Beruflich Dokumente
Kultur Dokumente
COMPREHENSIVE
Section 1. THE PRACTICE AND THEORY OF KINETICS
Volume 1 The Practice of Kinetics
Volume 2 The Theory of Kinetics
Volume 3 The Formation and Decay of Excited Species
Section 2. HOMOGENEOUS DECOMPOSITIONAND ISOMERISATIONREACTIONS
INORGANIC REACTIONS
POLYMERISATION REACTIONS (2
Section 6.
volumes)
(2 volumes)
Additional Sections
HETEROGENEOUS REACTIONS
SOLID STATE REACTIONS
KINETICS AND TECHNOLOGICAL PROCESSES
CHEMICAL KINETICS
EDITED BY
C. H. BAMFORD
M.A., Ph.D., Sc.D. (Cantab.), F.R.I.C., F.R.S.
Campbell-Brown Professor of Industrial Chemistry,
Unioersity of Liverpool
AND
C. F. H. TIPPER
Ph.D. (Bristol), D.Sc. (Edinburgh)
Senior Lecturer in Physical Chemistry,
Uniuersity of Lioerpool
VOLUME
ELSEVIER P U B L I S H I N G C O M P A N Y
AMSTERDAM
- L O N D O N - NEW Y O R K
1972
336 I A N V A N G A L E N S T R A A T
P.O. B O X 211. A M S T E R D A M , T H E N E T H E R L A N D S
A M E R I C A N ELSEVIER P U B L I S H I N G C O M P A N Y , I N C .
52 V A N D E R B I L T A V E N U E
N E W Y O R K , N E W Y O R K 10017
L I B R A R Y OF CONGRESS CARD N U M B E R
ISBN 0-444-40861
WITH
COPYRIGHT
@ 1972
76-151731
35 I L L U S T R A T I O N S A N D 228 T A B L E S
BY ELSEVIER PUBLISHING COMPANY, AMSTERDAM
A L L R I G H T S RESERVED
N O P A R T OF T H I S P U B L I C A T I O N M A Y BE R E P R O D U C E D ,
S T O R E D I N A R E T R I E V A L SYSTEM, O R T R A N S M I T T E D I N A N Y F O R M O R BY A N Y M E A N S
ELECTRONIC, MECHANICAL, PHOTOCOPYING, RECORDING, O R OTHERWISE,
W I T H O U T THE PRIOR WRITTEN PERMISSION O F THE PUBLISHER,
E L S E V I E R P U B L I S H I N G C O M P A N Y , J A N V A N G A L E N S T R A A T 335, A M S T E R D A M
C O M P R E H E N S I V E C H E M I C A L KINETICS
ADVISORY BOARD
Professor S. W. BENSON
Professor SIR FREDERICK DAINTON
Professor G. GEE
the late Professor P. GOLDFINGER
Professor G. s. HAMMOND
Professor W. JOST
Professor G. B. KISTIAKOWSKY
Professor v. N. KONDRATIEV
Professor K. J. LAIDLER
Professor M. MAGAT
Professor SIR HARRY MELVILLE
Professor G. NATTA
Professor R. G. W. NORRISH
Professor s. OKAMURA
Professor SIR ERIC RIDEAL
Professor N. N. SEMENOV
Professor z. G. SZABO
Professor 0. WICHTERLE
Contributors to Volume 7
D. BENSON
Department of Chemistry,
Widnes Technical College,
Widnes, Lancs., England
L. J. C S ~ N Y I
T. J. KEMP
M. PARRIS
Department of Chemistry,
Carleton University,
Ottawa, Canada
P. J. PROLL
Department of Chemistry,
Widnes Technical College,
Widnes, Lancs., England
Preface
The rates of chemical processes and their variation with conditions have been
studied for many years, usually for the purpose of determining reaction mechanisms. Thus, the subject of chemical kinetics is a very extensive and important
part of chemistry as a whole, and has acquired an enormous literature. Despite
the number of books and reviews, in many cases it is by no means easy to find
the required information on specific reactions or types of reaction or on more
general topics in the field. It is the purpose of this series to provide a background
reference work, which will enable such information to be obtained either directly,
or from the original papers or reviews quoted.
The aim is to cover, in a reasonably critical way, the practice and theory of
kinetics and the kinetics of inorganic and organic reactions in gaseous and condensed phases and at interfaces (excluding biochemical and electrochemical kinetics, however, unless very relevant) in more or less detail. The series will be divided
into sections covering a relatively wide field; a section will consist of one or more
volumes, each containing a number of articles written by experts in the various
topics. Mechanisms will be thoroughly discussed and relevant non-kinetic data
will be mentioned in this context. The methods of approach to the various topics
will, of necessity, vary somewhat depending on the subject and the author(s) concerned.
It is obviously impossible to classify chemical reactions in a completely logical
manner, and the editors have in general based their classification on types of chemical element, compound or reaction rather than on mechanisms, since views on
the latter are subject to change. Some duplication is inevitable, but it is felt that
this can be a help rather than a hindrance.
Section 3 deals with reactions in which at least one of the reactants is an inorganic compound. Many of the processes considered also involve organic compounds, but autocatalytic oxidations and flames, polymerisation and reactions of
metals themselves and of certain unstable ionic species, e.g. the solvated electron,
are discussed in later sections. Where appropriate, the effects of low and high energy radiation are considered, as are gas and condensed phase systems but not fully
heterogeneous processes or solid reactions. Rate parameters of individual elementary steps, as well as of overall reactions, are given if available.
In volume 7 reactions of metallic salts, complexes and organometallic compounds are covered. Isomerisation and group transfer reactions of inert metal
complexes and certain organometallics (not involving a change in oxidation state)
are considered first, followed by oxidation-reduction processes (a) between different valency states of the same metallic element (b) between salts of different
VIII
PREFACE
C. H. BAMFORD
C. F. H. TIPPER
Contents
Preface
................................
VI i
Chapter I (C H . LANGFORD
A N D M PARRIS)
...............................
. STOICHIOMETRIC MECHANISMS . . . . . . . . . . . . . . . . . . . . . . . . .
3 . REACTIONS OF CO(II1) COMPLEXES . . . . . . . . . . . . . . . . . . . . . . .
4 . Cr(ll1). Rh(ll1).
3
7
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5 . COMPLEXES OF Pt(1I). Pd(11). AU(II1) AND Rh(1)
. . . . . . . . . . . . . . . . .
6. COMPLEXES WITH B CLASS LIGANDS: THE BINARY CARBONYLS . . . . . . . . . . . .
7. COMPLEXES WITH B CLASS LIGANDS: THE SUBSTITUTED CARBONYLS . . . . . . . . . .
8. THEORETICAL CONSIDERATIONS . . . . . . . . . . . . . . . . . . . . . . . . .
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
RU(II1). I T ( I I 1 ) AND
Pt(1V) COMPLEXES
17
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25
31
43
52
Reactions in solution between various metal ions of the same element in different oxidation states . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
2 . COPPER.
...............................
SILVER AND GOLD . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1 The exchange reaction between Cu(II) and Cu(1) . . . . . . . . . . . . .
2.2 The exchange reaction between Ag(I1) and Ag(1) . . . . . . . . . . . . .
2.3 The exchange reaction between Au(II1) and Au(1) . . . . . . . . . . . .
2.4 The exchange reaction between Au(II1) and Au(I1) . . . . . . . . . . . .
2.5 The disproportionation of Au(1I) . . . . . . . . . . . . . . . . . . . . .
3. MERCURY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
56
1 INTRODUCTION
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3.1 The exchange reaction between Hg(l1) and Hg(l); the disproportionation reaction of Hg(I1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 The exchange reaction between Hg(I1) and Hg(1) in non-aqueous media . . . .
4
. THALLIUM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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5 . T I N AND LEAD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1 The exchange reaction between Sn(IV) and Sn(I1) in aqueous media . . . . .
4.1 The exchange reaction between TI(III) and TI(1)
5.2 The exchange reaction between Sn(IV) and Sn(I1) in non-aqueous media
5.3 The exchange reaction between Pb(lV) and Pb(I1) in aqueous media . .
5.4 The exchange reaction between Pb(IV) and Pb(1l) in non-aqueous media
56
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68
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70
70
71
CONTENTS
6.
ARSENIC A N D ANTIMONY
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8 . TRANSITION METALS . . . . . . . . . . . . . . . . . . .
8.1 Vanadium and tantalum . . . . . . . . . . . . . .
TELLURIUM
7.1
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96
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103
105
106
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110
110
110
111
111
111
114
119
119
121
121
122
122
CONTENTS
XI
8.6 Platinum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8.6.1 The exchange reaction between Pt(1V) and Pt(1l); Pt(I1)-catalysed substitution reactions of Pt(1V) . . . . . . . . . . . . . . . . . . . .
9.
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122
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9.2 The exchange reaction between Eu(II1) and Eu(l1) . . . . . . . . . . . . .
128
128
130
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130
CERIUM A N D EUROPIUM
10.
122
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10.2
10.3
10.4
10.5
10.6
10.7
10.8
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REFERENCES . . . . . . . . . . . . . . . . . . . .
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132
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135
138
138
141
141
142
INTRODUCTION
2.
OXIDATIONS BY VANADIUM
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2.1 Oxidations by vanadium(V) . . . .
2.2 Oxidations by vanadium(1V) . . . .
2.3 Oxidations by vanadium(l1l) . . .
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3 . OXIDATIONS
BY C H R O M I U M AND MOLYBDENUM
3.1 Oxidations by chromium(V1) . . . . . . . . . . . . . . . . . . . . . .
3.2 Oxidations by chromium(ll1) . . . . . . . . . . . . . . . . . . . . . . .
3.3 Oxidations by molybdenum(\/) . . . . . . . . . . . . . . . . . . . . . .
4 . OXIDATIONS BY MANGANESE A N D R H E N I U M . . . . . . . . . . . . . . . . . . .
4.1 Oxidations by manganese(VI1) . . . . . . . . . . . . . . . . . . . . . .
4.2 Oxidations by manganese(lI1) . . . . . . . . . . . . . . . . . . . . . .
4.3 Oxidations by rhenium(VI1) . . . . . . . . . . . . . . . . . . . . . . .
5.
6.
OXIDATIONS BY I R O N ( I I I ) AND R U T H E N I U M ( I I I )
153
154
154
157
159
162
162
167
169
169
169
172
175
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176
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188
188
OXIDATIONS BY COBALT(III)
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188
206
213
227
228
228
230
241
243
253
253
257
261
267
CONTENTS
XI1
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2 . OXIDATION BY cr(vr1) AND Mn(vII) . . . . . . . . . . . . . . . . . . . . . .
2.1 General features . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2 Solution equilibria of oxy-anions of Cr(V1) and Mn(VI1) . . . . . . .
2.2 Oxidation of inorganic covalent species . . . . . . . . . . . . . . . . .
2.2.1 Halide ions . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2 Cyanide ion . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3 Oxides of hydrogen . . . . . . . . . . . . . . . . . . . . . . .
2.2.4 Oxy-acids of sulphur . . . . . . . . . . . . . . . . . . . . . .
2.2.5 Nitrite ion . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.6 Trivalent phosphorus compounds . . . . . . . . . . . . . . . .
2.2.7 Arsenious acid . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.8 Carbon monoxide . . . . . . . . . . . . . . . . . . . . . . . .
2.2.9 Molecular hydrogen . . . . . . . . . . . . . . . . . . . . . . .
2.3 Oxidation of monofunctional organic molecules . . . . . . . . . . . . .
2.3.1 Aliphatic hydrocarbons . . . . . . . . . . . . . . . . . . . . . .
2.3.2 Olefins and acetylenes . . . . . . . . . . . . . . . . . . . . . .
2.3.3 Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.4 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.5 Phenols . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.6 Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.7 Monocarboxylic acids . . . . . . . . . . . . . . . . . . . . . .
2.3.8 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.9 Nitroalkanes . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Oxidation of polyfunctional organic molecules . . . . . . . . . . . . .
2.4.1 Glycols . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.2 Allylic alcohols . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.3 Ketols, keto-aldehydes and keto-acids . . . . . . . . . . . . . .
2.4.4 Dicarboxylic acids . . . . . . . . . . . . . . . . . . . . . . . .
2.4.5 Hydroxy-acids . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.6 Boronic acids . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.7 Furfurals . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5 Some metal-ion catalysed reactions of chromic acid . . . . . . . . . . .
3.
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3.3
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287
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316
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324
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327
327
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3.1
3.2
274
274
276
General features . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidation of inorganic species . . . . . . . . . . . . . . . . . . . . .
3.2.1 Halide and pseudohalide ions . . . . . . . . . . . . . . . . . .
3.2.2 Oxy-acids of sulphur . . . . . . . . . . . . . . . . . . . . . .
3.2.3 Hydrazine . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.4 Nitrite ion . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.5 Hypophosphorous acid . . . . . . . . . . . . . . . . . . . . .
3.2.6 Carbon monoxide . . . . . . . . . . . . . . . . . . . . . . . .
3.2.7 Molecular hydrogen . . . . . . . . . . . . . . . . . . . . . . .
Oxidation of monofunctional organic molecules . . . . . . . . . . . . .
3.3.1 Olefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.2 Arylcyclopropanes . . . . . . . . . . . . . . . . . . . . . . . .
3.3.3 Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.4 Hydroperoxides . . . . . . . . . . . . . . . . . . . . . . . . .
329
329
330
331
332
332
333
334
334
335
336
336
342
343
344
XI11
CONTENTS
3.4
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406
XIV
CONTENTS
6.
. 407
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Simple electron acceptance by inorganic molecules . . . . . . . . . . . . .
6.2.1 Perchlorate ion . . . . . . . . . . . . . . . . . . . . . . .
. .
6.2.2 Chlorate and bromate ions . . . . . . . . . . . . . . . . . . .
6.2.3 Chlorite ion and chlorine dioxide . . . . . . . . . . . . . . . . .
6.2.4 Molecular oxygen . . . . . . . . . . . . . . . . . . . . . .
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6.2.5 Water . . . . . . . . . . . . . . . . . . . . . . . . . . .
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REDUCTION
6.1
6.2
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428
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452
452
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456
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466
470
471
473
475
xv
CONTENTS
6.4.8
6.4.9
6.4.10
6.4.1 1
6.4.12
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482
486
487
488
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ACKNOWLEDGEMENTS
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REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
488
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Chapter 5 (L J. C S ~ N Y I )
Induced reactions . . . . . . . . . . . . . . . . . . . . . . . .
I . INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . .
1.1 Definitions . . . . . . . . . . . . . . . . . . . . . . .
1.2 Types of induced reactions . . . . . . . . . . . . . . . .
1.2.1 Coupled reactions . . . . . . . . . . . . . . . . .
1.2.2 Induced chain reactions . . . . . . . . . . . . . .
2.
2.2
2.3
2.4
2.5
2.6
2.7
3.
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519
Chromium(1V) and chromium(V) species as coupling intermediates . . . . . 519
2.1.1 Reaction between arsenic(II1) and chromium(V1) . . . . . . . . . . 521
2.1.2 Reaction between isopropyl alcohol and chromium(V1) . . . . . . . 525
2.1.3 Oxidation of other alcohols by chromic acid . . . . . . . . . . . . 528
2.1.4 Oxidation of aldehydes and organic acids by chrornium(V1) . . . . . 529
2.1.5 Reaction between iron(1I) and chromium(V1) . . . . . . . . . . . . 532
2.1.6 Oxidation of vanadium(I1) and vanadium(1V) by chromium(V1) . . . . 533
2.1.7 Chromium(V1) as indicator in the induced oxidation of arsenic (111) by
534
molecular oxygen . . . . . . . . . . . . . . . . . . . . . . . .
2.1.8 Properties of the chromium(V) and chromium(1V) intermediates . . . 536
Induced reactions caused by arsenic (IV) intermediates . . . . . . . . . . . 538
2.2.1 Iron(l1)-arsenic(II1)-peroxydisulphate system . . . . . . . . . . . . 538
2.2.2 Iron(1I)-hydrogen peroxide-arsenic(II1) system . . . . . . . . . . . 542
2.2.3 Arsenic(II1)-peroxydisulphate reaction catalyzed by iron(II1) and copper(I1) 543
2.2.4 Polarographic behaviour of the system containing peroxydisulphate,
547
arsenic(II1) and copper(I1) . . . . . . . . . . . . . . . . . . . .
2.2.5 The induced reduction of chlorate by arsenic(II1) . . . . . . . . . . 550
2.2.i Properties of arsenic(1V) intermediate . . . . . . . . . . . . . . . 552
Induced reactions involving H 0 2 and OH radicals . . . . . . . . . . . . . 554
2.3.1 Induced reactions occurring in the H 2 S Z 0 8 - H 2 0 2system . . . . . . . 554
2.3.2 Induced reactions involving other peroxy compounds . . . . . . . . . 563
564
2.3.3 The Fenton reaction . . . . . . . . . . . . . . . . . . . . . . .
Induced reactions involving sulphate radicals . . . . . . . . . . . . . . . 567
Induced reactions involving intermediates produced by partial oxidation of
thiocyanate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
569
Induced reactions effected by reduction of permanganate ions . . . . . . . . 573
Induced reactions involving tin(II1) intermediate . . . . . . . . . . . . . 575
2.7.1 Reaction between iron(II1) and tin(I1) . . . . . . . . . . . . . . . 576
2.7.2 Reaction between tin(I1) and chromate . . . . . . . . . . . . . . 576
2.7.3 Reaction between tin(I1) and perrnanganate . . . . . . . . . . . . 576
2.1
. . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
CONCLUSIONS
REFERENCES
577
577
581
Chapter I
1. Introduction
This chapter is concerned with the simplest reactions of inert transition metal
complexes. Fig. 1 shows a typical compound. This is Co(II1) coordinated to six
NH, molecules to form a triply positive cation [ C O ( N H , ) ~ ] ~It+ is
. indicated in
Fig. 1 to be in aqueous solution where water molecules occupy positions in what
Outer sphere
may be called the outer or second coordination sphere. The reactions in question
are typified by the replacement of one of the NH, molecules by a water molecule
from the outer sphere. Inert will be considered to mean any complex whose
reactions occur slowly enough for conventional experimental kinetic techniques
tG be applied; in general this means half times longer than 10 sec. The inert
complexes have sometimes been called robust but this term seems to be more
suggestive of thermodynamic stability than kinetic non-lability .
This chapter is restricted to treatment of the inert complexes because these
References pp. 52-59
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
STOICHIOMETRIC M E C H A N I S M S
the nature of the entering group, it is clear that the energy of the bond being
formed is important to the activation process; and its influence must be in the
nature of an entering group assistance to activation. If otherwise, then the entering
group could not influence the rate, and the minimum requirement for a substitution reaction is that the bond to the leaving group be broken.
The question of the sensitivity of the rate of substitution to the nature of the
entering ligand provides a basis for the mechanistic dichotomy. A reaction which
is clearly insensitive to the nature of the entering group must reach its transition
state principally by the internal accumulation of the energy to break the bond to
the leaving group within the ground state complex because any significant assistance (in the sense of formation of a new bond) should be selective with respect
to the ligand assisting. Such a reaction, insensitive to the nature of the entering
ligand, will be said to have a dissociative mode of activation. Reactions which are
sensitive to the nature of the entering group will be characterized as having an
associative mode of activation because the assistance of the entering ligand does
play an important part in the determination of the free energy of activation,
although not necessarily to the exclusion of the leaving ligand. As the discussions
of particular cases will suggest, the dichotomy between dissociative and associative
activation does encompass the secondary effects on the energy of activation by
other groups in the complex or by the factors of the environment of the complex
(e.g. solvent effects).
A discussion of ligand exchange reactions of organometallic compounds associated with oxidation-reduction processes leading to free-radical formation
will be found in Volume 14 (Free-radical polymerization).
2. Stoichiometric mechanisms
So far nothing has been said about rate laws. This has been intentional, for there
is no simple relationship between the modes of activation and the concentration
dependencies that determine the rate law. The form of the rate law for a reaction,
that is, the dependence of rate on concentrations over the widest possible variations, tests hypotheses concerning the stoichiometric composition of the transition
state and the number of elementary steps of the reaction. These aspects may be
called the stoichiometric mechanism3. There I S enough variation in activation
mode among reactions of similar stoichiometric mechanism to recommend classifying reactions in two separate ways, first according to stoichiometric mechanism,
then according to activation mode. Moreover, these two distinguishing classifications follow the natural evolution in experiment. Stoichiometric mechanism is
inferred from analysis of rate laws; mode of activation is inferred from consideration of relative rates.
Note that the three transition states, a , b and c , in Fig. 3 all contain both the
References pp. 52-55
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
Reaction coordinate
Fig. 2. Free energy vs. reaction coordinate for the concerted ( I ) and two-step ( A , D ) reactions.
+Y
I
+X
M
\Y
MY+X.
S T O I C H I O M E T R I C MECHANISMS
entering and leaving ligands, Y and X in addition to the remaining metal complex
moiety. All three of these must be reached uia an initial encounter with the entering groups. Since we consider here only slow reactions of non-labile complexes we might write a simple mechanism in all three cases as
MX +Y
K
+
MX, Y
MX, Y
MY + X
(fast equilibrium)
(slow)
(1)
Here MX, Y designates an outer sphere or second sphere complex. There is every
reason to suppose that formation and dissociation of MX, Y occurs at rates approaching the diffusional-control limit so that the slow conversion to MY is a
negligible perturbation on the equilibrium of the first step. There is a similarity
here the Langmuir, the Michaelis-Menten and the Lindemann-Hinshelwood
schemes.
Two common limiting forms of the rate law for mechanism (1) are encountered
experimentally. In the event that the equilibrium constant, K , for outer sphere
complexation is small in relation to the concentration of MX and Y, the rate law
becomes
d[MX1 - k,,,[MX][Y]
dt
where kobs,the second-order rate coefficient, is kK. If K is large, the outer sphere
equilibration may become saturated and the rate law reduce to
dCMX1 - k:,,[MX]
dt
(3)
where kAbs now equals k , the rate coefficient for the slow step. It has not always
beerl realised that these two forms may arise from the same mechanism. Choosing,
as is usual, Y to be in excess, a general expression under mechanism (1) may be
written
Recall that three transition states m:ght be considered as falling within the
pattern (1). Transition state a of Fig. 3 involves strong binding of both X and Y.
In this case, it is quite possible that an intermediate of increased coordination
number is formed during the reaction. Since the initial attack of Y determines
the stereochemical course of any reaction obeying the rate law (4) there is no
References pp, 52-55
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
MX
+ M+X
(slow)
kx
M+Y
5 MY
(fast)
STOICHIOMETRIC MECHANISMS
which is not easily distinguished experimentally from expression (4) for mechanism (1). Table 1 summarizes the mechanistic categories described and Fig. 2
indicates their relationships on an energy-reaction progress diagram.
TABLE 1
CLASSIFICATION O F L I G A N D S U B S T I T U T I O N MECHANISMS
Mode of activation
Stoichiornetric niechanisrn
Associative activation
Dissociative activation
Interriiediaie of increased
roordinotion number
One-step process
1,
Id
Interniediute of reduced
coordination number
sN1
(lim)
s N 2
= 1,
sN1
= 1,
(Iim)
them especially attractive for the systematic kineticist and the reactions of Co(II1)
systems have served as the model for development of most of the key concepts
about substitution reactions of octahedral systems.
A good starting place for discussion is the rate law for substitution reactions
in acidic aqueous solutions. One typical reaction is
CO(NH,)~CI'++ H 2 0 + CO(NH,),OH,~++Cl-
(8)
which is of course expected in this case from almost any mechanistic picture. When
the solvent is a potential ligand, the perpetual encounter between solvent molecules
and complex severely limits the cases in which the rate equation is directly informative. However, one limit of mechanism is available. The general reaction
(where Y is an arbitrary anionic ligand)
and related ones, in which CI- is replaced by another leaving group, or the NH,
ligands are replaced by others inert to substitution, all follow a rate law similar
to equation (9)'-'. Significantly, the Concentration of Y - does not appear i n the
rate law in any case except when Y - = OH-. Overlooking the exception of OHfor the moment, Y - is not a stoichiometric participant of transition state(s)
leading to its entry and there must be an intermediate in the reactions. There are
two choices of pathway, viz.
I/
-cox
slow
'I
I/
faSt
yco
+Y
I/
-Co'I
X + H,O
I/
-Co-0H2
/I
slow
1,
-/?o
+x
I/
>~o-Y
I/
-CO/I
OH2 + X
I,
+ Y fa51_ 7$o-Y+H20
The first possibility, (1 l), clearly is concerned with a dissociative mode of activation ( d ) . The second, (12), might beassociative led by water attack. But, this interpretation of (12) involves commitment to the proposition that no nucleophile
(possibly excepting OH-) has been discovered which is better than water, i.e. the
associative attack must always involve water in the first instance. The proposition
R E A C T I O N S OF
CO(II1) COMPLEXES
Perhaps the closest definition of the role of the leaving group emerges from correlation of rates with equilibria in reactions of the family CO(NH~)~X.In a
dissociative mode the leaving group in the transition state strongly resembles
the leaving group in the product state. If X is an anionic ligand, in the transition
state it should resemble the free anion. The activation free energy should respond
to changes in leaving group in much the same way as the free energy difference
for the overall reaction responds. A linear free energy relationship (see Vol. 2,
Chapter 4) is suggested between the activation energy AG and the free energy of
reaction AGO of the form A(AG) = j?A(AGo)), where A(AG) denotes change in the
free energy quantity with change of X. In the ideal dissociative case, j? would be
unity. This has been realised for the Co(NH,),X2+ family as shown in Fig. 4.
A persuasive reason for preferring the dissociative over the associative interpretation of equation (12) has emerged from recent work on reactions of Co(II1)
References p p . 52-55
10
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
TABLE 2
Co(ll1) COMPLEXES
The labile ligand is italicized.
RATES OF A C I D H Y D R O L Y S I S OF SOME
Complex*
Co(NH3)5 op(ocH3)1
Co(NH3)s NO3
Co(NH3)5 1
Co (N Ha) Br
C O ( N H ~OH2+
)~
Co(NHj)5 CI2+
C O ( N H ~SO4+
)~
CO(N H3) 5 O P 0 3H2
Co(NH3)s NOzZ
Co(NH3)5 N C S 2
Co(NH3)S O H Z +
CO(N H3)63
trans Coen20H CI+
cis CoenzOH Cl+
trans Coen,BrCI+
cis Coen,BrCI+
trans Coen,CI2+
cis CoenzCIz
trans CoenzN3CI+
cis CoenzN3CI+
trans CoenzNCSCI+
cis CoenzNCSCl+
trans Coen,NH3CIZC
cis Coen,NH3C12+
trans Coenz0HZClZ+
cis Coen20H2CI2+
trans Coen,CNCI+
trans CoenZNOzCI+
cis Coen,NO,Cl+
trans Coen2NOzEr+
trans Coen, Br2
trans C O ( N H ~ ) ~ C I ~
cis CO(NH,),CI,
+
AT
k(sec-)
AHX(kca1)
2.5 x 10-4
2.7 x 1 0 - 5
8.3 x I O - ~
6.3 X ~ O - ~
5.8 x I O - ~
1.7 x 1 0 - 6
1.2 x10-6
2.6 X I O - 7
1.15 x
5.0 x I O - O
very slow
25.5
23.5
27
23
19
+6
-9
-24
31
26.2
23.1
24.9
23.5
26.2
21.5
22.5
21.3
30.2
20. I
23.2
24.5
0
-
-lO-*O
1.6 X I O - 3
1.2 x10-2
4.5 X I O - 5
1.4 X I O - 4
3.5 X I O - 5
2.4 x 10-4
2.2 x 10-4
2.0 ~ 1 0 - 4
5 x10-8
1.1 X I O - 5
3.4 X I O - 7
5 XIO-7
2.5 x I O - ~
1.6 x I O - ~
8.2 X I O - 5
9.8 x 10-4
1 . 1 XIO-4
4.0 ~ 1 0 - 3
1.2 x10-6
1.8 X I O - 3
fast
22.5
20.9
21.8
-
250 C
ASt(eu)
ReJ
13
+6
14
14
-4
14
15
+20
+ 10
+2
+ 14
+I4
-5
0
-4
+9
- 14
-11
-6
-
-2
-2
-3
-
14
14
13
16
17
14
18
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
18, 19
20
20
21, 19
18, 19
18, 19
18, 19
18
23
23
~~-
complexes in solvents other than water. Work of Tobe, Watts, Langford and their
respective collaborators has demonstrated that these solvents, dimethyl formamide, dimethyl sulphoxide, dimethyl acetamide and methanol also function as
preferred nucleophiles. This reinforces the suggestion that it is the high solvent
concentration and not solvent nucleophilicity that is important. Furthermore, it
is found that in these solvents some direct replacement by an anion may be
observed but that such replacement is always associated with ion pair formation
and that reaction rates show very little sensitivity to the nature of the entering
ion12.
REACTIONS OF
cO(III)
COMPLEXES
11
-3 -
-4-
.-C
X
0
J
-5-
LOP H
eq
12
sociative model when the leaving group is anionic. For the associative model, one
might expect opposite or at least very small charge effects (see the discussion of
Pt(II), p. 20).
In this catalogue of structure variation experiments to test the hypothesis of
a dissociative activation mode, the last is the role of non-labile ligands. This
question has been examined using the hydrolysis reactions of the family of complexes cis and trans Coen,ACI+ where CI- is the leaving group and A is a variable
non-labile substituent (see rates in Table 2). The first approach taken to the
analysis of the data was to classify the ligands A as electron donors or electron
acceptors on the basis of organic chemical precedent and then to plot the observed
25" rate coefficients as a function of decreasing electron donor-increasing electron
acceptor proper tie^^^. The two branches of the curve (Fig. 5) were given a two-
-1 -
"
-2-
P)
rn
a-- 3 m
J
-4-
-5-
-6-
-'t
NHZ
OH-
N;
CI-
NCS-
NHJ
H,O
CN-
NO,
Fig. 5. Rates of hydrolysis of a series of Coen,ACI" complexes. The abscissa represents the
electron-donating or -accepting power of A .
R E A C T I O N S OF
CO(II1) COMPLEXES
13
reviewed. 26. No direct support has emerged for the postulation of an associative
transition state. Fortunately, there is an alternative account of the situation. The
dissociative transition state is an incipient five coordinate complex. In the extreme
case there are two possible geometries, trigonal bipyramidal and square pyramidal
and different ligands may stabilize geometrically different transition states. Note
(Fig. 6 ) that the square pyramidal form cannot lead to cis-trans isomerization
a-M
trans
cis ; t r a n s
=2.1
cis
14
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
-M
R E A C T I O N S OF
CO(lI1) C O M P L E X E S
15
outer coordination sphere as well as the ligand X. Even if the rate of dissociation
of water is unaffected by the presence of X in the neighborhood, the most probable
result of water loss will be water exchange and not X entry. Thus on the path we
expect all ion pairs tc show closely similar rates of conversion to aniono complexes, but we expect these rates t o lie below the solvent exchange rate by the appropriate statistical factor for the population of the outer sphere. Recently 9 , l 3
the rates of formation of Co(NH,),X from Co(NH,),OH, . . . X have been
reported relative to the water exchange rate for X = SO4, C1-, SCN-, and
H2P04-. The values are 0.24, 0.21, 0.16 and 0.13, respectively. The values span
a range of a factor of two which must be admitted to be a little larger than the
experimental uncertainty and also easily within the differences among the anions
in their probability of occupancy of the crucial outer sphere site adjacent to the
leaving water molecule. All are nearly a factor of five below the water exchange
rate. These results conform neatly to the I d predictions.
Examining the relationship between the probability that a ligand occupies an
outer sphere site, the rate of ligand incorporation, and the solvent exchange rate,
appears to be the most general method for identifying the I,, pathway. It has
been applied to several other systems recently. Rates of anion entry into cis[Coen2NO2(DMS0)I2+in dimethyl sulphoxide (DMSO) have been compared
to the DMSO exchange rate obtained from the deuterium tracer NMR experiments
of Lantzke and Watts29. The pattern is very akin to that for CO(NH,),OH,~
in water. Similarly the rate of sulphate anation in the pair ~ i s - [ C o e n , ( O H ~ ) ~ l ~ +
. . . SO4- has been found to be 0.25 times the water exchange rate of the free
ion 9a.
Several authors have suggested that the Id pathway may prove to be the most
common mechanism in substitution reactions of octahedral complexes generally.
However, the D path can be clearly demonstrated in some cases including at least
two examples from Co(II1) chemistry. The path (I -+ 111 -+ IV, Fig. 7) through the
fivecoordinate intermediate would lead, in the case of rate studies in the presence of
excess anionic ligand, to observed first-order rate constants governed by equation
(13)
References p p . 52-55
16
I N E R T C O M P L E X E S A N D METAL O R G A N I C C O M P O U N D S
Co(NH,),SO,+. The order of reactivity toward this five coordinate species is:
OH- > NO,- > CN- > NH, > H,O and spans six orders of magnitude.
These two five coordinated Co(II1) species are, to date, the only ones clearly
established from detailed knowledge of the rate law for substitution (a situation
very clearly subject to change). Strongly suggestive evidence for others has been
accumulated from another approach. Loeliger and Taube3, and Sargeson et al.,,
have examined reactions of a complex where there is a distribution of products
(i.e. 6O and l8O aquo complexes or stereoisomerically different complexes). They
argue that a constant product ratio strictly independent of the nature of the
leaving group implies product formation ufler the leaving group is removed from
the scene of reaction and the existence of an intermediate. The key word here is
strictly. Leaving group effects may often be quite subtle. In I , processes, for
example, they would appear only to the extent that they modified outer sphere
populations. Some persuasive indication of D reaction has been presented for
some of the so-called induced aquations of Co(II1) amine complexes. Induced
aquations include Hg2+-catalyzed halide loss and rapid azide loss catalyzed by
nitrous acid.
Before leaving Co(II1) chemistry we must consider the base hydrolysis reaction
Co(NH,),X+OH-
--+
(14)
Co(NH,),OH+X-
Co(NH,),(NH,)Cl+
C O ( N H ~ ) ~ ( N H ,+H,O
)~+
s Co(NH,),(NH,)CI+ + H,O(fastequilibrium)
+ Co(NH3),(NH2)
+
Co(NH,),OHZf
fC1- (slow)
(16)
(fast)
The mechanism allows for a slow step analogous to the d process observed in
AND
Pt(IV)
17
COMPLEXES
TABLE 3
R A T E S O F B A S E H Y D R O L Y S I S OF S O M E
cO(III)
COMPLEXES
koH(l.mole- '.see-')
Cottiplex*
Co(NH3)512+
Co (N H 3) 5Br
Co (N H Cl
Co(NH3)5 N 3 2
CO(NH~)~NO~*+
trans Coen2CI2+
trans Coen,OHCI+
trans Coen2NO2CI+
cis Coen2C12+
cis Coen20HCl+
cis Coen2N02Cl+
trans Co(d,I-bn)2C12+
trans Co(Meso-bn), C12
+
23
7.5
0.85
3 x 10-4
4.2 x
85
0.017
0.080
15.1
0.37
0.03
2100
9800
T("C)
25
25
25
25
25
0
0
0
0
0
0
25
25
29
28
29
33
38
23.2
22.8
24.4
24.6
22.4
23. I
AS(eu) Ref.
+42
+40
36
+35
30
-
+
+
35
35
35
35
35
36
36
36
36
36
36
31
37
bn represents 2,3-diaminobutane.
acid hydrolysis, and the extensive evidence of a parallel between acid and base
hydrolytic reactivity has been reviewed3'. It has also been established by measurement of H-D exchange on the ammine l i g a n d ~ ~ ' . that
~ ' the conjugate base
can be formed sufficiently rapidly. The most telling experiments, though, are those
that establish that product formation occurs in a step independent of the initial
hydroxide involvement. Green and T a ~ b have
e ~ shown
~
that the 160/180
isotope
fractionation factors in base hydrolysis are more easily explained assuming in~ ~ shown
corporation of 0 from H 2 0 than from OH-, and Sargeson et u I . have
that other anions (Y-) can effectively compete with OH- in the base catalyzed
pathway to give products C O ( N H , ) ~ Y ~in+ addition to Co(NH3),OH2+.Thus,
there seems little doubt that direct OH- attack on Co(I1I) is excluded.
The reason for high reactivity on the base-catalyzed pathway remains something
of a puzzle. The simplest, but not entirely convincing interpretation, suggests
that the NH2- ligand functions as an electron donor similar to OH-.
has suggested, on spectroscopic and stereochemical grounds, that the conjugate
base species may be labile because it is a high spin d6 complex. This view is rendered
more attractive by Watt and Knifton's recent report45 of a paramagnetic solid
Co(II1) conjugate base species isolated from liquid NH,. Gillard46 has made the
interesting suggestion that OH- may not function as a base but as an electron
donor, to produce a transient OH radical and a labile Co(I1) species.
4. Cr(III), Rh(III), Ru(III), Ir(II1) and Pt(1V) complexes
The related octahedral non-labile complexes which have received some attention will be grouped together simply because there is much less information
References p p . 52-55
18
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
(17)
AND
Pt(IV)
19
COMPLEXES
TABLE 4
25 "C
RATES OF H Y D R O L Y S I S R E A C T I O N S OF SOME O C T A H E D R A L C O M P L E X E S A T
k(sec- l )
E,(kcal.rnole-
Cr(NH3)JZ+
Cr ( N H ) Br
Cr ( N H 3 )sC12
Cr(NH3)63
Cr(OH2)5 F 2+
Cr(OHZ),Cl2+
Cr(OH2)SBr2+
Cr(OH2)5ZZ
Cr(OH2)sN32+
trans Cr(OH2)4C12+
cis Cr(OH2)4CIZ+
trans Cren2CI2+
cis Cren2C12
trans Cren20H2CI2+
cis Cren20H2C12+
Cr(NCS)63Ru(NH3)SCI'
I . O X 10-3
6.8 X
7.3 x 10-6
21
24
24
26
29
25
24
23
33
27
RU
ci63-
trans Ru (OHZ)3C13
Ru(OH2)SCI'
R h (N H 3 ) Br
Ir(NH3)sBr2+
Rh(OH2)CIsZIr(OH2)C152IrC163-
I.OX 10-7
6 . 2 ~
2.8 x 1 0 - 7
3.1 x
8 . 4 1~0 - 5
4.6~
8.3 x 1 0 - 5
4.3 x 1 0 - 5
2.2 x 1 0 - 5
3.3 x 10-4
< 10-6
-3 x
5.3 Y 1 0 - 5
7 . o ~10-7
-1
2.1 x 10-6
Ref.
52
53
53
54
55
55
56
55
55
57
57
58
58
58
58
59
60
61
61
61
62
51
63
23
21
-
23
'.)
26
21
10-8
2x10-'0
3 x 10-4
64
9.4 x 10-6
30
64
Complex
Ea(hcal.ttiole- I )
ReJ
Cr(NH3)5/2+
Cr(N H 3 ) Br2
Cr(NH3)5CIZ+
Ru(NH~)~CI'
Rh(NH3)s/Z+
Rh(NH3)sBr2+
Rh(NH3)5C12+
3.6
6 . 9 ~lo-'
1.7~10-3
4.9
7.3 x lo-'
3.4~10-4
4.1 x 10-4
21
26
27
52
52
52
B. Base hydrolysis
60
33
31
29
-
.-
65
65
65
~
20
is smaller71. Of course, this may be as expected for the larger Rh(I1I) ion. Limited
data7 on the effect of changing charge on the ion is contrary to expectation, for
the more highly-charged species react the faster. It is not here at all clear that only
overall charge effects are being measured.
TABLE 5
R A T E S OF:
k x I05(sec-)
X
OH- (0.1 M)
5.1
4.2
4.2
5.2
NOL-(0.1 M)
NOz- (0.05 M )
I - (0.1 M)
I-(0.05 M)
36c1-(0.01 M)
Thiourea (0.1 M)
NH3(5 M)
5.1
4.0
4.9
4.0
21
COMPLEXES
(kj + k2[36C1-])[A~C14-]
(19)
+ Pt(dien)Y+Br-
(20)
(dien = 1,4,7-triazaheptane,diethylenetriamine;
a tridentate ligand). The figure
shows apparent first-order rate coefficients in the presence of excess Y as functions
of Y, values of k, ranging from "0" and 8.8 x l o w 4I.mole-'.sec-' for OHand C1- to 4.3 x lo-' and 8.3 x lo-' I.mole-'.sec-' for SCN- and thiourea.
The pathway characterized by k , is clearly selective with respect to entering groups
and must be associative. This result raises the interesting question of what comI
"
I
*-
0
X
0
0
NOP,Py.CI
,
0.01
rY1.M
OH-
0.02
0.0 2
Fig. 8. Relative reactivities of different entering groups Y with PtdienBr+ in aqueous solution
at 25 "C. Data from ref. 74.
Referrtires pp. 52-55
22
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
prises a good nucleophile for Pt(I1). Apparently OH-, which is both a strong base
and a good nucleophile for attack at carbon is quite unreactive toward Pt(I1).
Of course, reactivity of nucleophilic reagents is quite sensitively dependent upon
the nature of the substrate. A good deal of effort has been directed toward the
exploration of the correlation of nucleophilic reactivity with easily measurable
characteristics of the nucleophile. A two-parameter approach based on the
basicity (toward H) and polarizability of the nucleophile meets with considerable
success. Nucleophilicity toward Pt(I1) is clearly most dependent upon polarizability, but it should be emphasized that the exact connection between the bulk
polarizability of a species and its nucleophilic reactivity is far from clear.
Nucleophilic reactivity toward Pt(I1) complexes may be conveniently systematized via linear free energy relationship^^^ established between reactions of trans
Ptpy2C1, (py = pyridine) with various nucleophiles and reactions of other Pt(I1)
complexes with the same nucleophiles. First, each nucleophile is characterized by
a nucleophilicity parameter, nopt derived from its reactivity toward the common
substrate, trans PtpyzC1,. Reactivity toward other Pt(I1) substrates is then quite
satisfactorily represented by an equation of the form (21), wherein k, is the value
of k, in the reaction with nucleophile Y
> S=C(NH,), > SeCN- > CN- > SCN- > I - >Br- > Py
> NH, > CI- > CH,OSome values of s (or NDF) fall in the order76
trans Pt[(C,H,),P],CI,
-+
L,Pt-S+X
(slow)
L,Pt-S+Y
--*
L,Pt-Y+S
(fast)
AND
Rh(1)
COMPLEXES
23
H,O departs about lo5 times as fast as CN-. A good attacking group is a poor
leaving group with very few exceptions. O H- is notable, for it is a very poor
nucleophile for Pt(I1) but is only very slowly replaced. In the main, lability also
corresponds to thermodynamic instability, for example in the series
The third ligand which plays a major role in determining rates of substitution
at Pt(I1) is the ligand which is trans to the leaving group. Its effect is as spectacular
as the effect of the directly involved entering and leaving ligands, and, since first
being recognized and explored by Wernera2 and ChernyaevE3, it has fascinated
students of Pt chemistry. The trans effect has been crucial to the control of synthesis in the square planar series. A fairly constant order of labilizing effect of
tram ligands can be given. If we could study the rate of release of a single leaving
group being replaced by a single entering group with the trans group varied from
CN- to OH-, the rate would decrease by a factor 01 about lo6. A trans effect
ordera4 is given in Table 6. Inspection of the table reveals that a good trans
labilizing ligand corresponds to a good nucleophile and a poor leaving group in
the great majority of cases.
The complementary roles of trans, entering, and leaving ligands when contrasted
with the much smaller role of variable cis ligands suggest an explicit model for
RrJrrenLrs pp. 52-55
24
TABLE 6
Trans EFFECT O R D E R I N G O F L I G A N D S
Relative rates
very large
co
CN-
>c-c <
>
large
>
1-
>
moderate
c1-
>
small
>
FH3
OH-
SCNPMe3
25
This section so far has concentrated on the evidence for a and possibly A reactivity at Pt(I1). Little has been said of the other square planar systems. This is
because much more data are available on Pt(I1) and where data for other complexes exist, they exhibit the pattern made familiar by Pt(I1). The rate coefficients
for reactions of AuC1,- are larger73 than those for PtC1,- suggesting increased
bonding by the entering group in the transition state. It is also true that square
planar Pd(I1) and Ni(I1) complexes react faster than the corresponding Pt(I1)
systems. Probably this reflects easier achievement of five-coordination. Axial
perturbations in solution are more pronounced for these square planar systems.
Some rates of reaction of complexes with pyridine are compared in Table 7. The
Rh(1) and Ir(1) square planar complexes Rh(CO),(p-anisidine)Cl and Ir(CO),
(p-to1uidine)Cl undergo second-order exchange with 14C0 at - 80 C in ethanol,
with k, approx. 2 l.mole-.sec- in both cases.
TABLE 7
R A T E S O F R E A C T I O N S OF A N A L O G U E S OF
[Py] ( M )
Complex
Ptdien SCN
O.OOO10
Pddien SCN
0.00123
Ptdien NO2+
0.00592
Pddien NO2+
0.00124
tr~ns-Pt
[ ( C Z H ~ ) ~ P ] ~ ( O - ~ O I ~0.0062
I)CI
trans-Pd [(C2H5)3P]2(o-to1yl)CI 0.0062
trans-Ni [(C2H5)3P]2(o-tolyl)CI 0.0062
+
Pt(1l)
COMPLEXES W I T H PYRIDINE
Soloent
H20
HzO
H2O
H20
C2HSOH
C2H5OH
C2H5OH
25
25
25
25
-25
-40
- 65
6.2 X lo-
4 . 2 lo-
~
5 . 0 ~
3.3 x 1 0 - 2
1.7~10-~
5.8 x 10-3
1 . 6 lo-
~
ReJ
81
81
81
81
90
90
90
26
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
say, that ligand-metal association tends to form well-matched systems in the sense
that B class ligands combine preferentially with B class metals and even promote
association with other B class ligands. The main virtue of a B class ligand appears
to lie in its minimizing interelectron repulsion, so promoting all of the above
characteristics. There is an independent criterion of this effect, namely the position
of the ligand in the nephelanxetic series94. We will here be concerned primarily
with organometallic rather than coordination compounds, generally, that is,
uncharged complexes with weakly basic ligands in the Brsnsted sense. Thus neither
complexes nor ligands will require a particularly polar solvent environment which
might interfere with kinetic interpretation. Against this advantage must be set,
firstly, the ambiguity which may arise in the oxidation number of the metal and,
secondly, the possibility that ligand reaction or rearrangement may occur without
normal substitution on the metal, and this may dominate the observations. The
stereochemistry of organometallic compounds is more varied9 than that of coordination compounds, and it is evident that more unorthodox substrates are open
to investigation. However, the kinetic information available to date concerns
compounds of conventional, especially octahedral and tetrahedral, stereochemistry. The greatest body of information concerns the carbonyl complexes - in
a sense these may perhaps be characteristic of the whole group of B type compounds, as the ammines have been conveniently taken as characteristic of the A
type compounds.
Some initial assessment of the metal-carbonyl bond may first be made. The
simpler neutral binary carbonyls fall conveniently into three eighteen-electron
classes, uiz. the octahedral chromium group hexacarbonyls, the trigonal bipyramidal iron group pentacarbonyls and tetrahedral nickel tetracarbonyl. In
addition, dimers or polymers with metal-metal bonds are formed by the elements
of groups VII and VIIl while carbonylate anions and some cations are fcrmed
which are structurally akin to the three basic monomeric types. Table 8 indicates
some of these formal relationships between the different carbonyls. Replacement
of CO by other ligands, anionic such as the halides or neutral such as the group V
ligands, hydrocarbons and the like, or a change in the charge on the complex or
a change in its geometry will result in a change in the nature of the M-C bond.
This has been adequately reviewed96: briefly, the total M-C bond owes its peculiar
TABLE 8
SOME B I N A R Y C A R B O N Y L C O M P O U N D S
C L A S S L I G A N D S : THE B I N A R Y C A R B O N Y L S
27
Fe(C0)42I786
Mn(C0)51895
I863
v(c0)6I859
Cr(CO)6
1985
cO(c0)41886
Ni(C0)4
2057
Fe(CO)S
2034
2014
Mn(CO)6+
2090
MO(CO),
I990
W(C0)6
1980
100.
28
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
'
' 9
Ni(CO),
Ni(CO),
Ni(C0)3 CO
+ L fast_ Ni(CO),L
( 24)
29
T A B L E 10
RATES OF THERMAL SUBSTITUTION I N SOME BINARY CARBONYLS
Corrtpoiind
1L-t CO
k,[M(CO).]
C'80
(C6H5)3P
(C6HshP
(C6H 5)3p
14co
14co
14co
1 4 ~ 0
14co
Benzene
Mesitylene
Toluene
Hexamethyl
benzene
Cycloheptatriene
Norbornadiene
(n-B~t)3P
(EtOhP
(C6H 5 )3p
Solvent
Hexane
Hexane
Cyclohexane
Toluene
HzO
Hz0
Gas
Gas
Gas
n-Decanecyclohexane
n-Decanecyclohexane
n-Decanecyclohexane
n-Decanecyclohexane
n-Decanecyclohexane
n-Decanecyclohexane
Decalin
Decalin
Decalin
AH:(kcal. ASI(eri)
mole- I )
0.5
0.5
25
25
60
60
117
116
142
I I2
2.45 x 10-4
24.3
2.45 x 10-4
24.2
6.87 x 10-3
26.6
1 . 9 4 ~ 1 0 - ~20.4
very slow
very slow
2 XIO-5
38.7(E,,)
7.5 X I O - 5
30.8(E,,)
2.6 x I O - ~ 39.8 (E.)
2 XIO-5
1 I2
2.75 x 1 0 - 5
I I2
Ref.
108
108
113
113
130
130
106
107
107
110
110
1 . 7 4 1~0 - 5
110
112
1 . 3 4 10-4
~
110
106
5.6 x 1 0 - 5
30.0(E,)
110
110
112
130.7
112.0
165.7
XIO-4
14
13
20.9
2.0
1.38 x 10-4
2.13 x 10-4
1.15 X
40.2
31.7
39.9
22.6
6.7
13.8
10-5
8.54~
25.5
21.7
29.2
-
- 14.3
- 14.9
-6.9
112
112
112
Decalin
Decalin
Decalin
Decalin
Decalin
Decalin
Decalin
Decalin
Decalin
130.7
112.0
165.7
130.7
112.0
165.7
130.7
112.0
165.7
2.05 x 10-4
7.1 XIO-5
4.5 X I O - 5
6.96 x 10-4
1.7 X I O - 4
4.31 x 1 0 - 5
1.77 x 10-4
8.88 x
112
112
112
112
112
112
112
112
112
30
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
'
The experimental results are equally consistent with an initial attack taking
place upon one of the coordinated ligands. A faster nucleophilic attack at the metal
by stronger bases is unexpected in view of the fact that these are electronically
saturated compounds. For this reason base attack upon the coordinated CO should
not be excluded from consideration as a possible mode of activation, and it is
worth noting here that oxygen exchange but not CO exchange occurs' in aqueous
solutions of Re(C0)6f. There will be available empty orbitals, largely located on
the ligands and electron donation into these will promote a loss of the ligands.
In effect, it is likely that the C of the CO ligand bears a net positive charge and as a
''
31
''
32
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
Cr(C0)6
Mn(COk+
Mn(C0LNO
Fe(CO)5
Mn(CO)(N0)3 Fe(C0)2(N0)2
and CO(CO)~NONi(CO)b
CO(CO)~(NO)L
ArCr(CO)3
*
Ar
CpMn(CO),
Ni(CO)3L
Ni(C0)2L2
halide ligand;
33
(NO), the 14C0 exchange is again first order although there is some possibility
of a confusing gas-phase reaction for the former"'. A first-order reaction between
Co(CO),NO and (C6Hs),As apparently occurs, but the remaining tetrahedral
nitrosyl carbonyls (the pseudo-nickel carbonyls) react according to a second-order
rate law. Tables 12 and 13 contain some rate data for these nitrosyl compounds
and show that the rate coefficient generally increases with the basicity of the
entering ligand. Those rates of CO exchange which have been measured are slower
than the second-order substitutions except for the doubtful case of Co(CO),NO,
and it has appeared reasonable to conclude that the substitutions are associative.
There are, indeed, many examples known of pentacoordinated complexes containing B type ligands"'. In the nitrosyl carbonyls, the formal oxidation number
falls: Co( -I), Fe( - 11), Mn( - 111), and it has been argued that this would cause
an increase in the M-C bond order and so reduce the possibility for dissociative
reaction. The decrease in rates in the series (n-But),P > (C,H,),P > (C6H,),As
is consistent with either smaller basicity or, equivalently here, polarizability.
T A B L E I2
(1. mole-'sec-I)
M(CO)4-,(NO)x+L
M(C0)3-,(NO),L+CO
9 x lo-'
2.6 x 10>200
CO(CO)~(NO)~
Fe(CO)Z(NOLa
Mn(CO)(N0)3b
FOR T H E REACTIONS
10-3
10-3
-54
2.3 x
125
126
127
slow
-5.6
at 25 "C; at 22 "C.
T A B L E 13
SOME DIFFERENCES I N KINETIC BEHAVIOUR BETWEEN
Co(CO),(NO)*
L
(C6H5)3AS (0.1 M )
(C6HshAS (0.1 M )
170.
AT
F e ( C O ) 2 ( N O ) zA N D
Solvent
Fe
co
Fe
co
Fe
co
toluene
toluene
THF
THF
toluene
toluene
Fe
co
toluene
toluene
kl(sec-')
0
0
k2(l.rnole-'.sec-')
10-3
10-3
10-3
0
0
0
1.6X
1.3 x 10-3
5.6 x 10-3
4x
kabr
km
1.5 Y l o y 6 sec-'
sec-'
34
I N E R T COMPLEXES A N D M E T A L O R G A N I C C O M P O U N D S
(27)
+L + Ni(CO),LL + L
(28)
Ni(CO),L+L
-+
or
Ni(CO),L,
While the rate is independent of both the concentration and the nature of L, it
varies with L as: L = Cl,P > (C6H5),P > (n-But),P > (C,H,O),P
>
> (C6H,0),P. The decrease in rate parallels an increase in basicity (a-donation)
and/or a decrease in nephelauxetic effect (n-acceptance) with the exception, that
is, of the phosphite, which appears an anomalously stable compound on both
counts.
Further second-order substitutions can take place also in the cobalt series of
compounds
Co(NO)(CO),L
L
+ L -,Co(NO)(CO)L, + CO
>> (C6H,),P
or
Co(NO)(CO),L
+ L -+
Co(NO)(CO),L
+L
L = CH,C(CH,O),P
(30)
Generally, the more basic and more polarizable nucleophiles enter into the
complexes more readily, while, as in the case of the nickel compounds, initial
presence of these same ligands aids the reaction. Steric hindrance in entering or
already present ligands markedly reduces the rates. The best entering groups
appear to be small, polarizable bases in which a-donating power appears to be of
more immediate importance than polarizability, while the most readily labilized
complexes are those of the same types of ligands in which lo^ polarizability
becomes more important. These two criteria are no more than general indications
however. It has been previously mentioned that, in a tetrahedral complex, the
presence of the NO ligand could quite readily reduce any dissociative contribution
relative to associative, and this could be explained quite adequately in terms of
an increase in the M-C bond order; this is supported by IR data with regard to the
C-0 bond order. However, it would not be expected to increase the (nucleophiles)
associative contribution by, in effect, reducing the positive charge upon the metal.
An alternative explanation may be that the presence of polarizable non-labile
B CLASS L I G A N D S :
THE S U B S T I T U T E D C A R B O N Y L S
35
M(CO)sX+L -+ M(C0)4LX+CO
M
Mn
Mn
Mn
Cr
Mo
W
Ref.
14co
130
131
132
107
110
107
(C6HS)JP, CsHSN
14co
1 4 ~ 0
R3P
14co
Mn
Mn
Cr
Mo
W
Br
H
CI, Br, I
cis byridine),
dipyridyl
~~
L, L-L
--f
M(C0)4L2, M(CO),(L-L)-I2 x
Ref.
133
I34
135
136
137
36
v1
z
3
0
z
0
>.
-1
z
0
a
4
u
a
-I
0
w
E
c
i,
0
w
2
I&
0
I
n
z
L,
0
4
z
3
0
c
c
v1
v1
m
3
y1
.-
s-
Y
4
L UM
ru u
IY
uJ
7
N
d
0-
;I
o\
ci
W
m
W
z,
0"
z+
2-1
ReJerences ,up. 52-55
v,
37
38
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
The two-term rate law for substitution reactions of the group VI hexacarb ~ n y l s ' ~has
' been previously mentioned (see p. 29) and it will be useful to
summarize the evidence for associative activation in this case.
i. There is reasonably good agreement between the rate of 14C0 exchange in
the gas phase and the jrirst-order rate of substitution in decalin, suggesting that
this term represents a dissociative reaction.
ii. AH', is significantly higher for Cr than for either Mo or W, and this is in
agreement with the generally observed order of stability for those group VI
compounds which are seven-coordinated.
iii. ASs is positive for the first-order rate, negative for the second-order and these
values are expected for, respectively, dissociative and associative activations.
Substitution in the pentacarbonyl manganese and rhenium compounds
(XM(CO),, where X is formally anionic) is invariably more rapid than in the
M(CO),+ cations. The reactions are complicated by the further replacement
steps but, in the first instance, produce cis Mn(CO),XL at a rate independent of
the nature and concentration of the entering ligand (i.e. first-order) and largely
determined by the nature of X','. Usually, the rate of substitution is very much
faster than the exchange in M(CO),+ and when X is a halogen the rates are
d e m ~ n s t r a b l y ' ~ ~ .the same. Ligands which particularly labilize the CO's are
those of type A, of relatively high polarizing power but low polarizability, that is
the halides and NO3-, while no significant acceleration is noted for the type B
ligands. There is one especially interesting exception, for HMn(C0)5 and
HRe(CO), both undergo extremely rapid I4CO exchange. The same effect is
noticed in HCo(CO), and HFe(CO),+ and it has been suggested'54 that the
extreme labilizing ability of H, which is unexpected since H is an extreme type B
ligand', lies in its being able to take part in an insertion (migration) reaction'53
HMn(CO),
(HCO)Mn(CO),+CO
s (HCO)Mn(CO),
e (HCO)Mn(CO),
(31)
+ A,P
-+
M(CO),(A,P)X-
+ CO
(32)
First-order: M
39
W, Mo > Cr. X
(33)
Br > CI, I
M(CO),LX
(35)
(36)
(M(CO),X), $ c i s
M(CO),LX
- co
cis M(C0)3L,X
(37)
One factor which promotes all reactions is the electronegativity of X(C1 > Br > I),
although an extensive study of reaction (34) has not been carried out. Release of
CO, reaction (37), is greatly accelerated when L is a basic or a N-donorligand,
(n-But),P rather than (C6HS),P and aniline rather than CNC6Hs, (n-ButO),P.
For a given donor atom, the rate increases with the bulk of the remainder of the
ligand. The reactions
Mn(CO),X
+ cis Mn(CO),LX
(or Mn(CO),LLX)
R e f i ~ t i c epp.
s 52-55
40
2 Mn(CO),XL,
undergo
(39)
There is no real indication of the part which the solvent plays i n these reactions.
The intermediate generated in the fast pre-equilibrium (40) may, for example, be
more or less solvated (as also the species M(CO),X). The effects of varying the
solvent are small, however.
In the case of replacement of CO from the group VI carbonyl compounds there
is additional evidence to the effect that the type A ligands labilize CO whereas the
type B d o not, but rather promote a second-order reaction. For the group VII
octahedral compounds there is no strong evidence in favour of an associative
activation step, except when interpretation is obscured by subsequent or concurrent
reaction (but see ref. 146). There is, however, good reason to believe that such
an associative reaction does occur in certain of the group VI compounds.
The rate of replacement of CO by phosphines and phosphites
M (CO)5L+ L
+ cis
M(CO),LL
+ CO
(43)
does not generally differ greatly from that in the unsubstituted carbonyl when
L = R,P, (RO),P or CNC,H5110. When L = halide or pyridine, that is a type
A ligand, the substitution is very much faster135but it is still first-order, independent of concentration and nature of the entering nucleophile. There ist indeed, a
B CLASS LIGANDS:
41
cis Cr(CO),L(N-N)+CO
(44)
-3.2-
-34-
-3.6-
4.0
50
6.0
P Ka
42
I N E R T C O M P L E X E S A N D METAL O R G A N I C C O M P O U N D S
THEORETICAL CONSIDERATIONS
43
(ii) A dissociation of one end of the bidentate ligand, followed by a ratedetermining entry of L, viz.
Alternative (ii) corresponds to the [Re(CO),X], case, equations (41) and (42)
above. However, it was here favoured largely because no second-order term
was observed for the Re(CO),X42 and Re(C0),LX15 substitution. In the case
of Mo(CO),Py, expected to be closely similar to Mo (CO),dipy, a second-order
dependence has been observed.
8. Theoretical considerations
In the final section of this chapter, we shall attempt to give a brief rationalization
of the regularities and peculiarities of the reactions of non-labile complexes which
have been discussed in the previous sections. The theoretical framework in which
the discussion will be conducted is that of molecular orbital theory (MOT).The
MOT is to be preferred to alternative approaches for it allows consideration of
all of the semi-quantitative results of crystal field theory without sacrifice of interest in the bonding system in the complex. In this enterprise we note the apt
remark56: Kinetics is like medicine or linguistics, it is interesting, it is useful,
but it is too early to expect to understand much of it. The electronic theory of
reactivity remains in a fairly primitive state. However, theoretical considerations
may not safely be ignored. They have proved a valuable stimulus to incisive
experiment.
Two remarkably successful generalizations from the preceding pages deserve
attention first of all. Octahedral complexes show a pronounced tendency to react
Re/erciices pp. 52-55
44
THEORETICAL CONSIDERATIONS
45
stand in sharp contrast. The metal p r orbital is part of the 0 bonding system in
the ground state and, as long as there are three or more d electrons the dn orbitals
are filled and not readily available for 0 bonding in the transition state. Orgel
noted several years ago that an associative mechanism would be quite plausible
if there were fewer than three d electrons. So far, there has been no definitive
evidence in support of this suggestion, although there are some indications in the
results of fast reaction kineticists on the behaviour of V(III)58~ When the
ligands can act as strong n acceptors then the situation may become modified.
n donors, that is, halide ions, amines, oxy ligands can only destabilise the dorbitals
of x symmetry. n accepting ligands on the whole may considerably stabilise these,
to a degree which depends markedly upon the matching (or lack of it) of metal
(dx) and ligand (n*) orbitals. If there is good matching, particularly in the cases
of CO and NO, to a less degree perhaps PF,, the filled orbitals will concentrate
into the internuclear regions leaving in the region of the ligand atom a net positive
References p p . 52-55
46
charge. The orbital system of the octahedral B-type complexes should be qualitatively similar to that of the square-planar d8 complexes.
Moving from consideration of general trends to specific phenomena, perhaps
the most fruitful problem for the theoretician of ligand substitution is the remarkable trans labilizing effect encountered in Pt(I1) chemistry. The molecular
orbital theory of this effect developed by Gray'60 serves admirably as a starting
point for a more general molecular orbital theory of the effects of the non-labile
ligands in a complex. If we appeal to the observation that the leaving group, the
entering group and the group trans to the leaving group play similar roles in square
planar substitutions, we may with reason postulate a transition state approaching
a trigonal bipyramid structure. The theoretical problem becomes comparison of
bonding in the square planar ground state and the trigonal bipyramid activated
state.
First the n bonding may be analyzed. Of the four metal valence orbitals involved
in strong n bonding in a square planar complex, only the p orbitals have trans
directional properties. The trans group and the leaving group must share the same
p orbital and a trans ligand with a strong n interaction with the p orbital must
weaken the bonding to the leaving group. Moreover, when the complex is converted
from the square planar form to the activated trigonal bipyramid an additional
p orbital (thep,) is involved in n bonding to the entering, leaving and trans ligands
(see Fig. 13). It follows that the trans ligand which had approximately a halfshare in a metal p orbital in the ground state may have approximately a twothirds share in a metal p orbital in this transition state. The energy difference
between ground state and transition state should be relatively small for good ligand
(n) to metal ( p ) donors located trans to the leaving group. Calcu1ationsl6' have
shown that ligands such as H - , PR, and CH,- have unusually large overlap
integrals with the Pt 6p orbital. It is probably safe to conclude that the large trans
effect of these ligands is a consequence of the n bonding effect described. Other
trans labilizing ligands must also depend for their effectiveness to a large extent
on this effect.
PZ
Fig. 13. Change in the metal p . orbital structure in square- planar substitution.
THEORETICAL CONSIDERATIONS
47
Some ligands may supplement this CT effect with one operating through the n
bonding system. Three d orbitals have proper symmetry for n interaction, xy, zx
and yz. Assuming coordinates chosen as before, it is clear that the x z and yz
interact only with a pair of trans disposed ligands in the square planar ground
state. For example, the x z orbital may be shared between the leaving and trans
ligands. In the trigonal bipyramid, four d orbitals are of n symmetry (xz, yz,
x2-yz and x y ) and all are shared in n interaction with ligands in the trigonal
plane, viz. the trans, entering and leaving ligands. NOW,in d 8 complexes (all of
the square planar cases we have discussed) all of the n antibonding orbitals derived
from the metal d orbitals are filled. In this case, it is a great advantage for the
trans ligand to have empty, reasonably low-lying ( n ) orbitals which can contribute
to delocalization of the charge in the antibonding n orbitals as a new ligand (the
entering ligand) is attached at the metal. Thus the effect of a good n acceptor
trans ligand is to lower the activation energy for the reaction. Table 16 gives
T A B L E 16
R E L A T I V E U-
A N D Z-trUns E F F F E C T S O F L l G A N D S
> PR3 > --SCN- > I-, CH3-, CO, CN- > Br- > C1- > NH3 > OH-
-NOz-
> -SCN- > I- > Br- > C1- > NH3 > OH-
theoretical estimates of the CT and n trans effect orders as derived from overlap
integral calculations16'. It can be seen from comparison of these orders with the
experimental order of trans effect that both (T and n effects are important. Earlier
emphasis had been placed on n effects but it is important to notice not only that
a very large part of the experimental trans effect order can be discussed using the
CT order alone, but that some ligands (e.g. H-) absolutely require consideration
of the CT effect.
The MOT discussion of the trans effect immediately illuminates the part played
by entering and leaving groups. The ligand which functions effectively in the trans
position should do so also in the other two positions in the trigonal plane; the
entering and the leaving positions. There should be a parallel between the trans
effect series and both the order of effectiveness (nucleophilicity) of entering groups
and the order of inertness of leaving groups, and these correlations are, of course,
well known.
Now, consider leaving group orders in general. The order of inertness at Pt(I1)
(which corresponds to the theoretically comprehensible trans effect series) is
largely opposite to the order of ligands in the well-known spectrochemical seriesL6'.
References pp. 52-55
48
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
Those ligands which are strong field i n the sense of producing a large splitting
between the dn antibonding (xz, y z , x y ) and d a antibonding (x2-y, z) orbitals
of an octahedral complex are frequently ones readily displaced from square
planar complexes of Pt(I1). This circumstance is the opposite of that observed
in the octahedral complexes of Co(1II) and Cr(II1). In these latter two cases the
ligands high in the spectrochemical series are the ones which are least readily
replaced.
The spectrochemical series reflects the splitting of molecular orbitals derived
from the metal d orbitals and a large ligand field splitting is expected in the event
that strong a bonding occurs between metal d and ligand a orbitals. However,
strong a bonding, ligand to metal p orbital, does not make a direct contribution
to the ligand field splitting. In the n bonding framework of the complex the most
important effects are directly reflected in the ligand field splitting. Interaction of
filled metal dn orbitals with lone pair electrons on the ligands in orbitals of n
symmetry makes the dn orbitals antibonding. As this interaction increases in
importance, the ligand field splitting decreases. Conversely, for ligands with lowlying empty TC orbitals (e.g. the n* levels of CO and CN-) the interaction with
the dn orbitals of the metal lowers these levels and increases the ligand field splitting. We can expect, then, that this easily accessible spectroscopic parameter might
provide a general guide to the role of a ligand in d orbital bonding of both a
and n types but little direct information about the important matter of a bonding
involving s a n d p orbitals. More detailed analyses of optical and magnetic resonance spectra promise parameters offering more direct guidance concerning the role
of the s and p metal orbitals. Some recent work is suggestive124*162-164.
Returning to the leaving ligand orders, that order observed for the third transition series metal, Pt(II), could be explained on the hypothesis that changes in a
bonding to metal p orbitals are more important than changes in a bonding to d
orbitals as the leaving group is changed (this hypothesis is implicit in the trans
effect theory). Correlation of lability at Cr(II1) and Co(II1) centres with the
spectrochemical series suggests importance of d orbital a bonding for the lighrer
first transition series metals. Only one later period metal octahedral system has
been studied extensively enough for a definite statement concerning leaving group
orders. In the Rh(1II) complexes the lability order C1- > Br- > I - has been
established6. This is opposite to the Co(II1) order and opposite to that expected
from the ligand field splitting as discussed above. It does correspond, however,
to the lability order for the three ligands at Pt(I1) centres and suggests that this
second transition series metal reflects changes in a binding through metal p orbitals
in its lability order.
As the trans effect theory indicates, there should be some relationship between
lability of a ligand and its role as a labilizing group in another position in a
complex. In an octahedral complex reacting via a dissociative mode of activation,
the transition state has five strongly bound ligands. This state will be stabilized
THEORETICAL CONSIDERATIONS
49
if there should be present within the complex a group which binds strongly with
orbitals formerly utilized by the leaving group. That is, in octahedral as in square
planar complexes, a non-labile group should function to labilize other groups.
In a very rough sense the data given above on the systems Coen,ACl+ where A
is a variable group influencing the rate of loss of CI- could be construed to agree
with this proposition. The labilizing order was
CJ
50
I N E R T COMPLEXES A N D METAL O R G A N I C C O M P O U N D S
Fig. 14. The overlap of (1igand)p orbital with avacant cis (meta1)p orbital without rearrangement.
Fig. 15. The overlap of (ligand) p orbital with a vacant orbital upon rearrangement of the rrans
compound to a trigonal bipyramid.
THEORETICAL CONSIDERATIONS
51
52
give rise to first-order kinetics if the solvent is a good nucleophile and secondorder kinetics if the entering ligand should be
M-C-O+S
M-C-0
I
M-C-0
I
S
+ B + M-I3 +CO +S
(slow)
(49)
(fast)
(50)
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REFERENCES
55
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170 D. E. MORRIS
Chapter 2
1. Introduction
This chapter attempts to survey the studies which have been made on the various
electron transfer reactions, occurring between metal ions (of the same element)
in homogeneous solution. These reactions include the types known as exchange
reactions
c o 3 ++ c o 2 + + c o 2 ++ c o 3 +
NpO;++NpO:
Mn(CN)i- +Mn(CN):-
+ NpO;+NpO:'
+ Mn(CN):- + Mn(CN)i-
+ 2 Np(1V)
Cr(VI)+3 Cr(I1)
=4
Cr(II1)
+ NH3
+c o 2
+ Fe(II)X+Fe(III)Y
+ IrC1;- + IrBri+ c o 3 + COCI+
+
The latter are often included with the exchange reaction type. Both inner- and
INT RO DUCT I ON
57
[X][Y]
CXI+[Yl
.-0.693 - -In
t+
(1 - F ) . -~
[X][Y]
t
[XI + CYI
where X and Y are the two exchanging species. The rates of exchange obtained
for a wide variety of conditions are then used to obtain the rate law, rate coefficient and mechanism in the usual manner. In some systems non-linear McKay
plots have been found and a modified treatment of exchange data has to be
employed. Separation of the two oxidation states of the metal ion can be achieved
using the physical methods of ion migration, ion exchange, diffusion, solvent
extraction, and various chemical methods - usually involving precipitation of one
of the exchanging species. The possibility of separation induced exchange, which
can lead to erroneous results, is usually investigated and corrections applied,
if necessary, to the exchange data. More than one separation method should, if
possible, be used.
Exchange reactions can be sometimes investigated by the techniques of polarimetry, nuclear magnetic resonance and electron spin resonance. The optical
activity method requires polarimetric measurements on the rate of racemization
in mixtures of d-X (or I-X) and I-Y (or d-Y).
The reactions
+ d-Y + I-X
d-X + I-X
I-Y + d-Y
d-X + I-Y
occur. The various kinetic possibilities resulting have been observed and discussed
in papers by Eichler and Wahl' and Im and B u ~ c h ~The
, ~ . nuclear magnetic
resonance method requires measurements on a suitable spectral line (either proton
or metal resonance). From either the position or the broadening, brought about
References pp. 142-152
58
I O N S O F SAME M E T A L I N D I F F E R E N T O X I D A T I O N S T A T E S
CU(I1) A N D CU(1)
McConnell and Weaver, using the NMR line width method, have obtained a
value for the observed rate coefficient, for the reaction in 12 M hydrochloric acid
media, of 5 x lo7 1.mole-.sec-. The width of the 63Cu NMR line from copper(1)
(- 1 M ) was observed in the presence of copper(I1)
to lo- M ) . In this
media the exchanging species are probably C U C ~ , ~and
CuCl,-. Optical
interaction effects have been observed in mixtures of Cu(1) and Cu(I1) in chloride
media.
2.2
Ag(I1) A N D Ag(1)
Gordon and Wahl have used the radioisotope OAg as a tracer for a study of
the exchange of silver between Ag(I1) and Ag(1) in acidic media. The precipitation
of Ag(phen)2(C104)2,brought about by the addition of o-phenanthroline, formed
the basis of the separation method. The experimental data were obtained using a
COPPER, S I L V E R A N D
59
GOLD
flow apparatus with reaction times of < 10 sec. Owing to the instability of silver(TI), media 6 M in H + and temperatures in the range - 14.8 to 11.4 "C were
employed. From measurements of the half-times (t,) and the generalised expression
where a and b are orders of the reaction with respect to Ag(1) and Ag(II), a rate
law
rate
~,,,[A~(II)]~
was obtained. The value of kobs (0.2 "C) for media 5.87 M in HC104 was 1020
].mole-'.set-'. An Arrhenius plot led to an activation energy of 12.5 kcal.mole-'
k'[Ag(II)]2/[H+]4
2 Ag(OH),"-")+
2.3
Au(II1)
AND
Au(1)
Under conditions where the dismutation reaction is slow the exchange between
Au(II1) and Au(I) has been shown to proceed at a measurable rate; at 0 "C in
0.09 M HCl, an exchange half-time of about 2 min was observed. The isotopic
method ("*Au) and a separation method based on the precipitation of dipyridine
-chloroaurate(III) was used to obtain data. An acceleration in the exchange rate
was observed as the HCI concentration was increased'.
60
2.4
Au(II1)
AND
Au(I1)
No direct studies have been made on this exchange system, but Rich and Taube'
have been able to propose a limit of > 1.7 x lo6 I.mole-'.sec-' at 0 "C for the
rate coefficient k i of the reaction
2.5
THE DISPROPORTIONATION OF
in the presence of
AU(I1)
A limit has been proposed by Rich and Taube' for the rate coefficient k ; of the
process
2A~(II)
A ~ ( I+) A ~ ( I I I )
at O "C.
3. Mercury
3.1
Hg(I1)
P R O P O R T I O NATION R E A C T I O N O F
AND
Hg(1);
T H E DIS-
Hg(11)
The earliest reported studies on the exchange, by King', and Haissinsky and
Cottin2, utilised the isotopic method (205* '03Hg) and showed the rapid nature
of the process. Complete exchange was observed within 2 min at room temperature
in acidic nitrate media2. Similar results were obtained with acidic perchlorate
media'. The separation methods used the insolubility of Hg(1) as (u)chloride',',
( b ) chromate' and ( c ) sulphate'.
Wolfgang and Dodson3 in a further study suggested a method of separation
using the picrolonic acid precipitation of Hg(1). In perchlorate media even with
reactant concentrations as low as lo-' M , complete exchange was always observed
by these workers, except in the presence of added CN- (- [Hg(II)]) when the
kinetics could be examined. With reactant concentrations in the ranges Hg(1)
6x
to 7 x lo-' M , and Hg(I1)
1.6 x
M the rate law
to 1.6 x
found was
N
61
MERCURY
3 . 2 10'
~ sec-' at 25 "C.
and have calculated a theoretical rate coefficient of
In the presence of cyanide, however, a new rate -determining step, involving a
neutral Hg(I1)-CN complex, possibly
Hg;++HgCN(C104)
is present. King4 and Adamson' have pointed out that the equilibria
Hg2++CN-
+ HgCN'
and
Hg2++ HgCN'
+ HgCN' + Hg2+
must not be rapid for the above mechanisms to be valid, and the observed zerotime exchange should be related to the concentration of free Hg2+.
Wolfgang and Dodson6 have since made a study of the exchange reaction
between H g 2 + and HgCN+ using 203Hg and 10; precipitation of the species
Hg2+.They have proposed a mechanism involving the steps
Hgz+ HgCN'
Hg( CN),
--*
HgCN'
+ Hg2'
ki
+ Hg2 +
HgCN' + HgCN
+
k2
(K)
to account for the experimental observations on the slow exchange. A value for
the equilibrium constant K of 20 at 25 "C has been obtained. With the aid of this
value of K, it was found possible to calculate the zero-time exchange (Z,) mentioned
previously. Good agreement was obtained between the calculated and observed
values of Z , . The rate coefficients k , and k , have values (at 0 "C, p = 0.12 M )
of 1.7 x
and 8.3 x
I.mole-'.set-', respectively, both activation energies
being 17 kcal.mole-'. For the exchange HgCN+-Hg(I), a rate coefficient (0 " C )
References pp. 142-152
62
of 7.0 x
l.mole-'.sec-'
and activation entropy of -18 cal.deg-'.mole-'
have been calculated.
Peschanski', during the course of a further study on this exchange in the
presence of cyanide, has obtained results which are in fair agreement with those
above.
3.2
Hg(I1)
AND
Hg(1)
IN
N 0 N-A QU E O U S M E D I A
Peschanski', using the isotopic method (z O'Hg), has found complete exchange
(0 "C) in methanol and various other non-aqueous media. The separation methods
used were, (u) paper and column chromatography, ( b ) paper electrophoresis, and
(c) precipitation of Hg(1) with chloride. In the presence of cyanide ions, however,
less than complete exchange could be observed. Zero-time exchange was again
found to vary in the same manner as for aqueous media. Similar effects were
observed in the presence of chloride ions.
4. Thallium
4.1
T H E E X C H A N G E R E A C T I O N B E T W E E N TI(II1) A N D
Tl(1)
Although attempts have been made to study this reaction using ThC as an indicator'P2, the stability of ThC has restricted these investigations. In 1948 the
production of
z06T1enabled more detailed studies to be made by Harbottle
and Dodson3 and by Prestwood and Wah14. In preliminary reports, these authors
presented data for the exchange in perchloric3, 4, hydrochloric3 and nitric4 acid
media, obtained using separation methods involving precipitation of (u ) TI(1)
as chromate3 or bromide4 and (b) Tl(II1) as hydroxide4. A rate law
' 0 4 3
rate
kobs[Tl(IIl)][Tl(I)]
was observed for each of the above three media. In 0.4 M HCIO, kobs (49.5 " c )
has a value of 5.6 x
l.mole-'.sec-' and an associated activation energy3 of
12 kcal.mole-'.
Prestwood and Wahls, in a report of a more detailed study conducted at an
ionic strength of 3.68 M (ClO,-) and temperatures in the range 10 to 50 "C, have
presented results consistent with a more complicated rate expression
rate
( k , k;[H+]-')[TI(III)][TI(I)]
63
THALLIUM
(plots of kobsversus [H+]-' were linear with a positive intercept). This was interpreted in terms of two exchange pathways (rate coefficients k, and k,), viz.
TI3++H,O
+ TIOH'+
+H+
K,
TIOH,+ + ~ i -%
+
with k , > k , and K, having a small value. The values of k, and k;(= k,K,)
at 25 "C are 4.3 x lo-' I.mole-l.sec-' and 2 x 10-6sec-', respectively, with corresponding activation energies of 17.6 and 10.3 kcal.mole-'. The thallium concentration employed in this work was 5 x
to 5 x lo-, M.
Harbottle and Dodson6, have presented data obtained during a study of the
exchange in perchlorate media, under constant high ionic strength conditions
(p = 6.0 M ) . From results obtained with Tl(II1) 1.4 x
to 1.7 x lo-, M ,
TI(1) 1 x
to 2 x
M and H + 3 x lo-' to 6.0 M , it was concluded that
only the step defined by k, was operative and the extent of hydrolysis was large
(plots of k:,: versus [H'] were linear with a positive intercept). On this basis, a
value fork; (25 "C) of 2.6 x 10- I.mole-'.sec-' and an associated activation energy
and entropy of 14.7 kcal.mole-' and - 32 cal.deg-'.mole-' were calculated.
Dodson', in an attempt to resolve the difference in interpretation, carried out
further experiments at various acidities and constant ionic strengths at 50 "C.
He was able to show that the data given by Prestwood and Wahl' and by Harbottle
and Dodson6 were in good agreement with his own, and the additional data he
obtained at p = 2.0, 4.0 and 6.0 M could be interpreted in terms of exchange via
T10H2+ and Tl'. The rate was found to decrease with increasing ionic strength
and a revised activation energy for the process involving k , of 16 kcal.mole-'
was given.
In 1955 Rossotti', utilising the data available at that time on the hydrolysis of
TI(II1)' and Tl(1)' was able to show that the interpretation given by Prestwood
and Wah15 of their data (p = 3.68 M ) was feasible. Estimates were made of k,
and k, (25 "C, p = 3.68 M ) of 4.28 x lo-' and 3.4 x
I.mole-'.sec-', respectively.
In 1961, Roig and Dodson" carried out a further study of the exchange in
perchlorate media under identical conditions (25 "C, p = 3.0 M ) to those in the
Tl(II1) hydrolysis study'. The isotope 'TI was used, with a separation procedure
based on extracting Tl(II1) from reaction mixtures with either methyl isobutyl
ketone or diethyl ether. The exchange was examined in the absence of light,
and a correction procedure to eliminate the catalytic effects of traces of chloride
ions was used since Tl(II1) concentrations of
M were necessary at the
very low acidities employed. Using the known values of the first and second
hydrolysis constants of TI(II1) ( K , and K 3 )
'
.64
T10H2
+ H 2 0 + Tl(0H); +H
K3
the values of the rate coefficients k , , k,, and k , for the steps
TI OH^+ +TI+ -%
T~(oH): +TI+ -%
were calculated to be 7.0 x 10- 5, 2.5 x
and < 2.8 x l o p 5 l.mole-'.sec-',
respectively. Activation parameters obtained for the first step ( k , )were E, = 17.4
kcal.mole-' and A S f = -21 cal.deg-'.mole-'.
Gilks and Waind12 have examined the exchange in heavy water and have found
the exchange rate to be about two-thirds of that in ordinary water. A similar
dependence, at constant ionic strength, on D + as on H f was observed and the
rate of exchange was found to decrease as the ionic strength was increased. The
isotope O4TI and chloroplatinate precipitation of TI(1) was employed in this
study. Waind', has discussed the role of water molecules in these exchange reactions.
The accelerating effect of nitrate ions (over the range lo-' to 1.0 M , at p = 3.68
M ) has also been studied5. An additional pathway involving the species TlN032+,
viz.
~ 1 , ++NO,
+ TINO:+
K4
k4
TINO;++TI+ ---+
was thought to occur at [NO;] < 0.4 M . At higher [NO;], pathways involving
'TI(N0,): were also thought likely. The full rate law found by Prestwood and
Wahl' was
rate
( k , k;[H+]-'
+ k~[NO,])[Tl(III)][Tl(I)]
65
THALLIUM
k3
+T1' -%
TICIT + TICiiTlCI,
k7
--+
+TICIi- %-
and it was concluded that k , and k , were less than k , or k , and that k , and k 8
were larger than k , or k,. For the exchange in 0.4 M HCI ( p = 6.0 M ) at temperatures 31.8 to 41.8 "C, an overall activation energy 29.6 kcal.mole-' was found.
Gilks et a l l 4 have since confirmed the above observations and have found a
similar effect to operate in deuterated solvent. At high [Cl-] the rate in D,O is
equal to that in H,O.
Challenger and Masters" have made some observations on the exchange in
to 1.7 x
M
0.4 M H,S04 solution using concentrations of Tl(II1) 8.5 x
and of Tl(1) 1.7 x
to 8.5 x
M , with the tracer ,O4TI and a chloroplatinate precipitation of TI(1). The rate law
rate
0.0345 + k;[H+]'[SO:-]
[H']'
+ k~o[H']~[SO~-~3[T1(III)][Tl(I)]
+ K,[H'] + K 2 K 3 + K,[H']'[SO:-](l+
KIO[SO:-])
66
and have numerical values (25 "C) of 0.012 and 0.2, respectively. Measurements
on the exchange at other temperatures were made and the exchange rate was
found to be dependent on the ionic strength.
In a further study, Brubaker et aI.l7 have reported on the effects of the addition
of chloride ion to the sulphate exchange system at virtually constant ionic strength
(3.68 M ) , sulphate and hydrogen-ion concentrations. For the concentration ratio
[CI-]/[Tl(III)] of 9 . 2 ~lo-' to 9.5 at 24.9 "C results analogous to the effect
observed in perchlorate media6 were obtained. The minimum in the rate corresponded to a ratio of
2.5. Results were also presented for the conditions,
constant [CI-] and variable [SO:-] and [H'] ( p = 3.68 M ) . Brubaker et a / . 1 7
have suggested that the exchange paths most likely to occur in sulphate media are
TISO: +T1+
TI(S0,);
+ TISO;
kto
for which activated complexes involving sulphate bridges are likely. Wiles", has
made a further study of this system in the presence of small amounts of added
sulphate and has observed a first order dependence on this anion. Results at higher
concentrations of added sulphate agree with those mentioned previously. A
sulphate bridge activated state was again proposed.
The effect of the addition of cyanide to the exchange reaction in perchlorate
media has been reported by Penna-Franca and DodsonL9.An effect similar to the
addition of chloride was observed with a minimum occurring at a ratio [CN-I/
[Tl(III)] of 3.5 ( p = 0.5 M , 30 "C). It was concluded that the pathways involving
T1+ and TlCN2+ or TI(CN)l are slow whereas the pathways involving T1+ or
cyanide complexes of TI(1) [TlCN, TI(CN);, Tl(CN):-] and TI(CN), or
TI(CN); are more rapid.
Dodson et ~ 1 . ~have
'
also studied in detail the effect of added bromide on the
exchange reaction using precipitation and extraction separations and 04Tl and
202T1as indicators. The variation in the rate of exchange was found to be governed
by the law
rate
k,[T13+][T1+]+ k2[T10H2+][TI+]+k,,[TIBr~]
ki4
-+
THALLIUM
67
the possibility of a symmetrical activated complex was suggested and the steps
having rate coefficients k l i and k , , were proposed as
TlBr:
%T1
TIBr,
%TI
+ Br,
+ Br, + Br-
Brubaker and Andrade have made a study of the effects of acetic and succinic
acids on the exchange; a reduction in the exchange rate was observed.
Some conclusions on the exchange reaction have been made as a result of studies
on the redox reactions between Tl(1) and Ce(TV) and between V(IV) and
Tl(III)23. Gryder and Dorfrnan, have pointed out that TI(II) cannot be invoked
for both the exchange between Tl(II1) and Tl(I) and the reaction of Tl(I) with
Ce(IV) which is slower than the exchange. S y k e ~ has
, ~ shown, on the basis of a
mechanism proposed for the reaction between TI(II1) and V(IV), that Tl(I1)
cannot be involved in the exchange reaction as this would lead to Tl(I) accelerating the above redox reaction. It is interesting to note that as long ago as 1949,
McConnell and DavidsonZ5reported the lack of interaction absorbance phenomenon between TI(II1) and Tl(1). This might be expected if Tl(I1) was absent.
Radiation-induced exchange reactions which are more rapid than the thermal
exchange reactions are thought to involve TI(I1) 5 * 2 6 .
Challenger and Masters have made a detailed study ot the X-ray-induced
exchange reaction in 0.4 M H,S04 solution, over the ranges TI(II1) 2 x lo- to
7 x lo-, M a n d TI(1) 1.4 x
M , with X-ray intensities ( I ) 1.7 x l o i 9
to 7 x
to 4 x 10, eV.l-.min-. The rate law observed was
rate
k,,,[TI(I11)]0510.67
+ TI(Il)+OH-
Tl(III)+H
+ TI(II)+HS
TI(I1) + Tl(1)
TI(II)+TI(IZI)
2 TI(I1)
+ exchange
-+
exchange
+ Tlf+Tl3+
68
I O N S O F SAME M E T A L I N D I F F E R E N T O X I D A T I O N S T A T E S
mechanism
~ i ~ + ++ T hI ~ + + O H + H +
T 1 0 H Z f + h v + T12++OH
T I + + O H .+ TI'++OHTi3++T1'+
T1'
+T12
exchange
exchange
2 TP+ -+ TI++ ~ 1 3 +
The value of the ratio k,,/k,, (at 25 "C) is 1.2 (see also Stranks and Yandel12*).
Sn(IV)
AND
Sn(I1)
IN AQUEOUS
MEDIA
In aqueous solution this exchange has been studied, in the absence of oxygen,
in chloride'*' and sulphate3 media. The isotope 'I3Sn was used as the indicator
and the separation of Sn(IV) and Sn(I1) was achieved by the formation of the
insoluble salts caesium hexachlorostannate(1V)' - 3 and stannous oxalate3.
Davidson et al.' have investigated the exchange reaction in chloride media,
where the rate law obeyed is
rate
k,,,[Sn(IV)][Sn(II)]
69
strongly) from a high intensity source. Uranyl oxalate, which has similar absorption characteristics to the complex (Sn,Cl?;), was used for the actinometer.
Quantum yields for the process were found to be
0.2. It was concluded that
exchange occurs uiu an activated complex which is unsymmetrical.
The exchange in sulphate media, where a similar rate law is obeyed and the
exchange rate is slower than in chloride media, has been studied by Gordon and
Brubaker3. At p = 4.98 M , kobs (25 "C, [ H + ] = 3.99 M and [SO:-] = 0.99 M )
has a value 1.7 x
l.mole-'.sec-'. The effect of variation in the hydrogen ion
(3.30 to 5.0 M ) and sulphate ion (0.70 to 1.40 M )concentrations at constant ionic
strength (LiClO, and Li,SO,) was found to conform to a relationship
suggesting the involvement of two exchange pathways. The possible steps proposed
were
SnOH' -+
SnO(S0,):-
Sn(OH)(SCl,); +Sn(OH)SO,
Sn(OH),SO,+Sn(OH)SO,
-+
-+
The main species of Sn(IV) and Sn(I1) in sulphate media were thought to be
SnOH' and Sn(S0,)2. The overall activation energy (over the range 25-50 "C, in
3.0 M H2S04 with p = 4.98 M ) was calculated as 19 kcal.mole-'.
The addition of chloride ion was found to increase the rate of reaction and, if
present in the range 0-0.5 M , to lead to abnormal orders with respect to Sn(IV)
and Sn(I1). Above 0.5 M C1- a rate law
rate
ko,,[Sn(IV)][Sn(II)][C1-]
was concluded to occur3. At high temperatures, McKay plots were found to show
deviations from linearity for exchange in presence or absence of chloride, suggesting more than one exchange path is operative.
Interaction absorbance data have also been reported by Gordon and Brubaker3
for mixtures of Sn(IV) and Sn(I1) in sulphate media. Exchange uiu interaction
dimers, Sn(IV)-Sn(II), seems likely.
References p p . 142-152
70
5.2 T H E E X C H A N G E
REACTION BETWEEN
Sn(IV)
AND
Sn(II)
I N NON-
AQUEOUS MEDIA
The exchange of I2'Sn between SnCI, and SnCl, in anhydrous methanol and
ethanol in the absence of oxygen has been investigated by Meyer e l ul.'.'. From
the linearity of plots o f t + uersus the inverse of the total tin concentration, which
was varied over the range
4 x lo-* to
3 x lo-' M , a rate law
rate = k,,,[Sn(IV)][Sn(II)]
was suggested. The kinetic parameters found were: (u) methanol solution';
kobs (33 "C) 7.12 x lo-' l.mole-'.sec-', activation energy (over range 33-47 "C)
21 kcal.mole-' and activation entropy - 11.5 cal.deg-'.mole-';
(b) ethanol
solution2; kobs (25 "C) 6.03 x lo-' I.mole-'.sec-', activation energy (over the
range 25-42 "C) 23.7 kcal.mole-' and activation entropy -0.4 cal.deg-'.mole-'.
The separation of Sn(I1) and Sn(IV) was based on the insolubility of the oxalate
of Sn(1I) in alcoholic media.
The mechanism proposed for ethanol media, which.is similar to that for
aqueous media, was
SnCI,
or SnCl:
+ SnCl, + Sn2c16
+SnCl, + Sn2C16
rapid
rapid
5.3 THE
Pb(1V)
AND
Pb(I1)
I N AQUEOUS
MEDIA
5.4
71
ARSENIC A N D ANTIMONY
Pb(1V)
AND
Pb(I1)
I N NON-
A Q U E O U S MEDIA
Exchange between Pb(W) and Pb(I1) as acetates in acetic acid solution has been
observed' using the isotopic method (Th B). However, Evans et ul. ', using Ra D
to lo-' M ,
as the indicator, with reactant concentrations in the range
concluded that there was no exchange at 80 "C in a period of several hours. The
reaction was carried out in a dry-box system and anhydrous acetic acid was used
as the solvent. Three separation procedures were used: (u) conversion of the lead
species to the plumbate and plumbite anions, followed by precipitation of barium
plumbate (a method used previously for the aqueous exchange system), (6)
precipitation of lead(1V) as the dioxide, and ( c ) rapid cooling and consequent
crystallisation of the lead(1V). Method (b) was reported to bring about induced
exchange.
THE E X C H A N G E R E A C T I O N
BETWEEN
AS(V)
AND
AS(I1I)
6.2
T H E E X C H A N G E REACTION BETWEEN
Sb(V)
AND
Sb(II1)
I N AQUEOUS
MEDIA
'
SbCl;
+ SbCI, + Sb,Cl:;
Observations on Sb(V) solutions, in the same media, have shown that the absorbance is dependent upon (u) time, and ( b )hydrochloric acid concentration' - 3 .
This has been shown to be due to reactions
SbCI,+x H,O
References p p . 142-152
+ SbC1,-,(OH),+x
H + + x C1-
72
rate
k'[Sb(111)]0'6[Sb(V)]'.l [HfI4[C1-l9
was found to be consistent with the experimental data. Concentrations were varied
over the ranges: Sb(1II) = Sb(V), 8 x
to 4 x
M ; C1-, 5.4 to 6.1 M;
li3.'.
H', 4.7 to 6.1 M . The value of k' (25 "C) was calculated as 2 . 4 ~
mole 3.7.sec-' with the overall activation energy
27 kcal.mole-'.
Neumann and Brown6, have suggested that the only species of Sb(V) that can
exchange with Sb(II1) is the ion SbCI,. Numerous reasons for this assumption
have been discussed. These authors have shown that the observed half-times of
exchange in media 6-12 M with respect to HCl'-' can be satisfactorily predicted
on the basis of a mechanism
SbCI;
(2)
where B represents species of Sb(V) which are present in equilibrium with SbC16-,
in which either reaction (1) or reaction (2) can be rate determining depending on
the conditions. In concentrated HCI the order of the reaction with respect to
[Sb(111)] was demonstrated to be unity. Various transition states, involving
chloride bridges, have been suggested6.
Cheek et al. ', have since published data for HCI media showing ( a )a maximum
exchange rate ( 9 M HCI), (b) non-linear exchange-time plots ( - 7 M HCI),
(c) an order in Sb(l1I) of 1.0 (1 1.8 M HCI) and 0.9 (9.5 M HCI), ( d ) an activation
energy which depends on the acidity, and ( e ) details of rate dependence upon
chloride and hydrogen ion concentrations. The observed rate coefficient (25 "C)
and activation energy are 5.7 x lo-, I.mole-'.sec-' and 17.2 kcal.mole-', respectively, for media 11.8 M in HCI. These authors conclude that exchange occurs
between Sb(1II) and two Sb(V) species which are present in slow equilibrium with
each other.
Kambara et ~ l have
. ~reported data for the exchange in media 0.8 to 4.0 M
with respect to HCI, the highest rate being observed at 2.0 M HCI. Added lithium
chloride and the previous treatment of reactants was also found to affect the rate
of exchange.
Bonner and Goishi" have reviewed the complex exchange kinetics and the
73
hydrolysis reactions of Sb(V), and have made a further study of the exchange in
the region
7 M HCI. The exchange data were treated according to a reaction
scheme in which Sb(II1) could exchange with two forms of Sb(V) which are
themselves in a slowly established hydrolysis equilibrium. For a medium 7.04 M
in HCl, the values of k , and k, the rate coefficients for exchange between Sb(II1)
and the two forms of Sb(V), are 2.32 x lo-' I.mole-l.sec-' and 2 6.7 x lo-' 1.
mole-'.sec-', respectively, at 24.95 "C. Energy of activation for the step with
coefficient k , is 17.2 kcal.mole-', with an entropy of activation of - 10.3 cal.deg-I.
mole-'. Some evidence was also obtained for a photochemical effect which only
shows itself at low [Sb(III)]. Bonner and Goishi have also pointed out that the
interaction dime? and the Sb(II1)-catalysed hydrolysis of Sb(V)4 must have unsymmetrical activated complexes, which are different from each other and from
the exchange activated complex.
Turco and Faroane" and Turco" have investigated the effect of bromide ions
on the Sb(V)-Sb(II1) exchange reaction in 3.15 M HCI media and have found a
complex rate law"
rate
k,,,[Sb(V)]
1~1[Sb(III)]o~15[H+]4~2[Br-]3~5
which was attributed to the exchange occurring via two pathways, one independent
of Sb(II1) (the main pathway) and one involving both Sb(V) and Sb(II1). A
simplified rate law
rate
k;[Sb(V)]
+ k;[Sb(V)][Sb(III)]
was also found to fit the experimental data. At low [Sb(III)] and [Br-1 (7.5 x
to 1 x lo-' M and 1.0 M, respectively), only the first term in the above rate law
sec-'. The step postulated
was observed. The value of kj (22 "C) is 1.3 x
to account for this exchange was
Sb(V)Br,(X)
+ Sb(III)Bq,,-,)(X)+
Br,
74
6.3
Sb(V)
AND
Sb(II1)
I N NoN-
AQUEOUS MEDIA
Barker and Kahn' have made a detailed study of the exchange in carbon
tetrachloride media using the isotope 124Sbto label the Sb(II1) species. The reaction was carried out in sealed ampoules covered with A1 foil in the presence of an
atmosphere of He or Ar gas. The separation method used involved complexing
the Sb(V) with fluoride (brought about by addition of ethanol, HCl and HF)
followed by precipitation of the Sb(II1) with H2S and finally addition of boric acid
and HCI, removal of the CCI,, and treatment with H2S to remove the Sb(V).
Zero-time exchange was
5 %.
Concentration ranges employed in this study were Sb(III), 1.5 x lo-' to
M , the chloride salts being
to 6 . 7 ~
1 . 2 lo-'
~
M , and Sb(V), 5 . 5 ~
used. The experimental data led to a rate law
N
rate = k,[SbCl,]
+ k;[SbC1,]2[SbC1,]
+ SbCl, + C12
ki
+ SbzCI,,
(rapid)
SbzClIo + SbCl, + SbSbzC113
(rapid)
SbSb2C113 SbCI, + SbSbCllo
2 SbCl,
k2
--t
was proposed to account for these observations. A suggestion was made concerning
the structure of the complex (SbSb,CI,,).
Price and Brubaker'9 have examined the catalytic effect of hydrogen chloride
on the rate of exchange in the same media. Over a range of HCl concentrations,
M , the data obtained was consistent with a rate law
6 x lo-, to 6 x
+ SbCI,
k3
--f
75
TRANSITION METALS
It is of interest to note that the 3 2 P exchange between PCl, and PCI, also
proceeds, in CC14 media, via a dissociation step4
k4
PCl, =$ PCl,
+ C12
6.4
THE
Sb(III)-CATALYSED
HYDROLYSIS OF
Sb(V)
Te(V1) A N D Te(1V)
The exchange between the acids H6Te06 and H2Te0, has been investigated
using the radioisotopes 12'Te, '29Te' and I3'Te2. No exchange was detected over
periods of many hours at 95 "C in acidic chloride or perchlorate solution up to
6 M with respect to H+. Separation was achieved using the precipitation of the
tellurite anion which occurs at pH 4.20.
8. Transition metals
8.1
King and Garner', using the isotopic method ("*V), made an attempt to study
this exchange reaction in both aqueous sulphate and perchlorate media. The
separation methods tried were (a) ion exchange, and ( b ) precipitation of the
vanadium (111) with ammonia, after first complexing the vanadium (11) in
aqueous ethanol as V(dipy):+. Complete exchange was observed within minutes
lo-' M .
at 2"C, in the absence of oxygen, with reactant concentrations of
Evidence was obtained that the exchange of V3+ with V(dipy):+ is slow.
76
exist. Analysis c,f the exchange data obtained at an ionic strength 2.0 M led to
I.mole-'.sec-'
and 3 . 5 ~
sec-',
values of k , and k2K2 of 1 . 0 2 ~
respectively, where K2 refers to
V3++H20
+ VOH2+H+
K2
Furman and Garner' have measured the rate of this exchange reaction in
aqueous perchlorate media using the isotope 48V as indicator. Numerous methods
77
T R A N S I T I O N METALS
of separation were tried, kinetic data being obtained using an ion exchange
technique. The rate law obeyed, over the concentrations range V(IV), 1 x lo-'
M , and in the absence of oxygen,
M , and V(III), 8 x
to 5 x
to 5x
was
rate
kobs[V(IV)][V(III)]
The observed rate coefficient kobswas found to be dependent on the hydrogenion concentration (plots of kobsversus [H+]-' were linear passing through the
origin), suggesting that only an acid dependent pathway for exchange occurs.
The pathway suggested was
VOz
+ VOH2+ -%
V3++Hz0
+ VOH2++Hf
Kl
78
2 V(V)
(V(V)),
+( V ) ) ,
2 V0:+2
H+
+V , O ~ + + H , O
in perchlorate media, in the absence of air, has been made by Newton and Baker
using a spectrophotometric method, a wavelength of 760 mp (absorption by
V(1V)) being used to obtain rate data. The rate law, obeyed over a range of conditions, was
-d[ V( IV)] /d t
= - d [V( I I)]/d t =
(k + k[H+])[VO+] [V21
VO2++V++Hf +
T R A N S I T I O N METALS
79
enthalpy and entropy were 12.3 kcal.mole-' and - 16.5 cal.deg-'.mole-', and
for that represented by k", 9.8 kcal.mole-' and -31.6 cal.deg-'.mole-'.
During this study, an intermediate absorbing at 425 mp was detected and shown
in a further study2 to be a dimer (VOV4+), with nearly two-thirds of the V(1V)V(I1) reaction proceeding uia this species in an inner-sphere step, the remainder
reacting via an outer-sphere pathway. The mechanism proposed for the reaction
was
V 0 2 ++ V 2 + + 2 H + -P 2 V3++ H 2 0 (k,)
vo2++v2++ vov4+
VOV4+ + H +
VOH2
+ V 3 ++VOH2+
+ H + + V3++ H,O
(k2)
(k3)
(rapid)
From spectrophotometric measurements (at 425 mp) on the appearance and disappearance of dimer, values for the rate coefficients k2 and k , were found to be
and 3.3 x lo-' l.mole-'.sec-',
(at 0 "C and ionic strength 1.0 M ) 6.7 x
respectively. Under the same conditions k , was calculated to be 3.9 x
1.
mole - .sec - I .
Both sulphate and chloride ions were found to accelerate the reaction under
constant ionic strength conditions and, although medium effects may operate,
pathways involving chloride and sulphate ions are possible. For the sulphate ion
addition Newton and Baker' conclude that the step
+ k4[VOHHSO:+][V2+]
Daugherty and Newton4 have examined the reaction between VO: and V3+
and have found their results to be consistent with a rate law
the major part of the reaction proceeding via a pathway associated with the
coefficient k 5 .
References pp. 142-152
80
The reaction
V2++VO:+2Hf
V3++V02++H20
has been investigated by Espenson and Krug', using the stopped-flow technique.
Results indicating a rate law
were obtained. The values of the rate coefficients k,(l.mole-'.set-') and kb(I2.
mole-2.sec-'), at 25 "C and p = 1.01 M , with the associated activation enthalpies
(kcal.mole-') and entropies (cal.deg-'.mole-')
in parentheses are 2.58 x lo3
(1.9, -36.8) and 2.16 x lo3 (1.8 and -37), respectively.
estimate^^,^ for the rate coefficient of 2 5 x lo7 and 6.8 x lo7 I.mole-'.set-'
have been recently reported.
For the reaction
8.2
CHROMIUM, MOLYBDENUM A N D T U N G S T E N
81
TRANSITION METALS
which was considered by Anderson and Bonner to arise from the exchange pathways
cr3+ +cr2+
+ CrOH2++H+
Cr3++H20
K2
with k ; given by the product K2k2. On this basis k , and k , were evaluated as
2 x lo-' and 7.0 l.mole-'.sec-', respectively (at 24.5 "C p
1.0 M ) . The value
obtained for the overall activation energy was 22 kcal.mole-'. For the second
step (k,) a hydrogen atom transfer mechanism was suggested.
The effect of chloride ion on the exchange was found by these workers to be
very small, whereas Plane and Taube' had estimated a rate coefficient about
five times larger in the presence of lo-' M chloride ion than in perchlorate
solution. Van der Straaten and Aten3 have studied the exchange in media 1 M
with respect to HCl and have estimated a rate coefficient 2 3.0 x lo-, I.mole-'.
sec-l. The isotopic method (51Cr)and a separation procedure based on the precipitation of Cr(I1) as the acetate complex was used.
The exchange reactions
whereXis, F-, C1-, Br-, N;, NCS-, CN-, and H2PO; have beeninvestigated4-*.
ReJerciices pp.
142-IS2
82
The radioisotope "Cr was used to tag the C r 2 + species and the separation of
C r 2 + from CrX2+ was achieved using an ion-exchange method, after oxidation
of the C r 2 +to Cr3+ with Fe(II1) or oxygen. The reactions were carried out in the
absence of oxygen in perchlorate media. For the systems involving chloride,
fluoride4, and azide6, King et al. have found a rate law
rate
k3[CrX2+][Cr2+]
CrNCS2++ C r 2 + + C r 2 ++CrSCN2+
CrSCN" + C r 2 + -+ C r 2 ++CrNCS2+
occurs.
Espenson et aI.'s8 have found for X
dependent rate law
rate
k,b,[~r~2+][~rZ+]
where the observed rate coefficients are given by kobs = kk [H+]-' for X = H,PO;,
(over the range of concentrations, CrH2PO:+ 3.7 x lo-, to 4.0 x
M, Cr2+
1.8 x lo-, to 2.5 x
M , and H + 2.6 x
to 1.0 M ) and by kobs= k , +kk
[ H + ] - ' for X = C N - (over the concentration ranges, CrCN2+ 4.5 x lo-, to
M , and H' 1.2 x l o F 2to 3.5 x lo-'
M , Cr2+ 1 . 0 ~
2.6 x
to 1.9 x
1.
TRANSITION METALS
83
cis-Cr(N,): +Cr'+ +
and have suggested two azide groups participate in the transition state bridging.
The isotopic method ( 51 Cr) and ion-exchange separation of reactants (after
treatment with HzOz)was used. The observed second-order rate coefficient has
a value 60I.mole-'.sec-' (0 "C, p = 0.5 M ) . The effect of increasing the hydrogen
ion concentration was very small.+
Stranks' has reported the activation energy and entropy for the exchange
system Cr(urea);+-Cr(urea):+, to be 13 kcal.mole-' and -40 cal.deg-'.mole-'.
+ Data for the exchange of 5'Cr between Cr2+ and the Cr(II1) species Cr(OAc)2+ and cis-
12.
84
+ Cr(V)+Cr(III)
Cr(II1) +Cr(V)
+ Cr(IV)+ Cr(IV)
or
+ Cr(1V) + Cr(V)
also occurring.
8.2.3 The reaction between Cr( V I ) and Cr(IZ)
Hegedus and Haim have examined the reaction of Cr(V1) with Cr(I1)
3 Cr2++Cr(VI) = 2 Cr3++Cr2(0H)42+
using the isotopic method (51Cr)in an attempt to verify the reaction mechanism
proposed by Ardon and Plane, viz.
Cr(V1) Cr2
Cr(V)+Cr+
Cr(V) + Cr3
-+
Cr(IV)+Cr3i
+
Cr(V) + Cr(1I)
Cr3
+ Cr(1V)
TRANSITION METALS
85
the former step being about four times faster than the latter. No kinetic measurements have been made.
have been studied and found to be catalysed by Cr(II), usually in the form (3::.
The reactions are usually carried out in a sealed container, in perchlorate media
and in the presence of an inert gas which prevents atmospheric oxidation of the
Cr2 ;the rate data are usually obtained from spectrophotometric measurements.
Studies have been made on the complex ions Cr(II1)X for X = C1- (Taube and
King', Adin and Sykes', and Pennington and Haim3), Br- (Adin et aL4, and
Pennington and Haim,), I- (Adin et uL4, and Pennington and Hairn,),' F- (Adin
et aL4), N; (Doyle et al.'), and NH, (Espenson and Carlyle6). The wavelengths
used in the absorbance studies were 608 mp (Cl-), 622 mp (Br-), 306 or 475 mp
(I-), 408 mp (F-), 433 mp (N;), and 504 to 522 mp (NH,).'+ Since these aquation
reactions can also occur via pathways which are not catalysed by Cr(II), terms
from both catalysed and non-catalysed reactions appear in the rate law, which is
usually of the form
+
d[Cr(III)X]/dt
(k, + k;[H+]-'
+ k'[Cr"])[Cr(III)X]
The rate coefficients k , and k; relate to the non-catalysed process and k' is the
apparent rate coefficient for the catalysed pathways. For the systems where X = C1-,
Br- and I - , k' is given by k ; [H'I-', and a reaction pathway
CrX( OH)+ + Cr2+%
was postulated, with the species Cr(X)(OH)' produced oiu the equilibrium
CrX2+ H,O
+ Cr(X)(OH)+ + H'
K,
and k ; = k,K,. Values of the observed rate coefficient k ; (sec-') are 3.2 x
(Cl-)',
1.74~
(Br-)4, 2.13 x
(I-)4 (at 25 "C, p = 2.0 M ) and
4x
((21-),
2 x lo-, (Br-), and 2 . 2 ~lo-' (I-), (p = 1.0 M , 25 'c),.
Activation parameters (AH* and AS*) of 20.2 kcal.mole-', -7.4 cal.deg-'.mole-'
86
I O N S OF S A M E M E T A L I N D I F F E R E N T O X I D A T I O N S T A T E S
- 3a
K3e
the related value of K,, has been determined and an estimate of k,, (at 20 "C,
p = 2.0 M ) of 20 I.mole-'.sec-' has been made'. The observed rate coefficient
k - 3 a has been evaluated as 3 . 4 lo-,
~
1'. mole-'. sec-' ([H'] = 1 . 0 ~
lo-' M
and CI- = 1.0 M a t 40 0C)2.
Sykes et
have proposed a transition state involving a hydroxide bridge
for the processes defined by k , .
For the systems X = F-, N;, and NH,, two catalysed pathways were indicated by the rate law, which took the same form as previously, with
~
k'
= (k;[H+]-'+k,)
2 C r 2 + + 2 H + + H N 3 = 2Cr"+NH3+N2
before evaluation of the rate data from the absorbance measure~nents~.
Aquation reactions of some disubstituted aquo ions of Cr(II1) have also been
found to be catalysed by C r 2 + ,viz.
Kinetic studies on the reactions (in the absence of oxygen, in perchlorate media)
have been made'-'' for the ions C r X l where X = CI-, F-, N; and CN-;
the rate data was obtained using spectrophotometric measurements for the
Deutsch and TaubeZ5and Nordrneyer and Taube26 have recently obtained data for the similar
Cr(1II)X systems, X = acetate25and nicotinarnidez6.
87
T R A N S I T I O N METALS
= k"[CrX:][CrZ+]
CrC12++ Cr2
Taube and King' have obtained a rate coefficient of (50.2 12.mole-2.sec-' at 0 "C
(media 1 M in HCIO,).
Haim' has found a value of k" of 7.6 I.mole-'sec-' at 25 "C (media 0.2 M in
HCIO,) for the aquation of cis-Cr(N,):. Corresponding activation parameters
of 8.1 kcal.mole-' and -27 cal.deg-'.mole-' werealso obtained. For the aquation ofcis-Cr(CN)l, Birk and Espenson" have reported a value of 4.19 I.mole-'.
sec-' at 25 "C (p = 1.0 M ) .
I.mole-'.sec-' at 25 " c (cisChia and King' have evaluated k" as 1 x
CrF:) and 1.5 x
I.mole-'.sec-' at 25 "C (trans-CrF:). The activation
enthalpq and entropy for the aquation of cis-CrF: are 13 kcal.mole-' and -24
cal.deg-'.mole- ' , respectively.
The species Cr(CN), also undergoes a catalysed aquation
Cr(CN),+Cr2+
C r 2 + + C r C N 2 + + 2CN-
C r X 2 + + 5NH:
+ For the similar system involving the species Cr(0x);- see Hutchital".
Relerrnces pp. 142-15.2
88
where X is the fluoride, chloride, bromide or iodide group. Ogard and Taube',,
using a spectrophotometric method (detecting the appearance of the product
CrX") have obtained rate data for these reactions, which were carried out in
perchlorate media in the absence of oxygen. The rate law found was
- d [Cr(NH3),X2+]/dr =
k, [Cr(NH,)5X2+]+ k, [Cr(NH,),X'+][Cr2+]
Cr(NH,)z+ +X-
and k, (the rate coefficient for the catalysed steps) has values (1.mole-'.sec-'
at 25 "C, p = [ H + ] = 1.0 M ) of 2.7 x l o W 4(F-), 5.1 x
(Cl-), 0.32 (Br-),
and
5.5 (I-). For the species Cr(NH,),Cl2+ k , was found not to be affected
by variation in [H'] but was reduced by change in the solvent from H 2 0 to D 2 0 .
Activation parameters of 13.4, 11.1, 8.5 kcal.mole-' and -30, -23, -33 cal.
deg-'.mole-' were calculated for the species Cr(NH3),F2+, Cr(NH,),Cl'
and
Cr(NH,),Br2+, respectively. The reaction (NH,),CrOHCr(NH,)4C14+ 5H+ =
(NH3),Cr2++5NH: +CrCIZ+ has been found by Hoppenjans et
to be
catalysed by Cr2+.
Cannon14 has made a study of the Cr(I1) catalysed reaction
Cr(NH3),C12++ n OAc-
+ 5 H'
C ~ ( O A C ) ~ ~ -5"NHf
)+
+ C1-
k"'[Cr(NH,)5C12+][Cr(II)]f
+ 2 Cr(0Ac);
-%Cr(OAc),Cl--+
Cr(OAc),
Cr(OAc),
--+
polymer
+ Cr(0Ac);
K,
+Cr(II)+5 NH;
+ C1-
T R A N S I T I O N METALS
89
CrCl" +4 NH,f
which are also catalysed by Cr2+.In perchlorate media in the absence of oxygen
a rate law
rate
k , [Cr(NH,),C12+][Cr2+]
was found. In the presence of chloride ions the rate law became
rate
( k , kb[C1-])[Cr(NH3),Cl2+][Cr2+]
Values of the kinetic parameters k,, AH' and AS' are 1.16 I.mole-'.sec-' at
25 "C (p = 1.0 M ) , 9.7 kcal.mole-' and 26cal.deg-'.mole-' for the truns-isomer
and 1.14 x lo-' l.mole-'.seL-', 10.6 kcal.mcle-' and -27.6 cal.deg-'.mole-'
for the cis-species. Both pathways associated with k , and kb are thought to occur
via chloride bridge transition states.
Pennington and Haim" have investigated the similar Cr2+-catalysedaquations
of the cis- and truns-Cr(en),C12+, and the cis- and trans-Cr(en),Cl: species of
Cr(III), in perchlorate media, uiz.
cis- or trans-Cr(en),Cl;
In the absence of oxygen the rate law obtained from spectrophotometric measurements at wavelengths 382 mp (trans-isomers) and 510 or 512 mp (cis-isomers)
was found to be of the form
-d[X]/dt
k,,[X][Cr2+] +k;,[X]
where X represents the Cr(II1) species mentioned and k,, and k',, are the rate
coefficients for the catalysed and non-catalysed pathways, respectively. (Only
for the cis-isomers was the term involving k ; , large enough, under experimental
conditions, to appear.) Values of the kinetic parameters k,, (l.mole-'.sec-' at
25 "C,p = 1.0 M ) , AH' (kcal.mole-I) and AS'(cal.deg-'.mole-') are 1.16 x
References pp. 142-1 5 2
90
I O N S O F SAME METAL I N D I F F E R E N T O X I D A T I O N S T A T E S
CrL+
k"" [Cr3'][Cr2+][HL-] [ H + ] - 2
was found to account for the experimental data. At 25 "C and p 1 .O M , k"" has
sec-'. The mechanism proposed by these workers was
a value 2.2x
H,L ;r HL- + H i
HLCr2 + + L2 Cr3++ H,O
+ L2-+H'
$ CrL
_-
CrOH2++ H t
C r 2 ++CrCN2+
CrSCN2++ C r 2 + = Cr2++CrNCS2+
have been studied using spectrophotometric techniques at wavelengths of 520 mp
91
T R A N S I T I O N METALS
twocatalysed pathways
CrSCN2++Cr2+%CrSCN2++H,0
+ Cr(SCN)(OH)++H+
K,,
Cr(SCN)(OH)+ +Cr2+
the observed rate coefficient being given by
Values of k,, and k,,K,, at 25 "C (p = 1.0 M ) were calculated by Haim and
Sutin2' as 40 I.mole-'.sec-' and 2 sec-', respectively;
For the species CrNC2+,Birk and Espenson22 have found a rate law
-d In [CrNC*+]/df
kob3 = k',,+k;,[Cr2+]
where the terms k i 4 and k',, [Cr"] relate to the non-catalysed and catalysed
processes. The value of k i 5 is 5.7 x lo-' I.mole-'.sec-' at 15 "C ( p = 1.0 M ,
[H'] = 4 x l o - ' M ) . Hutchital" has recently obtained kinetic data for the
Cr2
reaction trans-Cr(Ox), =-cis-Cr(0x);.
+
The exchange of Mo between the anions Mo(CN);- and Mo(CN);- has been
investigated by the isotopic method (99Mo) and the separation methods (a)
precipitation of Mo(CN);- with either ethanol or cadmium ions, and ( 6 ) precipitation of Mo(CN);- with tetraphenylarsonium chloride. Complete exchange
5x
M.
was observed by Wolfgang' even with reactant concentrations
An estimate of the rate coefficient at 2 "C of > lo3 I.rnole-'.sec-' has been sug-
gtsled.
More recently, a value of 3 x lo4 I.mole-'.sec-' has been calculated for the
exchange rate coefficient at 10 "C and zero ionic strength by Campion et a/.'
using the Marcus theory and rate coefficients for the reactions
Mo(CN)i-
+ Os(dipy):+ $
Mo(CN);- + Os(dipy):+
kr
k, and k, for the above reactions were measured by the temperature jump method.
ReJerences pp. 142-IS2
92
8.3
MANGANESE
Polissar' has observed 100 % exchange between Mn(III), as the oxalato ion
Mn(0x); , and manganous sulphate. Adamson', using manganic chloride as the
source of Mn(III), has observed the exchange to be incomplete in a time
15 sec
M. Both workers',' used a separation
with reactant concentrations
technique based on the precipitation of Mn(lV), present via the equilibrium
2 Mn(II1)
+ Mn(II)+Mn(IV)
as the oxide, with perchloric acid solutions as reaction media and the isotope
54Mn as the indicator.
93
TRANSITION METALS
Diebler and Sutin3, using perchlorate salts of Mn(II1) and Mn(1I) and the
isotopic method, have also observed complete exchange, in media 6 M in HClO,,
within a time of one min. Two additional separation techniques were employed:
extraction of the Mn(II1) into benzene as the complex dibutylphosphate and precipitation of the Mn(I1) as the salt MnNH,P04. However, using Marcus theory,
Diebler and Sutin3, have been able to calculate a value for the exchange rate
I.mole-'.sec-', from data obcoefficient at 25 "C (3 M in HC104) of 3 x
tained during a study of the reactions of Co(1II) with Mn(I1) and of Mn(II1) with
numerous Fe(I1) complexes.
Adamson, has reported the exchange between the manganese anions Mn(CN)i and Mn(CN);- to be measurable.
The kinetic parameters for the reaction between the Mn(II1) complex with
EDTA and the Mn(I1) complex with truns-l,2-diaminocyclohexanetetraacetate
have recently been reported by Wilkins and Yelin5 as 1.2l.mole-'.sec-', 7.1
kcal.mole-' and -34 cal.deg-'.mole-'.
8.3.3 The exchange reaction between Mn( VZZ) and Mn( VZ)
This exchange in alkaline media has been studied, using the isotopic method
(54Mn and 56Mn),by many workers. Libby', using the separation afforded by the
insolubility of barium manganate, has found 100% exchange. Hornig et aL2,
attempted to study the exchange using pyridine extraction of the permanganate
but observed 100 % exchange, as did Adamson3, who in addition to the above
separation methods, used a method based on the precipitation of manganese
dioxide. Bonner and Potratz,, using reactant concentrations
lo-, to
M
and extraction of Mn(VI1) as the triphenylsulphonium salt with either ethylenedichloride or chloroform, were able to suggest a limit of > 1500 l.mole-'.sec-'
for the rate coefficient at 0 "C for the exchange in 2 M NaOH.
Sheppard and Wah15 were the first workers to make rate measurements on this
exchange reaction. They used triphenylsulphonium bromide and tetraphenylarsonium chloride as the separating agents; both reagents remove the permanganate
anion. The radio-isotope 54Mn was used to label the manganate ion. In a further
report, Sheppard and Wah16 give details of their special reaction vessel and the
quenching solution. The rate law obeyed is
where kobs has a value of 710 l.mole-'.sec-' at 0.1 "C for 0.16 M NaOH. The
energy and entropy of activation were calculated as 10.5 kcal.mole-' and -9
cal.deg-'.molerespectively.
The addition of various cations (Cs", K", Na' and Li') was found to alter
',
94
the value of kobs,the highest value being observed in the presence of Cs'; various
anions were also added but only slight effects were noted. The suggestion of a
cation bridge transition state was made.
A detailed investigation of the catalysis by the caesium cation has been made
by Gjertsen and Wahl', who were able to show from the linear plots of kobstlersus
[ C s + ]that the rate law could be rewritten as
rate
At an ionic strength of 0.16 M the values of k' and k" (0 "C) were 7.1 x lo2 1.
mole- '.sec-' and 1.2 x lo4 12.mole-'.sec-', respectively. Sodium hydroxide was
used to maintain the ionic strength constant.
Meyers and Sheppard' have since made a study of this exchange using the
nuclear magnetic line-broadening method (55Mn). From the results obtained the
rate law
rate
k,,,[MnOi][MnO:-]
was confirmed and, as shown in previous work6, the value of kobswas found to
depend on both the concentration and nature of the cation. I n media 0.57 M with
respect to KOH, kobs(20 "C) has a value 5.6 x lo3 l.mole-'.sec-' ,with an associated activation energy of 8.3 kcal.mole-'.
Britt and Yeng, using the pulsed nuclear resonance technique, have obtained
exchange data comparable to those obtained by the isotopic method. An observed
rate coefficient at 0 "C and p = 1.06 M of 1.23 x lo3 I.mole-'.sec-' has been
calculated for the exchange in the presence of 1.0 M Na+.
and
Using the isotope 56Mnas a means of labelling the oxidation states of manganese,
Polissar' has made a preliminary study of the exchange reaction in perchlorate
media between Mn(VI1) and Mn(I1). He concluded that no measurable exchange
M ) in a time of 15 min.
occurred between these two oxidation states (The reactants were separated by the addition of sodium hydroxide which precipitated manganese dioxide. Adamson2, however, using reactant concentrations
95
TRANSITION METALS
rate
kobs[MnOJ113[Mn2+]4/3CH+]4'3
l2.mole-'.sec-I
Mn0,+3Mn2++6H+ $Mn02++3Mn3++3H,0
Mn3++H,0
MnO+ +2H+
Mn4++H20 $ Mn02++2H+
K,
K2
K3
M n O + + M n 0 2 +%exchange
Mn02++H,0
-+
MnO,(s)+2 H +
M n 0 2 + + M n Z + + 2 H +$ 2 M n 3 + + H 2 0
Mn4+ + M n Z + $ 2 Mn3+
which leads to a theoretical rate expression
rate
( k : K , Kf/3)f[Mn0,]f[Mn2+]3[H+]
5 Mn3+ + 4 H 2 0
The reaction to produce the hydrated manganese dioxide has been studied by
References pp. 142-IS2
96
many
The reaction in the presence of oxalate4 or periodate' ions has
also been investigated. Oxalato and iodato complexes of Mn(II1) are formed as
intermediates in the reactions.
Rosseinsky and Nico16 have investigated in detail the reaction in highly acidic
perchlorate media which leads to the production of Mn3+. Using [Mn(II)] in the
to 1 x lo-' M with [MnO,]
M the rate law, found from
range 2 x
absorbance measurements at a wavelength of 525 mp, is
-d[MnO;]/dt
k,,,,[MnO,][Mn(II)]*
The variation in the value of the observed rate coefficient kobswith acidity was
found to be of the form
8.4
8.4.I The exchange reaction between Fe(ZZZ) and Fe(ZZ) in aqueous media
The earliest attempts to measure the rate of exchange between ferrous and ferric
ions in aqueous media utilised the diffusion separation technique. Little agreement was obtained by the different workers' -4. Diffusion separation factors,
found to be
OS',
1.42, 3S3 and
l.24, illustrate the difficulty of the
technique. The isotopes used to label the iron were either "Fe or 59Fe,and exchange was found to be complete in hours2r4 or many days1p3 in perchlorate
media.
Silverman and Dodson' made the first detailed isotopic study of this exchange
system using the separation afforded by the addition of 2,2'-dipyridyl at pH 5,
followed by the precipitation of the ferric iron with either ammonia or 8-hydroxyquinoline. Dodson6, using this separation method, had previously obtained
an overall rate coefficient of 16 1.mole-'.sec-' at 23 "C for 0.4 M perchloric
acid media. The exchange in perchlorate and perchlorate-chloride media was
found to conform to a rate law, first order with respect to both total ferrous and
ferric ion concentrations, with an observed rate constant (kobo)dependent on the
hydrogen-ion concentration, viz.
kobs = k l +k;[H+]-'
TRANSITION METALS
97
F e 3 + + F e 2 +-+
and an [H+]-dependent pathway
k2
F e O H 2 + + F e 2 ++
the FeOH2+ being produced by the rapid hydrolysis reaction
K2w
'
98
Reynolds and Lumry have discussed the role of water in this exchange and
have suggested, for both steps, a mechanism involving water bridges.
Horne has studied the kinetics of exchange in aqueous perchlorate media
at temperatures down to -78 C by the isotopic method (59Fe) and dipyridyl
separation. The same rate law in these ice media as in aqueous solution was
observed, although the acid dependence was small. Horne concluded that the same
exchange mechanism occurs in solid and liquid solvent. Evidence for a Grotthustype mechanism has been ~ummarised~.
8.4.2 The efSect of inorganic ions on the exchange reaction between F e ( l I I ) and
Fe(ll)
The effect of the addition of inorganic ions has been investigated using the
isotopic method (55Fe or 59Fe) and the 2,2-dipyridyl separation. The rate law
in the presence of inorganic anions is given by
rate
kobs[Fe(III)][Fe(I1)]
where kobsis the observed second-order rate coefficient, which is related to the
rate coefficients for the individual reaction pathways and the formation constants
of the species involved in these pathways. The latter constants must be known for
the evaluation of the rate coefficients and constant ionic strength conditions must
be maintained. The reaction pathways
Fe3++ Fe2+
ki
_f
FeOH2++Fe2+
kZ
__f
k3
ks
+ Fe2+-+
+
Fe21
TRANSITION METALS
99
+ FeCI2+
FeCI2++C1- + FeCl:
Fe3++C1-
K3
3.01 I.mole-'
K4 = 0.94 I.mole-'
with k3 being the sum of 2 k j and kj'. Calculations have led to the evaluation of
k;' as 33.4 I.mole-'.sec-' ( p = 3.0 M a n d 25 "C). Home4 has shown that chloride
paths are unimportant at low temperatures in ice media.
Hudis and Wahl' have examined the effect of fluoride ion on the exchange
rate and have found it necessary to include three fluoride exchange paths
FeF2++ Fe2+
+Fe2
FeF, + Fe2+
FeF:
k5
_f
k6
_f
k7
_f
Values obtained for the rate coefficients k , , k6, and k7 (I.mole-'.sec-' at 0 "C
and p = 0.5 M ) were 9.7, 2.5 and 0.5, with activation parameters for the first
References p p . 142-152
100
I O N S OF SAME METAL I N D I F F E R E N T O X I D A T I O N S T A T E S
two steps (k, and k 6 ) of AS' -21 and -22 cal.deg-'.mole-' and E, 9.1 and
9.5 kcal.mole- ', respectively. A hydrogen-atom transfer mechanism was proposed
for these steps.
Menashi et d 6 have examined the exchange when only the FeFZ+ of the
Fe(II1) fluoro-species was present and when the rate of formation of FeFZf and
the rate of the 59Fe exchange are of the same order of magnitude. The results
obtained led these workers to conclude that exchange occurs via an activated
complex [Fe2F4+]*.
Thiocyanate ion also provides additional pathways for exchange, viz.
The rate law found by Laurence', for the exchange i n the presence of thiocyanate
ion in the range 3.2 x lo-, to 8.6 x lo-' M was
rate = k,[Fe3+][Fe2+] +k,[FeOHZ+][Fe2+] +k8[FeSCNZ+][Fe2+]
2 FeZ++FeSCNz'
FeNCS"
$ Fe2++FeNCSZf
+Fez+
FeN:+ +Fez+ +
TRANSITION METALS
101
3 Fe3+N;Fe2'
Fe3+ N 3Fez 2 Fe2 N 3 Fe3
Fe2+N;Fe3+ 2 Fe2++-N3Fe3+
Fe3+N; + F e 2 +
k-
14
k-IS
k-16
with the relative magnitudes of k-.14 and k,, accounting for the curvature of the
Arrhenius plot.
The presence of phosphoric acid also provides an additional pathway
Sheppard and Brown" have evaluated the rate coefficient k I 7 as 4180 ].mole-I.
sec-' with 0.53 M HCIO, at 20 "C. The overall activation energy and entropy
corresponding to the term K1,k17,where K17is the equilibrium constant of the
react ion
Fe3++HPOi-
+ Fe(HP0,)'
K17
uiz.
FeBr2++ Fe2+ -%
FeBr:
+ Fez
102
FeSO:
+ Fe2+ %
Fe(S0,); +Fe2+
FeOH2++ FeSO,
At an ionic strength of 0.75 M the calculated values of the rate coefficients k,,,
at 25 " C ) are 5 . 8 6 lo2,
~ 2.07 x lo4 and 1 . 4 lo6,
~
respectively. Although the rate of the step associated with k,, was found to vary
with the ionic strength of the medium, kzl and k Z 2would not appear to depend
on this property. In this study the concentration ranges used were Fe(I1) 6.2 x
to 3.16 x
to 1.1 x
M , SO:- 'up to 8 x loW3M ,
M , Fe(II1) 2 x
and H + 3.8 x lo-, to 1.25 x lo-' M .
Sheppard and Brown', have estimated a value of k,, of 9 . 8 0 ~10, 1.mole-'.
M
sec-' (at 28 "C and p = 1.0 M ) from data obtained with total iron
and sulphate ion up to 8 x lo-, M . Activation energy and entropy for the cornbined term K 2 , k,, , where K , , refers to
Fe3++SO:-
+ FeSOl
K2,
TRANSITION METALS
103
8.4.3 The effect of organic ligands on the exchange reaction between Fe(III) and
Fe(II)
The effect of some organic acids on the exchange in perchlorate media has been
investigated' -3. Fumaric'. ,, benzoic and o-phthalic acids' have been shown to
cause little or no alteration in the rate, whereas acetic, succinic, carbolic', oxalic'r
and tartaric acids3 have an accelerating influence. The isotopic method (59Fe)
and the 2,2'-dipyridyl separation have been used. The rate law observed was1-,
rate
k,,,[Fe(III)][Fe(II)]
At constant ionic strength and acidity (- 0.55 M ) , with oxalic acid (H20x) up
to 9 x lo-' M , and at temperatures in the range 0.02 "C to 20.57 "C,the rate data
were found by Horne' to be consistent with an expression
rate
R , + k3[FeOx+][Fe2+]
+ k4[Fe(Ox);][Fe2+]
where R, represents the exchange rate at zero oxalate ion concentration. Values
of k , and k4 were calculated as 2140 and 4250 l.mole-'.sec-', respectively, at
20 "C. For the step associated with k , the entropy and energy of activation were
estimated as - 14 cal.deg-'.mole-' and 9.2 kcal.mole-'. Sheppard and Brown2
have reported values of k , (20 "C) of 3300 1.mole-'.set-', and of the entropy of
activation of 28 cal.deg-'.mole-' and the energy of activation of 21 kcal.mole-'
for the overall process associated with k , K , where K3 refers to the equilibrium
Fe3++Ox'-
+ FeOx'
McAuley and Brubaker, have found that for added tartaric acid (H2Tar) up
to 5 x
M , at temperatures in the range 0 to 10 "Cwith constant acidity (0.11
M ) and ionic strength 0.55 M , rate data were consistent with an expression
rate = R,+ k,[FeHTar2+][Fe2+]+k,[Fe(HTar):][Fe2+]
The term defined by k , is relatively unimportant, since plots of kobsversus [H2TarI2
were linear. The pathways for exchange in the presence of tartaric3 and oxalic
acids' are
F e O x+ + F e 2 +
Fe(0x); + F e2 +
FeHTar2++ F e 2 + %
Fe(HTar)l + F e2 + -%References pp. 142-152
I 04
R,+k,[FeQ2+][Fe2+]
F e Q 2 + + F e 2 +--+
At 25 "C and p = 0.5 M the value of k , is 450 l.mole-'.sec-'.
100 % exchange of iron, between the ethylenediaminetetraacetate complexes of
iron(II1) and iron(1I) ( F e y 2 - and Fey-), has been observed within the time
required (15 sec) for either, precipitation, or ion exchange separation of the species
of iron5. Reynolds et d 6have since investigated the exchange of Fe2+ with F e y - ,
which they have found to be measurable and to follow a rate law
rate
k,,,[H
'3
1.7[Fe2+]o.7[FeY -3
'
105
T R A N S I T I O N METALS
8.4.4 The exchange reaction between Fe(ZZZ) and Fe(ZZ) in non-aqueous and mixed
solvents
An isotopic investigation (59Fe) of the exchange of iron (111) and iron (11) as
perchlorates in absolute ethanol, with chromatographic separation on an alumina
column, led to complete exchange being observed within the separation time'.
However, Horne', using the 2,2'-dipyridyl separation method and the isotope
55
Fe has observed a decrease in the exchange rate as water is replaced by acetone,
methanol, ethanol and propanol. The rate tending to zero in the absence of water.
In aqueous ethanol the rate law was found to be
rate = ko,,[Fe(III)][Fe(Il)]
with activation parameters at low water concentrations of about 10 kcal.mole-'
( A H ' ) and -20 cal.deg-'.mole-' (AS'). Increase in the ionic strength led to an
increase in the rate, whereas increase in HC104 concentration brought about a
reduction. The rate of exchange has also been reported to be much slower in
isopropano13 and nitromethane, than in aqeous media. Various reasons for the
slow rate in alcohol media have been put forward2.'.
Menashi et a f . 5have made a detailed isotopic study (59Fe) of the exchange in
dimethylsulphoxide, in the absence of oxygen, using the 2,2'-dipyridyl separation.
to
to 2.8 x lo-, M and 1 x
With Fe(I1) and Fe(II1) in the ranges 1 x
1 x lo-, M , respectively, the rate data was found to conform to a first order
dependence on both oxidation states of iron. The value of the observed rate
coefficient (20 "C), in the presence of 2.5 x
M H,O and 2 x lo-' M HC104,
at p = 0.2 M (NaCIO,), was 18 I.mole-'.sec-'.
Reference5 pp. 142-152
106
+ Fe3+ -%Fe3' + F e z +
FeCl' + Fe3 %Fe3 + FeCI'
KI
Fe''+Cl+
FeCl'
(K, = 1 . 4 ~
Fez'
I.mole-')
On this basis, a value of the rate coefficient k , was estimated as 3.2 x lo2 1.mole-'.
sec-' (at 20 "C and p = 0.1 M ) . The energy and entropy of activation corresponding to the term k,K, were calculated as 8.7 kcal.mole-' and -0.5 cal.
deg-'.mole- I , respectively.
The earliest attempts to measure the rate of this exchange reaction met with
little success, 100 % exchange being found to occur during the time necessary for
mixing and separating the two species of
The radioactive indicator used
was usually a mixture of isotopes (59Fe and 55Fe), and the media ranged from
molar aqueous hydrochloric acid to 0.05 M sodium hydroxide. The separation
methods tried included (a) precipitation of the ion Fe(CN);- as the insoluble
salts KCeFe(CN)i, Pb,Fe(CN)i and KFez(CN): and ( b ) physical methods based
on diffusion, ion exchange and electrophoresis4.
T R A N S I T I O N METALS
107
'
rate
ko,,[Fe(CN)~-][Fe(CN):-]
and the exchange paths involving all species of iron which occur, viz.
+ Fe(CN)i- --+
MFe(CN)i- + Fe(CN):- %
Fe(CN):- + MFe(CN)i- %MFe(CN)i- + MFe(CN)i- --+
Fe(CN);-
ko
k2
I08
TRANSITION METALS
109
Sutin et a / . ' - 3have found iron(l1) to catalyse the aquation of the iron(II1)
ions, FeCI2+ (refs. 1,2) and FeNCS2+ (ref. 3), in perchlorate media. A flow
technique, with spectrophotometric detection at 336 mp (disappearance of FeCl' )
and 460 mp (disappearance of FeNCS2+), was used to obtain rate data. The rate
law
+
'-d [FeX2+]
--____~- kob,([FeX2'1 - [FeX2'],,)
dr
where X is either the chloride or thiocyanate ions, was used to treat the data
obtained. The observed rate coefficient kobsis related to the reactions
FeX2+ + Fe3++XFeX'
+ Fe2++X-
2 F e X + + F e3 +
F e X 2 + + F e2 +
k-
110
and in the case of the chlorocomplex, following the study of the effect of hydrogen
ion', the additional reactions,
FeCI2+ H 2 0 $ ClFeOH'
ClFeOH'
ClFeOH++Fe'+
+H +
(K2)
+ FeOH++Cl-
2 FeCl++FeOH2'
k-2
Fe(IV)+Fe2+ + [Fe(III)J,
has been postulated to occur in the oxidation of iron(I1) by various two-equivalent
oxidants'.
8.4.9 The exchange reaction between Ru(VZZ) and Ru(V1)
The exchange between the ruthenium anions RuO, and RuO:- in aqueous
hydroxide media has been found rapid. A limit for the rate coefficient at 0 "C
of > 1.7 x lo3 I.mole-'.sec-' has been proposed by Luoma and Brubaker'.
The isotopic method (' 06Ru), and separation procedures based on the preci pitation of the RuOi- or RuO, species with barium or tetraphenylarsonium ions,
respectively, were used. Attempts to use an ESR technique failed.
8.4.10 Ru(IZ)-catalysed substitution reactions of Ru(IIZ)
Ru(1I) in the form of Ru(NH3)gC catalyses the substitution reactions'
Ru(NH3),0H3" +C1Ru(NH3),C1'+ +H,O
k'
__f
k'i
111
T R A N S I T I O N METALS
At an ionic strength 0.1 M the values of the catalytic rate coefficients k; and k;
(25 "C) were estimated from spectrophotometric measurements to be 4 x lo3
1'.rnole-'.sec-' and 2 x 10' I.mole-'.sec-', respectively.
8.4.1 I The exchange reaction between Os(IZZ) and Os(IZ)
The exchange between I-Os(dipy);+ and d-Os(dipy):+ has been studied by the
optical activity method by Dwyer and Garfas', and Eichler and Wahl'. The former
authors reporting complete exchange in 95 sec at 5 "C for reactants 5 x
M,
while the latter authors report complete exchange in a time < 15 sec at 4 "C under
comparable conditions.
Eichler and Wah12 have attempted an isotopic study (I9lOs and ' 8 5 0 s ) of the
exchange reaction between Os(dipy): + and Os(dipy): + using a direct injection
technique so that reaction times
7x
sec were possible. With total osmium
M in aqueous sulphate media at 0 "C complete exchange was observed.
The separation methods used were, ( a ) perchlorate precipitation (in presence of
iron(I1) carrier) and ( b ) extraction with p-toluenesulphonic acid in nitromethane,
of the osmium(I1) complex. A lower limit of 1 x lo5 1.mole-'.sec-' was placed
on the rate coefficient (0 "C, 3.0 M H'SO,). Dietrich and Wah13 using the line
broadening effect produced by Os(dipy): + on the NMR spectrum of Os(dipy):
have been able to propose a value of > 5 x lo4 I.mole-'.sec-' at 6 "C in D,O
(0.14M [Cl-] and 5 x
M [D']).
Campion et aL4 have calculated a value for the exchange coefficient (10 "C,
zero ionic strength) of 1 x lo7 I.mole-'.sec-' from the observed rate coefficients
for the reactions
Os(dipy):+
obtained by a temperature jump method, and the application of the Marcus theory.
8.5
8.5.1 The exchange reaction between Co(ZIZ) and Co(ZZ) in aqueous media; the
112
The first rate measurements on this system were made by Bonner and Hunt'
who, in a preliminary study, were able to show the exchange in perchlorate media
was overall second-order. The observed rate coefficient (0 "C, 1 M in HCIO4)
was 0.77 I.mole-'.sec-'. The separation method involved complexing with EDTA
at pH 8 before extracting the Co(II), after addition of thiocyanate ions, with
methyl isobutyl ketone. In a further article3 these two authors report in detail
their studies on this system. Overall activation energy and entropy values of 13.2
kcal.mole-' and - 13 cal.deg-'.mole-' are given. From results obtained at
varying acidity and constant ionic strength, Bonner and Hunt3 concluded that
the rate law could be of the form
rate
( k , +k;[H+]-l)[Co(III)][Co(II)]
where k , and k ; have values of 0.83 I.mole-'.sec-' and 0.14 sec-', respectively,
at 3.2 "C and ,LL = 1.0 M . The rate of exchange was found to be influenced by the
addition of nitrate or sulphate ions and ionic strength but not by the presence of
chloride ions, oxygen, light or platinum surfaces. In D 2 0 the rate was found to be
much slower than in H20.
Shankar and De Souza4. ', in a similar study using the isotopic method (60Co),
employed mainly ethylenediamine and ammonia to stop the reaction and a
separation based on the extraction of Co(I1) (as the thiocyanate) with amyl
alcohol-ether mixtures. These two workers were able to prove that the exchange
was accurately first order in both Co(I1) and Co(II1) over a wide range of conditions. Results in general agreement with those mentioned previously3 were
obtained for the effect of ionic strength, heavy water and hydrogen ion concentration on the exchange reaction. The mechanism suggested involved the two exchange pathways
c o 3 ++co'+
ki
-+
CoOH2++ Coz+ -+
k2
Co3+ H,O
$ CoOH2'
+ H+
K2
From a detailed study of the exchange, at various temperatures (in the range
0 to 20 "C) and acidities at a constant ionic strength of p = 1.0 M , the kinetic
parameters were calculated'. k , and k ; ( k ; = k 2 K z ) have values of 0.48 I.mole-'.
sec-' and 0.22 sec-', respectively, at 0 "C. For the exchange pathway associated
with k, , values of the activation enthalpy and entropy of 12.6 kcal.mole-' and
- 14 cal.deg-'.mole- ', respectively, were reported. For the second pathway
113
TRANSITION METALS
rate
( k , + k ; [ H + ] - ' +k;[SO~-])[Co(III)][Co(II)]
+c o z
k3
+
---f
co3 + so:- + C O S O ~
+
At p = 0.5 M the value of k j is 5.2 x 10' 12.mole-2.sec-' (0.15 "C); the corresponding activation enthalpy and entropy values are 20.5 kcal.mole- and 28.5
cal .deg - '.mole - I.
Shankar and De Souza' have also recently investigated the effect of the additions of various anions to this system in both water and heavy water solvent.
Fluoride was found to have very little influence on the exchange rate while acetate,
nitrate and sulphate ions produced an increase. For the addition of sulphate ions
an estimate of the rate coefficient k , of 20 I.mole-'.sec-' (at 14 "C and p = 2.0
M ) was made. For the addition of nitrate and acetate, values of the coefficients
kk and k; (where kk = k4K4 and k; = k 5 K 5 ) ,viz.
CoNO:++Co2+
kq
ks
CoOAc" +Co2+ -+
+ CONO:+
Co3++OAc- + CoOAc"
c o 3 ++NO;
K4
K5
114
+ Co2++Ag2+
co3+
+CI-
+COCI~+
have been able to evaluate the rate coefficients for the analogous reactions
coc12++co2+
c03++ C ~ C I +
ki
+ c1 + COCl+
+ Co(CN):-
I.mole-'.sec-'
has been evaluated as < 1 x
using data obtained by Adamson".
8.5.2 Exchange reactions involving complexes of Co(ZZZ) and Co(ZZ) with ammonia and organic ligands
The early work' - 4 on exchange reactions involving the complex hexammino
species Co(NH,):+ and Co(NH,);+ led to the conclusion that the 6oCoexchanges
115
T R A N S I T I O N METALS
between Co(NH,);+ and Co(NH,):+, and Co(NH,);+ and Co2+ were extremely
slow. The reactions were studied in the absence of oxygen, which catalyses the
exchange, and in media varying between acid and aqueous ammonia. The separation method used was the extraction of Co(II), as the thiocyanate complex, with
a mixed organic solvent.
Subsequently, Stranks' has investigated a series of cobaltammines with regard
to the electron exchange between cobalt(II1) and cobalt(II), using the isotopic
method 6oCo. The systems studied included the Co(1II) complexes and ion-pairs
Co(NH,):+, Co(NH,):+ OH-, Co(NH,);+ * C1-, Co(NH,),0H2+, trans-Co
and cis-Co(NH,),(OH): with Co(1I) complexes of the type
(NH,),(OH):
Co(NH3); where n has values 3, 4, 5 and 6.t All exchanges refer to perchlorate
13.5 kcal.mole-' and
media in the absence of oxygen. Energies of activation
activation entropies between -28 and -37 cal.deg-'.molehave been found
for these exchanges. The rate coefficients (I.mole-'.set-' at 64.5 "C, U
, = 1.0
M) evaluated from necessary kinetic and ion-pair association data are for the
exchange of Co(NH3):+ with Co(NH,):+.OH- 5.5 x lo-,, with Co(NH,);+.CI7.3 x lo-,, with Co(NH,),0H2+ 9.0 x lo-,, with truns-Co(NH,),(OH):
4.2 x loW3and with cis-Co(NH,),(OH)i 2.5 x
Under the same conditions
is < 1.7 x lo-''
the rate coefficient for the exchange Co(NH,);+-Co(NH,):+
I.mole-'.sec-'. The mechanism proposed by Stranks was
Co(NH3):++H2O
'
+ Co(NH3)2+.OH-+H'
Co(NH,);+.OH-+Co(NH,):+
-+ Co(NH,):++Co(NH,);+
+OH-
kobs[Co(NH3),0H2+][Co(NH,)f+]
was found from the data obtained over the range of [NH,] 0.092 to 0.167 M,
[Co(II)] in the range 1.5 x
to 9 x l o w 3M with [Co(III)] 4 x lo-, M. The
value of x was found to vary with the ammonia concentration. For the exchange
occurring under conditions when x = 5 the value of kobs(35.5 "C, p = 2.28 M )
is 4.4 x lo-, I.mole-'.sec-' with corresponding activation parameters of 15.6 kcal.
116
T R A N S I T I O N METALS
117
rate
k;[CoY -][COY
-1
+ I-COY- k
+ CoY2-+I-CoY-
k,
The equation -ln(at/g,,) = kobst was used to treat the experimental data
(kobs = k;[CoY2-]+2 k ) and it was found that k; (the apparent rate coefficient)
had a value of 1.5 x
l.mole-'.sec-' at 85 "C (pH = 2.0). Variation of the
solvent from H 2 0 to D,O did not bring about any change in the rate of racemization, whereas increase in the p H of the medium decreased the rate. This was
explained in terms of the formation of the species Co(H-Y)Co(H-Y)-
+ Coy2- +H +
k4
_f
ks
_f
K4
118
j-PY)-
D-cO( l-PY)-
k.,D-cO(I-PY)2- +L-CO(d-PY)-
and L, and d and I, refer to the rotational properties of the compound and the
ligand, respectively. Values of the rate coefficientsk, and k , at 100 "Care 7.0 x
and 2.0 x
1.mole-'sec-', respectively.
Baker et aLi3, have obtained some kinetic data on the exchange reactions
between the 1,lO-phenanthroline, 2,2'-dipyridine and 2,2', 2"-tripyridine complexes
of Co(11I) and Co(I1) in both H 2 0 and D 2 0 solution. The isotopic method (60Co)
and separations involving either extraction of Co(I1) with organic solvents (nhexanol-ether or saturated sodium acetate in n-hexanol) or precipitation of Co(II1)
as Co(phen),(I,), were used. For the 1,lO-phenanthroline system, a rate law
D
rate
'
T R A N S I T I O N METALS
119
',
8.5.3 The exchange reaction between Co(ZZZ) and Co(IZ) in non-aqueous media
Grossman and Garner' have investigated the exchange reaction between the
species Co(NH3);+ and Co(NH,):+, in the form of their nitrate salts, using the
isotope 6 o Co with anhydrous liquid ammonia as solvent. The reaction was carried out in a sealed system at temperatures of 25" and 45 "C, with a separation
procedure based on ether-pentanol extraction of the thiocyanate complex of
3x
M , observed rate coefficients of
Co(1I). With Co(lI1) and Co(11)
6x
(25 "C) and 7 x
(45 "C) 1.mole-'.sec-' were obtained. The activation energy for the exchange process is 23 kcal.mole-'. Grossman and Garner'
have pointed out that the exchange mechanism could involve the dissociation of
the species Co(NH3)zf, since the rate of ammonia exchange with this species is of
the same order of magnitude.
West2 has observed very slow exchange reactions in pyridine solvent between
Co(II) in the form of Co(OAc), and Co(II1) in the forms tris-(1-nitroso-2napht ho1)cobalt(111) and tr is-(acety1acetone)cobalt (111).
Baker et aL3 have obtained some evidence for a decreasing rate of exchange,
as water is replaced by acetone, with the system Co(phen):+-Co(phen)i+.
Co"'(CN),X+5 NH3
Co"'(NH3),X+6 CN-
Co(CN)2-+5 NH3 + X
and
the former by an inner-sphere mechanism with the group X acting as a bridge, uiz.
Co(CN):- +Co1"(NH3),X kl_ [(CN),Co"-X-Co1"(NH3),]'
rate
References p p . 142-1 52
-3
120
+ Co(CN):-
Co(CN):- +Co"'(NH,),X
rate
K2
[(CN),Co"(CN)(X)Co'"(NH,),I:
k , K , [Co"'(NH,),X] [Co(CN):
-1[CN -1
The nature of the group X determines the type of reaction which is the most
important. For X = azide, thiocyanate, hydroxide, chloride', bromide and
iodide' the inner-sphere bath operates while for X = ammonia or oxyanions
(including carboxylates)' the main pathway is the outer-sphere reaction. For X =
fluoride or nitrite the concentration of the cyanide ion present determines which
is the major reaction pathway.
Halpern et a l l , from data recorded using a stopped flow technique with
spectrophotometric detection, have obtained values of k , and k , K2 for each of the
above-mentioned anions.
For the Co(I1I) complex Co(NH,),NO;+, Halpern and Nakamura3 have
obtained spectrophotometric evidence for the inner-sphere reaction occurring via
C O ( C N ) ~ O N O ~which
isomerises to give the product Co(CN),NOl-. The
species Co(NH3),CN2+ also reacts in this manner to give Co(CN)'NC3- and
finally Co(CN):-.
Birk and Halpern4 have studied the Co(II), Co(CN):-, catalysed substitution
reactions
121
T R A N S I T I O N METALS
'.
3 2 Co(II1)
Co(IV)+Pb(II)
$ Co(II)+Pb(IV)
Whilst no direct measurements have been made on these Co(IV) reactions, the
ratio (k2/2 k , ) has been evaluated' as 0.15 at 25 "C.
+ 3 C1-
+(Rh
py4-C1-RhC1,)-
+trans-Rh
_f
slow
py4C12++Rh(I)
trans-Rh py4C1:
Other
have proposed steps involving catalysis by species other than
Rh(1) for some similar reactions.
References p p . 142-IS2
122
The isotopic method ( I 921r)has been used to investigate the exchanges between
the anions IrCli- and IrClz-. The separation methods used by Sloth and Garner'
were: ( a ) extraction of IrCli- with either 2-butanone or acetone-chloroform,
and (6) precipitation of the iridium (IV) as the ammonium salt. These authors
observed complete exchange in less than 42 sec, with reactant concentrations
M , at 1 "C in the absence of light with 1 M HCl as solvent. This corresponds to a rate coefficient in excess of 290 I.mole-'.sec-'.
Recently, Hurwitz and Kustin' have reinvestigated this exchange reaction using
the same isotopic procedure and the 2-butanone separation method, in conjunction
with a stopped flow apparatus. A rate coefficient of 2.3 x lo5 I.mole-l.sec-' was
obtained for the conditions, temperature 25 "C and ionic strength 0.1 M. Application of the Marcus theory to results obtained for the reaction
IrCli-
by the temperature jump method3 had led previously tc an estimate for this rate
coefficient of 2.5 x lo4 I.mole-'.sec-'.
8.5.8 The reaction between complexes of Zr(ZV) and Zr(IIZ)
Hurwitz and Kustin' have investigated the reactions
IrCIt-
k2
using the temperature jump method, with spectrophotometric detection (495 mp).
With potassium nitrate media ( p = 0.1 M)values ofk, and k2 (10 "C) are 1.1 x lo7
and 1.5 x lo6 I.mole-'.sec-', respectively, with energies of activation of 5.7 ( k , )
and 7.5 (k,) kcal.mole-'. The rate coefficients were found to depend on the ionic
strength of the medium and possibly on the size of the cation present. Hurwitz
and Kustin' have also obtained a value for the exchange rate coefficient (Marcus
theory) from this data of 1 x lo5 I.mole-'.sec-'.
8.6
PLATINUM
8.6.1 The exchange reaction between Pt(ZV) and Pt(ZI); Pt(ZI)-catalysed substitution reactions of Pt(ZV)
Two types of mechanism have been postulated to explain the experimental
observations on this exchange system.
123
T R A N S I T I O N METALS
Rich and Taube', using the isotopic method and a separation achieved by
precipitation of the ion PtCIi- as Cs,PtC16, have found Pt exchange in lo-, M
HCI media, at 25 "C, to occur in minutes in the presence of uv light and in many
hours under normal conditions. On this basis and using additional information
obtained from experiments on chloride exchange with the ions PtC1:- and
PtCI;-, a mechanism involving a Pt(II1) species, uiz.
+ 2 PtC1:PCCIZ - 5 PtCIi - + c1
PfCI:- +PtClZ-
+ PtC1:-
PtC1:-
+exchange
exchange
5Pt(en)Br, + Br
exchange
_ _ f
Pt(en)Br,
__f
rate
k'[Pt(IV)][Pt(II)][Cl-J
+[~1(en),~t-~1-~t(en),~l]~+
[Cl(en)2Pt-CI-Pt(en)2Cl]3 + ~t(en),Cl++ Pt(en),CI:
Pt(en),C~:+ +Pt(en),CI+
which, as Basolo et
have pointed out, provides a pathway for platinum
exchange. This has since been confirmedsp6.
Cox er d 5 using
,
the isotope 195Ptto label the species and tetraphenyl boron
References pp. 142-152
124
- -
Wen):+
+ trans-~t(l-pn),~:++ truns-~t(en),~:++Pt(/-pn):+
+ trans-Pt(l-pn),X:+
+Pt(en)2, +2 CI+
where X- is Br-, CNS-, CN-, CI-, CNO- and NO;, half times of minutes,
whereas for X- = OH-, SO:-, ClO;, C2H30;, F-, and NO; the half times are
hours. These reactions, which involve exchange and substitution, are also thought
to occur via a bridged dimer mechanism. Polarimetry was again used to obtain
the experimental results.
Ellison et aZ.* have reported that the substitution of one nitrite ion for one
chloride ion in the Pt(IV) species, trans- and ~ i s - P t ( N H ~ ) ~ Cand
l i + trans-Pt(en),
Cl$+,is catalysed by Pt(1I). In the absence of light, a rate law,
rate = k'[Pt(IV)][Pt(II)][NO;]
125
T R A N S I T I O N METALS
and a mechanism similar to that proposed for the chloride exchange reactions
with Pt(1V) was thought to occur. The values of k' (l'.mole-'.sec-')
at 50 "C
and truns-Pt(NH,),CJ,
are: truns-Pt(en)'Clq+, 10.1 ; cis-Pt(NH,),CI:+, 2.1 x
3.25. The species trans-Pt(tetrameen),CI, was found not to undergo substitution.
Other platinum(I1) catalysed substitution reactions which have been reported
are
trans-Pt(NH,),Cl:+ + Br- = truns-Pt(NH,),ClBr'+ + C1(1)
trans-Pt(NH,),ClBr'+ +Brtrans-Pt(NH,),Br$+
+ C1-
trans-Pt(NH3),BrC1'+
+ C1+ NH,
rruns-Pt(NH,),Br:+
= truns-Pt(NH,),Cl:+
+ Br-
(2)
(3)
(4)
Pt(NH3)5C13++ C1-
Pt(NH3)513++C1-
truns-Pt(NH,),ICl'+
+ NH,
(6)
Pt(NH,),13++Br-
trans-Pt(NH,),IBr'+ +NH,
(7)
Pt(NH3)513f + I -
t r ~ n s - P t ( N H ~ ) ~+NH3
Iq+
(8)
Pt(NH3),Br3+ + Br-
trans-Pt(NH,),Br:+
+NH,
(9)
trans-Pt(NH,),CI~+ +NH,
(10)
truns-Pt(NH,),Cl:+
Pt(NH3),CI3+ C1-
(5)
for which rate data has been obtained using spectrophotometric methods, by
Rettew and Johnson' for reactions (l), (2), (3) and (4), Johnson and Berger"
for reaction (5) and Mason and Johnson" for reactions (6), (7), (8), (9) and (10).
Values of the apparent rate coefficients (I'.mole-'.sec-')
at 25 "C for reactions
(1) to (lo), with the corresponding activation enthalpies (kcal.mole-') and
entropies (cal.deg- '.mole-') and ionic strength in parentheses, are : 108(8,- 24;
U
, = 0.2 M ) , 1 . 9 lo4
~ (3, -30; p = 0.2 M ) , 6.3 (11, -20; ,U = 0.2 M ) , 4 . 2 lo3
~
(6, -22; ,U = 0.2 M ) , 1.21 (6, -37; p = 0.375 M ) , 5.6 x 10' (11, - 10; p = 0.016
M ) , 1 . 2 lo4
~ (8, -15; ,U = 0.016 M ) , 3 . 9 10'
~ (6, -29; p = 0.016 M ) , 12
(10, -19; ,U = 3.2 M ) and 1.2 x lo-, (18, - 13; p = 3.2 M ) , respectively. In
all the above reactions a halide-bridged species participates. Johnson and Berger'
have made some rate measurements on the similar catalysed system
trans-Pt(NH,),pyC13+
+ C1- + trans-Pt(NH,),CIZf
+py
126
+Pt(diars):+
+ Y - = Pt(diars),XY'+
+ trans-Pt(PEt,),X,
+ Xu
where X- and Y - are either chloride or bromide ions, also occur via a
halide bridge mechanism. Peloso and Ettore", who have made a study of these
reactions using a spectrophotometric method, have found a rate law
rate = k; K[Pt(diars):+][Pt(PEt,),X,][Y-]/(l+
K[Y-1)
+ Pt(diars),Y'
to be applicable. Values of k; at 30 "C (p = 0.0385 M ) and the associated activation parameters (AH* and AS') obtained by these workers are: 4 . 1 4 ~lo-' I.
mole-'.sec-', 6.4 kcal.mole-' and -39 cal.deg-'.mole-'(X- = C1-, Y- = Cl-)
7.65 1.mole-'.sec-', 5.3 kcal.mole-' and -41 cal.deg-'.mole-'
(X- = Cl-,
Y- = Br-); 2.65 x lo3 1.mole-'.set-', 3.4 kcal.mole-' and -32cal.deg- '.mole-'
(X-= Br-, Y - = Cl-); and 3.9 x lo3 l.mole-'.sec-', 3.8 kcal.mole-' and -30
cal.deg-'.mole-' (X- = Br-, Y- = Br-). The mechanism proposed was
trans-Pt(PEt,),X,
+Pt(diars),Y+ + X,(PEt,),Pt-X-Pt(diars),Y+
X,(PEt,),Pt-X-Pt(diars),Y
+ +
trans-Pt(PEt,),X, +Pt(diars),XY2
+ X-
+ 2Br-
= trans-Pt(dien)NH,Br:
+CI- = trans-Pt(CN),C1Br2-
trans-Pt(en)(NO,),Cl,
trans-Pt(NO,),Br~ -
+ 2Br+ CI-
+ 2C1-
+ Br-
= trans-Pt(en)(NO,),Br,
trans-Pt(NO,),C1Br2-
(1 1)
(12)
-I-2C1-
+ Br-
(13)
(14)
by Mason',, reactions (12) and (14), and Syamal and Johnson14, reactions (11)
T R A N S I T I O N METALS
+ Pt(dien)Br+ +2Br-
trans-Pt(dien)BrCl;
trans-Pt(dien)NO,Cl;
trans-Pt(NH,),Cl;
trans-Pt(NH,),CI:
+ 2C1-
+ 2Br-
trans-Pt(dien)NH,Bri
+ Pt(NH,): + 2Cl+
+ +Pt(dien)Br+ +2Br-
trans-Pt(dien)NH,Cl:
rate
trans-Pt(dien)NO,Br: +Pt(NH3):+
+Pt(dien)NH:+
=
+2C1-
+ Pt(dien)NO: + 2Br-
trans-Pt(NH,),Cl:+
trans-Pt(dien)Br+ +Pt(NH,):+
+2CI-
trans-Pt(dien)Br:
+ Pt(dien)NH:+ + 2C1-
k'[Pt(IV)][Pt(II)][X]
where X is either the chloride or bromide ion, has been ~ b t a i n e d ' ~ . 'For
~ . reactions (11) and (12) the rate laws obtained were
rate
(k'[Br] +k"[Br]')~t(IV)][Pt(II)]
rate
( k , +k'[Cl-])[Pt(IV)][Pt(II)]
and
respectively.
For reactions (1 1)-(20) the values of the rate coefficients ( k ' ) (12.mole-'.sec-')
with the associated activation enthalpy (kcal.mole- ') and entropy (cal.deg. mole-') and ionic strength in parentheses are: 3.0 x 10' (4.2, -33; p = 0.1 M)I4,
7.2~
10 (2.5, -42; p = 1.01 M)',, 1 . 6 4 ~10' (5.8, -29; p = 0.1 M)',, 7 . 6 ~
lo-' (-1.6, -64; p = 1.01 M ) ' , at 25 "C, and 2 . 0 10'
~ (6.2, -27; p = 0.2 M ) ,
~ (7.6, -23; p = 0.2 M ) , 1 . 2 lo2
~
9 . 3 10'
~ (5.0, -28; p = 0.2M), 1 . 3 10'
(8.4, -21; p = 0.2 M ) , 4 . 0 lo2
~ (5.9, -27; p = 0.2 M ) , and 1.7 x 10' (8.0,
-21; p = 0.2 M ) 1 5 at 24.2 "C, respectively. The corresponding values associated
with the rate coefficients k , and k" (at 25 "C) are 7.8 l.mole-'.sec-' (-0.5,
'
128
I O N S O F SAME M E T A L I N D I F F E R E N T O X I D A T I O N S T A T E S
Ce(IV)
AND
Ce(II1)
rate = k'[Ce(III)]
+ ki[Ce(IV)][Ce(III)]
For media 6.18 M [HCIO,] at 0 "C, k' and k; have values 8.3 x
sec-' and
6.7 x
l.mole-'.sec-' with activation energies for these steps (k' and k ; ) of
19.4 and 16.8 kcal.mole- ', respectively. The mechanism proposed involved the
exchange steps
Ce(IV) + Ce(I1I)
-+
Ce(lV)+Ce(III)*
-+
+ + Ce(III)* + S
Ce(II1) S
From the dependence of the rate on [H'] it was concluded that hydrolysed species
are involved in the excitation step. For nitrate media where the step associated
with k ; predominates under the experimental conditions, the effect of variation in
the [H'] (1-6 M ) at ,u = 6.18 M was studied and results were interpreted on the
basis of a rate law
rate = k ; [Ce(Iv)][Ce( III)]
CERIUM A N D E U R O P I U M
129
was consistent with two exchange pathways, one involving fully aquated ions and
one hydrolysed species. At 0 "C k, and k;' have values of 2.5 x lo-' 1.mole-'.
sec-' and 0.3 mole.1-'.sec-' with activation energies of 7.7 and 24 kcal.mole-',
respectively.
Using a separation method based on the extraction of Ce(IV) by butyl phosphate
Parchen and Duke4 have made a further study of this exchange reaction. In
perchlorate media (- 6 M ) , at 0 "C, with Ce(1V) and Ce(II1) in the ranges 8 x
to
A4 and 8 x
to 8 x lop3M , respectively, the exchange data indicated
a rate law
rate
k ; [Ce(III)][Ce(IV)]
+ k;[Ce(III)][Ce(IV)]'
+ Ce(II1)
ki
k2
CeOCeOH5++Ce(III)+
It is interesting to note that a dimer of Ce(rV) has also been invoked to account
for observations on this exchange system at a platinum surface5. The rate of exchange between the fully aquated ions of Ce(1V) and Ce(II1) was concluded to
be relatively slow4.
Observations, made by Sigler and Masters6, on the exchange in 0.4 M H2S04
solution, have led to a rate law
rate
kobs[Ce(IV)] [Ce(III)]
M and Ce(III), 5 x
to
which was obeyed over the ranges Ce(IV),
to 1.1 x lo-' M . kobsat 0 "C has a value
4 . 2 ~lo-' 1.mole-'.set-'. These
authors have also reported their results for the exchange reaction induced by
hydrogen peroxide. A mechanism
H 0 2 +Ce(IV)
References pp. 142-IS2
+ H"
-+ Ce(III)+O,+H+
130
Eu(II1)
AND
Eu(I1)
The isotope ls2Eu has been used as a tracer in the study of this exchange
system'*2. In view of the instability of the Eu(1I) species the absence of both light
and oxygen are necessary. Separation of the two species, Eu(II1) and Eu(II),
was achieved using a hydroxide precipitation of the trivalent europium, brought
about by the addition of aqueous ammonia. Observations on the exchange in
perchlorate media were found to be obscured by the ClO; oxidation of Eu(1I).
However, in the presence of chloride ions the exchange rate could be measured in
perchlorate-containing media. A rate law for constant ionic strength (2.0 M )
rate
kob,[Eu(III)][Eu(I1)][Cl-]
',
EuC12
+ EuZ+
which is much more rapid than any involving the fully aquated or hydrolysed ions
of Eu(II1) and Eu(II), to occur.
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
131
containing hydrochloric acid4-' has been studied. The isotopic method (with
233Uas the tracer) was used with separations of the two oxidation states achieved
by ( a ) precipitation of the U(IV) as either the cupferron ~ o m p l e x or
~ , as
~ the
fluoride UF2 4 , 5 p and (b) aqueous extraction of U(IV) after the addition of
thenoyltrifluoroacetone in benzene3.
Betts' obtained evidence for the exchange in sulphate media being catalysed
by light of wavelengths
340 mp, the region of absorption of U(V1). In the presence of light a rate law, approximately
'
The rate was found to be unaffected by light and either [CI-] or [CIO,]. The
overall activation energy obtained was 33.4 kcal.mole- I. The mechanism of exchange suggested by Rona' was
+UOH3++H+
UOH3++ UO; + 2 H 2 0 +
U4++HZ0
(or,
OH
O=U-0-U-OH
O=U-0-U-OH
(K)
+ UOH3
OH d H
+
+2 H'
exchange
Masters and Schwartz3 have made a study of the exchange in perchlorate media
and have found two exchange pathways operate. One pathway involves exchange
via the process
U(V1) U(1V)
+ 2U(V)
with an activation energy of 38 kcal.mole-', the other via the pathway observed
for hydrochloric acid media with an activation energy of
28 kcal.mole-'. For
the former pathway a rate law
rate = kOb,[U(VI)][U(IV)]
where kobs = k"'([H+]3+K[H+]2)-1, was found to be obeyed over the range of
References p p . 142-152
132
conditions [U(Vi)] 2 x
to 4 x
M , [U(iV)] 1 x
to 5 x
M,
[H'] 6 x
to 2 x lo-' M , at temperatures of 25.1 to 47.1 "C. At 25.1 "Cand
p = 2.0 M , k"' hasavalue of 2 . 1 3 ~
mole2.1-2.sec-'. Values of the activation parameters of 37.5 kcal.mole-' and - 36 cal.deg-'.mole-' were calculated.
Ultraviolet radiation was found to increase the exchange rate in perchlorate media.
~ , found with various mixtures of aqueous hydrochloric acid
Amis et u I . ~ - have
with e t h a n ~ l ~acetone6,
.~,
or ethylene glycol7, exchange dependences with respect
to U(VI), U(IV) and H + which vary with the organic solvent content. Values of
2.70, 0 and - 1.26 (100 % ethanol) and 0.85, 0.66 and -0.53 (100 % ethylene
glycol) have been reported for the orders with respect to U(VI), U(IV) and H + .
With aqueous ethanol the activation energy was also found to depend upon the
solvent content; light was found to have no effect on the exchange rate'. Changes
in the mechanism are thought to O C C U ~ ~ * ~ * ' .
The rate coefficient for the exchange between U(Vi) and U(V) has been estimated as 52 I.mole-'.set-', at 25 "C in 1.0 M HC104, by Gordon and Taube',
from observations of the U(V)-catalysed water exchange reaction of aqueous
U(Vi).
10.2
R E A C T I O N S BETWEEN U R A N I U M IONS
Numerous studies have been made on the forward reaction of the equilibrium,
2 U(V)
+ U(Vi)+ U(iV)
using polarographic'
potenti~metric'.~
and spectrophotometric techniques'
-7,
O-
'
and a mechanism
UO: + H +
UO: + U O O H 2 +
UOOH'
+ UOOH2+
--f
UO;++UOOH+
U(IV)
The value of the rate coefficient k', (12.mole-2.sec-') has been calculated as 130
(p = 0.4 M ) ' , 1800 (p = 3.8 M ) 2 , 156 ( p = 0.5 M ) 4 , 260 ( p = 0.5 M , D20)4,
143 (p = 0.4
436 (p = 2.1 M ) 6 , 192 (p = 1.0 M ) 7 , 417 (p = 2.0 M ) 9 ,
150 (p = 0.5 M)" and 135 (p = 1.0 M)" at 25 "C in perchlorate media. Imai6
has also reported that addition of the anions C1-, Br-, I- and NO; accelerates
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
I33
K2
2 U(VI)+U(IV)
The dimer U,(XI), U20:+, was detected by its absorption at 737 mp. Analysis
of spectrophotometric data using the rate law
- -
10.3
The exchange reaction between Np(V1) and Np(V) has been investigated using
the isotopic method (239Np) and an extraction separation (Np(V1) with tributylphosphate or thenoyltrifluoroacetone in toluene)'-3. Cohen et al.' have
found, for the exchange in perchlorate media, a rate law
to 9 . 2 7 ~
M , [Np(V)]
134
2.6~
M , and [H'] 0.32 to 0.99 M . At p = 1.0 M and a
to 1 . 0 4 ~
temperature of 0 "C, kobshas a value of
30 I.mole-'.set-', with an associated
energy and entropy G f activation of 8.3 kcal.mole-' and -24 cal.deg-'.mole-',
respectively.
Cohen et aL2 and Sullivan et aL3, in further articles, report some data obtained
under higher ionic strength conditions and have suggested that kobs depends on
[H+] in the manner3
Values obtained for the coefficients k , and k ; at 4.5 "C ( p = 3.0 M ) were 73.5
1.mole- '.sec-' and 15 12.mole-2.sec-', respectively, with corresponding activation energies of 12 and 15 kcal.mole-'.
In deuterated solvent the rate of exchange was found to be lower than in aqueous
media; ths ratio kob,(H20)/kob,(D20)was found to be dependent on the acid
concentration. Sullivan et aL3 have suggested a hydrogen atom transfer process
and a water bridging process
NpO:
+H + + N p 0 2 H 2 +
N p 0 2 H 2 ++NpO:+
NpO:+ +NpO:
K2
5exchange
+ H 2 0 +exchange
ki
with values of the rate coefficients k b , k 3 and k, at 0 "C ( p = 3.0 M , [H'] = 3.0
M ) of 88.8, 215, and 86 I.mole-'.sec-', respectively. The energies and entropies
of activation were found to have values of 10.6 kcal.mole-', - 12.6 cal.deg-'.
mole-' (kb), 15.4 kcal.mole-', 6.7 cal.deg-'.mole-' (k3) and 15.3 kcal.mole-',
5 cal.deg- '.mole- ' (k,). A chlorine-atom transfer mechanism has been discussed.
Cohen et ~ l . have
~ , also made some observations on the exchange in watersucrose and water-ethylene glycol mixed solvents containing perchloric acid
(0.106 M ) . Over a range of dielectric constant 68 to 88, no alteration in the exchange rate was observed.
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
135
Sullivan et aL5, have studied the perchlorate media exchange reaction between
Np(V) and Np(1V) using the isotopic method (239Nptracer) and a separation
based on the extraction of Np(IV) with thenoyltrifluoacetone in benzene. Data
to 4.9 x lo-' M , [Np(IV)] 3.9 x
obtained over the ranges [Np(V)] 5 x
to 3.2 x
to
4.5
x
lo-'
M were found to fit a rate expresM a n d [H'] 4 x
sion
rate
'
The rate coefficients k ; and k i at 25 "C (p = 1.2 M) have values and corresponding activation parameters of 1.10 x
12.mole-2.sec-', 17.6 kcal.
mole-', -22 cal.deg-'.mole-' and 6.45 x lo-' mole.l-l.szc-', 36.8 kcal.mole-',
32 cal.deg-'mole- ', respectively. Some surface catalysis was found; the above
results relate to teflon reaction vessels. The processes suggested by these authors
were, for the path associated with k ; ,
2NpO:+H+
+ NpO:'+NpOzH+
+ Np( OH):'
exchange
NpO,H+
+ NpO:++Np3'
+exchange
+ NpOH3++ H +
N p O H 3 + + H 2 0+ Np(OH):++H'
Np4+ H,O
10.4
2 2 Np4'
136
et
-d[NpO:]/dt
= k;[NpO:][Np3+][H+]
to 1 . 0 ~
was found to be obeyed over the ranges [NpOl] 2.5 x
M,
[Np3'] 2.98 x
M and [H'] 1.08 x lo-' to 1.98 M . At 25 "C
to 1.04 x
and p = 2.0 M , k ; has a value 43.2 12.mole-2.sec-' (HzO solution) and 34.3 1'.
mole-'.sec-' (D'O solution). The activation energies obtained in this study were
6.52 (H'O) and 5.62 (D'O) kcal.mole-l. The mechanism suggested by these
workers involves reaction of the species Np(O)(OH)'+, which is produced by the
equilibrium
NpO:
+ H + + Np(O)(OH)'+
Kl
2 2 Np(V)
k4
k,,,[NpO:+][Np4+]"
'
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
137
+ N p 0 2 ++ 2 H + or
+ Np(OH)z++2 H +
Np4+ H 2 0
N p 4 + + 2 H,O
N p O f + + N p 0 2 ++N p O i + N p 0 3 +
Np03++H20
NpOZf+Np(OH)ff
Np(O)(OH),+
+ NpO:
--f
+ 2 H + or
2 Np(O)(OH),'
+ NpOl +H+
kobs = k;[H+]-2+k;'[H+]-3
was more accurate. Values of k; and k;' at 24.9 "C ( p = 2.2 M ) obtained were
4.27 x lo-, mole.l-'.sec-' and 5.04 x
mole2.1-2.sec- respectively.
For sulphate media much more complex rate laws for both the forward and
reverse steps of the reaction were found by Sullivan et a ~ the~ observed
,
rate
coefficient (kobs)being dependent on both [H'] and [HSO;]. For the forward
reaction
',
The values of the coefficients k;, k , , k6, k, and k, at 25 "C ( p = 2.2 M ) are
4 . 4 8 ~lo-, mole.l-l.sec-', 7 . 1 2 ~lo-' I.mole-'.sec-', 0.119 1.mole-'.sec-',
3.6 mole2.1-, and 1.7 mole3.1-j, respectively. The value of the overall activation
energy for the reaction in sulphate media is 23 kcal.mole-'.
For the reverse process the rate law obtained (sulphate media) was
-d[Np(V)]/dt
k'[Np(V)]2[H']o'09[HSO~]
(k,[HSO,I
+ k10[HS0,l2)(kI 1 + kl2[H+I)"P(V)l2
138
I O N S O F SAME METAL I N D I F F E R E N T O X I D A T I O N S T A T E S
energy for the reaction of 26.85 kcal.mole-' was also calculated from the experimental data. For the forward reaction in either perchlorate or sulphate media,
the reaction rate ratio (H,O: D20) lies between 4.33 and 5.65 depending on the
temperature. For the back reaction the same ratio has a value of 0.4, and the values
of the terms k , and k , , at 25 "C (p = 2.0 M ) for deuterated sulphate media are
1.17 x
12.mole-2.sec-' and 5.8 x
13.mole-3.sec-', respectively3.
10.5
~,,,[Pu(IV)][PU(III)]
For 0.5 M perchloric acid kobs has a value 1.8 x lo2 I.mole-'.sec-' at 0 "C'.
From results obtained at p = 2.0 M , [H'] = 0.40 to 2.0 M , Keenan concluded
that the pathways operative were
ki
PU4+ +pu3+ +
kz
PuOH~++PU~+
Pu4+ + H,O
+ PuOH3++ H +
K,
Using known values of the constant K 2 , the values of k , and k 2 were calculated
as 1.8 x lo2 and 1.3 x lo4 I.mole-'.sec-',
respectively, at 0 "C and p = 2.0 M.
The activation energies and entropies obtained for the k , step were 7.7 kcal.
mole-' and -31 cal.deg-'.mole-'; for the k 2 step values of 2.8 kcal.mole-'
and -32 cal.deg-'.mole-'were found.
10.6
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
puo;+ + pu3+
3.puo:
7
139
+pu4+
k2
-d[Pu3+]/dt
k l ( l - K/K*)[PuO;+][Pu3+]
3 P~(IV)
occurs, owing to the instability of Pu(V) in this media. Alexi et u I . ~have used a
spectrophotometric method to make a brief investigation and have suggested that
the steps
are amongst the processes occurring. The reaction appears to depend on the concentration of the Pu present.
From spectrophotometric studies on 0.5 A4 HCI solutions of plutonium containing Pu(V), Connick4 attempted to investigate the disproportionation reaction
of this species
k'a
2 Pu(V) $ Pu(IV)+Pu(VI)
k's
From his results, Connick concluded that the reactions also occurring were
Pu(V)+Pu(III)
22Pup)
k.6
Pu(V)+Pu(IV)
References pp. 142-152
2 Pu(VI)+Pu(III)
k'
140
I O N S OF SAME METAL IN D I F F E R E N T O X I D A T I O N S T A T E S
and he was able to obtain values of the rate coefficients k; and k ; at 25 "C of
5.8 x lo-' and < 2 x
Lmole-'.set-', respectively; in conjunction with
equilibrium data, estimates of kk and kk for the same conditions, of 3 . 5 ~
and < 1.2 x
I.mole-'.sec-', respectively, were made.
Rabideaus, using EMF measurements to obtain rate data, has since reinvestigated
the disproportionation reaction of Pu(V), using solutions containing very small
amounts of Pu(IV) and Pu(II1). He was able to conclude from the dependence
of the rate coefficient (kj) on the first power of [H'] that the steps and equilibrium
present were
PuO:
+ H + + Pu(O)OH'+
p = 1.0 M , [H']
3Pup)
+ Pu(VI)+2 Pu(rI1)
3 k~(l-K*/K)[Pu(IV)IZ
+ Pu(OH):+ + H +
--+Pu3++Pu0:
+H30+
10
U R A N I U M , N E P T U N I U M , P L U T O N I U M A N D AMERICIUM
141
'.
10.7
Keenan et a[.' have carried out a brief survey on the exchange reactions
A m O l + Am3+ -+
AmO:'
+AmOz
-+
In perchlorate media the latter reaction was found to be rapid (100 % exchange
in < 60 sec) and the former reaction slow (half times of > 200 hours at 100 "C).
The isotopic method was used (242Am).
10.8
-d[AmOl]/dt
k,,,[Am0~]'[H+]4
was ~ b e y e d ' . ~ - ~ .
In 1962, Coleman6, using the relatively stable 243Am, was able to study the
reaction of Am(V) in various media in more detail and found a rate law
-d[AmO:]/dt
k;[AmOl]2[H+]'
+ k',"Am0:]2[H+]3
142
I O N S OF S A M E M E T A L I N D I F F E R E N T O X I D A T I O N S T A T E S
+ Am(V1) + Am(IV)
Am(IV)+ Am(V)
+ Am(III)+Am(VI)
The reaction between Am(V1) and Am(1II) has been detected6 but no kinetic
data has been reported.
Americium(1V) has been found to undergo similar reactions, viz.
+ Am(V)+ Am(II1)
Am(IV) + Am( V) + Am(111) + Am( VI)
2 Am(1V)
Penneman et ~ l . have
~ , studied these reactions in acidic sulphate, nitrate and
perchlorate media, and have found that only in sulphate media is the latter step
relatively important. The disproportionation reaction rate coefficient has been
I.mole-'.sec-' at 0 "C (media5 x lo-' M i n HNO,).
estimated as > 1.03 x
REFERENCES
1. Introduction
REFERENCES
143
2
3
4
5
6
7
8
9
10
I1
12
13
14
15
16
17
144
5.1 The exchange reaction between Sn(1V) and Sn(l1) in aqueous media
1
2
3
4
C. I. BROWNE,
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M. A. MELNICK,
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A N D M. KAHN,J. Am. Chem. SOC.,73 (1951) 4950.
2 E. G. MEYER
5.3
5.4 The exchange reaction between Pb(1V) and Pb(l1) in non-aqueous media
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A N D L. ZECHMEISTER,
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2 E. A. EVANS,J. L. HUSTON
6.1 The exchange reaction between As( V ) and As(ll1)
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P. DAUDEL,
R. DAUDEL
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2 M. MARTIN,
6.2 The exchange reaction between Sb( V ) and Sb(ll1) in aqueous media
1
2
3
4
5
6
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9
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11
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13
14
15
J. E. WHITNEY
A N D N. DAVIDSON,
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H. M. NEUMANN,
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H. M. NEUMANN
AND R. W. RAMETTE,
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N. A. BONNER,
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H. M. NEUMANN
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K. YAMAGUCHI
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6.3 The exchange reaction between Sb( V ) and Sb(III) in non-aqueous rnediu
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K. R. PRICEA N D C. H. BRUBAKER,
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I
2
3
4
8.1.2
1 S . G. FURMAN
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5.1.3
I H. A. TEWES,J. B. RAMSEY
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I
2
3
4
5
8. I .5
T. W. NEWTON
A N D F. B. BAKER,
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8.2.1
2
3
4
5
6
7
8
9
146
10 D. R. STRANKS,
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11 E. DEUTSCH
AND H. TAUBE,
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Inorg. Chem., 9 (1970) 486.
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c. s. GARNER,
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1 E. L.GOODENOWAND
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AND R. A. BAILEY,
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2 D. S. MATTESON
8.3.2 The exchange reaction between Mn(III) and M n ( I I )
1 M. POLISSAR,
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2 A. W. ADAMSON,
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6
7
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2
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6
M. J. POLISSAR,
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8.4.1 The exchange reaction between Fe(III) and Fe(II) in aqueous media
I
2
3
4
5
6
7
8
9
10
148
8.4.2 The effect of inorganic ions on the exchunge between Fe(III) and Fe(II)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
J. SILVERMAN
AND R. W. DODSON,
J. Phys. Chern., 56 (1952) 846.
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AND R. W. DODSON,
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J. J. CONOCCHIOLI
AND N. SUTIN,
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C. Foxx AND W. L. REYNOLDS,
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A N D E. H. AXELROD,
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A N D S. DUCKWORTH,
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AND S. DUCKWORTH,
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A N D L. C. BROWN,
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8.4.3 The effect of organic ligands on the exchange between Fe(III) und Fe(II)
2
3
4
5
6
7
8
9
10
II
12
8.4.4 The exchange reaction between Fe(II1) and Fe(II) in non-aqueous and mixed soluents
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2
3
4
5
6
I
2
3
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5
6
7
A. C. THOMSON,
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A N D E. WICKLER,
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A N D N. SUTIN,
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.
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Inorg. Chern., 5 (1966) 1618.
8.4.10 Ru(II)-catn/ysedsubstitution reactions of Ru(II1)
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8.5.2 Exchange reactions involving complexes of Co(II1) and Co(II) with ammonia and organic
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2
3
4
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8
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11 Y . A. 1 M AND D. H. Busca, J. Am. Chem. Soc., 83 (1961) 3357.
12 Y.A. 1M A N D D. H. BUSCH,J. Am. Chern. SOC.,83 (1961) 3362.
F. BASOLO
AND H. M. NEUMANN,
J. Phys. Chem., 63 (1959) 371.
13 B. R. BAKER,
AND M. J. G. WILLIAMS,
J. Chem. SOC.,(1957) 4456.
14 P. ELLIS,R. G. WILKINS
15 N. S. BIRADAR,
D. R. STRANKS
AND M. S. VAIDYA,
Trans. Faraday SOC.,58 (1962) 2421.
A N D J. P. HUNT,J. Am. Chem. Soc., 90 (1968) 7210.
16 T. J. WILLIAMS
17 S. BRUCKNER,
V. CRESCENZI
AND F. QUADRIFOGLIO,
J. Cheni. SOC.,A (1970) 1168.
8.5.3 The exchange reaction between Co(III) and Co(I1) in non-aqueous media
1 J. J. GROSSMAN
A N D C. S. GARNER,
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2 B. WEST,J. Chem. SOC.,
(1952) 3115.
3 B. R. BAKER,
F. BASOLO
AND H. M. NEUMANN,
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HALPERN
AND S. NAKAMURA,
J. Am. Chern. SOC.,
85 (1963) 2517.
A. W. ADAMSON,
J. Am. Chern. SOC.,78 (1956) 4260.
J. HALPERN
AND S. NAKAMURA,
J . Am. Chern. SOC.,87 (1965) 3002.
J. P. BIRKAND J. HALPERN,
J. Am. Chern. SOC.,90 (1968) 305.
R. FARINA
A N D R. G. WILKINS,
Inorg. Chem., 7 (1968) 514.
1 J. P. CANDLIN,
J.
2
3
4
5
29 (1960) 60.
2 P. J. PROLL,Ph. D. Thesis, Liverpool University (1962).
8.5.6 Rh(I)-catalysed substitution reactions of Rh(III)
1 J. V. RUND,F. BASOLO
AND R. G. PEARSON,
Inorg. Chem., 3 (1964) 659.
J. A. OSBORNEAND
G. WILKINSON,
J. Chem. SOC.,(1965) 1951.
2 R. D. GILLARD,
3 R. D. GILLARD,
J. A. OSBORNE
A N D G. WILKINSON,
J. Chem. Soc., (1965) 4107.
REFERENCES
151
Pt(IV)
1 R. L. RICHAND H. TAUBE,
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D. S. MARTINAND L. T. Cox, J. Inorg. Nucl. Cheni., 7 (1958) 113.
2 R. E. MCCARLEY,
P. H. WILKS,R. G. PEARSON
AND R. G. WILKINS,
J. Inorg. Nucl. Chem.,
3 F. BASOLO,
6 (1958) 161.
A. F. MESSING,P. H. WILKS,R. G. WILKINS
A N D R. G. PEARSON,
J. Inorg.
4 F. BASOLO,
Nucl. Chern., 8 (1958) 201.
5 L. T. Cox, S. B. COLLINS
AND D. S. MARTIN,
J. Inorg. Nucl. Chem., 17 (1961) 383.
6 F. BASOLO,
M. L. MORRISA N D R. G. PEARSON,
Discussions Faraduy Soc., 29 (1960) 80.
AND F. BASOLO,
J. Inorg. Nucl. Chem., 13 (1960) 36.
7 R. C. JOHNSON
8 H . R. ELLISON,
F. BASOLO
AND R. G. PEARSON,
J. Am. Chem. Soc., 83 (1961) 3943.
9 R. R. RETTEW
AND R. C. JOHNSON,
Inorg. Chem., 4 (1965) 1565.
10 R. C. JOHNSON
AND E. R. BERGER,
Inorg. Chem., 4 (1965) 1262.
Inorg. Chem., 4 (1965) 1258.
11 W. R. MASONA N D R. C. JOHNSON,
AND R. ETTORE,
J. Chem. Soc. A, (1968) 2253.
12 A. PELOSO
13 W. R. MASON,Inorg. Chem., 8 (1969) 1756.
14 A. SYAMAL
AND R. C. JOHNSON,
Inorg. Chem., 9 (1970) 265.
AND R. C. JOHNSON,
Inorg. Chem., 8 (1969) 2596.
15 S. G. BAILEY
AND E. R. BERGER,
Inorg. Chem., 7 (1968) 1656.
16 R. C. JOHNSON
V. J. LINNENBOM
AND A. C. WAHL,J. Am. Chem. Soc., 71 (1949) 2589.
J. W. GRYDER
AND R. W. DODSON,
J. Am. Chem. Soc., 71 (1949) 1894.
J. W. GRYDER
AND R. W. DODSON,
J. Am. Cheni. Soc., 73 (1951) 2890.
F. R. PARCHEN
AND F. R. DUKE,
J. Am. Chem. Soc., 78 (1956) 1540.
S. FRONAEUS
A N D C. 0. OSTMAN,
Acta Chem. Scond., 10 (1956) 769.
P. B. SIGLER
AND B. J. MASTERS,
J. Am. Chem. Soc., 79 (1957) 6353.
G. E. CHALLENGER
A N D B. J. MASTERS,
J. Am. Chem. Soc., 77 (1955) 1063.
H. C. HORNIGAND W. F. LIBBY,J. Phys. Chem., 56 (1952) 869.
2
3
4
5
6
7
8
2
3
4
5
D. M. H. KERNAND E. F. ORLEMAN,
J. Am. Chem. Soc., 75 (1953) 3059.
K. A. KRAUS,F. NELSON
A N D G. L. JOHNSON,
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F. R. DUKEAND R. C. PINKERTON,
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J. KORYTA
AND J. KOUTECKY,
CON.Czech. Chem. Cornmun., 20 (1955) 423.
152
I O N S O F S A M E METAL IN D I F F E R E N T O X I D A T I O N STATES
6
7
8
9
10
11
12
13
1 D. COHEN,
J. C. SULLIVAN
A N D J. C. HINDMAN,
J. Am. Chem. Soe., 76 (1954) 352.
J. C. SULLIVAN
A N D J. C. HINDMAN,
J. Am. Chem. SOC.,77 (1955) 4964.
2 D. COHEN,
3 J . C. SULLIVAN,
D. COHEN
AND J. C. HINDMAN,
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4 D. COHEN,
J. C. SULLIVAN,
E. S. AMISAND J. C. HINDMAN,
J. A m . Chem. SOC.,78 (1956)
1543.
5 J. C. SULLIVAN,
D. COHENA N D J. C. HINDMAN,
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10.4 Reuctions between neptunium ions
1
2
3
4
5
J. C. HINDMAN,
J. C . SULLIVAN
A N D D. COHEN,
J. Am. Chem. Soc., 80 (1958) 1812.
J. C. HINDMAN,
J. C . SULLIVAN
AND D. COHEN,
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J. C . SULLIVAN
A N D D. COHEN,
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D. COHEN
AND J. C. HINDMAN,
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A N D J. C. HINDMAN,
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1 T. K. KEENAN,
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2 T. K. KEENAN,J. Phys. Chern., 61 (1957) 1 117.
10.6 Recictions between plirtonirim ions
1 0. E. OCARDA N D S. W. RABIDEAU,
J. Pliys. Chem., 60 (1956) 812.
2 s. W. RABIDEAU
A N D R. J. KLINE,J . Phys. Cheni., 62 (1958) 617.
3 M. ALEXI,Q. C. JOHNSON,
H. D. COWANA N D J. F. LEMONS,
J. Inorg. Niicl. Chem., 29
(1967) 2327.
J. Am. Chem. Soe., 71 (1949) 1528.
4 R. E. CONNICK,
5 S. W. RABIDEAU,
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7 R. E. CONNICK
A N D W. H. MCVEY,
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8 S. W. RABIDEAU
A N D H. D. COWAN,
J. Am. Chem. SOC.,77 (1955) 6145.
10.7 Exchiinye reactions bet ween americiiim ions
1 T. K. KEENAN,
R. A. PENNEMAN
A N D J. F.
SU1 TLE,
G. R. HALLAND P. D. HERNIMAN,
J. Chem. Soe., (1954) 2214.
G. R. HALLA N D T. L. MARKIN,
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S. R. G U N NA N D B. B. CUNNINGHAM,
J. Am. Chem. Soc., 79 (1957) 1563.
R. A. PENNEMAN
A N D L. B. ASPREY,
Intern. Con5 Peaceful Uses Atomic Energ), Vol. 7,
1955, p. 355.
5 A. A. ZAITSEV,
V. N. KOSYAKOV,
A. G . RYKOV,Yu. P. SOBELEV
A N D G . N. YAKOVLEV,
Radioklziniiyci, 2 (1960) 339.
6 J. S. COLEMAN,
Inorg. Chem., 2 (1963) 53.
7 R. A. PENNEMAN,
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AND T. K. KFENAN.J . Inorg. Nircl. Chem., 17 (1961 ) 138.
Chapter 3
Oxidation-Reduction Reactions
Between Complexes of Different Metals
D. B E N S O N
1. Introduction
The last two decades have seen a growing interest in the mechanism of inorganic reactions in solution. Nowhere is this activity more evident than in the
topic covered by this review: the oxidation-reduction processes of metal complexes. This subject has been reviewed a number of times previously, notably by
Taube' (1959), Halpern' (1961), Sutin3 (1966), and Sykes4 (1967). Other articles
and books concerned, wholly or partly, with the topic include those by Stranks',
Fraser6, Strehlow7, Reynolds and Lumry', Basolo and Pearson', and Candlin
et af.'Ot. Important recent articles on the theoretical aspects are those by Marcus"
and Ruff 12. Elementary accounts of redox reactions are included in the books by
Edwards13, SykesI4 and Benson". The object of the present review is to provide a
more detailed survey of the experimental work than has hitherto been available.
The material included is organised according to the periodic table as follows.
Classification, in the first place, is on the basis of oxidants, arranged in order of
their position across the periodic table, i.e., from vanadium to lead. The reactions
of the lanthanide cerium(1V) and the actinides are treated last. Within each section
the order for each oxidant is of decreasing oxidation number. In general, reductants
within each section and sub-section are arranged, again according to the periodic
table, but in order of increasing oxidation number. However, in sections (6.1)
and (6.2), dealing with oxidations by cobalt(III), the subject matter is such that
no classification on the basis of reductant has been attempted.
In terms of gross features of mechanism, a redox reaction between transition
metal complexes, having adjacent stable oxidation states, generally takes place in
a simple one-equivalent change. For the post-transition and actinide elements,
where there is usually a difference of two between the stable oxidation states, both
single two-equivalent and consecutive one-equivalent changes are possible.
AS regards intimate mechanism, electron transfer reactions of metal complexes
are of two basic types. These have become known as outer-sphere and innersphere (see Chapter 4, Volume 2). In principle, an outer-sphere process occurs
with substitution-inert reactants whose coordination shells remain intact in
t See, also, S ~ t i n ~ ' ~ .
References pp. 267-273
154
C O M P L E X E S O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
forming the activated complex. In other words, electron transfer proceeds more
rapidly than substitution in the coordination shell of one of the reactants. Conversely, in inner-sphere processes substitution takes place prior to electron
transfer. The direct and indirect criteria used in distinguishing between inner- and
outer-sphere mechanisms have been discussed in detail by Sutin3.
2. Oxidations by vanadium
2.1
OXIDATIONS BY VANADIUM(V)
V 0 2 + Fe( 11) + 2 H +
V 0 2 + + Fe(III)+ H 2 0
-d[Fe(II)]/dt
k'[V(V)][Fe(II)]
k' = u / [ H+ ] + b + c [ H + ]
The three terms of this expression indicate three competitive activation processes,
respectively
V 0 2 + + F e 2 + +H 2 0 +
V 0 2 + +Fe2+
_f
(V02FeOH2+)'+H+
(V02Fe3+)*
V 0 2 ++ Fe2++ H + +(HV02Fe4+)*
assuming inner-sphere structures for convenience. The term in a is barely significant, and the c term ytrongly predominates over the b term. At 25 "C and
p = 1 M the value of c [the rate coefficient for the most important path (2.3)]
is 3400 12.mole-2.sec-'. Under the same conditions a value of 60 I.mole-'.sec-'
can be assigned tentatively to b. The activation parameters corresponding to
155
OXIDATIONS BY V A N A D I U M
step (2.3), AH' and AS', are 1.52 kcal.mole-' and -37.3 cal.deg-'.mole-',
respectively. It is noteworthy that the following reduction reactions of the analogous MOz+ actinide ions show a similar first-order hydrogen-ion dependence:
( N p 0 2 ++Fe2+)17, ( N p 0 2 + + N p 3 + ) ' * , ( P U O , + + P U O ~ ~ )and
' ~ , ( UO z + +
U 0 2 + ) 2 0 .In Table 1 the activation parameters of the V(V)+Fe(II) reaction are
TABLE 1
ACTIVATION PARAMETERS FOR REACTIONS H A V I N G
AH '(kcal.
mole-')
+4
A C T I V A T E D COMPLEXES"
st
Ref.
corpku
-~
VO,+ + F e 2 + + H + + (HV02Fe4+)I
NpO,+ + F e z + + H + + (HNpO2Fe4+)'
Fez --Fe3
H zO (FeOH Fe4 )' 4-H
Cr2+T C ~ +~H+z O + (CrOHCr4+)'+H+
Fez+ L C o 3 + + H z 0 + (FeOHCo4+)X+H+
V 3 + + V O Z + + H z 0+ ( V O H V 0 4 + ) ' + H +
v3 'voZ + ( v o 2 v 4 +):
+
1.52
8.6
19.4
22
18.8
20. I
16.6
-37.3&0.6
-38
9.9*1.4
- 2 +5
+I6 ~ t 4
- 3 k5
5 1 6
-7Ofl
-69
-70+1
-79f5
-66*4
-77+5
-6516
16
17
22
23
24
25
26
contrasted with those of other redox reactions for which the net charge on the
activated complex is +4. The V(V) + Fe(I1) reaction is remarkable in having a
very low enthalpy of activation, considerably smaller than AH' for the Np(V)+
Fe(I1) system (which also involves the breaking of a metal-oxygen bond), and
rather surprisingly, lower than AH' for the exchange between Fe(CN)63- and
Fe(CN),4-. The AS' values in Table 1 are seen to vary widely from -38 to 16
cal.deg- '.mole-'. However, the (formal) ionic entropies (S'complex)
of the + 4
activated complexes are similar (-65 to -79 cal.deg-'.mole-') and comparable
to those for reaction between two actinide ions". Thus it is apparent that the
prime factor in deciding the entropy of these types of activated complexes is the
charge and not the size of the complex.
The reduction of V(V) to V(1V) by Fe(I1) has been also studied by Nicol and
Rosseinskyz7.z8. These authors used a polarographic method employing a
rotating platinum electrode-calomel electrode pair. Under certain conditions of
applied voltage, the diffusion current depends only upon the concentration of
Fe(1I). Nicol and Rosseinsky conclude, after studying the reaction over wider
ranges of conditions than those of Daugherty and Newton16, that the complex
dependence on hydrogen-ion concentration is better described by
k' = ~ + c [ H + ] + ~ [ H + ] ~
They attribute this to the existence of three reaction paths, given by eqns. (2.2)
References pp. 266273
156
(2.4)
V(V)+Sn(IIl) -+ V(IV)+Sn(IV)
(2.5)
V(V)+Sn(II)
V(IV)+Sn(III)
V(V)+V(III)
-+
--f
V(III)+Sn(W)
(2.6)
2 V(N)
(2.7)
in which the reactant species undergo one-equivalent changes. Tnstead, an alternative scheme, made up of a primary two-equivalent change
V(V)+ Sn(1I)
V(111) Sn(IV)
(2.8)
coupled with steps (2.4), (2.5) and (2.7), is more in accord with the experimental
results on stoichiometry. From a detailed analysis of the kinetic implications of
this reaction sequencc it is concluded that about 90 % of effective encounters
between V(V) and Sn(1l) result in the direct formation of V(I1I)and Sn(IV), whilst
the remaining 10 7; yield V(1V) and Sn(II1). It is conceivable that the reaction
involves an association complex represented as (V+ Sn)"" which, in addition
to dccaying to V([Il)+Sn(lV), or V(IV)+Sn(III) (steps (2.8) and (2.4), respectively), can persist for a sufficient time in solution to react further with V(V) to
generate V(1V) and Sn(IV), viz.
Evidence has been cited for a similar 1 : 1 complex formed between Sn(I1) and
U(V1) in hydrochloric acid3'. Path (2.9) is expected to become morc important
at relatively high initial concentrations of V(V). For conditions in which the
t Although the rate was found to be too great to measure in hydrochloric acid media, the
V(V) i-Sn(l1) reaction has been investigated more recently in perchloric acid2".
O X I D A T I O N S BY V A N A D I U M
I57
2.2
OXIDATIONS BY
VANADIUM(IV)
'
Kinetic data were obtained over wavelengths ranging from 260 to 760 mp. The
presence of an intermediate is readily apparent: on mixing pale-blue solutions
of V(1V) and Cr(I1) a bright green colour develops immediately, and then fades
slowly to the blue-purple colour characteristic of V3+ and Cr3+.From the response
of the rate to variations in acidity, it is deduced that the reaction proceeds mainly
via a rapid "direct" route and that only a small portion occurs via the intenselycoloured intermediate at a measurable rate. It is clear that the direct path cannot
be a two-equivalent change, involving V(11) and Cr(IV) as intermediates, since the
product Cr(II1) species is the aquo ion, and not the dimer which would be produced
from the interaction of Cr(IV) and Cr(II)33. Also, as the dimeric species VOV4+
(formed from V(IV) +V(II)34) is not detectable at 425 mp, appreciable concentrations of V(I1) cannot be present. The rate of disappearance of the intermediate
{which follows first-order kinetics) increases as the hydrogen-ion concentration
increases although the dependence is complex: over ranges of 0.010 to 0.99 M
HC104 and 5" to 25 "C at p = 1.00 M the following expression applies
k' = ( A K + B[H+])/(K+ [H'])
(2. lo)
where A and B are constants, and K is the equilibrium constant for equilibrium
between acid and base forms of the intermediate. Formulating the intermediate
as VO(OH),,Cr("-")+ and the equilibrium as
(koK+kl[H+])/(K+ [I+])
158
can be obtained by assuming that the intermediate decays by the two competitive
processes
VO(OH),+ ,Cd3-")+
products
- -
Wavelength (mp)
159
OXIDATIONS B Y V A N A D I U M
TABLE 2
DECOMPOSITION RATES OF BINUCLEAR METAL COMPLEXES'
Mode of formation
Binuclear species
Specific decomposition
rate at 25.0 "C (sec-')
Ref.
Cr(IV) +Cr(ll)
and
Cr(III)+OH-
CrOHCrS
1.5 x I O - ~
Cr(IlI),
-5.7
33b, 36
Np(V1) +Cr(lII)
and
N p (V) Cr (11)
Np02Cr4+
2.3 x
Cr(III),
-5.7
37
V(IV)+V(II)
and
V(II1) + O H -
vov4+
0.03 +1.54[H+]
V(III),
t1.8
34
VO(OH).Cr(4-n)+
0.017+0.645[Ht]
V(III),
+1.8
32
0.35 + 3 . 5 [ H + ]
Fe(III),
+2.1
38
V(1V) +Cr(II)
Fe(IV)+Fe(II)
and
Fe(III)+OHa
FeOFe4+
From Espenson3*.
2.3
OXIDATIONS BY VANADIUM(III)
- d[V3+]/dt = k'[V3+ ] [ C r Z f ]
over wide ranges of wavelengths and reactant concentrations. No direct evidence
could be adduced for the existence of intermediates. The rate response to variations
in acidity demonstrates that the observed rate coefficient, k', can be considered in
terms of two empirical parameters q and r
k' = q / ( r + [H'])
References p p . 266-273
(2.11)
160
COMPLEXES O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
To account for the inverse dependence of k' on [H'], Espenson4' has proposed
the following general mechanism
V 3 + + C r 2 + + nH 2 0
+ V(OH),Cr(5-")++n H +
ki
(2.12)
k-i
V(OH),Cr(5-")++(n-lj H + 3 (e.g., V 2 + + C r O H 2 + )
(CrOH2++Hf
(2.13)
C r 3 + + H 2 0 ,rapid equilibrium)
(2.14)
rate
q[v3+][cr2+]
-.
r
+ [H']
It follows that the reaction proceeds via two consecutive activated complexes:
OXIDATIONS BY VANADIUM
161
(VCr")'
and (V(OH)Cr4+)'. In Espenson's mechanism, equations (2.12) to
(2.14), (VCr")' is formed directly from the interaction of V 3 + + C r 2 + ,an event
which is followed by the spontaneous aquation of (V(OH)Cr4+)t. However, as
Haim points out, (V(OH)Cr4+)', formed from VOH" +Cr2+, may precede
(VCr5+)*,formed from V(OH)Cr4++ H + , as shown by
(2.16)
(2.17)
k-3
(2.18)
On this mechanism
rate
k , k4 K[V3+][Cr2+]
k-3 +k4[H+]
162
COMPLEXES OF DIFFERENT
M E T A L SO :X I D A T I O N - R E D U C T I O N
''
ks
V O H ~ ++ E ~ -f
~ +
(2.19)
products
(2.20)
OXIDATIONS BY
CHROMIUM(VI)
Cr3'+3V02++H20
That HCr04-, V 0 2 + and V 0 2 + are the predominant species under the conditions
of Espenson's kinetic study5' originates from evidence cited by Tong and King5',
No binuclear species are detectable
and Rossotti and R o ~ s o t t i respectively.
~~,
in the Cr(lI1) product. Vanadium(V) retards the reaction and the full form of the
rate law is
OXIDATIONS BY
Cr
AND
163
Mo
tion number for Cr and V of 4.5, i.e., 0.5 (2x4+6-5). Such a transition state
could stem from a V(II1) + Cr(V1) or V(IV) Cr(V) combination. In terms of
oxidation numbers the possible mechanisms involve either disproportionation
of V(1V) followed by a two-equivalent oxidation of V(II1) ( A ) , or a sequence of
three one-equivalent steps ( B ) ;viz.
2 V(IV)
2 V(V)+V(III)
rapid, K
k-i
slow
V(IV)+Cr(IV)
+ V(V)+Cr(III)
rapid
V(IV)+Cr(VI)
+ V(V)+Cr(V)
rapid, unfavourable
(3.2)
slow
(3.3)
rapid
(3.4)
or
( B ) V ( I V ) + C r ( V ) d V(V)+Cr(IV)
V(IV)+Cr(IV)
+ V(V)+Cr(III)
VOz+ HCr0,-
V 0 2 ++H3Cr0,
(H3Cr0,VO2+)'
rapid
slow
are in equilibrium by
2 HCr04- $ C r , 0 7 2 - + H , 0
as 98 ].mole-' at 25 "C
The equilibrium constant has been measured spectroph~tometrically~'
and ,u = 1 M .
References pp. 267-273
164
C O M P L E X E S 0 F D I FF E R E N T M E T A L S: 0 X I D AT I 0 N-R E D U C TI 0N
Cr3++3Fe3++4H 2 0
+ FeCrO," + H +
K,
received detailed study and a value of Kl = 1.4 was assigned at 0 "C and ,u =
0.0839 M t . Effectively, this result means that under these conditions 8 to 40 %
of Cr(V1) is present as Fe(II1)-chromate complex. Rate measurements on the
Cr(V1) Fe(I1) reaction were made both by a direct spectrophotometric approach,
and by the titrimetric method first used by B e n ~ o n(utilising
~~
the induced oxidation of iodide ion). Iron(II1) retards the reaction and the corresponding rate law
takes the form
- -
Cr(V1) Fe(I1)
Cr(V)+ Fe(l1)
Cr(IV)+Fe(II)
2.2 x
1OI2
ls.mole-s.sec-'
at
+ Cr(V) + Fe(III)
4
Cr(IV)+Fe(lII)
rate-determining
Cr(lII)+ Fe(1II)
rapid
The first term of (3.5) implies a corraponding net activation process" represented
+ See, also, ref. 278.
,.
OXIDATIONSBY
Cr A N D Mo
H C r 0 4 - + 2 F e Z + + 3H + + ( n - 2 ) H,O
-+
165
[FeOCrO(OH,),3+]t+Fe3+
That is, the activated complex contains one Cr(V) atom and one Fe(I1) atom.
Espensonsobhas shown, from a consideration of the induced oxidation of iodide
ion, that the reaction between Cr(V1) and Fe(I1) requires one added proton.
Consequently, the [H+I3-dependence of the rate can be viewed as the addition
of two protons in a pre-equilibrium followed by the addition of a further proton
in the slow step, viz.
HCr04-+FeZ++2H +
H3Cr04+Fe2++ H +
+ H3Cr04+Fe3+
rapid
(H4Cr04Fe3f)t
slow
-+
HCrO,-+3 Fe(phen),'++7 H+
C r 3 + + 3 Fe(phen),"+4
H,O
have been studied by Espenson and King5* over the temperature range 0-40 "C
by a spectrophotometric method. No unequivocal conclusions can be drawn
about the mechanism from the rate data except the lack of effect of F e ( ~ h e n ) , ~ +
concentration on the rate suggests that reduction of a Cr(V) species is not ratedetermining. In addition, the rate of the Cr(V1) + Fe(phen),'+ reaction is much
smaller than the Cr(VI)+FeZ+ reaction. This may be due to different thermodynamic tendencies in the primary and rate-determining step
Cr(VI)+Fe(II)
-+
Cr(V)+Fe(ITI)
166
2 Cr(Ill)
+ 3 Sn(IV)
there is some evidence for the presence of Sn(II1) or a related reducing species59.
In the Mo(V) + Sn(I1) system, however, formation of intermediates seems insignificantz8'.
Mason and Kowalak6O have examined the oxidation of As(I1I) by Cr(V1)
i n 0.2 M acetic acid-0.2 M potassium acetate buffers. When As(II1) is in large
excess over Cr(V1) the rate law is
-d[Cr(VI)]
dt
~
- k , K,[Cr(VI)][As(III)]
-~
+ K,[As(III)]
As(III)+ HCr04As(III).HCrO,-
+ As(III).HCrO,k3
--+
products
pre-equilibrium, K ,
rate-determining
At 25 "C, and with the ionic strength adjusted to 1.5 M with potassium nitrate,
sec-' and 22.4 l.mole-', respectively.
the values of k 3 and K , are 3 . 7 6 ~
At higher concentrations of Cr(VI) an analogous mechanism applies, HCr04being replaced by Cr,072-. No evidence is cited for the formation of As(1V);
it seems likely that As(V) and Cr(IV) are formed in the slow step.
Kinetic data for the oxidation of neptunium(V) by chromium(VI), uiz.
Cr(V1)+3 Np(V)
Cr(III)+3 Np(V1)
O X I D A T I O N S BY
Cr
AND
Mo
167
i n which the subscripts refer to initial concentrations of reactants, and the parameters A and B are defined in terms of initial concentrations and rate coefficients
k' and k". Values for A , B and C , computed from rate data (concentration of
Np(V) z'ersus time) using equation (3.7), were used to evaluate k' and k". Agreement was attained between these results and those calculated directly from equation (3.6). The rate law was checked by observing the constancy of k' and k"
(at constant perchloric acid concentration and ionic strength) over a range of
initial concentrations of Cr(VI), Np(V) and Np(V1). The average values are
k' = 8.26 I.mole-'.sec-'
and k" = 0.42 at [H'] = 1.51 M , ,D = 2.00 M and
25 "C. As a mechanism, Sullivan6' has proposed a sequence of one-equivalent
steps
Cr(VI)+NpO,+
+ Cr(V)+NpOZ2+
k4
k-4
Cr(V)+NpO,+
Cr(lV)+NpO,+
3 Cr(IV)+NpO;+
+
Cr(III)+Np022+
rapid
On this basis Cr(V), not Cr(IV), is the kinetically important intermediate such
that k' = 3 k , and k" = k-,/k,. The hydrogen-ion dependence of the reaction
rate has been discussed. Furthermore, comparisons are drawn with the rate of
the Cr(VI)+ F e ( ~ h e n ) , ~reaction",
+
and Sullivan has speculated on the intimate
nature of both mechanisms in the light of Marcus theory4j.
3.2
OXIDATIONSBY CHROMIUM(III)
occurs in two
(3.8)
VNCS2+ kz_ V 3 + + SCNA value for k , of 9.8 I.mole-'.sec-', at [H'] = 1.0 M , p = 1.0 M and 25 "C,
was obtained by following the rate of disappearance of CrSCN" at 262 mp2".
By contrast, the rate coefficient for the reaction of CrNCS2+ with V 2 + is 1.7 x lo-,
l.mole-'.sec-' under the same conditions62. The formation and subsequent disReferences pp -767-273
168
C 0 M P L E X E S OF D I F F E R E N T MET A L S: 0 X I D A TI 0 N-R E D U CT I O N
is negligible in comparison to reaction (3.8). Baker et a1.62suggest that the reaction of CrSCN" with V2+ takes place by a thiocyanato-bridged transition state,
in which the anion is bonded to both metal atoms.
The equilibrium constant of the system
2 Cr(II)+ Eu(II1)
Cr(III)+ Eu(I1)
k-3
is e ~ t i m a t e d ~(from
~ , ~ ' redox potentials) to be 2.2. Spectrophotometric measurements (at 575 mp, the absorption maximum for C r 3 + )reveal both forward and
backward reactions to be extremely slow (5 % reaction in one day). Approximate
1 . 7 lo-'
~
I.mole-'.sec-'
and k-,
1 . 4 lo-'
~
values ( f 2 0 % ) are k,
I.mole-'.sec-' at 25 "C and 0.5 M HCIO,. The addition of chloride ion, whilst
having no influence on k,, catalyses the back reaction appreciably, and
d[Cr(Ztl)]/dt
k - , [Cr(II)][Eu(IIl)] [CI - ]
k - , being 9.8 x lo-, 12.mole-2.sec-' under the same conditions. The substitutioninert CrC12+ species is formed as a product. With CrC12+ as the Cr(II1) species,
the reduction
OXIDATIONS BY
Mn
AND
Re
169
uiz.
Cr3++ X -
Cr 2 + + C r X 2 ++ c r 3 + + C r 2 + + X At 25 "C the rate coefficients @mole-'.set-') for the reductions are given as
> CrBr"
( 3 . 4 ~lo-,) > CrCI2+ ( 1 . 4 ~
> CrF2+
Cr12+ (4.1 x
(6.0 x
The reactivity sequence follows the "normal" order of bridging
efficiency (see p. 194) andisthe reverse to that found in the reactions of Eu(I1)
and Fe(1I) with C O ( N H ~ ) ~ X '(p.
+ 190).
3.3
OXIDATIONS BY MOLYBDENUM(V)
by octacyanomo-
4 Mo(CN)$- + O ~ ( b i p y ) , ~ +
kr
OXIDATIONS BY MANGANESE(VII)
170
c oM P L E x E s oF
D I F F E R E N T M E T A L s : O X I D A T I o N-R E Du c T I o N
E'CI
log -L
[At:
5ck't
2.303
=-.-
+ constant
E'
K++Fe(CN),,MnO,-+KFe(CN)?-
+ KFe(CN):4 MnO,'-
rapid,
K,
+KFe(CN)62-
350 I.mole-*
slow
H'
Fe(CN),"H'
HFe(CN)63-
Mn0,-
+ HFe(CN)63+ H2Fe(CN),'-I
rapid equilibria
slow
OXIDATIONS BY
Mn
AND
171
Re
-+
and
k , [CO(NH,),.OCHO~~][M~O,-]
Mn0,-
co M P LEX E s OF
1 72
4.2
D I FF E R E N T M E T A L s : ox I DA T I ON-RED
u C T IO N
OXIDATIONS BY MANGANESE(III)
Mn(III)+V(IV) = Mn(II)+V(V)
by following the rate of appearance of V(V) at 325 mp
A simple second-order rate law
(E =
284 l.mole-'.cm").
obtains over the range 0.8 to 3.0 M perchloric acid at temperatures from 5 "C
to 20 "C. With
M reactant concentrations, half-lives were of the order
of 10-20 sec. At 20 "C and 3 M HC104, kobsis 1.53 x lo2 l.mole-'.sec-'. The
rate increase with decrease in hydrogen-ion concentration is i n keeping with a
mechanism in which a hydrolysed species of Mn(II1) takes part, uiz.
Mn3++V02++H20
M n 2 + + V 0 2 + + 2H +
Mn3+ H 2 0 + MnOH2++ H +
rapid equilibrium, K h
M n O H 2 + + V O Z +3 M n 2 + + V 0 2 + + H t
The rate data were fitted to the relationship
OXIDATIONS BY
Mn
AND
173
Re
Although the activation parameters corresponding to steps k,, and k , are given,
there is some doubt over the correct value for Kh (and the accompanying AH,,)
under the conditions employed. There seems to be no special kinetic feature
about the oxygen ligand in V 0 2 + , since the rates of reaction of the latter oxocation
withvarious oxidants follow the same sequence (V(V)" > Mn(III)79 > C0(111)~~
> Fe(lX)28 > T1(III)26) as the corresponding reactions of Fe(lI)22,24,28~79*81.
An important study of Mn(II1) reactions is that by Diebler and Sutins2.
Mn(lI1) was prepared by anodic oxidation of up to 0.1 M Mn(II) in 1 to 6 M
HCIO,. The nature of Mn(I1I) in perchloric acid is discusseds3. The oxidation
of Fe(I1) by M n ( m ) is kinetically second-order with corresponding rate coefficients
of 1 . 4 6 lo4
~ and 1 . 6 7 lo4
~ I.mole-l.sec-' in 3.0 and 1.0 M perchloric acid,
respectively, at ,u = 3.1 M and 25 "C. The latter rate coefficient is consistent with
the value of 6 . 9 2 lo3
~ 1.mole-'.sec-' at 15 "C (1.04 M HClO,, p = 3.04 M )
recorded by Rosseinskys4. The oxidation of various substituted 1,lO-phenanthroline complexes of Fe(I1) was investigated also; a linear relationship exists
between log k l , 2 and log K l , 2 (Fig. 2). The gradient of the plot is 0.45, a value
close to the theoretical value of 0.5 given by the Marcus equation [eqn. (12.6), p.
2471. Rate coefficients for the oxidation of Fe(I1)-phenanthroline complexes in
pyrophosphate-sulphate media are presented. A linear relationship is observed
between log k l , 2 and the formal oxidation potentials of the Fe(I1) complexes
(Fig. 3). A rapid-mixing and flow apparatus44 was employed for all the above
reactions. In a recent paper, Rosseinsky and Nico17' confirm that the Mn(IlI)+
Fe(I1) reaction is second order from measurements on the changes in the diffusion current of iron(I1) at a rotating platinum electrode. In the ranges 0.54-3 M
perchloric acid and 0.3-15 "C the observed rate coefficient has an acid dependence
0 in 3M HCIO4
I in
4.0
6.0
8.0
1M HCQ
10.0
log Kip
Fig. 2. Relationship between the logarithms of the rate coefficients (k,,2) and the logarithms of the
equilibrium constants ( K , , 2) for the oxidation of various substituted Fe(I1)-phenanthroline
complexes by Mn(II1) in 1 M and 3 M HC104 at 25.0 "C. (From Diebler and Sutins2,by courtesy
of The American Chemical Society.)
References pp. 267-273
174
085
090
095
100
105
110
E: (volt)
Fig. 3. Relationship between the logarithms of the rate coefficients ( I ? , . ~ ) for the oxidation of
various substituted Fe(I1)-phenanthroline complexes by Mn(1II) pyrophosphate (pH I .O,
ionic strength
0.5 M ) at 25.0 ' C and the formal oxidation potentials ( E ; ) of the Fe(11) c o m plexes. (From Diebler oiid S i i f i i i s Z ,by coiirti'sy uf The Aiiiericuti Chcriiicul Sociery.)
M n 3 + + F e 2 + -+ Mn2++Fe 3+
Mn3+ H 2 0
+ MnOH2++ H +
M n O H 2 + + F e 2 +-+ M n 2 + + F e 3 + + O H As noted above (p. 173), a lack of certainty over the correct value of Kh under
the prevailing conditions gives rise to ambiguities in the values of individual
rate coefficients.
Ro~seinsky'~has examined the oxidation of Hg(1) and Mn(II1) in aqueous
perchloric acid at 50 "C by a method involving titration of Mn(1II) with Fe(I1).
At constant acidity ([H'] = 3.0 M ) his rate data can be expressed as
OXIDATIONS BY
Mn
AND
Re
175
and
2 Mn(1II)
+ Mn(IV)+Mn(II)
K2
lo-,
--%Mn(II)+Hg(I)
slow
Mn(IV)+Hg(I),
3 Mn(II)+2Hg(II)
slow
together with
Mn(lTI)+ Hg(1) .--,Mn(II)+Hg(II)
rapid
In this scheme Hg(1) is presenta5 as Hg+ ions (possibly ion-paired with CIO,-),
and Mn(1V) is likely to be M n 4 + + M n O Z + .Step (4.2) may proceed either as
written (two-equivalent change) or via two consecutive one-equivalent stages
with HgZ3+,or Hg(l), +Hg(II), as intermediates. On this basis k' and k" are
identified as k , K , and k, K 2 , respectively. Very approximate values of k 2 and k,
were estimated (on the basis of a number of rather drastic assumptions) as 5 x lo3
I.rnole-'.sec-' and 2 50 I.mole-'.sec-', respectively, at 50 "C. Other possible
mechanisms tested and found inadequate in explaining retardation of the reaction
by products include (a) reactions Mn(II1) Hg(I), and Mn(IV)+ Hg(O), and
( b ) a back reaction in step (4.1) and omission of (4.2). It is of interest to note that
Mn(1II) is capable of oxidising both Hg(0) and Hg(1) whereas Tl(I11) oxidises
only the formera6 and Co(Il1) the latters0. Also, of the three oxidants, only
Co(1II) is capable of oxidising HgZ2+,a result which has led R o ~ s e i n s k yto
~~
speculate on the ability of Co(IJ1) to react via a high-spin species which can tZsoverlap with HgZ2+.
4.3
OXIDATIONS BY RHENIUM(VII)
+ H2SnCI,
---f
Re(OH)C152- +HSnCI,
+SnCI,
176
co M P L E x ES OF D I F F E R E N T M E T A L S : ox I DA T I o N-RE D u c T I o N
5. Oxidations by iron(I1I) and ruthenium(IT1)
5.1
OXIDATIONS BY IRON(III)
Fe(H20)5XZ+A N D V ( H Z O ) Q ~A+T 2 5 C
1.0 M (ref. 6 2 )
X
HzO
OHCI NCSN3-
k(l.mole-.sec- * )
1.8 x lo4
<4 xi05
4.6 x 1 0 5
6.6 x lo5
5.2 x 105
X = H,O, OH-, C1-, NCS-, and N 3 - ; in all these cases the rates of reduction
are rapid compared with the rates of substitution of X- in Fe(H,0)63+. No
evidence is evinced for formation of VX+ complexes. It is noteworthy that
OH- exerts little effect on the rate of this reaction although it has a pronounced
influence on the rate of other reactions of Fe(IlI)89. This result, together with the
observation that the other anions have similar effects on the rate, would seem to
indicate that the FeX2++V2+ reactions proceed via an outer sphere path. The
suggestion is made, however, that, although the Fe3++ V 2 + reaction is undoubtedly of the outer-sphere type (since the rate of water replacement in V2+ is much
slower than the electron-transfer), the FeX2++V+ reactions occur through
inner-sphere, water-bridged activated complexes resulting from the loss of a
water molecule coordinated to Fe(lI1).
Fe(II1) oxidises V(111) to V(1V). Superficially the reaction is unexceptional:
the stoichiometry is simple
Fe(III)+V(III) = Fe(lI)+V(IV)
(5.1)
and the process is first-order in each reactant (Fig. 4;plot A). However, a number
of interesting features have been revealed by Higginson and Sykes in the course
of a detailed kinetic studyg0. Measurements were made at 755 mp (where V 0 2 +
absorbs strongly). Precautions were taken against atmospheric oxidation. Reduction of perchlorate to chloride by V(III) was slight under the conditions prevailing. On the assumption that the reaction proceeded as a single-stage process
V(IV) was added (in concentrations similar to those of the reactants) in an effort
OXIDATIONS BY
Fe(II1)
AND
Ru(II1)
177
Fig. 4. Effect of initial presence of products upon the rate of the Fe(III)+V(III) reaction. Initial
M (A, B, C),
concentrations: [Fe(III)] = 0.0226 M ; [V(III)] = 0.022 M, [Fe(II)]
0.07-0.12 M (D); [V(IV)]
M (A, D), 0.057 M (B), 0.094 M ( C ) ; [ H +] = 1.00 M,
ionic strength, 3.0 M, temp., 20.0 "C. (From Higginson and Sykesg0, by courtesy of The Chemical
Society.)
N
-d [V(III)]/dt =
= k, [Fe(II1)][V(lII)]
+k'[Fe(IIl)] [V(TII)][V(IV)]/[Fe(II)]
(5.2)
The first term in (5.2) corresponds to the simple path represented by (5.1), rate
coefficient k, . The form of the second term can be understood on the basis of the
sequence
Fe(III)+V(IV)
$ Fe(II)+V(V)
k-z
(5.3)
V(V)+V(III) 5 . 2 V(IV)
(5.4)
Although k2/kd2 is very small ([V(V)] 0.1 % of [V(III)] and [Fe(III)]), the
forward reaction in (5.3) is sufficiently rapid for (5.3) and (5.4) to make a significant contribution in the absence of large amounts of Fe(I1). The presence of
added Fe(1I) so reduces the amount of V(V) that (5.3) and (5.4) are no longer
References pp. 267-273
178
Equation (5.5) reduces to the form of (5.2) if k - , [Fe(II)] >> k , [V(III)], whereupon k' = k 3 k , / k - , . Equation (5.5) can be written as
CFe(W1[V(IV)I
- k-,[Fe(II)]
( - d [V( I I I )]/d t ) - k [Fe( III)] [V( I1I)]
kz k3[V( 111)]
+ -1
k2
Plots of the left-hand side of this equation uersus corresponding ratios of [Fe(II)]/
[V(IlI)] are linear. Such plots appear to pass through the origin so that k , must
be large. The gradients of the plots ( k - , / k , k , ) yield a value for k3 since k - , / k ,
was determined separately by measurements on the EMF of a cell composed of
Fe(III)+Fe(II)andV(V)+V(IV) half-cells. At 25 "C, /A = 3.0 M a n d [H'] = 1.0
M , k , is calculated to be 260 l.mole-'.sec-'. Step (5.1) was found to be acid
dependent
kl
b+(~/[H+l)+(d/[H+]~)
(5.6)
rapid
(5.7)
OXIDATIONS BY
Fe(II1)
AND
Ru(II1)
179
180
a detailed kinetic study of the Cl--catalysed oxidation (at 25 "C) based upon the
use of flow technique^^^'. The reaction is first-order in both Fe(ll1) and Cr(II),
the second-order rate coefficient being 7.7 x lo3 l.mole-'.sec-'
for 1.00 M
HClO,. The acid dependence of the rate can be expressed as
rate = k, [Fe3+][Cr"] +k,fFeOH2'][Cr2+]
Since Kh as defined by
Fe3'+H20
+ FeOH2++H'
A plot of k' versus l / [ H f ] is linear. Using a value9, for Kh of 1.69 x 1O-j enables
k, and k, to be calculated from the slope and intercept: k, = 2.3 x lo3 l.mole-'.
sec-' and k, = 3.3 x lo6 I.mole-'.sec-', at 25 "C and p = 1.00 M. The effect
of chloride was examined systematically as followstt. The formation and dissociation of Fe(H20)5C12' by
Fe(H20)63++c1-
ks
+
Fe(H2O),CI2+
k-9
has rate coefficients k, and k-9 of 19.4 I.mole-'.sec-' and 6.7 sec-', respectively,
at 25 "C and p = 1.00 M9,. With Cr(I1) present, the rate of disappearance of
Fe(H20),CI2+is given by
-d[FeCI2 +]/dt = k-, [FeCI'
'1 - kg[Fe3'][CI-]
+ klo[FeCl2+][Cr2'1
(5.8)
kio
__f
products
It was shown that k , , is much larger than both k, and k-9 whereupon equation
(5.8) becomes
-d [FeCI2+]/dt = k,,[FeCIZ+] [Cr2']
Fe(H20)J12+ was followed spectrophotometrically at 336 mp and k,, was
t The comparable reaction between FeBr*+ and CrZ+ has been examined by Carlyle and
EspensonzsS.
t t Catalysis by chloride has been examined for the comparable Fe(II1) fNp(I1I) reactionzs9.
O X I D A T I O N SBY
181
Fe(II1) A N D Ru(II1)
k , [Fe3+][Cr"] + k 6 [FeOH2+][Cr2+]
Plots of k' versus [Cr"] at fixed [Cl-] are linear and allow k , , to be calculated
from the slopes as 2 . 2 ~lo4 12.mole-2.sec-', at 25 "C and p = 1.00 M . Product
yields of Cr(H,0)5C12+ and Cr(H,0),3+ obtained experimentally were in excellent agreement with those calculated on the basis of the kinetic scheme. Dulz
and S ~ t i conclude
n ~ ~ that two routes exist for the chloride-catalysed oxidation,
Cr(H20),Cl2+ being formed in both paths, viz. inner-sphere process
Fe(Hz0)5C12+ Cr(H,O),'+
+[(HzO)5Fe-CI-Cr(H20)54+1'
Fe(H20),'+ +Cr(Hz0)5C12+
(or [(H20)5FeH20-CrCI(H20)$+]*)
+Fe( HZO),,
+ Cr(H,0),C12
or
(H20),Fe3+C1-
+ Cr(H20)62 +[(H,0),FeH20-Cl-Cr(H20)54+]*
+
+Fe(H,O),,
+Cr( H20),C12
182
TABLE 4
K L L A T I V E R A T E C O E F F I C I E N T S FOR T H E F e ( I I I ) + C r ( I l )
H2O
OH -
CI -
From rcl'. 2 3 .
I
>8 <IO4U
> 2 Y 106b
A N D RELATED REACTIONSg6
I
1.4 4 103
1
1.1
6.2d
104
\
,
I O X L
Co(EDTA)'-
'.
2Co(EDTA)- + Fe(CN),,-
C O ( E D T A).F~(CN),~-
rate-determining
OXIDATIONS B Y
Fe(II1)
AND
Ru(III)
183
and A , are the absorbance values at 420 mp, the absorption maximum of
Fe(CN)63-, at time I and after complete reaction. Furthermore, the form of the
rate law is verified from the linearity of plots of l/kobsversus l/[Co(EDTA)'-].
Slope and intercept values of such plots yield values for k,, and K , at 25 "C of
6.2 x
sec- and 670 1.mole-', respectively. An independent value of K , (710 1.
mole- ') was obtained spectrophotometrically. The overall activation energy and
entropy are estimated to be 26 kcal.mole-' and 16 cal.deg- '.mole-', respectively.
Adamson and Gonick"' are of the opinion that the reaction sequence is more
correctly a three-stage process involving the formation of the species (EDTA)Co"NC-Fe111(CN),5- which first undergoes charge-transfer to (EDTA)Co"'-NCFe"(CN),'and then breaks down to Co"'(EDTA)- and Fe11(CN),4-. The
second of these binuclear species is taken to be the intermediate, since magnetic
susceptibility measurements reveal the intermediate to be diamagnetic. Structurally
the intermediate resembles (NC) ,CO"'-NC-F~"(CN),~- formed between
C O ( C N ) , ~ -and Fe(CN),'-'O'.
The same system has been investigated in greater
detail by Huchital and Wilkin~"~,using rapid reaction techniques to characterise
the intermediates formed. The kinetics of formation and decomposition of the
bridged cyanide intermediate, (EDTA)CO"'-NC-F~"(CN),~-
'
Co(EDTA)'-
+ Fe(CN);-
k-
(EDTA)CO"'-NC-F~"(CN),~K,
(5.9)
I3
have been studied with the aid of temperature-jump and stopped-flow equipment.
It is suggested that the intermediate is formed by replacement of water from the
Co(l1) complex, which may react as Co(EDTA)(H,O)'-.
In addition, evidence
from stopped-flow measurements is presented for the inclusion of a second intermediate, viz.
(EDTA)CO"'-NC-F~"(CN)~~+Fe(CN),3-
2 (EDTA)Co"'-NC-Fe"'
k-14
(CN),4-+Fe(CN),4-
K,
(5.10)
TABLE 5
R A T E P A R A M E TE R S F 0 R
(5.9)
1.3 105
0.9 1 0 5
/
Fe(CN)63-
+Co(EDTA)'-
8 6"
b
RE ACT I 0 N I o 3
1 . 5 103
~ =
1.6 x 103 b
1.6 x lo3
Direct spectrophotometry.
184
Rate parameters, at 25 "C, for reactions (5.9) and (5.10) are collected in Table 5.
Reaction (5.10) is analogous to"'
(CN),Co1"-NC-Fe"(CN),6-
+Fe(CN);-
$(CN),Co"'-NC-Fe"'
k-15
(CN),'- +Fe(CN)64- K 3
Huchital and W i l k i n ~ " ~report k15 = 1.1 x lo3 1.mole-'.sec-', k - 1 5 = 1.6 x lo4
I.mole-'.sec-l and K3 = 0.07, at p = 0.1 M and 25 "C. These results are close
to those for reaction (5.10).
The reaction between Fe(U1) and Sn(I1) in dilute perchloric acid in the presence
of chloride ions is first-order in Fe(lI1) concentrationlo4. The order is maintained
when bromide or iodide is present. The kinetic data seem to point to a fourthorder dependence on chloride ion. A minimum of three C1- ions in the activated
complex seems necessary for the reaction to proceed at a measurable rate. Bromide
and iodide show third-order dependences. The reaction is retarded by Sn(I1)
(first-order dependence) due to removal of halide ions from solution by complex
formation. Estimates are given for the formation constants of the monochloro
and monobromo Sn(I1) complexes. In terms of catalytic power I- > Br- > C1and this is also the order of decreasing ease of oxidation of the halide ion by
Fe(1lI). However, the state of complexing of Sn(1I)and Fe(I1I)is given by C1- >
Br- > I-. Apparently, electrostatic effects are not effective in deciding the rate.
For the case of chloride ions, the chief activated complex is likely to have the
composition (FeSnCl,+)*. The kinetic data cannot resolve the way in which the
C1- ions are distributed between Fe(I11) and Sn(I1).
The problem has been partially resolved in a later note by Peterson and Duke'"
describing their investigation of the reaction between Sn(I1) and the ferricinium
ion. Ferricinium perchlorate was prepared by oxidation of ferrocene with AgCIO,
in aqueous perchloric acid; from the nature of the ferricinium structure, Fe(II1)
is unlikely to complex with more than one chloride ion. The reaction, followed by
absorbance measurements on the ferricinium ion at 615 mp, is first-order in both
reactants. The chloride-ion dependence indicates a total of five C1- ions in the
activated complex, four of which are deduced to be associated with Sn(1I) as
SnCI,-.
Wetton and Higginson5' have briefly investigated the reaction between Fe(II1)
and Sn(I1). Spectrophotometric data for the rate of disappearance of Fe(II1)
were obtained at 335 mp. In the absence of substantial amounts of Fe(I1) and
Sn(IV) the kinetics in 1.0 M hydrochloric acid are of simple second order, indicating that Sn(I1) is present as the monomeric species. The addition of Fe(l1)
to the reacting system produces a pronounced retardation, the second-order plots
showing curvature after 75 "/, reaction. The appropriate mechanism is
OXIDATIONS BY
Fe(II1)
AND
Ru(II1)
185
Fe(III)+Sn(II) 3 Fe(II)+Sn(III)
k-16
Fe(II1) + Sn(II1)
Fe(I1) + Sn(1V)
This mechanism gives a quantitative fit with the observed kinetics: at 25 "C,
k , , / k - 1 6 is 1280 and k,, is 4.4 l.mole-'.sec-'. Furthermore, experiments in which
the Co(II1) complex, Co(YOH)H20, is included in the reacting system provide
evidence for the presence of Sn(II1) intermediates (H4Y = EDTA).
By means of a stopped-flow technique, Carlyle and E ~ p e n ~have
~ subn ~ ~ ~ ~ *
jected the reaction between europium(I1) and iron(II1) to a detailed examination.
In perchloric acid solution two processes are discerned, viz.
and
Fe(H,O):++Eu:l
+ H 2 0 -+-[FeEu(H,O),OH4+]*+Ht
_f
Fe(H,O)z++Eui;
+Cl-
2 Fe(II)+U(VI)
186
Fe(ll)+ U(V)
slow
(A)
rapid
or
Fe(III)+ U(1V) -+ Fe(lI)+ U(V)
slow
(B)
rapid
* FeOH + H +
U 4 + + H 2 0 + UOH3++H+
KR
F e 3 + + 2 H,O ;= Fe(OH),++2 H +
K,
.+u ( o H ) ~+ ~2 +H +
K,
Fe3+ H 2 0
u4++ 2
H,O
K4
F e 3 + + U O H 3 +%Fe++U(V)
FeOH
F e O H 2 + + U O H 3 +% Fe 2++U(V)
k21
Fe(OH),+ + U 4 + --+
Fe3+ U(OH)+
k22
Fe++U(V)
(5.11)
+ U(V)
(5.12)
+Fez+
so that
(5.13)
OXIDATIONS BY
Fe(II1)
AND
Ru(III)
187
k'D
K'[H+]+K"
and plots of k'D (calculated from known values of Kh and K 4 ) against [H'] are
linear at temperature between 3.1 "C and 24.8 "C. The constants K' and K",
evaluated from the slopes and intercepts of such plots, are 2.98 sec-' and 20.6
mole.1- l.sec-', respectively, at 24.8 "C; the corresponding apparent activation
energies are 22.5 and 24.5 kcal.mole-'. If Fe(OH),+ and U(OH),'+, known to
be present in extremely low concentrations, are insignificant kinetically ( k Z 1=
k,, = 0) then
AH"
E2,+AH,,+AH4
where AHh and AH4 are the enthalpies of hydrolysis of Fe(1II) and U(IV),
respectively, and E,, is the true activation energy for FeOH2++UOH3+. On
this basis E,, = 24.2- 12.3- 10.6 = 1.3 kcal.mole-', a most unrealistic figure
for electron-transfer processes. It is concluded, therefore, that the sequence involving two OH groups is, in fact, made up of (5.11) and (5.12). Maximum rates
and activation parameters of the paths involving one OH group are given in
Table 6. The Fe(III)+ U(1V) reaction is greatly accelerated by HS04- ions"'.
This is ascribed to the participation of sulphate complexes of both reactants, e.g.
U4++ HS04-
+ US04'+ + H +
+ Fe(II)+Np(V)
TABLE 6
MAXIMUM VALUES OF
Condition
kls
AND
k I 9 I N Fe(IIl)i-U(lV)
REACT1ONlob
Rate coeficient(l.inole- I.
sec-', 25" C )
E(kcaLmole- I )
ASt(cal.degmole- I )
107
11.9
-11.2
1860
10.2
- 11.3
I.
188
C O M P L E X E S 0 F D I F F E R E N T M ETA L S: 0 XI D A T 1 0 N-R E D U C T I O N
is reported to be
d [Np(IV)]/dt = k"[Np(V)] [Fe(II)][H' 1-k' [Np(IV)][Fe( 1II)]/[H'l3
The value. given by Huizenga and Magnusson" for k' and k" are 3.4 mole2.1-'.
min-' and 4.7 12.mole-2.min-', respectively, at 25 "C in 1.0 M perchlorate
solutions. The apparent activation energy corresponding to k' is 35 kcal.mole-'.
Nitrate complexing of Np(1V) reduces the forward rate.
5.2
OXIDATIONS BY RUTHENIUM(III)
( k +k'[Cl-])[Ru(
] [Cr2+1
At p = 0.022 My k = 28 l.mole-'.sec-',
k' = 6 x 10' 12.mole-'.sec-'.
exchange experiments indicate that CrCI2+ is the major product species.
Ion-
6. Oxidations by cobalt(II1)
A great deal of attention has been given t o the oxidation-reduction reactions
of cobalt(Ir1). For convenience this section is subdivided into three parts: reactions involving inorganic bridging ligands (some outer-sphere systems are discussed also for comparison), reactions involving organic bridging ligands, and reactions of aquo complexes.
6.1
INORGANIC BRIDGING
LIGANDS I N OXIDATIONS BY
COBALT(III)
COMPLEXES
OXIDATIONS BY
CO(II1)
189
and Gorbitz'", confirming the earlier results of Taube"', have shown that
the principal path of reduction of Co(NH3),ClZ+ by Cr2+ in the presence of
pyrophosphate yields product Cr(I1I) incorporating both chloride and pyrophosphate.
The rates of oxidation of V2+ by complexes of the type CO(NH,)~X,where
X = HzO, NH, and C1-, have been examined by Zwickel and Taube1I2 in HzO
and in D,O solution. These workers have compared the results on such systems
with data on the CrZ++Co(NH,)63+reaction in HzO and D,O. The product
V 3 + , unlike Cr3+, is substitution-labile. Consequently, a different approach is
necessary for V2+ oxidations than is customary for CrZ+ oxidations. The specific
rate coefficients for Co(NH,),,
V2 and CO(NH,)~,++CrZ+ vary with CIconcentration according to
+
kobs = k k"C1-l
The rate coefficients, k and k', and the corresponding activation parameters are
given in Tables 7 and 8. Cr(H2O),Cl2+ is the primary product in the chloridedependent path for the co(NH3),,+ Cr2+ reaction. The specific rate coefficient
for the Co(NH3),CIzf +V2+ reaction was determined as 342 I.mole-'.min-' at
p = 1.00 M and 25 "C. In general, reactions of V2+ contrast sharply with those
of Cr2+ (except for CO(NH,),~+ CrZ+)and Cr(bipy),'+ by exhibiting chloride
TABLE 7
R A T E D A T A F O R C O ( N H J ) ~ ~ R+E A C T I O N S 1 1 2
Temp.("C)
Reductant
Cr2
k'(12.mole-2.min-')
0.0053
0.014
0.01 1"
0.22
0.41
0.24"
0.74
1.70
1.35"
1.27
3.27
1.95"
25.0
37.0
37.0
25.0
37.0
37.0
V2+
k(l.mole-'.min-')
In 100 % DzO.
TABLE 8
A C T I V A T I O N P A R A M E T E R S F O R C O ( N H J ) ~ ~R+E A C T I O N S L L Z
Reductant
Path
A H t (kcalmole- l )
Cr2
Cr2
V2+
V2+
k
k'
k
14.7
12.4
9.1
14.1
k'
-20
TABLE 9
_
S E C O N D - O R D E R R A T E C O E F F I C I E N T S (I.mole-'.sec-'
~
C r z +a
Oxidant
8 . 9 1~0 - 5
CO(NH~)~'+
0.5
Co(NH3)50Hz3+
1.5 x lo6
CO(NH~)~OH'+
9 xi05
Co(NH 3 ) F2
2.6 x lo6
Co(NH &I2+
> 2 XI06
Co(NH3),Br2+
> 2 x106
Co(NH3)512+
C O ( N H ~ ) ~ N ~ ~ + 3 xi05
19
Co(NH,),NCS'+
18
CO(NH~)~SO~+
0.18'
Co (N H 3 ) OAc2
90
CO(NH~)~NO~''
Co(NH3)5S203+
Co(NH 3 ) ,(maleate)
4.8 x 109
Co(NH3) d'04
8.3 x 103
Co(NH3)5P04H
C O ( N H ~ ) ~ P O ~ H ~ ~0.3
+
C O ( N H ~ ) ~ P O ~ H ~ ~0.3
+
-2 ~ 1 0 - 5
C~(en)~~
3 . 7 10-3
~
d,=
0.5'
-
0.3
7.8'
0.43'
2 x10-2
0.15
2.6 x 104
3.9 x 102
2.5 x lo2
1.2x102
1.9 x 10'
0.7
1 . 4 ~10'
0.18'
-1
x 10'
I .4 x 107
1 . 6 lo2
~
2.3
4.5
d
COMPLEXES
cr(bipu)32'
'RU(NH3)S2+ '
Fe2+ a
m
X
m
CA
13
Co(l11)
zP
P
2.6
-5
25
1.2 x 102
Eli2+ a
y2+ a
at 25 " C ) F O R
-2
XIO-4
6.9 x loz
5 xi04
1.1 x 10-2
3.0
4 x10-2
1.8 x 103
2.6 x lo2
I .6 x 103
6.7 x 103
1.2
8 x105
5 XI06
-
4.1 x 104
1 . 0 104
~
4.5 x 104
1 . 2 103
~
8 xi04
L O X 103
6.6~
1.3 x 10-3
7.3 x 10-4
-
8.8 x
<3
XIO-6
<5
XIO-5
tJ
5 XIO'
6
-3
-5
XIO-3
1.8 x 103
tJ
C
Data from refs. 113, 125 and 126, unless otherwise specified.
0.2 M.
,u = 0.1 M, C104- medium. ,LL
1.0 M , C104- medium, unless otherwise noted.
from ref. 114. 8 from ref. 127.
from ref. 128.
from ref. 122. j from ref. 129. Ir from ref. 130.
a /A =
n
/I =
0.4 M.
=!
0
z
191
CO(1II)
OXIDATIONS BY
T A B L E 10
A C T I V A T I O N P A R A M E T E R S FOR R E D U C T I O N O F V A R I O U S
.
~~~~
Cr2+
AH:
Oxidant
+
14.7"
2.9b
-
ASZ
References p p . 267-273
AH:
- 30"
9.1"
- 52b
-
6.2
6.9
- 32
9.1
(4.6)
11.7
6.1'
-29
Eu2
AS:
~~
V2+
~-
CO(NH~)~NH~~
CO(NH~)~OH~~+
Co(NH3)SCI2+
CO(NH~)~B~'+
Co(NH3)512
CO(NH~)~N~~+
CO(NH3) 5 S 0 4
Co (N H 3 ) NCS2
CO(II1) C O M P L E X E S 1 1 3
-40"
-
-22
(- 32)
- 14
-34'
5.0
4.7
- 30
-32
-
5.5
6.1
-30
-26
From ref.
192
o -Cr(biPY)j2*
3
O-V2'
-g
mercury electrode
:I
-2
- 3 t C i ,
i , i ,
-4
C o ( e n ) p ROAc2+ RNCS2* RS04*
RNHJ3*
RF2'
RCIZi
R O H P RN?'
R12*
RBr2+
OXIDATIONS BY
193
cO(III)
containing certain conjugated organic ligands takes place by remote attack on the
ligand"9, I2O
Diebler and Taubel2, have quoted rate parameters for the reduction of
halopentaamminecobalt(I1I) complexes by Fe(II) and V(II). Rate coeffients for
V 2 + reductions are in reasonable agreement with those reported by Candlin
et ~ 1 . ' '(except
~
for C O ( N H , ) ~ B ~ ~So
+ )also
. are Fe2+ reductions, taking into account differences in conditions. At 25.5 "C and p = 1.7 M , the second-order rate
coefficients for Fez+ reduction of Co(NH3),F2+, Co(NH3),CI2+ and
C O ( N H , ) ~ B ~ are
~ + 7.6 x lo-,, 1.6 x lo-,, and 0.92 x
I.mole-'.sec-',
respectively (compare results in Table 9). The respective values of AH* are 13.4,
14.5 and 15.6 kcal.mole-', and of AS* are -23, -23 and -20 cal.deg-'.mole-'.
The observed reactivity pattern F- > CI- > Br- is the reverse of the pattern
encountered in the oxidation of Cr2+ with CrX2+ (ref. 99) and Cr(NH,),X2+
(ref. 124) and in the reduction of CO(NH,)~X'+ by C r ( b i ~ y ) , ~ +
(ref. 114),
R u ( N H ~ ) (ref.
~ ~ +125) and V2+ (ref. 113)+.However, the pattern F- > C1- > Brapplies also in the Co(NH3),X2++Eu2+ ~ y ste m "~ . In the case of the
Co(NH,),X2+ + Fe2+ systems there seems to be a correlation between rate and
the thermodynamic stability of the complexes of Fe3+ with X-: the relevant
stability constants are 1.5 x lo5, 4 and < 0.1 for FeF", FeCI2+and FeBr2+,
respectively. The reactions are assisted by free halide ions, as shown by
rate
k'[FeZf][Co(NH3),X2+][XJ
Co2++ F e 3 + + X - + 5 NH,'
It proved necessary to correct the rate data in the case of X = Cl- and Brfor the simultaneous aquation of the complex. Rate coefficients are essentially
in agreement with those given in Table 9. Activation parameters are quoted when
X = F - , CI-, Br-, and also for CO(C,O,),~-.
t Parker and E ~ p e n s o n 'find
~ ~ the pattern BrReferences p p . 26 7-273
194
Candlin and Halpern comment that the sequence of rapid rates observed
for Cr2+ as a reductant (i.e. C O ( N H ~ ) ~ I >+ CO(NH,)~B~+
> CO(NH,)~CI+
> Co(NH,),F+) is contrary to that found for the slow reactions of Fez+
(ref. 126) and Eu (ref. 113). All three reductants would appear to favour innersphere mechanisms, but in the case of Fez and Eu the order of reactivity seems
to be connected with the stability of the product halide complex (FeX or
EuX2+) which increases in the order X = I- to X = F-. Or in other words, as
pointed out by Halpern and Rabani131, in the generalised inner-sphere reaction
Co-X
0
I
(NH3) ~CO-0-S-S
I
0
I
(NH3)sCo-S-S-0
0
I1
195
CO(II1)
OXIDATIONS BY
TABLE 11
REDUCTION OF
C O ( N H ~ ) ~CX
OMPLEXES
BY
so42so32-
ReJ
-25
-26
-39
3
113
132
132
132
8.3
8.3
4.2
24.6
18
18.6
13.3
0.18
I11 to a maximum value at Group V, and then decreases. Furthermore, for a given
ligand, the rate increases as the atomic weight of the central atom increases.
The reduction of cyanopentaamminecobaIt(I1I) by Cr2+ in acidic perchlorate
297
media proceeds in two distinct
Co(NH3),CN2++Cr2++5H +
_f
Coz++CrNC2++5NH4+
CrNC2++CrCN2+
(6.1)
(6.2)
_f
Cr2++CrCN2+
(6.3)
*]
and
rate
(4.4+ 82[H+])[FeZ+]
[trans-Co(NH,),(N,),+ ]
196
C O M P L E X E S O F D I F F E R E N TM E T A L S : O X I D A T I O N - R E D U C T I O N
T A B L E 12
RATE
COEFFICIENTS FOR
THE
REDUCTION OF
Co(ll1)
AZIDE
COMPLEXES BY
Fez+
(25 0C)138
k (Lrnole- .set- ')
Complex
Co(NH3)5N3"
rr~ns-Co(NH~)~(N~)~
cis-Co(N H 3)4(N3)2 +
cis-Co(N H3)4(0HZ)N32
~~U~S-CO(NH~)~(N~H)N~'
rr~ns-Co(NH3)4(0HZ)N3'
+
0.0057
0.0733
0.185
0.355
> 1.37
24
* A direct test of this mechanism is awaited. Haim'38 notes that the primary Fe(II1) product
of reduction of t r u n s - C 0 ( N H ~ ) ~ ( 0 H ~ )should
N ~ ~ + be detectable using a suitable flow apparatus.
OXIDATIONS BY
197
CO(lI1)
C o 2 + + F e 3 + + X - + 5 NH,'
71 [(NH,),CO-X-F~(H,O),~+]'
H,O
inner-sphere
li [(NH,),CoX H,O Fe(H,0),4+]*
outer-sphere
On this basis AV' should be more positive for an inner-sphere than for an outersphere reaction since a water molecule occupies a greater volume in the liquid
phase than if it is coordinated. Second-order rate coefficients were determined
at various pressures in the range 0.001 to 3.5 kbars, the rate decreasing with increase in pressure. The apparatus used was a modification of that first described
by Osborn and Whalley14'. Values of AV' were calculated from the slopes of
plots of log k versus pressure, since
-d log, kldP
AVf/RT
pp.
267-273
198
COMPLEXES O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
T A B L E 13
VOLUMES OF ACTIVATION
(Avt) F O R
cO(III)
REDUCTION OF VARIOUS
COMPLEXES BY
~e(11)13
9
A V~(cm3.rnole-')
Complex
+I1
+8
+8
+ 14
++2.2
14
+2.8
+3
HC104 media; temp., 25 "C except when noted. a At 35 "C.
HC104.
At 20 "C; Y4- = ethylenediaminetetraacetate.
0.001 M HC104.
0.02 M
C O ( N H , ) , B ~ ~ + + R U ( N H , +) ~5 ~H+
+ =
C O ~ + + R U ( N H , ) ~NH,++Br~++~
(k')
C ~ ( ~ ~ ) , C ~ , ~ + R U ( N H ,H+
) ~ '=+ + ~
C O ~ + + R U ( N H , )+~2~enH+
+
+ 2 cl-
(k")
OXIDATIONS BY
cO(III)
199
kb
and
log k"
2.5 +'p
log k y
200
COMPLEXES OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
T A B L E 14
COMPARISON
OF
THE
R A T E OF
REDUCTION
O F SOME
CHROMIUM(I1) A N D IRON(I1) A T
CO(en)2XY"+
2 5 0c64
COMPLEXES
RY
Reductarit
Co(en)zNH3(NCS)Z
+
Co(en)z(NCS)2
Co(en)20H2(NCS)Z+
Co(en)2NH3C12+
Co(en),(NCS)CI+ a
Co(en)zOHZCIZ+
+
Cr2
Cr2
Cr2
Fez
Fez
Fez
trans-Xlcis-X
1.2
9 xlo-1
3 '<I01
3.7
8 x10-1
5.2 x 10'
cis-Xlcis-NH3
1 .o
4.8
1.5 x 101
1 .o
10
2.6 x 10'
trans-Xltraris-N H 3
1.o
3.7
3.1 x 10'
1 .o
2
3.6 x lo3
OXIDATIONS BY
20 1
cO(llI)
tr~ns-Co(en),OH,(NCS)~~ trans-Co(en),(NCS)OH+
+H+
+CrSCN2+
1, where, for example, k,,, and K1,, are the rate coefficient
assumingf,,,lf,,,
and equilibrium constant for the C O ( N H , ) ~ C I ~++Cr2+ reaction, k,, and K1,3
are the corresponding constants for the Co(NH,),CI2+ + Fe 2 + reaction, andf,,,
References pp. 267-273
202
T A B L E 15
RATE
COEFFICIENTS
(1.mole-'sec-'.)
FOR
I R O N ( I I ) W I T H C O B A L T ( I I I ) C O M P L E X E S AT
C O ( N H ~ ) ~ C+Fez+
P+
C O ( N H ~ ) ~ C+Cr2+
I~+
C O ( N H ~ ) ~+Fe2
F~
C O ( N H ~ ) ~+Cr2+
F~+
C O ( N H ~ ) ~+Fez+
N~~
C O ( N H ~ ) ~ +Crz+
N~~+
cis-Co(en)z(NCS)C12++Fez
~is-Co(en)~(NCS)Cl'+Cr2
rruns-Co(en)z(NCS)C12 +Fez+
fruns-Co(en)z(NCS)C12++Cr2 +
+
-2.9
6.4
-2.2
5.9
-2.0
5.5
-3.8
6.3
- 3.9
6.4
6.6
5.5
5.7
5.1
-
5.6
andf,,, are as defined by Marcus". Although equation (6.4) was first derived
for outer-sphere processes, evidently it can be applied as well to inner-sphere
reactions since observed and calculated rate coefficients are in good agreement
(particularly among the pentaammine series).
Cannon and E a r l e ~ ' ~have
' measured the rates of reduction of cis- and transX = NH, or H,O) by Cr2+. From the observed inC O ( ~ ~ ) , X ( H , O )(where
~+
verse dependence on hydrogen-ion concentration it is concluded that the ratedetermining step is the attack of the reductant on the conjugate base of the aquo
ion. A bridged mechanism is supported by the work of Kruse and T a ~ b e ' ~ ~
who showed that the Cr2+ reduction of cis-Co(en),(H20)OH2+ results in the
transfer of a single oxygen atom. Table 16 allows results of Cr2+ and Fe2+
reductions141 to be compared; the data on the FeZf reactions refer to the corresponding chloro complexes. There is a vast difference in rates between these
two systems: the rates of the Co(en),(NH,)OH2+ +Cr2+ reactions are about
10" times greater than the rates of the Co(en),(NH,)CI2+ +Fez+ reactions.
Assuming that this disparity in rate arises entirely from free energy differences
in the Cr(III)-Cr(lI) and Fe(III)-Fe(rI) couples (A(AG) = 27.6 kcal.mole-I),
it is interesting that the Marcus treatment43 gives
although the equation was intended originally to describe the behaviour of outersphere reactions. For both Cr2+ and Fe2+ reductions the most reactive complex
is the trans-aquo one. However, the effect of the trans ligand is less pronounced
when Cr2+ is the reductant. Outward motion of the trans ligand in the formation
of the activated complex is present in both Cr2+ and Fe2+ reductions but is much
OXIDATIONS B Y
203
CO(111)
TABLE 16
Co(en)2XC1"+ A N D C O ( ~ ~ ) ~ X O H
C O"M
+P L E X E S
Fez+ A N D Cr2+
Fez+ reductant a
X
1 04k ( I . mole-
.set- I )
Cr2+ reductant
10 - 6k ( h o l e - '.set - )
trans-isomers
NH3
NCS
C1
Br
N3
H2O
cis-isomers
NH3
NCS
H20
CI
Chloro complexes141:[C104-]
0.66
1.3
320
360
620
2400
0.22
-
0.18
1.7
4.5
16
0.20
1.0 M , 25 "C.
2.6
0.79
more important in the latter case. This is consistent with the low isotopic fractionation factor found for trans nitrogen in Cr2+ reduction^'^^.
E ~ p e n s o n ' ~has
' shown that the reaction of ~ i s - C o ( e n ) ~ ( N ~
with
) ~ +V2+ takes
place by an inner-sphere mechanism. This Co(II1) complex was selected for investigation because it is particularly reactive towards V2+,and also the dissociation of monoazido vanadium(lI1) is relatively slow. At low V2+ concentrations
(2-20 x
M ) the second-order rate coefficient is 32.9 I.mole-'.sec-' at 25 "C,
[H'] = 0.10 M and p = 1.0 M . At higher VZf concentrations (- 0.1 M ) ,
using a stopped-flow apparatus, the kinetics are apparently first order at 520 mp,
a wavelength where VN32f shows negligible absorbance. The rate coefficient under
these conditions agrees with that obtained at low V 2 + concentrations. However,
the data obtained by monitoring the reaction at 350 mp, an absorption maximum
for VN32+,deviates from first-order behaviour. Subtraction of the absorbances
of stable reactants and products from the net absorption at 350 mp gives the
absorbance due to the VN3'+ entity. Fig. 6 shows the formation and decay of
the latter in a typical experiment. The variation of VN32+ concentration with
ime was calculated on the basis of an inner-sphere sequence
+V2+
ci~-Co(en),(N,)~+
-% VN32+
V3+ + N 3 -
where k,, and k,, are the rate constants for the redox and aquation reactions,
respectively. As shown in Fig. 6, the calculated and observed values agree nicely.
That the VN," intermediate does not originate from interaction of the Co(I1I)
Rejercnres pp. 267-273
204
COMPLEXES O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
30
02
06
04
Time b e c )
Fig. The formation and decay (at 350 mp) of the VN32 intermediate tmed in the cis-Co(en)2(N3)2+- 1 - V2 reaction. The points are the observed concentrations and the line is calculated from
the known rate parameters. [ C O ( I I I ) ]=
~ 1.5 x
M , [ H + ] = 0.10 M , [ V 2 + ] 0.1 M . The
+
intermediate attains a maximum concentration of 2.7 x l o w 5M a t 0.17 sec; calculated, 2.74 'i
M at 0.113 sec. (From E~penson'~', by courtesy of The American Chemical Society.)
complex with VN,' was proved by the observation that added HN, has no effect
on the rate.
It is of incidental interest that a little work has been done on dicobalt systems.
Doyle and Sykes14* have made a study of the reduction of decammine-p-amidodiby V(I1). Since the rate is independent
cobalt(IIl), (NH3),Co~NHz~Co(NH,)ss+,
of hydrogen-ion concentration the mechanism cannot involve an amide bridge
and must be outer-sphere, as it is in the case of the reduction of CO(NH,),~+
by V(11)112~
149. Both the binuclear complex and C O ( N H , ) ~ , +
are inert to substitution but the former is capable of functioning as a two-equivalent oxidant.
Thus the two likely mechanisms are
n+
CO'++CO(NH,),~+
+V3+
+ 5 N H 4 + (6.5)
H+
CO(NH,),~+f V 2 + -+ C o 2 + + V 3 + + 6NH,'
(6.6 1
and
(NH3)5C~.NH2Co(NH,),+
5+
V 2 + -f 2 Coz++V(IV)+ 1 1 NH4+ (6.7)
v(Il)+v(rv~
_f
2 V(II1)
55
(6.8)
cO(III)
OXIDATIONS BY
205
T A B L E 17
ANION EFFECTS I N THE REDUCTION OF
BY
(NH3)5Co.NH2.Co(NH3)5s+A N D C O ( N H & ~ +
vz+A T 25 'CL4*
Uncatalysed
+CI-
+sod2+F-
k'(12.mole-z.sec-')
k'lk
0.149 a
2.1
14
1000
8600
6700
58000
CO(NH3)6
k'(12.niole-2.sec-')
0.00441
0.035
8.50
91.7
k'lk
-
8
1930
2 1000
k values in I.mole-'.sec-L.
The side reaction can be obviated by setting aside the V(I1) before commencing a reaction,
thus removing traces of oxygen301.
References pp. 267-273
206
c o M P L E x ES o F
D I F F E R E N T METALS:
ox I DA T I o N-RE D u C T Io N
= k,[Co(HY)Cl-][FeZ+]
where log k, = log ko+AIH+], and k, and A are constants. The complexes
Co(Y)C12- and Co(HY)CI- react with Fez+ at comparable rates. Comparisons
are instructive between this redox reaction and other cation-catalysed chlorideabstraction reactions154 which occur without simultaneous oxidation-reduction.
The intimate mechanisms are likely to be
+Fe"'C1'
- - Fe"] +[Co(HY) - - C1
* *
Fe]*
and
+ [Co"'(HY)CI MI']
C1 - MI1]*
Co"'(Y) + H + + M"CI+
Co"'(HY)CI- + M 2 +
+[Co"'(HY)
* *
* * *
where M2+ = Mn2+, Co2+, NiZ+, Cd2+, Pb2+ and Hgz+. The fact that the
reduction by Fe2+ has a lower activation energy may be a consequence of the
weakening of the Co-Cl bond in the activated complex on reduction of the charge
on the Co centre.
6.2
ORGANIC
B R I D G I N G LIGANDS
IN
OXIDATIONS
BY
COBALT(III)
COMPLEXES
T A B L E 18
h,
u
h
TE P
R A M E T E R S ~F O R R D U C T I O N O F C
Reductant
Ligand
From Fraser13'.
0.35'
0.10
0.11
0.074
0.15'
0.074
0.082
-
0.075'
0.093'
0.21
-
0.13
0.18
7d (7.2')
0.052"
8.2'
7.9
4.0
2.5
9.0'
6.0
2.8
5.1'
2.6'
10.0
9.6
7.5
8.3'
-
Co(II1) C O M P L E X E S B Y Cr2+,V + ,
VZ+
CfZ+
Acetato
Chloroacetato
Cyanoacetato
Dichloroacetato
Benzoato
o-Chlorobenzoato
o-Iodobenzoato
Salicylato
o-Phthalato
m-Phthalato
p-Chlorobenzoato
p-Iodobenzoato
p-Hydroxybenzoato
p-Cyanobenzoato
Formato
Trifluoroacetato
a
RBOXYLATOPENTAAMMINE
ASt(cal. kb(l.mole-'.
deg-'.rnole-') sec-')
-33'
-37
-49
-55
-33'
-43
- 54
0.43
1.25
1.13
1.03
0.52
0.57
0.90
-45'
- 56'
-28
1.01
0.60
0.60
0.37
0.53
0.88
- 30
-37
-27'
From ref. 156.
AHt(kca1.
mole-')
5.8
9.4
9.4
9.6
6.7
10.5
15.8
9.3
10.2
9.0
8.0
9.0
9.3
10.2
-
Euz
ASt(ca1.
deg-'.mole-')
-41
- 27
-27
-26
-31
-24
- 5
-27
-24
-29
kb(l.mole-'
sec-')
0.18
3.16
2.08
0.24
0.39
0.28
2.16
0.64
AHz(kca1.
mole-')
4.4
9.3
-
6.9
6.2
3.2
3.3
-51
-
- 30
-33
-
2.1
-24
-
-47
-25
-35
-40
-50
8.2
7.9
0.27
-
ASt(ca1.
deg-'.rnole-')
-33
Eu2+
-30
-28
ND
208
C O M P L E X E S OF D I F F E R E N TMETALS: O X I D A T I O N - R E D U C T I O N
and the path for electron transfer is Co-0-C-0-red. The two oxygen atoms in
the carboxylato complexes are not equivalent'5s (a result in conflict with a previous
report'59). In a systematic study, FraserI3' has investigated the effect of varying
the substituent R. The rates are, in general, independent of hydrogen-ion concentration. viz.
-d[Co(NH3),L2+]/dt
k[Co(NH3),L2+][red]
C o 2 + + C r L 2 + + 5NH4+
LYAH'+P
O X I D A T I O N S BY
cO(III)
209
The rate of reaction is enhanced if the ligand is able to chelate with the reductant. Examples of chelating ligands are u-hydroxy acids, e.g., glycolate ( B ) and
lactate'61; and those ligands containing a carbonyl group ( C ) or a hydroxy group
( D ) in an ortho position to the co-ordinated carboxyl
157*161-164
(Table 19). o-Nitrobenzoato ( E ) (but not o-aminobenzoato) pentaammine complexes provide further examples. Chelation with Cr(I1) can take place via a
sulphur atom15" 164 , as in the S-benzylthioglycolato complex (F). The efficiency
of such ligands in promoting electron transfer from reductant to cobalt is imperfectly understood but is probably related to the provision of a firm route
along which an electron may move. Good evidence for the existence of chelation
is reported by Butler and Taube16' in the case of reduction of glycolatopentaamminecobalt(II1) by Cr2+. The first product of reaction is a metastable Cr(1II)
species which has a higher absorptivity than the stable glycolatochromium(II1)
ion, and reverts to the latter with a half-life of
22 h. Chelation of Cr2+ by the
u-hydroxy group seems to explain the rate sequence glycolate < lactate < methyl-
T A B L E 19
R A T E P A R A M E T E R S F O R R E D U C T I O N OF S E L E C T E D C A R B O X Y L A T O P E N T A A M M I N E
COMPLEXES B Y
S H O W I N G EFFECT O F C H E L A T I O N ' 5 5
cr2+,
Ligand
Glycolato
Methoxyacetato
Lactato
Methyllactato
a-Malato
p-Malato
Malonato
Salicylato
Phthalato ion
Salicylato ion
k (I.mole - .set- l )
9.0
9.3
3.1
0.42
6.7
11.8
2.7
0.36
0.29
0.15 a
2.7
2x108 =
9. I
ASf(cal.deg- '.mole- I )
-26
-23
-24
-
AH f (kcal.mole- )
cO(III)
210
COMPLEXES OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
lactate since replacement of H by CH3 on the ct carbon should increase the basicity
of the O H group. Chelation is an important factor in the reduction by C r 2 + of
a variety of heterocyclic complexes (derived from pyridine, pyrazole and pyrazine)
as is evidenced by marked spectral effects'63. Huchital and T a ~ b e 'have
~~
examined the rate of ring closure of malonatopentaamminecobalt(II1). They
find that a chelate ring is formed before oxidation of C r Z +occurs. It is considered
that the hydrogen-ion dependent path is not to be conceived in terms of a remote
attack mechanism but that the activated complex is probably of the type ( G ) , uiz.
is formed which can decompose by rupture at the Cr-0 bond (to form the half-
OXIDATIONS BY
cO(III)
21 1
H/C+cCH
I
o'/c\OH
(I)
212
COMPLEXES OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
direct evidence of this kind. The subject of remote attack is discussed at length
by Taube','.
Halide effects have been reported for the Cr2+ reduction of Co(NH,),L"+
complexes (where L = NH,, acetato or fumarato, FuH-)lE2. Chloride exerts a
stronger catalytic effect than bromide; in all cases the second-order rate coefficient takes the form kobs= k+k,[X-] where k is pH-independent for L = NH,
or OAc-, but not for L = FuH-. When L = NH, or FuH-, halide is captured
into the inner coordination sphere of chromium, and products of the type XCr2+
and XCrFuH' result. CO(NH,),NH,~+ is known to react via an outer-sphere
mechanism'12, whereas CO(NH~)~OAC'+
and Co(NH,),FuH2+ use bridge
mechanism^"^*'^^ . It is surprising that C1- and Br- have similar influences on
both outer- and inner-sphere processes (Table 20). This similarity suggests that a
Cr(I1) halide complex, CrX', is formed rapidly and that this species takes part
in the formation of the activated complex.
T A B L E 20
KINETIC
L
NH3
FuHOAc-
PARAMETERS
IN
THE
p(M)
k(l.mole-'.
sec-')
2.60
3.4
1.65
0.0072
HALIDE-CATALYSED
B Y CrZ+(AT 25 oC)'82
REDUCTION
kc,(12.mole-2. kB,(12.mole-2.
sec-I)
sec- l)
0.60
0.69
0.20
1 .oo
0.34
0.3 1
0.30
0.064
kc,/kB,
1.9
2.3
3.1
OF
CO(NH3)sL"'
kc,/k(l. kBr/k(l.
mole-') mole-')
83
0.69
0.59
43
0.30
0.10
T A B L E 21
RATE PARAMETERS FOR
T H E OXIDATION OF
CO(1II)
Complex
co(Y)Co(HY)H,O
Co(Y)HZOCo(Y0H)HZO
Co(Y0H)OHCo(HY)CI-
A H i (kcal.mole- ')
11.8
11.1
22.1
14.2
13.7
11.3
Fe(I1)
B Y VARIOUS
EDTA
AND
HEDTA
COMPLEXES'84
OXIDATIONS BY
cO(III)
213
6.3
The course of the oxidation of V(II1) by Co(II1) has been the subject of an investigation by Rosseinsky and Higginson". Fig. 7 illustrates the dependence of
the concentrations of reactants and products upon time when Co(II1) is in excess
over V(II1). Under the conditions applying in Fig. 7, V(Il1) is oxidised to V(1V)
until 90% of V(II1) has been used up (i.e. at
28 min). Then V(V) begins to
be produced, and after V(II1) has been totally consumed (- 37 min) the reaction
corresponds to the oxidation of V(1V) by Co(II1). Co(II1) reacts with V(II1) and
V(1V) at a similar rate under the same conditions*. It is clear that Co(lI1) is
reduced by V(IV) as well as by V(II1) during the reaction, and that reduction by
5*0h
4.0
3 .O
Co (ID)
c\
20
40
60
00
Time (rnin)
Fig. 7. Dependence of concentrations of reactants and products upon time in the Co(lII)+V(IlI)
reaction. Initial concentrations: [Co(III) J = 4.99 x
M ; [V(III)] = 2.93 X
M , [V(lV)]=
3 x lo-' M ; [H+]
= 2.96 M, ionic strength = 3.0 M ; temp., 5.0 "C. (From Rosseinsky and
Higginsonso, b y courtesy of the Cheniical Society.)
* The redox potentials of the V 0 2 + - V 0 2 + and V02+-V3+ couples are 1.00 and 0.36 V,
respectively.
References pp. 267-273
214
V(1V) becomes progressively more important as the reaction proceeds. The fact
that V(V), the product of oxidation, is not detectable until all the V(II1) is consumed is ascribed to the rapid reaction V(III)+ V(V) + 2 V(IV) with a rate coef5 x lo3 I.mole-'.min-' at 5 "C, [ H f ] = 3 M and p = 3 M. When the
ficient of
initial concentration of V(I1I) is greater than that of Co(III), the reaction between
V(II1) and V(V) is unimportant and
Values of k, were derived from plots of this equation using known values of kb (see
below). At 0 "C, [H'] = 1 M and ,u = 3 M , k, is equal to 0.192 I.mole-'.sec-'.
k, varies inversely with hydrogen-ion concentration, the precise form of the
function being uncertain but of the type k, = k, +k'/[H+].
The reaction between Co(II1) and V(IV)
Co(III)+V(IV)
co(Il)+v(v)
OXIDATIONS BY
cO(III)
215
concentrations the observed rate coefficient (kobs)is proportional to Ag(1) concentrarion. In addition, plots of l/kobsversus l/[Cr(III)] and 1/k& versus [cO(II)]
are linear. Variations in acidity and perchlorate concentration have no effect on
the rate. The kinetic results are discussed on the basis of the following mechanism
Co(III)+Ag(I)
2 Co(II)+Ag(II)
k-3
Cr(III)+Ag(II) 3 Cr(IV)+Ag(I)
Cr(IV)+Ag(II)
--+
Cr(V)+ Ag(1)
- d[Cr( VI)]
3 dt
dt
III)]
+ 3 k,[Cr(III)]
k-,[Co(II)]
Since
dt
d[Cr(VI)]
-3 dt
d[Co(III)]
3
kob,[Co(III)]
PARAMETERS FOR
THE Ag(l)-CATALYSED
References p p . 267-273
CO(I1I)+Cr(III)
AHt(kcal.mole-
I)
REACTION
AT
25
"c"
'
ASt(cal.deg- '.mole- )
7jI 6
-32+10
- 14120
2 16
-d[Fe(II)]/dt
-d[Co(III)]/dt = k'[Co(III)][Fe(II)]
OXIDATIONS B Y CO(II1)
217
Fe3+ C1-
*FeC12+
The rate of oxidation of Fe(I1) by Co(I1I) has been studied in the presence
of Ag(I) by means of a stopped-flow apparatus'". Under conditions of excess
Ag(1) and Fe(II), Ag(I1) competes with Co(1II) for Fe(II), and the reactions are
Co(II1) Ag(1)
k-3
Co(11) Ag(I1)
A Ag(I)+Fe(III)
Co(III)+Fe(II) A Co(II)+Fe(III)
Ag(II)+Fe(II)
218
Values of kobsvary linearly with [Co(Il)], at constant [Ag(L)], and k , and k-,
were obtained as 37+4 I.mole-lsec-' and 1.75 x lo3 I.mole-'.sec-', respectively
(cf. Table 22). The two independently-determined values of k , are seen to be
in close agreement. The equilibrium constant, k , / k _ , , of the Co(III)+ Ag(1)
system is, thus, 2.1 x lo-* (using average k , ) in 4 M perchloric acid at 25 "C. A
value of 4 + 2 x lo-' is arrived at by considering the oxidation potentials of the
Ag(I)-Ag(LI) and Co(11)-Co(II1) couples.
Despite the lability of Fe(II1) complexes, Haim and Sutin192 have been able
to study the rapid reductions of some Co(I1I) complexes by Fe(I1) and identify
the primary Fe(II1) products. A flow apparatus, described by Dulz and S ~ t i n ~ ~ ,
enabled the rate of formation and decay of the spectra of the Fe(II1) products
Fig. 8. Transmittance uersus time curves for the C O ( C ~ O ~+)F~e z~+- reaction. Upper curve
shows disappearance of
(wavelength, 600 mp; abscissa scale, 500 msec per major
division). Lower curve shows formation and decay of the intermediate FeC2O4+ (wavelength,
310 mp; abscissa scale, 2 sec per major division). [ C O ( C ~ O ~ )=~ ~
1 -. ]0 ~
M ; [Fez+] =
2.5 X lo-' M ; [HC104] = 0.92 M ; ionic strength = 1.0 M ; temp., 25 "C. (Froin Haim and
Sutin' 92, by courtesy of The American Chemical Society.)
OXIDATIONS BY
cO(III)
219
to be observed and recorded (Fig. 8). A two-stage mechanism holds for the
C O ( C ~ O , ) , ~ -Fe2+ reaction, uiz.
CO(C,O,),~- + F e 2 +
F e C 2 0 4 + + 2H +
_f
+ Fe3++H2Cz04
T A B L E 23
S E C 0 N D 0 R D E R R A T E C O E F F I C I E N T S F O R T H E 0 XI D A T I 0 N 0 F
COMPLEXES B Y
CO(1IL)
IN
Ligand
5-Methyl-l , 10-phenanthroline
I ,lo-Phenanthroline
5-Chloro-I, 10-phenanthroline
5-Nitro- 1,lO-phenanthroline
References p p . 267-273
3 M
Fe(l1)- P H E N A N T H R 0 L1 NE
25.0 0c'95
PERCHLORIC ACID AT
E"( b')
I .02
1.06
1.12
1.25
10- 3k12(l.mo/e'.set- l )
15.0
14.0
5.02
1.49
220
C O M P L E X E S OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
T A B L E 24
FOR OXIDATIONSLOPES A N D INTERCEPTS O F PLOTS O F ( A G t , , , + l . l 5
1ogf)vs.
R E D U C T I O N RE A C T I O N S I N V O L V I N O S U B S T I T U T E D Fe(Il)-PH E N A N T H R O L I N E C O M P L E X E S
AT
25.0 "C
Slope
Reaction
Intercepr(kcal.mole- I )
Observed Calculated
F e ( ~ h e n )+Fez
~~
a
Ce(IV)+Fe(phen)32+
Mn(IIl)+Fe(phen)3Z+
Co(III)+Fe(phen),Z+
+
0.56
0.48
0.49
0.51
Observed
14.8
14.8
17.6
19.5
0.50
0.50
0.50
0.50
Calculated
Medium
0.5 kfH2SO4
0.5 M HzS0.t
1 and 3 M HC104
13.0
13.0
15.8
12.9
3 M HCIO,
et u Z . ' ~ ' , this deviation may stem from non-cancellation of the non-electrostatic
contributions to the work required to bring together the various pairs of reactants.
The reduction of Co(II1) by Ag(1) in perchlorate solutions has been studied
by Sutcliffe el
Since the initial product of reaction is the very reactive
Ag(1l) species, all solutions were subject to preliminary ozonolysis to remove
traces of reducible impurities. The final products of reaction are Co(I1) and Ag(1).
Kinetic data were obtained spectrophotometrically by following the disappearance
of Co(II1) at 605 mp, a small correction being applied for the absorbance of
Co(l1). With Ag(1) in excess, the disappearance of Co(II1) is second order, i.e.,
plots of the reciprocal of the corrected absorbance uersus time are linear. The rate
is directly proportional to the concentration of Ag(I), and inversely proportional
to the square of the concentration of Co(II). These results can be understood in
terms of the mechanism
Co(III)+Ag(I)
Co(II)+Ag(II)
K2
k-3
Ag(l1)
+ products
+ Ag' +Ag3+
A g 3 + + H 2 0+ A g 0 + + 2 H +
2 Ag2'
Ago+ %Agf
+to,
rapid equilibrium, K3
rapid equilibrium, K4
slow
O X I D A T I O N S BY
CO(II1)
22 1
- -d[Ag2+]
dt
under conditions where [Ag(I)] > [Co(III)]. In keeping with this relationship,
the rate is dependent on [H+]-' at constant ionic strength; the observed rate
3.3 M perchloric acid. The
constant goes through a pronounced minimum at
overall A H f values for the Ag(I1) d e c o m p o s i t i ~ n ' and
~ ~ the Co(III)+ Ag(1)
r e a ~ t i o n ' ~ are
'
1 1 + 2 and 34+4 kcal.mole-', respectively. Thus K2 has an associated overall AH of 12 kcal.mole-'. The value of 0.76 obtained for K2 is in
poor agreement with the value of 2.1 x l o v 2 given in ref. 191 (see p. 218).
The slow reduction of cobalt(I1I) by mercury(1)
= -d[Co(III)]/dt
= 2 k,,~s[C~(III)][Hg(I)~]
is maintained in the presence of a large excess of Co(I1) and Hg(II), the products
of reaction. Kinetic data were obtained in most cases by monitoring the disappearance of Co(111) at 603 mp. Variation in perchlorate-ion concentration does
not affect the rate. This last observation contrasts with the behaviour shown by
the TI(III)+ H B ( I ) ~system, where the rate varies inversely with C104- concentrationS6. It follows from the observed acidity dependence that the second-order rate
coefficient kobs can be written as kobs= k+k'/[H+] where k = 0.02 I.mole-'.
sec-' and k' = 0.36 sec-' at 19.9 "C and p = 3.0 M. The corresponding activation
References pp. 267-273
222
C O M P L E X E S O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
energies and activation entropies are 22.1 and 29.2 kcal.mole-', and 9 + 6 and
37 + 4 cal.deg-'.mole-', respectively. Either of the following schemes is likely
Co(III)+ Hg(I),
-+
Co(II)+Hg(II)+ Hg(1)
Co(IIl)+Hg(I) -+ Co(II)+Hg(ll)
or
Co(IlI)+Hg(I),
slow
rapid
C0(11)+Hg,~+
slow
rapid
Since the rate does not display an inverse dependence on Hg(1I) concentration,
the oxidation of Hg atoms, in equilibrium with mercury(1) and mercury(II), can
be discounted, although Hg atoms are kinetically important in the reduction of
thallium(II1) by mercury(I)86. It seems likely that the acid-dependent path ( k ' )
involves CoOH2+.Anion effects were not investigated.
Co(1II) oxidises TI(1)'l according to
2 Co(III)+TI(I)
2 Co(II)+TI(IIl)
in a manner resembling the oxidation of Fe(I1) by Tl(III)199. Owing to the instability of Co(II1) in aqueous perchloric acid solutions, the kinetics of the reaction were examined under conditions where TI@) was in excess over Co(III), the
disappearance of the latter being followed by titration. By employing low initial
concentrations of Co(II1) relative to TI(I), and by avoiding low hydrogen-ion
concentrations, the rate of decomposition was reduced to less than 10 % of the
overall rate of disappearance. The presence initially of high concentrations of
Co(II1) causes a marked reduction in rate; on the other hand, TI(II1) has little
effect. The simplest scheme is
where TI(I1) is competed for by Co(1I) and Co(II1). At low Co(1I) concentrations
-d[Co(III)]/dt
2 k,,bs[C~(III)][Tl(I)]
and the pH-dependence of kobs was investigated over the range 0.25-2.50 M
HCIO, between 0 "C and 25 "C at p = 2.70 M . First-order plots (of log [Co(III)]
versus time) deviated slightly, but significantly, from linearity at the beginning of
reaction. This is thought to come about from the reaction of dimeric species
OXIDATIONS BY
cO(III)
223
Plots of kobsversus l/[H+] allow k,, to be evaluated, but k,, cannot be defined
exactly due to doubt over the value of K , , the hydrolysis constant of Co3+, and
I.mole-'.sec-' at 15 "C, and 2.5 x
also to scatter in the data. k , is 6.8 x
l.mole-'.sec-'
at 25 "C. Using a value of 5 x
mole.l-' for K , (ref. 200),
k,,
1 . 7 lo-*
~
I.mole-'.sec-'
at 15 "C. Unsuccessful attempts were made to
correct for the reduction of Co(II1) by water, and thus errors of up to
10%
may be present in the quoted values of k,,. The latter has an associated activation
energy and entropy of 26.4 kcal.mole-' and 2 2 5 7 cal.deg-'.mole-l, respectively.
The rate of the Co(m)+Tl(I) reaction is increased by the addition of sulphate.
It is deduced that the SO4,- ion, and not the HS04- ion, is responsible for the
catalysis, although the latter is present in much larger amounts. The back-reaction
of Co(I1) with TI(I1) is much less important in the presence of sulphate. Ashurst
and Higginson" make a tentative suggestion that perchlorate ions participate
in the Co(III)+Tl(I) system, i.e., the activated complex contains one or more
CI04- ions.
The binuclear complex of Co(III), bi-p-hydroxobis(bioxaIatocobaltate(II1)
[(C204)2Co"'(OH)2C01'1(Cz04)24-],
is reduced by Sn(1I) in dilute hydrochloric
acid solutions2". The products of reaction are the mononuclear complexes,
probably cis-bioxalatodiaquocobaltate(II1). If trioxalatocobaltate(II1) is included
in the reaction mixture, then a considerable fraction of it is consumed during the
course of the reaction of Sn(I1) with the binuclear species. Since trioxalatocobaltate(111) does not react with Sn(1I) under the prevailing conditions, this result indicates
that the reactive reducing species is Sn(III), generated by a one-equivalent process.
bring
~ + about oxidaThe Co(I1I) complexes CO(NH,),~+and C O ( N H ~ ) ~ O H
tion of stannate(I1) ion in strongly basic solution202.The rates were found to
be independent of the concentration of the Co(II1) complex. It is proposed that
stannate(I1) exists as a dimer, and that the monomer is the reactive species, the
rate being close to half-order in stannate(I1). Cyanide and thiosulphate catalyse
the reaction but CO(CN),~-is immune to attack by stannate(II) ion. The experimental difficulties encountered in this study preclude a full analysis as regards
mechanism.
The reaction between Co(I1I) and Ce(II1) has been the subject of a detailed
study in a series of papers by Sutcliffe and Weber's8~20s~206.
Of particular value
is the thorough investigation of the influence of anions on the rate in perchlorate
media. The reaction was followed by meaeuring the disappearance of Co(II1) at
its absorption maximum of 650 mp, a wavelength where both oxidation states of
cerium are transparent and Co(T1) absorbs only slightly. Changes in temperature
and ionic strength affect the spectrum of Ce(II1) at the 296 mp maximum, but the
References p p . 267-273
224
C O M P L E X E S OF D I F F E R E N T ME r A L S : O X I D A T I O N - R E D U C T I O N
k'
= a/[HCIO,]
l/k' = b+c/[CIO,-]
where b and c are constants. Since previous work had precluded the possibility
of a reactive hydrolysed species of cerium(III), the hydrogen-ion dependence was
taken as evidence for the existence of CoOH2+.The equilibrium constant for
Co3
+ H 2 0 +-CoOHZ++ H +
Kl
COOH~ C~CIO,~
+
co(11) Ce(IV)
OXIDATIONS BY
CO(II1)
225
since K , is less than [H']. The empirical parameters. a, b and c, are then evaluated
as follows
TABLE 25
RATE PARAMETERS F O R T H E
CO(III)+Ce(III)
REACTION188*20s*206
CoOH2++CeC1042+
CoOH2++CeNOJ2+
CoOHZC+CeFZf
CoS04+ +CeS04+
CoS04+ +CeC104*+
coSO4+ +Ce3+
c o 3 ++CeS04+
95
93
8500
12000
250
5 350
I
200
ASf(cal.deg- '.mole- I )
14&7
-5*l
19&2
14*2
The true rate coefficient, derived from these relationships, is given in Table 25,
along with the corresponding AH' and AS' terms. A later spectrophotometric
study'*' of Co(II1) perchlorate solution has cast some doubt over the value of
the formation constant (Kl) for CoOH". It is suggested that CoOH" undergoes
slow dimerisation to C0-O-Co4+ and/or Co-0-CoOH3 , although further
hydrolysis and/or polymerisation is possible. Furthermore, reaction between
hydrolysed and dimeric species has been proposed as the rate-determining step
in the reduction of Co(1II) by waterZo0.A kinetic study of the formation of
the monochloro complex of Co(II1) has given a considerably higher value for Kl
ot 0.22 mole.1- at 25 OCZo4.Nitrate ion increases slightly the rate of the Co(II1)
Ce(l1I) reaction in terms of a first-order dependenceZo5.The effect is attributed
to the introduction of a step involving CoOH" and CeN032+.The formation
constant of the latter ion received a spectrophotometric study. In contrast to the
slight effect of NO,-, the addition of fluoride ion increases the rate markedly:
M F- is sufficient to double the rate coefficient. The linear
the presence of
dependence of rate on F- concentration is discussed on the basis of reaction
between CoOH" and CeF2+. Rate parameters are collected in Table 25: experimental difficulties arising from the insolubility of cerium(I11) fluoride did not
allow calculation of the AH' and ASf values for the fluoride-catalysedpath. That
the product Ce(IV) is strongly complexed is shown by the observation that spent
reaction mixtures were colourless instead of yellow. Sulphate complexes of both
reactants participate in the Co(III)+ Ce(lI1) reaction in bisulphate media; a
linear relationship is found between the rate and the anion concentrationZo6.
+
226
The predominant reactive species of Co(lI1) are C0S04+ at 20 "C, and Co(SO,),at higher temperatures than 30 "C. Rate data (in the form of maximum rate
coefficients) are given in Table 25 for the various mechanistic steps.
The oxidation of Np(V) by Co(II1) has the stoichiometry
Co(III)+Np(V) = Co(lI)+Np(VI)
and a rate law
-d[Np(V)]/dt
~'[N~(V)][CO(III)][H+]-~"'
Co(II)+Np(VI)+ Cr(II1)
Kinetic data were obtained by following the rate of disappearance of the complex
at 993 mp, and the Cr(II1) product was identified"' as Cr(H20)63+.The rate is
described by
-d[Np(V)Cr(III)]/dt
k"[Co(III)][Np(V)Cr(III)][H+]
Co(II)+ Cr(IV)*Np(V)
t At 25 "C, the Np(V).Cr(llI) complex has an equilibrium constant of 2.62, and a rate coeffisec-' (p. 259). The dissociation of this species during the
cient for decomposition of 2.32 x
course of the redox reaction is negligiblezo8.
Pt(IV)
OXlDATlONS BY
227
7. Oxidations by platinum(1V)
Beattie and B a s o 1 0 ~ ' ~have investigated the reactions of the substitutioninert octahedral complexes of Pt(1V) with tris(bipyridine)chromium(II). A rapidmixing, stopped-flow apparatus"' was made use of in the majority of experiments.
Kinetic data were obtained by following the disappearance of Cr(bipy),''
at
562 mp, usually with Pt(IV) in excess. The stoichiometry corresponds to
Pt(IV)+2 Cr(1I) = products
and the rate law is simple second-order. The rate coefficients obtained are given
in Table 26. The complex Pt(en),,+ is reduced 20 times more rapidly than its
conjugate base, Pt(en),(en-H),
(where en-H represents ethylenediamine minus
a hydrogen atom). A comparison of the rates of reduction of Pt(1V) and C0(111)"~
(see Table 9, p. 190) by the common reductant Cr(bipy),'+ reveals: (a) the
order of halogenopentaamminecobalt(III) complexes is F- < C1- < Br-,
whereas that for the analogous Pt(1V) complexes is C1- < I - < Br-, ( b )
Pt(en),,+ is reduced ten times faster than Pt(NH3)64+ whereas Co(en),,+ reacts
four times slower than CO(NH,)~,+.The presence of a hydroxo ligand imparts
inertness to Pt(IV), truns-Pt(NH,),CIOH'+ reacting nearly lo4 times slower
than truns-Pt(NH,),ClZZ+. There is a general correlation between the rates of
reduction of Pt(1V) complexes and their polarographic half-wave potentials.
Beattie and BasoloZo9suggest that the rate-controlling step in the reductions is
the formation of a Pt(II1) intermediate by a one-electron, outer-sphere process,
cf. the oxidation of Pt(I1) complexes by hexachloroiridate (IV),06.
+
T A B L E 26
RATES OF REDUCTION OF
Pt(1V)
COMPLEXES BY
AT
25 "C AND^
k (I.mole-'.sec-')
Complex
Pt(NH3)5C13
Pt(NH3)5Br3+
Pt(NH3)513+
+
(2.9*0.3) x lo5
(8 &4 )x106
(3 f l )x106
(7.7 I .o) x 103
( 4+1 )x102
(7.7*1.0)x10~
Pt(en),(er~-H)~
Pt(NH3)64+
trans-Pt(N H3)4CIZZ
rrans-Pt(NH3),C10H2 +
+
Cr(bipy):+
107
(2 *I
)xi03
= 0.1 MZo9
228
c o M P L E x E s OF D I F F E R E N T M E T A L s: O X I D A T I o N-R
E D u cT I oN
8. Oxidations by copper(I1)
The rate of reduction of Cu(I1) by Cr(I1) has been measured in aqueous
perchloric
3 0 7 . With Cu(I1) in excess and in the absence of oxygen, the
reaction corresponds to
Cu2++Cr'+ = C u + + C r 3 +
and is first-order in each reactant, the rate showing an acid dependence given by
d [Cu' ]/dt
= (a
+b/[H+])[Cu2+][Cr"
9. Oxidations by mercury(I1)
The rate law for the oxidation of V(I11) by Hg(1I)
2 Hg(1I) + 2 V(I1I) = Hg(I),
is complexz6,viz.
+2 V(IV)
OXIDATIONS BY
Hg(I1)
229
The second term contributes only 10-20 % of the overall rate and its precise form
is uncertain. The kinetic parameters have been evaluated for the reaction at 15 "C.
The first term is consistent with the sequence of steps
Hg(I1) V(I11)
Hg(I)+V(III)
+ Hg(l)+ V(1V)
Hg(O)+V(IV)
-+
Hg(I1) Hg(0)
-+
Hg(I),
rapid
+ V(IV)+V(II)
Hg(O)+V(IV)
-+
Hg(II)+ Hg(0)
-,Hg(I),
rapid
-+
Hg(1) + Cr(II1)
rate-determining
230
-+
Hg(O)+ Cr(II1)
rapid
(9.2)
In this respect the final Cr(I1I) product is the monomeric species and not the green
dimer. Furthermore, if Hg(1I) is not i n excess then reaction (9.3) cannot occur,
and mercury precipitates. The reaction is appreciably catalysed by chloride ions.
At 10 "C, the specific rate coefficients for the reaction of C r 2 + with HgCl',
I.mole-'.sec-', respecHgOH', and Hg2' are 1.5, 2.3 x lo3, and 1.75 x
tively. The species HgCI, is much less reactive than HgCI'.
A slow reaction takes place between Hg(I1) and Fe(1I) in perchloric acid solution
viz.
2 Hg(I1) + 2 Fe(I1)
Hg(I),
+ 2 Fe(C1I)
Hg'
-+
+ Fe3+
slow
+ Hg2'+
rapid
-+
Hg + Fe3
Hg+Hg2+ -+ Hg2"
rapid
rapid
In dilute perchloric acid solution the reaction between Hg(l1) and Sn(I1) is
M . After a detailed
complete within 1 min for reactant concentrations of
consideration, Wetton and Higginson' conclude that a two-equivalent primary
reaction is likely.
10
OXIDATIONS B Y
23 1
Tl(III)
AHT.(kcal. AST(cal.deg- I .
mole- ')
mole- l )
S:,,,,,,.
-lS~+ZSo,,,,,,,,,zl.
13.9
17.6
13.4
4.1i-2.4
-10.2i-5.3
-8.3
St complex
-86
- 128
- 124
ReJ
213
90
b
TI(III)+V(tII)
+ TI(I)+V(V)
rate-determining
(A)
V(V)+V(III)
2 V(1V)
rapid
rate-determining
(B)
-rI(rr)+v(rrr)
Ti(r)+v(rv)
'
Higginson ef a1.26 have observed the formation of V(V) in dilute sulphuric acid media in
the presence of an excess ofTl(II1). More V(V) is formed if V(1V) is present initially. In this media
they suggest that mechanism ( B ) operates together with
TI(II)+V(IV) + TI(I)+V(V)
V(V)+V(11l) + 2 V(1V)
ReJcrenws p p . 267-273
232
c o M P L E x E s o F D I F F E R E N T M E T A L S:
O X I DA T I o N-R E D u c T I o N
This proposal is supported by the observation that the normally slow reaction
between TI(II1) and Fe(1I) can be induced by V(II1) (p, 233). Consequently,
Fe(1I) must react with an active intermediate, which is likely to be TI(I1).
The rate of oxidation of V(1V) by Tl(II1) is unaffected by the presence of TI(1)
but is considerably decreased by the addition of V(V)". The rate law is
~"CV(V)l+L-V(~V)l
where k'
2.2 x lo-' I.mole-'.sec-'
and k"
42 at 80 "C, [ H f ] = 1.8 M
and p = 3 M . Consequently, the mechanism is similar to the TI(III)+Fe(Il)
i.e.
+
+ T1(11) +V(V)
TI (11) + V(IV) .+ Tl(1) + V(V)
TI(II1) V( IV)
This scheme has a bearing2I4 on the TI(II1) + Tl(1) exchange reaction where,
on the basis of the observed rate law only (rate a[TI(III)][TI(I)]), it is impossible
to discriminate between a single-stage and a two-stage two-equivalent process.
Since the rate of the exchange reaction is comparable to the rate of oxidation of
V(IV) by TI(III), appreciable exchange occurs during the course of the latter
reaction. It is argued2I4 that the addition of TI(1) should increase the rate of the
TI(III)+V(IV) reaction if Tl(I1) were an intermediate in the exchange. However,
as noted above, TI(1) has no such effect, and it is concluded that the exchange takes
place by a single two-equivalent step.
The rate of reduction of TI(II1) by Fe(I1) was studied titrimetrically by Johnbetween 25 "C and 45 "C in aqueous perchloric acid (0.5 M to 2.0 M ) at
p = 3.00 M . At constant acidity the rate data in the initial stages of reaction conform to a second-order equation, the rate coefficient of which is not dependent
on whether TI(I1I) or Fe(I1) is in excess. The second-order character of the reaction confirms early work on this system216. A non-linearity in the second-order
plots in the last 30 % of reaction was noted, and proved to be particularly significant. Ashurst and Higginson' 9 9 observed that Fe(II1) retards the oxidation,
thereby accounting for the curvature of the rate plots in the last stages of reaction.
On the other hand, the addition of TI(1) has no significant effect. On this basis,
they proposed the scheme
TI(II1) + Fe(II)% Tl(I1) + Fe(II1)
k-
TI(II)+Fe(II)
Tl(I)+Fe(III)
10
OXIDATIONS BY
TI(II1)
233
in which Fe(II1) and Fe(I1) compete for the TI(1I) intermediate. The derived rate
law, applicable to the whole course of the reaction, is then
-d[Fe(II)]
dt
k, k2[Fe(II)]'[TI(III)]
k,[Fe(II)]
k-,[Fe(III)]
-2
-
k;'K2
(k" m)
T A B L E 28
RATE
COEFFICIENTS A N D
25.0
35.0
45.0
References p p . 267-273
EQUILIBRIUM
6.4
9.4
12.7
CONSTANTS
I .41
3.91
9.96
OF
TI(III)+Fe(ll)
I .24
4.44
12.8
234
COMPLEXES O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
of TI(IrI) and V(III), and that this intermediate is capable of reacting with Fe(I1).
The TI(III)+U(IV) system is also subject to induction by V(III), although TI(I1)
is not as reactive towards U ( W ) as it is to Fe(II). Induction experiments on the
effect of V(I1) on the TI(III)+U(IV) system reveal that TI(I1) reacts much more
rapidly with V(I1) than with V(1II). Alternatively, they imply that Tl(II) is not
formed in the TI(III)+V(II) reaction. Spectrophotometric data for the rate of
oxidation of V(I1) by TI(II1) were obtained from measurements at 760 mp, a
wavelength where V(IV) absorbs more strongly than V(lT), V(III), and TI(lI1).
As the reaction proceeds the observed second-order rate coefficient increases. This
effect is attributable to the catalytic influence of V(II1). The following sequence
of reactions is an appropriate mechanistic framework
Tl(III)+V(Il)
-+
TI(I)+V(IV)
(10.1)
+
TI (11) + V(II1)
TI (111) + V( I I I ) -+ TI (11) + V( IV)
TI(I1I) V( I I)
TI(II)+V(II)
TI(II)+V(I11)
T1(111)+2 V(I1)
2 Tl(I1)
v(rr)+v(iv)
--+
(10.2)
(10.3)
Tl(T)+V(III)
(10.4)
TI(I)+V(IV)
(10.5)
T1(1)+2 V(1II)
(10.6)
TI(I)+TI(III)
(10.7)
2 vpn)
(10.8)
Of these steps, the last three can be discounted: (10.6) on the grounds that there
is no significant V(I1) dependence, (10.7) is considered unimportant since TI(I1)
is present only in minute concentrations, (10.8) is slow by comparison with the
other steps in the set (k 0.13 I.mole-l.sec- in 1 M HCIO, at 0 OC)l. Both
rate and stoichiometric data infer that the reaction between TI(IT1) and V(II)
occurs essentially by a two-electron oxidation (step (10.1)). In the presence of
chloride, less V(IV) is produced. It is interesting to note that oxidation of V(II)
by molecular oxygen or hydrogen peroxide generates V(IV). However, the
oxidation of V(1II) by Tl(II1) does not occur as a two-electron step (see p. 231).
The kinetics of the oxidation of tris(bipyridyl)osmium(II) by T1(III)223
TI (111) + Os(bipy ),
TI (11) + Os(bipy ),
r TI(11) + Os(bipy ),
-+-TI( I)
+Os(bipy ),
+
+
10
OXIDATIONS BY
TI(III)
235
The reaction was followed by means of the strong absorption of the Os(1I)
complex at 480 mp. Unlike the TI(III)fFe(II) system, there is a slight increase
in rate as the hydrogen-ion concentration is increased. The kinetic data were
interpreted on the basis that both TI3+ and T10H2+ react with Os(bipy),2+
(with rate coefficients k, and k,, respectively). At 24.5 "C and p = 2.99 M ,
k, = 36.0 I.mole-'.sec-' and k, = 14.7 I.mole-'.sec-'; corresponding activation
energies are 6.90 and 11.5 kcal.mole-l. The latter values are considerably smaller
than those for the Tl(III)+T1(1) exchange,,, and for the TI(III)+Fe(II) react i o 1 1 l ~ On
~ . the other hand, all three reactions are subject to retardation by C1ions.
Ce(IV), although a strong oxidant, reacts only very slowly with Hg(I), whereas
TI(III), a two-equivalent oxidant, reacts relatively rapidlyE6,2 2 5 according to
Tl(III)+Hg(I),
TI(I)+2 Hg(1I)
where the subscript o refers to initial concentrations. Plots of the left-hand side
of this equation versus time are linear over a wide range of concentrations of reactants and products. The observed rate coefficient k', obtainable from the slopes
of such plots, is found to be inversely proportional to HCIO, concentration
(2.4 to 6.0 M at p = 6.0 M ) , and also to ClO,- concentration. The following
scheme accounts very adequately for the observed kinetics
Hg,,+ +CIO,-
+ Hg,CIO,+
K3
HgZ2+$ H g 2 + + H g
(10.9)
rapid equilibria
2 TIOH,+ + H +
TIOH2++ Hg 2T I + + H g 2 + + O H - rate-determining
TP+ +H,O
References p p . 267-273
(10.10)
(10.11 )
(10.12)
236
c o M P L E x E s o F D I F F E R E N T M E T A L S:
O X I DA T I o N-R E D u c T I o N
= k , [T10H2'][Hg]
or, alternatively
E,+AH,+AH,-AH,
(10.13)
Estimated values of A H 3 , AH4 and A H 1 are -0, 10.6 and -0.5 kcal.mole-',
respectively, and E' is 24.4 kcal.mole-' and therefore E , is given as -14+3
kcal.mole-'. The corresponding A S f term is 13 f10 cal.deg-'.mole-'.
It is
noteworthy that the kinetics demonstrate the direct reaction
+ TI++Tl3'+OH-
particularly as the TI' and Hg species are isoelectronic. However, this step is
lo9 to 10" times slower than (10.12) even though the activation energies are
similar. The profound difference in rate strongly suggests that the principal factor
responsible is the charge of the reactant ions: this is reflected in disparate AS'
10
O X I D A T I O N S BY
TI(II1)
237
terms. Chloride and bromide ions catalyse the Tl(III) + Hg(I)2 reaction (showing
non-linear dependences) by complexing with HgZ+,thus increasing the concentration of Hg atoms by displacing the dismutation step (10.10).
Wetton and HigginsonSg report that the reaction between Tl(JI1) and Sn(I1)
is complete in less than 10 sec at -6 "C in
1.3 M HCI for
lo-' M reactant
concentrations. It appears that it takes place as a single-stage two-equivalent
process without the intervention of Sn(III), since added CO(NH~)~(H,O)CI~+
is not consumed during the course of the reaction.
The two-equivalent oxidation of U(IV) by Tl(III), viz.
TI (111) U(IV)
T1(I) U( VI)
= [T13+][U4+](k;[H+]-'
+ k;[H']-2)
can be written in terms of K , and Kl , the hydrolysis constants of U4+ and TI3+,
viz.
-d[U(IV)]/dt
= [Tl(III)][U(IV)](k;[H+]
+k;)/([H+] +K,)([H+l+ K I )
Use was made of known values of K 5 = 0.021 mole.l-' and Kl = 0.073 mole.1-'
at 25 "C and p
3 M , along with estimated values of these constants at other
temperatures (assuming, in each case, an enthalpy of hydrolysis of 11.0 kcal.
mole-'). Plots of kobs([H']+K,)([H']+Kl) uersus [H'] are linear, and k',
and k ; are obtained from the slopes and intercepts. At 25 "C and p = 2.9 M , the
rate parameters for the first path are: k; = 2.11 x
sec-', A H f = 24.6 kcal.
For the second path, the cormole-' and A S f = 16f7 cal.deg-'.mole-'.
responding values are: k; = 2.13 x
mole.l-'.sec-', A H f = 21.7 kcal.mole-'
and ASf = 7+7 cal.deg-'.mole-'. Paths 1 and 2 involve the activated complexes
(UOHTI6+)' and (UOTI5+)', respectively. The formation of U-0 bonds is a
necessary requirement since changes in coordination occur from U(IV) to U(V)
( U 0 2 + )to U(V1) (UOZ2+).Addition of NaC104 increases the rate of the reac-
References p p . 26 7-273
238
c oM P L E X E s oF
D I F F E R E N T M E T A L s:
ox I D A T I o N-R
E Du c T I o N
tion. The effect of various anions and cations on the reaction is summarised as
follows. C1- inhibits the reaction whereas SO4- enhances the rate, results ascribed to the formation of complexes of Tl(111): parallel behaviour is noted in
the T1(TII)+TI(I) exchangezz9, and in the TI(III)+Fe(ll) r e a ~ t i o n ~ Ad.
dition of small amounts of Cu(lI), Ag(I) and Hg(I1) leave the rate unaffected.
These ions have a marked effect on the rate of oxidation of U(IV) by oxygen, a
reaction known to proceed by a chain mechanism230. It is concluded that the
general features of the Tl(III)+ U(1V) reaction are in accord more with a single
two-electron step than with successive one-electron steps for the following reasons:
(a) The reaction is considerably faster than the TI(III)+ Fe(I1) system, generally
accepted to occur via one-electron steps;
( b ) The reaction shows no abnormality in AHt and AS which seems to be
characteristic of processes, e.g. TI(II1) Fe(ll), involving TI(I1).
( c ) If the primary process generated TI(II), then a chain process of the sort
U(IV)+TI(II)
--+
U(V)+T1(1)
5( T I . H O . U ~ ++) H~ +
2 T 1 3 + + U 4 + + 2H z O ~ ( T I . H 0 . U . 0 H . T l s + ) : + 2H f
T A B L E 29
TI(III)+U(1V)
W V )
TI(III)
Hf
1.oo
1 .oo
1 .oo
1.50
1.25
0.67
-1.39 to -1.48
- 1.33
-0.25
-0.67
25
50
75
0.50
0.33
10
OXIDATIONS BY
239
TI(III)
3 [H'I-
+k" [Ti3
1' [U4+] [H
]-
'
and
Using values of K , and K , , identical with those made use of by Harkness and
Halpernz2*, the rate coefficients k' and k" were evaluated from the slopes and
intercepts of linear plots of the left-hand side of equation (10.14) versus ([H']
T A B L E 30
Tl(III)+U(IV)
2 5 % METHANOL-75 % W A T E R
MEDIAz3'
Path
AHZ(kcal.mole-')
ASt(cal.deg-'.mole-')
k'
k"
0.0041
0.98
3.11
4.47
-59.0
-43.6
Kl)/[Tl(III)]. Table 30 contains these results together with AH' and A S f values.
The reaction in 25 % methanol is faster than in water, although ASs is strongly
negative. To some extent this may be rationalised in terms of the structure of the
activated complex (TI.HO.U-OH.TI*')*, since the formation of U0,'+ would
appear to be facilitated by the positions of the two oxygen atoms relative to the
U atom. The role of the solvent in governing the progress of the reaction is discussed by Jones and A m i ~ ' ~ ' In
. contrast to the reaction in aqueous solution,
chloride is ineffective as an inhibitor and sulphate is a poor catalyst in 75 %
methanol media. Moreover, Cu(1I) and Hg(I1) exert a marked catalytic effect
whereas Ag(I) strongly retards the reaction. These latter observations recall those
recorded for the U(IV)+02 system230.A step-wise process, involving U(V) and
TI(II), is advanced, uiz.
+ U(VI)+Cu(I)
240
colloidal suspension of metallic Ag is formed, and after this is complete the reaction proceeds at its normal rate.
Wearz3' has subjected the TI(III)+U(IV) reaction to a close scrutiny, the
kinetics being studied over a 2000-fold range of reactant concentrations. Solutions
were kept under nitrogen. The range of concentrations examined by Harkness and
Halpernzz8 were U(1V) = 3.5 x
to 11.0 x
M , TI(rI1) = 5 x
to
21 x
M. Wear finds that the orders with respect to the reactant vary with
T A B L E 31
TI(III)+U(IV)
Region
I
I1
111
IV
REACTION:
V A R I A T I O N OF K I N E T I C O R D E R S W I T H C O N C E N T R A T I O N
1-50
5.0
0.02-1.0
0.12-0.36
0.25-2.75
0.90
0.90
0.50-1.90
0.88
1.2
0.88
1.6
0.90
0.90
0.67
0.38
-1.4
-1.4
-1.4
-1.5
IoNc strength, 2.9 M ; temp., 25 "C. From Wearf32 (by courtesy of Sandia Laboratories and
TI(Il)+U(V)
2 U(V)
+ TI(I)+U(V)
-+
TI(I)+U(VI)
U(IV)+U(VI)
2 TI(I1) + Tl(T)+Tl(ITI)
Tl(III)+U(V)
+ TI(II)+U(VI)
The rate laws reported by Wear2j2 have been criticised by Newton and Bakerzs0.
11
OXIDATIONS BY
24 1
Pb(IV)
',
20
I
40
60
[H20] ( M I
Fig. 9. Effect of water o n the stoichiometry of the Pb(LV)+Co(lI) reaction in acetic acid at
and 37 "C ( 0 ) .(From Benson et
by courtesy of The Faraday
temperatures of 23 "C (0)
Society.)
References pp. 267-273
242
co M P L E x ES o F D I F F E R E N T METALS: ox I DA T I o N-R E D u c T I o N
volving a Co(l1) dimer, and Pb(Il1) and Co(IV) as intermediate species, ciz.
CO(II)+C~(II) [co(rr)12
Pb(IV)
Pb(rv)+ [c0(11)],
-+
Pb(IV)+ [Co(II)],
-+ Pb(Il)+Co(IV)+
Pb(IV)+ Co(1I)
Pb(IV)+Co(II)
Co(1I)
+ Pb(II)+ Co(IV)
-+
Pb(III)+Co(III)
co(rv)+co(r~) 2 c O ( q
Pb(III)+Co(II)
-+
Pb(II)+ Co(1II)
-+
2 Co("1)
12
OXIDATIONS BY
Ce(IV)
243
--t
Pb(lII)+Ce(IV)
slow
Pb(IlI)+Ce(III)
Pb(II)+Ce(IV)
rapid
-+
products
-+
products
3 Ce(rrr)+ Cr(V1)
takes place at a convenient rate for spectrophotometric measurements239. HowReferences pp. 267-273
244
co M P L E x ES o F D I F F E R E N T M E T A L s: O X I DA T I o N-RE D u c T 10N
ever, the reaction was found to be inconveniently fast in perchloric acid solutions.
Kinetic results were obtained at 492 mp and 500 mp, wavelengths where Ce(II1)
is transparent but Ce(IV), Cr(II1) and Cr(V1) absorb to varying degrees. No
evidence was obtained for the presence of dimeric species of Ce(1V); this reactant
is presumed to be highly complexed with sulphate (or bisulphate) ions240t. Although dimers of Cr(V1) are possible, monomer and dimer have similar absorptivity values at the chosen wavelengths''. The reaction demonstrates an inverse
dependence on the concentration of Ce(III), and a square dependence on Ce(IV)
concentration, viz.
k,[Ce(IV)][Cr(IV)]
(12.4)
k-lCWWI
Thus the observed rate coefficient kobsis equivalent to k, k z / k - , . Because of the
limitations of the kinetic procedure, there is some small doubt over the inclusion
of a term in Ce(IV) concentration in the denominator of (12.4). However, the
relative insignificance of this term means that k - , [Ce(III)] > k2[Ce(IV)]. Also,
the inequality k3[Ce(IV)] >> k - , [Ce(III)] is a consequence of the observed
kinetics. A? in the Cr(VI)+Fe(II) system5*, the slow stage involves the inter+ See, also, ref. 309.
12
OXIDATIONS BY
Ce(1V)
245
conversion of Cr(IV) and Cr(V). There is strong evidence that such a transformation requires a change in coordination number of the metal ion. The observed
rate coefficient shows a n approximate inverse dependence on the square of HSO,concentration.
The cerium(1V) oxidation of Mn(I1) has been briefly reported on by Aspray
et ~ 2 1 . ~ The
~ ' ~ reaction
.
was followed from the rate of appearance of Mn(II1) at
505 mp, using solutions in 4.5 M sulphuric acid. The results indicate the occurrence
of an equilibrium
Ce(IV)+ Mn(I1)
+ Ce(III)+ Mn(lT1)
- d[Fe(II)]/dt
However, the intercepts of log [Fe(II)]/[Ce(IV)] versus time plots deviate from
the values expected for the initial concentrations of the reactants. This "apparent zero-time oxidation", which is reproducible, is believed to result from a
finite quenching time, and the reaction of Fe(l1) with a very reactive Ce(IV)
species. Added amounts of Ce(1II) and Fe(II1) leave the rate unaffected. At
constant ionic strength, k' varies inversely with hydrogen-ion concentration in
the range 0.05 to 1.00 M ; for [H'] > 1.0 M , k' increases with increasing [H'].
In general
k'
= u [ H + ] + b + c/ [ H + ]
246
coM P L E x E s oF
D I F F E R E N T M E T A L S: O X I D A T I o N-RED
u cT I O N
In accordance with this relationship, plots of k' versus K 2 / ( K 2+ [H']) are fairly
linear, using a value of 0.08 for K 2 . Values of k , and k6 are obtained from the
slopes ( = k,-k,) and intercepts ( = k,) of such plots. At 0.3 "C and p = 2.0 M ,
k, = 5865+ 1500 1.mole-'.sec-',
k , = 1000+200 I.mole-'.sec-',
and k , =
4830+500 I.mole-'.sec-'. At unit ionic strength, k' has an associated AH'
of 9.4 kcal.mole-', and a AS' of -6+3 cal.deg-'.mole-'.
Dainton et uLZ4',
suggest that the similarity between k , and k , may arise from common transition
states of the type (CelV-OH3+ . . * Fe") and (OHCe1"-OH2+ * * Fe"). Electron
transfer may take place by hydrogen-atom transfer, or electron conduction through
a hydrogen-bonded intermediate. The possible mechanism of the direct aciddependent path is discussed in terms of
( a ) charge transfer through symmetrical bridges of protonated water molecules,
i.e.
H
(H,O),,CeiVO . . H-0'-H
I
H
*
OFe"(H,O),
I
and
( 6 ) electron tunnelling through extended acid chains of the type -(HClO,-),
which may exist in cold, concentrated acid solutions.
The Ce(lV)+Fe(II) system is catalysed by HS04- and F - , but not by CIions. Since there is a linear relationship between k' and [HSO,-], the pathway
CeS0,"
+Fez+
5Ce(III)+Fe(III)
12
OXIDATIONS BY
Ce(1V)
247
Ce4+ HS04-
+ CeS04'+ + H+
then k , is
5 x lo3 I.mole-'.sec-' at 0 "C and p = 0.23 M. This value agrees
quite well with that calculated from the data of Dulz and S ~ t i for
n ~the~ reaction
in sulphuric acid solution.
Dulz and S ~ t i have
n ~ ~measured the rates of oxidation of Fe(I1) and tris(1,lOphenanthroline) Fe(I1) complexes by Ce(IV) with a view to test the linear free
energy relationships' predicted by M a r c u 244
~ .~ Th
~ ese
~ ~rapid reactions were
studied in sulphuric acid media using a stopped-flow apparatus. In 0.50 M
H2S04 at 25 "C the Ce(IV)+Fe(II) and Ce(IV)+Fe(phen),'+ systems have
~ I.mole-'.sec-'
and 1 . 4 2 ~10' 1.
(second-order) rate coefficients of 1 . 3 lo6
mole- '.set- respectively. The corresponding activation energies are 9.5 kcal.
mole-' and 6.5 kcal.mole-'. According to the Marcus theory of electron transfer
reactions43, if k l , z and Kl,2 are the rate and equilibrium constant, respectively,
for the oxidation-reduction reaction, and kl, and k z , z are the rate coefficients of
the exchange reactions, then
',
where f is defined by
(12.7)
(12.8)
where AG' represents the free energies of activation of the various processes,
and AGO,, is the standard free-energy change of the redox reaction. Consequently,
a linear relationship between (AG;,,-0.5
AG;, 1 ) and AG?, is predicted.
Fig. 10 contains such a plot for the Ce(1V) oxidation of a number of Fe(I1)
phenanthroline complexes. Similar data are included for the oxidation of Fez+
by various Fe(II1) phenanthroline complexes in 0.50 M HC104 at 25 0C196.Rate
coefficients and (formal) oxidation potentials are set out in Table 32. A straight
* Other linear free-energy relationships are those for the oxidation of a series of Fe(I1)
phenanthroline complexes by Co(II1)' 9s and Mn(III)S2.
References pp. 267-273
248
C 0M P L EX E S 0F D I F F E R E N T M ETA L S : 0X I D A TI 0N-R E D U C T I 0N
54-
3-
21-
-2
-4
-6
-8
I
-10
I
-12
I
-14
A G$(kcal mole-')
Fig. 10. Relationship between (AG:,,,-0.5 AG',.,) and the standard free energy change (AGOlz)
of the redox reactions at 25 "C. Open circles, Ce(IV)+Fe(phen)32+ reactions in 0.50 M H 2 S 0 4 .
Closed circles, Fez++ F e ( ~ h e n ) , ~ reactions
+
in 0.50 M HC104. Numbers refer to complexes in
~ ~courtesy
,
of The American Chemical Society.)
Table 32. (From Dulz and S u ~ i nby
T A B L E 32
Fe(l1)
HZS04A T 25.0 0C44
Complex
Iron (11)
Tris(3,4,7,8-tetramethyl-l ,lo-phenanthroline)iron(lI)
Tris(5,6-dimethyl-l ,lo-phenanthroline)iron(II)
Tris(5-methyl-1,1O-phenanthroline)iron(II)
Tris(1,IO-phenanthroline)iron(lI)
Tris(5-phenyl-l,lO-phenanthroline)iron(lI)
Tris(5-chloro-I, 10-phenanthroline)iron(ll)
Tris(5-nitro-1 ,lo-phenanthroline)iron(lI)
COMPLEXES BY
E o of coniplex (V)'
(1)
(2)
(3 )
0.68
0.83
0.99
(5)
1.04
1.08
1.10
(6)
(7)
1.14
1.26
(4)
Ce(IV)
IN
0.50 M
k(l.mole-'.sec- ')
1.3 \
1.6 x
4.3
2.2 x
1.42
1.2 x
2.5 Y
3.9
10'
lob
105
105
105
105
104
103
line of slope 0.50 has been drawn through the data for reactions which have
AGO,, close to zero, when equation (12.8) simplifies to
A G S2 = 0.50 AG:, +0.50 AGis 2+o.50 AGO,,
(12.9)
The intercept, 6.5 kcal.mole-', leads to a value of 13.0 kcal.mole-' for the
(average) AG' of the various phenanthroline Fe(I1)-Fe(lI1) exchanges. Such a
AG:, value corresponds to an average rate coefficient, k2, 2 , of 2 x lo3 1.mole-'.
12
OXIDATIONS BY
Ce(1V)
249
T A B L E 33
COMPARISON OF OBSERVED A N D CALCULATED RATE COEFFICIENTS AT
Reaction
k , . , (/.molesec- I )
k2,2(l.mole-I .
sec-I)
4.0
5 2 XIO-5
1.ox 1 0 - 2
II XIO-4
5 2 ~10-
4.4
4.0
4.0
4.0
-.
-5
-5
1.0 Y 1 0 - 2
s 2 XIO-5
4.0
k l , 2 calculated
(Lmole- '.see- I )
-.
Fe(I1) +Ce(IV)
Cr(II)+Fe(III)
V(II)+Fe(III)
Eu(II)+Fe(III)
Cr(I1) +Co(III)
V(II)+Co(III)
Cr2 +V3
FeZ++Co3+
k , ,2 observed
(/.mole-'.set- I )
25.0 V4
1.3 x lo6
8 X103
> 105 a
> 105 a
> 3 x 102a
> 3x102"
I . O v 10-2
42 a
-5
6 x lo5
1 6x
lo5
9 X lo5
2 2 x 106
51 x 10'0
-2X1010
2-2 x 10-2
-6x1O6
sec-'. The curve (AGO,, more negative than 5 kcal.mole-') was calculated from
equation (12.8) using this value for k z , in equation (12.7). The general conclusion
is that the data adequately comply with the predictions of the Marcus theory.
Table 33 is a collection of observed and calculated rate coefficients for a variety
of redox reactions. Adamson et ~ 1 . ~have
~ ' criticised the value of kl,z for the
Ce(IV)+Fe(II) system, as calculated by Dulz and S ~ t i non
~ ~the, grounds that
the rate of the Fe(JII)+Fe(II) exchange (kl, 1) and the corresponding oxidation
potential relate to HC104 media, whereas the rate ( k 2 , 2 )and oxidation potentia
of the Ce(IV)+Ce(III) system are for H2S04 media. Adamson e l ~ 2 1 . ~arrive
~'
at
a calculated value of 1.3 x lo6 l.mole-'.sec-' for the rate coefficient (k1,2)of the
Ce(IV)+Fe(II) reaction in 0.5 M HC104 at 0 "C. Since this value is very much at
variance with the observed value (700 1.mole- '.sec-'), they conclude that this
oxidation takes place by an atom-transfer mechanism, to which the theoretical
treatment of Marcus is not appropriate.
Rate coefficients (and oxidation potentials) are given in Table 34 for the Ce(IV)
T A B L E 34
SECOND-ORDER
RATE COEFFICIENTS
Ce(1V)
IN
Fe(phen),2+
Fe(phen)2(CN)2
Fe(phen)(CN)+'Fe(bipy),2+
Fe(bipy)2(CN)Z
Fe(bipy)(CN)42Fe(CN)64a
0.5 M
FOR
1.07
0.79
0.65
I .05
0.81
0.67
0.69
O F Fe(l1)
25.0C195
THE OXIDATION
SULPHURIC ACID AT
0.142 a
7.1 1
8.88
0.196
8.40
12.5
I .90
COMPLEXES
BY
250
C O M P L E X E S OF D I F F E R E N T METALS:
ox I DA T I O N-RE
DU CTION
TABLE 35
C O M P A R I S O N OF O B S E R V E D A N D C A L C U L A T E D R A T E C O E F F I C I E N T S ' 9 5
kl.' obserued(l.rnole-'.sec-')
Reaction
> 108
1.9~10~
1 . 4 107
~
6.1 X lo7
3.8 x 105
1.9 x lo6
5 . 0 lo6
~
3.0 x 104
4.3 x 104
k l B zcalculated(l.rnole- '.set-')
6.1 x lo8
6.0 x
1.3 x
8.1 x
5.7 x
lo6
107
107
105
1 .o x 106
1.7 x 107
2.1 x 104
5.1 x 104
- d[Ce(IV)]/dt
k'[Ce(IV)][Hg(I),]
obtains, Hg(I1) and Ce(II1) having no effect on the rate. Mechanistically the reac-
12
OXIDATIONS BY
25 1
Ce(1V)
-+
Ce(III)+Hg(I)+Hg(II)
slow
Ce(III)+Hg(II)
rapid
a scheme in which the Hg-Hg bondis broken simultaneously with electron transfer.
At 50 "C in 2.0 A4 HClO,, the rate coefficient of the slow step is given as 0.14
I.mole- '.set- ';the corresponding apparent activation energy is 14.4 kcal.mole-'.
Silver(]) is effective as a catalyst in the oxidation of mercury(1) by Ce(IV)26.
In dilute HCIO, solutions no direct reaction takes place between Ce(1V) and
mercury(I), or between Ce(IV) and Ag(1). The catalysed reaction obeys, in the
presence of excess Hg(l),, the expression
-d[Ce(IV)]/dt
=
= -2 d[Hg(I),]/dt
(12.10)
2 ki[ce(Iv)] = 2 k,[Ce(IV)][Ag(I)],
2 Ce(II1) +Ag(I1)
k-8
Ag(II)+Hg(I),
2Ag(l)+Hg(I)+Hg(II)
Ce(IV)+Hg(l)
-+
Ce(IlI)+Hg(ll)
rapid
-= k9
In mixed solutions, 2.0 M i n HC104 and 0.1 M i n H2S0,, the rates of oxidation
of Hg(I), by Ce(IV), as catalysed by Ag(1) and Mn(Il), are 247
- d[Ce(IV)]/dt = 0.304[Ce(IV)] [Ag(l)] +O.O218[Ce(IV)][Ag(l)]/[Hg(I),]
and
- d [Ce(lV)/dt
252
co M P L E x E s o F D I FF E R E N T M E T A L S :
O X I D A T I ON-R E D u c TI O N
activation energies are 13.5 and 12.1 kcal.mole-'. In the latter case the scheme
suggested is
Ce(IV)+ Mn(I1)
Mn(III)+ Hg(I),
+ Ce(IlI)+Mn(III)
-+
Hg(I)+Hg(Il)+ Mn(I1)
-+
Ce(II1) Hg(I1)
rapid
-+
Mn(U)+2 Hg(I1)
although this does not explain the inverse dependence on [Hg(I),] at low concentrations. Spectrophotometric evidence was adduced for the presence of
Mn(1II) as an intermediate. The Ce(IV)+ Hg(I)2 reaction, doubly catalysed by
Ag(I)+ Mn(II), was examined in both HC104 and H2S04.In the former medium,
the kinetics are complex, and the rate shows an enhanced catalytic effect; in the
latter medium, the kinetics are analytically soluble, and the catalytic effect is
additive. Tentative mechanisms are proposed.
The mechanism proposed by Dorfman and G r ~ d e r , ~to
' account for the reduction of Ce(IV) by Tl(I), in 6.18 A4 nitric acid at 54 "C, includes a dimeric species
of Ce(IV) and a Ce(1V)-Ce(II1) binuclear species, viz.
+ [Ce(IV)],
Ce(III)+ Ce(1V) + [Ce(Ill)Ce(lV)]
2 Ce(IV)
klo
+
k-
Ce(lV)+ OH-
K3
K4
Ce(III)+ OH
10
T1( I) + OH
kr
+
T1( 11)+ OHk-it
I
k12
Ce(IV)+TI(I)
f
k-12
Ce(III)+Tl(II)
2 Ce(Ill) +TI(III)
Using concentrations in mole.1-' and time in sec, Dorfman and Gryder find
K , = 18, K4 = 2, k , , = 1 . 3 3 lo-',
~
k 1 2 = 3.81 x
k-.lo/kll = 0.021,
k - l o k - , , / k l 1k , , = 5.4 x lo-', k - , , / k , , = 2.6 x lO-,,and k - , 2 / k , , = 1.52 x lo-,
The Ag(1)-catalysed oxidation of Tl(1) by Ce(IV) can be explained26 by a
series of reactions
Ce(IV)+Ag(I)
ks
+
Ce(III)+Ag(II)
k-8
2 Ag( I) +T1(11)
-+
Ce(III)+TI(III)
rapid
13
OXIDATIONS BY
u , Np,
PU
253
However, the term k-,[Ce(III)] cannot be neglected since k-8/k14 is 35.7. Neither
can k, be evaluated from first-order plots for the disappearance of Ce(1V). The
integrated form of equation (12.12) allows k-,/k,, and k, to be obtained. The
ratio k,lk,,, obtained from k-,/k9 and k-,/k14, is 180 at 1.5 M [H'] and
20 "C. This corresponds to the ratio of the rate coefficients for the oxidation of
Hg(I), and of Tl(1) by Ag(I1). Higginson et dZ6
quote a value of 185 for the ratio
of rate coefficients for oxidation of these two species by Co(II1). The dependence
of k, on hydrogen-ion concentration is described. Schenk and Bazzelle31 have
studied the Ce(1V) +TI([) system, both uncatalysed and catalysed by Ag(1) and
Mn(III), in sulphuric acid media.
Cerium(1V) oxidises tin(I1) in aqueous sulphuric acid probably by a two-step
path involving Sn(III)249. At low Sn(1V) concentrations and low sulphate concentration the reaction is second order, and the suggestion is made that the reactant species are Ce(SO,),'- and SnSO,. In mixed chloride-sulphate media the
Ce(1V) Sn(I1) reaction, in the presence of trioxalatocobaltate(lII), produces
an intermediate which consumes the Co(II1) complex5'. This result is interpreted
as being evidence for the presence of Sn(II1) in the reacting system.
13.1
OXIDATIONS BY URANIUM(VI)
U(V)+V(lII)
(13.1)
(13.2)
254
C O M P L E X E S O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
2 U(V)
( 1 3.3)
U(IV)+ U(V1)
and
U(V)+V(III)
U(IV)+V(IV)
( 13.4)
However, in the presence of excess V(1V) the U ( V ) formed in reaction (13.1) can
be reoxidised to U(V1) by
U(V)+V(lV)
U(VC)+V(III)
(I 3.5)
Since reaction (13.5) is more rapid than (13.2), (13.3), or (13.4), reactions (13.1)
and (13.5) are predominant under these conditions, and the overall process corresponds to the U(V1)-catalysed reaction of V(1I) and V(IV). In the absence of
U(V1) this reaction is relatively slow221. Kinetic data were obtained spectrophotometrically at 760 mp (where V(IV) is the principal absorbing species) in
0.05 to 2.0 M perchloric acid between 0.6" and 36.8 "C. The rate law is
- d IV( IV)]/dt
= - d[V(II)]/dt =
UO,'+
+ v 2 ++ (uo2v4+):
and the corresponding AS' and AH' values are quoted as -26.1 f 0 . 4 cal.deg-'.
mole-' and 7.1 kcal.mole-' at p = 2.0 M . It is not known whether the reaction
is of the inner-sphere type or not, as no evidence was obtained for a binuclear
intermediate. The reaction is catalysed by chloride and sulphate ions; the former
effect receives a detailed discussion by Newton and Baker2", as does the ionic
strength dependence.
U(V1) oxidises V(111) slowly in acid perchlorate solutions, the first step being
U(V1) + V( 111)
(13.6)
k-2
(13.7)
13
OXIDATIONS BY
u, Np, PU
255
2V(IV)+Fe(II)
V(IV) + Fe(II1)
V(V) + Fe(I1)
k-s
V(III)+V(V) 2.
2 V(IV)
V(III)+Fe(III)
(13.8)
(13.9)
(13.10)
The catalysed reaction was followed by measuring the rate of appearance of V(IV)
at 760 mp. Comprehensively, on the basis of reactions (13.6) to (13.10), the
rate law is
In equation (13.1 l), the first term corresponds to the catalysed part of the reaction
and the remaining terms, which make a relatively small contribution, apply to the
uncatalysed part. Kinetic data at constant acidity were in good agreement with the
integrated form of the calculated rate expression. The rate coefficients k,, k,, k, ,
and the ratio k - s/k6 were evaluated. Almost linear plots of log k z versus log [H']
were obtained at four temperatures with slopes close to - 1.8. This result suggests
that the dominant activated complex is that formed by loss of two H f ions, uiz.
U O Z z f + V 3 + + H Z O+ (VO*UOz3+)'+2H +
(13.12)
although the alternative path, involving the loss of one H + ion, viz.
UOzz+ + V 3 + + H Z O+ (VOH-UOZ4+)'+H+
(13.13)
must be present also. The rate data are shown to be more in accord with consecutive reactions and an inner-sphere binuclear intermediate, rather than with
parallel reactions. A number of mechanisms are possible, e.g.
v3++H,O + VOH,+ + H +
rapid equilibrium
+ VO.UOz3++ H +
V O ~ U O ~+~voz+
+
+uo,+
rate-determining
UOzz++VOHZf
References p p . 267-273
rate-determining
256
C O M P L E X E S O F D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
T A B L E 36
ACTIVATION
PARAMETERS2"
FOR
AH!(kcal.rnole- ' )
17.710.3
13 1 2
16 + I
NP
PU
M02''+V3++H2O
A S (cal.deg -9
-5
--f
(VOHM024+)s+H*
.mole- )
3.8h0.9
j=6
+3
ReJ
252
a
254
This contrasts with the Pu(V1) + V(II1) reaction which occurs by parallel paths.
The activation parameters corresponding to the net activation processes (13.12)
and (13.13) are A H f = 22.1 and 17.7 kcal.mole-', and ASs = 12.9k0.5 and
3.8 k 0 . 9 cal.deg-'.mole-'. respectively. Table 36 contains similar data for the
analogous reactions of NpOz2+ (ref. 253) and P u O ~ (ref.
~ + 254) with V3+. The
positive AS* value for the UOzz++V3+ reaction has led Newton and BakerZS2
to suppose that the U(VI) reaction is inner-sphere, whereas the Np(V1) and Pu(V1)
reactions are outer-sphere.
On mixing acid solutions of U(V1) and Cr(I1) at 0 "C, a rapid reaction takes
place and a bright green solution is produced. A slower reaction then occurs to
yield a solution having the darker green colour characteristic of U(W) and
Cr(lI1). The appearance of the absorption spectrum of the principal intermediate
leads to the conclusion3' that it is a complex formed between U(V) and Cr(lll),
viz.
U(Vl)+Cr(lI)
U(V).Cr(III)
--t
2 Cr(III)+U(IV)
proceeds rapidly with half-lives between 4 and 8 min at 0 "C. The intermediate
species is reactive towards TI(II1) and V(IV), displaying rates which are proportional to the concentration of the intermediate, but independent of the concentration of oxidant. Efficient transfer of oxygen from U 0 2 2 +to Cr(H20)63f
takes place2s5.Evidence was sought for an analogous intermediate in the Pu(VI)+
Cr(I1) system but the results were negative.
B a e ~ has
~'~
briefly investigated the reduction of U(V1) by Fe(l1) in the strongly
complexing medium of phosphoric acid.
Moore" has made a brief study of the slow reduction of U(V1) by Sn(I1) in
hydrochloric acid media. Chloride ion has a pronounced effect on the rate.
Spectrophotometric evidence is cited for the complexing interaction of U(V1)
and Sn(I1).
13
OXIDATIONS B Y
u , Np, PU
13.2 OXIDATIONS B Y
257
NEPTUNIUM
The reaction between Np(V1) and V(1II) in perchlorate media proceeds via
consecutive steps of comparable ratez53,viz.
Np(VI)+V(III) -% Np(V)+V(IV)
Np(VI)+V(IV) -% Np(V)+V(V)
At 25 "C and in 2.0 M HC104, k, is estimated as 17.5k1.6 1.mole-'.sec-' and
k, as 30f: 15 1.mole-'.sec-'. The hydrogen-ion dependence of the reaction is
rate
(k+ k'/[H+])[Np(VI)][V(III)]
where k and k' have values of 6.3 Lmole-'.sec-' and 20.3 sec-', respectively.
Likely steps are between NpOZ2++V3+, together with NpOzz++VOH2+ and/or
NpO,OH+ +V3+. The activation energies and entropies of the k and k' routes
are, respectively, 32 kcal.mole-' and 52+ 16 cal.deg-'.mole-',
and 13 kcal.
mole-' and -9+6 cal.deg-'.mole-' (as recalculated by Newton and Baker "').
Np(V1) oxidises U(1V) in a two-equivalent process
el
al.257is
2 k'[NpOzZ+][U4+]/[H+]
+ UOH3++ H + Kl
NpOzZ++ UOH3+
N p 0 2 ++ U(V)
rate-determining
rapid
NpOzz++ U(V) NpOz++ U02'+
U4++ HzO
coM P L E x E s oF
258
D I F F E R E N T M E T A L s : o x I D A T I o N-R E D u c T I o N
in acid media'". A value of 0.690 I.mole-' has been derived for the equilibrium
constant of the complex N p 0 2 + * U 0 2 2 +
at 25 "C.
Np(V) oxidises V(II1) to V(IV) in perchloric acid according to
Np(V)+V(III) = Np(IV)+V(IV)
that is
Np02++V3++2H+
Np4++V02++H20
where K2 6 x
the main reaction is
- d"PO2
dt
+I = ( k , + k ' X 1 )
[V02 +I
K2
[Np02+][V3+]
Plots of (-d[Np02+]/dt)/[NpOz+][V3+]
versus [Np4']/[V02+] are linear with
intercepts k, and slopes k'. The following mechanism accounts fairly adequately
for the kinetics
N p 0 2 + + V 3 +-% N p 0 2 + + V 0 2 +
Np0'++2 H +
-+N p 4 + + H 2 0
rapid equilibrium
+' N p 3 + + V 0 2 + + 2H +
rapid equilibrium, K 2
Np4++V3++H20
N ~ ( v+
) N~(III+
2~ p p )
Thus
+H 2 0
13
OXIDATIONS BY
u, Np, PU
259
&
...,....-'----..I.
400
500
,
-\
600
700
800
Wavelength ( m p )
Wavelength ( m p )
The complex has been separated by ion exchange and characterised by direct
analysisz0*. The complex has a distinctive absorption spectrum (Fig. 1l), quite
unlike that of Np(V) and Cr(II1). The rate coefficient for the first-order decomposec-' at 25 "C in 1.0 M HCIO,. Sullivan37
sition of the complex is 2.32 x
has obtained a value for the equilibrium constant of the complex, K = [Np(V)
-Cr(III)]/[Np(V)] [Cr(III) 1, of 2.62 & 0.48 at 25 "C by spectrophotometric
experiments. The associated thermodynamic functions are: AH = - 3.3 kcal.
mole-' and A S = -9.0 cal.deg-'.mole-'. The rates of decay and aquation of
the complex, measured at 992 mp, were investigated in detail. The same complex
is formed when Np(V1) is reduced by Cr(II), and it is concluded that the latter
reaction proceeds through both inner- and outer-sphere paths. It is noteworthy
that the substitution-inert Rh(lrI), like Cr(III), forms a complex with NP(V)'~'.
This bright-yellow Np(V).Rh(III) dimer has been separated by ion-exchange
References pp. 267-273
260
Np(1V) Cr(II1)
(1 3.14)
Np(IV)+Cr(II) ~ N p ( I I I ) + C r ( I I I )
(13.15)
Np(V)+Np(III) -% 2 Np(IV)
(13.16)
+
+Cr(1V)
Cr(II) + Cr(IV) --+ 2 Cr(II1)
Np(V) Cr(1I) + Np(lI1)
Np(V)+Np(IZI)-
2 Np(rV)
is rejected on the grounds that (u ) no dimeric Cr(II1) species was detected, and
( b ) for agreement with the empirical rate data, the Np(III)+Np(V) reaction
would require to have a rate coefficient
40 times greater than the observed
value. The rate law for the one-equivalent reduction of Np(V) by Cr(II), reaction
(13.14), is
13
OXIDATIONS B Y
u , Np,
PU
261
~~[N~(V)][NP(III)][H+]~.~~
where k 5 = 5.40 (mole, 1 and sec units) at 25 "C and p = 0.2 M (see also refs.
18 and 259). The effect of C1- and HSO,- ions on the rate of the Np(V)+Np(III)
and Np(V)+Cr(II) reactions are similar in that C1- is ineffective as a catalyst,
whereas both reactions are sensitive to HS04-.
Shastri et aLZ6' have examined the kinetics of the reduction of Np(V) by U(1V).
The rate of the reaction, zero order in Np(V) and first order in U(IV), shows
an inverse dependence on the square of the hydrogen-ion concentration. The
gross features of the mechanism are believed to be
Np(V)+U(IV)
Np(IV)+U(IV)
Np(V)+Np(III)
Np(V)+U(V)
Np(1V) U(V)
-+
-+
-+
-+
-+
Np(lV)+U(V)
Np(III)+U(V)
2 Np(IV)
Np(lV)+U(VI)
Np(1II) U(VI)
At [H'] = 0.1 M , U(IV) reacts about six times more rapidly with Np(IV) than
with Np(V). Unlike nitrate and sulphate, chloride ion accelerates the reaction.
The reaction between Np(1V) and Cr(II), reaction (13.15), has been the subject
of a separate investigation by Thompson and Sullivan263.The rate law is
-d[Np(IV)]/dt = k'[Np(lV)][Cr(II)][H+]-'.27
in perchloric acid solutions at 25 "Ct. At the same temperature, p = 1.00 M
and [HCIO,] = 1.00 M , k' is 4.29 I.mole-'.sec-'. In the presence of 1.0 x
M
C1- and 1 . 0 ~
M HS04-, the k' values are 4.33 and 6.26 I.mole-'.sec-',
respectively.
13.3
OXIDATIONSBY PLUTONIUM
In contrast to the reactions of Pu(VI) and Pu(1V) with Ti(III), the reaction
between Pu(V) and Ti(II1) was found by Rabideau and Kline264 to be immeaThe Np(IV)+V(II) reaction shows a quite different hydrogen-ion dependence and is thought
to be outer-sphere in type.
References p p . 267-273
262
C O M P L E X E S OF D I F F E R E N T M E T A L S : O X I D A T I O N - R E D U C T I O N
surably fast, and therefore they consider the overall reduction of Pu(V1) to Pu(1II)
as being composed of two consecutive second-order reactions, viz.
Pu(VI)+2 Ti(1II) = Pu(lV)+2 Ti(1V)
(1 3.17)
Pu(IV)+Ti(III) = Pu(III)+Ti(IV)
( 13.18)
- d[Pu(VI)]/dt
= k; [Pu(VI)] [Ti(III)]/[H+ ]
as the rate-controlling step. Using a value of 65.5 sec-' for k ; , the observed rate
coefficient of (13.18), the kinetic data were given an iterative treatment by a
computer method. At 25 "C in 1 M perchloric acid, the average value of k; was
shown to be 108 sec-'. For the net process
PuOz2++Ti3+ HzO -+ ( P u O , T ~ O H ~+
+H
) ~+
A H f and ASs are 10.3 kcal.mole-' and - 14.7+ 1.3 cal.deg-'.mole-'. A practical
difficulty is that Ti(II1) slowly reduces perchlorate ions to chloridez65. However,
added chloride ion was demonstrated to have no effect on the rate of the Pu(VI)+
Ti(lI1) system. It remains unclear why the reduction of Pu02'+ by Ti(II1) should
be more difficult to bring about than is the reduction of P u 0 2 + . It is interesting
that, with V(II1) as reductant, the reduction of Pu02+ takes place slowly254.
Pu(V1) oxidises V3+ by
P u O z Z + + V 3 + + H 2 0= P U O ~ + + V O ~ H
+ ++ ~
The progress of the reaction was followed at 830 mp254.Kinetically, the oxidation
is second order and it proceeds via parallel paths showing a dependence on both
the inverse first and inverse second powers of [H'], the respective rate coefficients
being 2.12 sec-' and 0.228 1.mole-'.set-' at 25 "C and p = 2 M. The route in
which a single hydrogen ion is liberated predominates at 25 "C, and has AH' =
15.5 kcal.mole-' and ASf = -5+2 cal.deg-'.mole-'.
R a b i d e a ~suggests
~~~
the following scheme as likely
v~++H+
~ oV O H ~ + + H +
rapid
(13.19)
slow
(13.20)
(13.21)
Pu02'+
+ VOH2+ + P u 0 2 ++ VOz++ H +
13
OXIDATIONS BY
u , Np, PU
263
The kinetics are equally in accord with the replacement of reaction (13.20)
by one between P u 0 2 0 H f +V3+, and reaction (13.21) by PuO,OH+ +VOH2+.
M ) Pu(V1) is reduced by Fe(I1) to Pu(V), viz.
At low concentrations ( c
(13.22)
(13.23)
The inverse hydrogen-ion dependence of the rate of reaction (13.22) is exceptionally complex and is summarised by
-d[Pu(VI)]/dt
[Pu(VI)][Fe(II)]{A
+ (B+C[H+I)-'}
from experiments in the range 0.05 to 2.0 M HC104 at p = 2.0 M (ref. 42). Rate
data were obtained by spectrophotometric measurements of Pu(V1) at 830 mp
between 0 "C and 25 "C. The existence of a binuclear intermediate, of the type
Pu(V).Fe(III), is inferred from the form of the rate law. Thermodynamic quantities of activation are reported for the three activated complexes through which the
reaction proceeds. Ionic strength effects were investigated, as also was the influence of chloride ions on the rate. The Pu(V).Fe(lIl) dimer is analogous to
the complexes formed between Np(V) and Fe(III)208,and U(V) and Cr(III)31.
Likewise, chloride ion has a marked accelerating effect on the two-equivalent
reduction of Pu(V1) by Sn(1I). On the assumption that the rate-determining step is
Pu(Vl)+Sn(II)
Pu(V)+Sn(IlI)
Pu(V)+Sn(IV)
+ Pu(IV)+Pu(VI)
(6) the reduction of a second Pu(V1) takes place, along with reduction of Pu(V)
by Sn(Il), viz.
Pu(VI)+Sn(III)
Pu(V)+Sn(II)
-+
Pu(V)+Sn(IV)
-+
Pu(IV)+Sn(III)
Pu(V)+Sn(III) + Pu(IV)+Sn(IV)
References pp. 267-273
264
COMPLEXES OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
Neither of these possibilities are likely: the disproportionation of Pu(V), and the
Pu(V)+Sn(II) reaction are too slow to account for the rapidity and kinetics of
the overall reaction. That the Pu(VI)+Sn(II) reaction is very much faster than
the Pu(V)+Sn(II) reduction is taken as evidence for the occurrence of a single
two-equivalent process, viz.
Pu(VI)+Sn(II)
--f
Pu(IV)+Sn(IV)
k'
a[CI-I3 +b[C1-I4
Newton41 has shown that no complications ensue from the reaction of the intermediate U(V) with oxygen, since the latter has no effect on the rate. A simple
second-order rate equation applies, the disappearance of Pu(V1) being followed
at 830 mp, and the probable mechanism is
Pu(V1) + U(IV)
Pu(V)+ U(V)
rate-determining
( 13.24)
rapid
(13.25)
followed by
Pu(V1) U(V)
-P
Pu(V)
+ U(V1)
or
2 U(V)
-,U(IV)+U(VI)
rapid
( I 3.26)
13
OXIDATIONS BY
265
u , Np, PU
(13.27)
+ ~( H O U O H P U O ~ ~ + )H
' ++~
P u O ~ ~ + + U H~ 2+0 +
(13.28)
and
The respective A H f and AS' values of (13.27) and (13.28) are 17.6 kcal.mole-'
and 3.4+ 1.5 cal.deg-'.mole-', and 21.4 kcal.mole-' and 18.1k 1.0 cal.deg-'.
mole- '. Newton4' discusses the apparent similarities between the U(V1) U(IV)267
NP(VI)+NP(IV)~~*,
P u ( V I ) + P U ( I V ) ~and
~ ~ , Pu(VI)+U(IV) systems.
The reduction of Pu(1V) by Ti(IT1) to blue Pu(JI1)
k;[Pu4+][Ti3+]/[H+]
At 2.4 "C and p = 2.02 M , k; is 12.7 sec-'; at 25 "C and p = 1.02 M , k; is 65.5
sec-'. In terms of the net activation process
P u 4 + + T i 3 + + H 2 0+ (PuTiOH6+)'+Hf
AH' and AS' are 16.7 kcal.mole-' and 5.9$.2 cal.deg-'.mole-', respectively.
Chloride ion has a slight accelerating influence on the reaction.
Pu(IV) oxidises V(II1) stoichiometrically in perchloric acid solution, uiz.
- d [Pu(IV)]/dt
270
= k'[Pu4+][V3+]/[H+]
=
+~ " [ P u ~ [V3+]/
']
[H']'
kobs[ P ~ )[v3
I +1
Spectrophotometric values for k' and k" at 2.4 "C ( p = 2 M ) are 1.70 sec-' and
1.71 mole.l-'.sec-', respectively. The corresponding activation parameters, AHS
and AS*, are 17.1 kcal.mole-' and 4.8k1.7 cal.deg-'.mole-' for the k' path,
and 21.5 kcal.mole-' and 20.8f 1.4 cal.deg-'.mole-' for the k" path. The rate of
reaction is not susceptible to the addition of chloride ions. This result is of importance because C104- is reduced to C1- by V(II1).
References pp. 26 7-273
266
C O M P L E X E S OF D I F F E R E N T M E T A L S : O X I D A T I O N - R E D U C T I O N
-d [Pu(l V)]/dt
k , [Pu4+][Fe2+]+k' [Pu4+][Fe2+]/[H+]
where k3 = 0.177 1.mole-'.sec-' and k' = 3.12 sec-' at 2.5 "C. The activated
complex (PuOHFeS+)' has AH' = 19.1 kcal.mole-', and AS' = 13.3 cal.deg-'.
mole-'. The pronounced increase of rate on the addition of chloride ion is attributed to the provision of a new reaction path involving (PuClFe")', for which
AH' = 14.4 kcal.mole-' and AS' = 0.6 cal.deg-'.mole-l. Sulphate ion also
increases the rate.
Sn(I1) reduces Pu(IV) by
2 Pu(IV)+Sn(II) = 2 Pu(III)+Sn(IV)
In perchloric acid media the reaction is extremely slow and is complicated by the
formation of polymeric species of tin, and by heterogeneity. R a b i d e a ~has
~~~
examined the kinetics in mixed perchlorate-chloride solutions, in which media
no turbidity is apparent. The rate expression is complex, viz.
- d [Sn(II)l)/dt
pu4+ Sn2
+4 ~ 1 -,
- ( P U C I , S +~ )'~
has AH' and AS' equal to 26.9 kcal.mole-' and 44.7 cal.deg-'.mole-',
the process
pu4+ +Sn2++ 5 CI-
-+
whereas
(PuClsSn+)'
A possible
REFERENCES
267
mechanism is
~[Pu~+][U~+]/[H+]~
and
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16
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24
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c o M P L E x E s OF
D I F F E R E N T M E T A L S:
ox I D A T I o N-R
E D u cT I oN
118 .I.
HALPERN
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213.
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272
C O M P L E X E S OF D I F F E R E N T METALS: O X I D A T I O N - R E D U C T I O N
224 G. HARBOTTLE
A N D R. W. DODSON,
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AND W. C. E. HIGGINSON,
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225 A. M. ARMSTRONG,
in Kinetics and Mechanism of Inorganic Reactions in Solution, Chemical Society,
226 K. W. SYKES,
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AND L. G. SILLEN,
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AND J. HALPERN,
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229 See, for example, C. H. BRUBAKER
AND J. P. MICKEL,
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AND J. G. SMITH,
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AND C. H. BRUBAKER,
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60.
AND A. W. DAVIDSON,
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L. H. SUTCLIFFE
AND J. WALKLEY,
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237 See also, D. BENSON,
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239 J. Y. P. TONG
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241 b G. A. RECHNITZ,
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AND P. GLENTWORTH,
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AND R. H. PRINCE,
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AND W. H. MCCURDY,
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247 G. G. GUILBAULT
AND J. W. GRYDER,
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AND M. K.
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DORFMAN,
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AND F. B. BAKER,
in Advan. Chem. Ser., No. 71, Am. Chem. SOC.,1967,
250 T. W. NEWTON
p. 268.
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AND F. B. BAKER,
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AND F. B. BAKER,
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AND J. C. HINDMAN,
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A N D A. J. ZIELEN,
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AND J. C. SULLIVAN,
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AND J. C. SULLIVAN,
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260 R. K. MURMANN
AND J. C. SULLIVAN,
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261 R. C. THOMPSON
E. S. AMISAND J. 0. WEAR,J. Inorg. Nucl. Chem., 27 (1965) 2413.
262 N. K. SHASTRI,
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AND B. J. MASTERS,
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267 See for example, S. W. RABIDEAU,
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AND D. COHEN,
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AND H. D. COWAN,
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273 T. W. NEWTON,
REFERENCES
273
SUPPLEMENTARY REFERENCES
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
Chapter 4
1. Introduction
1.1
275
INTRODUCTION
N4H6 -+ N 2 + 2 NH,
2 30;
(c)
-+
(3)
S 2 0 i - (dithionate)
(5)
M"++[(NH,),CO(III)-OCOCO~H]~+M("-')+
+[(NH,),CO(III)-OCOCO~-]~+
+H+
-+
[(NH,),CO(III)-OCOCO,-]~+
-+
[(NH,),CO(II)OH~]~+
+ 2 C 0 2 (very fast)
References p p . 493-SO9
c o v A L E N T c o M P o u N D S,
276
M E T A L I o N S : O X I D A T I o N-R E D u c T I o N
Two-equivalent oxidant
M"++ N2H4
(a)
-+
N,H,
+ M("-2)++ 2 H +
2 N2Hz -+ N4H4
NZ
N4H4
(c)
+ N2H4
NH3+HN3
M"++[(NH,),CO(III)-OCOCO~H]~+
+ M("-')'
+[(NH,),CO(III)OH~]~'+~C 0 2 + H +
1.2
C A T E G O R I S A T I O N O F O X I D A N T S AS O N E - OR T W O - E Q U I V A L E N T
INTRODUCTION
277
The use of sulphite has, however, been called into question recently. According
to the scheme all one-equivalent oxidants should produce at least some dithionate
(eqns. 4 and 5). However, Vepkek-SiHka et a1.l2-I4 have found that while substitution-labile one-equivalent oxidising metal complexes give sulphate and
dithionate, substitution-inert one-equivalent oxidising complexes give sulphate
only.
The following mechanisms for generation of both products were suggested
278
cov A L E N T C O M P O U N D S ,
METAL IONS:
0 x 1D AT ION-RED U C T I O N
G E N E R A L FEATURES
+ 14 H + + 6 e- + 2 C r 3 + + 7 H,O
M n 0 4 - + 8 H + + 5 e - + M n 2 + + 4 H,O
MnO,-+e- + MnO2-
Cr,O,r
M n 0 4 - + 4 H + + 3 e-
+ Mn OZ+2 H,O
+1.33 V
+1.51 V
+ 0.564 V
+ 1.695 V
OXIDATIONBY
Cr(V1) A N D Mn(VI1)
279
+ H + + HCrO,
+ Hf+CrO:-
2HCrO; + C r 2 0 , 2 - + H 2 0
mole.1-'
K,
= 4.1
K,
1.3 x
K3
155
mole.l-'
H+ HO-Cr-0- + X -
29
0
II
+ X-Cr-0- + H 2 0
II
II
Addition of acetic acid27or trifluoroacetic acid3' also influences the acid chromate
ion (oide infra).
It transpires2' that Cr20,'- plays a minor part in oxidation mechanisms and
that H2Cr0, is the reactive form of Cr(V1) and accordingly most reactions are
acid-catal ysed.
Permanganic acid has a pK of -2.25 in perchloric acid3' and one of -4.6 in
sulphuric acid3, when the Hammett acidity function, H,, is used. Accordingly
HMnO, is present to a significant extent only in strongly acidic solutions and
comparatively few of the reactions which have been examined involve anything
other than MnO;.
2.2
O X I D A T I O N O F I N O R G A N I C C O V A L E N T SPECIES
280
Iodide ion is very slowly oxidised by Fe(II1) and the iodide must therefore be
oxidised by some species other than Cr(VI) or Fe(II1). For a large excess of iodide,
the stoichiometry has been reported to be3,
Cr(VI)+2 I-+Fe(II) = Cr(III)+I,+Fe(III)
from which it is clear that the Fe(I1) is not acting as a true catalyst, but that it is
probably involved in a scheme
Cr(VI)
Cr(V)+I10-+I-+2Hf
(10)
Cr(III)+IO-
(1)
-+
12+H20
(12)
This is an example of an induced reaction, which is the subject of the next chapter
of this book. That step (1 1 ) is involved rather than
Cr(V)
+ I-
Cr (IV) 1.
is argued by Westheimer from the relative effects of arsenious acid upon the
chromic acrd oxidations of manganous and iodide ions. The latter has an induction
factor, defined as the number of equivalents of substrate oxidised to the number
of equivalents of inductor oxidised, of 2 but the former has one of 0.5. The reactions involved are:
Manganous ion
H,AsO,
Cr(N)+ Mn(II)
H,AsO,+Cr(VI)+Mn(II)
-+
Cr(III)+Mn(III)
= H3A~O4+Cr(III)+Mn(III)
Iodide ion
H,AsO,
+ Cr(VI)
H3As04 Cr(rV)
-+
2 Cr(V)
2 [Cr(V)+I-
-+
Cr(III)+IO-]
2 [10-+1-+2H+
-+
12+H20]
H3As0,+2 Cr(VI)+4I-
H,As0,+2 Cr(III)+2 I,
Cr(N)+Cr(VI)
It is assumed that Cr(IV) reacts quickly with Mn(II) but slowly with iodide ion
for otherwise the induction factors would not be as found.
OXIDATION BY
28 1
Cr(V1) A N D Mn(VI1)
= k[HCrOJ[I-]2[H30+]'
k 2
k-13
Cr(IV) + Cr(VI)
Cr(V)+I2H++IO-+I-
1'
+ Cr(IV)
(13)
3 2 Cr(V)
(14)
k-14
IO-+Cr(III)
+ H20+12
Further analysis of the kinetics over the course of reaction afforded values for
k14/k-13, e.g. 0.10 at 20 "C (p = 0.1).
Measurements over a wider range of reactant concentration^^^^ favour a more
complex rate law
-d[HCrOJ/dt
[HCrO,-](k,
[H30+][I-]
+ k2[H30+]2[J-]2
+ k 3 W 3 0+ 1"1- 1)
282
The permanganate oxidation of iodide has been the subject of a recent detailed
study by a rapid mixing technique3'. At 35 "C and at an ionic strength of 0.9 M
over the p H range 3-6 the rate expression is
-d[MnO,]/dt
[Mn0,][I-]{k,+k3a,+}
+ (03MnOI)2-
(O,MIIOI)~-+ H 2 0 -, HOI+HMnOz-
(rapid)
(slow)
pH-dependent path
( 03P/lnOI)2- + H,O+
-, HOI
+ H2Mn0,
(slow)
The HOI would be rapidly reduced by iodide and the Mn(V) species would be
expected either to disproportionate or to oxidise further iodide. This reaction
scheme has features in common with the analogous reaction with cyanide ion
discussed below.
The oxidation of bromide ion by Cr(V1) has been examined at length by
Bobtelsky et a1.38-40.The rate equation is
d[Br2]/dt
k[Cr(VI)l[Br-If"H2S041
The apparent first-order rate coefficient obtained using excess oxidant increased
exponentially with increase in acidity in the range 5 N < [ H 3 0 + ] < 12 N . The
reaction is first-order with respect to added manganous ions (k increasing sharply),
but the activation energy (1 1.0 kcal.mole-') remains unchanged. At appreciable
catalyst concentrations the reaction becomes almost zero-order with respect to
bromide ion. The mechanism appears to be a slow oxidation of Mn(I1) to Mn(II1)
followed by a rapid reduction of the latter by bromide. This reaction is considered
further in the section on Mn(1I)-catalysis of chromic acid oxidations (p. 327).
OXIDATION B Y
283
Cr(V1) A N D Mn(VI1)
Only the permanganate oxidation of this ion has been studied kinetically. At
pH 12-14.6 the reaction has the stoichiometry
2MnO;+CN-+2
OH- = 2MnO:-+OCN-+H,O
- d[MnOJ/df
k,[MnO,][CN-]
but at lower basicity and at higher reactant concentrations a more complex and
pH-dependent path dominates, the rate law being
- d[MnOJ/d
f =
k ; [Mn 0, ][CN - ] [H 1
k;MnO,][CN-][HCN]
Freund4, has reported similar kinetics for the simple reaction and gives k , as
6.4 x lo7 exp( -9.0 x 103/RT)I.mole-.sec-.
Stewart and Van der Linden4 also examined the incorporation of 0 into
the cyclnate from labelled permanganate. The percentage of transfer varied with
alkalinity and the authors believe that significant oxygen-transfer occurs in the
second-order reaction, but not in the complex reaction. Accordingly the mechanism
for the second-order reaction is proposed to be
MnO, + C N - -+ [O,Mn
. . . 0 . . . CN12- + MnO;
+ OCNMnO,
+ MnO,
+ 2 OH-
-+
2 MnOi-
+ H,O
(slow)
(fast)
+ H(CN),
+ H(CN);
+ (CN),
+
+ H + + Mn0:-
CN-+OCN-+HZO
H,O = 2 M n 0 2 + M n 0 i + 8 OH-
(fast)
(slow)
(fast)
(fast)
284
C O V A L E N T COMPOUNDS, M E T A L IONS: O X I D A T I O N - R E D U C T I O N
The slow step of this reaction corresponds to removal of hydride from an anion
and finds several counterparts in oxidations of organic compounds by MnO; .
The anion may have the structure
H-C-NI
C=N
+ H + + H2Cr04
H2Cr04+H,0,
-, H 2 C r 0 , + H 2 0
H 2 C r 0 5 + H 2 0 2+ CrO,+2 H20
(slow)
(fast)
= k;[Cr0,][H+]2
- 12.8 x 103/RT)I2.mole-'.sec-',
2.7 at 25 "C.
OXIDATIONBY
Cr(V1) A N D Mn(VI1)
285
Permanganate does not form a stable peroxy compound with hydrogen peroxide
but oxidises it rapidly to oxygen and water. The stoichiometric equation depends
on pH, with Mn(II), Mn(1V) and Mn(V1) being formed in acidic, neutral and
alkaline solutions respectively. Chang4* found DzOz to react with MnO; in D,O
with a rate only 15 % of that for H 2 0 2 in H 2 0 , the reaction being auto-catalysed
by Mn2+ ion. At 0.1 Macidity k , equals 2 . 9 ~lo3 I.mole-'.sec-' (18 0C)49.
2 C r 3 + + 2 SO:-+S,0,2-+6 H 2 0
(15)
2 HCrO, + 3 HSO; + 5 H +
2 C r 3 + + 3S 0 : - + 5
(16)
2 HCrO;+4
HzO
The observed rate law, which applies only to (15) in 0.5 M sodium acetate
buffer in the pH range 4.18-5.05 is
K , , which has a value of 36 1.mole-' at 25 "C, is interpreted as being the equilibrium constant for the reaction
kobs is 1.37 X lo8 13.mole-3.sec-' at 25.0 " c and the activation energy and entropy
are 4.5 kcal.mole-' and - 13 eu, respectively. A further point is that the sulphate
formed during the reaction is bound to Cr(II1) at its conclusion.
The presence of the denominator term in the rate equation (17) suggests that
the equilibrium (18) precedes the oxidation step. Two sequences of reactions are
proposed (see below), depending on whether the sulphite radical ion dimerises
(20) or attacks further acid chromate ion (21). It should be noted that of the
species prevalent in dilute aqueous chromic acid, namely CrO:-, Cr,O:-,
HCrOg and H2Cr04, only the last is regarded as possessing oxidising powers.
This fact, noted by Westheimer", is tacitly assumed in all recent discussion of
References pp. 493-509
286
+S02+H20 K
+ {[O~SOC~O,OSO,]~-}'
(slow)
s20;-
(20)
-+
SOz-+Cr(V)
(21)
-+
O,CrOCrO,OSO:-
2.s0,
-+
-SO, +HCrO,
H + + HCrO, +CrSO;-
+ H,O
(22)
O,C~OC~O,OSO:Cr(V)+S(tV)
-+
-+
2 Cr(V)+SO:-
(23)
Cr(III)+S(VI)
(24)
is unusually high ( 1 . 2 4 ~lo4 I.mole-') and essentially all Cr(V1) is in the form
of the complex under the reaction conditions of high [S,Oi-]. The activated
complex contains one Cr(V1) and two S,OZ - species and two-electron reduction
of Cr(V1) occurs with concomitant one-electron oxidation of both S,Oi - species
O X I D A T I O N BY
Cr(V1) A N D Mn(VI1)
287
k [Cr(VI)] [S,0:-]2(H30f]
'
]/dt
k[Mn04- I [NO,-
I( 1 + k ' /[ H 3 0 +I)
-9.9 eu.
288
c o v A L E N T c o M P O u N D S,
MET A L I o NS : O X I D A T I o N-R E D u c T I o N
+ HP(OH),-O + -OCr02-O-PH(OH)-O+
-Hf
H20
I1 + H +
HOCr0,-0-PH(0H)-0
II
HO-Cr0,-0-P-OH
-+
HO-CrO, - 0-P-OH
+ BH
H:B
2 Cr(1V) -+ Cr(V)+Cr(III)
P(III)+ Cr(V) -+ P(V)+ Cr(TZ1)
(B is a base, e.g. H,O or H,P03-)
This is entirely analogous to the Westheimer mechanism for isopropanol
oxidation (Section 2.2.3).
Clearly for P(II1) to be oxidised, the P atom must be bonded simultaneously
to (i) a hydrogen atom, (ii) an oxygen atom linked to the oxidant and (iii) a free,
unioniyd hydroxyl group [for otherwise H2P03- would reduce Cr(VI)]52.In
conformity with these conclusions replacement of the hydroxylic protons in H3P03
by ethyl groups to give diethyl phosphite results in a reduction of Cr(V1) characterised by rate-determining ester-hydrolysis to ethanol and monoethyl phosphite,
both of which are oxidised normally52b.Also DP(OC,H5),-0 is oxidised at
virtually the same rate as HP(OC,H,),=O but oxidation of C,H5P(OC2H,),-0
proceeds very slowly.
A r e i n v e ~ t i g a t i o nof~ ~the
~ hypophosphite oxidation produced rather slower
rates and a differing rate law including a term k o [HCrO; ][H,PO,] corresponding
to a complex H,PCrO; for which optical measurements provided support.
OXIDATION BY
Cr(VI)
AND
Mn(V1I)
289
observations are best accommodated in the following scheme, which does not
involve the unstable As(1V)
HCr04-+As(III)
Cr(IV)+AsO,
Cr(tV)+Cr(VI)
-+
2 Cr(V)
Cr(V)+As(III)
-+
Cr(IIt)+AsO,
Edwards5 has also re-examined De Lurys data and finds evidence for an extra
term in the rate law, which becomes
+ k[HCrO,][H,AsO,][H+]
- d[Cr(VI)]/dt = k[HCrO,][H,AsO,][H+]
- d[Cr(VI)]/dt =
sec- and K
+ As(III).HCrO,
+ products
(slow)
A second series of experiments was conducted with [Cr(VI)] > [As(III)] and
a modified rate law was obtained, viz.
-d[Cr(VI)]/dt
1.68 x lo-2[As(IIIj][HCr0,]
1 +22.4 [HCrOJ
+2.47 x 10-2[Cr20~-][As(III)]
The authors believe that a similar mechanism to the above operates for the
dichromate-ion dependent path, but that the equilibrium constant K is much
smaller. This oxidation presents two novel features, namely the lack of an acidity
dependence of the rate and the participation of a term involving dichromatic ion.
Kolthoff and Fineman have examined the reaction in alkaline media in the
presence and absence of oxygen, obtaining the rate law
-d[Cr(VI)]/dt
References pp. 493-509
= k,[CrO~-][As(III)]
290
cov A L E N T COMPOUNDS,
METAL
I O N S:
0x1D A T I ON-RED u C T I o N
with k , = 1.61 x
I.mole-'.sec-' at 30 "C, pH 9.1 and an ionic strength of
1.75. k , was independent of acidity above this pH, but the reaction was acid
catalysed at lower pH. This conclusion was based on a single measurement,
however, and the disagreement with the results of Mason and K ~ w a l a kis ~not
~
serious. The cr(vr)-As(rrr) reaction was found to induce the reduction of
molecular oxygen, thereby confirming the early work of Kessler5*. For further
details, the reader is referred to the chapter on induced reactions.
Wiberg5' has reviewed this oxidation and suggests that the complex of Mason
and Kowalak is a mixed anhydride, cf. the oxidations of sulphur dioxide (p. 285)
and formic acid (p. 316). The anhydride cannot be of neutral charge, however, as
no acidity dependence is observed and a possibility is
H3As03 HCrO;
+ H,O
+ HO-As-0-Cr0,-0I
OH
HO-As-O-CrO,-O-
-+ As(V)+Cr(IV)
(slow)
OH
Further complication is apparent when the reaction is investigated in
H,PW-HPO:while the rate shows a first-order dependence on
total [Cr(VI)] and [As(III)], a complex dependence on the buffer composition
is found, indicating two activated complexes of composition H,PO, .HCrO,.
As(II1) and HPO:-*HCrO,*As(III), which correspond to attack of HCrP0:upon neutral As(II1) and As(OH),O- respectively.
k[CO][MnOJ
with E = 13.6 kcal.mole-' and AS' = 17 eu over the p H range 1 to 13. Catalysis
by Agf and Hg2+ ions was observed (cf. oxidation of hydrogen by MnO;)
following a general rate law6'
-d[CO]/dt
k[CO][MnO;][cat]
OXIDATION BY
29 1
Cr(V1) A N D Mn(VI1)
the type
[-Hg-CO-OMnO,]
are involved. It is pertinent6 that CO is readily oxidised by solid AgMnO,.
2 C r 3 + + 7 H,O
k[AgI2[H2]
+ AgH:
+ (Ag, . . . H,)
. . . H2)++3 Cr(V1) -+
2 A g f + 3 C r 3 + + 2 Hf
(fast)
(slow)
(fast)
= 2Mn0:-+2Hz0
k,[H,][MnOh]
c o v A L E N T c o M P o u N D S,
292
M E T A L I O N S: O X I DA T I o N-R E D u c T I O N
with k2 = 4 . 2 lo9
~ exp[-(14.7&0.5) x 103/RT]I.mole-'.sec-'
(p = 0.3 M ) .
The reaction is subject to slight acid catalysis. In neutral solution the rate expression has the same f ~ r m ~ ~but
. ~ k' ,is lower by 15 %. In basic solution also no
change in the law was observed and no significant salt effect was found at any pH.
The reaction has the same velocity in deuterium oxide66.
The authors favour a two-equivalent oxidation in order to avoid the necessity
to postulate free hydrogen atoms as intermediates in the reaction, viz.
MnO,+H,
Mn0;-+2 H + or HMnO:-+H+
or
MnO,+H,
MnO;+H,O
The reaction was also found to be catalysed by silver ion6,, being of the third
order, with k , = 7.5 x lo7 exp[( -9.3f.0.5) x 103/RT]I2.mole-'.sec-' (p = 0.3
M ) . Ag+ is thought to form a complex with MnO, (a process for which there is
spectroscopic support), which attacks the hydrogen molecule, viz.
Ag'
*
*
+ MnO, + AgMnO,
+ H 2 + AgH+ + Mn0:- + H +
AgH+ + MnO,
Ag+ + H + Mn0:AgMnO,
--f
2.3
(fast)
(slow)
(fast)
O X I D A T I O N O F MONOFUNCTIONAL O R G A N I C MOLECULES
It is not within the scope of this review to deal with products of oxidation
of organic molecules in cases other than those for which a kinetic analysis has also
been attempted. However, much insight into the modes of reactivity of Cr(V1)
and Mn(VI1) is to be gained from such information and the reader is referred to
the recent excellent reviews of Wiberg67 on Cr(V1) and Stewart6' on Mn(VII1).
One major difference between the published accounts of oxidation of inorganic
and organic species is the more prevalent use of non-aqueous solvents for the latter,
which gives rise to several complicating features.
2.3.1 Aliphatic hydrocarbons
(b)
OXIDATION BY
toluene ethylbenzene
1
7.2
Cr(V1)
AND
isopropylbenzene
71.1
Mn(VI1)
293
tert-butylbenzene
0.019
nkCHz
where kCH2= 5.73 x lo-' I.mole-'.sec-'. The same rate law was found for
c y c l ~ h e x a n e and
~ ~ the oxidations of both cyclohexane and n-heptane were
greatly retarded on addition of 4 % of water to the acetic acid medium. This effect has been found subsequently for many oxidations of organic substances by
chromic acid in acetic acid (vide infra).
RoCek et ~ 1 have
. also
~ measured
~
rate coefficients for a series of cyclo-alkanes,
(CH,),(n = 4 to 14), and find the analogue of kCH2
in equation (25) to fluctuate
with ring size in a manner corresponding exactly to the enthalpy of combustion
of the cycloalkane concerned per methylene group, provided n is greater than five,
i.e. there exists a direct correlation between reactivity and thermochemical strain.
For straight chain and cycloalkanes, RoCek et ~ 1 . ' prefer
~
a mechanism involving hydride ion abstraction to give a partly-developed carbonium ion which
suffers further reaction with the Cr(rV) portion before it can become free to give
acetate or olefin
294
(CH3),CH(neo-C5Hii) CH,CH(neo-C,H,,),
0.674
0.104
k, (relative)
cyclohexane
1
bornane
2.0
isobornane
8.0
These effects are very much smaller than those found for the first-order solvolyses
of bornyl and isobornyl chlorides, which differ in relative rate by several orders of
magnitude. However, the authors argue that this does not necessarily disprove
participation by a carbonium ion in the mechanism which they proposed for the
oxidation of straight-chain alkanes (see above).
Wiberg and Foster75 oxidised (+)-3-methylheptane in 91 % acetic acid with
chromic acid and obtained (+)-3-methyI-3-heptanol with 70-85 % retention of
Configuration. This implies that should the initial product of oxidation be either
MeEtPrC' or MeEtPrC., then neither diffuses away from the solvent cage before
reacting further. Slow initial formation of [R3c.Cr(V)] would be expected to be
followed by rapid transfer of a second electron to give [R,C+*Cr(IV)]. The latter
could be an ester of Cr(1V) which suffers Cr-0 fission to give R,COH with
retention of configuration.
Closely related to this work is that of Wiberg and Evans69 on the Cr(VI)
oxidation of diphenylmethane in 95 % acetic acid. This has the rate law
- d [Cr(VI)]/df
= k [substrate] [ C r 0 3 ] h ,
OXIDATION BY
Cr(V1)
AND
Mn(VI1)
295
kinetics and the C-H cleavage implied by the isotope effect, viz.
A.
B.
C. Ph,C
-H
H\
O=Cr03H,
0.
OH
E.
0 = Cr0,H2
PhfCH-Ph
I
H
>
Ph2C--H
HO8H
+ Cr(lV)
Ph,C-H
5'-
OH
bH
0 -Cr(OH),O'
I
Ph-CH-Ph
296
Evans69. The more recent result is to be preferred in view of the wider range of
Cr(V1) concentration employed.
Electron-releasing groups facilitate the oxidation of a series of para-substituted
toluenes, although determination of the rate coefficients again depended on a
second-order decay plot of the concentration of Cr(VI)83.
Chromyl chloride combines with arylalkanes in inert solvents to deposit an
Etard complex of the general formula ArH.2 CrO,CI,. On hydrolysis this yields
the expected oxidation product. Study of the reaction has been from three standpoints, namely the formation and the spectroscopy of the complex and the products
of its decomposition. The latter aspect has been covered by Wiberg67, who gives
details of the reaction of o-nitrotoluene to give an apparently normal complex
which, on hydrolysis, reverts mainly to the starting compound84. This implies
that oxidation occurs only during hydrolysis. However, both the magnetic
susceptibility85*8 5 a (3.2+_0.06 Bohr magnetons per Cr atom) and the ESR spectrum86 of the complex with toluene, indicate the presence of Cr(IV)67.
The oxidations of toluene, diphenylmethane and triphenylmethane are second
order, relative rates at 22 C being
PhCH,
k,(l.mole-.sec-)
1.28 x
Ph,CH2
Ph,CH
1 . 6 7 ~lo-
0.16
OXIDATION BY
Cr(V1) A N D Mn(VI1)
297
likely67*", viz.
Ar3CH+ CrO2CI2 + [Ar3c.0Cr(OH)C121
[Ar3~.0Cr(OH)CI,]+ Ar,C-O-Cr(OH)CI,
Ar,CH, would react further to give Ar2C[OCr(OH)CI,]2, hydrolysis of which
would give the observed products.
NecSoiu et al.79.9 s dispute these conclusions and prefer an S,2 process, viz.
\
\
-C-H
o:c/rcl,
:
'
-C
/ ' ,
H..-O
CI
L-o-&-cl
I
OH
The transition state does not involve a large degree of charge separation and hence
the relative rates of oxidation of toluene, diphenylmethane and triphenylmethane
may be explained in terms of an ionic mechanism.
The aqueous permanganate oxidation of hydrocarbons has been relatively
neglected for reasons of low solubility, and discussion of the oxidations of C-H
groups has derived largely from studies of certain carboxylic acids or alcohols
when the functional group is not directly involved. The oxidations of 4-methylhexanoic acid, 5-methylheptane sulphonic acid and p-sec-butylbenzoic acids are
of a total kinetic order of
at pH 13. Oxidation of 4-methylhexanoic acid
proceeds with 35 % retention of configuration at pH 13, but that of p-sec-butylbenzoic acid displays only 6 % retention. About 25 % of l80was transferred to
the product, 4-hydroxy-4-methylhexanoate lactone, from labelled MnO,, but
only 0.6 to a-hydroxy-p-sec-butylbenzoic acid. As in the case of chromic acid,
three modes of electron-transfer deserve consideration
R3CH
MnO,
R3C+ + M n ( V )
The factor of seven variation between k, for the ordinary and benzylic tertiary
hydrogen is too small to be associated with carbonium ion formation. The observed degrees of retention and l8O transfer imply a caged radical rapidly reducing
Mn(V1) to Mn(V) by accepting oxygen
[R3C.MnO4H-] + R,C-O-Mn03H
Solvolysis follows, with carboxyl participation where this is feasible, to yield
R3COH, although several modes are involved. Other stereochemical work has
been summarised by Stewart6'.
References pp. 493-SO4
298
k,
1.9 x lO"exp(-
- d [Cr(VI)]/df
k , [Cr(Vr)][olefin][H,O+]
The reaction is insensitive to steric effects, but k , increases with the number of
alkyl substituents although it is not influenced by position of the alkyl groups
(unlike oxidation by TI(T11))97b.In these respects Cr(V1) oxidation resembles
bromination, chlorination and epoxidation and a symmetrical transition state of
the type depicted is favoured.
OXIDATION B Y
Cr(V1)
AND
Mn(VI1)
299
some c y c l ~ a l k e n e swith
~ ~ ~E and A S f values in the ranges 6.0-7.6 kcal.mole'-'
and 27-41 eu, respectively. Formation of rearranged products
R3
I
RIR,C=CR,R,
-+
Rl-C-COR,
1
R,
suggests alkyl migration on hydrolysis of the adduct.
The oxidation by permanganate has been investigated both at pH 6.5 and
13 using salts of unsaturated carboxylic acids to facilitate d i s s ~ l u t i o n ~At~ .low
substrate concentrations (M ) and pH 13, the reaction is first-order with
respect to both oxidant and substrate but at 2-3 x
M substrate concentration
significant deviation is apparent, especially at 0 "C. The initial rate is independent
of base concentration but the rate at later stages is strongly affected. This suggests
that the reduction of a second permanganate ion is influenced by hydroxide ion
as in the following scheme
MnO, +crotonate ion
5B
(26)
II
/c\
+ MnO;
C'-O,
c
,-,0
M
, "'
0"0
300
c o v A L E N T c o M P o u N D S,
M E T A L I o N s : o x I D A TIo N-R E D u c T I o N
TABLE 1
R A T E P A R A M E T E R S FOR F I R S T S T A G E O F T H E O X I D A T I O N O F O L E F I N S B Y P E R M A N GANATE
Temperature
Olefin
Ally1 alcohol
Acrylate ion
Crotonate ion
Vinylacetate ion
4-Bromocrotonate ion
2-Pentenoate ion
3-Pentenoate ion
4-Pentenoate ion
Cinnarnate ion
p-Methylcinnamate ion
p-Methoxycinnamate ion
p-Chlorocinnarnate ion
Oleate ion
= 25
k (I.mole- '.set- l )
C; pH 13.
E
137f7
330f 17
220f 11
111*6
325j=16
242k 12
455f23
167f8
503525
278k 14
264% 14
302+ 15
70
(kcal.mole-)
ASt(eu)
8.1 f0.7
5.9f0.7
5.4f0.7
7.0k0.7
-24f2
-3Of2
-32f2
-28k2
7.2&0.7
3.9f0.7
-27f2
-36f2
__
second-order kinetics7 lo. Although the removal of MnO, (A,,, 540 nm) under
conditions of excess substrate showed clean first-order behaviour, a transient
built up and then decayed at ca. 250 nm, the region of absorption by Mn(II1).
Quenching the reaction at this point in time enabled identification of oxalic acid
as another intermediate. At pH > 3, when the dianion of the substrate is the only
significant species, E = 6.7 kcal.mole- and ASt = -32 eu.
2.3.3 Alcohols
( a ) Products
In general, the substrate RlR2CHOH, where R, or R, and R, may be H, is
OXIDATION BY
Cr(V1) A N D Mn(VI1)
301
- d[ Cr(VI)]/d t
= k , [HCr OJ
+ k,[HCr0,][R2CHOH][H30+]z
The dependence on [HCrO,] is a feature of many other oxidations by chromic
acid and is characterised by a falling-off of the apparent first-order rate coefficient for disappearance of Cr(V1) at higher concentrations of oxidant. In more
strongly acidic solutions the kinetics are1"*
- d [Cr(VI)/dt
k[Cr(VI)] [R,CHOH]h,
~ exp(-13.1 x 103/RT)I.mole-'.sec-'. At
At an ho value of 1, k = 1 . 4 lo7
acidities Ho = -3 to -9, the rates of oxidation of 2-propanol, l,l,l-trifluoro2-propanol and 1,1,1,3,3,3-hexafluoro-2-propanol
reach maxima' O 5 at different
values of h,.
Primary isotope eflect
At low acidity the relative rates of oxidation of isopropanol and (CH,),CDOH
(contaminated with "light" isopropanol) were found to be 6.4+ 1.9 at 40 "C after
correction for incomplete deuteration' 0 6 . k,/k, has also been determined and the
results are in agreement'O7. Under extremely acid conditions k,/k, decreases to
1.3'05.
(c)
Results on the relative rates of oxidation in light and heavy water were considered' O8 in terms of the two components of the rate expression. k,(D,O/H,O) is
2.44 and k,(D,O/H,O) is 6.26.
( e ) Replacement of hydroxylic hydrogen by an alkyl group
This replacement (by an isopropyl group to give di-isopropyl ether) reduces
the oxidation rate'" by a factor of about 1500.
302
c o v A L E N T c o M P o u N D S,
M E T A L I o NS: OX I D A T I o N-RED
ucT I o N
( 9 ) Base catalysis
An o b s e r ~ a t i o n that
' ~ ~ the oxidation is subject to marked catalysis by pyridine
was later refuted'0'*'''.
( h ) Induced oxidation
The oxidation induces the oxidation of manganous ion to MnOz with an induction factor (see p. 280) of 0.5'12. The rate of reduction of Cr(V1) is reduced
simultaneously to a maximum extent of 50 %lo3.
=H2Cr04
H20
(28)cfast)
R2C-0-Cr -OH
I
11
H
O
(29) (fast)
0
II
R2CHOH
H2Cr04
0
I1
R2C-OpCr-OH
IJ
H20)
R,C=O
0
&-OH
H30t
0-
(30)(slow)
OXIDATION BY
Cr(V1) A N D Mn(VI1)
303
C r ( I I I ) + R 2 c O H+ HS
+
+
Cr(V) + R2CHOH + R,C = 0 + Cr(II1)
The two major differences are: (i) the absence of any complex or ester in the
second mechanism, and (ii) the direction of the movement of the electron pair
of the C-H bond, the hydrogen becoming proton-like in the transition state of
the Westheimer scheme but hydride-like in that of the RoCek mechanism.
Both schemes accommodate the kinetics, the primary isotope effect and the
induction factor, which indicates that Cr(IV) is the initial stage of reduction of
the oxidant. RoCek's mechanism does not accord with the solvent isotope effect
of 2.5 per proton, which has just the value to be expected for acid-catalysis, for
the 0-H bond cleavage should be subject to a primary isotope effect of about
7. The ester mechanism is not open to this criticim.
The main objections to the ester mechanism are based on the substituent effects
and, to a lesser degree, the kinetics in strongly acidic solutions. The departure of
the hydrogen as a proton in the slow step should be facilitated by electron-withdrawing groups, but the converse is found. Substituents are, of course, bound
to affect both the esterification equilibrium (29) and the oxidation step (30) and
the observed p is the sum of the individual values. Spectroscopic evidence has been
~ b t a i n e d " ~ . ~, ho
" wever, for the existence of 1 : 1 complexes in solution between
alcohols and acid chromate ion, e.g. KzsOfor isopropanol is 0.083 I.mole-'
( p = 0.001 M ) . These esters can be extracted into benzene'04 and are rapidly
decomposed therein on addition of pyridine to give the oxidation product, although
hydrolysis is a competing reaction' 16. The pyridine-catalysed oxidative breakdown in benzene has a primary kinetic isotope effect of about 5 (ref. 116).
References pp. 493-509
304
c o v A L E N T co M PO u N D s, M E T A L I o N S : o X I D A T I o N-RE D u c T 10N
These results do not prove that the ester is an essential intermediate in aqueous
solution even though it is present, but the result with the hindred triterpene is
convincinglo2. In this case the esterification step, which is normally fast, has
become rate-determining and the disappearance of the isotope effect must mean
that C-H cleavage occurs after the formation of the ester and not independently of
it. The generality of this result is apparent from the stopped-flow investigation of
isopropanol oxidation ' 1 3 .
The h, dependence of the oxidation in strongly acidic media was taken by RoCek
as implying that no water molecule is involved in the transition state and that
consequently the ester mechanism as portrayed above cannot hold. However,
the Zucker-Hammett hypothesis upon which this argument is based, i.e. that a
reaction forming a transition state containing a water molecule will follow a
[H,O+] dependence, but that otherwise an h, dependence will be followed, may
not be valid, and in any case the ester can be depicted as breaking down as foll o W s 1 l 7 , 118
The maximum rate reported at very high acidity accords with protonation of the
ester' 0 5 . To summarise, the ester mechanism has gained general acceptance,
although the substituent effects have yet to be explained wholly satisfactorily and
the exact nature of the transition state, i.e. whether it is of considerable or only
slight carbonyl character, remains a contentious issue67, '.
Many interesting observations not bearing directly on the general mechanism
have been reported. Certain secondary alcohols undergo cleavage' 2 0 , e.g.
''
H
I
C6H ,-C-C(CH,),
I
OH
Cr(V1)
--f
C,H ,C-C(CH,),,
C 6 H 5 C H0and (CH,),COH
II
OXIDATION BY
Cr(VI) A N D Mn(VI1)
C6H5CH(OH)C(CH,)3 Cr(V)
305
+ C6H5-CH-C(CH,),
I
I
0-Cr (V)
C6H5-CH-C(CH,), + C6H5CHO+Cr(lII)+ (CH3),C+
I
0-Cr(V)
(CH3),Cf H 2 0 4 (CH,),COH
+H +
+
Cr(IV) + RCHOHR' -,Cr(II1) + RCHO + R',
Cr(V) + R'OH
Cr(V1) + R'.
2Cr(V) + Cr(V1) + Cr(IV)
Cr(V1) + RCHOHR'
Cr(1V) RCOR'
Interest has been shown by several groups on the effect of solvent and of added
anions upon the oxidation of alcohols. The oxidation of isopropanol proceeds
2500 times faster in 86.5 % acetic acid than in water at the same hydrogen ion
c ~ n c e n t r a t i o n ~The
~ . kinetics and primary kinetic isotope effect are essentially
the same as in water. Addition of chloride ion strongly inhibits the oxidation and
the spectrum of chromic acid is modified. The effect of chloride ion was ratioin terms of the equilibrium,
H++Cl-+HCrO;
+ CICrO;+H,O
306
c o v A L E N T c OM P o u N D s, M E T A L I o N s: O X I D A TI o N-R
E D u CTI o N
acid, viz.
H,CrO,
+ HA + H,O + HCr0,A
+ CH3COOCr0,0H + H,O
OXIDATION BY
307
Cr(V1) A N D Mn(VI1)
primary kinetic isotope effect, the Hammett p value and salt effects are largely
unaltered, but the rate is enhanced by a factor of 7 x 10 in 93.3 % acetone compared with that in water and depends on the h, function. These observations cannot
be accommodated by invoking substitution of an anion into HCrO, and the enhancement may originate in a shift of the equilibrium (29) to the right.
A number of effects of conformation have been reported118. Crowding of
the hydroxyl group results in faster oxidation and alcohols with axial hydroxyl
groups are oxidised more readily than the equatorial isomers, e.g. cis-4-tertbutylcyclohexanol is oxidised about three times fasterlZ7than the trans isomer at
25 C.
TABLE 2
OXIDATION OF SUBSTITUTED PHENYLTRIFLUOROMETHYLCARBINOLS BY CHROMIC
A C I D AT
Substituent
25C
CH3
H
m-Br
m-NO2
3,5-Dinitro
kl,/kD
7.4040.20
8.53&0.15
9.803=0.20
12.20*0.20
I2.93f0.78
One further striking kinetic feature is the magnitude of the primary kinetic
isotope effect for the oxidation of certain aryltrifluoromethylcarbinols18 (Table
2 ) . It is clear that a correlation exists between the isotope effect and the oxidation
rate, slow oxidations exhibiting large isotopes effects. The magnitude of the
isotope effects may be due to one of several effects including loss of bending
frequencies in the transition state or quantum-mechanical t~nnelling~.That
large isotope effects are often associated with neighbouring groups of fluorine
atoms is apparent from the analogous results with permanganate (p. 308).
The oxidation of tertiary alcohols by chromic acid is comparatively slow and
shows a zero-order dependence of the rate upon oxidant concentration130*1 3 1 . For
l-methylcyclohexanol31 the kinetics are
-d[Cr(VI)]/dt = k[alcohol]h,
Clearly the rate-determining step is the elimination of water from the protonated
alcohol to form a carbonium ion, which loses a proton to give the readily oxidised
olefin.
The Cr(V1) oxidation of di- and triarylcarbinols in acetic acid-sulphuric acid
mixtures shows normal kinetics (first-order each in alcohol and Cr(V1) and an
h, dependence up to H,
- l)131a. Electron-donating substituents appear in the
phenolic component and the rate-determining step is believed to involve a 1,2-
References p p . 493-SO9
308
a+
Ar3C-O-Cr03H,+
--+
Ar&-O..
;a+;
. Cr03H,
-+
Ar,C-0-Ar
Is';
k[R,CHOH][MnO,][OH-]
+ R,CHO- + H +
H
16.0
57.1 & 2.4
p-CH3
16.1
rn-Br
16.2
OXIDATION BY
Cr(V1) A N D Mn(VI1)
309
That reaction rates are barely affected by the nuclear substitution ill-accords with
the hydride abstraction mechanism. However, nuclear substitution affects both
the ionisation of the alcohol as well as the oxidation step. The value of kH/kT
agrees well with that of 55.5 calculated from k,/k, by means of the Swain rel a t i ~ n s h i p , 'i.e.
~ ~ ~( k ~ / k , ) " ~ ~=' kH/kT.
A few results have been reported on the oxidation of cyclohexanol by acidic
permanganateZ4*13'. In the absence of added fluoride ions the reaction is firstorder in both alcohol and oxidant',', the apparent first-order rate coefficient
(for excess alcohol) at 25 "C following an acidity dependence k = 3.5+ 16.0
[H,O+]sec-'. k,/k, depends on acidity (3.2 in dilute acid, 2.4 in 1 M acid) and
kDzO/kH20
is 1.74. Addition of fluoridez4 permitted observation of the reaction
for longer periods (before precipitation) and under these conditions methanol is
attacked at about the same rates as di-isopropyl ether, although dioxan is oxidised
over twenty times more slowly. The lack of specificity and the isotope effect indicates
that a hydride-ion abstraction mechanism operates under these conditions. (The
reactivity of di-isopropyl ether towards two-equivalent oxidants is illustrated by
its reaction with Hg(II).) Similar results were obtained with buffered permanganate.
An analogous study668of the oxidation of benzyl alcohol by permanganate in
aqueous perchloric acid yielded a rate law
-d[MnO,-]/dt
k, [MnO4-][C6H5CHZOH][H3O+
]
+ H+ + ArzCH++ H,O
2.3.4 Aldehydes
RCH=O HZO
+ RCH(OH),
(31)
and in any example the solute may act either as a gem-diol or a carbonyl compound.
References pp. 493-SO9
310
k[RCHO][HCrO,]h,
For the latter reaction E = 13.2 kcal.mole-' and ASt = -28 eu.
Both groups reported a sharp decrease (40-65%) in the rate on addition of
Mn(I1) ions. Wiberg and
reported a deuterium isotope effect of 4.3
(30 "C) and that electron-withdrawing groups facilitate reaction ( p = 1.02),
the latter result confirming the data of L ~ c c h i ' ~ ' , ( p = + 1.06). The opposite
effect of electron-withdrawing groups for aliphatic aldehydes has been reported
by ROC^^'^^ (p* = - 1.2), who explains the difference in terms of the hydration
pre-equilibrium (3 1 ) which favours the gem-diol form for aliphatic aldehydes and
the carbonyl form for aromatic aldehydes. Otherwise the oxidation of aliphatic
aldehydes strictly parallels that of benzaldehyde as regards kinetics'40* 14'
(formaldehyde), Arrhenius parameters (f~rmaldehyde'~', acetaldehyde, nbutyraldehyde, i~obutyraldehyde'~~),
primary kinetic and solvent isotope effects
(f~rmaldehyde'~',a ~ e t a l d e h y d e ' ~ ~and
) , retardation by Mn(I1) with induced
oxidation (f~rmaldehyde'~').
Accordingly, the most reasonable mechanism is the exact analogue of that
proposed for alcohol oxidation
''*
RCHO + H'
HCr 04-
?H
R-C-OCr03H
I
Although the fate of Cr(1V) is uncertain, (cf. the alcohol oxidation), some characteristics of the intermediate chromium species have been obtained by Wiberg and
Richards01-1'~~
from a study of competitions between benzaldehyde and each of
several substituted benzaldehydes. The competition between the two aldehydes
for Cr(V1) is measured simply by their separate reactivities; that for the Cr(V) or
Cr(IV) is obtained from estimation of residual aldehyde by a ''C-labelling
technique. If Cr(V) is involved thenp values for oxidation by Cr(V1) and Cr(V) are
0.77 and 0.45, respectively. An isotope effect of 4.1 for oxidation of benzaldehyde
by Cr(V) was obtained likewise.
Wiberg and L e p ~ e have
' ~ ~ examined the oxidation of benzaldehyde by chromyl
OXIDATIONBY
31 1
Cr(V1) A N D Mn(VI1)
acetate in an acetic anhydride medium. The orange colour of the oxidant changes
to dark brown on addition of the aldehyde. Analysis showed that each chromium
atom retains one equivalent of oxidising power and the spectrum rules out the
possibility of a Cr(V1): Cr(1II) complex. Isotope dilution analysis indicated that
almost 25 % of the oxidant was consumed by the solvent under some conditions
and this effect was minimised by employing excess aldehyde. The oxidation
proceeds in two stages, both steps displaying a total kinetic order of two. Some
substituted benzaldehydes show detailed differences of order in one step or the
other. The p values for the two steps were estimated to be -0.2 and -0.9
respectively, and both display a moderate primary kinetic isotope effect. "0 is
transferred from labelled oxidant to the aldehyde and an ESR spectrum obtained
from the reaction mixture was assigned to Cr(V). The authors prefer a oneequivalent oxidation mechanism to give an acyl radical (corresponding to the
first step); the resulting Cr(V) effects a similar one-equivalent oxidation (corresponding to the second step), viz.
RCHO +(CH,CO),CrO,
-+
Rc-O+ Cr(V)
+
RCHO + Cr(V) + R e 0 + Cr(IV)
R e 0 +(CH,CO),CrO,
RcO+Cr(V)
-+
R e 0 Cr(V)
+ R6O+Cr(IV)
3 12
co v A L E N T c OM P ou N D S,
M E T A L I o N s : ox I D A T I ON-R E D u CTIo N
+ MnO, + H 2 0 +
ArCHO
OH 0
I
I1
Ar-C-0-Mn-0
OH
I
II
+OH-
OH
I
Ar-C-0-MnO,
I
+ B: + Ar-C=O+
Mn(V)O;
HB
H
3MnO;+H20
2Mn02+MnO;+20H-
H,O may be replaced by any acid, HA, and a cyclic mechanism for the breakdown of the ester is quite feasible. For oxidation in alkali the fractional order in
hydroxide ion, the low k,lk, and low degree of oxygen-transfer from oxidant are
taken as symptomatic of a free-radical chain reaction of the type
MnO;
+ OH-
MnOt-
+ OH.
-+
RCO,H+MnO;
+ OH*
with termination by dimerisation of OH.. This particular scheme does not fit the
observed kinetics and it should operate for any organic substrate readily oxidised
by hydroxyl radical, of which there are a large number. The kinetics are, however,
unique to aromatic aldehydes.
Investigation of the oxidation of aliphatic aldehydes32 has been confined to
gem-diols which behave as secondary alcohols, being most easily oxidised in the
anionic forms, e.g.
CF3CH(OH) and CF3CH-OI
I
0-
0-
although in very strong acid the permanganic acid itself effects rapid oxidation.
All these routes for fluoral hydrate display a substantial primary kinetic isotope
effect and Arrhenius parameters have been obtained (Table 3).
As has frequently been the case, the evidence at present available does not
permit discrimination between the possibilities of hydride ion- or hydrogen atomabstraction by Mn(VI1).
O X I D A T I O NBY
Cr(V1) A N D Mn(VI1)
313
TABLE 3
K I N E T I C ISOTOPE EFFECTS AND
A R R H E N I UPSA R A M E T E R S F O R T H E
Mn(VI1) A N D Mn(V1)
~E (kcal. mole-')
kH/kD
OXIDATION OF
FLUORAL HYDRATE BY
~~
Reaction
~~
MnOa2--dianion
MnO,--dianion
Mn0,--monoanion
H Mn04-neutral
aldehyde
pH 10.2
DH 7.6
ASt(eu)
_____~
4.8
5.1
10.1
13.6
1.2
13.0
-31.4
-18.4
6.3
13.5
- 17.8
2.3.5 Phenols
a+b[H,O+]
+ c[H3OfI2
',
'
2.3.6 Ketones
The chromic acid oxidation of cyclohexanone to adipic acid via 2-hydroxycyclohexanone and cyclohe~ane-l,2-dione~~~
is third order' 53, viz.
-d[Cr(V1)l
dt
References pp. 493-509
k[ketone][HCrO,][H,O+]
3 14
c o v A L E N T c o M P o u N D S,
M E T A L I O N S: O X I D A T I o N-R E D u c T I o N
where k = 1.05 x
12.mole-2.sec-' at 50 "C (p = 0.646 M ) . The rate of
oxidation is considerably lower than that of enolisation at the same temperature
and the question arises at to whether oxidation proceeds via attack of Cr(V1)
upon the ketone or the enol, and the observation of a primary kinetic isotope
effect of 4.0 (50 "C) on changing the substrate to 2,2,6,6-tetradeuterocyclohexanone does not clarify matters, for the enolisation itself is subject to an isotope
effect of the same order of magnitudelS4. However, the reaction proceeds four
times faster in heavy than in light water and this increase, which is considerably
larger than the factor of 2.0 to 2.5 for proton-catalysed reactions, was taken
as evidence by the authors that enolisation must be taking place as a necessary
pre-requisite for reaction, for this equilibrium is favoured by a factor of 2.0-2.5
on changing to heavy water. The mechanism therefore becomes
(last)
+H'+HCrO~
(last)
O - croz- OH
-rf r0, -% H
+ CrO,
H20
+ OH-
(slow)
(fast)
RoCek and Rieh1lS5 have pointed out that the enolisation scheme leads to
kinetics
- d[Cr( VI)] - k ,
-
dt
k,,,[acetone][OH-][MnOJ
where kobs= 107 12.mole-2.sec-' at 25 "C. These kinetics suggest the mechanism
acetone + OHenolate + MnO;
+ enolate + H,O
ki
k-
4 product + Mn(V)
,2 Mn( VI)
Mn(V) + Mn(VI1) "
OXIDATION B Y
Cr(VI)
315
Mn(VI1)
AND
-.
- 2 k , k,[MnO,][acetone][OH-]
-
k - *[H20] k[MnOi]
dt
acetol
pyruvic acid 27 %
pyruvaldehyde 0 %
lactic acid
6%
19 %
acetic acid
47 %
oxalic acid
CHO - C H 3 C 0
CO,H
'(CO2H),
/OHCH3C H (0H)CO;
Rate laws and coefficients were determined for the oxidation of all intermediate
compounds by MnO, and were compatible with the scheme as presented, i.e.
including a route for direct oxidation to pyruvaldehyde. An estimate of k2
(- 5 x lo7 I.mole-'.sec-') suggests an initial electron-transfer to give CH3
COCH,. . This can then be rapidly oxidised in two ways
0
II
CH,CCH,.
0
II
+ Mn(V1) -+
+ CH,CCH:
CH,COCH,OH
CH3C-CH-OMn( VI)O;
I
H
OH-
0
11
CH,C-CHO
+ H 2 0+ Mn(1V)
316
COVALENT
C O M P O U N DMSE, T A L
IONS: O X I D A T I O N - R E D U C T I O N
Formic acid is rather atypical and should be considered separately. The chromic
acid oxidation has been examined in some detail by Kemp and water^'^', following the earlier work of St~ethlage'~'.At acidities of up to 3.6 M (HC104) the
reaction follows kinetics
-d[Cr(V1)l
dt
- k[formic a~ i d l [ H C r O J[ H , 0 + ] ~
with E = 11.6 kcal.mole-' and AS* = -38 eu. However, at an ionic strength
of 6.0 M (CIO;), the [ H 3 0 + l 2term reverts t o h,. Several effects associated also
with the Cr(V1) oxidation of alcohols were noted, including a primary kinetic
isotope effect of 7.15 at 25 "C, a solvent isotope effect of 5.74 and a retardation
of rate by Mn(lI), the latter in a sulphate-ion medium only. It is probable, therefore
that a Westheimer-type mechanism operates through a n intermediate formylchromic anhydride, HCOOCrO,H, which undergoes protonation before breaking
down to C 0 2 and Cr(IV), cf. reactions (28)-(30).
The permanganate oxidation of formic acid has attracted much attention. The
reaction is pH-independent above pH 5 and involves formate ion. At lower pH's
the rate is much lower until permanganic acids begins to be formed at very low
pHls9.
Above pH 5 the reaction presumably involves two anions and, indeed, a positive
salt effect is found'60*16' and the rate expression is
164,
Alargeprimary kineticisotopeeffect has been reported by several
the most comprehensive study having been made by Bell and Onwood160in an
attempt to assess the role of quantum-mechanical tunnelling. This was found to
be unimportant and the rate coefficients at infinite dilution were expressed as
k,
k,
=
=
A small solvent isotope effect was found by Bell and OnwoodL6' (kH20/kD20=
1.08) in contradiction to that of only 0.38 reported by Taylor and H a 1 ~ e t - n ' ~ ~ .
Over one-third of the oxygen present in the carbonate originated from the oxidant
when "0-labelled permanganate was used'63. The reaction is subject to pronounced catalysis by ferric ions'63.
The available data do not permit a conclusive mechanism to be formulated.
C-H cleavage is clearly rate-determining but no choice between a one- or two-
OXIDATIONBY
Cr(V1) A N D Mn(VI1)
317
k[(NH,),Co.02CH2+][Mn0,]
++MnO;
(NH,),Co*O2CHZ+
= CO,
+ Coz+++MnO,
++MnO,
C-deuteration of the captive formate reduces the rate by a factor of 10.5 without
affecting the stoichiometry. The ratio of unreduced to reduced cobalt was found
to depend on oxidant concentration
[ ( N H , ) , C O . ( - O ~ C H ) ] ~ + + M ~O,, [(NH,),CO(III)(CO;)]~++HM~O~
''
co2
[(NH3),C~(III)(CO;)]2+
MnOT
+ co2
[(NH,),CO(~~I)~H~]~++C~~
3 18
c o vA LEN T
COM P O U N D S. M E T A L I O N S : O X I DA T I ON-R E D u C T I o N
H02C(CH2),C02H it was found that beyond a certain point the increment in the
rate coefficient for an increases of one i n n is constant at 5.2 x l o p 3 I.mole- '.set- ',
which compares with a value of 5.73 x
I.mole-'.sec-' for n-paraffin oxidation
(p. 293). It is clear that carboxylic acids behave as paraffins except that a slight
retardation due to the inductive effect of -C02H is apparent. Permanganate
behaves in much the same way and some examples of carboxylic acid oxidation
have been cited in the section on hydrocarbons.
2.3.8 Amities
A comprehensive account of the oxidation of benzylamine by both neutral and
alkaline permanganate has been published recently'66. The neutral amine is the
active reductant at all pH values and at pH 9.9 good second-order kinetics were
obtained. Under these conditions the stoichiometry is
3 C6H5CH2NH2+2MnO,
=:
3 C6H5CH=NH+2M n 0 2 + 2 OH-
+ 2 H2O
The pH-dependence of the rate is complicated. The rate increases very rapidly
between pH values of 8 and 10 and the authors correlate this with the literature
value of pKBH+ of benzylamine of 9.34. The rate levels off at pH 11-12, but at
pH 13-14 a reaction the rate of which is linearly dependent on hydroxyl ion concentration occurs.
In the pH range 8-10 the reaction shows a deuterium kinetic isotope effect of
7.0 for oxidation of C6H5CD2NH2.C6H5CH2ND2(in D,O) is oxidised at the
same rate as the light compound. A series of ring-substituted analogues were
examined and the data afforded a p + value of -0.28. Activation parameters were
determined for a series of benzylamines and all fell in a range of 11.0 to 12.3
kcal.mole-' (E) and -21.6 to -24.8 eu (AS'). These large negative values are
of interest as they resemble those found for permanganate oxidation of both
neutral molecules (H2, HC02H) and of anions (alkoxides). For this path the
authors propose a transition state formed thus
C6H5CH2NH2 + Mn0,-
----C
OXIDATION BY
Cr(VI) A N D Mn(VI1)
319
The present information does not allow discrimination between these two routes.
The high-pH path probably involves concerted attack of OH- and MnO, upon
neutral amine because the possibility of attack of oxidant upon C6H5CH2NHor C6H,CHNH2 is too remote in view of known acidities of amines.
In the same paper the authors list the responses of a number of amines and
amides towards permanganate and record the effect of freezing the medium upon
the oxidation of benzylamine.
TABLE 4
R A T E D A T A FOR T H E P E R M A N G A N A T E O X I D A T I O N O F SOME A L K Y L A M I N E S
P Ka
3.08
0.944
0.0828
10.65
10.98
10.63
9.92
10.155
3.36
1.82
MnO, +N(CH,),
+
"(CH,),
H2C . . . N(CH,),
+ MnO,
+ H2C=N(CH3I2+
(slow)
(fast)
(fast)
H,C-N(CH,),+ + H 2 0 + H2CO+HN(CH3),
2.3.9 Nitroalkanes
A stopped-flow examinati~n'~'' of the alkaline permanganate oxidation of
phenylnitromethane
3 C,H5CH-NO;+2
= k2[Mn04][C6H5CH=NO;]
320
co v A L E N T c o M PO u N D s,
M E T A L I o N s : ox I D A T I o N-RE D u c T I o N
Substrate
Phenylnitromethane
Nitrocyclo hexane
Nitrocyclopentane
2.4
E(kcal.mole8.1 5 0 . 2
8.05
11.1
180&20
310*20
52&10
I)
ASi(eu)
-20*1
-27.8
-20.0
O X I D A T I O N O F P O L Y F U N C T I O N A L O R G A N I C MOLECULES
2.4.1 Glycols
Oxidation of glycols can proceed by two routes: (i) formation of an a-hydroxycarbonyl compound and (ii) carbon-carbon fission. In the case of chromic acid,
successive C-methylation of ethylene glycol increases the degree of cleavage16'
until, with pinacol, cleavage is at least 70 % q ~ a n t i t a t i v e ' ~Chatterji
~.
and Mukherjee169 - 1 7 1 have examined four glycols obtaining rate laws and Arrhenius
parameters. In all cases the oxidation rate depends on the first powers of the
glycol and acid chromate ion concentrations. The remaining data are summarised
in Table 5. Manganous ion strongly retards the oxidation of all the glycols except
pinacol. Despite its much larger activation energy, the oxidation of pinacol is
cu. 400 times faster than that of ethylene glyc01'~'. It is clear that an ordinary
TABLE 5
ACIDITY-DEPENDENCES
O F C(-GLYCOLS
Glycol
Ethylene glycol"
Propylene glycol
2.3-Butylene glycol
Pinacol
IH30+12
[H30+1
2.2 x i 0 5
8.1 x i 0 5
4.5 x 107
b1.07 x l o L 2
10.7
10.4
12.2
17.2
Ref.
170
169, 171
169, 171
169, 171
OXIDATION BY
Cr(VI)
AND
Mn(VI1)
321
alcohol type oxidation mechanism operates almost exclusively for ethylene glycol,
but that increasing C-methylation favours the second (cleavage) mechanism. This
view is supported: (i) by the fitting of the result for ethylene glycol to the Taft
plot for oxidation of primary alcohols and ( i i ) by its proximity to the point for
2-methoxyethanol on this plot" '.
The oxidation of pinacol was studied in further depth by Chang and Westheinier'72. The total kinetic order of three was confirmed and the reaction was
found to proceed 2.7 times faster in heavy than light water. In contrast with
ethylene glycol, 0-methylation of one group reduces the oxidation rate by a factor
of the order of 1500, producing complex kinetics containing an essentially zeroorder term in chromic acid. The reaction is not sensitive to oxygen, but induces
the oxidation of Mn(I1) ion to MnO, with a factor just under 0.3. The oxidation
rate is reduced by Mn(I1) by a factor of about 2.5 at chromic acid concentrations
of 6 x
M . At high oxidant concentrations (0.145 M ) no retardation is found.
This probably accounts for the failure of Chatterji and Mukherjee to observe
retardation' '.
The solvent isotope effect suggests that no 0-H cleavage is involved in the slow
step and the effect of 0-methylation indicates that a cyclic complex is involved.
The induction factor is probably obscured by the reaction of Mn(I1I) and MnO,
with pinacol itself. The typical glycol-cleavage mechanism advocated for oxidations
by Pb(IV) and I(VI1) (p. 349) may well operate, uiz.
H 2 C r 0 4 + RC
,
R2C
R2C
R,
-OH
- OH
- 0,
C -' 0
R2C-0,
R2C
- 0'
Cr
+ 2H,O
(fast)
CrO,
(slow)
\O
R2C = 0
\O
R2C=0
Strong support for the cyclic ester intermediate comes from the measurement
of the relative rates of oxidation by chromic acid of cis- and truns-1,2-dimethyl1,2-~yclopentanediol~~~.
In water and in 90 % acetic acid kcis/k,,,,,is 17,000 and
800, respectively. Both oxidations are first order both in glycol and HCrO;.
The rate with the cis-isomer involves a hydrogen ion concentration dependence;
the reaction with the trans-isomer was examined in more acidic solutions and the
rate followed an h, dependence. The solvent isotope effect of kD20/kH20
of 2.0 is
also normal. Oxidation of some diastereoisomeric 1,2-diols has revealed lower
k(dl)/k(meso)ratios than expected on the basis of decomposition of a cyclic ester.
This has been i n t e r ~ r e t e d " in
~ terms of rate-determining ester formation (cf. the
hindered triterpene study of Westheimer et al.lo2,p. 302). A similar proposal
has been made by Kwart and B r e t ~ g e r " to
~ explain the relative rates of oxidation
of cyclohexyl and cyclopentyl pinacols.
References pp. 493-509
322
faster than the axial 3a-hydroxyandrost-4-ene and 6.9 times faster than its 3deuterated a n a l ~ g u e " ~The
.
greater speed of oxidation of the equatorial isomer
is in contrast to the pattern observed for saturated alcohols and probably arises
from resonance between the double bond and the incipient carbonyl group.
Ally1 alcohols behave essentially as olefins towards MnO; (p. 300).
k,[substrate][MnO;]
+ k,[substrate][MnO;][OH-]
acetol
pyruvaldehyde
50
1 . 2 103
~
5.6 x 10'
9.3 x 10,
k,[substrate][MnO;][OH-]
+ k,[substrate][OH-]
OXIDATIONBY
Cr(V1) A N D Mn(VI1)
323
Early work of Dhar'77 established that oxidation of oxalic acid by chromic acid
occurs readily, but some of his kinetic data are unreliable as the substrate itself
acted as the source of hydrogen ions. The reaction is first-order in oxidant and is
subject to strong manganous ion catalysis (as opposed to the customary retardation), the catalysed reaction being zero-order in chromic acid. This observation
is related to those found in the manganous-ion catalysed oxidations of several
organic compounds discussed at the end of this section.
' ~ ~also Bakore and Jain178adetermined the rate law for
Chandra et ~ 1 . and
the uncatalysed reaction to be
-d[Cr(VI)]/dt = k,[HCrO; ][oxalic a ~ i d ] ' [ H , O + ] ~
with k, = 3.7 x lo7 e x p ( l 2 . 0 ~103/RT) I'.mole-'.sec-'.
tain a different rate law
-d[Cr(VI)]/dt
( k , [ C , O 2 - ] + k2[C204'-]2)[H30+]3[HCrOq]
Of the various results, these appear to the reviewer to be the most meticulously
obtained and they do not fit the other two rate laws suggested. At 25 "C ( p = 1 .O M
perchlorate), k, = 5 . 1 0 ~
lo5 14.mole-4.sec-' and k, = 4.78 x 10" I ' . m ~ l e - ~ .
sec- The corresponding reaction intermediates are a neutral chelate monooxalato complex and a (non-chelate) bis-oxalato complex of Cr(V1).
The permanganate oxidation of oxalic acid has been studied exhaustively and
has been reviewed by Ladbury and C u l l i ~ ' ~It~is. characterised by an induction
period and a sigmoid dependence of rate upon time. Addition of manganous
ions eliminates the induction period and produces first-order decay kinetics"'. l E 2 .
Addition of fluoride ions, however, practically eliminates reaction"'.
It is clear that some slow reduction of permanganate occurs during the induction
period to give lower valency states of manganese which form oxalato complexes of
varying stability. Oxidative break-down of these gives manganous ions which
react rapidly with permanganate unless removed by complexing, e.g. with fluoride.
Oxidation of malonic acid by Cr(V1) has been noted briefly by SnethlagelE3
and later by Kemp and WaterslS4. The kinetics are simple second-order but the
acidity dependence is complex. Heckner et ~ 1 . ' ~find
~ ' the alkaline permanganate
oxidation of malonic acid (and also of 0- andp-toluic acids and of p-toluenesulphonic acid) to be retarded by added Mn(VI), uiz.
'.
-d[MnO;]
dt
References p p . 493-SO9
- k[MnO~][OH-][sub~trate]~.~-~.~
- ____
[M n 0,'
-1
324
c o v A L E N T c o M P o u N D S,
M E T A L I o N s : O X I D A T I o N-R E D u CT I O N
+ MnO,- + Mn04,-
+OH.
the validity of which rests on the value of no for the couple OH*/OH-. Latimer's
value'' of +2.0 V, compared with that of +0.56 V for the Mn(VII)/Mn(VI)
couple, would seem to exclude it but Stein's value of +1.25 V (pH 14)'34d increases its plausibility. However, the extreme sensitivity of alkaline permanganate
to trace metal
renders Heckner's conclusions suspect as no special precautions to remove these ions appear to have been taken.
2.4.5 Hydroxy-acids
Bakore and Narain"' obtained the following kinetics for the oxidations by
chromic acid of lactic, malic and mandelic acids
- d[Cr(VI)]/dt = k[HCr O i l [ hydroxy-acid] [H,
0'1
The rate of oxidation is reduced by one half on addition of manganous ions and
the following Arrhenius parameters were recorded
Lactic acid
Malic acid
Mandelic acid
A(l2.mole-*.sec-')
E(kcal.mole-
5.2 x 104
6.6 x lo4
2.2 x 104
9.04
8.96
7.90
Kemp and Waters'86 found a primary kinetic isotope effect of 8.7 for oxidation
of C-deuterated mandelic acid and noted a large difference in rate between the
oxidations of mandelic acid ( k , at 24.4 "C = 1.7 I.mole-'.sec-') and u-hydroxyisobutyric acid ( k , at 24.4 "C = 5 . 6 ~
I.mole-'.set-') - a difference not
reproduced for the oxidation of these compounds by the one-equivalent reagent,
manganic sulphate. The various data are fully in accord with a Westheimer-type
mechanism, viz.
RtH(OH)CO2H
HCrOi
+ H,O+
H,C,R
H02C'
R
C'
I,,,
r /
\\o
II
'0-Cr-OH
II
0
OH
I
Cr-OH
II
2H20
(slow)
OXIDATION BY
Cr(V1) A N D Mn(VI1)
325
Fig. 1. Isotope effect for acid permanganate oxidation of mandelic acid. Temperature = 16.2 C;
~
M ; [H2S04] = 1.69 M .
[Mn04-] = 1 . 4 lo-
lo3 [C6H5CH(OH)C02H]
lo3 [C6H5CD(OH)C02H]
References pp. 493-SO9
10.4
9.9
1.3
6.9
5.2
4.9
326
Fig. 2. Relative rates of oxidation of some a-hydroxy acids by acid permangante. Temperature =
25.6 "C; [MnO,-] = 1 . 4 ~ 1 0 -M~; [HZS04]= 1.69 M . 0,C6H5(OH)C02H (0.0693 M ) ;
0,(CH3)2C(OH)COzH (0.0630 M ) ; X , CH3CH(OH)COzH (0.0704 M ) ; A, CHz(0H)COZH
(0.142 M ) .
+ t-C,H,B(OH),
"Ao t-C,H,OH+
B(OH),
+ Cr3+
- d[Cr(VI)]/dt
= k[HCrO~][t-C,H,B(OH)z]
The acidity dependence is complex and indicates that no extra proton to give
H,CrO, is required, but that H,CrOf is an active oxidant in this reaction. The
rate is very sensitive to the nature of the alkyl group, uiz.
R
CH3
CZH5
t-C,H,
2.4
6600
750,000
OXIDATION BY
327
Cr(V1) A N D Mn(VI1)
H C r O i t RB(OH)2 F
B (OH),
+O
; H + C r (P)
2.4.7 Furfurals
Examination of the permanganate oxidation of furfural anc 5-substituted
furfurals, at pH 11.5-13.3 in a stopped-flow apparatus, viz.
- d [MnO,-]/dt
k , [furfural] [MnO,-]
+ k , [furfural][MnO,-
][OH-]
OH
OH
2.5
D h a ~ - noted
~
that the oxidation of oxalic acid by chromic acid is markedly
accelerated on adding manganous ions, the reaction order in Cr(V1) changing
from one to zero. Bobtelsky and Glasner4 found the oxidation of bromide ions
by chromic acid in aqueous sulphuric acid to follow kinetics
-d[Cr(VI)]/dt
References p p . 493-509
k[Mn(II)][Cr(VI)]f [H,O+]
328
C 0 V A L E N T C 0 M PO U N D S, M E T A L I O N S: OX1 D A TI ON-R E D U C T I 0 N
i.e. to be independent of the concentration of bromide (p. 282). Their results were
confirmed by Kemp and Watersxs4using aqueous sulphuric acid (2.4 M ) and are
readily rationalised in terms of the scheme
+ Cr(V)+ Mn(II1)
Cr(V)+ Mn(I1) + Cr(IV)+Mn(III)
Cr(IV)+ Mn(I1) + Cr(III)+ Mn(1II)
Cr(VI)+3 Mn(I1) + Cr(II1)+3 Mn(1II)
Cr(V1) + Mn(I1)
Mn(III)+Br2 Br.
--$
Mn(II)+Br.
Br2
(35)
The slow step is (32), which excludes any participation by bromide in determining the overall rate.
Kemp and WaterslS4 also found the oxidations of cyclohexanone and of
mandelic, malonic and a-hydroxyisobutyric acids by Cr(V1) to be Mn(I1)catalysed. In these cases, as with oxalic acid, the [Cr(VI)] versus time plots are
almost linear and the reaction becomes first order in substrate (or involves
Michaelis-Menten kinetics), and, except at lowest catalyst concentrations, approximately first order in [Mn(II)]. Detailed examination of the initial rate of
oxidation of a-hydroxyrobutyric acid as a function of oxidant concentration
revealed, however, that the dependence is
-d[Cr(VI)]/dt
= k[substrate][Mn(II)][HCrO~]*
- d[Cr(VI)]/dt
SPECIES
329
and a-hydroxyisobutyric acids by Cr(V1) are in the ratio 300 : 1, the ratios for
oxidation by the couple and by Mn(II1) are, respectively, 2.9 and 2.3. Furthermore,
the values of k,/k, for oxidation of C-deuteromandelic acid by Cr(VI), Mn(Il1)
and Cr(V1)-Mn(II) respectively are 8.7, 1.1 and approximately 1 .O.
More detailed results on the less strongly-catalysed oxidation of mandelic
acid186a shows that here the catalytic effect depends on the initial [Mn(II)]/
[Cr(VI)] ratio; at ratios less than lo2 Mn(I1) retards reaction. At high ratios the
catalysed reaction is not retarded by a hundred-fold excess of Cr(II1) ions, which is
evidence against the multiple equilibria (32)-(34), and for this substrate the reaction order in substrate is fractional. Step (33) is discounted in a modified reaction
scheme which attributes part of the oxidation to attack by Cr(IV) and Mn(II1)
upon the substrate, the Cr(1V) being formed during initial attack on substrate by
Cr(V1). At low [Mn(II)], the more strongly oxidising Cr(IV) is replaced by
Mn(II1) via reaction (34); at high [Mn(II)], Cr(V1) is reduced by Mn(1I) as well
as by mandelic acid.
Preliminary results have been reported'86b of oxidation of cyclobutanol by
the Cr(V1)-V(IV) couple to 4-hydroxybutyraldehyde. This proceeds at the same
rate as the oxidation of V(IV) by Cr(VI)la6" and cannot involve attack of Cr(V)
upon the alcohol, for this oxidation state is formed in a rapid pre-equilibrium:
but rather attack by Cr(IV), uiz.
Cr(VI)+V(N) f: Cr(V)+V(V)
Cr (V) V( IV)
Cr(IV)+C,H,OH
R.+V(V)
(fast)
+ Cr (IV) +V(V)
(slow)
Cr(III)+R.
(fast)
HOCH,CH,CH,CHO+V(IV)
(fast)
+
--f
The oxidation by chromic acid alone leads to a mixture of cyclobutanone and 4hydroxybutyraldehyde; the existence of an isotope effect for the oxidation of
1-deuteriocyclohexanol suggests that Cr(V1) produces the ketone and lower
oxidation states of chromium produce the cleavage product.
GENERAL FEATURES
The first three members of this series appear at the bottom of the B subgroups
of the periodic groups 4, 3 and 2. They exhibit the so-called "inert-pair'' effect and
normally assume oxidation states of +4, + 2; + 3, + 1 and + 2,O respectively, i.e.
differing by two units. The species Hg', TI2+ and Pb3+ are of high energy and
References pp. 493-SO9
330
co v A L E N T C O M P O U N D S ,
M E T A L I O N S : O X I DA T I O N-RED U C T I O N
Reaction
Pb4+ $ 2
TI3++ 2
2 Hg2++ 2
Hgz2++ 2
Au3++ 2
PtC162-+2
PdZC+ 2
PbZ+
(Yolr)
=2
ca. +1.7
iI.25
+0.920
+0.789
cu. +1.41
e- =
eeeee-
no
= TI+
= HgzZ+
Hg
Auf
= PtC142-+2 CI-
e- = Pd
+0.68
$0.987
Pb(1V) is most usually employed as the tetraacetate and the action of this
compound is complex in that it can function either as a two-equivalent oxidant
giving Pb(I1) or as a source of acetoxy radicals, uiz.
Pb(O.COCH,),
Pb(O.COCH,),*+ CH,C02.
3.2
O X I D A T I O N OF INORGANIC SPECIES
33 1
SPECIES
+5 I-
trans-[Pt(AsEt,)I,] + 4 C1-
+ i;
TABLE I
RATE D A T A FOR T H E O X I D A T I O N O F IODIDE ION BY COMPLEXES O F
Complex
k2
(I.niole-'.sec-')
trans- [ P ~ ( A S E ~ ~ ) ~ C I ~
(0.5
] 10.03) x
trans- [Pt(AsEt&Br4]
1.56k0.04
trans- [Pt(PEt&CI4]
(3.5 &0.15) x
Temperature
("C)
E
(kcalmole- ')
35
25
35
20.1 f 0 . 6
10.6k0.4
16.2k0.4
pt(lV)'93
A.Si(eu)
- 1 1 k3
-25 + 2
- 19.5+2
The authors acknowledge that the present data are insufficient to allow a detailed
mechanism to be given but they reject the possibility of slow S,2 substitution
followed by a rapid redox process.
The oxidation of potassium thiocyanate by AuBr, is first-order in oxidant and
the pH dependence indicates that it is also first-order in thiocyanate ion, which is
oxidised much faster than HCNS19,. The activation parameters are E = 6.4k0.4
kcal.mole-' and AS' = 26+2 eu.
Bi(V) in aqueous perchloric acid is very strongly oxidising but kinetic studies
have been confined to a few stopped-flow measurements on oxidation of iodide,
bromide and chloride ions6 '. The appearance of Bi(II1)-halide complexes was
first-order with respect to Bi(II1) and in all cases the first-order rate coefficient, k,,
was the same, i.e. 161+8 sec-l at 25 "C ([H,Of] = 0.5 M , p = 2 . 0 M ) , irrespective of the nature or concentration of the halide. A preliminary attack on
solvent is compatible with these interesting results, viz.
Bi(V) + H,O
Bi(IV)+XOH*+X-
$ Bi(IV)
+H + +OH.
Bi(III)+X.
OH-+X.
2x. + x,
These authors also cite unpublished work on Sb(V) oxidation of I - which follows
a rate law involving the term [Sb(V)][1-l2.
References pp. 493-509
332
c o v A L E N T c o M P o u N D S,
M E T A L I o N s : o x I D A T I ON-R E D u c T I o N
+ 2 S,O:-
+ S402- + 2 C1-
trans-[Pt(AsEt,),CI,]
TABLE 8
R A T E D A T A F O R T H E O X I D A T I O N O F T H I O S U L P H A T E ION B Y C O M P L E X E S O F
Complex
k2 (l.mole-'.sec-')
r r ~ n s - [ P t ( A s E t ~ ) ~ C l ~ ] 0.86&0.03
(2.6 f 0 . 1 ) ~ 103
tr~ns-[Pt(AsEt~)~Br,]
2.06&0.08
trans- [Pt(PEt3)2C14]
35
25
35
15.5+0.4
9.8+0.5
14.5+0.4
- d[AuBr,]/dt
94
pt(IV)'93
ASt(eir)
--10.5&2
-12 *3
-12 +2
is pH-dependent
k,[HSO;][AuBr,]
3.2.3 Hydrazine
333
SPECIES
N,H,+
Mo(VI)+Mo(IV) + 2 Mo(V)
+ [Mo(V)],
(slow)
(fast)
(fast)
k[Mo(V),]
~
sec-' and E = 23.4k0.2 kcal.mole-'. These
where k (25 "C) = ( 8 . 6 k 0 . 4 ) lo-,
figures are very similar to those reported for oxidation of Mo(V) dimer by iodine
and oxygen (pp. 468 and 450) and suggest a rate-determining first-order dissociation of the dimer to yield a reactive, monomeric Mo(V).
P Pt(en),NO:
lllow
fast
[CIPt(en),
slow
ethylene-
(fast)
. . . C1.. . Pt(en),NOz13+
11 fast
ClPt(en):
Pt(en),Cl+
(en
+ CIPt(en),NO:+
+ Pt(en)2,++CI-
(fast)
334
Mitchell' 96 has shown that mercuric chloride oxidises this substrate to phosphorous acid
H
I
slow
O=P-OH
+ HO-P-OH %
fast
P(OH),
+ M("-')+
H+
335
SPECIES
+ CO -+
[H,O-Hg-CO-OH]+
Hg+Hg+
[HzO-Hg-CO-OH]+
+H +
(Slow)
-+
Hg+ COZ H +
(fast)
-+
Hg;+
(fast)
Pd+COz+2Hf+4Br-
The appearance of COz in the gas phase before precipitation of metal implies the
production of a soluble Pd(0) complex such as [Pd(CO)zBr,]2-. This receives
support from the observation that three times as much CO is consumed as CO,
liberated before deposition of Pd. The following reactions may be involved
PdBri[PdBr,CO]-
336
c o v A L E N T c o M P o u N D S,
M E T A L I o N s : O X I D A T I o N-R E D u c T I o N
(Hg(1) should fall into Class I on this basis but it is regarded as a source of two
oxidising ions per molecule.)
The first kinetic class probably corresponds to heterolysis of the H-H bond,
the second class to homolysis. Hg(I1) falls, with Cu(II), Ag(1) and MnO,, into
Class I and Hg(I), with Ag(1) and the Ag(1)-MnO, couple, into Class 11. The
activation energies for Hg(1) and Hg(I1) are 20.4f0.6 and 18.1 f0.6 kcal.mole-l,
respectively, and the activation entropies are, respectively, - 10.2k2 and
- 12.2+2 eu. The rate-determining steps are believed to be
H g Z + + H 2-+ H g H + + H +
Hg;+
+ H,
2 HgH+
The configuration of the transition state for Class I reactions is seen aszo3
(L = any other ligand). Strong complexing of the mercury atom, e.g. by CI- or
ethylenediamine, reduces the rate by 2 or 3 powers of tenzo4, but this is in any
case a general feature of Hg(I1) oxidations.
PdCIi-, Rh(II1) and Ru(II1) act as homogeneous catalysts for reduction of
The kinetics of all three activation reactions
FeCI, by molecular
fall into Class I. The Arrhenius parameters are
A(I.mole-'.sec-
PdQ2Rh(II1)
Ru(II1)
l)
E(kcal.mole- ')
6.6 x 10"
2.3 x 1015
4.0 x 1014
20
25.2
23.8
3.3
O X I D A T I O N O F M O N O F U N C T I O N A L O R G A N I C MOLECULES
3.3.1 Olefns
These ions, with the exception of Pb(IV), form complexes with olefins and this
process is a preliminary to oxidation when this occurs. A recent reviewZo8of the
action of Pd(I1) covers aspects of structure and bonding as well as kinetics, and
a similar but older, review exists for Hg(II)Z09.The oxidation of olefins by thallic
337
SPECIES
species was discovered only recently and no previous review has included discussion of it.
Acetoxylation at an allylic position2' is the typical reaction of lead tetraacetate
but no kinetic data are available. Product studies favour a heterolytic mechanism2' .
Henry has examined in detail the oxidation of several olefins both by thallic
perchlorate in an aqueous perchloric acid
2 1 3 and by thallic acetate in
aqueous acetic acid214. The reaction displays mixed stoichiometry
'
-d[Tl(III)]/dt = k 2 [TI(III)][olefin]
k 2 increases with increase of acidity but this is a salt effect and the dependence is
really an inverse one with respect to the activity of water. The relative rates in
the two media (but not between the media) are
Ethylene
Propene
1 -Butene
cis-2-Butene
1
1
I67
153
162
157
58
60
Perchloric acid
Acetic acid
trans-2-Butene Isobutene
13.6
35
-200,000
-230,000
The product distribution is also largely unaffected by change of medium. The basic
kinetics in acetic acid are also unchanged but the effect of addition of acetate ions
indicates a linear relationship between k2 and [TI(OAc); ]/[TI(III)]. TI(0Ac); is
regarded as the most significant oxidising entity over a wide range of acetate
concentration although TI(OAc)'+ and TI3+ become important at low acetate
concentrations. The mechanism, which is basically the same for both sets of reaction conditions, is
H20
k2
2*TI-CRlR2-CR3R40H
+ H'
k-2
H'
33 8
c o v A L E NT c o M P o u N D S,
M E T A L I o N s : O X I D A T I o N-R E D u c T I o N
the slow step because the acid-retardation implied by step (38) is not found. Reaction (38) is probably, therefore, the slow step. Several schemes for the breakdown
of the oxythallation adduct are considered to account for the shift of the group
R,, and it is probable that more than one mechanism operate^"^.
The reaction between Hg(1I) and olefins has been examined from several angles
and work prior to 1950 has been summarised by ChattZo9.Several types of complex
and product are formed, depending on the olefin, which involve no change in the
oxidation state of the mercury atom. Propenyl ethers have long been known to
produce the corresponding glycol plus metallic mercury but no kinetics are
available215.
It has been shown recently216that the 1 : 1 complexes between Hg(II) and a
number of olefins are themselves subject to allylic oxidation by Hg(I1) at 80 "C.
Typical stoichiometry is
CH3CH(OH)CHZ.Hg+ + 3 Hg2+ = CH,=CH.CHO-t2 Hgi+ + 3 H t
The kinetics, which involve examination of two species containing Hg(1I) are of
the form
+ d[acraldehyde]
- -
!d14
dt
k,[adduct][Hg2+]
dt
This could be oxidised by a second Hg(I1) species in the slow step, which must involve two molecules containing Hg(I1).
The stoichiometry of the oxidation of ethylene by palladous chloride is
C2H,+PdC12+HzO
CH,CHO+Pd+2 HCI
Products from very many other olefins have been detailed by Smidt et aLZ1'.
All monoolefins with at least one hydrogen atom on each carbon atom of the
339
SPECIES
double bond yield the corresponding ketone, with the carbonyl group appearing
at the carbon atom initially subject to the higher inductive effect. Reaction in
acetic acid produces complex mixtures of compounds including glycol acetates.
Considerable kinetic and other data are available, and are summarised below
for the reaction in aqueous solution.
(i) The kinetics for the oxidation of ethylene, propene and the three butenes
are of the form219-223
+ RCH=CHR +
RCH
_f
PdCl,
1-
+ CI-
k-2
(K2 = k2/k-2)
[PdC12(H20)C2H4] H 2 0
.+ [PdC12(OH)C2H4]- + H 3 0 +
k-3
(K3
[PdC12(OH)C2H4]-
(42)
k3
k,/k-,)
(slow)
(43)
(44)
k-4
CH20H-CH2-PdCl
References pp. 493-509
(45)
340
C O V A L E N T C O M P O U N D S , METAL IONS: O X I D A T I O N - R E D U C T I O N
in agreement with experiment. The slow step (44) corresponds to the transformation of a n-complex into a a-complex, viz.
CI,
CL/
CH\
Pd
OH
H 0
CH2
\ Pd /
CI'
H2\
HO'
CH2
OH2
ClPd
H
I
CH,-C=O
OH2
CIPd-
H30+
with E = 10.4 kcal.mole-'. The agreement with the uncatalysed reactions and
the non-involvement of Cu(1I) concentration supports the catalytic role. The
situation may, however, be more complicated (vide infra).
The oxidation of ethylene by palladous acetate in acetic acid has been examined
by Moiseev et a l.z2 8 -2 3.0This reaction shows mixed stoichiometryZz8
C2H4 PdClz
+ 2 CH3CO;
= CH3COzCH-CHZ +Pd(O)
+CH3C02H
+2
C,H4+PdClz+2 CH3CO;
c1-
(CH3COz)zCHCH3+Pd(O)+2 C1-
k,[Pd(II)][C,H4]
341
SPECIES
One interesting difference between Pd(I1) in aqueous and acetic acid solutions
is that whilst oxidation of C2D4 by aqueous Pd(I1) displays no primary kinetic
isotope effect, the oxidation of CH,-CD-CH, by PdCl, in acetic acid-isooctane
affords aZ3' k,/k, value of 2.8. The products are a mixture of propenyl and
isopropenyl acetates in a 64 : 36 ratio unaffected by deuteration and with isotopic
retention. A hydride-ion shift in the slow step is proposed to account for the
isotope effect. This would be expected to result in a lower yield for labelled
isopropenyl acetate compared with propenyl acetate. Agui16208has commented
that Pd(I1)-catalysed isomerisation of the olefin could account for the isotopic
pattern of the products.
Moiseev et al., who proposed initially232that ethylidene diacetate was produced
from addition of acetic acid to vinyl acetate, later showed this to be impossible
from the result of reaction in CH3C02D,preferring the following mechanism230
+
CH,CO,H
[C~3Pd-CHz-CHzOzCCH3]2-+
H*
1 .
3 C I - + Pdo+CH3-CH-OzCCH3
C
, Hz=CH
-O,CCH,+
H+
(46)
C H3CH02CCH3
\CH,COZH
'(CH3C0z)z
CHCH, + H '
(47)
PdCI,
C,H4+CuCl,+CH3CO;
Palladium metal is not produced in the new reaction and the substitution of a
twenty-fold excess of lithium chloride for cupric chloride prevented reaction;
kinetic data revealed first-order dependences upon both Pd(1I) and Cu(1I). The
distribution of products varied in an unpredictable way with reactant concentrations. The following mechanism was proposed by Henry233(X = C1- or CH,CO;)
+ XPdCH2CH202CCH3 +X-
XPdCHZCH202CCH3 + HPdX
XPdCH2CH202CCH3 + 2 CUX,
+ CH2=CHO,CCH3
342
cov A L E N T co M P O u N DS,
M E T A L I o N S: O X I D A T I o N-R E D u c T I O N
k[Rh(III)][C
H 4]
-2
'""
[a-I
ki
+ Rh(III)Cl,,k-
+Cl-
Rh(lII)CI,-,(C2H4)+H,0
Rh(I)CI,-
-, Rh(I)CI,- I
+CH3CHO+2 H +
(fast)
(fast)
dt
kl k2[Rh(II1)CInICC2H4I
k- I [cl-]fk2[C2H4]
The observed results fit this equation reasonably well, and at 80 "C k , z
sec-', k-,[Cl-]/k, z 0.025 mole.l-' with (for k , ) E = 10.1 kcal.mole-I and
AS' = -46 eu.
3.3.2 Arylcyclopropanes
Thallium(I[I) triacetate oxidatively cleaves phenylcyclopropane and its ringsubstituted analogues in anhydrous acetic
to yield mainly (> 90 %) the
corresponding I -aryl-1 , 3-diacetoxypropane together with a little of the cinnamyl
acetate. The reactions are of the first order in each component provided account
is taken of the double salt formation between TI(I1I) and TI(1) which renders an
additional TI(II1) molecule inactive following the reduction of each TI(II1) in a
two-equivalent process. For phenylcyclopropane E = 13.0k0.2 kcal.mole-' and
AS' = -29.2k0.6 eu. Electron-releasing groups facilitate reaction ( p = -4.3).
By analogy with Hg(I1) acetate which cleaves the ring to yield an organomercurial
compound, the proposed mechanism is
C 6 H 5 u
TI(OAC)~
C6H5
&
Tl(OAc),
fast
C 6 H 5 5 OAc + C 6 H 5 v O A C
+ T lOlc
343
SPECIES
Kinetic studies have been reported only for the oxidations by Hg(I1) and
TI(III), although the oxidation by Pb(IV) is receiving mechanistic study at the
present time.
1-Propanol reacts with lead tetraacetate in boiling benzene solution to give a
complex mixture of products including 1-propylacetate (35 %) and 1,l-dipropoxypropane (10 %)*". The intermediate RCH2CH2-0-Pb(OAc), is considered to
decompose both homolytically and heterolytically on the basis of observed
products, e.g. 2-propanol gives 2 % of isopropyl phenyl ether in benzene solution
and the reaction is subject to catalysis by pyridine. The production of substituted
tetrahydrofurans from long-chain alcohols236 has been reviewed2j7. Triphenyl
methanol gives high yields of hemiketal ester238*2 3 9 ; in general the course of
reaction is
e.g.
X = NO2
X=NOz,
Y=n
X=H.
Y = NO2
+ Ar,C-0-Pb(OAc), + HOAc
+
Ar,C-O. +Pb(OAc),.
+ Ar,t]OAr
+ product
+ Ar3COPb(OAc),
-+ Pb(OAc),
+ product
(slow)
+Ar,CO*
+ Pb(OAc),
344
C O V A L E N T C O M P O U N D S , METAL I O N S : O X I D A TI O N - R ED U C TI O N
3.3.4 Hydroperoxides
Only tert-hydroperoxides have been examined kinetically and discussion will
be restricted to these. The stoichiometry of the lead tetraacetate oxidation is not
straightforward, but the main product is the corresponding t e r t - a l ~ o h oand
l ~ ~one
~
mole of tert-butyl hydroperoxide consumes just over two moles of oxidant245.
The kinetics with this substrate are245
-d[Pb(IV)]/dt
k3 [ P ~ ( I V ) ] [ ~ - B U O O H ] ~
'.
345
Pb(0Ac);- +ROOH
$ Pb(OAc)i-.ROOH
Pb(0Ac); +ROOH
+ [Pb(OAc),.ROOH]
[Pb(OAc),.ROOH]-
+ROOH
-+
R0,.
Pb(OAc)~-.ROOH+ROOH -+ R 0 , .
Added alcohol can replace ROOH in its purely coordinative capacity.
A non-kinetic study of the oxidation of cumyl h y d r ~ p e r o x i d eby
~ ~Pb(1V)
~
to acetophenone and dimethylphenylcarbinol gives useful complementary data.
Kinetics are obtained directly for Hg(II), Hg(1) and TI(III). With Pd(I1) a catalytic
system was
depending on the continuous reoxidation of Pd(0) by a
Cu(II)-02 couple. The inverse acidity dependence could result from a hydrolysis
of the type
TI3++H,O
+ TIOH'' + H +
where only T10H2+is strongly oxidising, but is more probably due to ionisation
of the substrate to the readily oxidised HCO; ;thus
- d[HCO,H]/dt
k,[HCO;][Ox]
The data are summarised in Table 9. At high concentrations of formic acid the
reaction becomes less than first-order in substrate248;this indicates the possibility
of complex-formation, but a medium effect may also be influential in the vicinity
of 1 M formic acid. Complex-formation affects the kinetics of the TI(IrI) oxidation
at all but the lowest reactant concentration^^^^.
References pp. 493-SO9
c o v A L E N T c o M P ou N D S,
346
M E T A L I o N S: OX I D A T I o N-R E D u CTI o N
TABLE 9
SUMMARY OF DATA FOR OXIDATION OF FORMATE 1 0 ~ 2 4 7 . 2 4 9 3
Oxidant
E (kcal.mole-
l)
AS:(eu)
~~~~
Hg2
Hg2
~
1 +3
Pd(I1)
36-61
60-80
65-85
100-1 25
20.6
21.6
26.6
22.7
kHlkD
~
3
0
21
-6
HCO;
K
+ M"+ +
HCO,.M'"-')+
H C O , . M ( ~ - ~ ) + H + + co , + M ( " - ~ ) +
(fast)
(slow)
In the case of TI(III) the overall rate coefficient has been resolved into a product
k K for the two steps247*249. The large positive AS' is due almost entirely to the
initial association, which was also studied spectroscopically. An alternative rate
determining step in the Pd(II) oxidation is hydride ion transfer to Pd(II)249a.
Oxidation of formic acid by mercuric chloride is the subject of several early
kinetic studies. D h a ~ - "showed
~
the reaction to be first-order in oxidant and substrate and to be subject to strong retardation by added chloride ions in agreement
with earlier work. The reaction is also subject to retardation by added acid and
presumably involves formate ion as the principal reactant.
SPECIES
347
AcO-Pb(OAC)p
\
6 7 ,/
ACO.CH,CO;
+ BH+
pb(oAc)z
CHz-CO
3.3.7 Ketones
Pb(IV), Tl(II1) and Hg(1I) attack ketones at rates approximating to the corresponding rate of enolisation
OH
11
-C-CHR-
+ -C=CR-
k[ketone][Pb(IV)]O
Clearly a two-equivalent oxidation of the enol is taking place. Product work has
been summarised by Criegee 53 and in general a-acetoxylation occurs.
Oxidation of cyclohexanone by thallic per~hlorate~has similar kinetics but
includes an acidity dependence of the form (at 25 C, p = 1.3 M )
k
k ( 4 . 8 ~I O - + l l . l
10-[H30+])
The rate of oxidation is, however, considerably slower than the rate of enolisation
as measured by iodination.
References pp. 493-SO9
348
co v A L E N T C O M P O U N D S , M E T A L I O N S:
O X I D A TI ON-RED
u C T IO N
-CH=C-
-CH-C-
Hg+
I1
0
3.3.8 Ethers
The ready oxidation of di-isopropyl ether by Hg(l1) p e r ~ h l o r a t eis~ a~ good
indication that this oxidant can function as a hydride-ion acceptor, uiz.
CH3
Hg2+ H-C-O-CH(CH,),
CH
HgH+ +
--f
Hg22++ H +
CH3
HgH'
+ Hg2+
3'C=(;-CH(CH3)2
CH3/
CH3\
+
,C-O-CH(CH,),
CH3/
+ H 2 0 --*
CH3\
'C=O+ (CH3)zCHOH
CH3/
(slow)
(fast)
(fast)
3.4
SPECIES
349
O X I D A T I O N OF P O L Y F U N C T I O N A L MOLECULES
3.4.1 Glycols
Lead tetraacetate is an important reagent for glycol cleavage, which has the
stoichiometry
RZC-OH
1
RZC-OH
+ Pb(OAc),
2 RzC-O+ P b ( 0 A ~ ) z 2 HOAC
It can be used both in polar and non-polar solvents and complements the Malaprade oxidation with periodate, with which it has been compared and contrasted256.
Much has been published on the mechanism of its action, particularly on the
stereochemical aspects of its reactivity, and only a summary of the main features
can be presented.
The rate equation for the oxidation of ethylene glycol in acetic acid isz5'
-d[Pb(lV)]/dt
k,[Pb(IV)][glycol]
with k, = 1.95 x 1014 exp(-20.9 x 103/RT) I.mole-'sec-'. This has been confirmed for a series of glycols by Cordner and PausackerZ5*,who also showed that
electron-releasing substituents accelerate oxidation of benzpinacols while electronwithdrawing groups retard it.
Acidification with trichloracetic acid catalyses oxidationz59 , the fractional increase in the rate coefficient per mole of acid added, uiz. (Ak/k,)/[acid], being
of the order of two. Strong catalysis by alkali metal acetates has been observed for
several oxidations, e.g. of cis-cyclohexane-1,2-diolz60.formic acidz6', methyl
mannoside and galactoside261 and several a-hydroxycarboxylic acidsz6'.
Retardation by acetic acid itself, which reduces the oxidation rate of transcyclohexane-l:2-diol by three orders of magnitudez6', suggests the existence of
a pre-equilibrium
RZC-OH
I
+Pb(OAc),
RZC-OH
RzC-O-Pb(OAc),
I
RZC-OH
+ HOAc
Changing the reaction medium from acetic acid to water does not reduce the
efficiency of the oxidant263and, indeed, gradual dilution of an acetic acid medium
with water, methanol or benzene increases the rates of oxidation of several glycols
of factors of 500 to 1000 (ref. 260). This effect raises the question of whether the
catalysis by trichloracetic acid (uide supra) is solely an effect of acidity.
The main discussion of mechanism has been centred around the stereochemical
specificity of the fission, particularly with respect to the role of cyclic intermediates
References p p . 493-SO9
350
R2C - O H
Pb(OAC),
+ Pb(OAc),
HOAC
R2C-OH
R2C - O H
It
R2C- 0
'PbiOAlc)p
R2C--0
HOAC
(48)
Criegee et ~ 1 . have
' ~ ~ measured the oxidation rates of a series of cyclic 1 :2-diols.
For up to seven-membered rings the cis form is more reactive than the trans,
k,i,/kr,ons reaching lo3 for cyclopentane-l:2-diol but falling to 22 for cyclohexane-1 :%-dial and becoming less than one for nine-membered and larger rings.
Racemic forms of the diols R-CH(0H)-CH(0H)-R are oxidised 20-40 times
faster than the meso forms265. However, dihydrophenanthrene-9,lO-diols(l)
'
T A B L E 10
SECOND-ORDER
(20-c)
RATE COEFFICIENTS
SYMMETRlCA L
9, IO-DI S U B ST1.T U T E D
---
~~~
h,,,
~~
~-
~~
~-
BY
R
~
Ph(1V)
D I H Y D R O P H E N A N T H RENE-9,10-D 10LS265
ktron,
-~~
(I.rnole-'.sec -')
_ _ ~ ~
I30
192
1310
24.7
32.4
OF
351
diol cholestane-3/?,6/?,7~-triol(III)
is immeasurably slow at 50 C.
HO
(Ill)
are oxidised at least 6 x lo4 times faster than the pair (VI) and (VII)
It is clear then that more than one mechanism is operative for glycol fission.
In the case of cis-cyclopentanediols and camphanediols a cyclic ester is a necessary intermediate. For trans-decalin-9,lO-diol a non-cyclic mechanism must
operate which cannot function for cholestane-3/?,6/?,7cc-trioland is inefficient for
trans-camphanediols. It is pertinent that while the fission of glycols capable
of forming cyclic esters proceeds several hundred times faster in benzene than in
acetic acid, the reactions of trans-decalin-9,lO-diol and trans-hydrindane-l,6-diol
are 4-5-fold slower in benzene265.
A solution of lead tetraacetate in pyridine rapidly oxidises the most recalcitrant
trans-diols, especially if a considerable excess of oxidant (3-4 moles) is used,
implying yet a further mechanism for the action of this versatile oxidantz7,.
The normal oxidation, i.e. that of cis-diols, occurs by an oxidative breakdown of the cyclic complex, viz.
352
C O V A L E N T C O M P O U N D S , M E T A L IONS: OXIDATION-REDUCTION
A few rate coefficients for oxidation by lead tetraacetate have been reported.
These, together with those for some carbohydrates, are referred to in the section
on glycols (p. 349).
The oxidation of oxalic acid by mercuric chloride to give CO, and mercurous
chloride is a classic example of an induced reaction. This reaction is extremely
slow unless small quantities of chromic acid and manganous ions are added,
whereon facile reduction takes place7, 2 7 3 . Addition of permanganate or persulphate and some reducing agents is also effective and the oxidation proceeds
readily under photo- or X-irradiation (Eders reaction). The large quantum
yield points to a chain mechanism274,which could also function with an inducing
oxidant, uiz.
+ (CO,H),
.C02 + HgCI,
-+
-+
CO,
HgC1.+(CO2H),
--+
Hg+C1-+C02-+C02+2 H+
Oxidant
+ HgCl. + C1-
The oxidation of oxalic acid by AuC1,- represents one of the few examples of
a kinetic
of Au(II1) oxidation falling within the present category, uiz.
AuCI;
A slow, second stage leads to metallic gold. The rate law was determined, under
conditions unfavourable to hydrolysis of chloraurate ion, to be
-d[Au(lII)]/dt
k[H,C,04][A~C1,]/{([H30+]/K)+ l}
k,[HC204-][A~Cl,]
Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 353
+ H 2 0 + [AuCI,OH]- + C1- + H +
the reaction becomes faster. k, for the reaction between the hydroxotrichlorogold(111) ion and HC204- is 0.9f0.1 I.mole-'.sec-'
at 20 "C (1.1 = 0.15 M), the
Arrhenius expression being k, = 1 x 10" exp(- 13.5 x 103/RT)I.mole-'.sec-'.
This represents a further example of the greater reactivity of a hydroxo-ion as
compared with its fully aquated or chlorinated counterpart.
and Pu(VI)
4.1
I N O R G A N I C C H E M I S T R Y O F T H E S E O X I D A T I O N STATES
Complex
Medium
Ag2++ e - = Ag+
Co3++e-
= CoZ+
Ce4++ e -
Mn3++e-
Ce3+
Mn2+
HCI
1 MHC1
no (Volr)
1.970
1.927
1.842
1.70
1.61
1.44
1.28
1.56
1.51
1.U4"
1.017
1.oo
1.15
0.93
354
C O V A L E N T C 0 M P 0 U N D S, MET A L I O N S : 0 X I D A TI 0 N-R E D U C TI 0 N
M ~ M i l l a has
n~~
reviewed
~
the chemistry of Ag(I1) and Ag(II1). Paramagnetism
and electron spin resonance studies confirm the presence of Ag(l1) (as opposed
to equimolar Ag(I)+Ag(III)). The colours of Ag(I1) solutions in various mineral
acids indicate the existence of complexes, the oxidising power of which is apparent
from their decomposition even at 0 "C, although high acidity promotes stability.
Rapid isotope exchange277between Ag(1) and Ag(I1) is considered to result from
the equilibrium
2 Ag(I1)
+ Ag(1) +Ag(I1I)
Both Ag(1I) and Ag(I1I) have been considered to be the active species in the
Ag(1)-catalysed oxidation of many compounds by persulphate ion. Salts of
Ag(II1) have been prepared but only a single kinetic study (of the decomposition
of water by the ethylene dibiguanide nitrate) has been reported (p. 366).
Oxidations by persulphate ion have been reviewed by
Silver-ion
catalysed reactions normally obey the rate expression
-d[S,O;-]/dt
k,[S,O;-][Ag(I)][red~ctant]~
[Ag(I)] is, of course, unchanged during reaction. For reducing agents which are
positive ions, all values of k2 fall in a narrow range, particularly after correction
for ionic ~trength"~.k , for reductants bearing zero or negative charge is up to
lo2 times greater and varies over a much wider range. Within a given class of
organic substrate, e . g . alcohol, a-hydroxy acid, variations in k2 are
Several mechanisms have been put forward which are consistent with the
kinetics
(A)
(B)
Ag++S20i-
s20;- + 2 .so;
2 -SO; +Ag+
(C)
(slow)
+ A g 3 + + 2 SO:-
Ag++S20i-
(fast)
(slow)
+ AgS20,
(slow)
-+
A g S 2 0 i + Ag3++ 2 SO:or
AgS20,
+ SO:-
+ Ag2+
+*SO,
(fast)
(fast)
The species A g S 2 0 i may represent only a transition state and not a reactive intermediate.
References to the numerous substrates which have been oxidised by
Ag+-S,Oi- are given by House. Additional data have been reported more re-
4 Ag(II), Ag(lII), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 355
. Since all the oxidations follow the same basic kinetics and involve
an oxidising metal ion in trace quantities, the details are not reiterated here.
The simple oxidation of Ag(I) by persulphate is discussed on p. 475.
4.1.2 Cobalt (ZZZ)
The chemistry of Co(II1) in dilute aqueous acidic solution is complicated by
( i ) oxidation of the solvent, (ii) complex formation with counter-ions, (iii) hydrolysis and ( i v ) apparently extensive dimerisation. These phenomena are discussed
further in the section on oxidation of water.
4.1.3 Ceriurn(1V)
The redox potential and the reactivity of this oxidation state depend strongly
upon the anion (Table 11). Strong complexes are formed279ewith SO:-. Even in
perchloric acid, hydrolysis and polymerisation greatly complicate kinetics. The
co-ordination number of Ce(1V) in solution is not e ~ t a b l i s h e d ' ~ ~ .
4.Z.4 Manganese(ZZ1)
This oxidation state is stable only when complexed by anions, e.g. PO:-, or in
moderately acidic solutions. Perchloric acid solutions of Mn(II1) perchlorate have
been prepared2"; these are fairly stable, although the omnipresent equilibrium
2 Mn(I11)
+ Mn(II)+ Mn(1V)
MnOH2++ H 3 0 +
356
cov A L E N T co M P O U N DS,
M ETAL IONS:
ox I DA T I ON-R
E D uCTION
4.1.6 Iridium(IV) as IrC1:This oxidant, which has been utilised only recently284, is almost substitutioninert, and any reaction proceeding via substitution would be expected to have an
activation energy of the order of 30 kcal.mole-'. Those oxidations which have
been examined have much lower activation energies. The reduction product is
IrCIi- which is also solvolysed slowly.
4.2
O X I D A T I O N OF I N O R G A N I C SPECIES
- d [Ce(IV)]/dt
= k[Ce(IV)]f[H,O+]f'[CI-]
The chloride ion dependence indicates the participation of several chloro-complexes of Ce(1V); the acid catalysis was ascribed to the suppression of the hydrolysis
Ce( H20):
+ Ce(H20)"-
OH3
+H '
Study of the Co(I11) oxidation of C1- has been restricted to observation of the
CoCI2+ intermediate complex and measurement of it5 formation rate7 704.
0 3 9
= [ce(rv)l
~
[so:-]
{k3[Br-]2+k,[Br-]}
Ag(II), Ag(IJI), Co(III), Ce(IV), Mn(IIl), V(V), Ir(IV), Np(VI), Pu(V1) 357
The dominant species of Ce(IV) existing under the reaction conditions is Ce(S04): and the activated complexes for the two paths must have compositions Ce(S04)2
Bri- and Ce(S04)2Br-. The latter path is subject to chloride-ion catalysis of the
form k,,,,, = k, +k'[CI-] which suggests a n activated complex Ce(S0,)2CIBr22-.
Slow oxidative breakdown of the complexes containing bromide gives Ce(II1)
and Br atoms or .Br;. The latter go on to form molecular bromine; however,
their presence has been detected in this reaction from their ability to add to butadiene to form dibromo~ctadienes~~'.
A stopped-flow examination of the Co(II1) perchlorate oxidation produced
kinetics6 7 3
- d [Co(III)]
dt
[Co(III)] [Br- ]( k,
-+
Co(II)+Br.
CoOH2++Br-
--t
Co(II)+Br-
- d [Mn (I I I)] /d t =
k [Mn (I I1 )] [Br - ]
-d[Mn(III)]/dt
k,[Mn(llI)][Br-]
The stoichiometry A[Mn(III)] : A[Br-] : A[Br2] is 2 : 2 : 1 and induced polymerisation indicates the intermediacy of bromine atoms or radical ions, viz.
Route (1)
Mn(III)+BrMn( 1II)Br-
+ Br-
Mn(III)+.Br;
Route (2)
Mn(II1)Br2 Br.
References p p . 493-509
+ Mn(II1)Br-
+ .Br;
(fast)
-+
Mn(I1)
(slow)
-+
Mn(II)+Br,
(fast)
-+
Mn(lI)+ Br-
(slow)
-+
Br,
358
CO V A L E N T C 0 M P 0 U N D S , M ETA L I 0 N S : O X I D A T I 0 N-R E D U C T 1 0 N
Both reaction paths are acid-catalysed and are subject to retardation by specific
ions probably by removal of free Br-. The second-order dependence with respect
to reductant has several precedents, e.g. Fe(II1) oxidation of 1- and Mn(I1I)
oxidation of HN,. The acid catalysis results from suppression of the hydrolysis
to MnOH2+ which is ineffective in this oxidation.
Strongly acidic vanadium(V) oxidises bromide in a sulphate ion medium289.
The reaction is first-order in both oxidant and sulphuric acid. The dependence
of the rate on bromide ion concentration is complex and a maximum is exhibited
at certain acidities. A more satisfactory examination is that of Julian and Waters290
who employed a perchlorate ion medium and controlled the ionic strength. They
used several organic substrates which acted as captors for bromine radical species.
The rate of reduction of V(V) is independent of the substrate employed and almost
independent of substrate concentration. At a given acidity the kinetics are
- d[V(V)]/dt = k[V(V)] [Br-
l3[substrate]'
The rate depends on the square of the acidity function ha at constant ionic strength
(5 MI.
A mechanism based on multiple pre-equilibria was proposed
+ V(OH):+
V(OH):+ +Br- + V(OH),Br+
V(OH),Br++H+ + V ( O H ) 2 B r 2 + + H 2 0
VO: + H 3 0 +
V(OH),Br2+ +Bri.e.
[V(OH),Br;]
e V(OH),Br;
Kl
K2
K,
K4
K , K 2 K, K4[VO:][Br-]2[H+]'
V(IV)(OH),Br+ +.Br;
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 359
eliminates the induction period, thus
k[V(V)][I-][H30+]2
360
c o v A LE N T c OM P o u N D S,
M E T A L I o N S : O X I D A T I o N-R E D u c T I o N
- d [Co(III)]/dt
k' [Co(III)][HN, ]
k'
'
+ HN,
+ Co(III)HN,
2Co(I1) + .H,N6+
(slow)
(fast)
Co(III)+*H,N~ Co(II)+3 N 2 + 2 H +
The kinetics and mechanism bear some resemblance to those reported by the same
workers for the Mn(ll1) oxidation of HN, ; Co(II1) may be in a dimeric form.
This apparent duality of mechanism has been reinvestigated carefully by one of
the groups involved697 , using experimental conditions very similar to those employed by the other (Wells and
and a sharp discrepancy is revealed
both as regards the rate law and activation energy. A further stopped-flow investigati01-1~~'
supports the results of Sullivan et al.296b'6 9 7 .
Mn(II1) in perchloric acid forms a pink complex with hydrazoic acid, which
decomposes thermallyz97to give nitrogen with stoichiometry A[Mn(IlI)]/A[HN,]
= 1.0 and with kinetics
-d[Mn(III)]/dt
k,b,[Mn(III)][HN,]2
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 361
kobsincreases with acidity. The following mechanism was suggested
Mn3++H,0
ki
$
MnOHZ++H+
(fast) K,
(49)
(fast) K ,
(50)
(slow)
(51)
(fast)
(52)
k-1
Mn3++HN3
MnHN33
+ HN,
kz
+
MnHN,,'
+ Mn(11)+ -HzN6+
k-z
k3
kq
Mn3++.H,N6+ + Mn(II)+3 N 2 + 2 H +
The rate of disappearance of total Mn(II1) is given by
-d[Mn(III)]
dt
- 2k3 Kz[Mn(III)][HN3]2
1+( k l /[H 'I)
+ kdHN31
Mn3+ HN,
-+MnN3'+ + H +
- k[Mn(III)]2[HN3]2f'[H30+~
dt
f [Mn(II)l
+N;
+ [Mn(III).EDTA.N,12- + H,O
362
COVALENT
C O M P O U N DMSE, T A L I O NS:O X I D A T I O N - R E D U C T I O N
4.2.5 Bromine
The oxidation to bromate by Co(II1) perchlorate
96a,
viz.
Br2+10Co(III)+6 H 2 0 = 2 BrO;+lOCo(II)+12
H+
- d[Co(lII)]/dr
k[C0(lI1)][Br,]/[H,0+]~
Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(1V). Np(VI), Pu(V1) 363
N4HS2+(or N,H:++NHl)+2
Mn(II)+2 H + (or H + )
4 Mn(1II) CH,N,H:
= CH3NH2N=NNH2CH:++4 Mn(II)+4 H'
2 Mn(III)+2 N,N-(CH,),N,H:
=
(CH3),NHNHNHNH(CH3)$++2 Mn(II)+2 H +
2 Mn(III)+2(CH3),N,Hl
=
(CH3),NHN(CH,)N(CH,)NH(CH3)$+ + 2 Mn(II)+2 H+
2 H , 0 + 2 Mn(III)+2(CH3),N2H:
=
(CH,),NHN(CH,)N(CH,)NH(CH,)$+
+ 2 Mn(lI)+2 H + + 2 CH,OH
have been determined298b in acid perchlorate media. All reactions are simple
first-order in both oxidant and hydrazine but the second order rate coefficients
are acid-dependent, normally decreasing with increasing [HC104] except for
tetramethylhydrazine when an increase is found. All the hydrazines are almost
entirely monoprotonated under the reaction conditions and the reactions are
viewed as the combined attacks of Mn3+ and MnOH2+ upon the protonated base,
BH:, viz.
Substitution of a value of 0.93 for the hydrolysis constant of Mn3+ (as) yields the
individual values for k, and k ; at 25 "C (accuracy L- 10 %) below.
References p p . 493-509
364
c O V A L E N T c o M P o u N D s, M E T A L I o N s: O X I D A T I ON-R
Substrate
10-
kl ( h o l e - '.set- I)
E D u c TI o N
I)
10.3
3.0
4.0
0.73
0.43
0.03
As is quite often the case, the hydrolysed form of the oxidant is more reactive
than the hexa-aquo species. The stoichiometries suggest dimerisation, rather than
secondary oxidation, is the normal fate of the hydrazoyl radical. The variations in
k , and k ; suggest oxidation occurs at the non-protonated nitrogen atom.
NH30H+
NH30CH3'
HNOz
( 1 . 4 k O . l ) ~lo3
< 0.5
(2.2$0.2) x 104
MnOHz
The mechanisms of all three oxidations involve initial slow one-equivalent oxidation
to a radical (NH,O., .NHOCH, and NO,.) followed either by rapid secondary
oxidation (of NH,O. or NO,.) or by radical dimerisation (.NHOCH3).
Ce(1V) sulphate oxidation of N H 3 0 H f shows a stoichiometry depending on
the relative initial concentrations, but at low [Ce(IV)]/[NH,OH+ 1, the conditions
for kinetic experiments, a value of 1.0 is realised for A[Ce(tV)]/A[NH30H+]298d.
The reaction orders with respect to oxidant and substrate are both one but k, is
reduced by addition of sulphate ions, indicating Ce(SO,),'-,
the dominant
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(1V). Np(VI), Pu(V1) 365
species present, to be less reactive than Ce(S04)2. An inner-sphere oxidation to
NH,O. is proposed, the radical then dimerises (at low [Ce(IV)]) or is oxidised
by Ce(1V) to HNO which decomposes to NzO. E, = 14.8 kcal.mole-' and
ASf = -7eu.
The rate expression for the oxidation of water by silver(I1) perchlorate is299s3 0 0
with E = 11.Ok2.0 kcal.mole-'. The inverse dependence upon Ag(1) concentration indicates a rapid pre-equilibrium
+ Ago'
+2 H+
Ag+ ++0,
at [Ag(II)] >
366
COVALENT
(B)
at [Ag(II)] <
C O M P O U N DMSE, T A L I O N S O: X I D A T I O N - R E D U C T I O N
which holds for both perchlorate and sulphate ion media. In a perchlorate medium
+ (CO-O-CO)~++H,O
and that the slow oxidation step involves both dimer and monomer, uiz.
CoOH2++(CO-O-CO)~+ + 3 C o 2 ++HO,*
followed by a fast reduction by H02., uiz.
+ O2
367
H+
Co3+ H 2 0 + CoOH"
( C O - O - C O ) ~+~2 H 2 0 $ (HOCO-O-COOH)~++ 2 H +
Spectroscopic support exists both for hydrolytic equilibria of this kind3''*
and for the presence, especially at high oxidant concentrations, of a further
species, probably of a polynuclear type3I2. The most convincing support for the
dimer theory, however, comes from the elegant study of Anbar and Pecht3I3
who used '80-labelled Co(1II) to oxidise H2160, making the due correction for
ligand exchange in this substitution-inert complex. Anbar and Pecht conclude
that nearly all the oxygen evolved originates from the inner sphere of Co(II1)
and not from the solvent. It is concluded that the oxygen is formed from binuclear
complexes
4+
H
H z O ~ 4 C0~ < ~ ~ C d O H z ~ 4 ]
Very little hydrogen peroxide was found as a product (by isotope dilution
analysis), and it was ruled out as an intermediate by addition of '80-labelled
H 2 0 2 before reaction.
A preliminary account of the kinetics of the oxidation of hydrogen peroxide
by Ag(I1) nitrate in 3 M H N 0 3 has appeared3I4,the rate law being
where k = 1 . 0 10''
~ exp( -26.0 x 103/RT) 1.mole-'.sec-'.
Spectrophotometric
examination revealed rapid reversible complex formation, e.g.
Co(III)+Hz02
References p p . 493-509
+ [CO(III)-HOZ-]~++H+
368
cov A L E N T co M P O U N DS.
M E T A L I o NS: O X I DA T I ON-R E Du c T I O N
If a dimer of Co(I1I) is present then two one-equivalent oxidations of H0,can occur synchronously to give Hf and 0, ; otherwise HO,. is an intermediate.
The reaction between isothiocyanatopentaminecobalt(II1) and hydrogen
peroxide has been studied k i n e t i ~ a l l y ~Although
~'.
Co2+ (aq) is formed as one of
numerous products, the overall reaction is essentially an oxidation of ligand by
the pcroxide. The reaction is first-order in both oxidant and reductant although
there is a complex acidity dependence.
The Ce(IV) sulphate oxidation has a s t o i ~ h i o m e t r y ~ ' ~
2 Ce(IV)+ H,O,
2 C e ( l I I ) + 0 , + 2 Hi
Ce(IV)+H,O,
kT,
Ce(III)+HO,*+H'
Ce(lV)+HO,*
2Ce(III)+O,+H+
When [Cc(IIt)] >> [Ce(IV)] or [Ce(IV)] > H,O, the expression is simplified and
tests using various concentrations of oxidant and peroxide confirmed both the
simple laws. k , was found to be lo6 I.mole-'.sec-' at 25.0 "C. ESR flow studies
confirm the presence of HO,. in the reaction318o3 1 9 .
The rate of oxidation with Ce(lV) perchlorate depends on the method of preparation3,'. The material from certain preparations gives a deep red complex,
containing two equivalents of Ce(IV) to one molecule of H , 0 2 , which decomposes
in second order fashion-presumably by means of two concerted one-equivalent
oxidations of the substrate. Other preparations give no complex and decompose
peroxide much faster. The difference is thought to lie in the degree of association
of the oxidant (cf. the Ce(1V) oxidation of iodide ion, p. 359).
Oscilloscope traces obtained on mixing Ce(IV) perchlorate and H 2 0 2 in a
stopped-flow apparatus reveal an initial build-up of absorption at 350 nm complete
within a few msec, suggesting formation of a complex, followed by a first-order
decay almost complete within 20 msec and independent of initial [Ce(IV)],
[H,0,] and [ H 3 0 + ]and of added Ce(II1); at 25 "C k, = (2.8f0.2) x 10, sec-'
and a similar value is found over a temperature range of 1 8 4 3 "C implying
E = 0. Breakdown of a Ce(1V)-peroxide complex to HO,. followed by oxidation
of H 0 2 *to 0, is proposed6".
M n O H 2 + + H , 0 2 k ~Mn2+
1
+HOz.+H20
4
M n O H 2 + + . H 2 O 2 +2 M n 2 + + H 3 0 + + 0 2
M n 3 + + - H 2 0 2 + M n 2 + + 2H + + 0 2
H 2 0 2 + . H 2 0 2 +% O H . + H 3 0 + + 0 2
Mn2++ O H .
2 Mn(IIl)+ OH-
370
where k = 5.5 x 10' 12.mole-2.sec-1 at p = 3.5 M and 25.0 "C. This provides
a contrast to other Ag(1I) oxidations mentioned in this review which involve
Ag(IL1). The simplest mechanism consistent with the kinetics is
+H +
(fast)
(slow)
(fast)
- d [Co(IIL)]/dt
k3 is considered to relate to the active form of the neutral acid (p. 334) and k,
to the predominant form. k3 is much smaller than the value reported for halogenation of the active form. Further details are available in the original thesis.
The analogous work with Ce(lV) perchlorate has been reported by Carroll and
Thomas326.The rate expression is complex, uiz.
"=3
-d[Ce(IV)]/dr
= k[H,0']'~-[Ce(H,P02),'4-")+]
n=l
Ag(ll), Ag(lll), Co(lII), Ce(lV), Mn(lll), V(V), Ir(lV), Np(VI), Pii(V1) 371
+ Ce(S0,),(H3P02)
+ Ce(S0,)32- + H 3 0 +
K
K'
and for the overall reaction E = 17.2 kcal.mole-'. The mechanism is presumably
the same as for Ce(IV) perchlorate, involving
+ Ce(III)+
Ce(SO,),(H,PO,)
radical
(slow)
Again, therefore, the Mitchell type of mechanism (p. 334) is not operating.
4.2.12 Arsenious acid
The Ce(IV) oxidation of arsenite has been examined in various acids for which
the sequence of rates is HCIO, > H N 0 3 > H,S0,328. The kinetics are simple
second order. E in HC10, is 9.55 kcal.mole-'. The chief kinetic interest in this
reaction is, however, centred on its remarkable acceleration on addition of minute quantities of iodine3,', R U ( I V ) ~ ~ ' ,Ru(V1)
~~'
or O S ( V I I I I ) ~3~3 3~. * The
kinetics are complicated and although catalysis is not the subject of this review, the
above references have been included.
The V(V) sulphate oxidation of a r ~ e n i t shows
e ~ ~ ~an interesting second-order
dependence on oxidant concentration, the rate expression being
+d[V(IV)]/dt
~[As(III)][V(V)]~~[H~O+]
The reaction is catalysed by adding phosphoric acid. Presumably two V(V) entities are bound to the arsenite in the transition state and effect concerted oneequivalent oxidations to avoid formation of the energetic As(IV).
4.2.13 Antimony(ZZZ)
dt
References p p . 493-509
+ CeSO,,+ + H +
+ Ce(SO,), + H +
+ Ce(S0,):- + H +
+ CeS04Cl+
(Kl)
(K21
(K3)
(K4)
1-2 M H2S04
372
COVALENT
C O M P O U N DMSE, T A L
IONS: OXIDATION-REDUCTION
where at 25 "C, K , = 3.5 x lo3, K , = 2.0 x 10, and K 3 = 20 (ref. 278e). CeSO,CI+
is regarded as the active species in the oxidation but Ce(S0,);- is predominant
under these conditions, hence
== [Ce(IV)][H+]/K, K3[HSOJ2
[CeSO,"]
and
~~
i.e. k' = k K 4 / K 2K3 and K ' = K , . A chloride ion bridge mechanism is favoured
for the electron transfer to give Ce(II1) and labile Sb(1V). Composite Arrhenius
0.
parameters were found to be E = 16.0 kcal.mole-', AS'
In a perchlorate medium the kinetics are found to be676
where k , and k , refer to oxidation by CeOH3+ and Ce(OH),,+ and are 35 and
300 I.mole-'.sec-' respectively at 25 "C ( p = 2 M ) and K , is the second hydrolysis constant of Ce4+, i.e. to Ce(OH),'+. Also E, = 19.7 kcal.mole-', AS: =
7.2eu, E , = 9.6 kcal.mole-' and AS: = -27.6eu. The rate-acidity profile
shows a maximum at 0.15 M acid, a phenomenon related to hydrolysis of HSb0,
to SbO'. Strong catalysis by halide ions is considered to favour a mechanism of
atom-transfer rather than of electron-transfer.
4.3
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 373
The one-equivalent oxidation of an organic molecule should yield a free radical
or radical-cation. Direct or indirect evidence for the intermediacy of these species
has been obtained in certain cases.
4.3.1 Alkanes
The slow oxidation of cyclohexane by Co(II1) is mentioned in the following
section.
+H+
C O ( H ~ O ) ~ ~CO(OH)(H,O),~+
+
with the hydroxopentaaquo complex deemed the reactive species.
The following outer-sphere oxidation mechanism is favoured over the radicalcation formation which is a feature of similar oxidations by Mn(II1) acetate
(p. 375). With toluene
C6H5-CH2
9H O - Cfo i( m )
(H,O),
CgH5CH,*
CO(H$)l+
This is consistent with the observed products of oxidation, i.e. benzyl alcohol,
benzaldehyde and benzoic acid and with the observed oxidation of cyclohexane.
Radical-cations are, however, probably formed in oxidation of napthalene and
anthracene. The increase of oxidation rate with acetonitrile concentration was
i n t e ~ r e t e din~terms
~ ~ of a more reactive complex between Co(I1I) and CH3CN.
The production of substituted benzophenones at high CH,CN concentration indicates the participation of a second route of oxidation.
At 15 "C (70 % CH3CN, 0.77 M H + , p = 0.9 M ) k2 for the Co(1II) oxidation
of toluene is 4 x
I.mole-'.sec-', E = 28.0 kcal.mole-' and AS' = 24 eu.
References pp. 493-SO9
374
C O V A L L N T COMPOUNDS, METAL
IONS: O X I D A T I O N - R E D U C T I O N
-d[Co(III)]/dt
~[A~H][CO(II~)]~/[CO(II)]
4.3.3 Olefins
375
RCH-CH2
+ C O ( H ~ O ) ~ ~RcH-CH2
+
+ Co(I1)
-+
The products formed are a complex mixture, but it appears that initially the double
bond is split to give aldehydes which suffer subsequent oxidation. Glycol formation
may precede C-C fission.
Addition of a Co(II1) sulphate solution in sulphuric acid to an olefin dissolved
in acetic acid results in reduction of Co(II1) at a rate commensurate with that
observed for aqueous solution and with identical kinetics341. Prior treatment of
the Co(II1) solution with acetic acid, however, causes the rate of reduction of
Co(I1I) to become almost independent of olefin concentration. Evidently a
Co(II1)-acetate complex is formed in the mixture of acids which oxidises only
after a rate-determining dissociation. However, this complex cannot be formed
instantly, and uncomplexed Co(II1) can attack olefins in acetic acid in a manner
similar to that in water.
4.3.4 Benzene
The oxidation by Co(II1) is first-order in oxidant and in
the acidity dependence has the form
343
and
k 2 = k'+k"/[H+]
where k' = 1.8 x 10'' exp( - 19.0 x 103/RT)I.mole-'.sec-' and k" = 8.7 x lo'*
exp( -29.0 x 103/RT) 12.mole-2.sec-'. The products were identified spectroscopically to be p-benzoquinone and muconic acid. The oxidation presumably
involves the production of phenyl radicals, viz.
376
C 0 V A L E N T C 0 M P 0 U N D S , M ETA L I 0 N S : 0 X I D A TI ON-RE D U C T I 0 N
4.3.5 Alcohols
All the oxidants convert primary and secondary alcohols to aldehydes and
ketones respectively, albeit with a great range of velocities. Co(1II) attacks even
tertiary alcohols readily but the other oxidants generally require the presence of
a hydrogen atom on the hydroxylated carbon atom. Spectroscopic evidence indicates the formation of complexes between oxidant and substrate in some instances
and this is supported by the frequence occurrence of Michaelis-Menten kinetics.
Carbon-carbon bond fission occurs in certain cases.
It has been demonstrated spectroscopically that Ce(IV)344,3 4 5 and V(V)346
perchlorates and Ce(IV) nitrate346aform complexes with alcohols of composition
[ROHCe(IV)I4+ and [ROH-V(OH)3]2+.The agreement between the determined
formation constant and the Michaelis-Menten constant for Ce(IV) oxidation is
good evidence for the role of these complexes in the oxidation process. The
oxidations by C O ( I I I ) ~and
~ ' V(V)346perchlorates have kinetics
- d [Co(III)]/dt =
- d[V(V)]/dt
k [ROH][Co(III)]{a+ b/ho}
k [ROH] [V(V)][H,O+]
k k'[Ox] [R OH]
~
+K[ROH~
4 Ag(II), Ag(lII), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 377
The other main piece of kinetic evidence concerns the primary kinetic isotope
effect. 1-Deutero alcohols are oxidised more slowly than the corresponding protio
compounds in all cases, the values of k,/k, being: C O ( I I I ) ~ ~ '1.72
,
(10 "C);
Ce(IV) ~ u l p h a t e ~ ~1.9
' , (50 "C); Mn(I1I) perchlorate3", 3.0 (25 "C); Mn(II1)
~ u l p h a t e ' ~ ' ,1.6 (50 "C); V(V) ~ u l p h a t e 4.5
~ ~ ~(50
, "C); V(V) p e r ~ h l o r a t e ~ ~ ~ ,
3.6 (50 "C). These imply rate-determining C-H cleavage, although the significantly low values of k,/k, probably originate in the geometry of the transition
state.
These data have been interpreted3 5 2 as favouring the following general mechanism
:slow)
H
I ox
(fast)
L is a ligand which may be further H,O and the oxidant will have gained a proton
in the case of V(V), or lost one in the case of Co(II1).
The very fast oxidation of the radical precludes its detection and identification
by ESR; however, reacting mixtures are capable of initiating polymerisation of
a~rylonitrile~
The
~ ~ .oxidations of allylic alcohols by V(V) perchlorate are ca.
thirty times faster than those of saturated
This is supporting evidence
for radical intermediates in view of the expected delocalisation of the free electron
This type of fission has been observed in a detailed examination of the oxidation
of tertiary alcohols by C O ( I I I ) ~ ~The
' . kinetics are similar to those reported for
cyclohexanol (vide supra) although the rate is about 40 times less. The possibility
of alkoxyl radical formation seems attractive, for Co(II1) is known to oxidise
References p p . 493-509
378
COVALEN
water at an appreciable rate, unlike the other oxidants which are also inert towards
tertiary alcohols (although it has recently been found that Ce(1V) perchlorate
oxidises t e r t - b ~ t a n o l ~The
~ ~ ) radical
.
R,R,R,C-O. would then undergo rapid
fission to give the mixture of ketones found e ~ p e r i r n e n t a l l y ~Replacement
~~.
of
one or more methyl groups of tert-butanol by higher alkyl groups results in a
30-40 fold increase in the rate ~oefficient~~,
which is more readily explained in
terms of a synchronous decomposition of the incipient alkoxyl radical (cf. the
V(V) oxidation of a-tert-butylbenzyl alcohol) than a subsequent breakdown.
Product studies show (i) that the ease of elimination of R,. from R,R,R3COH
depends on the relative stabilities of R,., R,. and R,. and (ii) that R,. can be
eliminated from R,R,HCOH, i.e. that secondary alcohols can undergo a measure
of C-C fission via an alkoxyl radical. The extent of C-C fission increases when
R,R,DCOH is employed, but the k,/k, values for several alcohols do not accord
with the observed products358. This paradox has been discussed at length359.
4.3.7 Hydroperoxides
Cobaltic acetate oxidises tert-butyl hydroperoxide to a mixture of tert-butanol,
di-tert-butyl peroxide and oxygen with essentially second-order kinetics360. The
reaction does not involve 0-0 fission, the mechanism suggested being
Co(III)+ROOH + Co(II)+ROz*+H+
2 RO,. + ROOR+ 0,
RO,-+ROOH +. R O - + R O H + O ,
RO.+ROOH + ROH+RO,*
RO. + Co(I1) -+ RO- + Co(II1)
Simple second-order kinetics have also been found for the Co(lr1) sulphate
oxidation of the hydroperoxide of 2-methyl-but-2-ene in aqueous solution, although the reaction also shows both acid-inverse and acid-independent routes361.
Co(II1) in aqueous sulphuric acid oxidises tert-butyl hydroperoxide with kinetics
-d[Co(II[)]/dt
= ~[ROOH][CO(III)]/[H~O+]
It is not clear whether the inverse acidity dependence stems from ionisation of
ROOH or from hydrolysis of Co3+ aq.
4.3.7 Aldehydes
These comprise two classes, namely enolising and non-enolising. The former
can undergo oxidation in either or both tautomeric forms; the latter exist partly
or, in some cases, wholly as gem-diols.
Ag(ll), Ag(III), Co(lll), Ce(lV), Mn(III), V(V), Ir(lV), Np(VI), Pu(V1) 379
k , [substrate]{ [V(V)][H30+l+k2[V(V)12(H30f12}
The second term relates to the simultaneous reduction of two V(V) species by the
aldehyde, possibly via the mechanism
RCH(OH)? + V(OH):*
F=X?
RCHOH
( f ast 1
HO -V(OH):+
+ V(0H):'
R CH OH
P d -V(OH):*
OH
H 0-
$-
--V(OH):+
(fast)
-V(OH):+
OH
R \ (0
-H
H290
-H
H;;\-r? ,2
O
,H
R-CH
\OH
_c
"vO
+
2V(IV)
(slow)
\OH
0H
OH
The oxidation of formaldehyde by V(V) has an isotope effect of ca 4.5 which accords with the depicted C-H ~leavage'~'.
The Co(II1) perchlorate oxidation of substituted and unsubstituted benzaldehydes has kinetics and a low isotope effect (2.3 at 10 "C) in complete analogy
with cyclohexanol and formaldehyde367. Ring-substitution by electronegative
groups accelerates reaction.
Two studies of the Ce(IV) perchlorate oxidation of benzaldehyde in aqueous
acetic acid have been reported363.364, 364a . The rate law is of the form
+k' [ArCH0I2)
380
cov A L E N T
o X I D A T I ON-REDU C T IO N
and is the same as the rate of bromination and iodination under the same conditions. Evidently acid-catalysed enolisation is rate-determining, uiz.
CH3
H,O+
'CH-CH-o
CH3\
C-CH-OH
(slow)
CH3
CH3'
Propionaldehyde and n-butyraldehyde are oxidised more slowly then they enolise
and the rate expressions are368
- d[V( V)]/dt =
The acidity dependences are not simple. V(V) is thought to form a complex with
the enol which undergoes slow oxidative breakdown. Propionaldehyde and nbutyraldehyde are, however, oxidised by Mn(II1) pyrophosphate with a zeroorder dependence on oxidant c ~ n c e n t r a t i o n ~but
~ first-order dependences on
substrate and H 3 0 + concentrations. Here oxidation immediately follows enol
formation. Ce(IV) sulphate oxidises acetaldehyde at a rate much faster than
enoIisation3'O.
4.3.8 Ketones
These exist in several tautomeric forms, if the carbonyl group is flanked by two
different a-CH bonds, uiz.
RICHzCCH2R2
II
+ R,CH=C-CH2R, + R,CH2C=CHR,
I
OH
OH
Discussion of ketone oxidation has centred around the identity of the molecule
undergoing oxidation. This has been clearly resolved in some, but not all, cases,
the evidence resting on (i), the relative rates of enolisation and oxidation, (ii)
kinetic orders and (iii)isotope effects. A general feature ofthe oxidations of ketones
by one-equivalent reagents is that the rate for a given oxidant exceeds that for
oxidation of a secondary alcohol by the same oxidant. The most attractive explanation is that the radical formed from a ketone is stabilised by delocalisation,
uiz.
RcH-C-R
11
c,
RCH=C-R
I
0.
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 381
T A B L E 12
KINETIC
DATA
Oxidant
Rnte expression
kdkv
6.0 (1 1 "C)
kD20/kn20
ReJ
311,312
188,313
314
310, 312, 375
312, 714
316
311
312,317
318
more effectively than the radical from an alcohol. This situation is reversed for
two-equivalent oxidants, e.g. chromic acid.
Kinetic data exist for all these o ~ i d a n t s ~and
~ l some
- ~ ~ are
~ given in Table 12.
The important features are: ( i ) Ce(1V) perchlorate forms 1 : 1 complexes with
ketones with spectroscopically determined formation constants in good agreement with kinetic values373;(ii) only Co(I1I) fails to give an appreciable primary
kinetic isotope effect371*3 7 2 (Ir(J.V) has yet to be examined in this respect); (iii)
the acidity dependence for Co(J.11) oxidation is characteristic of the oxidant371.3 7 2
and (iu) in some cases [ C O ( I I I ) ~3 7~2 ,~Ce(IV)
*
p e r ~ h l o r a t e Mn(II1)
~~~, ~ u l p h a t e ~ ~ ~ ]
the rate of disappearance of ketone considerably exceeds the corresponding rate
of enolisation; however, with Mn(I1I) p y r ~ p h o s p h a t eand
~ ~ Ir(IV)378
~
the rates
of the two processes are identical and with Ce(IV) sulphate and V(V)372the rate of
enolisation of ketone exceeds its rate of oxidation. (The opposite has been stated
for Ce(IV) ~ u l p h a t e ~but
~ ' , this was based on an erroneous value for k(eno1isation)
for c y c l ~ h e x a n o n e ~The
~ ~ . )oxidation of acetophenone by Mn(II1) acetate in
acetic acid is a crucial step in the Mn(I1)-catalysed autoxidation of this substrate.
The rate of autoxidation equals that of enolisation, determined by isotopic exchange37', under these conditions, and evidently Mn(I1I) attacks the enolic form.
Products detected or isolated from these oxidations include the corresponding
a-hydroxy ketone and a-diketone and also adipic acid (from cyclohexanone) in
up to 95 % yield. However, IrCI6'- gives a-chloroketone in quantitative yield378.
Evidently when the rate of oxidation exceeds enolisation attack is on the keto
form, probably via a complex, although this is definite only for Ce(IV) perchlorate,
to give a radical, e.g.
References p p . 493-509
382
covA L E N T c o M P O u N DS,
M E T A L I O N S: O X I D A T ] ON-R E D u c T I o s
This is in accordance with the primary kinetic isotope effect for Mn(ll1) ~ u l p h a t e ~ ~ .
With Co(I1I) electron abstraction may occur to give a radical-cation which suffers further oxidation. The alternative explanation of the lack of an isotope effect
is that formation of the Co(1II)-ketone complex is rate-determining; this lacks,
however, other kinetic support3.
The mode of oxidation by Mn(II1) p y r ~ p h o s p h a t ealso
~ ~ seems
~
clear cut from
(i) the agreement between oxidation and enolisation rates for cyclohexanone and
(ii) the tendency for the rate to become independent of Mn(1II) concentration
at high concentrations. Several other ketones, however, were oxidised rather
more slowly than they e n ~ l i s e d ~ ~ ~ .
Preliminary results on the anaerobic oxidation of cyclohexanone by IrC162suggest that, although enolisation is rate-determining at pH 3 (when the oxidation
rate is equivalent to the enolisation rate and the reaction is zero-order in oxidant
but first order in acidity), the subsequent reaction of the radical is one of ligandcapture378,viz.
Evidence for (56) includes the almost quantitative formation of chlorocyclohexanone and the production of 50 % of the Ir(II1) in the form of [IrCI,0H2]2-.
At pH 1 an acid-independent reaction predominates with the rate parameters,
E = 16.4 kcal.mole- and ASt = -12.6 eu. [IrCI,OH,]- also oxidises cyclohexanone by an acid-independent path, with E = 16.6 kcal.mole- and ASt =
-7.3 eu.
The oxidations of 2-chloro- and 2-hydroxycyclohexanone by IrCIi - show the
same general kinetic behaviour, indicating prior enolisation, and analogous
products, i.e. dichlorocyclohexanone and IrCI,0H2- from chlorocyclohexanone
(ref. 699).
The main mechanistic difficulty involves Ce(IV) sulphate and V(V), which
attack ketones at rates less than those of enolisation. The kinetics and relative
oxidation rates are of little assistance in discriminating between attack on keto
and enol forms. However, the solvent isotope effects in these oxidations are in
strict accord with the measured acidity-dependences: if attack had occurred on the
enol then the change of solvent should have enhanced the expected kD20/kH20
by a
factor of 2.5, because Keno,
is favoured to such a n extent in D 2 0 as compared
and attack is, therefore, on the keto
with H,O. No such enhancement is
Ag(II), Ag(III), Co(lll), Ce(lV), Mn(III), V(V), Ir(lV), Np(VI), Pu(V1j 383
form in both cases, in contrast to the oxidation by Cr(V1) for which similar
considerations lead to the opposite conclusion. (p. 314).
4.3.9 Ethers
-+
(CH3),c0Pri + Co(1I) + H +
-+
(CH,),CO
(slow)
+Pr'.
Pr'.+Co(III)aq
-+
Pr'OH+Co(II)+H+
(CH,),cOPr'+ Co(I1I)aq
-+
(CH,),CO +Pr'OH
+ Co(II)+ H+
The oxidation step may be of an inner sphere type, and the first two steps may be
concerted. Some acetone is produced in a path not involving consumption of
Co(lI1) and a short chain reaction may participate, including the step
Pr'.+Pr'OPr'
-+
Me,~OPr'+C,H,
Co(II1) -+ CICH,cHOCH,CH,Cl+
+ Co(1II)aq
-+
+ ClCH,CH,-
CICH,CH,OH+Co(II)+ H +
Co(lI)+ Hf
384
k,K[Co(III)][KCO,H]
w+1+
K[RCO,Hl)
Similar kinetics are given by phenylacetic acid, but with isobutyric and pivalic
acids the rates are given by the simple expression k, [Co(IIl)] [RCO,H]/[H+ I.
The oxidation of C,H5CD,C02H proceeds at 8 0 % of the rate of the protio
compound. The relative rates of oxidation of a series of acids of formula RC0,H
at 10 C" are
R
Kk,(HCIO,)
C2H5
0.0034
(CH3)2CH
0.33
(CH3)3C
0.68
C6H5CHZ
1.25
(fast)
(slow)
R.+Co3+ + R + + C o 2 +
(fast)
R f + H 2 0 + ROH+H+
(fast)
Cup) Co(1II)
CU(II)+Co(l1)
Fig. 3. Electron spin resonance spectrum of ethyl radical generated during photolysis of an
aqueous acidic solution of Ce(IV) and propionic acid at 77 "C. The scale at lower right-handside = 50 G .
References pp. 493-509
386
c o v A L E N T c o M P O u N D S,
M E TA L I
o N S: O X I D A T I o N-R
E D ucT I
oN
meter. The appropriate alkyl radical was obtained in each case; the production
of C2H5.from propionic acid is illustrated (Fig. 3).
Kinetics for Ce(IV) perchlorate oxidation of acetic acid in HC104 media at
50-60 "C approximate to first-order in both oxidant and substrate and a plot of
k; versus [H,O+]-' is linear7". A complex was identified (A,,
286 nm) and
more detailed examination of the substrate dependence revealed MichaelisMenten kinetics. At 50 "C and unit acidity, k , for oxidation of several acids was
determined,
CICHZCOZH
Substrate mid
CHjCOzH
I .26
0.71
C Z H S C O ~ H(CH-,)ZCHC02H
3.26
17.5
-+
Mn(O,CCH,),
+ CH,CO,.
-&-M
0
~(OAC)~
H?9
CH-C
2 \
OH
CH3CO-0
Mn(OAc)p
.CH -C
0
//
\
OH
The oxidations of formic acid by CO(III)'~',3 8 2 and V(V),', are straightforward, being first-order with respect to both oxidant and substrate and acidinverse and slightly acid-catalysed respectively. The primary kinetic isotope effects
(25 "C)forCo(III) and 4.1 (61.5 C") for V(V). The low value for Co(1II)
are
is analogous to those for Co(II1) oxidations of secondary alcohols, formaldehyde
for the Co(TI1) oxidation is
and m-nitrobenzaldehyde (vide supra). kDZ0/kHz0
about 1.O, which is curiously high for an acid-inverse reaction3',. The mechanisms
clearly parallel those for oxidation of alcohols (p. 376) where R, and R, become
doubly bonded oxygen.
The oxidation by Mn(II1) sulphate shows remarkable kinetics366,viz.
387
- kK[Mn(III)][HCO,H]
1 K[HC02H]
+ (1 +k'K'[Mn(III)]3[HC02H]
K'[HC0,H])[Mn(II)]'.25
The first term is analogous to the rate expression for the Mn(I1t) oxidation of
cyclohexanol (vide supra) and displays a primary isotope effect of similar magnitude
(2.2 at 50 "C). The second term shows an isotope effect of 4.3 for replacement of
~ Hg(1)"'
~ ~ *in-~
HC0,H by DC0,H. The oxidations of malonic a ~ i d and
volve [Mn(I1I)l2/[Mn(lI)] terms and these are readily explained by the equilibrium
2 Mn(II1)
+ Mn(IV)+ Mn(I1)
and attack of the two-equivalent oxidant Mn(1V) upon the substrate. The formic
acid oxidation probably involves concerted attack of Mn(lI1) and Mn(lV), viz.
+ Mn(lV)"+
HC0,H
Mn(1lI)
&
HCO,
-Mn(lV)("-')'
+ H'
Mn(I1) + H*
CO,
Mn(Il1)
4.4
O X I D A T I O N O F P O L Y F U N C T I O N A L O R G A N I C MOLECULES
3SS
C O V A L E N T C O M PO U N D S , M E T A L I O N S : 0 X I D A T I 0 N-R E D U C T I O N
4.4.2 Glycols
The oxidations of these by Ce(IV), Mn(II1) and V(V) have been studied ext e n ~ i v e I y ~ ' ' - ~Kinetic
~ ~ . data are summarised in Table 13. The main tasks are
those of ( i ) discriminating between C-C cleavage and oxidation of ;CHOH
groups to > C - 0 and (ii) assessing the role of cyclic complexes.
1 : 1 complexing affects the kinetics in several cases and with Ce(1V) perchlorate
and nitrate oxidations, K(kinetic) equals K (spectroscopic). Some evidence exists
for higher complexes, which break down less easily than the 1 : 1 complex390.
The cleavage of pinacol to acetone in good yield in all cases is clear evidence
for C-C fission, and polyhydric alcohols yield formic acid as the end product.
Isolation of 2-hydroxycarbonyl compounds from reaction mixtures is difficult
because of their much greater case of oxidation once formed, and evidence for
the oxidation of >CHOH to >C-0 is mainly kinetic. k,/k, for the Ce(IV)
sulphate oxidation of butane-2 : 3-diol to (mainly) acetaldehyde is too low
(1.17)390 to be of diagnostic value. However, the V(V) oxidation of this substrate
has a higher isotope effect (2.7) which indicates considerable, if not, preponderant,
C-H as opposed to C-C, cleavage390.
The acidity dependences of V(V) oxidations are significant. That of p i n a ~ o l ~ ~ ~ ,
which undergoes 100 % C-C cleavage, is (a+bh,). The first (acid-independent)
term is rare in V(V) oxidations and implies that VO,' is the active oxidant; the
second term implies, on the basis of the Zucker-Hammett hypothesis, that the
transition state has the structure ( B ) , the mechanism being
- H~o+.)~ + H ~ G *
389
T A B L E 13
KINETICS O F T H E O X I D A T I O N S OF G L Y C O L S
Oxidant
Ce(IV) (HC lo4)
Glycol ( G )
2,3-butanediol
Ce(IV) (H C 10,)
pinacol
Mn(1II)(H,PO4)
Mn(III)(H,P04)
1.18
pinacol
pinacol monomethyl ether
pinacol
ethylene glycol
butane-2 : 3-diol
pinacol monomethyl ether
1.35
state, viz.
and with that of pinacol monomethyl ether which cannot form a cyclic ester like
( A ) and also shows an [H,O+] dependence394, the transition state being
References p p . 493-SO9
OH
393
393
394
394
390
390
390
390
390
co v A L E N T c OM P o u N D S, M E T A L I o N S: o X I D A T I o N-R
E D uc T I oN
Thus the acidity dependence of V(V) oxidations gives some guidance as to the
mode ot fission; chelation followed by C-C cleavage is associated either with zeroorder or an ho-dependence and C-H cleavage with a [H,O+] dependence.
Ditertiary glycols fall into the former category and disecondary into the latter3.
Steric effects in ditertiary glycol oxidation indicate that a cyclic ester is a neces1 : 2-diols are oxidised
sary intermediate, for example 1,2-dimethyIcyclohexaneat one-hundredth the rate of pinac01~~.
Evidence concerning the relative extents of C-C and C-H fission is less well
defined for Ce(1V) and Mn(II1) as compared with V(V). Pinacol is cleaved to
acetone in all cases, but while Mn(II1) pyrophosphate [like V(V)] oxidises pinacol
much faster than butane-2 : 3-dio1, the rate ratio with Ce(1V) is only approximately
3 and the production of acetaldehyde from butane-2 : 3-diol by Ce(IV) oxidation
demonstrates C-C cleavage390. It is probable, therefore, that Mn(II1) oxidises
the disecondary glycol by C-H fission.
Relative rate studies395of cyclic cis- and trans-1 : 2-diols give no clear pattern
of results. Cis-cyclohexane-1 : 2-diol is oxidised by V(V) faster than the trans
isomer, but the reverse is found for the isomers of 1 : 2-dimethylcyclohexane1 : 2-diol.
4.4.3 Unsaturated aldehydes
- d[Mn(Ill)]/dt
+ H
H+ HO-CH2-CH=CH-OH
HO-CHp-CHZCH-OH
slow
Mn(lI1)
fast
HOCH2. CHOH.CH(OH)2
glyceraldehyde hydrate
4 Ag(II), Ag(IlI), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 391
is unlikely per se and cannot account for the comparable oxidation of a-methylacraldehyde.
Benzaldehyde and related compounds are dealt with under aldehydes (p. 379).
/c
,c-c
I\
(CH3),C0
CHJ
CH3C0
VO;
OH
"+'
392
Acetoin consumes 4 equivalents of V(V) to produce some biacetyl via C-H fission;
however, this cleavage is not accompanied by a hydronium-ion concentration
dependence of the rate thereby differing from a secondary alcohol oxidation.
The mechanism of breakdown of the complex is depicted as follows
CH3C0 CO CH3
It is noteworthy that while V(V) attacks a-hydroxy ketones faster than unsubstituted ketones by two orders of magnitude377,Mn(1l'I) pyrophosphate oxidises
a-hydroxycyclohexanone more slowly than cy c l~ h e x a n o n e ~ ' ~ .
OH
+H30+
O=C-0'
o=c
O
'H
-0
The existence of a transient complex between malic acid (HA) and Co(II1)
has been demonstrated optically (Amax 275 nm)398,
ki
+ Co.HA3+
COOH,++HA + C O O H . H A ~ +
Co3++ H A
k-I
ki
Kl
K,
k-2
/OH
/ O.
R CH
'C02H
\ C02H
II
/OH
RCH
\co;
Ill
./OH
RCH
+co2
1v
4 Ag(ll), Ag(lll), Co(lll), Ce(lV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 393
T A B L E 14
KINETIC D A T A FOR THE OXIDATION OF U-HYDROXY ACIDS
Oxidant
Subsfrate
Co(II1)
mandelic acid
k[Co~III)][substrate]
(at low substrate concentration only)
Co(II1)
rnalic acid
k { [Co3+substrate]
+k[CoOHZ+substrate]{(a+b/[H+])
k[Ce(lV)] [substrate]
{I + K [HSOa-] +K[HSO4-I2}
Ce(IV)
(sulphate) glycollic acid
rnandelic acid
Rate law
E (kcalmole- )
1153*10
(k)
25.1 f1.0 (k)
10.1k0.8
AS+c)
Ref.
188
15.752 (k)
398
-42.1 + 2
k[Ce(IV)] [substrate]
399
400
[HzS04I2
Ce(1V)
(sulphate) lactic acid
Ce(1V)
(sulphate) benzilic acid
k K [Ce(IV)] [substrate]
- ~(1 + K [substrate])[H+ I z
k [Ce(IV)][substrate]
~
[HzS04I2
(+)-tartaric acid
k[Mn(III)] [substrate]
dl-malic acid
rneso-tartaric acid (1 + K [substrate])f[Mn(II)]
rnandelic acid
k p ( V ) ] [substrate](a+ bho)
dl-malic acid
latic acid
a-hydroxyk[V(V)] [substrate][H,O+]
isobutyric
k(V(V)] [substrate]f[H,O + I
acid
(Plot of k-versus [ H 3 0 + ] -
linear with intercept)
As for V(V)(HC104)
a-hydroxyisobutyric acid
22.8
3.1
40 1
22.3
-8.14
402
403
394
21.8
22.0
- 2.8
23.0
1.5
-1.0
Radical I can be ruled out because it would be oxidised to a a-keto acid which
would be rapidly further oxidised to R C 0 2 H ; in fact the stoichiometry for V(V)
oxidation is 2 V(V) : 1 molecule substrate in all cases and the major product is
always RCHO (or R , R 2 C 0 from R,R,C(OH)CO,H). These data, are, however,
compatible with the production of radicals n-IV and discrimination can be made
only with the aid of kinetics.
Krishna and Tewari400 favour I1 in Ce(1V) oxidation; Waters et ~ 1 . 394
~ ~prefer
C-C fission to give IV for both V(V) and Mn(II1). Kemp and WaterslS6 have
established two main features of these oxidations, namely, (i) k,/k, for the oxidations of C6H,CD(OH)C0,H and the light compound are: V(V), 2.0; Mn(II1)
sulphate, 1.2; Ce(IV) sulphate, 1.1; and (ii), that the trend of rates of oxidation
of mandelic, a-hydroxyisobutyric, lactic and glycollic acids is as expected for
Ce(1V) and Mn(II1) if stabilisation of the radical R c H O H is important, but is
altered for V(V) (Fig. 4). It appears from the latter observations that the presence
of a-hydrogen atoms causes a drop in rate by a factor of almost 10 per a-hydrogen
References pp. 493-SO9
404
404a
404a
394
\
\
\
C6H5
R' H
CH3
CH 3
CH3
H
H
H
for Mn(II1) oxidation, the drop is less marked with Ce(IV) and is reversed for
V(V). The isotope effects reveal that C-H breakage is of some importance in the
V(V) oxidation, but much less significant for the other oxidants; indeed, at 35 "C
the oxidation of benzilic acid by Ce(1V) sulphate is about 9 times faster than that
of mandelic acid402.
One anomaly is the [H,O+] dependence found for the V(V) oxidation of ahydroxyisobutyric acid to acetone404, because the C-H fission normally associated
with such an acidity dependence cannot occur. This dependence has been disputed
in a recent r e - e ~ a m i n a t i o n ~ ' ~ ~ .
4.4.7 a-Mercaptocarboxylic acids
4 Ag(II), Ag(III), Co(lII), Ce(lV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 395
with the kinetic parameters, [H,O+] = 0.512 Mgiven below (k, at 23.4 "C)
thiomalic acid
k Z (I.mole-'.sec-')
E (kcal.mole-')
ASt(eu)
thioylycollic acid
1.15~
thiolactic acid
7 . 0 4 lo-*
~
7.9
-27k4
1.6
-3Ok4
4.12~
lo-*
6.8
-3113
.
. -~
~-
VO:.RSH
VO:-RSH+RSH
hi
+
VOl*RSH
k-
K,
5 VO~++RS.+OH-
2V(III)+RSSR+2 OH-
CH3COzH+2 Mn(1I)+CO2+2 H +
396
cov A L E N T
C O M P O u N DS, M E T A L I O N s: O X I D A T I O N - R E D
u CTION
f H+l
f[Mn(II)]
The retardation by Mn(1I) is only 18 % at most. The mechanism proposed involves acetyl radicals and does not incorporate enolisation, uiz.
CH,-C=O
CH3-?=0
+ Mn(l1)
co,
The lack of exchange between C-labelled oxalate i n solution and bound oxalate
rules out the existence of free .C,O, in this reaction. The same intermediate is
thought to participate i n isotopic Co(11)-Co(1ll) exchange in oxalate solution407.
Themostrecentstudy76indicatesthatbothCo(C,O4),(H2O)~andCo(C,04):decompose by the dissociation of on end of the chelate to give an intermediate (I)
capable of attacking a second molecule of complex to give Co2+ and CO, without
participation of free radical intermediates, oiz.
Co(C,O,),(H,O)i
kt
+I
k-1
2 2 Co2++2C02+3C20:-
I+Co(C204),(H20)~
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(lV), Np(VI), Pu(V1) 397
which on integration gives
In[Co(III)]- (k- ,/k2)/[C0(111)j
-2k,1 +constant
concentration^^'^.
The oxidation by Mn(II1) chloride involves three complexes and the kinetic
data of Taube413*414are summarised in Table 15. The greater thermal stability
of the tris-complex is considered to result from the lowering of the free energy
relative to the transition state as compared with bis- and mono-complexes. The
study of MnCZ0,+ was based on the Mn(II1)-catalysed chlorine oxidation of
oxalic acid414.
One study has been made with a chelate complex, trans-l,2-diaminocyclohexanet e t r a a ~ e a t o ma n g a n a t e( I I I ) ~which
~ ~ , is either pentadentate or hexadentate, a
water molecule occupying the sixth or seventh coordination position respectively,
and hence chelation of the oxalate is very unlikely. The reaction is first-order both
in oxidant and oxalate and is retarded by increase of acidity. The HC204- ion
is, therefore, attacked more slowly than the C204'- ion but both forms are
oxidised as follows
Mn(chelate)- + HCz04Mn(chelate)- + .C204-
Mn(che1ate)'+ Mn(che1ate)'-+
+ H + + .Cz04+ 2 COz
T A B L E 15
DECOMPOSITION OF MANGANIOXALATES
~.
Mn(C2 04) +
k , (sec-') at 25.2 "C
E (kcalmole-')
A (sec- ')
ReJ'Prencesp p . 493-509
0.197
18.3k0.5
2 xi014
Mn(C2O4)2 -
Mn( C2 04)s3 -
7.7 x 10-4
3.4 x 10-4
22.2+0.5
xi014
398
cov A L E N T c o M P o u N D S ,
M E T A L I o N S: O X I D A TIo N-R E D u c T I o N
E (kcal.mole-)
(eu)
HC204-
21.5h0.2
+ 3.5h0.7
CZO4-
16.6f0.4
-13.0h1.3
The V(V) oxidation has some interesting kinetic features. The dependence of
rate upon acidity shows a sharp minimum in the region of 3 M3348416
, and the
early determinations of Bobtelsky and G l a ~ n e showing
r ~ ~ ~ second- and firstorder dependence upon oxalic acid and V(V) concentration, respectively, have
been confirmed416for conditions of low acidity (1 M ) . At high acidity (> 4 M )
the kinetics revert to a normal form, uiz.
-d[V(V)]/dt
k[V(V)][oxalic acid][H,O+]
At low acidity a complex is formed417 between oxalic acid and the feeble oxidant
VOz +,uiz.
/O - C O
+~
HO\ + ,O
2 ~ 2 0 4
HO&COO/
-CO
+H~O
0-CO
and slow decomposition of the V(V)Ox, complex would produce the unusual
kinetics. At lower acidities ionisation of this complex produces an uncharged
complex in which the oxidising power of V(V) would be greatly reduced. However, combination with a third molecule of oxalic acid produces the complex
H02C.C0.0,
+/
0-CO
I
-02c.coo/ \o-co
which retains a positively charged V(V) centre and can undergo internal oxidationreduction.
The oxidation by V(V) is also subject to strong catalysis by Mn(II)418. The
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(lV), Np(VI), Pu(V1) 399
kinetics are changed to
- d[V(V)]
dt
- kK,[V(V)][oxalic acid]
1 + K,[oxalic acid]
+ V(IV)+ Mn(III)C,O,+.aq
[H,O+I
Admixture of the reactants caused the pink colour of NpO:' to change to yellow,
suggesting complex formation, and one mole of oxalic acid consumed four moles
of oxidant to give Np(V) as the final product, identified optically. k is independent
of ionic strength and is 0.012+0.001 sec-' at 25 "C ( p = 1 M ) with E = 15.5
kcal.mole- '. Breakdown of an oxalatoneptunium(V1) complex of low formation
constant is presumably the mechanism.
--t
OHC.C02H + HCO,H
420
400
T A B L E 16
KINETICS OF OXIDATION OF MALONIC ACID
Oxidant
E (kcal.mole-)
AS(eu)
Ref.
419
9.2h0.4
11.5~t0.5
-38.6*1.2
-31.4k1.0
420
420
16.1 1 0 . 5
-
-16.5kl.O
-
420
188
385
3 84
19.7
383
kK [Co(III)] [substrate]
1 + K [substrate]
Co(II1)
Ce(IV) perchlorate
Ce(lV) nitrate
Ce(IV) sulphate
Ce(1V) sulphate
k [Ce(IV) J [substratelo
f [H30+1
13.2+ 1.O
The kinetics are straightforward only in the case of Co(II1) oxidation, which
involves slow breakdown of a malonato
viz.
HO 9
-co(lll)
\
CO(I1)
\
0
H20
c-c=o
H
C0,H
CO,H
Oxidative decarboxylation, after the manner of RCOzH (vide supra), is ruled out
because the product, glycollic acid, is only slowly oxidised by Mn(II1) pyrophosphate yet all equivalents of Mn(II1) are consumed rapidly384.
Sengupta and A d i t ~ a find
~ ~ the usual reactivity sequence for Ce(IV) salts,
uiz. C104- > NO3- >>
but note that plots of log (Ce(lV)] versus time
are linear even when equal molar concentrations of Ce(IV) and malonic acid are
taken. This implies a first-order dependence on [Ce(IV)] and zero-order dependence
on malonic acid concentration. Kemp188, however, has found a clear first-order
dependence on malonic acid concentration for the Ce(IV) sulphate oxidation,
using a n excess of reductant and making a four-fold variation in reductant concentration. Moreover, consumption of Ce(lV) was intermediate between first- and
second-order. Further work is needed to resolve this discrepancy.
Waters et al. have found the remarkable kinetics for the Mn(1II) oxidation in
both H,P04 (ref. 384) and H,S04 (ref. 385) media, which implies a mechanism
dependent upon the nature of Mn(II1) rather than a mere one-equivalent oxidation,
for Mn(lI1) pyrophosphate and sulphate have very different redox potentials of
1.15 (ref. 421) and 1.51 (ref. 19), respectively. An original mechanism384 for
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 401
the pyrophosphate oxidation depends on a reversible equilibrium (ignoring inorganic ligands), uiz.
Mn(III)+CH,(CO,H),
+ CH,(CO,H),.Mn(III)
(fast) (57)
CH2(C02H)2.Mn(III)s~~CH(C02H),
slow
+ Mn(I1)
Mn(III)+-CH(CO,H),+H,O
+ H+
(58)
Mn(II)+HO.CH(CO,H),
+ H + (slow)
(59)
This has the attraction of explaining other characteristic features of this reaction,
namely: (i) the sensitivity to oxygen of the rate and course of reaction (because
of capture of 0, by -CH(CO,H),), (ii) acceleration by added acrylonitrile to
produce a carboxyl group-containing polymer, and (iii) powerful induced oxidations by the reaction mixture of molecules inert to Mn(II1) pyrophosphate, e.g.
ethanol, diethyl ether.
The latter effect is presumed to result from oxidation by CH(CO,H),. Of
relevance also are the kinetics of the Mn(II1) pyrophosphate oxidation of ethyland benzylmalonic
the order in Mn(1II) is approximately one, no
retardation by Mn(I1) is found and induced oxidations do not occur. This has
been explained in terms of a lowering by R of the redox potential of RC(C0,H)
to a value insufficient to reoxidise Mn(I1) pyrophosphate in reaction (58).
The free-radical scheme, however, fails to account for the following: ( i ) It
cannot be easily generalised to cover the identical kinetics of the Mn(lI1) sulphate
oxidation; if CH(COZH) has an oxidation potential comparable with Mn(IIl)/
Mn(I1) pyrophosphate then it cannot appreciably reoxidise Mn(l1) sulphate,
(ii) If *CH(C02H)reoxidises Mn(I1) sulphate then it should be capable of reoxidising both V(1V) sulphate (of the V(V)/V(IV) pair, potential 1.0 v ) and
Mn(I1) sulphate in the V(V) oxidation of malonic acid; that it does neither can be
seen from the rate laws of these oxidations which show no Mn(I1)-retardation
(vide infra). (iii) The not dissimilar kinetics of the Mn(II1) sulphate oxidation of
formic acid (vide supra) and mercurous ionz8.
Waters et al.385s422 have overcome these objections, whilst preserving the
principal feature of the oxidising radical mechanism, by proposing formation
of a malonato Mn(1V) complex stabilised by extensive delocalisation, uiz.
M n (111 ) + CH2(C0,H )2
==CH2(CO2Hh. Mn (11I
(fast)
0-c
Mn(lV$*
//
CH-Mn(III)
\o-c@
0
<O-c\.
0-c
,o - c0
CH
CH -Mn(IlI)+
-c,
0.
(fast)
402
c ov A L E N T coM P ou N D S ,
M E T A L I o N S : O X I D A T I o N-R E D u c T I O N
The second of the resonance structures is the source of the radical reactivity
displayed during oxidation and the Mn(II1) in this structure must be low-spin to
preserve multiplicity. Substitution at the meso-position could provide steric
hindrance to analogous decompositions and reactions of the Mn(IV) complexes
of ethyl- and benzylmalonic acids, and a conventional one-equivalent oxidation
step becomes dominant.
The V(V) oxidation383is about lo' and lo3 times slower than those by Mn(rI1)
sulphate and pyrophosphate respectively. The [V(V)I2 dependence indicates two
concerted one-equivalent oxidations; one possible mechanism involves oxygentransfer, uiz.
k[Co(llI)][substrate]/[H30+]
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(Vl), Pu(V1) 403
at 20 "C
trations this step is rate-determining, with k , = 40 l.mole-'.sec-'
( E = 10.5 kcal.mole-' and ASs = - 18 eu), for reaction with 2,6-dimethylphenol,
and with corresponding values of 8.3 x 10' l.mole-'.sec-', 3.1 kcal.mole-' and
- 11 eu for reaction with 2,6-dimethylphenoxide anion. At higher Ir(II1) concentrations the reverse of the electron-transfer step becomes significant and the following kinetics are obtained
- d[Ir(IV)] - 4 K , 2kz[ArOH]Z[Ir(IV)]2
- ~-
dt
4 K , 2k,[ArOH][Ir(IV)]Z
[H,0+]2[Ir(111)]2
4 K , K4k,[ArOH]2[Ir(IV)]Z
+-
[H,O+I[Ir(III)I
CH3OI + r m 0 1
kl
Ir(lV)
ArO.
ArO.+Ir(lV) L I r ( I I I )
H' + Ir (111)
+ ArO+
2 I r ( l V ) 3@
:=O
fast
CH3
k4
ArO. + A r O H
d i r n e r r a d i c a l k,/k-,
= K4
k-4
dirner r a d i c a l
Ir(lV) L d i r n e r
2Ir(lV)
r
CH3
Also significant is the reverse of the first step but involving phenoxide ion, viz.
ArO.+Ir(IIl) %ArO-+Ir(IV)
The following values of the coefficients at 20C have been deduced423: k, =
5.6 x lo9 I.mole-l.sec-' (ref. 424), k, = 6 x lo4 l.mole-'.sec-', k 5 K 4 = 6 x lo*
12.mole-2.sec-', k-, = 4 . 8 ~
lo6 12.mole-2.sec-', k'-, = 2 . 2 lo3
~ l.mole-'.
sec-'.
Trisacetylacetonecobalt(II1) oxidises phenols to phenoxyl radicals at 71-120 "C
in chlorobenzene with simple second-order kinetics, ( E = 33 kcal.mole- and
ASs = 13.6 e ~ ) ~ When
' ~ . 2,4,6-tert-butylphenol was employed, the characteristic
ESR spectrum of the phenoxyl radical was obtained with an intensity corresponding
to almost quantitative conversion, viz.
ArOH Co(acac),
404
C O V A L E N T C O M P O U N D S , METAL IONS: O X I D A T I O N - R E D U C T I O N
The main oxidation product from dibenzyl ether is benzaldehyde (up to 80%
yield) with smaller amounts of benzyl alcohol and benzoic acid. The rates of
oxidation are only slightly affected by major stereochemical changes, and it is
considered that an outer-sphere oxidation of the ether is followed by radical
breakdown, uiz.
4 Ag(II), Ag(III), Co(III), Ce(IV), Mn(III), V(V), Ir(IV), Np(VI), Pu(V1) 405
CH30C6H4CH3+ 2 Mn(OCOCH,),
CH30C6H4CH20COCH,
+ C H 3 C 0 2 H + 2 Mn(OCOCH,),
k is unaffected by added sodium acetate but deuteration of the CH, group reduces
k by a factor of 5 at 70 "C. The retardation by Mn(I1) is rationalised as follows427
PMT+Mn(III)
+ .PMT++Mn(II)
+
C H , 0 C 6 H 4 C H ~+ Mn(I1)
CH,0C6H4CH20COCH3+ H +
*PMT+-+ CH30C6H4CH2* H +
CH30C6H4CH2.+Mn(1II)
-+
CH,0C6H4CH2+ CH3C02H -+
(fast)
(slow)
(fast)
(fast)
The acetate ion relinquished by the metal atom in the first step probably remains
Refert-nces pp 493-SO9
406
C O V A L E N T C O M P O U N D S , METAL IONS: O X I D A T I O N - R E D U C T I O N
in the vicinity of the radical-cation to promote the removal of the proton in the
slow step.
Identical kinetics are exhibited in the analogous oxidations of 1- and 2methoxynaphthalene to 4-methoxyl-1-naphthyl acetate and 2-methoxy-l,4naphthoquinone re~pectively~~'.
In these cases the radical-cations may react
with acetate ion thus
H' 6COCH3
mo=
H OCOCH3
O ~ O C H ~
Mn(ll1)
Similar acetoxylations have been reported for several other aromatic ethers,
amines and polynuclear hydrocarbons4' and more complex reaction products
have also been identified, although kinetic data are lacking.
The Ce(1V) oxidation of the leuco-base of Malachite Green yields a dye, uiz.
1
Swain and Hedberg292have shown that the tertiary alcohol is not an intermediate,
for the dehydration process is slower than the rate of formation of dye. Instead
it is proposed that the tertiary hydrogen is removed to give a radical-cation which
is further oxidised to the carbonium ion. The oxidation involves two steps; one
fast and one very much slower. This parallels the Ce(1V) oxidation of iodide ion
and is therefore probably a function of the oxidant.
4.4.14 Thioureas
Oxidations by CO(III)~~'"
and Ce(IV)429bto the corresponding disulphides
require stopped-flow techniques for kinetic study. All oxidations are first-order
T A B L E 17
RATE A N D A C T I V A T I O N D A T A FOR ONE-EQUIVALENT O X I D A T I O N S OF THIOUREAS
Thiourea
Oxidant
Unsubstituted
EthyleneDiethylDimethylThiosemicarbazide
Ce(1V) sulphate
co3
k,(l.mole- '.see- I )
I
I
CoOH2+
Temperature("C) E(kcal.mole- I )
163
37.0
403
490
227
ASt(eu)
23.9
26.3
24.7
25.5
23.7
7.96 k0.2
9.61 1 0 . 2
8.9010.5
9.10h0.5
9.8 1 0 . 5
-32.71 3
-25.4f3
-28.5*4
-29.3f5
-28.8*3
-29
-30
-29
-26
+5
-22
-19
-12
-14
1 3
h3
f3
&3
Unsubstituted
EthyleneDiethylDimethyl-
712
2016
36h10
22h4
25.0
25.0
25.0
25.0
8.6
7.8
7.8
7.6
k1.5
h1.4
11.6
Unsubstituted
EthyleneDiethylDimethyl-
380f20
360f30
1600h 150
3000+150
25.0
25.0
25.0
25.0
9.0
10.9
10.6
9.8
f0.5
h1.5
h0.5
~t0.4
k0.4
both in oxidant and substrate. Acidity dependences were determined for the
Co(II1) oxidations to be of the type
k , = k;+k;'/[H,O+]
The two terms are considered to correspond to one-equivalent oxidations by
Co3+ and CoOH", respectively, of the monoprotonated thiourea (RSH') to
give a sulphur radical, uiz.
2C o Z + + * R S + + H +
C ~ O H Z+RSH+
+
2.c O z + +.Rs+ + H ~ O
Co3++RSH+
2 .RS+--f RSSR"
The Ce(IV) oxidation occurs by the first type of path ( k l ) . Kinetic data are collated in Table 17.
+4
+5
+4
408
C O V A L E N T COMPOUNDS, M E T A L
I O N S:O X I D A T I O N - R E D U C T I O N
T A B L E 18
REDOX
POTENTIALS
OF R E L A T I V E L Y W E A K
(phen)
ONE-EQUIVALENT
Medium
Reaction
OXIDANTS
],lo-orthophenanthroline.
,zo
(Volt)
ReJ
._____
Fe3+4-e-
Fez+
0.772
0.772
0.355
1 M H2S04
1.06
= Ag
(calculated value)
Cu2+$ 2 e- = Cu
(calculated value)
Cu++e- = Cu
(calculated value)
Cu2++ e - = Cu+
(calculated value)
N p 0 2 ++ e - = Np(1V)
1.0 M HCl
M o ( C N ) ~ +~ e- - = M O ( C N ) ~Natural
~pH, extrapolated
to zero ionic strength
Ag+ +e-
0.799
0.337
0.521
0.153
0.737
0.7260
430
430
43 I
19
19
19
19
19
432
432a
a quite different reactivity towards compounds such as pinacol, oxalic acid and
acetoin from other one-equivalent oxidants433.The difference probably stems from
the inability of the substitution-inert ferriin to form chelate complexes with these
substrates.
Ag(1) and Cu(I1) are readily used in neutral solution, although oxidations by
Ag(1) are often affected by the deposition of silver metal. Theoretically Cu(I1)
can behave either as a two- or a one-equivalent reagent, but it usually functions
as the latter6. The tendency of Cu(1) to disproportionate is normally suppressed
by working with solvents such as pyridine which form stable complexes with this
oxidation state.
5.1
OXIDATION O F I N O R G A N I C MOLECULES
The kinetics of the oxidation of iodide ion by Fe(II1) have been investigated
by many groups. The early studies are unreliable as guides to mechanism because
of the disregard of the effects of hydrolysis, complexing, ionic strength, etc.
Fudge and S y k e rectified
~ ~ ~ ~these errors by using ferric nitrate in moderately
strong acid at constant ionic strength. The rate law was determined to be
- d[Fe( III)]
dt
k,[Fe( 111)][1-]2
1 k,[Fe(II)]/[Fe(lII)]
+ Fe12+
Fe12++I- + Fe2++.12-
Fe(lIl)+I-
Fe(III)+.I,-
+ Fe2++I2
Specific retardation of this reaction by ions able to form weakly oxidising complexes with Fe(II1) has been noted435.
Identical kinetics have been noted for the oxidation of iodide by ferricyanide
iOn436-438 . H owever, the mechanism cannot be identical because FC?(CN),~is substitution-inert. A one-equivalent oxidation of I - to an iodine atom would
be followed by the rapid reactions
but this does not lead to the observed kinetics. However, the hypothesis of outersphere electron flow is supported by the observed catalysis by added platinum
metals439.
The reaction is specifically catalysed by hydronium ion440. This catalysed path
shows a rate law
- d [Fe(CN),]/dr
References p p . 493-509
k [Fe(CN)63-][I-] [K+]
410
c o v A L E N T co M P o u N D S,
M E T A L I o N S: O X I DAT I o N-R E D u c T I O N
The ion-triplet oxidises I- in the slow step to yield *I2-. The non-participation
of any ligand substitution step is confirmed by the absence of any incorporation
of activity from added 14C-labelledfree cyanide ion into the product f e r r ~ c y a n i d e ~ ~ l
Specific catalysis by sodium ions is also found in the oxidation of iodide ion
by octacyanomolybdate(V) which otherwise shows simple, second-order kinetiCS441a
with E = 5.68f2.57 kcal.mole-I and AS' = -39k8.5 eu and k, =
3.52k0.13 I.mole-'.sec-l, at 25.7 "C and p = 0.1 M . Mo(IV), which is produced
stoichiometrically exerts slight retardation upon the reaction. An outer-sphere
one-electron transfer is proposed.
Essentially identical results were obtained by a second group682with k, =
1.4k0.3 I.mole-'.sec-' at 25 "C (p = 0.02 M ) . Specific cation effects were also
found with rate sequences K + > Na+ N(C2H40H)4+ > Li+ and positive
deviations of the reaction orders above unity were also noted.
The oxidation of iodide ion by Np(V), which exists in solution mainly as
NpO:, viz.
2NpO:+21-
= 2Np(IV)+I,
follows kinetics442
d [Np(IV) ] / d t = k [NpO: ][I- ]* [H']'
where, at 25 "C (p = [H+] = 3.29 M ) , k equals 1.71 x
14.mole-4.sec-1
and E equals 28.3 kcal.rnole-'. The fractional orders are not significant and the
data are equally well represented by a law
d[Np(lV)]/dt = k[NpO:] [H+I2[I-]
This suggests little more than the importance of protonated forms of Np(V).
The kinetics are complex, but the following features are apparent437: (a) order
in Fe(CN),,- between 1 and 2, tending to 1 in presence of Fe(CN)64-; (b) firstorder retardation by Fe(CN)64-; ( c ) order in CN- between 1 and 2; ( d ) rate
independent of pH between pH 9 and 11 ; ( e ) E zero or negative. The following
mechanism was proposed437
and the rate law i n ammoniacal aqueous solution was found to be444
- d[Cu(II)]/dt
k[Cu2+][CN-I4
A complex was detected in these solutions with the composition CuCN' but this
was not formed in significant quantities under the conditions employed. The role
of ammonia molecules could not be assessed, although it was found that the rate
showed a strong inverse dependence in ammonia concentration, indicating
competition between NH, and CN- for coordination sites.
The thermal oxidation of thiocyanate by Fe(II1) in a perchlorate medium involves two thiocyanato complexes of Fe(III)445. The stoichiometry is thought
to be
6 Fe(III)+SCN-+4 H 2 0
and the rate law is given as
References p p . 493-SO9
6 Fe(II)+CN-+S042-+8 H+
4I 2
c o v A L E N T c o M P O u N D s, M E T A L I o N s:
O X I D A T I ON-R
E D u c T I oN
At 25 "C, k , = 1 . 8 ~
I . m ~ l e - ~ . s e c - ' ,k , = 1 . 4 ~
1.mo1e-'.sec-',
El = 26.2 kcal.mole-', E2 = 27.05-3.0 kcal.mole-', k J k , = 3.55-1.0 (independent of temperature), K , = 114 (p = 1.28 M ) and K , = 205-5 (both in
I.mole-' units).
The following mechanism was proposed
+ FeSCN2+
+ Fe(SCN),+
Fe3++SCNFeSCN" +SCN-
(Kl
(K2)
+
+
Fe2++.(SCN),Fe2++.(SCN),- +SCN-
Fe2++.(SCN),-
F e 3 + + 2 SCN-
(62)
Fe2++(SCN),
(63)
-+
C N - , SO4,-, etc.
(64)
Fe(rrl)+(scN),-
H 2 0 + (SCN),
(slow)
(slow)
(60)
(61 1
Reaction (61) implies that the transition state contains 3 SCN- ions. A steady
state approximation for [*(SCN),-] leads to the observed rate law. A temperature
variation study of K , and K2 is included in this paper. It was also concluded that
simple redox breakdown of FeSCN2+ is of negligible importance.
5.1.4 Pseudohalides; azide ion
[ H 3 0 +I
Fe(rrr) + HO, -
-+
OH.+Fe(ll)
Fe(llI)+OH-
to H 0 2 *
However, A n d e r ~ e n ~noted
~ , a new rate law at lower values of [H2O2]/[Fe(1II)]
with a higher order dependence on peroxide.
The reaction scheme as presented is of a non-chain variety provided OH.
~ ~ 'included further
is removed by Fe(1I) rather than by peroxide. Barb et ~ 1 . have
steps in the scheme, viz.
Fe(Il)+H,O,
Fe(1II) HO,.
Fe(III)+OH.+OH-
(69)
0,
+ H + + Fe(I1)
(70)
k[Fe(III)]*[H,02]3
Fe3++HO;
+ [FeHO2I2-
4 14
c o v A L E N T c o M P O u N D s, M E T A t I o N s : O X I D A T I o N-R
ED ucT I oN
has been
as a model for the catalytic activity of copper-containing
proteins. The overall reaction rate at pH 7.0 is given by
where the subscripts denote total molar concentrations. Variation of rate with p H
indicates that
kobs = k,[CuHm2+][H0,-]
+ k2[CuHm(H02-)'][H02-]
2 Fe(II)+S4062-
rate =
k[FeS2O3+]*[S2OJ2-If
s [Fe(II>l
+ FeS203+
FeS203++ S 2 0 3 2 - +' FeS203+ * S 2 0 3 FeS203++ . S 2 0 3 - -+ Fe(Il)+ S40b2Fe(III)+S2032-
(fast)
(slow)
(slow)
H,S03 is oxidised to two sets of products by both ferric ion and ferricyanide
depending upon the reaction conditions, e.g.
H,SO,
+2 Fe(I1I) + H,O
2 H,S03+2 Fe(II1)
= 2 Fe(I1)
=
+ 4 H + + SO,'
2 Fe(II)+4 H + +S206,-
When a large excess of ferric ion was employed to promote the sulphate-forming
reaction under nitrogen, it was found46' that a plot of t+ versus {[Fe(II)],+
2 [H2S03],} is a straight line and in general the rate equation
[Fe(III)]2t+ = k[H,O'I{ [Fe(II)l,+2 [H,SO,],} +k'[Fe(HI)l[H30fl
expresses the observed data very adequately. Such an equation may be obtained
by applying a steady-state approximation to HSO,. in the following mechanism462
- d[S0,2-]/dt
k, [Fe(CN)63-][S0,2-]
with k, strongly dependent upon pH, becoming virtually zero at pH 3.5 but at
pH 8.4 being given by 1 . 4 lo8
~ exp(- 1 4 . 0 ~
103/RT) I.mole-'.sec-'.
These
authors object to free radical intermediates on the grounds of non-production of
References p p . 493-509
416
cov A L E N T
COMPOUNDS. M E T A L IONS:
0 x 1D ATION-R
E DU C T I O N
Fe(CN),,- + C N -
Fe(CN),4-
(slow)
(fast)
(fast)
(fast)
Swinehart4,, believes that specific ion-pairing effects are important with both
Na' and K + and that the rate law should be written
-d[Fe(CN),,-]/dt
k , [Fe(CN),3-][S0,2-][M+]
'so,- + Fe(CN),,2.S0,-
+.so,-
Fe(CN),4-
-+
so3 + Fe(CN)64-
--f
S2062-
V e ~ f e k - S i S k a ascribes
~ ~ ~ " the accelerative effects of "inert" electrolytes to catalysis
by trace quantities of Cu2+ ions.
Wiberg et ~ 1 . have
~ ~ ' performed the reaction in the presence of ''C-labelled
cyanide ion and find no incorporation of activity into product ferrocyanide.
Evidently the reversible ligand displacement proposed by the Czech workers does
not take place and the electron-transfer scheme of Swinehart is preferable. Recent
spectroscopic
indicate that a complex [Fe(CN),(CNSO,)]' - functions
as an intermediate in this reaction.
417
5.1.10 Phosphorothioic acid
+ H,P03S-S03PH, + 2 Fe(CN),4-
+ 2 H+
Several of these features remain unexplained but it is clear that here we have an
example of a relatively well-behaved reversible electron transfer reaction involving
radical intermediates.
5.1.11 Hydrazine
The oxidation by simple salts of Fe(II1) has been studied by several groups. Two
overall routes are apparent
, y l / 2
N2 + NHJ
+ HI
N2H4
'b +
N2
4H+
(Cahn and
omit
kr
Fe(III)+N,H4~rFe(II)+N,H3~+H+
5N4H6
2 N2H3-
Nz + 2 NH,
(72)
aNzHz+Fe(I1)
Fe(II1) N2H3*
(73)
fast
N2
dCNH,I/dt
References pp. 493-509
2 k,
=l+-+
kz
4 k,[Fe(III)]
Jk,d[NH,]/dt
(74)
418
COVALENT
C O M P O U N DMSE, T A L I ONS:
OXIDATION-REDUCTION
In the presence of sufficient F e y 2 - then k-, [Fey2-] >> k,[FeY-] and the
kinetics observed with added F e y 2 - result. Phenanthroline removes all Fe(I1)
from solution thereby suppressing the back-reaction in (71) and the change in
order is explained. Cu(11) exerts a catalytic effect, as in the oxidation by ferric
ion, by oxidising N,H3*, thereby reducing the importance of the back-reaction.
A few data exist on the oxidation by ferricyanide. This is simple ~ e c o n d - o r d e r ~ ~ ~
(in oxidant and neutral hydrazine), and leads to quantitative production of
nitrogen' 4 7 3 in accordance with scheme (71k(74) with k, >> k3 and k-, . No
scrambling occurs during oxidation of "N-labelled NZH4 indicating that all N,
is formed via di-imir~e,~'. Di-imine so prepared is capable of hydrogenating added
unsaturated compounds, for example, phenylpropiolic acid gives cis-cinnamic
6s
419
5.1.12 Hydroxylamine
+ +
2 Ag+ 2 N H 2 0 H = 2 Ag Nz 2 H 3 0 +
A dependence of d[N,]/dt upon [Ag(I)I2 is considered to result from heteropneous
catalysis.
The rapid insertion of CO, which recalls the Hg(l1)-CO reaction (p. 334), is followed by
[CU-CO-OH]'
2 H + + [Cu-CO-OH]++HOz-
Cu(II)+COz+2 H 2 0
(slow)
(fast)
420
cov A L E N T co M P O u N D S,
M E T A L I O N S : O X I D A T I ON-R E D u C T I O N
expression being477a
(k1)
(k2)
Cu(II)-C02H++Cu(II)
-+
C 0 2 + 2 Cu(L)+H+
( k 3 ) Cu(lI)-C02H22f+Cu(II)
C 0 2 + 2 Cu(I)+2 H +
each of which is preceded by equilibria between the metal ion, CO and H,O, e.g.
Cu(l1) + CO H,O
+ (Cu-CO-OH)' + H +
5 .I . 14 Molecular hydrogen
Cu(11) and Ag(I), in common with other oxidising ions with d9 or d' configurations react readily with H, in aqueous solution, giving the following rate laws:
( a ) cupric p e r ~ h l o r a t e ~ ~ '
= k2[Cu2+][H2]
-d[H,]/dt
(75)
-d[Cu(OAc),]/dt
k,[Cu(OAc);?l[H21
(76)
k , = 1 . 6 loL2
~ exp{-24.2+0.8)~ 103/RT}I.mole-'.sec-'.
( c ) silver perchlorate (see also p. 291)63n480
-d[H,]/dt
k3[Ag+I2[H2]+
k1CAg+12CH21
[&+I + k - l/k2[H+I
(77)
=
1 . 2 lo',
~
exp
cu2
kHZ0/kDzO
(fO.l)
Cu(OAc),
0.93 (100 "C)
Ag'
1.23 (50 " C )
ki
+
AgH+H+
k-
(78)
followed by
AgH + Ag+
1:further intermediates
422
C O V A L E N T C O M P O U N D S , M E T A L I O N S: O X I D A T I ON-R E D U C T I O N
5 .I . 15 Antimony(III)
Sb(II1) is oxidised by alkaline ferricyanide with complex kinetics including
variable reaction orders4". It is proposed that the reacting form of Sb(I1I) is
dimeric, and, that subsequent to an initial one-equivalent reduction of Fe(CN)63-,
a further form of Sb(II1) is involved, uiz.
Sb(III), +Fe(CN),3-
Fe(CN),4- +Sb(IV)+Sb(III)
Sb(LI1) + Sb(II1)'
Sb(III)'+ Fe(CN)63-
Sb(IV)+ Fe(CN)64-
Sb(IV)+ Fe(CN)63-
Sb(V)+ Fe(CN),4-
k2[H30'][BH4-]
-d [OH- ]/dt
with k,
k , [ BH4- ] [Fe(CN)63- ]
8.2~
I.mole-'.sec-'
ferricyanide although those of Na+BH,(OH),- are inactive. The rate law with
borohydride was found to be
- d [Fe(CN)6, - ]/df
= k , [ H 3 0 ] [Fe(CN),,
+
] [BH4- ]
The authors believe hydrolysis to be rate-determining but do not account for the
presence of ferricyanide in the transition state.
5.2
These are oxidised by both Fe(lII) and Cu(l1) octanoates (denoted Oct) in nonpolar solvents at moderate temperatures492.80-90 % yields of the corresponding
disulphide are obtained with Fe(Il1) and this oxidant was selected for kinetic
study, the pattern of products with Cu(I1) being more complex. The radical nature
of the reaction was confirmed by trapping of the thiyl radicals with added olefins.
Simple second-order kinetics were observed, for example, with 1-dodecane thiol
oxidation by Fe(Oct), in xylene at 55 "C ( k , = 0.24 I.mole-'.sec-'). Reaction
proceeds much more rapidly in more polar solvents such as dimethylformamide.
The course of the oxidation is almost certainly
RSH
+ Fe(Oct),
RS.
+ RSSR
Dithiodipropionic acid was without effect o n the reaction rate but the reaction
went faster at high pH, suggesting the participation of species HRS- (thiolate)
and RS2- (thiolate carboxylate). The retardation by ferrocyanide suggests the folReJerrrrres pp. 493-SO9
424
c o v A L E N T c o M P o u N DS, M E T A L I o N S:
O X I D A T I o N-R E D u c T I o N
HRS-
(fast)
(slow)
(fast)
A steady-state treatment for the radical (and inclusion of similar reactions incorporating RS2- + -RS-) produces the observed rate law.
Aqueous acidic ferricyanide oxidises thioglycollic acid, HSCH,COOH, to the
disulphide with identical kinetics, and a similar reversible initial step is proposed493a.
The aqueous ferricyanide oxidation of 2-mercaptoethanol to the disulphide is
also complex kinetically494. In the pH range used (1.84.1) no complication from
ionisation of the thiol is expected. Individual decays of oxidant concentrations are
initially second-order but eventually become almost zero-order. For both secondand zero-order paths the rate depends on the first power of the thiol concentration and the former path is retarded by increasing the acidity, an approximately
inverse relation existing above p H 3.2. Addition of ferrocyanide transforms the
kinetics; the rapid, second-order path is inhibited and the zero-order path is acM ferrocyanide, the whole of the disappearance of oxidant
celerated until, at
is zero-order. Addition of Pb(CIO,), , which removes product ferrocyanide,
greatly enhances the oxidation rate and the consumption of oxidant becomes
first-order. Two routes are considered to co-exist (taking due account of the acidity
of ferrocyanic acid), viz.
F ~ ( C N ) G ~RSH
-
+ HFe(CN),3- + RS.
(slow)
Fe(CN)63-+RS-+H+ + HFe(CN)63-+RS+
(fast)
+ RSH + RSSR + H +
Fe(CN)64- + RSH + Fe(CN),SR4- + HCN
Fe(CN)63- + Fe(CN),SR4- + Fe(CN)64- +Fe(CN),SR3RS
(fast)
(slow)
(fast)
k[Fe(CN)63-][RSH][OH-]
425
(slow)
(fast)
and then further reactions as above. The "residual" reaction at high cyanide concentrations is regarded as a simple non-substitutional redox process.
The displacement of CN- by RS- in surprising since l4C-Iabelled cyanide ion
does not exchange with unlabelled f e r r i ~ y a n i d e ~ 'Wiberg
~.
et al.441 have shown
that no exchange occurs under the conditions of the oxidation and that the effect
of added cyanide is to be attributed t o nucleophilic addition of cyanide to the
thiol, uiz.
RSH+ HCN
HC(SR)=NH + RSH
HC(SR)=NH
-+
HC(SR)zNHz
- d [Fe(CN),3-]/dt
R2CH-CO-R'.R2C=C-R'e
R 2 C = C - ~ ' + ~~0
I
I
OH
0-
Rp?-C
References p p . 493-SO9
-R'
,.
I1
( f ast or slow)
426
co v A L E N T c o M P o uN D s,
M E T A L I o NS: OX I D A T I o N-R E D u c T I o N
- d[Fe(CN)63-]/dt
k (25 "C) is 44.9 and 11.1 12.mole-2.sec-1 for acetone and methylethyl ketone
respectively498a.A slow two-equivalent attack of Os(V1II) upon enolate ion followed by a fast reoxidation of Os(V1) by Fe(CN)63-, uiz.
RZCH-CO-R'+ OH-
kr
+
R*C=C-R'+H,O
k-
(K)
0-
2Os(VI)+ products
fast
0Os(VI)+2 Fe(CN):-
~[CU(II)][CH,O][OH-]~
- 2 k , k,LCH,O][OH-][Fe(CN);-]
k - ,[H,O]+k,[Fe(CN);-]
(excluding an initial rapid reaction). The rate coefficients refer to the steps
H,C(OH),+OHH,C(OH)-O-
ki
+
H,C(OH)-0-+H,O
k-
+ Fe(CN);- 2H,C(OH)-0-+
H,C(OH)-O*+Fe(CN);-
Fe(CN):-
HCO,H+Fe(CN):-
+H +
(fast)
when [H,O] >> k2[Fe(CN),3-]/k-l then the observed third-order rate coefficient becomes 2 k,k,/k-,[H,O]. At 40 "C its value is 1.5 x
12.mole-2.sec-'
(p = 2.0 M ) and E = 12.0 kcal.mole-'.
Cupric chloride oxidises isobutanal in 80 % acetone-20 % water according to
the s t ~ i c h i o m e t r y ~ ~ ~
(CH,),CHCHO+ 2 CUCI,
~
12.mole-2.
where, at 30 "C, k , = 2.1 x lo-' I.mole-'.sec-' and k, = 1 . 4 lo-,
sec- k 2 has an activation energy of 23 kcal.mole- Addition of LiCl accelerates
reaction but the effect levels out at a LiCI:CuCI, ratio of 2, suggesting CuCI,'may be an active species.
Rate-determining enolisation is discounted by the authors on the grounds of
the appearance of cupric ion in the rate law and of the value of the rate coefficient,
which shows oxidation to be faster than enolisation. However, it is known that
Cu(11) catalyses enolisation and an intermediate radical (CH3),eCHO could
abstract chlorine from CuCI, .
The oxidation of rz-butanal by CuCI, in dimethylformamide showed simple
second-order kinetics in the presence of lithium chlorideso0. At 83 "C, k, is
2 x lo-, I.mole-'.set-'. cr-Monohalogenation occurs in 97 % yield. Cu(11)catalysed enolisation followed by ligand-transfer is proposed.
a-Halogenation of acetone is accomplished by CuCI, , viz.
'.
'.
428
COVALENT
c O M P O U N D S,
The radical is rapidly oxidised to a carbonium ion which is hydrolysed to 2hydroxycyclohexanone. Electron transfer is compatible with the observed Arrhenius parameters ( E = 12.6 kcal.mole-', AS' = -31 eu).
Oxidation of butan-2-one in nitrate media by [Fe"'(H,O),phen, j is reported
to proceed much more slowly than e n o l i ~ a t i o n moreover
~~~;
Fe(phen): is said
to be even less reactive, in total contrast to the results on cyclohexanone.
+
k3[HC02-][Ag'I2
R C E C - C K R + ~Cu(I)+2 Hi
8.84 x 10-4[RC-CH][base][Cu(
[base]*[CH3C02H]q1+ 1.49[RC=CH]
I)]
17.3[Cu(I)])
A mechanism consistent with this rate expression was put forward, viz.
RC3CH
+B
RC3C-+Cu(CHSCO2)
RC3C-+BH+
(slow)
R C 3 C C u tCH3CO;
(slow)
C
RCZCCu+ Cu(CH,C0,)FtI[~CU(CH3C0,)
C
R C X Cu + Cu(CH,CO,),2 RC EC.
cu
R C Z C . + 2CU(CH,C02)
R C E C -CGCR
(fast)
(fast)
(fast)
An analogous study has been reportedso3 of the oxidation of 2-methyl-but-3yn-ol by Cu(I1) chloride in aqueous ammonia to give 2,7-dimethylocta-3,5-diene2,7-diol. Simple, second-order kinetics were obtained, but a very sharp increase
in rate occurred when the pH was increased from 8 to 10. Addition of ammonium
ions retarded reaction but Cu(1) was without effect. The reaction mechanism put
forward is similar to that given above.
The methanolic cupric bromide oxidation of propargyl a l c o h 0 1 ~to~ ~
trunsBrCH=CBrCH,OH (30 %) and Br2C=CBrCH20H (18 %) and, under other
reaction conditions, Br,C=CBr-CH,OH (93 %) follows simple second-order
kinetics with a rate coefficient of 1.5 x l o w 2I.mole-'.sec-' at 64 "C. A mechanism
of ligand-transfer in a n-complex is proposedt.
The analogous quantitative oxidation of methanolic allyl alcohol to 2,3-dibromopropan-1-01 shows unusual kinetics5", viz.
-d[Cu(II)l/dt = k2 [CuBr2I2[allyl a l c ~ h o l ] ~
t Some of the formulae for the oxidation products (in the original papcr) are obviously incorrect.
References pp. 493-SO9
430
+ 2 CuBr + Br,
followed by fast bromination of the olefinic group. This hypothesis could easily
be tested with related compounds.
- d[Fe(III)l/dt
= k [Fe(III)][acetoin](a+ b/[H+ 1)
The two terms correspond to oxidation by Fe3+ and Fe(OH)'+ which exist in a
hydrolytic equilibrium. A radical intermediate CH,COC(OH)CH,, which suffers
rapid oxidation by a second ferric ion, is proposed.
Ferricenium ion oxidation of acetoin in acidic aqueous ethanol (50 % v/v)
involves rate-determining enolisation ,, producing a zero-order decay of oxidant.
The oxidation rate approximates to that of deuteration under similar conditions.
Several studies have been made of oxidations of ketols by Cu(I1). Simple cupric
salts deposit cuprous oxide, but this has been overcome by using a citrate complex
of Cu(II) or a 1 : 1 (mole) pyridine-water mixture. A recent detailed account is
that of Wiberg and Nigh505, who found the stoichiometry and rate law for the
oxidation of a-hydroxyacetophenone by Cu(J3) acetate to be, respectively,
'
The first term was found to correspond to the rate of enolisation (measured by
an NMR study of hydrogen-deuterium exchange at the methylene group). The
second term predominates at [Cu(II)] > lo-' M and is characterised by a primary
kinetic isotope effect of 7.4 (25 "C) and a p value of 1.24. Addition of 2,2'-bipridyl
(bipy) caused an increase in k, up to a bipy: Cu(1I) ratio of 1 : 1 but at ratios
greater than this k, fell gradually until the enolisation term dominated. The
oxidation of a-methoxyacetophenone is much slower but gives a similar rate
43 1
expression. These various data suggest the following mechanism
RCO~HOH
+ CU(II)
R C O C H O + CU(I)+
H+
(fast)
- d[Cu(II)]/dt = k[a-ket~l][OH-][Cu(II)]~
In several instances an induction period has been observed but this has been
shortened by elimination of dissolved oxygen O. Deposition of cuprous oxide
(Fehlings test) does not appear to influence the zero-order disappearance of
Cu(IT), but the induction period can be eliminated by adding copper powder
(but not C U , O ) ~ ~ .
The rate expression suggests a rate-determining step not involving the oxidant;
this is very probably enolisation, viz.
CH,CH(OH)COCH,
CH3C(OH)COCH,
+ H,O + CH,C(OH)=C(OH)CH, + O H -
(slow)
(fast)
CH,C(OH)=C-CH,
I
0The rapid oxidation of the enediol then ensues. Marshall and Waters propose
that a Cu(1) complex of the enediol is the active reductant in order to explain the
induction period (during which O2 reoxidises Cu(I)), but Wiberg and Nigh O 5
believe that it is unlikely that the enediol can displace citrate or tartrate from
copper ions. The report of Marshall and Waters that the oxidation proceeds at
about one-third of the rate of enolisation is also discounted by Wiberg and Nigh
on the grounds of experimental inaccuracy in determining [OH-] in strongly
basic solutions with dioxan-water mixtures.
The faster cupric ion oxidation of ketoses compared with aldoses is due to
the more strongly reducing nature of the a-hydroxyketone group. Pre-treatment
References p p . 493-SO9
432
cov A L E N T C O M P O U N D S , M E T A L
I O N S : O X I DA T I ON-REDU CTION
- d[Fe(CN)63- I/dt
k , [Fe(III)][ascorbate ion]
21.5
4.0
1.30
0.88
5.6f0.2
5.1h0.2
4.9f0.2
4.7+0.2
AS(eu)
no(V )
-21&1
-27fl
-30fI
-322~1
+0.30
fO.10
f0.08
+0.06
The rate sequence is determined by the entropy term and correlates with the
oxidation potential of the chelate complex, indicating an outer-sphere electron
transfer.
The anaerobic V(IV) oxidation of ascorbic acid (H,A) in the pH range 1.75-2.85
follows a rate law 513b
d[A]/dt = k3[H,A][V02+][H30+]
A two-equivalent process is proposed, yielding V(1I). In the presence of oxygen
433
k4[H2A][V02+][H,0'][0,1
k 3 ( 2 9 8 = ( 1 . 8 k 0 . 1 ) ~lo2 l.mole-'.sec-'
( p = 0.10 M KNO,), k 4 ( 2 9 8 OK)
= ( 4 . 4 k 0 . 3 ) ~lo3 I.mole-'.sec-'.
atm-'; E, = 7.6k0.5 kcal.mole-', AS! =
-25+2 eu, E4 = 14.4k0.7 kcal.mole-' and AS: = 4.1k0.2 eu. Complexes
VOH,A3+ and VOH3A(02),+ are regarded as breaking down in the ratedetermining steps
VOH3A3+ + V 2 ++ A + H 3 0 +
VOH,A(02)3+ + V 0 2 + + A + H 2 0 2 H +
Identical kinetics are found for the uranyl ion-catalysed aerobic oxidation of
ascorbic acid and a similar mechanism has been put
These results
and others afford a sequence of catalytic activity for the aerobic oxidation of ascorbic acid'
'
- d [Fe(CN)63- ]/dt
k [H2A][Fe(CN),,-
31 [ H 3 0 +]
2.1 x
sec-', E
= 10.8
5.2.7 Phenols
~ been superseded by that of Baxendale et ~ 1 . " ~
The early work of P ~ r r e t ' ' has
who found the oxidation of hydroquinone (QH,) by Fe(lI1) perchlorate to follow the rate law
-d[QH,l/dt
kotdFe(III)I[QH21
kobs is sharply reduced by added ferrous ion and by increased acidity; plots of
kobs-' versus [Fe(II)] are linear with an intercept and the retardation, which is
too severe to be ascribed to the Fe(II)+Q back-reaction, is considered to result
from re-oxidation by a semi-quinone intermediate, viz.
ki
+
Fe(II)+QH-+H+
Fe(II1) + QH. + Fe(I1) + Q + H +
Fe(III)+QH,
k-I
k2
k-2
References p p . 493-SO9
434
ki k2[Fe(III)12 CQHzI
k-,[Fe(II)]+k,[Fe(III)]
i.e.
kobs = k,k2[Fe(III)]/k-l[Fe(II)]
+ k2[Fe(III)]
This accords with both [H'] and [Fe(II)] dependences and gives values for k ,
and k,/k- ; their variations with temperature yield
k , = 1.9 x lo2' exp(-25.6 x 103/RT)I.mole-'.sec-'
and
kJk-
Waters et
detected retardation by added ferrocyanide and found the reaction to be approximately first-order in hydroxide ion; the order in phenol, while
complex, is greater than unity. The isolation of polymeric products is sure indication of the irreversible secondary reactions which follow the initial equilibrium.
An (EMF) study of the ferricyanide oxidation of phloroglucinol revealed kinet i c ~ ~ ' ~
- d[Fe(CN),3-]
dt
- k[phloroglucinol][Fe(CN)~- ]
- -
kf[Fe( CN)64-]
+ k"
'
435
5
yield, viz.
is kinetically complex520.Oxygen is absorbed during the reaction after an induction period and its presence strongly influences the course of reaction as well as
the kinetics. The phenol concentration has to exceed a critical value of ca. 4 x
M before the reaction proceeds and the concentration of Cu(1I) influences the
induction period. Small amounts of H z 0 2eliminate the induction period. The rate
law is complex: the dependence on oxygen pressure is approximately linear:
the reaction order in the other reactants (Cu(II), phenol, morpholine) is initially
unity but at moderate concentrations decreases to zero or becomes negative.
H,O, , which is produced during autoxidation of hydroquinones, is considered to
play a crucial role in the reaction, and ortho-hydroquinone and ortho-benzoquinone are the reaction intermediates. The initial step is an attack of Cu(I1) 011
phenol to give phenoxyl radical.
5.2.8 Atnines
1 1.64 71'-
5.78
More general forms of this equation incorporating the ionisation potential of the
amine also give a good degree of correlation with several aliphatic amines.
The oxidation of N , N-dimethylaniline by aerated, ethanolic cupric chloride to
give a mixture of products including methyl and crystal violets is simple secondorder when an excess of amine is used"'. Presumably Cu(1) is re-oxidised by
dissolved oxygen, for otherwise the observed linearity of log [residual amine]
versus time plots would not be found as Cu(I1) disappears. Under nitrogen the
kinetics are complex, but a new optical absorption (472 and 1007 nm) appears
immediately on mixing the reactants. This absorption decays whilst a new one at
740 nm develops. The latter absorption originates from a 1 : 1 complex formulated
References pp. 493-509
436
c o v A L E N T c o M P o u N D s, M E T A L
I O N s: O X I D A T I o N-R E D u c T I o N
as
Treatment of the complex with further amine produced the violet dyes. The
importance of this complex in the mechanism is suggested by the inability of cupric
acetate, nitrate or sulphate to achieve the oxidation.
+2Cu(I) + 2 H +
has kinetics 2 2
d[Cu(I)]/dt = k[aminoazo compound] [Cu(II)]
The order in oxidant is considered to result from attack of Cu(1I) upon a chelate
complex of the azo-compound and a second Cu(I1) species. Systematic variations
11
HOx
11
S . H S 4 -
II
k-l
The following rate coefficients were determined at 30 "C: k , < 3 x lo5 I.mole-'.
sec-', k ; = (7.3+2)x lo8 I.mole-'.sec-',
k - , = ( 3 . 3 k 0 . 8 ) ~lo7 I.mole-'.
sec-' and kL2 = ( 1 . 2 k 0 . 3 ) ~ lo4 l.rnole-'.sec-'.
= k,[Y4-][Fe(CN)63-]
438
An irreversible outer sphere electron transfer is thought to be the most likely ratedetermining step in view of the lack of retardation by Fe(CN),,- and CN- ions.
Sixteen other nitrogen-containing chelates were examined by Lambert and
Jones524, and a very good correlation is observed between E and A S f indicating
a single effect to predominate in all instances.
The stoichiometries of the oxidations of thiourea and thioacetamide, respectively. by alkaline ferricyanide are526
8 F c ? ( C N ) ~ ~ -CS(NH2)2
8 Fe(CN),3- +CH,CSNH,
+ 10 OH-
= CO(NH,), +SO,'-
+ 11 OH-
+ 8 Fe(CN),,- + 5 H2O
= CH3C0,- + N H 3 + SO,,+ 8 Fe(CN)6,- + 5 H2O
- d [Fe(CN)63- ]/dt
- d [Fe(CN)63- ]/dt
- d[CuY2- ]/dt
439
REDUCTION
6. Reduction
6.1
INTRODUCTION
to the me 11 ion
The erm reductant is relative but in this Section it is applied
~(which becomes oxidised) irrespective of its reduction potential (Table 19). The
stages of oxidation may differ by one [Ti(III), Cr(II), Co(II), Cu(lI)] by two
[Sn(rr), TI(I)] or by one and two [V(II), Mn(II)], and in some cases, e.g. certain
reductions by Fe(II), the issue is in doubt.
The field of reduction is much less well charted than that of oxidation but a
substantial literature exists nonetheless and is growing rapidly. Reductions are
conveniently classified into (i) those involving and initial electron acceptance by
the substrate (possibly followed by rapid protonation) and (ii) those involving
electron acceptance concerted with, or followed very rapidly by, homolysis of the
substrate; the latter includes the important Fenton and silver-persulphate reactions, as well as reductions of halogens, hydrazine and possibly NO; and NO;.
T A B L E 19
S T A N D A R D E L E C T R O D E P O T E N T I A L S FOR R E D U C I N G I O N S I N A Q U E O U S S O L U T I O N
?Go
(Volt)
+0.43
+0.41
en. +0.37
+0.255
en. -0.1
-0.147
-0.15
-0.153
-0.334
-0.355431
-0.361
-0.521
-0.53
-0.712
-0.97
-1.017
-1.15
- 1.25
-1.51
-1.61
440
Within each group relatively simple molecules will be discussed first. In some cases
a given substrate may be reduced by modes ( i ) and (ii) depending on the reductant
and in other cases the mechanism is unknown, for example the reduction of
perchlorate ion may involve either electron-acceptance or oxygen atom transfer.
6.2
8 V(II)+CI04-+8 Hf
8 V(II'I)+Cl-+4 H 2 0
8 V(III)+C104-+4 H2O = 8 V 0 2 + + C 1 - + 8
HS
- d [V(II)]/dt
= k , [V2'] [CIO,- ]
+ 2 k , [V3'] [ClO,-]
The second term corresponds to the concurrent reduction of ClO,- by the product,
V(III), to give V(IV), which oxidises further V(I1) very rapidly to V(II1). k , is
almost acid-independent but k , is doubled by a 15-fold variation in [H,O+]. At
1.mole-'.sec-' and
50 "C and an acidity of 1 M (p = 2.5 M ) , k , = 2.12 x
k 2 = 4.2 x
1.mole-'.sec-'.
Ti(II1) also reduces aqueous acidic C10,- in accordance with the stoichiometry
given for V(II)528,5 2 9 and with kinetics
-d[Ti(III)]/dt = [Ti(III)][C1O,-](kl + k Z [ H 3 0 + l )
Chloride ion retards reaction, presumably by forming less reactive chlorocomplexes
with Ti(II1). At 40 "C (p = 0.5 M ) , k , = ( 8 . 8 9 k 0 . 9 ) ~lo-, l.mole-'.sec-'
and k , = ( 3 . 4 0 k 0 . 3 ) ~lo-, 12.mole-2.sec-2. El = 26.0 kcal.mole-' (+ 15 %),
AS: = 20 eu (f 15 %), E, = 6 + 3 kcal.mole-' and AS: = -46523 eu. Rate
and activation data are also listed5, for the reduction by TiCI2 .
Reduction by Ru(NH,):+ is simple second-order and a~id-independent'~'.
k , is 2 . 5 lo-,
~
I.mole-'.sec-' at 25 "C (p = 0.142 M ) . Reduction by the corresponding hexammine is about 100 times slower.
Reduction by Eu(1I) in a perchlorate medium is too fast for conventional study
but chloride ion retards the reaction531.
These various reductions may involve transfer of oxygen from substrate to
+
441
REDUCTION
Ti3+ C10,-
+ Ti.C104'+
T i 0 2 ++ CIO,.
(slow)
followed by rapid reduction of CIO,. However, alternative schemes are consistent with available data, for example, an electron-transfer mechanism.
6 V(III)+CI-+3 H,O
-d[V(II)]/dt
k , [V(II)][ClO,-]
= k>[Cr(lI)][ClOi]
k3[Cr(lI)][C10;][H30+]
k , [II-CI,~-][C103- I [H+lo
(3.2k0.1)~
I.mole-'.sec-'
at
acidities below 0.2 M . k , is in good agreement with a value at the same temperature
obtained polarographically (3.0 x
I.mole-'.sec-' )5 3 5 . The stoichiometry was
found to be
6 IrC163-+C103-+6 H+
References pp. 493-SO9
6 IrC1,2-+C1-+3
H,O
442
C O V A L E N T COMPOUNDS, METAL
IONSO
: XIDATION-REDUCTION
A simple electron transfer was proposed. Ir(V1) does not retard reaction and
evidently the initial species
must oxidise further I r p r ) very rapidly.
The reduction of bromate by V(IV) shows a stoichiometry
2 Br0,-
+ 10 V 0 2 + + 4 H,O
= 10 V 0 2 + Br,
+ 8 Ht
- _d[V(IV)]
_ _ _ _ _- kK[V(IV)][BrO;]
dt
1+ K[BrO;]
At 20 "C ( p = 0.10 M ) k = 0.125 sec-' and K = 88.8 l.mole-'; E = 19+ 1
kcal.mole- '. An intermediate BrO; .V02+ is considered to break down via
oxygen-atom transfer to give BrO,. and VOz+.
The U(IV) reduction of bromate follows two paths in acid perchlorate or
nitrate media535b,the rate law being
- d[U(IV)]/dt = k,[U(IV)][BrO;]
+ k4[U(IV)][BrOS][H30t]2
with corresponding activation parameters E, = 27.8 k0.6 kcal.mole= 27+2 eu, E4 = 23.9k1.0 kcal.mole-' and AS: = 16+3 eu.
',
AS:
A.St(eu)
k z (27 "C)(l.mole-'.sec-')
E(kcal.mole- ')
(6.3fo.5) x 104
( 6 . 2 1 0 . 2 )x 104
(3.ofo.3) x 104
4413.7
13
13
t 2.5+0.2
-11.210.2
443
REDUCTION
-+
.O,H
e-
-+
H 2 0 2 --t OH.+OH-
e-
--t
H,O+OH-
e-
However, the kinetics of the reduction are often simplified in that the first step
(production of HO,.) is rate-determining; the ensuing reactions, however, may
confer radical-chain behaviour on the system. Hydrolysis of the reductant can
also modify the kinetics.
These possibilities are featured in the autoxidation of U(IV) in perchloric
The rate law is
with k = 2 x l O I 4 exp(-2.2f 103/RT)sec-'. This is evidence for slow oneequivalent reduction of 0, preceded by a rapid hydrolysis, uiz.
u4++ H 2 0 + UOH3++ H +
2 UO,++HO,.+2 H +
U 0 2 + + 0 2 + H 2 02 U 0 2 2 + + H 0 , . + O H H 0 2 * + U O H 3 + + H 2 02 U 0 2 + + H , 0 2 + 2 H +
U 0 2 ++ H 0 2 - +H 2 0 2 U 0 , 2 + + H 2 0 , + OH'
u4++H,o, 1: uo22++ 2 H +
UOH3++02+H20
initiation (slow)
propagation (fast)
termination (fast)
(fast)
Steady-state treatment for the transients (H02. and UO,') leads to the observed
rate law. The chain reaction is indicated by (i) strong catalysis by Cu2+ ions and
(ii) partial and complete inhibition respectively by added CI- and Ag+ ions.
The inhibition by Ag+ is not indefinite, however, and takes the form of an induction period, during which time metallic silver is deposited.
The effects of additives are accounted for by the following reactions536
References p p . 493-509
444
C 0 V A L E N T C 0 M P 0 U N D S , MET A L I 0 N S : 0 X I D A T I ON-R E D U C T 1 0 N
-+
Cu+ -t U 0 2 ++ 3 H +
CU++02 H + + Cu"
+ HO,.
U 0 2 + + C I - + 2 H 2 0 -, UOH3++C1.+3 OH-
CI- inhibition
H 0 2 * +C1-
U 0 2 + + A g + -+ U02'++Ag
Ag+ inhibition
H02.+Ag+ + 0 2 + H + + A g
Gordon and TaubeS3', however, have found only one oxygen atom of U02'+
is derived from labelled O2 and Fallab538prefers an initial two-equivalent oxidation to U(V1).
The rate law for the autoxidation of Ti(II1) chloride to Ti(1V) in aqueous HCl
was found to be539
The first term is identical with that observed for autoxidation of U(W) and a
similar mechanism involving hydrolysis is probable for the initial stage, although
the authors prefer an initial three-equivalent oxidation of Ti(1II) to give Ti(VI),
OH. and OH-.
The autoxidation of V(1II) to V(IV) in aqueous HCIO, also displays the
kineticss4'
'
-d [V(III)]/dt
k[V(rII)][Cu(II)]/[H,O+
This slow process generates Cu(1) which rapidly reduces 0, to H 0 2 *(uide infra).
The kinetics of autoxidation of ferrous ion depend on the acidity of the medium
445
REDUCTION
d[Fe(III)]/dt = k[Fe(II)][O2][OH-I
i.e. Fe(I1) resembles U(IV), Ti(II1) and V(II1) in its mode of reduction and
FeOH2+ is presumed to be the active species.
The rate expression for the reaction in a perchlorate ion medium at higher
acidities is quite differents4,, viz.
-d[Fe(II)]/dt = k[Fe(I1)l2 [02]/[H30+10.23
(The acidity dependence is regarded as too slight to have any substantial bearing
on the mechanism.) Cu(I1) is a weak catalyst for the reduction. A mechanism
involving attack of ferrous ion upon a Fe(1I)-0, complex accounts for the
kinetics, viz.
+ Fe02,+
(fast)
+ Fe2+ .+ 2 Fe3++02,-
(slow)
Fe2++0,
FeO,"
This concerted reduction by two ferrous species eliminates HO,. (or 02-)as an
intermediate and explains the weak catalysis by Cu(I1) (which is strong for V(I1I)
and V(1V) autoxidations). we is^^^,' has suggested that the species Fe2+.02.Fe2+
may be a stable intermediate, but Wells542aexplains the presence of two Fe(Z1)
species in the rate law in terms of a pre-existing dimeric form of Fe(l1) containing
an H 2 0 bridge, for which there is evidence542b.The reduction is completed via
the Fenton reaction (vide infra). The hydrogen peroxide dianion is probably never
free but is protonated whilst complexed to Fe(II1).
Both of these rate laws combine in that for the autoxidation of ferrous sulphate
at 140-180 C" in dilute sulphuric acid solution543*s44, viz.
2 Fe2+ 0,
-, 2
Fe(1II)
+H202
F e S 0 4 + F e 2 + + 0 2 -, 2 Fe(III)+H,O,
Pronounced acid-retardation occurs at acidities lower than 10- Ms44. The reaction is catalysed by cupric ions (unlike that in HC104)543*s44, viz.
-d[Fe(II)]/dt = k2 [Fe(II)][Cu(II)]
References p p . 493-509
446
c o v A L E N T c o M P O u N D S,
M E T A L I o N s: O X I D A T I o N-R E D u c T I o N
T A B L E 20
A U T O X l D A T I O N OF F E R R O U S I O N S I N P R E S E N C E O F C O M P L E X I N G
Medium
Acidity
IONS
Rate expression
Other effects
Ref.
k[Fe(lI)] [Oz][HzP04-]z
Cu2+ catalysis
545
k [Fe(Il)l [021f
[HCII
( E = 14.6 kcal.mole-')
k tFe(lI)I[021
k[Fe(WI [021
[F- 1
Charcoal
catalysis
-
546
541
548
Further data on this reaction are summarised in Table 20. The role of complexing
anions is clear from the kinetics and also from relative rates. It appears that
strongly bound ligands are associated with second-order reduction but that weakly
bound ligands such as H,O result in a third-order reaction. One
of the
third-order term for dilute sulphuric acid (as for aqueous HCIO,) is that the active
reductant is a bridged species of the type ( F e Z +S0 4 Z - Fe Z f ) Z f .
It has also been observed541 that sulphosalicylic acid strongly catalyses autooxidation of Fe(I1) at pH 6. A complex of the chelate, Fe(I1) and molecular oxygen
is believed to be formed and to break down. Ethylenediaminetetraacetic and its
analogues behave similarly548a.
The fast interaction of 0, with Fe(I1)-cysteine complexes to give an oxygen
adduct which rapidly undergoes one-electron breakdown to an Fe(II1)-cysteine
complex and .O; has been examined by stopped-flow spectrophotometry at
570 nm685,Subsequent decomposition of the Fe(ll1) complex to yield Fe(I1) and
the disulphide, cystine, was much slower. Both mono- and bis-complexes of Fe( 11)
are involved and the reaction is first-order i n both Fe(I1) complex and 0 2 ;
k (mono) = (55 1) x lo3 1.mole-'.set-' and k (bis) = (2k0.5) x lo4 1.mole-'.
sec-' at 25 "C, corresponding to factors of lo5 and lo7 times faster than the
analogous reactions with sulphosalicylic acid complexes 5 4 1 of Fe(II), a feature
attributed to Fe(I1)-S bonding in the cysteine complexes686.
Autoxidation of Fe(CN),,- proceeds only in acidic solution, being first-order
M and rather less than first
in Fe(CN),,- but only first-order in acid up to
order at higher acidities (up to 6 x loe5 M ) ; however the acidity dependence can
be rationalised in terms of the sum of the concentrations of HFe(CN),3- and
H,Fe(CN),'-. No dependence upon oxygen concentration was obtained548'.
Autoxidation of ferrous chloride in nonaqueous solvents is much faster than in
water. The rate law is
- d [O,]/dt
= k [Fe(L1)l2[O,]
447
REDUCTION
ion and is attributed to competition between Fe(I1) and Fe(lI1) for CI-. The
relative rate sequence for different solvents is
CzHSOH 20.0
(CH,),SO
(CH,OH), 0.06
2.6
C H 3 0 H 1.0
H z O < 0.02
+ FeC1,
FeOCl2+C,H,CHOHCOC6H,
2 FeOCI,
-+ 2
+
Fe(III)
(slow)
(fast)
- d[Pu(III)]/dt
At high cuprous ion concentrations the reaction becomes zero-order in reductant5 5 5 3 and is determined by the rate of passage of O2 from the gaseous to
the liquid phase. A mechanism involving a Cu(1)-0, complex is proposedss2, uiz.
References pp. 493-509
448
C O V A L E N T COMPOUNDS, M E T A L IONS: O X I D A T I O N - R E D U C T I O N
O,(gas)
kl
+
0, (solution)
k-1
kr
F
CU(I)+O,
k-2
CuO,'
cuo,+
+ H + + Cu2++ H 0 2 .
kn
k-3
At 25 "C k , is 250 I.mole-'.sec-' and in general is given by 10" exp( - 12.0 x lo3)
/ R T ) I.mole- '.sec-'. With slurries of cuprous chloride in acetic acid containing
excess chloride, however, the following relation is
- d [CU([)]/dt
k [CU(I)j2pOz
'.
+ C u + + 2 CH,CN
c u + +o,+ cuo2+
C U O ~++H + + C u 2 ++ HO,.
C U ++ HO,. + C u 2 ++ H 0 2 -
(fast)
Cu(CH,CN),+
(fast)
(slow)
(fast)
ki
+ L k+
CUL,
-
either ligand)
(fast)
+ 0, + CUL302+
c~L,o,+
+ L 1:C ~ L , + .o,CUL,+
kz
k-r
(slow)
(fast)
REDUCTION
449
-+
+ ~ o , ( t r i en ) , . o , ~ +
ki
k-
+
k2
* COL2022+
ki
k-
~ 0 ~ +~
cOL0
,~+ , ~
(c~L,),o,~+
+
k-2
450
ki
k2
k-2
The reaction rate is identical with that of reduction of iodine,,' and discussion
of the mechanism is deferred t o that section (p. 468).
Although the kinetic studies summarised here are useful guides to the gross
features of mechanism it is evident from apparently closely related autoxidations,
e.g. those of V(II1) and U(IV), that subtle factors operate. Fallab538has pointed
out that these reductants give similar kinetics and possess similar reduction
potentials, yet differ in autoxidation rate by a factor of 3 x lo5, and has discussed
differences of this type in terms of the stereochemistry of the electron-transfer
process in the coordination sphere.
An altogether different interaction is that between chelates of oxidising, as well
as reducing, metal ions and oxygen at 100 "C in diphenyl ether s o l ~ t i o n ~ ~ ~ - ~ ~ ~
Attack is on the ligand although the precise site remains unestablished; however,
deuteration of the 3-position of tris-acetylacetone iron(III), (Fe(acac)3), leaves
the rate unchanged. Only chelates with metal ions capable of oxidation or reduction undergo autoxidation but these cover only a relatively small range of reactivity. The products are a complex mixture, thus Fe(acac), absorbs 3.86 moles of
oxygen to yield CO, , H,O, biacetyl and acetic acid as major products and smaller
amounts of mesityl oxide and acetylacetone, and a residue is left of empirical
formula FeC7H,04,85 . Other chelates may enhance the rate for Fe(II1) compared
with acetylacetone, e.g. dibenzoylmethane and 3-methylacetylacetone, whilst
others suppress reaction, e.g. 3-phenylacetylacetone, 3-benzylacetylacetone and
45 1
REDUCTION
= k[~helate]~~~[O,]~.~~
L*+O,
+ R.+Fe(Il)(acac),
kr
k-
(K,)
4 LO2.
(81)
2L02.2P
LO2*+ Fe(II)(acac),
Fe( II)(acac),
ks
+
(82)
(83)
$ Fe( II)o.c.
(84)
k-6
Fe(Il)o,c, O2 2 (acac),FeOO-
References p p . 493-SO9
(79)
Fe-acac
(85)
452
co v A L E N T c o M P O u N D S,
M E T A L I O N S: O X I D A T I o N-R E D u C T I o N
k,(K, [Fe(a~ac),])~.'
3Hz+HzO
0
2 Co(CN),,-
+ SO, -+
2 2 Co(CN),0H3-
++S204'-
6 Pu(II1) XeO,
+ 6 H + = 6 Pu(1V) + Xe + 3 H 2 0
453
REDUCTION
k , [Pu(III)][XeO,] [ H 3 0 f ] 0
with k , = 1.6 x
I.m~le-'.sec-~at 30 "C (p = [H'] = 2 M ) .
The thermal reduction by Np(V) is a slow reaction of complex kinetics, but it
proceeds readily under the influence of light with kinetics565
-d[Np(V)]/dt
k , [XeO,]
Cr(I1) readily reduces a wide range of (but not all) acetylenic compounds to
give mainly the corresponding trans-olefin. Propargyl alcohol is reduced with
kinetics5
-d [Cr(II)]/dt
k[HC=CCH,OH] [Cr(II)]'
The activation energy is almost zero, but ASt = -60 eu. The effect of acidity is
very slight at constant ionic strength, but kDzO/kHzO
= 2.86. The following
mechanism was proposed
Cr(ll) + RCGCR
RC_=CR
R
[kCfCR]
Cr(l1)
References p p . 493-SO9
Cr(II)--2Cr(Iri)
+ )c =c'
H
(fast.
Cr(J
H
;510w1
' R
454
C O V A L E N T C O M O P U N D S . METAL IONS: O X I D A T I O N - R E D U C T I O N
> HCZCBU>> C H ~ C Z C C H Z C H ~
for the ability of the acetylene group to form a n-complex with Ag+ decreases
on a l k y l a t i ~ n ~ Chelation
~.
of Cr(I1) with ethylenediaminetetraacetic acid reduces
the reaction velocity and a new rate law is found, viz.
- d[Cr(lr)]/dt
k [Cr(I1)l3[acetylenelo
- d[Cr(Tl)]/dr
k [acetylene] [Cr(Tr)]2/[H30+]
The reaction of the red complex to give species TI is first-order, but the rate is
dependent on acidity, uiz.
Ilk = a + b / [ H 3 0 + ]
(sec)
-+
species 111
-+
(86)
(87)
(88)
Cr(III)+fumaric acid
(89)
The inverse acidity dependence of step (86) probably stems from dissociation
REDUCTION
455
of the substrate rather than from hydrolysis of CrZ+ in view of the slight acidity
dependence of the reduction of propargyl alcohol. Stepwise coordination of two
Cr(rr) species to HO2CC=CCO2- would given rise to the observed kinetics,
although the authors suggest the second Cr(I1) may be sited at the COz- moiety
rather than at the triple bond.
This reaction is currently under further e ~ a m i n a t i o In. ~ ~
6.3.2 Quinones
The reduction by Fe(T1) is one step of the equilibrium considered in the section
on oxidation of phenols by Fe(III)51', (Q = p-benzoquinone), viz.
Fe( 111) QH -
QH.
.Q-
Fe(IIr)+Q-
+H+
+ Fe(II)+Q
k'
C[Fe(CN)Q-]
[Fe(CN)2-]
where C is some function of pH, depending on the quinone employed. AG' was
obtained using an A factor of 10" and agreed well with calculated values.
Pentacyanocobaltate ion reduces p-benzoquinone in several stages573. An
initial, fast reaction produces the bridged species
[(CN) ,CoOC, H40Co(CN)5]6-
456
COVALENT
C O M P O U N DMSE, T A L I O N SO: X I D A T I O N - R E D U C T I O N
ArCHOH+2 V(I11)
I
ArCHOH
and in acetone-acetic acid mixture the kinetics of both reductions are of the type575
-d[V(II)]/dt = k , [ArCHO][V(II)]f[H,O+]
Simple electron transfer followed by rapid protonation would give the ketyl
radical which dimerises very rapidly.
Cr(I1) reduction of benzaldehyde in aqueous acidic ethanol also yields largely
hydrobenzoin although other products were characterised, e.g. hydrobenzoin
monoethyl ether, and a 1 : 1 stoichiometry is preserved. The rate law in ethanol
acidified both with HC104 and HCl is complex; for example, in H C l - e t h a n ~ l ~ ~ ~ ,
-d[Cr(II)]/dt
+k, [Cr(II)][PhCHO][H,O+][Cl-]+
k4[Cr(II)][PhCH0]2[ H , O f ] [Cl- ]
but, in HCIO,-ethanol, k , = k, = 0. At 25 "C (HC1-ethanol), k , = 5.9 x 10-'
12.mole-*.sec-', k, = 2.4 x
13.mole-3.sec-', k, = 6.3 x 10-' I3.moleC3.
sec-, and k4 = 7.6 x
14.mole-4.sec-'. The complexity of the individual
terms of the rate law is attributed to pre-equilibria giving rise to protonated
hydrate, hemiacetal and halohydrin structures, and ethers derived from these,
6
e.g.
457
REDUCTION
(R
H or C2H5)
PheH(OR)
+Cr3+
PheH(0R)
tCrCI*+
PhCH
*/O'CHPh
+ Cr3+
OR
Maleic acid
.-
Firmaric acid
~~~~
Citraconic acid
-~
~
_
0.018
0.003
0.014
0.005
k3
0.420
0.100
0.059
k4
0.393
0.044
0.178
458
co v A L E N T co M P O u N DS,
6.4
M E T A L I O N S:
0x1D A T I o N-R
E D uCTI oN
However, no evidence for even a transitory existence of .(X-Y)- has been obtained except in the cases of X = Y = halogen or CNS- (ref. 575a). and it is
probable that the breakdown is concerted with reduction. The mole of cleavage
appears to be governed by the relative electron affinities of X. and Y., for example,
hypobromous acid576and h y d r o ~ y l a m i n eare
~ ~ ~cleaved by reducing ions as
follows
HOBr+ Fe2+ + HO-
+ Br.+ Fe3+
N H 2 0 H + T i 3 + -+ HO-+NH2.+Ti4'
The most celebrated example of this process is the Fenton reaction which is
discussed at some length to illustrate the general characteristics of such reductions.
An interesting recent example is the reduction of organic halides, viz.
2 Fe(rrr)+2 N 2 0
but it has long been known that a reacting mixture is capable of oxidising a wide
range of compounds unreactive towards H 2 0 2 alone. Several detailed kinetic
investigations have been made. Barb et al.448determined the rate law
- d[Fe(II)]/dt
= 2 k [Fe(U)][H,O,]
(90)
-+
Fe(lll)+OH.+OH-
(91)
REDUCTION
459
(90) holds even in weakly acid solution (pH 3) when excess Fe(1I) is present,
with k (0 "C) = 12.6f0.3 l.mole-'.sec-' and k (25 " C ) = 53.010.7 Lmole-'.
sec-'. It also holds in very acidic solution even when peroxide is in excess but
at lower acidities and in the presence of excess peroxide, deviation occurs as the
reaction proceeds. This deviation increases with increasing peroxide concentration, but reaches a limit, and has been shown to be associated with the presence of
Fe(l1I); however, addition of Cu(I1) results in deviation from (90) from the outset.
Evolution of oxygen takes place with excess peroxide and the volume obtained
increases with peroxide concentration, but reaches a limit, which can, however,
be increased by adding Fe(Ill) or Cu(II). However, the deviations from the rate
law and the oxygen evolution occasioned by Fe(I1r) were suppressed by adding
fluoride ions. Barb et ~ 1 . modified
~ ~ '
the original scheme of Haber and Weiss4"
as follows
Fe(II)+H202 2 Fe(III)+ O H - + OHFe(Il)+OH.
OH*+H202
-+
Fe(ITI)+OH-
(93)
-+
H2O+ HO2.
(94)
(92)
2 Fe(I1) + O2+ H +
(95 )
(96)
as a sources of oxygen. k92 may be represented as 4.45 x 10' exp( -9.4 x 103/RT)
I.moIe-'.secAt low peroxide/Fe(II) ratios only (92) and (93) occur. As the ratio increases,
OH. increasingly attacks H 2 0 2to give the observed kinetic deviation and evolution
of 0 2 .At high ratios the competition between Fe(I1) and Fe(rrI) for H 0 2 *
dominates and the evolution of O2 becomes independent of peroxide concentration. The effect of Cu(1I) is ascribed to reactions
C u 2 + + H 0 2 -? C u + + O 2 + H +
(98)
C u + + F e 3 ++ C u 2 + + F e 2 +
(99)
where k , , > k 9 6 .The greater prevalence of kinetic deviation and oxygen evolution at higher pH is believed to originate in hydrolysis of Fe3+ and ionisation of
H 0 2 . . A further possibility noted by the authors, following Bray and Gorrin'",
is the oxidation of Fe(I1I) to Fe(IV), viz.
OH.+Fe3+
References pp. 493-509
FeOH3+ + F e O * + + H +
(100)
460
co v A L E N T C O M P O u N DS,
M E T A L I O N S : O X I D A T I ON-R E D U c T 1 0h
+
-+
F e 0 2 ++ H , 0 2 -+
Fe2+ H 2 0 ,
FeO,+
+ H,O
Fe2+ H,O+ 0,
This has received support from work with '80-labelled peroxide under conditions
when 0, is evolved579, but a stopped-flow examination580 indicated the immediate product to be at least 99 % Fe3+ +FeOH2+; in contrast, reduction of
HOCl and O3 gave significant quantities of the dimeric (FeOH),4+ formed very
probably as follows
Fe2'+HOCl
-+
Fe(IV)+OH-+CI-
(very fast)
The absence of dimer i n the Fenton reaction is regarded as evidence for almost
complete one-equivalent reduction.
Subsequent studies have been concerned mainly with questions of detail.
Wells and Salam"' have explored the increase of rate with pH at pH > 3 and
their data are consistent with Fe(OH), as reductant in the region of high pH. The
rate with Fe(OH), can bc summarised as
k, = 3.7 x 10" exp(- 12.0 x 103/RT)I.mole-'.sec-'
"'
FeF, ;
k,,
FeCl+;
k92
1 I8
68.5
'.set- '
1 . 2 10'
~ exp( - 8 . 4 ~ 103/RT); k (25 "C)
I.moIe-
'.set-
46 1
REDUCTION
FeBr';
k,,
78.5
1 . 6 10"
~ exp(-ll.Ox lo3/RT); k (25 "c)= 124
I.mole-'.sec-
Po and Sutin688have disputed both the extent of the catalytic effect of chloride
ion reported by Wells and Salam586and the formation constant of 5.54 (25 "C,
[Cl-] = 0.300 M , p = 1.00) for FeCI' estimated thereby. Wells6" has replied
that the value of k , of Po and Sutin at zero chloride concentration is artifically
increased because of the presence of stabiliser in their peroxide, consequently
masking the catalysis.
and
Chelates of Fe(II), for example with 2,2'-bipyridyl,9,lO-phenanthr01ine~~~
N-(2-pyridylmet hy1ene)aniline' '.
react with hydrogen peroxide at the natural pH of the system with kinetics
- d[Fe(II)]/dt = k[complex][H,O,]'
The slow step is thought to be loss of one ligand from the complex. These chelates
and those with a series of ring-substituted Schiff bases undergo acid fission at
exactly the same rate as oxidation by peroxide.
The effect of adding 2,2'-bipyridyl is more complicated589; it does seem that
the mono- and bis-complexes of Fe(I1) are capable of reducing peroxide although
the rate coefficients can only be given within limits.
U(IV) reduction of acidic H 2 0 2 to give U(V1) has a stoichiometry A[H,O,]/
A[U(IV)] slightly in excess of unity even at high peroxide/reductant ratioss9'.
The reaction is second-order with k, (25 "C,2 M HC104) equal to 0.95 I.mole-'.
sec-'. Slight catalysis by dissolved oxygen was detected and E is of the order of
16 kcal.mole-l. Mild retardation by Cu(1I) and Co(I1) indicate at least partial
chain character.
The Cr(I1) reduction of H,O, involves transfer of one oxygen atom from the
peroxide into the coordination shell of the resulting hexaaquochromium(III)591.
It would seem that 0-0 fission is an inner-sphere process, uiz.
Cr(H20)62+ HzOz
+ [(Hz02)sCr-0-OH]+ + H+
(fast)
[(H,O)sCr-O-OH]+
-+
[(H,O)SCr-O-]+ +OH*
(slow)
I
[(H,O) SCrOH]2+
References p p . 493-SO9
462
dt
[ CN -l +k l +k2KcKa/[H30+1[CN-1) 0 ])(I
+
+ K , [CN- I) + KcKa [H2O2I t o t a J W 3 0 + I [CN- I
2[H2021total[Cr(II)l(kOK1
(1 + ~
a / W 3
+ Cr(CN)g- + H 2 0
H 2 0 2 + H++HO;
[Cr(CN)5H,0]3- +CN-
[Cr(CN),H,0I3- +HOT
* [Cr(CN),H20HO2l3- + CN-
[Cr(CN)4H20H0z]3- + products
The final step is
Cr(II)+OH.
Cr(III)+OH-
2 Co(CN)S3-
+ H 2 0 2 = 2 Co(CN)SOH3-
-d[Co(CN)S3-]/dt = 2 ~ [ C O ( C N ) , ~ - ] [ H ~ O ~ ]
where k = 7 . 4 10'
~ l.mole-'.sec-'
at 25 "C ( p = 0.5 M NaClO,, pH < 10)
and E = 4.820.5 kcal.mole-', ASt = -31 f 2 eu. k falls off at pH > 10 in a
manner indicating H 0 2 - to be unreactive towards C O ( C N ) ~ (pK,
~ - for H 2 0 2 =
11.62)19. Addition of iodide ion (- 0.1 M ) changes the stoichiometry to
463
REDUCTION
(slow)
(fast)
(fast)
(fast)
2 Cr042-+OH-+H20
- d[Cr(III)]/dt
k[Cr(rII)] [H02-]h-*
k2[Cu(I)I[H2O21
C/t,
CH2
-CH
,NH2
INH2,
F
\
% \
C
2.;,
NH;
,C,u2+
..
- O;
N.H*
References p p . 493-SO9
y 2 ,
,
I
74,
CH2
464
COVALENT
C O M P O U N DMSE,T A L I O N SO: X I D A T I O N - R E D U C T I O N
( b ) C~~+-diethylenetriamine(dien)~~~~
(pH ca. 7.5-9.5)
- d [H202]/dt = k[Cu(dien)2 + ] [ H 2 0 2][H,O+]-*
5'
0
OH
_c.
b i p y CU*+
H2O
b i p y CU)'
a
0
bipy Cu2'
02
OH-
6.4.2 Hydroperoxides
-+
CzH6
(fast)
(103)
-+
CH,++Fe(II)
(fast)
(104)
(fast)
(105)
H 2 0 + CH3+ -+ CH,OH
+ OH-
465
REDUCTION
T A B L E 21
A R R H E N I UDSA T A
Hydroperoxide
Fe(I1)comnplex
aquo
aquo
aquo
aquo
aquo
aquo
aquo
aquo
aquo
EDTA
pyrophosphate
pyrophosphate
pyrophosphate
diethylenetriamine
diethylenetriamine
diethylenetriamine
triethylenetriamine
triethylenetriamine
triethylenetriamine
tetraethylenepentamine
tetraethylenepentamine
tetraethylenepentamine
pentaethylenehexamine
pentaethylenehexamine
pentaethylenehexamine
pentaethylenehexamine
Fe(I1)
pH
AND HYDROPEROXIDES
A (I.mole-'.sec-l)
3.9 xi09
1.07 x l o L o
3.53 x 108
9.25 x lo8
4.0 x 109
1.8 X lo9
8 x10'O
6.3 xi09
2.4 x 109
5.36-10
4.8
6.8
8.8
10.0
11.0
11.6
9.8
11.0
11.6
9.I
10.9
11.7
10.0
11.0
11.5
10.0
5.0
xlOIO
2.0 x 108
2.7 x 109
1.6
xIO9
1.2 X I O L Z
7.1 xlOL1
6.7 x10"
4.8 x 1013
3.6 xlO1'
1.4 >:lo11
1.0 ~ 1 0 1 3
2.7 x 1 0 1 3
1.3 xi014
2.8 x 10'
8.0 x 1010
9.0 x 1 O 1 O
3.2 x 1013
E (kcd.mole-l) ReJ
11.1
12.0
9.97
10.84
10.8
9.90
13.1
11.1
10.6
10.4
8.2
8.9
8.4
16.6
15.0
31.2
16.0
14.3
12.4
14.8
14.9
15.4
7.15
11.3
11.3
15.0
k [Fe(CN)64- ] [ROOH] [ H 3 0 +]
k [ROOH]"' [ C O ( I I ) ] ' . ~ ~
595
596
597
597
598
598
599
599
599
600
600
600
600
601
60I
601
601
601
601
601
601
60I
601
601
60I
601
466
-+
+ Co(I11)
Co(II)+H++RO,*
-+
RO2.
+ O2+ Co(I11)
2 RO-+02
- d[ROOH]/dt
~.~~[CO(II)][CO(III)]~~~
[ROOH]
when steady-state concentrations of Co(I1) and Co(II1) have been reached6 90.
Benzaldehyde is the main product, implying dehydration, rather than reduction,
is the course of reaction. Initial rate studies on the Co(I1) reaction indicate
kinetics
d[Co(III)]/dt
~[CO(II)]~[ROOH]
but [Co(III)] reaches a stationary level and the "normal" kinetics then prevail.
The mechanism proposed is
+ Co(III)*ROOH
Co(III).ROOH +Co(II)
Co(I1I) + Co(I1) + C6H5CH0+ H 2 0
[CO(III)], + 2 Co(II1)
Co(II1) + ROOH
-+
which leads to the observed law. The initial rate studies indicate a mechanism
Co(II).ROOH
-+
(slow)
(fast)
467
REDUCTION
(3.2f 0.4) x lo3 I.mole-'.sec-', yields mainly monomeric Fe(rI1) species but gives
some dimeric (FeOH),4+, which suggests Fe(IV) as an intermediate5".
A conventional study of the ferrous ion-chlorine reaction in a chloride medium
indicates the kinetics603
d[Fe(III)]/dt = 2 k1 [Fe(II)][C1,]+2 k2[Fe(II)][C13-]
with kl = ( 9 . 1 f 1 . 0 ) ~10, I.mole-'.sec-' and k, = ( 1 . 6 3 f 0 . 2 ) ~10, I.mole-'.
sec-' at 30 "C (p = 1 M ) . No inhibition by Fe(III), which is a characteristic of the
Fe(I1)-bromine reaction, was detected. Catalysis by Cu(I1) was found.
The appearance of FeC12+ in the Fe2+(aq) reduction suggests an inner-sphere
path. By contrast, the reduction by tris-1 : 10-phenanthrolineiron(I1) or ferroin
is ~ u t e r - s p h e r e ~ 'for
~ ~ ,ferriin is formed in high yield. The kinetics are simple
second-order with k2 (25 "C, p = 1 M ) = 2.2k0.2 (independent of acidity).
The reduction of bromine by Fe(1I) at acidities of0.5 to 0.8 M follows kinetics604
-dcBr2'
dt
k,[Fe(II)][Br;]
,[Br] [Fe( I I I )]
{ + kk,[Fe(II)I
1
k2
Fe(ll)+.Br,-
Fe(II1) +Br-
i
+
k-2
+ -Br,-
5 Fe(III)+2 Br-
k, = 3 . 9 lo7
~ exp(-8.4+0.5x 103/RT) l.mole-'.sec-'
and k-Jk3
(kO.01) at 30 "C. Outside this acidity range extra terms are required.
Reduction of Br, by U(1V) in perchloric acid has the kinetics605
0.11
-d[U(IV)]/dt = k[U(IV)][Br,]/[H'l2
At 25 "C, k = ( 5 . 3 k 0 . 3 ) ~lo4 moles 1-l.sec-l and the reaction is strongly
catalysed by Fe(II1). Br, and Br,- appear to be equally reactive. The acidity
dependence may originate in the pre-equilibrium
U 4 + + 2 H 2 0 + U(OH),,++2 H'
The catalysis presumably involves a reduction of Fe(II1) by U(IV).
Reduction of bromine by TI(1) is important in the bromide-catalysed isotopic
exchange between TI(1) and TI(II1). A potentiometric examination606 revealed
that the reaction was first-order both in Tl(1) and in Br, with k2 = 7 . 2 ~
lo3 I.
mole-'.sec-' (25 "C) and acid-independent. This is in passable agreement with
References pp. 493-509
468
co v A L E N T c o M PO u N D S,
M E T A L I o N S : O X I D A T I o N-R E D u c T I O N
a value of k - , of 4 . 7 lo4
~ l.mole-'.sec-',
constant for the reaction
ki
+
TI(I)+Br,(K
T1(111)+2 Br-
k-
= 2x
lo-" at 25 "C, p
0)
k [Fe(II)][I2]{1
2 Mo(VI)+3 I-
Mo(V),
ke2 Mo(V)
ki
(slow)
(106)
(fast)
(107)
(fast)
(108)
Mo(V)+I,-
2.1,-
2 Mo(VI)+.I,k,
-,
I,-+I-
+I-
469
REDUCTION
The third term is minor. The first two terms are considered to refer to reactions
between TiOH2+ and I, and 13-, respectively. One-equivalent processes involving
.I,- are favoured.
The V2+ ion reductions of iodine, triiodide ion and bromine are all simple
second-order61Ob, with no acidity dependence. The rate and activation data can
be summarised (p = 1.0 M ) as
Oxidant
k,,
0~
(I.mole-'.sec-')
(7.5k0.5) x 1 0 3
(9.7h0.2) x 10'
(3.oi-0.4) x 104
> 5 x lo2
12
13-
Brz
CJ2
E (kcal.mole-')
6.6k0.5
9.7*0.2
4.111.2
ASt(eu)
-21 *2
-1411
-26k4
V3+ was produced in each oxidation. The low values of E preclude the ratedetermining loss of water from the Vz+ coordination shell found for V2+ reductions of several metal
The kinetics of the C1, reduction were not
reproducible.
Cyanogen iodide is reduced by penta~yanocobaltate(I1)~
92a
2 Co(CN)S3- + I C N
Co(CN),13- +Co(CN),,-
2 k [CO(CN)~~-][ICN]
with kinetics
-d[Co(CN)5I3-/dt
470
cov A L E N T
C O M P O u N DS. M E T A L I O N S : O X I D AT ION-RE D u C T 1 0N
Higginson et a1.577,
have used vinyl monomers to capture the radical intermediate,
which turned out to be NH,. when Ti(III) was employed as reductant. Brown and
Drury61 measured the k,,/k, nitrogen isotope effect for the reduction of several
molecules containing N-0 bonds, obtaining a value of 1.034f 0.002 for the reduction of hydroxylamine by Fe(I1) at 25 "C. The lack of enrichment of the I5N
content of residual NH,OH during reduction in the presence of added enriched
'5N-labelled NH4+ rules out a back-reaction involving this ion.
Two studies have been made of the reductions of NH,OH and its analogues by
Cr(I1) perchlorate which differ seriously both as regards the results and their
interpretation. The results of both studies are combined in Table 22. Wells and
salarn6
1 2 . 6 1 2 a find NH,OH and N2H4 to be much more reactive towards Cr(I1)
than do Taube et
(who find no reaction with NzH4 in 24 h at 25 "C).
T A B L E 22
A R R H E N I UPSA R A M E T E R S F O R T H E R E D U C T I O N O F S P E C I E S
N - 0 B Y C H R O M O U S I O N ( p = 1.0 M )
Substrate
NHzOH
NH 3 0 H C
(CH3)3NOH+
(CHj)ZC6HSNOH
N2H4
N2H4
HN3
N3-
I .oo
0.0141
0.66
36
1.32
N O
14
4.2
8.6
1 1 . 1 *0.5
8.5f0.3
6.350.2
10.7
-
13.6
17.5
CONTAINING
ASi(eu)
- 30
-3712
-33f1
-33fl
- 22
-
-7.5
3.1
N-N
AND
Ref.
612,612a
6I2b
612b
612b
612, 612a
612b
612,612a
612,612a
47 1
REDUCTION
However both groups agree on the stoichiometries, which are all of the type 2
Cr(II) : 1 reductant molecule, and on the rate laws, which are generally
d[Cr(III)]/dt = k, [Cr(II)][oxidant]
k, depends on acidity only for HN3 above pH 5 when the active oxidant is N;.
The efficient transfer of '*O from labelled NH20H6'2b to Cr(1I) rules out the
mechanism proposed by Salam and Wells612a,uiz.
2 k [Co(CN):-][NH,OH]
with k = ( 5 . 3 k 0 . 3 ) ~
I.mole-'.sec-' at 25 "C (p = 0.2 M KCI); E
10.9k0.5 kcal.mole-' and ASf = -35+2 eu. The stoichiometry is
2 Co ( C N ) : - + N H 2 0 H + H 2 0 = Co(CN),0H3-+Co(CN),NH:-+
OH-
The absence of any effect of added iodide upon the products is in contrast with
the reduction of H,O, by pentacyanocobaltate (p. 462) and confirms that NH2.
is the free radical intermediate rather than OH.
Co(CN):-+NH,OH
Co(CN)Z- +NH,*
Co(CN),NH:-
-+
Co(CN),OH3-+NH2.
-+
Co(CN),NH;-
2Mo(VI)+2 H 2 0 + 2 N 0
-d[Mo(V),]/dt
= ~[NO~-][H~O+][MO(V)~]O
472
c o v A L E N T c o M PO u N D S,
M E T A L I o N S: O X I D A T I o N-R E D u c T I o N
H 3 0 + NO,HNO,
Mo(V)
NO'
+ HNO, + H,O
+
-+
NO' + O H N O + Mo(V1)
(fast)
(slow)
(fast)
Pu(lV)+NO+H,O
The rate law and the rate coefficient are the same in the two media; the former
being
+ NO++H,O
(fast)
In nitric acid the rate law includes an additional term, k,[Pu(III)] [H+][HNO,]
[NO;], with k , equal to 1.5k0.313.mole-3.sec-1 and E equal to 14.050.5
kcal.mole-'. This term dominates at nitrate concentrations in excess of 1 M and
is attributed to the further equilibrium
HNO,
(fast)
followed by
N,O4+Pu(I1I)
Abel et
law
-+
Pu(1V)+NO2- +NOz-
(slow)
413
REDUCTION
(6)
+ + NO.
HNOz + H + + NO+ + H,O
Fe(I1) HNO,
-+
Fe(II)+NO+
(c)
-+
Fe(III)+NO*
2 HNO,
Fe(II)+ NO,.
-+
Fe(IIT)+ NO,-(etc.)
(slow)
(fast)
(slow)
(fast)
(slow)
The nitrogen kinetic isotope effect for this reaction is 1.034+0.002, which indicates that breaking of the N-0 bond occurs in the slow step6' '.
The As(II1) reduction of nitrite has the kinetics616
d[As(V)]/dt = k [H3A~03][HN02]2
with k = 9 . 6 ~
12.mole-2.sec-' (25 "C). A fast equilibrium is followed by
a slow redox process, viz.
2 HNO,
N,O3+As(III)+2 H +
+ N203+H20
-+
As(V)+2 NO.+H,O
(fast)
(slow)
6.4.6 Nitrate
The reduction by Ce(IZ1) of nitric acid is a reversible reaction, and in a kinetic
investigation6" it was found necessary to remove the oxides of nitrogen with a
stream of nitrogen. The overall reaction is
Ce(III)+H,O++HNO, = Ce(IV)+N02.+2 H 2 0
At 100 "C and with a substrate concentration range of 12 to 16 M the rate law
was found to be
d[Ce(ZV)]/dt
k[Ce(ZII)]f[HNO,]
474
C O V A L E N T C O M P O U N D S , M E T A L I O N S : O X I D AT ION-RED U C T I O N
and ASt
2 N 0 3 - + 3 Mo(V), = 2 N 0 + 6 Mo(V1)
The immediate product of reduction is NO2. which disproportionates to NO3and NO'; however, the latter is very rapidly reduced by further Mo(V) to NO.
Only in a tartrate buffer is the rate appreciable and it is significant that only
in this buffer does the normally diamagnetic Mo(V) display ESR signals (g = 1.937
and g = 1.945) indicating the presence of monomeric Mo(V) which is regarded
as the active species in the proposed mechanism, viz.
Mo(V),
Mo(V)+ NO,2 NO,.
Mo(V)+NO+
NO'
+ Mo(V)
NO2*+ Mo(V1)
-, N 2 0 4 + NO+ +NO,-+
-+
Mo(Vl)+NO.
+ H 2 0 -,H N 0 2+ H+
HNO,
+ Hf
-, NOf
+H20
(fast)
(slow)
(fast)
(fast)
(fast)
(fast)
5 Re(V) 2NO;
3Re0,
+ 2 [Re"'CI,N0]2-
REDUCTION
475
k2[S20a2-][Agf J [ r e d u ~ t a n t ] ~ [ H , O ' ] ~
The observation of Fronaeus and Ostman6,1 that the first-order decay coefficient
of persulphate in the presence of Agf is quite unchanged by adding cerous ions
(which are oxidised) indicates the decomposition of persulphate and the redox
process to have the same rate-determining step. These workers obtain values for
k, and k, of ( 8 k 3 ) x
sec-' and (3.75k0.17)~lo-, I.rnole-'.sec-',
respectively, at 25 "C,and they prefer the mechanism
Ag++SzOa2- -+ A g 2 + + S 0 , 2 - + . S 0 4 It is pertinent that S,OS2- accepts an electron generated by pulse radiolysis of
sec6',.
water to give optically detectable -SO4- within 1.5 x
The ability of the stable free radical diphenylpicrylhydrazyl (DPPH) to act as
an efficient trap for reactive radicals such as -SO4- and OH. has been utilised by
Bawn and M a r g e r i ~ o nin~ their
~ ~ examination of the Ag+-S,OaZ- couple. The
disappearance of the intensely coloured DPPH gave excellent zero-order kinetics;
the rate as a whole was identical with that found by Fronaeus and Ostman6"
and kz was given by 3.1 x 10'l exp(- 17.9 x 103/RT)I.mole-'.sec-'. Sengar and
Gupta62a-626 have also determined Arrhenius parameters for this reduction
and have compared them with those for some redox processes (Table 23).
The oxidations by persulphate of certain complexes of Ag(I) to stable forms of
Ag(T1) or Ag(CI1) have recently been examined626a.Bipyridyl (bipy) and ethylenebisbiguanide (enbig) were selected as ligands. The stoichiometry of the oxidation
References pp. 493-SO9
476
co v A L E N T co M P O U N DS,
M E T A L I o N s: O X I D A T I ON-R E D U c T I O N
T A B L E 23
K I N E T I C P A R A M E T E R S F O R R E A C T I O N S OF T H E S I L V E R - P E R S U L P H A T E
Reactioii
Oxidation of Mn(1l)
Oxidation of TI(1)
Uncatalysed
COUPLE624
0.637
0.772
0.740
9.00~lo-'
9.11 x 10-3
9.58 x
6.45 x lo6
4.3 X I 0 6
2.0 x 107
15.0
13.2
14.2
625
626
624
of Ag(bipy),+ to A g ( b i ~ y ) ~ ' +
is A[Ag(I)]/A[S2082-] = 0.5 (as expected) and
the reaction is first-order in each of the two reactants, yielding an expression for
the rate coefficient in 50 % acetone-water mixture as
k,
A (l.mole-'sec-')
5.0 x 107
4.0 x 109
E (kcal.mole- ')
13.1k0.7
14.3k3.8
3 H + + f S 2 0 8 2 - + C o ( N H 3 ) , 0 H 2 3 += S 0 4 2 - + C o 2 + + 5 N H 4 + + j 0,
which proceeds with the customary rate law under the influence of Ag+ ions and
at the same rate as the Ag(I)-S2OS2- reduction of Mn Z +ions625,reveals that at
least 70 % of the oxygen emanates from the coordinated water molecule. Only a
fraction of the persulphate consumed is effective in production of C o 2 + .The reaction in the absence of Ag+ (p. 481) produces nitrogen and it is proposed626bthat
neither OH. nor .SO4- attack the complex but that the active oxidant is Ag(I1)
or Ag(I11).
Bawn and M a r g e r i ~ o n ~have
, ~ observed cupric ion catalysis of the persulphate-DPPH reaction although the effect is smaller than that with Ag'. The kinetics are complex and few details are given.
477
REDUCTION
k[S2OS2-][Cu(II)]*[~xalate]~
- d[As( III)]
~[CU(II)]*[S~OS~-][AS(III)]
1+ K[As( III)]
dt
As(III)+Cu(II)
-+ CU(II)+SO,~-
As(V)+H02.
H 0 2 - +Cu(I1)
-+
H + O2 Cu(I)
Cu(1)+HO2.+H+
-+
Cu(II)+H,Oz
As(IV)+O2+H+
+ +
propagation
termination
478
COVALENT
C O M P O U N DMSE,T A L IONS:O X I D A T I O N - R E D U C T I O N
-+
SO:-+As(V)
k[S,O,]'
[CU(~I)]'[S~(III)]~[H~O+]~
s20g2-2 2 *so,
initiation
-SO,
propagation
termination
cu(I)+s,og~-c u s , o s -b
CUS,O,-
-b
C U ( I I ) + S O ~+.SO4~-
(slow)
(fast)
The reductions by ferrous ion and mono- and bis-bipyridyl complexes of Fe(1I)
are also simple second-order with (for the Fez+ reaction at zero ionic strength630).
k , = 1 . 0 10"
~ exp(- 12.1 x 103/RT)I.mole-'.sec-'.
This reaction generates
an intermediate capable of oxidising ethanol631,but the effect is suppressed by addition of C1-, Br- and acrylonitrile, the latter being polymerised.
An attempt to correlate reduction rate with redox potential of the metal ion
479
REDUCTION
T A B L E 24
A R R H E N I UPSA R A M E T E R S F O R
THE REDUCTION
OF PERSULPHATE BY
COMPLEXED
D I V A L E N T M E T A L I O N S 6 5 2 '6 3 3
Reductant
Tri~-4,4'-dimethyIdipyridyliron(11)
Tri~-2,2'-dipyridyliron(II)
Tris-o-phenanthrolineiron(I1)
Tris-5-methylphenanthrolineiron(II)
Tris-2,2'-dipyridylruthenium(II)
Tris-2,2'-dipiridylosmium(II)
3.2 x lo8
10.6
12.4
13.3
12.6
14.6
9.4
5.1 x 10'
1.5 x 109
1.6 x 10'
5.0 x lo8
2.8 x 10'
2 M2++S20S2-
2 M 3 + + 2 SO4,-
Substituent
None
5-Nitro
5-Methyl
5-Chloro
5-Methyl-6-nitro
5,6-Dimethyl
4,7-Dimethyl
3,5,6,8-Tetramethyl
References pp. 493-509
A (I.mole-'.sec-')
E (kcatmole- ')
1014
13.5
21.5
11.9
20.1
10'9
21
108
13.3
109
10'9
108
105
6.9
106
9.1
480
co v A L E N T co M P O u N DS,
M E T A L I O N S: O X I D A T I O N-RED
u CT I oN
Cr2++.S04- + C I - ~ + + S O , ~ Br- merely reacts with -SO4- to produce Br., which is oxidised by Cr2+ by an
inner-sphere route, possibly in the form of *Br2-.
Both kinetic and product studies have also been made626bof the reductions
~ +the
. concentration of the
of S2OS2- by CO(NH,),OH,~+ and C O ( N H ~ ) ~As
48 1
REDUCTION
dt
S z 0 8 2 - + 2 *SO4-
+As(IV)
+ As(V)+HOz*
+ H++02+S042-+.S04-
+ +
As(IV) + H 0 2 - + As(II1) H+ 0,
References p p . 493-509
482
C 0 V A L E N T C 0 M P 0U N D S , M ETA L I 0 N S: OX I D A TI 0 N-R E D U C T I 0 N
-d[HSO,-]/dt
k , [HSO;]
-d[HSO,-]/dt
k , [HSO;]
+ ~,[CO(II)-J"[HSO,-]~
(pH 6-6.7)
Mn(I1) catalysis
Mo(V1) catalysis
-d[HSO;]/dt
+k
[M n( I 1I)]* [H S 05]
~,[HSO;]+~,[MO(VI)]~[HSO,-]
The latter reaction displayed an induction period independent of reactant concentrations and pH. The initial decompositions may be
HSO,-
+ M"'
+ M("+' ) + +.SO,- + O H -
Production of the oxidised ion has been observed for Mn(I1) catalysis642.
REDUCTION
483
in 1 : 1 solvent mixture and at 7 M acidity (HC104) the second-order rate coefficients are 0.02 and 0.04 l.mole-'.sec- ', respectively643.The stereochemical course
of reaction is illustrated by the reduction of optically inactive a-phenylethyl
chloride and bromide to diphenylbutanes of composition 85-90 % meso and
10-15 % d,l. The mechanism is thought to involve transfer of a halogen atom, uiz.
Halide always appears in the coordination sphere of Cr(I11) immediateIy following reduction. Castro and Kray643 propose that the organochromium compound is formed by subsequent attack of R. upon further Cr(I.1).
Similar kinetics are exhibited by the reduction of vicinal dihalides by Cr(II)645,
which proceeds 10-40 times faster than that of the allylic halides. Such activation
by a second halogen atom suggests645a neighbouring group effect, viz.
The dehalogenation of the a-haloalkyl radical is a fast step which can take place
by several possible routes645.Dibromides are reduced much faster than dichlorides
and truns-l,2-dibromocylohexaneis reduced 100 times faster than the cis-isomer.
This accords with neighbouring group assistance which bromine seems particularly
capable of offering (see subsection 6.4.10).
Attempts have been made647to trap the intermediate radical with a monomer,
particularly in the reduction of benzyl chloride by Cr(I1) to benzylchromium ion
(and ultimately to toluene and dibenzyl). The results were ambiguous, however,
as benzylchromium ion itself reacts with butadiene and acrylonitrile. This reduction shows second-order kinetics with E = 14.6 kcal.mole-' and ASt = 14.3 eu.
The rate coefficients for benzyl chloride, bromide and iodide follow the expected
sequence647
C,H,CH,Cl
3.2 x
C6H5CH,Br
4.1 x lo-'
C6H,CH21
1.8
484
covA L E N T
C O M P O U N DS, M E T A L I O N S : O X I D A T I O N - R E D U C T I O N
n-butyl bromide
n-butyl iodide
10,000
isopropyl chloride
3.6
isopropyl bromide
1,100
isopropyl iodide
63,000
f-butyl bromide
5.800
sec-butyl iodide
110,000
t-butyl chloride
29
140
+ H,O
-, R-
+ Cr"'en,X2+
RCr"'en:
--f
RH+Cr"1en2(OH)2+
2 Co(CN):;+RX
Co(CN),R3- +Co(CN),X3-
but for ethyl, isopropyl and t-butyl iodides an additional path is apparent649a
of the type
- ~ [ C O ( C N )-]/dt
,~
2 k, [CO(CN),~
- 3 [RX]
are listed in Table 26. The reduction of methyl and benzyl halides resembles that
by Cr2 (as), uiz.
+
485
REDUCTION
T A B L E 26
RATE COEFFICIENTS FOR T H E REDUCTION
ANOCOBALTATE(II)ION^^^^
Temp., 25.0&0.2 "C; medium, 20 % HzO-80 % C H 3 0 H (v/v); p H > 11, / I = 0.02 M (NaCIO,).
kz (I.niole- '.see-')
Halide
~~~~
3800
9.1
I .20
0.059
0.043
0.0095
105
7.5
2.33
0.00049
63
0.99
0.68
0.30
0.12
+
Co(CN),H3- + CH3CH21
C O ( C N ) , ~ - CH3CH,*
--f
-+
Co(CN),H3- + CH,=CH,
Co(CN),13-
+ C,H,
486
E D u C T IO N
T A B L E 27
R A T E C O E F F I C I E N T S FOR T H E R E D U C T I O N O F O R G A N I C H A L I D E S B Y
cO(l)
CHELATES649c
Halide
CH3CI
CH,Br
CH3I
CH3CHZCl
(CH3)ZCHCI
CH3CH2Br
(CH,),CHBr
CBHSCH~CI
k2 (rriburylphosphitie-cobaloxiine,)
(I.mole-.sec- * )
5.0
1 . 6 lo3
~
3.4 x 104
4.7 x 10-2
-
3. I
1 . 1 x 10-1
10-
2.2 x
2.3 x
9 . o
3.2 x
1.6
102
8.5
103
10-3
~
10-4
1.8
4.4 x 1 0 2
[ C o . . . R . . . XI-
Co-R+X-
Closely related to the reductions by Cr(I1) of vic-dihalides are those of the comp o u n d ~ ~ ~ ~
X Y
where X = halogen and Y = OH, CH3COz, NH, and Cr(I1) refers either to the
ethylenediamine complex of Cr(I1) or the aquo species. For a series of 3-Ysubstituted-7-butyl bromides the rates given in Table 28 were obtained. With the
exception of the dibromides the composition of the butenes obtained from a given
pair of diastereoisomers is the same, although the &/trans ratio depends on Y.
Only the dibromide is highly stereospecific, giving up to 97 % trans elimination
under some conditions, and it appears that only Br is capable of forming the bridged
487
REDUCTION
T A B L E 28
RATES O F R E D U C T I O N O F 3 - S U B S T I T U T E D B U T Y L B R O M I D E S B Y
erythro
H
OH
CH3COZ
~ - T o s ~ ~ o x ~
CI
Br
CI'(II)aq
M.
= 0.9
threo
0.68
2.0
6.0
25
660
0.14
0.56
2.1
7.7
51
1600
species in reaction (109). This is supported by the rate difference both in these
reductions and in those of cis- and trans-dibromocy~lohexanes~~~
(preceding
section).
6.4.11 Carbon tetrachloride
A,,, 532 nm
The overall oxidation is first-order in Fe(lI), and the main product is tetrachlorethylene, indicating a stoichiometry
2 CC14+4 FeCl,
C2C14+4 FeCI,
At 22 "C the overall second-order coefficient for reductions by Fe(TI) and Cu(1)
are, respectively, 4 x lo-, and
5x
I.mole-'.sec-'.
Products in the
presence of olefins demonstrate unequivocally the intermediacy of carbenoid
transients, and a complex mechanism is put forward, viz.
FeC1:-
+ CCI4
2 cc1,CCI,.
CT
- -
C T -FeCL4-
CCI,.
+ CL-
(slow)
C2C16
+ FeCIi-
2 [FeCI,(CCI,)I-
C1-
-2FeCI;
CFeCl,(CCl,)I'
+ C2CI4
488
c o v A L E N T c o M P O u N D S.
M E T A L I o N s: O X I D A T I o N-R E D u c T I O N
Propagation
Termination
ArS0,CI
+ CuCl
kz
ArSO,.
k-2
ArS0,-+ Cu(1)
+ CuCl,
ArSO,-. Cu(I1)
k-
(slow)
-+
Cu(II)+ products
there is evidence that they can function as oxidising agents (vide infra), uiz.
Reactions of e-aq and OH. are dealt with later in this series.
7.1
489
STABLE R A D I C A L S
Diphenylpicrylhydrazyl (DPPH)
(C6H5)2N-N
b
0
NO2
NO2
is a well-known stable free radical which reduces the acetates of several oxidising
metal ions in acetic
the second-order coefficients at 25 "C revealing
remarkably low specificity, particularly towards the two-equivalent oxidant Pb(IV)
Metal acetate
k , (I.mole-'.sec-')
Pb(IV)
35
Co(r1I)
22
Ce(IV)
55
Fe(I1I)
88
Fe(II)+C,H,OH+DPPH
[C2H,0-Fe(I11)]2+ +DPPH,
(DPPH, represents the corresponding hydrazine). The kinetics are simple secondorder with a rate coefficient, k,, in l/l(v/v) ethanol-water of 2.73 x 10" exp
(13.5 x 103/RT)I.mole-'.sec-', independent of pH and of ionic strength. Log k ,
is inversely proportional to the dielectric constant of the medium. The small
entropy of activation and the rather large activation energy are taken as favouring
a hydrogen-atom transfer as opposed to an electron-transfer process.
Ions also reducing DPPH include Sn(II), Cr(II), Fe(CN)64- and Mo ( C N) , ~ - .
However, Ag(I), Pb(II), Mn(lI), Co(I1) and Ce(1II) are inert. These data enabled
an approximate estimate of 1.1 V for the redox potential of DPPH/DPPH, to
be made652.
The reduction of 2,2,6,6-tetramethyl-4-piperidol N-oxide (RNO.)
OH
490
COVALENT
COMPOUNDS, M E T A L
IONS: O X I D A T I O N - R E D U C T I O N
reaction. Anions exert a specific catalytic effect, in the order: SO:- > CI- > ClO;,
probably through formation of more reactive complexes of Fe(I1) as in the Fenton
reaction. The effect of pH is complex, being related to the prevailing anion, but
the acidity dependence in perchlorate media is zero. E is ca. 7 kcal.mole-' under
most conditions.
7.2
GROWING POLYMER R A D I C A L S
FOR
Metal ion
Acidity
Fe3+aq
Cu2+aq
Ce4 aq
&+aq
Hg2+aq
T13 aq
+
vo2
FeOH2
FeC12
FeClz
FeC13
FeBr2
FeN3'+
FeNCS2+
Fe(di~y),~
F e ( ~ - p h e n') ~ ~
Fe(CN)63Ti3+aq
Euz+aq
V2+aq
Cr2+aq
Fez aq
~ o ~ + a q
+
0.1+O.I)XIO~
(8.5 1 0 . 2 ) x 1 0 5
( 5 . 8 1 0 . 3 ) x 10'
(8 1 4 ) x 1 0 4
(1.1 f0.6)x105
(2.8
1.4) x 105
O<k,<1
(7
h o . 7 ) ~1 0 3
1.45 x 1 0 5
1 . 1 x 107
2.3510.6
5.4 *l.3
4.2 x 104
21
-
0.37h0.3
0.7 h 0 . 6
XIO"
4
2.7 Y 1 0 5
-
-1.2
2.3 Y 105
3.6 x106
2.4 x 1 0 5
2.2 i:10'
1.6 ~ 1 0 7
h0.3
0.5 1 0 . 2
-2.4
h0.9
10'2
-4.3 &0.5
1.2 1 1 . 0
11.1 &2.0
108-1 0'0
6.0 f1.5
R E D O X R E A C T I O N S B E T W E E N R A D I C A L S A N D M E T A L IONS
49 1
Fe2
+X +R +
-
R.
k, at 60 "C
(I.mole-'.sec-')
acrylonitrile
methacrylonitrile
styrene
6.53 x lo'
6.15 x 10'
5 . 4 ~104
7.3
C4H9CO-O-O-COC4H9
CU([) + C,HgCO,.+ Cu(Il)O,CC4H,
C4H9C02. + C4H,.+C02
+
C4H9*+C U ( H ) O ~ C C ~+HCH,CH,CH=CH,
~
C4H9C0,H+Cu(I)
i.e. in toto (C4H9C0,), = CH,CH,CH=CH, + C4H9C0,H + CO,
R e f e r o i ~ c ip. ~p . 493-509
492
C O V A L E N T C O M P O U N D S , M E T A L IONS: O X I D A T I O N - R E D U C T I O N
k R . + C u ( l l ) / k R . +DH
kR.+DH
CH,(CHz)ZCHz* + CHj(CH2),CHO
C4HIo CHj(CH2)3CO.
and from the known activation energy for this reaction a value of k R . + C u ( l l ) at
57 "C, the temperature at which the competition was staged, of 1.1 x 10' Lmole- '.
sec- was derived. More generally, for this particular oxidation
'
k,
k, was determined for several analogous reactions, always falling in the range
log k, = 8.2f0.6, but correlating roughly with the ionisation potential of the
radical. This compares with a value of 1.17 x lo3 I.mole-l.sec-l (25 "C) for Cu(I1)
reacting with growing polyacrylamide radical which is a much larger molecule
carrying an electronegative group near the radical site654.
The reaction between CH,cHOH and Cu(I1) has been examined by pulse
radiolysis661.The reduction of CuCI, followed the beam pulse shape even down
to 2 x
M oxidant, from which it follows that k, > lo9 I.mole-'.sec-'.
CH,CO,H reduces Cu(O2CCH3), with a similar rate coefficient but fails to reduce
the dimeric Cu,(O,CCH,),.
It was also shown that reaction between ethanolic
Cu(1) and CH,CH(OH)O,., monitored by pulse radiolysing oxygenated ethanolic
Cu,Cl,, is diffusion-controlled.
By pulse radiolysis of nitrous oxide-saturated aqueous solutions of ferricyanide
(2 x lo-, M ) and various alcohols (0.1 M ) , Adams and W i l l ~ o were
n ~ ~able
~ to
obtain absolute rate coefficients for the ferricyanide oxidation of the radicals
derived from the alcohols by attack of the solvent irradiation product, OH..
T A B L E 30
S E C O N D - O R D E R R A T E C O E F F I C I E N T S F O R SOME O X I D A T I O N S OF FREE R A D I C A L S
Oxidant
Radical
Medium
Cu(1I)
CH3CHOH
Cu(l1)
Cu(l1)
Fe(CN),3Fe(CN)c,3-
n-butyl
acrylamide (polymer)
acrylamide (monomer)
acrylamide (polymer)
-20
1109
66 1
51
25
-20
25
1 . 1 x 108
1 . 1 7 103
~
6.8*0.4 x lo6
8.5 x 1 0 5
65F
654
662
654
REFERENCES
493
ACKNOWLEDGEMENTS
Dr. J. S. Littler is thanked for reading the manuscript, for making many usefu
comments and for disclosure of unpublished results. The author's wife, Sheila
is thanked for her support during the preparation of this chapter. The encouragement of Professor T. C . Waddington, formerly Chairman of the School of
Molecular Sciences, University of Warwick, is also acknowledged.
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REFERENCES
509
Chapter 5
Induced Reactions
L. J. C S A N Y I
1. Introduction
1.1
DEFINITIONS
I t has been well known for a long time that some reactions taking place at :I
very slow rate may be markedly accelerated by the simultaneous occurrence of
another reaction of measurable velocity. On the suggestion of Kessler' this
phenomenon is called chemical induction and it is said that the reaction of
measurable velocity induces the other slow reaction.
An induced reaction may be represented by the following scheme.
A+I = C
A+Ac
While in separate solutions only reaction (1) occurs, in a common solution of the
three constituents reaction ( 2 ) also takes place.
Reaction (1) is called the primary, main, or inducing reaction, which brings
about induced reaction ( 2 ) . Substances A, I and Ac taking part in both reactions
(1) and (2) are called actor, inductor, and acceptor, respectively. The extent of
the induced change is conventionally expressed by the induction factor Fi,defined as the ratio of the equivalents of the induced reaction to those of the primary
reaction.
In the majority of cases both the primary and the induced reactions are oxidation-reduction reactions. In such reactions the actor can have either reducing or
oxidizing properties. The chemical characteristics of the inductor and acceptor
are always identical and opposite to that of the actor. When the latter is a reducing
agent the acceptor and inductor are oxidants and vice versa.
Besides induced oxidation-reduction reactions we often speak of induced dissolution, induced precipitation, as well as of induced complex formation; there is
even a reference to an induced reaction caused by neutralization. It is only necessary to examine briefly the latter cases.
Induced precipitation is a collective name for processes accompanying the
formation of solid phase, such as occlusion, adsorption, compound formation,
formation of isomorphous mixtures, mixed crystals, colloidal solutions, etc. In
INTRODUCTION
51 1
our opinion induction occurring at precipitations does not fall within the
category of chemical induction since coprecipitation is determined by different
crystal-physical and -chemical factors.
As far as we know there is only one reference to induced change caused by
neutralization. Raschig observed a strong air oxidation during the conversion
of bisulphite-sulphite. We are of the opinion that, here, not the air oxidation of
sulphite induced by neutralization but the pH dependence of oxidation is involved.
Induced dissolution is also a well known phenomenon and frequently applied
in chemical analysis. To dissolve platinum easily it was suggested by Ropp3
that the sample should be alloyed with silver or copper, the alloys being easily
soluble even in dilute acids. Anhydrous chromic chloride, insoluble in water
and dilute acids, becomes easily soluble by adding metallic magnesium or zinc to
the dilute acid4. In this case the chromium(I1I) compound is reduced to chromium(II), which will be oxidized by the solvent to water-soluble chromium(II1)
CrClz+3 H 2 0 + H 3 0 + = [Cr(H2O),C1:]+3H,
(3)
1.2 T Y P E S
O F I N D U C E D R EA C TI O N S
In the early years of this century Luther and Schilow attempted to classify
induced reactions. This classification was based on the specific nature of substances
taking part in the induced reaction. Thus they distinguished two groups: coupled
and induced chain reactions (this term was adopted later).
References p p . 577-580
512
I N D U C E D REACTIONS
ired
C I ~
u A, + ab Iox
513
INTRODUCTION
Since Pa + (1 - P)a
F.' =
equivalents of Ac reacted
(1 - P ) a
= (1 -p)(l - a ) sum of equivalents of I reacted
crb + P( 1 - a)b
c1+ P( 1 - a )
Knowing Fi and
CI,
Fi (FJcI)
F, = Fi(cl 1) CI-F~ l-(Fi/cl)
If Fi/cl 1, then F, -+ 00.
From the foregoing it can be seen that F, refers to the rate ratios of competing
reactions (6) and (5). A knowledge of F, makes it possible in certain cases to
obtain the relative rate coefficient, k , / k 5 .
Denoting the equivalents of the actor converted in reactions (4), (5) and (6)
by x 4 , x 5 , and x6, and the initial concentration of the actor (also in equivalents)
by cA, then
-+
CA
x4+X,+xfj
The rate equations of the competing reactions (6) and ( 5 ) , assumed second order,
are
References p p . 577-580
514
INDUCED REACTIONS
Dividing we obtain
Hence
If the initial concentrations of Ac and I are high so that the amount of substance
converted can be ignored, i.e. if the concentration of the actor is low, then
The utility of this approximation (9) can be judged by the figures in the last
columns of Tables 4, 6 , 8 , 9 and 10.
In practice, however, it may happen that w 5 w6, even when concentrations
of I and Ac are commensurable. In such cases, even with the greatest ratio of
(Ac/I), which can be realized experimentally, Fi cannot reach a limiting value,
i.e. the characteristics of coupled reactions cannot be observed.
(a, ii) When the actor is a reducing agent and is oxidized by the inductor in
steps Ared+ At -+ A,,, the considerations are similar to those in the previous
case. Obviously, the problem is more involved when the reduction or oxidation
of the acceptor is taking place in two or more steps. Cases are particularly complicated when the inductor also has more than two oxidation states.
From the above it can generally be concluded that the basic condition of the
occurrence of coupled reactions - if the coupling intermediate is derived from the
actor-is that the actor has at least three (including zero) oxidation states.
Case a, i is well illustrated by the arsenite-induced oxidation of manganese(I1)
by chromic acid, studied by Lang and Zwerina. The overall equation of this induced reaction is
=-
2 Cr(VI)+2 As(rrr)+Mn(rr)
According to eqn. (lo), CI
2 Cr(III)+2 As(V)+Mn(IV)
(10)
INTRODUCTION
515
CI = -
u-x
Hence
x =
c1u+
-0
~-
1 +CI
Refercncev p p . 577-5610
516
INDUCED REACTIONS
c(
= 6, o = 3, and C I = 0.5
0.5 x 6 + 3
=4
1 +0.5
CI = -
and so
y = n+cI(n-rn)
Induced chain reactions occur when the very slow reaction between acceptor
and actor is catalyzed by the inductor. Actually it means that primary reaction
between actor and inductor induces a chain reaction between actor and acceptor.
That is why this group of reactions is called induced chain reactions.
Assuming that the actor forms its stable end-product through steps A,, + A,
+ Ared, and the acceptor is oxidized according to Acred+ Ac, + Acox, and
furthermore, for the sake of simplicity, that the inductor is transformed directly
to the end-product according t o Ired + I,, which is a reversible reaction, we can
write
Aox+lred
+Iox
+Ired = Ared
+I o x
(13)
(14)
A, +Acre,
Ared+Ac,
(15)
AC, +Iox
ACox+Ired
(16)
INTRODUCTION
517
The above scheme represents a closed-chain reaction showing that, at a high concentrations of Ac if the chain carrier A, reacts only with Acred,Fi never reaches
a limiting value: the plot of Fiversus ([AC]/[I])~is exponential. If the concentration of Acredis high enough, the competing reaction (14) is practically negligible;
thus, in the overall equation of the induced reaction, composed of steps (13),
(15) and (16)
only the acceptor and thc actor take part, in contrast to coupled reactions, in the
overall process of which the inductor is also involved. This fact is often emphasized
as a characteristic difference between the two types of induced reactions. To stress
the point is, however, not reasonable, for it is valid only in special cases when rate
w15
>> w 1 4 .
From the above scheme it is evident that the extent of the induced change here
as well as in the case of coupled reactions depends on the rate ratios of competing
reactions (14), (15) and (16). Thus any factor influencing these rates will also
affect the value of the induction factor. According to our experience of investigating induced reactions by titration methods, e.g. titrating the common solution
of the actor and the acceptor with the solution of the inductor, the delivery rate
of the titrant, the dilution of the solution, the stirring rate, the hydrogen ion concentration, the order of addition of the reagents, the temperature, the presence of
several, apparently indifferent substances - all considerably influence the value of
Fi .
The principal characteristic of induced reactions of this type which have not
been stressed so far, is that the extent of the induced change greatly decreases and
in most cases reaction even ceases in the presence of chain-breaking substances.
The induced reaction can be suppressed by any substances reacting with chain
carriers at a higher rate than does the acceptor, and the product of the reaction
of the suppressor can easily react with the inductor. Since the concentration of
the chain carriers is generally low, the supressors of induced chain reactions exert
considerable effect even in small quantity. The effect is particularly pronounced
when the suppressor reacts reversibly.
From the above it is obvious that merely the magnitude of the numerical value
of Fi and the shape of the plot of Fi uersus ([Ac]/[I]), do not make it possible
to classify induced reactions correctly. It is necessary to learn more about the
mechanism of induced reactions. The schemes presented show clearly that a
genuine coupled reaction can be regarded as an open-chain, and an induced
catalysis as a closed-chain reaction. However, these limiting types of reactions
occur only rarely.
The examples mentioned illustrate well the peculiarities of induced reactions,
i.e. a hardly oxidizible substance can be oxidized when a simultaneous reduction
References p p . 577-580
518
I N D U C E D REACTIONS
519
EXAMPLES
CHROMIUM(V)
S P E C I E S AS
COUPLING INTER-
MEDIATES
520
I N D U C E D REACTIONS
TABLE 1
INDUCED REACTIONS WITH
Inductor
-
Cr(V1)
AS ACTOR
Acceptor
Fi
Ref
Mn(I1)
Itartaric acid
Mn(I1)
Mn(I1)
Mn(l1)
Mn(II), Ce(II1)
Mn(l1)
Mn(I1)
Mn(I1)
Mn(1I)
Mn(I1)
Mn(I1)
Mn(l1)
Mn(I1)
Mn(II), Ce(II1)
IBr-
0.5
2
12
0.5
0.5
19
20
21
21
22
22
23
24
24
25
26,27
28
29
30-33
15
As( I I I )
As (I I I)
As(II1)
iso-propanol
sec-butanol
n-butanol
sec-hexanol
n-propanol
caprylalcohol
ethyleneglycol
propyleneglycol
2, 3-butyleneglycol
pinacol
benzaldeh yde
formaldehyde
formic acid
Fe(I1)
Fe(1l)
V(W
V(II1)
V(I1)
Ti(Il1)
Ti(II1)
15
15
15
1-
IIIBrIindigo
tartaric acid
tartaric acid
tartaric acid
loxalic acid
glycerol
lactic acid, citric acid
maleic acid
uo2+
oxalic acid
Sn(I1)
Sb(II1)
[Fe(CN)614-
34
34
15, 3 5 , 36
17, 37
1
1
1
hydroquinone
38
TABLE 2
I N D U C E D REACTIONS WITH
Cr(VI)
Actor
Acceptor
As(II1)
As(II1)
As(lI1)
As (111)
As(ll1)
Sn(1I)
0 2
HBr03
Fe(lI1)
HClOj
HzSz08
0 2
18
1
AS l N D U C T O R
ReJ
1, 15, 39
15
IS
15
15
15
52 I
EXAMPLES
+ H z O + 2 HCrO,
it was found that the rate of disappearance of chromic acid is proportional to the
first power of the concentration of arsenous acid and of hydrogen chromate and
approximately to the second power of the hydrogen ion concentration.
Edwards42 has pointed out that, at low acid chromate concentrations, the plot
of k/[HCr04][H+]2 against 1/[H+] is linear but not horizontal. Therefore the
rate law
rate
k,[HCrOJ[H,AsO,][H+]
+ k,[HCr04][H3AsO3][H+]*
-~
_
I
+ As(III).HCrO,
--f
product
pre-equilibrium, K
rate determining, X-
2kK, B = K , k
3.76~
sec-l,
22.4 I.mole-'
d[Cr(VI)]
- A[As(III)][HCrO,]
~dt
1+ B[HCrO,]
+ k'[Cr,O:-][As(
Ill)]
522
I N D U C E D REACTIONS
where
k'
2.47 x
I.mole-'.sec-'
'
'
TABLE 3
OXIDATION
OF
MANGANESE(1I) I N D U C E D
BY
REACTION
BETWEEN
CHROMIC
ACID
A N D ARSENOUS ACID
.-. -
Initial ratio
57.3
37. I
28.8
23.0
19.2
17.7
16.4
15.4
14.4
12.9
0.49
0.49
0.41
0.46
0.45
0.41
0.39
0.33
0.27
0.14
73.5
73.5
23.5
13.3
13.6
6.8
5.3
2.9
1.8
0.9
523
EXAMPLES
TABLE 4
A R S E N I T E - I N D U C E D O X I D A T I O N O F I O D I D E B Y DICHROMATE A C C O R D I N G TO
DE LURYI*
Conditions:
-
__
1.96
2.94
3.95
4.92
5.90
7.38
9.88
14.77
24.62
34.42
0.0
1 . 6 6 lo-'
~
__ ~
1.24
1.41
1.41
1.50
1.51
I .77
I .86
2.05
2.12
2.1 I
-
M AsZO3;1 . 1 1 x
~
1.15
1.34
1.46
I .54
1.60
I .67
1.74
I .82
I .89
1.92
-
4.07
6.1 I
8.21
10.23
12.27
15.35
20.55
30.72
51.21
7 I .59
-
M KZCr2O7,8 . 0 ~
_
4.93
5.23
5.28
5.42
5.50
5.67
5.77
5.78
5.98
5.80
-
~~
M HzS04.
4.05
3.73
3.78
3.67
3.30
3.23
3.13
2.87
2.87
2.78
8.93
1.21
I .40
I .39
1.47
1.66
1.75
I .84
2.01
2.08
2.08
-
2.07
2.07
2.08
2.09
2.08
2.07
2.08
2.08
2.08
2.08
-
t F, is calculated by eqn. (8) (p. 513) using values of (Fi),,bs. The value of
Considering the limiting values of the induction factor it may be postulated that
in the case of iodide and bromide the induced oxidation is caused by chromium(V),
whereas for induced oxidation of manganese(I1) chromium(1V) is the coupling
intermediate. Therefore, one has to assume that in the course of reaction between
arsenic(II1) and chromium(V1) both chromium(V) and chromium(1V) intermediates are involved. The mechanism below, proposed by Westheimer4', seems
to be in agreement with experiment.
Cr(V1)
Cr(IV)+Cr(VI)
Cr(V)+ As(111)
-+ 2Cr(V)
+
Cr(I1I) + As(V)
(18)
(19)
(20)
524
INDUCED REACTIONS
O1t
I
15
10
Id25
25
x 10.~M K I
Cr(V)+ I -
10- Cr(III)
IO-+I-+2H+
I,+H,O
Cr(lII)+ Mn(II1)
(23),
Mn(IV)+Mn(II)
(24)
From the stoichiometric point of view the above induced reactions can be
described equally well if the formation of arsenic(IV) is assumed, viz.
Cr(VI)+As(III)
Cr(V)+As(IV)
(25)
525
EX A M P L ES
reaction should be autocatalytic. However, omission of step (25) from the mechanism of induced oxidation of manganese(I1) leads to the difficulty that reaction
(19) involves a positive standard free-enthalpy changes6, and, consequently, will
be too slow to be significant.
2.1.2 Reaction between isopropyl alcohol and chromium( VZ)
Oxidation of isopropyl alcohol (H,R) by chromic acid has been studied in det ai
by Westheimer and N o v i ~ kand
~ ~ it
, was found that acetone (R) is formed nearly
quantitatively. The reaction proved to be first order with respect to hydrogen chromate and second order with respect to hydrogen ions. Measurements using 2deutero-Zpropanol under identical conditions as those for the oxidation of ordinary isopropyl alcohol showed the rate of reaction to be of that with the hydrogen compound. This fact is considered to prove that the secondary hydrogen atom
is removed in the rate-controlling step and that the assumption of hydride-ion
abstraction can be excluded. The data are consistent with the following mechanism
(26)
Cr(IV)+H,R = Cr(II)+R
(27)
HCrO,
Cr(IV)+Cr(VI)
Cr(V)+H,R
Cr(V)+Cr(IIT)
(28)
Cr(III)+R
(29)
in which only chromium intermediates are assumed and neither organic free radicals nor reaction of chromium species with the solvent molecules are taken into
account. The absence of organic free radicals seems to be supported by the fact
that oxygen has no influence on the oxidation. Reaction between the solvent and
the chromium species is unlikely because it would lead to the production of OH
radicals and hydrogen peroxide. If hydrogen peroxide were formed, it would
cause the oxidizing capacity to decrease, i.e. no quantitative formation of acetone
could be observed.
A recent study by Lee and Stewart4 confirms the previous observations that
with rather low acid concentrations the oxidation rate of H2R depends only on the
acidity of the medium and not on the nature of the proton-supplying mineral acid.
On the contrary, at rather high acid concentrations the rate of oxidation depends
not only on the acidity but also on the nature of the acids. This can be explained
by the fact that the hydrogen chromate and the acid present interact with each
other
HCrO;
+ H ++ HB = HCr0,B + H 2 0
where HB and B represented the acid and acid radical, respectively. The incorporaReferences pp. 577-580
526
I N D U C E D REACTIONS
TABLE 5
APPARENT
PK,
VALUES
OF
CHROMIC
ACID
IN
Acid
AQUEOUS
SOLUTIONS OF
pK,,(H, scale)
Species formed
-1.91
-0.83
+0.34
-t0.52
HCrNOs
HCrC107
HCrS0,
HCrC103
H3CrP07
t1.74
VARIOUS
LEE A N D
tion of the acid radical increases the electron-accepting power of chromium. The
oxidizing ability of the protonated species, HCrO,B, increases in the order:
H2CrP0, < HCrC10, < HCrSO, < HCrClO, < HCrNO, for a given H,
value. This is the same order in which the apparent pK, values of these species vary
(Table 5).
The first step in the oxidation of the alcohol is the formation of a chromate ester
which probably decomposes unimolecularly to products, uiz.
Oxidation of isopropyl alcohol by chromic acid in concentrated acetic acid solution has recently been studied by Wiberg and Schafer4'* lZ3 spectrophotometrically. At 385 nm a rapid increase in absorbance (with a half life of about 6 sec) due
to mono- and diester formation was noted. When the reaction was examined at
510 nm124, first a rapid increase, then a decrease of the absorbance was found.
Since at this wavelength only chromium species can absorb, the intermediate could
be chromium(V) or (IV). The ESR spectra of reaction mixtures showed a relatively
sharp signal with a g = 1.9805 value corresponding to chromium(V). The fact
that the relative concentrations of the intermediate determined from the spectral
data agree well with the intensity of ESR signals, indicates that the same species is
responsible for the both phenomena. It is then clear that the oxidation of isopropyl
alcohol proceeds via chromium(V).
It is also interesting to note that kinetic data of Wiberg and Schifer are in-
527
EXAMPLES
+ Cr(IV) -+ HR + Cr(1II)
HR+Cr(VI)
H,R
-+
+ Cr(V) -+
R+Cr(V)
R + Cr(II1)
Cr(W)+Cr(VI)
2{H,R+Cr(V)
9,
+ 2Cr(V)
R+Cr(III)}
ALCOHOL-INDUCED OXIDATION
OF
MANGANESE(II) BY
CHROMIC ACID
MnS04
(rnole.1- I )
0.053
0.106
0.213
0.331
0.426
Milliequiu.
Milliequio. Mn2+
chromic acid reduced oxidized
Fi
0. I37
0.141
0.148
0.153
0.149
0.036
0.040
0.047
0.050
0.048
0.36
0.40
0.47
0.50
0.48
3.87
6.0
23.4
12.7
9.9
15.5
co
36.0
14.0
Average = 13.3
References p p . 577-580
528
INDUCED REACTIONS
-+
Cr(V)+Cr(III)
(30)
Cr(VI)+Cr(lV)
(31)
529
EXAMPLES
n[cr(vl)l
dt
~~
[H][HCrO~][C6H5CHO]{0.147+0.95[H+]}
H
I
(32)
OH
H
I
C6H5COCr03H: + H 2 0
-+
C6H5C0,H + H 3 0 ++ H,Cr03
OH
Cr(W)+Cr(Vr)
(33)
(rate-determining)
-+
2Cr(V)
C6H5CHO+Cr(V) = C6H5C02H+Cr(III)
(9)
(34)
k[RCHO][HCrO,]h,
where
h,
a--f B
fBHf
The value of the second-order rate coefficient is considerably decreased by increasing the ionic strength as well as by increasing the water concentration. If the water
References p p . 577-580
530
INDUCED REACTIONS
content of the solvent is more than 25 %, the rate of reaction decreases more than
the acidity function.
The rate coefficient was found to be (5.98f0.06) x
I.mole-'.sec-' at
I.mole-'.sec-' at 59.94 "C, indicating that the
30.01 "C and (4.28f0.4) x
reaction has an activation energy of 13.2f0.3 kcal.mole-' and ASf = -28 eu.
To decide whether the reaction involves 1- or 2-electron transfers, i.e. chromium(IV)or chromium(V) is formed first, the induced oxidation of manganese(I1) was
investigated. When sodium perchlorate was used to maintain a constant ionic
strength, the rate of oxidation of benzaldehyde dropped to one-half of the original
rate in the presence of manganese(I1) ions. On the contrary, when magnesium
perchlorate was used as the neutral salt, the rate was reduced to 3 of its original
value. This peculiar observation, however, has not been interpreted.
Knowledge of stoichiometry of the induced reaction could help to distinguish
whether chromium(V) or chromium(IV) species are involved in the oxidation of
benzaldehyde. Thus, the Cr(V) hypothesis predicts that for each molecule of benzaldehyde oxidized two molecules of manganese dioxide should be formed, whereas
the Cr(IV) predicts that one molecule of manganese dioxide should be formed for
each two molecules of benzaldehyde oxidized. Unfortunately, the attempt to determine the stoichiometry of the induced reaction failed because the oxidized
manganese species was not precipitated during the reaction presumably due to
formation of acetate complexes in the concentrated acetic acid solution.
6. Formaldehyde
It was found by Chatterji and Mukherjee2* that the rate law for the oxidation of
formaldehyde indicated that the chromic acid was esterified by the aldehyde
hydrate formed, although they did not succeed in isolating the ester. The hypothesis
of ester formation seems to be supported by the experience that the rate of reaction is increased by addition of pyridine.
Just as for the oxidation of alcohols by chromic acid, the rate of oxidation of
TABLE 7
FORMALDEHYDE-INDUCED OXIDATION OF
MANGANESE(II)
BY
CHROMIC ACID
[HCHO]
( Mx lo3)
Equiv. of
M n 2 + oxidized
Equiv. of
H C H O oxidized
F1
8.20
5.56
4.92
3.28
I .64
0.870
0.891
0.809
0.119
0.603
5.145
4.596
3.441
2.298
1.149
0.15
0.19
0.23
0.34
0.51
._
kHC"0
~
F C
0.645
0.96
1.27
3.18
h *1n2 +
26.5
18.3
21.8
13.5
-
E X A M PL E S
53 1
aldehyde will be decreased by addition of manganese(I1) and cerium(Il1). The limiting value of Fi is about 0.5, which points to the occurrence of chromium(1V)
intermediate (Table 7).
c. Formic acid
The mechanism of the oxidation of formic acid by chromic acid4' is far from
being solved yet. The reaction in many respects reminds one of the oxidation of isopropyl alcohol. The induced oxidation of manganese(I1) can also be observed during the reduction of chromium(V1) by formic acid. The stoichiometry of the induced reactions, however, cannot be given, because the oxidized product of manganese cannot be separated from the solution. The rate of oxidation of formic acid
is reduced to one-third of its original value by adding manganese@) in a sufficient
quantity; thus it might be assumed that a chromium(1V) species is the active intermediate. The factor by which manganese(I1) reduces the rate was explained by
Wagner'37, who suggested that manganese(I1) ion catalyzes the disproportionation
of chromium(IV) or chromium(V) to chromate and chromic ions. The experimental facts can be explained by steps analogous to reactions (18), (19) and (20).
Cerium(II1) also proved to be an effective inhibitor of the oxidation of formic
acid. As the oxidation of cerium(II1) to cerium(IV) is a 1-equivalent process, the
inhibition furnishes additional evidence for the chromium(1V) species as intermediate.
d. Other acids
The kinetics of the initial stages of the oxidation of some a-hydroxy-carboxylic
such as lactic, malic and mandelic acids by chromic acid have been studied by
Bakore and Narain'26. The initial reaction resembles the oxidation of a secondary
alcohol to ketone. The authors concluded that the rate determining step involves
C-H bond rupture at the a-carbon atom. The rate of oxidation of these acids is
reduced to one-half by the addition of manganous ions, when the concentration of
the latter is commensurable with that of the acids.
The oxidation of t a r t a r i ~ " and
~ glycollic acid'28 by chromic acid also induces
the oxidation of manganous ions. In the presence of higher concentrations of
manganese(I1) the rate of oxidation of the acids is diminished to about one-third
of that in the absence of manganous ions. The decrease of the rate has been attributed to manganese(I1) catalysis of the disproportionation of the intermediate
valence states of chromium probably chromium(1V).
It was observed by Gopala Rao and Sastri3' that the reaction between hydroquinone and chromic acid leads to the induced oxidation of oxalic acid, glycerol,
lactic acid, glucose, citric acid, and malic acid. If the concentrations of the above
acceptors are [en times that of that of the hydroquinone inductor, the values of Fi
found are, respectively, 0.51,0.46,0.35,0.27 and 0.17. The numerical values of the
induction factor do not permit us to discuss the nature of coupling intermediate.
References p p . 577-S80
532
INDUCED REACTIONS
Gopala Rao and Venkateswara Rao37 found that the oxidation of indigo to
isatin by chromic acid is accelerated by the presence of oxalic acid, and at the same
time the extent of the oxidation of oxalic acid by chromic acid is increased. This
observation is an example of mutual induction.
Benson31 has found that, for the reaction between iron(I1) and chromate, the
following rate law holds
-
d[Cr( VI)]
= k
[Cr(VI)]'~7[Fe(II)]'[H+]z
CFe(II 111
dt
The order of greater than unity with respect to chromate concentration suggests
that here the active oxidizing agent is the dichromate ion. The concentration of this
ion must vary as the square of the gross concentration of chromic acid, whenever
that concentration is small.
The fact that the rate of reaction is inversely proportional to the concentration
of iron(Il1) is explained by Wagner and P r e i ~ son~ the
~ basis of an equilibrium
between chromium(V1) and iron(II), uiz.
Cr,O:-+Fe(II)
Cr,O:-
+ Cr,Oj-+Fe(III)
(35)
(36)
(37)
In the presence of iodide ions the reaction of iron@) with chromate induces the
formation of iodine. The induced formation of iodine can be represented by reaction (21) and (22).
Relative rate coefficient, k37/kZ1,has been calculated by Wagner end Preiss
from the expression
-3 - Y *
"-1,"
-- -__
k, I
Y
[Fe(wl,"
k37
fc-y.
-~
Y
b-
Y
~
a-HC-Y)
where a, b, and c are the initial concentrations of iron(II), iodide and chromate
and x and y represent the equivalents of iodine formed and of iron(1I) converted.
Values of k21/k37 for the initial stages of the reaction, at constant acidity, are
satisfactorily constant. In Table 8 both the values of F, and Fc([Fe(II)]/[I~l)o
are listed, and it can be seen that they agree satisfactorily with the kZl/k37 ratio.
The induced iodine formation can be formally explained by the following reac-
533
EXAMPLES
TABLE 8
IRON(I1)- INDUCED OXIDATION OF IODlDE B Y DICHROMATE
Data of Wagner and Preiss,,. Conditions: 0.95 M KCI; 1.91 x lo- M HCI; 1.91 x lo- MKI;
1.91 x
M FeCI,; 1.58 x
M K2CrZ07.
(&I).
Fi
Fc
-__
I .00
0.50
0.33
0.25
0.20
0.166
0.133
0.10
1.299
0.852
0.653
0.534
0.465
0.401
0.356
0.282
5.557
2.225
1.454
1.092
0.909
0.752
0.649
0.492
5.780
4.694
4.587
4.587
4.761
4.716
5.076
5.102
5.557
4.45 I
4.361
4.377
4.546
4.532
4.883
4.924
tions
Cr(V)+Fe(III)
Cr(III)+Fe(IV)
(38)
Fe(IV)+Fe(rI)
2Fe(III)
(39)
- d[Cr(V1)l
dt
+ V(V)+Cr(V)
Cr(V)+V(nl-) + V(V)+Cr(IV)
V(IV)+Cr(VI)
(rate determining)
5 34
I N D U C E D REACTIONS
TABLE 9
V A N A D I U M ( I V ) - I N D U C EODX I D A T I O N O F
IODIDE BY
DICHROMATE
1.875
1.945
1.962
1.993
45.00
106.09
154.89
854.14
-
~~~~
t Corrected by extrapolation
~~
4.1 I
20.57
41.15
82.30
M VOS04;
10.948
5.157
3.764
10.378
~~~~~~~~
~~
of original plots.
T A B L E 10
VANADIUM(II)-INDUCED
OXIDATION
OF I O D I D E B Y D I C H R O M A T E
4.50
8.70
19.80
39.30
91.2
182.4
459.0
903.0
1530.0
Fi
1.13t
I .375t
1.41t
1.477
1.61
I .68
1.87
I .96
1.99
3.896
6.600
7.169
8.320
12.384
15.75
43.153
147.0
597.0
0.8657
0.7586
0.3620
0.2117
0.1357
0.0863
0.0940
0.162
0.3901
EXAMPLES
535
For the induced reaction Kolthoff and Fineman3 suggested a mechanism similar
to that proposed for isopropyl alcohol, uiz.
Cr(VI)+As(III) = Cr(IV)+As(V)
+
Cr(II) + Cr(V1) = Cr(V) + Cr(1II)
Cr(I1) 0,
2 C r 0 2 = (Cr02)2
(CrO,),
+ 2 ~ ~ ( r r r ) + 4=~2As(V)+
+
2Cr(III)+ 2 0 H - + H 2 0 2
H202+As(III)
As(V)+20H-
According to this scheme the Cr(I1) species is responsible for the induced reduction
of oxygen, though its occurrence cannot be supported by independent experimental
evidence.
Abel has assumed that the reaction between arsenite and molecular oxygen is
catalyzed by a chromium intermediate. He suggested that chromium(1V) is converted by oxygen into chromium(VI) which causes the excess oxidation of arsenic(II1).
Howevzr, this mechanism is also devoid of experimental support.
We are of the opinion that the reaction can be explained without assuming the
reduction of chromium(1V) to chromium(I1) by arsenic(III), although this step is
References pp. S77-S83
536
INDUCED REACTIONS
Cr(V)+As(IV)
-+
Cr(V)+As(III) -+ Cr(III)+As(V)
As( IV) + 0,
O;+As(III)
As(IV)+O;-
--+
O~-+As(III)
_ _ _ _ ~ _ _
As( V) + 0;
-+
-+
202-+As(V)
_.
Cr(III)+3+As(V)+ 2 0 , -
+ Fe(III)+Cr(V)
Since the reaction is markedly displaced to the left, the standard potential of
Fe(III)/Fe(II) couple (0.77 V) must exceed that of the Cr(VI)/Cr(V) couple; therefore E6q5 must be < 0.6 V. This estimate seems reasonable. Regarding the oxidation potential of chromium(1V) there is an estimate, also by Westheimer, that the
Cr(IV)/Cr(III) couple has a value of E:,, 3 1.5 V. This was based on the fact that
537
EXAMPLES
15-
10-
.>
.
0.5-
ril
00-
-05-
En,
538
INDUCED REACTIONS
2Cr(V)
(19)
+ Cr(V1) . As(II1)
Cr(V1). As(ITI)+Cr(VI)
-+ 2Cr(V)+As(V)
2Cr(V)
-+
Cr(VI)+Cr(IV)
Cr(V)+As(III)
-+
Cr(III)+As(V)
Cr(1V) As(II1)
-+
Cr(III)+ As(IV)
Cr(VI)+As(IV)
-+
Cr(V)+As(V)
Induced reactions
Cr( V) + Acre,,
Cr( I V) + Ac;,,
-+ Cr( 111)
+Ac;,
This scheme accounts for both the induced oxidation of iodide (where CI = 2)
and that of manganese(I1) (where CI = 0.5) without including step (19). Furthermore it can be seen that in the presence of iodide the rate of disappearence of
chromate will not be altered, whilst the rate of oxidation of arsenic(lI1) will be
reduced to one-third of its original value, as found experimentally.
It should be mentioned that problems of chromic acid oxidations are discussed
in detail in recent excellent reviews by Wiberg and Stewart13.
2.2
ARSENIC(IV
I N)T E R M E D I A T E S
EXAMPLES
539
dt
k[S20:-]
k'[Fe(II)][S,Oi-]
k' = 30 I.mole-'.sec-' at 25 "C. The induction factor, Fi (= equivalents of arsenic(II'1) oxidized/equivalents of iron(1I) oxidized), depends considerably on
the experimental conditions.
( a ) Fidecreases on increasing the acid concentration.
( b )Addition of iron(1II) ions results in the increase of Fito infinity. Copper(I'1)
ions have a similar ,,catalytic" effect but, their activity does not depend on the
acid concentration of the solution.
(c) Increasing the iron(1I) concentration decreases Fi .
( d )Fluoride was found to reduce the induction factor to values approaching zero.
However, the rate of the iron(1I)-peroxydisulphate reaction is not influenced by
fluoride ions.
( e ) The value of Fi is independent of the arsenic(I11) concentration, when
[As(III)]/Fe(II)] 2 2.
The results can be explained by the following mechanism
Fe(1I) + S20: Fe(II)+SO,
As(III)+SO,
+ Fe( 111)
+ SO:- + S 0,
(43)
Fe(III)+SO:-
(44)
+ As(IV)+SO:-
(45)
As(V)+Fe(lI)
(46)
(46' )
(46")
As(IV)+Fe(III)
As(lV)+ Fe(l1)
-+
As(lLI)+ Fe(II1)
(47 1
According to this mechanism only iron(I'1) reacts with peroxydisulphate and gives
an SO, radical. With respect to reactions of the SO, radical, reaction (44) becomes
insignificant compared with (45) at [As(III)]/[Fe(II)] ratios greater than two, and
then Fi will no longer depend on the arsenic(II1) concentration.
The relative rate coefficient, k4,/k4,, can be determined by assuming a steadystate with respect to arsenic(1V). According to the data given in Table 11 the value
of k46/k47depends on the ionic strength and the pH. Dependence on the pH can
be explained by the fact that arsenic(1V) reacts with FeOH2+ ions, present at low
acid concentrations, 90 times faster than with Fe3+ ions.
References p p . 577-5880
540
I N D U C E D REACTIONS
TABLE I 1
VARIATION OF INDUCTION FACTOR WITH VARYING ACIDITY A N D IONIC STRENGTH
FOR THE
IRON(II)-ARSENIC(III)-PEROXYDISULPHATE
SYSTEM
0.002
0.002
0.005
0.010
0.50
1.32
0.002
1.54
5.1
0.50
0.50
I .07
0.88
1.23
0.32
0.23
2.6
0.01
0.50
0.50
0.010
0.10
0.50
lo- M; [S,O,]
3.8
1.8
3.3
0.27
0.14
-+
As(V)+Cu(I)
(48)
Cu(I)+Fe(III)
-+
Cu(II)+Fe(Il)
(49)
cu(I)+s,o;-
+ cu(II)+so:-
+so;
(50)
(A)
EXAMPLES
54 I
(B)
A s ( I I I ) + S ~ O ~=- As(V)+2SO:-
The initiation step in the chain oxidation, reaction (43), is not affected by the
presence of oxygen. SO; radicals formed in (43) give arsenic(IV), reaction (45),
initiating the following propagation cycle which leads to the reformation of As(1V)
+ +
+H 0 2
Fe(II)+ H 0 2 + H + + Fe(III)+H202
Fe(lL)+ H 2 0 2
As(lII)+OH
--f
.+
Fe(lII)+OH-+OH
As(N)+OH-
.+
Fe(lI)+O,+H+
(55)
Cu(I)+02+H+
(56)
followed by either
Cu(I)+ Fz(III) .+ Cu(II)+ Fe(1I)
(49 1
or
CU(I)+S,O;-
CU(II)+SO:-
+so;
If the initiation and termination steps are excluded because the chain is long, the
sum of the propagation reactions gives the stoichiometric relationship (A).
At sufficiently high concentration of iron(I1I) and copper(II), the induced oxidation by oxygen is eliminated because all the HOz radicals are oxidized by steps
(55) or (56). In such cases Fiapproaches infinity and XAsbecomes equal to 1, i.e.
arsenic(II1) is oxidized according to equation B. Consequently, iron(I1) is reformed
at the same rate as it is oxidized.
The extent of induced oxidation increases with increasing hydrogen ion concentration. This is a consequence of the fact that both iron(I1) and iron(II1) are present in the solution and compete for H 0 2 radicals, reactions (52) and (55). The
rate of reaction (52) increases as the acidity is increased, whereas that of (55) is
independent of hydrogen ion concentration.
The extent of the oxygen-induced oxidation passes through a maximum at a
certain [As(rrI)]/[Fe(rr)] ratio. When the arsenic(1II) concentration is low with
respect to that of iron, the induction is decreased because of the enhanced role of
References p p . 577-580
542
INDUCED REACTIONS
-+
Fe(III)+OH-
(57)
Under these conditions the ratio, X,,/X,, , becomes significantly greater than 2.
When [As(lIl)] > [Fe(II)], there is a competition between arsenic(II1) and
iron(1I) for hydrogen peroxide and the reaction
As(111)
+ H20,
As(V) + HzO
(58)
also results in chain termination. In this case X,,/X,, becomes smaller than 2.
Photoreduction of iron(II1) in the absence of oxygen may induce the iron(II1)arsenic(Il1) reaction. The initiating steps (59) and (60)
primary step F e 3 + . 0 H -
2 Fe2+OH
OH+HSO;
EXAMPLES
543
Fe(III)+OH-+OH
As(IV)+OH-
As(IV)+Fe3+ -+ As(V)+FeZf
As(IV)+FeOH2+ -+ As(V)+Fe(TI)
As(IV)+Fe(Il)
As(III)+Fe(IIl)
+H+
Fe(IIl)+OH- +OH
-+
As(IV)+OH-
-+
As(V)+H02
Fe(III)+ H,O,
Fe(II)+O,+H+
-+
Fe(III)+OH-
H202 =
As(V) H2O
d In [S,Oi-]
dt
are listed in Table 12. It has been observed that the extent of the oxygen effect
was reduced by the addition of ally1 acetate and acrylonitrile.
The rate of reaction between arsenic(II1) and peroxydisulphate is markedly increased by iron(II1) ions. In the absence of air
References p p . 577-580
544
I N D U C E D REACTIONS
T A B L E 12
RATE
OF
REDUCTION
OF
PEROXYDtSULPHATE
Absence of oxygen
0.9
0.0
10-3
3.0
2 'i 1 0 - 2
6.0
6.1
A ir-saturated
0.0
10-3
4x10-'
10-2
2 x 10-2
0.9
35
35
41, 35, 40
46
k = 4.2 x 10-3[Cu(II)]isec-'
I n the presence of air
k
2.8 x 10-2[Cu,II)]fsec-1
s20,2-+ 2s0,
H++S20i-
SO,+HSOh
k = k 6 1 + k 6 2[H'], and k B 1= 1 . 3 ~
sec-' at 25 'C the activation energy
being 33.5 kcal.mole-'. The overall rate coefficient at 25 "C was found to be
k = 9x
sec-' at a hydrogen ion concentration of 0.01 M and an ionic
EXAMPLES
545
s20;-+ 2 so,
As(1II) + SO,
(61)
+ SO:As(IV) + 0, + H + + As(V) + H 0 2
HOz + S,OiH + + 0, +SO:+
+ As(1V)
--*
(45)
+SO,
-+
2 so,
-+
SO:-+O,+Hf
s20:-
-, As(III)+O2+Hf
(66)
the overall process would be of first order in peroxydisulphate and zero order in
arsenic(II1) as found experimentally, and half order in oxygen.
Catalysis by iron(III)
In the presence of iron(II1) ions and in the absence of oxygen,[reaction (61) is
followed by steps (45), (46) or (46') and by reaction (43) with chain termination
by reaction (47), uiz.
s,o;-
2 so,
(61 1
As(1II) + SO,
As(1V) + SO:-
(451
+ +
+
As(1V) + Fe(1II) + As(V)+ Fe(l1)
As(IV) + FeOH'
As(V) + Fe(I1)
As(1V) O2 H + + As(V) HOz
(46)
(46')
--f
Fe(I1) + S,Oi-
-+
As(1V) + Fe(1I)
+ As(II1)
(5')
Fe(II1) + SO:-
+ SO;
+ Fe(II1)
(43)
(47)
546
I N D U C E D REACTIONS
In the presence of oxygen, reactions (46) and (46) will be replaced in the chain
propagation cycle by reactions (63) and (55); consequently, there will be no change
in the overall stoichiometry of the reaction. The chain reactions will be terminated
by steps (52), (53), (54) and (58)
H02+S20s2-
H++O2+SO:-+S0;
Fe(III)+HO, + Fe(II)+O,+H+
Fe(ll)+ HO,+H+
Fe(II)+H,O,
As(III)+OH
-+ Fe(III)+H,O,
-+
Fe(III)+OH-+OH
-+
As(TV)+OH-
As(III)+ H 2 0 2 = As(V)+ H 2 0
Assuming a steady state for the chain carriers, in the absence of oxygen we obtain
Catalysis by copper(l1)
In the presence of copper(I1) ions and in the absence of oxygen, steps (48),
(50) and (67)
As(IV)+Cu(II)
As(V)+ Cu(I)
+so,
A ~ ( I I I ) +cu(rr)
A ~ ( I v ) +CU(I)
-+
will replace reactions (46), (43) and (47), respectively. By a steady-state treatment
we obtain
In the presence of air, reactions (55), (43), (52) and (53) are replaced by reactions (56), (50), (68) and (69), viz.
EXAMPLES
547
Cu ( II ) + H 0 2 + Cu(l)+O,+H+
cu(I)+S,oCu(I)+ H 0 2 + H +
+
--f
cU(rI)+so:-
+so,
Cu(II)+ H 2 0 2
At high copper(1I) concentrations the rate of reduction of peroxydisulphate becomes independent of copper(I1) concentration and is unaffected by the presence
of oxygen. This can be explained by the occurrence of the termination reaction
Cu(I)+ so,
Cu(II)+
so:-
( 70)
2.2.4 Polarographic behaviour of the system containing peroxydisulphate, arsenic(ZZZ) and copper(ZZ)
Copper(I1) ions in the presence of chloride ions are reduced at the dropping
mercury electrode (DME) in two steps, Cu(I1) + Cu(1) and Cu(1) + Cu(0)
producing a double wave at +0.04 and 0.22 V versus SCE half-wave potentials.
In the presence of p er o x y d i ~ u l p h a t e~
when
~ , the chloride concentration is large
enough, two waves are also observed; the first limiting current corresponds to the
reduction of the Cu(I1) to Cu(I) plus reduction of a fraction of peroxydisulphate
and the total diffusion current at a more negative potential is equal to the sum
of the diffusion currents of reduction of Cu(I1) to C u ( 0 ) and of the peroxydisulphate. There is evidence that peroxydisulphate is not reduced at the potential
of the first wave because of the adsorption of the copper([) chloride complex at
References pp. 577-580
548
I N D U C E D REACTIONS
the electrode surface. In the presence of thiocyanate a similar effect was observed.
An adsorbed layer of copper@) complex at the DME also prevents the electroreduction of hydrogen peroxide65.
The kinetic current, ik, of peroxydisulphate exalting the Cu(I1) to Cu(1) wave
is caused by a regenerative reaction consisting of the following steps
Cu(II)+e
Cu(1)
Cu(I)+s,o;-
cu(I1)+so:-+so,
Cu(I)+SO,
cU(rI)+so:-
SO:-
SO, + e
= 0.812(ak,, t [ s , o ; - ] ) + ~ H ( u i )
id
where id is the first diffusion current of copper(II), i = id+ik is the current found
experimentally, CY is the stoichiometric factor which is 2 in this case, t is the drop
time,
EXAMPLES
549
s,o;-
-+
2 so;
As(III)+SO,
-+
As(IV)+SO:-
As(IV)+Cu(II)
As(V)+Cu(I)
-+
cu(Ir)+so:-
cu(I)+s,o:-
+so,
+ +
-+
Cu(I)+02+H+
-+
Cu(I)
(71)
--___
dt
where the subscript e refers to concentrations on the electrode surface. At potentials at the beginning of the reduction of Cu(I1) to Cu(1) the concentration of
the copper([) ions at the surface of DME is proportional to the copper(I1) concentration, and thus
5 50
I N D U C E D REACTIONS
Fe(III)+SO:-
(44)
(47)
d[C1o'l
-~
dt
= k,[CIO;][As(III)]
+ k,[CIO;][CI-]
-+
CIO,+As(IV)
(73)
CIO; +As(III)
-+
ClO, +As(V)
(74)
can be assumed to be the rate-determining step, followed by the fast disproportionation of chlorite'32
4 Cloy
+ 2H'
2 C10,
+ C1- + C l o y + H 2 0
(75)
EXAMPLES
551
(76)
-+
As(V)+ClO2
(77)
Then, in fast consecutive steps, chlorine dioxide is reduced to chloride. The induced reduction of chlorate is quantitative within a few minutes. At the beginning
of the titration not only the special smell but also the faint-yellowish colour of
chlorine dioxide can be observed after the complete disappearance of the cerium(1V)
reagent.
The induced reduction of chlorate can be inhibited by iodide, bromide and
chloride ions. The effectiveness of these ions is about 400 : 10 : 1 in the given
order. The order and the magnitude of the effect agree fairly well with the catalytic
activity of these ions in the arsenic(III)<erium(IV) reaction. This inhibition by
halides is presumably connected with the opening of a new two-electron route for
the arsenic(III)-cerium(IV) reaction.
During the induced reduction of chlorate a considerable oxygen effect was
observed. The air oxidation of arsenic(1II) is also an induced reaction, the extent
of which decreases with increasing acid concentration and is increased by decreasing
the rate of primary reaction. The induced oxidation caused by air also can be
observed69 during the osmium tetroxide-catalyzed chlorate-arsenic(II1) reaction.
It may be assumed that the induced air oxidation is caused by reactions (51),
(78) and ( 5 8 ) , uiz.
As(IV)+O,+H+
-+
As(V)+H02
+ 3 0 2 HzOz + 0 2
As(1II) + HZ02 -+ As(V) + H 2 0
HO2
(51)
(78)
(58)
552
INDUCED REACTIONS
+ Ce(lV)
-+
0, H + + Ce(II1)
(79)
is formed, may offer an explanation. However, the formation of CIO is not supported by direct experimental evidence.
According to experiment the induced air oxidation can be suppressed by silver(1)
or copper(IC) if added in sufficient quantity6.
This order of the potentials indicates that arsenic(IV) is an intermediate irk the
oxidation of arsenic(lI1) and reduction of arsenic(V) which is unstable from
thermodynamic point of view and disproportionates easily according to
+ + H + + As(V) + HO,
As(IV) 0,
(51)
553
E X A >MP L ES
T A B L E 13
OXIDATION-REDUCTION REACTIONS
OF
__
ARSENIC(IV)
Eo ( V )
A s ( I V ) as reducing agent
0 2 +
HOz
-0.13
CUZ+ + c u +
0.15
0.11
0.79
Fe3 + Fez+
Ag+ + A g
V 0 3 - + VOz+
c103- + ClOZ
1.oo
1.15
A s ( I V ) as oxidant
HOz
cu+
+0
-0.13
0.15
0.17
CuZ+
Fez+ + Fe3+
--f
OH
I
HO-AS
1
OH
I
+ H-As=O
OH
a
OH
b
and form b is favoured. The oxidation of the latter by hydrogen abstraction can
occur easily, because the heterolysis, such as
I-I+ H-AsO(OH),
-+ I-
+I-H
+ +AsO(OH),
(8211
HO H-AsO(OH),
References pp. 577-580
HO-H
+ .AsO(OH),
554
I N D U C E D REACTIONS
However, this method of oxidation differs considerably from the effect of strong
oxidizing ions such as cerium(lV), manganic(II1) etc., because these merely gain
electrons from the reducing partner.
This proposed structure of arsenic(1V) could also explain why the FeOH2+
ion reacts faster with arsenic(1V) than does Fe3+(aq). The former can react by
direct transfer of hydroxyl, viz.
Fe(OH)2
+ AsO(OH),
Fe2
+ HO-AsO(OH),
(46')
while the reaction of the latter will involve a n electron transfer followed by the
addition of hydroxyl ion, viz.
OH-
2.3
I N D U C E D REACTIONS INVOLVING
HO2
AND
OH
RADICALS
+O2
(83)
(or cerium(LV) sulphate)
EXAMPLES
555
556
I N D U C E D REACTIONS
silver(I), iron(III), and fluoride ions. The copper(I1) ions catalyze the induced
reaction without modifying its characteristics.
( b ) The induced reaction is inhibited by iodide, bromide and chloride, the
magnitude of the effect being in the order given, as well as by acetate,
manganese(II), cerium(III), and uranyl ions. Cations of groups I, I1 and I11 also
exert a slight inhibiting effect.
To understand this induced reaction it is necessary to examine the reaction
between hydrogen peroxide and peroxydisulphuric acid. The rate equation based
on the careful experiments of Tsao and Wilmarth7 is
-
dcs20;-1
dt
k,[S,O;-]
dt
(c) 1.0 M H,O, and 0.1-0.25 M K,S,O,
+ H,O
-+
H + +SO:-
+ OH
O H + H 2 0 z -+ H 0 2 + H 2 0
HO, +S20;-
-+
0,
+ HSO, + SO,
HOz+H202+ 0 2 + H 2 0 + O H
EXAMPLES
557
HOz+OH
02+Hz0
SO; + O H -+ HSO;
(87)
(88)
HOz+SO,
-+
02+HSO,
(64)
so,+so,
--t
szo,2-
(65)
From these relations it can be concluded that k s s > k63 > k84, which implies
that the concentrations of SO, and H 0 2 radicals are relatively large compared
to that of OH. It is striking, however, that for kinetic reasons this mechanism does
not involve termination steps (78) and (89) which are widely favoured in the
chemistry of H 0 2 and OH radicals
558
I N D U C E D REACTIONS
SO,
+H 2 0 2
HO,
+ H f +SO:-
(90)
559
EXAMPLES
H02+H++Red
(91)
HO,+Ox
02+H++Red
(79')
HSO;+O,+SO,
(63)
The sulphate radical formed either reacts directly with H,O2 or, according
to the assumption of Tsao and Willmarth", is converted to O H (step 84) which
reacts with hydrogen peroxide, the H 0 2 radical being reformed, uiz.
OH(or S O i ) + H 2 0 ,
--t
H 0 2 + H 2 0 ( o r SO:-)
(85)
560
I N D U C E D REACTIONS
or dissociated
HO,
+ H + + O2
KH02
O2 +HSO, + H + +SO,
H20: + S 2 0 i -
-+
o;+s,o:-
o2+so:-+s0,
-+
(63')
(63")
-+
SO:-(or
OH)+As(IV)
(45)
EXAMPLES
56 1
-+
As(V)+SO:-
+SO,
(92)
and that chain carried by arsenic(1V) and sulphate radicals is nearly as long as
that by H 0 2 and OH (or SO,) radicals, one can understand that the H2 0 ,
error decreases, while the S 2 0 i - error remains the same as it was in the absence
of arsenic(III), but an As(II1) error also appears.
If reaction (92) occurred during the cerimetric (or permanganometric) titration
of arsenic(II1) in the presence of peroxydisulphate negative errors in concentration
determinations should also appear contrary to experience. Therefore step (92)
is presumably replaced by a reaction in which the As(IV) radical is oxidized by the
oxidant according to
As(IV) Ox
-+
As(V)+ Red
(93)
The occurrence of reaction (93) results in a shortening of the chain causing the
S 2 0 i - error to be considerably reduced.
Considering, however, that the solution contains oxygen from the beginning
of the titration and oxygen is evolved during the reaction as well, the effect of
oxygen should not be overlooked. In fact, it was found that the extent of induced
reaction differs considerably in the presence or absence of oxygen. When oxygen
was removed by bubbling N2 through the solution, the H 2 0 2 error remained the
same in the presence as in the absence of arsenic(1rI). However, in the presence
of oxygen, as was mentioned above, the H 2 0 2 error was decreased by adding
arsenic(II1). This observation indicates that reaction (51) takes place
+ +
As(IV) O2 H +
-+
H 0 2 As(V)
(51)
accounting for the variation in the H202error and the constancy of the As(1II)
error.
In connection with the role of arsenic the reaction
(94)
(95)
562
I N D U C E D REACTIONS
the As(1II) and S,O;- errors. However, if reaction (51) occurs, the HO, radical
formed sustains the chain leading to the reduction of peroxydisulphate by arsenic(I11).
The results of the inverse titrations can be interpreted as follows. On titrating
cerium(IV) sulphate with hydrogen peroxide in the presence of peroxydisulphate,
owing to the great excess of cerium(1V) present a much larger proportion of HO,
radicals are removed by reaction (79) than in the case of direct titration; therefore the value of Fi considerably decreases. Fiis decreased further because there
will be no hydrogen peroxide present to remove SO, radicals, which oxidise
cerium(II1) ions, formed during titration, to cerium(1V). Thus the amount of
cerium(1V) increases on adding a charge of peroxydisulphate. However, this increase is significant only in the presence of copper(I1) ions, being due to the
oxidation reaction of peroxydisulphate markedly accelerated by the latter. Halides,
just as in direct titrations, strongly inhibit the induced reaction.
It was found that the value of Fi is markedly increased by ions which are effective catalysts of oxidation reactions of peroxydisulphate. These are silver(1)
copper(II), and iron(I1I). Cobalt(I1) and nickel@) ions, although they are good
catalysts for the decomposition of hydrogen peroxide, exert their effect merely
as inert electrolytes in the induced reaction. Therefore it can be concluded that, in
this process, activation of the rather less reactive S20;- is more important than
that of hydrogen peroxides4.
The induced change is decreased by ions of groups I, I1 and 111. The effect of
these ions in decreasing Fi can be ascribed to an increase i n the rate of primary
reaction (91).
The inhibiting effect of halide ions and other easily oxidizable and reducible
substances can be interpreted by assuming that these substances scavenge the
chain carriers, HO, and SO, (or OH) radicals. The role of uranyl ions is different,
a weak 1 : 1 adduct with hydrogen peroxide is formed, which reacts with permanganate more slowlys6. Owing to this slow reaction the local concentration
of the oxidant will be increased, therefore the removal of HO, radicals by reaction
(79) will be favoured. In the presence of great excess of uranyl ions the induced
change practically ceases.
Summarizing our findings, the induced reaction occurring in the H,O,-H,S,OsKMnO,, or Ce(S04), , system can be illustrated by the following reaction scheme
Ox
H202
-Hop
+ Ox
563
EXAMPLES
H 2 0 2 , Os04 A N D KMnO.,
Data of Csiinyi ef ~ 1 . ~ .
REACTION BETWEEN
0.01
0.10
1 .o
1 .o
5.0
5.0
10.0
10.0
50.0
50.0
100.0
100.0
500.0
500.0
A H 2 0 2 (ml)
0.1 N H 2 0 2 ( m l )
[Os041(Mx106)
Taken
Found
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.30
9.15
8.96
8.15
8.15
6.20
6.22
5.06
5.12
3.45
3.41
2.99
2.9 1
1.83
1.86
0.00
-0.15
-0.34
-1.15
-1.15
-3.10
-3.08
-4.24
-4.18
-5.85
-5.83
-6.31
-6.39
-7.47
- 7.44
~~
564
I N D U C E D REACTIONS
-+
Os(VII)+02+H+
Os(VII)+H202 -+ Os(VIII)+OH-+OH
(96)
(97)
+ OH-
Fe(I1) + OH
Fe(III)
OH + H202
HO2 H2O
Fe(Il)+HO,
Fe(llI)+HO;
Fe(III)+HO,
Fe(II)+02+H+
At a low ratio of [H202]/Fe2'] only reactions (53) and (57) take place, oxygen
is not evolved and a second order rate law is operative. In dilute perchloric acid
solution (pH = 1.35) and at 25 "C, k,, was found to be 53.0k0.7 I.mole-'.
EXAMPLES
565
HA+H20
HA+Fe(III)
A + H + +Fe(11)
-+
Fe(rIr)+OH-
Fe(rr)+OH
The sum of steps (53) and (99) gives the direct reaction of the organic radical
with hydrogen peroxide, uiz.
HA+H,O2
References pp. 577-580
-+
A+OH+H,O
(100)
566
INDUCED REACTIONS
T A B L E 16
IRON(II)-INDUCED
O X I D A T I O N O F E T H A N O L EY
HYDROGEN
PEROXIDE
1.0~10-4
i . o x 10-3
I.OX 10-3
I . O X 10-3
1.ox 1 0 - 2
1.0 x 1 0 - 2
1.0 X 10-2
1.o~
10-3
1 . o 10-3
~
Initial
0.52
0.52
0.52
0.52
0.52
0.52
0.90
2.0
2.0
2.0
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.027
3.8
3.8
3.8
7.6
1.9
3.8
0.85
2.0
4.1
3.8
1.98
1.64
0.54
0.56
0.58
0.15
0.19
0.2 I
0.70
0.49
0.01
0.22
2.7
2.6
2.5
12.3
9.5
8.5
1.86
3.08
The suppressing effect of the acetic acid can be interpreted by reactions (101) and
(102)
+
CH3COO- + Fe(III)
(101)
CH,COO+ Fe(1I)
(102)
OF
VARIOUS
ORGANIC
SUBSTANCES
BY
HYDROGEN
P E R O X I D E IN T H E P R E S E N C E O F A I R
Substance added
Methanol
Methanol
Methanol
Acetic acid
Acetic acid
Acetone
Acetone
Ethanol
Ethanol
Concentration ( M )
10-4
10-2
10-2
10-4
10-2
10-4
10-2
10-4
10-2
Initial
[Fe' ]
( M x 103)
+
I .o
I .o
I .0
1.3
I .o
1 .o
I .o
1 .o
1 .o
2.0
Initial
[Fe'
[Fe+ ] reucted
__.__
[ H z O , ] rakeri
+
[ H z O z1
3.75
3.75
3.75
9.28
3.75
3.75
3.75
3.75
4.16
4.24
2.04
2.22
2.10
3.21
2.07
2.41
2.09
3.04
2.19
2.06
EXAMPLES
567
oxygen. This phenomenon has been studied by Kolthoff and Medaliato5.The increase in the amount of iron(I1) reacted is caused by autoxidation of the organic
compound present. Some relevant data are included in Table 17. All the organic
substances studied, unlike their effects in the absence of oxygen, show similar
behaviour. Chloride ion, however, proved to be an effective suppressor of the
induced reaction in the presence as in the absence of oxygen. The induced reaction occurring in the presence of oxygen can be described by the following scheme
Fe(II)+H,O,
-+
Fe(III)+OH-+OH
H,A+OH -+ HA+H,O
(53)
(98)
H A + 0 2 -+ HAO,
(103)
HA02+H++Fe(11) .+ HAO,H+Fe(lII)
(104)
HA0,H
+ Fe(II)
HAO+H2A
HAO,
+ H2A
-+
(105)
-+
HAOH+HA
(106)
-+
H A 0 2 H+ HA
(107)
HAO+Fe(II)+ H + -+ HAOH+Fe(IlI)
Fe(II)+OH
-+
Fe(lI1)fOH-
(108)
(57)
2.4
Fe(II1)
568
INDUCED REACTIONS
Fe(III)+SO:-+SO,
(43)
-+
Fe(III)+SO:-
(44)
+ H2A + HA + HSO,
(109)
Fe(II)+SO,
SO;
HA+S20:-+
A+HSO,+SO,
(110)
- kl09lIH2Al
-d[H2AI 2 k,,[Fe(II)]
-d[Fe(II)]
must be independent of the rate of addition of peroxydisulphate to the reaction
mixture. On the other hand, if iron(I1) is added to an alcohol-peroxydisulphate
mixture, the extent of the oxidation of alcohol is determined by the rate of addition of iron(I1). If the instantaneous concentration of iron(I1) is very low- which
can be attained by very slow addition-the value of -d[H2A]/-d[Fe2+] should
become infinite. This is supported experimentally. With ethanol the value of
klOg/k,, was found t o be 0.006 by Merz and Waters"' and 0.015 by Kolthoff
et allo7.The difference was ascribed by the latter to traces of oxygen, as the value
of kIo9/k4, decreases in the presence of 02.
Dilution of the reaction mixture with water or acid results in a decrease in the
consumption ratio. This result cannot be interpreted by the above mechanism
because the induced oxidation depends on the relative and not on the absolute
concentrations. But assuming that reaction (109) is reversible we obtain for the
consumption ratio
I f k l l o >> k-109, or the concentration of the oxidizing agent is high, eqn. (112)
reduced to eqn. (1 11). On the contrary, with a very low concentration of oxidizing
agent the consumption ratio becomes dependent on the concentration of the
oxidizing agent.
During the induced reactions involving peroxydisulphate in the presence of
oxygen, the induced oxidation of iron(I1) by oxygen can be observed just as with
the hydrogen peroxide-iron(I1) system. Chloride and particularly bromide ions
are effective inhibitors in the iron(I1)-peroxydisulphate system.
569
EXAMPLES
so;
OH
AND
RADICAL, RESPECTIVELY
___.
C2H50H
n-CaH70H
iso-C3H70H
0.0022
0.0062
0.0061
0.0089
1.14
2.05
1.30
CH,OH
~~
_.
~~~~~~~~~
(SO,)
h109/k44
(OH)
k9dk57
--~~____.
2.5
INDUCED
~~
REACTIONS
PARTIAL
--.
INVOLVING
OXIDATION
1.77
~
lNTERMEDIATES
OF
PRODUCED
BY
THIOCYANATE
570
I N D U C E D REACTIONS
T A B L E 19
DEPENDENCE OF I N D U C E D
C O N D I T I O N SI N T H E
H202-H2S05-SCN-
SYSTEM
Data of Csrinyi and Solyrnosi"o. Initial amounts taken: 2.83 ml 0.01 N H 2 S 0 5 , 7.46 ml 0.01 N
H , 0 2 . Total oxidising capacity taken: 10.29 ml 0.01 N .
0.I N K S C N
PH
Time of reaction
(see)
(l?ll)
3.00
2.50
2.10
I .30
0.90
3.6
3.6
3.6
3.6
3.0
3.0
3.0
3 .O
3.0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Total oxidising
cnpncity found
s tnlO.01 N
8.30
7.90
7.65
6.98
6.86
8.70
8.06
7.35
6.90
8.30
7.50
7.14
6.86
6.86
15
15
15
15
15
15
45
120
180
15
0.5
1.5
2.0
3.0
4.0
15
15
15
15
Difference
10.29-x
I .99
2.39
2.64
3.31
3.43
1.59
2.23
2.94
3.39
I .99
2.79
3.15
3.43
3.43
'
SCN- +(3 - 2 m
=
(4-
3/17
+ f)
+ /) SO:-
57 1
EXAMPLES
T A B L E 20
DEPENDENCE OF
INDUCED
REDUCTION OF
HYDROGEN
H202-CH3COOOH-SCN-
SYSTEM
Trrken
PH
Found
CH3COOOH
HzO2
( n i l 0.01 N ) (mlO.01 N )
~~~~~~~
4.97
4.97
4.97
4.91
4.97
4.97
4.91
4.97
4.03
4.03
4.03
4.03
4.03
4.03
4.03
4.03
4.03
4.03
4.97
4.97
4.97
4.97
4.97
4.97
4.97
6.73
6.73
6.73
6.73
6.73
6.73
6.13
6.73
4.03
4.03
4.03
4.03
3.03
4.03
4.03
4.03
4.03
4.03
6.73
6.73
6.73
6.73
6.13
6.73
6.73
Diference
( n il 0.01 N )
~
~~
0.25
0.50
3.05
3.05
3.05
3.05
3.35
3.05
3.05
3.05
3.34
3.23
3.10
2.92
2.75
2.62
2.54
2.10
1.70
1.27
3.05
3.05
3.05
3.05
3.05
3.05
3.05
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
45
60
90
I20
180
240
0.15
1.oo
1S O
2.00
2.50
3.00
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
11.70
11.70
11.70
11.70
I 1.70
I 1.70
11.70
11.70
7.23
7.23
7.23
7.23
7.23
7.23
7.23
7.23
7.23
7.23
11.70
11.70
11.70
11.70
1 1.70
11.70
11.70
8.38
6.90
5.93
4.45
3.78
3.10
2.93
2.93
4.80
4.70
4.23
3.40
3.00
2.82
2.70
2.30
2.18
2.15
7.17
6.15
5.17
4.40
4.25
4.24
4.24
~~
3.32
4.80
5.77
7.25
7.92
8.60
8.77
8.77
2.34
2.53
3.00
3.83
4.23
4.41
4.53
4.93
5.05
5.08
4.53
5.55
6.53
7.30
7.45
7.46
7.46
-k,
C N -S
( CN )2
The rate of reaction depends in a fairly complex way upon concentrations. In the
pH range from 2.3-3.7 (which is the interesting range from the aspect of the induced reaction), the initial rates were shown to obey the relation
572
I N D U C E D REACTIONS
where K = (5.0+ 1.6) x lo-'' mole.l-' is the formal ionization constant for
HSO;.
Since the measurements of conductance change are not directly related to the
composition of the solution, as an alternative method numerical integration of the
differential rate equations implied by the proposed mechanism was employed.
The second order rate coefficients obtained by this method are
30.1 "C
2.8
2300
0.0052
0.1
10.1 "C
1.o
1000
0.0040
0.04
~~~~~
__
HSO;
(1 13)
HSO; +SCN-
+ HS0,.SCN2-
is equally consistent with the initial rate data. The two possibilities (113) and
( 1 14) are in principle distinguishable. If ( 1 13) is occurring, then increasing the
sulphate ion concentration should produce a decrease in the initial rate, while there
is no sulphate dependence in the case of step (114). Unfortunately, at present
there are no results reliable enough to distinguish between these two possibilities.
The acid-catalyzed reaction between hydrogen peroxide and thiocyanate ions
has been investigated by several authors, most thoroughly by Wilson and Harris114.
The rate law has the form
R
+ c1 [HCN])
EXAMPLES
SCN-
573
+ H 2 0 2+ H 3 0 + + HOSCN + 2 HzO
HOSCN+ H 2 0 2 -+ HOOSCN+ H 2 0
HOSCN + HCN
S(CN), + H 2 0
(118)
(119)
+2 H 2 0 = HCO; + NH;
(122)
reaction (120) being rate determining, account for the stoichiometry and kinetics
of the non-catalyzed reaction.
The reactions of peroxysulphuric acid and of hydrogen peroxide with the
thiocyanate are obviously very similar. In both reactions the reactive intermediate
is the same or at least has a very similar structure, and the subsequent reactions
of this entity are equally fast either with peroxy acid or with hydrogen peroxide.
Accordingly it can be said that if both peroxy acid and hydrogen peroxide are
present in the solution a competition between these two substances for the intermediate occurs, as a result of which not only the peroxy acid but also the hydrogen peroxide will be reduced.
In solutions of pH > 3, when the rate of reduction of peroxy acid is much lower,
the induced disappearance of hydrogen peroxide will be considerably reduced.
2.6
IONS
5 74
INDUCED REACTIONS
100
200
300
400
500
600
700
[MeOH]
[ w 2 ]
Fig. 3. Induced oxidation of methanol by permanganate in the H 2 0 2 - K M n 0 4 system. ACcording to data of Waters ef uI."*.
575
EXAMPLES
the presence of pyrophosphate ions, not only the rate of reduction of permanganate
but also the rate of the oxidation of alcohol was decreased.
The data for this induced reaction can be interpreted as follows. In the course
of the permanganate-iron(I1) or permanganate-hydrogen peroxide reaction a
manganese intermediate [presumably maganese(IV)] is formed which reacts both
with the inductor (iron(11) or hydrogen peroxide), and with the acceptor (alcohol).
The suggestion that manganese(1V) is the active intermediate is supported by the
value of CI = 0.6 and by the limiting value of the oxidation ratio, (equiv. of
alcohol/mole of KMnO,) = 3, found experimentally. This assumption is also in
accordance with the fact that addition of manganese(II), by both displacing the
equilibrium
Mn(ITI)+ Mn(1I)
+ 2 Mn(IV)
to the right, and increasing the rate of the primary reaction, greatly decreases the
rate of the alcohol oxidation.
The mechanism of the induced oxidation of alcohol is assumed by the authors
mentioned to be analogous to that of oxidation of isopropyl alcohol by chromic
acid, viz.
Me2C-6I
Me2C=0
2.7
+ Mn4*
-C
H I
M e 2 C - 6 I -Mn3+
TIN(II1)
INTERMEDIATE
The formation of tin(II1) intermediate during the oxidation of tin(I1) has been
postulated earlier in some cases, although direct evidence has not been quoted.
Recently a couple of cobalt(II1) complexes were supposed by Higginson et al.' '
to demonstrate the presence of tin(II1).
Generally to detect strongly reducing intermediates it is necessary to have a
substrate which is not a strong oxidizing agent, or it is likely to react fairly rapidly
with the reduced form of the oxidizing partner under investigation. (Mutatis
mutandis- the same is valid for detection of oxidizing intermediates.) The
suitability of some cobalt(II1) complexes, e.g. in order of sensitivity: trioxalato- >
> aquo-chloro-tetramino- > (hydroxyethylethylenediamine-triacetato)aquo-(Co
(YOH)H,O) > ethylenediamine-tetraacetato cobaltate(II1)-(Co(Y)), arises from
the fact that they are weak oxidizing agents, and that cobaltous ions produ :ed are
inert towards oxidation, or further reduction. The ease of determination of
cobalt(II1) complexes by spectrophotometry is an additional advantage.
References pp. 577-530
576
INDUCED REACTIONS
121, l
was
+ Fe(II)+Sn(IV)
In perchlorate media, a marked decrease in the apparent second-order rate coefficients was found as the reaction proceeded if tin(lI) was present in excess,
whereas only little change occurred when iron(I1I) was in excess. This behaviour
indicates that there is a competition between iron(1I) and iron(III) for tin(1II).
In experiments with added Co(YOH)H,O a considerable consumption of this
complex was found56.
The fact that the results of kinetic study are in good agreement with the above
mechanism, together with the additional evidence obtained by using the cobalt(II1)
complex, makes it highly probable that tin(II1) is, in fact, the only intermediate
involved in this reaction.
2 Cr(III)+3 Sn(IV)
unlike the reaction between arsenous acid and chromate, takes place in l-equivalent steps. Thus, a considerable consumption of added trioxalato cobaltate(II1)
complex has been observed56. This finding also supports the authors opinion
that it is necessary to reconsider some steps in the widely accepted mechanism
of chromic acid oxidations.
2.7.3 Reaction between tin(ZI) and permanganate
REFERENCES
577
place. According to the meagre kinetic data it seems likely that the fast stage of
the reaction is the formation of Mn(V) by a 2-equivalent change. The step
Mn(V)+Sn(I")
Mn(IV)+Sn(lII)
3. Conclusions
This short and far from complete survey shows that the previously obscure field
of chemical induction is becoming more and more understood. The accelerating
pace of progress has furnished from the forties onwards a great deal of interesting
information about the chemistry of unstable intermediates, e.g. chromium(V),
chromium(IV), arsenic(IV), tin(III), HOz , OH, SO, radicals. These results were
obtained mostly by conventional methods. Therefore, it may be expected that the
more extensive application of methods suitable for detection and estimation of
short-living entities (e.g. resonance methods, fast reaction techniques) will enable
our somewhat qualitative knowledge (as i t is today) to be put onto a quantitative
basis.
REFERENCES
1 F. KESSLER,
Pogg. Ann., 119 (1863) 218.
Z. Angew. Chem., 17 (1904) 580, 1407.
2 F. RASCHIG,
3 A. VON DER ROPP, Z. Anal. Chem., 40 (1901) 482.
4 F. FEIGL,Chemistry of Specific Selective and Sensitive Reactions, Academic Press, New
York, 1949, p. 156.
5 F. FEIGL,Chemistry of Specific Selective and Sensitive Reacrions, Academic Press, New York,
1949, p. 159.
6 R. L. RICHAND H. TAUBE,
J. Am. Chem. SOC.,76 (1954) 2608.
7 R. LUTHER
A N D N. SCHILOW,
Z. Physik. Chem. Leipzig, 46 (1903) 777.
8 R. LIVINGSTON,
in S. L. FRIESA N D A. WEISSBERGER,
Eds., Technique of Organic Chemistry,
Vol. VIII, Interscience, New York, 1953, pp. 219 and 224.
9 W. C. BRAYAND J. B. RAMSEY,
J . Am. Chem. Soc., 55 (1933) 2219.
10 W. MANCHOT,
Ann., 213 (1882) 312.
1 1 A. 1. MEDALIA,
Anal. Chem., 27 (1958) 1678.
Z. Anorg. Allgem. Chem., 170 (1928) 389.
12 R. LANGA N D J. ZWERINA,
13 L.J. C S ~ N Y
AN
I D M. SZABO,Talanta, 1 (1958) 359.
14 W. NERNST,Theoretische Chemie, 4th ed., ENKE, Stuttgart, 1903, p. 656.
15 R. LUTHERA N D T. F. RUTTER,Z. Anorg. Allgem. Chem., 54 (1907) 1.
16 P. A. SCHAFFER,
J. Am. Chem. Soc., 55 (1933) 2169; J. Phys. Chem., 40 (1936) 1021.
J. Prakr. Chem., 75 (1858) 108.
17 C. F. SCHONBEIN,
578
I8
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
INDUCED REACTIONS
REFERENCES
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
I17
118
119
120
121
122
123
124
125
126
579
580
INDUCED REACTIONS
127 G. V. BAKORE
A N D S. NARAIN,
Z. Pliys. Cheni., 227 (1964) 8.
A N D A. A. DESHPANDE,
Z. Phys. Chern., 227 (1964) 14.
128 G. V. BAKORE
129 K. B. WIBERG,
Oxidation in Organic Chemistry, Part A , Academic Press, New York, N.Y.,
1965.
Oxidation Mechanism: Applicatiori to Organic Chemistry, W. A. Benjamin,
130 R. STEWART,
New York, N.Y., 1964.
131 A. 0. ALLEN,private communication.
132 C. C. HONGA N D W. H. RAPSON,
Can. J. Cheni., 46 ( I 968) 2053.
A N D M. C. R. SYMONS,
The Structure of Inorganic Radicals, Elsevier, Amster133 P. W. ATKINS
dam-London-New York, 1967, p. 175, 210.
J. Phys. Chern., 71 (1967) 268.
134 H. A. CATHERINO,
J. Phys. Cheni., 70 (1966) 1339.
135 H. A. CATHERINO,
136 J. Y. TONGAND E. L. KING,J. Am. Chern. Soc., 82 (1960) 3805.
Z. Anorg. Allgem. Ctiern.,168 (1928) 279
137 C. WAGNER,
-,
-,
-,
-,
-,
+
+
582
INDEX
-, reaction + Fe(lll)/02, 45 1
acetylene dicarboxylic acid, reaction +Cu(II),
454,455
acetyl radicals, from Mn(III)+ MeCOCOOH,
396
acraldehyde, reaction+Hg(II), 338
-, - Mn(III), 390
acrylonitrile, effect on As(III)+S20s2-, 543
-, -on Ce(IV), Mn(VII)/H202/S2082-,555
-, - on Cr(II)PhCH,, 483
-, - on Cr(VI)+Me,CCHPhOH, 528
-, - on Fe(II)/EtOH/S2082-, 478
-, -on Fe(II)+PhCMe,OOH, 464,465
-, - on metal ions+ROH, 377
-, - on Mn(III)+CH2(COOH),, 401
activated complex, see transition state
activation energy, see also enthalpy of activation
-, of Ag(I)/Ag(II) exchange, 59
of Ag(I), Cu(II)+HZ, 420, 421
ofAg(I)+S2082-, 475, 476
Of Ag(II)+HzO, H202, 365-367
-, of A s ( ~ ~ ~ ) / C U ( I I ) + S477
~O~~-,
-, Of Au(III)+CNS-, 331
-, of Au(III)+(COOH)2, 353
-, of Au(III)+SO,-, 332
-, of Ce(lI)/Ce(lV) exchange, 128, 129
-, ofCe(IIl)+NOJ-, 473
-, of Ce(IlI)+Pb(IV), 242, 243
-, of Ce(lV)+As(III), 371
-, of Ce(lV), Co(IIl)+mercaptoacids, 395
-, of Ce(lV), Co(IlI), Mn(VI)+C6H4(OH),,
404
-, of Ce(IV), Co(lll)+thiourea, 407
-, Of C e W ) , Co(Ill), V(V)+hydroxyacids,
393
-, of Ce(lV)+Fe(ll), 247
-, of Ce(IV)+Hg(I), 251, 252
-, of Ce(lV)+HN,, 362
-, of Ce(lV)+H202, 368
-, of Ce(IV)+H,PO,, 371
-, of Ce(IV), Mn(III)+(COOH)2, 397, 398
-, of Ce(lV), Mn(lll), V(V)+CH,(COOH),,
400,402
-, of Ce(lV)+Sb(llI), 372
-, of Co(ll)/Co(lI1) exchange, 112, 114-1 I 7
-, of Co(II)+Fe(III), 183
OfCO(II)+H20,, 462
-, of Co(II)+ICN, 469
-, of Co(lI)+NH2OH, 471
-3
Of Co(lI)+O,, 449, 450
-, of Co(lI)+organic halides, 485
-, of Co(ll)+Pb(lV), 241
-, of Co(llI)+alkylbenzenes, 373, 374
-, of Co(III)+ArOH, 403, 404
-, of Co(llI)+Br-, 357
-9
-3
-9
-9
-, of Co(III)+Br,, 362
-, Of CO(III)fC6H6, 375
-, of CO(I~I)+CIO,,363
-, of Co(lII)+Fe(II), 216
-, of Co(III)+Hg(I), 222
-, of Co(III)+HN,, 361
-,
Of
Co(III)+H202, 367
-, of Co(III)+olefins, 375
-,
O f CO(llI)+PhCH-CHCOOH,
391
-,
-,
-,
-,
-,
-,
Of CO(III)+V(IV), 214
of Cr(lI)/Cr(lII) exchange, 81-83
of Cr(ll)+CH=CCH,OH, 458
of Cr(lI)+HN3,
NH20H, 470
of Cr(II), Ir(IlI), v ( I I ) + c ~ o , - , 441
of Cr(OAc),Cr(NH3)sC12+,88, 89
-, of Cr(lI)+PhCH,CI, 483
-, of Cr(VI)+Br-, 282
-, Of Cr(VI)+C6H4(OH)2, 313
-, of Cr(Vl)+glycols, 320
-, of Cr(VI)+H2, 291
-, of Cr(VI)+HCOOH, 316
-, ofCr(VI)+H202, 284
-, of Cr(Vl)+HSO,-, 285
-, of Cr(VI)+hydroxyacids, 324
-, of Cr(VI)+I-, 281
-, of Cr(VI)+Ph,CH,, 294
-, of Cr(VI)+RCHO, 310, 530
-, of Cr(VI)+ROH, 301, 308
-, of Cr(VI)+S2032-, 286, 287
-, of Cr02CIZ+C-C, 298, 299
-, of Cu(I), Fe(II)+CIO,-, 442
-, of Cu(1) +O,, 448
-, Of C U ( I I ) + ~ - C ~ H492
~.,
-, of CU(II)+CO, 420
-, Of Cu(II)+CS(NH2)2, 439
-, O f Cu(II)+HCHO, 426
-, of Cu(II)+Me,CHCHO, 427
-, of Cu(II), Sb(lII)+S2082-, 478
-, of decomposition of CrOS, 284
-, of dissociation of Np(V) . Rh(lll), 260
-, of Eu(II)/Eu(IlI) exchange, 130
-, of exchange reactions of carbonyls, 29
-, of Fe(lI)+Br,-, 467
-, of Fe(II)+C6H402,455
-, of Fe(ll)+DPPH, 489
-, of Fe(ll)+Fe(Ill) exchange, 97, 99-103,
106-1 08
-, of Fe(II)+Fe(lII) reactions, 108
-, of Fe(lI)+Hg(ll), 230
-, of Fe(II)+H2O2, 459-461, 565
-, of Fe(Il)+02, 445, 446
-, of Fe(ll)+RNO., 490
-, of Fe(l1) +ROOH, 465
-, of Fe(lI)+S208Z-,478, 480
INDEX
-, of Fe(ll)+Tl(Ill), 233
-, of Fe(III)+BH4-, 422
-, of Fe(1ll) chelate+02, 451
Fe(II1)+CyClO-C6HloCO, 428
Of Fe(III)+C6H4(0H)2, 434
-, of Fe(III)+C8H1,SH, 424
-, of Fe(Ill)+CN-, 411
-, of Fe(IlI)+CS(NH2),, MeCSNH,, 428
-, of Fe(lIl)+HCHO, 427
-, of Fe(III)+H202, 413
-, of Fe(III)+N2H4, 419
-, of Fe(IIl)+Np(IV), 188
-, of Fe(lII)+SCN-, 412
-, of Fe(lII)+S03z-, 415
-, of Fe(III)+U(IV), 187
-, of Fe(III), V(IV)+ascorbic acid, 432, 433
of M I ) , Hg(II)+HZ, 336
-, of Hg(l)+TI(III), 236
-, of Hg(Il)+acraldehyde, 338
Of Hg(CN)2+HgZ+, 61
-, of Hg(lI)+CO, 334
-, of Hg(ll)+cyclohexanol, 344
-, of Hg(II), Pd(III), TI(III)+HC02-, 346
-, of Hg(II)+Pr,O, 348
-, Of HzOz+SCN-, 572
-, of lr(lll)+Ir(lV), 122
-, of Ir(lV)+ArOH, 403
Of IrC16C Y C I O - C ~ H ~ 382
~CO,
-, of hydrolysis of Co(1ll) complexes, 17
-, - of Cr(lll), Rh(II1) and Ru(II1) complexes, 19
-, of metal ions+polymer radicals, 490
-, of Mn(lll)+HN,, 361
-, of Mn(llI)+MeCOOH, 386
-, of Mn(lll)+PhMe, 374
-, of Mn(VII)+ArCH2NHz, 318
-, of Mn(VII)+CN-, 283
-, of Mn(Vll)+CO, 290
-, of Mn(VII)+furfural, 327
-, of Mn(VII)+H,, 292
-, of Mn(VII)+HCOOH, 316, 317
-, of Mn(VII)+l-, 282
-, of Mn(VII), Mn(VI)+CF3CH(OH)z, 313
-, of Mn(VII)+N02-, 287
-, of Mn0,C-C, 299, 300
-, of Mn0,C2(COO-)2, 300
-, of Mn04-/Mn0,2- exchange, 94
-,of Mn(VII)+PhCHO, 311
-, of Mn(VII)+PhEt, 298
-, of Mn(VII)+RNO,, 320
-, of Mn(VII)+ROH, 308, 309
-, of Mo(V)+methylene blue, 332
-, Of Mo(V)+NOJ-, 474
-, of Mo(V), Np(V)+I-, 410
-, of Mo(V), Pu(IIl)+NOZ-, 472
-, O f M o ( V I ) + N ~ H ~332
,
-9
Of
-9
-I
-1
-3
+
+
583
-, of Np(V)+V(III), 257
-, of Np(VI)+EDTA, 402
-, ofNp(VI), V(V)+(COOH)Z, 399
-, of OS(II)+TI(III), 235
-, of Pb(lI)/Pb(IV) exchange, 70
-, of Pb(IV)+t-BuOOH, 344
-, of Pb(IV)+(CH2OH)z, 349
of Pb(IV)fPhC3Hs, 343
-, of PC13/PCI5 exchange, 75
-, of Pd(Il)+oletins, 339, 340
-, Of Pt(IV)+S20A2-, 332
-, of Pu(lII)+Oz, 447
-, Of Pu(~II)+Pu(IV), 138
-, of reactions of Np ions, 134, 137, I38
-, of Rh(IlI)+CzH4, 342
--, of Ru(II)+HZO, 452
-, of Sb(IlI)/Sb(V) exchange, 72-75
-, of Sn(lI)/Sn(lV) exchange, 68-70
-, of Sn(lI)+S2082-, 480
-, of TI(I)/TI(III) reactions, 62-65
-, o f T I ( I I I ) + C I O ~ ~440
,
-,
-,
-,
-,
-,
-,
-,
-,
o f TI(III)+HF, 469
of TI(III)+H3P04, 334
Of TI(III)+PhC3H~,342
Of U(IV) H202,46 I
of U(lV)+O,, 443
of U(lV)/U(Vl) exchange, 131, 132
of U(IV), V(IV)+Br03-, 442
of V(11)+Br2, IT, 469
-, of V(II)/V(lII) exchange, 76
-, of V(Il)+V(IV), V(V), 79, 80
-, of V(III)+O,, 444
-, of V(III)/V(IV) exchange, 77
-, of V(V)+1-, 359
actor, in induced reactions, 510, 512, 514, 516,
517
-, - with Cr(VI), 520
-, - with Fe(l1)+H,O2, 565
adipic acid, from Cr(Cl)+cyclohexanone, 313
adjacent attack, and Co(1lI) oxidations, 206,
21 1
p-aldehydobenzoate ion, oxidation of, in
Mn(VII) +Co(lll), I71
allyl acetate, effect on A s ( I I I ) + S ~ O ~ ~543
-,
allyl alcohol, reaction+Cr(VI), 322
-, - Cu(ll), 429, 430
-, - Mn(VIl), 300
allyl chloride, reaction+Cr(ll), 482
alpha radiation, effect on reactions of Am(V),
141
amide ion, and Co(l1I) complexes, 12, 17
-, labilizing effect on, 49
++
584
INDEX
+
+
+
+ NOz-, 473
_ ,- + S2OS2-. effect
-, -
+
+
B
barium ion, effect on Fe(CN)64-/Fe(CN)63exchange, 107
benzaldehyde, from Ce(lV)i-ArPhC2H3 0 H ,
388
-,from Ce(IV), Co(lll), V(V)+PhMe, 374
-, from Co(II)+PhCH200H, 466
-, from Co(llI)+Bz20, 404
-, from Co(lII)+BzOC6HI,, 405
-, from Co(lll)+PhCH=CHCOOH, 391
-, from Cr(VI)+Me,CCHPhOH, 528
-, reaction+Ce(IV), Co(lII), 379
585
INDEX
-, reaction+Au(Ill), 332
-, -, -
bond order, and exchange reactions of carbonyls, 28, 30, 31, 34, 42
bornanes, reaction+Cr(Vl), 294
borohydride ion, reaction+Fe(lll), 422
bromate ion, reaction+U(IV) and V(IV), 442
bromide ion, and carbonyl compounds, 35-39,
42
-, and Co(1ll) complexes, 9, 10, 14, 15, 17,
50, 51
-, and Co(11l) oxidations, 188, 190-194, 198200, 203, 212
-, and Co(ll1) substitution reactions, I20
-, and Cr(II)/Cr(lIl) exchange, 81, 82
-, and Cr(II)EDTA+Cr(llI), 90
-, and Cr(II)+Fe(lll), 180
-, and Cr(ll)+Pt(IV), 227
-, and Cr(ll)+S2OS2-, 480
-, and Cr(1II) aquation, 85, 86
-, and Cr(lII)+Eu(ll), 169
-, and C r ( l l I ) + H + , 88
-, and Cr(lll), Rh(lll), Ru(1ll) complexes,
18, 19
-, and Cu(lI)+unsaturated alcohols, 429
-, and Fe(Il)/Fe(IIl) exchange, 101
-, and Fe(Il)+H202, 461
-, and Fe(lI)+polyacrylamide radicals, 490
-, and Fe(II)+S2082-/EtOH, 478, 568
-, and Fe(IIl)+Sn(ll), 184
-, and Pt(l1) complexes, 22-24
-, and Sb(lIl)/Sb(V) exchange, 66, 67
-, and U(V)i-U(V), 132, 133
-, effect on As(lII)+CIO3-, 551
-, - on Co(ll)/Co(lll) exchange, 117
-, - o n HzO2+S2Os2-,556
-, - on Pd(ll)i-CO, 335
-, - on Pt(lI)/Pt(lV) reactions, 123-127
-, - on Tl(III)+Hg(I), 237
-, - on TI(III)/TI(I) exchange, 66, 67
-, lability of, 48
-, reaction+Bi(V), 331
-, - -tCe(IV), Co(lll), Mn(lII), V(V),
356-358
-, - I Cr(VI), 282, 288, 327, 328
-, train effect of, 47, 49
bromine, reaction+Co(lll), 362
-, - I Fe(II), TI(I), U(IV), 467
-, - I V(II), 469
586
INDEX
+
+
+
+
+
+
C
cadmium ion, reaction+Co(III), 206
caesium ion, effect on Fe(CN)e3EDTA,
437
-, - on Fe(CN)e3- Fe(CN)e4-, 107
-, - on Fe(CN)e3- f I - , 409
-, - on Mn(VI)/Mn(VII) exchange, 93, 94
calcium ion, effect on Fe(CN)63-/Fe(CN)e4exchange, 107
camphane diols, reaction+Pb(IV), 351
carbonate anion, and Co(lI1) oxidation of
metal ions, 194
carbon dioxide, complex+Pd(O), 335
-, from Co(III)+RCOOH, 384
-, from Mn04- CN-, 283
-, from Mn04- Co(III)HCO2, 171
-, from Mn(III)+RCOOH, 386, 387
carbonium ions, and Cr(V1) hydrocarbons,
293-296
-, and Mn(VII)+ROH, 309
carbon monoxide, and orbital matching in
complexes, 45, 48
-, exchange with carbonyls, 28,29, 32, 33, 35,
38, 51
-, -with Ir(1) and Rh(1) complexes, 25
-, labilizing effect of, 51
+
+
-,
-,
-,
-,
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
587
INDEX
+
+
+
+
+
+
588
INDEX
+ DPPH, 489
+ Fe(III), 179-182, 249
- + Hg(Il), 229, 230
- + HN3,86
- -1- H202, 461, 462
- + Np(lV), Np(VI), 259-261
- + 02,447
-, -
-, -
-.
-I
-,
-,
-1
-,
-,
-,
-,
a
,
+
- + V(III), 159-161, 249
- + V(IV), 157, I58
+
+
+
+
+
+
+
+
+
-.
-,
-,
-,
-,
-,
-,
-,
-,
+ hydrocarbons, 292-297
+ Mn(II), 514
- + Np(V), 166, 167
+ olefins, 298, 299
P(III), 287, 288
+ RCHO, 310, 31 I, 529-531
+ Sn(II), 165, 166, 576
+ SZOs-, 286, 287
--
-,
-, --, -- -1-, -, -, -
+
+
+
+
+
5 89
INDEX
-, - + CC14,487
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-,
+ HZO, 366
-,
+ H202, 367, 368
+ H3P02, 370
-, - + hydroxy acids, 392-394
-, - + I - , 358, 359
-, - + ketones, 381, 382
-, - + Mn(Il), 215, 216
-, - + Np(V), 226, 227
-, - + olefins, 374, 375
-, - + phenols, 403, 404
-, - + RCHO, 379
-, - + RCOOH, 384-386
-, - + ROH, 376, 377
-, - + Sn(lI), 223
-, - + Sn(II), and FeUII),
Mn(VII), 576, 577
-, - + SzOs2-, 476,480,481
-, - + thiomalic acid, 395
-, - + thioureas, 407
-, - + TI(I), 222, 223
-, - + unsaturated acids, 391
-, - + V(II), 189-193, 249
-, - + V(III), V(IV), 213, 214
-, -, -, -,
-, -,
-I
Cr(V1)
or
-, reaction+Co(lI), 121
cobalt carbonyls, exchange reactions of, 27-29,
32-34, 51
-, structure of, 26, 27
concerted reaction, of inert complexes, 4
conjugate base, in reactions of inert complexes,
20
coordination spheres, in complexcs, 1
copper(I), effect on C u ( I I ) + C H K C H , O H ,
429
-, exchange with Cu(II), 58
-, reaction+ArS02C1, 488
+ Co(III), 198
+ Fe(III), V(IV), 178, 179
+ H2,421
+ HzOz, 463
+ 02,447449
+ S2OSz-,478
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
590
INDEX
+
+
+
+
-, - + Mn(VII), 315
-, - + TI(III), 347, 348
1,5-cyclooctadiene, and carbonyl exchange
reactions, 41
cyclopentadiene, as ligand in carbonyls, 32
-, effect on Fe(II)/Fe(lII) exchange, 105
cyclopentane-1,2-dioIs, reaction+Ce(lV),
Mn(lll), 389
cysteine, and Fe(III)+02, 446
D
decalin, exchange reactions of carbonyls in,
29, 36, 38
decaIin-9,IO-diol, reaction+Pb(IV), 350, 351
deuterium, effect o n reactions of Co(II1) complexes, 15
-, exchange with Co(III), Cr(III), Rh(III),
R u ( ~ I I ) ( N H ~ ) ~20
CI,
deuterium oxide, Ag(l), Cu(II)+H2 in, 421
-, Ce(IV), Co(III), V(V)+ketones in, 381,382
-, Co(ll)/Co(llI) exchange in, 112, 113, 117,
118
-, C O ( I I ) + S ~ O ~in,~ -481
-, Co(III)+HCHO in, 379
-, Co(III), Mn(III)+HCOOH, 386, 387
-, Co(lII)+V(II) in, 189
-, Cr(ll)+CH&CH,OH in, 458
-, Cr(II)(NH3)5CI+H+ in, 88
-, Cr(V1)fcyclohexanone in, 314
-, Cr(VI)+ Me2CHOH in, 301
-, Cr(VI)+pinacol in, 321
-, Cr(VI)+S2OJ2- in, 287
-, Fe(II)/Fe(III) exchange in, 97, 99, 101, 104
-, Fe(II)+PhCMe200H in, 465
-, Mn(VII)+H, in, 292
-, N p ion reactions in, 134, 136-138
-, Pd(II)+CZH4 in, 339
-, Pu ion reactions in, 139, 140
-, reaction+Ru(II), 452
-, TI(I)/TI(III) exchange in, 64, 65
-, TI(III)+cyclohexanol in, 344
3p,28-diacetoxy-6p-hydroxyI 88- I2-oleanene,
reaction Cr(VI), 302
2,3-diaminobutane, as ligand in Co(II1) hydrolysis, 11, 17
-, - in Pt(l1) complexes, 22, 23
1,2-diaminocyclohexanetetraacetate,and
Fe(Il)+Fe(III) reaction, 109
-, and Mn(ll)/Mn(III) exchange, 93
-, and Mn(III)+(COOH)2, 397, 398
-, reaction+Cr(II), 90
di-2-aminoethylene, and Co(I1) +OZ, 449
1,2-diamino-2-methylpropane,and carbonyl
exchange reactions, 37,41,42
dibenzyl ether, reaction+Co(lll), 404
INDEX
59 1
-, - + Pb(IV), 346
di-i-propyl ketone, reaction+ Fe(lII), 425
dipyridyls, and Ag(I)/Ag(II) exchange, 59
-, and Ag(l)+SzOsz-, 475, 476
-, and Au(I)/Au(lll) exchange, 59
-, and carbonyl exchange reactions, 35, 37,
41-43
-, and Ce(lV)+Fe(II), Ru(II), 249, 250
-, and Co(ll)/Co(Ill) exchange, 118, 119
-, and Co(III) oxidation of metal ions, 189191, 197, 198
-,and Co(lI1) substitution reactions, 120, 121
-, and Cu(l), Cu(ll)+H2O2, 463, 464
-, and Cu(l)+Oz, 449
-, and Cu(II)+ketols, 430, 431
-, and Fe(lI)+Fe(lII), 108-1 10
-, and Fe(lI)+S2Os2-, 479, 480
-, and Fe(III)+radicals, 490
-, and Mo(V)+Os(II), 91, 169
-, and Os(I)/Os(II) exchange, 1 1 1
-, and Os(II)+TI(III), 234, 235
-, and Pt(IV)+Cr(II), 227
dissociative mode of activation, and carbonyl
exchange reactions, 38, 43
-, and reactions of Co(II1) complexes, 8, 9,
11, 13
-, - of Cr(lll), Rh(III), Ru(1ll) complexes,
18-20
-, - of inert complexes, 3, 6, 7, 51
2,5-dithiahexane, and carbonyl exchange reactions, 41
dithiodipropionic acid, from Fe(CN)63HSCZH4COOH, 423
dithionate, from oxidation of SOJ2-, 275, 277
-, reaction+Ag(II), 369, 370
dithionic acid, reaction+Cr(VI), 287
dodecane thiol, reaction+ Fe(llI), 423
E
electron spin resonance, and Ce(IV)+H2O2,
368
-, and Co(Ill)+aromatic hydrocarbons, 374
-, and Co(11I) oxidations, 211, 212
-, and Co(llI)+PhOH, 403
-, and Cr(VI)+Me2CHOH, 303, 526
-, and Cr(VI)+PhCHO, 31 1
-, and CrO2CI2+PhMe, 296
-, and detection of Ag(ll), 220
-, and Fe(Il)+RNO ., 489
-, and Mn(VII)+quinolphosphates, 313
-, and Mo(V)+N03-, 474
-, and study of exchange reactions, 5,7,8, 10
-, of C2H5, 385
enolisation, and Ce(lV), Mn(lII), Ir(IV),
V(V)+ketones, 381
INDEX
-,
-,
-,
-,
of Ag(l)/Ag(Il) exchange, 59
of AS(III)/CU(II)+SZO~~-,
477
of Au(III)+CNS-, 331
of base hydrolysis of Co(I1I) complexes, 17
-, of Ce(III)+Pb(IV), 243
-, o f Ce(lV), Co(IIl)+thioureas, 407
-, of Ce(IV), Co(IlI), V(V) +hydroxyacids,
43M32
393
116-118, 155
-, of Co(III)+Cr(IIl), 215
-, of Co(II1) oxidation of metal ions,
189, 191,
121
-,
-,
-,
-,
-,
36-38
-,of
-, of Mn(I)/Mn(ll), Mn(lI)/Mn(IIl),
Mn(II)/Mn(VII) and Mn(VI)/Mn(VII) exchange, 92, 93, 96
-, Of Np(VI), Pu(VI), U(VI)+V(III), 256
-, of Np(VI)+U(IV), 257
-, of Pu(VI)+Ti(lII), V(III), 262
-, of reactions of Np ions, 135, 136
-, - of Pt(I1) complexes, 24
-, - o f Pt(IV), 124-128
-, - of Pu ions, 139-141
-, - of U ions, 132, 133
-, Of Tl(IlI)+U(lV), 237-239
-, Of U(VI)+V(II), 254
-, of V(III)/V(V) exchange, 155
entropy of activation, see also pre-exponential
factor
-, of acid hydrolysis of Co(1II) complexes, 10
-, of Ce(IV)+NH30H+, 365
-, of Ce(IV)+Sb(III), 372
-, of Co(II)/Co(llI) exchange, 112, 113, 115118
-,
-,
-,
-,
-,
-,
-,
-,
-,
-,
-,
of Co(lI)+Fe(IIl), 183
of C0(11)+H202, 462
of Co(ll)+lCN, 469
of Co(lI)+NHzOH, 470
O f C0(1l)+02,450
of Co(lI)+organic halides, 485
of Co(Il)+Pb(lV), 241
of Co(lIl)+ArOH, 403
of Co(III)+Br-, 357
ofCo(III)t-Brz, CIOz, 362
of Co(lIl)+Ce(lIl). Hg(L), TI(]), 222, 223,
225
-, of Co(lII)+Cr(IIl), 215
-, ofCo(III)+Fe(lI), 216
-, of Co(III)+HN,, 360
-, of Co(III)+Me3CCOOH,
384
C O ( I I I ) + C ~ H ~ ( O H404
)~,
-, of Co(1II) oxidation reactions, 189, 191
-9
-, of Fe(IIL)+V(III),
-,
-,
-,
-,
Of
-, Of Co(IlI)+PhCH=CHCOOH, 391
-, of Co(lII)+PhMe, 373
-, of Co(II1) substitution reactions, 121
-, of co(rII)+v(rv),
214
-, of C r ( I I ) + C H S C H Z O H , 458
155
-, of Cr(ll)+PhCHzCI,
-,
-,
-,
-,
-,
-,
-,
-,
-,
-,
483
593
INDE X
-.
of Cr(VI)+ROH, 308
-, of Cr(VI)+S2032-, 286
-, of Cu(I), Fe(lI)+CIO,-, 442
-,
Of
-, of Pt(lV)+I-, 331
-, of Pt(lV)+S20aZ-, 332
-, of Pu(IV)+Fe(II), Sn(lI), Ti(llI), U ( I V ) ,
Cu(Il)+CS(NH2)2, 439
-, of Cu(Il)+HCHO, 426
-, of Pu(VI)-kSn(II), 264
-, of Pu(Vl)i-Ti(III), U(III), 262
-, of Pu(VI)+U(IV), 265
-, of Pu(VI)+V(III), 256
-, of reactions in TI(I)/TI(III) systems, 63-65
-, - of Np ions, 134, 136
-, - of Pt(I1) complexes, 24
38
-,of Fe(ll)+Fe(IlI), 97, 99, 101-103, 106109. 153
-, of Fe(ll)+Hg(lI), 230
-, - o f Pu ions, 138-141
-, o f Fe(ll), S r ~ ( l l ) i - S ~ O480
~~-,
-, - of U ions, 132, 133
-, of Fe(II)+Ti(lII), 23 I
-, of redox reactionswith -1-4transition states,
-, of Fe(1l)-+TI(lII), 233
155
-, of F e ( l I ) + V 0 2 + , 155
-, of Sb(lII)/Sb(V) exchange, 73
-, O f F~(II~)-~-CYC~O-C~HI~CO,
428
-, of Sn(ll)/Sn(IV) exchange, 70
-, of Fe(Ill)i-CS(NH2)2, MeCSNH,. 438
-, of TI(III)+C104-, 440
-, of Fe(lIl)+Cu(II)/V(lll), 178, 179
-, of Tl(lII)+H3P02, 334
-, of Fe(Ill)-{-U(IV),187
of TI(III)+PhC3HS, 342
-, of Fe(Ill), V(V)+ascorbic acid, 432, 433 -, of Tl(III)+U(IV), 237, 239
-, of Hg(I)-tHgCN+, 62
-, of U(IV)+Br03-, 442
-, of Hg(l), Hg(II)+H2, 336
-, of U(Vl)+V(II), 254
--, of Hg(l)-l TI(III), 236
-, of V(ll)i-Brz, 12, 1 3 - , 469
-, of Hg(ll)+cyclo-C~H1OCO, 344
-, of V(II)/V(lIl) exchange, 76
-, of Hg(Il)+-CO, 334
-, of V(II)+V(IV), V(V), 79, 80
-, o f Hg(ll), Pdcll), TI(11I)~-HCOz-,346
-, of V(IlI)+Fe(lll), TI(III), 231
-, of hydrolysis of C r ( H 2 0 ) s X Z + ,18
-, of V(lII)/V(lV) exchange, 77, 155
-, of Ir(IV)+ArOH, 403
--, of v ( v ) + I - , 359
-, o f I ~ C L +- ~ Y c I ~ - c , Hoco,
,
382
entropy of complex formation, for Np(V)
-, ofMn(l)/Mn(Il), Mn(II)/Mn(lll),
Cr(III), Rh(lII), 259, 260
Mn(VI)/Mn(VlI) exchange, 92, 93
entropy of complexes, in Fe(IlI)i-Ti(lII) and
-, of MnZ+ MnO,-, 96
V(lll)+Fe(Ill), TI(III), 231
-, of Mn(111)+Cz042-, HC204-, 398
entropy of hydration, of ions and hydrolysis of
-, of Mn(111)+HN3, 361
Cr(HzO)sXZ+,18
-, of Mn(VII)+ArCH2NHZ,318
entropy of +4 transition states, 155
-, of Mn(VII)+CF3CH(OH)2, 313
equilibrium constant, for acid hydrolysis o f
-, o f MII(VII)+CO, 290
Co(I1I) complexes, I I
-, o f Mn(VIl)+furfural, 327
-, for Ag(I)/Co(lII), 218, 221
-, of Mn(VIl)+HCOOH, 317
-, for As(1ll)+HCrO4-, 166, 289, 521
-, of Mn(Vll)-i-I-, 282
-, for Ce(1ll)i-Ce(lV), Ce(lV)i-Ce(lV), 252
--. o f Mn(VII)-t NOz-, 287
-, for Ce3+ C104-, 224
-, of Mn(V1I)i-PhCHO, 31 I
-, for Ce4+ HS04-, 247
-, of Mn(VII)-FRNO,, 320
-, for Ce(1V)i- Mn(lI), 245
-, o f Mn(Vll)t-ROH, 308, 309
-, for Co(II)/Fe(III) systems, 183
-, of M n 0 , )C=C<, C2(COO-)2. 300
-, for Co(Ill)+malic acid, 392
-, of Mo(V)+I-, 410
-, for Cr(III)+Eu(ll), 168
-, of Mo(V)+N02-, 472
-, for Cr(Ill)+Np(V), 226, 259
-, of Mo(V)-tNOa-, 474
-, for Cr(III)+V(lII), 158
-, of Mo(VI)+N~H,, 332
-, for [Cr(CN)sHz013- CN-, H 0 2 - . 462
-, of Np(VI)+EDTA, 402
-, for C r 2 0 7 2 - -1- HCr04-, 163
-, of Np(VI)-I-U(IV), V(III), 256, 257
-, for Cr(VI)/Mn(ll)/H+, 279
-, of Pb(IV)+MeCOOH, 347
-, for dissociation of HCrO,, 526
-, of Pb(IV)+PhC3HS, 343
-, - of HO2, 558, 560
-, of Pd(Il)t-olefins, 339, 340
-, - of HSOS-, 572
---,of Pt(ll)/Pt(lV) reactions, 124-178
--, for Fe(I1) I V 0 2 + , 154
-.
+
+
594
INDEX
-,
-,
-,
-,
-,
-.-.
+
+
+
+
+
-,
- in
Hg(II)+HZ, 336
Pt(ll)/Pt(lV) reactions, 123-126
-, - in Pt(lV)4-NO2-, 333
ethylene diamine tetraacetic acid, and Co(ll)/
Co(1ll) exchange, 117, I18
-, and Co(ll)+Fe(lll), 182, 183
-,and Co(lll)+Fe(ll), 198,205, 212,213,219
-, and Cr(ll)/Cr(lI1) reactions, 90
-, and Cr(I1) 1-RCzCR, 454
-, and Cu(lI)+CS(NH2)z, 438, 439
-, and Fe(11)-l-C102-, 442
-, and Fe(ll)-1-02,446
-, and Fe(ll)+-PhCMezOOH,464, 465
-, and Fe(ll1)i-ascorbicacid, 432
-, and Fe(lll)i-N2H4,418
-, and Fe(1ll)i-Sn(ll), 185
--, and Mn(ll)/Mn(lll) exchange, 93
-, and Mn(lll)+HN3, 361
-, complexi-Fe(Ill)/H,O,, 413
-, reaction4 Fe(CN)63-, 437, 438
-, - $- Np(VI), Pu(VI), 402
ethylene dibiguanidine, and A g ( l ) i - S 2 0 s z - ,
475, 476
-, and Ag(ll)fHzO, 366
ethylene dichloropalladium(lI) dimer, in
Pd(II)+CzH4, 339
ethylene glycol, effect on Np(V)/Np(VI) exchange, 134, 136
-, Fe(ll)+Oz in, 447
-, reactionfCe(lV), V(V), 389
-, - f Cr(VI), 320
-, U(lV)/U(Vl) exchange in, 132
ethyl halides, reaction+Co(l), Co(ll), 485, 486
ethylidine diacetate, from Pd(OAc), CZH4,
340, 341
europium(ll), exchange+Eu(lll), I30
-, reaction-tCIO,-, 130, 440
-, - Co(lll), 190-194, 205
-, - f Co(lll), and bridging ligands, 207,
208, 210, 21 I
-, - i- Cr(lII), 168, 169
-, - C ~ ( l l )228
,
-, - Fe(lII), 185, 249
-, - radicals, 490
-, - f V(I11), V(IV), 158, 161, 162
europium(llI), exchange+ Eu(ll), I30
extinction coefficient, of VOV4+, 205
-, - i n
+
+
+
F
ferricinium ion, reaction facetoin, 430
-, - Sn(ll), 184
ferricyanide ion, effect on Fe(1l)+CsH4O2,
455
-, - o n Fe(lll)+H2O2, 413
-, exchange t ferrocyanide, 106-108
595
INDEX
+
+
-7
-7
-,
-,
-,
-t
-,
+
+
+
+
+ H3P03S, 417
+ I-, 409, 410
+ NzH4, 418
- + phenols, 434
- + PhNHNH2, 436
-
+
+
+
+
+
-1
- - ~ , a I l dEu(l1) I F c ( l l l ) , 185
-, and F e ( l l ) i CI,, 466
-, and Fe(ll)/Fe(lll) exchange, 105, 108, 109
-, and Fe(Il)+Mn(llI), 173
-, and F e ( l l ) + 0 2 , 446
-, and Fe(IlI)i-V(ll), 176
-, and Ir(Ill)/lr(lV) exchangc, 122
-, and M n ( l I l ) - t H N 0 2 ,NHZOH, 364
-, and Mn(Vll)+furfurals, 327
-, and Mn0,Cz(COOH),, 299
-, and V(II) I C103-, 441
-, and V(I1)i V(V), 80
fluoral hydrate, reaction -1 Mn(VI) and
Mn(VII), 312, 313
fluoride ion, and Co(ll1) oxidation of metal
ions, 188, 190, 192-194, 198,202, 205, 216,
225, 226
-, and Co(ll1) substitution reactions, 120
-, and Cr(ll)/Cr(IIl) exchange, 81, 82
-, and Cr(ll1) aquation ( H + ) , 85-88
-, and Cr(lIl)+Cr(ll)EDTA, 90
-, and Cr(lll)+Eu(ll), 169
-, and Pt(lI)/Pt(IV) reactions, 124
-, effect on Ce(ll)/Ce(lV) exchange, 130
-, - on Ce(IV)-t-Fe(ll),246
-, - on Fc(II)/As(I11)+S20e2-, 539
-, -on F e ( I l ) + H 2 0 2 , 460
-, -on F e ( l l ) + 0 2 , 446
-, - on H2O2+SzOs2-, 556
-, - on Mn(V11)+(COOH)2, 323
-, -on Mn(Vll)+ROH, 309
-, replacement of, from co(ll1) complexcs. 9
-, -, from Cr(OH,),F2+, 19
formaldehyde, reaction-tCo(lll), V(V), 379
-, - Cr(VI), 310, 520, 530, 531
formate ion, and Co(l1) oxidation of metal
ions, 207, 208, 21 I
-, oxidation of, i n Co(lll)+Mn(Vll), 171
-, reaction+Mn(VlI), 316, 317
formic acid, from Ce(lV), Mn(lIl), V(V)
CHZ(COOH)2, 399
-, reaction+Ce(lV), Co(llI), Mn(lll), V(V),
386, 387
-, - Co(ll)-tS2082-, 481
-, - Cr(VI), 316, 520, 531
--, - Hg(Il), Pd(II), TI(111), 345
free energy, and Co(IIl)+-Cr(lI), Fe(Il), 202
-, and reactions of inert complexes, 4
frec energy of activation, and Marcus theory,
247-249
fumarate ions, and Co(ll1) oxidation of nietal
ions, 21C212
funiaric acid, effecto n Fe(ll)/Fe(lll) exchange,
103
-, from Cr(II)+C2(COOH)Z,454
-, reaction+Co(lll), 402
+
+
+
596
- , - - I V(II), 457
furfurals, reaction-I-Mn(VII), 327
60
--, complex with PPhJ and cdrbonyi exchdnge
reactions, 35
-, exchange with Au(l), Au(ll), 59,60
-, reaction+CNS-, 331
-~,- (COOH)2, 352,353
-, - S03-, 332
+
+
59,70
-, in Cr(ll)-t U(VI), 256
-, of Am3+ + A m O z + , 141
-, of Co(lll)+Cr(ll), 209
-, o f Co(lll)+Fe(ll), 216,219
-, of FeCI2+,217
-, of F e C 2 0 4 + ,219
-, o f Mn(lll)+V(IV), 172
half-wave potentials, of Cr(ll)-I-Pt(lV),227
279
Hammett relationship, and Ce(lV), Co(lII),
V(V) +aromatic hydrocarbons, 374
-, and Ce(lV), V(V)+alcohols, 388
-, and CH,COOH +toluenes, 376
-, and Cr(V1) X - C < , 298
-, and Cr(Vl)+RCHO, 310,31 I , 529
-, and Cr(VI)+RH, 294-296
-, and Cr(VI)+ROH, 305,307,308
-, and Cu(l)+ArSOZCI, 488
-, and Cu(I1) ketols, 430
-, and Mn(VII)+ArCH,NH,, 318
-, and Mn(VII)+furfurals, 327
-,and Mn(VII)+RCHO, 311
-, and Mn(VII)+ROH, 309
-, and Pb(lV)+ArC3HS, 343
n-heptane, reaction Cr (VI), 293
+
+
38
-,
47
131, 132
420,421
-, - Cr(VI), 291,292
-, - Hg(l), Hg(ll), 335,336
-, - Mn(VI), 291, 292, 335,336
+
+
+
-, - on Ag(l)+Co(Ill), 221
-, - on Ag(l)+H2, 420
-, - on Ag(Il)+HzO, 365,366
-, - o n Ag(ll)+Sz06z-, 370
-, - on As(lll)+Cr(Vl), 521,522
-, - on As(llI)/Fe(ll)/Sz082-, 539,541
-, - on As(Ill)+V(V), 371
-, - on Ce(llI)/Ce(lV) exchange, 128,129
-, - on Ce(lll)-tCo(lll), 224
-, - o n Ce(IV), Co(lll)+H3POZ,370
-, - on Ce(lV), Co(lll), Ir(lV), Mn(I11),
V(V)+ketones, 381,382
-,
597
INDEX
-,
- 011
-, - on Ce(IV)+MeCOOH, 386
--, - on Ce(lV), Mn(lll), V(V) ICHz(COOH)2, 400
- on Ce(lV), Mn(111), V(V) tglycols,
388-390
-, - on Ce(1V) t PhCHO, 379
-, -on Ce(lV)+Sb(lll), 371, 372
- O n CO(ll)-t-C6H40~,456
-, - on Co(II)/Co(lll) exchange, 112, 113,
117, I I8
-, - o n Co(ll), C r ( l l ) + H z 0 2 , 462
--, - o n Co(lll)+Ar,CO, 404
-, - on Co(lII)+aromatic hydrocarbons,
373, 375
-, -on Co(lIl)+Br2, CIOz, 362
-, - 011 Co(lII)+r-BuOOH, 378
-, - o n Co(lll~-kCr(ll),200, 201
-, -on Co(lll)+Fe(ll), 195, 216
-, -on Co(lIl)HC02- M n 0 4 - , 171
-, - on Co(1lI)t Hg(l), 221
-, -on Co(III)+HN,, 360
- on Co(llI)+H,O, H202, 366, 367
-, -on Co(lll)fNp(V), 226
-, - on Co(llI)+olefins, 375
-, -on Co(II1) oxidation of metal ions, 204,
208, 211, 212
-, - on Co(llI)+PhCH=CHOOH, 391
-, - on Co(lll)+thiomalic acid, 395
-, - O n Co(lll)+thioureas, 407
-3
- 011 CO(~II)+TI(I),223
-, -on Co(lII)+V(lII), V(IV), 214
-, - on Co(III), V(V)+ROH, 376
-, - on Cr(II)+Cz(COOH)Z. 454
-, - on Cr(II)/Cr(lll), Cr(IIl)/Cr(Vl) exchange, 81-83
-, - on Cr(Il)+Cu(lI), 228
-,-on
Cr(II)+Fe(lll), 180, 181
-, - on Cr(II)+Hg(Il), 229
-, - o n Cr(ll), l r ( l l l ) + C 1 0 3 ~ 441
,
-, - on Cr(ll), V(II)+ArCHO, 456
-, - on Cr(Il), V(Il)+Np(IV), Np(VI), 260,
261
-, -on C r ~ l l ) + V ( l l l ) V(IV),
,
157, 159-161
-, - on Cr(l11) aquation, 85, 86
-, - On Cr(ll1) isomerisations and substitutions, 90, 91
-, - on Cr(VI)-tBr-, 282
-, - o n Cr(VI)-tFe(ll), 164, 165, 532
-, - on Cr(VI)+glycols, 320, 321
-, - on Cr(VI)+H2Oz, 284
-, - on Cr(VI)+HSO,-, SZO3,-, 286, 287
-, - on Cr(Vl)+hydroxy acids, 324
-, - o n Cr(V1)t I-, 281
-, - o n Cr(VI)+Me,CHOH, 301, 303, 304,
306, 525
-,
-3
-9
-, -on
Cr(VI)+Np(V), 167
-, - on Cu(1)i-0,, 447,448
-, - on Cu(II)+CS(NH,), 438
-,
-,
-, -on
INDEX
-, - o n
Mn(Vll)+PhCH2NHz, 318
Mn(VII)+PhCHO, 31 I
Mo(V)+I,, 468
Mo(V)+NO,-, NOs-, 471,474
Mo(V)+O,, 450
-, -on Np(V)+I-, 410
-, - on Np(V). Np(VI)+V(III), 257, 258
-, - o n Np(VI)S-(COOH),, 399
-, - on Np(VI)+EDTA, 402
-, -on Pt(lV)fS2OsZ-, 332
-, - on Pu(lV)+Ti(lII), U(IV), V(III), 265,
267
-, - on Pu(VI)+Sn(ll), U(IV), 264
-, - on reactions of N p ions, 134-137
-, - on reactions of Pu ions, 140
-, - o n reactions of U ions, 131-133
-, - on Sn(lI)+CIC6H4N0,, 456
-, - on Sn(II)/Sn(lV) exchange, 69
-, -on Ti(III)+Iz, 469
-, - on Ti(III), V(11)+CI04-, 440
-, - on Ti(III), V(III)+O,, 444
-, - o n TI(I)/TI(III) exchange, 62-65
-, - on T I ( 1 1 1 ) + ~ y c l o - C ~ H ~ ~347
CO,
-, - 011 T I ( I I I ) + c ~ c I o - C ~ H ~ ~ 344
OH,
-, -on T I ~ I I I ~ + U ~ I IuI()I,v ) , 231, 237-240
-, - on U W f B r , , 467
-, - o n U(IV)+BrO,-, 442
-, - o n U(IV)+O,, 443
-, - on U(VI)+V(II), V(III), 254, 255
-, - on vanadium ion exchange and reactions, 76-80
-, - on V(II)+unsaturated acids, 457
-, - on V(IV)+ascorbic acid, 432
-, - o n V(V)+(COOH),, 398
-, - on V(V)+hydroxyketones, 391
-, - o n V(V)+I-, 359
-, - on V(V)+RCHO, 379, 380
hydrogen peroxide, and As(llI)/CIO3-/O2, 5 5 1
-, and As(lll)/S2082-/02, 541,542,546,547
-, and Cu(II)/PhOH/O,, 435
-, and U(IV)+O,, 443
-, catalysis ofCe(llI)/Ce(lV)exchange by, 129
-, from C u ( l ) + 0 2 , 449
-, from Pu(lII)+Oz, 447
-, reaction+Ag(lI), Ce(lV), Co(llI), Mn(lI1)
V(V), 367-369
-,- Co(W, Cr(II), Cr(lll), Cu(l), Cu(ll),
U(IV), 4 6 1 4 6 4
-, - Cr(VI), 284
-, - Fe(lI), 458461, 564, 565
-, - f Fe(II), and As(lII), 542, 543
-, - 4-Fe(II), and organic compounds,
565-567
-, - Fe(llI), 412, 413
-, - f H2S05/MeC03H+SCN-, 569-573
-, - -k M n 0 4 - , 285
-, - on
-, - o n
-, - o n
-, - on
+
+
-+
+
+
+
+
599
INDEX
-, -
V(V), 393,394
hydroxyethylethylenediaminetriacetic acid, and
Co(lll)+Fe(II), 212,213
-, and Cu(ll)+Cs(NH,),, 438,439
-, and Fe(Ill)+ascorbic acid, 432
hydroxylamine, reaction-tCe(lV), Mn(lll),
364,365
-, - Co(ll), Cr(ll), Fe(lI), 470,471
-, - + Fe(Ill), 419
-, - -t- Ti(Ill), 458,470
217
-, and Co(II1) substitution reactions, 119,120
-, and electron transfer, 56, 153, 154
-, and Ce(lV)+NH30H+, 364
hydroxyl radicals, in As(] I I)/Fe( I I ) / S z 0 , 2 - /
-, and Co(lII)+Cr(lI), 188,194
0 2 , 541,542
-, and Co(llI)+HN3, 360
-, in Co(lI), Cr(1l) I-HzOZ,461-463
-, and Cr(II)+Fe(lll), 179,182
-, in Fe(lI)+H20z, 458,459,543,564-567
-, and Cr(II)+Np(VI), 259
-, in Fe(lII)+HzO2, 412,413
--, and Cr(lI)+V(lll), 160
-, in H2O2+SZOsZ-,556-562
-, and Cu(Il)+H202, 463
-, in induced TI(I)/TI(IIIexchange,
)
67,68
-, and Eu(Il)+Fe(lIl), 185
-, in Mn(llI)+H2O2, 369
-, and Fe(ll)+CIz, 467
3-hydroxy-3-methylbutan-2-one, reaction t
-, and Fe(ll)/Fe(III) exchange, 101
V(V), 391
-, and Re(V)+N03-, 474
hypochlorous acid, reactioni Fe(ll), 460,466 -, and U(VI)+V(IlI), 256
hypophosphorus acid, reaction i Ce(lV),
-, and V(Il)+V(IV), 79
Co(Ill), 370
interaction absorbance, and Cu(l)/Cu(II), 58
-, - Cr(VI), 287,288
-, and Sb(III)/Sb(V), 71,73
-, - -t C ~ ( l l )416
,
-, and Sn(II)/Sn(IV), 69
-, -Hg(ll), TI(III), 334
-, and TI(I)/Tl(III), 67
interchange reactions, of inert complexes, 6
I
intermediates, in Cr(I1) +V(III), V(IV), 157160
midazole, as ligand in Cu(l)+O,, 448,449
-, in Cr(III)+ U(VI), 256
ndigo, reactionSCr(V1). 531
-, in Cr(Vl)+ROH, 302,303
induction factor, 280,510, 517
-, in Hg(ll)+C3H6, 338
--, for As(IIl)/Cr(Vl)/Mn(lI), I-, 522,523
-, in H 2 0 2 + S Z 0 8 2 - ,555
-, for As(lIl)/Cr(VI)/02, 535
-, in Pd(II)+olefins, 339
-, for As(lll)/Fe(ll)/S2OsZ-,539,540,542
-, in reactions of inert complexes, 5,6,14-18,
-, for Cr(V1) as actor, 520
24
-, for Cr(Vl)/Fe(ll)/I-, 280,288
-, in V(II)+V(IV), 79
-, for Cr(VI)/Mn(Il)/alcohoIs, 302,321,520, iodide ion, and carbonyl compounds, 35-39,42
-, and Co(II)/Co(III) exchange, 117
527
-, for Cr(VI)/Mn(II)/HCHO, 530,531
-, and Co(II1) complexes, 9,10, 15
-, for Cr(Vl)/V(ll), V(lV)/I-, 534
-, and Co(l11) oxidation of metal ions, 190-, for Fe(lI)/H2O2/EtOH,565,566
192,194,199
-, for H202/Mn(VII)/Os04, SzOe2-, 555, -, and Co(ll1) substitution reactions, 120
559,560,562-564
-, and Cr(ll)+Pt(lV), 227
-, for induced oxidations by Cr(Vl)/
-, and Cr(IlI)+Eu(II), 169
-, and Cr(lII)i-H+, 89
C ~ & ( O H ) Z ,531
-, for V(V)/I-/Oz, 359
-, and Cr(lII), Rh(ll1) complexes, 18-20
induction period, in Co(ll), Mn(Il), Mo(V1) t
-, and Fe(IlI)+Sn(lI), 184
HSOS-, 482
-, and Pt(l1) complexes, 22-24
-, in Cu(I1)frr-ketols, 431
-, and Pt(ll)/Pt(lV) reactions, 125,126
-, in Cu(ll)+PhOH+02, 435
-, and U(V)+U(V), 132
-, in decomposition of Co(lll)(NH3)~1,358 -, effect on As(lll)+CIO~-, 551
-, in Mn0,(COOH)2, 323
-, - on Co(II)+HzOZ, 462,463
-, in U(IV)+02, 443
-, - on CrlIII) aquation, 85,86
-, in V(111)+02, 444
-, - on Fe(CN)6,12,468
inductor, 510, 512,514,516,517
-, in induced reactions, 520,523, 524
+
+
600
INDEX
+
+
+
+
+
+ C6H402, 455
+ 12,468
+ Mn(lll), 173, 174,247
-- + M n W I ) , 169
- + Mn(VII), and ROH, 573-575
- + Mo(III), 250
- + NHzOH, 470
- + NOZ-, NO3-, 472, 473, 475
- + Np(V), 155
- + 02,444447
-, -, -,
-,
-,
-,
-,
-,
-,
-, - -1- Pu(IV), Pu(VI), 263, 266
--, - i -ROOH, 464,465, 567
--, - 4-Sz08'-, 478-480, 538-542, 567, 568
-, - -t T1(111), 232-234
-, - i~U(VI), 256
-, - i -V(V), 154-156
iron(lll), complex with Pu(V), 160
SCN-, 159
-, effect on As(Il1) l - S 2 0 8 2 - , 539-541, 543546
-, - o n Cr(VI)/Fe(ll)/I-, 532
-, - on Fe(ll)+Br2, 467
--, - on F ~ ( l l ) + O z ,446
-, -on H 2 0 2 i - S 2 0 8 2 - ,556, 562
-, - on U ( V I ) ~ t V ( I l l )254,
,
255
-, exchange Fe(ll), 96-108
-, reaction+As(lV), 554
-, - -~
I ascorbic acid, 432,433
-, -- BH4-, 422, 423
-, ~-. I - CN-, 410,411
-, -~-1. Co(Il), 182-184
--, - -1- Cr(lI), 179-182, 249
-, - -1- dichlorophenol indophenol, 437
-, - -1- DPPH, 489
-, - -1- EDTA, 437, 438
-, -~-1 Et3N, 435
-+
-- -1 Eu(II), 185, 249
-, - -1 H202, 412, 413
--, - -I H3P03S, 417
--, - -1 HzS03,415,416
-, - hydroxy ketones, 430,432
-, -- -1 I - , 4 0 8 4 1 0
-,
- 1 ~ N3-, 412
--, ~-1- NZH4. NHZOH, 417-419
-, - -1- Np(lll), 180
--, -with
+-
60 1
INDEX
-, - Np(IV), 187,188
-, - phenols, 433,434
-, - 4-PhNHNHz, 436
-, - radicals, 49W93
-, - t RCHO, RzCO, RNOZ, RSH, 423428
-, - Ru(lI), 198
-, - Sb(III), 422
-, - SCN-, 411,412
-, - i Sn(lI), 184,185,576
-, - T S,03-, 414,415
-, - - Ta6ClIz2+,179
-, - Ti(III), V(III), 231
-, - U(IV), 185-187
V(II), 176-179,249
-, - W(IV), 250
iron(IV), in Fe(II)+CI,, 467
-, in Fe(l1)+HzO2, 459,460
-, in Fe(II)+OZ, 447
-, reaction+Fe(ll), 110
iron carbonyls, exchange reactions of, 28,29,
32,33, 51
-, structure of, 26,27
isocyanide, isomerisation of CrNCZ+,91
isomerisation, cis-trans of Cr(CZO4)-, 91
-, in Co(l11) substitution reactions, 120
-, of CrNC2+ and CrSCN2+, 90,91
isonitriles, and Mn(I)/Mn(lI) exchange, 92
isothiocyanate ion, and Co(lII)+HZ02, 368
isotope effect, and Ag(l), Cu(II)+H,, 421
-, and Ce(IV), Co(III), Mn(III), V(V)+ketones, 381
+
+
+
+
+
+
+
~
-3
-,
-,
-,
-,
-,
L
labilizing order, of ligands, 48,49
lactate ion, and Co(II1) oxidation of metal
ions, 209
-, reaction+Mn(VII), 325
lactic acid, reaction+Ce(IV), V(V), 393
-, - Cr(VI), 324,531
lanthanum ion, effect on Fe(CN)e3- + I - , 409
lead(II), exchange with Pb(IV), 70,71
-, reaction+Co(Ill), 206
lead(III), in Pb(1V) oxidations, 242,243
Iead(IV), exchange with Pb(II), 70, 71
-, reaction+ArC3H5, 343
-, - t-BuOOH, 243
-, - Ce(III), 242,243
-, - CO(II), 121,241,242
-, - i
DPPH, 489
-, - glycols, 349-352
-,
ketones, 347
-,
MeCOOH, 346,347
-,
olefins, 336,337
-,
ROH, ROOH, 343-345
ligaad field splitting, 48
h e a r free energy relationship, and Marcus
theory, 247,248
-, for carbonyl exchange reactions, 41,42
-, for hydrolysis of Co(NH&X2+, 9,11
-, for reaction of Pt(II)+nucleophiles, 22
lithium chloride, effect on Cu(II)+PrCHO,
+
+
+
+
-+
-+
-+
-+
427
- on Sb(IIl)/Sb(V) exchange, 72
lithium ion, effect on Fe(II)/Fe(IIl) exchange,
-,
107
-,
-,
-,
-,
- on Fe(CN)6- + I - , 409
- on Fe(III)+EDTA, 437
- on Mn(VI)/Mn(VII) exchange, 93
- on Mo(V)+I-,
410
M
McKay equation, 57,69,118
602
INDEX
+
+
-9
-9
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
603
INDEX
+
+
+
+
-9
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-.
+
+
+
+
N
naphthalene, reaction+Co(lll), 373
nephelanxetic series, and labilizing effect of
ligands, 49
-, and metal carbonyls, 26
neptunium(IlI), reaction +Fe(III), 180
-, - Np(VI), 136
neptunium(lV), reaction +Cr(ll), V(II), 261
-, - Fe(III), 187, 188
-, - Np(VI), 136, 137
neptunium(V), complex+Cr(Ill),
Rh(III),
228, 258-260
-, reaction+Co(IIl), 226, 227
-, - Cr(III), V(III), 258, 259
-, - Cr(VI), 166, 167
-, - I-, 410
-, - of complexes of, 133-138
+
+
+
+
+
+
604
INDEX
+ U(IV), 261
+ XeO,, 458
neptunium(VI), reaction +(COOH)2, 399
-, - + Cr(lI), 159, 160, 259-261
-, - + EDTA, 402
-, - of complexes of, 133-137
-,
+ U(IV), V(IlI), 256-258
-, -, -
190,
194, 225
-,
-,
-,
-,
-, - + M n 0 4 - , 287
-, - + Pt(IV), 333
+
+
+
-,
-,
-,
-,
- Pt(dien)Br+, 21
- Re(V), 474
- RhenzCl2+,20
tram effect of, 47
nitrobenzene, exchange reactions of carbonyls
in, 36
m-nitrochlorobenzene, reaction +Sn(II), 456
nitrocyclohexane (and pentane), reaction+
Mn(VII), 320
nitroethane, reaction+Fe(IlI), 425
nitrogen, from Fe(III)+N2H4, 417, 418
nitromethane, and reactions of Pt(I1) complexes, 23
-, and Fe(II)/Fe(III) exchange in, 105
nitropropane, reaction +Fe(III), 425
I-nitroso-2-naphthol, and Co(II)/Co(III) exchange, 119
nitrosylcarbonyls, exchange reactions of, 32,
33
605
INDEX
+
+
+
+
+
+
606
INDEX
-, and Fe(II)+H20Z,460
-, and M n 0 4 - + C N - , 283
-, and M n 0 4 -
-, reaction
+ Co(III)HCOz, 21 1
+ Fe(lI)+ROH, 573, 575
+ furfurals,327
+ H2,291, 292, 335, 336
+ HCOz-, 316, 317
- + HzOz,285
- + O.S.04, 563, 564
- + ROH, 574,575
- + hydrocarbons, 297,298
- + hydroxyacids, 325, 326
- + I-, 282
- + MnZ+,95, 96
- + N 0 2 - , 287
- + phenols, 313
- $- RCHO, 311-313
- + Sn(lI), 171, 576, 577
-, -, -, -, -, -
-,
+ ;)C-C(,
-,
-,
-,
-,
-,
-,
-,
-,
-,
-,
+
+
+
+
+
+
+
607
INDEX
of metal
-, - t I - , NOz-, s203*-,331-333
--, - + Pt(II), 122-128, 511
plumbate/plumbite, exchange of Pb, 70
plutonium(lll), reaction +NO2-, 472
-, - 02,447
-, - Pu ions, 138, 139
-, - Xe03, 452, 453
plutonium(IV), reaction +Fe(ll), Sn(II),
Ti(III), U(IV), V(III), 265-267
-, - Pu ions, 138-140
plutonium(V), complex+Fe(III), U(V), 160
-, reaction+Pu ions, 139
-, - Ti(III), 261, 262
plutonium(Vl), reaction+Cr(lI), V(III), 256
-, - EDTA, 402
-, - Fe(II), Sn(ll), Ti(III), U(IV), V(III),
262-265
-, - Pu(III), 138, 139
polarimetry, and exchange reactions, 57, 104,
116-118, 124
polarography, and A s ( l l l ) / C ~ ( I l ) / S ~ 0 ~ ~ - ,
547-550
-, and Cu(l), Fe(ll)+CI02-, 442
-, and IrCI6- C D - , 441
-, and reactions of Co(llI), 192
-, - of U ions, 132
-, - of V ions, 79, 155
polymer radicals, reaction+metal ions, 490492
potassium ion, effect on F ~ ( C N ) G ~ - /
Fe(CN)63- exchange, 107
-, - on F ~ ( C N ) G ~ -s2osZ-,480
-, - On F ~ ( C N ) G-1
~ -C ~ H I ~ S 424
H,
-, - on F C ( C N )3~- + EDTA, 437
-, - on Fe(CN)63- I-, 409, 410
-, - o n Fe(CN)63SOs-, 416
-, - on Mn(VI)/Mn(VII) exchange, 93
-, -on Mo(V)+I-, 410
pre-exponential factor, for Ag(l), Cu(l1) t H2,
420, 421
-, for A g ( I ) + s ~ 0 8 ~ 475,
- , 476
-, for Ag(ll)+H20, H 2 0 2 , 366, 367
-, for Au(III)+(COOH)~, 353
-, for Co(lI)+O,, 449
-, for Co(III)+C6Hs, olefins, 375
-, for Co(Ill)+RCOOH, 384
-, for Cr(Vl)+glycols, 320
-, for Cr(Vl)+H2, 291
-, for Cr(VI)+hydroxyacids, 324
-, for Cr(VI)+Me,CHOH, 301
-,for C r 0 5 formation and decomposition,284
-, for Cu(I)+02, 448
-, for Cu(ll)+n-C4H9 ., 492
-, for decomposition of Mn(l1) oxalates, 397
-, for Fe(II)+CsH402, 455
-, for Fe(II)+DPPH, 489
+
+
+
+
+
+
+
+
+
+
608
INDEX
-,
-,
-,
-,
-,
-, C u ( I I ) + C H ~ C C H z O Hin, 428,429
-, Cu(II)+ketols, 430
-, effect on Cr(V1) +HCHO, 530
_ ,_ on Pb(IV)+glycols, 351
_ ,- on Pb(IV)+PrOH, 343
-, reaction+Pt(dien)Br+, 21
Q
quantum yield, in photolysis
of Ce(IV) carboxylates, 385
quinoline, Cu(II)+H2 in, 421
quinolinol, effect on Fe(lI)/Fe(IIl) exchange,
104
quinol phosphates, reaction MnOc -, 3 13
R
rate coefficient, and exchange of metal ions,
58,59976,77,81-84,91-97,99-108,111-119,
128-130
-, in Au~II)/Au(III),Hg(I)/Hg(Il),
SWII)/Sb(V), Sn(ll)/Sn(IV), TI(I)ITI(IlI)
systems, 60-66, 68-70, 72-74
of Ag(l)+SzOsz-, 475, 476
-, ofAg(lI)+HzOz, 367
OfAg(lI)+SzOsz-, 370
-, ofAs(lII)+Cr(Vl), 166, 521, 522, 524
-, of As(III)/CU(II) -tSZ082-, 544
-, ofAs(III), Fe(lI), Pu(l1l) +NOZ -,473,474
-, of Au(III)+(COOH)Z, 353
-, of Au(lII)+HS03-, 332
-, ofBi(V)+Br-, CI-, I - , 331
-, of Ce(llI)+Co(lll), 225
-, o f Ce(IIl)+Pb(lV), 242, 243
-, o f Ce(lV), Co(IlI), Fe(ll), Fe(llI),
Pb(IV)+DPPH, 489
-, ofCe(lV), C o ( l l l ) + l ~ ,358, 359
-, o f Ce(lV), Co(IIl)+thioureas, 407
-, of Ce(IV), Co(lII), V(V) +mercaptoacids,
395
-, 0f Ce(lV)+Fe(II), Hg(I), Mn(lI), TNI),
245-25 3
-, of Ce(IV), Mn(llI)+CsH4(0H)2, 404
-, ofCe(lV), Mn(III)+H,OZ, 368, 369
-, ofCe(IV)+ROOH, 386
-, of Ce(IV)+Sb(III), 372
-, of Co(I),.Co(II)+halides, 485, 486
-9
-9
609
INDEX
complexes, 159
_ ,-
-9
-9
-9
-I
-1
of SZO8-, 544
-, of Eu(II)+V(III), 162
-, of Eu(II)+V(IV), 158
-9
-,
-,
-,
-,
-,
-9
-.
-9
610
INDEX
-, of Np(V)+V(III), 258
-, of Np(VI)+(COOH)z, 399
-,
-,
-,
-,
of Pt(II)Br+Y, 21
Of Pt(II)+CSHgN, 25
of Pt(lI)+CO, 335
of Pt(lV)+I-, NOz-, s203-, 331-333
-, of Pu(lV), Pu(Vl)+Fe(ll), Sn(ll), Ti(III),
V(Ill), 262, 264-266
-, of reactions in H202+SzOs2-, 557, 558
-, of Am, Np, Pu and U ions, 132-142
-, ofAs(lV), 554
_ ,- of Cr(lII), 85-90
- _, of tantalum cluster ions, 80
-, of Re(V)+N02-, NO3-, 474
-, of Re(VI)-tSn(ll), 175
-, of Ru(V1) RuWII), 110, 111
-, of SO4- . +HCOOH, MeOH, 48 I
-, of Ti(lll)+HF, 469
-, ofTI(l), U(1V)+Br2, 467, 468
-, of Tl(lll)+Fe(lI), Hg(l), Os(lI), U(IV),
V(IV), 232,233,235-237,239
-, of u(VI)+V(II), V(I11), 254
-, of V(ll)+acids, 457
-, ofV(11)+Br2, C12, 1 2 . 469
-7
ofV(11)+V(IV), V(V), 78-80, 163,234
o f V(V) k l - , 359
rate-determining step, i n Ag(II)+H20, 365
-, in As(1Il)i ClO3-, 550
-, in As(lll)-kCr(Vl), 521
-, in As(lll), Fe(ll), Mo(V), Pu(III)+N02-,
472
-, in Ce(lV)+-Cr(lll), 244
-, in Cr(l1) t H g ( l I ) , 229
-, in Cr(llI)/Cr(VI) exchange, 84
-, in Cr(V1) t dithionic acid, 287
-, in exchange reactions of carbonyls, 40
-, in Fe(ll)+Hg(lI), 230
-, in Hg(I)/Hg(ll) exchange, 61
-, in Hg(l)fTI(II1), 235
-, in Hg(ll)4-H2, 336
-, in Mn(lll)i-HzOz, 369
-, in Pu(Vl)+-Ti(lll), U(IV), 262, 264
-, in Tl(lll)+olefins, 338
-, in Tl(III)+V(III), 231
-, in U(Vl)+V(lll), 255
rate law, for aquation of Cr(lII), 85-87
-, for aquation of Fe(lII), 109
-, for As(IIl)+Cr(vI), 166,288-290, 521,522
-, for AuCl,-+CI-, 21
-, for Co(III)+OH-, 16
-,for Co(ll1) oxidations with bridging ligands,
208,211
-1
-, for Fe(lII)+BH,-,
61 I
INDEX
-, reaction+Ce(lV), 250
_ ,- i C 1 0 4 - , 4 4 0
- _, +C0(111), 190, 198, 199
-,- +Fe(lll), 198
-.,- +H20,452
_ ,- -i-SzOs2-, 479
ruthenium(lll), reaction +Cr(ll), 188
+H2, 336
-, reactions of inert complexes of, 19, 20
-, substitution reactions of, 110, I I 1
ruthenium(lV), catalysis of As(ll1)-t Ce(lV),
371
ruthenrum(Vl), catalysis of As(ll1) kCe(lV),
371
-, exchange+Ru(VII), 110
ruthcnium(VII), exchange+-Ru(VI), 110
_ ,_
S
salicylate ions, and Co(II1) oxidation of metal
ions, 207, 209
second sphere complex, see outer sphere
selcnate ion, and Co(1ll) oxidation of metal
ions. 194
-, effect on Fe(ll)+H2O2, 565
selenite ion, and Co(1ll) oxidation of metal
ions, 194
selenocyanatc ion, and Pt(1l) complcxes, 22
silver(I), and Ag(II)+H20, 365
-, catalysis o f Ce(lV)+Hg(l), TI(I), 251-253
-,- of Cr(V1)i H , , 291, 421
_ ,- of Mn(V1l)i-CO, 290
-, of Mn(VI1)-I H 2 , 292
- _, of SzOsz- reactions, 354
-, complex+acetylenes, 454
-, effect on As(lll)/C1O3-/OZ, 552
- _, on Co(lI)/Co(lll) exchange, 114
-,- on C o ( l l l ) f C r ( l I I ) , Fe(ll), 214, 215,
217,218
-, on H2O2-kS2OsZ-.556, 562
- _,
on U ( I V ) + 0 2 , 443,444
_ ,_ ,-
+radicals, 490
+S2Os2-, 475, 476
silver(II), 354
-, decomposition of,220, 221
-, cxchange+Ag(l), 58, 59
-, in Ag(I)/Ce(lV)/Hg(l), 25 I
-, reaction+Co(ll), 217, 218
_ ,- +H2O, 365, 366
- _, +HzOz, 367
_ ,- i S 2 O S z - ,369, 370
_ ,- +Tl(l), 253
silver(lll), in decomposition of Ag(ll), 220
s o d i m ion, effect on Cr(Vl)+PhCHO, 530
_ ,_ on Fe(II)/Fe(lll) exchange, 107
_ ,_ on Fe(lll)+EDTA, 437
-_
, on Fe(Ill)+l-, 210
_ ,- on Fe(lII)+S032-, 416
_ ,- on Mn(VI)/Mn(VII) exchange, 93, 94
_ ,- on Mo(V)+I-, 410
spectrochemical series, and ligand lability, 47,
48, 51
square planar complexes, 20-25
-, and molecular orbital theory, 44, 46, 47
steric crowding, and reactions of inert complexes, 9, I I , 18, 19, 23, 44
steric effects, and Co(1II) oxidations, 208
-, and Cr(V1) oxidations, 298, 302
strontium ion, effect on F C ( C N ) ~ ~ - /
Fe(CN)63- exchange, 107
styrene, and Cu(l)+ArSO,CI, 488
-, reaction+CrO2CI2, 298
succinate ion, and Co(l1l) oxidation of metal
complexes, 210
succinic acid, effect on Fe(II)/Fe(IIl) exchange,
103
-,- on TI(I)/TI(III)exchange, 67
-, reaction-tCo(lll), 402
sucrose, effect on Np(V)/Np(VI) exchange, 134
sulphate ion, and Ce(ll)/Ce(lV) exchange, 128
-, and Ce(lV)+CH,(COOH),, 400
-, and Ce(lV)+Cr(lll), Mn(ll), 243-245
-, and Ce(lV)+Sn(ll), 253
-, and Co(lI)/Co(lI1) exchange, I1 I , 113, 117
-, and Co(ll1) complexes, 10, 15
-, and Co(ll1) oxidation of metal ions, 188,
190, 191, 194, 195, 205
-, and Cr(VI)+ROH, 305, 306
-, and F e ( l l ) + 0 2 , 445, 446
612
INDEX
_ ,_ on TI(III)I-U(IV), 240
275-277
-, r ea~ t i o n + F e( C N ) 6 ~ -415
,
sulphosalicylic acid, effect on Fe(lI)+O,, 446
sulphur dioxide, reaction+Co(II), 452
sulphuric acid, and Mn(III)+CHz(COOH)2,
400
-,
-,
-,
-,
-,
117,135
183
-,
for Fe(IIl)+dichlorophenolindophenol,
437
-, for Ir(lI1) +Ir(IV), 122
-, for Mo(V)+Os(Il), 1 1 1 , 169
terephthalate ions, and Co(lI1) oxidation of
metal ions, 210,21 1
tetrachloroethylene, from Fe(II)+CC14, 487
tetraethylenepentamine, and Co(II1) oxidation
of metal ions, 21 1
-, and Fe(lI)+ROOH, 465
tetrahydrofuran, carbonyl exchange reactions
in, 30, 51
tetramethylethylenediamine, and Pt(II)/Pt(IV)
reactions, 124,125
2,2,6,6-tetramethyl-4-piperidol-N-oxide,
reaction+Fe(II), 489,490
tetraphenylarsonium ion, effect on
Fe(CN)64-/Fe(CN)63- exchange, 107
thallium(I), and Ag(I)+S20s2-, 476
-, exchange+Tl(III), 62-68
-, reaction+Brz, 467,468
-, +Ce(IV), 67,252,253
- _, +Co(llI), 222,223
- _ +Sz08-, 481,482
thallium(II), in Fe(Il)+Tl(lIl), 233,234
-, in TI(I)/TI(III) exchange, 67,232
thallium(III), exchange+TI(I), 62-68
-, reaction +cyclo-C6Hl ,,O, 347,348
, +CyCIO-C6HI10H, 344
, +Co(Ill), 194
, +Fe(II), Fe(lIL), Hg(I), Os(II), Sn(I1).
U(IV), V(III), 230-240
-,-- t H C O O H , 345,346
-- +H3POz, 334
, +olefin% 337,338
-, +radicals, 490
, +V(IV), 67,232
thioacetamide, reaction+ Fe(III), 438
thiocyanate ion, and Co(ll1) complexes, 9,10,
9
-----7
14, 15,51
-,
19Sl92,199-203
T
-,
-,
-,
-,
-, reaction+Fe(III), 179
tartaric acid, effect on Fe(lI)+C1O2-, 442
Fe(II)/Fe(III) exchange, 103, 104
Mo(V)+NOp-, 474
-,- on
-,- on
and
and
and
and
-, and
INDEX
-,
-,
-,
-,
_ ,_
_ ,_
613
614
INDEX
u-
+
+
+ Np(V), 261
+ 238,239,443,444
-, - + Pu(IV), 267
-, - + Pu(VI), 264,265
--, - + TI(III), 237-240
0 2 ,
- U(VI), 130-132
uranium(V), complex with Pu(V), 160
-, reaction+U(V)/U(Vl), 132, 133
uranium(VI), catalysis of ascorbic acid-t 0 2 ,
433
-, reaction+Cr(II), Fe(lI), 256
-, - Sn(lI), 156, 256
-, - i-U(lV)/U(V), 130-133
-, - V(11), V(III), 253-256
uranium(X1) dimer, in U(V)+U(V), 133
urea, and Cr(Il)/Cr(llI) exchange, 83
urethane, an d Co(llI)+Cr(ll), 21 1
-,
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-3
msB?E;
ultra-violet radiation, effect on exchange reactions, 123, 132
uranium(IV), reaction+Br2, 467
-, - BrO3-, 442
-, - Fe(III), 185-187
- H202r 461
-9
-, -, -
+
+
+
+
+
+
61 5
INDEX
-,
-,
-,
+
+
+
+
+
+
+
+
+
+
+
+
+
+
2
zero-time exchange, and Hg(l)+Hg(Il), 61, 62
-, and Sb(III)+Sb(V), 74
zero-time oxidation, and Ce(1V) +Fe(II), 245
-, and Co(III)+Fe(ll), 216