ric acid (1 :4) containing 0.01% sodium lauryl sulphate and again a suitable aliquot
was wet-ashed. Finally the extracted fruit was cut into small pieces and weil mixed
and a lOOg portion wet-ashed, using 150m! of nitric acid and 40ml of sulphuric
acid. Tin in the three fractions was determined photometrically with dithiol.
Getzendaner and Corbin [ 182] showed that separation of tri-, di- and mono-
cyclohexyltin compounds present together in the 'surface organic tin' fraction ob-
tained by extraction with hexane-acetic acid as above, was possible by re-extraction
240 Organatin Compounds [Ref.p. 243

of the mono- compound with dilute hydrochloric acid (1 :4), and of the di- compound
with alcoholic potassium hydroxide (5% in 50% ethanol), leaving the tri- compound
in the hexane layer. Tin in theseseparate fractions was then determined with dithiol
after wet-ashing as above.
More recently Gau er et al. [ 183] have described the determination of the tri- and
di- compounds on strawberries, apples and grapes treated with Plictran. A finely-
chopped SOg sample was treated with enough water to form a slurry, 30rnl of hydro-
bromic acid added and the mixture swirled mechanically for 30min to convert the
organotin hydroxides to bromides. After the addition of SOml of benzene swirling
was continued forafurther 30min and the benzene layer separated by centrifugation.
The extraction with benzene was repeated twice, the combined extracts reduced to
Sml by distillation and further to 1 ml under a stream of nitrogen at room tempera-
ture. This solution was analysed by gas-liquid chromatography on a 60cm column
containing 2% OV-225 (a cyanosilicone) on Chromosorb G and operated at 200°C.
The method was not suitable for the determination of the mono- compound owing
to irreversible column losses. Retention times for the di- and tri- compounds were
about 5 and 10 min respectively.

8.2.2 Residues in soils

The only work so far reported has been concerned with the extraction on a Iaba-
ratory scale of triphenyltin acetate or hydroxide from soil samples, combined with
assessment of the rate of breakdown under various conditions.
Cenci and Cremonini [ 184] added 8 mg of triphenyltin acetate or hydroxide to
1 kilo samples of different types of soil and, after exposure in the open air for up to
30 days, extracted the organotin compounds with a 1:1 mixture of ethanol and
diethyl ether. The extract, after concentration by evaporation in a rotary evaporator,
was examined by TLC on silica gel, using as developing solvent a mixture of n-buta-
nol, ethanol and water (4:2:1). The spray reagent used to detect the triphenyltin
'spots' was prepared by mixing 1 g sodium metavanadate with 0.5 g di-potassium hy-
drogen phosphate, dissolving in water with dropwise addition of ammonia to effect
complete solution and diluting to 1 1. This reagent gave an orange-brown colour with
amounts of triphenyltin down to 0.05 pg. The authors found a fairly rapid breakdown
to inorganic tin which they attributed entirely to photolytic action.
A more detailed study was made by Poller et al. [ 185], who followed the biologi-
cal degradation of triphenyltin acetatein soil radiometrically using (14 C] (see Sec-
tion 6). They found that, while all the added triphenyltin could be recovered initial-
ly by Soxhlet extraction for 2h of a 20g sample of soil with SOrnl of methanol, the
amount decreased with time, and that any diphenyltin added could not be extracted.
The leaching of triphenyltin through a column of sterile soil was investigated by
passing waterat a rate of 12ml/hr. through the column for 6 weeks; no radioactivity
was detected in any of the fractions eluted. Degradation was studied by treating soil
samples (microbial count 11 x 10 6 organisms/g) with rt 4 CJ triphenyltin acetate at
Ievels of 5 and 10pg/g, placing in 2 cm diameter columns shielded from the light and
passing a slow stream of air through the columns. Evolution of [ 14 C]C0 2 was moni-
tared by absorbing in an ethanolamine-2-butoxyethanol (1: 1) trap (2rnl). It was found
that half of the carbon in the phenyl groups was converted to co2 in about 140 days,
the rate of evolution then falling off, while on using sterile soil very little evolution of
co2 took place (0.4 7%) in 60 days.
 Ref.p. 243] 8.3 Wood 241

No comparable work on the trialkyltins has so far been published but it is reason-
able to expect similar results. Bollen and Tu [ 186] have reported that Ievels of TBTO
up to 1OOppm in soils have no effect on the microorganisms present.

8.3 Wood
Salutions of bis( tri-n-butyltin) oxide (TBTO) in organic solvents are fmding in-
creasing use for the protection of timber against fungal and insect attack, and for can-
trot purpose it is usually sufficient todeterminetotal tin in a sample by wet-oxida-
tion or by X-ray fluorescence spectrometry [18 7]. TBTO can be extracted from
freshly impregnated samples in the form ofthin sections or as wood flour by reflux
or Soxhlet extraction into such solvents as chloroform, ethanol or methylisobutyl
ketone and total tin determined in the extract by e.g. atomic absorption spectroscopy.
In examining aged timber, however, extraction is incomplete and some degradation
has probably taken place with the formation of a dibutyltin compound. However,
complete recorvery can be obtained with a 0.5% solution of hydrochloric acid in eth-
anol [ 188] and separation of tri- and di- butyltin chlorides in this solution carried out
by adsorption on a cation-exchange P~sin (Amberlite CG 120). The tri-compound
is then recovered from the resin with a solution containing 10% water and 0.3%
hydrochloric acid in ethanol, and the di- compound subsequently eluted with a 5%
solution of hydrochloric acid in ethanol. The compounds in the two eluates were
then determined either directly by atomic absorption or by polarography.
Anti-Fouling Paints
The evalution of these paints involves measurement of leaching rates of toxic agents
from a paint film in sea-water and for paint containing organotins - usually trib-
utyl or triphenyl compounds - this involves determination of concentrations of a
few micrograms per litre. Determination of residual tin in a paint film after prolo).l-
ged soaking in sea-water has been suggested [ 189] but can only serve as a rough guide.
Chromy et al. have used an extraction procedure which allowed deterrnination of
amounts down to 1JLg/ml ofTBIO in sea-water using a 50sample. They extracted
twice with 5 ml of carbon tetrachloride and determined the compound in the com-
bined extracts with dithizone [ 190] or spectrographieally [ 191] as follows:
3m! of the carbon tetrachloride extract were mixed with 0.5g carbon powder containing
0.5% of a solution of copper ch!oride in methanol to act as internal standard, and after drying,
the powder was placed in a crater in the lower carbon electrade af a medium resalutian spec-
tragraph. Camparisan with the phatametric procedure shawed this ta be the mare accurate
methad.
Another extraction procedure was used by Pettis et al. [192] to determine 0.1
- 1 mg/1 of TBTO in sea-water. They extracted the sample with half its volume of
methylisobutyl ketone by shaking for 2h. A solution of haematin in the same solvent
was prepared by dissolving 0.5 g of haematoxylin in 1OOrnl, adding 0.2g dibenzoyl
peroxide and refluxing for 2h; 2m! of this solution were added to the extract and
the volume made up to 100m! with the solvent. This solutionwas then heated for 2h
at 60°C to produce a blue colour, the absorbance of which was measured at 570nm.
This method appears to rely on the degradation of the tributyltin compound to form
a dibutyltin complex, as the same blue colour is produced immediately in the cold
with a dibutyl compound, but, providing the experimental conditions are followed
carefully, accurate results are stated to be obtained.
242 Organetin Compounds (Ref.p. 243

8.4 Environmental

8.4.1 Air
In 1964 Selivokhin [ 193] determined diethyl- and dibutyltin compounds in air by
passing 20- 80 l of the air a rate of 11/rnin through 5 rnl of butanol maintained at 0°.
The dissolved compound was then determined colorimetrically by the addition of
diphenylcarbazone and direct comparison with standards covering the range 2 - 30,ug
of the compound.
Luskina and Syatsillo [ 194] adsorbed the organotin compounds on a column of
silica gel at- 70°, and after desorption at 100° followed by wet-ashing, determined
tin photometrically with phenylfluorone.
In 1968 a threshold limit value of 0.1 mg/m 3 was recommended in the U .S .A. for
'organic tin' in air and methods were put forward by Jettes (195] for the deterrnina-
tion of TBTO at levels approaching this limit. He assumed that the TBTO was pre-
sent as an aerosol and so could be collected on a filter. A high volume air sampler
fitted with two glass fibre fllter discs, 16cm dia., was used and a sample of25m 3 of
air passed through them at a rate of 30 -40m 3 /hr. Two methods of analysis were
used, the second of which is specific for butyltin compounds.
1. The filters were extracted with methylisobutyl ketone in a Soxhlet apparatus
and the extract examined by atomic absorption spectroscopy using a nitrous Oxide-
acetylene flame. Calibration was carried out with solutions ofTBTO in the same Sol-
vent and covering the range 10- 50mg/l.
2. The fllters were extracted as above with toluene and the solution (1.5,ul) inc
jected into a gas chromatograph through an injection port packed with glass wool
and maintained at 390°C. The 6ft. column packed with Parapak Q was at 240°C and
the detector at 340°C. Complete pyrolysis of the TBTO to olefines took place and
the I-butene peakwas used for measurement. Calibration was carried out with solu-
tions of TBTO in toluene covering the same range as above.

8 .4.2 Water
The determination of organotin compounds in waste waters presents some diffi-
culty, particularly in view of the very low amounts to be expected, e.g. a tolerance
limit of 0.003 ,ug/ml TBTO has been suggested [ 196]. At these low concentrations
TBTO is likely to be adsorbed on particles of soil or organic matter and on the walls
of any glass vessels used for sampling purposes, and also to suffer degradation, ulti-
mately to hydrated tin oxide, which is itself firmly held by soil particles and sedi-
ments. If a determination of total tin gives sufficient information, evaporation and
wet-oxidation of a large sample of waste water can be carried out and the resulting
solution analysed for inorganic tin. If, however, TBTO itself is tobe deterrnined, ex-
traction and Separation become necessary, and, although some methods have been
published, all the problemsarenot yet solved and further work is necessary.
Vrestal and Havir [ 197] have described a method for the determination of trial-
kyltin compounds by extraction with chlorobenzerre from a water sample that has
been made 0.1 M in sodium hydroxide and 0.01 M in EDTA, so that other alkyltin com-
pounds and inorganic tin are not extracted. The trialkyl compound in the extract
was then determined by photometric titration of the solution with a 10-4M solution
of dithizone in the same solvent. In this way it was found possible to determine as
little as 3 ,ug of TBTO with good accuracy.
 8.4.2 Water 243

Removal of TBTO from waste waters has been suggested by adsorption on to

cellulose [198] or active carbon [199) and monobutyltin chloride has been removed
by extraction into a solution of tributyl phosphatein butanol [200], but little infor-
mation is available on the quantitative aspects of these systems.
The position with the phenyltin compounds is more satisfactory in that extrac-
tion techniques are available for the separation of small amounts of tri-, di- and
monophenyltins from each other and from inorganic tin, and although there have
been no publications dealing explicitly with waste waters, the methods developed by
Freitag and Bock [201] for the separation and determination of 2 - 50pg of each of
these compounds present tagether in solution by using a sample size of 25ml would
no doubt be applicable. Their procedure is as follows: to the 25rnl sample add an
equal volume of citrate/phosphate/EDTA buffer solution (pH 8.5) and extract twice
with lüml of methylene chloride; triphenyltin is then determined in the combined
extracts photometrically with dithizone. Diphenyltin is then extracted from the
aqueous solution by shaking with a complexing agentsuch as dithizone, PAR, o:-ben-
zoinoxine or acetylacetone and also determined photometrically. Monophenyltin
compounds can then be extracted with tropolone or diethyldithiocarbamate and are
then best determined by wet-oxidation followed by photometric measurement with
e.g. dithiol.
A procedure has recently been described for the determination of trace amounts
of TBTO and triphenyltin in surface waters [202). lt differs from other methods in
that TBTO is separated from di- and mono- butyltin and from triphenyltin by steam
distillation rather than by extraction with a solvent. A llitre water sample is steam-
distilled after the addition of 30ml of 1M hydrochloric acid and 200rnl of distillate
collected; this is acidified with 5 rnl of the acid and the TBTO extracted in to 5 rnl of
cyclohexane. Then after isolation by TLC from a 500,ul aliquot and detection with
quercetin after UV ir:radiation, the 'spot' is extracted with 25 ml of 12% hydrochlo-
ric acid and the compound converted completely to inorganic tin by UV irradiation
for 60min. Finalanalysis is by inverse voltammetry (see Section 4.3.3), allowing
determination of amounts ofTBIO down to 0.01 ppm. Degradation products can be
determined by solvent extraction, followed by t.l.c. separation as above. Triphenyl-
tin in a llitre sample is determined by concentration by evaporation to a volume of
200ml after the addition of 0.25 g EDT A and extraction with cyclohexane after the
addition of 5 ml M hydrochloric acid. Separation from butyltin and other phenyltins
is performed by TLC and the determination completed as above.

In the case of sea water containing TBTO compounds, concentration of the sam-
ple by direct evaporation is precluded owing to the volatility of tributyltin chloride.
Ch1orides must first be removed e.g. by ion-exchange, but extraction procedures
are to be preferred. Most of the published work on organotin compounds in sea water
arises from studies of leaching rates from anti-fouling paints, a number of which rely
on these compounds as toxic agents. Theseare dealt with in Section 8.3.

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244 Organetin Compounds

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246 Organatin Compounds

121. Braun, D., Heimes, H.-Th.: Z. Anal. Chem., 239, 6 (1968)

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 Referenees 24 7

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CHAPTER 20

TIN AND TIN ALLOY PLATING SOLUTIONS

By J.W. Price

1. Introduction
Large amounts oftin- ofthe order of 80,000 tonnes per annum- are electro-
deposited on to steel sheet by a continuous process in the production of tinplate (see
Chapter 18). The electroplating solutions used, generally of the acid type, have been
specially developed for high-speed strip plating and arenot suitable for 'still"baths;
their analytical control is also somewhat specialised and will not be considered here.
Tin and tin alloy plating is used on a great variety of fabricated articles, often in
relatively small units, and here control methods must be rapid and capable of being
carried out, if necessary, on the shop floor and so methods of analysis are usually
volumetric. In the case of tin plating solutions, bath composition is not particularly
critical and an accuracy of ± 10% is generally all that is required; with tin alloy
processes, particularly where deposit composition is important, e.g. with tin-copper
or tin-zinc alloys, higher accuracy may be required. Where the equipment is available
atomic absorption methods are of value for routine solution and deposit analysis
and some details are given in Section 8 of procedures that have been found suitable.
Other instrumental methods of analysis of plating solutions have been put forward
and of these the direct polarographic determination of tin in stannate solution [ 1] and
of meta! concentration in alkaline cyanide baths, used for producing alloy deposits
of tin with zinc, cadmium amd· copper [2] are of interest.
Detailed accounts are not given in this chapter of electrolyte compositions or
operating conditions, as these are available in the relevant literature. Brief descriptions
are, however, given of methods of routine control, some of them empirical, which
can be carried out rapidly with a minimum of apparatus and which, over a lang period,
have been found to give reproducible results. In using other methods, care should be
taken to make sure that no interference is caused by impurities that accumulate in
the plating solutions over lang periods of use. This applies particularly to the alka-
Hne cyanide alloy baths.
In determining coating thickness and composition a !arge choice of methods, both
destructive and non-destructive, is available and the method selected will depend on
a number of factors. A detailed discussion of the methods and equipment available for
the testing of metallic coatings in general has been given by Plag [3] and referee meth-
ods for the evaluation of tin and some tin-alloy coatings have been published [4]. It
should be noted that in applying the method of measuring metallographic specimens
using a microscope to coatings of tin or tin-lead alloy, the sample must be pre-plated
with a harder coating of e.g. copper or nicke! because of the ease with which these
soft coatings can be smeared.
 Ref.p. 252] 3. Tin-Lead Plating Salutions 249

2. Tin Plating Solutions

a) Alkaline stannate solutions. These baths are based on either sodium or potassi-
um salts and for routine purposes it is only necessary to analyse the solutions for
their tin and free alkali content, although periodic checks are required for the pres-
ence of stannite and alkali carbonate.
Tin is determined iodometrically after acidification with hydrochloric acid of a
suitable sample and reduction of the tin(IV) to tin(II) with nicke! as described in
Chapter 4. The free alkali is determined by precipitating the tin and alkali carbonate
as their barium salts by the addition of barium chloride solution and titration with
0.25M hydrochloric acid using thymolphthalein as indicator, the titration being car-
ried out in the presence of the precipitated barium salts.
b) Acid Tin Solutions. All acid tin plating solutions are based on tin(II) salts and
all require the presence of organic addition agents to produce smooth adherent
deposits. The most generally used electrolytes are based on sulphuric/cresolsulphonic
acid or fluroboric acid and for routine control purposes determination of the tin con-
tent and free acid is all that is required. Determination of the addition agent by che-
mical methods is unsatisfactory and this is best controlled by use of the Hull cell.
In both baths the stannous tin content is determined by adding 25 ml of 20%
hydrochloric acid to a suitable aliquot and titrating with iodate/iodide solution (see
Chapter 4).
Free acid is determined by titration with standard alkali to a permanent turbidity,
in the case of the sulphate bath after the addition of 50ml of arnmonium oxalate
solution (SOg/!); with the fluoraborate bath the titration is carried out on the undil-
uted sample.

3. Tin-Lead Plating Solutions

Tin-lead electrolytes are based on fluoroboric acid solutions containing tin(Il) and
lead fluoroborates, free fluoroboric acid, free boric acid and organic addition agents.
As with the acid tin baths, only the meta! content and free acid are determined for
rou tine con trol.
Stannous tin is determined in the same way as for the acid tin baths. Lead is
determined volumetrically with EDTA after oxidation of the tin(II) and organic matter
as follows:
To 5 ml of the plating bath add 10 ml hydrochloric acid and 5 ml nitric acid and evaparate the
solution to ab out 5 ml. To the cooled solution add 20m! of 20% tartaric acid solution 80 ml of
water and 2 drops of Methyl Red indicator. Neutralise with 50% ammonia and add 40,ml excess.
Add 5 ml of 20% potassium cyanide solution, 1 ml magnesium-EDTA salt (3%) and sufficient Erio-
chrome Black T (1 g in 100 g sodium ch!oride) to give a purple colour. Titrate the solution to a
blue end-point with 0.05M EDTA solution.
Im! 0.05 M EDTA =2.07g/l Pb
Free acid is determined with standard alkali as in the stannous fluoroberate bath.
250 Tin and Tin Alloy Plating Solutions [Ref.p. 252

4. Tin-Copper Plating Solutions

Commercial baths are usually based on sodium or potassium stannate-cyanide
solutions, although cyanide-pyrophosphate baths have been suggested. For routine
purposes it is essential in order to obtain the required alloy composition that the
meta! content and both the free alkali and cyanide are controlled. Tin content is
determined iodometrically after wet-oxidation of the cyanide with sulphuric/nitric
acids and separation from copper by coprecipitation of the hydroxide with iron;
details are similar to those for the determination of tin in bronze (see Chapter 16).
Copper is determined by thiosu1phate titration after wet-oxidation with acid fol-
lowed by volatilisation of the tin as the bromide.

5. Tin-Nickel-Plating Solutions
These solutions contain stannous and nicke! chlorides, tagether with sufficient
ammonium bifluoride to complex all the tin present. Routine control requires the
determination of meta! content (stannous as weil as total tin) and also fluoride.
Stannous tin is determined by direct titration as in the acid tin baths, total tin
by titration after nicke! coil reduction (Chapter 4) and nicke! by an EDTA titration
in ammoniacal solution after oxidation of the tin with peroxide. Fluoride is also
determined by an EDTA titration, Iead chlorofluoride being precipitated at pH 5 - 6
in the presence of 0.01 M potassium chloride by the addition of a known excess of
standard Iead nitrate solution. Afterfiltration the excess Iead is determined with EDTA
as described in Section 3.

6. Tin-Zinc Plating Solutions

Commercial baths are of the alkaline cyanide type, the deposit composition being
controlled by meta! content and the amounts of cyanide and free alkali present.
Tin is determined iodometrically after decomposition of cyanide with nitric/
sulphuric acids and a nicke! coil reduction (Chapter 4).
Zinc cannot be determined by a direct EDTA titration owing to interference by
impurities, but titration in alkaline solution with ferrocyanide is possible without the
need for Separations. In this method a ferric salt and citric acid are added to the So-
lution after wet-oxidation as above and the solution made just alkaline with ammonia.
The end-point of the ferrocyanide titration is detected by the first appearance of a
blue colour in a drop of acetic acid used as external indicator.

7. Other Tin Alloy Plating Solutions

Although tin has been co-deposited with a number of other metals e.g. antimony,
bismuth, gold, indium, iron and silver, the only other alloy in commercial use is tin-
cadmium, which is of some value for corrosion protection, the 50/50 alloy being the
most important. It is deposited from a stannate-cyanide bath in the same way as tin-
zinc and methods of control are similar to those given in Section 6.
 Ref.p. 252] 9.1 Destructive Methods 251

8. Atomic Absorption Methods of Analysis

The meta! content of tin and tin-alloy plating solutions can be readily determined
using this technique. In a1l cases the sample will require dilution to obtain a metal
concentration within the range suitable for analysis, but in order to prevent hydro-
lysis all dilutions must be made with acid or alkalias follows:
a) For alkaline tin, tin-copper and tin-zinc solutions, dilute with 1% sodium hy-
droxide solution.
b) F or acid sulphate and for tin-nicke! solutions, dilute with 5% hydrochloric
acid.
c) For tin and tin-lead fluoraborate solutions, dilute with 10% fluoroboric acid.
Standard metal solutions for these determinations should have approximately the
same composition matrix as the sample to be analysed.
In the detertnination of tin it should be bome in mind that the atomic absorption
method gives the total tin content i.e. tin(II) plus tin(IV). In the case of the acid tin
baths the amount of tin(IV) likely tobe present (1 - 2g/l) will not cause serious error
but with tin-nicke! solutions the tin{IV) content of a bath may build up during use
to as much as I OOg/1 and so for control of this bath the tin(II) content must be de-
termined by iodometric titration.
Atomic absorption offers an easy way of determining metallic impurities in plating
solutions, particularly in the case of the tin-nickel bath in which Iead cannot be tol-
erated above about 20p.g/ml. The undiluted sample can be aspirated into the flame and
the lead peak compared with those obtained with standards containing the same
amount of salts as the sample.

9. Coating Thickness
Briefdetailsare given below of some destructive and non-destructive methods
that have been found satisfactory.

9.1 Destructive Methods

9 .1.1 'Strip and weigh' methods measure average rather than local thickness. A know-
ledge of sample surface area is necessary so they are particularly suitable for sheet
samples.
a) Coatings on steel. Coatings of tin, tin-lead and tin-zinc are stripped in cold con-
centrated hydrochloric acid containing 20g/l of antimony trioxide. Tin-nickel coatings
can be stripped anodically in hot alkaline cyanide solution.
b) Coatings on brass and copper. Tin coatings can be stripperl in hot concentrated
hydrochloric acid, the weight loss including any tin-copper alloy layer that may be
present. Tin-lead is dissolved in a cold solution containing a mixture of 50ml of fluo-
roboric acid and 50ml of 6% (20vol.) hydrogen peroxide. Tin-nickel is dissolved in
hot (180- 200°) phosphoric acid:
In all cases deposit thickness, t, is given by the expression
t (J..tm) = loss in weight (g) 2 xF
surface area of sample (cm )
where F = 1370 for tin coatings
1170 for 60/40 tin-lead coatings
1380 for 75/25 tin-zinc coatings
1190 for 65/35 tin-nicke! coatings
252 Tin and Tin Alloy Plating Salutions

9 .1.2 The 'Jet Test' measures time of penetration of a jet of a solution through the
coating to the basis metal, a calibration curve being required relating this time to
coatings of known thickness.
For tin coatings on steel or copper alloys the solution used contains 1OOg/1 of
trichloracetic acid, while for tin-zinc coatings a solution of SOg/1 of the same reagent
is suitable. A method of test for tin-nickel coatings has been suggested [5] in which
the jet solution is 0.03M hydrochloric acid and the specimen is made anodic. With
a current of 1OmA the coating is dissolved at a rate of ab out 1J.l.m/sec.

9.1.3 Coulometric methods. Commercial equipment is available for the determination

of tin coatings on steel by dissolving the coating anodically in 10% sodium hydrox-
ide [6] or in 1M hydrochloric acid [7]. These can also be used for tin-zinc and tin-
lead coatings.

9.2 Non-destructive Methods

Tin being non-magnetic, coatings on steel may be measured by using magnetic or
electromagnetic thickness gauges [3]. B-backscatter gauges or X-ray fluorescence
methods are suitable for tin and tin-lead deposits on both ferrous and non-ferrous
su bstra tes.

References
1. Diaz, R.: Plating, 40,45 (1953)
2. Knotowicz, A.E., Petrocelli, J. V.: Plating, 44, 602 (1957)
3. Plog, H.: Galvanotechnik, 56, 261 (1965)
4. British Standards Institution: B.S. 5411 'Methods of test for metallic and related coatings'
Part 5, 1976
4a International Standards Organization: ISO/DIS 3882: 1976
5. Kudryavtsev, N.T., Tyutina, K.M., Chvankin,l. V.: Zavod. Lab., 26, 301 (1960)
6. Francis, H.T.: J. Electrochem. Soc., 93, 79 (1948)
7. Kunze, C.T., Willey,A.R.: J. Electrochem. Soc., 99,354 (1952)
CHAPTER 21

TIN CHEMICALS

By J.W. Price

1. Introduction

Tin chemieals of industrial importance include the halides, particularly the chlo-
rides, of both tin(II) and tin(IV), the salts used in electroplating-tin(II) sulphate and
fluoraborate and the alkali stannates - and also tin(II) octate which is used as a
catalyst in the production of polyurethanes. As most tin(II) salts are oxidised on
exposure to air, commercial material can be expected to contain small amounts of
tin(IV) and in their analysis a knowledge of both tin(II) and tin(IV) content may be
necessary. While the tin(II) content can readily be found by direct titration with
iodate, there exist no reliable methods for the determination of the accornpanying
small amounts of tin(IV) and the most accurate procedure involves careful determina-
tion of tin(II) and of total tin, the amount of tin(IV) being found by difference.
In the iodometric determination of tin(II) it is sornetimes recommended that
during the titration the solution should be protected frorn air-oxidation by passing
a current of inert gas through the flask. However, this refinernent is seldorn neces-
sary, provided that the cold solution is titrated rapidly without violent shaking. A
rnechanical stirrer rotated slowly provides adequate rnixing.

For routine analysis of tin salts it is convenient to use a standard iodate solution
of such strength that l rnl is equivalent to 0.01 g Sn and for this purpose potassium
iodate rnay be regarded as a primary standard. The solution is prepared as follows:
dissolve 6.02 g of potassiurn iodate (previously dried at 105 - 110°) in 400rnl of
water containing 1g sodium hydroxide. Add 30g of potassiurn iodide and dilute to
1 litre in a volumetric flask.

2. Tin(II) Chloride
This is available commercially as the dihydrate SnC1 2 .2H 2 0 or as the anhydrous salt
SnCl 2 • Both salts undergo hydrolysis and oxidation on exposure to rnoist air.
a) Tin(II): Dissalve a 0.5 g sample in the cold in 20rnl of 5 M hydrochloric acid,
dilute with an equal volurne of water, add 2 - 3rnl of 0.5% starch solution and titrate
immediately with the standard iodate to a permanent blue colour.
b) Total Tin. Transfer a 0.5 g sample to a 500ml conical flask, add 75 rnl of hydro-
chloric acid and 175rnl of water, introduce a nickel coil and boil the solution gently
for 30rnin. Cool in the absence of air (see Chapter 4}, add starch solution and titrate
with the standard iodate.
254 Tin Chemieals [Ref.p. 255

3. Tin(IV) Chloride
This is avaüable as the solid pentahydrate SnC4 .5H 2 0 or as the anhydrous SnC14 ,
which fumes in moist air. Tin is determined by titration after reduction to tin(II)
with a nicke! coil as above.ln dealing with the anhydrous material it should be
weighed in a sealed glass ampoule and the ampoule placed in a glass-stoppered flask:
containing 20ml of SM hydrochloric acid. On breaking the ampoule the solution in
the flask: should be shaken to dissolve all traces of stannic chloride vapour.

4. Tin(II) Sulphate
The anhydrous salt SnS0 4 undergoes hydrolysis and oxidation on exposure to
moist air and for use in electroplating a minimum quantity of acid-soluble tin(II) is
usually specified [ 1]. Procedure: dissolve 0.8g of the sample in 20ml of 2% (v/v)
sulphuric acid without heating. To the cold solution add 5ml ofhydrochloric acid,
20m! of water and 2- 3ml of starch solution and titrate immediately with a minimum
of shaking with the standard iodate solution to a permanent blue colour.

5. Sodium and Potassium Stannates

The technical materials approximate to the trihydrates Na 2 Sn0 3 .3H2 0 and
K2 Sn0 3 .3H 2 0. They both hydrolyse and absorb carbon dioxide in moist air, tending
to become less soluble in water in consequence; they usually contain a few per cent
of free alkali in order to mitigate this effect. For electroplating purposes a minimum
amount of soluble tin is usually specified [ 1]. Procerlure: dissolve a 25 g sample in
250m! of a 1% solution of the corresponding alkali hydroxide by heating at 80° for
30 min. Filter, washing the fllter with the 1% alkali hydroxide solution followed by
water, and dilute the combined flltrate and washings to 500ml. Transfer a 20m!
aliquot to a 500ml conical flask, add 75ml ofhydrochloric acid and 175m! of wa-
ter, reduce with a nicke! coil and titrate with iodate as above (Section 2b ).

6. Tin(II) Fluoroborate
The material used for electroplating is in the form of a concentrated aqueous so-
lution containing ab out 300g/l of tin(II) [2]. This is determined by direct titration
with iodate after addition of hydrochloric acid as described above (Section 2a).

7. Tin(II) Octoate
Small amounts of tin(IV) in this material are considered deleterious and accord-
ingly the commercial salt usually contains a stabiliser; this does not interfere in the
detmmination of tin.
a) Tin{ll). Dissalve a 1g sample in 15 ml of chloroform, add 25 ml of 2M hydrochlo-
ric acid and 2- 3ml of starch solution, and titrate with the standard iodate solution,
 7. Tin (II) Octoate 255

stirring mechanically throughout the titration. The reaction is rather slow near the
end-point and titration should be continued until the blue colour persists for 2min.
b) Total Tin. Dissalve a 1g sample in 75 ml of hydrochloric acid and 175 ml of wa-
ter, reduce with a nicke! coil and titrate with iodate as described above (Section 2b ).

References
1. TinAnodesand TinSalts for Electroplating: B.S. 1468; 1967
2. Fluoroboric Acid and Meta! Fluoroborates for Electroplating: B.S. 2657; 1974
SUBJECT INDEX
Acetylacetone and related compounds, solvent
extraction of tin with 7 3
Agricultural applications of organotin compounds
237
- determination in crop residues 237
- determination in soils 240
Aluminium and magnesium alloys, detection
of tin in 6
-, determination oftin in by atomic absorp-
iion spectroscopy 92
-,- by emission spectroscopy 107
-, - by solvent extraction 89
-, - by X-ray fluorescence 142
Amberlite LA-1, determination of tin in copper
base alloys with 71
-, separation of tin from Iead with 71
-, solvent extraction of tin with 71
Ammonium benzoate as gravimetric reagent for
tin 10
Ammonium pyrrolidinedithiocarbamate, solvent
extraction of tin with 7 6, 88
Amperometry, 63
-, determination or organotin compounds
by 217, 224
-, determination of tin in Zircaloy by 64
Anodic Stripping Voltammetry, 64
- - -, determination of tin in copper
alloys by 64
- - -, determination of tin in gallium
arsenide by 64
- - -, determination of tin in organotin
compounds by 224, 238
Antimony determination in ingot tin 194, 196
- - in solders 186
- - in white meta! 186
- - of tin in by emission spectroscopy 108
- separation from tin by ion-exchange 147
- - from tin by solvent extraction 67, 70
Aqueous solutions, detection of tin in 4
- -, spot tests for tin in 5
Are discharges, behaviour of tin -ili- 104
Arsenic determination in ingot tin 194
- determination in solders 187
- determination in white meta! 187
- determination of tin in by emission
spectroscopy 108
- separation from tin by solvent
extraction 70
Arsonic acid derivatives as gravimetric
reagents 10
- as photometric reagents 55
Atomic absorption spectroscopy, 80, 225
- - -, analysis of tin and tin-alloy
electroplating solutions 251
- - -, applications 92
- - -, parameters for tin in different
flames 80, 86
- - -, separation procedures 87
- - -, wavelengths of tin 82
Atomic flame emission 83
Atornie fluorescence 86
Atomic line interferences 98
Benzene and toluene, iodide extraction of tin 69
N-Benzoylphenylhydroxylamine as gravimetric
reagent 10
- solvent extraction of tin with 7 5
Bismuth, determination of tin in by emission
spectroscopy 109
Bromide, solvent extraction of tin as 67
-, volatilisation of tin as 187
Cacothelene, detection of tin with 5
-, photometric reagent for tin 43
Cadmium, determination of tin in by emission
spectroscopy 109
Carbon tube or fllament atomisers 87
Cassiterite, 1
-, decomposition of 156
-, mining of 1
Cast iron, determination of tin in by atomic
absorption 208
- -, determination of tin in by photometric
method 206
- -, determination of tin in by volumetric
method 206
Catechol Violet, 51
- -, determination of tin with in copper base
alloys 52
- -, determination of tin with in
effluents 52
- -, determination oftin with in foods 52
- -, deterrnination of tin with in iron and
steel 52, 207
- -, determination of tin with in seawater 53
- -, photometric reagent for tin 51
258
Chemiluminescence atomic emission 85
Chloride, solvent extraction of tin as 67
Chromatography, inorganic tin compounds 3
-, organotin compounds, gas-liquid 227
-, - -, paper 228
-, - -, thin layer 230
Coating thickness, tin and tin alloy coatings 251
- -, tinplate 210
Complexometric titration of tin, 35
----,back 37
- - - -, direct 35
- - - -, displacement 39
- - - -, indirect 38
Concentrates, see Tinares
Copper, determination of in ingot tin 195, 196
-, determination of in solders 187
-, determination of in white meta! 187
Copper base alloys, 2, 199
- - -, composition 200
- - -, determination of tin in by anodic
stripping voltarnmetry 64
- - -, determination of tin in by atomic
absorption 203
- - -, determination of tin in by coprecip-
itation with lanthanum hydroxide 90
- - -, determination of tin in by coprecip-
itation with manganese dioxide 203
- - -, determination of tin in by coulometric
analysis 61
- - -, determination of tin in by emission
spectroscopy 109
- - -, determination of tin in by nitric acid
attack 8
- - -, determination of tin in by photometric
methods 203
- - -, determination of tin in by polaro-
graphy 63
- - -, determination of tin in by solvent
extraction 69
- - -, determination of tin in by volumetric
methods 202
- - -, determination of tin in by X-ray
fluorescence 141, 203
- - -, sarnpling and sarnple treatment 199
Coulometric analysis, 61
- -, determination of tin in copper alloys 61
- -, determination of tin in glasses 62
- -, determination of tin in tinplate 213
Crop residues, determination of organotin
compounds in 237
Cupferron as arnperometric reagent 64
- as gravimetric reagent 10
- solvent extraction of tin(IV) complex
with 45, 74
Detection of tin 3
- - - in aqueous solutions 4
- - - in metals and alloys 5
- - - in ores and minerals 3
- - - in organic matter 7
- - - in slags and residues 4
- - - in surface coatings 6
Subject Index
Dibutyldithioph osphate acid, solvent extraction
of tin with 72
Diethylarnmonium diethyldithiocarbarnate,
photometric reagent for tin 4 3
- -,solvent extraction of tin(II) complex
with 43, 45, 76
Diethyldithioph osphoric acid, solvent extraction
of tin with 72
Diethylether, bromide extraction of tin with 67
-, chloride extraction of tin with 67
-, fluoride extraction of tin with 66
-, iodide extraction of tin with 69
-, thiocyanate extraction of tin with 70
Di-isopropyl ketone, fluoride extraction of tin
with 66
Di-n-butylphosphoric acid, solvent extraction of
tin with 71
Di-n-butylthiop hosphoric acid, solvent extraction
of tin with 72
Diphenylcarbaz one, determination of organotin
compounds with 221
Distillation separation of small arnounts of tin
by 44,233
Dithiocarbamates, solvent extraction of tin
with 76
Dithiol, see Toluene 3, 4 Dithiol
Dithizone, solvent extraction of organotin
compounds with 76, 219, 238
-, solvent extraction of tin with 45, 75
Drosses and ashes, analysis of 17 3
- - -, sarnpling and pretreatment of 173
Effluents, determination of organotin
compounds in 242
-, determination of tin in 122
Electrochemical methods 61
- -, organotin compounds 222
Electrodepositi on, determination of tin by 61
Electrolysis, controlled potential 61
-, analysis of copper base alloys by 62
-, mercury pool cathode 62
Electroplating solutions 248
E!ectrothermal atomisation 87
Emission spectroscopy, 96
- -, applications 107
- -, determination of tin by in
environmetal materials 122
- - , determination of tin by in
inorganic materials 119
- -, determination of tin by in metals 107
- -, determination of tin by in ores and
minerals 117, 166
- -, determination of tin by in organic
materials 121
- -, determination of tin by in organotin
compounds 226
- -, interferences 97
Environmental analysis, determination of
organotin compounds in air and water 242
- -, determination of tin by emission
spectroscopy 122
Subject Index
F erric chloride as Redox titrant for tin 32
Ferrous alloys 205
Flame ernission spectroscopy 83, 96
Flavonal, determination of triphenyltin
cornpounds with 56, 225, 239
-, fluorirnetric reagent 56
Fluoride, solvent extraction of tin as 66
F!uorirnetric rnethods 56, 225, 239
F oods, determination of tin in by atornic
absorption 89, 94
-, determination of tin in by photornetric
rnethods 48, 51, 53, 54,55
-, determination of tin in by
polarography 63
-, determination of tin in by solvent
extraction 8 9
Flue dusts and furne, sampling analysis of 176
Gallein, 53
-, determination of tin with in food
products 53
-, deterrnination of tin with in metals and
alloys 53
-, determination of tin with in rnine
sarnples 53
-, determination of tin with in ores 53, 164
-, photornetric reagent 53
Galliumarsenide, determination of tin in 119,
142
Gravimetrie methods 8
Haematoxylin and haernatin, 54
- - -, deterrnination of tin with in Iead
alloys 55
- - -, deterrnination of tin with in
organotin compounds 55
- - -, deterrnination of tin with in
steels 55
- - -, photornetric reagent 54
Hardhead and irony interrnediates, sampling and
analysis of 17 8
Heteropoly rnolybdic acids as photornetric
reagents 43
Hydrous tin(IV) oxide, 8, 46
- - -, coprecipitation of with lanthanurn
hydroxide 90
- - -, coprecipitation of with rnanganese
dioxide 45, 90
- - -, precipitation with alkali 8
Hydroxamic acids, solvent extraction of tin
with 75
4-Hydroxy-3-nitrophenylarsonic acid, 55
- -, detection of tin with 5, 10
- -, deterrnination of tin with in alurniniurn
alloys 55
- -, deterrnination of tin with in copper
alloys 55
- -, determination of tin with in foods 55
- -, deterrnination of tin with in iron and
steel 55
- -, deterrnination of tin with in zinc base
alloys 55
- -, photornetric reagent 55
259
8-Hydroxyquinoline, determination of tin with
in steels 43
-, fluorirnetric reagent 56
-, gravirnetric reagent 11
-, photometric reagent 43
-, solvent extraction of tin with 43, 74
Irnpurities in tin ores and concentrates 166
-, deterrnination of As, Ca, F, Fe, Si, Ag, S,
W etc. 166
Ingottin 1, 192
- -, deterrnination of irnpurities in by
ernission spectroscopy 196
- -, deterrnination of irnpurities in by
neutron activation 147, 195
- -, determination of irnpurities in by
photornetric rnethods 194
- -, determination of irnpurities in by
X-ray fluorescence 14 3
- -, determination of tin in by volurnetric
rnethod 193
- -, production 1
- -, sampling 192
- -, specifications 192
Inorganic rnaterials, determination of tin in by
emission spectroscopy 119
Interferences in the atornic absorption method
82
Iodide, solvent extraction of tin as 44, 45, 69
Iodine rnonochloride titrations of tin 34
Iodometrie titration of tin
- - -, by aluminium reduction method 15
- - -, by hypophosphite reduction method
19
- - -, by Iead reduction method 17
---,nicke! reduction method 13, 16
- - - end-point detection 23
- - - interferences 26
- - - standardisation 24
Ion-exchange, organotin cornpounds 23 2
-, separation of srnall arnounts of tin by 46
-, separation of tin by in Iead 46
-,Separation of tin by in seawater 122
Iron and steel, 205
- - -, detection of tin in 6
- - -, determination of tin in by atomic
absorption 89, 92, 208
- - -, determination of tin in by ernission
spectroscopy 111
- - -, determination of tin in by neutron
activation 145
- - -, deterrnination of tin in by photometric
rnethods 206
- - -, determination of tin in by solvent
extraction 8 9
- - -, determination of tin in by volurnetric
rnethods 206
- - -, deter1nination of tin in by X-ray
fluorescence 14 2
Lanthan um hydroxide, coprecipitation of tin
with 90
Lead deterrnination of in ingot tin 195, 196
 260
Lead determination of in solders 185
- determination of in white meta! 185
- determination of tin in by emission
spectroscopy 113
Lead base alloys, 8 8
- - -, detection of tin in 6
- - -, determination of tin in 43, 184
Manganese dioxide, coprecipitation of tin
with 90
Mercuric chloride as gravimetric reagent for
tin 9
Metals and alloys detection of tin in 5
- - - determination of tin in by atomic
absorption 89, 90, 94
- - - determination of tin in by photo-
metric methods 43, 49, 51, 53, 54,55
- - - determination of tin in by solvent
extraction 74, 75, 76
Metastannic acid, determination of tin by
precipitation as 8, 45
Methyl isobutyl ketone in bromide extraction
of tin 67
- - - in chloride extraction of tin 67
- - - in fluoride extraction of tin 66
Molecular emission 83
Morin fluorimetric reagent 54, 165
- photometric reagent 54
Mossbauer spectrometry, analysis of ores and
minerals by 147, 166
Mud, slimes and de-tinning residues, sampling
and analysis of 17 8
Naphthol sulphonic acids as fluorimetric
reagents 56
Nickel - determination of tin in by emission
spectroscopy 114
Ores, see Tin Ores
Oil fJ.im weight on tinplate - determination
of 212
Organic matter detection of tin in 7
- - determination of tin in by emission
spectroscopy 121
- - determination of tin in by photometric
methods 48, 51, 52, 53, 54, 55
- - determination of tin in by radiochemical
methods 146
Organic reagents, precipitation of tin with 10
Organetin carboxylates, determination of 217
Organetin compounds 2, 214
- -, applications 214, 235
- -, -, agricultural residues 237
- -, -, anti-fouli!tg paints 241
- -, -, environmental 242
- -, -, stabilisers 235
- -, -, wood 241
- ~. determination of by atomic
absorption 225
- -, determination of by electrochemical
methods 222
- -, determination of by fluorimetric
methods 225, 239
Subject Index
- -, determination of by photometric
methods 219
- -, determination ofby physical 226
- -, determination of by volumetric
methods 218
- -, determination of functional groups
in 217
- -, determination of tin in by dry-ashing 215
- -, determination of tin in by solvent
extraction 23 2
- -, determination of tin in by wet
oxidation 215
- -, determination of tin in by X-ray
fluorescence 142, 226
- -, eiemental analysis 215
- -, radiometry of 233
- -, separations of by chromatography 226
- -,Separations of by distillation 233
--,Separations ofby ion-exchange 232
- -, Separations of by solvent extraction 23 2
- -, spectroscopy of 234
Organetin hydrides, determination of 218
Organetin hydroxides and oxides, determination
of 218
Oxide fJ.im on tinplate, determination of 212
Paints, anti-fouling, determination of organotin
compounds in 241
PAN- solvent extraction of tin with 78
PAR-reagent for organotin compounds 222
Phenylfluorone 49
- determination of tin with in copper base
alloys 49
- determination of tin with in iron and
steel 51, 207
- determination of tin with in organic
materials 49, 51
- determination of tin with in rocks 51, 164
- determination of tin with in slags 51
- photometric reagent 49
- - - applications 51
Phenylfluorone derivatives 50
- - determination of tin with in copper
base alloys 50
- - determination of tin with in hydrogen
peroxide 50
- - determination of tin with in organotin
compounds 50
- - determination of tin with in steels
50,207
- - determination of tin with in zinc base
alloys 50
- - photometric reagents 50
Phosphorus-containing extractants 71
Photometrie methods 43
- - for organotin compounds 219
- - reagents 46
Polarography, 62
-, D.C. for the determination of tin in
copper base alloys 6 3
-, - for the determination of tin in
foods 63
-, - for the determination of tin in
ores 63, 165
Subject Index
-, A.C. for the detennination of tin in
geochemical materials 6 3
-, of organotin compounds 222, 238
Potassium bromate and related compounds as
Redox titrants 31
Potassium ferricyanide as Redox titrant 32
PVC stabilisers, organotin detennination of 235
- -, - migration of from PVC 236
Quercetin 54
- detennination of tin with in bismuth 54
- determination of tin with in copper alloys
54
- detennination of tin with in foods 54
- determination of tin with in indium 54
- determination of tin with in Iead 54
- detennination of tin with in organotin
compounds 221,231
- determination of tin with in steels 54
- photometric reagent 54
Radiochemical methods 145
- -, neutron activation analysis of
agricultural residues 146
- -, neutron activation analysis of
biological materials 146, 226
- -, neutron activation analysis of
geological materials 146, 147, 166
- -, neutron activation analysis of
iron and steel 145
- -, neutron activation analysis of
nicke! alloys 146
- -, neutron activation analysis of
organotin compounds 226, 233
- -, neutron activation analysis of
tinmetal 147
Rhodamine B as fluorimetric reagent for tin 56
Sampling procedures for copper base alloys 199
- - - drosses and ashes 173
- - - flue dusts and fume 176
- - - hardhead and irony intermediates 178
- - - ingot tin 192
- - - mud, slimes and detinning residues 178
- - - ores and concentrates 150
- - - slags 175
- - - solders and white metals 180
- - - turnings and borings 176
Seawater, determination of tin in 46, 53, 122,
146,241,243
Secondary materials and intermediates 173
Selenous acid as gravirnetric reagent for tin 9, 10
Separation procedures in atomic absorption 87
Slags and residues 4
- - -, detection of tin in 4
- - - , determination oftin in 175
- - -, sampling of 175
Sodium and potassium stannates, analysis of 254
Sodium pyrrolidine dithiocarbamate as photo-
metric reagent for tin 43 . solvents 45, 52, 69, 89
Soils, determination of organotin compounds
in 240
261
Solders 2, 18 0
- analysis by density methods 188
- composition 180
- detection of tin in 6
- detennination of antirnony in 186
- detennination of arsenic in 187
- detennination of copper in 187
- detennination of Iead in 185
- detennination of tin in 184
- determination of tin in, by density
methods 188
- preparation of standards, calibration
and matrix correction for X-ray fluorescence
analysis 13 7
- sample preparation 136, 180
- segregation and ageing of 134, 182
Solvent extraction 45, 66, 87
- -, ion association systems 66
- -, procedures for foods 89
- -, procedures for organotin compounds
232
Spectral characteristics of tin in emission
spectroscopy 96
- - of tin in X-ray fluorescence 126
Spectroscopy of organotin compounds 234
Spot tests, detection of tin by means of 5
Steam distillation, separation of organotin
compounds by 233
- -, separation of small amounts of tin by 44
Surface ·coatings,
- -, detection of tin in 6
- -,detenninationoftinin 210,251
Tannin as amperometric reagent for tin 64
- as gravirnetric reagent for tin 11
Thermally excited atomic emission 84
Thiocyanate, solvent extraction of tin as 70
Tin and tin-a11oy electroplating solutions 248
Tin base alloys, 180
- - -, detection of tin in 6
- - -, detennination of antirnony in 186
- - -, determination of copper in 187
- - -, determination of Iead in 185
- - -, determination of tin in 184
- - -, determination of other elements 187
- - -, sampling of 180
- - -, specifications for 180
Tin chemicals, analysis of 253
- -, sodium and potassium stannates 254
- -, tin(Il) chloride 25 3
- -, tin(Il) fluoraborate 254
- -, tin(Il) octoate 254
- -, tin(Il) sulphate 254
- -, tin(IV) chloride 254
- -, tin(lv) halide complexes - photometric
determination of tin as 44
- -, tin hydride - volatilisation of tin as 91
- -, tin(IV) iodide •
- -, tin(IV) extraction of into organic
- -, tin(IV) separation by sublimation 90,
160
262
Tin detection 3
Tinminerals 3, 149
Tin ores and concentrates 3, 149
- - - -, decomposition procedures, acid
attack 161
- - - -, decomposition procedures,
fusion 156
- - - -, decomposition procedures,
reduction 159
- - - -, decomposition procedures,
sublimation 90, 160
- - - -, determination of impurities in 166
- - - -, determination of maisture in 154
- - - -, determination of tin in by
atgmic absorption 166
- - - -, determination of tin in by D.C.
arc spectrography 166
- - - -, determination of tin in by
emission spectroscopy 117
- - - -, determination of tin in by
Mossbauer spectrometry 14 7
- - - -, determination of tin in by neutron
activation 166
- - - -, determination of tin in by
photometric methods 164
- - - -, determination of tin in by
polarography 165
- - - -, determination of tin in by
vanning assay 166
- - - -, determination of tin in by
volumetric methods 161
- - - -, determination of tin in by
X-ray fluorescence 128, 166
- - - -, pre-treatrnent of 156
Tinplate 2, 209
-, determination of oil film weight 212
-, determination of oxidefilm 212
-, determination of tin by anodic dissolution
method 210
-, determination of tin by Bendix method
210
-, determination of tin by coulometric
method 210
-, determination of tin by 'strip and weigh'
method 211
-, determination of tin by volumetric
method 211
-, determination of tin by X-ray method
210
-, performance tests 213
-, production 2, 209, 248
Tin, small amounts of separation by
coprecipitation 45
-, small amounts of separation by
distillation 44
:-, small amounts of Separation by
!On-exchange 46
-, small amounts of separation by
solvent extraction 45, 87
-, small amounts of Separation by
Sublimation 53, 90
Tin sulphide, separations of 4, 9
Toluene 3,4 Dithioi" 48
Subject Index
- - -, determination of tin with in canned
foods 48
- - -, determination of tin with in silicate
rock 48, 165
- - -, photometric reagent 48, 238
- - -,solvent extraction of tin with 49, 77
- - -, spottest for tin with 5
3,4, 7-trihydroxyflavone as fluorimetric reagent
56
Tri-n-octylphosphine oxide, determination of tin
with in aluminium, iron and nicke! base
alloys 89
--,solvent extraction of tin with 73
Triphenyltin compounds, determination of in
crop residues 237
- -, fluorimetric determination of 225, 239
- -, radiometry of 233
Tris (2-ethylhexyl)phosphine oxide - solvent
extraction of tin(IV) complex 45, 73
Turnings and borings, sampling and analysis
of 176
Volumetrie methods 12
Volumetrie titrants, 12
- -, complexometric titrations 35
- -, ferric chloride 32
- -, iodide/iodate 12, 21
- -, iodine monochloride 34
- -, potassium bromate and related
compounds 31
- -, potassium ferricyanide 32
- -, other titrants 33
White metals, determination of antimony in 186
- -, determination of arsenic in 187
- -, determination of copper in 187
- -, determination of Iead in 185
- -, determination of tin in 184, 188
Wood, determination of organotin compounds
in 241
Xanthates, solvent extraction of tin with 77
X-ray fluorescence 126
- -, analysis of aluminium and magnesium
alloys 142
- -, analysis of copper base alloys 141
- -, analysis of ingot tin 143
- -, analysis of iron and steel 142
- -, analysis of ores and concentrates 128
- -, organotin compounds 142, 226
- -, analysis of solders and white metals 134
- -, analysis of tinplate 21 0
- -, instrumentation for 126
- -, other applications 142, 210
Zinc base alloys, determination of tin in by
emission spectroscopy 116
Zircaloy, determination of tin in 51, 92
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