Gmelin Handbook of Inorganic Chemistry

8th Edition
Gmelin Handbook
of Inorganic Chemistry
8th Edition

Gmelin Handbuch der Anorganischen Chemie

Achte, voLLig neu bearbeitete AufLage

Prepared Gmelin-Institut fur Anorganische Chemie

and issued by der Max-PLanck-GeseLLschaft
zur Forderung der Wissenschaften
Di rector: Ekkehard FLuck

Founded by Leopold Gmelin

8th Edition 8th Edition begun under the auspices of the
Deutsche Chemische Gesellschaft by R. J. Meyer
Continued by E.H.E. Pietsch and A. Kotowski, and by
Margot Becke-Goehring

Springer-Verlag Berlin Heidelberg GmbH 1986

Gmelin-Institut fUr Anorganische Chemie
der Max-Planck-Gesellschaft zur Forderung der Wissenschaften

ADVISORY BOARD

Dr. G. Breil, Chairman (Ruhrchemie AG, Oberhausen-Holten), Prof. Dr. K. Dehnicke

(Philipps-Universitat Marburg), Prof. Dr. N. N. Greenwood (University of Leeds), Prof. Dr.
H. GrOnewald (Bayer AG, Leverkusen), Prof. Dr. H. Harnisch (Hoechst AG, FrankfurtlMain-
Hochst), Prof. Dr. H. Noth (Universitat MOnchen), Prof. Dr. H. Offermanns (Degussa AG,
Frankfurt/Main), Prof. Dr. G. zu Putlitz (Universitat Heidelberg), Prof. Dr. A. Rabenau (Max-
Planck-Institut fUr Festkorperforschung, Stuttgart), Prof. Dr. A. Simon (Max-Planck-Institut
fUr Festkorperforschung, Stuttgart), Prof. Dr. Dr. A. H. Staab (Prasident der Max-Planck-
Gesellschaft, MOnchen), Prof. Dr. Dr. h.c. mUlt. G. Wilke (Max-Planck-Institut fUr Kohlenfor-
schung, MOlheim/Ruhr)

DIRECTOR DEPUTY DIRECTOR

Prof. Dr. Dr. h.c. Ekkehard Fluck Dr. W. Lippert

CHIEF EDITORS

Dr. K.-C. Buschbeck - Dr. H. Bergmann, J. FOssel, B. Heibel, Dr. H. Katscher, Dr. R.
Keim, Dr. E. Koch, Dipl.-Phys. D. Koschel, Dr. U. KrOerke, Dr. H. K. Kugler, Dr. P. Merlet,
Dr. E. Schleitzer-Rust, Dr. F. Schroder, Dr. A. Slawisch, Dr. B. v. Tschirschnitz-Geibler,
Dr. R. Warncke

CORRESPONDENT MEMBERS OF THE SCIENTIFIC STAFF Dr. J. R. Clark, Dr. J. L. Grant,

Dr. V. Haase, Dipl.-Ing. G. Kirschstein,
Dr. K. Rumpf, Dr. U. Trobisch,
Dr. B. Vance

EMERITUS MEMBER OF THE INSTITUTE Prof. Dr. Dr. E.h. Margot Becke

CORRESPONDENT MEMBERS OF THE INSTITUTE Prof. Dr. Hans Bock

Prof. Dr. Dr. Alois Haas, Sc. D. (Cantab.)
STAFF GMELIN HANDBOOK

D. Barthel, Dr. N. Baumann, Dr. W. Behrendt, Dr. L. Berg, Dipl.-Chem. E. Best, Dipl.-Ing.
V. A. Chavizon, E. Cloos, Dipl.-Phys. G. Czack, I. Deim, Dipl.-Chem. H. Demmer, R. Dowideit,
Dipl.-Chem. M. DroBmar, U. Duggen, M. Engels, Dr. H.-J. Fachmann, Dr. J. Faust, Dr.
W.-D. Fleischmann, V. Frick, G. Funk, Dipl.-Ing. N. Gagel, E. Gerhardt, Dr. U. W. Gerwarth,
M.-L. Gerwien, C. Gorr, Dipl.-Phys. D. Gras, Dipl.-Bibl. W. Grieser, H. Hartwig, Dipl.-Min.
H. Hein, G. Heinrich-Sterzel, H.-P. Hente, H. W. Herold, U. Hettwer, Dr. I. Hinz, Dr. W.
Hoffmann, Dipl.-Chem. K. Holzapfel, Dr. S. Jager, Dr. R. Jotter, Dr. J. von Jouanne, Dipl.-
Chem. W. Karl, H.-G. Karrenberg, Dipl.-Phys. H. Keller-Rudek, A. Klusch, Dipl.-Phys. E.
Koch, Dipl.-Chem. K. Koeber, Dipl.-Chem. H. Kottelwesch, R. Kolb, E. Kranz, Dipl.-Chem.
I. Kreuzbichler, Dr. A. Kubny, Dr. P. Kuhn, Dr. W. Kurtz, M. Langer, Dr. A. Leonard, Dipl.-
Chem. H. List, H. Mathis, E. Meinhard, K. Meyer, Dr. M. Mirbach, Dr. U. Neu-Becker, K.
Noring, Dipl.-Chem. R. Nohl, Dipl.-Min. U. Nohl, Dr. W. Petz, I. Rangnow, Dipl.-Phys. H.-J.
Richter-Ditten, Dipl.-Chem. H. Rieger, B. Riegert, E. Rieth, A. Rosenberger, E. Rudolph,
G. Rudolph, Dipl.-Chem. S. Ruprecht, V. Schlicht, Dipl.-Chem. D. Schneider, Dipl.-Min.
P. Schubert, A. Schwarzel, Dipl.-Ing. H.M. Somer, E. Sommer, M. Teichmann, Dr. W. Topper,
Dipl.-Ing. H. Vanecek, Dipl.-Chem. P. Velie, Dipl.-Ing. U. Vetter, H.-M. Wagner, Dipl.-Phys.
J. Wagner, R. Wagner, Dr. E. Warkentin, Dr. C. Weber, Dr. B. Wobke, K. WOlff, U. Ziegler

STAFF GMELIN ONLINE DATA SYSTEM

Dr. L. KieBling - Dr. R. Frobose, Dr. B. Roth

Dipl.-Min. M.-B. Cinarz, Dr. J. Fippinger, Dr. G. Friedrich, Dr. B. Frohlich, I. Gullich,
M. Kloffler, R. Lohmeyer, Dr. M. Pauluth, Dr. H.-J. Schroder, Dr. K. Schucke
Volume published on "Beryllium" (Syst. No. 26)
Main Volume: Element and Compounds - 1930
Gmelin Handbook
of Inorganic Chemistry
8th Edition

Be
Beryllium
Supplement Volume A1

The Element. Production, Atom, Molecules,

Chemical Behavior, Toxicology

With 68 illustrations

AUTHORS Ingeborg Hinz, Karl Koeber, Irmingard Kreuzbichler,

Peter Kuhn
Arnulf Seidel
Institut fOr Genetik und fOr Toxikologie von Spaltstoffen,
Kernforschungszentrum Karlsruhe

EDITORS Ingeborg Hinz, Hans Karl Kugler, Joachim Wagner

CHIEF EDITOR Hans Karl Kugler

System Number 26

Springer-Verlag Berlin Heidelberg GmbH 1986

 LITERATURE CLOSING DATE: 1985

Library of Congress Catalog Gard Number: Agr 25-1383

ISBN 978-3-662-10319-7 ISBN 978-3-662-10317-3 (eBook)

DOI 10.1007/978-3-662-10317-3

This work is subject to copyright. AU rights are reserved, whether the whole or part of the material is concerned, specifically
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fee is payable to "Verwertungsgesellschatt Wort", Munich.

© by Springer-Verlag Berlin Heidelberg 1986

Originally published by Springer-Verlag, Berlin . Heidelberg · New York ·Tokyo in 1986
Softcover reprint ofthe hardcover 8th edition 1986

The use of registered names, trademarks, etc., in this publication does not imply, even in the absence of a specific statement,
that such names are exempt from the relevant protective Laws and regulations and therefore free for general use.
 Preface

The present voLume is the first in a series of suppLement voLumes to the beryLlium
voLume which appeared in 1930. This voLume" BeryLLium" SuppLement VoLume A 1 is divided
into the following chapters:
1. The Production of Beryllium
2. Uses
3. Nuclides
4. Atoms and Ions
5. MoLecuLes
6. ChemicaL Reactions
7. The ChemicaL Behavior of BeH in SoLution
8. ToxicoLogy of Beryllium
Chapter 1 describes the steps from ore dressing to obtaining the metaL and then further
refining and preparing speciaL forms. No differentiation is made between processes per-
formed on an industriaL scaLe and a Laboratory scaLe.
In Chapter 2 are shown various uses, taken from review literature, of Be as a metaL,
in aLLoys, and in compounds.
Chapter 6 presents the reactions of Be metaL with various eLements and compounds.
In the section on the reactions with metaLs is incLuded its behavior in binary metaL systems
(e.g. diffusion).

In Chapter 7 the behavior of Be 2 + in soLution is limited to hydration, hydroLysis, and

a short survey of the anaLytically most important precipitation reactions. The compLex chemi-
caL behavior will be described in detaiL Later in a speciaL voLume.
The crystallographic and physicaL properties, and the eLectrochemicaL behavior will be
treated in a Later voLume of the series" BeryLLium" SuppLement A.

Frankfurt/Main, June 1986 Hans KarL KugLer

x
Table of Contents

Page

Beryllium

1 The Production of Beryllium 3

1.1 Mineral Dressing 3
1.1.1 Picking 3
1.1.2 Electrostatic Separation 4
1.1.3 Separation by Heavy Liquids 4
1.1.4 Enrichment of Beryllium Ores by Fuming and Magnetic Concentration 5
1.1.5 Flotation 5
General . . . . . . . . . . . . . . . . . 5
Flotability of Beryl . . . . . . . . . . . . 5
Flotation of Synthetic Beryl-Mineral Mixtures 8
Flotation of Beryl Bearing Ores ..... . 9
Flotation of Bertrandite, Phenacite, and Other BeryLlium Minerals 14

1.2 Chemical Decomposition of Beryllium Minerals 16

1.2.1 With Clorinating Agents . 16
1.2.2 With Fluorinating Agents ..... . 18
HF and SiF4 . . • . . . . . . . . . . . 18
With Alkali Fluorides, CaF 2 , FeF 3, and ZnF2 19
With Alkali Hexafluorosilicates and/or Na3FeF 6 20
1.2.3 With Alkaline Agents . . . . . 25
1.2.4 With Aqueous CO 2 . . . . . . 28
1.2.5 With Organic (Carboxylic) Acids 29
1.2.6 With Mineral Acids and S03 29
1.2.7 The Sulfate Process ..... 32

1.3 Separation of Beryllium from Solutions 35

1.3.1 Extraction of Beryllium from Aqueous SoLutions 35
With Fatty Acids . . . . . . . . 35
With Long-Chain Aliphatic Amines . 36
With Acetylacetone and Derivatives . 37
With Acidic Esters of Phosphoric Acid 38
With Various Extractants from Thiocyanate Solutions 42
1.3.2 Ionic Flotation . . . . . . . . . . . . . . . 43
1.3.3 Extraction of Beryllium by Cation or Anion Exchange Resins 44
1.3.4 Separation of Beryllium by Sublimation of the Acetylacetonate 45

1.4 Production of the Metal . . . . . . . . . . . . . . . 45

Review . . . . . . . . . . . . . . . . . . . . . . . . 46
1.4.1 Reduction of BeryLlium Oxide with Metals or Nonmetals 48
Reduction with Metals ..... 48
With Calcium 48
With Zirconium and Other Metals 49
Reduction with Nonmetals 51
With Carbon . 51
With Hydrogen . . . . 52
 XI

Page

1.4.2 Reduction of Beryllium Halides with Metals or Hydrogen 53

Review . . . . . . . . . . . . . . . . . . . . . . . . 53
Reduction of Beryllium Fluoride and Double Fluoride with Metals 54
Introduction . . . . . . . . . . . . . . . . 54
Reduction of Beryllium Fluoride with Magnesium 56
Basic Process Design . . . . . . . . . . . 56
Commercial Scale Production Processes 58
Small Scale Investigations on the Reduction Process 63
Reduction of Beryllium Double Fluoride with Magnesium or Calcium 66
Reduction of Beryllium Chloride 66
With Metals . . . . . 66
Basic Process Design 66
Industrial Procedure 68
With Hydrogen . . . . 73
1.4.3 Reduction of Beryllium Sulfide with Metals or Hydrogen 74
1.4.4 Miscellaneous Reductions of Beryllium Compounds 74
1.4.5 Reduction of Beryllium Compounds by Electrolysis 75
Review . . . . . . . 75
Fusion Electrolysis . . . 76
From Beryllium Oxide . 76
Basic Process Design 76
Electrolysis 77
Isolation of Beryllium Metal 77
Other Processes . . . . . 77
From Beryllium Fluoride and Oxide Fluoride 78
From Beryllium Chloride ....... . 79
Basic Process Design . . . . . . . . . 80
The" High Temperature" Electrolysis Process 80
The" Low Temperature" Electrolysis Process 81
The" Standard Process" and Modifications 81
Various Plant Practices . . . . . . . . . 84
Further Variants of the" Standard Process" 85
From Beryllium Sulfide . . . . . . . . . . 88
Electrolysis in Solutions with Various Solvents . 88
1.4.6 Thermal Decomposition of Beryllium Compounds 89
Beryllium Iodide . . . . . . . . . . . . . . . . 89
Beryllium Nitride, Beryllium Carbide, Diethylberyllium 91
1.5 Separation of Metal from Slag and Refining of Metal 91
Review . . . . . . . . . 91
1.5.1 Milling and Leaching 93
1.5.2 Melting and Casting 95
1.5.3 Melting Under a Flux 100
1.5.4 Vacuum Distillation . 100
1.5.5 Refining by Transport Reaction 106
1.5.6 Refining by Zone Melting 107
1.5.7 Refining by Recrystallization from Aluminium Melts 109
1.5.8 Refining of Be by Spinel Forming Oxides 110
1.5.9 Electrolytic Refining with BeCl2 in Eutectic KCl-LiCl Melts 110
1.5.10 Electrolytic Refining in Eutectic BeCl 2 -NaCl Melts . . . 112
XII

Page

1.6 Preparation of Special Forms 113

1.6.1 Powders ....... . 113
1.6.2 BeryLlium with Low Density 114
1.6.3 FiLamentary CrystaLs 114
1.6.4 FiLms and Foils ..... 115
1.6.5 SingLe CrystaLs . . . . . . 117
Growth from Melts and by Evaporation 117
SingLe CrystaLs by VerticaL FLoating Zone MeLting 118
SingLe CrystaLs by HorizontaL Zone MeLting 121
BicrystaL Grown by Zone MeLting . . . . . . . 121

2 Uses . . . . . . . . 123
2.1 Beryllium Metal . . 124
2.1.1 NucLear Technique 124
2.1.2 Aircrafts and Space VehicLes 126
2.1.3 Other Uses ...... . 127
2.2 Alloys and Compounds of Beryllium 127
ALLoys . . . . . . 128
BeryLLia . . . . . 130
Other Compounds 131

3 Nuclides 132

3.1 Atomic Weight. Isotopic Abundance 132

3.2 Properties of Nuclides 132

BeryLLium-5 133
BeryLlium-6 133
BeryLLium-7 133
BeryLLium-8 134
BeryLLium-9 134
BeryLLium-10 134
BeryLLium-11 134
BeryLLium-12 135
BeryLLium-13 135
BeryLlium-14 135

4 Atom and Atomic Ions 137

4.1 The Be- Ion 137

4.2 The Be Atom 139
4.2.1 Ground State. Ionization Energies 139
4.2.2 ELectron Affinity ..... . 140
4.2.3 Atomic Structure CaLcuLations 140
4.2.4 X-Ray Spectra . . 141
4.2.5 Auger Spectra . . . 143
4.2.6 FLuorescence YieLd . 145
4.2.7 PhotoeLectron Spectra 145
4.2.8 Atomic Energy LeveLs. OpticaL Spectra (Be I) 145
 XIII

Page

4.2.9 Interaction Constants . . . . . . . . . . . . . . . 153

4.2.10 Electric Dipole Polarizability . . . . . . . . . . . 154
4.2.11 Photon Cross Sections. Mass Attenuation Coefficients 154
4.2.12 Interaction with Electrons 157
4.2.13 Thermodynamic Functions 157

4.3 The Be + Ion ...... . 158

4.3.1 Ground State. Ionization Energies 158
4.3.2 Atomic Structure Calculations 159
4.3.3 X-Ray Spectra . . 159
4.3.4 Auger Spectra . . . . . . . 160
4.3.5 Fluorescence Yield . . . . . 161
4.3.6 Atomic Energy Levels. Optical Spectra (Be II) 162
Be+ 1 S2 nl (Singly Excited Be+) 162
Be+ 1 s nln'l' (Doubly Excited Be+) 166
4.3.7 Interaction Constants 170
Electron-Electron 170
Electron-Nucleus . . . . . . . 170
4.3.8 Electric Dipole Polarizability 171
4.3.9 Interactions with Photons and Electrons 171
4.3.10 Thermodynamic Functions 172
4.4 The Be2 + Ion . . . . . . . 172
4.4.1 Ionization Energy Ej 172
4.4.2 Atomic Structure Calculations 173
4.4.3 X-Ray Spectra . . . . . . . 173
4.4.4 Auger Spectra . . . . . . . 174
4.4.5 Atomic Energy Levels. Optical Spectra (Be III) 175
Be 2 + 1 s nl (Singly Excited Be 2 +) . . . 175
Be 2 + nln'l', n~2 (Doubly Excited Be 2 +) 177
4.4.6 Interaction Constants . . . . . . 179
4.4.7 Electric Dipole Polarizability . . . 179
4.4.8 Interactions with Photons and Electrons 179
4.4.9 Thermodynamic Functions 179
4.5 The Be 3 + Ion 180

5 Molecules 182
5.1 The Be2 Molecule 182
5.2 Ions Be! and Be2". Molecules Ben, n > 2, and Ions 184

6 Chemical Reactions . . . 185

6.1 Reactions with Nonmetals 185
6.1.1 With Helium . . . . . 185
6.1.2 With Hydrogen . . . . 186
Adsorption and Chemisorption 186
Permeation, Diffusion, Solubility, Implantation 188
General Reactions . . . . . . . . . . . . 190
XIV

Page

6.1.3 With Oxygen and Air 191

Adsorption and Solubility of Oxygen 191
Reactions with Oxygen . . . . . 192
With Dry Oxygen below Atmospheric Pressure 192
With Dry Oxygen at Atmospheric Pressure 196
With Moist Oxygen 197
With Liquid Ozone 198
Reactions with Air 199
Powder . . . . . 199
Thin Layers 199
Compact Beryllium 200
Structural Studies and Oxide Growth in Oxygen and Air 203
Ignition and Combustion ......... . 204
6.1.4 With Nitrogen .............. . 209
6.1.5 With Fluorine, Chlorine, Bromine, and Iodine 211
6.1.6 With Sulfur, Selenium, Tellurium, and Polonium 213
6.1.7 With Boron ........... . 213
6.1.8 With Carbon . . . . . . . . . . . . 214
6.1.9 With Silicon, Phosphorus, and Arsenic 216
6.2 Reactions with Metals 218
6.2.1 With Antimony 218
6.2.2 With Bismuth 219
6.2.3 With Lithium . 219
6.2.4 With Sodium . 221
6.2.5 With Potassium, Rubidium, and Caesium 222
6.2.6 With Alkaline Earth Metals 223
6.2.7 With Zinc, Cadmium, and Mercury 225
6.2.8 With Aluminium 226
6.2.9 With Gallium and Indium 228
6.2.10 With Rare Earth Metals 228
6.2.11 With Titanium, Zirconium, Hafnium, and Thorium 229
6.2.12 With Germanium, Tin, and Lead . . . . . . . . 231
6.2.13 With Vanadium, Niobium, and Tantalum 232
6.2.14 With Chromium, Molybdenum, Tungsten, and Uranium 235
6.2.15 With Manganese ..... 237
6.2.16 With Nickel, Cobalt, and Iron . . . . . . 237
6.2.17 With Copper, Silver, and Gold . . . . . . 241
6.2.18 With Ruthenium, Rhodium, and Palladium 243
6.2.19 With Osmium, Iridium, and Platinum . . . 243
6.2.20 With Technetium, Rhenium, and Transuranium Elements 244

6.3 Reactions with Nonmetal Compounds ..... . 244

6.3.1 With Liquid Water and Aqueous Hydrogen Peroxide 244
At Room Temperature 244
At 30 to 100°C . . . 245
Above 100 °C 246
6.3.2 With Water Vapor 249
At Low Pressures 249
At High Pressures 253
 xv

Page

Ignition and Combustion ............ . 253

6.3.3 With NH3 and Ammonium SaLts . . . . . . . . . 254
6.3.4 With NO, N20 4 , N02F, NOF·3HF, and N20 4 +NOCL 254
6.3.5 With Nonaqueous HF, HCL, HBr, and HI 255
6.3.6 With H2S, H2Se, S2CL2' B20 3, BF3, and BCL 3 256
6.3.7 With CO . . . . . . . . . . . . . . 257
6.3.8 With CO 2 . . . . . . . . . . . . . 259
With Dry CO 2 beLow Atmospheric Pressure 259
With Dry CO 2 at Atmospheric Pressure 263
With Dry CO 2 above Atmospheric Pressures 266
With Moist CO 2 . . . . . . . . . . . 268
With CO Containing Dry and Moist CO 2 273
6.3.9 With Si0 2 and SiC ...... . 274
6.3.10 With Organic Liquids, CooLants, and Explosives 275
6.3.11 With Acids . . . . . . . . . . . . 276
With HN03 . . . . . . . . . . . . . . . 277
With HF, HCL, HCL04 , HBr, H2S0 4 , and H3P0 4 278
6.4 Reactions with Metal Compounds 279
6.4.1 With NaH, NaNH 2, KNH 2, and Pb(N 3)2 279
6.4.2 With MetaL Oxides . . . . . . 280
With Na20 . . . . . . . . . . . . 280
With BeO, MgO, CaO, SrO, and BaO 280
With AL 20 3 . . . . . . . 280
With Rare Earth Oxides . . 281
With Ti0 2, Zr0 2, and Th0 2 . 281
With Pa 20 5 , U0 2, and U30 a 281
With Oxides of the Transuranium ELements 281
6.4.3 With ALkali Hydroxides 282
6.4.4 With ALkaline Aqueous SoLutions 283
6.4.5 With MetaL Halides . . 283
With Solid or Liquid Halides . . . 283
With Gaseous Halides . . . . . . 284
6.4.6 Reactions with SaLt SoLutions 285
With SoLutions of Ammonium FLuoride 285
With SoLutions of NaCL and Seawater 286
6.4.7 With CeS, FeS, PbTe, TiB2' and MetaL Carbides 288
6.4.8 With Hg(CH 3)2 290
6.4.9 With GaP . . . . . . . . . . . . . . . . . 290
6.4.10 With GaAs 291
7 The Chemical Behavior of the Be 2 + Ion in Solution 292
7.1 Hydration . . . . . . . . . . . . . . . . . . 292
7.1.1 Hydration Number H . . . . . . . . . . . . 292
7.1.2 Thermodynamic Data of Hydration and Formation 293
7.1.3 Water Exchange and Substitution 294
7.2 Hydrolysis of the [Be(H 20)4F+ Ion 295
WeakLy Acid Medium 295
Basic Medium 297
Thermodynamic Data 298
XVI

Page

7.3 Precipitation 299

8 Toxicology of Beryllium 300

8.1 Historical Survey 300
8.2 Biological Behavior of Be in Mammals 300
8.3 Beryllium Toxicity In Man . . . . . . 304
8.3.1 Acute Beryllium Disease ..... 304
8.3.2 Chronic Beryllium-Induced Lung Disease: Epidemiological and Clinical Aspects 304
8.3.3 Immunological Aspects . . . . 308
8.3.4 Carcinogenic Effects . . . . . 309
8.3.5 Beryllium and Chelating Agents 312
Table of Conversion Factors . . . . . 316