(Austral) Cementation of Gold From Bromide Solutions

Cementation of gold from bromide solutions
Author:
Armoo, Kwesi Buah-Mensah
Publication Date:
1994
DOI:
https://doi.org/10.26190/unsworks/5912
License:
https://creativecommons.org/licenses/by-nc-nd/3.0/au/
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THE UNIVERSITY OF NEW SOUTH WALES
SCHOOL OF MINES
CEMENTATION OF GOLD FROM BROMIDE SOLUTIONS
A Thesis by
Kwesi Buah-Mensah Armoo, BSc (Hons)
Submitted in fulfilment
of the requirements for the degree of
Doctor of Philosophy
October, 1994
ii
CANDIDATE'S CERTIFICATE
I hereby declare that this submission is my own work and that, to the best of my
knowledge and belief, it contains no material previously published or written by
another person nor material which to a substantial extent has been accepted for
the award of any other degree or diploma of a university or other institute of
higher learning, except where due acknowledgement is made in the text.
KWESI BUAH-MENSAH ARMOO
CERTIFICATE OF ORIGIN
ALITY
l hereb y declare that this

submission is my own wor
be st Of my knowledge and k and that ' to the
· contain
belief' It · s no material previously
published or written by
ano ther person nor materiel
substant1. el extent has been which to e
accepted fo th e awa of
or diploma of a universit � � any other degree
or other . strtute of h g
where due acknowledgem�nt ·1 l� i her learning, except
s ma d e in the t ext.
(Signed)
iii
ACKNOWLEDGEMENTS
I gratefully acknowledge the award of a Special Commonwealth African

Assistance Plan (SCAAP) Scholarship by the Australian International
Development Assistance Bureau for this research study at the University of New
South Wales, Australia.
I am highly indebted to my supervisor, Dr. Tam Tran, the Director of the Centre
for Minerals Engineering, U.N.S.W., for suggesting this thesis topic and his
invaluable guidance throughout this study.
I wish to express my profound gratitude to Professor R.G. Robins, formerly of

the Department of Mineral Processing and Extractive Metallurgy, U.N.S.W.,
and Dr. Josick Commarmond of ANSTO, Lucas Heights, for the many helpful
discussions and assistance in this study. I also wish to thank Dr. Augustine
Davis of Hydromet Corporation for his continued assistance and support
throughout this study.
My sincere thanks are also due to Dr. P. Wong, Ms Viera Piegerova, Fred Scott,
John Buddon and John Sharp, all of the School of Materials Science and
Engineering, U.N.S.W., for their help at various stages of this research study.
Mr. Steve Rayner (Metcon Pty Ltd.), Ms. 1k Ling Lau, Mr. J.K. Song, and the
staff of the Centre for Minerals Engineering also deserve many thanks for their
encouragement and assistance in diverse ways. My sincere acknowledgements
are also due to Hong Dy Hsu, Javad Koleini, Basil Marasinghe, Raghvendra
Desai and Glen Noble (postgraduate students) of the Centre for Minerals
Engineering for their support and assistance while completing this thesis.
I am also grateful to the following: Mrs Kate Davis, Paul and Dorcas Appiah,
Napoleon and Gina Obi1i-Asare, Joseph and Felicia Boateng, Louis and Gladys
Owusu-Mensah, Edmund and Winifred Aikins, Joseph and Catherine Afful,
Judy Burgess and all friends for their concern, encouragement and prayerful
support throughout this study and my stay in Sydney. My thanks also to my
parents, brothers and sisters for their moral supp01t.
Finally I would like to thank the Almighty God for seeing me through my stay
and study in Australia.
iv
ABSTRACT
Recent research efforts have developed several and improved bromine-bromide

systems as alternatives to the cyanidation process. Bromine-bromide leaching
routes have been found to extract gold significantly faster than the cyanide
leaching and offer a lot of potential benefits such as simplicity, easily controlled
leach chemistry, higher extraction efficiency, adaptability to a wider range of
pH values and lower toxicity over cyanidation process.
A fundamental study has been conducted on zinc cementation of gold from

bromine-bromide solutions as a recovery option for the extraction of gold by
bromine/bromide media.
Electrochemical measurements (scanning voltammetry) usmg rotating-disc

electrodes were used to evaluate the various factors which influence the two
half-cells involved in the process: the reduction of gold and the dissolution of
zinc. The kinetics of the cementation reaction by both zinc rotating-disc
geometry and suspended zinc particles were investigated. The role of bromide
and the effect on the kinetics of variables such as pH, temperature, gold
concentration, rotational speed, amount of particulate zinc and zinc particle size
(in the case of suspended zinc particle study) were determined. The structural
characteristics of the resultant deposits were evaluated by scanning electron
microscopy. The structure and morphology of the deposits at the various
experimental conditions were analyzed in conjunction with the respective rate
constants.
Various computer packages/programs (DIAST AB, SYSTEM, CHEMIX) were

also used to determine the various equilibria governing the reduction/oxidation
process. The potential-pH and equilibrium species concentration versus pH
diagrams developed identified the predominant species in the cementation
reaction. The gold(ill) bromide complex, AuBq-, is more stable in the
bromine/bromide system in the acidic conditions. Under the same conditions
(low pH) at low bromide concentrations, zinc dissolves to give Zn 2+.
Evans diagrams constructed from the current-potential curves of the two half-
cells showed that the cementation process is controlled by the diffusion of the
V
Au(ill) bromide ions to the zinc surface. The Au(ill) bromide/Zn (rotating-disc)
cementation reaction was found to follow two-stage first-order kinetics for most
conditions as observed for most cementation reactions. The initial reaction rate
constants corresponded to expected (or predicted) magnitude of the limiting
mass-transfer coefficients (from electrochemical measurements). The
experimental activation energies were 2.50 kcal/mol (10.50 kJ/mol) and 3.13
kcal/mol (13.12 kJ/mol) for the initial and enhanced periods respectively. The
kinetics of the Au(ill) bromide cementation using suspended zinc particles
supported the analysis of the reaction kinetics under zinc rotating-disc geometry
and from polarization measurements at the different conditions. The reaction
velocity constants also exhibited strong dependence on the inverse of particle
diameter and the square-root of stirring speed.
Increasing initial Au(ill) bromide concentration from 10 mg/I to 100 mg/I

improved significantly the kinetics of the cementation reaction (using both zinc
rotating-disc and suspended zinc particles). The reaction rates/velocities were
greatly impaired at pH values below pH:4.00. Hydrogen evolution became
predominant under such conditions and excessive amounts of zinc dissolved
under corrosion effect. An optimum bromide concentration of 0.50/0.10 M
prevailed for cementation periods associated with higher gold recoveries. At low
bromide concentrations, (especially at low gold concentrations) the reaction was
inhibited due to a change in mechanism from diffusion control to
electrochemical (charge transfer) mechanism or pore diffusion control. Higher
bromide concentrations at high gold concentrations, increased the stability of
AuBq- and reduced the reaction.rate/velocity.
At 0.10 M bromide concentration, shrinking core kinetics confirmed a film

diffusion mechanism at the initial stages of the reaction followed by a product-
layer-diffusion mechanism. At low gold concentration, the diffusion through the
product layer dominated the reaction.
A change in the surface roughness of the reacting zinc surface and hence in the
effective deposition smface area as a result of modification to the deposit
morphology for the different experimental conditions was found to be the major
reason for variations in the reaction rate/velocity. For most conditions, the
deposits were bulbous/botryoidal crystal masses (for low initial gold
concentrations) and dendritic structures (for high initial gold concentrations) of
different degrees of texture and size.
vi
LIST OF PUBLICATIONS
1. Armoo, K., Oo, M.T. and Tran, T., Application of cementation for precious
metal recovery, DITAC Workshop on New Developments in electrodes,
University of Wollongong, (Feb.1990).
2. Armoo, K. and Tran, T., Cementation of gold from bromine-bromide liquors,

DITAC Workshop on New Developments in electrodes, University of
Wollongong, (Feb. 1990).
3. Armoo, K., Puvvada, G. and Tran, T., Recovery of precious metals by

cementation, Proc. Aus IMM. 5th Ext. Metall. Conf., Perth, Western Australia,
(1991), pp.191-196.
vii
TABLE OF CONTENTS
ACKNOWLEDGMENT 111
ABSTRACT IV
LIST OF PUBLICATIONS VI
LIST OF FIGURES XIV
LIST OF TABLES xxxm

LIST OF APPENDICES XXXVI
CHAPTER ONE
INTRODUCTION 1
CHAPTER TWO
GENERAL & THERMODYNAMIC PROPERTIES OF
BROMINE, ZINC AND GOLD.
2-1 Bromine 4
2.1.1 General Chemistry/Properties 4
2-1-2 Thermodynamics 5
2-1-2-1 Speciation/aqueous solution 7
2-1-2-2 Eh (potential) - pH relationship 11
2-1-2-2-1 Bromine - water system 11
2-1-3 Toxicity 14
2-2 Zinc 14
2-2-1 General Chemistry/Properties 14
2-2-2-1 Speciation/aqueous solutions 16
2-2-2-2 Bromide species of zinc 20
2-2-2-3-1 Zinc - water system 21
2-3 Gold 22
2-3-1 General Chemistry/Properties 22
viii
2-3-2-1 Aqueous gold complexes/solution chemistry 23

2-3-2-2 Bromide species of gold 27
2-3-2-2-1 Gold - water system 28
2-3-2-2-2 Gold - bromine - water system 29
CHAPTER THREE
HYDROMETALLURGY OF GOLD
3-1 Introduction/Review of historical development 34
3-2 Gold Minerals/Ore deposits 38
3-3 Extraction/Leaching of Gold 41

3-3-1 Cyanidation 42
3-3-2 Non-cyanidation methods 50
3-3-2-1 Thiourea 50
3-3-2-2 Halides 54
3-3-2-2-1 Chloride leaching 54
3-3-2-2-2 Bromide leaching 57
3-3-2-2-3 Iodide leaching 62
3-3-2-3 Thiosulphate 63
3-3-2-4 Thiocyanate 65
3-3-2-5 Others 65
3-4 Separation/Recovery of Gold from Aqueous solutions 66

3-4-1 Zinc precipitation/Cementation 66
3-4-2 Carbon adsorption 74
3-4-3 Electrowinning 78
3-4-4 Ion-exchange technique 83
3-4-5 Solvent-extraction technique 85
CHAPTER FOUR
ELECTROCHEMISTRY 88
4-1 General theory 88

IX
4-2 Electrochemical techniques 98

4-2-1 Voltarnrnetry 98
4-2-2-1 Experimental technique 99
4-3 Electrode systems 100

4-3-1 Rotating disc electrode 101
4-3-2 Electrode kinetics and mechanism 104
4-4 Current - potential relationships 106

4-4-1 Hydrogen evolution 109
4-5 Evans diagram 110
CHAPTER FIVE
CEMENTATION
5-1 Introduction/Definition 114
5-2 Theory/fhermodynamics 115
5-3 Electrochemistry 118

5-3-1 Electrode Systems 118
5-3-2 Hydrodynamics/Mass transfer 118
5-3-2-1 Rotating disc 118
5-3-2-2 Rotating cylinder 119
5-3-2-3 Suspended particles 120
5-3-3 Kinetics/Mechanism 122
5-4 Deposit/Morphology 130

5-4-1 Deposit 130
5-4-2 Morphology 130
5-5 Suspended particles/Shrinking-Core model 133

X
CHAPTER SIX
SUMMARY OF LITERA TORE REVIEW AND
RESTATEMENT OF AIMS 137
CHAPTER SEVEN
THERMODYNAMIC STUDY
7-1 Introduction 140
7-2 Thermodynamic data and computational methods 140

7-2-1 CSIRO Thermochemistry system 141
7-2-1-1 Chemix 142
7-2-1-2 System 144
7-2-2 The DIAST AB program 146
7-3 Equilibrium solution chemistry 148

7-3-1 The Br- - Br2 - H20 system 148
7-3-2 The Zn - Br21Br- - H20 system 151
7-3-3 The Au - Br/Br2- H2o system 158
7-3-4 The Au(III) - Zn - Br-1Br2 - H20 system 167
CHAPTER EIGHT
ELECTROCHEMICAL STUDY
8-2 Experimental 172

8-2-1 Chemical reagents 172
8-2-2 Equipment and Instrumentation 173
8-2-2-1 Electrochemical equipment 173
8-2-2-2 Instrumentation/Data acquisition 174
8-2-3 Electrodes 175
8-2-4 Apparatus/Others 176
8-2-5 Solutions preparations/Analysis 177
8-2-5-1 Stock solutions 177
8-2-5-1-1 Determine of bromine 178
xi
8-2-5-1-2 Determine of bromide 178

8-2-5-2 Test solutions 178
8-2-6 Experimental procedure 178
8-2-6-1 Anodic studies 180
8-2-6-2 Cathodic studies 181
8-3 Scanning (Linear sweep) Voltammetry 181

8-3-1 Anodic oxidation/dissolution of zinc 181
8-3-2 Cathodic reduction of gold bromide ions 184
8-4 Evans diagrams 191

8-4-1 Effect of residual bromine 193
8-4-2 Effect of dissolved oxygen 194
8-4-3 Effect of bromide concentration 195
8-4-4 Effect of pH 197
8-4-5 Effect of gold concentration 201
8-5 Rate measurements/kinetics 203

8-5-1 Diffusivity 203
8-5-2 Rate constant/kinetics 204
CHAPTER NINE
CEMENTATION STUDIES
9-2 Experimental 205

9-2-1 Materials 205
9-2-1-1 Chemical reagents 205
9-2-1-2 Zinc 206
9-2-2 Equipment and Instrumentation/Analytical methods 206
9-2-2-1 Experimental apparatus/equipment 206
9-2-2-2 Analytical instrumentation/methods 208
9-2-3 Preparations 209
9-2-3-1 Solutions/Reaction mixtures 209
9-2-3-2 Polishing of electrodes 209
9-2-3-3 Particle size analysis 209
xii
9-2-3-4 Smface area determination 210

9-2-4 Experimental procedure 210
9-2-4-1 Zinc disc geometry experiments 210
9-2-4-2 Suspended zinc particles experiments 211
9-3 Cementation onto zinc rotating discs 211

9-3-1 Reaction kinetics/Rate measurements 211
9-3-1-1 Effect of rotational speeds 211
9-3-1-2 Effect of temperature 213
9-3-1-3 Effect of initial gold concentration 215
9-3-1-4 Effect of NaBr concentration 217
9-3-1-5 Effect of hydrogen ion concentration 221
9-3-2 Zinc dissolution/stoichiometry 224
9-3-3 Deposit morphology/Surfaces studies 227
9-3-3-1 Effect of rotational speed 227
9-3-3-3 Effect of pH 233
9-4 Cementation onto suspended zinc particles 246

9-4-1 Reaction rate/velocity measurements 246
9-4-1-1 Effect of particle size 246
9-4-1-2 Effect of zinc amount 249
9-4-1-3 Effect of stirring speed 251
9-4-1-7 Effect of hydrogen ion concentration 261
9-4-2 Deposit nucleation and morphology 264
9-4-3 Shrinking core model/kinetics 275
xiii
CHAPTER TEN
CONCLUSION AND RECOMMENDATION
10-1 Conclusion 280
10-2 Recommendation/Suggestion for future work 285
REFERENCES 287
APPENDICES 316
xiv
LIST OF FIGURES
Chapter Two
Figure (2-1.1) The potential-pH diagram for the bromine - water

system at 25°C (Mussini and Faita, 1973).
Equilibria considered are: (a) H+fH2(g)
(b) O2(g)/H2O (c) HBrO)!BrO3- (d) Br3/Br
(e) BrO3-1Br(f) Br2(aq)/Br3- (g) BrO3-1Br3-
(h) HBrO3/Br2(aq) (i) BrO3-1Br2(aq) (1) Br2(1)/Br3-
(m) HBr03/Br2(1) (n) Br03-1Br2
(o) BrO4-1Br03-
(p) BrO4-1HBr03_ 12
Figure 2-1.2 The potential - pH equilibrium diagram for the

bromine - water system at 25°C for solutions
containing (a) 1.0 M Br2 (b) 10-2 M Br2
(c) 104 M Br2 (d) 10-6 M Br2 (Pourbaix, 1966).13
Figure (2-2.1) The potential-pH diagram for the Zn-H2O at

25°C (Pourbaix, 1966). 21
Figure (2-3. I) The potential - pH equilibrium diagram for the

Au-H 20 system at 25°C. The concentrations of
all gold species= 10-4 M (Puddephat, 1978). 30
Figure (2-3.2) The potential - pH diagram for the Au-Br-H2O

system at 25°C [Au]= 10-5 Mand [Br-] = 10-2 M
(Hiskey and Atluri, 1988). 32
Figure (2-3.3) Eh-pH diagram for the Au-Br-H2O system at 25°C

(a) [Au] = 10-3 M, [Br] = 10-5 M (b) [Au] = [Br-] =
10-3 M (c) [Au] = I0-3 M, [Br] = 0.1 M (d) [Au] =
10-3 M, [Br-] = 1.0 M (Dadgar, 1989). 33
xv
Chapter Three
Figure (3-3.1) A schematic gold recovery process flowsheet 42
Figure (3-4.1) A general flowsheet for Merrill-Crowe

process (A vraamides, 1989). 68
Chapter Four
Figure (4-1.1) Flow of electrons and ions between electrode and

electrolyte for net cathodic and net anodic
processes (Wadsworth, 1969). 91
Figure (4-4.1) Current density-potential electrochemical reaction

which achieves a mixed potential, Em (Miller, 1981). 107
Figure (4-5.1) Typical polarization curves for an arbitrary metal

showing cathodic and anodic reactions (Power, 1975). 112
Figure (4-5.2) Idealized Evans diagram showing the transition from

mass transfer control to electrochemical reaction
control (Power, 1975). 113
Chapter Five
Figure (5-2.la) Schematic diagram showing anodic and cathodic

regions in cementation (Power and Rithchie, 1975). 116
Figure (5-2.lb) Cementation reaction mechanism (Strickland and

Lawson, 1970). 117
Figure (5-3.1) Plot of mass transfer coefficient vs. particle diameter

for free-falling spheres; minimum mass transfer
coefficient, k* (Wadsworth and Miller, 1979). 121
xvi
Chapter Seven
Figure (7-3.la) The equilibrium profile of bromine species of initial

[Br2 (aq)] = 6.07x 10-4 Min 10-3 M bromide solution
(constructed using the CHEMIX program). 149
Figure (7-3.lb) The equilibrium profile of bromine species of initial

[Br2 (aq)] = 6.07x 10-4 Min 10-2 M bromide solution
Figure (7-3.lc) The equilibrium profile of bromine species of initial

[Br2 (aq)] = 6.07x 10-4 Min 10- 1 M bromide solution
Figure (7-3.ld) The equilibrium profile of bromine species of initial

[Br2 (aq)] = 6.07x 10-4 Min 1.0 M bromide solution
Figure (7-3.2) The potential - pH diagram for the Zn-Br-H2O system

at 25°C. [Zn] = 10-4 Mand [Br] =1.0 M
(constructed using the SYSTEM program). 152
Figure (7-3.3) The solubility diagram for the Zn-Br-H2O system at

25°C. [Zn] = [Br-J = 1.0 M (constructed using
the DIASTAB program). 153
Figure (7-3 .4) The distribution-pH diagram for the Zn-Br-H2O

system at 25°C. [Zn] = 10- 2 and [Br] = 1.0 M
(constructed using DIASTAB program). 153
Figure (7-3.5) The distribution - log [Br-J diagram for the

Zn-Br-H 2O system at 25°C [Zn] = 5x 10-s M
and [Br] = 10-3 M to 30.0 Mand pH= 3.50
X vii
Figure (7-3.6a) The equilibrium concentration profile of zinc species

of initial [Zn] = 10-2 Min bromide-bromide solution
of [Br-] = 10-3 Mand [Br2 (aq)] = 6.07x 10-4 Mat
25°C (constructed using the CHEMIX program) 155
Figure (7-3.6b) The equilibrium concentration profile of zinc species

of initial [Zn] = 10- 2 Min bromide-bromide solution
of [Br-] = 1.00 Mand [Br2 (aq)] = 6.07xlo-4 Mat
25°C (constructed using the CHEMIX program). 155
Figure (7-3.7a) The equilibrium concentration profile of zinc species

of initial [Zn] = 10-4 Min a bromine-bromide solution
of [Br-] = 0.10 Mand [Br2 (aq)] = 6.07xlo-4 Mat
Figure (7-3.7b) The equilibrium concentration profile of zinc species

of [Br] = 0.10 Mand [Br2 (aq)] = 6.07x 10-4 Mat
Figure (7-3.7c) The equilibrium concentration profile of zinc species

of [Br-] = 0.10 Mand [Br2 (aq)] = 6.07xl0-4 Mat
Figure (7-3.7d) The equilibrium concentration profile of zinc species

of initial [Zn] = 0.10 Min a bromine-bromide solution
of [Br] = 0.10 Mand [Br2 (aq)] = 6.07x 10-4 Mat
Figure (7-3.8a) The distiibution - log [Br] diagram for the

Au-Br-H20 system at 25°C, [Au]= 1000 mg/1,
[Br2] = 0.1875 M, [Br] = 10- 3 M to 10.0 Mand
pH= 2.00 (constructed using the CHEMIX program). 159
xviii
Figure (7-3.8b) The distribution - log [Br-] diagram for the

Au-Br-H20 system at 25°C, [Au]= 1000 mg/I,
[Br2] = 1.875x 10-3 M, [Br-] = 10-3 M to 10.0 Mand
pH= 2.00 (constructed using the CHEMIX program). 159
Figure (7-3.9) The solubility diagram for the Au-Br-H2O system at

25°C (constructed using the DIASTAB program). 160
Figure (7-3.l0a) The equilibrium concentration profile of the gold

species of initial [Au] = 1000 mg/I in
bromine-bromide solution of [Br] = 0.10 Mand
[Br2] = 6.07x 10-3 Mat 25°C (constructed using
the CHEMIX program). 161
Figure (7-3. l0b) The equilibrium concentration profile of the gold

species of initial [Au] = 1000 mg/I in
bromine-bromide solution of [Br-] = 0.10 Mand
Figure (7-3. l0c) The equilibrium concentration profile of the gold

species of initial [Au]= 1000 mg/I in
bromine-bromide solution of [Br-] = 0.10 Mand
Figure (7-3 .11 a) The equilib1ium concentration profile of gold

species in gold-bromide solution of initial
[Au]= 10 mg/I, [Br] = l.00x 10-4 Mand
[Br2 (aq)] = 6.07x 10-s Mat 25°C (constructed
using the CHEMIX program). 163
Figure (7-3.11 b) The equilib1ium concentration profile of gold

[Au]= 10 mg/I, [Br] = 0.10 Mand
[Br2 (aq)] = 6.07x 10-s Mat 25°C (constmcted
xix
Figure (7-3.1 lc) The equilibrium concentration profile of gold

[Au]= 10 mg/1, [Br-J = 1.0 Mand
[Br2 (aq)] = 6.07x 10-5 Mat 25°C (constructed
Figure (7-3.12a) The equilibrium concentration profile of gold

[Au]= 100 mg/1, [Br-] = 1.00x 10-4 Mand
[Br2 (aq)] = 6.07x 104 Mat 25°C (constructed
Figure (7-3.12b) The equilibrium concentration profile of gold

[Au]= 100 mg/1, [Br-J = 0.10 Mand
Figure (7-3.12c) The equilibrium concentration profile of gold

[Au] = 100 mg/1, [Br-] = 1.00 Mand
[Br2 (aq)] = 6.07x 104 Mat 25°C (constructed
Figure (7-3.13a) The equilibrium concentration profile of Au/Zn

species in solution of initial [AuBq-J = 100 mg/1,
[Zn] = 10-4 M, [Br-] = 0.10 M,
[Br2 (aq)] = 6.07x10-4 Mat 25°C (constructed
Figure (7-3.13b) The equilibrium concentration profile of Au/Zn

species in solution of initial [AuBq-J = 100 mg/1,
[Zn] = 10-3 M, [Br-J = 0.10 M,
XX
Figure (7-3.13b) The equilibrium concentration profile of AufZn

species in solution of initial [AuBq-] = 100 mg/I,
[Zn] =2.3x 10-3 M, [Br-J =0.10 M,
Figure (7-3.14a) The equilibrium concentration profile of AufZn

[Zn] = 104 M, [Br-J =0.10 M,
Figure (7-3 .14b) The equilibrium concentration profile of AufZn

[Zn] = 2.3x 104 M, [Br] =0.10 M,
Chapter Eight
Figure (8-2.1) Front view of the electrochemical equipment showing:

Pine Instrument RDE 4 Potentiostat; MSRX
Speed Controller, Electrode rotator and YEW
X-Y Recorder. 173
Figure (8-2.2) Front view of data acquisition unit showing:

386-PC and TLC 548/9 Analog-to-Digital Converter. 174
Figure (8-2.3) Gold and Zinc rotating-disc electrodes for

electrochemical half-cell studies. 176
Figure (8-2.4) Metrohm Automatic titrator unit

(682 Titroprocessor and 665 Dosimat). 177
Figure (8-2.5) A schematic diagram of the equipment arrangement

for electrochemical studies. 179
XXI
Figure (8-2.6) Front view of electrochemical cell showing the

arrangement of the three electrodes. 180
Figure (8-3.1) Current-potential curve for zinc dissolution in

0.05 M NaBr at pH:5.00, 20°C and 200-2500 rpm. 182
Figure (8-3.2) Current-potential curves for zinc dissolution

in NaBr solutions (0.01 M to 0.50 M) at pH:5.00,
20°c and 1000 rpm. 182
Figure (8-3.3) Current-potential curves for zinc dissolution in

0.05 M NaBr solution at 20°C, 1000 rpm and
pH:2.00 to pH:7 .00. 183
figure (8-3.4) Current-potential curves for 100 mg/I Au(III)

bromide solution containing 0.01 M NaBr and
90 mg/I Br2 (aq) at pH:5.00, 10°C and rotational
speed from 200 to 2500 rpm. 184
Figure (8-3.5) Current-potential curves at gold rotating-disc

electrode in 0.01 M NaBr at pH:5.00, 10°C,
1000 rpm and (a) absence of atmospheric 02,
Br2, Au (ie., background electrolyte) (b) presence
of atmospheric 02, (c) presence of atmospheric 02,
Br2 (aq) ((40 mg/1)) (d) presence of Au (100 mg/1),
Br2 (aq) ((90 mg/1)). 185
Figure (8-3.6) Variation of limiting current densities with the

square-root of rotation speed for the reduction of
100 mg/I Au(III) bromide solution containing 0.01 M
NaBr and 90 mg/I Br2 (aq) pH:5.00, at 10°C. 187
Figure (8-3.7) Current-potential curves for the reduction of 100

mg/I gold bromide ions in 0.05 M NaBr
solution (containing 90 mg/I Br2 ( aq)) at 20°C,
1000 rpm and pH's 3.00 to 7.00. 187
XXll
Figure (8-3.8a) Current-potential profile in 0.05 M NaBr solution,

pH:5.00 at 20°C 1000 rpm for the reduction of
(a) 0 mg/I Au(III) bromide ions (b) 100 mg/I
Au(III) bromide ions. 188
Figure (8-3.8b) Current-potential profile in 0.05 M NaBr solution,

(a) 0 mg/I Au(III) bromide ions (b) 100 mg/I
Figure (8-3.8c) Current-potential profile in 0.05 M NaBr solution,

(a) 0 mg/1 Au(III) bromide ions (b) 100 mg/1
Figure (8-3.9) Current-potential curves for the reduction of

H+fH2SO4 ions at gold rotating-disc surface at 20°C,
1000 rpm and pH: 3.00, 4.00 and 5.00. 190
Figure (8-4.1) Evans diagram for the reduction of 100 mg/I

Au(III) bromide ions/Zinc dissolution in 0.05 M
NaBr solution at 20°C, pH 5.00 and 1000 rpm.
A: reduction of bromine species;
B: reduction of Au(III) bromide ions;
C: reduction of dissolved oxygen. 192
Figure (8-4.2) Polarisation curves (I vs E) for the zinc

dissolution (oxidation) in 0.05 M NaBr and the
reduction of 100 mg/I Au(III) bromide in 0.05 M
NaBr (containing 90 mg/I Br2 (aq)); at 20°C,
pH 5.00, 1000 rpm showing the mixed potential and
the difference in electrode potentials ( I'). E 0 ) of the
half-cell reactions. 192

NaBr solution in (a) presence of 02,
xxiii
(b) absence of 02; at 20°C, pH 5.00 and 1000 rpm. 194

Au(III) bromide/Zinc dissolution (oxidation) in
(a) 0.01 M NaBr (b) 0.05 M NaBr (c) 0.10 M NaBr
(d) 0.50 M NaBr; at 20°C, pH:5.00 and 1000 rpm. 195

Au(III) bromide/Zinc dissolution in 0.10 M NaBr at
20°C, 1000 rpm and (a) pH 2.00 (b) pH 3.00
(c) pH 4.00 (d) pH 5.00. 197
Figure (8-4.6a) Evans diagram for the reduction of (a) 0 mg/I

Au(l11) bromide (b) 100 mg/I Au(l11) bromide;
and Zinc dissolution in 0.10 M NaBr at
20°C, pH:5.00, 1000 rpm. 198
Figure (8-4.6b) Evans diagram for the reduction of (a) 0 mg/I

Au(III) bromide (b) 100 mg/I Au(III) bromide;
20°C, pH:4.00,1000 rpm. 198
Figure (8-4.6c) Evans diagram for the reduction of (a) 0 mg/I

Au(III) bromide (b) 100 mg/I Au(III) bromide;
20°C, pH:3.00,1000 rpm. 199
Figure (8-4.6d) Evans diagram for the reduction of (a) 0 mg/1

Au(III) bromide (b) 100 mg/1 Au(III) bromide;
20°C, pH:2.00,1000 rpm. 199
Figure (8-4.7) Evans diagram for the reduction of 100 mg/1

NaBr at 20°C, 1000 rpm and (a) pH:5.00
(b) pH:6.00 (c) pH:7.00. 201
xxiv
Figure (8-4.8) Evans diagram for the reduction of (a) 10 mg/1

Au(III) bromide ions (b) I 00 mg/1 Au(III) bromide
ions and Zinc dissolution in 0.10 M NaBr at
20°C, pH:5.00, and 1000 rpm. 202
Figure (8-5.1) Variation of limiting current densities with rotation

speed for the reduction of Au(III) bromide ions in a
solution containing 100 mg/1 Au, 0.05 M NaBr,
90 mg/1 Br2 (aq) at 20°C, (a) pH:5.00 (b) pH:6.00
(c) pH:7.00. 203
Figure (8-5.2) Variation of the diffusion coefficient of Au(III)

bromide ions with pH ([Au(l11)]: 100 mg/1,
[NaBr]:0.05 M, 20°C). 204
Chapter Nine
Figure (9-2.1) Rotating disc system for the Au(III) bromide/Zinc

cementation experiment (zinc rotating-disc geometry);
from left to right: zinc disc; brass rod; teflon/
plexiglass holder. 206
Figure (9-2.2) A schematic diagram of the equipment/apparatus

arrangement for the Au(III) bromide/Zinc cementation
experiment using zinc rotating-disc geometry. 207

arrangement for the Au(l11) bromide/Zinc cementation
experiment using suspended zinc particles. 208
Figure (9-3.1) Variation of log([Au]i/[Au] 0 ) ratio with time for

10 mg/1 Au(III) bromide/Zn cementation in 0.10 M
NaBr (containing 9.8 mg/1 Br2 (aq)); 20°C; pH:5.00;
at different rotational speed. 212
XXV
Figure (9-3.2) Variation of reaction rate constants with the square-root

of rotation speed for 10 mg/I Au(III) bromide/Zn
cementation in 0.10 M NaBr solution (containing
9.8 mg/I Br2 (aq)); at 20°C and pH:5.00. 212
Figure (9-3.3) Variation of log (concentration ratio) with time for

10 mg/I Au(l11) bromide/Zn cementation in 0.10 M
NaBr solution (containing 9.8 mg.I Br2 (aq)); at
pH:5.00; 1000 rpm and (i) 10°C (ii) 20°C (iii) 30°C
(iv) 40°C. 214
Figure (9-3.4) Arrhenius plots for 10 mg/I Au(III) bromide/Zn

cementatiion in 0.10 M NaBr (containing 9.8 mg/I
Br2 (aq)) at pH:5.00 and 1000 rpm. 214

(i) 10 mg/I (ii) 20 mg/I (iii) 50 mg/I (iv) 100 mg/I
Au(III) bromide/Zn cementation in 0.10 M NaBr
solutionat 20°C, pH:5.00 and 1000 rpm. 216
Figure (9-3.6) The effect of initial gold concentration on Au(III)

bromide/Zn cementation in 0.10 M NaBr, at
20°C, pH:5.00; 1000 rpm. 216
Figure (9-3.7a) Variation of log([Au]t/[Au] 0 ) with time for 10 mg/I

Au(III) bromide/Zn cementation in (i) 0.001 M
(ii) 0.010 M (iii) 0.050 M (iv) 0.100 M (v) 0.500 M
NaBr (Br2 (aq):9.8 mg/I); 20°C; pH:5.00; 1000 rpm. 218
Figure (9-3.7b) Variation of log([Au]t/[Au] 0 ) with time for 100 mg/1

Au(III) bromide/Zn cementation in (i) 0.001 M
(ii) 0.010 M (iii) 0.050 M (iv) 0.100 M (v) 0.500 M
NaBr (Br2 (aq):9.8 mg/1); 20°C; pH:5.00; 1000 rpm. 218
Figure (9-3.8) Variation of reaction rate constants for I 0 mg/I

Au(III) bromide/Zn cementation with NaBr
concentration (Br2 (aq):9.8 mg/1) at 20°C;
xxvi
pH:5.00 and 1000 rpm. 219

Figure (9-3.9) Variation of reaction rate constants for 100 mg/1
Au(ID) bromide/Zn cementation with NaBr
concentration (Br2 (aq):98 mg/1) at 20°C; pH:5.00
and 1000 rpm. 219

10 mg/1 Au(l11) bromide/Zn cementation in 0.10 M
NaBr solution (Br2 (aq): 9.8 mg/1 at 20°C, 1000 rpm
and (i) pH:2.00 (ii) pH:3.00 (iii) pH:4.00 (iv) pH:5.00
(v) pH:7.00. 221
Figure (9-3.11) Variation of reaction rate constants and Zn(II)

concentration with pH for 10 mg/1 Au(III)
bromide/Zn cementation in 0.10 M NaBr
solution (containing 9.8 mg/1 Br2 (aq)) at 20°C;
1000 rpm. 222
Figure (9-3.12) Zinc dissolution rate versus time for (i) 10 mg/1
(ii) 20 mg/1 (iii)50 mg/1 (iv) 100 mg/1 Au(l11)
bromide solution containing 0.10 M NaBr at
20°C, pH:5.00 and 1000 rpm. 225
Figures (9-3.13a-d) Scanning electron micrographs showing the effect

of rotational speed on Au(III) bromide/Zn cementation
(10 mg/1 Au(III); 0.10 M NaBr (containing 9.8 mg/1
Br2 (aq)); 20°C; pH:5.00), (a) 200 rpm (b) 500 rpm
(c) 1000 rpm (d) 1500 rpm. 229
Figures (9-3.14a-d) Scanning electron micrographs showing the effect

of temperature on Au(III) bromide/Zn cementation
(10 mg/1 Au(III), 0.10 M NaBr (containing 9.8 mg/1
Br2 (aq)), pH:5.00, 1000 rpm), (a) 10°C (b) 20°C
(c) 30°C (d) 40°C. 232
xxvii
Figures (9-3.15a-d) Scanning electron micrographs showing the effect of

pH on Au(III) bromide/Zn cementation (10 mg/1
Au(III), 0.10 M NaBr (containing 9.8 mg/1 Br2(aq)),
20°C, 1000 rpm); (a) pH:2.00 (b) pH:3.00 (c) pH:4.00
(d) pH:7.00. 235
Figures (9-3 .16a-d) Scanning electron micrographs showing the effect of

initial gold concentration on Au(III) bromide/Zn
cementation (0.10 M NaBr, 20°C, pH:5.00, 1000 rpm);
(a) 10 mg/1 (b) 20 mg/1 (c) 50 mg/1 (d) 100 mg/1. 238
Figures (9-3 .17 a-e) Scanning electron micrographs showing the effect of
NaBr concentration on Au(l11) bromide/Zn cementation
(10 mg/1 Au(III), 9.8 mg/1 Br2 (aq), 20°C, pH:5.00,
1000 rpm); (a) 0.001 M (b) 0.010 M (c) 0.050 M
(d) 0.100 M (e) 0.500 M. 242
Figures (9-3 .18a-d) Scanning electron micro graphs showing the effect of
NaBr concentration on Au(l11) bromide/Zn cementation
(100 mg/1 Au(III), 98 mg/1 Br2 (aq), 20°C, pH:5.00,
1000 rpm); (a) 0.01 M (b) 0.05 M (c) 0.10 M
(d) 0.50 M. 245
Figure (9-4. la) Variation of log([Auh/[Au] 0 ) with time for 10 mg/1

Au(III) bromide/Zn (suspended particles) cementation
in 0.10 M NaBr (containing 9.8 mg/1 Br2 (aq)) at 20°C,
500 rpm, pH:5.00, (i) 38x45 µm (ii) 45x63 µm
(iii)63x 106 µm. 246
Figure (9-4.1 b) Variation of log([Auh/[Au] 0 ) with time for 100 mg/1

in 0.10 M NaBr (containing 98 mg/1 Br2 (aq)) at 20°C,
500 rpm, pH:5.00, (i) 38x45 µm (ii) 45x63 µm
(iii) 63x 106 µm. 247
xxviii
Figure (9-4.2a) Variation of reaction velocity constants with the

reciprocal of particle diameter for 10 mg/I Au(III)
bromide/Zn (suspended particles) cementation in
0.10 M NaBr (9.8 mg/I Br2 (aq)) at 20°C, pH:5.00
and 500rpm. 248
Figure (9-4.2b) Variation of reaction velocity constants with the

reciprocal of particle diameter for 100 mg/I Au(l11)
0.10 M NaBr (9.8 mg/I Br2 (aq)) at 20°C, pH:5.00
and 500rpm. 249

100 mg/I Au(l11) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr (containing 98 mg/I
Br2 (aq)); 20°C; pH:5.00; 500 rpm at different
zinc amounts. 250
Figure (9-4.4) Variation of reaction velocity with particulate zinc

amount for 100 mg/I Au(III) bromide/Zn (suspended
particles) cementation in 0.10 M NaBr (containing
98 mg/I Br2 (aq)); at 20°C; pH:5.00; and 500 rpm. 250

100 mg/I Au(III) bromide/Zn (suspended patticles)
cementation in 0.10 M NaBr (98 mg/I Br2 (aq));20°C;
pH:5.00; at (i) 100 (ii) 300 (iii) 500 (iv) 700 rpm. 252
Figure (9-4.6) Va1·iation of reaction velocity constants with the

square-root of stirring speed for 100 mg/1
Au(III) bromide/Zn (suspended particles) in 0.10 M
NaBr solution (containing 98 mg/I Br2 (aq)); at 20°C
and pH:5.00. 252
xxix
Figure (9-4.7a) Variation of log([Au]t/[Au]o) with time for 10 mg/1

in 0.10 M NaBr (containing 9.8 mg/1 Br2 (aq)); at
pH: 5.00; 500 rpm and (i) 10°C (ii) 20°C (iii) 30°C
(iv) 40°C. 254
Figure (9-4.7b) Variation of log([Au]t/[Au]o) with time for 100 mg/1

in 0.10 M NaBr (containing 9.8 mg/1 Br2 (aq)); at
pH: 5.00; 500 rpm and (i) 10°C (ii) 20°C (iii) 30°C
(iv) 40°C. 254
Figure (9-4.8a) Arrhenius plots for 10 mg/1 Au(III) bromide/Zn

(suspended particles) cementation in 0.10 M NaBr
(containing 9.8 mg/1 Br2 (aq)) at pH:5.00 and 500 rpm. 255
Figure (9-4.8b) Arrhenius plots for 100 mg/1 Au(III) bromide/Zn

(suspended particles) cementation in 0.10 M NaBr
(containing 98 mg/1 Br2 (aq)) at pH:5.00 and 500 rpm. 255
Figure (9-4.9) Variation of log([Au]r/[Au] 0 ) with time for (i) 10 mg/1

(ii) 20 mg/1 (iii) 50 mg/1 (iv) 100 mg/1 Au(III)
0.10 M NaBr solution at 20°C, pH:5.00 and 500 rpm. 256
Figure (9-4.l0a) Variation of log([Au]r/[Au] 0 ) with time for 10 mg/I

in (i) 0.001 M (ii) 0.01 M (iii) 0.05 M (iv) 0.10 M
(v) 0.50 M NaBr (Br2 (aq): 9.8 mg/1); 20°C; pH:5.00;
500rpm. 258
Figure (9-4.l0b) Variation of log([Au]r/[Au] 0 ) with time for 100 mg/1

in (i) 0.001 M (ii) 0.01 M (iii) 0.05 M (iv) 0.10 M
(v) 0.50 M NaBr (Br2 (aq): 9.8 mg/1); 20°C; pH:5.00;
500rpm. 258
XXX
Figure (9-4.11) Variation of reaction velocity constants for 10 mg/I

with NaBr concentration (containing 9.8 mg/I Br2 (aq))
at 20°C; pH:5.00 and 500 rpm. 259
Figure (9-4.12) Variation of reaction velocity constants for 100 mg/I

Au(l11) bromide/Zn (suspended particles) cementation
with NaBr concentration (containing 98 mg/I Br2 (aq))
at 20°C; pH:5.00 and 500 rpm. 260

100 mg/I Au(III) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr solution (Br2 (aq):
98 mg/l)at 20°c, 500 rpm and (i) pH:2.00 (ii) pH:3.00
(iii) pH:4.00 (iv) pH:5.00 (v) pH:7 .00. 262
Figure (9-4.14) Variation of reaction velocity constants with pH for

100 mg/I Au(l11) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr solution (containing
98 mg/I Br2 (aq)) at 20°C and 500 rpm. 262
Figure (9-4.15) Typical optical micrograph of gold-coated zinc

particles (polished to I µm) as obtained from Au(III)
bromide/Zn (suspended particles) cementation,
625Xmag. 264
Figure (9-4.16) The scanning electron micrograph of gold-coated zinc

particle (polished to 1 µm) obtained from Au(III)
bromide/Zn (suspended particles) cementation,
3000Xmag. 265
Figure (9-4. l 7a-d) Scanning electron micrographs showing the effect of

initial gold concentration on Au(l11) bromide/Zn
(suspended particles) cementation (0.10 M NaBr,
20°c, pH: 5.00, 500 rpm); (a) 10 mg/I (b) 20 mg/I
(c) 50 mg/I (d) 100 mg/I Au(III). 267
xxxi
Figure (9-4.18a-b) Scanning electron micrographs showing the effect of

zinc particle size on Au(III) bromide/Zn (suspended
particles) cementation (10 mg/I Au(III) in 0.1 M
NaBr (containing 9.8 mg/I Br2 (aq)), 20°C, pH: 5.00,
500 rpm) (a) 45X53 µms and (b) 63X 106 µms. 269
Figure (9-4.19a-b) Scanning electron micrographs showing the effect of

zinc particle size on Au(III) bromide/Zn (suspended
particles) cementation (100 mg/I Au(III) in 0.1 M
NaBr (containing 98 mg/I Br2 (aq)), 20°C, pH: 5.00,
500 rpm) (a) 45X53 µms and (b) 63X 106 µms. 270
Figure (9-4.20a-c) Scanning electron micrographs showing the effect of

stirring speed on Au(l11) bromide/Zn (suspended
particles) cementation (100 mg/I Au(III), 0.10 M
NaBr (containing 98 mg/I Br2 (aq)), 20°C, pH: 5.00);
(a) 100 rpm (b) 300 rpm, (c) 700 rpm. 272
Figure (9-4.2la-b) Scanning electron micrographs showing the effect of

amount of zinc particles on Au(III) bromide/Zn
(suspended particles) cementation (100 mg/I Au(III),
0.10 M NaBr (containing 98 mg/I Br2 (aq)), 20°C,
pH:5.00, 500 rpm); (a) 0.0604 g Zn and
(b) 0.500 g Zn 274
Figure (9-4.22a) Plots of l -(r/r0 )3 versus time for 10 mg/I Au(III)

0.10 M NaBr ( 9.8 mg/I Br2 (aq)), at 20°c, pH:5.00,
500 rpm and (i) 38x45 µm (ii) 45x63 µm
(iii) 63x 106 µm zinc particle size ranges. 276
Figure (9-4.22b) Plots of l -(r/r0 ) 3 versus time for 100 mg/I Au(l11)
0.10 M NaBr (98 mg/I Br2 (aq)), at 20°C, pH:5.00,
(iii) 63x 106 µm zinc particle size ranges. 276
xxxii
Figure (9-4.23a) Plots of l-(2/3)a-(l-a) 213 versus time for 10 mg/I

in 0.10 M NaBr (Br2 (aq): 9.8 mg/I) at 20°C, pH:5.00,
(iii) 63x 106 µm zinc particle size range. 277
Figure (9-4.23b) Plots of l -(2/3)a-(l-a) 213 versus time for 100 mg/I
in 0.10 M NaBr (Br2 (aq): 98 mg/I) at 20°C, pH:5.00,
(iii) 63x 106 µm zinc particle size range. 277
xxxiii
LIST OF TABLES
Chapter Two
Table (2-1.1) Basic thermodynamic functions for bromine at

different oxidation states at 25°C (Mussini and
Faita, 1973). 6
Table (2-2.1) Equilibrium constants for some typical anionic

complexes of zinc (Cotton and Wilkinson, 1972). 18
Table (2-2.2) Overall formation constants for various zinc

complexes (Brodd and Leger, 1976). 19
Table (2-2.3) Thermodynamic data on zinc bromide species

at 25°C (Wagman et al, 1982). 20
Table (2-3.1) Standard potentials (E0 , Au 0 +/Au), volts, for

gold complexes in aqueous solutions and
possible oxidants for the dissolution (Adamson,
1972; Puddephat, 1978; Schmid, 1985). 25
Table (2-3.2) Stability constants for selected Au(l) and Au(III)

complexes (Adamson, 1972). 25
Table (2-3.3) Thermodynamic data on gold-bromide species

at 25°C.(Schmid and Curley-Fiorino, 1975;
Schmid, 1985). 27
Chapter Three
Table (3-3.1) Summary of oxidative pre-treatment processes

(Marsden and House, 1992). 49
xxxiv
Chapter Four
Table (4-4.1) Kinetic parameters for hydrogen evolution

(Rieger, 1987). 110
Chapter Five
Table (5-3.1) Activation Energies, Ea, of cementation systems

limited by aqueous phase mass transfer. 129
Chapter Eight
Table (8-4.1) Calculated H+ and measured current densities

of the reduction of 100 mg/I Au(l11) bromides
ions in 0.10 M NaBr at different pH's and
rotationalspeeds. 200
Chapter Nine
Table (9-3.1) Rate constants from cementation experiments

(kc(l); kc(2)) and as predicted from Evans
diagrams (kp)· 220
Table (9-3.2) The influence of pH on the kinetics of Au(III)

bromide/Zinc cementation (initial Au(l11): 10 mg/I;
0.10 M NaBr (containing 9.8 mg/I Br2 (aq));
20°c; 1000 rpm). 223
Table (9-3.3) Total zinc consumption. 225
Table (9-4.1) The reaction velocity/rate constants for different

zinc particle sizes in the Au(III) bromide/Zn
system (0.10 M NaBr; pH:5.00; 20°C; 500 rpm;
Au(III): (i) I 0 mg/1 (ii) I 00 mg/1). 247
XXXV
Table (9-4.2) The experimental activation energies (LiE) for the

Au(l11) bromide/Zn (suspended particles) system
(0.10 M NaBr; pH: 5.00; 20°C; 500 rpm; Au(l11):
(i) 10 mg/I (ii) I 00 mg/I). 256
Table (9-4.3) Comparison of the reaction velocity/rate constants

for different concentrations of gold (0.10 M NaBr;
pH:5.00; 20°C; 500 rpm). 257
Table (9-4.4) Variation of velocity/rate constants with pH

(100 mg/I Au(III); 0.10 M NaBr; 20°C; 500 rpm). 263
Table (9-4.5) The shrinking-core kinetics/mass transfer

coefficients calculated for the different zinc
particle size ranges (0.10 M NaBr; pH:5.00;
20°C; 500 rpm; Au(l11): (i) 10 mg/I (ii) 100 mg/I). 278
xxxvi
LIST OFAPPENDICES
Appendix (7-2.1) A typical CHEMIX input statement. 317
Appendix (7-2.2) A typical SYSTEM input statement. 325
Appendix (7-2.3) A typical DIASTAB input statement. 330
Appendix (8-4.1) Calculation of the mass-transport limited

currents iL of H+ 331
Appendix (8-4.2a) Evans diagram for the reduction of 100 mg/I

Au(III) bromide/Zinc dissolution in 0.10 M
(b) pH:3.00. 332
Appendix (8-4.2b) Evans diagram for the reduction of 100 mg/I

Au(III) bromide/Zinc dissolution in 0.10 M
(b) pH:5.00. 333
Appendix (8-4.3) Evans diagram for the reduction for (a) 10 mg/I
Au(III) bromide ions and (b) 100 mg/I bromide
ions and Zinc dissolution in 0.10 M NaBr
at 20°c, pH:5.00, and 1000 rpm. 334
Appendix (8-5.1) Calculation of diffusion coefficient. 335
Appendix (8-5.2) The prediction of cementation rate constant, (kp) 336
Appendix (8-5.3) Variation of limiting current densities with rotation

speed for the reduction of 100 mg/I Au(III) bromide
ions in 0.05 M NaBr, (90 mg/I Br2 (aq)) at 20°C,
(a) pH:5.00, (b) pH:6.00, (c) pH:7.00. 337
xxxvii
Appendix (9-2.1) Surface area measurements (BET methods). 338
Appendix (9-2.2) Measurements of mean particle size. 340
Appendix (9-3.1) Variation of log([Ault/[Au] 0 ) ratio with time for

10 mg/I Au(III) bromide/Zn cementation in 0.10 M
NaBr (containing 9.8 mg/I Bri (aq)); 20°C; pH:5.00;
at different rotational speed. 343
Appendix (9-3.2) Variation oflog([Au]r/[Au] 0 ) ratio with time for

10 mg/I Au(III) bromide/Zn cementation in 0.10 M
NaBr (containing 9.8 mg/I Br2 (aq)); at pH:5.00;
1000 rpm and (i) 10°c (ii) 20°c (iii) 30°C (iv) 40°C. 344
Appendix (9-3.3) Variation oflog([Au]tf[Au] 0 ) ratio with time for

(i) 10 mg/I (ii) 20 mg/I (iii) 50 mg/I (iv) 100 mg/I
Au(III) bromide/Zn cementation in 0.10 M NaBr
at 20°C, pH:5.00; and 1000 rpm. 345
Appendix (9-3.4a) Variation oflog([Au]r/[Au] 0 ) ratio with time for

10 mg/I Au(III) bromide/Zn cementation in
(i) 0.001 M (ii) 0.010 M (iii) 0.050 M
(iv) 0.100 M (v) 0.500 M NaBr (Br2 (aq):
9.8 mg/I); at 20°C; pH:5.00; and 1000 rpm. 346
Appendix (9-3.4b) Variation of log([Au]r/[Au] 0 ) ratio with time for

100 mg/I Au(III) bromide/Zn cementation in
(i) 0.001 M (ii) 0.010 M (iii) 0.050 M
(iv) 0.100 M (v) 0.500 M NaBr (Br2 (aq):
98 mg/I); at 20°c; pH:5.00; and 1000 rpm. 347
Appendix (9-3.5) Variation of log([Au]r/[Au] 0 ) ratio with time for

1O mg/I Au(III) bromide/Zn cementation in O.10 M
NaBr (Br2 (aq): 9.8 mg/1); at 20°C; pH:5.00;
1000 rpm. and (i) pH:2.00 (ii) pH:3.00
(iii) pH:4.00 (iv) pH:5.00 (v) pH:7.00. 348
xxxviii
Appendix (9-3.6) A typical ED AX chart. 349

Appendix (9-3.7) A typical XRD chart. 349
Appendix (9-4.la) Variation of log([Au]tf[Au] 0 ) ratio with time for

10 mg/I Au(III) bromide/Zn (suspended
particles) cementation in 0.10 M NaBr (Br2 (aq):
9.8 mg/I); at 20°C; pH:5.00; 500 rpm. and
(i) 38x45 µm (ii) 45 x 63 µm (iii) 63 x 106 µm
zinc particle size ranges. 350
Appendix (9-4.1 b) Variation of log([Au1t/[Au] 0 ) ratio with time for

98 mg/I); at 20°C; pH:5.00; 500 rpm. and
(i) 38x45 µm (ii) 45x63 µm (iii) 63x 106 µm
Appendix (9-4.2) Variation of log([Au]t/[Au] 0 ) ratio with time for

98 mg/I); 20°C; pH:5.00; and 500 rpm at different
zinc amounts. 352
Appendix (9-4.3) Variation of log([Ault/[Au] 0 ) ratio with time for

98 mg/I); 20°C; pH:5.00; at (i) 100 (ii) 300
(iii) 500 (iv) 700 rpm. 353
Appendix (9-4.4a) Variation of log([AuJt/[Au] 0 ) ratio with time for

9.8 mg/I); at pH:5.00; 500 rpm and (i) 10°c
(ii) 20°c (iii) 30°C (iv) 40°C. 354
Appendix (9-4.4b) Variation of log([Ault/[Au] 0 ) ratio with time for

xxxix
9.8 mg/1); at pH:5.00; 500 rpm and (i) I0°C

(ii) 20°c (iii) 300c (iv) 400c. 355
Appendix (9-4.5) Variation of log([Au]tf[Au] 0) ratio with time for

(i) 10 mg/1 (ii) 20 mg/1 (iii) 50 mg/1 (iii) 100 mg/1
in 0.10 M NaBr at pH:5.00;and 500 rpm. 356
Appendix (9-4.6a) Variation of log([Ault/[Au] 0) ratio with time for

10 mg/1 Au(III) bromide/Zn (suspended
particles) cementation in (i) 0.001 M (ii) 0.010 M
(iii) 0.050 M (iv) 0.100 M (v) 0.500 M NaBr
(Br2 (aq):9.8 mg/1); at 20°C; pH:5.00; and 500 rpm. 357
Appendix (9-4.6b) Variation of log([Au]r/[Au] 0) ratio with time for

particles) cementation in (i) 0.01 M (ii) 0.10 M
(iii) 0.10 M (iv) 0.20 M (v) 0.50 M NaBr
(Br2 (aq):98 mg/1); at 20°C; pH:5.00; and 500 rpm. 358
Appendix (9-4.7) The solution potential of 10 mg/1 Au(III)

(i) 0.001 M (ii) 0.010 M (iii) 0.050 M (iv) 0.100 M
(v) 0.500 M NaBr (containing 9.8 mg/I Br2 (aq))
at 20°C, pH:5.00, 500 rpm. 359
Appendix (9-4.8) The solution potential of 100 mg/I Au(III)

(i) 0.01 M (ii) 0.05 M (iii) 0.10 M (iv) 0.20 M
(v) 0.50 M NaBr (containing 98 mg/1 Br2 (aq))
at 20°C, pH:5.00, 500 rpm. 360
Appendix (9-4.9) Variation of log([Au]r/[Au] 0) ratio with time for

98 mg/1); at 20°C, 500 rpm and (i) pH:2.00
(ii) pH:3.00 (iii) 4.00 (iv) pH:5.00 (v) pH:7 .00. 361
xl
Appendix (9-4.I0a) Variation of l-(r/r0 )3 with time for 10 mg/I

Au(III) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr (Br2 (aq):
9.8 mg/I); at 20°C; pH:5.00; 500 rpm. and
Appendix (9-4.l0b) Variation of 1-(r/r0 )3 with time for 100 mg/I

Au(III) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr (Br2 (aq):
98 mg/I); at 20°C; pH:5.00; 500 rpm. and
Appendix (9-4.lla) Variation of 1-(2/3)a-(l-a)213 with time for

9.8 mg/I); at 20°C; pH:5.00; 500 rpm. and
Appendix (9-4.1 la) Variation of 1-(2/3)a-(1-a)213 with time for

98 mg/I); at 20°C; pH:5.00; 500 rpm. and
CHAPTER ONE
INTRODUCTION
Cyanidation using cyanide and air has been widely used to extract gold from its
ores and concentrates for over one hundred years, and still remains the
overwhelming option. This has been reflected in simplicity of its application,
high pH, well defined complexation chemistry and small reagent addition,
making it generally effective in treating a wide range of ores at relatively low
cost.
However, the process lends itself to potential environmental restrictions on the

use of cyanide in some areas. The potential toxicity of cyanide and its
complexes are high requiring careful monitoring and control of process purge
streams. Spent cyanide liquors may be subjected to waste treatment operations
before being discharged to the environment.
In addition, it is not a suitable technique for ores and concentrates that are
considered refractory. Host minerals like pyrite, arsenopyrite, chalcopyrite,
pyrrhotite, galena and other lead minerals which are ubiquitous in primary ores
tend to react and consume excessive cyanide during leaching or exhibit poor
dissolution rates. Carbonaceous gold ores generally contain naturally active
carbon which adsorbs dissolved gold during cyanidation. In some other ores of
this type, the gold is chemically combined with the organic matter and requires
pre-oxidation before leaching. A few ores containing gold telluride minerals are
also resistant to cyanidation. Also, leaching rates with alkaline cyanide solutions
are generally low (with contact times of more than 24 hours) especially with
gold concentrates. For these applications, a faster leaching system is required.
Other leachants have been considered as alternatives and especially in

applications where the use of cyanidation is impractical. Of these, thiourea,
thiosulphate and the halides have shown exciting prospects and extensive
research has been undertaken to investigate the fundamental conditions for the
various processes. The use of oxidants such as iron(lll), ammonia, hypochlorite
and other halogens to dissolve gold in these systems respectively has been
established.
2
The halides in particular offer special properties for the processing of gold ores
and concentrates and recent significant advances claim a lot of potential benefits
for the halogens/halides couple over cyanide/air. Chlorine, bromine, iodine and
the respective salts have all been suggested their applications in various niche
processes and form both Au(I) and Au(ill) complexes with gold depending on
the solution chemistry conditions. In aqueous solutions, the stability of the gold-
halide complexes increases in the order Cl-< Br- < 1- which shows a preference
for gold to bond with large polarizable ligands. The bromine-bromide system
has evolved to be the most reactive and extract gold significantly faster than
cyanide-air. Its adaptability to a wide range of pH values, low toxicity and the
reasonably known bromine chemistry represent a competitive technique for gold
extraction. The development of several and improved bromine-bromide systems
has therefore been topical among many researchers. These advances have also
identified the different recovery techniques (zinc and aluminium precipitation,
carbon adsorption/electrowinning, ion-exchange, solvent extraction) for
recovering gold from the pregnant bromide-leach liquors.
In gold metallurgy, the two most popular techniques for recovering gold from
the solutions obtained after extraction have been by zinc cementation and
carbon adsorption/electrowinning. Zinc cementation grew out of the same
fashion as the development of cyanidation and in its common form, the Merrill-
Crowe process, by far the oldest method for recovering gold from cyanide
solutions. The process has therefore been widely used in the industry. The
remarkable versatility of the zinc cementation as a recovery technique seems to
be outstripped with the advent of the carbon adsorption/electrowinning for gold
extraction and recovery. However, it still accounts for a significant portion of
gold recovery in South Africa, Canada, United States of Ame1ica and some parts
of South America and is applied widely around the world as an alternative to
electrowinning. It is particularly advantageous for gold plants employing non-
agitation leaching methods in the treatment of low-grade ores. In milling
systems, it is prefen-ed to carbon adsorption for treating leach solutions
containing significant amount of silver and for small operations in which gold
recoveries cannot justify the relatively high cost of carbon elution and
reactivation equipment.
In the case of the bromine-bromide system, the only recovery techniques that
have been considered in parallel with its fundamental study are the carbon
adsorption and the ion-exchange methods. Typically, these are likely to be
3
unsuitable for the entire gold recovery. The gold precipitated on activated
carbon or resin is, however, in a metallic form hence abrasion can cause
significant losses. Competitive adsorption of bromine species may limit carbon
or resins loadings. Nevertheless, electrowinning or electrolysis might not also be
suitable as the presence of bro~ine will offset the current efficiency of the
operation and cause cell hardware problems such as anode corrosion and cell
distortion.
Invariably, zinc cementation has been identified to be highly efficient with gold
recoveries up to 99.5 percent. Hence, it is highly imperative that a fundamental
study of the zinc cementation process is carried out to reveal the kinetics and
mechanism of the process to enable a complete assessment of the bromine-
bromide system as an alternative to cyanidation. The precursor to the zinc
cementation technique is its electrochemical nature which allows for its
application, understanding and determination of the characteristics of the
reaction. Accurate data on the kinetics and mechanism of the reaction can be
obtained from electrochemical measurements.
This study therefore endeavours to:
(1) Investigate the electrochemical nature of the respective half-cell reactions:

the reduction of gold and the oxidation of zinc in bromine-bromide solution.
(2) Determine the factors controlling the zinc cementation process with the aim
to optimise the conditions for gold recovery.
(3) Determine the kinetics (reaction rates) of the gold reduction and the zinc
oxidation.
(4) Determine the mechanism of the reaction and the factors controlling the rate
determining steps.
(5) Identify the predominant species m the reaction to reveal the various
equilibria governing the recovery process.
CHAPTER TWO
GENERAL & THERMODYNAMIC PROPERTIES OF

BROMINE, ZINC & GOLD
2-1 BROMINE
2-1-1 General Chemistry /Properties
The element bromine belongs to the group of halogens (meaning "salt former")
comprising of fluorine, chlorine, bromine, iodine and the very rare radioactive
element, Astatine, and which collectively constitute the fluorine family (Group
VII) of the periodic table.
Bromine was discovered by Balard in 1826 who recognised it as a new element,

after its isolation in 1825 from Kreuznach mineral water (Bloch, 1929).
Bromine is a fuming, highly corrosive, reddish-brown, diatomic liquid with a

specific gravity of 3.12 at 20°C. It is the only non-metallic element which is
liquid at room temperature, freezing at -7 .3°C and boiling at 58.8°C. The atomic
number of bromine is 35, thus giving an electronic configuration of ls 2 2s 2 2p6
3dl0 4s2 4p5 and a normal oxidation state of -1 and an electronegativity of 2.8.
It also has two stable isotopes with mass numbers of 79 and 81 occurring in the
ratio 50.5:49.5 and has atomic and ionic radii of 0.114 and 0.196 nm
respectively.
Bromine has a total solubility of 0.2141 moles/litre in water. The solubility of

bromine in water is increased by the presence of chlorides and particularly of
bromides. The density of bromine solutions in the presence of bromides is very
high. A solution containing 408.3 g/1 NaBr and 10.43 moles/litre Br2 has a
density of 2.42 g/1. Other properties of bromine include a bond dissociation
energy of 192.5 kJ/mol.(46 kcal/mol.) and an electron affinity of 3.363 eV.
In nature, it appears in the form of bromide salts. Aqueous salts are found in the
sea, rivers, lakes, wells and springs. The concentrations can vary from a few
parts per billion to a few parts per thousand. The greater part of bromine is
5
found as a trace level in the rocks which comprise the earth crust. (Neufeld,
1936; Jolles, 1966). Bromine is generally manufactured from bromide in sea
water, with chlorine as the oxidizing agent. The sea water is first acidified to
pH:3.5 with hydrochloric and sulphuric acid to prevent disproportionation of the
bromine to be formed, and then a slight stoichiometric excess of chlorine is
passed through the solution to oxidise the bromide ions to bromine. The
bromine formed is swept out with a current of air and led into a basic solution
(NaOH), where it disproportionates into bromide and bromate ions. When the
concentration of bromine in this solution is sufficiently high, the solution is
acidified to recover the elemental bromine.
Chemically, bromine (as well as chlorine and iodine) is well known to be

extremely reactive. With a given reagent, bromine commonly gives analogous
reaction products to chlorine and iodine. Bromine has thus found applications in
numerous niche processes and is its ability to dissolve gold to an appreciable
extent (Schaeffer, 1882; Hinman, 1895; Cassel, 1903; Fink and Putnam, 1942;
Bahl and Leach, 1983).
The chemistry of bromine is dominated by a tendency to gain a completely

filled outermost electron shell. Reduction of bromine thus leads to the formation
of bromide ion with the closed-shell configuration and electronic ground state of
ls.
Consequently, bromine reacts with most metals to form ionic compounds
containing the bromide ion. With non-metals, semi-conducting elements and
some metals in high oxidation states, it tends to form simple molecular
compounds. In these, bromine is limited by a single covalent (van der Waals)
bond to the other elements.
2-1-2 Thermodynamics
The most common oxidation state of bromine is -1. In addition, there are known
in the presence of strong electrophilic anions (eg. oxygen), many de1ivatives in
which positive oxidation states of + 1, +3, +5 or +7 are associated with the
bromine atom. Some common compounds and ions of the various oxidation
states are: -1, hydrobromic acid (HBr) and its salts, the bromides (Br-); +l,
hypobromous acid (HBrO) and its salts, the hypobromites, (Bro-); +5, bromic
acid (HBrO 3) and its salts, the bromates (BrO3-); +7, perbromic acid (HBrO4)
6
and its salts, the perbromates (Br04-). There is also evidence for the existence
of the oxides, Br20, BrO, Br02 with oxidation numbers for bromine of+ 1, +2,
and +4 respectively (Mussini and Faita, 1973). Bromous acid (+3) forms as an
intermediate step in several reactions (Mussini and Faita, 1973; Moeller et al,
1989). The values of the fundamental thermodynamics for the more significant
bromine species at different oxidation states at 25°C are listed in table (2-1. l ).
Table (2-1.1) Basic thermodynamic functions for bromine at different

oxidation states at 2s0 c (Mussini and Faita, 1973).
Formula State AG~ AH 0f so

(kcal/mole) (kcal/mole) (caVdeg/mole)
Br g 19.701 26.741 41.805

Bf2 liq. 0 0 36.384
Br2 aq 0.94 -0.62 31.2
Br- g -55.9
Br- aq -24.85 -29.05 4.1
HBr g -12.77 -8.70 47.463
HBr aq -24.85 -29.05 19.7
Br3- aq -25.59 -31.17 35.9
Br5- aq -24.8 -34.0 60.1
BrO g 25.87 30.06 56.75
Bro- aq -8.0 -22.5 -5.6
HBrO aq -19.7 -27.0 34.0
BrO2 s 11.6
BrO3- aq 0.4 -20.0 23.4
HBrO3 aq 0.4 -20.0 39.0
BrO4- aq 29.18 3.19 29.1
HBrO4 aq 29.18 3.19 44.7
where s = solid, aq. = aqueous, g = gaseous state.

7
2-1-2-1 Speciationlaqueous solutions
The reaction chemistry is characterised by the ease with which its atoms acquire
an electron to form either the uninegative ion Br or a single covalent bond -Br.
The potential of the reversible bromine/bromide couple can be expressed in
terms of either the electrode reaction:
(2-1.1)
or
(2-1.2)
for which the standard potential E0 for equation (2-1.1) is 1.0652 V and the
standard potential E 0 for equation (2-1.2) is 1.0874 V (Mussini and Faita, 1973)
and these establish the strong oxidizing power of bromine. For this reason,
redox couples with E0 values less than that of the 1t2Br2/Br couple are usually
subject to oxidation by bromine. In particular, the oxidation strength of bromine
relative to that of the other halogens (ie. F- >Cl-> Br > I-) makes it possible for
bromine to oxidize iodide ions.
(2-1.3)
Similarly, chlorine oxidizes bromide ions.
(2-1.4)
and in the presence of excess chlorine, bromide ion can be oxidised to bromate
I On.
(2-1.5)
In aqueous solution, bromine disproportionates to give hydrobromic and

hypobromous acids.
(2-1.6)
8
(2-1.7)
The HOBr so produced is a weak acid and undergoes slow decomposition.
2HOBr(aq) = O2(g) + 2H+ +2Br- (2-1.8)
so that oxidation of water is the overall result. The reaction (2-1.8) is greatly
accelerated by sunlight (or photolysis) and by catalysts such as platinum and
metallic oxides.
The concentration of HOBr could be decreased by the addition of Br which

shifts the equilibrium of reaction (2-1.6) to the left in favour of Br2 and H2O.
Similarly, the yield of HOBr may be improved by the judicious choice of
conditions where pH is increased (adding OH- to react with the H+ to form
water) or by adding a cation that forms soluble salt with Be The formation of
HOBr will therefore be favoured by the absence of Br ions.
Hypobromous acid, HBrO, is a strong oxidizing agent especially in acid

solutions but rather unstable. Moreover, it is generally metastable with respect
to bromic acid and bromine, into which it decomposes.
5HBrO(aq) = HBrO3(aq) + 2Br2(aq) + 2H2O (2-1.9)
HBr notably, undergoes virtually complete ionization m aqueous solution

according to the reaction:
HBr(aq) = H+ + Br- (2-1.10)
with a free energy LiG~98 = -49.79 kJ/mol. The reactions of HBr in aqueous
solutions may be classified, according to the outcome, as either addition or
substitution. Addition reaction may be further sub-divided into those wherein
the HBr bond remains intact and those wherein the bond is broken. Substitution
reactions are exemplified by protonation, halogenation, oxidation or reduction.
9
1e.
HBr --) H+ Br
I I
Protonating Halogenating
agent agent
Reducing Oxidizing
agent agent
(eg. metal)
1/2Ri 1/2Bri
Substitution reactions inevitably entail cleavage of the H-Br bond. In keeping

with the standard potential of the couple 112Br2/Br-, HBr is a strong reducing
agent. For the HBr/Br- couple,
log PHBr = -8.70 - pH+ log(Br-) (2-1.11)
Thus, solutions of hydrobromic acid or bromides, even when very acidic, exert
only a very small partial pressure of gaseous hydrogen bromide (Pourbaix,
1966). HBr is a strong acid with pKa value of approximately -9.00. Agents with
the capacity to oxidize HBr to bromine include atomic nitrogen, oxygen,
fluorine, hypochlorite, permanganate, hot concentrated sulphuric acid and
chlorine. The thermodynamics of the reaction of oxygen with HBr:
(2-1.12)
for example, is favourable but does not proceed at room temperature. The
reaction (2-1.12) is accelerated by photolytic action.
In alkaline solution, bromine disproportionates into bromide and hypobromite

ions according to the equilibrium reaction:
(2-1.13)
(2-1.14)
10
However the situation 1s complicated by the tendency of Bro- to

disproportionate further to produce the corresponding bromate ions:
3BrO- = 2Br + BrO3- k = 10 15 2-1.15)
This reaction (2-1.15) occurs even at room temperature and therefore an

aqueous alkaline solution of bromine contains a mixture of all three possible
ions (ie. Br-, Bro-, BrO3-). At temperatures of 50-80°C the Bro 3- ion is formed
quantitatively according to the equation.
(2-1.16)
Thus bromine is thermodynamically stable in acid solutions with respect to

disproportionation into bromate and bromide, but unstable at high pH. The
bromates are powerful oxidizing agents but are generally slow in reaction. They
are often sparingly soluble in the cold. The acids (bromic acids, HBrO 3) are
strong acids (pK = 0. 70) and are also powerful oxidizing agents. Likewise, the
perbromates, Br04-, emerge as powerful oxidants, but appear to be sluggish in
their formation and reactions. Perbromic acid, HBrO4, is also described as a
sluggish oxidizing agent, but is a strong acid. In aqueous solution, it is
completely dissociated into aquated protons and tetrahedral BrO4- anions.
Solutions more than 6 moles/litre (55%) in HBrO4 are unstable in air,
undergoing an apparently autocatalytic· decomposition. Its decomposition is also
catalysed by metal ions (eg. Ag+).
In aqueous solutions, bromide ions become hydrated and thus break down the
water structure in the immediate neighbourhood. This effect tends to increase
the mobility of adjacent molecules. Bromine reacts with bromide to form the
tribromide ion, according to the reaction:
(2-1.17)
At high concentrations, in addition to Br3-, the pentabromide ion B1y, might

form according to:
(2-1.18)
11
These reactions allow for the high solubility of bromine in aqueous solution of
bromide ions. Thus in common with chloride and iodide ions, bromide ions
function as ligands to form bromo complexes (eg. with majority of metal ions or
other ligands).
The oxidation of bromide to bromine can be brought about chemically using

nitric acid, concentrated sulphuric acid, metallic peroxides, dichromate or
hypochlorous acid. Under certain conditions, the oxidation of bromide ions may
give rise to oxybromine ions. However, this is more easily accomplished in
alkaline media. Most reactions involving oxybromine anions also involve
hydrogen or hydroxide ions and the position of an equilibrium such as the
disproportionation of bromine:
(2-1.19)
is very dependent on the pH of the medium. Latimer (Latimer, 1952) gave a

potential diagram for bromine at unit hydrogen ion activity as:
OXIDATION
+7 +5 +3 +1 0 -1
STATE
SPECIES/ r---+1.51
EQUILIBRIUM -
+1.76 BrO3
- +1.49 HOBr +1.59 Br 2 +1.07 Br
POTENTIAL (V) Br04
2-1-2-2 Eh (potential) - pH relationship
The equilibria governing the 112Br21Br- redox couple (such as the

disproportionation of bromine) and the formation and stability of the bromine
species are in essence also illustrated by Eh - pH diagrams.
2-1-2-2-1 Bromine - water system
Figure (2-1.1) shows the Eh - pH diagram for a bromine - H20 system

containing 1.0 M total dissolved bromine. Bromide is in equilibrium with
bromine (at 1 atm) from a potential above 1.07 V (vs SHE). The domain of
12
predominance of the bromides, Br-, covers entirely the domain of stability of

water (except where the media are very acid and oxidizing). The position of the
stability window of bromine, characterises it as an oxidizing substance in the
neutral, alkaline and slightly acid solutions. The diagram also demonstrates the
existence of the polybromides (eg. Br3-).
The effect of dissolved bromine concentration ( I o-6 M to 1.0 M) on the

bromine-bromide equilibrium is shown in figure (2-1.2a-d). The oxidation of
bromides at potentials above those indicated by line (9') leads to the formation
of bromate, BrO3- accompanied in acid media by the intermediate formation of
bromine and possibly tribromide, Br3-. The Br3- ion has a domain of relative
predominance only in solutions whose concentration is greater than 8.04x 10-2
M dissolved bromine.
222,--.0_ _---,-2_ _4,-----;6;--_--.:;:8_ _1.:,.:0:_____:.;:
1.0
~ 06 --- --- --- --- ---®-- 0.6

0
> --- --- --- ---
w 0.2
---
0.2
-®--
--- --- --- --- i
-0.2 --- --- --- 1-0.2
0.6
--. . __ --. . __ --. . __ - . . __ --. j_ 0. 6
-1~-~-~--~ ~--J_
'
- - --- ---
1 -._ I..__ ..__ --.
j J
2 0 2 4 6 8 10 12 14 16
pH~
Figure (2-1.1) The potential-pH diagram for the bromine - water system at
2soc (Mussini and Faita, 1973). Equilibria considered are:
(a) H+fH 2(g) (b) O2(g)/H2O (c) HBr03'Br03· (d) Br3'Bi- (e)
Br0 3·/Br(f) Br2(aq)/Br3· (g) Br03·/Br3· (h) HBrOJffir2(aq)
(i) BrO 3·/Br2(aq) (I) Br20)/Br3· (m) HBrOJffir2(1) (n) BrO3·
/Br2 (o) BrO 4·/BrO3· (p) BrO4·/HBrO3
2 3 4 5 6 7 -1 0 3 4 2
5 6 7
2 .---...-~. .---~---- -..--..--- ~~2
1,8 1,8
Br03 1,6 l,6
1,4 1,4
1,2
Q8 0,8 Br- 0,8

0,6 0,6 0,6
0, 4 '-------L.-- '----'--'---- -'----'-----L __J 0,4 '-------L.---' -------'----'-- -'---_L__--- '-----' 0,4
-1 o 2 3 4 5 iH 7 -1 0 2 3 4 5 6pH 7
u. b.
3 4 5 6 7 -1 0 2 3 4 5
2
1,8
Bro 3 1,6
1,4
1,2 1,2
08
, Br- Q8 8~ Q8
~6 Q6 Q6
0, 4 L,__.___L ..--.L-~'--- -'----'-----'- -----' 0,4 '-----'--'-- -'----'----- -'---'---'-- ---' 0, 4.
-1 o 2 3 '+ 5 iH
7 -1 0 2 3 4 5 iH 7
c. d.
Figure 2-1.2 The potentia l - pH equilibrium diagram for the bromine -

water system at 25°C for solutions containing (a) 1.0 M Brz
(b) 10- 2 M Br2 (c) 10-4 M Br2 (d) 10- 6 M Br2 (Pourbaix,
1966).
14
2-1-3 Toxicity
Through the oxidizing action of bromine, concentrations as low as 0.3 mg/1 of

the vapours are highly irritating to the entire respiratory tract, mucous
membranes and the eyes, producing responses such as coughing and smarting of
the eyes. An exposure of half an hour to one hour to high concentrations of the
vapours of bromine (about 7 mg/1) is likely to cause fatal illness (eg.
inflammation and congestion of the respiratory system and oedema of the lungs)
in man. The toxicity threshold level for gaseous bromine (highest concentration)
after eight (8) hours continuous exposure is 1 mg/1. However, the properties of
bromine (ie. its pungent, irritating nature and dark brown colour) help in
preventing dangerous exposure of humans to the vapours (Downs and Adams,
1973; Van Leeuwen and Sangster, 1987).
Likewise, liquid bromine presents a serious hazard in handling. It rapidly attacks

the skin and other tissues to produce irritation and necrosis. Nevertheless,
bromine has a long history of use as a disinfectant for water, limited only in
comparison to chlorine principally due to cost. Brominated compounds are
considered to be less of an environmental problem as they are easily degradable
than their chlorinated analogues (Price, et al, 1988).
The toxicity of sodium bromide is similar to that of sodium chloride. At low

concentration levels, bromide and chloride are virtually indistinguishable by
most organisms with regard to toxicity. Acute poisoning is rare because of its
low toxicity. The allowable discharge levels of bromide in fresh water is 250
mg/1 (Dadgar and Howarth, 1992).
2-2 ZINC
2-2-1 General Chemistry/Properties
The element zinc belongs to the zinc family (comprising zinc, cadmium and
mercury) or group IIB elements of the period table which follows copper, silver
and gold. The atom of zinc has an electronic structure which ends with 3d 104s 2
and does not form ions with incomplete d shell.
15
Zinc is a silvery-white metal, very lustrous but tarnishes rapidly on exposure to

air because of the formation of a thin film of oxide. The atomic mass is 65.37.
The metal is rather brittle at room temperature but becomes quite ductile and
malleable at 100-150°C. Further heating to above 200°C makes it so brittle that
it can be pulverized by grinding. Zinc melts at 420°C, and its boiling point of
907°C makes it one of the most easily volatilized metals. It does not have the
close-packed structure characteristic of true metals but has distorted hexagonal
close-packed (h.c.p.) structure in which the distances between layers of atoms
are about 15% larger than ideal. Consequently, it has a low tensile strength
(compared with the d-block metals) and a density of 7.13 glee. The atomic and
ionic radii are 1.3IxI0-4 µm and 7.4xI0-5 µm respectively. The vapours of the
metal are nearly completely monatomic above 1000°C, but there are sufficient
diatomic molecules to produce a characteristic band spectrum. Vapourised
mixtures of zinc with cadmium or mercury or with the alkali metals, also give
characteristic spectra.
Whereas in Cu, Ag and Au, the filled d shells may lose one or two d electrons to
give ions or complexes in the I, II and ill states, there is no evidence for
oxidation states higher than II for zinc. This follows from the fact that the third
ionization potential of zinc is extremely high (ie. 40.0 e V) and the energy of
solvation or lattice formation cannot suffice to render the ill oxidation state
chemically stable. Therefore, the only important oxidation state of Zn is the +2
state. There is little evidence that Zn forms a strongly reducing univalent ion
zn+, but is highly unstable and can be obtained when aqueous solutions of Zn 2+
are irradiated.
The chemistry of zmc 1s what is expected for bivalent, moderately

electronegative element. On the whole it follows closely the chemistry of
magnesium. The element has relatively low abundance in nature (0.02% of the
earth crust) and occurs almost entirely as the sulphide, which has two forms, the
commoner, cubic zinc blende or sphalerite and the rarer, hexagonal wurtzite.
Iron and cadmium are nearly always present as substitutional impurities. The
metal is used for galvanising steel. An alloy with -4% Al and 0.15-1.25% Cu is
being increasingly employed for die-casting. Zinc dust is used to cement out
gold from solution and as a chemical reagent in dyestuff production.
16
2-2-2-1 Speciationlaqueous solutions
Zinc is an active metal above hydrogen on the electromotive force (EMF) scale.
The value for the standard potential (calculated from thermodynamic data) is
zn2+ +2e- = Zn (2-2.1)
E0 25oc = -0.7628 V (Brood and Leger, 1976). Thus, it is a reasonably strong

reducing agent (stronger than Cu, but weaker than Mn and the elements at the
left of Mn in the first transition series). It is also thermodynamically unstable in
the presence of water and aqueous solutions and tends to dissolve easily in non-
oxidising acids, releasing hydrogen and giving the divalent ions. It also dissolves
in very alkali solutions, liberating hydrogen and forming zincate ions:
Zn + 2OH- = ZnOi- + H2 (2-2.2)
Solid zincates, Na2Zn(OH)4 and NaZn(OH)3 can be crystallised from the

solutions according to reaction (2-2.2).
The dissolution of zinc (except in strongly acid or alkali solutions), in actual

fact, often takes place extremely slowly when the zinc is very pure. This is due
to the high hydrogen overpotential (or overvoltage)(about -0.8V) exhibited by
zinc, and a direct consequence of the weak interaction between zinc and
hydrogen. Metallic impurities in the solution or on the zinc surface, (eg. Cu and
Fe), usually lower the hydrogen overpotential as their overpotential is less than
that of zinc. That impurities lead to increased zinc corrosion couples is well
known. Several other metal additions too ( eg. Hg, Cd and Sn) raise the
hydrogen overpotential on zinc. Specific adsorption of anions lowers the
hydrogen overpotential on zinc, while specific adsorption of cations raises the
hydrogen overpotential. Tsa and lofa (Tsa and Iofa, 1960) found that iodide
addition to HCl lowered the hydrogen overpotential on zinc single crystals due
to adsorption of the iodide. Also, the large value of electronegativity of zinc
(1.6) indicates a high degree of water orientation at the zinc surface. This
behaviour is an exception to that exhibited by most s-p type metals. Thus, it
appears that while the free energy for reaction of zinc and water is large, water
17
retains the prope1ties of an isolated molecule on the surface even though

chemisorbed.
On account of the electronegative character and the small "self-corrosion"
nature of zinc, it lends itself well for use as a reactive anode for the sacrificial
protection of metals (eg. iron). Zinc reacts directly with oxygen when heated, to
give the oxides and reacts readily with the halogens and non-metals such as
sulphur, phosphorus and selenium. It also forms many alloys, some, such as
brass, being of technical importance. At high temperatures zinc reduces water
Zn + H20 = ZnO + H2 (2-2.3)
In the presence of moderately alkaline solutions (between pH 8.5 - 10.5),

various crystalline forms of the hydroxide (Zn(OH)z) form, the proportions
depending on concentrations, pH and temperature. Of the six modifications
(a,p 1 ,p 2 ,y,o,ande) the E-form is the only one stable in contact with water
below 312K The hydroxide passivates the zinc surface. Zinc dissolution(or
corrosion) is actually a minimum under these conditions of pH.
Zinc hydroxide is nearly insoluble in water (solubility product, ksp = 10- 14),but
it dissolves in acid solutions to give zincic ions, Zn 2+ and in excess alkaline
solutions to give anionic hydroxo species, ie. bizincate, HZnOz-(or Zn(OH)3-)
or zincate ions, Zn022-(or Zn(OH)4 2-). At high hydroxide concentrations,
Zn(OH)4 2- is the only species. In neutral solution, the tendency to form hydroxo
species is small as depicted by the value log k = -8.96 for the equilibrium:
Zn 2+ + HzO = Zn(OH)+ + H+ (2-2.4)
Zinc oxide, ZnO, is formed when the hydroxide is heated (or at temperatures
above 39°C) and is insoluble in water. ZnO is an intrinsic semiconductor with
an energy gap of 316 kJ moI-1 but when heated in zinc vapour the solid becomes
a metal- excess n-type semiconductor with an energy gap of only 5.0 kJ/mol.
The aquo ions of zinc are quite strong acids and aqueous solutions of its salts
are hydrolysed. In solutions, in the presence of a ligand (or a complexant), the
zinc ions form sp3 hybridized orbitals giving tetrahedrally coordinated
complexes. The primary coordination number is four, although others (eg. 6-co-
ordinates) have been shown to exist. Apparently, due to the complete inertness
18
of the d-orbital electrons in Zn and not used in bond formation, no ligand field
stabilization effects occur in zinc complexes. Ligand bonding, thus occurs in
zinc complexes presumably via covalent sigma bond formation of the sp3
hybrids and yields relatively stable tetrahedrally co-ordinated complexes. The
stereochemistry of the zinc complexes is determined by the ligand size, and
electrostatic and covalent bonding forces.
The stability of the various complex ions influences the reactions of the zinc
ions in solution. The stabilities of selected anionic complexes, [ZnX4J2- (where
X = Ligand), as measured by the equilibrium constants of the reaction
zn2+ + 4X- = [ZnX4]2- (2-2.5)
are given in table (2-2.1).
Table (2-2.1) Equilibrium constants for some typical anionic complexes of

zinc (Cotton and Wilkinson, 1972).
Ligand
c1- 1
Br- 10-1
1- 10-2
CN- 1021
However, there is evidence for the attainment of all four stages of complexation
by zinc with most possible ligands (eg. Cl-, Br- and 1-) (Cotton and Wilkinson,
1972). The formation of fluoro complexes is restricted, and none has been
isolated as a solid. Generally, complex formation follows the pattern given
below for a ligand X, of negative charge n.
19
Zn 2+ + xn = ZnX2-n (2-2.6)
znx 2-n + xn = znxi2-2n (2-2.7)
(2-2.8)
(2-2.9)
The respective formation constants for several common ligands are also given in
table (2-2.2).
Table (2-2.2) Overall formation constants for various zinc complexes

(Brood and Leger, 1976).
Ligand Log formation constants

k1 k2 k3 k4
F- 0.92
c1- 0.72 -0.49 -0.19 -0.18
Be 0.22 -0.10 -0.74 -1.00
1- -0.47 -2.00 -0.74 -1.25
CN- 11.07 26.05 35.67
OH- 6.31 11.19 14.31 17.70
SCN- 1.57 1.56 1.51 3.02
so/- 2.08
The zn2+ ion is a hard acid (the term "hard acid" will be used when Zn 2+ tends
to form more stable complexes with fluorine and oxygen donor atoms).
Complex cations with ammonia and amine ligands (eg Zn(NH3)42+) are well
defined and can be obtained as crystalline salts. These are principally tetrahedral
complexes.
20
2-2-2-2 Bromide species of zinc
The thermodynamic properties of zinc-bromide species are shown in table (2-

2.3 ).
Table (2-2.3) Thermodynamic data on zinc bromide species at 25°C

(Wagman et al, 1982).
Formula State ~HO ~GO ~so

(kJ/mol) (kJ/mol) (J/mol)
ZnBr+ aqueous -247.7

ZnBr2 aqueous -349.4
ZnBr2 solid -328.65 -312.13 -138.5
ZnBr3- aqueous -448.9
ZnBr2.2H 20 solid -937.2 -799.5 -198.7
ZnBr2.4Zn0.13H20 solid -5436.7
ZnBr2 is a colourless hygroscopic substance with a solubility of 20.9 mol/litre in

water at 25°C (Cotton and Wilkinson, 1972). It crystallizes in a close-packed
array in which the Zn atoms are tetrahedrally co-ordinated to bromine atoms. A
concentrated solution of ZnBr2 deposits ZnBr2.2H2O. The bromate
Zn(BrO3)2.6H 2O is known. It melts at I00°C, loses all its water at 200°C. and
decomposes to ZnO, oxygen and bromine at about 250°C. From the ~G0 r
values shown in table (2-2.3), there is therefore a small but definite tendency to
form bromo complexes· of zinc in solution. However, ZnBr+, ZnBr2(aq) and
ZnBr3- complexes have relative stabilities in aqueous solutions depending on
the concentration of the bromide ions and all contain four-coordinate zinc, in a
somewhat distorted tetrahedral arrangement.
21
2-2-2-3 Eh (potential) - pH relationship
The thermodynamic equilibrium conditions for the dissolution of zinc (increase

or decrease conosion) in water is depicted by the Eh - pH diagrams.
2-2-2-3-1 Zinc - water system
Figure (2-2.1) shows the schematic Eh - pH diagram for Zn-H 2O system at

25°C. The diagram shows zinc corrosion (dissolution) domains at low and high
pH values and the formation of Zn(OH)i between the corrosion regions. It also
shows no domain of stability of zinc in common with that of water. Thus, zinc is
very unstable in water and easily dissolves.
-z -I 0 2 J 4 5 6 7 8 9 JO II 12 13 14 15 15
2.2 2.2
E.(v)
2 2
1.8
0 ~ 1.'l
1.6 u::
Zn 02
1.4
,~
0
1.2
---®-- ·2
·O ;, ?
-5
6
-6
'
0.8
--4, ' 0.8
·?
..__ 7
'' 0
0.6 ' 0.6
'' 8
0.4
'
,-
----t
0.4
0.2
- 0.2
0 %_ Zn
+,
zA(oH) 2 0
-0,2 -o_z
-0.4 - C, 4
---'- -0.G
-0,6 ~:_Zn0 2
' ''
'
---,_
'
'
- fnoz- ·';_8
-!
-1 0 -? -4 • 6 ''
-1.2 -1,2
.-1.~ -1, 4
Zn
-1,6 -1,6
0-2-<. -6
-1,8 -1,8
-z -1 0 2 J 4 5 5 7 8 5 10 11 12 13 14 15 16
pH
Figure (2-2.1) The potential-pH diagram for the Zn-H20 at 25°C

(Pourbaix, 1966).
22
2-3 GOLD
2-3-1 General Chemistry/Properties
Gold is the 79th element in the periodic table, classified with Cu and Ag in
group 1B. It has a single s electron outside a completed d shell (outer electron
configuration being 5d106sl).
In the massive form, gold is a soft, yellow metal with a moderately high melting
point (1063°C) and a high electrical and thermal conductivity exceeded among
the elements by silver and copper. It is the most malleable and ductile of the
metals. It has an atomic weight of 196.97 and a density at 20°C of 19.3 g cm-3.
Like the other group 1B elements, gold crystallises in the face-centred cubic
lattice and the closest inter-nuclear distance is 288.4 pm.
Gold is usually found in one of three oxidation states: 0 (native/Au(0)), +1

(aurous/Au(I)), and +3 (auric/Au(ill)). However, there are claims that Au(II)
species are formed as transient intermediates in redox reactions between the
stable oxidation states +1 and +3.(Rich and Taube, 1954; Cotton and Wilkinson,
1972).
Gold in the native state is the most noble of the metals. It is chemically
unreactive and is not affected by water or most acids (eg. hydrochloric acid) and
is not attacked by oxygen or sulphur. Gold does however react with tellurium at
high temperatures and reacts readily with all the halogens. It also dissolves
readily in aqua regia (HCl/HNO3) and in alkali cyanide solutions in the
presence of air. Also, mercury amalgamates about 0. 70% by weight of gold at
25°C. This amalgamating effect of mercury is essentially the result of
mechanical mixing, wetting, and smface reactions between gold and mercury.
In its compounds, gold as Au(I) and Au(III) has the closed-shell electronic
configuration of d 10-type and d8-type respectively and exhibits mainly a
covalent character because of the high ionisation potentials of the two states of
oxidation.
23
2-3-2-1 Aqueous gold complexes/Solution chemistry
Gold is unreactive in pure water. The free aurous ion Au(I) is not stable in water
and the free Au(ID) is a strong oxidant. For this reason, the standard potential
for Au(l)/Au(0) couple cannot be determined directly and probably the best
value that can be obtained for the reaction:
Au++ e- = Au (2-3.1)
is E0 = 1.85 ± 0.05 V (Schmid and Curley-Fiorino, 1975). The acceptable

standard potential for:
Au3+ + 3e- = Au (2-3.2)
is E 0 = 1.50 V and the free energy of formation of Au(ID) according to Latimer

(Latimer, 1952) is Gr= 433.5 kJ/mole. Thus Au(l)/Au(0) has a higher E0 value
than Au(ID)/Au(0) and consequently gold is rapidly oxidised to Au(ID) without
Au(I) forming to any significant extent. Also the reactions (2-3.1) and (2-3.2) all
occur at potentials greater than that required for the reduction of oxygen:
E = 1.229 V (2-3.3)
which accounts for the stability of gold in aqueous solutions (Marsden and
House, 1992). The activity of gold is reduced in the presence of certain
complexing ligands by the formation of stable complexes and hence the aqueous
chemistry of gold is essentially that of complex ions.
Gold dissolves in aqueous solutions containing a good ligand and an oxidising

agent, but neither condition alone is sufficient. The complexant or ligand
governs its stability in a potential range within the water region and the oxidant
b1ings the gold surface to a mixed potential which provides an essential driving
force for the dissolution and establishes the rate. Thus gold will dissolve as
Au(I) according to the general reaction:
(2-3.4)
24
and as Au(ill) according to the general reaction:
(2-3.5)
where Lis the complexing ligand (and may be ions such as CN-, Cl-, SCN-,Br-
or uncharged molecules (eg. NH3, H2O, (NH2) 2CS)). It is also possible, in the
presence of complexing ligands for the oxidation of Au(I) to Au(ID) according
to the reaction:
(2-3.6)
This shows that Au(I) generally has the preference to form a linear complex
with two fold co-ordination and Au(ID) has a marked tendency towards the
formation of a four fold coordination complex.
Representing the standard electrode potential for reaction (2-3.4) as E 0 1,0 and
that of reaction (2-3.5) as E0 3,o, it can be easily shown that:
(2-3.7)
The standard potentials, E0 3,1 for reaction (2-3.6) for oxidation of Au(I) to
Au(ID) in the presence of a complexing ligand can be deduced. The standard
potentials for species which form stable gold complexes are listed in Table (2-
3.1 ). The standard potentials show that these species or ligands form water-
stable complexes with gold. In the case of CN- the lowering of the reduction
potential (E0 , Au(I)/ Au(0)) is about 2.46 volts relative to the simple Au+ ion in
water.
Such effects are a function of the large stability constants associated with these
gold complexes . A selection of stability constants have been listed in Table (2-
3.2). These stability constants also show that there is a direct relationship
between standard potential and the magnitude of the stability constant and that
some complexing ligands form more stable complexes with Au(I) and others
with Au(ID). A useful generalisation for this preferred oxidation state is related
to the electron configuration of the donor (or complexing ) ligand atom (ie., the
atom in the ligand which is bound directly to the gold).
25
Table (2-3.1) Standard potentials (E 0 , Au 0 +/Au), volts, for gold complexes

in aqueous solutions and possible oxidants for the dissolution
(Adamson, 1972; Puddephat,1978; Schmid, 1985).
Ligand Eo1,o Eo30 Eo3,1 Possible oxidants

'
Au(l)/Au(O) Au(ill)/Au(O) Au(ill)/Au(I)
H2O +1.85 +1.50 +1.325

(+1.70) (+ 1.40)
c1- +1.15 +1.00 +0.93 0 2, c1O-
Br- +0.96 +0.86 +0.81 Br2
1- +0.56 +0.57 +0.57 I21I3-, H2O2
SCN- +0.67 +0.64 +0.62
NH3 +0.563 +0.325 +0.206
S2O32- +0.20 +0.10 +0.05 Oz, H 2O 2
CS(NHz)z+ +0.38 +0.30 +0.26 Fe3, H 2O2, MnO2
CN- -0.61 -0.50 -0.445 02, H2O2
Table (2-3.2) Stability constants for selected Au(I) and Au(ill) complexes
(Adamson, 1972).
Ligand Au(I), k1 Au(III), k2
CN- 2X lQ38 IQ56

SCN- l.3X 10 17 IQ42
S2Ol- 5X IQ28
c1- 109 IQ26
Br- 1012 IQ32
1- IQ19 5X 1047
CS(NH 2)z+ 2X 1023
Both Au(I) and Au(III) are B-type metal ions which means that the stability of
their complexes tends to decrease as the electronegativity of the ligand donor
atom increases (i.e. as the tendency of the atom to attract electrons increases).
This accounts for the stability order for the halogen complexes, 1- > Br- > Cl- >
26
p-, where the order of electronegativities is F- > Cl- > Br- > 1-. It also accounts
for the stability orders such as Bi> Sb> As> P, Te> Se> S > O and CN- >
NH3 > H2O and explains why gold tellurides, gold bismuthide and aurostibnite
are stable enough to be found in nature. Thus both Au(I) and Au(ID) prefer to
bond to large polarizable ligands. However, Au(I) ion discriminates more than
Au(ID) ion between hard ligands (Ligands, containing hard donor atoms (i.e.
NR3, N=N=N-, NO2-, RCOO-, NO3-, SO/-, F and Cr) preferring metals ions of
high valency, that preferentially form stable complexes of Au(ID) to the gold
will be referred to as "hard (a-bonding) ligands) and soft ligands (the term "soft
(1t-bonding) ligands" will be used when ligands, containing soft donor atoms
(i.e. CN-, PR3, SR2, S=C(NH2)2, SCN-, S2O3 2-, Se=C(NH2h, SeCN- and r)
preferring metals ions of low valency, preferentially form stable complexes of
Au(I) to the gold), and has the greater B-type metal character. Soft electron
donor ligands such as cyanide, thiourea, thiocyanate and thiosulphate, prefer
metal ions of Au(I) whereas hard electron donor ligands (eg., chloride,
bromide.) prefer Au(ID) ions. By and large, the oxidation of gold to Au(I) or
Au(ID) in the presence of a particular ligand will also depend on the strength of
the oxidizing agent or oxidant and on the relative magnitudes of E 0 1,o and E 0 3,0·
Some possible oxidants are also shown in table (2-3.1).
Au(I) complexes, in particular, show a tendency to disproportionate into Au(0)

and Au(ID) complexes, according to equation (2-3.7). The equilibrium constant
for equation (2-3.7) is given by:
log k = 2F/2.303RT(E0 1,o -3E0 3,o) (2-3.8)
which shows that in general, disproportionation of Au(I) to Au(III) will be

favourable if E0 1,0 > E0 3, 1. The calculated values of K are for L = H2O, K =
1Ql0; L = Cl-, K = 5X 107; L = Br-, K = 105; L = SCN-, K = 2.1; and for L =
CN- is estimated as 10-25 (Puddephat, 1978). It is apparent that the
disproportionation of Au(I) complex becomes less favourable as the ligand
becomes more polarisable. This is also probably in part due to Au(I) having a
relatively greater affinity than Au(ID) for soft polarisable ligands. As a result,
the most important stable Au(I) complex is the cyano complex, Au(CN)z-.
Au(ill) complex is not normally formed, but can be formed under strongly
oxidising conditions as well as excess cyanide. It forms compounds or
complexes with all the halides but Auric fluoride is not stable in water and is
rapidly decomposed. The chemistry of the gold chloride, bromide and iodide are
27
similar. Amie chloride and bromide are soluble in water and excess chloride or
bromide ion yields the complex AuCl4- and AuBq- respectively. In solutions
containing excess cyanide, Au(CN)4-, Au(CN)52- and Au(CN) 63- are formed.
Au(ID) thiocyanates are known, but the most common of these, Au(SCN)4- is
insoluble in water. Au(ID) salts of oxyanions are not particularly stable, but
solutions containing complex auric nitrates, sulphates, and others, (eg.
[Au(N03)4]-, [Au(S04)i]-) can be prepared. Gold selenate, Au2(Se04)), and
gold selenite, Au2(Se03)) are relatively stable. In strongly alkaline solutions,
pH > 13, the soluble hydroaurate species, Au(OH)4- (or H2Auo 3-) and
Au(OH)5 2- (or HAu03 2-) are formed.
Gold complexes in aqueous solutions may be reduced to metallic gold by the

addition of a species with a lower standard potential (eg. cementation) or by
providing a potential difference from an external source (eg. electrowinning). A
number of metals (eg. Zn, Mg, Al, Cr, Fe) are thermodynamically suitable for
gold recovery. Zinc is used for gold recovery from cyanide solutions. This has
been in practice for a century now (MacArthur et al, 1889; Rose and Newman,
1937; Habashi, 1970).
2-3-2-2 Bromide species of gold
Au(I) and Au(ID) species for bromide have been identified (Latimer, 1952;
Schmid and Curley-Fiorino, 1975; Schmid, 1985). The thermodynamic
properties of the gold- bromide species are given in Table (2-3.3).
Table (2-3.3) Thermodynamic data on gold-bromide species at

25°C.(Schmid and Curley-Fiorino, 1975; Schmid, 1985).
Formula State ~uo ~so ~GO

kJ/mol J/mol kJ/mol
AuBr2- aqueous -128.0 220.0 -115.0

AuBr4 - aqueous -192.0 336.0 -167.0
AuBr3 aqueous -39.30
AuBr3 solid -53.26
AuBr solid -14.00
HAuBr4.5H2O solid -166.8
28
AuBr can be prepared but the bromide slowly disproportionate in water to yield
metallic gold and auric bromide. Aurous bromide dissolves in alkaline bromide
solutions to form the aurous bromide complex, AuBr2-- Auric bromide is soluble
in water and in excess bromide ion yields the auric bromide complex, AuBq-.
Gold dissolves in a mixture of hydrobromic acid and nitric acid to form
tetrabromoauric(ID) acid, H[AuBq], which can be isolated in the hydrated form
as HAuBr4.5H2O by evaporation of the solution. In aqueous solution AuBq-
ions are hydrolysed to some extent as:
(2-3.9)
with an equilibrium constant K = 3.4X 10-6.
Thermodynamically, as shown in Table (2-3.3) the gold-bromide system is

characterised by AuBr2- and AuBq- complexes. However, the more important
stable gold-bromide complex is the AuBq-. AuBr2- shows a tendency to
disproportionate according to the equilibrium reaction:
(2-3.10)
and may be stabilised in the presence of excess bromide.
2-3-2-3 Eh (Potential) - pH relationship
The thermodynamic behaviour of gold under different conditions and the

selection of reagents and conditions that will favour the dissolution of metallic
gold, or alternatively, its precipitation from solution are well demonstrated by
Eh - pH diagrams (Osseo-Asare et al, 1984a).
2-3-2-3-1 Gold - water system
The Eh - pH relationship for the Au-H2O system conveniently illustrates the

extreme nobility of gold in the absence of co-ordinating ligands and the
conditions under which particular species are expected to be formed. Figure (2-
3.l) shows the Eh - pH diagram for pure gold at 25°C.
29
Au (OH) 5
--.... --~-
...... ......
Eh ID ---- -._
.............................
-- --- ---
0.0
..... _ Au
-...-... ........ ..._ .......
---- ----
--- -- --
--- -- -
- I .O-----L.__ _.____...J.____ _.l._,_--L_--1... _-..J.._-1_
--- ___]
-2 0 2 4 6 8 10 12 14 16
pH
Figure (2-3.1) The potential - pH equilibrium diagram for the Au-H 2 o

system at 25°C. The concentrations of all gold species = 10-4
M (Puddephat, 1978).
30
The diagram shows that metallic gold covers a very large area of predominance
including the entire domain of water stability and that Au3+ and other oxidized
forms of gold only occur at potentials above the upper stability limit of water.
At these potentials, water will be oxidised to oxygen (according to equation (2-
3.3)) and the various oxidised gold species will be reduced simultaneously to the
metallic state. As a result, Au(ill) is unstable in pure water and will be reduced
to the metallic state by very weak reductants. Au(I) has a higher E0 value than
Au(ill) and makes this ionic species even relatively less stable in water than
Au(ill). Au(I) does not appear on the diagram because it disproportionates
spontaneously according the reaction (2-3 .1 ). The equilibria governing the
Au(I)/Au(0) and Au(ill)/Au(0) couples are therefore represented by (Marsden
and House, 1992):
E = 1.85 + 0.0597log[Au+] (2-3.11)
and
E = 1.50 + 0.0197log[Au3+] (2-3.12)
respectively, where Eis the reduction potential. This means that any decrease in
the concentration of free gold ions will decrease the reduction potential, E, and
enhance the stability of the dissolved gold relative to water.
2-3-2-3-2 Gold - bromide - water system
An Eh - pH for the Au-Br-H2O system emphasizes the need for complexing

ligands in effecting the dissolution of gold. Figure (2-3.2) shows the Eh - pH
diagram for [Au]= 10-5 Mand [Br] = 10-2 M (Hiskey and Atluri, 1988).
In contrast to the situation existing in pure water, Figure (2-3.1), the presence of
the bromide ligands significantly increases the range of conditions over which
dissolved gold is stable. More importantly, the reduction potential for the
dissolved gold species is now less than that of water over at least some part of
the diagram.
31
Metallic gold is oxidised in the presence of bromide to yield AuBr2- at a

standard reduction potential of approximately 0.90 V and the AuBq- complex is
formed at about 0.95 V. AuBr2- complex occupies a very narrow stability field
up to about pH:9.00. There is a wider stability field for AuBr-4- and is centred in
the acidic region. Dissolved gold exists in the shaded area of the diagram.
The magnitude of the complexation is apparent from an examination of the

equations:
Au+ + 2Br- <=> AuBr2 - (2-3.13)

K= [AuBr2-] = 1012 (2-3.14)
[Au+][Br-]2
Au 3+ +4Br- <=> AuBr4 - (2-3.15)
K= [AuBr4 -] = 1032 (2-3.16)

[Au 3+][Br-]4
Figure (2-3.3a-d) also shows the Eh - pH diagrams for Au-Br-H2O at 25°C for
[Au] = 10-3 M and varying concentrations of bromide. Increasing the bromide
concentration forces the Au/AuBq- boundary to lower potentials. Thus, at a
concentration of [Au] = 10-3 M, varying the concentration of [Br-] from 10-5 to
1.0 M, the AuBq- stability region is expanded and Eh (potential) values for
Au/AuBq- are lowered from 1.20 V to 0.80 V. Also the equilibrium for AuBq-
/Au(OH)) couple moves up from pH:4.00 to pH: 11.00, thus widening the
AuBq- window. This indicates that AuBq- stability increases with increasing
bromide concentration in the solution.
From figures (2-3.2) and (2-3.3) the reaction paths for the dissolution of gold in
bromide solution can be synthesized. Similarly, gold extraction from bromide
solution can also be described.
32
2.0
Au(OH) 3
I. 5
AuBr; HAuo;-
H2Auo;
1.0
Eh ..........
..........
AuBr; ..........
..........
.......... ........_
..........
0.5 ' -.......... ........_
..........
Au ..........
0.0
- 0. 5 . . _ _ _ _ . . _ _ _ _ . . _ _ _ _ . . _ _ _ _ . J . . . _ _ _ . . h _ _ _ l . . _ _ L _ _ _ J_ __J
-2 0 2 4 6 8 10 12 14 16
pH
Figure (2-3.2) The potential - pH diagram for the Au-Br-H 2O system at

25°C [Au] = 10· 5 M and [Br-] = 10-2 M (Hiskey and Atluri,
1988).
33
2.0 2.0
a) (b)
1.2 1.2
0.4 - 0.4
Au(OH) 52 -
Eh
-0.4
-------------- ~ - -
[Au3+] = 1 o-3 M Au
Eh
-04
---------- -
[Au3+] = 10-3 M
Au(OH)s2 -
-1.2 [B, J = 10-s M -1.2 [Br- ] = ,o-3 M
-2.0 -2.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 00 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH pH
C) (d)
1.2
0.4
Au(OH) 5 2 - Au(OH) 5 2 -
Eh -- -----
Eh -0.4 -
-0.4 --~-
Au
[Au 3•j ~ 1o-3 M Au [Au3• 1= 10- 3 M
-1.2 [8,]=10- 1 M -1.2 [Br· ) = i .0 M
-2.0 -2.0 .___..___ _.____..,___ _,___ _ t __ __.___ __,

00 2.0 4.0 6.0 8.0 10.0 12.0 14.0 00 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH pH
Figure (2-3.3) Eh-pH diagram for the Au-Br-H 2O system at 25°C (a) [Au]
= 10-3 M, [Br] = 10-5 M (b) [Au] = [Br-] = 10-3 M (c) [Au] =
10-3 M, [Br] = 0.1 M (d) [Au] = 10-3 M, [Br] = 1.0 M
(Dadgar, 1989).
CHAPTER THREE
HYDROMETALLURGY OF GOLD
3-1 INTRODUCTION/REVIEW OF HISTORICAL

DEVELOPMENT
Hydrometallurgical processing consists usually of leaching followed by the

treatment of the resulting pregnant aqueous solution by chemical or
electrochemical means to obtain the separation, purification and recovery of the
metals (Jackson, 1986). Cyanide leaching, chlorination, zinc precipitation and
carbon/charcoal adsorption are processes used for gold extraction which have
been known for at least a hundred years and combination of these remain as the
basis for most gold hydrometallurgical flowsheets (Marsden and House, 1992).
Historically, the early metallurgy of gold was almost totally involved with
gravity techniques (due to its high specific gravity), from placer-type deposits,
sometimes aided by amalgamation with mercury (Eisele, 1988). These advances
were unsuitable for the recovery of fine gold and gold associated with sulphide
minerals and consequently became unpopular and prompted the search for an
effective hydrometallurgical process. The first hydrometallurgical approach for
the dissolution of gold from its ores was the chlorination process which was
proposed by Plattner in 1851 (Liddell, 1945). This consisted of passing chlorine
gas over crushed ore to produce a soluble gold chloride which was then leached
out with water and precipitated with ferrous sulphate, hydrogen sulphide or
charcoal. The properties of several other chemicals or reagents for dissolving
gold and silver were known in the late l 800's and early 1900's. These included
bromine/bromide, cyanide, thiosulphate and thiourea solutions (Plaksin and
Kozhukhova, 1941; Preisler and Berger, 1947).
The dissolution of gold by potassium cyanide (in the presence of oxygen) was
discovered in 1846 by Elsner, patented between 1887 and 1889 by McArthur
and Robert and William Forrest and was studied in detail subsequently by
Bodlander in 1896 (Habashi, 1970; Eisele, 1988). This event radically changed
the hydrometallurgical processing of gold although the action of cyanide on
precious metals had been noted years earlier (Clennell, 1915) and rapidly
35
developed into a commercial process. The first commercial use of cyanide for
gold extraction was in New Zealand in 1889 (Shoemaker, 1984; McNulty,
1989). This followed in South Africa in 1890, United States of America in 1891,
Mexico in 1900 and in France in 1904 (Shoemaker, 1984; Marsden and House,
1992). These early operations involved percolation leaching in vats. During the
following decades, the development of agitated tanks/thickeners and classifiers
for leaching and washing allowed development of the countercurrent
decantation cyanide leach plant.
In parallel with the cyanidation process, recovery of gold from the pregnant
cyanide solution was by zinc precipitation (or cementation) using zinc shavings
which was patented by McArthur and the Forrest brothers (McArthur et al,
1889). This process was improved by Merrill and Crowe with the use of zinc
dust (rather than zinc shavings in zinc boxes), the introduction of de-aeration
and the addition of small quantities of soluble lead salts to solutions prior to
precipitation. Cyanidation, thus continued in this fashion with only
improvements in the mechanical and physical handling aspects of the process
until about 1950 when hydrocyclones started to replace mechanical classifiers in
gold mills. Organic flocculants were also developed for the thickening and
washing of cyanide pulps, improving clarification of pregnant solutions for the
zinc cementation step.
Electrolytic recovery processes using lead foil cathodes (Siemens and Halske
process) and carbon sheet cathodes (Tainton process) were used in the late
1800's but did not prove economic. Precipitation by aluminium powder had a
very brief spot those early days. The use of carbon (wood charcoal) for
recovering gold from cyanide solutions was patented in 1894 and was
commercially used at Youanmi Mine, Western Australia in 1916 as an
alternative to zinc cementation. Various investigators experimented with
activated carbon over the years (Crabtree et al, 1950). However, the only known
means to recover gold from carbon at that time was to burn it. This was difficult
to accomplish and sometimes the loaded carbon was sold to a smelter. Hence,
the process became uncompetitive and was usually only resorted to when zinc
precipitation could not be used.
At this time, an all important research began at the United States Bureau of
Mines (USBM) for methods to strip gold (or silver) from loaded carbon which
would then allow the carbon to be re-used to make the entire carbon process
36
very economical for the recovery of gold. Initially, an alkaline Na2S stripping
method (that eluted the gold but not the silver from carbon) was described
(Zadra, 1950). This method was not satisfactory because most ores contain some
silver and the carbon would eventually be loaded with unstrippable silver. In
1952, this process was modified by the USBM researchers to use hot caustic and
cyanide which could desorb both gold and silver from loaded carbon (Zadra et
al, 1952). Concurrently with stripping, the leach solution was passed through an
electrolytic cell (known as Zadra's cell) where the gold and silver were
recovered on a steel wool cathode. An important feature, was that, the hot
NaOH-NaCN solution desorbed more than 90% of the gold and silver in 4-6
hours, and the carbon could be re-used a number of times ( <10 times) without
thermal reactivation and significant activity losses. The carbon adsorption
permitted gold and silver recovery from slimy ores by eliminating the
requirement of a clarified solution and was invariably an efficient means for
collecting gold from dilute solutions. This was therefore a precursor for two
important developments in gold and silver ore processing; carbon-in-pulp, CIP (
including carbon-in-leach, CIL) cyanidation and heap leaching.
Apparently, commercial plant practice adopted coarser carbons made from

coconut shells and electrowinning was always done simultaneously with elution.
This resulted in much longer elution times, 24-48 hours, (instead of 4-6 hours as
described by Zadra et al, 1952) to desorb more than 90% of the precious metals.
The need to decrease the desorption time evolved the development of two
methods, pressure stripping and alkaline-alcohol stripping by the United States
Bureau of Mines. In 1973, it was shown that by using a pressure vessel and
increasing the temperature of the caustic cyanide stripping solution to I 50°C
gold was removed form the carbon in about 2 hours (Ross et al, 1973). In the
alkaline-alcohol stripping method, developed a few years later, 20% ethanol in
addition to the alkaline cyanide was used at ambient pressure (Heinen et al,
1976). At 80°C, gold and silver, were desorbed in 6 hours. A concmTent
development was the separation of gold and silver by precipitating silver as
sulphide (Heinen et al, 1978). For pregnant solutions containing high values of
silver, silver was precipitated before loading the carbon (Heinen et al, 1975) and
this practice reduced the carbon usage by maintaining a capacity for only gold
adsorption.
In 1969, Heinen, and other researchers at the USBM developed heap leaching as
a low-cost method for recovering gold values from low-grade materials
37
containing micron-size particles of gold which otherwise would not have been
exploitable economically by conventional agitation cyanidation (Heinen and
Potter, 1969; Potter, 1969). This permitted the recovery of gold and silver from
crushed ores and wastes heaped on an impermeable pads or membrane and had
the advantage of very low capital and operating costs. However, ores that
contained high clay content were untreatable by heap leaching. These ores
swelled on contact with the leaching solution and affected heap permeability.
Similarly, crushing the ore to the liberation size for gold-silver extraction
generated large amounts of fines that were washed into the voids by the
percolating leaching solution, caused channelling, and resulted in partial
leaching of gold and silver from the heap material. For these reasons, in the late
1970's, an agglomeration process was developed also at USBM, that
successfully overcame these problems (Heinen et al, 1979; McClelland and
Eisele, 1982). Agglomeration was achieved by mixing the ore with lime and/or
cement and water in an agglomeration drum, or by conveyor handling in the
crusher plant ore stacking system. This simple pretreatment increased the flow
of solution through some ores several thousand-fold and decreased the leaching
cycle very significantly. Heap leaching took advantage of the concurrent
development of carbon adsorption processes by using carbon-in-columns for
gold recovery from solution followed by electrowinning. Zinc precipitation is
preferred in the case of high silver concentrations or when the cost of a carbon
stripping/reactivation circuit cannot be justified.
During the 1970's and 1980's, major efforts were directed at the treatment of
ores (refractory ores) which could not be effectively treated by simple
cyanidation. These ores contain minerals (sulphide minerals, carbonaceous
materials, tellurium minerals) which are present at much greater concentrations
than the gold, often cause problems because they dissolve in solution and hence
consume cyanide and oxygen (cyanicide) (Finkelstein, 1972). Historically,
severely refractory ores and concentrates, have been roasted to completely
oxidize the refractory portion of the ore and render the contained gold leachable.
In 1971, carbonaceous ore was treated by chlorination, followed by cyanidation
and zinc precipitation (later replaced by CIP). In 1977, the process was altered
to a double oxidation circuit by incorporating a pre-aeration stage ahead of
chlorination. Pressure oxidation was established for the treatment of gold-
bearing sulphides. A bio-oxidation process to partially oxidize flotation
concentrates was developed and practised. The motivation for the continued
development of bio-oxidation process is the potential cost savings over pressure
38
oxidation and the considerable environmental advantages over roasting

(Marsden and House, 1992).
Metallurgical research and development work have been prolific in the 1980's.
These have been towards the need to treat lower grade ores with more complex
mineralogy coupled with the increasing environmental requirements placed on
mining operations. The continued development of refractory ore projects has
encouraged renewed interest in lixiviants for gold that could be used in acidic
media to avoid the high neutralisation costs required by alkaline cyanidation of
oxidized products. Thiourea and ammonium thiosulphate have received
significant attention. Several studies have shown promising results for these
leachants (Chen et al, 1980; Tozawa et al, 1981; Hiskey, 1984; Charley, 1984;
Filmer et al, 1984; Gabra, 1984; Block-Bolten et al, 1985; Block-Bolten and
Torma, 1986; Loveday, 1986; Sandberg and Huiatt, 1986). The use of
halide/halogen systems for extracting gold has been tested lately. Various
iodine/iodide systems have been evaluated by Davis, Tran and Young (Davis,
1991; Davis and Tran, 1991; Davis et al, 1993). Hiskey and Qi also reported on
similar systems (Hiskey and Qi, 1991). Several bromine/bromide systems have
also been evaluated (Sehic, 1988; Dadgar, 1989; Pesic and Sergent, 1990; Pesic
and Sergent, 1991; Pesic, 1992; Dadgar and Howarth, 1992). The Great Lakes
Chemical Corporation (USA) and Kaljas Limited. (Australia) (Sehic, 1988),
have developed a series of reagents which can provide bromine for gold
dissolution (Pesic and Sergent, 1990; Pesic and Sergent, 1991).
3-2 GOLD MINERALS/ORE DEPOSITS
Gold is inert at ambient temperatures and pressures and consequently there are
very few naturally occun-ing compounds of the metal. The average
concentration of gold in the earth's crust is 0.005 git, which is much lower than
most other metals, for example, silver (0.07 g/t) and copper (50 git). In nature,
gold occurs predominantly as native metal or as ~ major constituent of various
alloys, primarily, silver, copper, or platinoid metals. Its other main occun-ence is
as gold-silver tellurides. However, it occurs in small amounts in a number of
silver minerals (tetrahedrite, tennanite, argentite, hessite etc.) and as a common
constituent of copper (an average of 0.3-0.9 git) and base-metal ores (an average
of 0.4-0.9 mg/1). Gold also occurs in lead-zinc-silver ores. Gold does not f01m a
separate sulphide mineral but is found in various types of ore deposits (primary,
39
secondary or metamorphic) mostly associated with quartz and sulphide minerals

which may be oxidized in surface deposits. Also, there are no common naturally
occurring gold oxides, silicates, carbonates or sulphates (Marsden and House,
1992).
Gold ores are broadly classified as primary hydrothermal or magmatic and as

secondary (placer). The hydrothermal deposits are generally divided into those
associated with volcanic or hot spring activity and those in metamorphic
(usually precambrian) rocks. Magmatic deposits are usually polymetallic in
nature. For metallurgical purposes gold ores are generally classified as placer
ores, free milling ores, oxidized ores and refractory ores. The type of ore ( the
exact mineralogy and occurrence of gold) is important in deciding suitable pre-
treatment and metallurgical process options. Each of these classes of gold-
bearing materials has special mineralogical characteristics which affect their
processmg.
Placer ores are alluvial, eluvial or colluvial deposits for which diagenetic
processes have occurred to a limited extent. Gold normally occurs as free
(particulate or loosely consolidated) gold alloyed with silver. These require no
milling (crushing and grinding) and are treated by washing, gravity
concentration and amalgamation. The amalgamation process is however, almost
obsolete now. Cyanide leaching, in fact, is not at all necessary for the treatment
of such ores.
Free milling ores are palaeo-placers (lithified conglomerates) or quartz vein gold
ores. The gold is unliberated and the ore is consolidated. The essential feature is
that the gold is relatively coarse and does not contain an excess of interfering
elements. Crushing and grinding is therefore required to liberate the gold to an
extent which allows efficient gold extraction. Cyanidation, in particular, can
extract approximately 95% of the gold when the ore is ground to a size of 80%
passing 75 µm, without incmTing prohibitively high reagent consumption.
Frequently, some of the gold is recovered by gravity concentration and
amalgamation and gangue mineral composition does not significantly affect the
processing requirements.
Oxidized ores are weathered (or oxidized) primary ore/deposit for which some
processing steps may be employed. Generally, the degree of gold liberation is
increased by oxidation resulting in increased permeability which often allows
40
high leaching extractions. However, in some cases protective coatings of

secondary and hydrated oxides (eg. iron oxides) on gold are commonly
encountered which are quite detrimental in leaching circuits ( they act as
cyanicides). Oxidized ores may also contain various copper minerals, many of
which dissolve in alkaline cyanide solution and may, depending on the
concentration, interfere with gold leaching and recovery processes (Baum,
1985). Clay minerals such as pyrophyllite (Al2Si4010(0H)i), talc
(Mg3Si4010(0H)i), kaolinite (Al4Si4010(0H)g) and montmorillonite
(A14Sig020(0H)4).nH20) are often abundant in oxidized ores and can have
important process implications (eg. in heap leaching and CIL/CIP circuits).
Carbonate minerals, calcite (CaC03), dolomite (Ca,Mg(C03)i) and siderite
(FeC03) are also more common in oxidized ores and affect pH control
especially in oxidative pretreatment processes.
Refractory ores almost always come from primary and secondary zones and
contain complex minerals in which the gold is principally unliberated and
occluded in their matrices. They interfere with amalgamation and leaching
processes in terms of process selection or operating conditions and require
pretreatment. In particular, they are not amenable to direct cyanidation without a
pretreatment (Seymour et al, 1989; Foo et al, 1989; Dry and Coatzee, 1986;
Beattie et al, 1988). These are classified as sulphidic, carbonaceous or telluride
ores. The important sulphide minerals are pyrite, marcasite, pyrrhotite,
arsenopyrite, chalcopyrite, chalcocite, stibnite, galena and sphalerite. In the
sulphidic ores, the gold may be free milling but the sulphides tend to decompose
cyanide. Pyrrhotite and marcasite consume cyanide (cyanicide) and oxygen in
cyanidation. Pyrite is usually only a problem in processing if it reduces gold
liberation and rarely a significant cyanicide. Fine gold occlusions in pyrite
require more extreme conditions to be liberated. Gold/stibnite associations are
rare, though stibnite can occur at sufficiently high concentrations in gold ores to
cause problems as a cyanicide.
Carbonaceous ores contain carbonaceous components (organic carbon or

graphite) which tend to "preg-rob" or re-adsorb the gold during leaching thereby
resulting in low recove1ies. Carbon content as little as 0.1 % may produce preg-
robbing properties (Osseo-Asare et al, 1984). These ores usually require
oxidative pretreatment prior to leaching.
41
Gold tellurides usually contain some native gold, together with gold and other
metal tellurides, often with complex intergrowths. They occur as calaverite
(AuTe2), krennerite ((Au,Ag)Te2), petzite (Ag3AuTe2), muthmannite
((Ag,Au)Te), sylvanite ((Au,Ag)Te4), nagyagite ((Pb5Au(Te,Sb)4S 5_g),
kostovite (AuCuTe4) and montbrayite ((Au,Sb)Te3) and are the only gold
minerals other than metallic gold and Au-Ag which are of economic significance
(Boyle, 1979). Ores containing gold tellurides have unique, and generally poorly
optimised, processing requirements. Gold tellurides, with or without silver,
dissolve extremely slowly in cyanide solutions and usually require an oxidation
stage to obtain commercially viable extractions. The presence of clay minerals
such as pyrophyllite in gold ores also produce refractory properties (Marsden
and House, 1992). They are capable of absorbing gold complexes.
Another group of gold ores which are of metallurgical importance are those with
high silver content. Although, gold is almost always associated with silver,
when the silver grade is high (> 10 git) and/or the gold is present as electrum
(silver-rich ores) the processing may need to be modified. The greater reactivity
of silver particularly influences the behaviour of gold in flotation, leaching
and/or recovery processes. Gravity and cyanide methods do not generally
remove all of the silver from such ores (Boyle, 1979; Marsden and House,
1992).
3-3 EXTRACTION/LEACHING OF GOLD
Gold metallurgy covers many facets including leaching and recovery. In the
context of gold extraction, leaching is the dissolution of the metal or mineral in
aqueous solution which requires both a complexant and an oxidant to achieve
acceptable leaching rates. Only a limited number of ligands form complexes of
sufficient stability for use in gold extraction processes, some of which are
shown in table (2-3.1 ). Figure (3-3.1) is a schematic gold extraction/recovery
process flowsheet showing in essence the important metallurgical units of gold
processing.
42
Grinding and Gravity

Crushing Separation
gold cone.
Flotation
- roasting
Pre-treannent - chemical oxidation
,....__----.-_ __. - bio-oxidation
- Cyanidation
- Non-cyanidation
~=;;;;;;;;;;;;.==.;:;;,I
Solid/Liquid
Separation
- carbon adsorption/electrowinning
- zinc precipitation-Merril Crowe
Gold
Figure (3-3.1) A schematic gold recovery process flowsheet.
3-3-1 Cyanidation
Cyanidation since its invention about 100 years ago, has been the standard
method for gold and silver extraction. It involves the dissolution of gold by
alkaline cyanide solution in the presence of oxygen (as an oxidant). The cyanide
most commonly used is sodium cyanide due to its greater dissolving power and
lower cost. Oxygen is introduced as air. In the conventional mode of cyanide
leaching, the gold ore is first crushed and finely ground. It is subsequently
subjected to long hours (for up to 24 hours) of leaching with the alkali cyanide
solution. This is effected in a number of ways which are all variations of
percolation or agitation leaching (Stewart, 1984; Marsden and House, 1992).
Percolation leaching takes place in vats, heaps and dumps, in which the
comminuted ore is placed in vats or on an impervious base such as clay or
polyurethane ( eg. heap leaching) and cyanide solution is percolated upwards or
downwards through the bed until the effluent reaches an economically high
enough value. It is essential that the charge is sufficiently permeable for the
solution to percolate evenly and must not be too fine or contain clay.
43
Conventional agitation leaching of a pulp is the more common method in which

a pulp consisting of a suspension of cyanide solution and suitably ground ore is
mechanically agitated with air passed through for a predetermined period. This
is done in mechanical or air agitated pachucas and may be done on a continuous
basis.
The mechanism of gold dissolution by CN-/atmospheric 02 which has been

discussed by many researchers (Kudryk and Kellogg, 1954; Cathro, 1963;
Cathro and Koch, 1964; Habashi, 1966; Nicol, 1980), involves simultaneous
anodic dissolution of gold via passivating films and oxygen reduction. The
reaction scheme (Muir, 1987) is illustrated as:
CN-
Anodic: Au + CN- =[AuCNlacts---Au(CNh-+e- (3-3.1)
Au+OH
- ow
= [AuOHlacts---Au(OHh+3e- (3-3.2)
or
Cathodic: (3-3.3)
Thus, the dissolution of gold in cyanide solution is essentially an

electrochemical corrosion process in which anodic and cathodic zones are
formed on the gold surface.
The overall reaction as proposed by Elsner (Elsner, 1846) is:
(3-3.4)
with a free energy change of -376 kl/mole. Bodlander (Bodlander, 1896)

suggested that the dissolution of gold proceeds in two steps as follows:
(3-3.5)
and
(3-3.6)
where hydrogen peroxide is formed as an intermediate product.

44
According to Christy (Chiisty, 1900), at least 0.001 % CN- is required for any
gold dissolution to occur. Habashi (Habashi, 1970) reported that the rate of gold
dissolution increases linearly with increasing cyanide concentration until a
maximum is reached, beyond which a further increase in cyanide concentration
does not increase the amount dissolved, but, on the contrary, has a slight
retarding effect. The decrease in rate at high cyanide concentration is due to the
increase in the pH of the solution via hydrolysis of the cyanide ion:
(3-3.7)
Kudryk and Kellogg (Kudryk and Kellogg, 1954) also reported (or proposed)
that, the dissolution of gold is controlled by the diffusion of dissolved oxygen
and the cyanide ion species through a diffusion boundary layer. At low cyanide
concentration (0.01 % or 0.004M CN-), the dissolution rate is dependent on the
cyanide concentration (increasing linearly with cyanide concentration). At a
mole ratio of cyanide to oxygen greater than 10, the dissolution of gold is
dependent on the diffusion rate of oxygen and not that of cyanide ions. In
addition, the solubility of oxygen decreases as cyanide concentration increases,
meaning less available oxygen for the leaching reaction (Law, 1982). Thus, in
the presence of excess free cyanide, increasing dissolved oxygen concentration
increases the rate of dissolution. However, higher dissolved oxygen
concentrations (>20 mg/litre), may cause passivation of the gold surface due to
oxide layer formation (Cathro and Walkley, 1961; Cathro, 1963).
Therefore, the dissolution rate of gold in cyanide solution will be directly

proportional to agitation and temperature. Increased intensity of agitation will
increase the rates of reactions, but will not change the ratio [CN-him/[O2J1im at
which agitation the change over from control by cyanide to control by oxygen
diffusion takes place. This is also limited to a maximum, above which agitation
has little or no further benefit and may cause passivation of the gold surface
(Cathro, 1963). Increase in temperature also improves the gold dissolution rate
as a result of increased activities and diffusion rates of reacting species.
However, due to lower oxygen solubility at higher temperatures, a temperature
of the order of 85°C is considered optimum (Caruso, 197 5; Gupta and
Mukherjee, 1990). The dissolution rate is also affected by the efficiency of the
comminution processes preceding leaching. In general, the rate increases with
decreasing particle size due to an increase in gold liberation and/or surface area
of gold particles (Marsden and House, 1992). Typically, cyanide leaching is
45
performed at pH values above pH:9.40 to prevent excessive loss of cyanide by

hydrolysis according to equation (3-3.7) and decomposition by Co 2 in the
atmosphere according to:
(3-3.8)
HCN has a relatively high vapour pressure of 100 kPa at 26°C (Huiatt et al,
1983). When the pH is reduced to below pH:9.40, the equilibrium between CN-
and HCN favours the formation of gaseous HCN. This (pH> 9.40) is achieved
by the addition of lime or caustic soda to the slurry during leaching to maintain
a protective alkalinity of pH:10.00 to 11.00. A too high pH value is also
detrimental because the rate of dissolution falls sharply due to increase in the
rate of interfering reactions such as the dissolution of sulphides, antimony and
arsenic-bearing materials.
The successful extraction of gold by cyanidation is often dependent not only on

its behaviour but also on the response of the associated minerals (foreign
constituents) to the cyanide solution. The presence of trace amounts of lead,
mercury, thallium and bismuth has significant effect on the dissolution rate.
According to Kameda (Kameda, 1949), the presence of lead in very small
amounts accelerates the dissolution process. Nicol (Nicol, 1980), also reported
that mercury and lead reduce the passivation effect (ie. disrupts [AuCN] film)
and increase the dissolution rate. Thallium was also found to decrease the
passivity of gold and hence accelerate the dissolution rate spectacularly (Cathro
and Koch, 1964). Many other metals and minerals besides gold also dissolve in
the dilute cyanide solutions. These reactions tend to consume cyanide and
oxygen, as well as producing a variety of solution species which retard gold
dissolution rate, interfere with subsequent recovery processes and contaminate
the final product. The presence of metallic cations like Fe 2+, fe3+, Cu 2+, Ni 2+,
Mn 2+, zn2+, Ca2+, Ba2+ retard the dissolution process (Beyers, 1936; Kameda,
1949). These cations principally form stable complexes with cyanide, thereby
lowering the activity of cyanide in the solution.
Also, sulphides (copper sulphides and some arsemc and antimony-bearing

minerals) which are associated with primary gold ores decompose quite readily
in aerated alkaline cyanide solution to form metal ions, metal oxides or metal
cyanide complexes and various sulphur containing species including
thiocyanate, sulphide, thiosulphate and polythionate ions. Pyrite (FeS2),
46
marcasite (FeS2), pyrrhotite (FeS), chalcolpyrite (CuFeS2), chalcocite (Cu2S),

galena (PbS), arsenopyrite (FeAsS), sphalerite (ZnS), stibnite (Sb2S3) are the
common sulphide constituents of gold ores. They decompose to some extent in
aerated alkaline cyanide solutions which results in high cyanide and/or dissolved
oxygen consumption. Pyrrhotite and marcasite are the most reactive of the iron
sulphides in alkaline cyanide and consume both cyanide and dissolved oxygen.
Pyrrhotite readily gives up part of the sulphur content (which is loosely bound)
in cyanide and react to form iron(II) cyanide and the various aqueous sulphur
species (thiocyanate, thiosulphate and polythionates) (Marsden and House,
1992) according to equations:
(3-3.9)
and
(3-3. 10)
Thiosulphate and polythionates react slowly with cyanide in the presence of

dissolved oxygen to form thiocyanate;
(3-3.11)
and therefore consume both cyanide and oxygen. Thiocyanate has been recorded
variously as being inert towards, an inhibitor and an accelerator of the
cyanidation of gold (Kameda, 1949; Habashi, 1967). Pyrite usually causes
relatively a less significant effect but catalyses the oxygen reduction step and
may cause gold passivation (Muir, 1989; Marsden and House, 1992). The
copper minerals (eg., chalcocite and chalcopyrite) generally represent more of a
problem in cyanidation than do the corresponding iron minerals. Contents as
little as 0.10% Cu in the ore form a variety of extremely stable soluble Cu(I)
complexes in cyanide solution and in turn have adverse effect on the dissolution
and precipitation. The quantities of cyanide and oxygen consumed are
correspondingly high (Finkelstein, 1972). However, chalcopyrite is the least
objectionable of the copper minerals. Under the conditions applied for gold
leaching in cyanide solutions, the arsenic sulphides (eg., arsenopyrite) and the
antimony sulphides (eg., stibnite), also contribute to excess consumption of
leach solution. They form vanous arsenites/arsenates and
antimonites/antimonates in alkaline cyanide solution, which consume oxygen
47
from solution. Sulphide, thioamonite and thioarsenite ions are frequently formed
as intermediate products and inhibit cyanidation due to their action at the gold
surface (Finkelstein, 1972). Sulphide ions adsorb strongly at the surface of gold
and the adsorption density increases, the gold surface is rendered passive which
significantly retards the gold dissolution rate. Sulphide ion concentrations of
about 0.05 mg/litre have been shown to produce an observable decrease in the
rate of gold dissolution (Fink and Putnam, 1950).
Many metal oxides, carbonates, sulphates and other compounds are also soluble
in alkaline cyanide solutions, with the solubility dependent on specific solution
conditions. These minerals generally consume smaller quantities of cyanide and
oxygen than sulphides but the species formed may affect precipitation reactions
and overall process efficiency. In some cases, metal oxide minerals such as iron
oxides form protective coatings on gold which are virtually insoluble in alkaline
cyanide solutions and inhibit gold cyanidation (Marsden and House, 1992).
A number of naturally occurring carbonaceous materials also reduce gold

extraction (low/poor recoveries) during cyanide leaching by adsorbing (preg-
robbing) dissolved gold from the leach solution (Urban et al, 1973; Hausen and
Bucknam, 1985). There have been only a few reported attempts to characterise
the carbonaceous matter (Radtke and Scheiner, 1970; Zaitseva et al, 1973;
Afenya, 1976; Zumberge and Sigleo, 1978; Nelson et al, 1982). The available
information suggests that carbonaceous matter consists of a predominantly
elemental carbon component which behaves like activated charcoal and
therefore adsorbs gold from solutions, heavy hydrocarbons which do not interact
with gold and organic acids (akin to humic acids), which are capable of forming
strong chemical bonds or complexes (chelates) with dissolved gold. Radtke and
Scheiner (Radtke and Scheiner, 1970) reported the ability of surface coatings of
organic compounds to modify the gold uptake of carbonaceous ores and
concluded that the hydrocarbon fraction is present in the natural material as a
film around the activated carbon fraction resulting in poorer gold extraction by
conventional cyanidation.
Tellurium does not form stable complexes with cyanide and therefore gold-
tellurium minerals (Aux Tey) dissolve slowly in alkaline cyanide solution.
Leaching rates vary for the different minerals, with leaching time requirements
in excess of 14 days in some cases (depending on particle size) (Cornwall and
Hisshion, 1976; Jackman and Sarbutt, I 990).
48
Flotation reagents and other surface reagents also inhibit cyanidation. Thiol
collectors (eg. xanthates and dithiophosphates) are poisons of the cyanidation
reaction and are as powerful as the sulphide ions. Xanthates adsorb at gold
surfaces and render the surface passive to cyanidation (Plaksin and Bessonov,
1948; Kameda, 1949; Barbin, 1963; Ashurst and Finkelstein, 1970). At high
concentrations (order of 10- 2 M), ketones, ethers and alcohols compete with
oxygen for sites at the gold surface in cyanide solutions and retard the
dissolution rate (Barbin, 1963).
The use of cyanide as a leachant is acceptable therefore providing there is not a

rapid consumption of oxygen in the leach, the consumption of cyanide is within
economic constrainsts and the gold is physically accessible to the leachant.
Consequently, such materials or gold ores termed "refractory" are successfully
treated for gold recovery by using a modified cyanide leaching technique or by
carrying out a pre-treatment of the ore prior to its conventional cyanide
leaching. Recent studies by several workers reveal a range of assessments of
different alternatives available for the pre-treatment (Berezowsky and Weir,
1983; Jha and Kramer, 1987; Kontopoulos and Stefanakis, 1989). Several
factors have to been taken into account including costs and environmental
constraints which have dominant influence on process selection. The central
objective of the pre-treatment process is to liberate gold particles from the
refractory materials, to prevent adsorption or to destroy it entirely. This is
usually accomplished by oxidative processes (hydrometallurgical and
pyrometallurgical). The options (thermal or chemical/autoclave/biological)
within these processes are summarised in table (3-3.1). Pyrometallurgical
oxidation of sulphidic and carbonaceous ores by roasting has been practised
around the world for decades and is thoroughly proven. However, increasingly
stringent roaster emissions control legislature for environmental protection
worldwide has increased the complexity and cost of roasting processes.
Hydromet.allurgical met.hods, other than simple pre-aeration techniques have
been developed during the past 25 years and these present attractive alternatives
to roasting for many refractory ores and concentrates (Marsden and House,
1992).
Neve1theless, the cyanidation process has been widely pract.iced and its long
acceptance as the overwhelming option for gold processing is in view of its
relative economy and technological simplicity. However, a major concern is the
slow kinetics of the dissolution of gold.
49
Table (3-3.1) Summary of oxidative pre-treatment processes (Marsden

and House, 1992).
Process type Oxidation method Ore types treated
Hydrometallurgical Low- pressure oxygen Mildly refractory - contain

(per-aeration) small quantities of reactive
sulphides(eg. pyrrhotite and
marcasite).
High-pressure oxygen Refractory sulphidic and

(acidic media) arsenical ores - low
carbonate, high sulphur
High-pressure oxygen Refractory sulphidic and

(non-acidic) arsenical ores - low sulphur,
high carbonate.
Chlorine, Nitric acid Carbonaceous ores

(chemical) Refractory sulphidic- low
sulphur telluride ores and
refractory sulphidic ores.
Biological Refractory arsenical and

sulphidic ores. Gold
preferably associated with
arsenopyrite, marcasite.
Pyrometallurgical Roasting Refractory sulphidic,

(thermal) arsenical, carbonaceous and
telluride ores.
Theoretical consideration indicates that this disadvantage cannot be overcome

without a considerable increase in the consumption of reagents and operating
costs. Another major concern involving the cyanidation process is the health and
environment problems associated with it. Cyanide and its complexes are very
50
toxic. Hydrogen cyanide and simple salts such as sodium, calcium, and
ammonium cyanide dissociate readily to release CN- ion. This group of cyanide
compounds are among the most rapidly acting poisons known. Thus, slightly
elevated changes (increases) in atmospheric concentrations or amounts of
exposure dermally or orally may cause or contribute to instantaneous collapse,
cessation of respiration and/or death. Also, cyanide readily interacts with a
number of biologically active metal ions such as Fe3+ which results in the
inhibition of the enzymatic activity of cytochrome oxidase. Cytochrome oxidase
is the key enzyme in a cell's ability to utilize molecular oxygen. Inhibition of
this proces rapidly leads to loss of cellular functions and then cell death. If the
concentration of cyanide ion is not great enough to cause death, thiocyanate ions
(SCN-) are formed later and at chronically high enough levels in the blood can
inhibit the uptake of iodine by the thyroid gland (Hartung, 1982). The
cyanidation process therefore lends itself to severe environmental restrictions on
the use of cyanide in most places. Stringent environmental guidelines must be
observed requiring careful monitoring and control of process purge streams.
Spent cyanide effluent must be degraded before being discharged to the
environment.
3-3-2 Non-cyanidation methods
There has been considerable interest m the development of non-cyanide

lixiviants for gold leaching during the last decade for a variety of reasons such
as faster rates of leaching, lower toxicity and application to the more refractory
ores. Thiourea, thiosulphate, thiocyanate and the halides have shown exciting
prospects and various processes have been described or developed for use of
these lixiviants for gold processing. Recent reviews indicate that although these
lixiviants/processes are not widely practised at present, interest still remains
high as they offer several advantages over conventional cyanidation (Von
Michaelis, 1987; Hiskey and Atluri, 1988).
3-3-2-1 Thiourea
The use of acidified thiourea to leach gold and silver was initially reported by
Plaksin and Kozhukhova in 1941 (Plaksin and Kozhukhova, 1941) and by
Preisler and Berger in 1947 (Preisler and Berger, 1947) and has received
51
significant attention since 1960 as a potential substitute for cyanide leaching

solution. Several reviews describe the different aspects of gold dissolution with
acidified thiourea (Plak:sin and Kozhukhova, 1960; Tartaru, 1968; Pachenko et
al, 1975; Groenwald, 1976; Groenwald, 1977; Chen et al, 1980; Pyper and
Hendrix, 1981; Hiskey, 1981; Schulze, 1984; Gabra, 1984; Filmer et al, 1984;
Hilston et al, 1984; Moussoulos et al, 1984; Sandberg and Huiatt, 1986;
Deschenes and Ghali, 1988). The strong interest in this leaching system is
attributed to its lower toxicity, greater dissolution rate compared to cyanide and
less sensitivity to cyanicides such as Cu, As, Sb, Pb and other impurities in gold
ores.
Thiourea, CS(NH2h, is an organic compound which dissolves readily in acidic

solution in a stable molecular form. Gold is oxidized and complexed in dilute
acid solution of thiourea according to the reaction:
(3-3.12)
The reduction potential for this reaction is E0 = 0.38 V and the gold exists as the
bis(thiourea) gold(I) complex cation. The process generally requires an
oxidizing agent such as fen-ic ion, hydrogen peroxide, manganese dioxide,
ozone or potassium permanganate (Woodcock, 1987). Among these oxidants,
fen-ic ion is the most effective and produces the fastest initial rate (Groenwald,
1976; Chen et al, 1980; Gabra, 1984). In the presence of ferric ion as an
oxidant, the overall equation for the dissolution reaction is:
2Au + 4CS(NH2h + 2Fe 3+ = 2Au[CS(NH2h] 2+ + 2Fe 2+ (3-3.13)
The leach rate depends on pH, and thiourea and oxidant concentrations. In use
thiourea decomposes to formamidine disulphide as follows (Hiskey, 1984 ):
(3-3.14)
In view of this, formamidine disulphide is considered the active oxidant (rather

than Fe(ID)) for the dissolution of gold in thiourea solutions (Hiskey and Atluri,
1988). Thus:
2Au + 2CS(NH2h + NH2(NH)CSSC(NH)NH2 + 2H+

= 2Au[CS(NH2h] 2+ (3-3.15)
52
However, formamidine disulphide disproportionates ineversibly to thiourea and

sulphinic acid or a compound which further decomposes (also ineversibly) to
elemental sulphur and cyanamide, CN(NH2), according to the overall reaction:
NH2(NH)CSSC(NH)NH2 = CS(NH2h + S + CN(NH2) (3-3.16)
In an acidic medium, cyanamide undergoes hydrolysis to form urea. Sulphur

reduces the leaching of soluble gold by poisoning the gold surface. These
iITeversible reactions consume thiourea (via formamidine disulphide) and are
responsible for the high thiourea consumptions that are typically experienced in
a thiourea leaching system. For this reason, close control of solution potential is
required through all stages of leaching to control the formation of formamidine
disulphide. In a practical sense, the addition of minor amounts of sulphur
dioxide, S02, in the form of sodium bisulphite (Na2S205) to the leaching
system stabilizes thiourea and is an important control measure to reduce
thiourea consumption. This partially reverses (or inhibits) the thiourea oxidation
reaction (3-3 .14) before the formamidine disulphide is oxidised further to
elemental sulphur(Hiskey, 1984; Schulze, 1984) according to:
[(NH2)2CSSC(NH2)i] 2+ + S02 + 2H20

= 2CS(NH2h + S04 2- + 4H+ (3-3.17)
Further reduction in thiourea consumption is obtained with a combination of

high temperature (eg. 313K) and low reagent concentration (Caldeira and
Ciminelli, 1993).
Thiourea leaching is carried out at a pH of 1.40-1.50 (Raudsepp and Allgood,

1987; Marchant et al, 1988). A trend towards a decrease in gold extraction with
increase in pH above this pH was found by many researchers (Gabra, 1984;
Hilston et al, 1984; Deschenes and Ghali, 1988). Consumptions of thiourea due
to hydrolysis or dissociation of formamidine disulphide also increase at high pH
as follows (Filmer et al, 1984; Marsden and House, 1992):
(3-3.18)
CS(NH2h = NH4+ + SCN- (Dissociation) (3-3.19)

53
Bilston, La Brooy and Woodcock (Bilston et al, 1984) also observed higher
thiourea consumption at lower pH (<l) and attributed this to the fact that the
hydrolysis of thiourea to urea is catalysed by the hydrogen ion. The reaction
may be represented as:
(3-3.20)
The dissolution rate of gold in thiourea is generally very rapid (much faster than
in cyanide) and extractions of about 95% to 99% can be achieved in two hours
(Finkelstein, 1972). The rate is usually controlled by diffusion of reactants to
the gold surface and is consequently related to the concentrations of Fe(ill),
formamidine disulphide and thiourea species. Optimum kinetics are achieved
when approximately half the thiourea present in the solution is converted to
formamidine disulphide (Marsden and House, 1992).
At the present time, the major drawback of the method appears to be the high
cost of reagents, stemming principally from the instability of thiourea under the
conditions of leaching (Finkelstein, 1972). Thiourea is more expensive than
cyanide. Advantages in the rate of gold dissolution in thiourea solutions must be
weighed against possible high reagent consumption. Nevertheless, interest in the
thiourea system has remained high and it is likely, the technique will remain
restricted to very few situations and to ores/concentrates with sufficient value to
justify the costs of the reagent. The gold thiourea complex is cationic and as
such is more susceptible than anionic species to adsorption on clays. The
adsorption is minimised by operating under acidic conditions but for some
orebodies can substantially reduce the dissolution of gold (Filmer et al, 1984 ).
Eisele (Eisele, 1989) compared gold and silver extractions from fourteen
different ore samples, some containing sulphides, with thiourea and cyanide
leaching, and concluded that if most ores cannot be treated with cyanide they
will not be leached better with thiourea. The lixiviant therefore is applicable to
special cases as reported by Hisshion and Waller (Hisshion and Waller, 1984)
for an antimony ore, and by Zegan-a, Huyhua and Gundiler (Zegan-a et al, 1989)
for manganiferous ores. In these cases the ores are not amenable to cyanidation.
Several studies have also reported that activated carbon, solvent extraction, ion
exchange, hydrogen reduction and electrolysis can be used to recover gold from
thiourea solutions (Zegan-a et al, 1989; Deschenes et al, 1989; Dupius and
Ghali, 1989). Competitive adsorption of other cationic species may limit the
54
resin loadings and activated carbon adsorbs both thiourea and soluble gold
(Filmer et al, 1984). Gold could also be recovered by precipitation with S02 or
by cementation onto aluminium, lead, iron powders or steel wool (Hiskey, 1984;
La Brooy, 1989). Invariably, the downstream recovery of gold from cyanide
solutions appears to be much better characterised and probably simpler than that
for thiourea.
3-3-2-2 Halides
The use of halide/halogen systems for extracting gold has been explored over
the past 100 years as an alternative to cyanidation. The complexation of gold by
halide has long been recognised where Au(I) complex exists for iodide and
Au(ill) complexes exist for bromide and chloride. These systems are strongly
oxidizing and dissolution rates are typically several orders of magnitude faster
than those achieved with cyanide and oxygen under ambient conditions (Hiskey
and Atluri, 1988).
3-3-2-2-1 Chloride leaching
This is commonly known as the Plattner or theis process (Habashi, 1970), and
was applied extensively in the 1800's, prior to the introduction of cyanidation,
for the treatment of ores containing fine gold and occurring with sulphides,
which were not amenable to gravity concentration and amalgamation. Chloride
media have also been applied in electro-plating processes since the early 19th
century and for the oxidative pre-treatment of some carbonaceous refractory
ores. Although, chlorine/chloride is no longer used for leaching of primary ores,
and only limited to refining processes, several processes have been proposed for
the treatment of refractory or semi-refractory ores as an alternative to cyanide
(Marsden and House, 1992). More recently, chloride/chlorine (or hypochlorite)
system has been suggested by Fagan (Fagan, 1992), in an in-situ leaching
system for recovering gold from oxide gold ores as an answer to the major
operational difficulties faced with cyanide for such a hydrometallurgical
extraction process.
Gold will dissolve in the presence of chloride ion and a strong oxidant when the
solution is highly acidic (< pH:4.00). Dissolved chlorine, hypochlorous acid and
55
hypochlorite ion are all capable of oxidizing gold in chloride media (Hiskey and
Atluri, 1988). Nitric acid is also a sufficiently strong oxidant to dissolve gold in
chloride media, and this is applied as aqua regia (a mixture of 33% HNO 3 and
66% HCI) in a well-established technique for gold analysis. Fundamental
studies have shown that although the gold-chloro complex is more stable as
AuCl4-, gold can also exist as AuCl2-, especially at high chloride concentrations
( > 0.10 M Cl-). Thus:
(3-3.21)
AuCl4- + 3e- = Au + 4Cl- E0 =0.994 V (3-3.22)
These equilibria are well established by Eh - pH diagrams for Au-Cl-H2O

system prepared and reported in the literature (Hiskey and Atluri, 1988;
Marsden and House, 1992). Several mechanisms have been proposed for the
formation of these species in gold dissolution in aqueous chloride solutions. The
most likely theory suggests that AuCl2-, is formed as a secondary intermediate,
which then is either oxidized further to Au(ill), or diffuses into solution as
AuCl2-, depending on the oxidizing potential of the solution (Nicol, 1980).
Increasing the chloride concentration forces the Au/AuCl4- equilibria to lower
potentials. At about 0.10 M Cl-, the chloride activity for these conditions is
sufficient enough to establish the AuCl2- complex. At solution potentials above
approximately 1.40 V the gold surlace becomes passivated with an oxide layer.
At ambient temperatures, the dissolution of gold in chloride solutions is

favoured at low pH (Putnam, 1944) and the dissolution rate is proportional to
the chloride ion concentration (Finkelstein, 1972; Nicol, 1980(1) ). In practice,
the mass transport of chloride ions to the gold surlace is the rate-determining
step and the chemical reaction rate is fast. Chloride ion mass transport rates are
maximized by high chlmine/chloride concentrations and by increased
temperatures. The rate of dissolution of gold in aqueous chlmide solutions is
much faster (about two orders of magnitude) than its rate of dissolution in
aqueous alkaline cyanide solutions (Putnam, 1944; Tran et al, 1992). In
addition, the chloride media provides a promising prospects for various gold
extraction applications and as a potential alternative to cyanidation.
Carbonaceous ores are more amenable to chlorination. Its application
deactivates gold-adsorbing organic carbon which occurs naturally in these ores.
Carbonates and other acid-soluble minerals dissolve to varying extents in acidic
56
chlorine/chloride media. The decomposition of these minerals may enhance gold

extraction by exposing locked gold. The leaching system is also potentially
attractive for the treatment of some copper-gold ores. Chloro-complexes of
copper (as well as zinc and most of the other transition metal series) are less
stable than gold(ill) chloride. Thus, for a particular ore, less copper will be
dissolved in chloride media than in cyanide media. Also, for completely
oxidized gold ores, the chloride media possesses a clear advantage over
cyanidation for applications where a high dissolution rate is required. The
leaching system is also significantly useful for extracting coarse gold. In
particular, the chloride leaching system is applied at Emperor (Fiji) for the
recovery of gold and tellurium from an ore that is not amenable to direct cyanide
leaching (Marsden and House, 1992).
However, the principal restriction of the chlorine-chloride systems is the high

reagent consumption in the presence of oxidizable materials in the ore or leach.
Pyrite and other sulphides commonly associated with gold are readily oxidized
by aqueous chlorine, and cause excessive chlorine consumption (Filmer et al,
1984; Marsden and House, 1992). For example:
2FeS2 + 15HOC1 + 7H2O = 2Fe(OH)3 + 23H+ +4SO4 2- + 15Cl- (3-3.23)
An ore containing 1% sulphide as pyrite will consume 82 kg chlorine/tonne ore,

if the pyrite is completely oxidized (Marsden and House, 1992). At a level of
sulphur in the orebody the cost of chlorination will obviously exceed that of
cyanidation and hence chlorination will become unattractive. In practice, ores
and concentrates with higher sulphide content may need to be pre-treated by one
of the alternative options ( eg., pre-aeration, pressure oxidation or roasting). The
highly oxidizing character of the system creates a corrosion problem and
requires special materials of construction (eg., stainless steels and rubber-lined
equipment). Considerable importance attaches to the behaviour of silver and
lead contents of the ore which react to form insoluble chlorides in
chlorine/chloride solutions. These insoluble products can reduce the solubility
of gold due to the formation of an insoluble passivating layer and in the case of
silver results in loss of metal recovery. Thus, the system may be seriously
jeopardised when the combined silver-lead content of gold exceeds
approximately 13% (Nicol, 1980). The chlorine vapour phase could also
become a problem in open systems contributing to reagent losses and health
risk. Chlorine gas must therefore be contained to allow optimum utilisation of
57
the gas. As a result, chlmine leaching is usually restricted to agitated or

intensive agitated systems where closed tanks can be used in closely controlled
environment. The process is also carried out at a pH of 2.0 to 2.5 to achieve
both fast gold dissolution and a low vapour pressure. Chlorine gas absorption
rate is maximised by decreasing pH but the solution becomes increasingly
difficult to handle as pH decreases. In general, chlorine/chloride leaching is
more difficult to apply commercially than cyanide leaching.
Nevertheless, in the chloride system, the chloride complex of gold is much

weaker than either the cyanide or thiourea complexes. The gold is therefore
readily precipitated from the resulting pregnant solution by reducing with
hydrogen sulphide, sulphur dioxide, ferrous sulphate or by carbon adsorption.
3-3-2-2-2 Bromide leaching
The use of bromine/bromide for leaching gold from ores was first documented
by Shaeffer in a 1882 patent (Shaeffer, 1882). It was demonstrated that, ores
which contained gold, silver and copper can be successfully treated with
brominated aqueous solutions, after pre-treatment by roasting. Subsequent
patents by Hinman (Hinman, 1895) and Cassel (Cassel, 1903) described
processes for the application and regeneration of bromine which improved
Shaeffer's process. The next important development occurred in the 1940's when
Fink and Putnam (Fink and Putnam, 1942) in a patent, re-evaluated the effect of
various background solutions on the dissolution of gold using bromine. Bahl and
Leach in two patents (Bahl and Leach, 1980; Bahl and Leach, 1983 ), used a
mixture of bromide ions and elemental bromine to recover gold from gold-plated
materials.
The extraction of gold in bromide solutions has attracted much interest in

Australia and the U.S.A. recently and over the past five years several bromine
systems have been evaluated (Sehic, 1988; Dadgar, 1989; Dadgar and Howarth,
1992; Pesic, 1992). In the U.S.A., the Great Lakes Chemical Corporation,
patented its process in 1987, which uses a proprietary dibromo-dimethyl-
hydantoin (Geobrom 3400) (Pesic and Sergent, 1990) or a mixture of
bromate/bromide compounds (Pesic, 1992) for leaching gold from various
sources. In the same period, the Kaljas Limited in Australia also patented the K-
Process which used a mixture of bromine-caustic to dissolve gold (Sehic, 1988).
58
The dissolution of gold in a bromide solution is an electrochemical process as

described by the reaction (3-3.24).
Au + 4Br = AuBq- + 3e- E 0 =0.87 V (3-3.24)
The dissolution of gold in a bromide solution will be affected by many factors

such as a bromide and gold concentrations, pH and the electrochemical
potentials of the anodic and cathodic processes. An Eh - pH analysis of the Au-
Br-H20 system (figures (2-3.2) and (2-3.3)) emphasises the AuBq- equilibria
and the increased stability of AuBq- complex with increase in bromide
concentration. The Eh - pH diagrams also establishes that AuBq- is stabilised at
25°C in the range of E0 = 0.8-1.0 V and pH of 2.0-10.0 (Dadgar, 1989).
The most suitable oxidants for bromide leaching are bromine, chlorine and
hypochlorite. In the presence of bromine, the reaction can be represented as
(Marsden and House, 1992):
E0=0.95 V (3-3.25)
However, bromine demonstrates the existence of tribromide ions in reaction

with bromide according to the equation (2-1.17). Consequently, Br3- (i.e. as Br-
+ Br2 = Br3-) can serve as the active oxidant for gold leaching in bromide
solution in the presence of bromine (Hiskey and Atluri, 1988). The anodic half-
cell by combining equation (3-3.25) with Br3- can be represented as follows:
(3-3.26)
Other reactions have also been described for the dissolution of gold m
bromine/bromide solutions, based on the reaction chemistry of bromine with
gold and aqueous bromide (Dadgar, 1989; Pesic and Sergent, 1991 ). For
example:
(a) i. 3Br2 + 3H20 = 3HOBr + 3HBr (3-3.27)

ii. 2Au + 3HOBr + 5Br + 3H+ = 2AuBq- + 3H20 (3-3.28)
(b) i. 2Au + 3Br2 = 2AuBr3 (3-3.29)

ii. AuBr3 + Br- = AuBr4- (3-3.30)
59
In practice, bromide leaches gold at acid, neutral or slightly alkaline pH. Gold
dissolution rate decreases linearly with pH increase in the range 7.00-9.50, and
there is no good dissolution above pH:10.0. Below pH:6.0, the gold dissolution
is insensitive to pH (Pesic and Sergent, 1990; Pesic and Sergent, 1991). The
gold dissolution in the bromine/bromide solution is also a function of
bromine/bromide concentration and temperature. Increasing bromine/bromide
concentration generally increased the rate of gold dissolution. For fixed bromine
reagent (eg., Geobrom 3400) concentration, gold dissolution improved as the
bromide concentration increased up to a value (between 5-20 gn, depending on
the type of ore) above which, bromide did not appear to be beneficial (Sergent et
al, 1988; Pesic et al, 1992). Temperature is not a critically important parameter
for dissolution of gold in bromine/bromide solutions. However, increasing
temperature increased gold dissolution under acidic conditions and certain
potential commercial applications would be favourable at high temperatures
(40°C - 50°C) (Pesic and Sergent, 1991; Pesic et al, 1992).
The use of bromine/bromide to extract gold offers a significant increase in the

extraction rate than other lixiviants, especially with gold concentrates.
Typically, the gold dissolutions are achieved within 4 - 6 hours of leaching time
(Dadgar, 1989). Pesic and Sergent (Pesic and Sergent, 1991) also showed that,
bromine/bromide dissolves gold about 21 times faster than cyanide/air and about
10 times faster than thiourea. In general, the bromine/bromide leaching system
besides fast kinetics, has the additional advantages of simplicity, easily
controlled leach chemistry, high extraction efficiency, adaptability to a wide
range of pH values (Sergent, 1988, Sergent et al, 1988, Dadgar, 1989; Pesic and
Sergent, 1990; Pesic and Sergent, 1991). In addition, bromine can easily be
regenerated electrochemically from solution with the potential for simultaneous
recovery of gold (Dadgar et al, 1990; Hiskey and Qi, 1990; Howaith et al,
1991). Furthermore, due to the applicability of the bromine/bromide leaching
system in the acid pH region, the reagents can be added directly into the
discharged pulp after pre-treatment without the need for prior solution
neutralisation of the acid. The system has also been shown to be effective for
both ore and scrap recovery and more applicable to ores which contain high
levels of cyanicides such as copper and iron (A vraamides, 1982; Sergent et al,
1988). The development of the K-Process by Kaljas Limited has been promoted
as having high selectivity for gold from metallic copper substrates or gold ores
containing copper (Sehic, 1988; Muir et al, 1989). Gold extraction and
recoveries from refractory concentrates (containing carbon (10-13 % ) and
60
sulphur (12-15% )) and black sand concentrates (an "alluvial" gravel consisting
predominantly of magnetite and haematite and small amounts of nickel,
manganese, chromium and titanium) using bromine reagents have been reported
(Dadgar, 1989; Dadgar et al, 1990). In each case gold extractions ranged from
94-96%.
However, the overall economics of the bromine/bromide system depend on

reagents costs and for more expensive bromine reagents the potential benefits of
high extraction rates will be more attractive for higher grade operations.
Practically, if the ore is completely pre-oxidized, as during pressure oxidation or
roasting, bromine reacts only with gold and consequently the bromine
consumption becomes negligible. In a broad sense therefore, bromine/bromide
system is most applicable for recovery of gold present in the oxidized ores
(Pesic and Sergent, 1990; Pesic and Sergent, 1991). The commercial application
of the bromine/bromide system for gold leaching is also invariably restricted by
high cost of materials of construction to withstand the severe conditions
imposed by the corrosive nature of bromine.
The various studies have also demonstrated that the recovery of gold from the
bromine/bromide leach solutions can be achieved readily by the different
conventional methods such as carbon adsorption, solvent extraction, ion
exchange, cementation or chemical precipitation. Reid and Mensah-Biney (Reid
and Mensah-Biney, 1988) evaluated several absorbents for gold bromide
leaching. Several ion-exchange resins and activated carbon were examined by
Reid, Bereuter, Mensah-Biney and Sergent (Reid et al, 1988). Dadgar (Dadgar,
1989) reported that any one of the conventional methods is a viable option for
gold recovery from Geobrom pregnant solutions with recoveries in excess of
99%. Several studies evaluated the loading characte1istics and adsorption
kinetics of gold-tetrabromide species onto ion-exchange resins and activated
carbon (Dadgar and Sanders, 1990; Mensah-Biney et al, 1991; Pesic and
Storhok, 1991; Dadgar and Howarth, 1992). Dadgar, Sanders, McKeown,
Sergent and Jacobson (Dadgar et al, 1990) also described the gold loadings and
recoveries with Geobrom 3400 from black sand concentrates using both ion-
exchange and solvent extraction methods. The commercial ion-exchange resins
PAZ-4, Dowex-21K, Amberlite XAD-7 and Great Lakes Chemical experimental
GLR-30 were evaluated in this work. Diethylene glycol dibutyl ether was used
for the solvent extraction studies. Most of these studies focused on the process
61
optimisation parameters and offered a comparison with recovery from alkaline

cyanide solution.
Although the ion-exchange resms can successfully recover gold from

bromine/bromide leach solutions, the ion-exchange method will require a direct
application of resins in the pulp (RIP) in order to be practical. The mechanism
for gold loading onto resins is generally visualised as consisting of ion-exchange
adsorption of the anion, AuBr4-, from solution onto the resin surface and the
reduction of the highly oxidized gold ion Au(III) to metallic gold via electron
exchange reduction (Mensah-Biney et al, 1991). Thus, the gold precipitated on
the resin is in a metallic form and may lead to significant attrition losses. Also,
for weak base resins, the gold is so strongly loaded to the resin (eg. PAZ-4) that
elution is difficult to achieve and usually not quantitative. Elution of gold from
the loaded resin is only feasible provided the resin is not loaded to high values
and is accomplished with 4.0 M hydrochloric acid and acetone (Green et al,
1986). For high loading values complete elution becomes impractical and the
gold may be recovered by ashing the loaded resin. The maximum loading
capacity is also inhibited by the concentration of bromine species in solution
and initial gold concentration. Bromine competes for sites on the resin surface
and adsorption of AuBq- by ion-exchange processes is prevented. Also, the
surface of the resin may be degraded by oxidation with bromine and efficient
reduction cannot take place at the surface (Mensah-Biney et al, 1991). However,
according to Dadgar and Howarth (Dadgar and Howarth, 1992), the adsorption
kinetics of AuBr4- on Dowex-21K ion-exchange resin was found to be
independent of the initial gold, bromine and base metals concentrations.
Activated carbon has also demonstrated its applicability for direct recovery of
gold from bromine/bromide solutions too. Gold adsorption is fast and follows
the first reaction order. Also, Cu, Fe, Mg and bromide ions which are most
probable to be present in the leach solutions do not interfere with the gold
recovery (Pesic and Storhok, 1991). However, recovery of gold from
bromine/bromide solutions by carbon in pulp is likely to be unsuitable (Filmer et
al, 1984) There is evidence that, the gold precipitated onto the activated carbon
is in the elemental form similar to that on ion-exchange resins and consequently
susceptible to significant gold losses through abrasion. Activated carbon is also
a well known scavenger for bromine gases. Another major drawback associated
with the use of activated carbon is the presence of residual bromine in the
solution, which suppresses the gold adsorption rate because of its competitive
62
adsorption on carbon. Bromine adsorption on carbon reduces the availability of

surface active sites for gold bromide adsorption (Pesic and Storhok, 1991).
Therefore, with respect to application of bromine/bromide for gold recovery,
zinc cementation is likely to emerge as an alternative to electrowinning.
Unfortunately, there is no detailed study or reported literature on the recovery of
gold by cementation from bromine/bromide leach solutions extended beyond the
initial claim by Dadgar in 1989.
3-3-2-2-3 Iodide leaching
The iodine/iodide system was suggested for extracting gold from vanous
sources. McGrew and Murphy in 1985 (McGrew and Murphy, 1985) claimed
for In-situ Corporation a patent which covered a process using iodine/iodide for
recovering gold by solution (in-situ) mining. Other patents were granted on
various iodine/iodide techniques for dissolving gold from electronic scraps
(Hormick, 1973; Wilson, 1973; Wilson, 1974; Falanga and MacDonald, 1982).
Several fundamental studies on gold extraction in iodide systems were also
reported (Davis, 1991; Davis and Tran, 1991; Hiskey and Qi, 1991; Davis et al,
1993).
The dissolution of gold in an iodide electrolyte is represented by:
(3-3.31)
with E0 = 0.578 V. The Eh-pH behaviour of Au-I-H2o system for 10- 2 M 1- and
[Au] = 10-5 M, reported by Hiskey and Atluri (Hiskey and Atluri, 1988),
illustrates the stability of the AuI2- complex with a solubility field up to about
pH=12. It also shows that above 0.69 V Au4- complex becomes stable with a
stability region greater than that of either AuCl4- or AuBq-. Nevertheless, the
gold iodide complexes are the most stable complexes of all the halogens m
aqueous environments.
Suitable oxidants for iodide leaching are iodine and hypochlorite. According to
Davis and Tran (Davis and Tran,1991), iodine performs better than hypochlorite
on a molar basis because higher gold dissolution rates can be achieved over a
wider pH range. In the presence of dissolved iodine of about 1o- 3 M, I3- ions
form according to the reaction (Hiskey and Atluri, 1988):
63
(3-3.32)
In this case, the tri-iodide ions serve as the oxidant for gold dissolution
2Au + l3- +I-= 2AuI2- (3-3.33)
The gold dissolution rate is strongly dependent on the iodide concentration,

oxidant concentration and solution pH. The gold dissolution rate increases with
an increase in the concentration of iodide or the oxidant (eg. iodine). At a given
iodide concentration, there exists an optimum iodide-iodine mole ratio for the
best practical conditions for gold dissolution. The optimum iodine-iodide
mixture of 40.0 mM iodine and 0.10 M iodide (mole ratio of 0.35-0.40) could
dissolve gold at a rate of 17 mg/cm2/h with pH ranging from 2.7-10.0. This rate
drops to 4 mg/cm2/h at pH: 11.5. A mixture having equal concentrations of
iodide (within the range of 0.02-0.10 M) and tri-iodide will give the best
dissolution rate. The dissolution rate in a hypochlorite-iodide mixture is strongly
dependent upon the solution pH. At 0.10 M iodide, the maximum dissolution
rate is 6.8 mg/cm2/h achieved at pH:2.7 and 25 mM hypochlorite (Davis and
Tran, 1991). Thus, the conditions for extraction (with respect to oxidant/iodide
molar ratio, concentration and pH) have to be optimised to maximize the
dissolution rate and to avoid the passivation of gold by the formation of solid
gold, Aul.
The advantages claimed for the iodine/iodide leaching system are faster kinetics
(compared with cyanidation) (Davis and Tran, 1991), high solution stability
over a wide pH range, low oxidation potential, its effectiveness even at low
concentrations in leaching gold and which makes it selective in leaching other
minerals and low reactivity between iodine and sulphides (Hiskey and Atluri,
1988). However, the high cost of iodine (about $15.5/kg.) demands its efficient
recovery and recycling in a leaching process. It has been demonstrated that
iodine can readily be regenerated electrolytically from iodide ions in a
diaphragm cell and also with the potential for simultaneous recovery of gold
(McGrew and Murphy, 1985; Hiskey and Qi, 1990).
The recovery of gold from the iodine/iodide solutions, so far, has been by
electrolytic method and by precipitation especially with concentrated solutions,
by alkali solutions (or pH adjustment) (McGrew and Murphy, 1985; Falanga
64
and MacDonald, 1982; Murphy and Wyo, 1988; Hirako and Kikinzoku Kogyo,
1990).
3-3-2-3 Thiosulphate
The use of thiosulphate to extract gold was reported in the patents by

Berezowsky, Sefton and Ormely in 1978 (Berezowsky et al, 1978) and Kerley
in 1981 (Kerley, 1981). Thiosulphates are compounds containing the group,
S2O3 2-, which is a structural analog of sulphate with one oxygen atom replaced
by a sulphur atom. The two most important salts of thiosulphate are sodium
thiosulphate, Na2S2O3 (or Na2S2O3.SH2O), and ammonium thiosulphate,
(Nl4)zS2O3. Gold dissolves in alkaline thiosulphate solution, using dissolved
oxygen as the oxidant, to form the Au(I) complex as follows:
(3-3.34)
Alkaline solutions are necessary due to the decomposition of thiosulphate at a

low pH. This has the further advantage of minimising the solubility of
impurities, particularly iron compounds. The rate of dissolution is dependent on
thiosulphate and oxygen concentrations and temperature. It has been shown that
leaching rates are enhanced in the presence of copper (ie. ammoniacal copper-
thiosulphate solutions), with the following reactions proposed (Tozawa et al,
1981):
4Cu(S2O3)z 3- + l6NH3 + 02 + 2H2O

= 4Cu(NH3)4 2+ + 8S2O/- + 4QH- (3-3.35)
Au + 4S2O3 2- + Cu(NH3)4 2+
= Au(S2O3)z 3- + 4NH3 + Cu(S2O3)z 3- (3-3.36)
One maJor problem is the susceptibility of thiosulphate species to several

oxidation and association reactions according to the overall equation (3-3.37)
(Zipperian et al, 1986):
(3-3.37)
65
However, thiosulphate can be stabilized to some extent by the addition of small

amounts of sulphite (SO3 2-) ions which react with sulphide and regenerate
thiosulphate (Kerley, 1983 ):
(3-3.38)
A process for the treatment of sulphidic gold ores has been proposed whereby
thiosulphate ions are generated in-situ under alkaline oxidation conditions.
Nevertheless, there are no commercial scale ore treatments using the reagent at
present.
3-3-2-4 Thiocyanate
Gold dissolves in aqueous, acidified thiocyanate (SCN-) solutions to form both

the Au(I) and Au(ill) complexes, depending on the solution potential (Barbosa
and Monhemius, 1988):
Au(SCN)i- + e- = Au+ 2SCN- E 0 = 0.662 V (3-3.39)
Au(SCN)4- + 3e- = Au+ 4SCN- E0 =0.636 V (3-3.40)
Oxidants such as ferric ion, Fe(ill), or oxygen may be used. Thiocyanate is

oxidized very rapidly in the presence of hydrogen peroxide. The optimum pH
range for the reaction is pH:2.00-3.00.
The rate of gold dissolution increases with increasing thiocyanate. The stability
of thiocyanate is strongly potential dependent, with stability achieved below
approximately 0.64 V. On the other hand, a potential greater than 0.64 V is
required to achieve satisfactory gold leaching rates at practical thiocyanate
concentrations. A compromise between these two requirements is necessary in
any leaching system. Increasing temperature increases the rate of thiocyanate
consumption and, in view of the high reagent consumption even at ambient
temperatures, elevating slurry temperature is not a viable option. A drop in gold
extraction has been reported at temperatures above 40°C. (Marsden and House,
1992). Thiocyanate forms complexes with cations (eg. Fe(SCN) 2+) and such
reactions could lead to high reagent consumptiom especially in acidic solutions
where the metal ion concentrations may be high.
66
3-3-2-5 Others
Leaching systems using polysulphide, cyanamide, cyanoform, organic

nitrile/malonitrile-related compounds for gold dissolution have been proposed.
However, despite some potential advantages, there is little prospect for
commercial development and they are currently of academic interest only
(Woodcock, 1988; Hiskey and Atluri, 1988).
3-4 SEPARA TI ON/RECOVERY OF GOLD FROM AQUEOUS

SOLUTIONS
Recovery processes remove gold and other metal values from solutions into a
concentrated form. The high grade solid product may then either be sold directly
or treated further by refining to improve the grade. Recovery may be achieved
from a wide range of solutions, varying dramatically in gold concentration and
purity.
Recovery of gold from dilute solutions has been a common subject of

investigation in gold metallurgy. Carbon adsorption/carbon in pulp (CIP) has
become an extensively used process for gold recovery from dilute cyanide leach
slurries and solutions. Prior to this, zinc precipitation was used exclusively for
direct recovery of gold from clarified cyanide leach solutions. Subsequently,
both electrowinning and zinc precipitation have been used to treat the more
concentrated gold solutions produced by carbon elution. Direct recovery of gold
from high gold concentration solutions by zinc precipitation is still preferred
over carbon adsorption for high gold concentrations. Ion exchange and solvent
extraction techniques have been introduced into hydrometallurgy of gold within
the last two decades. It is claimed that, with suitable design, both techniques are
more effective than the zinc precipitation process for the treatment of highly
contaminated solutions (Finkelstein, 1972). Other processes have been revealed
to recover gold from dilute aurocyanide or chloroaurate solutions by ion
flotation (IF) using collectors (Charewicz and Niemiec, 1969; Charewicz. 1975;
Walkowiak and Grieves, 1976; Walkowiak et al, 1976; Berg and Downey, 1980;
Engel et al, 1991). Precipitation by soluble reducing reagents (hydrogen
sulphide, sulphur dioxide, sodium sulphite, ferrous sulphate) has been used
industrially to precipitate gold from chloride solutions (Finkelstein, 1972).
67
3-4-1 Zinc Precipitation/Cementation
Precipitation or cementation of gold with zmc powder was introduced

commercially for the treatment of cyanide leach solutions in parallel with the
development of the cyanidation process and has subsequently been applied
widely in the industry (Marsden and House, 1992). The process, which is
traditionally referred to as 'Merrill-Crowe' precipitation after its pioneers has
evolved to be highly efficient, with gold recoveries in excess of 99.5% routinely
achieved and is in use at several large gold mines in Canada, United States of
America and South Africa (Jha, 1984). Zinc precipitation was also first used to
treat hot, high grade solutions produced by carbon elution in 1981 in U.S.A. and
South Africa and has subsequently been applied in Papua New Guinea (at Ok
Tedi gold mine) and widely around the world as an alternative to electrowinning
(Marsden and House, 1992).
Zinc precipitation/Cementation of gold from aurocyanide solution takes place by

a direct replacement reaction and can be represented in the simplest form as
(Julian and Smart, 1921; Finkelstein, 1972; Jha, 1984):
2Au(CN)z- + Zn = 2Au + Zn(CN)42- (3-4.1)
For this reaction, the operation is generally carried out under strongly reducing
conditions and at pH of about 10.5 - 11.5 so that zinc cyanide ions are the stable
species in solution. At a too high pH, zinc hydroxide and zincate ions may be
formed. Under optimum conditions the process, however, is extremely efficient
in precipitating gold from cyanide solutions to 0.01 mg/I level (Jha, 1984). The
generalised flowsheet for Merrill-Crowe process is represented in figure (3-4.1)
(Muhtadi, 1988; Avraamides, 1989).
The first step in this process is a solid/liquid separation to remove the bulk of
the leached solids. This is conducted initially in counter current thickeners
and/or in drum or belt vacuum filters. The pregnant solution produced by these
methods is then further clarified using sand clarifiers, leaf, candle (eg. stellar) or
plate-and-frame filters. The leach liquor or filtrate is then de-aerated in vacuum
towers, the cyanide strength raised, alkalinity adjusted to optimal level and lead
salt is added, followed by zinc dust. The gold is precipitated immediately as a
68
finely divided metal (together with excess zinc) and is separated from the barren
solution in pressure filters. The banen solution is returned to the mill for re-use.
Adamson (Adamson, 1972) reported that cla.1ification is required to remove the
slimy and colloidal constituents from the solution as those materials will inhibit
the precipitation of gold. De-aeration is necessary to minimize prima.1·ily the zinc
consumption and the re-dissolution of precipitated gold (Finkelstein, 1972;
Avraamides, 1989). Gold dissolves in the presence of oxygen and is most
effectively re-precipitated in its absence.
Leached Pulp
t
cco Solids to Tailings
Liquor
T
Filtration
l
l"Polisheci" Liquor
r
Deaeration
( Crowe To•,.,,er)
I
ILiquor
r
Barren Liquor --(-Zinc (po'wder, dust}
. ---< Gold Prec1r:l!tation
Return ro Mill --<-Pb(t10 3 ) 2 (ophonal}
BULL\Oi~
Figure (3-4.1) A general flowsheet for Merrill-Crowe process (A vraamides,

1989).
69
The addition of lead (as lead nitrnte, (Pb(NO3)i)) is to prec1p1tate soluble

sulphides as lead sulphide and to form a lead-zinc electrocouple on the zinc
surface which has a stronger precipitating action than pure zinc.
Like cyanidation, zinc precipitation/cementation is a heterogeneous redox

reaction. Zinc is dissolved at the anodic areas of the surface and the electrons
released serve to reduce the aurous ions at the cathodic areas. Thus, the two
electrode half-cells involved are:
Au(CN)i- + e- = Au + 2CN- EO =-0.67 V (3-4.2)
and
Zn(CN)42- + 2e- = Zn + 4CN- EO = -1.26 V (3-4.3)
Therefore, the resulting potential for the reaction is 0.59 V with .1.G0 = -113.87
kJ/mole (Jackson, 1986). This value, (.1.G 0 ), indicates that the process is
thermodynamically feasible. In practice, the reaction rate depends on many
factors such as concentration of gold in solution, pH of solution, temperature,
concentration of free cyanide, rate of stirring and the presence of other metal
ions in the solution.
A detailed electrochemical study by Nicol, Schaich, Balestra and Hedegus

(Nicol et al, 1979), investigated the effect of the various parameters on the
efficiency of this technique that forms the basis of the zinc cementation process.
According to Barin, Barth and Yaman (Barin et al, 1980), the overall chemical
reaction for the cementation in the presence of the side reaction of reduction of
water to give hydrogen is:
(3-4.4)
In dilute solutions, the gold concentration has a direct influence on the rate of
cementation. This is essentially a first-order effect controlled by the mass
transport with film diffusion of Au(CN)i- ions to the zinc surface under
conditions typical of those applied industrially (Nicol et al, 1979; Barin et al,
1980). Thus, the rate has a small positive temperature coefficient and the overall
activation energy is about 13 kJ/mol (Finkelstein, 1972). Other work has
indicated a deviation from this behaviour but this is most prevalent in high grade
70
solutions and is attributed to the morphology of the prec1p1tate formed,

formation of passivating layers/coatings on the zinc surface (ie. Zn(OH)z) or a
particle agglomeration phenomenon (which occurs at high gold concentrations
and low temperatures) (Paul and Howarth, 1986; Parga et al, 1988; Miller et al,
1990). Elevated temperatures (>50°C) also increase the rate of zinc dissolution
and hydrogen evolution, with an associated decrease in precipitation efficiency
(Paul and Howarth, 1986). At a temperature lower than 10°C the cementation
process will change from a diffusion-controlled to a kinetic-controlled process,
especially when the gold concentration is at 5 mg/1 or less (Oo and Tran, 1991).
The effect of the morphology on the cementation process was first noted by Paul
and Howarth (Paul and Howarth, 1986). The deposit formed from a solution
containing 80 mg/1 Au is more porous than the compact precipitate formed at
higher gold concentrations.
A variation of pH from 9.00 to 12.00 has no noticeable effect on the rate of

cementation (Nicol et al, 1979; Paul and Howarth, 1986; Parga et al, 1988).
Leblanc (Leblanc, 1942), showed that the recovery using zinc dust dropped
sharply for pH values below 8.0 at cyanide concentrations of 2 to 3X 10-3 M.
Above pH:8.0, the recovery increased gradually to a maximum at a pH of about
11.5. In practice, however, the pH should be maintained above pH of 10 to
minimize the formation of HCN by hydrolysis of cyanide. Excessively high
concentrations of OH- will result in copious evolution of hydrogen and a high
consumption of zinc. A minimum free cyanide ion concentration is necessary
for the cementation process. This critical cyanide concentration is 0.002 M CN-
(0.10 g/1) according to Nicol, Schaich, Balestra and Hedegus (Nicol et al, 1979)
and 0.035 M CN- (1.7 g/1) according to Barin, Barth and Yaman (Barin et al,
1980). Below these concentrations, the rate of zinc dissolution is decreased and
the rate of cementation is low (ie. controlled by the diffusion of free cyanide
ions to the zinc surface). A too low concentration causes the cementation to
operate in the passive region where the dissolution of zinc is retarded by the
formation of Zn(OH)i (Paul, 1986). A study by Miller, Wan, and Parga (Miller
et al, 1990) using zinc powder also confirmed the formation of zinc hydroxide at
a low cyanide concentration (0.001 M) which accounted for the decrease in the
reaction rate with time. A too high free cyanide concentration also results in an
increase in the rate of hydrogen evolution which leads to an increase in the rate
of consumption of zinc.
71
The presence of oxygen in solution affects the cementation process adversely. In

potable water solubility in equilibrium with the atmosphere is about 10 mg/1,
although at a high salinity this level drops to about 3 mg/I. The solution
containing less than 10 mg/I gold should be de-aerated, although such an action
might not be necessary for those solutions containing gold higher than 100 mg/1
(Paul and Howarth, 1986). Oxygen reacts with zinc resulting in lower gold
recovery and/or excessive zinc consumption (Finkelstein, 1972; Avraamides,
1989). The reduction of dissolved oxygen occurs at a rate controlled by the mass
transport of oxygen to the zinc surface for potentials more negative than -0.30
V. Consequently, alternative mechanisms are established for the dissolution of
zinc (Finkelstein, 1972; Marsden and House, 1992):
2Zn + 8CN- + 02 + 2H2O = 2Zn(CN)42- + 4OH- (3-4.5)
2Zn + 02 + 2H2O = 2HZnO2- + 2H+ (3-4.6)
These reactions, equations (3-4.5) and (3-4.6), markedly consume zinc. The
reaction (3-4.5) also consumes cyanide and might cause the passivation of the
zinc surface. Also, in the presence of dissolved oxygen, there is the tendency for
the re-dissolution of precipitated gold by the standard cyanide leaching
mechanism according to equation (3-3.5). However, if the precipitated gold
remains in electrical contact with the zinc, as is usually the case, it will form the
cathodic member of a local electrochemical cell, and zinc will preferentially
corrode. Nevertheless, the severity of the effect of dissolved oxygen depends on
the dissolved oxygen concentration and other precipitation conditions,
principally the temperature and gold concentration. In dilute gold cyanide
solutions at ambient temperatures, the effect becomes significant at dissolved
oxygen concentrations above 0.50-1.00 mg/I (Marsden and House, 1992). There
is some evidence that low concentrations of dissolved oxygen (<1.0 mg/I)
enhance gold precipitation from dilute gold cyanide solutions (Plaksin and
Budnikova, 1951 ). This is attributed to the depolarizing action of oxygen at
cathodic areas of the zinc surface by reaction with hydrogen that is evolved
(according to reactions (3-4.7) and (3-4.8)) (Finkelstein, 1972; Marsden and
House, 1992):
Zn + 4CN- + 2H2O = Zn(CN)i- + 2OH- + H2 (3-4.7)
Zn + 2H2O = HZnO2- + H+ + H2 (3-4.8)

72
The dissolved oxygen concentration 1s unlikely to be a problem in gold

precipitation from hot, high grade gold cyanide solutions, such as those obtained
from carbon elutions systems (Paul and Howarth, 1986; Marsden, 1990), and
de-aeration is unnecessary because of the low solubility of oxygen at normal
operating temperatures and the consumption of residual oxygen during carbon
elution.
The beneficial effect of lead ions on gold precipitation from dilute gold cyanide
solutions at low temperatures has been evaluated in several studies (Leblanc,
1942; Nicol et al, 1979; Paul and Howarth, 1986; Nicol et al, 1987; Miller et al,
1990; Oo and Tran, 1991). Most studies agreed that lead affects the cementation
process in many ways. In the presence of lead the passivation of zinc due to the
formation of zinc hydroxide is reduced. However, the lead addition rate is
critical and is most effective at a Pb:Zn weight ratio of between 1:7 and 1:10.
Pb 2+ concentrations between 0.001 and 0.01 g/1 are optimal for the process from
solutions containing 1.0-10.0 git Au (Marsden and House, 1992). Nicol,
Schaich, Balestra and Hedegus (Nicol et al, 1979) showed that an increase in the
rate of cementation by 30 % was observed when 5 mg/I lead as nitrate was
added to the solution containing 5 mg/I gold. Oo and Tran (Oo and Tran, 1991)
also showed that the addition of 3 mg/I Pb to a 5 mg/I gold solution maintains
the cementation reaction in the diffusion-controlled zone and makes it more
effective. At a temperature of 40°C or higher the addition of lead (at 3 mg/I Pb)
decreases the zinc consumption as the hydrogen evolution reaction is
suppressed. Excess additions are detrimental and can completely stop the
precipitation, probably due to complete coating of the zinc surface by a lead
film. Other divalent metal cations, such as Hg, Th, Bi, and Cd at very low
concentrations have also been shown to enhance the cementation rate (McIntyre
and Peck, 1976). Although, Nicol, Schaich, Balestra and Hedegus (Nicol et al,
1979) and Oo (Oo, 1990) also reported that Cu, Ni, and Co have no effect on
the cementation rate, it can be expected that the presence of these metals will
result in higher zinc consumption as well as in poorer grade of gold product.
According to Leblanc (Leblanc, 1942) and Plaksin, Suvorovskaya and Bunikova
(Plaksin et al, 1948), the presence of copper cyanide at a concentration of
6.0x 10-3 M adversely affects the cementation process. Paul (Paul, 1986) also
reported that the presence of common impurities such as cyanide complexes of
iron, nickel and copper increased the consumption of zinc but did not affect the
efficiency. Many of the common constituents of gold cyanidation solutions also
influence the cementation reaction. According to Finkelstein (Finkelstein, 1972),
73
sulphate, sulphite, thiosulphate and feITocyanide ions present in the

concentration range of 10-3 M to 10- 2 M can reduce the recovery of gold by 1-2
% from 10-3 M cyanide solution. Calcium sulphate forms insoluble gypsum
which tends to precipitate on the zinc surlace and deactivate it. In the absence of
sulphate, calcium ions alone appear to have a small beneficial effect on the
precipitation (Leblanc, 1942). The presence of sulphide ions at concentration as
low as 10-4 M causes a definite detrimental effect by passivating the zinc
surlace (forms zinc sulphide). This effect may be reduced to some extent in the
presence of lead due to preferential precipitation of lead sulphide. Antimony and
arsenic compounds however, have the most severe detrimental effect on the
precipitation (Leblanc, 1942; Plaksin et al, 1948). Their presence even at 1 mg/I
level can reduce the rate of cementation by 20% (Jha, 1984).
Invariably, the oxidative dissolution of metallic zinc in alkaline cyanide

solutions to soluble cyanide complexes (eg. Zn(CN)42-) promotes the
precipitation of metallic gold (Osseo-Asare et al, 1984). However, high zinc
concentrations can result in formation of Zn(OH)i which tends to take place at
the surlace of the zinc and severely reduces the precipitation rate or stops it
entirely. The maximum zinc concentration depends on pH and cyanide
concentration. At a total cyanide concentration of 3 g/1 CN-, the limiting zinc
concentration below which no precipitation of zinc hydroxide takes place at a
pH of 11.0 is 0.75 g/1 Zn 2+ (Marsden and House, 1992). Nevertheless, the
surlace area of the zinc precipitant is one of the most important variables in the
system. An increase in the available zinc surlace area increases the kinetics
(Marsden and House, 1992). Also, since most inhibitors act by forming bamers
at the surlace, their effects can be reduced by increasing the surface area of zinc
(Finkelstein, 1972). On the other hand, increase in surlace area also increases
the rate of side reactions, which increases zinc consumption. The fineness of
zinc is also limited by the filtration requirements and the filtration properties of
the precipitate (Marsden and House, 1992).
Zinc precipitation seems to lose popularity with the advent of carbon

adsorption/electrolysis for gold extraction and recovery. MeITill-Crowe
precipitation is known to be adversely affected by the sensitivity of the reaction
towards impurities and the need for liquor purification for an effective
operation. Consequently, it suffers from greater capital and operating costs due
to the filtration/decantation step. Storage capacity is necessary in order to cope
with surges in throughput (Avraamides, 1989; Marsden and Fuerstenau, 1993).
74
It is more susceptible to upset conditions which can severely reduce metal

recovery efficiency. The use of zinc and lead presents some additional operating
problems. The zinc and lead may be significant contaminants in detoxification
of the spent liquor. Also, zinc is known to inte1fere with cyanide titration when
present in cyanide solutions which can have an adverse effect on process control
and leaching efficiency (Marsden and Fuerstenau, 1993). However, cementation
offers faster kinetics and is quite simple to operate. It is particularly
advantageous for gold plants employing non-agitation leaching methods in the
treatment of low-grade ores and is most economic on small scale. It is also
applicable for the recovery of gold from carbon-in-pulp eluates and is best
suited to batches of low gold tenor eluates (Avraamides, 1989). In milling
systems, Merrill-Crowe precipitation is prefened over carbon adsorption in the
following cases (Marsden and Fuerstenau, 1993 ):
(1) For treating leach solutions containing silver:gold ratios above

approximately 10: 1.
(2) For high-grade solutions above approximately 10-15 git gold equivalent.
(3) For small operations recovering less than 25 ounces per day of total precious
metal which cannot justify the relatively-high cost of carbon elution and
reactivation equipment.
3-4-2 Carbon Adsorption
The alternate scheme of adsorption of gold and silver on activated charcoal from
pregnant solutions has found a worldwide acceptance in the last decade. This
preference over the Merrill-Crowe zinc dust precipitation system is primaiily
due to more effective recovery of precious metals from lower grade leach
solutions emanating from lower grade ores and lower capital and operating
costs. A majority of the new plants designed in the last ten yeai·s in the United
States, Australia and South Africa incorporate one or the other modifications of
the carbon based gold recovery. These modifications include Carbon-in-Leach
(CIL), Carbon-in-Pulp (CIP) and Cai·bon-in-Column (CIC).
The CIP process has been used commercially and is applied to slimes or ground
ores and calcines cyanided in agitated tanks. The biggest advantage of this
75
process is that it eliminates the expensive solid/liquid separation step needed in

the case of Merrill-Crowe process. The leach pulp is first screened on a coarse,
generally about 0.6 mm screen to remove any large particle or wood chips. The
pulp then flows through a series of stirred tanks countercurrent to the flow of
activated carbon. Solid/liquid contact is provided in each of the tanks by
mechanical agitation. Interstage screens are used to separate coarse carbon from
the pulp, with the two being moved in opposite directions. The pulp depleted of
gold is discarded from the last tank which receives fresh reactivated carbon and
the loaded carbon from the first tank is sent for elution (Jha, 1984). The CIL
process is a modification of the CIP process that allows adsorption to be carried
out directly in the cyanide leaching tanks. As leaching is a slower process than
adsorption, one or two of the first leaching tanks contain no carbon and are used
solely for leaching. The remaining tanks, however contain carbon and therefore
act as both leaching and adsorption vessels. Carbon inventory in a CIL syatem is
larger than in a CIP system of the same plant capacity, due to lower gold
concentration in solution and therefore a smaller driving force. This increased
carbon inventory represents an increase in locked-up gold values and is
probably the most serious drawback of the process (Jha, 1984 ). CIC process
involves the contacting of the activated carbon with relatively clear pregnant
solution (usually leach liquors generated in most heap-leaching operations) in
vertical columns partitioned horizontally with the carbon being moved counter-
currently and intermittently to the flow of solution. A series of columns is used.
The solution enters the first column containing carbon most loaded with gold
and leaves as barren solution from the last column containing fresh or least
loaded carbon. The first column is removed from the circuit when it reaches a
predetermined gold loading and freshly eluted column is added to the tail end of
the circuit.
The behaviour of various activated carbons in adsorption and de-adsorption of

gold and silver has been discussed in detail (Jha, 1984 ). The mechanism of
adsorption of gold or silver cyanide on activated carbon appears to be diffusion
controlled with available adsorption sites varying in potential, the lowest
potential sites adsorbing last (Davidson, 1974 ). Thus, high surface areas and
pore diffusion are important aspects of the adsorption process. Activated
carbons can be manufactured from wood, nut shells, coal, petroleum coke, and a
variety of organic products. Coconut shell carbon, however, is the preferred
brand with commendable durability and high adsorption capability for gold and
silver cyanides (Bhappu, 1986).
76
The normal ranges of carbon size from 1.2 x 2.4 to 1.7 x 3.4 mm have proved to
be effective in practice depending on CIL, CIP or CIC system used. While fine
particles give faster kinetics, they are more likely to cause high pressure drops in
loading and elution columns. The finer particles can also increase gold loss in
tailings in CIP operations. The normal loading varies from 600 to 10,000g
gold/silver per ton of carbon. The loaded carbon can then be stripped readily
using hot caustic-cyanide (1 % NaOH, 0.1 to 0.2% NaCN) at about 95-98°C at
atmospheric pressure. The kinetics of stripping is slow under these conditions
and may require 48 hours for completing a stripping cycle (Zadra et al, 1952).
The slow kinetics necessitates large size stripping plants and represents a
significant lock-up of gold values in the plant. The elution rate may be
accelerated by refluxing and recycling hot methanol at temperatures around 60
to 80°C with a stripping time of 4 to 6 hours. The elution of loaded carbon may
also be enhanced by using pressure elution (50 to 70 psig) at about 120 to 130°C
in 6 to 8 hours. An interesting variation of this method involves the pretreatment
of the loaded carbon with a strong cyanide solution (10% NaCN stabilized with
1% NaOH) followed by elution with water at high temperature (110°C) in a
pressure vessel. It is claimed that elution can be completed in a few hours. The
Anglo elution process virtually uses all the South African plants and many
Australian plants since the mid-1970' s.
The gold/silver values from the rich stripping solutions (5.0 oz per ton) can be
recovered by electrowinning on steel cathodes using 2.50 to 3.50 V per cell and
amperage consistent with 30 to 40 percent current efficiency (Bhappu, 1986).
Electrowinning is the most common recovery method used. However, there are
a few plants which have adopted zinc dust cementation in preference to
electrowinning (Jha, 1984). It is claimed that this process reduces the high gold
inventory normally associated with electrolytic gold deposition. Carbon is
usually acid washed (3% v/v HCl at ambient temperature) to remove lime and/or
certain metal complexes prior to elution in non-oxidizing atmosphere for about
half-hour, generally in an indirectly heated rotary kiln (Jha, 1984 ).
Studies pe1formed at United States Bureau of Mines (Hussey et al, 1982) and at
Anglo American Research Laboratories (Davidson et al, 1982) have confirmed
that the equilibrium capacity of carbon to load gold is related to pH, gold
concentration, and free cyanide concentration. Typical isotherms are almost
linear between equilibrium concentrations of 10.0 and 0.10 mg/I gold in
77
solutions but starts curving at lower concentrations. The pregnant solution

entering the circuit at 1.0 to 10.0 mgn equilibrates with the loaded carbon
leaving the circuit. At the other end of the circuit, freshly regenerated carbon
entering the circuit can scavenge gold down to 0.02 ppm level or less from the
barren solution to be discarded. The carbon adsorption process does not reach
equilibrium. Attainment of equilibrium with granulated carbon takes days or
weeks, whereas the pulp residence time in the adsorption section of a CIP plant
is no more than 6 hours to achieve solution gold concentrations around 0.01
mgn. The effect of residence time and number of stages on percent gold
extraction on one hand, and gold holdups costs on the other hand are very well
explained by process models developed by Fleming at National Institute for
Metallurgy, South Africa (Fleming, 1982). In general higher solution grades
result in higher loading. Also, the adsorption capacity increases with a decrease
in pH (Davidson et al, 1982). An extreme case in this respect was
Witwatersrand gold plant solution which had to be acidified to a pH of 5.00 in
order to get optimum adsorption rate and loading (Davidson et al, 1979).
Davidson, Douglas and Tumilty (Davidson et al, 1982) found that the successive
addition of free cyanide lowered the equilibrium capacity of carbon. Their work
also showed that the effect of increasing cyanide concentration was worse at
higher temperatures. This may be part of the reason why higher temperature and
NaCN concentrations are used in eluting the carbon. The rate of adsorption is
also affected significanty by the quality of agitation or mixing (Fleming, 1982).
In the Grootvlei CIP pilot-plant operation, replacement of air agitation by
mechanical mixing, doubled the rate of gold extraction. The efficiency of
mechanical agitation as carbon contactors is also reported for Masbate operation
in the Phillippines (Pizarro and Antonio, 1981 ).
Based on literature so far and experimental work at Mintek, South Africa,

McDougall, Hancock, Nicol, Wellington and Copperthwaite (McDougall et al,
1980) concluded that the mechanism appears to have an initial adsorption stage
that involves the adsorption of an ion pair Mn+ Au(CN)2n-, where Mn+ is a
metal ion (for example Na+, K+ and Ca 2+).
The presence of high concentrations of silver will significantly increase the

requirements of activated carbon and thereby increase the cost of the process.
Copper behaves in a way similar to that of silver. It is loaded on the carbon as a
cyanide complex at low pH. Nickel reduces the gold loading on the activated
carbon. The amount of nickel loaded onto carbon is primarily a function of the
78
concentration of nickel in solution. Calcium also loads on the activated carbon,

the amount increasing with increasing concentration of calcium in solution and
increasing contact time (Sceresini, 1982). The origin is generally the lime used
for maintaining the pH during cyanidation. A serious fouling problem arises due
to precipitation of calcium carbonate on the activated carbon, particularly when
air is used for agitation.
3-4-3 Electrowinning
Electrowinning for recovery of gold from cyanide solutions was practised in the
early days of the development of the cyanidation process. It was then abandoned
due to extremely low current efficiencies experienced with conventional cells.
During the past ten years, as the carbon adsorption process proliferated through
the gold mining industry, interest in electrolysis/electrowinning has been
renewed for the treatment of the high-grade strip solutions (carbon eluates). The
popularity of the process stems from the advantage of a greater selectivity for
gold and silver from copper in comparison to zinc-dust cement.at.ion and hence
the product is generally of higher purity which simplifies the melting and
fluxing operation to produce dore bullion. Also, electrons are used to reduce
gold directly and as such no new chemicals or metals are introduced into the
process (Jha, 1984; Marsden and House, 1992).
Electrowinning is generally an integral part of the overall flowsheet comprising

of activated carbon adsorption and is performed in cells containing a number of
cathodes and anodes. The gold-beruing solution is fed into one side of the cell
and passes out at the opposite end and the direction of flow may either be
parallel or perpendiculru· to the orientation of the electrodes depending on the
specific cell design. Thus, the cell is a function of the flow- through properties
of the electrodes and the cell geometry. In recent years there has been a
significant development in electrolysis cell design and the operations of
electrowinning in a Carbon-In-Pulp circuit vary from one plant to another
depending on the type of practice used to strip gold from the loaded carbon (eg.,
Zadra and Anglo-American). Accordingly, variations in the electrowinning cells
developed include the Zadra and Mintek cells. Basically, all of these cells
employ porous packed-bed electrodes and are of two types of design (Paul,
1986).
79
The Zadra type cell (designed by the United States Bureau of Mines and
developed by Homestake Mine) consists of three concentric containers, the
cathodic compartment, the overflow container, and the outside container which
are placed in cascade and connected in series. The inside container is perforated
and contains steel wool to serve as the cathode. The anode is made of stainless
steel screen placed in the overflow compartment. The cyanide solution is
allowed to enter and flow at right angles to the flow of current, upwards and
through the steel wool into the anode compartment. The possibility of the
electrolyte by-passing the cathode bed is minimized by introducing it inside the
bed by means of a delivery tube provided with orifices along its length (Jha,
1984). The Anglo-American cell (devised by the Anglo American Research
Laboratory of South Africa) is a modified version of cylindrical cell. A strong
alkaline solution circulates through the anode compartment and the pregnant
electrolyte circulates through the cathode compartment. In the second type of
cell design developed by the National Institute for Metallurgy, South Africa, the
cell is of rectangular shape and the solution flows parallel to the passage of
current. The Mintek cell consists of a stainless steel rectangular tank enclosing a
number of removable anodes (stainless steel 316) and cathodes (filled with steel
wool) positioned alternately within the tank so that each cathode is effectively
'sandwiched' between two anodes. The fronts and backs of the cathodes are
perforated so that the electrolyte can flow down the length of the cell through
each alternate anode and cathode (Paul et al, 1983). The design features of the
cell, materials of construction and operating results have been reported in detail
(Paul et al, 1983). Other cell designs have also been tested on pilot plant scale.
The Chemelec cell originally designed for recovering metal from electroplating
rinse water (Paul, 1986) was also tested with CIP eluates. The cell consists of a
tank containing stainless steel cathodes, platinized titanium anodes and a
fluidized glass bead bed between the electrodes. This design claims to yield a
high purity gold deposit which can be easily stripped from the cathode sheets.
Another development being pursued in Australia involves the use of the Siltech,
an Australian-designed electrolytic cell for recovering silver from spent
photographic solutions but no Siltech has been put into practice.
Electrowinning is an integral part of the Zadra elution process. Although, the

cmTent efficiency is usually low, electrowinning is specific for Au and Ag. The
efficiency of the Zadra process, however, is linked to the efficiency of the
electrolytic cell and flowrate. High flow rates improve the elution of Au(CN)i-
from carbon but cause a decrease in single pass efficiency of the electrolytic
80
cell. The multi-compartment flow-through Anglo or Mintek cell achieves a very

high cell efficiency enabling batches of eluates from Anglo elution to be
processed (Muir, 1989).
Typically, gold is electrowon on knitted or woven steel wool. Like any other
electrowinning process, gold is electrolytically displaced from the aqueous
alkaline cyanide solution. Oxidation reactions taking place at the anode generate
electrons which are consumed at the cathode to deposit gold. In alkaline cyanide
solution, the major reaction at the anode is the oxidation of water to oxygen
represented as:
4OH- = o2 + 2HzO + 4e- (3-4.9)
and the cathodic reduction of gold is illustrated as:
Au(CN)z- + e- = Au + 2CN- (3-4.10)
Side reactions involve the deposition of other metals (ie. Ag, Cu, Pb, Hg, Ni, Fe,
Zn) as well as evolution of Hz (according to reaction 3-4.11) and the reduction
of 02 (according to reaction 3-4.12) at the cathode:
2H2O + 2e- = H2 + 2OH- (3-4.11)
Oz+ 2HzO + 4e- = 4OH- (3-4.12)
The anodic reactions may include the kinetically slower oxidation of cyanide
ions to cyanate according to (Kirk and Foulkes, 1984; Muir, 1982; Brandon et
al, 1987; Marsden and House, 1992):
CN- + 2OH- = CNO- + H2O + 2e- (3-4.13)
Cyanide can also be oxidised in bulk solutions by dissolved oxygen. Sulphide

ions, which may be present in low concentrations in gold electrolytes, are also
oxidized to polysulphide at the anode. These ions may then be transported to the
cathode where they may react with deposited gold to form stable complexes (ie.,
causing re-dissolution of the deposited metal) (Marsden and House, 1992).
81
The variables affecting these reactions are the cell voltages, current density,
solution flow rate (electrolyte hydrodynamics) and solution composition. The
voltage and current that must be applied to a cell for most efficient gold
recovery depends on the cell design and the solution conditions, including
conductivity, pH, temperature and concentration of all ionic species (or
impurities) present. In industrial cells voltages of the order 2-4 V are applied to
allow for solution losses and side reactions (Raub, 1984).
Deposition of gold from an alkaline-cyanide electrolyte does not occur until a

potential of about -1.00 V is attained (the exact potential depends on the
solution composition, temperature, etc.). Over the potential range -1.00 to about
-1.30 V the rate of deposition is determined by the electrode potential (ie.
kinetic control). At potentials greater than -1.30 V the rate of deposition is
controlled by the mass transport with diffusion of gold(I) cyanide to the
electrode (cathode). The optimum current for gold deposition is therefore that at
which the deposition rate is just mass transport controlled (Paul et al, 1983;
Raub, 1984). Thus, the rate of deposition increases with increasing current up to
the limiting current, at which point maximum current efficiency is obtained in
the system. Above the limiting value the excess current is consumed by side
reactions, principally the reduction of water to hydrogen, but also potentially the
reduction of oxygen and other metals. Currents of between 200 and 8000 A are
applied depend.ing on the cell configuration, gold concentration, electrolyte
composition and hydrodynamic properties of the electrolyte (Halbe, 1984 ).
The operating solution flow rate is a balance between single-pass efficiency and
the total volume that must be treated to recover a fixed amount of gold. The
single pass efficiency decreases with increasing solution flowrate. Beyond some
velocity, the physical abrasion of gold may also become significant. Usually
solution flowrates of 38-150 l/min in the range 250-500 l/m 2 cathode are
employed. The efficiency of electrowinning will depend on whether using
constant current or constant voltage electrolysis. This basically determines the
size of the electrowinning cells for a given production rate (Paul et al, 1983; Jha,
1984).
The eluates from CIP plants are relatively low gold (and silver) cyanide
solutions (ie. 100-500 mg/1) containing some free cyanide ions and sodium
82
hydroxide (Jha, 1984; Avraamides and Haynes, 1988). Paul, Filmer and Nicol
(Paul et al, 1983) showed that deposition efficiency remained practically
constant at about 75% when the gold concentration was in the range 10 to 200
mg/I. However, this efficiency decreased at both lower and higher
concentrations. Below 10 ppm, the deposition potential for gold shifts
cathodically (-0.12 V per 10-fold decrease in gold concentration) and an
increasing fraction of the cathode bed becomes electrochemically inactive
towards the reduction of the aurocyanide ions. For concentrations above 154
mg/I, they showed that the electrochemical reactions such as reduction of
oxygen and silver compete for the limited amount of available current thereby
decreasing the deposition efficiency, but it is still not clear why oxygen and
silver will compete at high gold concentrations. The presence of sodium
hydroxide (NaOH) increases the conductivity of the solution and thereby the
single-pass extraction efficiency. The solution conductivity determines the
ohmic drop across the cell, and therefore the potential distribution throughout
the cathode (ie. electroactive cathode volume) (Paul et al, 1983; Brandon et al,
1987). The higher the conductivity, the lower the electrical loss (or electrical by-
passing) in the solution. Gold recovery (or single-pass extraction efficiency)
also decreases with increasing free cyanide concentration (Brandon et al, 1987).
Harrison and Thompson (Harrison and Thompson, 1973) showed that an
increase in cyanide concentration (ie. from 5 g/1 to 50 g/1 NaCN) shifts the
potential for deposition cathodically by approximately 0.2 V. Thus, a higher
voltage must be applied at higher concentration to ensure that the system is
operated at, or slightly above, the limiting current (Marsden and House, 1992).
Electrowinning efficiency is also maximized by large or maximizing cathode

surface area and voidage. The presence of any particulate material in the
electrolyte that builds up in the cathode will tend to reduce voidage rest1icting
flow and reducing cell efficiency. In addition, as the amount of gold deposited
onto the cathode increases, the smface area of the cathode is also increased,
which in turn increases the rate of water and oxygen reduction at the cathode.
Hydrogen evolution increases the ohmic potential drop across the cathode bed,
which causes the potentials within the bed to move in an anodic direction and
may produce regions within the electrode where gold deposition cannot occur
(Paul et al, 1983 ). Thus, as the amount of gold deposited on the steel wool
increases, the efficiency goes down. While the steel wool cathodes can be
loaded up to twenty times their weight with gold, in practice, the cathodes are
pulled out much before that (Jha, 1984). Loadings of 1-2 kg Au/kg steel wool
83
are typically achieved (Marsden and House, 1992). The gold-to-steel wool mass
ratio is therefore another important variable affecting the single-pass deposition
efficiency. In addition, pH is also important for electrode stability. Below a pH
of approximately 12.5, the electrodes (eg. stainless steel) corrode in solution.
This corrosion increases the concentrations of chromium and iron species in

solution which may undergo side reactions and reduce efficiency. Chromium
concentrations above 100 git have been observed to completely prohibit gold
electrowinning. Iron cyanide species set up redox system across the cell
(Marsden and House, 1992). The presence or addition of sodium hydroxide
reduces the rate of corrosion (Paul et al, 1983 ).
Elevated electrolyte temperature will also increase the deposition rate and
improve the cell current efficiency. This is due to an increase in solution
conductivity, higher diffusion coefficient of gold(I) cyanide ions and a lower
solubility of oxygen in the solution at higher temperature (Paul et al, 1983 ).
Therefore a minimal cooling of eluate solution should be allowed before
electrowinning (Jha, 1984; Marsden and House, 1992). However, these effects
are quite small, particularly when compared with effects of gold concentration,
the degree of mixing of the electrolyte and the cathode surface area (Marsden
and House, 1992).
Various gold electro winning innovations include integrated high temperature-

pressure, elution-electrowinning, improved mass transport cells and
electrorefining with stainless steel wool. Each has particular advantages (Muir,
1989). Despite these extensive innovations fmther improvements are required
especially with the cell hardware, since operating problems such as anode
coITosion and cell distortion are still experienced in certain plants. Application
of existing electrowinning technology to more dilute solutions (ie. 1.0-10.0 git
Au), for example those produced by direct leaching of ores results in much
lower cmTent efficiencies ( ~0.33% ), making the process uneconomic (Brandon
et al, 1987; Marsden and House, 1992). In addition, the process lends itself to
low single-pass efficiencies at high flowrates per unit cell volume and most
systems rely on recirculating solutions to achieve acceptable gold extractions.
The process is also sensitive to metal impurities such as iron, zinc copper and
mercury. Mercury is particularly detrimental to gold recovery and may present
more of a health hazard in electrowinning systems than in closed zinc
84
precipitation circuits (Paul et al, 1983; Brandon et al, 1987; Marsden and
House, 1992).
3-4-4 Ion-Exchange Technique
One of the emerging technologies deserving attention involves the recovery of

precious metals from pregnant solutions by ion-exchange resins using the resin-
in-column (RIC) technique (Gilmore, 1967). The flowsheet for this system is
similar to that of carbon-in column (CIC) plant. The active group on the surface
of the resin exchanges with the complex ion. Adsorption takes place rapidly
until the surface of the resin is fully reacted. One major exception involves the
operation of the elution (Stripping) stage which does not require elevated
temperatures and pressures for removal of precious metals from loaded resins.
Process analogs of CIL have been investigated in Russia in which cyanide
leaching and adsorption on ion-exchange resins are carried out simultaneously.
However, a more common possible use would be for gold recovery directly
from the pulps. The resin-in-pulp ion-exchange technology has been used
commercially in Russia to recover gold from cyanide pulp. The RIP technology
has two potential advantages over the CIP technology:
(1) The elution and regeneration processes for the resins may be simpler than for
activated carbon, making RIP the favourite for smaller plants (Fleming and
Nicol, 1981; Fleming, 1982).
(2) The RIP process may maintain its efficiency when organic matter (flotation
reagents, ash char, etc.) are present in the pulp (Fleming, 1982; Gupta and
O'Neil, 1982).
The process could also be attractive in comparison to the MeITill-Crowe process

for difficlut-to-filter pulps caITying high values and low concentrations of
competing ions such as copper, nickel and zinc.
Just as with activated carbon, the gold-recovery process with ion-exchange

resins involves three basic operations - loading, elution, and recovery. However,
the variations in each step are much less than in the activated carbon process.
85
Either strong or weak base resins may be used as presented in the loading and
stripping equations, respectively:
RCl + NaAu(CN)i i R Au(CN)i- + NaCl (3-4.14)
and
R Au(CN)i + NH4SCN i RSCN + NH4 Au(CN)i (3-4.15)
where R is an anion exchanger (Bhappu, 1986).
The strong-base resins contain quartennary amine functional groups and are
ionized over the full pH scale. They extract aurocyanide ions by an exchange
mechanism. Typical resins have total capacities of 0. 7 gram gold per gram dry
resin. Gold complexes tend to be displaced by copper cyanide complexes,
Cu(CN)42- and by iron complexes, Fe(CN)6 2- so that the loading will be
affected by the presence of these complexes. The weak-base anion exchange
resins exist with several different functional groups consisting of primary,
secondary, and tertiary amine groups. In their free-base form these resins are
uncharged. It is therefore necessary for the resin to be protonated prior to the
extraction of aurocyanide ions. Generally the protonation to a pH value between
7.0 and 9.0 is adequate to achieve maximum gold extraction.
The stripped gold/silver in solution is then electrowon as follows:
(3-4.16)
In general, the stripping of the loaded gold/silver values from the resins has
proved to be somewhat difficult. Weak base resins may be eluted by dilute
caustic solution at ambient temperature. On the other hand, the strong base
resins require a concentrated NH4SCN or Zn(CN)4 2- solutions as reported by
MINTEK, South Africa (Fleming and Nicol, 1981 ). In this case, the resin needs
to be regenerated using acid which breaks down the zinc cyanide complex
producing HCN gas which must be then collected and re-adsorbed into caustic
soda for recycling.
86
3-4-5 Solvent-Extraction Technique
The alternate technique of solvent-extraction (SX) of gold/silver from pregnant

solutions is also worthy of consideration, but it is still in its infancy. Mooiman
and Miller (Mooiman and Miller, 1983) identified a suitable extractant with an
organic phase consisting of a weak base amine whose basicity has been
increased by the addition of an organic phosphorus oxide modifier in an
appropriate carrier for gold/silver recovery. The loading stage reaction for a
secondary amine is as follows:
(3-4.17)
where R = C 10 - C 12 alkyl group. Maximum loading is achieved at pH about

9.50, even for a very weak gold bearing solution.
Stripping of the loaded solvent is affected at pH of 12.0-13.0 by deprotonating

the amine or with a 0.10 to 0.50 percent caustic solution. Both the loading and
stripping reaction rates are relatively fast making the technique very attractive
from design and cost considerations. Moreover, the system is very selective for
gold/silver complexes which should result in obtaining a relatively pure
gold/silver product. Additional research and development activities in the future
should prove the solvent-extraction to be quite attractive, practically and
economically.
CHAPTER FOUR
ELECTROCHEMISTRY
4-1 GENERAL/fHEORY
Electrochemistry is a surface science. In the broad sense, it is the

interrelationship of electrical and chemical phenomena. Its application requires
an understanding of the fundamental principles of electrode reactions and the
electrical properties of electrode-solution interfaces. Electrode reactions, as
distinct from chemical reactions, involve electrons which react at the interface
of a solid phase, capable of electron conduction, and a solution of electrolyte.
According to conventional usage, an electrode, in its simplest form, is defined as

a metal immersed in an electrolyte. Typically, when a metal is immersed in an
electrolyte solution, an electric potential difference is developed between the
metal and the solution. This potential difference is called electrode potential for
the metal/electrolyte combination. If the electrode is composed of more than two
conducting phases in series, the electrode potential is the difference between the
electrical potentials of the two terminal phases. Virtually any surface in contact
with an electrolyte solution acquires a charge different from that of the bulk
solution and is responsible for the electrical potential difference. This electrical
charge is transferred between the electrode and the electrolyte by electrons in
redox reactions and by positively charged metal ions in the case of metal-metal
ion electrodes (Vetter, 1959). It is therefore obvious that the electrode potential
depends on any excess charge that exists on the electrode and the energy
required to add or subtract an electron from the electrode can also be expressed
in terms of the electrode potential. Thus, in electrode reactions, the flow of
electrons at an electrode is directly proportional to the rate of reaction there and
as such the potential is very influencial on the rate of the reaction (Faulkner,
1983).
An electrode reaction takes place in a mechanism of several steps. In addition to

the heterogeneous electron-transfer step, associated equilibrium and sequential
chemical reactions may be involved in the total process. These reactions precede
or follow the electron transfer and include coupled heterogeneous processes of
88
other types, such as adsorption, desorption, or electrocrystallization and coupled

homogeneous processes such as protonation or dimerization in the solution.
(Wadsworth, 1969; Rieger, 1987). All of these chemical steps are kinetic events,
and they all proceed at rates described by rate constants. The overall rate of the
electrode reaction is determined by all of the individual rates together. Since the
electrode process can happen only at the electrode, another factor in the overall
reaction rate is the rate at which reactants can be brought to the electrode or the
rate at which products can be dispersed. Mass transport is therefore usefully
regarded as part of the overall mechanism and occurs by diffusion (microscopic,
random motion), by convection (bulk flow, stirring, movement of segments of
solution), or by electric migration (movement of ions along an electric field). As
such chemical information from a complex electrochemical mechanism can be
obtained by arrangement of conditions so that a single step, such as mass
transfer or heterogeneous electron-transfer controls the overall rate. Non-
electrochemical reactions may, in fact, be rate determining. Transport of ions by
diffusion may also be rate determining even though influenced by potentials
associated with the electrical double layer (the structure of the array of charged
species and oriented dipoles) at the electrode-electrolyte interface (Wadsworth,
1969). The influence of potential in the electrical double layer is a fundamental
feature of electrode reactions since it will increase or diminish activation free
energies of individual reactions depending upon the sign and magnitude of the
charge of the reacting species and its position within the double layer.
Mathematically, the flux (mass transport) to the electrode is described (in one
dimension) by the Nernst-Planck equation:
J( x,t) -__ D -
bC(x,t)
- - _ ~DC( x,t ) -
b<j)(x,t)
-- + C( x,t )vx (x,t ) (4-1.1)
bx RT bx
where J is the flux (mol cm-2 s- 1); Dis the diffusion coefficient (cm 2 s- 1), C is
the concentration (mol cm-3 ), <j> is the electrostatic potential, and v x is the
hydrodynamic velocity. In simple terms, this partial differential equation states
that the flux of material toward the electrode is proportional either to the slope
of the C or <j> profiles or the v x profile (Maloy, 1983 ).
Any electrode process is characterized by its own standard potential E0 . On the

positive side of E0 , the oxidized form of the couple is stable at the electrode,
and the reduced form tends to undergo oxidation if it reaches the electrode.
Likewise, the zone of potential more negative than E0 is a region where the
89
reduced form is stable and the oxidized form tends to be reduced. Actually, in a
zone about 100 mV wide centred on E 0 , statistical equilibrium of electrons on
the electrode and on the species in the solution permits mixtures of oxidized and
reduced forms with appreciable amounts of both species (Faulkner, 1983). As an
oxidation or reduction predominates at the electrode, a flow of electrons or ions
(either to or from the electrode) gives rise to a cmTent which is related to the
rate of the electrochemical reaction.
The development of an electrochemical potential difference between the two

phases(metal and the electrolyte) requires the transport of the electrically
charged particles, ions or electrons, in either direction. The direction is a
function of the initial state. When the equilibrium potential is reached, this
reaction apparently ceases macroscopically, as in the analogous case of a
chemical equilibrium. However, on a molecular scale, there is constant
exchange of charge (ions or electrons) in both directions through the phase
boundary. The forward reaction rate does not become zero, but is compensated
by a reverse reaction of identical rate even though the reaction has
macroscopically come to a complete standstill at the equilibrium potential. The
equilibrium potential can be calculated from the change in Gibbs free energy
(llG) in the course of the reaction. If an electrode process involves a series of
reactions of which one or more may be rate controlling, and there are n such
steps of which steps n; to n1 are rate controlling, then the free-energy difference
is given by the chemical potentials such that
(4-1.2)
Furthermore, if all steps prior to ni and following n1 are essentially at

equilibrium, the free-energy difference is the same as that for the overall
process, or:
~G = µ.J -µ.:::::: µ -µ a
I - C
(4-1.3)
where µc and µa are the cathodic and anodic chemical potentials for the total
process. At equilibrium the chemical potentials are equal and ~ G = 0, resulting
in zero net current density.
Figure (4-1.1) depicts the flow of electrons and ions between the electrode and
electrolyte. The net current density / is the sum of the partial current densities / +
90
and/- (Vetter, 1959). If II-1 > I+' I is negative, and the net process is cathodic.
If II-I < I+' I is positive, and the net process is anodic. It follows that for a net
cathodic process the potential of the electrode E is less than £ 0 and for a net
anodic process E > E 0 , where Eis the voltage when there is a net current density
and £ 0 is the voltage when the net current density is zero (equilibrium value).
By definition, the deviation (difference) of the electrode potential E from the
equilibrium value £ 0 is the overvoltage 'Tl:
11= E - Eo (4-1.4)
and is positive for anodic cmTents and negative for cathodic currents. Thus, the
overvoltage is a function of the net current density. At the equilibrium condition
where the partial current densities are equal, E = E0 and 'Tl = 0. The magnitude
of these mutually compensating current densities at equilibrium is called the
exchange-current density, / 0 . The overvoltage may result from any one of then
steps in the overall process.
When several electrode reactions take place simultaneously, a mixed potential,

Em, develops which differs from the equilibrium potentials of the participating
reactions. It is a non-equilibrium, steady-state value representing conditions
where the total anodic current just equals the total cathodic current (ie. /a = -le).
The anodic and cathodic regions or domains are in electrical contact (short-
circuited) so that the mixed potential, Em, falls between the equilibrium
potential values of the two electrode processes (Wadsworth, 1969; Wadsworth
and Miller, 1979). In the absence of significant internal and ohmic resistance,
each reaction sees the same mixed potential. Thus, a current will also cause a
change in the potential E(i) as compared to the zero current potential which in
this case given by E(o) =Em.This change 'Tl is given by:
1l = E(i) - E(o) (4-1.5)
and is known as polarization. Polarization is also a function of the cun-ent

density. When E( o) = E 0 , the polarization and overvoltage become synonymous.
Consequently, the region for which ll < 0 reacts cathodically, and the region for
which ll > 0 reacts anodically. The cun-ent densities la and le are normalized in
terms of the total area, A. Actually, the cun-ent passing through the cathode of
area Ac must be equal to the cmTent passing through the anode of area Aa.
91
NET CATHODIC PROCESS
(+)
electrons
{-)
I.+ I_ - I < 0
E < E0
I On$
NET ANODIC PROCESS
I+)
electron,
.
I+l-I>O
-
E > E
•
I On I
Figure (4-1.1) Flow of electrons and ions between electrode and electrolyte
for net cathodic and net anodic processes (Wadsworth,
1969).
92
If the anodic and cathodic areas are separate and distinguishable but electrically
in contact, the system represents a galvanic couple. If the anodic and cathodic
areas are part of the same surface, so that A = Aa + Ac, the system represents a
corrosion couple. Under steady-state conditions:
IaA = -IcA (4-1.6)
The transport of an ion to or away from the surface of an electrode is influenced

by the potential gradient at the interface. In passing over barrier ni, an ion goes
from state si to state Si-I which represent minima on either side of the transition
state. If t:,.Gi is the increase in free energy of si-J over Si as a result of the
localized potential gradient, a fraction a of ~ Gi will increase the free energy of
Si-I and the fraction (1-a) of t:,.Gi will lower the free energy of si (Eyring and
Eyring, 1963 ). Thus, if t:,. <1> is the increase in potential across the electrical
layer, the free energy is increased by the amount of zf f:,.<j>, where F is the
Faraday constant and z is the charge, to the value Ga. It is apparent that the
~+
potential decreases the activation energy for the anodic direction ( Ll G + ) by (1-
~+
a )zFt:,.<j> and increases the activation energy for the cathodic direction ( Ll G + )
by the amount azFt:,.<j> where a is the transfer coefficient. The potential
difference t:,.<j> is given by:
(4-1.7)
where l; is the zeta potential. If l; = 0, f:,.q> = E. Other influences such as fluid

flow or temperature gradients may also produce an increase in free energy
between the two states resulting in a similar bias. However, internal
concentration adjustments may take place rapidly enough that steady state
conditions prevail even though localized variations of potential, fluid flow or
temperature exist. Each ion is influenced by its own localized environment. At
electrode interfaces ions experience large variations in potential as they pass
through the electiical double layer.
The kinetics of transfer (electrochemical) reactions thus involve the activation

energy effect associated with the transport of charge carrier (metal ion or
electron) (ie. charge-transfer process) through an inte1facial electrical potential
gradient developed by the system. This potential gradient exists between the
electrode surface and the Outer Helmholtz plane and is essentially linear
93
(Butler, 1951). The separate anodic or cathodic reaction kinetics can be

considered in terms of the absolute reaction-rate theory which considers the rate
process, in which the reactant species are transformed to the product species, to
involve an intermediate high-energy state referred to as the activated complex.
The reactants are assumed to be in equilibrium with the activated complex and
the rate at which the reaction proceeds in a given direction is determined by the
concentration of the activated complex, which in tum is determined by the
magnitude of the energy barrier (Miller, 1981).
If/ is the electron current resulting from the transfer of a metal cation of charge
z, the rate process for an oxidation/reduction reaction can be formulated in
terms of the anodic (or anodic partial current density) and cathodic (or cathodic
partial current density) directions of the reaction. The anodic partial current
density t, and the cathodic partial current density /_ are given by:
--i- kT
I = zF'A,C+ - K (4-1.8)
+ h
and
I= -zFAC+
f-+ -kTK (4-1.9)
- h
~ 7-
where C+ and C+ are the concentrations of the activated complex for the
cathodic and anodic directions respectively, A is the distance between the
minima on either side of the transition (activated) state, K is the transmission
coefficient, k is the Boltzman constant, h is the Planck constant, and T is the
absolute temperature. Assuming the transmission coefficient to be unity. the net
cmTent density I for the reaction is given by:
7-
I= -zFA ( C+-C+
f-+) -kT (4-1.10)
h
7- ~ 7- ~
If C + > C + the electrode reaction is a net anodic process and if C + < C + the
electrode reaction is a net cathodic process. Considering the equilibrium
established with the activated complex for both the cathodic and anodic
directions of the reaction, the equilibrium constants are given by:
94
f+ f-+
~+ C+ ( ~G+)
K+ =-=exp - - - (4-1.11)
Cc RT
and
-t.. ~+
~+ C+ ( ~G+)
K+ =-=exp - - - (4-1.12)
Ca RT
where Cc is the concentration of the metal ion at the Outer Helmholtz plane and
Ca is the effective surface concentration of the metal sites capable of reacting in
~+ +-+
the anodic direction. If ~G 0 + and ~G 0 + are the activation free energies for the
reactions in the anodic and cathodic directions when E is zero, then the specific
rate constants for the anodic and cathodic reactions, k: and k~ are given by the
following expressions from transition state theory (Rieger, 1987):
(4-1.13)
An increase in E favours the anodic process and a decrease in E favours the

cathodic process such that:
-t..
K! = C+
C
=k'(ex [azFE])(~)
a p RT kT
(4-1.14)
a
and
(4-1.15)
Combining equations (4-1.10), (4-1.14) and (4-1.15) gives:
, [azF] , [ (1-a)zF] (4-1.16)

I= zFACaka exp --E - zFACckc exp - - - - E
RT RT
95
(4-1.17)
Equation (4-1.17) is known as the Butler-Volmer (Butler, 1924; Erdey-Gruz and

Volmer, 1930) equation. When the electrode is in equilibrium with the solution,
I =0, E = E 0 , and / + =I/_
j = / 0 . The equilibrium exchange-cmTent density, / 0 ,
is thus given by:
(4-1.18)
and the Butler-Volmer equation (4-1.17) in terms of 10 is:
azF ] [ (1-a)zF ])
1=10 ( exp [ -11 -exp ----11 (4-1.19)
RT RT
where 11 = E - E0 and lo is the exchange-cmTent density when

7- ~
C+ = C+ .Equation (4-1.19) reduces to the Tafel equations (Tafel, 1905) for
large anodic currents (11 >>0):
RT RT
11 = - ln 10 + - ln I (4-1.20)
aF aF
and for large cathodic currents (11 <<0):
11 = RT In I + RT In / (4-1.21)
(1-a)F O (1-a)F
such that:
lril = ~ + ~ lnlII (4-1.22)

a' a'
or
TI = b log ( I/1 0 ) (4-1.23)
where b = -(a/In lo)= RT/zF and a'= a for anodic currents and a' =(1-a) for
cathodic currents (Wadsworth, 1969). For smaller currents both terms of
96
equation (4-1.19) are important. If the overvoltage is a result of energy barrier ni

and µi and µi-l are the chemical potentials for the i and i-1 states equations (4-
1.2) and (4-1.18) result in the important general equation:
(1-a)zF
l=-10 exp [ - - - 1 1 ] ( I-exp [ -~G J) (4-1.24)
RT RT
where ~G is the free energy change for the total cathodic process. At ~G = 0,
equilibrium is attained and I = 0. It is possible to estimate the importance of
back reactions for the total process using equation (4-1. 23). For practical
application to metallurgical systems back reactions would be negligible for
values of ~G such that exp(~G/RT) < 0.01 which corresponds approximately
to ~ G values where ~ G < 1OT, or ~ G < -3 kcal/mole at room temperature. For
sufficiently small overvoltages as 11-----tO, zF11-----t ~G and equation (4-1.23)
becomes:
1=10 zF
-n
-I ~G (4-1.25)
RT 01
- 0 RT
which is equivalent to the irreversible thermodynamic approximation for

processes near equilibrium (Wadsworth, 1969).
For electron transfer equation (4-1.16) becomes:
I= nFACrkr, exp[ --E

anF ] - nFAC k , exp[ -(1-
0 0 - -a)nF
-E ] (4-1.26)
RT RT
where n is the number of electrons in the transfer reaction, Cr is the

concentration of reduced ion and C0 is the concentration of the ion in the
oxidized state. If the electrode process (eg. reduction of ion) involves both metal
ion and electron transfer, equations (4-1.16) and (4-1.25) may be combined for
steady-state conditions which for divalent cations results in the equation:
a F (2-a )F
21 0 M(exp[ ____M_11]-exp[ - M 11])
I= ' RT RT (4-1.27)
Io,M
1 + --exp (1 + ae - aM)F ]
[ - -----=------==------11
l 0 ,M RT
97
If the energy barriers are approximately symmetrical such that

= = =
aM 1- aM ae 0.5 = a, equation (4-1.25) becomes:
aF (2-a)
21 0 M(exp[-11]-exp[ ---11])
I= ' RT RT (4-1.28)
loM F
1+-·-exp[--]
Ioe RT
For large anodic currents equation (4-1.27) becomes:
aF ] (4-1.29)
I = 21 0 ,M exp[ RT 11
and for large cathodic currents:
I= -21 (1-a)F ,, ]
exp [ ____
o,e RT 'I (4-1.30)
If the exchange current density l 0 ,efor electron transfer is very smaller than the
exchange current density l 0 ,M for the ion transfer reaction equation (4-1.28)
becomes for cathodic current densities and small anodic current densities:
(2-a)F ] - exp [ --11

I= 2l 0 e ( exp [ ---11 aF ]) (4-1.31)
' RT RT
The denominator of equation (4-1.28) would approach unity at sufficiently large

anodic current density, but equation (4-1.31) would apply for example up to an
anodic overvoltage of 100 mV for the ratio 10 .M/Io.e of approximately 103.
4-2 ELECTROCHEMICAL TECHNIQUES
In p1inciple, all electrode reactions occur to some degree at all potentials, but in
some cases the rate is too slow to be interesting. The electron transfer rate
increases exponentially with the applied potential. This is a very powerful tool
and a unique feature of experimental electrochemistry. The electrochemical cell,
consisting of two or more conducting electrodes, is an extremely versatile
device, the basic properties of which give rise to experimental observables.
98
Non-equilibrium electrochemical methods such as conventional polarography at

the dropping mercury electrode (DME), cyclic voltammetry, linear sweep
voltammetry, normal pulse and differential pulse voltammetry or polarography,
chronopotentiometry, chronoamperometry, chronocoulometry, conductimetry,
and others abound in modem electrochemistry. The uses range from highly
sensitive assay work, to fundamental kinetic-mechanistic studies of electrode
reactions (Smith, 1983).
4-2-1 Voltammetry
Voltammetry, is concerned with the study of current-voltage relationships at an

electrode immersed in a solution containing electroactive species. More
specifically, it is the determination of the potential of a single electrode during
the course of a sustained electron transfer reaction at the electrode surface
(Adams, 1969).
Studies in this field began in 1897 with the work by Salomen (Salomen, 1897;
Salomen, 1898) who obtained current-voltage curves for the electrolysis of
silver ion and indicated the existence of limiting currents. Caspari (Caspari,
1899) examined the anodic oxidation of bromide and iodide at platinum
electrodes. Technical interest in the electrolytic reduction of organic compounds
had already developed at this time. Haber (Haber, 1900), and Russ (Russ, 1903)
examined the electrochemical properties of gold, platinum and other less noble
metal electrodes with respect to organic reductions and oxidations. The effect of
pretreatment techniques were noted qualitatively by these workers. Theoretical
studies of rotated electrodes and stirred solutions developed with the work of
Nernst and MeITiam (Nernst and MeITiam, 1905) and Brunner (Brunner, 1906),
among others.
Beginning in the 1950's, publications on solid electrode voltammetry parallels

the rapid increase of the general polarographic literature as cited by Kolthoff
and Ligane (Kolthoff and Ligane, 1952). Some of the increased activity can be
traced to an appreciation of modern electroanalytical techniques which employ
solid electrodes. A rise in the applications involving limiting cuITent
measurements for routine analytical work is evident. Solid electrode techniques
have played an increasing part in the recent interest in the chemical industry in
organic oxidation-reduction processes. Significant advances have been made in
99
the interpretation of complex electrode reactions to such a high level of

confidence at present that information from solid electrode determinations is
commonly used in theoretical studies.
4-2-1-1 Experimental Technique
The electrochemical experimental technique commonly involves studying the

influence of changes in applied voltage on the current flowing at the electrode,
but in some circumstances, the variation of current or potential with time may be
investigated (Vogel, 1989). The procedure normally involves the use of a cell
with an assembly of electrodes. Typically, the potential is determined by a
variable power supply voltage applied across the electrodes. This power supply
may be controlled by a potentiostat (Maloy, 1983; Rieger, 1987). The current
flowing through the cell is then plotted as a function of the electrode potential.
The kind of voltammogram that is observed depends on the way that the power
supply voltage is varied and the physical and electrochemical properties of the
cell. In experiments which require a constant current through the cell, the
potential of the electrode is controlled by a galvanostat (Rieger, 1987).
Voltammetry and related electrochemical techniques require an excess of inert
electrolyte to make the solutions conducting and to reduce the electrode double-
layer thickness. In principle, any strong electrolyte will satisfy these basic
requirements. The design of electrochemical cells for voltammetric experiments
depends on the technique and on the requirements of the chemical system being
studied. The details of two common designs have been described by Rieger
(Rieger, 1987).
4-3 ELECTRODE SYSTEMS
The three electrode polarographic system 1s the conventional practice m

voltammetry. The electrode at which the primary polarographic reaction occurs
is referred to as the indicator or working electrode (WE) and it is used
frequently to mean the platinum, gold or other electrode involved. There is an
opposite working electrode referred to as the auxiliary or counter electrode
(CE). If, for example, an oxidation polarogram is being studied at a platinum
working electrode, the counter electrode is the cathode of the polarographic cell
(Adams, 1969). The electrochemical properties of a counter electrode do not
100
affect the behaviour of the electrode of interest and may be any desired inert
electrode (ie. does not produce substances by electrolysis that will reach the
working-electrode smface and cause interfering reactions there). It is frequently
placed in a compartment separated from the working-electrode compartment by
a sintered-glass disk or other separator (Bard and Faulkner, 1980). The counter
electrode merely serves to complete the electrochemical cell. The potential of
the working electrode is measured relative to a separate reference electrode, the
third electrode of this system, positioned with its tip near the working electrode.
The internationally accepted primary reference is the standard hydrogen
electrode (SHE) or normal hydrogen electrode (NHE), which has all
components at unit activity:
Pt/H2 (a= 1)/H+ (a= 1, aqueous) (4-3.1)
In aqueous solutions, the saturated calomel electrode (SCE) is almost

universally used as a reference electrode. It is well characte1ized and gives
reproducible potential readings with a minimum of experimental difficulty. It
consists of Hg which is coated with a slurry of calomel, Hg2Cl2, in KCl solution
and is designated as follows (Bald and Faulkner, 1980):
Hg/Hg2Cl2/K.Cl (saturated in water) (4-3.2)
Its potential is 0.242 V(versus NHE). For certain purposes the silver-silver
chloride (Ag/AgCl) electrode is useful. Mercury-mercurous sulphate and lead
amalgam-lead sulphate half-cells have been used (Adams, 1969). The
anangement of the reference electrode is such that it does not pass cuITent and
hence its potential remains constant and equal to its open-circuit value. This
provides an invariant reference point against which working electrodes can be
measured. Also, the three-electrode configuration avoids the problem of
reference electrode polarization and somewhat reduces the iR contribution to the
measured potential (Bard and Faulkner, 1980; Rieger. 1987). However, iR drop
often remains a problem and most commercial electrochemical instruments
contain a circuit which partially compensates for iR drop by electrically
subtracting an adjustable voltage, proportional to the cuITent, from the measured
cell potential (Rieger, 1987).
101
For electroanalytical and mechanistic work two forms of working or indicator

electrodes commonly used are the dropping mercury electrode (DME) and the
rotating disc electrode (RDE).
4-3-1 Rotating disc electrode
The rotating disc electrode (RDE) is the most practical f01m of electrode for
which a completely rigorous hydrodynamic treatment can be given. The theory
of a rotating disc electrode applies to thin plane surface, so large in diameter
that the edges may be neglected with respect to the total surface. This plane is
rotated with constant angular velocity about an axis perpendicular to the plane
such that the experiment is done under steady-state (ie., time independent)
conditions. The rotational motion stirs the solution so that diffusion problem is
reduced to transport across a stagnant layer at the electrode surface. This
electrode is easy to construct and consists of a disc of the electrode material
imbedded in a rod of an insulating material. A commonly used form involves a
platinum wire sealed in glass tubing with the sealed end ground smooth and
perpendicular to the rod axis. More frequently the metal is imbedded into teflon,
epoxy resin, or another plastic. Although the literature suggests that the shape of
the insulating mantle is critical and that the exact alignment of the disc is
important (Riddiford, 1966), in practice what is more imp01tant is that there is
no leakage of the solution between the electrode material and the insulator (Bard
and Faulkner, 1980). The rod is attached to a motor directly by a chuck or by a
flexible rotating shaft or pulley arrangement and rotated at a certain frequency, f
(revolution per second). The electrical connection is made to the electrode by
means of a brush contact usually of carbon-silver (Graphalloy) materials. The
full details of the construction and application of RDEs have been given m
excellent reviews by Riddiford (Riddiford, 1966) and Adams (Adams, 1969).
A theoretical treatment of the rotating disc system is also given by Riddiford

(Riddiford, 1966). The rotating system has a well-defined hydrodynamic flow
pattern. Qualitatively, as the electrode rotates, adjacent solution is pulled along
by viscous drag and is thrown away from the axis of rotation (ie., in a radial
direction) by the centrifugal force. The expelled solution is replaced by flow
normal to the disc surface (ie., axial flow). The rotating disc, thus acts as a
102
pump which moves solution up from below and then away from the electrode.
Near the surface of the rotating disc:
(4-3.3)
where ro is the angular velocity of the disc given by: ro = 2rcf radians/sec, v is
the kinematic viscosity of the solution in cm 2/sec, 80 is hydrodynamic (or
momentum or Prandtl) boundary layer thickness and roughly represents the
thickness of the layer of liquid dragged by the rotating disc (Bard and Faulkner,
1980).
The region close to the surface of the rotating disc electrode can be considered
as two regions in order to describe qualitatively the mass transport of species to
the rotating surface. For a certain fluid having a finite viscosity, the solution
contacting the rotating disc adheres to its surface and has the same velocity
vectors as the rotating disc. In this adherent layer diffusion is responsible for the
mass transport of reactant species. The thickness of diffusion layer, measured
perpendicular from the rotating disc surface is inversely proportional to the
square root of rotational speed. Levich (Levich, 1942) showed that for a rotating
disc, under laminar flow conditions:
(4-3.4)
where, 8 is diffusion layer thickness (cm), D is the diffusion coefficient of

electroactive or reactant species (cm 2/sec), v is the kinematic viscosity
(cm 2/sec), and ro is angular velocity of rotating disc (rad/sec).
For a reaction controlled by only mass transfer (reversible), the limiting cmTent
is also given by Levich (Levich, 1942):
2 I I
iL = 0.62nFACbD 3 v- 0 w~ (4-3.5)
where iL is the limiting cmTent (mA), Cb is the bulk concentration of

elelctroactive species (moles/cm3), A is area of disc electrode (cm 2), D is the
diffusion coefficient of electroactive species (cm 2/sec), ro is angular velocity of
the disc (rad/sec), n is the equivalents of charge/mole, v is kinematic viscosity
of solution (cm2/sec) and Fis the Faraday constant (96485 coulomb/equivalent).
Equation (4-3.5) is known as the Levich equation and predicts that iL is
103
proportional to Cb and w½. The constant, idCbw½, is defined as Levich

constant and is the RDE analog of the diffusion current constant or current
function in voltammetry (Bald and Faulkner, 1980). However, a simple
I
evaluation like iL versus ro 2 behaviour is a necessary but not sufficient proof
that a given RDE is functioning according to theory. The real test of the RDE
lies in checking experimental iL's with theoretical values. The derivation of the
Levich equation also assumes that laminar flow exists near the disc surface.
Such conditions can be maintained apparently up to Reynolds numbers, NRe•
between 104 and 105. The value of NRe for a RDE is given by:
(4-3.6)
where r is the disc radius in cm and is the total radius of working plus non
working area.
For non-limiting current conditions:
(4-3.7)
where C0 is the concentration of electroactive species at the electrode surface.

Thus for a Nemstian reaction, combination of the Nemst equation for the 0
(oxidation), R (reduction) couple (assuming the simple reaction O + ne <=> R)
with the equations for the various currents and limiting currents yields the
familiar voltammetric wave equation:
RT (iLc -i)
E = E 112 + - I n . '. (4-3.8)
nF (1-1L.J
where iL,c is the limiting cmTent for a cathodic reaction and it,a is the limiting
cunent for an anodic reaction and:
E o RT DR½3
½- = E --ln(-)
nF D
(4-3.9)
0
Thus, the shape of the wave for a totally reversible reaction is independent of m.
However, since iL varies as w½, i at any potential should vary as w½. A
deviation of a plot of i versus w½ from a straight line that intersects the origin
suggests some kinetic step involved in the electron transfer reaction.
104
4-3-2 Electrode kinetics and mechanism
The most valuable applications of the RDE have been to investigations of the
rates and mechanisms of electrode processes. For a first-order electrode reaction
which is controlled both by mass transport and charge transfer, Levich equation
gives:
(4-3.10)
where k is the heterogeneous rate constant at the given potential. This relation
can be written as:
. nFADCb
I=--- (4-3.11)
8+(0/k)
where 8 is as defined in equation (4-3.4). The other symbols have been defined
in equation (4-3 .5) and have their usual significance. The equation (4-3 .10) or
(4-3 .11) is useful in defining the conditions for kinetic or mass transfer control
at the RDE depending on the relative magnitudes of 8 and the ratio D/k. If
8=10-3 cm, then for values of k > 10- 1 cm/sec, the term D/k can dropped to give
the familiar relation for the limiting current of a diffusion-controlled process at
the RDE, ie., equation (4-3.5). On the other hand, if under the same
experimental conditions, k < 1o-4 cm/sec, then 8 is negligible with respect to
D/k and equation (4-3.11) becomes:
i = nFAkCb (4-3.12)
and the observed cmTent in this case is independent of the mass transfer. ie., the
cmTent is entirely controlled by charge transfer or under kinetic (or activation)
control. The rate constant can be evaluated from equations (4-3 .11) and (4-
3. l 2). Thus if the RDE is to be used for kinetic measurements D/k should be
small. Under mass transfer conditions k can be calculated from:
(4-3.13)
105
In real situations, the diffusion coefficient D is mostly not known. A linear

relationship of k versus co½ demonstrates the diffusion control process.
It is also possible to determine the order of the electrochemical reaction from

RDE measurements. The order is actually reflected in the shape of i versus co½
curves for the charge transfer-controlled reactions. Alternatively, the order can
be found from the expression:
(4-3.14)
where m is the order of reaction, o is the thickness of the diffusion layer defined
in equation (4-3 .4 ), and j is the flux expressed as:
(4-3.15)
The determination of m involves measurement of i at two different rotation

velocities and evaluation of the various parameters (Galus and Adams, 1962;
Levich, 1962). Other techniques for evaluating reaction orders at RDE's have
been given by Frumkin and Tedoradse (Frumkin and Tedoradse, 1958).
From equation (4-3.5), the limiting current density (mA/cm 2), is given by:
2 _.1 .1 b
iL,j = 0.62nFD/v 6 co 2 Cj (4-3.16)
This equation (4-3.16) expresses a relation between the six quantities iL,j, n, Dj,
v, co, C/, any one of which could be determined experimentally by means of
the RDE. However, v and co are better determined directly. The evaluation of
the bulk concentration of the species j offers obvious analytical applications.
The electrode could be used for amperometric titrations to determine species
concentrations. The possibility of computing iL,j from a knowledge of the
remaining quantities has two advantages. First, such a computation avoids the
necessity for polarizing the electrode to the point where iL,j could be determined
experimentally. This may be undesirable in practice since the polarization may
result in changes in the activity of the electrode or in the case of
electrodeposition, in too heavy a deposit for satisfactory kinetic study. Second,
it may not be possible to determine the limiting current by direct measurement,
either because of the onset of a second electrode process or because the limiting
106
current 1s too high for convenient measurement. Given an experimentally

determined limiting current however, the number of Faradays associated with
the electrode process is easily obtained. Alternatively, if n is known, the
diffusion coefficient of the rate-limiting species may be determined. This latter
application of the RDE has been given more attention by researchers.
4-4 CURRENT - POTENTIAL RELATIONSHIPS
Electrochemical reaction kinetics can be analyzed in terms of the steady-state

mixed potential, Em, which the system develops. The anodic and cathodic curves
of a hypothetical electrochemical reaction are presented in the current-potential
diagram in figure (4-4.1). The position of these curves may be dependent on the
composition of the electrolyte, the concentration of Mt1 and M;22 •
Consequently, the current-potential diagram for the short-circuited system,
shown by the dashed line, also varies as the sum of the respective half-cell
current-potential curves. Under these circumstances the mixed potential can
vary between the two reversible potentials, E 0 ,M 2 and E 0 ,M 2 • The region for
which the overpotential 11 (ie., 11 = E - E 0 M) < 0 reacts cathodically and the
region for which 11 > 0 reacts anodically. The exact position of the mixed
Potential is determined by the fact that i M I = -i M 2 for a system at steady state.
As the reaction proceeds, the half-cell current-potential plots change and the
mixed potential drifts.
The mixed potential can be treated quantitatively by using the Butler-Volmer

equation for each half-cell:
(4-4.1)
(4-4.2)
107
I
I
I
I
I
I
I
I
E..,• I
T/2
'\
T) Eh(volt~)
.. Z I
M +ze--+-M
""i 2 (E)
I 2~·+2e _.._ H2
I
I
I
Figure (4-4.1) Current density - potential diagram electrochemical reaction

which achieves a mixed potential, Em (Miller, 1981).
108
For a symmetrical energy barrier, the transfer coefficient equals 0.5. Setting,
IM 1 = -IM 2 equations (4-4.1) and (4-4.2) can be solved to give:
(4-4.3)
and the complex nature of the mixed potential is revealed. The expression can
be greatly simplified if the back reaction is considered negligible, that is large
overvoltages exist. In this case the expression becomes:
(4-4.4)
In an actual system it is conceivable that not only the concentrations of the

metallic ions could vary, but also the anodic and cathodic areas.
4-4-1 Hydrogen evolution
The most striking feature of current-potential curves 1s the reduction of

hydrogen ions, H+ (aq), to form hydrogen gas. The mechanism has been the
subject of some controversy over the years and the details are still imperfectly
understood (Rieger, 1987). One of the important characteristics is the enormous
range in the exchange cmTent density with electrode material. Also, the apparent
cathode transfer coefficients vary from less than 0.5 to about 2.0. Some
representative results are shown in Table (4-4.1 ). Conside1ing the electrode
process:
2H+ (aq) + 2e- = H2 (g) (4-4.5)
The mechanism is likely to involve reduction of hydrogen ions to give hydrogen

atoms adsorbed on the electrode surface:
M + H+ (aq) + e- ~ M-H (4-4.6)

109
The hydrogen atoms then migrate on the surface and form hydrogen molecules:
2M-H ~ M· H2 (4-4.7a)
Alternatively, if the mobility of hydrogen atoms on the surface is slow, H-H

bond formation may be concerted with reduction of a second hydrogen ion near
an adsorbed atom:
M-H + H+ (aq) + e- ~ M· H2 (4-4.7b)
Finally, hydrogen molecules are desorbed from the surface:
M • H2 ~ M + H2 (g) (4-4.8)
Table (4-4.1) Kinetic parameters for hydrogen evolution (Rieger, 1987).
Metal* log(iofA m- 2 ) aapp
Pt (smooth) 1.0 1.5

Pd 0.3 2.0
Ni -1.4 0.5
Au -2.0 1.3
Fe -2.0 0.4
Mo -2.0 1.5
w -2.0 1.5
Cu -2.7 0.5
Cd -:to 0.3
Sn -4.0 0.4
Hg -7.7 0.5
Pb -8.7 0.5
* Metal in contact with 1.00 M HCl at 20oC.

110
If step (4-4.7a) is the rate limiting, in the absence of double-layer effects, the
anodic and cathodic transfer coefficients should be near ½. The data given in
table (4-4.1) are consistent with step (4-4.7a) being rate limiting for Pb, Hg, Zn,
Sn, Cd, Cu, Fe, and Ni. If step (4-4.7b) is rate limiting, the cathodic transfer
coefficient should be approximately ½ and the anodic transfer coefficient
should be about½- Step (4-4.7b) is probably rate limiting for Pt, Au, Mo, and
W. A strong M-H bond is expected to make step (4-4.6) more favourable but
hinder step (4-4.7a) or (4-4.7b). Conversely, a weak M-H bond would make step
(4-4.6) slow and (4-4.7a) or (4-4.7b) fast.
4-5 EVANS DIAGRAM
A convenient way to investigate electrochemical reaction kinetics is to plot the

current-potential curves for the respective half-cell reactions involved in the
process in an Evans diagram. An Evans diagram is a potential versus log
(current density) plot of the cmTent-potential (i-E) curves of the two half-cell
reactions. In essence the diagram is simply the superposition of the anodic and
cathodic current-potential (polarization) curves. From this diagram the
mechanism and reaction rate of the electrochemical process can be derived. A
typical polarization curve for an arbitrary metal is shown in figure (4-5.1). At
very low currents the potential, Ea, is equivalent to the reversible electrode
potential. As E is made more negative (cathodic) than Ea, the metal ions begin
to be reduced. At some point (intermediate cmTent densities) the potential
begins to vary linearly with log i. This region of the polarization curve is known
as the Tafel region and the slope of the linear portion of the curve is referred to
as the Tafel slope. For large negative values of potential, the cmTent density
reaches a maximum value, the limiting cmTent density. Under these conditions
the magnitude of the current is determined by the rate of transport of metal ions
to the electrode smface. Similar regions can be identified for the anodic
behaviour of the system when the potential is made more positive than Ea.
However, in this case, the limiting current density is reached only when the
metal surface becomes saturated with respect to a salt of the metal and as such
usually not observed. From the linear region of the polarization curves, the Tafel
equation is defined as:
111
anodic
-c.n
£ Eo I------ ~-::-: ::-'. Tafel slopes
w I
0 +r
cathod ic M-M
C
-Q)
0
Q_
diffusi on
log
Figure (4-5.1) Typica l polariz ation curves for an arbitra ry metal showin g
cathod ic and anodic reactio n (Powe r, 1975).
112
11 = a±blogi (4-5.1)
where a and b are constants and 11 is the overpotential. Alternatively, the Tafel
equation can be written from the Butler-Volmer equation (4-1.14) in terms of
the exchange-current density as defined in equation (4-1.20). The polarization
curves can be determined experimentally or calculated, provided the exchange-
current density and transfer coefficient are known.
An idealized Evans diagram is presented in Figure (4-5.2). In this diagram it is

assumed that the cathodic and anodic polariztion curves are independent, and
the cathodic and anodic areas are equal and are short-circuited. Under these
circumstances the mixed potential, Em, can be read directly from the diagram.
Another unique feature of this diagram is that it shows clearly whether the
reaction is controlled by diffusion or by a chemical process. The point of
intersection of the polarization curves determines the mixed potential for the
reaction and the rate controlling step. The criterion for mass transfer controlled
reaction is the intersection of the anodic and cathodic curves in the diffusion-
limited region while that for a chemical controlled reaction is the intersection of
these curves in the Tafel region or above it. The point at which rate control
switches from mass transfer to chemical reaction can be evaluated. When the
anodic curve intersects the anodic curve right on the "knee" (ie., the transition
point), the reaction is expected to be controlled by both diffusion and chemical
steps (mixed control). Solution of the respective Tafel equations for cathodic
and anodic half-cells at the transition mixed potential results in:
~ = b[loo(iL) + loo(iL) a]
0 b. C b.
(4-5.2)
lo lo
where b =0.03 V/decade cmTent density for many metals.

113
Eo .c
--
V)
---w>
-0
c
-d)
0
a_
0 6
log ilia
Figur e (4-5.2) Idealized Evan s diagr am show ing the transi tion from
mass trans fer contr ol to electr ochem ical reacti on
contr ol (Pow er, 1975)
CHAPTER FIVE
CEMENTATION
5-1 INTRODUCTION/DEFINITION
Cementation or metal displacement or contact reduction is the reaction in which

a noble metal ion in a solution or melt is precipitated (ie., reduced to the metal)
onto a less noble metal. This reaction is electrochemical in nature and is
represented as:
nMm+ + mN° = nM0 + mNn+ (5-1.1)
In this equation (5-1.1) a metal 10n m a solution (MID+) is reduced to the

metallic state by electrons which are released from the oxidation of a less noble
metal (N°) in the solution. The reaction is heterogeneous and takes place at the
surface of the metal N°.
According to Power and Ritchie (Power and Ritchie, 1975), the word
"cementation" used widely in literature for metal displacement reaction is
believed to be originated from the Spanish word "cementacion" which means
precipitation. Cementation has been known for centuries and is still an
important operation in hydrometallurgical processing. It is used extensively as a
means of primary metal recovery in the case of cadmium, copper, gold, and
silver, and as an electrolyte purification technique in electrolytic recovery
systems. Undoubtedly copper cementation from dump leach liquors represents
the greatest production of industrial cementation system. An important example
of its purification application process can be found during the electrolytic
production of zinc and nickel. In such cases a number of metallic impurities,
particularly Cu and Cd, are removed either by zinc dust for electrolytic zinc
production or by metallic nickel for electrolytic nickel production. Other
examples for this type of reaction include recovery of Bi, Ge, TI and Re from
their respective solutions, and recovery of Zr, Ti and Be from their respective
melts. Fe, Al, Zn, Mg and Na amalgam are used as common precipitants.
115
5-2 THEORYffHERMODYNAMICS
Microscopic observation of cementation reactions show that the cemented metal

is deposited onto a growing surface (cathodic area) while the dissolving metal is
ionized and enters the solution from separate anodic area. The electrochemical
nature can be seen more clearly if equation (5-1.1) is separated into oxidation
and reduction half-reactions. At an anodic site on the surface of metal N°,
oxidation is taking place:
mN° = mN°+ + mne (5-2.1)
At a cathodic site, the cation of the second metal is being reduced:
nMm+ + nme = nM0 (5-2.2)
Thus a condition for the displacement reaction is that the electrode (reduction)
potential of pure N° in the solution of N°+ ions is more negative than that of
pure M0 in the solution of Mm+ ions, ie.,:
(5-2.3)
or
(5-2.4)
where E0 (MID+fMO) and E0 (N°+fN°) are the standard electrode potentials, and
a(MID+) and a(N°+) are the activities of the cations in solution. If the reaction is
between metals of equal valence and goes to completion at room temperature
[say a(N°+)/a(MID+) = 1010 at equilibrium]:
(5-2.5)
This is the thermodynamic condition for the feasibility of a metal displacement

reaction.
The anodic and cathodic reactions are shown in figure (5-2.la), in which it has
been assumed for simplicity that no redeposition of metal N° has taken place.
116
The reaction, at least in a formal sense, can be considered as occurring via five
steps as shown in figure (5-2.1 b ):
(i) transport (diffusion) of MnH to the surface of N°;

(ii) adsorption of Mm+;
(iii) electron transfer from N° to MllH;
(iv) desorption of Nn+;
(v) transport (diffusion) of Nn+ away from the smface.
In principle, any one of these steps may be rate controlling. If the first or the last
step governs the reaction, it is said to be under diffusion control. If any of the
other steps is rate determining, the reaction is said to be under surface or
chemical control. Mixed control occurs when a diffusion step and a surface step
have comparable rates.
Arn+ sol u\ ,on
l
calrod,c : , \
s i \ .z
A Bn+ A
- - - - - -
Q
B
_____,.
anodic SI\ Q
Figure (5-2.la) Schematic diagram showing anodic and cathodic regions in

cementation (Power and Ritchie, 1975).
117
procipitonl deposit d lffusion bounder y bulk

metal ,urfoc,. I oyt,r ,::,Jut ion
Figure (5-2.lb) Cementation reaction mechanism (Strickland and Lawson,

1970)
It can also be seen that the anode and cathode are virtually shorted, and are
therefore at practically the same potential. This is a mixed potential, which
means that the cathodic process is taking place at a more negative potential than
the equilibrium potential of metal M0 in a solution of its ions, and so is
essentially one of electrodeposition. Correspondingly, the anodic process is
essentially one of dissolution. The complexity of the metal displacement
reaction is partly due to the fact that the metal surface is simultaneously subject
to deposition and dissolution (Power and Ritchie, 1975).
118
5-3 ELECTROCHEMISTRY
5-3-1 Electrode Systems
The first step in studying the kinetics of cementation or metal displacement

reactions, like all heterogeneous reactions, is to distinguish the mechanism and
to determine whether the rate of reaction is controlled by a diffusion or chemical
step (Power and Ritchie, 1975). The rate of a diffusion-controlled reaction
depends, inter alia, on the sample geometry and method of stining. In order to
test unambiguously for diffusion control, it is necessary to use a sample
geometry that provides a flow situation whose hydrodynamics is well-
characterized (ie., amenable to mathematical analysis). The only sample
configurations (or geometries) that appear to be satisfactory for these studies are
the rotating disc, the rotating cylinder, and the suspended particles (Power and
Ritchie, 1975; Miller, 1981)
5-3-2 Hydrodynamics/Mass transfer
5-3-2-1 Rotating disc
The rotating disc system is unique for kinetic studies of cementation reaction
with laminar flow being maintained up to quite high Reynolds numbers (of
order of 105 for a smooth disc). Furthermore, the hydrodynamic flow in this
system is well defined and can be calculated from first principles as done by
Levich (Levich, 1942). As a result of this, the rate constant for a reaction which
is controlled by ion transport to the surface of a rotating disc is given by
equation (4-3.13). This provides additional insight into distinguishing the rate-
limiting step for cementation reaction.
A number of cementation-rate studies have been successfully canied out using

the rotating disc geometry (Episkoposyan and Kakovskii, 1965; Shcherbakov
and Kakovskii, 1967; Strickland and Lawson, 1970; Strickland and Lawson,
1971; Power and Ritchie, 1975; Power and Ritchie, 1976; Nicol et al, 1979;
Ritchie and Staunton, 1984; Hughes et al, 1984; Paul and Howarth, 1986;
Miller, 1988). The results of these studies showed that for most cementation
systems the rate is limited by mass transfer (diffusion) and that the kinetics of
the reaction conformed well with equation (4-3.13), until the surface had
119
become sufficiently roughened by deposit formation to cause a significant

perturbation to laminar flow. The mass transport to a rotating disc is very
sensitive to the roughness of the disc surface since the roughness decreases the
critical Reynolds number above which the transition from laminar to turbulent
flow takes place (Bircumshaw and Riddiford, 1952). Furthermore, since the
Reynolds number is a function of the radius r (Re = r 2 m/v), the flow regime
will become turbulent at the outer section of the disc first (Chin and Litt, 1972),
and as the deposit grows, the turbulent region will move toward the centre of the
disc. Under these conditions, the flow situation is complex and can cause an
increase in the apparent reaction rate constant. The nature of this deposit can be
particularly sensitive to the temperature and electrolyte composition (Miller,
1981).
5-3-2-2 Rotating cylinder
Unlike the rotating disc system, the flow regune of the rotating cylinder
becomes turbulent at very low Reynolds numbers,
Re= Vd/v (5-3.1)
where V is the peripheral velocity of the cylinder, d is the cylinder diameter,

and v is the kinematic viscosity. On this basis the transition to turbulent flow
for a rotating cylinder begins to occur at Re = 10 and at very low rotation speeds
(Miller, 1981; Power and Ritchie, 1975). Thus, the mass transfer to a smooth,
rotating cylinder under laminar flow conditions is of limited applicability (Gabe
and Robinson, 1972). However, all points on the smface of the rotating cylinder
have equal linear velocity and equally accessible (Power and Ritchie, 1975). For
most purposes, the mass transfer coefficient for rotating cylinders (under
turbulent flow), k, is given by (Eisenberg et al, 1954 ):
k = o.079 yo.7 d-o.3 v-0.344 oo.644 (5-3.2)
where D is the diffusion coefficient (cm2/sec). The dependence on the

peripheral velocity to the 0.7 power has been demonstrated for Cu 2+/zn system
(Miller, 1981 ). A number of cementation rate studies have been made using
rotating cylinders (Power, 1975; Barin et al, 1980) but few investigators have
analyzed their results in terms of predicted mass transfer rates for turbulent flow
at a rotating cylinder. A major factor or complication which may lead to
120
erroneous interpretation of cementation rate data by this system is the surface

deposit and its morphology. This factor is common to all experimental
techniques. Another factor which may cause difficulty in the analysis of
cementation data for a rotating cylinder is the end effect. However, a review of
the literature indicates that for studies in which surface deposit effects have been
eliminated the calculated mass transfer coefficient agrees well with the
experimental values (Miller, 1981).
5-3-2-3 Suspended particles
Cementation on suspended particles is of considerably greater interest than the

rotating disc or the rotating cylinder systems. Most industrial cementation
reactions are accomplished in stirred reactors with particulate metal powder.
However, the theoretical treatment of mass transfer to particles suspended in a
stirred reactor has not been fully developed. Nevertheless, the minimum mass
transfer coefficient, k*, in which the slip velocity would be equivalent to that for
free-falling particles, can be calculated on a semitheoretical basis for monosize
spheres from the physical properties of the aqueous and solid phase and the
diffusion coefficient of the reactant. Basically, the semitheoretical correlation
takes the following form for free-falling spherical particles (Ranz and Marshall,
1952):
Sh = 2 + 0.6 Re0.5 Sc0.33 (5-3.3)
where Sh is the Sherwood number (k*d/D), Re is the Reynolds number (vd/Y),

and Sc is the Schmidt number (D/v). Figure (5-3.1) is a plot of the above
correlation in terms of the mass transfer coefficient versus particle size. In the
range of 100 to 1000µ the mass transfer coefficient is independent of particle
size. For large particles the mass transfer coefficient is dependent on the particle
diameter to the -0.25 power and for small particles, varies inversely with
particle size to the first power. The figure is constructed using the terminal
settling velocity to calculate the Reynolds number and should give the minimum
transfer coefficient for a suspended particle.
For a given system the actual coefficient is dependent on reactor design and
stirrer speed, or power input, and the effects of particle size, diffusivity, and
similar variables on the actual coefficient can be predicted from their effects on
121
the minimum coefficient or from figure (5-3. l). Haniott et al (Harriott et al,
1983) described a method for prediction of mass transfer coefficients in stined
reactors which has been reviewed (Wadsworth and Miller, 1979). This
procedure gives the HaiTiott coffelation which involves reactor design, stiITing
speed, and power input, and is expressed by the agitation intensity, I:
(5-3.4)
where N = stirring speed (min- 1); D 1 = impeller diameter (inches); T = tank

diameter (inches); and Z = suspension depth (inches). The prediction is made
for spherical particles and for irregularly shaped particles the coefficients would
be somewhat smaller (Miller, 1981). However, experimental reaction velocity
constants were found to be similar to the expected (calculated) mass-transfer
coefficients for suspended particles in the Au(CN)i-/Zn system (Miller et al,
1990).
u
.,a,
'E
u
.x
ca., density ( P8 ), '-/cm3
u
,._
,._
a,
0
u 001
,._
~-A ! 1
a.,
~=2+06(9W) (~) 2------.
,._
Vl
C -5 2
0,._
D= 10 cm/sec
I- -2
µ= K) Q/Cm5€C
Vl
"'0 P=
I
1.0 Q/cm 3
~
5 10 50 100 500 K)()()
Particle Diameter, d , micron
Figure (5-3.1) Plot of mass transfer coefficient vs. particle diameter for free-
falling spheres; minimum mass transfer coefficient, k*
(Wadsworth and Miller, 1979)
122
Calculation of mass transfer coefficients for paiticles suspended in stirred

reactors is not nearly as accurate as the calculation of mass transfer coefficients
for rotating discs and rotating cylinders. Again, for cementation systems, as
always, complications associated with surlace deposit formation must be
carefully considered in the analysis of rate data.
5-3-3 Kinetics/Mechanism
The kinetics of cementation are generally described in terms of the variation

with the electrochemical potential of the rates of the reduction (cathodic) or
oxidation (anodic) reactions, which are directly related to the current. A primary
and convenient way of studying cementation reactions is therefore by the
experimental measurements of the current as a function of the potential of the
respective half-cell reactions involved and plotting the results as curves of
current versus potential (polarisation curves). The data from these curves are
analyzed in terms of the electrochemical theory, using the concept of steady-
state mixed potential, Em, which the system develops as shown in figure (4-4.1).
Rickard and Fuerstenau (Rickard and Fuerstenau, 1968) demonstrated that the
cementation process is driven electrochemically by the galvanic coupling of the
two metals which assume the same mixed potential. Thus, the cementation
process occurs at a rate that is determined by the condition that the rate (or
current) of the anodic reaction must be equal but opposite to that of the cathodic
reaction (i.e., icathodic = -ianodi).
The cementation reaction is, in principle, very similar to corrosion process and
polarization studies of the individual half-cells therefore yield invaluable
information to explain the mechanistic features of the process. The data from the
cmTent-potential curves can be reprocessed to yield Evans diagrams as shown in
figure (4-5.2). From this the mechanism, the reaction cmTent density and the
reaction rate of the cementation process can be derived from the intersection of
the two curves. In general most cementation reactions are controlled by a
diffusion step although in some cases an electrochemical or a mixed step
controls the reaction kinetics. Under diffusion-control step the rate constant can
be evaluated from equations (4-3.12) and (4-3.13).
The potential difference (~E 0 ) of the two half-cell reactions involved in the
cementation process can also yield mechanistic details. Power and Ritchie
123
(Power and Ritchie, 1976) formalized the mixed potential model using Evans
diagrams and outlined conditions to predict the control mechanism. In most
cases where the cementation process is controlled by mass transfer (diffusion)
step, ~E 0 is generally greater than 360 mV, while for d£ 0 <60 mV the reaction
should be controlled by an electrochemical (electron transfer) step. Mixed
kinetics may be expected for voltages in between, depending upon the
exchange-current density. In reviewing the data of Strickland and Lawson
(Strickland and Lawson, 1971) for 18 systems, 15 had d£ 0 values greater than
360mV.
Power and Ritchie (Power and Ritchie, 1976) have also shown the important
role of the ratio of cathodic to anodic area in the electrochemical analysis of
cementation kinetics. In order for a certain cementation reaction to take place,
the total cathodic current must be equal to the total anodic current in which case,
(5-3.5)
where Ac & Aa are the cathodic and anodic areas respectively and ic & ia are the
cathodic and anodic current densities respectively. However, the cathodic and
anodic areas may differ from one another at the time of reaction initiation and
the fraction of the surface acting cathodically or anodically may change during
the reaction progress. In a cementation process, a tight, coherent surface
(cathodic) deposit may reduce the anodic area (ie., Aa < Ac). For a diffusion-
controlled reaction the total cathodic current is fixed and the effect of having a
decreased anodic area is to necessitate a higher anodic current density with a
subsequent increase in the mixed potential. When the anodic area is greatly
reduced the mixed potential shifts to a more positive position (into the Tafel
region) resulting in the change of the reaction mechanism to a chemically
controlled step. Chemical control results when the mixed potential is raised by
an amount~' given by:
~' = b (log ia' - log ic) (5-3.6)
where b is the Tafel slope for the anodic polarization curve, ia' is the anodic
current density (for Ac > Aa) and ic is the cathodic current density (Miller,
1981). Another possibility is that as the anodic area decreases, the limiting
anodic current density is reached before reaching the point of chemical reaction
control. Under these circumstances the anodic metal salt crystallizes at the
124
surface and the anodic cmTent density will be fixed by the concentration
gradient between the saturated solution surrounding the salt at the surface and
the bulk solution. Further decrease in the anodic area and the increase in mixed
potential will result in a transition to chemical reaction rate control. It is
therefore evident that as a cementation reaction proceeds, the cathodic/anodic
area changes and a variation in the mixed potential as a function of time can be
expected. In this regard, measurement of the mixed potential in cementation
reactions can be useful in the determination of the intrinsic reaction kinetics.
Another phenomenon which may be important in cementation systems is the

possible existence of an ohmic resistance between cathodic and anodic sites.
Such a resistance and the attendant potential drop may arise from the presence
or formation of oxide films during the reaction progress. A general analysis of
this phenomenon has been published by Hope, Ritchie and Wajon (Hope et al,
1976). During the course of a cementation reaction limited by transport of the
noble metal ion to the surface, the formation of an oxide film provides sufficient
resistance such that the system passivates and the kinetics become chemically
controlled.
For cementation systems, the electrochemical reaction kinetics can also be

analyzed using the Butler-Volmer equation. The theoretical analysis of the
electrochemical reaction will result in the equations (4-4.1) to (4-4.4 ).
Generally, the cementation reaction (equation (5-1.1 )) follows first-order

reaction kinetics, at least in the initial stages of the reaction. Thus, the rate
constant (or the reaction velocity), k, is described by the general first-order rate
equation:
dC -kAC
=--- (5-3.7)
dt V
where C is the concentration of the reactant solution (mol/cm 3), V is the volume
of the reactant solution (cm3), A is the surface area of the active metal (cm 2)
and t is the reaction time (sec). For a reactant solution of initial concentration
C0 , the integrated form of equation (5-3.7) is:
(5-3.8)
125
Hence:
log( C/C 0 ) = -kA t (5-3.9)
2.303V
where Cr is the concentration of the reactant solution at time t. Thus, the plot of
log(Cr/C0 ) against t should be a straight line (for a first-order kinetics) from
which slope the rate constant k can be calculated. Hence, measuring the rate of
disappearance of the noble metal is usually a convenient method of following
the reaction kinetics. This commonly involves the periodic withdrawal of
samples from the solution and subsequent analysis for the noble metal by an
appropriate analytical method. In practice, the reactant volume decreases during
the reaction as samples are drawn from it, and a small correction is therefore
necessary to compensate for this change in volume. The form of the corrected
first-order equation, to which most cementation reactions conform
approximately, is:
(5-3.10)
where Cn is the concentration in the nth sample, VO is the initial volume,
(5-3.11)
v is the sample volume, and ~t is the (constant) time between samples. The
value of Sn is the same for reactions of any order, and the equation assumes a
slightly more complicated form if ~t is not constant.
Nevertheless, deviation in kinetics from a slow first-order process to a more

rapid first order process has been observed by many investigators (Rickard and
Fuerstenau, 1968; Ingraham and Kerby, 1969; Strickland and Lawson, 1970).
According to Ingraham and Kerby (Ingraham and Kerby, 1969), the reaction
rate is controlled by the cathodic process, and the rate increase is due to an
increase in the cathodic area as the deposit grows. However, Strickland and
Lawson (Strickland and Lawson, 1970) attiibuted the enhanced rate to a
roughening of the growing surface. When the deposit becomes thick enough,
laminar flow is replaced by turbulent flow and mass transfer is increased. Dual
kinetic regimes at high and low temperatures have been explained by Miller and
126
Beckstead (Miller and Beckstead, 1973) on the basis of variable reduced metal
growth kinetics and its influence on the effective interfacial area.
Invariably, many investigators agree that the kinetics are controlled by rates of
diffusion at the interface and are dependent on sample diameter, solution
viscosity and stirring speed. Schaich and Nicol (Schaich and Nicol, 1978)
measured rates of cementation of copper on iron using a rotating disc of iron
plated on platinum and demonstrated diffusional kinetics based upon the effects
of stirring speed, copper concentration and temperature. For most systems that
have been studied using a rotating disc, a good agreement with the Levich
equation has also been obtained indicating diffusion control. The data of
Schaich and Nicol (Schaich and Nicol, 1978) illustrate the excellent correlation
of measured rates with the expected half-power dependence on (I) (stirring
speed). The measured rate constants for the various systems studied by
Strickland and Lawson (Strickland and Lawson, 1973) also show good
correlation with the rate constants calculated using the Levich equation.
Conformance to the Levich equation has also been demonstrated for
copper/cobalt (Ho, 1973), silver/iron (Episkoposyan and Kakovskii, 1966),
copper/iron and silver/iron in brine (Episkoposyan and Kakovskii, 1965) and
silver/zinc and gold/zinc in cyanide solutions (Shcherbakov and Kakovskii,
1967; Oo and Tran, 1991).
By and large, the first-order rate constants determined in cementation reactions

have been found to obey an Arrhenius equation:
k = Ae-E.IRT (5-3.12)
where Ea is the activation energy or the critical increment of energy, R is gas

constant and T is absolute temperature. In logarithmic form equation (5-3.12) is:
(5-3.13)
Thus, a plot of In k versus 1/T frequently results in a straight line, with -E/R as
the slope, from which the numerical value of Ea can be determined. In
differential form equation (5-3.13) becomes:
127
dE
d In k=--a dT (5-3.14)
RT 2
and upon integration,

In k2=dEa(T2-T1) (5-3.15)
k1 R T1 XT2
If the specific rate constant is known for two temperatures, dEa may be
calculated directly by equation (5-3.15). The apparent activation energy has
frequently been used as evidence for or against chemical control. For a process
controlled by a chemical step Ea exceeds 6 kcal/mol (25 kJ moI- 1), whereas for
reactions controlled by diffusion in a liquid phase, Ea is generally between 2 and
6 kcal/mol. The activation energies of most cementation systems reported in the
literature support a diffusion-controlled model (Wads worth, 1969; Power and
Ritchie, 1975; Miller, 1981). A few systems, however, exhibit rather large
activation energies and have been described as being chemically controlled. The
deposition of palladium onto copper in 0.1 M perchloric acid below 45°C is
described in this way, having an Ea of 40 kJ moI- 1 (Von Hahn and Ingraham,
1966). Similarly, the low temperature reaction of copper ions with nickel metal
is ce1tainly chemically controlled, since it has an Ea of about 270 kJ mol- 1
(MacKinnon et al, 1971 ). A non-diffusional process (ie chemical control) has
also been observed for the cementation of gold by iron from cyanide solution
between 25°C and 84°C (Ea= 50±5 kJ mol- 1) (Kenna et al, 1990). However, Ea
values of diffusion-controlled reactions are somewhat sensitive to hydrodynamic
conditions. In particular, they are generally higher when the flow is turbulent
(Riddiford, 1952). Therefore the apparent activation energies for rotating disc
studies (in a laminar flow regime) are usually lower (3-4 kcal/mol) than the
apparent activation energies for rotating cylinder (turbulent flow) studies (5-6
kcal/mol) (Strickland and Lawson, 1973 ). This is largely borne out in the
apparent activation energies for various cementation reactions limited by mass
transfer in the aqueous phase, as shown in table (5-3.1). On the other hand, high
activation energy may be obtained for a diffusion-controlled reaction if the form
of the deposit is temperature sensitive. Miller and Beckstead (Miller and
Beckstead, 1973) found that for the Cu++ /Fe system, the deposit roughness
increased with temperature between O and 35°C with an activation energy in this
temperature range being 42 kJ mol- 1. Above 35°C, a value of about 17 kJ mol- 1
128
was obtained, which was thought to be the true value for the diffusion process,
the deposit profile being invariant at the higher temperatures.
For an ideal first-order reaction, the rate constant should be independent of the
concentration of reactant in solution. However, in many systems a characteristic
effect of the noble metal ion concentration on cementation reaction kinetics has
been observed. Strickland and Lawson (Strickland and Lawson, 1973) showed
that the kinetics on deposit roughened, rotating disc depends very strongly on
the initial concentration. The same is presumably true for many rotating cylinder
studies which are carried out under turbulent flow conditions. Consequently, the
observed dependence of rate constant on initial concentration of noble metal ion
is related to the structural and mass density of the smface deposit. Alternatively,
the concentration dependence of the mass transfer coefficient can be
rationalized in terms of the concentration dependence of diffusion coefficient
and activity of diffusing species (Miller, 1979).
In fundamental kinetic studies using rotating discs or cylinders, it is important

that the surface be smooth initially, because roughness lowers the critical
Reynolds number above which turbulence effects become apparent (Cornet et
al, 1969; Kappesser et al, 1971). It is also essential that the smface is rendered
active. The production of an active smface means providing sufficient anodic
and cathodic sites available to the solution. This usually involves the removal of
protective surface films. On exposure to air, all active metals form a surface
oxide coating, which may inhibit reaction. Layers of other kinds can also be
troublesome(for example, on a sample that has been electropolished), so that the
sample should be thoroughly washed and degreased before use.
The kinetics of a cementation reaction may be modified by foreign cations,

anions and surfactants. Small amounts of foreign cations can significantly affect
the diffusion conditions and/or redissolve precipitated metal. Foreign cations
tend to modify the physical structure of the deposit. An increase in deposit
roughness as a result of the presence of a foreign cation can be expected to
increase the reaction rate, whereas cations that favour the production of smooth
deposits will inhibit the reaction. It has been found that Ag+ accelerates the
deposition of gold onto zinc (Shcherbakov and Kakovskii, 1967), and that Cu 2+
increases the rate of displacement of cadmium by zinc (Ingraham and Kerby,
1969). In the former case, the presence of silver favours the formation of a
powdery deposit, and in the latter, the alloy Cd3Cu is formed.
129
Table (5-3.1) Activation Energies, Ea, of cementation systems limited by

aqueous phase mass transfer.
System Geometry Ea, kJ/mole Reference
Ag+/Fe (Cl·) Disc 12.55 (Episkoposyan and Kakovskii, 1965)

Ag+/Fe (SOi·) Disc 12.97 (Episkoposyan and Kakovskii, 1966)
Ag+/Zn (CN·) Disc 12.97 (Kakovskii and Shcherbakov, 1967)
Ag+/Zn (Cl·) Disc 30.54 (Puvvada and Tran, 1992)
Ag+/Cu (Cl·) Disc 10.88 (Puvvada and Tran, 1992)
Au+/zn (CN·) Disc 10.88 (Oo and Tran, 1991)
Cd++/Zn(SOi·) Disc 15.90 (Lee et al, 1975)
Cu++/Fe (Cl·) Disc 12.97 (Episkoposyan and Kakovskii, 1965)
Cu++/Fe (SOi·) Disc 13.39 (Episkoposyan and Kakovskii, 1966)
Cu++/Zn(SOi·) Disc 12.55 (Strickland and Lawson, 1970)
Ag+/Cu (ClO4·) Cylinder 20.9+2.1 (Von Hahn and Ingraham, 1967)
Ag+/Cu (CN·) Cylinder 20.9±2.1 (Von Hahn and Ingraham, 1967)
Ag+/Zn (ClOf) Cylinder 25.10 (Von Hahn and Ingraham, 1968)
Ag+/zn (CN·) Cylinder 25.10 (Von Hahn and Ingraham, 1968)
Bi3+/Fe (Cl·) Cylinder 18.8-31.8 (MacKinnon, 1972)
Cd++/Zn(SOi·) Cylinder 19.7±3.3 (Ingraham and Kerby, 1969)
Cu++/AI (SOi·) Cylinder 24.27 (MacKinnon and Ingraham, 1971)
Cu++/Fe (SOi·) Cylinder 19.7-20.5 (Miller and Beckstead, 1973)
Pct+/Cu (CIO4·) Cylinder 31.0-39.7 (Von Hahn and Ingraham, 1966)
Ag+/Fe (Cl·) Powder (laminar) 14.23 (Hamdorf, 1961)
Cu++/Fe (SOi·) Suspended 20.9±2.9 (Nadkarni and Wadsworth, 1968)
plates (Turbulent)
Common impurities in reactant solutions (eg., Fe 2+) tend to lower the hydrogen
overvoltage on metals resulting in their loss by dissolution. Redissolution is a
problem in the extraction of copper with iron (Nadkarni and Wadsworth, 1968).
The most important impurity in reactant solutions is dissolved oxygen which
must be removed by extensive bubbling of the solution with nitrogen.
130
Anions and surfactants may affect the rate of cementation reaction in several
ways. Complex formation changes the effective concentration of the diffusing
ion, and may also modify the deposit structure (Von Hahn and Ingraham, 1967).
Species that adsorb to the surface can reduce the active surface, affect the
deposit morphology, or react with the surface. Strickland (Strickland, 1972)
showed that the second (enhanced) stage of the copper/zinc reaction has larger
rate constant in chloride than in sulphate solutions, due to changes in the deposit
structure.
The presence of the hydrated proton may also influence the cementation
reaction. A variation of deposition rate with pH has been observed in a number
of cementation systems. In general, this is attributed to a change in the reacting
species with pH. Gladyshev, Enikeev, Zakharchuk and Petrova (Gladyshev et al,
1970) studied the pH dependence of the thallium/zinc amalgam reaction over a
wide range of pH, and found large variations in rate depending upon the stable
zinc species at a given pH. The deposition rate decreased at pH = 9.0, due to the
formation of insoluble Zn(OH)i on the surface, but increased at pH = 11.0 as
[Zn(OH)J]- formed. The rate of the gold/zinc reaction decreased as the pH
increased (above pH: 13.0) at a constant cyanide concentration. Nicol, Schaich,
Balestra and Hegedus (Nicol et al, 1979) and Oo and Tran (Oo and Tran, 1991)
found this to be due to the formation of hydroxide ions in the zinc oxidation
process.
5-4 DEPOSIT/ MORPHOLOGY
5-4.1 Deposit
In cementation reactions, it might be expected that the solid product would

consist only of the more noble metal. While examples of such behaviour are
known (Straumanis and Fang, 1951) the deposit may be contaminated with
oxides, hydroxides and basic salts (Bratt and Gordon, 1967) and substantial
quantities of the less noble metal. The oxides, hydroxides and basic salts arise as
a result of secondary reactions between the metals, water and dissolved oxygen.
It is therefore important to exclude oxygen, not only in fundamental studies, but
also in many industrial applications.
131
5-4.2 Morphology
Invariably, the structure and morphology of the reaction product can have a
significant effect on the reaction kinetics, either enhancing the rate in some
cases or passivating the surface in other cases. During the past several years the
importance of the surface deposit in the interpretation of cementation rate data
has therefore been clearly demonstrated in quantitative manner. The cathodic
part of a cementation reaction is an electrodeposition reaction. Surface deposits
formed in cementations systems are therefore quite similar to electrolytic
deposits and may be influenced by the activity (or concentration) of depositing
ion, temperature, agitation (hydrodynamics), pH, nature of the anions present
(eg., ligand), presence of addition agents (eg., organic colloid), and the
condition of the substrate metal (Drozdov, 1958; Miller, 1981 ). Under special
circumstances the cementation reaction may be inhibited presumably because of
product ion diffusion resistance (Miller, 1981 ). A further complication is
introduced by the fact that simultaneous dissolution of the underlying metal is
taking place.
Broadly, surface deposits may be smooth or particulate deposits, although

intermediate structures are common (Power and Ritchie, 1975). Smooth (tight,
coherent) deposits are relatively uncommon and appear to be governed by low
cationic activity, low temperature, the presence of addition agents and
compatibility between substrate and deposit. In general, smooth deposits adhere
well to the substrate metal. For this deposit, the cathodic sites at which initial
attachment of the deposit takes place must be widely distributed over the
substrate, while the anodic sites must be confined to a few selected areas such as
grain boundaries or pits. If corrosion of the substrate over and above that
occasioned by the displacement reaction takes place, the formation of smooth,
adherent deposits is rendered less likely. The conditions which lead to the
formation of particulate deposits tend to be the reverse of those with which the
growth of smooth deposits is associated. Thus a high concentration of cation, a
high temperature, the absence of an addition agent, and a corroding substrate
help in the formation of a discontinuous product (MacKinnon and Ingraham,
1970; Miller and Beckstead, 1973).
Agitation (or solution flow) also affects the morphology of the deposit.
Generally, the surface deposit is either dendritic (treelike) or botryoidal
(bulbous) and the reaction kinetics are enhanced significantly due to the
132
presence of the deposit. However, it has been shown in the case of zinc
deposition from cyanide solution that, as the flow rate (and hence the Reynolds
number) of solution over the cathode increases at constant current density, the
nature of the deposit changes from a dendritic, to a botryoidal, to a smooth
deposit (Naybour, 1969). In stagnant or slowly flowing solutions, dendritic
growths have been reported in cementation reactions (Strickland and Lawson,
1970; Barth et al, 1973). In rotating-disc system the deposit has also been shown
to vary with respect to radial position on the disc surface (Calara, 1970). For
laminar flow, at all positions on the disc's surface there is a gradual change from
a coarse deposit at the disc centre to a finer textured deposit at the edge of the
disc. For the case in which the flow changes from laminar to turbulent at some
radial position of the disc, there is an abrupt rather than a gradual change in
surface-deposit character, and the influence of the transition to the turbulent
flow regime on the surface deposit is most pronounced. Fluid flow also
dete1mines at a microscopic level the basic character, namely nucleation, of the
surface deposit.
Since most cementation reactions are diffusion-controlled, the particulate

deposits commonly formed offer little resistance to the flux of reactants or
products and so must be porous. Without exception, for small initial
concentrations of the noble metal species in solution, while not affecting the
precipitation rate in the initial stage of the reaction, does cause marked changes
in the second stage (Strickland and Lawson, 1970; Annamalai and Murr, 1979;
Miller, 1981 ). The difference is attributed to physical changes in the deposit
structure due to differences in the nucleation and form of the initial crystal
growth. The initial stage of reaction corresponds to deposition on a relatively
smooth surface. During this stage of reaction the deposit structure and thickness
do not significantly affect the reaction kinetics. The deviation from the initial
smooth surface diffusion kinetics becomes significant when the specific deposit
mass exceeds its critical value (critical deposit mass per unit area). For most
cementation systems this was found to correspond to 0.35±0.05 mg/cm 2 (a
layer of 0.8 microns thick assuming a porosity of 50%) (Strickland and Lawson,
1971; Ingraham and Kerby, 1969). For quantities of deposit in excess of 0.35
mg/cm2 the deposit takes on a rough appearance. This roughness causes an
enhancement in cementation rate which may be several times that with a clean
surface. Precipitates from high initial concentrations of noble metal ions have
been observed to be coarser and more porous (Chizhikov, 1966) and would
therefore be expected to cause a greater enhancement in diffusion flux.
133
Consequently, the first-stage reaction kinetics may not be seen as the critical
deposit mass density is reached almost immediately. According to MacKinnon
and Ingraham (MacKinnon and Ingraham, 1970), the structure of the copper
deposited on aluminium at 70°C became coarse and granular at copper
concentrations in excess of 5X 10-3 M, although at intermediate concentrations
the deposit was a coherent film.
Surface deposits have been shown to also have a significant temperature

dependence (MacKinnon and Ingraham, 1970; Miller and Beckstead, 1973;
Parga et al, 1988; Puvvada and Tran, 1992). At lower temperatures, the coating
of copper on aluminium was much finer. In the copper/iron system, the
discontinuous nature of the deposit was also found to be enhanced by increasing
the temperature. A change in the morphology of the gold deposit with a change
in temperature was observed for the Au(CN)2-!Zn system (Miller et al, 1990).
At a lower temperature, a smooth deposit was produced whereas at a higher
temperature the deposit morphology changed significantly to botryoidal and
rough in appearance. Similarly, the morphology of silver on copper shifted from
dendrites formed at high temperature to an evenly fine deposit at 10°C (Puvvada
and Tran, 1992). The importance of pH in determining the roughness in the
cadmium/zinc system has also been demonstrated by Ingraham and Kerby
(Ingraham and Kerby, 1969).
5-5 SUSPENDED PARTICLES/SHRINKING-CORE MODEL
In heterogeneous systems, the rates of reaction are often related to both the total
surface and the number of reactive sites per unit area available for reaction
(Wadsworth, 1979). In considering the cementation of metals using suspended
particles, the fluid-particle is three dimensional and the reacting area is
subjected to great change (eg,. shrinks) dming the course of the reaction. It is
therefore possible to treat the kinetics using the shrinking-core model applied to
the leaching of mineral particles. The shrinking-core model visualized the
particle-fluid reaction as occurring primarily at the outer smface of the particle
and the net result is an unreacted shrinking core with a reacted diffusion (or
product) layer surrounding it. Considering monosized spherical particles the
reaction kinetics will therefore be controlled by diffusion at the boundary of
fluid-particle initially, diffusion through the reacted (or product) layer or surface
reaction at the inte1face.
134
For a fluid-particle reaction with the formation of a porous (solid) product as

the reacted layer, depicted by the equation,
aA(t) + bB(s) ~ cCcn + dD(s) (5-5.1)
if diffusion at boundary of fluid-particle is rate controlling the rate of reaction

may be expressed by:
dNA = -4 2 D[A] (5-5.2)

dt 7tfo b bulk
where NA is the number of moles, b is the boundary layer and r0 is the radius of
the original particle (sphere). From stoichiometry, the number of moles of
unreacted B with time is:
- dN 8 = -(12.) dN A = 4 7tf 2c12.~ [A] (5-5.3)

dt a dt o a b bulk
and the rate of the solid volume of B reacted is:
_ dN 8 I _dV_
___ = -4m· 2 dr (5-5.4)
dt V dt V dt
where V is the molar volume and is equal to M/p, where M is the molecular
weight and p the density and r is the radius of the unreacted B. If ex is the
fraction of B reacted, it may be shown that:
(5-5.5)
which upon differentiation with respect to time becomes:
da 3r 2 dr
-=--- (5-5.6)
dt r/ dt
Combining equations (5-5.3), (5-5.4) and (5-5.6) gives equation:
da 3V (b) (D) (5-5.7)

dt = -r- -;- 8 [A]bulk
0
135
and equation (5-5.7) may be integrated to give the conversion-time equation:
(5-5.8)
where km =~ = mass transfer coefficient.
Equation (5-5.8) indicates that for a film diffusion controlled process, a plot of
a versus t should yield a straight line. The mass transfer coefficient can be
determined from the slope of the plot.
The same calculational procedure as above can be used to determine the rate
equation for a product layer diffusion controlled process. The integrated rate
expression in terms of the fraction of solid reacted is shown by the following
equation:
2
1--a-(l-a) 213
= (2V)
- 2 (b)
- D[A]bulk t (5-5.9)
3 ~ a
where D is the effective diffusivity of species A into product layer. Equation (5-
5.9) will yield a straight line by plotting 1- 2 a -(1- a)213 versus t and the
3
effective diffusivity of species A can be determined from the slope. Another
unique feature for a product layer diffusion controlled reaction is that the
modified rate constant kp (i.e. kp = ( 2 ~) ( b) D[A]bulk) or rate of reaction is
ro a
sensitive to the particle size, ie., the rate decreases with an increase in particle
size.
Similarly, for a kinetic (or surface) reaction controlled process, the rate equation
can be calculated to be shown by the following equation:
1-(1 - a) 113 = ( V ) ( ~) k [A]° t (5-5.10)

ro a
where n is the order for reactant A. In this case, a plot of 1-(1- a) 113 versus t
will yield a straight line from which the specific rate constant, k, can be
136
determined from the slope. The rate equation (5-5.10) also indicates that the rate
is inversely proportional to the particle size.
When a fluid-particle reaction does not generate any solid product (eg., aA(f) +
bB(s) ---, cC(t)), the reacting particle shrinks during the reaction and finally
disappears. The reaction can be controlled by either a film diffusion process or a
surface (or kinetic/chemical) reaction. When surface reaction controls, the
behaviour is identical to that of fluid-particle reaction forming a solid product,
ie., equation (5-5.10). The integrated rate expression for a film diffusion process
for a shrinking spherical particle is shown by:
2V b
1-(1- a) 213 = ( -
2 ) (-) km[Ahutk t (5-5.11)
ro a
where km is the mass transfer coefficient. Thus, a plot of 1-(1- a) 213 versus t
will yield a straight line and km can be determined from the slope.
CHAPTER SIX
SUMMARY OF LITERATURE REVIEW

AND RESTATEMENT OF AIMS
The following points have been deduced from the literature review:
(1) Cyanide has been a powerful lixiviant in extracting gold from a wide range
of ores at a relatively low cost, especially when used in the carbon-in-pulp (CIP)
process and in the heap leaching process.
(2) As conventional ores continue to be depleted, different processes have

been developed for treating the increasing sources of refractory ores which are
not amenable to direct cyanidation process. Such materials or gold ores are
successfully treated for gold recovery at a much higher cost by using a modified
cyanide leaching technique or by pre-treatment of the ore to liberate gold from
the host minerals prior to the conventional cyanidation.
(3) Cyanide and its complexes are very toxic and present health and
environmental problems with cyanidation. Growing public paranoia imposes
severe government regulations on the use of cyanide in most places. Care must
be exercised to maintain cyanide solutions alkaline in order to prevent the
release of hydrogen cyanide gas and spent cyanide liquors must be degraded
before being discharged to the environment. Also gold dissolution rates with
alkaline cyanide solutions are generally low with contact times of about 24 to 72
hours.
(4) There has been considerable interest in the development of non-cyanide

lixiviants for gold leaching with faster kinetics, lower toxicity and applicable to
the more refractory ores. Thiourea, thiosulphate, thiocyanate and the halides
have demonstrated exciting prospects and various processes have been described
and developed for use of these lixiviants for gold processing. Although these
lixiviants/processes are not widely practiced at present, interest still remain high
as they offer several advantages over conventional cyanidation.
138
(5) The halides in particular form both Au(I) and Au(ill) stable complexes
with gold and dissolution rates are typically several orders of magnitude faster
than those of cyanide/air and other lixiviants under ambient conditions. Among
these, the bromine-bromide system claims other natural advantages of
simplicity, easily controlled leach chemistry, high extraction efficiency,
adaptability to a wide range of pH values, and low toxicity. In addition, bromine
can easily be regenerated electrochemically from solution with the potential for
simultaneous recovery of gold.
(6) The development of several and improved bromine-bromide systems has

been topical among many researchers as an alternative to the cyanidation
process. These advances have also identified the different conventional recovery
techniques (zinc precipitation/cementation, carbon adsorption/electrowinning,
ion-exchange, solvent extraction) for recovering gold from the pregnant
bromide-leach liquors. However, only carbon adsorption and ion-exchange have
been evaluated in detail in parallel with the fundamental studies on the bromide
leaching system.
(7) Although activated carbon and ion-exchange resms have demonstrated

their applicability for direct recovery of gold from bromine-bromide solutions,
the gold precipitated on activated carbon or resin is in the metallic form and
hence susceptible to significant gold losses through abrasion. The presence of
residual bromine in solution also suppresses the gold adsorption rate because of
its competitive adsorption on carbon or resin surface.
(8) Invariably, zinc cementation has been claimed to be a highly efficient

option for gold recovery from bromine-bromide. Gold recoveries in excess of
96% have been reported for various bromine/bromide liquors (Dadgar 1989;
Dadgar et al, 1990). Unfortunately, no detailed study or reported literature on
the recovery of gold by cementation from bromine/bromide leach solutions has
been extended beyond this initial claim. As zinc cementation still accounts for a
significant portion of gold recovery at several gold mines in Australia, Canada,
U.S.A. and South Africa and is applied widely around world as an alternative to
electrowinning, a study of the kinetics/mechanism of gold recovery by zinc
cementation from bromine/bromide liquors is highly imperative for complete
assessment of the system as an alternative to cyanidation.
139
(9) Zinc cementation is electrochemical in nature which allows for the

application of the electrochemical techniques for the understanding and
determination of the characteristics of the reaction. Accurate data on the kinetics
and mechanism of the reaction can be obtained from electrochemical
measurements.
The aims of this study are to:
(1) Investigate the electrochemical nature of the respective half-cell reactions;

the reduction of gold and the oxidation of zinc in bromine-bromide
solution.
(2) Determine the factors controlling the zinc cementation process with the
aim to optimise the conditions for gold recovery.
(3) Determine the kinetics (reaction rates) of the gold reduction and the zinc
oxidation.
(4) Determine the mechanism of the reaction and the factors controlling the
rate determining steps.
(5) Identify the predominant species m the reaction to reveal the vanous
equilibria governing the recovery process.
CHAPTER SEVEN
THERMODYNAMIC STUDY
7-1 INTRODUCTION
An important consideration in the zmc cementation of gold from aqueous

solutions is the chemical basis (chemical speciation) of the species involved in
the reaction. The successful exploitation of this method in extracting/recovering
gold from dilute aqueous solutions is often dependent on the oxidative
dissolution of the metallic zinc to soluble complexes or species which promotes
the precipitation of the metallic gold. In this regard, the solution conditions of
the background electrolyte such as concentration, pH, and temperature in
concert during the reaction are of paramount importance. Thus, the
thermodynamic constraints affecting the speciation of aqueous solutions need to
be delineated to determine the soluble species which favour the reaction.
Thermodynamic modelling represents a powerful/viable method for predicting

chemical speciation and hence of understanding the chemical reactions
occurring under such conditions. Furthermore, knowledge of the likely
predominating species form the basis of any kinetic model and is generally
indispensable for optimising operating conditions.
In this study, the solution chemistry (equilibrium conditions) of zmc

cementation of gold from bromine-bromide system is treated in terms of
aqueous equilibrium/stability diagrams such as Eh-pH, concentration of species
versus pH, distribution-pH, distribution-log [Br-]. As the bromine/bromide
system is complex, the thermodynamic equilibrium concentrations were
generated with the aid of a computer program.
7-2 THERMODYNAMIC DATA AND COMPUTATIONAL

METHODS
Two general computer packages; the CSIRO thermochemistry system (Turnbull,

1983) and DIAST AB (Robins and Stillman, 1989) were used for calculation of
141
equilibrium compositions in the system with thermodynamic data taken from the
literature (Pourbaix, 1966; Tyurin, 1966; Naumov et al, 1974; Wagman et al,
1982). All possible compounds which are known to exist in the system and for
which thermodynamic data could be found were considered.
7-2-1 CSIRO Thermochemistry System
The CSIRO Thermochemistry system is an integrated multipurpose program

developed by the Commonwealth Scientific and Industrial Research
Organisation (CSIRO) of Australia. The system consists of thermodynamic
databases and a set of compatible programs for equilibrium thermodynamic
calculations with the data. The current version, called Version V, is written in
Fortran 77 for the V AXNMS and IBM PC Computers.
The system has been designed to be as general as possible so as to handle any

type of chemical species or system, a wide range of thermodynamic properties
and a variety of equilibrium calculations. A modular method of construction
based on a shared subroutine library and a generalised file structure ensure that
extension to new properties and applications may be done in a simple manner.
An essential feature of the system is the ability to read chemical formulae and
names in a variety of formats and convert them to unique internal identifiers for
the species. A variety of physical units is used for internal computations.
The system is divided, for convenience, into a number of major application

programs each of which has access to the common directive language and to the
data bank:
1. FILER Fitting and storage of basic data (ie., data base

creation and management).
2. REACT Properties of species and reactions. A variable tool

for screening processes prior to more complex
thermodynamic and laboratory investigations.
3. SYSTEM Predominance area diagrams. Allows the compact

representation of the equilibrium stability and
associations.
142
4. CHEMIX : Equilibrium calculations on systems.
5. EXERGY : Analysis of efficiency of processes: - based on

second law energy analysis technique.
6. VAPOUR : Vapour pressure and related properties for pure

species.
7. ESTIMA Estimation of thermodynamic data: Makes available

11 estimation techniques for those cases where
experimental data are not available.
8. REFER Storage and retrieval of references.
The programs access thermodynamic databases or files compiled from JANAF

tabulations/the1mochemical tables (CPDJANDAT); Scientific Group
Thermodata Europe (CPDSGTDAT); the U.K. National Physical Laboratory
(CPDNPLDAT); a number of published critical compilations by CSIRO Mineral
Research Laboratories (CPDMRLDAT); and the U.S. National Bureau of
Standards data on aqueous species (CPDNBSDAT). In addition to these data
files, the system includes a bibliographic data bank (SLAGDATA) containing
references to the thermodynamic properties of slags, mattes and related
metallurgical solutions.
7-2-1-1 Chemix
The program allows a set of possible chemical species and phases present in a
chemical system to be easily defined using standard chemical nomenclature. The
initial state of the system may also be defined in terms of selected elements or
species and their amounts. The basic thermodynamic data for the set of species
are retrieved from the data bank or entered directly. For non-ideal solution
phases, the activity coefficients of the component species must then be defined
as functions of temperature and composition. A number of well-known methods,
including the extended Debye-Huckel and Pitzer methods, are provided for this
purpose.
143
The program calculates the particular species and phases and their quantities
which give the minimum total Gibbs energy for system at given temperature and
pressure by the Eriksson minimization method (Eriksson, 1975). In this method,
the quantity:
G go
-RT = I,n-[(-)-+ln
I RT I
a-]I (7-2.1)
is minimized with respect to the variables ni for constant temperature and

pressure values, where G denotes the total free energy of the system, R the gas
constant, T the thermodynamic temperature, ni the amount of the ith substance,
g0 the standard chemical potential, and a the activity. The ni-values
corresponding to the equilibrium mixture must be non-negative and as a further
subsidiary condition, the mass balance constraints must be satisfied (Eriksson
and Rosen, 1973 ). Langrange's method of undetermined multipliers is used for
determining the constrained minimum, and the logarithmic equations thus
obtained are expanded in a Taylor series about initially estimated ni-values,
neglecting terms involving derivatives of second and higher orders.
Following this, enthalpy balances between initial and equilibrium states, the
distributions of the elements among the equilibrium products and the
thermodynamic properties of the total system may be calculated. To explore the
effects of system variables, there are further options for various repetitive or
step-wise calculations. There are also options to fix, maximize or mm1m1ze
chosen properties of the system by systematically varying others.
In use, a typical input statement is as shown in Appendix (7-2.1) where the

directives for the program:
- SYSTEM defines all the possible phases and component species which may be
present in the system at equilibrium. The three reserved phasenames are GAS,
AQUEOUS and SINGLE.
- UNITS resets units for input and output.
- GIBBS enters Gibbs free energy for component species defined by the system.
- FILE searches data files for thermodynamic data sets. The first three
characters, CPD, identify the file type in use as thermodynamic data for
144
species and the second group of three characters define the source of the data
in the file.
- INSPECIES enters the phases and species for input.
- TEMPERATURE enters list of temperatures for input and output.
- PRESSURE enters list of pressures for input and output.
- INMOLE enters moles of input species.
- TRY enters trial equilibrium moles of species. This directive allows the setting
of estimates of the equilibrium moles of all possible species in the system. It
provides a starting point for the iterative calculation of equilibrium.
- EQUILIBRATE calculates equilibrium of the system.
- STEP calculates series of equilibria.
- OUTMOLE calculates moles of selected species in the system for a number of

steps of another property.
- VARY varies property to satisfy constraint.
- ACTIVITY calculates log (base 10) activity of a solution component species in

the system for a number of steps of another property.
7-2-1-2 System
The program system provides for the automatic calculation and plotting of
equilibrium stability and associations of chemical species in defined chemical
system to be compactly represented on various predominance area diagrams,
such as Pourbaix, Ellingham or partial pressure diagrams (Turnbull, I 977;
Turnbull and Wadsley, 1984 ).
The program allows the system for the diagram to be defined by entering the set
of species to be involved in the axes, areas and overlay lines. Chemical reactions
145
involving all valid combinations of these species are then set up and balanced
automatically. The basic thermodynamic data for the species are retrieved from
the data bank or are entered directly and the Gibbs energy changes of the
reactions calculated, including the effects of set activities and molar volumes.
The predominance areas are calculated by a routine named ST ABLE (Froning et

al, 1976) which has been revised and extended. The program first calculates
stable ligand areas, and then stable metal areas within each ligand area. When
more than one metal component is present in the system, the diagram is often
complicated by overlapping areas due to any compounds containing more than
one metal. This may be avoided by defining the limiting upper and lower ratios
of the metals, thereby restricting the system to certain areas of stoichiometry. A
number of sub-diagrams then cover the whole system.
The computed diagram, with axes scaled, marked and labelled and areas
identified, may then be plotted on single or multi-pen plotters. A typical system
input is as shown in appendix (7-2.2). The directives for the program:
- DIAGRAM enters the species used in diagram under axes, ligands, areas and
lines specifying the state and charge (for charged species).
- UNITS resets units for input and output.
- GIBBS enters coefficients for Gibbs free energy data for species.
- FILE searches files for thermodynamic data sets.
- COMPONENTS enters number of species per area.
- AXES enters definition of axes of diagram.
- LIMITS enters limits of axes of diagram.
- TEMPERATURE enters list of temperatures.
- PRESSURE enters list of pressures.

- ACTIVITY enters activities of species.
146
- AREAS calculates stable predominance areas.
- OVERLAY calculates overlay lines for diagram.
- PLOT generates plots from all programs.
7-2-2 The DIASTAB program
The DIAST AB program is a stability diagram generator developed by the

Department of Mineral Processing and Extractive Metallurgy of the University
of New South Wales, Australia (Robins and Stillman, 1989). The program
presents thermodynamic chemical equilib1ia in graphical form. The stability
diagrams include ionic distribution/pH, log activity/pH and potential/pH
diagrams for aqueous systems. It condenses voluminous amount of
thermodynamic calculations into concise, convenient and easily understandable
form, and predicts both equilibrium conditions and likely reaction paths in
organic/aqueous processes.
In use, the current version DIAST AB v 4.02, involves:
1 Data Entry: Data input can be created by any editor or word processor
which supports ASCII files. Two blocks of information define a valid input:
(a) Parameter block - contains parameter directives;
and
(b) Data block - contains chemical data (ie., types/free energies) on

elements/compounds in the system for which stability data is to be calculated. A
typical input statement is as shown in appendix (7-2.3) in which the directives
or labels:
- .P identifies/opens the Parameter block.
- .D identifies/opens the Data block.

- . delimits blocks and sub-blocks.
147
- X enters X-axis range and interval.
- Y enters Y-axis range and interval.
- T enters the temperature.
- R enters the gas constant.
- N enters name of the output file to store the stability diagram in.
- H enters heading on the diagram.
- G enters generation mode.
- M enters diagram and lettering sizes.
- 0 enters output mode.
- Q enters number of diagrams required.
2. Data Calculation: Three subprograms can be called as follows:
-CL DMB to calculate ionic distribution data by mass balance

solution. The calculations involve the generation of
balance expressions, and the solution of these using the
Newton Raphson iterative method.
-CL PMB to calculate predominance data by solving the mass

balances of the required chemical system. As the mass
balance is solved at each point in the X-Y space, the
equilibrium data generated are placed on disk. After the
g1id of points has been covered, the data is buffered back
into memory for the calculation of predominance areas.
-CL PRQ to calculate predominance data by reaction quotients. This
method is based on that described by Osseo-Asare and
Brown (Osseo-Asare and Brown, 1979) and, to use their
desc1iption, "is based on dissociation equations with
coITesponding log equilibrium constants and log reaction
148
quotients". Like PMB, the program scans the designated

X-Y space in the X and Y directions in order to determine
the predominance areas.
3. Data Output: The results of the calculations can be directed to a screen,

a printer, a plotter or to disc file.
7-3 EQUILIBRIUM SOLUTION CHEMISTRY
7-3-1 The Br- - Br2 - HzO system
The bromine-bromide equilibrium represents the reactivity/chemistry of bromine

in bromide media. Bromine exhibits disproportionation in bromide solutions and
the existence of the bromine species characterises its stability window.
Using the chemix program the equilibrium concentrations of bromine species

versus pH for the Br--Br2-H2O at 25°C were plotted at different conditions. The
effect of initial bromine (aqueous) concentration of 6.07X 10-4 M (or 0.6 mM)
on the bromine-bromide equilibrium (where [Br-] = 10-3 M to 1.0 M) is shown
in figure (7-3.la - d).
Under these conditions, the equilibria governing the Br--Br2-H2O system are
notably dependent on the bromide concentration and pH. Bromine is most stable
in acidic conditions and higher bromide concentrations. However, at 0.10 M Br-
concentration and above, the tribromide ion, Bq- emerges as the dominant
species as a result of the reaction of Br- with Br2 according to equation (2-1.17).
The initial concentration of bromide is thus reduced by this reaction. In effect,
the stability window of the Br2/Br- equilibrium is governed judiciary under such
conditions by the relative predominance of Br3- in the system.
In the neutral pH range, HBrO (aq) is the predominant species while above pH
of 9.00, Bro- is the predominant species. This indicates that in general Br2
disproportionates into the soluble oxy-bromo species in the neutral and basic
conditions causing the Br2/Br- equilibrium to destabilise. The positions of the
HBrO (aq)/Br- and BrO-/Br- equilibria shift to higher pH values as bromide
concentration increases. At 0.10 M Be HBrO (aq) ceases as the predominant
species in the neutral pH range, thus extending the BriBr- stability window
over pH's 1.00 to 9.00.
149
At low pH and especially low Br- concentration, it can be inferred that, bromine
undergoes less disproportionation and its high activity will influence or
jeopardise any system operating under such conditions. It can also lead to
potential corrosion (oxidation) problems.
Log Concentration (M)

-4~---------------------,
Br2 (AQ)
-+- Br3-
-¼- BrO-
-8
-a- HBrO (AQ)
-*- Br03-
-+ Br5-
-12
-16
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.la) The equilibrium profile of bromine species of initial [Br2

(aq)] = 6.07X 10-4 Min 10-3 M bromide solution (constructed
using the CHEMIX program).
150

-2.---------------------~
Br2 (AQ)
-+- Br3-
~ BrO-
--a- HBrO (AQ)
-8
-x- Br03-
~ Br5-
-14
-20 '---*-----,~_._*-'*-~!---'H-~f---H-----'-----a,...___'--____..::::al--'
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.lb) The equilibrium profile of bromine species of initial [Br2

(aq)] = 6.07X 10-4 Min 10-2 M bromide solution (constructed

o~-------------------~
Br2 (AQ)
-+- Br3-
-4 ~ BrO-
--a- HBrO (AQ)
-x- Br03-
-8
~ Br5-
-12
-16
-20 L--'k---------;j(__J_~,j(_~'-----'lll==--'--#--H-----A'---'fl---..::W--------'
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.lc) The equilibrium profile of bromine species of initial [Br2

(aq)] = 6.07X 10·4 Min 10- 1 M bromide solution (constructed
151

0...---------------------~
Br2 (AQ)
-+- Br3-
-5 ""*- BrO-
-a- HBrO (AQ)
""*- Br03-
-+-- Br5-
-10
-15
-20 L---¾-~,--*-""*"----';*-*-~~E-...J.._-Bi!l---l!l-..:::::aa-flf-----J
0 1 2 3 4- 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.ld) The equilibrium profile of bromine species of initial [Br2

(aq)] = 6.07X 10· 4 Min 1.0 M bromide solution (constructed
7-4 The Zn - Br2/Br· - H20 system
The stability of the various zinc complex ions influences the reactions of the
zinc ions in solution. A knowledge of the stability of the zinc complexes is
therefore vital in the control of the solution chemistry of zinc cementation
reactions.
The dissolution of zinc in bromine-bromide solution was modelled using the

various computer packages. Figure (7-3.2) shows the Eh - pH diagram for the
Zn-Br-H2O system at 25°C for [Bi:-] = 1.0 M and [Zn] = 10-4 M, constructed
using the SYSTEM program of the CSIRO - Thermochemistry package. It
shows no domain of predominance for the zinc-bromide species or complexes.
This is also quite obvious when compared with the Zn-H2O system as shown in
figure (2-2.1 ). Thus, under these conditions (low bromide concentration), the
dominant zinc species is the simple Zn 2+ ions. A similar equilibrium profile is
shown by the solubility diagram (figure (7-3.3)) for Zn-Br-H2O system at 25°C
and [Zn] = [Br-] = 1.00 M (constructed using DIASTAB).
152
Eh
2.0 r-------.-----,-----,--------.--..-----,---~~~
A Zn
B Zn E-2(AQ)
1.5
C Zn(OH)2(AQ)
D Zn(O H) 4E2 (AQ)
1.0 C
1 - - - - -
0.5 B
0.0 D
- - - -2.
-0.5
-1.0
-1.5 A
-2.0 . __ ___.__ __.___ __..'--_ ___,__ _....___ __,__ __,___ ___,

0 2 4 6 8 10 12 14 16
pH
Figure (7-3.2) The potential - pH diagram for the Zn-Br-H 2 O system at

25°C. [Zn] = 10-4 Mand [Br-] = 1.0 M (constructed using the
SYSTEM program).
Zinc dissolves (corrodes) readily in bromide solutions at low pH values to give

zincic ions, Zn 2+, and in high alkaline solutions to give the zincate ions,
Zn(OH)4 2- (or ZnO2 2-). Zn(OH) 2 forms in moderately alkaline conditions and
demonstrates no tendency to form hydroxo species in neutral conditions. Figure
(7-3.3) also shows that higher zinc concentrations favour the precipitation of
Zn(OH)i (s) at higher pH. The precipitation of such a solid as a reaction product
around zinc paiticles will passivate the zinc surface and restrict its use in
cementation processes.
Appai-ently, the existence and relative predominance of the zinc-bromide

complexes is well characte1ised in figure (7-3.4) which shows a distribution-pH
diagram for Zn-Br-H 2O system at 25°C for [Br-] = 1.0 M and [Zn] = 10- 2 M
(constructed using DIASTAB). At bromide concentrations of 1.0 mole/litre and
less the zinc-bromide complexes exist in very small quantities.
Figure (7-3.5) is also a distribution-log bromide concentration diagram for zinc-

bromide-water system at 25°C and pH of 3.50 for [Zn] = 5X 10-5. The change in
zinc-bromide species with solution concentration is depicted by this diagram.
The species ZnBr+, ZnBr2 (aq) and ZnBr3-, have relative stabilities only in high
bromide concentrations (ie., [Br] > 4.0 M).
153
p[Zn++)[Br]
0 .-----+----+---+---+-----ll- --+---+----+---+---+-----ll- ----1----1--~
I Zn++
1 ZnOII+
3 Zn (Oil) 2 (AQ)
2 4 ZnO112 (S)
5 ZnBr+
3
6 ZnBr2 (AQ)
4 7 ZnBr3-
8 Br-
5 9 IIBr (AQ)
pll2O:0/0/0
6
pH: o IOI .2
7 pZn++: O I .25 I o
3 Br: O / .25 I 0
8
10 +-----+---+----l--+--+-- +----+---+-:....+----l--+ --+----+---'
0 1 2 3 4 5 6 7 a 9 10 11 12 13 14
pH
Figure (7-3.3) The solubility diagram for the Zn-Br-H 2 O system at 25°C
[Zn] = [Br-] = 1.0 M (constructed using the DIASTAB
program).
7c..!-BR--r-i20
T· 298. 15
--+- - - +--- - - -+--- - +--
', 00 ... +- +- ---- --3 t- - ~ '. .'.r~--.-_,.
----------=-------- 1 2 :~:--~QH-"
3 :~N {OH) 2 (..:.G
90 l .i. 4 zr·JBR-+-
5 Zt-!8n2 (t~O}
, 5 ::NBR3--
GO
l 7 a.=.--
.! B YBR (,:.Q)
. oH20 Q. 0
l;:,H· 0/ .2
\ , o2'.-i· 2/0
60 1 1 oaR· 010
:,O i I
4C 'El
I
-~ \
5 / \
------ \2',
t t- t-- ---+- ·-t--- -+------+---

:J E 7 [3 g ·o 11 12 1:,
I
n
Figure (7-3.4) The distribution - pH diagram for the Zn-Br-H 2 0 system at

25°C [Zn] = 10-2 M and [Br] = 1.0 M (constructed using
DIASTAB program).
154
Further, the equilibrium concentration profiles of the zinc species versus pH in

bromine-bromide solution with changes in the solution chemistry ([Zn], [Br-])
are shown in figures (7-3.6) and (7-3.7). Figure (7-3.6a-b) also reveals the
strong dependence of the equilibrium concentration of the soluble species on
bromide concentration. In a solution of 10-3 M Br-, 0.607 mM Br2 (aq) and 10-2
M initial Zn, Zn 2+ is the only predominant species up to pH:6.79 as shown in
figure (7-3.6a).
% Zn ions
90
Zn l+
80
70 ZnBr 3
60
50
40
30
20
10
ZnBr +
o L--1=====1::===:c:===:::::i::==--=±::::::::::::==-===r::::::::::__----1..__ ____1:::::::::;~
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
log(Br-]
Figure (7-3.5) The distribution - log [Br·] diagram for the Zn-Br-H 2 O
system at 25°C [Zn] = SX 10-5 M and [Br] = 10-3 M to 30.0
Mand pH= 3.50 (constructed using the CHEMIX program).
At a higher concentration of Br- (ie., 1.0 M), the predominant equilibrium

species are zn2+, ZnBr+, ZnBr2 (aq), ZnBr3- (figure (7-3.6b)). The existence of
the bromo-species is influenced by the Br-/Br2 (aq) equilibria. In this solution
the zinc species are also more stable (although by a marginal difference) and the
solid, ZnO (s) is formed at a slightly higher pH of 6.90.
155
Concentration (M)
0.012 , - - - - - - - - - - - - - - - - - - - - - - - - ,
ZnBr3-
0.010 -+- ZnBr2 (AQ)
--+ ZnBr+
--e-- Zn++
0.008
-*- Zno (s)
~ Zn02--
0.006 -A- 02 (AQ)
---H-- Br2 (AQ)
0.004-
0.002
0 1 2 3 4- 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.6a) The equilibrium concentration profile of zinc species of

initial [Zn] = 10-2 M in bromide-bromide solution of [Br·] =
10-3 M and [Br2 (aq)] = 6.07X 10-4 M at 25°C (constructed
Concentration {M)
0.012 ~ - - - - - - - - - - - - - - - - - - ~
ZnBr3-
0.010 X
-+- ZnBr2 (AQ)
--+ ZnBr+
--e-- Zn++
-*- zno (s)
~ Zn02--
---H-- Br2 (AQ)
0 1 2 3 4- 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.6b) The equilibrium concentration profile of zinc species of

initial [Zn] = 10-2 M in bromine-bromide solution of [Br·] =
1.00 M and [Br2 (aq)] = 6.07Xt0· 4 M at 25°C (constructed
156
At initial conditions of 6.07X 10-4 M Br2 and 0.10 M Br concentrations (figure

(7-3.7a-d)), increasing zinc concentration from 10-4 M to 0.1 M lowers the pH
for the formation of ZnO (s) from pH =7.8 to pH= 6.20. The aqueous stability
window for Zn 2+ thus shifts to more acidic condition at higher zinc
concentrations. As such, in practical situations, zinc cementation in aqueous
bromine-bromide solutions, can only be conducted under acidic conditions
where zinc will be corroded (oxidized) especially at low pH's.
The distribution between the species, Zn 2+, ZnBr+, ZnBr2 (aq) and ZnBq- in
this pH range is also dependent on the concentration of zinc. The Zn-bromo
complexes are more predominant at higher concentrations of zinc. Similarly, the
soluble species, ZnOi2- (or Zn(OH)4 2-) is more predominant in alkali conditions
(pH> 10.0) at higher concentrations of zinc. However, ZnOi2- is only stable in
solutions of low zinc concentrations (ie., < 1o-4 M) above pH: 12.60. Also, the
Br2 (aq) equilibrium concentration can be seen to be greatly reduced in the
presence of excess zinc addition. The oxidizing properties of the Br2 (aq)/Br
equilibria are therefore highly impaired at zinc concentrations greater than 0.01
M, and contributes in part to the lower stability of the soluble species under
such conditions.

-3 . - - - - - - - - - - - - - - - - - - - - ,
ZnBr3-
-4 -+- ZnBr2 (AQ)

-¼- ZnBr+
-5 -B- Zn++
""*- zno (s)
-6 --+ Zn02--
-%- Br2 (AQ)
-7
-8
-9
O 1 2 3 4 5 6 7 B 9 10 11 12 13 14
pH
Figure (7-3.7a) The equilibrium concentration profile of zinc species of

initial [Zn] = 10-4 M in a bromine-bromide solution of [Br·]
= 0.10 Mand [Br2 (aq)] = 6.07xt0· 4 Mat 25°C (constructed
157

-3.--------------------------,
ZnBr3-
-4 -+-- ZnBr2 (AQ)
~ ZnBr+
-5 -a- Zn++
--*- ZnO (S)
-6 --4--- Zn02--
---H- Br2 (AQ)
-7
-8
-9
-10'--~~9------'--~9---'e>---l!I---H--Bi&--l!P---E----IF=---!IHIIIII---'
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.7b) The equilibrium concentration profile of zinc species of

=0.10 Mand [Br2 (aq)] = 6.07X10·4 Mat 25°C (constructed

o~------------------------.
ZnBr3-
-+-- ZnBr2 (AQ)

-2 ~ ZnBr+
-a- Zn++
--*- ZnO (S)
-4
-A- Br2 (AQ)
---H- Zn02--
-6
-8
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.7c) The equilibrium concentration profile of zinc species of

= 0.10 Mand [Br2 (aq)] =6.07Xl0· 4 Mat 25°C (constructed
158

0.--------------------~
ZnBr3-
-+- ZnBr2 {AQ)
-2 ~ ZnBr+
-a- Zn++
-4
-*- ZnO {S)
~ Zn02--
--¾- Br2 {AQ)
-6
-8
0 2 4 6 B 10 12 14
pH
Figure (7-3.7d) The equilibrium concentration profile of zinc species of

initial [Zn] = 0.10 M in a bromine-bromide solution of [Br]
= 0.10 Mand [Br2 (aq)] = 6.07xl0·4 M at 25°C (constructed
7-3-3 The Au - Br·/Br2 - H20 system
The thermodynamic behaviour of gold in bromine-bromide solution with respect

to the solution potential is well described in various Eh - pH diagrams reported
in literature and as shown in figures (2-3.2) and (2-3.3). As depicted by these
diagrams, the gold-bromide system is characterised by Au(I) bromide, AuBr2-,
and Au(III) bromide, AuBq-, complexes. The role of bromide in enhancing the
relative stability of these complexes is also demonstrated by these diagrams. The
magnitude of the equilibria describing the formation of these complexes are
given by equations (2-3.14) and (2-3.16).
The distribution of these species as a function of bromide concentration for a

total of 1000 mg/litre Au is shown in figure (7-3.8a-b). In the presence of
0.1875 M Br2, Be concentrations between 10- 3 M and 10.0 M, and pH of 2.00,
all the gold (ie., 100%) is present as AuBr4- complex. AuBr2- forms in trace
amounts at Be concentrations between 1.0 M and 10.0 M. At a lower Br2
concentration of 1.875X 10-3 M, pH 2.00 and 1000 mg/litre Au, 16% of the gold
exist as AuBq- at 10-3 M Br- concentration and increases to a maximum of 20%
AuBq- at 0.20 M Br- as shown in figure (7-3.8 b).
159
Log Concentration {M)

-2 , - - - - - - - - - - - - - - - - - - - - ~
AuBr4-
-+- AuBr2-
~ HAu03--
-4
-e- H2Au03-
-¾- Au03---
~ Au(OH)3 (AQ)
-6
-B
-10 L--------'---------l----19-ilFlllll--&I_____ _J
-4 -3 -2 -1 0 1 2
log [Br-]
Figure (7-3.Sa) The distribution - log [Br] diagram for the Au-Br-H 20
system at 25°C, [Au] = 1000 mg/I, [Br2] = 0.1875 M, [Br·] =
10-3 M to 10.0 M and pH = 2.00 (constructed using the
CHEMIX program).

-2.-----------------------,
AuBr-4,-
-+- AuBr2-
~ HAu03--
-e- H2Au03-
-3 -¾- Au03---
~ Au(OH)3 (AQ)
-4-
-5 '------B----l-----111---1. . . . . . . . . ._ _ _ _ _ __J
-4 -3 -2 -1 0 1 2
log(Br-]
Figure (7-3.Sb) The distribution - log [Br·] diagram for the Au-Br-H20
system at 25°C, [Au] = 1000 mg/I, [Br2] = 1.875X 10- 3 M, [Br·
] = 10-3 M to 10.0 M and pH = 2.00 (constructed using the
CHEMIX program).
160
At much higher Br- concentrations, lesser AuBq- forms respectively and is

completely inhibited at Br concentrations of 1.00 M and above. Under the same
conditions, AuBr2- increases from 0.41 % at 10-3 M Br- to 68.7% at 10.0 M Br
and predominates (over AuBq-) at Br- concentrations in excess of 0.40 M. This
shows that the equilibria governing the Au(0)/Au(I) bromide and Au(0)/Au(III)
bromide couples are strongly dependent on the Br21Br- equilibria. By and large,
the existence and relative predominance of AuBq- in bromine-bromide solution
will also depend on the strength of Br2 as an oxidant. AuBr2- may only be
stabilized in excess bromide concentrations.
Figure (7-3.9) shows the solubility of gold in bromide solution in relation to

Au(ill) bromide species (constructed using the DIASTAB program). As shown,
AuBq- is more stable in the acidic region at higher gold concentrations. At
lower concentrations of gold, AuBq- complex will precipitate as Au(OH)J (s) at
pH's higher than 4.00 and at much lower concentrations, form the soluble
Au(OH)4- at pH 5.70 and Au(OH)3 (aq) between pH 2.30 and 5.70. The Au(III)
bromide stability window thus shrinks to lower pH values at lower
concentrations. However, for the same initial conditions, no solubility windows
were identified for AuBr2- complex in a solubility diagram for gold-bromide
system. This indicates that AuBr4- is the more stable gold-bromide complex.
p[Au(m)][Br-]
0
1 Au+++
2 Au (OIi) 3
3 Au (OH) 4-
1
4 Au (OH) 5--
5 Au (OU) 6---
2 6 Au (OIi) 3 (S)
10 7 Br-
8 HBr
3 9 llAuBr4
10 AuBr4-
6 pll20: 0 / 0 / 0
4 pH: o / o / .l
pAu(lll): .507 I .25 I 0
pBr-: 0 / .25 I 0
5
3
2
6
0 1 2 3 4 5 6 7
pH
Figure (7-3.9) The solubility diagram for the Au-Br-H 2O system at 25°C
(constructed using the DIASTAB program).
160
161
Thus, the reaction path for the dissolution of gold in bromide solution yields
predominantly AuBq- complex. AuBr2- is unstable in aqueous bromide solution
and tends to disproportionate into AuBq- and Au(0) according to the
equilibrium reaction (2-4.10).
Figures (7-3.l0a-c) present the equilibrium concentration of predominant

species versus pH for the Au-Br-1Br2-H2O system at 25°C for initial conditions
of 1000 mg/litre Au (s), [Br-] =0.10 Mand [Br2] =6.07X 10-3 M (for figure (7-
3.l0a)), l.875X 10- 2 M (for figure (7-3.l0b)), 0.1875 M (for figure (7-3.l0c)
(constructed using the CHEMIX program). These figures illustrate further the
effect of Br2 concentration on the Au-Br-/Br2-H2O system. It can be seen that
AuBr2- complex is more predominant (increases in equilibrium concentration)
in the bromine-bromide solution at a higher Br-1Br2 ratio (ie., lower Br2
concentration or a lower solution potential). In figure (7-3. l0c), the predominant
soluble/aqueous equilibrium species are Bq-, Br2, AuBq-, below pH 7.00 and
Au (s) as the insoluble equilibrium species above pH 7 .00.

0
Br2 {AQ)
-+- AuBr4-
-¼- AuBr2-
-a- Br3-
-5
'"*"' Au
-4- 02 (AQ)
-A- BrO-
~ HBrO (AQ)
-10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
pH
Figure (7-3.lOa) The equilibrium concentration profile of the gold species of

initial [Au] = 1000 mg/I in bromine-bromide solution of [Br-]
= 0.10 M and [Br2] = 6.07X t0- 3 M at 25°C (constructed
162

0
02 (AQ)
-+- Br2 (AQ)

-¼- AuBr4-
-a- AuBr2-
-5
-¾- Br3-
~ Au
-A- BrO-
-H- HBrO (AQ)
-10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14- 15
pH
Figure (7-3.l0b) The equilibrium concentration profile of the gold species of

initial [Au]= 1000 mg/I in bromine-bromide solution of [Br·]
= 0.10 M and [Br2] = 1.87Sx10·2 M at 25°C (constructed

0
02 (AQ)
-+- Br2 (AQ)

-¼- AuBr4-
-a- AuBr2-
-5
-¾- Br3-
~ Au
-A- BrO-
-H- HBrO (AQ)
-10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
pH
Figure (7-3.l0c) The equilibrium concentration profile of the gold species of

initial [Au] = 1000 mg/I in bromine-bromide solution of [Br·]
= 0.10 M and [Br2] = 0.1875 M at 25°C (constructed using
the CHEMIX program).
163
The equilibrium concentration of AuBq- decreases in this pH range where it

predominates, in figures (7-3.l0a) and (7-3.l0b), as Bq-!Br2 equilibrium
concentrations decrease due to lower Br2 concentrations in the solution. In these
cases, solid Au predominates over a wider pH range while AuBq- stability
window narrows to below pH 5.00. The concentration profile of AuBq- is also
similar to that of Br3-1Br2. These indicate that gold dissolution to AuBr4- is
influenced by the concentration of Br3-1Br2 equilibria which dominates in the
solution below pH 7.00. Above pH 7.00, Br3-1Br2 disproportionates to HBrO
(aq) (pH 7.0-9.0) or BrO- (pH > 9.00) and AuBq- becomes unstable (or de-
stabilises). The gold dissolution in alkaline conditions at these conditions 1s
completely inhibited or the reaction path will lead to the formation of AuBr2--
The stability of Au(ill) bromide at different concentrations (10 and 100 mg/I)
with respect to changes in solution conditions (pH, [Br-]) are also shown in
figures (7-3.lla-c) and (7-3.12a-c). In figures (7-3.lla-c), the stability of 10
mg/I Au(ill) bromide solution can be seen to be strongly dependent on the
solution pH and the free bromide in the solution.
Concentration (lE-6 M)
60~---------------------,
02 (AQ)
50
-+- Br2 (AQ)
-¾- AuBr-4.-
-e- AuBr2-
4-0
--*- Au
~ HAu03--
30 -A- H2Au03-
-¾- Au03---
20
10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.lla) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au] = 10 mg/I, [Br-] = 1.00x 10-4
M and [Br2 (aq)] = 6.07X 10-5 M at 25°C (constructed using
164
Concentration (1E-5 M)
!Or-----------------------,
02 (AQ)
-+- Br2 (AQ)
8 -¾- AuBr4-
-e- AuBr2-
6
-*- Au
-+- HAu03--
-A- H2Au03-
4 --H- Au03---
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.llb) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au]= 10 mg/I, [Br·] = 0.10 Mand
[Br2 (aq)] = 6.07xl0· 5 M at 25°C (constructed using the
CHEMIX program).
Concentration ( 1E-6 M)
60~-----------------------,
02 (AQ)
50 -+- Br2 (AQ)

-¾- AuBr4-
-e- AuBr2-
40
-*- Au
-+- HAu03--
30 -A- H2Au03-
--H- Au03---
20
10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.llc) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au] = 10 mg/I, [Br·] = 1.0 M and
[Br2 (aq)] = 6.07x10· 5 M at 25°C (constructed using the
CHEMIX program).
165
At 104 M free Br and Br2 (aq) concentration of 6.07X 10-5 M (figure (7-
3.lla)), AuBq- (10 mg/1) complex is only stable below pH 2.00. At pH> 2.00,
Au (s) precipitates. At a higher concentration of free Br- (1.0 M), AuBq- is
more stable over a wider pH range (pH: 1.00-6.00) as shown in figure (7-3. llc).
Also, at [Br-J = 0.10 M, [Br2 (aq)] = 6.07X 10-5 M and pH > 4.00 (figure (7-
3.1 lb)), AuBq- decomposes to AuBr2- (on the basis of mass balance) where the
latter predominates in the solution between pH:5.00 and 6.00 and Au (s) forms
above pH:6.00. At higher Br concentrations (ie., [Br] > 0.10 M), AuBr2-
becomes more stable in the neutral pH range, and Au (s) can only be formed at a
higher pH as shown in figure (7-3.1 lc).
Similarly, as shown in figures (7-3. l 2a-c ), for a 100 mg/I Au(III) bromide
solution, the stability of AuBq- is enhanced as free Br concentration in the
solution increases from 10-4 M to 1.0 M ([Br2 (aq)] = 6.07X 10-4 M). However,
AuBr2- is only dominant in the Au(III) bromide solution of 1.00 M free Br-
concentration within a small pH range of 6.20 to 7 .00 and will predominate over
wider pH range at much higher Br- concentration.
These stability diagrams developed indicate that although the gold-bromide

complex is more stable as AuBr4-, gold can also exist as AuBr2- especially at
high bromide concentrations. The Au(III) bromide, AuBq-, is also more stable
at a higher pH range only in excess of bromide. In addition, the diagrams show
that the recovery of gold from Au(III) bromide solution by a cementation
process will only be effective in the acidic zone (pH < 6.00) where AuBr4- is
more predominant. In the neutral pH zone, a cementation kinetic model will be
complicated by the reduction of both AuBr4- and AuBr2- especially at low gold
and high bromide concentrations. In the alkaline zone, AuBq- is unstable
(decompeses into Au (s)) and a different recovery method will have to be
employed under such conditions.
This observation from thermodynamic modelling suggests that gold recovery

from Au(III) bromide solution can be achieved simply by adjusting the solution
pH within the alkaline range. However, such a consideration will require
seeding (or nucleation) of the gold particles and can only be applied
commercially with solutions of high soluble gold concentrations.
166
Concentration ( 1E-5M)
60.-------------------------,
02 (AQ)
50 -+- Br2 (AQ)

--+- AuBr,4,-
--e- AuBr2-
4-0
---*- Au
~ H2Au03-
30 -A- HAu03--
--¾- Au03---
20
10
o L_.,.....t:::::11&::::a~-----~--------1--------:111~
o 1 2 3 4 5 6 7a 9 10 11 12 13 14-
pH
Figure (7-3.12a) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au] = 100 mg/I, [Br] = 1.00X 10-4
M and [Br2 (aq)] = 6.07xto-4 M at 25°C (constructed using
Concentration (1E-5M)
60~---------------------
02 (AQ)
50 -+- Br2 (AQ)

--+- AuBr,4,-
--e- AuBr2-
4-0
---*- Au
~ H2Au03-
30 -A- HAu03--
20
10
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.12b) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au] = 100 mg/I, [Br-] = 0.10 M
and [Br2 (aq)] = 6.07x10-4 Mat 25°C (constructed using the
CHEMIX program).
167
Concentration (E-4 M)
6.....-------------------~
- Br2 (AQ)
5
-+- AuEr4.-
""* AuEr2-
-e- HAu03--
-*- H2Au03-
-4- Au03---
3 ---A- Au
--*- 02 (AQ)
2
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.12c) The equilibrium concentration profile of gold species in gold-

bromide solution of initial [Au] = 100 mg/I, [Br-] = 1.00 M
and [Br2 (aq)] = 6.07xto-4 Mat 25°C (constructed using the
CHEMIX program).
7-3-4 The Au(III) - Zn - Br-!Br2 - HzO system
Figures (7-3.13a-c) represent the equilibrium concentration of gold(III) bromide

species versus pH for the Au(III)-Zn-Br-1Br2-H2O system at 25°C, for initial
conditions of [AuBq-] = 5.08X 10-4M (100 mg/litre), [Br] = 0.1 M, [Br2 (aq)] =
6.07X 10-4 M and [Zn] = 10-4 M (figure (7-3.13a)), 10-3 M (figure (7-3.13b))
and 2X 10-3 M (figure (7-3. 13c)) (constructed using the CHEMIX program).
In the presence of 10-4 M Zinc, only 02 (aq) Br2 (aq) and Br3- equilibrium
concentrations decreased in the pH regions where they are stable, comparing
figures (7-3.13a) and 7-3.12b). The equilibrium concentration of AuBq- is
specifically not affected by this zinc addition in the gold-bromide solution. At
higher zinc concentration of 10-3 M, as shown in figure (7-3.13b), AuBq-
decomposes into Au and AuBr2- (by mass balance) below pH:5.00 and
predominantly Au between pH:5.00 and pH:7.00. Br2 (aq)/Br3- and 02 (aq) are
completely reduced in this pH range. Above pH:7 .00, the equilibrium
concentrations of the species Au and ZnO (s) are of the same equilibrium values
as those of Au and ZnO (s) for the thermodynamic conditions shown in figures
(7-3.12b) and (7-3.7b) respectively.
168
Concentration ( lE-4-M)
6,--------------------------~
02 (AQ)
5 -+- Br2 (AQ)

~ AuBr4-
-a- AuBr2-
4-
~ Zn++
--+- Au
3 -A- Zn0 (S)
-H- Br3-
2
o L-__.--,__-1..:~----------.1...ji~HilllF::::::.lat-•--1-••~
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.13a) The equilibrium concentration profile of Au/Zn species in

solution of initial [AuBr4-] = 100 mg/I, [Zn] = 10-4 M, [Br-] =
0.10 M, [Brz (aq)] = 6.07Xl0- 4 Mat 25°C (constructed using
12.------------------------,
02 (AQ)
10 -+- AuBr4-
~ AuBr2-
-a- Zn++
8
~ Au
--+- ZnO (S)
6 -A- Br2 (AQ)
-H- Br3-
4
0 1 2 3 4- 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.13b) The equilibrium concentration profile of Au/Zn species in

solution of initial [AuBr4·] = 100 mg/I, [Zn] = 10-3 M, [Br-] =
0.10 M, [Br2 (aq)] = 6.07x10-4 Mat 25°C (constructed using
169
Concentration ( 1E-4M)
25r-------------------~
AuBr2-
--t- Zn++
20 ~ Au
-a- ZnO (S)
15
-*- 02 (AQ)
~ Br2 (AQ)
-A- Br3-
10 -H-- AuBr4-
00 '------.l!l-----------l-------'----1----~--------.--------__J
1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.13c) The equilibrium concentration profile of Au/Zn species in

solution of initial [AuBr4·] = 100 mg/I, [Zn] = 2.3xto·4 M,
[Br] = 0.10 M, [Br2 (aq)] = 6.07x10· 4 M at 25°C
(constructed using the CHEMIX program).
However, for the zinc condition of 2.3x 10-4 M (figure (7-3.13c), it can be seen
that, in addition to Br2 (aq)/Br3·, 02 (aq), AuBq· and AuBr2· are completely
reduced to Au over the pH range of 1.00-7 .00 where they are stable in the
Au(III) bromide solution for the stated conditions, in comparison with figure (7-
3.l 2b ). Similarly, as shown in figures (7-3. l 4a-b ), 10 mg/litre Au(III) bromide
in a solution of 0.10 M Br-, 6.07X 10-5 M Br2 (aq), is also completely reduced
to Au in the presence of zinc amount of 2.3x 10-4 M.
These results show that, the reduction of the Au(III) bromide, AuBq·, to Au(0)
by zinc (ie., zinc cementation of Au from bromine-bromide solution) will be
more cost effective at pH's 5.00-7.00 and high gold concentrations. Below
pH:5.00, reduction of Au(III) bromide can only be effective at zinc amounts
more than the stoichiometric requirements. This simulation also indicates that
between pH's 1.0-4.0 and especially at high zinc amounts, zinc will be
conoded/oxidized (ie., reacts with hydrogen ions) first, before it reacts with
Au(III) bromide, Br2 (aq)/Br3· and 02 (aq).
170
1.2 , - - - - - - - - - - - - - - - - - - - - - - - - ,
02 (AQ)
1.0 -+- Br2 (AQ)

-¼- AuBr4-
-a- AuBr2-
0.8
-x-- Zn++
--4--- Au
0.6 -A- zno (s)
-¾f.- Br3-
0.4
0.2
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Figure (7-3.14a) The equilibrium concentration profile of Au/Zn species in

solution of initial [AuBr4-] = 10 mg/I, [Zn] = 10-4 M, [Br] =
0.10 M, [Br2 (aq)] = 6.07X 10-5 Mat 25°C (constructed using
25~---------------------~
AuBr2-
-+- Zn++
20 -¼- Au
-a- Zn0 (S)
-x-- 02 (AQ)
15
--4--- Br2 (AQ)
-A- AuBr4-
10 -¾f.- Br3-
0 1 2 3 4 5 6 7 6 9 10 11 12 13 14
pH
Figure (7-3.14b) The equilibrium concentration profile of Au/Zn species in

solution of initial [AuBr4-] = 10 mg/I, [Zn] = 2.3x 10-4 M, [Br-
] = 0.10 M, [Br2 (aq)] = 6.07xl0-5 M at 25°C (constructed
171
On the basis of the thermodynamic considerations, in the Au(ill)-Zn-Br-1Br2-

H2O system, the complete reductions of Br2 (aq)/Br3- and 02 (aq) to Br- and
H2o respectively precede the reduction of AuBq-, especially within the pH
1.00-4.00. This contributes in part to the higher zinc requirements for the
cementation reaction under these conditions. Thus, a kinetic model for zinc
cementation of gold from bromine-bromide solutions in this pH range, will be
controlled initially by the rate of reduction of these species.
At low zinc additions and low gold inventories, as the results also indicate, the
reduction of AuBr4- yields AuBr2-/Au(0). This means that, the reduction of
AuBq- to Au(0) involves the AuBr4-/AuBr2- and AuBr2-/Au(0) steps. As
depicted by figures (7-3.12a-c), this observation will be more pronounced at
higher Br- concentrations.
CHAPTER EIGHT
ELECTROCHEMICAL STUDY
8-1 INTRODUCTION
The anodic and cathodic reactions involved in the zinc cementation of gold from
gold-bromide solutions/liquors were studied separately as half-cell reactions by
electrochemical technique.
The objectives of these studies were to establish:
(1) the fundamental mechanistic features (current-potential relationships) to

describe the kinetic aspects of the initial dissolution of zinc in the bromide
solution and the reduction of the gold(III) bromo complex ion.
(2) the effects of bromide concentration, pH, temperature and other solution
conditions on the current-potential relationships of the reaction with the
aim of optimising the best conditions for recovery.
8-2 EXPERIMENTAL
8-2-1 Chemical reagents
The following chemical reagents were used in the experimental investigations:
Sodium bromide: (M&B) Analytical reagent; assay (on dried), 99 %

minimum NaBr; Molecular weight, 102.91.
Bromine (liquid): (BDH) Concentrated bromine solution; density, 3.12;

Br %, 99.5 minimum; Contents per millilitre at 20°c,
3g.
Sulphuric acid: (AJAX) H2SO4 solution; assay, 95.0 % to 98.0 %

w/w; Weight per millilitre at 20°C, about 1.84g.
173
Sodium hydroxide: (AJAX) NaOH pellets; assay, 98 % ffilmmum;

Molecular weight, 40.00.
8-2-2 Equipment and Instrumentation
8-2-2-1 Electrochemical equipment
The electrochemical study was conducted using a Pine Instrument RDE 4

Potentiostat in conjunction with a MSRX Speed controller and an Electrode
rotator as shown in figure (8-2.1).
The cmTent-potential curves (scanning voltammograms) were recorded on a

YEW type 3086 X-Y recorder with an effective recording area of 180 x 250
mm, a maximum sensitivity of 5 µ V/cm and pen speed of 500 mm/s (for both X
and Y axes) which provides excellent record of fast moving input signals (figure
(8-2.1)).
I_
--:J
'
k.,,~-J
.
Figure (8-2.l) Front view of the electrochemical equipment showing: Pine

Instrument RDE 4 Potentiostat, MSRX Speed Controller,
Electrode rotator and YEW X-Y Recorder.
174
8-2-2-2 Instrumentation/Data acquisition
Digitized data were also acquired with a 386-PC using Quick.log PC Data
Acquisition package through a TLC 548/9 LinCMOS 8-bit Analog-to-Digital
Converter, placed in parallel with the YEW 3086 X-Y recorder, as shown in
figure (8-2.2).
Figure (8-2.2) Front view of data acquisition unit showing: 386-PC and
TLC 548/9 Analog-to-Digital Converter.
The converter is a complete data acquisition system on a single chip. It is

designed for serial inte1iace with a microprocessor, peripheral, or digital logic
circuitry through 3-state Data output, chip select, and Input/Output Clock
control signals. Its additional features include:
175
Versatile control logic.

Data register.
An on-chip sample-and-hold circuit that can operate automatically or
under microprocessor control.
A high-speed converter with differential high-impedance reference voltage
inputs that facilitate ratiometric conversion and scaling, while isolating the
conversion circuitry from logic and supply noises.
The TLC 548/9 provides low error conversion of ±0.5 least significant bit
(LSB) in less than 17 microseconds.
The Quicklog PC software offers data logging and monitoring to disk in a text
format that is compatible with spreadsheets, data bases, and other analysis
programs. Multiple channels may be logged into one file including optional time
and date sampling. Multiple files may log data simultaneously.
8-2-3 Electrodes
All experiments were carried out using spectrographically high purity gold and
zinc rotating-disc electrodes with surface areas of 0.385 cm 2 and 0.0314 cm 2
respectively and fitted in teflon sleeves/shroud that could be rotated at various
speeds. Figure (8-2.3) shows these electrodes.
These electrodes were used (as working electrodes) in a conventional three-

electrode configuration with either a platinum (15-cm length of 22-ga) wire or a
graphite rod (0.5 mm diameter and 14.0 mm long) counter electrode (CE) and a
saturated calomel (as defined by equation (4-3.2)) reference electrode (SCE).
The counter electrode was shielded in a fritted glass compartment (Pine
Instrument model# ACOl 1420).
Prior to use, these electrodes (WE) were cleaned, polished with fine gram
(12µm) alumina powder and washed thoroughly with distilled water.
176
Figure (8-2.3) Gold (left) and Zinc (right) rotating-ruse electrodes for
electrochemical half-cell studies.
8-2---1- Apparatus/Othe rs
The electrochemical cell consisted of 125 ml round bottom pyrex glass cell
(Pine Instrument model # PRF696 l 6--1-) with ports/compartme nt s for elec trodes,
thermometer and gas dispersion.
The cell was imme rsed in a water hath (dimensions: 8x 8x 10 cm) with a
thermostat to control the tempe rature to t0. 5°C. /\n Orion model S/\ 520 pi I
meter was used to meas ure the pi I or the so lutio ns.
177
8-2-5 Solutions preparation/Analysis.
All solutions were prepared from analytical grade chemical reagents and
distilled water.
8-2-5-1 Stock solutions
A synthetic gold bromide stock solution (1000 mg Aull) was prepared from lg
of 99.99 % gold foil dissolved in 10 g/1 NaBr solution containing 10 ml of liquid
bromine and stined for about 12 to 24 hours. The solution was stripped off
excess bromine by bubbling air through for about 2 to 3 hours (ie., until bromine
vapour ceased to evolve).
The concentration of gold was determined by atomic absorption

spectrophotometry (Varian Spectra A-20) and that of bromine and bromide
concentrations by potentiometric titration using the Metrohm Automatic titrator
unit (682 Titroprocessor and 665 Dosimat) as shown in figure (8-2.4).
Figure (8-2.4) Metrohm Automatic titrator unit (682 Titroprocessor

and 665 Dosimat).
178
8-2-5-1-1 Determination of bromine
The total bromine (BrtotaI) in the stock solution was estimated against a 0.25 %
sodium thiosulphate (Na2S2O3) in the presence of 50% H2SO4 and 10% Kl
with combined platinum/saturated calomel electrode. The amount of bromine
was calculated according to the equation:
EPl x 1.265
Brtotal (g /1) = - - - - (8-2.1)
z
where Z is the volume (ml) of sample aliquot and EPl is the volume (ml) of
0.25% Na2S2O3 solution at equivalence point.
8-2-5-1-2 Determination of bromide
The bromide ions in the stock solution was also estimated against 0.03 M
AgNO3 solution with silver/KNO3 electrode. The bromide concentration was
calculated according to:
Br- (g/1) = EPl x 0.03 x 79.90 (8-2.2)

z
where Z is the volume (ml) of sample aliquot and EPl is the volume (ml) of
0.03 M AgNO3 solution at equivalence point.
8-2-5-2 Test solutions
The test (experimental) solutions of the required concentrations of Au and Br-

were prepared from gold bromide stock solutions using the respective acidified
NaBr solution.
8-2-6 Experimental procedure
The scanning voltammetry technique was used to study both the anodic
dissolution/oxidation of zinc in sodium bromide solutions and the cathodic
179
reduction of gold (ill) bromide complex 10ns from the bromine-bromide

solutions.
A schematic diagram of the equipment arrangement for the experimental work is

presented in figure (8-2.5). Figure (8-2.6) also shows the arrangement of the
three electrodes in the electrochemical cell.
The zinc and gold working electrodes were used for their respective half-cell
study. The working electrode was securely mounted on the metal shaft of the
electrode rotator and was submerged approximately 5 mm below the surface of
the solution in the cell to foster a well controlled rotating-disc electrode
hydrodynamics.
At the start of each experimental run, 120 ml of the test solution was adjusted to
the required pH (2.00-7 .50) by the addition of sulphuric acid or sodium
hydroxide and was allowed to obtain the required temperature in the water bath.
The solution was de-oxygenated (where necessary) with high purity (oxygen-
free) nitrogen for 30 minutes and then maintained under that atmosphere for the
duration of the experimental measurement.
1 Rotating disc electrode

2 Reference electrode
3 Counter electrode
4 Thermometer
5 Cell
6 Waterbath
7 Motor
8 Potentiostat
6
9 X Y Recorder
10 Data Acquisition unit
11 PC/IBM 386
Figure (8-2.5) A schematic diagram of the equipment arrangement for

electrochemical studies.
180
For each experiment, the RDE 4 Potentiostat was set to the required potential
range, scan rate and cunent conversion factor and the X and Y axes of the X-Y
recorder adjusted to the appropriate sensitivities. Cunent-potential curves were
recorded using a 386-PC using Quick.log PC Data Acquisition package through a
TCL 548/9 LinCMOS 8-bit Analog-to Digital converter. All potential scans
were started at the conesponding rest potential.
Figure (8-2.6) Front view of electrochemical cell showing the

arrangement of the three electrodes.
8-2-6-1 Anodic studies
For the anodic studies, the test solutions were sodium bromide solutions with no
bromine. It was difficult maintaining the same concentrations of bromine as the
res idual bro mine in the solutions for the cathodic studies in the sodium bromide
solutio ns for these studies.
181
The anodic experimental measurements were carried out in the potential range
of -1.20 V to -0.50 V (vs SCE), at a scan rate of 20 mV/s and electrode rotation
speed from 200 to 2500 rpm. The electrodes were polished between scans to
minimize variation in electrode area before each testing.
8-2-6-2 Cathodic studies
The test solutions were gold bromide solutions of the required concentrations of
Au (ID) bromide ions in the respective concentrations of NaBr solution (free Br-
ians of the same concentrations as in the equivalent anodic study) and residual
bromine (present from the stock solution).
The cathodic studies were carried out in the potential range of -1.80 to +0.80 V
(vs SCE) at a scan rate of 20 mv/s and electrode rotation speed between 200 and
2000rpm.
8-3 SCANNING (LINEAR SWEEP) VOLTAMMETRY
8-3-1 Anodic oxidation/dissolution of zinc
Figure (8-3.1) shows a typical current-potential curve for zinc dissolution of a

rotating-zinc disc electrode in a 0.05 M NaBr solution at a pH 5.00 and 20°C.
As shown, in the 0.05 M bromide solution, under these conditions, the zinc
rotating-zinc electrode (area 0.0314 cm 2 ) assumed a rest potential of about -
1.115 V (vs SCE).
The slow potentiodynamic sweeps on the zinc-rotating disc in the 0.05 M

bromide solution in the potential range of -1.115 V to -0.50 V reveal an initial
dissolution region where the current increases exponentially with potential and
an active dissolution region where the current increases rapidly in a linear
fashion. The currents in both regions are significantly independent of the disc-
rotation speed and show no passivation of the zinc.
However, as shown in figure (8-3.2), the cmTent-potential curve is dependent on

the concentration of bromide. There is a cathodic shift of the curves as bromide
increases from 0.01 M to 0.10 M.
182
Current {mA)
1.2 , - - - - - - - - - - - - - - - - - - - - - - - - -
1.0
0.8
0.6 [NaBr] = O.OCI M
0.4 pH= 5.00

Temp.= 293 K
0.2
RDE area = 0.0314 aq.cm.
0.0 L----'-------'-"""""--.L_----L--____IL-_ _...J___ ___J
-1.5 -1.3 -1.1 -0.9 -0.7 -0.5 -0.3 -0.1
E vs SCE {V)
Figure (8-3.1) Current-potential curve for zinc dissolution in 0.05 M NaBr

at pH:5.00, 20°C and 200-2500 rpm.
Current (mA)
5.0 ~ - - - - - - - - - - - - - - - - - - - - - - -
pH= 5.00 1 0.01 M NaBr
Temp.= 20 C 2 0.05 M NaBr
4.0 3 0.10 M NaBr
RDE area = 0.0314 sq.cm -' 0.50 M NaBr
3.0
2.0
3
1.0
o.o L_--1---=;;;;;;;;;~;;:;;;;~===.::ic=:::=::::1::==~==---__L__ _J
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4
E vs SCE {V)
Figure (8-3.2) Current-potential curves for zinc dissolution in NaBr

solutions (0.01 M to 0.50 M) at pH:5.00, 20°C and 1000 rpm.
At 0.50 M NaBr, the equilibrium potential tends to shift to a relatively less

negative value. The current in the active region, however, increases with
increasing bromide concentration from 0.01 M to 0.5 M and is therefore
controlled by the concentration of the bromide ions at the zinc electrode surface.
183
It is also apparent from figure (8-3.2) that the anodic dissolution of zinc will not
occur at an appreciable rate in low bromide solutions (ie., < 0.01 M). At high
bromide concentrations ( > 0.10 M) there will be accelerated corrosion
(oxidation) of zinc.
Figure (8-3.3) also shows the current-potential curves for the anodic dissolution
of zinc in 0.05 M bromide solution at various pH's, at 20°C and 1000 rpm.
Increasing the pH value at constant Br- concentration resulted in a cathodic shift
of the anodic curves. This indicates the influence of H+ ions in the rate-
determining step. At pH values less than 5.00, the participation of H+ ions leads
to high zinc corrosion as depicted by the observed high current values. At a pH
value of 2.00, increasing the pH value at constant B{ concentration resulted in a
significant cathodic shift of the anodic dissolution curves. This is due to the
participation of hydrogen ions in the rate-determining step of the dissolution
reaction. Much lower currents are obtained at pH values between 5.00 and 7.00.
It can be inferred that the dissolution of zinc in a strongly acidic bromide

solution occurs by means of a reaction in which both bromide and H+ ions are
involved. Thus, under such conditions, the reaction is under the influence of a
corrosion process.
Current (mA)
1.0 , - - - - - - - - - - - - - - - - - - - - - - - - ,
1 pH= 2.00 4 pH= 6.00
2 pH= S.00 0 pH= 8.00
0.8 S pH= 4.00 8 pH= 7.00
0.6 [N allr) = 0.05 M

Temp.= 20 C
0.4 RDE area = 0.0314 aq.cm
0.2
o.o L _ ~~:::::___--1.._ _
______J........ __.L__ __L__ __L__ _J
-1.2 -1.1 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5
E VS SCE (V)
Figure (8-3.3) Current-potential curves for zinc dissolution in 0.05 M NaBr

solution at 20°C, 1000 rpm and pH:2.00 to pll:7.00.
184
8-3-2 Cathodic reduction of gold bromide ions
Figure (8-3.4) shows typical current-potential curves obtained at a rotating-gold

disc electrode (area 0.385 cm2) in a 100 mg/1 gold (III) bromide solution
containing 0.01 M NaBr and 90 mg/1 Br2 (aq) (as Br total) at rotation speeds
from 200 rpm to 2500 rpm, pH of 5.00 and 10°C. These polarisation curves
exhibit three characteristic regions as indicated by A, B, and C and an
equilibrium potential of about 0.60 V (vs SCE). A comparison between these
curves and those obtained at the gold rotating-disc electrode in 0.01 M NaBr
solutions at various solution conditions (ie., presence/absence of atmospheric
02, Br2, Au(III)), pH:5.00, 10°C and 1000 rpm is also shown in figure (8-3.5).
Current (mA)
o.o~--~--~--~--~---~-~
1 100 rpm 8 1000 rp., e 1000 rpm
1 eoo rpm 4 1100 rpm e HOO rpm
B A
C
-0.2
2
8 pH• 8.00
-0.4 4 Temp.• 10 C
e
e
[AuBr-4-) • 100 mg/I
-o.e [NaBr[ • 0.01 M
ROE area • 0.385 eq.cm
-o.a~--~--~--~--~---~-~
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
Eva SCE (V)
Figure (8-3.4) Current-potential curves at gold rotating-disc electrode in

deaerated Au(ID) bromide solution containing 0.01 M NaBr
and 90 mg/I Br2 (aq) at pH:5.00, 10°C and rotational speed
from 200 to 2500 rpm.
It is apparent that the first cmrent rise (region A) in figure (8-3.4) (at potentials
cathodic to 0.60 V) results from the reduction of bromine (or aquo-bromide
species) to bromide ions according to:
185
-0.2
-0.4
pH • 15.00
-o.e a -02; -Br2(aq); -Au
Temp.• 10 C
b •02; -Br2(aq); -Au

[NaBrl • 0.01 M
-0.8 o •02; •Br2(aq); ·Au
ROE area • 0.3815 aq.om
d -02; •Br2(aq); •Au
RPM.• 1000
-1.0 ' - - - - - ' - - - - - ' - - - - - - - ' - - - - - - - - - ' - - - - ' - - - - - - '
-2.0 -1.6 -1.0 -0.6 0.0 0.5 1.0
Eva SCE (V)
Figure (8-3.5) Current-potential curves at gold rotating-disc electrode in

0.01 M NaBr at pH:5.00, 10°C, 1000 rpm and (a) absence of
atmospheric 0 2, Br2, Au (ie., background electrolyte) (b)
presence of atmospheric 0 2, (c) presence of atmospheric 0 2,
Br2 (aq) ((40 mg/I)) (d) presence of Au(ill) bromide (100
mg/I), Br2 (aq) ((90 mg/I)).
for which the reduction potential can be expressed by the Nernst equation as:
E O RT _ RT
(B _) = E(B _) - -ln[Br ]+-ln[Bri(aq)] (8-3.2)
r r F 2F
where E~Br-) = 0.60 V (vs SCE) (8-3.3)
The second wave (region B) at about -0.25 V corresponds to the reduction of the
gold (Ill) bromide ions to metallic gold (ie., Au (0)) according to:
(8-3.4)
which can also be expressed by the Nernst equation as:

186
(8-3.5)
where E(Au)= -0.25 V (vs SCE).
The current increases with decreasing potential until it becomes limited (limiting
current) at potentials cathodic to about -0.70 V (vs SCE). The third current rise
(region C) at -1.30 V also results from the evolution of hydrogen from the
reduction of H2O1H+ according to:
(8-3.6)
or
(8-3.7)
In addition, from the voltammogram (b) in figure (8-3.5) obtained in the

presence of atmospheric 02 (no N2 purging of the solution) cathodic reduction
of 0 2 can be explained as a result of the reduction of the gold(ill) bromide ions.
The excellent agreement of the shape of this voltammogram (b) with that of (c)
in figure (8-3.5) obtained in the presence of both 02 and Br2, lends further
support to the 02 assignment.
Furthermore, figure (8-3.6) shows the variation between the magnitude of the
limiting current densities and the square root of the rotational speeds of the disc
for the reduction of gold(ill) under the conditions in figure (8-3.4). The square-
root dependence of the limiting current densities follows the Levich's equation
(equation (4-3.5)), which describes the rate of mass-transport to a rotating disc
under laminar conditions. Thus, the cmTent-potential curves show a clear mass-
transp011 controlled (independent of potential) zone at potentials lower than -
0.70 V (vs SCE).
Figure (8-3.7) shows the typical current-potential scans at 1000 rpm for the
reduction of 100 mg/1 Au(III) bromide ions in 0.05 M NaBr solution (containing
90 mg/1 Br 2 (aq)), 20°C and various pH's from 3.00 to 7 .00.
187
limiting current density (mA/sq.cm)

0.5 , - - - - - - - - - - - - - - - - - - - - - - - - , , . - - - - ,
0.4
0.3
0.2
0.1
o.o-----~~----~-----~-----~
0.0 5.0 10.0 15.0 20.0
sq. root of rotation (rad/sec)-1/2
Figure (8-3.6) Variation of limiting current densities at gold rotating-disc

electrode with the square-root of rotation speed at constant
potential (E = -0.25V vs SCE) for the reduction of 100 mg/I
Au(ill) bromide solution containing 0.01 M NaBr and 90
mg/I Br2 (aq) pH:5.00, at 10°C.
Current (mA)
0.0 , - - - - - - - - , - - - - , - - - - - - - , - - - . - - - - - - r : 7 " " - - - - ,
l pH • 7.00 8 pH • Ii.DO Ii pB • 8.00
2 pH =Cl.00 4 pH =4.00
-0.6
[AuBr<i-] = 100 111&/l
[NaBr] = O.OCi M
a _ __
-0.9
Temp.= 293 K
RPM.= 1000
-1.2 RDE area = 0.385 aq.cm
-1.5 ~ - - - - ' - - - - ~ - - ~ - - - ~ - - ~ ~ - - ~
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
E VB SCE (V)
Figure (8-3. 7) Current-potential curves at gold rotating-disc electrode for

the reduction of 100 mg/I gold bromide ions in 0.05 M NaBr
solution (containing 90 mg/I Br2 (aq)) at 20°C, 1000 rpm and
pH's 3.00 to 7.00.
188
It can be seen that at pH's 4.00, and 3.00, the third steady-state current wave
(region C) in figure (8-3.4) at -1.30 V (vs SCE) is shifted negatively.
Figures (8-3.8a-c) also show the difference in E/1 profiles between the
background electrolyte (ie., 0.05 M NaBr) and those obtained in 100 mg/I
Au(ill) bromide solution containing 0.05 M NaBr at pH's 5.00, 4.00 and 3.00
respectively. In the potential range -0.25 V and -1.30 V (vs SCE), where the
reaction is believed to be limited by the mass-transport of Au(ill) bromide ions
to the electrode surface, the scans at pH 4.00 and 3.00 yield an additional
current rise. This effect is particularly more significant at much lower pH's
leading to higher limiting currents as pH decreases. Another feature of the
cathodic polarisation curves is that they demonstrate rather a progressive anodic
shift in the potential at which the additional current rise commences as pH
decreases.
Eva SCE (V)

o.o~-------------------~
--B-- [AuBr4•] • 0 mg/I
-A- [AuBr4-l • 100 mg/I
pH• 15.00
[NaBrl • 0.015 M
Temp.• 293 K
-1.2 RPM.• 1000
-1.4
ROE area • 0.3815 aq.om
-1.8
-1.8 L . . __ _ _ ___.___ _ _ ____,____ _ _ _____.___ _ _ __ _ .
0.00 0.02 0.04 0.06 0.08

Current (mA)
Figure (8-3.Sa) Current-potential profile at gold rotating-disc electrode in

0.05 M NaBr solution, pH:5.00 at 20°C 1000 rpm for the
reduction of (a) 0 mg/I Au(III) bromide ions (b) 100 mg/I
Au(Ill) bromide ions.
189
Eve SCE (V)

0.0,-----------------------~
-o. --e-- (AuBr4-( • 0 mg/I
-A- (AuBr4•l • 100 mg/I
pH• 4.00
(NaBrl • 0.015 M
Temp.• 283 K
RPM.• 1000
-1.4
ADE area • 0.388 1q.cm
-1.e
-1.8 .____ _ _ _ _ _ _ L_ _ _ _ __ _ , _ __ _ _ _ __ . __ _ _ __ _ _ ,
0.00 0.05 0.10 0.15 0.20

Current (mA)
Figure (8-3.Sb) Current-potential profile at gold rotating-disc electrode in

0.05 M NaBr, pH:4.00 at 20°C, 1000 rpm for the reduction
of (a) 0 mg/I Au(IIl) bromide ions (b) 100 mg/I Au(ID)
bromide ions.
E vs SCE (V)
o.o~---------------------~
-0.2 --e-- [AuBr4-I • 0 mg/I
-A- (AuBr4-) • 100 mg/I
-0.4
-o.e
pH• 3.00
-0.8
-1.0 (NaBrl • O.OCI M
-1.2 Temp.• 293 K
RPM.• 1000
-1.4
-1.e ROE area • 0.385 1q.cm
-1.8
-2.0 '------------'---------'-------_.__ _ _ _ ~
0.0 0.5 1.0 1.5 2.0

Current (mA)
Figure (8-3.Sc) Current-potential profile at gold rotating-disc electrode in

0.05 M NaBr, pH:3.00 at 20°C, 1000 rpm for the reduction
of (a) 0 mg/I Au(Ill) bromide ions (b) 100 mg/I Au(III)
bromide ions.
190
The change in the shapes of the polarisation curves for gold(ill) bromide
reduction at pH's 4.00, 3.00, is likely to be due to the preferential reduction of
H+ ions/protons on the surface of the electrode at these conditions and which
becomes more pronounced as pH decreases (ie., H+ increases as pH decreases).
This is in close agreement with the mechanism of the reduction of H+ to give
hydrogen atoms proposed by Rieger (Rieger, 1987) given in section (4-4.1 ).
The reduction of H+ ion may be catalysed on the surface of the gold electrode,
thereby lowering the reduction over-potential for the H+ ions on the gold surface
much further.
The effect of pH is also apparent from figure (8-3.9) showing the

voltammograms for the reduction of H+ ions at a rotating-gold surface at 1000
rpm, 20°C and pH's 3.00, 4.00 and 5.00. Thus, at low pH's the reduction of
Au(ill) bromide ions is superimposed by the hydrogen evolution reaction.
Hydrogen evolution becomes more predominant as the pH of the solution
decreases and the gold cathodic potential window is restricted or natTows in the
potential range -0.25 V and -0.5 V (vs SCE), as shown in figure (8-3.8 a-c).
These results indicate that Au(ill) bromide ions might not be reduced to Au(0)
at low pH's without hydrogen being copiously produced.
1 pH• 3.00
-0.05
2 pH• 4.00
-0.10 3 pH • 11.00
2
-0.15
Temp.• 293 K
-0.20 RPM.• 1000
-0.25
ADE area • 0.386 sq.cm
-o.so
-0.35 L . __ _
.1....__ _..1--_ _ _.__ _ __.___ _ _~ - - ~
-2.0 -1.5 -1.0 -0.6 0.0 0.5 1.0

E vs SCE (V)
Figure (8-3.9) Current-potential curves for the reduction of H+/HzSO4 ions

at gold rotating-disc surface at 20°C, 1000 rpm and pH 3.00,
4.00 and 5.00.
191
8-4 EVANS DIAGRAMS/1-E RELATIONSHIPS
The reduction of the Au(ill) bromide ions from bromine-bromide solutions and
the zinc dissolution in bromide solutions were further evaluated in terms of
Evans diagrams constructed from the current-potential curves (polarisation
curves) of the two half-cell reactions. Figure (8-4.1) shows a typical Evans
diagram constructed for a 100 mg/1 Au(ID) bromide ions/Zinc dissolution in
0.05 M NaBr solution at pH:5.00, 20°C and 1000 rpm. The polarisation curves
for the two half-cell reactions are also represented in a similar diagram as shown
in figure (8-4.2).
It can be seen from figure (8-4.1) that, the intersection of the anodic and
cathodic polarisation curves lie in the diffusion-control region of the cathodic
branch. Figures (8-4.1) and (8-4.2) reveal a large potential separation (L1E 0 >
0.36 V) of the equilibrium lines for gold(ill) bromide reduction and zinc
dissolution and the existence of a unique mixed (or corrosion) potential (-1.00
V) at which the rate of the anodic reaction is equal but opposite to that of the
cathodic reaction. These establish that under this condition, the Au(ill)
bromide/Zinc cementation reaction is mass-transport diffusion controlled and
there will be no thermodynamic restriction to the completion of the reaction.
Inefficient deposition of gold onto zinc cannot be attributed to the lack of
driving force. Consequently, the rate at which Au(III) bromide ions are reduced
in the displacement reaction is determined by the rate at which Au(III) ions
diffuse onto the zinc surface, provided the anodic and cathodic reactions
proceed independently on the zinc surface.
It is also clear from figure (8-4.1) that excess zinc has to be used to react with
the residual bromine and dissolved oxygen besides the Au(III) bromide ion
reduction reaction. At about -1.00 V (vs SCE) (ie., the mixed potential), the
COITesponding current density (0.935 mA/cm 2) involved in the reduction
process, is equal to the sum of the various current densities for the reduction of
the residual bromine (or aquo-bromide) species (A), gold(IIl) bromide ions (B)
and dissolved oxygen (C). In effect the reaction kinetics is strongly dependent
on the gold concentration, bromide concentration, bromine concentration, pH,
dissolved oxygen and temperature of the solution. The inter-related effect
between these factors as found from the study is discussed.
192
E vs SCE (V)
1.0
[AuBr4-I • 100 mg/I
Aelluollon
0.5 [NaBrl • 0.06 M
pH• 6.00
0.0
Temp.• 293 K
RPM.• 1000
-0.5
-1.0
-1.5
-2.0
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0
log current density (mA/sq.cm)
Figure (8-4.1) Evans diagram for the reduction of 100 mg/I Au(ill) bromide
ions/Zinc dissolution in 0.05 M NaBr solution at 20°C,
pH:5.00 and 1000 rpm. A: reduction of bromine species; B:
reduction of Au(III) bromide ions; C: reduction of dissolved
oxygen.
Current density (mA/aq.cm)

4.0.---------------------------,
INaBrl • 0.06 M
3.0 Oxlllatlon
pH• 6.00
2.0 Temp.• 293 K
1.0 RPM.• 1000
O.Ol-------''-----'--+e=•'-----'------'-------''-: :,,------;
t,•• - - - - -·
-1.0
Aelluctlon
-2.0 ' - - - - ~ - - - ~ - - - ~ - - - ~ - - - ~ - - ~
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
Eva SCE (V)
Figure (8-4.2) Polarisation curves (I vs E) for the zinc dissolution

(oxidation) in 0.05 M NaBr and the reduction of 100 mg/I
Au(III) bromide in 0.05 M NaBr (containing 90 mg/I Br2
(aq)); at 20°C, pH:5.00, 1000 rpm showing the mixed
potential and the difference in electrode potentials ( ~ E 0 ) of
the half-cell reactions.
193
8-4-1 Effect of residual bromine
The reduction of residual bromine as can be seen in figure (8-4.1) precedes the
reduction of the Au(ill) bromide species and is mass-transport controlled under
almost all conditions. In the bromide system depending on the bromide
concentration and the pH value, the bromine species predominant are Br 2 (aq),
Br3- (which forms as a direct reaction between Br2 and Br-), Bro- and HBrO
(aq).
The presence of Br2 (aq) or the aquo-bromide species m concert m the

cementation circuit will interfere with the Au(III) bromide ions reduction
reaction. In the reduction of 100 mg/I Au(ill) bromide ions in 0.05 M NaBr at
the solution conditions in figure (8-4.1), the presence of about 90 mg/I Br2 (aq)
led to a net current density of 0.86 mA/cm 2 and this accounted for the shift of
the Au(III) bromide reduction wave by that order.
Primarily, Br2 (aq) (or aquo-bromide) species reduction increases the Br-
concentration in the solution. Increasing Br2 (aq) (or aquo-bromide species)
concentration will undoubtedly aggravate its behaviour in the system. This will
lead to a shift in the mixed potential, change the rate step controlling the
reduction of Au(ill) bromide ions and jeopardise the gross efficiency of the
cementation reaction. In particular, its inherent oxidizing properties will
increase the dissolution of zinc in the bromide solution, causing an anodic shift
of the polarisation curve. This will result in a decrease in the magnitude of the
driving force necessary for the cementation reaction.
However, bromine is an essential component in the gold dissolution/oxidation in

bromide liquors. The logarithm of gold dissolution rates in bromide liquors is a
linear function of the logarithm of bromine concentration (Pesic and Sergent,
1991). Dissolved bromine in bromide leach liquors and for that matter in
cementation routes may be limited and its total removal in the system cannot be
warranted. In terms of the kinetics of the cementation reaction and for practical
applications, Br2 (aq) should be as low as possible.
194
8-4-2 Effect of dissolved oxygen
The reduction of dissolved oxygen to water in the entire reduction features of

gold(ill) bromide ions in bromine-bromide solutions as outlined in figure (8-3.5)
occurs in the same potential region for the reduction of Au(ill) bromide ions to
metallic gold (ie., Au (0)), and at a rate controlled by the mass-transport of the
dissolved oxygen.
Equilibrium oxygen solubility in potable water is around 8-9 mg/1, although at

high salinity this level drops to about 3 mg/I (A vraamides and LaBrooy, 1989).
Without de-oxygenation, the reduction of oxygen at a gold rotating-disc
electrode in 0.05 M NaBr solution at pH:5.00, 20°C and 1000 rpm was at 0.99
mA/cm2. After 30 minutes de-aeration, about 97% of the dissolved oxygen was
removed, leading to a net current density due to oxygen of 0.03 mA/cm2. In the
presence of Au(III) bromide ions in 0.05 M NaBr and at the same conditions,
the decrease in the rate of dissolution are due to the reduction of Au(III)
bromide ions to the metallic gold by this amount. Apparently, the current for the
reduction of oxygen in bromide solutions is directly proportional to the
concentration of dissolved oxygen and as such the extent of purging (de-
aeration). However, in highly acidic bromide solutions, purging with nitrogen
has little effect on the reduction curve, as the maximum oxygen solubility is
low.
Eva SCE (V)

1.0~---------------------,
Reduction --- 02 abHnt (N2 purge)

0.6 --e-- 02 prHent

0.0 [NaBrl • 0.01 M
-0.6 pH• 5.00

Temp.• 293 K
RPM.• 1000
-1.0
Oxidation
-1.6
-2.0 L..,__ _L.,____ _. _ _ _ - - ' ' - - - - - ' - - ~ - - ~ - - ~
-1.6 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0

log current denalty (mA/eq.cm)
Figure (8-4.3) Evans diagram for the reduction of 100 mg/I Au(l11) bromide
ions/Zinc dissolution in 0.01 M NaBr solution in (a) presence
of o 2 , (b) absence of 0 2 ; at 20°C, pH:5.00 and 1000 rpm.
195
The presence of dissolved oxygen also consumes zinc and causes a significant
shift in the reaction kinetics. Figure (8-4.3) shows the Evans diagram for the
reduction of 100 mg/I Au(ill) bromide ions and zinc dissolution in 0.01 M NaBr
solution in the presence of oxygen and without oxygen (purged with nitrogen for
30 minutes) at 20°C, pH:5.00 and 1000 rpm. The presence of oxygen caused the
anodic curve to shift to a more anodic direction and can be seen to change the
kinetics from a diffusion-control mechanism to a charge-transfer step. This will
lead to a less efficient cementation and the reaction might cease.
8-4-3 Effect of bromide concentration
Figure (8-4.4) shows the Evans diagram for 100 mg/I Au(ill) bromide/zinc
dissolution in different bromide solutions, pH:5.00, 20°C and 1000 rpm. It can
be seen that both the Au(ill) bromide ions reduction and zinc dissolution half-
cell reactions shifted in the cathodic direction as bromide increased from 0.01 M
to 0.10 M. However at 0.50 M bromide concentration the Au(III) bromide
reduction curve moved relatively in the anodic direction.
Eva SCE (V)

1.0
R•duotlon ---- (NaBrl • 0.01 M

0.5 -"*- (NaBrl • 0.0& M
-e-- (NaBrl • 0.10 M
0.0 -A- (NaBrl • 0.50 M
(AuBr4-) • 100 mg/I

-0.5
pH• &.00
-1.0 Temp.• 293 K

RPM.• 1000
-1.6
-2.0
-1.5 -1.0 -0.6 0.0 0.5 1.0 1.5 2.0 2.5
log current denalty (mA/aq.cm)
Figure (8-4.4) Evans diagram for the reduction of 100 mg/I Au(lll)
bromide/Zinc dissolution (oxidation) in (a) 0.01 M Nallr (b)
0.05 M NaBr (c) 0.10 M NaBr (d) 0.50 M Nallr; at 20°C,
pH:5.00 and 1000 rpm.
196
In addition, the respective potential for the evolution of hydrogen (due to the
reduction of water) shifted to less negative values as bromide concentrated
increased from 0.01 M to 0.50 M. The mixed potentials (where the anodic and
cathodic curves intersect) for 0.01 M NaBr, 0.05 M NaBr, 0.10 M NaBr, and
0.50 M NaBr are -0.98 V, -1.00 V, -1.07 V, -1.01 V (vs SCE) respectively and
the corresponding current densities are 0.89, 0.93, 1.05, 0.83 mA/cm2
respectively. As shown in figure (8-4.4 ), diffusion-control kinetics are
demonstrated by these concentrations of bromide solutions. It can be seen that
the effect due to the changes in bromide concentration (0.01-0.50 M) is only
marginal. However, at 0.50 M NaBr, a relatively lower current density (ie., rate
of reduction) is observed. Also, the intersections of the anodic and cathodic
curves at 0.10 M NaBr and 0.50 M NaBr are just at/closer to the respective
potentials for evolution of hydrogen. These imply that, at high NaBr
concentration(> 0.10 M) Au(ill) bromide ions will be reduced at a decreasing
rate, and accelerated corrosion of zinc. The decreasing rate of reaction at high
bromide concentration is probably caused by a decrease in the diffusivity of
Au(ill) bromide ions as NaBr solution becomes more concentrated, leading to a
shift in potential in the cathodic curve. This effect can be expected to be more
pronounced at lower gold concentrations.
On the other hand, the anodic behaviour of the zmc dissolution curve with
decreasing bromide concentration shows that, at lower NaBr concentration (ie.,
<0.0lM), the polarisation curves will intersect in the Tafel region of the Au(III)
bromide reduction branch and the reaction will proceed under an
electrochemical or charge transfer control step. Any changes in the reaction
(such as influence of bromine) under such conditions may lead to the complete
cessation of the reaction.
It is therefore obvious that the addition of free bromide solution (0.01 M to 0.10
M) during zinc cementation of gold from bromide leach liquors is essential.
Certainly, from the points of intersection of the polarisation curves in figure (8-
4.4 ), it follows that, best kinetics are obtainable at 0.01 M NaBr. However, for
practical applications, the concentration of bromide in this range (0.01 M to
0.10 M) can be rationalised in terms of thermodynamics to be dependent on the
bromide concentration necessary to stabilize the Au(III) bromide ions in
solution. Higher concentrations of bromide are required for more concentrated
Au(III) bromide solutions to be stable.
197
8-4-4 Effect of pH
Figures (8-4.5) and (8-4.6a-d) also show the Evans diagrams for the cathodic
reduction of 100 mg/I Au(ill) bromide ions and the anodic dissolution of zinc in
0.10 M NaBr at 20°C, 1000 rpm and different pH values (2.00 to 5.00).
These diagrams show that the kinetics/mechanistic features of the reduction of

Au(ill) bromide ions is largely affected by the proton concentration at pH:4.00
and below as discussed in section (8-3-2). A comparison (shown in table (8-
4.1)) of the measured values of the mass-transport limited cuffents, iL, for
solutions at pH's 2.00, 3.00 and 4.00 agree well (within experimental effors)
with the values calculated for the respective H+ concentrations from the Levich's
equation, using a diffusion coefficient, D, of 81. 7 x 1o-6 cm 2/s at 18°C (Marsden
and House, 1992) and a value of 0.01 cm 2/s for the kinematic viscosity, v
(Weast, 1986). Thus, as pH decreases the contribution of iL of H+ (calculated)
to the total (iH+ + iAu) as iL (measured) becomes more pronounced.
Also, as shown in figures (8-4.6b-d), the addition of 100 mg/I Au (III) bromide
ions in 0.10 M bromide solutions at pH's 4.00, 3.00 and 2.00 has no noticeable
effect on the cathodic polarisation curves for a blank 0.10 M NaBr solution.
Eva SCE (V)

1.0 . - - - - - - - - - - - - - - - - - - - - - - - - - ,
Reduction -4- pH• 2.00
0.5 -¼ pH• 3,00
-8- pH• 4.00
0.0 -B- pH• 5.00
-0.5 [NaBrl • 0.10 M
-1.0 Temp.• 2113 K

RPM.• 1000
-1.5
-2.0 ' - - - - - ' - - - - - ' - - - - - - ' ' - - - - ~ - ~ - - - - ' - - ~ - ~ - ~

-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Figure (8-4.5) Evans diagram for the reduction of 100 mg/I Au(Ill)
bromide/Zinc dissolution in 0.10 M NaBr at 20°C, 1000 rpm
and (a) pH 2.00 (b) pH:3.00 (c) pH:4.00 (d) pH:5.00.
198
Eva SCE (V)

0.0.-----------------------~
lleduollon - (AuBr4-I • O mg/I
-+- (AuBr4-I • 100 mg/I
-0.5
(NaBrl • 0.10 M
pH• 6.00
-1.0
Tamp.• 2g3 K
RPM.• 1000
-1.6
-2.0 L . . . - - - - - ' - - - - - ' - - - - - - ' - - - - _ . __ _ __.__ _____.

0.0 1.0 2.0 3.0 4.0 5.0 6.0
log current density (uA/aq.cm)
Figure (8-4.6a) Evans diagram for the reduction of (a) 0 mg/I Au(ID)
bromide (b) 100 mg/I Au(ill) bromide; and Zinc dissolution
in 0.10 M NaBr at 20°C, pH:5.00, 1000 rpm.
Eva SCE (V)

o.o~-----------------------,
lleduotlon - IAuBr4-I • 0 mg/I
-B- [AuBr4-I • 100 mg/I
-0.5
[NaBrl • 0.1 M
pH• 4.00
-1.0
Temp.• 293 K
RPM.• 1000
-1.5
-2.0 L . . . - - - - - ' - - - - - ' - - - - - - ' - - - - _ . __ _ __.__ ____,

0.0 1.0 2.0 3.0 4.0 5.0 6.0
Figure (8-4.6b) Evans diagram for the reduction of (a) 0 mg/I Au(l11)
bromide (b) 100 mg/I Au(III) bromide; and Zinc dissolution
199
Eva SCE (V)

0.0.--------------------------,
- [Au8r4-I • 0 mg/I
-a- (AuBr4-I • 100 mg/I
-0.5
(NaBrl • 0.1 M
pH• 3.00
-1.0 Temp.• 293 K
RPM.• 1000
-1.5
-2.0 L - - - - - ' - - - - - - ' - - - - - ' - - - - - ' - - - - - - ' - - - - - - - ' - - - - ' - - - - - - - - '

0.0 1.0 2.0 3.o 4.o 5.o e.o 7.0 8.0
Figure (8-4.6c) Evans diagram for the reduction of (a) 0 mg/I Au(l11)
bromide (b) 100 mg/I Au(ID) bromide; and Zinc dissolution
Eva SCE (V)

o.o~---------------------~
- (AuBr4-l • 0 mg/I
-a- (AuBr4-I • 100 mg/I
-0.6
(NaBrl • 0.1 M
pH• 2.00
-1.0 Temp.• 293 K
RPM.• 1000
-1.5
-2.0 L . . - - - - ' - - - - ' - - - - - ' - - - - - - ' - - - - - - - ' - - - - ' - - - - ' - - - - - - '

0.0 1.0 2.0 3.0 4.0 6.0 6.0 7.0 8.0
Figure (8-4.6d) Evans diagram for the reduction of (a) 0 mg/I Au(III)
bromide (b) 100 mg/I Au(Ill) bromide; and Zinc dissolution
200
The solution at pH 5.00 (figure (8-4.6a)) only showed a cathodic effect in

favour of the reduction of Au(III) bromide ions.
These results are strong indication that the mechanistic features of the cathodic
reduction of Au(ill) bromide ions at low pH's (< 4.00) are compatible with the
existence and the cathodic nature of protons (H+) on the surface of the gold
smface. Thus, at low pH's the rate of reduction of Au(ill) bromide ion is
controlled by the reduction of hydrogen ions.
Table (8-4.1) Calculated ff+ and measured current densities of the

reduction of 100 mg/I Au (III) bromides ions in 0.10 M NaBr
at different pH's and rotational speeds.
pH of solution RDE rotation speed iL (measured) iL of ff+ (calculated)

(RPM) mA/cm2 mA/cm2
2.00 600 19.48 19.20

1000 25.65 24.79
1600 31.49 31.36
3.00 600 1.75 1.92

1000 2.21 2.48
1600 2.86 3.14
4.00 600 0.19 0.19

1000 0.21 0.25
1600 0.26 0.31
5.00 600 0.116 0.019

1000 0.130 0.025
1600 0.135 0.031
201
Figure (8-4.7) also shows the Evans diagram for the reduction of Au(ID)
bromide ions/zinc dissolution in 0.05 M NaBr at 20°C, 1000 rpm and pH values
of 5.00, 6.00 and 7.00.
Eva SCE (V)

1.0
Reduction -H- pH• 7.00

0.5 -e- pH· e.oo
-A- pH • 6.00
0.0
(AuBr4-I • 100 mg/I
(NaBr) • 0.06 M
-0.5
Temp.• 2113 K
-1.0 RPM.• 1000
-1.5
-2.0
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5
Figure (8-4. 7) Evans diagram for the reduction of 100 mg/I Au(ill) bromide
ions/Zinc dissolution in 0.05 M NaBr at 20°C, 1000 rpm and
(a) pH:5.00 (b) pH:6.00 (c) pH:7.00.
As evidenced by figure (8-4.7), the pH of the solution in gold (III) bromide/zinc

cementation process should be maintained between pH:5.00 and 7.00 to avoid
the deleterious effect of H+ ions.
8-4-5 Effect of gold concentration
The effect of gold concentration on the kinetics/rate of gold (III) bromide

reduction at 10 mg/I Au in 0.10 M NaBr solution (containing about 9.8 mg/I Br2
(aq)) and 100 mg/I Au in 0.10 M NaBr solution (containing about 98 mg/1 Br2
(aq)) at pH 5.00, 20°c and 1000 rpm is shown in figure (8-4.8).
202
Eva SCE (V)

1.0.----------------------~
Reduction -A- (AuBr-4-) • 10 mg/I
0.5 -¼- (AuBr4-I • 100 mg/I
(NaBr) • 0.10 M
0.0
pH• 6.00
-0.5 Tamp.• 2g3
RPM.• 1000
-1.0
-1.5
-2.0~-~-~-~-~-~-~~-~-~-~---'
-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5
log currant danalty (mA/aq.cm)
Figure (8-4.8) Evans diagram for the reduction of (a) 10 mg/I Au(III)
bromide ions (b) 100 mg/I Au(ID) bromide ions and Zinc
dissolution in 0.10 M NaBr at 20°C, pH:5.00, and 1000 rpm.
The potentials cathodic to which the reduction of Au (ill) bromide ions is

controlled by mass-transport to the surface of the electrode are almost
independent of the gold concentration. Actually, the results show a ten-fold
increase in cathodic current corresponding to the ten-fold increase in the gold
concentration (10 to 100 mg/1), as expected. This indicates that the reaction rate
increases with increase in gold concentration at the same conditions of NaBr,
temperature and pH.
It can also be seen m figure (8-4.8) that the potential for the discharge of
hydrogen on gold due to the reduction of water shifts anodically at 10 mg/I Au
concentration. This results in the cathodic branch intersecting the zinc
dissolution curve in the hydrogen evolution region. Consequently, zinc will be
dissolving not only as a result of its reaction with Au(III) bromide ions, but also
as a result of its reaction with protons which are discharging on the smface of
the gold deposited during the displacement reaction. Thus, at low gold
concentration and under these conditions, the reaction would be inhibited by the
simultaneous hydrogen evolution.
203
8-5 RA TE MEASUREMENTS/KINETICS
Under ideal conditions, the rate of reduction of Au(ID) bromide ion by metallic
zinc is controlled by diffusion of the aurobromide ion to the zinc surface. In
essence, the rate constant can be predicted from the reduction half-cell reaction
via the Levich's equation (equation (4-3.5)).
8-5-1 Diffusivity
The variation of limiting current densities for gold reduction (obtained at a gold
RDE in a solution containing 100 mg/I Au, 0.05 M NaBr, 90 mg/I Br2 (aq), at
20°C) with square root of rotational speed at pH's 5.00, 6.00, 7.00 is shown in
figure (8-5.1).
At each pH, the linear relationship of limiting current density versus square root
of rotational speed, yields a slope from which the diffusion coefficient of
Au(ID) bromide species was calculated using the Levich's equation (refer to
appendix (8-5.1)). The kinematic viscosity value of 0.01002 cm 2/s for 0.05 M
NaBr (Weast, 1974) was used for the calculations.
Limiting current density (m.A/sq.cm)

0.10 ~ - - - - - - - - - - - - - - - - - - - - - - ,
__._ pH = 5.00
-f- pH= 6.00

0.08
¾ pH= 7.00
0.06
0.04.-
0.02
0 2 4 6 8 10 12 14 16
sq.root of rotation (rad/sec)-0.5
Figure (8-5.1) Variation of limiting current densities with rotation speed

for the reduction of Au(l11) bromide ions in a solution
containing 100 mg/I Au, 0.05 M NaBr, 90 mg/I Br2 (aq) at
20°C, (a) pH:5.00 (b) pH:6.00 (c) pH:7.00.
204
Diffusion coefficient {E-06) (sq.cm/s)

0.25 ,--------------'--=---___;__:__ _ _ _ _ _ _ _ __
0.20
0.15
0.10
0.05
0.00 .____ _ _ _..,__ _ _ ___,___ _ _ __ J __ _ _ ____J

4 5 6 7 8
pH
Figure (8-5.2) Variation of the diffusion coefficient of Au(III) bromide ions

with pH ([Au(III)]: 100 mg/I, [NaBr]:0.05 M, 20°C).
Figure (8-5.2) shows the plot of the diffusion coefficient values with pH. As
shown, the diffusion coefficient decreases significantly with pH in the pH range
5.00 to 7 .00. Thus, the diffusion coefficient of Au(III) bromide is represented
reasonably by 0.17x 1o-6 cm 2/s at 20°c, pH:5.00.
8-5-2 Rate constant/kinetics
The resulted diffusion coefficient values were used to predict the reaction rate
constant, kp, at the respective pH using equation (4-3.13). This yielded a
representative kp value of 4.2X 10-4 emfs for the reduction of Au(III) bromide
ions in 0.05 M NaBr at 20°C, pH:5.00 and 1000 rpm.
An analysis of the diffusion-limited currents using equation (4-3.12) (ie., kp =

iJnFC), for the reduction of Au(III) bromide ions to Au(0) at a gold rotating-
disc measured from the curves in figure (8-4.7) also yielded a kp value of
4.22x 10-4 cm/s for pH:5.00 at 20°C and 1000 rpm, which is in reasonable
agreement with the above value. Table (9-3.1) shows the kp values for different
experimental conditions.
CHAPTER NINE
CEMENTATION STUDIES
9-1 INTRODUCTION
The intrinsic reaction features (kinetics) of Au(ill) bromide/Zinc cementation

process from bromine/bromide solution were further studied by both rotating
zinc-disc geometry and suspended zinc particles.
The reaction rate was measured by following both the rate of disappearance of
gold and the rate of appearance/dissolution of zinc. The rate of cementation was
then compared with the predicted rate (from electrochemical studies) under the
same experimental conditions.
The relative merits of bromide concentration for the reduction of Au(III)

bromide ions and the effects of such kinetic variables as temperature, rotational
speed, gold concentration, pH (hydrogen ion concentration), amount of
particulate zinc and zinc paiticle size (in the case of suspended zinc paiticle
study) were evaluated to determine the optimum values of each parameter for
maximum cementation. The kinetic features of the process as influenced by
surface deposit characteristics at various experimental conditions were also
evaluated by scanning electron microscopy and X-ray diffraction. This was also
primarily to observe the mechanism of nucleation and subsequent growth of
gold deposits on zinc substrate.
9-2 EXPERIMENTAL
9-2-1 Materials
9-2-1-1 Chemical reagents
The chemical reagents as described in section (8-2-1) were also used for these
studies.
2()(,
Figure (9-2. 1) Rotatin g disc system for the A u(l ll) bromide/Zinc
cementation experiment (zinc rotating-d isc geometry); from
left to right: zinc disc; brass rod; teflon/plexiglass holder.
9-2-1 -2 Zinc
High purity (99.9%) zinc rotating zinc discs of area 7.069 cm 2 (diameter J.0 cm
by 2 mm thick) as shown in figure (9-2. 1) were used as wo rking
electrode/precipitant in the rotating-d isc geometry. The zinc disc s were
mach ined from cast zinc.
Also. of same purity (ie .. 99_9c1c ) zinc dust/particles or size ranges +38 ---1-:i pm:
+45-63 pm: +63- 106 µ m and surface areas 0.0906 m 2/g; 0.0547 111 2/g; 0.03--1-0
m2/g respectivel y were used in the suspended particles experiments.
9-2-2 Equipment and Instrumentation/Analytical methods
9-2-2- 1 Experimenraf Apparaws!Equipment
Figures (9-2.2) and t_9-2.3) show the sc hemati c diagr::ims or the experimental
apparatus used for the zinc rotating-disc geometry and the suspe nded 1111 (
p::irticles experiments respectivel y.
207
5
1 Zinc disc
3 Thermometer
4 Rotating shaft
5 Motor
4 6 DC/Speed controller
7 Multimeter
8 Water bath
2 9 Reactor/Cell
10 pH Meter
11 pH electrode
12 Thermostat
3

arrangement for the Au(ill) bromide/Zinc cementation
experiment using zinc rotating-disc geometry.
As shown in figure (9-2.2) the apparatus for the rotating-disc study consisted
essentially of a rotating-disc assembly, rotator/rotating shaft, a motor, a speed
controller, a reactor vessel, a water bath and a multimeter. The rotating-disc
assembly consisted of the zinc disc screwed into a brass rod and placed in a
bell-shaped teflon/plexiglass holder (shown in figure (9-2.1) mounted on a
stainless-steel shaft which could be rotated at various speeds. The rotating shaft
was in turn coupled to a DC motor and the speed was controlled by a DC
supplier. Similarly, the experimental apparatus for the suspended zinc particles
study, consisted of a stirrer, a combined stirrer motor and speed controller, a
reactor vessel, a water bath and a multimeter. The stirrer was a 30 cm long
PVC/Teflon rod with a 2-blade polyethylene impeller (dimensions: 2 cm x 4
cm).
In these studies, the rotating speed of the rotating shaft/stirrer was measured and
monitored by a TM-2011 Optical tachometer (RS Components Ltd). A high
impedance multimeter, model P7080B (Parameters Pty Ltd) with a maximum
sensitivity of 0.10 mV was used to measure the mixed potential of the test
solution during the course of the experiment. An Orion model SA 520 pH meter
was used to monitor the pH of the solution.
208
5
1 Stirrer impelers
3 Thermometer
4 Stirrer rod
5 Motor/Speed controller
4
6 Pt electrode
7 Multimeter
12 8 Water bath
2 9 Reactor/Cell
10 pH Meter
11 pH electrode
12 Thermostat
7

arrangement for the Au(III) bromide/Zinc cementation
experiment using suspended zinc particles.
All the batch experiments were canied out in a I-litre glass reactor vessel
(diameter: 10 cm , height: 15 .5 cm ) supported in a constant temperature water
bath controlled with a thermostat (of range: 0 - 100°C) and a constant speed
impeller. The lid of the reactor was a PVC stub (10-cm diameter and 2-cm
thick) with baffles/ports for the zinc electrode assembly/stiner, thermometer,
electrodes, nitrogen-dispersion tube (gas ingress) and sampling.
9-2-2-2 Analytical Instrumentation/Methods
The chemical analyses of the solution samples from the different cementation
experiments for gold and zinc concentrations were carried out with a Varian
(Spectra A20) atomic absorption spectrophotometer. Bromine and bromide
contents were also determined by potentiometric titration using the Automatic
titrator unit shown in figure (8-2.4) following the procedure described in
sections (8-2-5-1-1) and (8-2-5-1-2).
After each cementation experiment, the smface deposits of the gold-deposited

zinc discs/particles were observed in a JEOL JXA 840 scanning microanalyzer
fitted with an energy dispersive X-ray analysis system and operated at 20 kV in
209
the secondary electron emission mode. Prior to this study, each specimen was
coated with approximately 200 A (angstrom unit) of Au (in the case of the zinc
particles) and C (in the case of the zinc discs) in a JEOL vacuum coating unit
operated at a residual pressure of about 3X 10-5 Torr. Further examination of the
chemical nature of deposit on the zinc discs (beyond the limitations of the SEM)
was done using a PHILIPS X-ray diffractometer installed on PW 1140 X-ray
generator. The gold deposited on the zinc particles were also further examined,
in a cold setting resin polished to 1 µm, under a ZEISS optical microscope.
9-2-3 Preparations
9-2-3-1 Solutions/Reaction Mixtures
A synthetic gold bromide stock solution (1000 mg/1) was prepared following the
same procedure and analysis as described previously in section (8-2-5-1) for
electrochemical study. The reaction mixtures (or test solutions) of gold bromide
containing the required concentrations of Au(III) ions and Br- ions were
prepared by dilution of the stock solution using the desired amount of acidified
NaBr solution.
9-2-3-2 Polishing of electrodes
Prior to use, the zinc disc surface was initially roughly ground on 300, 600,
through 1200 grit wet emery papers followed by polishing with 4000 grit wet
emery paper to mirror appearance on a BUEHLER G1inder Ecomet V polisher.
The disc smface was then thoroughly washed with tap water rinsed with
distilled water and immediately dried with pressurised air. The prepared discs
were used immediately as soon as possible after cleaning to prevent
contamination.
9-2-3-3 Particle size analysis
Zinc dust/particles (-75 µm) was separated into the various size fractions (-45
+38 µm; -63 +45 µm; -106 +63 µm) by dry sieve analysis using Endecotts
210
laboratory test sieves (38, 45, 63, 106 µm) arranged m a stack or nest and
shaken on an Endecotts EVS I shaker for 30 minutes.
9-2-3-4 Surface area determination
The surface areas of the different size fractions of zmc particles were
determined by a multipoint BET method at 77 K with nitrogen as the analysis
gas. The BET smface area reports and plots of the different size fractions are
shown in appendix (9-2.1).
9-2-4 Experimental procedure
The batch reactor cementation experiments were can-ied out with an initial
reaction mixture/test solution of volume of 500 ml. Prior to any measurement,
the reactor vessel and the reaction mixture/test solution were allowed to attain
thermal equilibiium (at the required temperature) in the water bath. The test
solution/reaction mixture was adjusted to the desired pH (with H2S04/NaOH)
and de-oxygenated with high-purity (oxygen-free) nitrogen for 45 minutes. The
reactor was subsequently operated throughout the experiment with a continuous
purge of oxygen-free nitrogen over the surface of the solution.
In all experiments, solution samples of 5.0 ml were withdrawn from the reactor
vessel at regular intervals (using a 5 ml pipette) for gold and zinc analyses and
where required bromine/bromide contents. The mixed potential and pH of the
solution were also measured/monitored at each sampling time.
9-2-4-1 Zinc disc geometry experiments
These experiments were performed in the system shown in figure (9-2.1). The
principal and reference electrodes for the potential measurements were the zinc
rotating-disc and saturated calomel electrode respectively.
The zinc rotating-disc assembly was lowered into the Au(III) bromide solution-
filled reactor vessel and rotated at a desired rotational speed (measured by an
optical tachometer) to commence the cementation reaction. After two hours of
211
experimental run, the rotating-disc assembly was dismounted and the zinc disc
was detached from the teflon/plexiglass holder, washed with distilled water and
then dried in a vacuum desiccator prior to morphological study.
9-2-4-2 Suspended zinc particles experiments
The experimental procedure in these experiments followed the system shown in

figure (9-2.2). In these experiments, the solution potential of the reaction
mixture was measured/monitored relative to the saturated calomel electrode (as
reference electrode) using a Pt-wire electrode.
An experiment was initiated by the addition of known amount of particulate zinc

into the experimental gold bromide solution in the reactor vessel. The solution
was stirred with the stirrer at a desired rotational speed. The sample aliquots
taken periodically in the course of the experiments were centrifuged at a fixed
rotational speed for 5.0 minutes in a specially designed two-tube centrifuge to
arrest any entrained zinc particle before gold and zinc analyses.
The reaction product after 30 minutes run, in this case, was filtered, washed
with distilled water and dried in a vacuum desiccator for 24 hours.
9-3 CEMENTATION ONTO ZINC ROTATING DISCS
9-3-1 Reaction kinetics/Rate measurements
9-3-1-1 Effect of rotational speed
The cementation kinetics were followed by series of experiments canied out at

various stirring speeds. The data were analyzed according to first-order rate
equation (equation (5-3.8)) by plots of log([Au]t/[Au] 0 ) against time; where
[Au]t and [Au] 0 refer to Au concentrations at any time t and at t = 0
respectively.
Figure (9-3.1) shows the various behaviour of the first-order plots for 10 mg/1
AuBq-/Zn cementation in 0.10 M NaBr solution (containing 9.8 mg/1 Br2 (aq))
at 20°c, pH: 5.00 and stiITing speeds of 200, 500, 1000, 1500 rpm.
212
-0.1
[Ne.Br] = 0.1 M
pH= 5.00
-0.2
Temp. = 20 C
-0.3
Stlrri eed
-0.4 RPM= 200 Initial solution vol. = 600 ml.
-+- RPM= 500 RDE. area = 7.069 aq. cm
-0.5 -A- RPM = 1000
-a- RPM= 1500
-0.6 ~ - ~ - - ~ - - ~ - ~ - - ~ - - ~ - - ~ - ~ - - - '
0 20 40 60 80 100 120 140 160 180
Time, (mins)
Figure (9-3.1) Variation of log([AuJt/[Au] 0 ) ratio with time for 10 mg/I

Au(ID) bromide/Zn cementation in 0.10 M NaBr (containing
9.8 mg/I Br2 (aq)); 20°C; pH:5.00; at different rotational
speed.
kc(l)(E-04) {cm/s) kc(2}(E-03} (cm/s)

10.0 ~ - - - - - - - - - - - - - - - - - - - - ~ ~ 10.0
Initial rate, kc{l)
8.0
-+- Enhanced rate, kc(2)
8.0
[AuBr-'-] = 10 q/L
6.0 (NaBr] = 0.10 M 6.0
pH= 6.00
Temp.= 20 C
4.0 4.0
2.0 RDE. area = 7.069 sq.cm 2.0

Initial solution vol. = 600 ml
0.0 ~ - - ~ ~ - - - ~ ~ - - - ~ - - - - ~ - - - ~ 0.0
0 3 6 9 12 15
w-1\2 ((rad/s)-1/2)
Figure (9-3.2) Variation of reaction rate constants with the square root of
rotation speed for 10 mg/I Au(Ill) bromide/Zn cementation
in 0.10 M NaBr solution (containing 9.8 mg/I Br2 (aq)); at
20°C and pH:5.00.
213
These plots commonly are in a reasonable fit to a two-stage first-order rate

equation as observed for most cementation reactions. Thus, nucleation and
growth of the reduced gold (ie., Au(0)) occurs on the surface of the zinc
substrate and the kinetics shift from a slow first-order process (initial period)
(between 0 - 20 minutes) to a more rapid first-order process (enhanced period).
The second stage of accelerated rates according to Strickland and Lawson
(Strickland and Lawson, 1971) occurs when the deposit thickness exceeds a
specific deposit mass and is associated with the roughening of the growing
surface which causes perturbations of the hydrodynamics at the substrate
surface.
The rate constants, kc(l), calculated for the initial period (0 to 20 minutes) and
kc(2) for the enhanced period (20 to 120 minutes) (from the geometric slope of
the first-order plots) are plotted in figure (9-3.2) for the various stirring speeds.
As shown, the initial rate curve followed the Levich's equation (equation (4-
3.13)) based on hydrodynamic theory for laminar flow conditions, which, for
diffusional processes predicts that the rate will increase with square-root of the
rotation/stirring speed. The kc(l) values for rotational speeds of 200 and 1000
rpm are in reasonable agreement with the kp values (as shown in table (9-3 .1)
for the same conditions calculated from polarization measurements. Also, the
enhanced rates kc(2) are in strong dependence on the rotational speed and in
general confirms a mass transfer limited/controlled process for the Au(III)
bromide/Zn cementation reaction under these conditions.
The enhancement of the reaction rate constant at higher rotation speeds can also
be attributed to the changes in properties of the reacting surface with rotation
speed resulting in changes in deposit morphology.
9-3-1-2 Effect of temperature
The cementation kinetics of gold were also studied at different temperatures

ranging from 10°c to 40°C for an initial gold concentration of 10 mg/1 in 0.1 M
NaBr solution (containing 9.8 mg/1 Br2 (aq)) at pH: 5.00 and 1000 rpm.
The results are presented in log( concentration ratio) against time plots in figure
(9-3.3). These plots also show that the Au(III) bromide/Zn cementation reaction
follows a two-stage first-order kinetics.
214
-0.1
[Naik] = 0.1 M
pH= 5.00
-0.2
RPM. = 1000
-0.3
-0.4 10 C
-+- 20 C Initial aolution vol. = 500 ml.
-0.5 -A- 30 C RDE. area= 7.069 sq. cm
-a- 40 C
-0.6
0 20 40 60 80 100 120 140 160 180
Time, (mins)
Figure (9-3.3) Variation of log (concentration ratio) with time for 10 mg/I
Au(ill) bromide/Zn cementation in 0.10 M NaBr solution
(containing 9.8 mg.I Br2 (aq)); at pH:5.00; 1000 rpm and (i)
10°c (ii) 20°c (iii) 30°C (iv) 40°C.
ln kc(l) or kc(2)
-2 [AuBr4-] = 10 mg/1
--
-+-
Initial rate
Enhanced rate
[NaBr] = 0.10 M
pH= 5.00
-4- RPM. =
1000
-
-6 I-
-
-8 ~
RDE. area = 7.069 aq.cm

Initial aolution vol. = 500 ml
I
-10
3.0 3.2 3.4 3.6 3.8
1000/T ( 1/K)
Figure (9-3.4) Arrhenius plots for 10 mg/I Au(l11) bromide/Zn cementatiion

in 0.10 M NaBr (containing 9.8 mgn Br2 (aq)) at pH:5.00
and 1000 rpm.
215
It can also be seen that the rate of reaction improves with increasing temperature
from 10°C to 40°C and the enhanced rate occurs sooner at higher temperatures.
The differences in the dual kinetic regimes at high and low temperatures can be
explained on the basis of variable reduced metal growth kinetics and its
influence on the effective interfacial area. The plots of the natural logarithm of
the initial rate/enhanced rate against the inverse of temperature (Arrhenius plots)
are shown in figure (9-3.4). The slopes of these plots yield activation energies of
2.50 kcal/mol (10.50 kJ/mol) for the initial rate period and 3.13 kcal/mol (13.12
kJ/mol) for the enhanced rate period, confirming that the Au(ill) bromide/Zn
reaction is controlled by a diffusion mechanism as predicted by the Evans
diagrams (section 8-4).
9-3-1-3 Effect of initial gold concentration
The influence of initial gold concentration on the Au(III) bromide/Zn

cementation kinetics was also evaluated at 10, 20, 50, 100 mg/I of Au(III) in 0.1
M NaBr solution at 20°C, pH:5.00 and 1000 rpm. Figure (9-3.5) shows the first-
order plots of the expe1imental results. The initial and enhanced rates are also
plotted against the initial Au(III) concentration in figure (9-3.6).
Theoretically, if the reaction kinetics are limited by mass-transfer, boundary-

layer diffusion-control as revealed so far, the reaction rate constant should be
independent of the initial gold concentration. However, as depicted in figures
(9-3.5) and (9-3.6) there are significant changes in the initial and enhanced rates
of deposition of gold when the initial concentration is changed from 10 mg/I to
100 mg/I. Both the initial and enhanced rates increased as the initial gold
concentration was increased. Nevertheless, first-order kinetics are still evident in
each case and the results can be reconciled with diffusion as the rate-controlling
step.
The observed dependence of rate constant (especially with the enhanced rate
period) on the initial gold concentration is quite attributable to marked physical
changes in the deposit structure due to differences in the nucleation and form of
the crystal growth. At higher concentrations of initial gold, the deposits are
coarser and more porous as the deposition occurs on dendrites causing a greater
disturbance in the diffusion flux at a constant disc rotation speed.
216
[NaBr] = 0.1 M
pH= 5.00
Temp.= 20 C
RPM. = 1000
-1.0
lniUal [AuBr4-]
10 ppm AuBr4-
-1.5 -1- 20 ppm AuBr4-
-A- ISO ppm AuBr4- Initial aolution vol. = 500 ml.
-a- 100 ppm AuBr4- RDE. area = 7.069 aq. cm.
-2.0
0 20 40 60 80 100 120 140 160 180
Time, (mins)
Figure (9-3.5) Variation of log (concentration ratio) with time for (i) 10
mg/I (ii) 20 mg/I (iii) 50 mg/I (iv) 100 mg/I Au(ID)
bromide/Zn cementation in 0.10 M NaBr solution at 20°C,
pH:5.00 and 1000 rpm.
kc(l)(E-04) (cm/s) kc(2)(E-03) (cm/s)

10-----------------------~50
[NaBr] = 0.1 M
Intial rate, kc(1)
-1- Enhanced rate, kc(2) pH= 5.00 40
8
Temp.= 20 C
RPM.= 1000
6 30
4 20

2 Initial aolutlon vol. = 500 ml 10
+
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

[Au] mg/1
Figure (9-3.6) The effect of initial gold concentration on Au(III)

bromide/Zn cementation in 0.10 M NaBr, at 20°C, pH:5.00;
1000 rpm.
217
9-3-1-4 Effect of NaBr concentration
The role of free bromide in the Au(ill) bromide/Zn cementation reaction was
also studied at different sodium bromide concentrations for two different initial
gold concentrations. Figures (9-3.7 a-b) present the first-order plots for (a) 10
mg/I Au(III) bromide/Zn reaction in (i) 0.001 M; (ii) 0.010 M; (iii) 0.050 M; (iv)
0.100 M; (v) 0.500 M NaBr solution (each containing 9.8 mg/I Br2 (aq)) and (b)
100 mg/I Au(ill) bromide/Zn reaction in (i) 0.010 M; (ii) 0.050 M (iii) 0.100 M
(iv) 0.500 M NaBr (each containing 98 mg/I Br2 (aq)) respectively at 20°C,
pH:5.00 and 1000 rpm. Figures (9-3.8) and (9-3.9) also show the variation in the
reaction rate constants for (a) 10 mg/I Au(ill) bromide/Zn (b) 100 mg/I Au(ill)
bromide/Zn respectively.
It can be seen under the different initial gold concentrations that well-behaved
first-order kinetics were observed for free bromide concentrations between
0.010 Mand 0.500 M. However, at low concentrations of bromide as shown in
figures (9-3.7a) and (9-3.8), while the initial rate constant is highest at 0.001 M
Br-, an inhibiting effect on the reaction rate is observed at 0.001 M NaBr after
80 minutes of cementation leading to a deviation from first-order kinetics. This
phenomenon is attributed to the build-up of gold on the zinc surface increasing
the diffusion path length thereby restricting the diffusion to take place within the
open pores of the deposit. Thus, under these conditions, the gold cementation
will be associated with the dissolution of zinc under conditions which the rate is
controlled by the diffusion of free bromide to the zinc surface. In effect, while
the initial rate decreased with increase in free bromide from 0.001 M to 0.500
M, the enhanced rate slightly increased with free bromide from 0.001 M to
0.100 Mand decreased at 0.500 M.
On the other hand, for 100 mg/I Au(III) bromide/Zn cementation reaction, as
shown in figures (9-3. 7b) and (9-3. 9), the initial rate of cementation increased
with increase in free bromide from 0.01 M to 0.10 Mand decreased at 0.50 M
as predicted by the Evans diagrams in figure (8-4.4) obtained from polarization
measurements. These initial rate constants (kc(l)) agree well in most cases with
the predicted rate constants (kp) as measured from the cunent-potential data
following Levich's equation under these conditions as shown in table (9-3 .1 ).
218
-0.1 pH= 5.00

Temp.= 20 C
RPM. = 1000
-0.2 Initial [NaBr]
0.00lU NaBr
-t- 0.010 U NaBr
-0.3 -A- 0.050 U NaBr Initial •olulion vol. = 500 ml.
-6- 0.100 U NaBr RDE area= 7.069 sq.cm
--*- 0.500 U NaBr
-0.4~-~--~-~--~--~-~--~-~-~
0 20 40 60 80 100 120 140 160 180
Time, (mins)
Figure (9-3.7a) Variation of log([Au]tf[Au] 0 ) with time for 10 mg/I Au(III)

bromide/Zn cementation in (i) 0.001 M (ii) 0.010 M (iii)
0.050 M (iv) 0.100 M (v) 0.500 M NaBr ([Br2 (aq)]: 9.8
mg/I]); 20°C; pH:5.00; 1000 rpm.
pH= 5.00
Temp.= 20 C
RPM. = 1000
-1.0
Initial [NaBr]
0.0lM NaBr
-1.5 -t- 0.05M NaBr
-A- 0.10M NaBr
Initial aolulion vol. = 500 ml.
-a- 0.50M NaBr RDE. area = 7.069 sq. cm.
-2.0
0 20 40 60 80 100 120 140 160 180
Time, (mins)
Figure (9-3.7b) Variation of log([Au] 1/[Au] 0 ) with time for 100 mg/I Au(III)
bromide/Zn cementation in (i) 0.01 M (ii) 0.05 M (iii) 0.10 M
(iv) 0.50 M NaBr ([Br2 (aq)]: 98 mg/I); 20°C; pH:5.00; 1000
rpm.
219
kc(l)(E-04-) {cm/11) kc(2){E-03) (cm/11)

10.0 . - - - - - - - - - - - - - - - - - - - - - - - ~ 10.0
[AuBr4-] = 10 ~
lnJUal rate, kc(l)
8.0
--+- Enhanced rate, kc(2)
8.0
pH= 5.00
Temp. 20 C
6. o v--t---------1- RPM. = 1000 6 _0
4.0 4.0
2.0 2 •0
lnJUal aoluUon vol. = 500 ml.
RDE area = 7.069 1q. cm
0.0 .___ ___.__ __.__ _---'-_ _.....___ _..___ ____._ ___,__ __, 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
[NaBr], Mole/litre
Figure (9-3.8) Variation of reaction rate constants for 10 mg/I Au(ill)

bromide/Zn cementation with NaBr concentration ([Br2
(aq)]: 9.8 mg/I) at 20°C; pH:5.00 and 1000 rpm.
kc(l){E-04) {cm/s) kc{2)(E-03) {cm/s)

10.0 , - - - - - - - - - - - - - - - - - - - - - - - - - - . 60.0
(AuBr•-1 = 100 mc/L
lnlUal rate, kc(l)
8.0
--+- Enhanced rate, kc(2) 50.0
pH= 5.00
Temp. 20 C
40.0
RPM.= 1000
6.0
30.0
4.0
20.0
2.0
IniUal aolution vol. = 500 ml. 10.0
RDE area = 7 .069 aq. cm
0.0 .___ ___.__ __.__ _---'-_ _ ~ _ _.___ ___.__ ____,__ __, 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
(NaBr], Mole/litre
Figure (9-3.9) Variation of reaction rate constants for 100 mg/I Au(III)
bromide/Zn cementation with NaBr concentration ([Br2
(aq)]: 98 mg/I) at 20°C; pH:5.00 and 1000 rpm.
220
The enhanced rates in this case, however, decreased as free bromide increased
from 0.01 M to 0.50 M. This behaviour is probably caused by a decrease in the
diffusion coefficients (or mean activity coefficients) of gold-bromide ions due to
increase in the stability (or ionic strength) of the Au(ID) bromide solution as
bromide concentration increases. Nevertheless, the change in structural
characteristics of the deposit during the course of the reaction, over this
concentration range may be in the right direction to explain this variation in
enhanced rates.
Table (9-3.1) Rate constants from cementation experiments (kc(l); kc(2))

and as predicted from Evans diagrams (kp).
[NaBr] Rotation [AuBr4·] k p x10- 4 kc(l)X10· 4 kc(2)Xl0· 2

Mol/litre speed mg/L emfs emfs emfs
0.10 200 10 1.98 2.01 0.19

0.10 500 10 2.95 0.43
0.10 1000 10 3.94 4.13 0.64
0.10 1500 10 5.08 0.83
0.001 1000 10 4.38 4.72 0.59

0.010 1000 10 4.10 4.48 0.63
0.050 1000 10 4.00 4.37 0.64
0.100 1000 10 3.94 4.13 0.65
0.500 1000 10 2.00 2.36 0.60
0.01 1000 100 4.14 4.6 3.85

0.05 1000 100 4.22 4.96 3.76
0.10 1000 100 5.31 5.67 3.59
0.50 1000 100 2.11 2.95 3.06
0.10 1000 20 4.489 0.733

0.10 1000 50 5.075 2.059
221
The variation in initial rates with bromide concentration for 100 mg/1 Au(III)
can also be attributed to the influence of morphological changes with NaBr
concentration on the kinetics of Au(III) bromide/Zn cementation. Invariably, the
addition of free bromide ( > 0.01 M) is essential in the Au(III) bromide/Zn
cementation circuit and may be said to activate or influence the initial
dissolution of zinc substrate. However, at 0.50 M, as indicated by both
thermodynamics and electrochemical studies, there is an increased corrosion of
zinc.
9-3-1-5 Effect of hydrogen ion concentration
Figure (9-3.10) presents first-order plots of rate data obtained for various pH
values (2.00-7 .00) for 10 mg/1 Au(III) bromide/Zn cementation reaction in 0.10
M NaBr solution (containing 9.8 mg/1 Br2 (aq)) at 20°C and 1000 rpm. The
influence of pH on the specific rate constants kcO ); kc(2) and zinc dissolution
rate is also presented in figure (9-3.11).
(AuBr4-) = 10 mr/L
-0.1
[NllBr) = 0.1 M
Temp.= 20 C
-0.2
RPM. = 1000
Initial pH
-0.3 --- pH = 2.00

-+- pH= 3.00
¾ pH= 4.00 Initial solution vol. = 500 ml.
-0.4
-a- pH= 5.00 ROE. area = 7.069 aq. cm.
""*- pH= 7.00
-0.5 L...__ _ . _ __ __,___ _ _ _ ._ __ , _ _ _ - ' - - - - - ' - - - ' - - - - ' - - - - - '
0 20 40 60 60 100 120 140 160 180

Time, mins.
Au(III) bromide/Zn cementation in 0.10 M NaBr solution
([Br2 (aq)]: 9.8 mg/I at 20°C, 1000 rpm and (i) pH:2.00 (ii)
pH:3.00 (iii) pH:4.00 (iv) pH:5.00 (v) pH:7.00.
222
kc(l) or kc(2) (E-04-) (cm/s) ZN(II)(E-04-) (mg/sq.emfs)

120 , - - - - - - - - - - - - - - - - - - - - - - - - , 20
- Initial rate, kc{1)

[Aullri-] = 10 mc/l
100 -f- Enhanced rate, kc(2) [Na.Dr] = 0.1 Y
-0 Zn{D) 15
Temp. 20 C
80
RPM. = 1000
60 10
Q
4-0
Initial solution vol. = 500 ml. 5
20 D RDE area = 7.0611 aq. cm
0 0
0 1 2 3 4 5 6 7 8 9 10
pH
Figure (9-3.11) Variation of reaction rate constants and Zn(II) concentration

with pH for 10 mg/I Au(ID) bromide/Zn cementation in 0.10
M NaBr solution (containing 9.8 mg/I Br2 (aq)) at 20°C;
1000 rpm.
It can be seen from figure (9-3 .11 ), that the initial rates of cementation increased
slightly with decrease in pH from 7 .00 to 4.00 and then increased sharply for
further decrease in pH from 4.00 to 2.00. Clearly, hydrogen ion concentration is
of significance in the kinetics of Au(III) bromide/Zn cementation. The variation
in reaction rates between pH's 2.00 and 4.00 is probably connected with a
change in the nature and morphology of the deposit which may conceivably be
influenced by increased corrosion of the zinc substrate as H+ increased
according to:
Zn + 2H+ = Zn 2+ + H2 (9-3.1)
The effect would be to increase the number of anodic and active cathodic sites
for deposition thereby increasing the rate of nucleation and growth of the
deposit. Based on the information given by AAS measurements of zinc
concentration, the rates of zinc dissolution in the solution are determined in
figure (9-3.11) and table (9-3.2). At lower pH's (2.00 - 3.00), zinc dissolved in
the solution by several times the stoichiometric value. Also, as shown in table
(9-3.2), there was an appreciable change in the initial pH value at the end of
223
each experiment under this study which suggests the precipitation of hydrogen
during the reaction via equation (9-3.1).
Table (9-3.2) The influence of pH on the kinetics of Au(ID) bromide/Zinc
cementation.(initial Au(ill): 10 mg/L; 0.10 M NaBr
(containing 9.8 mg/L Br2 (aq)); 20°C, 1000 rpm).
Kinetic condition Rate constants Zinc dissolution rates

Initial Final Initial Enhanced Zn(Il)X l0-4 Zn(II)X l0-4
pH pHkc(l)X l0-4 kc(2)X 10· 4 Initial Enhanced
emfs emfs mg/cm2/s mg/cm2/s
2.00 2.56 16.565 67.723 34.253 9.283

3.00 3.97 11.820 72.694 5.952 3.365
4.00 5.24 7.0850 72.703 0.817 0.513
5.00 6.45 4.1340 64.495 0.397 0.291
7.00 7.29 1.4160 53.757 0.264 0.210
2 hours of cementation
Nevertheless, at higher pH (pH:5.00-7.00) the variation in reaction rates may be

due to the decrease in diffusion (or activity) coefficient as pH increases over this
pH range.
However, at pH:2.00, in addition to increased zinc consumption during the

reaction, a characteristic inhibiting effect on the reaction rate was observed after
80 minutes of cementation leading to a deviation from a well-behaved first-order
kinetics. In effect, the enhanced reaction rate at pH:2.00 (67.723x 10-4 emfs)
was lower than that at pH:3.00 (72.694X 10-4 emfs). This may be due to an
apparent change in the morphology of the growing deposit under the influence
of high H+ions and increased zinc consumption. This probably resulted in a
change in the diffusional process and perhaps a poor adherent deposit.
Invariably, this effect may be due to adsorption of atomic hydrogen (released via
equation (9-3.1)) on the precipitant, effectively reducing the cathodic area
available for the discharge of gold.
224
It could be inferred from these results that, although faster kinetics are
obtainable at low pH values (ie., pH:2.00 - 4.00), the corresponding high zinc
dissolution rates do not warrant a cost effective practical cementation process
under these conditions.
9-3-2 Zinc dissolution/stoichiometry
An examination of the gold and zinc Eh(potential) - pH, equilibrium

concentration versus log bromide concentration diagrams suggest that the
reaction between a Au(ID) bromide solution containing about 0.001-0.500 M
free bromide, and zinc metal will have the stoichiometry:
2AuBq- + Br- +3Zn = 3Zn2+ +2Au + 9Br- (9-3.1)
where a stoichiometric ratio of Au:Zn(II) 1s 1: 1.50. The dissolution of zinc

during the Au(ID) bromide/Zn cementation reaction was monitored and
quantified as dissolution factors defined as the ratio of the total amount of zinc
dissolved to the theoretical values calculated based on the stoichiometry of
equation (9-3.1). The dissolution factors obtained at different variables are given
in table (9-3-3).
As depicted by table (9-3-3), the zinc dissolution factors were higher at low
initial gold concentration (10 mg/1), low pH values (< pH:4.00) and higher
bromide concentration (0.500 M). At initial gold concentrations greater than 20
mg/1, dissolution factors close to 1.00 were obtained. The relatively higher
dissolution factor at low initial gold concentration (10 mg/1) is due to an
increased effect of H+ reduction in the solution. Thus, under this condition, zinc
dissolves along the reaction path of hydrogen evolution. It can also be seen that,
the dissolution factors increased greatly at low pH values, due to an increase in
the rate of hydrogen evolution. The dissolution factors also increased marginally
with increasing temperature as expected of a diffusion controlled reaction.
Figure (9-3.12) also shows the variation in the zinc dissolution rates with time
for (i) 10 mg/1 Au(l11) (ii) 20 mg/1 Au(III) (iii) 50 mg/1 Au(III) and (iv) 100 mg/1
Au(III) in 0.10 M NaBr solution at 20°C, pH:5.00 and 1000 rpm. These results
show that zinc dissolution rates in general increased with increase in initial gold
concentration. This phenomenon suppo11s the variation in kinetic behaviour
225
(increasing reaction rates) with increase in initial gold concentration and further
suggests that the deposited metallic gold on the zinc smface enhances the
dissolution of the substrate.
Zn dissolution rate(E-04-) (mg/sq.emfs)

12..--------------------------,
[NaBr] = 0.1 M
[AuBr4-] = 10 m.r/L
10
pH= 5.00 -+- [AuBr4-] = 20 m&/L
Temp.= 20 C -A- [AuBr4-] = 50 m.r/L

8 RPM.= 1000 -8- [AuBr4-] = 100 mc/L

6 Initial aolution voL = 500 ml.
0 20 4-0 60 80 100 120 14-0 160 180

Time, (mins)
Figure (9-3.12) Zinc dissolution rate versus time for (i) 10 mg/I (ii) 20 mg/I
(iii)S0 mg/I (iv) 100 mg/I Au(ID) bromide solution containing
0.10 M NaBr at 20°C, pH:5.00 and 1000 rpm.
226
Table (9-3.3) Total zinc consumption
Kinetic Variable Total Au Total Zn Stoich Dissolution.

condition deposited dissolved ratio factor
(xto-s moles) (x10·5moles) (Au/Zn(II))
-RPM: 200 1.2501 2.246 1.797 1.20
Au:lOmg/I 500 1.933 3.404 1.762 1.17
Temp. 20<>C 1000 2.473 4.523 1.829 1.22
pH:5.00 1500 2.948 5.104 1.731 1.15
NaBr:0.10 M
Au(III}: 10 mg/1 2.473 4.523 1.829 1.22

Temp. 20°C 20 mg/1 5.389 8.135 1.510 1.01
pH:5.00 50 mg/1 21.525 32.839 1.526 1.02
RPM:1000 100 mg/1 48.869 74.752 1.530 1.02
NaBr:0.10 M
TemQ. (°C}: 10 2.150 3.893 1.811 1.21

pH:5.00 20 2.473 4.523 1.829 1.22
Au:10 mg/I 30 2.810 5.171 1.840 1.23
RPM:1000 40 3.096 5.814 1.878 1.25
NaBr:0. 10 M NaBr
n.tl: 2.00 2.671 144.483 54.093 36.06

Au:lOmg/I 3.00 2.750 52.381 19.048 12.70
Temp:20<>C 4.00 2.704 7.990 2.955 2.00
RPM:1000 5.00 2.473 4.523 1.829 1.22
NaBr:0.10 M 7.00 2.178 3.274 1.503 1.00
NaBr 0.001 2.450 4.229 1.726 1.15

pH:5.00 0.010 2.487 4.907 1.973 1.32
Temp:20°C 0.050 2.496 4.543 1.820 1.21
Au:10 mg/I 0.100 2.473 4.523 1.829 1.22
RPM:1000 0.500 2.348 5.157 2.196 1.46
NaBr 0.01 49.279 74.305 1.508 1.01

pH:5.00 0.05 49.095 75.539 1.539 1.03
Temp:20°C 0.10 48.869 76.217 4.897 1.04
Au:100 mg/1 0.50 47.618 74.973 4.817 1.05
RPM:1000
227
9-3-3 Deposit Morphology/Surface studies
The recovery of metallic gold from Au(ill) bromide solutions by cementation

using zinc is an electrochemical process involving the oxidation of zinc and the
reduction of gold bromoanions.
The characterisation of the cementation reaction product on the zmc surface

after two hours of cementation in bromide solutions at different conditions by
both Energy dispersive X-ray analysis and X-ray diffraction showed only peaks
characteristic for synthetic gold and synthetic zinc. Typical EDAX and XRD
charts (after 20 min reaction time) are shown in appendices (9-3.1) and (9-3.2)
respectively. These findings endorse that the resultant deposit on zinc for
Au(ill) bromide/Zn cementation was pure gold and not an alloy of Au-Zn. Thus,
gold deposited at cathodic sites while zinc dissolved from anodic sites.
The effect of the gold deposit on the rate of the cementation reaction is quite
significant. Further examination of the cementation reaction product by
scanning electron microscopes showed that the gold deposit layer on the zinc
surface accounts for the observed boundary layer diffusion-controlled first-order
reaction kinetics. The structure of the surface deposit was found to be
characteristic of a two-stage growth phenomena as evident in many other
cementation reactions. An initial smooth deposit (corresponding to the initial
period/stage of reaction) over which a secondary coarser
particulate/botryoidal/dendritic deposit (corresponding to the enhanced
period/stage of reaction) formed. Once the amount of gold deposited was
massive enough (specific mass deposit) to cause disturbances in the diffusional
process, the secondary particulate/dendritic formation occurred which enhanced
the cementation rate by several times that of the initial period. The change in
smface character is vividly illustrated by comparison of the SEM
photomicrographs under different conditions.
9-3-3-1 Effect of rotational speed
The effect of disc rotational speed on the cementation deposit structure and
morphology is shown in figures (9-3.13a-d) corresponding to 200, 500, 1000
228
and 1500 rpm respectively for 10 mg/1 Au(ill) bromide/Zinc cementation

reaction in 0.1 M NaBr (containing 9.8 mg/1 Br2(aq)) at pH:5.00 and 20°C.
Figure (9-3.13a) 200 rpm, 500X mag.
Figure (9-3.13b) 500 rpm, 500X mag

229
Figure (9-3.13c) 1000 rpm, 500Xmag.
Figure (9-3. 13d) 1500 rpm, 500X mag.
Figures (9-3.13a-d) Scanning electron micrographs (shown after 120 mm

reaction time) showing the effect of rotational speed on
Au(ill) bromide/Zn cementation (10 mg/I Au(III); 0.10 M
Nallr (containing 9.8 mg/I Ilr2 (aq)); 20°C; pH:5.00), (a) 200
rpm (b) 500 rpm (c) 1000 rpm (d) 1500 rpm.
230
Figures (9-3-13a-d) illustrate clearly an appreciable change in surface

character/morphology of gold deposit for Au(ill) bromide/Zinc cementation as
indeed, a function of the rotational speed of the zinc disc and thus explains the
nature of the observed kinetic behaviour. The observed rotational speed
dependence of the enhanced rates in the range 200 to 1500 rpm is such that the
deposit roughness increases in this range.
Figure (9-3.13a) shows that the gold deposit obtained at 200 rpm consisted of
scattered thin crystallites on entirely smooth matrix/surface. The nature of this
deposit possibly created minimum turbulence in the boundary layer due to its
regular surface and smaller cathodic area and contributed to the lower reaction
rate constants associated with it. This deposit also revealed the initial smooth
deposit corresponding to the initial period of reaction.
An increase in the rotational speed from 200 to 500 rpm resulted in a change in
the nature of the deposit to a thicker growth, with the deposit growing outwards
from the disc (figure (9-3.13b)). The deposit also provided a more roughened
surface area and cathodic sites to facilitate further deposition as observed in
higher reaction rate than at 200 rpm. As the rotational speed was further
increased the deposit changed to a botryoidal structure at 1000 rpm and a
botryoidal-type of fine textured dendiitic growth at 1500 rpm. The physical
nature of these deposits at 1000 and 1500 rpm's contributed to increasing
turbulence in the boundary layer as well as higher surface areas which resulted
in progressively higher reaction rate.
The structural changes of the gold deposits on zinc discs at (a) 10°C (b) 20°C
(c) 30°C (d) 40°C for 10 mg/I Au(ill) bromide/Zn cementation in 0.10 M NaBr
solution (containing 9.8 mg/I Br2 (aq)) at pH:5.00 and 1000 rpm are shown in
figures (9-3.14a-d) respectively.
At 10°c (figure (9-3.14a)), the deposit was smooth/compact and coherent in

nature which supposedly contributed less roughness and less surface area
responsible for the low reaction rates. At 20°C (figure (9-3.14b)), the deposit
was more particulate/botryoidal and less coherent than at 10°C and possibly
contributed a higher reaction rate.
231
Figure (9-3.14a) lQOC, 2000X mag.
Figure (9-3.14b) 20°C, 2000X mag.

232
Figure (9-3.14c) 3QOC, 2000X rnag.
Figure (9-3.14d) 4QOC, 2000X rnag.
Figures (9-3.14a-d) Scanning electron micrographs (shown after 120 mm

reaction time) showing the effect of temperature on Au(ill)
bromide/Zn cementation (10 mg/I Au(ill), 0.10 M NaBr
(containing 9.8 mg/I Br2 (aq)), pH:5.00, 1000 rpm), (a) 10°C
(b) 20°c (c) 30°C (d) 40°C.
233
At higher temperatures (30°C and 40°C) as shown in figures (9-3.14c-d), the

deposit changed to a coarser crystalline type which became more prominent
over the electrode surface at 40°C than at 30°C. These crystalline variety of
different roughness and surface areas at these higher temperatures were
obviously accompanied by higher reaction rates.
9-3-3-3 Effect of pH
The scanning electron micrographs at initial pH values of (a) 2.00 (b) 3.00 (c)
4.00 (d) 7.00 for 10 mg/I Au(III) bromide/Zn cementation reaction in 0.10 M
NaBr (containing 9.8 mg/I Br2 (aq)) at 20°C and 1000 rpm are presented in
figures (9-3.15a-d).
The difference in the nature of the deposits m figure (9-3.15a)

(botryoidal/bulbous deposit) and figure (9-3. l 5e) (uniformly smooth crystallites)
offers support to the difference in the rate values between at pH:2.00 (kc(l) =
16.57X 10-4 emfs; kc(2) = 67.72X 10-4 emfs) and at pH:7.00 (kc(l) = 1.4X 10-4
emfs; kc(2) = 53.76X 10-4 cm/s).
Figures (9-3.15a-c) show unmistakably, the role of H+ ions in initiating the

Au(III) bromide/Zn cementation reactions by corroding the deposit surface. The
deposit surfaces show increased oxidation of the zinc surface with numerous
active cathodic sites for gold deposition as pH decreased from pH:4.00 to
pH:2.00. The deposit appeared to be small bulbous/botryoidal with secondary
fine textured dendritic growths, which contributed to the high reaction rates
observed under these conditions. Comparing figures (9-3.15b) and (9-3.1 Sc)
shows a more prominent secondary dendritic formation supporting a higher
reaction rate at pH:3.00 than at pH:4.00.
Figure (9-3.15a), however, shows that the deposit formed at pH:2.00 appeared
to lack the characteristic fine textured dendritic secondary structure common at
pH:3.00 and pH:4.00 and it is possible that this could have contributed to a pore
diffusion process which limits cementation rates. The enhanced cementation rate
at pH:2.00 (kc(l) = 67.72X 10-4 emfs) was lower than at pH:3.00 (kc(2) =
72.69X 10-4 cm/s).
234
Figure (9-3.15a) pH:2.00, 1000Xmag.
Figure (9-3.15b) pH:3.00, lOOOx mag.

23S
Figure (9-3. l 5c) pH:4.00, lO00X mag.
Figure (9-3.15d) pH:7.00, 1000Xmag
Figures (9-3.lSa-d) Scanning electron micrographs (shown after 120 min

reaction time) showing the effect of pH on Au(ffi)
bromide/Zn cementation (10 mg/I Au(ffi), 0.10 M NaBr
(containing 9.8 mg/I Br2 (aq)), 20°C, 1000 rpm); (a) pH:2.00
(b) pH:3.00 (c) pH:4.00 (d) pH:7.00.
236
The evidence of increased (much pronounced) corrosion of the zinc surface

(increasing both cathodic and anodic sites) supports that there was poor gold
deposit adherence to the fast dissolving zinc surface, thereby hindering the
growth of the deposit into well textured dendrites. According to Power and
Ritchie (Power and Ritchie, 1975), for a deposit to stick to a dissolving surface,
the cathodic sites at which initial attachment of the deposit takes place must be
widely distributed over the substrate, while the anodic sites must be confined to
a few selected areas such as grain boundaries or pits. If corrosion of the
substrate over and above that occasioned by the displacement reaction takes
place, the formation of smooth, adherent deposits is rendered less likely.
Figure (9-3.15d) seen at pH:7.00 shows a thinly grown smooth crystalline

deposit which presumably supports the low initial and enhanced cementation
rates.
9-3-3-4 Effect of initial gold co11centratio11
Figures (9-3.16a-d) also show the scanning electron micrographs for (a) 10 mg/1
(b) 20 mg/1 (c) 50 mg/1 (d) 100 mg/1 Au(III) bromide/Zn cementation reactions
respectively in 0.10 M NaBr solution at 20°C, 1000 rpm and pH:5.00.
These show that increasing the initial gold concentration from 10 to 100 mg/1
significantly changed the nature and morphology of the deposit from
particulate/thin botryoidal type of deposit to a coarser and more porous bulbous
growth and then to the formation of dendrites, contributing both surface
roughness and higher surface area towards increasing rates of reaction.
At 20 mg/1 Au(III) shown in figure (9-3 .16b ), the small botryoidal type of
structure seen in figure (9-3.16a) for 10 mg/1 Au(lll) became coarser and more
porous supporting a higher rate of reaction than at 10 mg/1. At higher Au(III)
concentrations (ie., 50 and 100 mg/I) shown in figures (9-3.16c-d), an initial
bulbous deposition was followed by a good growth of long bulbous-type of
dendritic deposits which invariably enhanced further the diffusional process. At
100 mg/I Au(lll) (figure (9-3.16d), these dendritic structures became more
prominent contributing a much higher rate of cementation than at 50 mg/1
Au(III).
237
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0111 20KlJ X2,000 10~m WD38
Figure (9- 3. l 6a) 10 mg/L Au(III), 2000X mag.
Figure (9-3 .16b) 20 mg/L Au(III), 2000X mag .

238
Figure (9-3.16c) 50 mg/L Au(III), 2000X mag.
Figure (9-3.16d) 100 mg/L Au(III), 2000X mag.
Figures (9-3.16a -d) Scannin g electron microgr aphs (shown after 120 min
reaction time) showing the effect of initial gold concen tration
on Au(ffi) bromid e/Zn cement ation (0.10 M Na13r (20°C,
pH:5.00 , 1000 rpm); (a) 10 mg/I (b) 20 mg/I (c) 50 mg/1 (d)
100 mg/I Au(III).
239
Figures (9-3.16a-d) therefore demonstrate very clearly that the nature and
morphology of the deposit control the rates of the Au(ill) bromide/Zn
cementation reaction. Both the initial and enhanced rates of reaction increased
with increase in Au(III) concentration.
The effect of NaBr concentration on the deposit morphology of Au(ill)

bromide/Zn cementation reaction is evident in the photomicrographs shown in
figures (9-3.17a-e) for 10 mg/I Au(ill) in (a) 0.001 M (b) 0.010 M (c) 0.050 M
(d) 0.100 M (e) 0.500 M NaBr solution (containing 9.8 mg/I Br2 (aq)) at 20°c,
pH:5.00 and 1000 rpm.
As discussed earlier in section (9-3-1-4), increasing free NaBr concentration

from 0.001 M to 0.500 Min the solution containing 10 mg/I Au(ill) ions, during
Au(ill) bromide/Zn cementation resulted in a decrease in initial reaction rates
but an increase in the enhanced rate from 0.001 M to 0,100 Mand a decrease at
0.500M.
At 0.001 M NaBr as shown in figure (9-3. l 7a), the gold deposit seems to
nucleate and grow only at isolated locations (ie, well localised) on the substrate
surface around the perimeters of large zinc dissolution pits; with
coherent/compact dendritic stmcture. This orientation (ie., restricted growth
area) on one hand prevails for rapid nucleation and growth for optimum initial
kinetic conditions. On the other hand, the resultant dense/compact deposit
possibly reduced the available surface area and inhibited the diffusion process
and perhaps zinc dissolution rate which caused the retarded cementation rate.
Similarly, at 0.010 M NaBr as shown in figure (9-3.17b), the relatively less
coherent, intertwined dend1itic structure was also localised, thus supporting a
lower initial reaction rate and higher enhanced rate than at 0.001 M NaBr.
At a higher NaBr concentration as shown in figure (9-3. l 7c) for 0.050 M NaBr
solution, the deposit was non-dendritic but coarser crystalline/botryoidal type
and occmTed over a wider area on the zinc substrate than at 0.001 M and 0.010
M NaBr which could support a lower initial reaction rate and a higher enhanced
reaction rate than at 0.010 M NaBr. The changes in reaction artes are apparent:
At low NaBr concentration, the increased rate of reaction is due to the
development of a structured surface deposit which acts as though the surface
240
area available for reaction has been increased. For high initial concentration of
NaBr concentrations, the enhanced rate may not be seen because the critical
deposit mass density is reached almost immediately.
Figure (9-3.17a) 0.001 M NaBr, 500Xmag.
Figure (9-3. 17b) 0.010 M NaBr, 500X mag.

241
Figure (9-3.17c) 0.050 M NaBr, 500X mag.
Figure (9-3.17d) 0.100 M NaBr, 500X mag.

242
Figure (9-3.17e) 0.500 M NaBr, 500X mag.
Figures (9-3.17a-e) Scanning electron micrographs showing the effect of NaBr

concentration on Au(ill) bromide/Zn cementation (10 mg/I
Au(ill), 9.8 mg/I Br2 (aq), 20°C, pH:5.00, 1000 rpm); (a)
0.001 M (b) 0.010 M (c) 0.050 M (d) 0.100 M (e) 0.500 M.
At 0.100 M NaBr (figure (9-3.17d)), as already described in previous sections,

the cluster-like growth of thin, smooth crystalline structure was also more
widely spread over the zinc substrate than at 0.050 M and furth er supports the
trend of the observed kinetic behaviour. Figure (9-3. l 7e) shows features of
thickly grown bulbous deposit with few needle-like growths a1·ound cracks
developed along the grain bounda1"ies, for 0.500 M NaBr concentration. It is
possible that such a deposit had an inhibiting effect o n the ceme ntation reaction
rate by blocking off high surface energy sites for zinc dissolution thereby
responsible for the low cementation rate constants.
However, for a solution containing 100 mg/I Au(III) ions , increasing the NaBr
concentration from 0.01 to 0.50 M exhibited a reverse kinetic behaviour to that
observed for a solution containing 10 mg/1 Au(III) ions at 20°C, pH:5.00 and
1000 rpm. Thus, the initi al reaction rate increased w ith increasing NaBr from
243
0.01 M to 0.10 M and decreased at 0.50 M, while the enhanced reaction rate
decreased with increasing NaBr concentration from 0.01 M to 0.50 M.
Figures (9-3.18a-d) shows the scanning electron micrographs for 100 mg/1
Au(ID) bromide/Zn cementation in (a) 0.01 M, (b) 0.05 M (c) 0.10 M (d) 0.50
M NaBr solution (containing 98 mg/1 Br2 (aq)) at 20°C, pH:5.00 and 1000 rpm.
Figures (9-3 .18a-c) show that the changes/differences in the nature of the
dendritic deposits obtained as free NaBr concentration increased from 0.01 to
0.10 Mare such that the deposits became more dense/compact and thicker with
decreasing deposit smface area and explains the various kinetic changes.
At 0.01 M NaBr (figure (9-3 .18a), a secondary finely textured dendritic deposit
with well dispersed branches fo1med over the substrate smface which was
responsible for the high enhanced period reaction rate. At 0.05 M NaBr (figure
(9-3.18b), the secondary dendrites formed were longer and more closely
intertwined in nature than those evident in figure (9-3.18a) for 0.01 M NaBr
solution, which supported a relatively lower enhanced period reaction rate. Also
at a higher NaBr solution as in figure (9-3.18c) for 0.10 M NaBr, the secondary
dendrites formed were more dense and had longer bulbous branches than the
dendrites formed at 0.05 M NaBr. This structure supposedly contributed a
relatively more pronounced effect on the diffusional process governing the
cementation reaction, thereby leading to a much lower rate of reaction than at
0.05 M NaBr.
Figure ( 9-3. 18a) 0.0 1 M NaBr, 500X mag.

244
Figure (9-3.1 8b) 0.05 M NaBr, 500X mag.
Figure (9-3.18c) 0.10 M NaBr, 500X mag.

245
Figure (9-3.18d) 0.50 M NaBr, 500X mag.
Figures (9-3.lSa-d) Scanning electron micrographs showing the effect of NaBr

concentration on Au(III) bromide/Zn cementation (100 mg/I
Au(III), 98 mg/I Br2 (aq), 20°C, pH:5.00, 1000 rpm); (a) 0.01
M (b) 0.05 M (c) 0.10 M (d) 0.50 M
Nevertheless, the observed increase in initial reaction rate as bromide

concentration increased from 0.01 M to 0.10 M may be due to the effectiveness
of initiating active nucleation sites by higher bromide concentration . Invariably,
this may also be caused by the changes in the initial deposition from fine
smooth crystallites (figure (9-3.18a)) to a bulbous structure (figure (9-3 .18c)) as
bromide increased from 0.01 M to 0.10 M.
Figure (9-3.1 8d) also shows that the deposit morphology had a distinct change
at 0.50 M NaBr solution where an initial scattered fine bulbous deposition took
place with secondary cluster-like thick bulbous-type dendrites. Certainly. this
deposition contributed immensely to the low initial and enhanced reaction rates
associated with the cement.at.ion at 0.50 M TaBr.
246
9-4 CEMENTATION ONTO SUSPENDED ZINC

PARTICLES
9-4-1 Reaction rate/velocity measurements
The Au(ill) bromide/Zn cementation reaction kinetics were further followed and
characterised at various kinetic variables using zinc suspended particles. The
cementation studies were conducted with large excess of zinc particles to ensure
that the surface area remained constant during reactions. The kinetics (reaction
velocity) were evaluated according to the first-order equation.
9-4-1-1 Effect of particle size
Figures (9-4. la-b) show the plots of log ([Au]tf[Au] 0 ) against time for (a) 10
mg/I (b) 100 mg/I Au(ill) bromide/Zn (suspended particles) cementation
respectively in 0.10 M NaBr solution at 20°C, pH: 5.00, 500 rpm using (i)
38X45 µm (ii) 45X63 µm (iii) 63X 106 µm zinc particles.
[NaBr) • 0.1 M
~0.6
pH • 6.00
Temp.· 20 C
RPM. - 600
-1.0
- 1.6 --- 38•45 um

-+-- •"5•83 um lnltlal aolutlon vol. • 500 ml.
-B- 83•108 um
-2.0 1 - - - - 1 - - - - + - - t - - - - + - - - - - + - - - - - t - - + - - - - + - - ~
0 6 10 15 20 26 30 35 40
Time, (mlna)
Figure (9-4.la) Variation of log([AuJt/[Au] 0 ) with time for 10 mg/I Au(III)

bromide/Zn (suspended particles) cementation in 0.10 M
NaBr (containing 9.8 mg/I Br2 (aq)) at 20°C, 500 rpm,
pH:5.00, (i) 38X45 µm (ii) 45X63 µm (iii)63Xl06 µm.
247
Log([Au)t/[Aulo)
-1 [NaBr] • 0.1 M
pH • 6.00
Temp.• 20 C
RPM.• 600
-2
Zinc particle alZII
-3 - - 38••5 um
lnltlel solution vol. • 600 ml.
-t- •5•83 um
-a- 83•108 um
-~~--~--~--~--~--~--~--~
0 5 10 15 20 25 30 35
Time, (mine)
Figure (9-4.lb) Variation of Iog([Au]tf[Au] 0 ) with time for 100 mg/I Au(ID)
NaBr (containing 98 mg/I Br2 (aq)) at 20°C, 500 rpm,
pH:5.00, (i) 38X45 µm (ii) 45X63 µm (iii) 63Xl06 µm.
Table (9-4.1) The reaction velocity/rate constants for different zinc particle
sizes in the Au(ID) bromide/Zn system (0.10 M NaBr; pH:
5.00; 20°C; 500 rpm; Au(III): (i) 10 mg/I (ii) 100 mg/I).
Initial Au Particle size Reaction velocity/rate constants

concentration Initial Enhanced
k(l)x10- 3 k(2)X l0-3
mg/I µm emfs emfs
10 38X45 6.009 6.342

45X63 5.125 5.501
63X 106 4.209 4.714
100 38X45 11.413 23.688

45X63 8.403 15.729
63X 106 5.262 13.305
248
These results conform to two-stage first-order reaction kinetics. The gold

formed a uniform layer around the zinc particles, apparently with sufficient
porosity to shift the initial slow first-order reaction velocity (between O - 5
minutes) to an enhanced first-order reaction rate/velocity. Table (9-4.1) lists the
values of the initial and enhanced reaction velocity constants for 10 mg/I and
100 mg/I Au(ID) bromide/Zn dust cementation reactions for each particle size
interval.
The reaction velocity constants can be seen to exhibit strong dependence on

particle size (shown in figure (9-4.2)). Clearly, the rate increased with decreased
particle diameter (increase surface area) and can be rationalised in terms of the
rate dependence of mass-transfer boundary-layer diffusion limited process on
surface area. The increase in reaction rate/velocity constants with decrease in
particle size may be due to the development of a structured surface deposit
which acted traditionally to increase the reaction velocity.
k(1);k(2)(E-03) (cm/s)
20~--------------------~
--- lnlUal rate, k(l) [AuBr•-J = 10 mc/1
+ Enhanced rate, k(2) [NaBr] = 0.10 ll
15
pH= 5.00
Temp.= 20 C
RPM.= 500
10
ln!Ual •oluUon vol. = 500 ml.
o~---~---~----~---~---~
0.00 0.01 0.02 0.03 0.04 0.05
1/do, um--1
Figure (9-4.2a) Variation of reaction velocity constants with the reciprocal of

particle diameter for 10 mg/I Au(III) bromide/Zn (suspended
particles) cementation in 0.10 M NaBr (9.8 mg/I Br2 (aq)) at
20°C, pH:5.00 and 500 rpm.
249
k(1);k(2)(E-03) (cm/s)
60.-------------------------,
(AuBr4-] = 100 me/I
--- InlUal rate, k(l)
(NaBr] = 0.10 K
50 -+- Enhanced rate, k(2)
40 pH= 11.00
Temp.= 20 C
30 RPII. = 1100
20
10
IniUal aoluUon vol. = 1100 ml.
o~---~---~---~----~---~
0.00 0.01 0.02 0.03 0.04 0.05
1/do, um--1
Figure (9-4.2b) Variation of reaction velocity constants with the reciprocal of

particle diameter for 100 mg/I Au(ill) bromide/Zn
(suspended particles) cementation in 0.10 M NaBr (98 mg/I
Br2 (aq)) at 20°C, pH:5.00 and 500 rpm.
9-4-1-2 Effect of zinc amount
The effect of particulate zinc on the reaction velocity/rate constants was

evaluated at different amounts of zinc (particle size: 38X45 µm) additions
2 2 2
(0.0604 g: 54.7cm; 0.1250 g: 113.3 cm; 0.2500 g: 226.5 cm; 0.5000 g: 453.0
cm2 Zn) for 100 mg/I Au(ID) bromide in 0.10 M NaBr solution (containing 98
mg/I Br2 (aq)) at 20°C, pH: 5.00 and 500 rpm.
The results are presented in first-order plots in figure (9-4.3). As expected, these
plots follow a two-stage reaction kinetics and reflect a dependence of the
reaction velocity/rate on the amount of particulate zinc. The first-order reaction
rates/velocities are dependent on surface area which is directly proportional to
the amount of zinc precipitant. At a fixed initial particle size, the rate expression
in equation (5-3.8) reflects the surface area effect through the zinc value (g).
Accordingly, the rate/velocity should be a linear function of amount of zinc.
However, as shown in figure (9-4.4), both the initial and enhanced reaction
rate/velocity constants decreased with increased amount of particulate zinc. This
means that the presence of excess amounts of zinc particles caused some sort of
diffusional resistance in the solution. Addition of a large number of suspended
particles significantly increase the reaction kinetics (Miller, 1981 ). The rate
250
enhancement should be proportional to the number of conductive particles and

the collision rate. There would be more collisions between particles, thus a
greater reduction in the boundary layer thickness and a greater diffusion rate.
Log([Au)t/(Aulo)
o.
-1.0
[NaBr] • 0.1 M
pH• 5.00
-2.0 Temp.· 20 C
RPM.• 600
-3.0 Initial amt. of Zinc
- o.oeo4g zn
Zinc particle size • 38"46 um.
-t- 0.1250g Zn
-4.0 lnl tlal solution vol. • 500 ml.
-A- 0.2600g Zn
-B- 0.6000g Zn
-s.o~--~--~---~--~--~------'~-~
0 6 10 15 20 26 30 36
Time (mlna)
Au{ill) bromide/Zn (suspended particles) cementation in
0.10 M NaBr (containing 98 mg/I Br2 (aq)); 20°C; pH:5.00;
500 rpm at different zinc amounts.
k(1);k(2)(E-03) )cm/s)
50~----------------------~
[AuBr4-] = 100 me/I
IniUal rate, k( 1)
[NaBr] = 0.10 I{
40
-+- Enhanced rate, k(2)
pH= 5.00
Temp.= 20 C
30
RPM.= 500
20 Initial aolutlon vol. = 500 ml.

Zinc particle ab:e = 38*45 um.
10
0'----.,___ _.,___ _.,___ _~--~-----'~-----'------'

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Zn, (g)
Figure (9-4.4) Variation of reaction velocity with particulate zinc amount

for 100 mg/I Au(III) bromide/Zn (suspended particles)
cementation in 0.10 M NaBr (containing 98 mg/I Br2 (aq));
at 20°C; pH:5.00; and 500 rpm.
251
This effect, may be due to a decrease in activity (or diffusion) coefficient as

particulate zinc amount increased over this range. An increase of the gold layer
thickness could not account for this effect, as the kinetics can be seen in figure
(9-4.3) to follow a well-behaved first-order plots. The slopes of the plots
increased with increase in zinc amount. This was more likely to be due to an
aggregation phenomenon (or cluster-effect) of the zinc particles as the amount
increased, thereby reducing the effective surface area for gold deposition.
Particle aggregation phenomenon was observed by Miller et al (Miller et al,
1990) in their study of gold cementation from alkaline cyanide solution by
suspended zinc particles.
Nevertheless, in the extreme case, the gold layer/deposit on an individual zinc

particle could become significant in this case. An increased amount of zinc or
number of particles caused either an increase in both the cathodic and anodic
sites for gold deposition or the available cathodic sites at which the deposition
took place to be widely distributed over and among the surfaces of the zinc
particles. The effect would be to hinder the growth of the deposit on an
individual zinc particle into well-textured dend1ites which could support a true
departure (or a more enhanced) in the reaction rate/velocity.
9-4-1-3 Effect of stirring speed
Figure (9-4.5) represents the first-order plots for a series of experiments carried
out for 100 mg/I Au(III) bromide/Zn (suspended particles) in 0.10 M NaBr
solution (containing 98 mg/I Br2 (aq)) at different stirring speeds of 100, 300,
500, 700 rpm (20°C; pH: 5.00).
Clearly, these first-order plots followed two-stage kinetics as observed using the
rotating-disc geometry. The reaction velocity constants (calculated from the
geometric slopes of the plots) are also plotted in figure (9-4.6) for the different
stiffing speeds. Both the initial and enhanced reaction rates/velocities are in
strong dependence on the square-root of the stiffing speeds which supports a
mass-transfer controlled process for the Au(Ill) bromide/Zn (suspended
particles) cementation reaction.
252
Log([Au)t/[Aulo)
[AuBr-4-1 • 100 mg/I
[NaBr] • 0.1 M
-1
pH• o.00
Temp.· 20 C
-2
Stirring epHd
- 100 RPM.
-3 -+- 300 RPM.
Zinc particle ela • 88•46 um.
-A- 1500 RPM.
lnltlal eolutlon vol. • 600 ml.
-a- 700 RPM.
-4
0 5 10 15 20 25 30 35
Time, (mlna)
Au(ill) bromide/Zn (suspended particles) cementation in
0.10 M NaBr (98 mg/I Br2 (aq)); 20°C; pH:5.00; at (i) 100 (ii)
300 (iii) 500 (iv) 700 rpm.
k(1)/k(2)(E-03) (cm/s)
50...--------------------------,
[A.uBr.(-] = 100 ma:/l
Initial rate, k(l)
[NaBr] = 0.10 M
40
pH= 5.00
Temp. = 20 C
30
Zinc parUclea size = 38•.(5 um.
20 Initial solution vol. = 500 ml.
10
0 2 4 6 8 10
w-1/2, {rad/s)-1/2)
Figure (9-4.6) Variation of reaction velocity constants with the square root
of stirring speed for 100 mg/I Au(III) bromide/Zn (suspended
particles) in 0.10 M NaBr solution (containing 98 mg/I Br2
(aq)); at 20°C and pH:5.00.
253
However, at lower strrnng speed (ie., 100 rpm), an inhibiting effect was
observed after 10 minutes of cementation resulting in a lower second-stage
reaction rate/velocity (0.569X 10-3 emfs) than the first-stage reaction
rate/velocity (1.155X 10-3 emfs). This may be attributed to the nature of the
deposit morphology under this condition.
Nevertheless, the reaction velocity constants can be seen to correlate well with
the reaction rate constants for 200, 500, 1000, and 1500 rpm observed using the
rotating-disc geometry as shown in table (9-3.1). The variation of the reaction
velocity with stirring speed can also be related to an increase in slip velocity (or
mass-transfer coefficient) resulting from the deposit growth as stirring speed
increased.
The effect of temperature on the reaction velocity/rate of the Au(III) bromide/Zn

(suspended particles) is illustrated in the first-order plots shown in figures (9-4.7
a-b) for (a) 10 mg/1 (b) 100 mg/1 Au(III) respectively in 0.10 M NaBr at pH:
5.00, 500 rpm and (i) 10°c (ii) 20°c (iii) 30°c (iv) 40°c.
The two-stage reaction kinetics corresponding to an initial slow first-order

process (between 0 - 7 minutes) followed by an enhanced first-order process are
evident in these plots. A significant change in the morphology of the gold
deposit with change in temperature was also observed.
The reaction velocity/rate constants for the cementation reaction at the various
temperatures and 500 rpm are plotted on an Arrhenius plot as shown in figures
(9-4.8a-b ). The activation energies calculated from the slopes of these plots for
both initial and enhanced rate periods are also shown in table (9-4.2). These ~E
(activation energy) values are consistent with that expected for film diffusion as
the rate-limiting step. The ~E (activation energy) values also compare well with
the ~E (activation energy) values of 2.50 kcal/mol (10.50 k.J/mol) for initial rate
pe1iod and 3.13 kcal/mol (13.12 kJ/mol) for the enhanced rate period obtained
from the Au(III) bromide/Zn (rotating-disc) cementation reaction.
254
Log((Au)t/(Au)o)
0,0A...,.....----------------------,
-0.5
(NaBr] • 0.1 M
pH • 6.00
-1.0 RPM.• 600
-1.6
- 10C
-+- 20 C
-2.0
~ 30C Zinc particle size • 38'46 um
-A- 40 C lnltlal solutlon vol. • 600 ml
-2.5
0 5 10 15 20 26 30 35 40 46
Time, (mlns)
Figure (9-4.7a) Variation of log([Au]tf[Au] 0 ) with time for 10 mg/I Au(III)

NaBr (containing 9.8 mg/I Br2 (aq)); at pH: 5.00; 500 rpm
and (i) 10°c (ii) 20°c (iii) 30°C (iv) 40°C.
Log((Au)t/(Au]o)
[NaBr] • 0.1 M
-2
pH • 6.00
RPM. • 600
-4
- 10C
-6 -+- 20 C
-A- SO C Zinc particle size • 38'46 um.
-a- 40 C Initial solution vol. • 600 ml.
-6
0 5 10 15 20 25 30 35
Time, (mlna)
Figure (9-4. 7b) Variation of log{[Au]tf[Au] 0 ) with time for 100 mg/I Au(III)
NaBr (containing 98 mg/I Brz (aq)); at pH: 5.00; 500 rpm
and (i) 10°c (ii) 20°c (iii) 30°C (iv) 40°C.
255
In k{l) or k(2)
-3.5 ~ - - - - - - - - - - - - - - - - - - - - - - ~
(AuBr4-] = 10 mc/1
lnltlal rate, k( 1)
[NaBr) = 0.10 M
-4.0 -+- Enhanced rate, k(2)
pH= 5.00
RPM. = 500
-4.5
~.o
-5.5 Zinc particle llize = 38"-'5 um.

lnlUal aoluUon vol. = 500 ml.
-6.0 ~ - - - ~ - - - - ~ - - - - ~ - - - - ~ - - - ~
3.1 3.2 3.3 3.4 3.5 3.6
1000/T, (1/K)
Figure (9-4.Sa) Arrhenius plots for 10 mg/I Au(ill) bromide/Zn (suspended

particles) cementation in 0.10 M NaBr (containing 9.8 mg/I
Br2 (aq)) at pH:5.00 and 500 rpm.
In k(l) or k(2)
o~-------------------------,
[AuBr4-] = 100 m1t/l
lnlUal rate, k( 1)
[NaBr) = 0.10 ),(
-1 -+- Enhanced rate, k(2)
pH= 5.00
-2
RPM.= 500
-3
- 4 'Zinc
_5 1
=particle
== ~--=========d
llize = 38"45 um.
lniUal aoluUon vol. = 500 ml.
-6 .___ ____,___ _ _.___ ____,___ _ _..___ ____,___ _ _.....___ ___,
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7
1000/T, (l/K)
Figure (9-4.Sb) Arrhenius plots for 100 mg/I Au(Ill) bromide/Zn (suspended
particles) cementation in 0.10 M NaBr (containing 98 mg/I
Br2 (aq)) at pH:5.00 and 500 rpm.
256
Table (9-4.2) The experimental activation energies (~E) for the Au(ill)
bromide/Zn (suspended particles) system (0.10 M NaBr; pH:
5.00; 20°c; 500 rpm; Au(III): (i) 10 mg/I (ii) 100 mg/I)
Initial Au concentration dE(activation energy)

Initial Enhanced
mg/I kcal/mol kJ/mol kcal/mol kJ/mol
10 1.96 8.20 2.88 11.83

100 2.89 12.07 6.76 28.27
9-4-1-5 Effect of initial gold concentration
The influence of initial gold concentration on the Au(ill) bromide cementation

reaction on suspended zinc particles (38X45 µm) is shown in first-order plots in
figure (9-4.9) for 0.1 M NaBr solution at 20°C, pH: 5.00 and 500 rpm.
Log([Au)t/(Aulo)
[NaBr] • 0.1 M
-1
pH • 5.00
Temp.• 20 C
-2
RPM. • 600
-3
lnltlal [AuBr4·)
--4 - 10 ppm
+ 20 ppm
-6 -A- 150 ppm Zinc particle size • 39•45 um
--a-- 100 ppm Initial solution vol. • 600 ml
-6
0 10 20 30 40 50
Time, (mlna)
Figure (9-4.9) Variation of log([Ault/[Au] 0 ) with time for (i) 10 mg/I (ii) 20
mg/I (iii) 50 mg/I (iv) 100 mg/I Au(lll) bromide/Zn
(suspended particles) cementation in 0.10 M NaBr solution
at 20°C, pH:5.00 and 500 rpm.
257
These plots also show a significant change in the reaction velocity as the initial
gold concentration changed from 10 mg/I to 100 mg/I, as observed under zinc
rotating-disc geometry. The two-stage kinetic reactions are also apparent in
these plots. Table (9-4.3) lists the reaction velocity/rate constants calculated
from figure (9-4.9) for the different initial concentrations of gold. The increased
rate/velocity of reaction was due to the development of a coarser, more porous
botryoidal/bulbous to dendritic deposits as initial gold concentration increased.
Table (9-4.3)Comparison of the reaction velocity/rate constants for different

concentrations of gold (0.10 M NaBr; pH: 5.00; 20°c; 500 rpm).
Initial Au concentration Reaction velocity/rate constants

Initial Enhanced
k(l)X 10· 3 k(2)X 10·3
mg/I emfs emfs
10 6.009 6.342
20 7.770 8.124
50 10.074 13.395
100 11.413 23.688
Figures (9-4.l0a-b) also show the effect of free bromide concentration on the
first-order plots for (a) 10 mg/I Au(III) bromide cementation in 0.001 M; 0.010
M; 0.050 M; 0.100 M; 0.500 M NaBr (b) 100 mg/1 Au(III) bromide cementation
in 0.01 M; 0.05 M; 0.10 M; 0.50 M NaBr respectively on suspended zinc
particles (38X45 µm) at 20°c, pH: 5.00 and 500 rpm.
258
[AuBr4-] = 10 me/I
-0.4
pH= 5.00
-0.8 Temp.= 20 C
RPM.= 500
Initial [NaBr]
-1.2 -t- 0.001M NaBr

~ 0.010M NaBr
-a- 0.050M NaBr Zinc particle me = 38°45 um.
-1.6
""* 0.100M NaBr Initial aolution vol. = 500 ml.
-+- 0.500M NaBr
-2.0
0 10 20 30 40 50
Time, (mins)
Figure (9-4.l0a) Variation of log([Au1t/[Au] 0 ) with time for 10 mg/I Au(ill)

bromide/Zn (suspended particles) cementation in (i) 0.001 M
(ii) 0.01 M (iii) 0.05 M (iv) 0.10 M (v) 0.50 M NaBr (Br2
(aq): 9.8 mg/I); 20°C; pH:5.00; 500 rpm.
Log([Aultt[Aulo)

-1
pH• 6.00
-2
Temp. • 20 C
RPM. - 600
-3 lnltlal [NaBr]
- 0.01 M NaBr
-4 -t- 0.011 M NaBr
-A- 0.10 M NaBr
-5 --e- 0.20 M NaBr Zinc particle size • 38"45 um.
~ 0.60 M NaBr Initial solution vol. • 600 ml.
-6
0 5 10 15 20 25 30 35
Time, (mlna)
Figure (9-4.l0b) Variation of log([AuJt/[Au] 0 ) with time for 100 mg/I Au(III)
bromide/Zn (suspended particles) cementation in (i) 0.01 M
(ii) 0.05 M (iii) 0.10 M (iv) 0.50 M NaBr (Br2 (aq): 9.8 mg/I);
20°C; pH:5.00; 500 rpm.
259
The variation in the reaction velocity/rate constants for (a) 10 mg/I (b) 100 mg/I
Au(ill) bromide /Zn (suspended particles) at the different free sodium bromide
concentrations investigated are also presented in figures (9-4.11) and (9-4.12).
These results also attest to the various kinetic behaviour of the first-order plots
observed for Au(ill) bromide cementation on zinc rotating-disc geometry. The
relative merits/importance of the addition of free bromide (>0.01 M )especially
at low initial gold concentrations are evident from these results. Figure (9-4.11)
indicate an optimum bromide concentration of 0.05 M to sustain a well-behaved
first-order kinetics. At lower bromide concentrations (<0.01 M) and at low gold
concentration, a deviation from the first-order kinetics was observed after 10
minutes of cementation. This was probably due to an inhibiting effect of the
deposit growth on the diffusional flux and presumably the dissolution of zinc
which tends to control the process. An initial growth of the deposit on dendrites
became dense and less distributed around the zinc particles as cementation
progressed.
k(1);k(2)(E-03) (cm/s)
12..--------------------------,
[AuBr4-] = 10 me/I
- - InlU&l rate, k(l)
pH= 5.00
Temp.= 20 C
6
RPM.= 1500
Zinc particle idze = 38°415 um.

lnlUal aoluUon vol. = 500 ml.
o~---'---~-~--~--~-~--~----'
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.6
[NaBr], mole/litre
Figure (9-4.11) Variation of reaction velocity constants for 10 mg/I Au(III)

bromide/Zn (suspended particles) cementation with NaBr
concentration (containing 9.8 mg/I Br2 (aq)) at 20°C;
pH:5.00 and 500 rpm.
260
This behaviour also corresponds to a big anodic shift in the solution potential
(from -0.636 V at 1 minute of cementation to -0.184 V at 10 minutes of
cementation for 0.001 M NaBr and from -0.727 Vat 1 minute cementation to -
0.532 V at 10 minutes of cementation for 0.010 M NaBr) (refer appendix (9-
4.1)), indicating a change in the controlling mechanism of the process from
mass-transport diffusion controlled to electrochemical (or charge transfer)
controlled. At higher NaBr concentration (0.050 M and 0.100 M), the gold
deposits formed on the zinc particles were sufficiently porous to maintain
structural integrity for a mass-transport boundary-layer diffusion-control
mechanism throughout the cementation reaction. Thus for extended times
associated with greater gold recovery from the Au(ill) bromide/zinc suspended
particles cementation circuits, under these conditions, higher concentration of
bromide (ie 0.05 M- 0.10 M) is essential.
However, for 100 mg/I Au(ill) bromide as shown in figures (9-4.l0b) and (9-
4.12), well-behaved first-order kinetics were followed at each NaBr
concentration considered but the enhanced reaction rate/velocity constant
decreased as bromide concentration increased.
k(l);k(2)(E-03) (cm/s)
50..----------------------,
(AuBr4-] = 100 mi/1
- Initial rate, k(l)
40
pH= 5.00
Temp.= 20 C
RPM.= 500
30
Zinc particle size = 38°45 um.

20 lnJUal solution vol. = 600 ml.
10
0 L-----'----'----~----'------'-----~-~-___.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
[NaBr], mole/litre
Figure (9-4.12) Variation of reaction velocity constants for 100 mg/I Au(III)
bromide/Zn (suspended particles) cementation with NaBr
concentration (containing 98 mg/I Br2 (aq)) at 20°C; pH:5.00
and 500 rpm.
261
The initial reaction rate/velocity constant increased with increase in bromide

concentration and decreased at 0.50 M NaBr. The change in the diffusion (or
mean activity) coefficients over this concentration range is sufficient in
magnitude and direction to explain the decrease in enhanced reaction rate as
bromide increased whereby it may be attributed to increased solution stability
(or ionic strength) effect as bromide concentration increased.
Nevertheless, the change in deposit morphology as bromide concentration

increased contributed to the decreasing variation in the enhanced reaction rates.
Since deposition in the enhanced region occurred on growing dendrites, there
was differential growth in those local areas which protruded further into the
boundary layer or provided increased surface area for further deposition. As
bromide concentration increased, the growing dendrites became
bulbous/botryoidal in nature leading to a decreasing surface area and thereby a
decreasing reaction rate/velocity. Under these circumstances too, the solution
potential varied far in the cathodic direction (refer to appendix (9-4.2)). It is
possible that such a variation pushed the zinc dissolution along the hydrogen
evolution path thereby leading to either increased zinc corrosion or the blocking
of high sites by the adsorption of atomic hydrogen on the zinc surface.
The variation of the reaction rate/velocity in the initial period as bromide

concentration increased can also be ascribed to the initial morphological
changes as influenced by the bromide concentration.
9-4-1-7 Effect of hydrogen ion concentration
The rate of the cementation reaction with respect to the concentration of pH ions
on the Au(IlI) bromide cementation reaction on suspended zinc particles (38X45
µm) is first order and shows in figure (9-4.13) for 100 mg/1 Au(IIl); 0.10 M
NaBr (containing 98 mg/1 Br2 (aq)); 20°C; 500 rpm and pH values from 2.00 to
7.00. Figure (9-4.14) shows the variation of the reaction velocity constants with
pH. Table (9-4.4) also lists the calculated initial and enhanced reaction
velocities/rates.
It is clear that, the initial reaction rates/velocities are significantly impaired at

pH values below pH: 4.00.
262
Log([Au)t/(Au)o)
-1 [NaBr) • 0.1 M
Temp.• 20 C
RPM. • 600
-2 lnltlal sol. pH
- - pH• 2.00
-+- pH• 3.00
-3 -A- pH • 4.00
Zinc particle size • 38"46 um.
-B- pH • 15.00
Initial solution vol. • 600 ml.
-•.____ __
--V-- pH•7.00
_._ ___,_ ____,____,_____._____.____,
0 6 10 16 20 26 30 35
Time, (mine)
Au(ID) bromide/Zn (suspended particles) cementation in
0.10 M NaBr solution (Br2 (aq): 98 mg/I) at 20°C, 500 rpm
and (i) pH:2.00 (ii) pH:3.00 (iii) pH:4.00 (iv) pH:5.00 (v)
pH:7.00.
k(1);k(2){E-03) (cm/s)
60,--------------------------,
[AuBr4-] = 100 me/I
InlUal rate, k(l)
[NaBr] = 0.10 M
50 -+- Enhanced rate, k(2)
Temp.= 20 C
40 RPM.= liOO
Zinc particle size = 38"41i um.

30
+ Initial aoluUon vol. = liOO ml.
20
10
O.___ _.__ ___,__ _~ - ~ - ~ . _ _ - ~_ _.___ _.___ _.__ _,

0 1 2 3 4 5 6 7 8 9 10
pH
Figure (9-4.14) Variation of reaction velocity constants with pH for 100 mg/I
/
Au(III) bromide/Zn (suspended particles) cementation in

0.10 M NaBr solution (containing 98 mg/I Br2 (aq)) at 20°C
and 500 rpm.
263
This is believed to be due to the competitive or preferential reduction of H+ ions

adsorbed on the surface of the zinc particles at pH: ~4.00, thereby reducing the
cathodic area available for the discharge of gold. This is evidenced by the big
change in the initial pH value at the end of each experiment as shown in table
(9-4.4). Thus, for solution pH's below pH: 5.00, the kinetics of the hydrogen ion
- zinc reaction dominate in the Au(III) bromide/Zn cementation reaction.
The variation in reaction rates/velocities between pH: 5.00 and pH: 7.00 is
likely to be due to the relative reduction in diffusion coefficient and activity of
diffusing species at pH:7.00 which is directly related to the rate of mass transfer
to the zinc surface.
Table (9-4.4) Variation of rate/velocity constants with pH (100 mg/I

Au(III); 0.10 M NaBr; 20°C; SOO rpm).
Kinetic condition Rate/velocity constants

Initial Final Initial Enhanced
pH pH k(l)X l0-3 k(2)X l0-3
cm/s emfs
2.00 2.53 5.835 1.420

3.00 6.48 6.382 17.231
4.00 7.50 8.212 23.688
5.00 7.21 11.413 23.688
7.00 7.27 9.782 14.963
20 minutes of cementation
However, the variation of the enhanced reaction rates/velocities indicates an

optimum condition at pH: 4.00(27.84X 10-3 cm/s) corresponding to 99.72%
overall gold recovery. The overall gold recovery at pH: 5.00 was 99.54%.
Again, at pH: 2.00, an inhibiting behaviour was observed after 10 minutes of
reaction leading to a deviation from first-order kinetics.
264
This can be reconciled with the variation of the solution potential (refer
appendix (9-4.3)) to be explained by a change in the diffusion controlled
mechanism to a smface reaction mechanism or pore diffusion process.
Nevertheless, the variations in the reaction rate/velocity under this study, can be
explained in terms of changes in the deposit morphology. The deposits were
seen to be botryoidal/bulbous types of dendritic structmes of different degrees
of texture and size (similar in structure to those obtained/observed for Au(III)
bromide cementation on zinc rotating-disc).
9-4-2 Deposit nucleation and morphology
The observation of the various structural char·acteristics of the gold deposit on

the suspended zinc particles after 30 minutes of cementation provide evidence to
account for the changes in the reaction rates/velocities at the var·ious
experimental conditions.
Figure (9-4.15) reveals the nature of the gold deposit on the reacted zmc
particles as observed under the optical microscope.
Figure (9-4.15) Typical optical micrograph of gold-coated zinc particles as

obtained from Au(III) bromide/Zn (suspended particles)
cementation, 625X mag.
Figure (9--U6) The scanning electron micrograph of gold-coated z111c
particle (polished to 1 µm) obtained from .\u ( lll )
bromidc/Zn (s uspended particles) ccmcntation, J000 X mag.
Further C\arni 11 at io11 or the deposit by scanning microscope (figu re (9--l.l(iL

shO\\·cd that the gold formed a layer around the zinc particle s. appare ntl y \\'ith
.;;utlic,cnt poros,t_v to sustain the first-o rder kineti cs . It appcars that in th e in1t1:1l
pcrI()d (JI the reaction. th e go ld nuclei were generated more o r lcs" ll\'CI thl'. 1111c
"urL1L·c-., and 11 wa-, not until a mass ive/critica l height o f depos i t w~h formed
\\'hich c(~ul d '- Jry w ith the bo und ary layer thi ckness th at seco ndary depositio11
1Kcurrcd coiTes po nding to the enhanced cementation r:.ite s/vclocitic-;_ rl1i -., '"
vi\·idl) 11lu-,tr:1tecl in ri gurcs (9---l . l 7a-d ) show ing the electron micrograph-, ro,
(a) 10 111~/l (bl 20 mg/ I (c) 50 mg/I (d ) 100 m g/I Au(IIT) bromide cemcntation on
-.,u.;;pcll(kd 1inc particles U8x ...is pm) in 0.10 :v1 Na Br at :w0 C. pl l: 5.00 a11d
500 , pm
J\t 10 rn g/1 /\u(III) brom ide conce ntration (ri g ure (9---l . 17a), an initial srnm)th
dcp1J-;1\11J11 ,tnlund the 1i11c particles \\J.S lollo\,ed hy J thin /sma ll -;cull'1cd
p11llrt1-,I\Hhl~r,rnth 1lf hotryoidal/crystalline type ()r " tru c turc. The i11l'Il',hl' 111
-.,url-tcL' ,lll'.t (d uL' to mughncs-,) in this ca-;c. had a 111ar~inal -.,ig11ificant cikL·t ,i11
thL' Il',tL'tHln r,11d,elnc 1t \.
266
Figure (9-4.17 a) 10 mg/1 Au(Ill), 500Xmag.
Figure (9-4.17b) 20 mg/1 Au(Ill), 500X mag.

267
Figure (9-4.17 c) 50 mg/1 Au(III), 500X mag.
Figure (9-4.17d) 100 mg/1 Au(III), 500X mag.
Figure (9-4.17a-d) Scanning electron micrographs showin g the effect of initial

gold concentration on Au(ill ) bromide/Zn (suspended
particles) cementation (0.10 M NaBr, 20°C, pH: 5.00, 500
rpm); (a) 10 mg/I (b) 20 mg/I (c) 50 mg/I (d) 100 mg/I Au(III).
268
At 20 mg/I Au(ID) bromide concentration, shown in figure (9-4. l 7b) the

botryoidal/crystalline nature of deposit seen at 10 mg/I Au(ID), changed to a
thicker growth (more widely spread on the zinc particles) with the deposit
growing outwards towards the formation of dendrites. The deposit, in this case,
possibly provided a more surface area (roughness) to facilitate further
deposition. At a higher Au(ID) bromide concentration as shown in figure (9-
4.17 c) for 50 mg/I Au(ID), the deposit developed dendrites and the physical
nature or morphology clearly indicates that, it contributed to both increased
perturbations in the boundary layer as well as higher surface area for a higher
reaction rate/velocity than at 20 mg/I Au(ID). Figure (9-4. l 7d) also shows that
the dendritic deposit obtained at I 00 mg/I Au(ID), was more pronounced than
that obtained at 50 mg/I Au(ID), thereby leading to a further enhanced reaction
rate/velocity.
These results also indicate that surface roughness was of major importance in
the Au(ID) bromide cementation on zinc suspended particles unlike the
Au(CN)i-/Zn (suspended particles) system reported by Miller, Wan and Parga
(Miller et al, 1990). Thus, the surface velocity (or slip velocity) was significant
in distorting the boundary layer or microstreaming at the surface of the particles.
Consequently, the nature of the smface deposit had great impact on the reaction
velocity constant. Similar results were observed for the Au(III) bromide
cementation on zinc rotating-disc.
Figures (9-4.18a-b) show the effect of zinc particle size on the deposit stmcture
for 10 mg/I Au(ID) bromide/Zn cementation in 0.10 M NaBr solution
(containing 9.8 mg/I Br2 (aq)) at 20°C, pH: 5.00 and 500 rpm. At zinc particle
size range of 45X53 µm, (figure (9-4.18a), compared with figure (9-4.17a) for
zinc particle size range, 38X45 µm, the deposit was much smoother with less
significant secondary crystalline growths. At higher zinc particle size range,
63X 106 µm, shown in figure (9-4.18b), the deposit lacked entirely any
secondary growth.
This effect is further illustrated in figure (9-4.19a-b) for 100 mg/I Au(III)
bromide/Zn cementation in 0.10 M NaBr solution (containing 98 mg/I Br2 (aq))
at 20°C, pH:5.00 and 500 rpm.
269
Figure (9-4.18a) 45X53 µm, 500Xmag.
Figure (9-4.18b) 63X75 µm, 500Xmag.
Figure (9-4.18a-b) Scanning electron micrographs showing the effect of zinc

particle size on Au(ID) bromide/Zn (suspended particles)
cementation (10 mg/I Au(III) in 0.1 M NaBr (containing 9.8
mg/I Br2 (aq)), 20°C, pH: 5.00, 500 rpm) (a) 45X53 µm and
(b) 63X 106 µm.
270
Figure (9-4.19a) 45X53 µm, 500Xmag.
Figure (9-4.19b) 63X 106 µm, 500Xmag.
Figure (9-4.19a- b) Scanning electron microgra phs showing the effect of zinc
particle size on Au(III) bromide/ Zn (suspend ed particles )
cementat ion ( 100 mg/I Au(ID) in 0.10 M Nailr (contain ing
98 mg/I Ilr2 (aq)), 20°C, pH: 5.00, 500 rpm); (a) 45X 53 µm
and (b) 63X 106 µm .
271
At zmc particle size range of 45X53 µm (figure (9-4.19a)), the dendritic

structure seen in figure (9-4. l 7d) was less prominent, more bulbous in nature
and with shorter branches contributing less smiace roughness in the mass-
transport boundary layer. At zinc particle size range of 63X 106 µm (figure (9-
4.19b) ), the deposit was much more bulbous than the deposit observed at zinc
particle size range of 45X 53 µm and lacked a well-textured dendritic structure.
These surface roughness factors, in both cases, explain the nature of the
observed kinetic behaviour under these conditions.
Figures (9-4.20a-c) also show the surface roughness influence on the

rate/velocity of the Au(ll) bromide cementation on zinc suspended particles as
a function of the applied stining speed. The increase in the reaction rate/velocity
constant as solution stining speed increased can be seen to relate strongly to the
change in the structure and morphology of the deposit formed. At 100 rpm
(figure (9-4.20a), the gold deposit consisted of an initial smooth deposition with
secondary small crystallites on the zinc particles. An increased stining to 300
rpm (figure (9-4.20b) led to a dendritic deposit which contributed to a higher
reaction rate/velocity due to its greater smface roughness. At a much higher
stirring speed as in figure for 700 rpm, the deposit was endued with thicker and
well-textured dendritic structure which provided a much greater surface
roughness and c01responding higher reaction rate/velocity than those obtained at
lower stining speeds.
Figure (9-4.20a) 100 rpm, 500X mag.

272
Figu re (9-4.20b) 300 rpm, 500X mag.
Figure (9-4.20c) 700 rpm , 500X mag.
Figu re (9-4. 20a- c) Scan ning elect ron micr ogra phs show ing the effec
t of stirr ing
spee d on Au(I II) brom ide/Z n (susp ende
d parti cles)
ceme ntati on (100 mg/I Au(I II), 0.10 M NaB r (con
taini ng 98
mg/I Br2 (aq)) , 20°C , pH: 5.00) ;(a) 100 rpm (b)
300 rpm , (c)
700 rpm.
273
Figure (9-4.2la-b) also show the scanning electron micrographs at initial

amount of zinc suspended particles of (a) 0.0604 g (2.43 times the
stoichiometric requirement) (b) 0.500 g (20.10 times the stoichiometric
requirement) Zn respectively for 100 mg/1 Au(III) bromide/Zn cementation
reaction in 0.10 M NaBr solution (containing 98 mg/1 Br2 (aq)) at 20°C, pH:
5.00 and 500 rpm. The difference in the nature of the deposits in figure (9-
4.2la) and figure (9-4.2lb) offers support for the anomalous behaviour in the
reaction rate/velocity constants obtained at initial amount of zinc of 0.0604 g
and 0.500 g Zn. At 0.0604 g Zn (suspended particles), the deposit was massive,
porous and fine textured dendritic in nature which exhibited the observed
departure in the initial kinetic rate/velocity. However, at 0.500 g Zn the deposit
was small bulbous/botryoidal in nature and lacking well characterised dendrites.
Although, the slope of the first-order curve under this condition was higher than
that at 0.0604 g Zn, it is possible that, this deposit reduced the available surface
area (roughness) on the individual particles to sustain the diffusional process
and hence resulted in the lower reaction rate character.
Figure (9-4.21 a) 0.0604 g Zn, 500X mag.

274
Figure (9-4.21b) 0.5000 g Zn, 500X mag.
Figure (9-4.21a-b) Scanning electron micrographs showing the effect of amount

of zinc particles on Au(ill) bromide/Zn (suspended particles)
cementation (100 mg/I Au(ill), 0.10 M NaBr (containing 98
mg/I Br2 (aq)), 20°C, pH: 5.00, 500 rpm); (a) 0.0604 g Zn
and (b) 0.500 g Zn.
Invariably, for the experimental conditions employed in this study under the
effect of free bromide, pH and temperature, the deposits on the zinc suspended
particles were bulbous/bot:ryoidal crystal masses (for low initial gold
concentrations) and dendritic structures (for high initial gold concentrations) of
different degrees of texture and size. Almost without exception, these deposits
under the various kinetic conditions were comparable to the deposits obtained
on zinc rotating-discs as discussed in section (9-3-2). The structure and
morphology of the deposits modified themselves according to changes in the
experimental parameters. A change in the smface roughness (ie., effective
deposition surface area) of the reacted zinc particles as a result of such
modification to the deposit morphology resulted in the observed variations in the
reaction rate/velocity.
275
9-4-3 Shrinking core model/kinetics
The Au(ID) bromide cementation on suspended zmc particles reaction was

further analyzed in terms of a shrinking core type model (with a product layer
formation) described in section (5-5) according to the equation:
2Au(Ill)(f) + 3Zn(s) = 3Zn(Il)ct) + 2Au(s) (9-4.1)
For a film diffusion controlled reaction, the relationship between the fraction of
zinc suspended particles reacted (a= {l -(rli"a) 3 }) and time (t) is well established
and is given by equation (5-5.7), such that:
(9-4.2)
where km is reaction rate constant (emfs), Mzn is the molecular weight of zinc
(g/mol), Pzn is the density of zinc (g/cm3).
The plots of a= {l-(r/r0 )3} against tare shown in figures (9-4.22a-b) for (a) 10
mg/I (b) 100 mg/I Au(ID) bromide/Zn (suspended particles) cementation
respectively in 0.10 M NaBr at 20°C, pH:5.00, 500 rpm and (i) 38x45 µm (ii)
45x63 µm (iii) 63x 106 µm zinc particle sizes
A product layer diffusion-controlled model (shrinking-core type) was also tested

graphically using equation (5-5.9). Figures (9-4.23a-b) also show the plots of
1--½ a-(1- a) 213 versus t for (a) 10 mg/I and (b) 100 mg/I Au(lll) bromide/Zn
(suspended particles) cementation respectively in 0.10 M NaBr at 20°C,
pH:5.00, 500 rpm and (i) 38x45 µm (ii) 45x63 µm (iii) 63x 106 µm zinc
particle sizes.
These results illustrate that, in the initial stages of reaction (0-7 minutes), the
reaction displays linear relationships/kinetics for the inverse of particle diameter
(l/d 0 ), which supports the assumption of film diffusion control mechanism. This
can be seen to be followed by diffusion-through-the-product-layer control
mechanism. Thus, in accordance with equations (9-4.2) and (5-5.9):
276
1-(r/ro)·s
0.10 . - - - - - - . - - - - - - - ~ - - - - - - - - - ~
0.08
(Au8r4-J • 10 mg/I
(NaBrl • 0.10 M
0.06 pH• 8.00
Temp.• 20 C
D
RPM.• 600
0.04
D
--- 38•45 um
Initial aolutlon vol. • 800 ml.

-t- 48•83 um
-B- 83•108 um
0 5 10 15 20 25 so 35 40 45 50
Time, (mlna)
Figure (9-4.22a) Plots of l -(r/r0 ) 3 versus time for 10 mg/I Au(ID) bromide/Zn
(suspended particles) cementation in 0.10 M NaBr ( 9.8 mg/I
Br2 (aq)), at 20°C, pH:5.00, 500 rpm and (i) 38X45 µm (ii)
45X63 µm (iii) 63X106 µm zinc particle size ranges.
1-(r/roJ-3
0.8 ,-------r--------r--------y------,
(Au8r4·) • 100 mg/I

0.6 (NaBr) • 0.10 M
+ pH• 6.00
0.4 * Temp.• 20 C
RPM.• 500
0.2 --- 38•45 um

-t- 46•83 um
+ 83•108 um
0 5 10 15 20 25 so 35 40 45
Time, (mlna)
Figure (9-4.22b) Plots of I -(r/r0 ) 3 versus time for 100 mg/I Au(ID)
NaBr (98 mg/I Br2 (aq)), at 20°C, pH:5.00, SOO rpm and (i)
38X45 µm (ii) 45X63 µm (iii) 63Xl06 µm zinc particle size
ranges.
277
1-(2/3)x-(1-x>-2l3 (E-04)
10.-----------------~-------,
IAuBr4-I • 10 mg/I pH• &.00
- 38•46 um INaBrl • 0.10 M T•mp. • 20 C
8
+ 4&•83 um
RPM.• 1500
D 83•108 um
Initial •olutlon vol. • 1500 ml.

0~ste1f.-:l:l"'---'=-----'----'-----'---....1.----'-----'-------'
0 5 10 15 20 25 30 35 40
Time, (mine)
Figure (9-4.23a) Plots of 1-(2/3)a-(1-a) 213 versus time for 10 mg/I Au(ID)
NaBr (Br2 (aq): 9.8 mg/I) at 20°C, pH:5.00, 500 rpm and (i)
38X45 µm (ii) 45X63 µm (iii) 63X106 µm zinc particle size
range.
1-(2/3)x-(1-xr213
0.08 . - - - - - - - - - - - - - - - - - r - - - - - - - - - - - - - - - - - , ,
• 38•46 um
(NaBrl • 0.10 M
+ 4&•88 um
0.06 0 83•108 um
0.04
Temp.• 20 C
RPM.• SOO
0.02
0 5 10 15 20 25 30 35 40 45
Time, (mlns)
Figure (9-4.23b) Plots of 1-(2/3)a -(1- a) 213 versus time for 100 mg/I Au(ID)
NaBr (Br2 (aq): 98 mg/I) at 20°C, pH:5.00, 500 rpm and (i)
38x45 µm (ii) 45X63 µm (iii) 63Xl06 µm zinc particle size
range.
278
(9-4.3)
where kr = JPM~n
Zn 0
km and t is time between O and 7 minutes, and
(9-4.4)
where k* = 3Mzn D (D is the diffusivity of AuBq-) and t is time> 7 minutes.

2
Pzndo
Further, from the slopes of the curves in figures (9-4.22a-b), the mass transfer
coefficients (or the reaction rate/velocity constants) calculated using equation
(9-4.3) are shown in table (9-4.5). These rate data are in reasonable agreement
with the calculated rate/velocity constants listed in table (9-4.1) for the different
zinc particle size ranges.
Table (9-4.5) The shrinking-core kinetics/mass transfer coefficients

calculated for the different zinc particle size ranges (0.10 M
NaBr; pH:5.00; 20°C; 500 rpm; Au(l11): (i) 10 mg/I (ii) 100
mg/I)
Initial gold Particle Mass transfer

concentration size range coefficient
km x10-3
mg/I µm emfs
10 38X45 7.120
45X63 3.509
63X 106 2.136
100 38X45 7.151

45X63 3.300
63X 106 2.144
From the slopes of the (38x45 µm) curves in figures (9-4.23a-b), the deviation
in the plots at longer times might be mass-transfer limitations. This should be
279
expected because the supply of reactants and the removal of products through
the layer becomes limiting.
280
CHAPTER TEN
CONCLUSION AND RECO!Vl!VIENDATION
10-1 CONCLUSION
A study was conducted to evaluate the fundamental aspects of the cementation

of gold from bromine-bromide solutions using zinc.
Thermodynamic modelling usmg vanous computer packages/programs

(CHEMIX, SYSTEM, DIASTAB) showed that, although gold-bromide complex
is more stable as AuBr4-, AuBr2- may be stabilized in excess bromide
concentrations. The equilibria governing Au(0)/ Au(I) bromide and Au(0)/Au(IIl)
bromide couples are strongly dependent on the Br2/Br equilibria.
The equilibrium species concentration versus pH diagrams developed by these

programs also showed that, the Au(III) bromide, AuBr4 -, is more stable at a
higher pH range only in excess of bromide. The recovery of gold from Au(III)
bromide solutions by a cementation process will only be effective in the acidic
zone where AuBr4 - is more predominant. Under the same conditions (especially
at low bromide concentrations), zinc dissolves (or corrodes) in bromide
solutions at low pH's to give zincic ions, Zn 2+. The zinc-bromide species,
ZnBr+, ZnBr2 (aq) and ZnBr 3- have relative stabilities only in high bromide
concentrations ([Br-] > 4.00 M). A similar equilib1ium concentration/pH profile
for Au(IIl)-Zn-Br!BrrH 20 system at 25°C, showed that, the reduction of
Au(III) bromide to Au(0) by zinc will be more cost effective at pH's 5.00 - 7.00
and high gold concentrations. Below pH:5.00, reduction of Au(III) bromide can
only be effective at zinc amounts more than the stoichiometric requirements.
Between pH's 1.00 - 4.00, and especially at- high zinc amounts, zinc will be
corroded/oxidized (ie., reacts with hydrogen ions) first before it reacts with
Au(III) bromide, Br 2 (aq)!Br 3- and 02 (aq). At low zinc additions and low gold
inventories, the reduction of AuBr4- to Au(0) will involve AuBr 4 -/AuBr 2 - and
AuBr2-/ Au(0) steps.
An electrochemical technique of scanning (linear sweep) voltammetry usmg

gold and zinc rotating-disc electrodes for the cathodic reduction of AuBr4 - and
2Xl
anodic dissolution of zrnc half-cell reactions respectively has provided

mechanistic/intrinsic features of the zinc cementation of gold from gold-bromide
solutions.
The polarization (1-E) curves from this study showed evidence of three reactions
involved in the reduction process corresponding to the reduction of residual
bromine species at 0.60 V (vs SCE), gold-bromide ions at -0.25 V (vs SCE) and
dissolved oxygen in the same potential region for the reduction of Au(III)
bromide ions. In addition, at potentials cathodic to -1.30 V (vs SCE), hydrogen
will evolve from the reduction of H20/J-{+ ions and the cunent becomes limited
at potential cathodic to about -0.70 V (vs SCE). The magnitude of the limiting
cun-ent densities for the reduction of AuBr4 - also showed a linear dependence
on the square root of the rotational speed of the disc, indicating a mass-transfer
controlled mechanism governing the reaction.
The Evans diagrams constructed from the polarisation curves of the oxidation
and reduction half-cell reactions confirmed that the Au(III) bromide/Zn system
is controlled by a diffusion step. The potential separation of the equilibrium
lines of the two half-cell reactions involved in the process is greater than the
typical value of 360 m V for a diffusion control system and there exists a unique
mixed (or con-osion) potential (around - 1.00 V (vs SCE)) at which the rate of
the anodic reaction is equal but opposite to that of the cathodic reaction. Under
ideal conditions, there will be no thermodynamic restriction to the completion of
the reaction. The kinetics controlling the cementation reaction will be
determined by the rate at which Au(III) ions diffuse onto the zinc surface. The
Evans diagrams also indicated that, excess zinc has to be used to react with the
residual bromine and dissolved oxygen besides the Au(III) bromide ion
reduction. In effect, the reaction kinetics are strongly dependent on the gold
concentration, bromine concentration, bromide concentration, pH, dissolved
oxygen and temperature of the solution.
For practical applications, Br 2 (aq) should be as low as possible and the solution
should be de-oxygenated. The addition of free bromide solution (0.01- 0.10 M)
during zinc cementation of gold from bromide leach liquors is essential. At
lower bromide concentrations ( < 0.01 M), the reaction will proceed under an
electrochemical or charge transfer control step and may lead to the complete
cessation of the reaction. Inordinate bromide concentrations (> 0.10 M) will
lead to accelerated con-osion of zinc and Au(lll) bromide ions will be reduced at
2X2
a decreasing rate. However, the concentration of bromide in this range should he

rationalised in tenns of thermodynamics to be dependent on the bromide
concentration necessary to stabilize the Au(III) bromide ions in the solution.
Higher bromide concentrations are required for more concentrated Au(lll)
bromide concentrations to be stable. The pH of the solution in the Au(III)
bromide/Zn cementation system should also be maintained between pH:5.00 and
pH:7 .00 to avoid the deleterious effect of H+ ions. At low pH's ( < pH:5 .00), the
reduction of Au(III) bromide 10n reaction proceeds at a rate
controlled/influenced by the copious discharge of hydrogen. An excessive
amount of zinc will also be dissolved under the influence of a conosion process.
Experimental cementation results indicated that gold cementation from bromine-

bromide solutions by zinc rotating-disc conforms .to well-behaved two-stage
(initial and enhanced periods) first-order reaction kinetics under certain
circumstances as observed for most cementation reactions. Under these
circumstances, initial reaction rate constants cones pond to expected (or
predicted) magnitude of the limiting mass-trarisfer coefficients based on the
Levich's equation and support the proposition that the cementation reaction is
limited by mass-transfer of the Au(III) bromide species to the zinc reaction
smface.
Increase in temperature (from I 0°C to 40°C) increased the reaction kinetics/rate.

The Anhenius plots of the reaction rates yielded activation energies of 2.50
kcal/mol (10.50 kJ/mol) for the initial rate period and 3.13 kcal/mol (13.12
kJ/mol) for the enhanced rate period, which are consistent with that expected for
mass-transfer-diffusion control mechanism. Both the initial and enhanced
reaction rates increased significantly as the initial gold concentration increased
from 10 mg/1 to 100 mg/1 Au(l11) at 20°C. The relative me1its of bromide
concentration for the reduction of Au(III) bromide ions and effects of such
kinetic variables as pH and rotational speed, under this study followed the
predictions from polarization measurements (electrochemical studies), under the
same conditions. At low gold concentrations an optimum bromide concentration
of 0.100 M was observed for extended times of cementation reaction associated
with greater gold recovery. At 0.001 M NaBr an inhibiting effect on the reaction
rate occuned after 80 minutes of cementation leading to a deviation from first-
order reaction. On the other hand, at 100 mg/1 ·Au(Ill), while the initial rate of
cementation increased with increase in free bromide from 0.01 M to 0.10 M
NaBr, the enhanced rates decreased as free bromide increased from 0.01 to 0. I 0
281
M NaBr. In this case, both the initial and enhanced rates decreased at 0.50 M.
Invariably, the initial rates of cementation increased slightly with decrease in pH
from 7 .00 and then increased sharply for further decrease in pH from 4.00 to
2.00. This kinetic behaviour was associated with high zinc dissolution rates at
low pH values. In addition, at pl-1:2.00. the second stage reaction rate was lower
than the initial rate. Thus, for cost effective cementation process, the reaction
should be conducted at close to neutral conditions (ie., between pH:5.00 to
7.00).
The characterization of the cementation product on the zinc slllface at different

kinetic conditions showed a significant effect of the gold deposition on the
reaction kinetics. Examination of the reaction product by scanning electron
microscope indicated that the structure and morphology of the gold deposits
over the zinc surface provide strong evidence to account for the change in the
reaction rates at the various experimental conditions. The structure was found to
be characteristic of a two-stage growth phenomena as evident in the first-order
plots. An initial smooth deposit (corresponding to the initial period/stage of
reaction) was followed by a secondary coarser particulate/botryoidal/dendritic
deposit (corresponding to the enhanced period/stage of reaction) which
enhanced the cementation rate by several orders of magnitude than that of the
initial period. In all cases, the structure and morphology of the deposit modified
themselves according to the changes in the experimental parameters. Of greater
significance, is the structural and morphological changes from thin botryoidal
type at 10 mg/I Au(III) concentration to coarser and more porous bulbous
growth at 20 mg/I Au(III) concentration and then to the formation of dendrites at
50 mg/I and 100 mg/1 Au(III) concentrations. Also at low bromide
concentrations (< 0.001 M) and especially low gold concentrations, the gold
deposit nucleate and grow only at isolated locations along compact/coherent
dendritic structure, thereby supporting a retarded cementation rate.
Further characterization/kinetic study of the Au(III) bromide cementation using

suspended zinc particles support the analysis of the reaction kinetics under zinc
rotating-disc geometry and from polarization measurements at the different
conditions. The experimental results under this study also conform to two-stage
first-order reaction kinetics for most conditions and demonstrate strong support
for mass-transfer diffusion control mechanism. The Arrhenius plots of the
reaction rates/velocities yielded activation energies of 1.96 kcal/mol (8.20
kJ/mol) for initial rate period and 2.88 kcal/mol ( 11.83 kJ/mol) for enhanced
284
rate period at I 0 mg/I Au(III) and 2.89 kcal/rnol ( 12.07 kJ/mol) for initial rate
period and 6.76 kcal/mol (28.27 kJ/mol) at I 00 mg/I Au(III) and 38x45 ~Lm
which are also consistent with the expected values for diffusion mechanism. The
reaction velocity constants also exhibited strong dependence on the inverse of
particle diameter and the square-root of stirring speed.
The nature of the gold deposit on the reacted zinc particles, under optical and
scanning electron microscopes showed that the gold formed a layer around the
zinc particles with sufficient porosity to sustain the first-order kinetics. The gold
deposits indicated that surface roughness was of major significance in the
Au(III) bromide cementation on zinc suspended particles unlike the Au(CNh-
/Zn (suspended particles) cementation process. An increase in particulate zinc
amount from 0.0604 g Zn (2.43 times the stoichiometric requirement) to 0.5000
g Zn (20.10 times the stoichiometric requirement) reduced the available surface
roughness on the individual particles to sustain the diffusional process and
hence resulted in lower reaction rate character. For the experimental conditions
tested in this study the deposits on the zinc suspended particles were
bulbous/botryoidal crystal masses (for low initial gold concentrations) and
dendritic structures (for high initial gold concentrations) of different degrees of
texture and sizes (similar in structure to those observed for the Au(III) bromide
cementation on zinc rotating-disc). The change in the nature and morphology of
the deposits corresponded to the observed kinetic behaviour.
The initial reaction rates/velocities were significantly impaired at pH values

below pH:4.00. Under these conditions, the kinetics of hydrogen ion-zinc
reaction dominated in the Au(III) bromidefZn cementation system. However, the
variation of the enhanced reaction rates/velocities yielded an optimum condition
at pH:4.00 (27 .839x I0-3 cm/s) coITesponding to 99.72% overall gold recovery.
An optimum bromide concentration of 0.050 M was also found to be critical to
sustain a well-behaved first-order kinetics for highest gold recovery. Lower
bromide concentrations ( < 0.01 M) inhibited .the reaction rate after I 0 minutes
of cementation leading to overall lower gold recoveries. Evidence for anodic
closure and a change in reaction mechanism from diffusion to electrochemical
(charge-transfer) kinetics were found from solution potential measurements at
lower bromide concentrations ( < 0.01 M) and low gold inventories. Higher
bromide concentrations at high gold concentrations, increased the stability of
AuBr4 - and reduced the reaction rate/velocity.
285
At 0. I O M bromide concentration, a shrinking core kinetics confirmed a film

diffusion mechanism at initial stages of the reaction followed by a product-
laycr-diffusion mechanism. At low gold concentration, the diffusion-through-
thc-product layer dominated the reaction.
I 0-2 Recommendation/Suggestions for future work
This study was conducted to provide fundamental kinetic data on gold recovery
by zinc cementation from bromine-bromide solutions as a recovery option for
the bromide/bromine leaching system for gold extraction. Zinc cementation was
claimed to be highly efficient method for gold recovery from bromine-bromide
solutions (Dadgar, 1989; Dadgar et al, 1990), but no detailed evaluation or
reported literature was extended beyond this claim.
Electrochemical techniques or measurements have allowed for the determination

of the characteristics and mechanistic/intrinsic features of the recovery process.
Morphology study of the reacted zinc surface after cementation experiments
using both zinc rotating-disc and suspended particles by optical and/or scanning
electron microscopes has also provided useful information on the nature of the
reaction products. Significant as it is, the optimum kinetic data from this study
using synthetic gold solutions (from high purity (99.99%) gold strips), could be
more applicable to the treatment or recovery of gold from leach liquors from
concentrates and electronic scraps.
Gold ores contain a number of impurity minerals which could be trapped in the
bromide leach liquors/solutions.
(1) To cope with the increasing complexity of these gold ores (due to these
impurities) further work is recommended/suggested to test the optimum kinetic
conditions against bromide leach solutions from gold ores of different
mineralisations. Electrochemical measurements should also be extended to
evaluate the effect of arsenic, antimony and sulphide ions on the rate of
cementation of gold from bromine/bromide solutions.
(2) In view of the significant role of lead in improving the kinetics and
extending the zinc cementation of gold and silver in cyanide systems (Oo and
Tran, 1991 ), the effect of lead on the reaction rate constants and the deposit
286
morphology of zinc cementation of gold from bromide-bromine solutions should

also be evaluated.
(3) Results of the work carried out in this study showed a marked deleterious
effect of H+ ions on the kinetics of the cementation of gold from the bromine-
bromide system, especially at low pH values. Although, faster kinetics are
obtainable under these conditions, excessive amounts of zinc dissolve under the
influence of a corrosion process. Hydrogen evolution becomes more
predominant as the pH of the solution is decreased. At low initial gold
concentration, the zinc cementation reaction is also inhibited by copious
evolution of hydrogen accompanying the reaction.
Since Au(III) bromide ions are more stable in acidic conditions, a comparative
study towards raising the hydrogen overpotential on both zinc and gold smfaces
for better kinetics is recommended.
(4) The study also indicated that, the presence of Br 2 (aq) or the aqua-bromide
species in the cementation circuit inte1fere with the Au(III) bromide ions
reduction reaction. However, bromine is an essential component of the gold
dissolution/oxidation in bromide liquors and its total removal in the system
cannot be waITanted. The existence and relative predominance of AuBr 4 -ions in
bromine-bromide solutions also depend on the strength of Br 2 . A more detailed
work on the effect of Br 2 may be worthwhile for the purpose of process design.
287
REFERENCES
Adams, R.N., Electrochemistry at solid surfaces, (Marcel Dekker, New York,

1969).
Adamson, R.J., Gold metallurgy in South Africa, (Cape and Transvaal Printers
Limited, Cape Town, 1972).
Afenya, P.M., Studies in the processing of a carbonaceous gold ore, Ph.D.

thesis, Imperial College, London, (1976).
Annamalai, V. and Murr, L.E., Influence of deposit morphology on the kinetics

of copper cementation on pure iron, Hydrometallurgy, 4 (1979), pp. 57-
82.
Ashurst, K.G. and Finkelstein, N.P., The influence of sulphydryl and cationic
flotation reagents on the flotation of native gold, J.S. Afr. Inst. Min.
Metall., Vol. 70, (1970), pp. 243-258.
Avraamides, J., Prospective for alternative leaching systems for gold, In: Proc.
C.I.P. Technology for the Extraction of Gold Symposia, Series No 32,
(Aus IMM, Melbourne, 1982), pp. 369-382.
Avraamides, J., Changing trends in gold ore treatment in Western Australia; the
problem of refractory ores, In: Gold Forum on Technology and Practices
- World Gold '89, Eds: Bhappu, R.B. and Harden, R.J., Proc. 1st Joint
Int. Meeting between SME and Aus IMM, Reno, Nevada, USA,
(SME/AIME, Littleton), (1989), pp. 333-336.
Avraamides, J., CIP carbons - selection, testing and pilot plant monitoring, Proc.
World Gold '89 Symp. AIME, (1989), pp. 288-292
Avraamides, J., Gold extraction and recovery process options, Australian

Mineral Foundation Workshop Course on C.I.P. and Gold Processing
Technology, (Feb., 1989).
288
Avraamides, J. and Haynes, P., Electrolytic recovery of gold from cyanide

solutions, In: ELECTROCHEMISTRY: Current and Potential
Applications, Eds: Tran, T. and Skyllas-Kazacos, M., Proc. Seventh Aust.
Electrochemistry Conf., UNSW., Kensington, Australia, (Feb. 15-19,
1988), pp. 134-140.
Bahl, S.K. and Leach, G.L., Gold etchant composition and method, U.S. Patent
No. 4,190,489 (1980); and 4,375,984, (1983).
Barbin, M.B., The influence of flotation agents on the dissolution of gold and
silver by a cyanide treatment, Sb. Nauchn. Tr. Uralsk. Politekhn. Inst.,
No. 134, (1963), pp. 101-102.
Barbosa, 0. and Monhemius, A.J., Thermochemistry of thiocyanate systems for

leaching of gold and silver ores, In: Precious Metals '89, Eds: Jha, M.C.
and Hill, S.D., TMS, (1988), pp. 307-339.
Bard, A.J. and Faulkner, L.R., Electrochemical methods, (Wiley, New York,
1980).
Barin, I., Barth, H. and Yaman, A., Electrochemical investigation of the kinetics
of gold cementation by zinc from cyanide solutions, Erzmetall, Vol. 33,
No. 7/8, (1980), pp. 379-403.
Barth, H., Gans, W. and Knacke, 0., An experimental contribution to the

kinetics of cementation, Int. Symp. on Hydrometallurgy, Chicago,
Illinois, USA., (1973), pp. 1081-1094.
Beattie, M.J., Balderson, G. and Foo, K., Application of the Arseno process
technology for refractory ores and concentrates, Randol Perth lnt. Gold
Conference, Oct. 28 - Nov. I, (1988), (Randol International, Colorado),
p. 123.
Berezowsky, R.M.G., Sefton, V.B. and Ormerly, L.S., Recovery of precious

metals from metal sulphides, US. Patent No. 4,070,182 (January 24,
1978).
289
Berezowsky, R.M.G.S. and Weir, D.R., Pressure oxidation pretreatment of

refractory gold ores, 7th Annual AIME Precious Metals and Uranium
Seminar, Lakewood, Col., (August 22-24, 1983), pp. 1-4.
Berg, E.W. and Downey, D.M., Ion flotation studies of the chlorocomplexes of
some platinum group metals, Analytica Chimica Acta, 120 (1980), pp.
237-248.
Beyers, E., Some of the factors which influence the dissolution of gold and
silver in cyanide solutions, J. Chem. Metall., Min. Soc., South Africa, 37,
(1936), pp. 37-89.
Bhappu, R.B., Hydrometallurgical advances in precious metals extraction, In:

Advances in Mineral Processing, Ed: Somasundarin, P., Proc. Symp.
New Orleans, Louisiana, March 3-5, 1986, (SME-AIME, Littleton,
Colorado), pp. 463-480.
Bilston, D.W., LaBrooy, S.R. and Woodcock, J.T., Gold and silver leaching
from an oxidized gold ore with thiourea under controlled conditions, In:
Extractive Metallurgy Symposium, (Aus IMM, Melbourne), (1984), pp.
51-60.
Bircumshaw, L.L. and Riddiford, A.C., Transport control in heterogeneous

reactions, Quart. Rev. Chem. Soc., 6 (1952), pp. 157-185.
Bloch, M., Das Buch der Grossen Chemiker, Vol. 2, Ed: Bugge, G., Verlag
Chemie, Weinheim, (1929), p. 99.
Block-Bolten, A., Daita, M.S., T01ma, A.E. and Steensma, R., Thiosulphate
leaching of gold from sulphide wastes, In: Complex sulphides, processing
of ores, concentrates and by-products, Eds: Zunkel, A.D., Boorman, R.S.,
Morris, A.E. and Wesley, R.J., (TMS, 1985).
Block-Bolten, A. and Torma, A.E., Thiosulphate leaching of gold from sulphide

wastes, Metall. (Berlin) (1986), 40(7), pp. 687-689.
Bodlander, G.Z., Angew. Chem., Vol. 9, (1896), p. 583.

290
Boyle, R.W., The geochemistry of gold and its deposits, (Canadian Gov't.
Publishing Centre, Quebec, Canada, 1979).
Brandon, N.P., Mahmood, M.N., Page, P.W. and Roberts, C.A., The direct
electrowinning of gold from dilute cyanide leach liquors,
Hydrometallurgy, 18 (1987), pp. 305-319.
Bratt, G.C. and Gordon, A.R., Research in Chemical and Extraction Metallurgy,
Aus IMM, (1967), p. 197.
Brood, R.J. and Leger, V.E., Zinc, In: Encyclopaedia of Electrochemistry of the
elements, Ed: Bard, A.J., Vol. V, (Marcel Dekker Inc., New York, 1976),
Chapter V-1, pp. 1-67.
Brunner, E., Z. Physik. Chem., 56, (1906), p. 321.
Butler, J.A.V., Trans. Faraday Soc., (1924), Vol. 19, pp. 729-733.
Butler, J.A.V., The electrical double layer and electrocapillarity, In: Electrical
Phenomena at Interfaces, Ed: Butler, J.A.V., (MacMillan Co., New York,
1951), pp. 30-74.
Calara, J.V., Kinetics of copper cementation on a rotating iron disc, MSc.

Thesis, University of the Phillipines, Department of Metallurgy, Manila.
Phillipines, (1970).
Caldeira, C.L. and Ciminelli, V.S.T., Thiourea leaching of a refractory gold

ores, In: XVIII Int. Mineral Processing Congress, Sydney, Australia, (Aus
IMM, May 23-28, 1993), Vol. 5, pp. 1123-1128.
Caruso, S.G., The chemistry of cyanide compounds and their behaviour in the
aquatic environment, Carnegie Mellon Inst. of Research, USA., (1975).
Caspari, W.A., Z. Physik. Chem., 30, (1899), p. 89.
Cassel, H.R., U.S. Patent No. 732,706 (1903); and 732,709 (1903).
291
Cathro, K.J., Effects of oxygen in the cyanide process for gold recovery, Aus
IMM Proceedings, 207, (1963), pp. 181-205.
Cathro, K.J. and Walkley, A., The cyanidation of gold, (CSIRO Publication,
Melbourne, Australia, 1961).
Cathro K.J. and Koch, D.F.A., The dissolution of gold in cyanide solutions-An
electrochemical study, Aus IMM, Proceedings, 210, (1964), pp. 111-126.
Charewicz, W and Niemiec, J ., Flotation of anions using cationic surfactants.

III. Flotation of chloroaurates, Nukleonika, 14 (1969), pp. 799-806.
Charewicz, W., Flotation of anions using cationic smfactants, IV: Flotation of

molybdates, perrhenates and chloroaurates from solutions of some
electrolytes, Nukleonika, 20 (1975), pp. 447-456.
Charley, W.R., Hydrometallurgical extraction of precious metals using thiourea

, In: Practical Hydromet "83, 7th Annual Symposium on Uranium and
Precious Metals, Ed: Chlumsky, G.F., (SME-AIME, 1984) pp. 75-81.
Chen, C.K., Lung, T.N. and Wan, C.C., A study of the leaching of gold and
silver by acid thioureation, Hydrometallurgy, 5 (1980), pp. 207-212.
Chin, D.T. and Litt, M., J. Fluid Mech. 54 (1972), p. 613.
Chizhikov, D.M., Cadmium, (Pergamon Press, Toronto, Canada, 1966).
Christy, S.B., The electromotive force of metals in cyanide solutions, Trans.

AIME, 30, (1900), pp. 864-946.
Clennell, J.E., The Cyanide Handbook, (McGraw-Hill, New York, 1915), 2nd
edition, pp. 10-24.
Cornet, I., Lewis, W.N. and Kappesser, R., Cathodic protection of a rotating
cylinder, Trans. Inst. Chem. Eng. 47 (1969), p. T222.
292
Cornwall, W.G. and Hisshion, R.J., Leaching of telluride concentrates for gold,
silver and tellurium - Emperor process, Trans. Soc. AIME, 260 (1976),
pp. 108-112.
Cotton, F.A. and Wilkinson, G., Advanced Inorganic Chemistry, 3rd editiion,
(lnterscience, New York, 1972), p. 1396.
Crabtree, E.H., Winters, V.M. and Chapman, T.G., Developments in the

application of activated carbon to cyanidation, Trans. Am. Inst. Min.
Engrs., (1950), pp. 187-217.
Dadgar, A., Extraction and Recovery of Gold from Concentrates by Bromine

Process, In: Precious Metals '89, Eds: Jha, M.C., Hill, S.D., (1989), pp.
227-240.
Dadgar, A. and Sanders, B .M., Recovery of gold from Geobrom 3400 leach
solution with ion-exchange resins, EPD Congress '90, Ed: Gaskell, D.R.,
(Anaheim, CA, TMS, 1990), pp. 355-391.
Dadgar, A., Sanders, B.M., McKeown, J.A., Sergent, R.H. and Jacobson, R.H.,
Leaching and recovery of gold from black sand concentrate and
electrochemical regeneration of bromine, In: Advances in Gold and Silver
processing, Proc. Gold Tech. 4, Eds: Fuerstenau, M.C. and Hendrix, J.L.,
Reno, Nevada, Sept. 10-12, 1990, (SME-AIME), pp. 75-89.
Dadgar, A. and Howarth, D., Advances in Bromide Gold leaching technology,

EPD Congress 1992, Ed: Hager, J.P., Proc. of TMS-AIME Conference,
(1992), pp. 123-136.
Davidson, R.J., The mechanism of gold adsorption on activated carbon, J. S.

Afr. Inst. Min. & Metall, (November, 1974), pp. 67-76.
Davidson, R.J., Douglas, W.D. and Tumilty, J., Aspects of laboratory and pilot
plant evaluation of CIP with relations to gold recovery, Presented at XIV
Int. Mineral Processing Congress, Toronto, Canada, (Oct. 17-23, 1982),
pp. II.6.1-11.6.9.
293
Davidson, R.J., and Veronese, J. and Nkosi, M.V., The use of activated carbon
for the recovery of gold and silver from gold plant solutions, J. South
African Inst. Min. Met., (May 1979), pp. 281-297.
Davis, A., Kinetic studies on gold extraction in iodide systems, Ph.D thesis,
School of Mines, University of New South Wales, (1991).
Davis, A. and Tran, T., Gold dissolution m iodide electrolytes,

Davis, A. and Tran, T., Fundamental aspects of gold on the leaching of gold in
halide media, In: Proc. EDP '92 Congress, Ed: Hager, J. (TMS-AIME,
1992), pp. 99-114.
Davis, A., Tran, T. and Young, D., Solution chemistry of iodide leaching of
gold, Hydrometallurgy, 32, (1993), pp. 143-159.
Deschenes, G. and Ghali, E., Leaching of gold from a chalcopyrite concentrate

by thiourea, Hydrometallurgy, 20 (2) (1988), pp. 179-202.
Deschenes, C., Ritchy, G.M. and Ghali, E., Reduction of gold and silver by
hydrogen from sulphuric thiourea solutions, ibid, (1989), p. 341.
Downs, A.J. and Adams, C.J., Bromine In: Comprehensive Inorganic

Chemistry, Ed: Trotman-Dickenson, A.F., Vol. 2, (Pergamon Press,
Oxford, 1973), pp. 1107-1594.
Drozdov, B.V., Conditions for the contact reduction of a metal from solution,
Zh. Prikl. Khim. 31 (1958), p. 211.
Dry, M.J. and Coetzee, C.F.B., The recovery of gold from refractory ores, Gold
100, Proc. Inter. Conf. on Gold, Eds: King, R.P., Fivas, C.E., (SAIMM,
1986), p. 259.
Dupius, C. and Ghali, E., Gold recovery from thiourea solutions by direct
electrowinning, In: Precious Metals '89, Eds: Jha, M.C., Hill, S.D. and El
Guindi, M., TMS-AIME (1989), pp. 359-376.
294
Eisele, J.A., Gold Metallurgy-A historical Perspective, Canadian Metallurgical

Quarterly, Vol. 27, No 4 (1988), pp 287-291.
Eisele, J.A., Comparative leaching of gold and silver with cyanide and thiourea
solutions, Precious Metals '89, Ed: Jha, M.C., Hill, S.D. and El Guindi,
M., (TMS-AIME, 1989), p. 253-260.
Eisenberg, M., Tobias, C.W. and Wilke, C.R., Ionic mass transfer and
concentration polarization at rotating electrodes, J. Electrochem. Soc.,
101 (1964), pp. 306-319.
Elsner, L., Uber das Verhalten vers Chiedner metalle in einer wassrigen losung
von zyankalum, Journal fuer Praktische chemie, 37, (1846), pp. 441-446.
Engel, M.D., Leahy, G.J., Moxon, N.T. and Nicol, S.K., Selective ion flotation
of gold from alkaline cyanide solutions, In: World Gold '91, (Aus IMM,
Melbourne), (1991), pp. 121-131.
Episkoposyan, M.L. and Kakovskii, I.A., An examination of copper and silver

cementation kinetics with metallic iron from chloride solutions, Soviet, J.
Non Ferrous Metals, 38 (10), (1965), pp. 16-21.
Episkoposyan, M.L. and Kakovskii, I.A., An examination of copper and silver

cementation kinetics with metallic iron from sulphate solutions, IZV,
UYSCH UCHEBN ZaVED, Tsvet. Metall, 9 (1), (1966), pp. 34-40.
Erdey-Gruz, T. and Volmer, M., Z Physik. Chem, (1930), Vol. A 150, pp. 203-
213.
Eriksson, G., Thermodynamic studies of high temperature equilib1ia XII,.

SOLGASMIX a computer program for calculation of equilibrium
compositions in multiphase systems. Chemica Scripta, No. 8, (1975), pp.
100-103.
Eriksson, G. and Rosen, E., Thermodynamic studies of high temperature

equilibria VIIl. General equations for the calculation of equilibria m
multiphase systems. Chemica Scripta, 4, (1973), pp. 193-194.
295
Eyring, H. and Eyring, E.M., Modern chemical kinetics, (Reinhold, New York,
1963).
Fagan, R.K., Chlorine based flooded pit leaching of oxide ores, In: Proc. Int.
Conf. Extractive Metallurgy of Gold and Base Metals, Eds: Misra, V.N.,
Halbe, D. and Spottiswood, D.J., Kalgoorlie, Western Australia, Oct 26-
28, 1992, (Aus. IMM).
Falanga, B.J. and MacDonald, D.I., Recovery of gold and/or palladium from an
iodide-iodine etching solution, US. Patent No. 4,319,923 (1982).
Faulkner, L.R., Understanding electrochemistry: Some distinctive concepts, J.

Chem. Educ., (April, 1983), Vol. 60 No. 4, pp. 262-264.
Filmer, A.O., Lawrence, P.R. and Hoffman, W., A comparison of cyanide,

thiourea and chlorine as lixiviants for gold, Aus IMM Regional
Conference proceedings on Gold Mining, Metallurgy and Geology,
(October, 1984), pp 1-8.
Fink, C.G. and Putnam, G.L., Bromine process for Gold Ores, U.S. Patent No.
2,283,198 (1942).
Fink, C.G. and Putnam, G.L., The action of sulphide ion and of metal salts on
the dissolution of gold in cyanide solutions, Trans. Soc. Min. Engrs.,
AIME, Vol. 187, (1950), pp. 952-955.
Finkelstein, N.P., The Chemistry of the Extraction of Gold from its ores, In:
Gold Metallurgy in South Africa, Ed: Adamson, R.J., (Cape & Transvaal
Printers Limited, Cape Town, 1972), pp. 284-351.
Fleming, C.A., Some aspects of the chemistry of carbon-in-pulp and resin-in-

pulp processes, In: Carbon-in-Pulp Technology for the Extraction of
Gold, Aus IMM, Parkville, Australia, (1982), pp. 415-440.
Fleming, C.A. and Nicol, M.J., Alternative processes to filtration: Carbon-in-

pulp and resin-in-pulp in the Metallurgical Industry, In: Hydrometallurgy
'81, Soc. Chem. Industry, London, (1981), pp. C2/1 - C2/16
296
Foo, J.R., Bath, M.D., Ismay, A. and Canterford, J.H., New gold processing
technologies: An Engineer's perspective, World Gold '89, Proc. of Joint
Symp. AIME-Aus IMM, Reno, Nevada, (September, 1989), p. 233.
Froning, M.H., Shanley, M.E. and Verink, E.D. Jr., An Improved Method for
Calculation of Potential-pH Diagrams of Metal-Ion-Water Systems by
Computer, Corrosion Science, 16, (1976), pp. 371-377.
Frumkin, A.N. and Tedoradse, G., Dokl. Akad. Nauk SSSR, 118, 530 (1958); Z.
Electrochem. 62, (1958), p. 251.
Gabe, D.R. and Robinson, DJ., Mass transfer in a rotating cylinder cell - 1,
Electrochim. Acta. 17 (1972), pp. 1121-1129.
Gabra, G., A kinetic study of the leaching of gold from pyrite concentrate using
acidified thiourea, In: PRECIOUS METALS: Mining, Extraction and
Processing, Eds: Kudryk, V., CoITigan, D.A., Liang, W.W. Proc. TMS-
AIME Int. Symp., Los Angeles, California, February, 27-29, 1984, pp.
145-170.
Galus, Z. and Adams, R.N., Anodic Oxidation Studies of N, N-Dimethylaniline.

II. Stationary and Rotated Disk Studies at Inert Electrodes, J. Am. Chem.
Soc., 84, (1962), pp. 2061-2065.
Gilmore, A.J., A proposed use for ion exchange in gold cyanidation, Can. Min.
J., 88 (1967), pp. 63-65.
Gladyshev, P., Enikeev, R.S., Zakharchuk, N.F. and Petrova, L.P., Zh. Prikl.
Khim. 43 (1970), p. 994.
Green, B.R., Schwellnus, A.H. and Kotze, M.H., Recent developments in resins
for the extraction of gold, GOLD 100, Proc. Int. Conf. on Gold, Vol. 2,
S. Afr. Inst. Min. & Metall.(1986), pp. 321-334.
Groenwald, T., The dissolution of gold in acidic solutions of thiourea,

Hydrometallurgy, Vol. 1, (1976), pp. 277-290.
297
Groenwald, T., Potential applications of thiourea in the processing of gold, J.S.

African Inst. Min. Met., (June 1977), pp. 217-223.
Gupta, A. and O'Neil, G.R., Concentration of gold and carbon contaminated

residue dumps in the Kalgoorlie Area, In: Carbon-in-pulp Technology for
the Extraction of Gold, Aus IMM., Parkville, Australia, (1982), pp. 99-
120
Gupta, C.K., Mukherjee, T.K., Hydrometallurgy in extractive processes, Vol. II,

(CRC Press Inc., Florida, 1990).
Habashi, F., Principles of Extractive Metallurgy, Vol. 2, Hydrometallurgy,

(Gordon and Breach, New York, 1970), Chapter 2.
Habashi, F., The theory of cyanidation, Trans. Soc. Engrs, AIME, 235 (1966),
pp. 236-239.
Habashi, F., Kinetics and mechanism of gold and silver dissolution in cyanide
solution, Mont. Bureau. Mines, Geol. Bull. No. 59, (1967).
Haber, F., Z. Physik. Chem., 32, 193, (1900), p. 271.
Halbe, D., Electrowinning cell efficiency, Custom Equipment Corp., Salt Lake
City, Utah, USA. (1984).
Hamdo1f, C.J., Precipitation of lead and silver from brine solutions by metallic
iron, Proc. Aust. Int. Min and Met., 199 (1961), p. 19.
Harrison, J.A. and Thompson, J., The electrodeposition of precious metals,

Electrochimica Acta., 18 (1973), pp. 829-834.
Hartung, R. Cyanide and Nitriles, Patty's Industtial Hygiene and Toxicity, Eds:
Clayton, G.D. and Clayton, F.E., (John Wiley and Son, New York, 1982)
Vol 2C, pp. 4845-4900.
298
Hausen, D.M. and Bucknam, C.H., Study of preg-robbing in the cyanidation of

carbonaceous gold ores from Carlin, Nevada, In: Applied Mineralogy,
Proc. 2nd. Int. Congress on Applied Mineralogy (1985), pp. 833-858.
Heinen, H.J. and Potter, B., Experimental leaching of gold from mine waste,
Bureau Mines, RI 7250, (1969), p. 5.
Heinen, H.J., Peterson, D.G. and Lindstrom, R.E., Silver extraction from
., Metall. Soc. AIME, New
marginal resources, 104th Annual Meeting,
York, (February 16-20, 1975), p. 14.
Heinen, H.J., Peterson, A.G. and Lindstrom, R.E., Gold desorption from
activated carbon with alkaline alcohol solutions, World Mining and
Metals Technology, Vol. 1, (AIME, New York, 1976), pp. 551-564.
Heinen, H.J., Peterson, D.G. and Lindstrom, R.E., Processing of gold ores using
heap leach-carbon adsorption methods, Bureau Mines RI 8770, (1978), p.
21.
Heinen, H.J., McClelland, G.E. and Lindstrom, R.E., Enhancing percolation

rates in heap leaching of gold-silver ores, Bureau Mines RI 8388, (1979),
p. 20.
Hinman, B.C., U.S. Patent No. 545,890 and 545,891 (1895).
Hirako, M. and Kikinzoku Kogyo, T., The new gold purification process,
Precious Metals News and Review, 14:(7), (1990), pp. 217-223.
Hiskey, J.B., Thiourea leaching of gold and silver-Technology update and

additional applications, In: Practical Hydromet '83, 7th Annual
Symposium on Uranium and Precious Metals, Ed: Chlumsky, G.F.,
(SME-AIME, 1984), pp. 95-99.
Hiskey, J.B., and Atluri, V.P., Dissolution Chemistry of Gold and Silver in
different Lixiviants, Mineral Processing and Extractive Metallurgy
Review, Vol. 4, (Gordon and Breach Science Publishers Inc., U.K.,
1988), pp. 95-134.
299
Hiskey, J.B. and Qi, P.H., Leaching and electrochemical behaviour of gold in
iodide solutions, Part I: Dissolution kinetics, AIME Preprint No. 90-112,
Presented at SME Annual Meeting, Salt Lake City, USA, (1990).
Hiskey, J.B. and Qi, P.H., Leaching behaviour of gold in iodide solutions,
World Gold '91, (Aus IMM, Melbourne, 1991), pp. 115-120.
Hisshion, R.J. and Waller, C.G., Recovering gold with thiourea, Min Mag.,
(Sept. 1984), pp. 237-243.
Ho, T.T.K., M. Eng. Thesis, Monash University, Melbourne, Australia, (1973).
Hope, G.A., Ritchie, I.M. and Wajon, J.E., The effect of oxide films on
cementation reactions, Trends in electrochemistry, (Plenum Press),
(1976), p. 341.
Hormick, R.P., Gold reclamation process, US. Patent No. 3,778,252 (1973).
Howarth, J., Dadgar, A., McKeown, J.A., Sanders, B.M. and Sergent, R.H.,
Electrochemical regeneration of bromine in a gold ore leach/recovery
circuit, EPD Congress '91, Ed: Gaskell, D.R., (TMS, New Orleans, LA.,
1991), pp. 709-718.
Hughes, J., Ritchie, I.M. and Singh, P., The silver(l)/copper reaction m
acetonitrile - water mixtures, Aust. J. Chem., 37, (1984), pp. 903-910.
Huiatt, J.L., Kerrigan, J.E., Olson, F.A. and Potter, G.L., Cyanide from mineral
processing, Proc. of Workshop Sponsored by Nat. Sci. Foundation,
USBM & Industry, Salt Lake City, USA, (1983).
Hussey, S.J., Salisburry, H.B. and Potter, G.M., Carbon-in-pulp gold adsorption
from cyanide leach slurries, RI 8368, US. Bureau of Mines, (1979).
Ingraham, T. and Kerby, R., Kinetics of cadmium cementation on zinc m

buffered sulphate solutions, Trans. TMS/AIME, 245, (1969), pp. 17-21.
300
Jackman, I. and Sarbutt, K., The recovery of gold from a telluride concentrate,
Proc. Randol Gold Forum Squaw Valley'90, (Randol Int. Ltd., Golden,
CO, USA, 1990), pp. 55-58.
Jackson, E., Hydrometallurgical Extraction and Reclamation, (Ellis Horwood

Limited, West Sussex, England, 1986), p. 25.
Jha, M.C. and Kramer, M.J., Recovery of gold from arsenical ores, Precious
Metals: Mining, Extraction, and Processing, AIME, New York, (1984),
pp. 337-365.
Jha, M.C., Recovery of gold and silver from cyanide solutions: A comparative
study of various processes, Proc. 1st. Int. Symp. on Precious Metals
Recovery, Reno, Nevada, (1984).
Jolles, Z.E. (Ed.), Bromine and its compounds, (E. Benn, London, 1966), p.
940.
Julian, H.F. and Smart, E., Cyaniding gold and silver ores, 2nd edition, (Charles
Griffin, London, 1921).
Kameda, M., Part I: Fundamental studies on solution of gold in cyanide

solutions; Part II: Equations of reactions and effects of cyanide strength
and other variables on dissolution rate, Sci. Rep. Res. Inst. Tohoku Univ.,
Ser. A. Vol. 1, (1949), p. 230.
Kappesser, R., Comet, I. and Greif, R., J. Electrochem. Soc. 118 (1971), p.
1957.
Kenna, C.C., Ritchie, I.M. and Singh, P., The cementation of gold by iron from
cyanide solutions, Hydrometallurgy, 23 (1990), pp. 263-279.
Kerley, B.J., Recovery of precious metals from difficult ores, US. Patent No.
4,269,622 (May 26, 1981).
Kerley, B.J., Recovery of precious metals from difficult ores. US. Patent No.
4,369,061 (1983).
301
Kirk, D.W. and Foulkes, F.R., A potentiometric study of metals affecting

precious metal recovery from alkaline cyanide solutions, J. Electrochem.
Soc., Electrochem. Sci. & Tech., (1984), pp. 760-769.
Kolthoff, I.M. and Lingane, J.J., Polarography, 2nd edition, (Interscience, New
York, 1952), Vol. 2.
Kontopoulos, A. and Stefanakis, M., Process selection for the Olympias

refractory gold concentrate, Precious metals '89, Eds: Jha, M.C., Hill,
S.D. and El Guindi, M. (AIME-TMS, 1989), pp. 179-210.
Kudryk, V. and Kellogg, H.H., Mechanism and rate-controlling factors in the

dissolution of gold in cyanide solutions, Journal of Metals, 6, (1954), pp.
541-548.
La Brooy, S.R., Alternative reagents: THIOUREA, In: Carbon-In-Pulp and Gold

Processing technology, Eds: Avraamides, J., La Brooy S.R., Muir, D.M.,
AMF Workshop Course, 613/89, (Feb., 1989).
Latimer, W.M., The Oxidation States of the Elements and their potentials in
Aqueous Solutions, 2nd edition, (Prentice Hall, New York, 1952).
Law, H.H., A new process for making potassium gold cyanide from gold
particles, In: Precious metals '82, Ed: El Guindy, M.I., (Pergamon, 1982)
pp. 169-184.
Leblanc, R., Precipitation of gold from cyanide solution by zinc dust, Can. Min.
J. 63, Parts I, II, III, April, May, June, (1942).
Lee, E.C., Lawson, F. and Han, K.N., Precipitation of cadmium with zinc from
dilute aqueous solutions: I - Under inert atmosphere, Trans. IMM. Vol.
84, (1975), C87-91; II - Under oxygen-containing atmospheres, Trans.
IMM. 84 (1975), pp. Cl49-153.
Levich, V.G., Acta Physicochim, URSS, 17, (1942), p. 257.
Levich, V.G., Physicochemical Hydrodynamics, Prentice-Hall, Eaglewood

Cliffs, N.J., (1962).
302
Liddell, D.M., Handbook of Non-ferrous Metallurgy, Vol. 2, Recovery of

Metals, (McGraw-Hill, New York, 1945), 2nd edition, p. 520.
Loveday, B.K., The role of electrochemistry in the extraction of gold, Mintek

Review No. 4, Ed: Pingram, G.J., (1986), pp. 23-31.
MacDougall, G.J., Hancock, R.D., Nicol, M.J., Wellington, D.I. and

Copperthwaite, R.G., The mechanism of the adsorption of gold cyanide
on activated carbon, J. S. Afric. Inst. Min. & Metall., 80 (9), (1980), pp.
344-356.
MacKinnon, D.J. and Ingraham, T.R., Can. Met. Quart. 9 (1970), p. 443.
MacKinnon, D.J., Ingraham, T.R. and Kerby, R., Can. Metall. Quart., 110,
(1971), p. 165.
MacKinnon, D.J., Recovery of bismuth from HCl leach solutions by

cementation on iron, Department of Energy, Mines and Resources,
Ottawa, Research Report R252, (September 1972), p. 18.
Maloy, J.T., Voltammetry: Factors affecting the shape of current-potential

curves, J. Chem. Educ., No. 4, (April, 1983), pp. 285-289.
Marchant, P.B., Broughton, L.M. and Lake, M.J., Comparative analysis of

cyanidation and acidothioureation, Proc. Randol Gold Forum -
Scottsdale, (Randol Int. Ltd., Golden, CO, USA, 1988), pp. 171-178.
Marsden, J. and House, I., The Chemistry of Gold Extraction, (Ellis Horwood
Limited, West Sussex, England, 1992).
Marsden, J.O., Practical aspects of the precipitation of gold from high

temperature carbon eluates, Proc. Randol Gold Forum-Squaw Valley'90,
Randol Int. Ltd., Golden, CO, USA, (1990), pp. 289-294.
Marsden, J.O. and Fuerstenau, M.C., Comparison of MeITill-Crowe

precipitation and carbon adsorption for precious metals recovery. In:
XVIII Int. Min. Proc. Congress, (Aus IMM, Sydney, Australia), Vol. 5,
May 23-28, 1993, pp. 1189-1194.
303
McArthur, J.S., Forrest, R.W. and Forrest, W., Process of obtaining Gold and
Silver from Ores, British patent No.14, 174 (1887), U.S. Patent No. 403,
202 418, 137 (1889).
McClelland, G.E. and Eisele, J.A., Improvements in heap leaching to recover

silver and gold from low-grade resources, Bureau Mines RI 8612, (1982),
p. 26.
McGrew, K.J. and Murphy, J.W., Iodine leach for the dissolution of gold, US.
Patent No. 4,557, 759 (1985).
McIntyre, J.D.E. and Peck, W.F., Electrodeposition of gold; depolarisation

effects of heavy metal ions, J. Electrochem. Soc. 123 (1976), pp. 1800-
1813.
McNulty, T., A Metallurgical history of Gold, American Mining Congress,

September 20, (1989), San Francisco.
Mensah-Biney, R., Hepw011h, M.T. and Reid, K.J., Loading characteristics of

gold-bromo species onto weak-base anion exchange resin, PAZ-4, EPD
Congress '91, Ed: Gaskell, D.R., (New Orleans, LA., TMS, 1991), pp.
687-707.
Miller, J.D. and Beckstead, W., Surface deposit effects in the kinetics of copper
cementation by iron, Trans. TMS/AIME, 4, (1973), p. 1967.
Miller, J.D., Cementation, In: Rate processes of Extractive Metallurgy, Eds:

Sohn, H.Y and Wadsworth, M.E., (Plenum press, 1979), pp. 197-241.
Miller, J.D., Solution concentration and purification, In: Metallurgical Treatise,

Ed: Tien, J.K. and Elliot, J.F., AIME, (1981), pp. 95-116.
Miller, J.D., The significance of electrochemistry in the analysis of mineral

processing phenomena, In: Electrochemistry Current and Potential
Applications, Eds: Tran, T. and Skyllas-Kazacos, M., Proc. 7th. Aust.
Electrochem. Conf., (1988), pp. 122-132.
304
Miller, J.D., Wan, R.Y. and Parga, J.R., Characterization and electrochemical
analysis of gold cementation from alkaline cyanide solution by suspended
zinc particles, Hydrometallurgy, 24 (1990), pp. 373-392.
Moeller, T., Bailer, J.C. (Jnr), Kleinberg, J., Guss, C.O., Castellion, M.E. and
Metz, C., Chemistry with Inorganic Qualitative Analysis, 3rd edition,
(Harcourt Brace Jovanovich Publishers, Orlando, Florida, 1989).
Mooiman, M.B. and Miller, J.D., The solvent extraction of gold from
aurocyanide solutions, Proceedings of ISEC '83, Denver, Colorado,
(1983).
Moussoulos, L., Potamianos, N. and Kontopoulos, A., Recovery of gold from

arseniferrous pyrite cinders by acidic thiourea leaching, In: PRECIOUS
METALS: Mining, Extraction, and Processing, Eds: Kudryk, V.,
Corrigan, D.A. and Liang, W.W., Proc. TMS-AIME. Int. Symposium,
Los Angeles, California, (Feb. 27-29, 1984), pp. 323-336.
Muhtadi, O.A., Metal extraction (Recovery system), In: Introduction to

Evaluation, Design and Operation of Precious Metal Heap Leaching
Projects, Ed: Vanzyl, DJ.A., Hutchison, I.P.G., and Kiel, J.E., SME-
AIME, Littleton, Colorado, (1988), pp. 124-136.
Muir, D.M., Recovery of gold from cyanide solutions using activated carbon - a
review, Proc. C.I.P. Technology for the Extraction of Gold Symposia,
No. 32, (Aus IMM, Melbourne), (1982), pp. 7-22
Muir, D., Recent advances in gold metallurgy, Research and Development in

Extractive Metallurgy, (Aus IMM, 1987), pp. 1-10.
Muir, D.M., Principles of leaching gold with cyanide and alternative reagents,
In: Carbon -In-Pulp and Gold Processing Technology-AMF Workshop
Course 613/89, Eds: Avraamides, J., La Brooy, S.R. and Muir, D.M.,
(Feb. 13-17, 1989).
Muir, D., La Brooy, S. and Cao, C., Recovery of gold from copper-bearing ores,
In: World Gold'89, Proceedings of Joint Symposium AIME-Aus IMM,
Reno, Nevada, (Sept., 1989), p. 365.
305
Murphy, J.W. and Wyo, L., Electrolytic process for the simultaneous deposition
of gold and replenishment of elemental iodine, US. Patent No. 4,734,171
(1988).
Mussini, T. and Faita, G., Bromine, In: Encyclopaedia of Electrochemistry of

the elements, Ed: Bard, A.I., Vol. 1, (Marcel Dekker Inc., New York,
1973) Chapter 1-2, pp 57-90.
Nadkarni, R.M. and Wadsworth, M.E., Kinetic study of copper with iron,
Advances in Extractive Metallurgy, IMM, (1968), pp. 918-941.
Naumov, G.B., Ryzhenko, B.N. and Khodakovsky, I.L., Handbook of

Thermodynamic Data, (Moskow: Atomizdat, 1971). Translated from the
Russian by the U.S. Geological Survey, NTIS PB-226, (1974), p. 722.
Naybour, R., The effect of electrolyte flow on the morphology of zinc

electrodeposited from aqueous alkaline solution containing zincate ions,
J. Electrochem. Soc. Electrochem. Technol. 116 (1969), p. 520.
Nelson, J.H., MacDougall, J.J., Eaglin, F.G., Freeman, D.W., Nadler, M. and
Hendrix, J.L., Characterization of Carlin-type gold ore by Photoacoustic,
Raman, and EPR Spectroscopy, Applied Spectr., 36, (1982), pp. 574-576.
Nernst, W. and Merriam, E.S., Z. Physik. Chem., 52, (1905), p. 235.
Neufeld, A.H., Contributions to the Chemistry of bromine, Can. J. Res., 14,

(1936), p. 160.
Nicol, M.J., Schaich, E., Balestrn, P. and Hedegus, H., A modern study of the
kinetics and mechanism of the cementation of gold, J. S. Afri. Inst. Min
& Metall. (Feb. 1979), pp. 191-198.
Nicol, M.J., The anodic behaviour of gold, Gold Bulletin, Vol. 13, No. 2, (Part
I) (1980), pp. 46-55; Part IT: Oxidation in alkaline solutions, Vol. 13, No.
7 (1980), pp. 105-111.
Nicol, M.J ., The anodic dissolution of gold, Part I: Oxidation in acidic solutions,
Gold Bulletin 13, (1980), pp. 46-55.
306
Nicol, M.J., Fleming, C.A. and Paul, R.L., The chemistry of gold extraction, In:
The Extractive Metallurgy of Gold, Ed: Stanley, G.G., S. Afr. Inst. Min
& Metall, (1987), pp. 831-905.
Oo, M.T., Study on the recovery of gold from cyanide solutions, MSc. Thesis,
U.N.S.W., School of Mines, Kensington, Australia, (1990).
Oo, M.T. and Tran, T., The effect of lead on the cementation of gold by zinc,
Osseo-Asare, K. and Brown, T.H., A Numerical Method for Computing

Hydrometallurgical Activity-Activity Diagrams, Hydrometallurgy, 4
(1979), pp. 217-232.
Osseo-Asare, K., Xue, T. and Ciminelli, V.S.T., Solution Chemistry of Cyanide

Leaching Systems, In: PRECIOUS METALS: Mining, Extraction and
Processing, Eds: Kudryk, V., Corrigan, D.A., Liang, W.W., (Proc. TMS-
AIME Int. Symposium Los Angeles, California, February 27-29, 1984a)
pp. 173-198.
Osseo-Asare, K., Afenya, P.M. and Abotsi, G.M.K., Carbonaceous matter in

ores: isolation, characterization and adsorption behaviour in aurocyanide
solutions, In: PRECIOUS METALS: Mining, Extraction and Processing,
Ed: Kudryk, V.V., Corrigan, D.A. and Liang, W.W., TMS-AIME, Los
Angeles, California, (February 27-29, 1984b), pp. 125-144.
Pachenko, A., Kakovskiy, I., Shamis, L. and Khmelnitskaya, 0., Dissolution

kinetics of gold, silver and their alloys in aqueous thiourea, Izv. Akad
Nauk. SSR, Met. 6, (1975), pp. 32-37.
Parga, J.R., Wan, R.Y. and Miller, J.D., Zinc dust cementation of gold from
alkaline cyanide solutions - analysis of Merrill-Crowe plant data, Min. &
Met. Proc. 5, (1988), pp. 170-176.
Paul, R.L., The role of electrochemistry m the extraction of gold, Mintek

Review No. 4, (1986), pp. 24-31.
307
Paul, R.L. and Howarth, D., Cementation of gold onto zinc from concentrated
aurocyanide electrolytes, Proc. of Int. Conf. on Gold, GOLD 100, Ed:
Fivaz, C.E., S. Afr. Inst. Min & Metall., Johannesburg, (1986), Vol. 2,
pp. 157-172.
Paul, R.L., Filmer, A.O. and Nicol, M.J., The recovery of gold from
concentrated aurocyanide solutions, In: Hydrometallurgy, Research,
Development and Plant Practice, Proc. 3rd. Int, Symp. Hydromet. 112th
AIME Meeting, Eds: Osseo-Asare, K. and Miller, J.D., TMS-AIME,
New York, (1983), pp. 689-704.
Pesic, B. and Sergent, R.H., The rotating disc study of gold dissolution with
Geobrom™ 3400, Refractory Gold, Silver and Precious Metals
Processing, TMS-AIME, Anaheim, California, (February 18-22, 1990),
pp.355-391.
Pesic, B. and Sergent, R.H., The rotating disc study of gold dissolution with
bromine, EPD Congress '91, Ed: Gaskell, D.R., Proc. of TMS-AIME
Conference, New Orleans, (February, 18-21, 1991), pp. 613-636.
Pesic, B. and Storhok, V.C., Adsorption of gold on activated carbon in bromide

solution, EPD Congress '91, Ed: Gaskell, D.R., (New Orleans, LA.,
TMS, 1991), pp. 591-611.
Pesic, B., The rotating disc study of gold dissolution with sodium bromate, EPD
Congress '92, Ed: Hager, J.P. Proc. of TMS-AIME Conference, (1992), p.
355.
Pesic, B., Smith, B.D. and Sergent, R.H., Dissolution of gold with bromine from
refractory ores preoxidized by pressure oxidation, In: Proc. EPD '92
Congress, Ed: Hager, J., (TMS-AIME, 1992), pp. 223-238.
Pizarro, R.S. and Antonio, The carbon-in-pulp plant of the Mesbate Gold
Operations, Phillippines, Proceedings of Asian Mining '81 Conference,
(1981), pp. 213-220.
Plaksin, I.N. and Kozhukhova, M.A., The solubility of gold and silver m
thiourea, Compt. Rend. Acad. Sci. U.S.S.R. 31, (1941), pp. 671-674.
308
Plaksin, I.N., Suvorovskaya, N.A. and Bunikova, O.K., Precipitation of metals

from solutions by metals, Otdel, Telch. Nauk., (1948), pp. 131-138.
Plaksin, I.N. and Bessonov, S.V., Influence of flotation reagents on the

hydrometallurgical processing of ore concentrates, Invest. Akad. Nauk,
S.S.S.R. Otdel. Tekj., Naulc, (1948), pp. 883-888.
Plaksin, I.N. and Budnikova, O.K., Oxidation-reduction processes during

precipitation of metals from cyanide solutions, Otdel: Tekh. Nauk.,
(1951), pp. 267-272.
Plaksin, I.N. and Kozhukhova, M.A., Dissolution of gold and silver in solutions
of thiourea, Sb. Nauchn. Tr. Inst. Tsvetn. Metal 33, (1960), pp. 107-119.
Potter, G.M., Recovery of gold from stripping waste and ore by percolation
cyanide leaching, Bureau Mines, TPR 20, (1969), p. 5.
Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous Solutions

(Pergamon Press, New York, 1966).
Power, G., Cementation Reactions, Ph. D. Thesis, University of Western

Australia, Nedlands, Western Australia, (1975).
Power, G.P. and Ritchie, I.M., Metal displacements reactions, Modem aspects
of Electrochemistry, Plenum Press, London, Vol. II, (1975), pp. 119-250.
Power, G.P. and Ritchie, I.M., A contribution to the theory of cementation

(metal displacement) reactions, Aust. J. Chem., 29, (1976), pp. 699-709.
Preisler, P.W. and Berger, L., Oxidation-Reduction Potentials of Thiol-Dithio

Systems: Thiourea-Formamidine Disulfide, J. Am. Chem. Soc. 69,
(1947), pp. 322-325.
Price, D., lddon, B. and Wakefield, B.J., (Eds), Bromine Compounds:

Chemistry and Applications, (Elsevier Science Publishers B.V.,
Amsterdam, 1988).
309
Puddephatt, R.J., The Chemistry of Gold, Monograph 16, (Elsevier Scientific

Publishing Co., Amsterdam, 1978).
Putnam, G.L., Chlorine as a solvent in gold hydrometallurgy, Eng. and Min. J.

145 (3), (1944), pp. 70-75.
Puvvada, G. and Tran, T., The cementation of Ag(I) ions from sodium chloride
solutions onto rotating copper and zinc discs, Proc. Int. Conf. Ext.
Metallurgy of Gold and Base Metals, Eds: Misra, V.N., Halbe, D. and
Spottiswood, D.J., Kalgoorlie, WA, Oct. 26-28, (1992), (Aus IMM,
Parkville, Victoria, Australia), pp. 361-367.
Pyper, R.A. and Hendrix, J.L., Extraction of gold from finely disseminated gold
ores by use of acid thiourea solution, Extraction Metallurgy '81, IMM
Symposium, London, Sept. 21-23, (1981), pp. 57-75.
Radtke, A.S. and Scheiner, B.J., Studies on hydrothermal gold deposition I.

Carlin Gold Deposit, Nevada: The Role of Carbonaceous Materials in
Gold Deposition, Econ. Geol. 65, (1970), pp. 87-102.
Ranz, W. and Marshall, W., Evaporation from drops, Chem. Eng. Prog., 48
(1952), p. 141.
Raub, J., Precious metal alloy electrodeposits, In: PRECIOUS METALS:

Mining, Extraction and Processing, Ed: Kudryk, V., Co1Tigan, D.A. and
Liang, W.W., Proc. Int. Symp. Los Angeles, California, (February 27-29,
1984), pp. 253-260.
Raudsepp, R. and Allgood, R., Thiourea leaching of gold in a continuous pilot

plant, Proc. of lnt. Symp. on Gold Metallurgy, Ed: Salter, R.S.,
Wyslouzil, D.M. and McDonald, G.W., (1987), pp. 87-96.
Reid, K.J. and Mensah-Biney, R., Gold bromine loading characteristics on

selected adsorbents, Randol Perth Int. Gold Conf., Randol Perth, Western
Australia, Oct. 28-Nov. 1, (1988), pp. 306-309.
310
Reid, K.J., Bereuter, L.W., Mensah-Biney, R.K. and Sergent, R.H., Gold
recovery from bromine solutions using ion exchange resins, In: Precious
and Rare Metals, Eds: Torma, A.E. and Gundiler, I.H., April 6-8, (1988),
Albuquerque, New Mexico, (Elsevier, New York, 1989), pp. 307-316.
Rich, R.L. and Taube, H.J., The Induced exchange of er and Auc4- evidence
for Au(II), J. Phys. Chem., 58, (1954), pp. 6-11.
Rickard, R.S. and Fuerstenau, M.C., Electrochemical investigation of copper

cementation by iron, Met. Trans., 242, (1968), pp. 1487-1493.
Riddiford, A.C., The rotating disc system, Advances in Electrochemistry and

Electrochemical Engineering, Vol. 4, (1966), pp. 47-116.
Riddiford, A.C., The temperature coefficient of heterogeneous reaction, Journal

of Physical Chemistry, London, 56 (June, 1952), pp. 745-748.
Rieger, P.H., Electrochemistry, (Prentice-Hall International, Eaglewood Cliffs,

N.J., 1987), p. 508.
Ritchie, I.M. and Staunton, W.P., Electrochemical investigations and electron

microscopy of silver(l)/copper cementation reaction, Proc. Int Symp.
electrochemistry in mineral and metal processing, Eds: Richardson, P.E.,
Srinivasan, S. and Woods, R., Electro. Soc., (1984), pp. 486-500.
Robins, R.G. and Stillman, R.W., DIASTAB, Version 4.02 User's Manual,
(1989).
Rose, T.K. and Newman, W.A.C., The Metallurgy of Gold, 7th edition (Charles
Griffin, London, 1937), p. 573.
Ross, J.R., Salisbury, H.B. and Potter, G.M., Pressure stripping of gold from
activated carbon, Annual Conference Soc. Min. Eng. AIME, Chicago,
IL., February 26 -March I, (1973), p. 14.
Russ, R., Z. Physik. Chem., 44, 641 (1903).
Salomen, E., Z. Physik. Chem., 24, 55 (1897).

311
Salomen, E., Z. Physik. Chem., 25,365 (1898).
Sandberg, R.G. and Huiatt, J.L., Recovery of silver, gold and lead from a
complex ore using ferric chloride, thiourea and brine leach solutions, US
Bureau of Mines, RI 9022, (1986).
Sceresini, B.J.S., The design, construction, and operation of a 500,000 tonnes

per annum Carbon-in-Pulp Plant at Kambalda, Western Australia, In:
Carbon-in-Pulp Technology for the Extraction of Gold, Aus IMM,
Parkville, Australia, (1982), pp. 237-278.
Schaich, E. and Nicol, M.J., An electrochemical investigation of copper

cementation on iron, Trans. IMM, Vol. 87, (1978), p. Cl 6.
Scherbakov, O.K. and Kakovskii, I.A., A study of the kinetics of co-

precipitation of gold, silver and copper from cyanide solutions, Metally,
Vol. 8, No. 2, (1967), pp. 10-14.
Schmid, G.M. and Curley-Fiorino, M.E., Gold, In: Encyclopaedia of the

Electrochemistry of the elements, Ed: Bard, A.J., Vol. IV (Mai-eel Dekker
Inc., New York, 1975), Chapter IV-3, pp. 87-178.
Schmid, G .M., Standard Potentials in Aqueous Solutions, In: Gold, Eds: Bard,
A.J., Parsons, R., Jordan, K., (Marcel Dekker, 1985), pp. 313-320.
Schulze, R.G., New aspects in thiourea leaching of precious metals, Journal of

Metals (1984), pp. 62-65.
Sehic, 0., An update on the K-Process, Proc. of Randol Perth, Int. Gold
Conference, (October, 1988), pp. 184-186.
Sergent, R.H., The use of brominated hydantoins for gold leaching, Randol
Gold Forum '88, Scottsdale, AZ, (January 23-24, 1988), pp. 167-169.
Sergent, R.H., Dadgar, A., Shin, C.C. and Reid, K.J., A comparison of bromine
and cyanide leaching for refractory gold concentrate, In: Precious and
Rare Metals, Eds: Torma, A.E. and Gundiler, I.H., (April 6-8, 1988),
Albuquerque, New Mexico, (Elsevier, New York, 1989), pp. 149-156.
312
Seymour, D., Ramadorai, G., Traczyk, F. and Hill, D., Rapid oxidation of
refractory gold-bearing ores by intense flash chlorination at Newmont
Gold Co., In: Precious metals '89, Ed: Jha, M.C., Hill, S.D., El Guindi,
M., (TMS-AIME, 1989), p. 165.
Shaeffer, C.A., Process of Extracting Gold and Silver from their Ores, U.S.
Patent No 267, 723 (1882).
Shoemaker, R.S., Gold, In: PRECIOUS METALS: Mining, Extraction and

Processing, Eds: Kudryk, V., Corrigan, D.A., Liang, W.W., Proc. TMS-
AIME lnt. Symposium, Los Angeles, California, February 27-29, 1984)
pp. 3-10.
Smith, R.E., Thermodynamic and kinetic properties of the electrochemical cell,

J. Chem. Educ., (1983), Vol. 60, No. 4, pp. 299-301.
Stewart, L.A., Gold ore processing today, International Mining (1984).
Straumanis, M.E. and Fang, C.C., The structure of metal deposits obtained by
electrochemical displacement upon zinc, J. Electrochem. Soc., 98,
(1951), pp. 9-13.
Strickland, P.H. and Lawson, F., Cementation of copper and zinc from dilute
aqueous solutions, Proc. Aus IMM, No. 236, (Dec. 1970), pp. 25-34.
Stiickland, P.H. and Lawson, F., The cementation of metals from dilute aqueous
solution, Proc. Aus IMM, No. 237, (1971), pp. 71-78.
Sti·ickland, P.H., Ph.D. Thesis, Monash University, Australia, (1972).
Strickland, P.H. and Lawson, F., The measurement and interpretation of

cementation rate data, Int. Symp. on Hydrometallurgy, SME,
TMS/AIME, (1973), pp. 293-330.
Tafel, J., Z. Physik. Chem., (1905), Vol. 50, pp. 641-712.
Tarta.ru, S., Dissolution of gold in thiourea solution, Rev. Roum. Chim., 13 (7),
(1968), pp. 891-897.
313
Tozawa, K., Invy, Y. and Umetsu, Y., Dissolution of gold m ammoniacal

thiosulphate solution, (TMS-AIME, 1981), pp. A81-25.
Tran, T., Davis, A. and Song, J. K., Extraction of gold in halide media, In: Proc.
Int. Conf. Extractive Metallurgy of Gold and Base Metals, Eds: Misra,
V.N., Halbe, D. and Spottiswood, D.J., Kalgoorlie, Western Australia,
Oct. 26-28, (1992), (Aus. IMM), pp. 323-327.
Tsa, C.S. and Iofa, Z.A., Doklady Akad. Nauk SSSR, 131, (1960), p. 137.
Turnbull, A.G., A general computer program for the calculation and plotting of
thermodynamic stability diagrams, Joint AusIMM/UNSW Extractive
Metall. Symp., Sydney, (1977), p. 10.
Turnbull, A.G., A general computer program for the calculation of chemical

equilibria and heat balances, CALPHAD, 7, (1983), pp. 137-147.
Turnbull, A.G. and Wadsley, M.W., Predominance-area diagrams by computer

methods, CSIRO Division of Mineral Chemistry, Research Report,
(1984), pp. 108-110.
Tyurin, N.G., Akad. Nauk. SSSR Izv., Ser. Geol., 8 (1966).
Urban, M.R., Urban, J. and Lloyd, P.J.D., The adsorption of gold from cyanide
solutions onto constituents of the reef and its role in reducing the
efficiency of the process, Chamber of Mines, South Africa, Project No.
503/67, Research Report No. 32/73, (1973).
Van Leeuwen and Sangster, B., The toxicology of bromide ion, Vol. 18, Issue 3
(1987).
Vetter, K.J., The determination of electrode reaction mechanism by the

electrochemical reaction orders, In: Trans. Symp. Electrode Processes,
Ed: Yeager, E., (John Wiley and Sons, Inc., New York, 1959), pp. 47-65.
Vogel, A.I., VOGEL'S Textbook of Quantitative Chemical Analysis, 5th edition,

Revised by: Jeffrey, G.H., Bassett, J., Mendham, J. and Denney, R.C.,
(Longman Scientific & Technical, Essex, CM20 2JE, England, 1989).
314
Von Hahn, E.A. and Ingraham, T.R., Kinetics of Pd(II) cementation on copper
sheet in perchlorate solutions, Trans. TMS/AIME, 236, (1966), pp. 1098-
1103.
Von Hahn, E.A. and Ingraham, T .R., Kinetics of silver cementation on copper in
perchloric acid and alkaline cyanide solutions, Trans. TMS/AIME, 239,
(1967),pp. 1895-1905.
Von Hahn, E.A. and Ingraham, T.R., Kinetics of silver cementation on zinc in
alkaline cyanide and perchloride acid solutions, Can. Met. Quart., 7,
(1968), pp. 15-26.
Von Michaelis, H., The prospects for alternative leach reagents, Eng. Min. J.,
(June, 1987), pp. 42-46.
Wadsworth, M., Reduction of metals in solution, Extractive Metallurgy Lecture,

Trans. TMS/AIME 245, (1969), pp. 1381-1394.
Wadsworth, M.E. and Miller, J.D., Hydrometallurgical processes, Rate

Processes of Extractive Metallurgy, Plenum Press, (1979), p. 133.
Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Halow, I., Bailey,
S.M., Chumey, K.L. and Nuttal, R.L., The NBS tables of Chemical
thermodynamic properties, Journal of Physical and Chemical Reference
data Vol. 11, (1982) Supplement No. 2, (Published by the American
Chemical Society and the American Institute of Physics for the National
Bureau of Standards, Washington, DC 20234).
Walkowiak, W. and Grieves, R.B., Foam fractionation of cyanide complexes of

Zn(II), Cd(ll), Hg(ll) and Au(ill), Journal of Inorganic and Nuclear
Chemistry, 38, (1976), pp. 1351-1356.
Walkowiak, W., Bhattacharyya, D. and Grieves, R.B., Selective foam

fractionation of chloride complexes of zinc(ll), cadmium(II), mercury(II)
and gold(III), Analytical Chemistry, 48, (1976), pp. 975-979.
Weast, R.C. (Ed), Handbook of Chemistry and Physics, 66th edition, (CRC
Press Inc., 1986).
315
Wilson, H.W., Process for separation and recovery of gold, US. Patent No.
3,778,252, (1973).
Wilson, H.W., Noble metals solvation agents - hydroxyketones and iodine and
iodide, US. Patent No. 3,826,750, (1974).
Woodcock, J.M., Recent advances in metallurgy, Aus. IMM. Conf. 5, (1987).
Woodcock, J.T., Innovations and options in gold metallurgy, Proc. XVI lnt.
Min. Proc. Congress, Ed: Forssberg, E.K.S., (Elsevier, 1988), pp. 115-
131.
Zadra, J.B., A process for the recovery of gold from activated carbon by
leaching and electrolysis, US Bureau Mines RI 4672, (1950), p. 47.
Zadra, J.B., Engel, A.L. and Heinen, H.J., A process for the recovery of gold
and silver from activated carbon by leaching and electrolysis, US Bureau
Mines RI 4843, (1952), p. 32.
Zaitseva, M.D., Ivanovskii, M.D. and Larina, N.K., An examination of the

sorption properties of carbonaceous substances during the cyanidation of
gold ores, Sov. J. Nonferrous Met. 14(1), (1973), pp. 78-80.
Zegana, C.R., Huyhua, J.C. and Gundiler, I. A., Thiourea leaching of

manganiferous gold-silver ore, In: Precious and rare metal technologies,
Ed: Torma, A.E. and Gundiler, I.H., (Elsevier, New York, 1989).
Zippelian, D., Raghavan, S. and Wilson, J.P., Thiosulphate technology for

precious metal recovery, Presentation at 115th AIME Convention, New
Orleans, (March 1986).
Zumberge, J.E. and Sigleo, A.C., Molecular and elemental analysis of the
carbonaceous matter in the gold and uranium-bearing vaal reef carbon
seams, Witwatersrand Sequence, Mineral Sci. Engng., 10 (10), (1978),
pp. 223-245.
APP END ICE S
317
Appendix (7-2.1) A typical CHEMIX input statement.
TITLE
CHEMIX CALCULATION OF GOLD BROMIDE CEMENTA TION
IN THE SODIUM BROMIDE-BROMINE SYSTEM
AT VARIABLE ACID CONCENTRATION
SYSTEM
GAS
02 (G)
N2(G)
Br (G)
Br2 (G)
H2 (G)
H Br (G)
Br O (G)
H2 0 (G)
AQUEOUS
H20
Br2
02 (AQ)
0 H <-> (AQ)
H <+> (AQ)
Br <-> (AQ)
Br2 (AQ)
Br3 <-> (AQ)
Br 0 <-> (AQ)
H Br 0 (AQ)
Br 03 <-> (AQ)
H Br 03 (AI)
Br 04 <-> (AQ)
Br5 <-> (AQ))
H Br (AI)
H Br 04 (AI)
Au 03 H3 (AQ))
Au Br2 <-> (AQ)
318
Au Br4 <-> (AQ)

Au 03 <3-> (AQ)
H Au 03 <2-> (AQ)
H2 Au 03 <-> (AQ)
Zn <2+> (AQ)
Zn 02 <2-> (AQ)
Zn OH <+> (AQ)
Zn 03 H3 <-> (AQ)
Zn 04 H4 <2->(AQ)
Zn Br <+> (AQ)
Zn Br2 (AQ)
Zn Br3 <-> (AQ)
H Zn 02 <-> (AQ)
Zn S 04 (AI)
Na<+> (aq)
S 04 <2-> (AQ)
H S 04 <-> (AQ)
H2 S 04 (aq)
SINGLE
Au [0 H]3
ZnO
Zn [0 H]2
Zn Br2
NaBr
Na OH
AuBr
Au
Zn
UNITS
JOULE
GIBBS
02(G)
0.0
N2(G)
319
0.0
Br(G)
82396.
Br2 (G)
3110.
H2(G)
0.0
H Br (G)
-53450.
Br O (G)
108220.
H2 0 (G)
-228572.
H20
-237129.
Br2
0.0
02 (AQ)
16400.
0 H <-> (AQ)
-157244.
H <+> (AQ)
0.0
Br <-> (AQ)
-103960.
Br2 (AQ)
3930.
Br3 <-> (AQ)
-107050.
Br O <-> (AQ)
-33400.
H Br O (AQ)
-82400.
Br 03 <-> (AQ)
18600.
H Br 03 (AI)
18600.
Br 04 <-> (AQ)
320
118100.
Br5 <-> (AQ)
-103700.
H Br (Al)
-103960.
H Br 04 (Al)
118100.
Au 03 H3 (AQ)
-283370.
Au Br2 <-> (AQ)
-115000.
Au Br4 <-> (AQ)
-167300.
Au 03 <3-> (AQ)
-51800.
H Au 03 <2-> (AQ)
-142200.
H2 Au 03 <-> (AQ)
-218300.
Zn <2+> (AQ)
-147060.
Zn 02 <2-> (AQ)
-384240.
Zn OH <+> (AQ)
-330100.
Zn 03 H3 <-> (AQ)
-694220.
Zn 04 H4 <2-> (AQ)
-858520.
Zn Br <+> (AQ)
-247700.
Zn Br2 (AQ)
-349400.
Zn Br3 <-> (AQ)
-448900
H Zn 02 <-> (AQ)
-457080.
Zn S 04 (AI)
321
-891590.
Na<+> (aq)
-261905.
S 04 <2-> (AQ)
-744530.
H S 04 <-> (AQ)
-755910.
H2 S 04 (aq)
-744530.
Au [0 H]3
-316920.
ZnO
-318300.
Zn [0 H]2
-553810.
ZnBr2
-312130.
NaBr
-348983.
Na OH
-379494.
AuBr
-6669.3
Au
0.0
Zn
0.0
FILE
CPDNBSDAT
CPDNPLDAT
CPDMRLDAT
INSPECIES
GAS
N2(G)
322
AQUEOUS
H20
Br2 (AQ)
Au Br4 <-> (AQ)
H2 S 04 (aq)
SINGLE
Zn
NaBr
Na OH
TEMPERATURE
298.15
PRESSURE
1.
INMOLE
.8
55.52
.0000607
.0000508
.0000005
.0001
1.
.1
try
.3E-81 .8 .6E-46 .lE-64 .99E-01 .74E-23 .55E-91 .29E-01
55.52 .35E-63 .93E-84 .991E-01 .IE-12 .1003 .6E-64 .12E-63 .lE-53 .441E-58
.78E-92 .7E-90 .69E-90 .25E-92. lE-13 .69E-90 .2E-73 .16E-30 .85E-85 .75E-75
.51E-72 .llE-71 .35E-16 .99E-06 .llE-12 .57E-06 .95E-06 .94E-17 .38E-18 .6E-21
.5E-04 .17E-20 .2 .5E-07 .49E-17 .5E-32
0.0 .687E-3 0.0 0.0 0.0 0.0 0.0 .508E-4 .lE-90
EQUILIBRATE
323
STEP
OUTMOLE
AQUEOUS
02 (AQ)
Br <-> (AQ)
Br2 (AQ)
Au Br4 <-> (AQ)
Au Br2 <-> (AQ)
Br3 <-> (AQ)
H Br (AI)
H BrO (AQ)
Zn <2+> (AQ)
Zn Br <+> (AQ)
VARY
INMOLE STEPSIZE .049968 .00000048 .049992
AQUEOUS
H2 S 04 (AQ)
EQUILIBRATE
step
activity
aqueous
H <+> (AQ)
VARY
INMOLE STEPSIZE .049968 .00000048 .049992
AQUEOUS
H2 S 04 (AQ)
equilibrate
step
outmole
single
Au
Au Br
324
ZnO
Zn
VARY
INMOLE STEPSIZE .049968 .00000048 .049992
AQUEOUS
H2 S 04 (AQ)
equilibrate
325
Appendix (7-2.2) A typical SYSTEM input statement.
TITLE
Eh vs pH diagram for Zinc-Bromine-water system
DIAGRAM
AXES
E(AQ)
H E-1 (AQ)
H20
LIGANDS
Br2 (G)
H Br (G)
Br2
Br E (AQ)
Br2 (AQ)
Br3 E (AQ)
Br OE (AQ)
H Br (AQ)
H Br0 (AQ)
Br 03 E (AQ)
Br 04 E (AQ)
Br5 E (AQ)
AREAS
Zn
Zn0
Zn Br2
Zn E-2 (AQ)
Zn Br2 (AQ)
Zn Br E-1 (AQ)
Zn Br3 E (AQ)
Zn [0 H]3 E (AQ)
Zn [0 H]2 (AQ)
Zn [0 H]4 E2 (AQ)
326
LINES
02 (G)
H2(G)
UNITS
JOULES
GIBBSDATA
Br2 (G)
3110.0
H Br (G)
-53450.0
Br2
0.0
Br E (AQ)
-103960.0
Br2 (AQ)
3930.0
Br3 E (AQ)
-107050.0
Br OE (AQ)
-33400.0
H Br (AQ)
-103960.0
H BrO (AQ)
-82400.0
Br 03 E (AQ)
18600.0
Br 04 E (AQ)
118100.0
Br5 E (AQ)
-103700.0
Zn
0.0
ZnO
-318300.0
Zn Br2
-312130.0
327
Zn E-2 (AQ)
-147060.0
Zn Br2 (AQ)
-349400.0
Zn Br E-1 (AQ)
-247700.0
Zn Br3 E (AQ)
-448900.0
Zn [0 H]3 E (AQ)
-694220.0
Zn [0 H]2 (AQ)
-553810.0
Zn [0 H]4 E2 (AQ)
-858520.0
FILE
CPDNBSDAT
CPDNPLDAT
CPDMRLDAT
COMPONENTS
1,1
AXES
ORD INA TES EH
E(AQ)
ABSCISSA PH
H E-1 (AQ)
LIMITS
ORDINATE -2.0 2.0
ABSCISSA 0.0 14.0
TEMPERATURE
298.15
PRESSURE
328
1.
ACTIVITY
1. 1. 1.
1.0 1.0 1.0
10. 10. 10. 10. 10.
10.0E-00 10.0E-00 10.0E-00 10.0E-00 10.0E-00
1.0E-04 1.0E-04 1.0E-04
1.0E-04 1.0E-04 1.0E-04 1.0E-04 1.0E-04 1.0E-04 1.04E-04
1. 1.
AREAS
COORDINATES
OVERLAY
H2O = 0.5 02 (G) + 2 H E-1 (AQ) + 2 E (AQ)
1. 0.21 1. 1.
OVERLAY
0.5 H2 (G) = H E-1 (AQ) + E (AQ)
1. 1. 1.
PLOT
HEWZNB7
PEN 1
MARK LOWER ABSCISSA 6
2. 4. 6. 8. 10. 12.
MARK LOWER ORDINATE 7
-1.5 - 1.0 -0.5 0.0 0.5 1.0 1.5
LABEL LOWER ABSCISSA 8
0.0
2. 2
4.4
6. 6
8. 8
10. 10
12. 12
14. 14
329
LABEL LOWER ORDINATE 9

-2. -2.0
-1.5-1.5
-1. -1.0
-.5 -0.5
0.0
.5 0.5
1. 1.0
1.5 1.5
2. 2.0
TITLE LOWER ABSCISSA 2
pH
TITLE LOWER ORDINATE 2
Eh
TITLE UPPER ABSCISSA 14
ZN-BR-H2O AT 25 C
OVERLAY
IDENT
LEGEND
330
Appendix (7-2.3) A typical DIASTAB input statement.
".P"
"XO 14 .2"
"YO 10 .25"
"T 298.15"
"R 1.98717"
"N ZN-BR-H2O(A)L"
"H ZN-BR-H2O"
"GL"
"M 20 2 .65"
"O ZNBR.PLT"
"Q 1"
II II
".D"
".00"
"H2O -56.675 H2 O"
II II
".HX"
"HOH"
II II
".ZNAY"
"ZN++ -35.15 ZN"
"ZN++ -35.15 ZN"
"ZNOH+ -78.9 ZN OH"
"ZN(OH)2(AQ) -124.94 ZN 02 H2"
"ZNOH2(S) -132.294 ZN 02 H2 (S)"
"ZNBR+ -59.20 ZN BR"
"ZNBR2(AQ) -83.51 ZN BR2"
"ZNBR3- -107.29 ZN BR3"
".BRAY"
"BR -24.85 BR"
"BR- -24.85 BR"
"HBR(AQ) -24.85 BR H"
331
Appendix (8-4.1) Calculation of the mass-transport limited currents iL of u+.
The mass-transport limited current iL of H+ was calculated using the Levich's

equation (4-3.5):
iJA = 0.62nFD2t3y-116ro112cb
where
IL = limiting current, mA
A = cathodic surface area, cm 2
n = number of electrons
F = Faraday's constant, 96,486, coulomb/mole
Cb = concentration of reducing ions, mole
V = kinematic viscosity, cm2/s
0) = rotation speed, (rad/s)l/2
For the reaction:
(i)
n = 1,. At pH:2.00, and 1000 rpm, using a diffusion coefficient, D = 81.7x 10-6
cm2/s and kinematic viscosity, v = 0.01 cm 2/s:
iJA = 0.62x96486x l.825x 10-3x2.154x 10.233x0.0l
iJA = 24.79 mNcm 2

332
Appendix (8-4.2a) Evans diagram for the reduction of 100 mg/I Au(ID)
and (a) pH:2.00 (b) pH:3.00.
pH:2.00 pH:3.00
Cathodic reaction Anodic reaction Cathodic reaction Anodic reaction
Evs log Evs log Evs log Evs log

SCE, current SCE, current SCE, current SCE, current
(V) density, (V) density, (V) density, (V) density,
mA/cm2 mA/cm2 mA/cm2 mA/cm2
0.563 -1.006 -1.033 -1.218 0.52 -1.00 -1.056 -0.333
0.398 -0.245 -1.011 -0.095 0.41 -0.403 -1.037 0.146
0.23 -0.042 -0.993 0.42 0.202 -0.093 -1.016 0.434
0.106 -0.027 -0.972 0.641 -0.045 -0.075 -0.996 0.633
-0.018 -0.0023 -0.95 0.794 -0.087 -0.071 -0.973 0.788
-0.100 -0.019 -0.931 0.914 -0.211 -0.058 -0.954 0.91
-0.224 -0.0016 -0.907 1.023 -0.331 -0.056 -0.935 1.01
-0.344 -0.014 -0.887 1.11 -0.413 -0.039 -0.915 1.095
-0.427 0.165 -0.847 1.25 -0.495 0.07 -0.893 1.168
-0.508 0.532 -0.807 1.355 -0.620 0.354 -0.853 1.277
-0.590 0.793 -0.706 1.562 -0.702 0.441 -0.811 1.376
-0.715 1.035 -0.603 1.709 -0.744 0.460 -0.71 1.565
-0.796 1.145 -0.500 1.821 -0.827 0.471 -0.609 1.701
-0.919 1.265 -0.909 0.473
-1.003 1.324 -0.99 0.474
-1.125 1.387 -1.114 0.478
-1.21 1.408 -1.199 0.479
-1.29 1.419 -1.319 0.492
-1.416 1.423 -1.402 0.501
-1.662 1.425 -1.525 0.543
333
Appendix (8-4.2b) Evans diagram for the reduction of 100 mg/I Au(ID)
and (a) pH:4.00 (b) pH:5.00.
pH:4.00 pH:5.00
Evs log Evs log Evs log Evs log

0.51 -1 -1.092 -0.0743 0.5 -1 -1.117 -1.082
0.392 -0.385 -1.0173 -0.208 0.304 -0.215 -1.094 -0.395
0.189 -0.094 -1.052 0.131 0.099 -0.077 -1.076 -0.01
0.066 -0.07 -1.031 0.397 0.015 -0.07 -1.054 0.301
-0.017 -0.068 -1.012 0.592 -0.107 -0.069 -1.035 0.528
-0.222 -0.06 -0.991 0.744 -0.19 -0.067 -1.014 0.707
-0.306 -0.058 -0.971 0.868 -0.314 -0.061 -0.993 0.841
-0.43 -0.052 -0.951 0.97 -0.48 -0.039 -0.952 1.043
-0.513 -0.033 -0.928 1.055 -0.604 -0.026 -0.911 1.188
-0.554 -0.009 -0.908 1.13 -0.727 -0.026 -0.85 1.346
-0.595 0.002 -0.847 1.293 -0.768 -0.026 -0.808 1.433
-0.676 0.019 -0.806 1.385 -0.81 -0.025 -0.707 1.599
-0.801 0.023 -0.705 1.559 -0.893 -0.02 -0.604 1.72
-0.966 0.023 -0.602 1.686 -1.016 0.001 -0.502 1.817
-1.009 0.028 -1.099 0.039
-1.134 0.08 -1.18 0.092
-1.213 0.143 -1.304 0.193
-1.298 0.21 -1.388 0.235
-1.421 0.26 -1.43 0.268
-1.502 0.345 -1.595 0.499
-1.624 0.534
334
Appendix (8-4.3) Evans diagram for the reduction for (a) 10 mg/I Au(ID)
bromide ions and (b) 100 mg/I bromide ions and Zinc
dissolution in 0.10 M NaBr at 20°C, pH:5.00, and 1000 rpm.
Au(III):10 mg/L Au(IIl):100 mg/L
Evs log E vs log Evs log Evs log

0.54 -2.000 -1.117 -1.082 0.5 -1 -1.117 -1.082
0.398 -1.435 -1.094 -0.395 0.304 -0.215 . -1.094 -0.395
0.191 -1.123 -1.076 -0.010 0.099 -0.077 -1.076 -0.01
0.067 -1.096 -1.054 0.301 0.015 -0.07 -1.054 0.301
-0.038 -1.076 -1.035 0.528 -0.107 -0.069 -1.035 0.528
-0.221 -1.045 -1.014 0.707 -0.19 -0.067 -1.014 0.707
-0.302 -1.045 -0.993 0.841 -0.314 -0.061 -0.993 0.841
-0.424 -1.005 -0.952 1.043 -0.48 -0.039 -0.952 1.043
-0.509 -0.985 -0.911 1.188 -0.604 -0.026 -0.911 1.188
-0.589 -0.955 -0.85 1.346 -0.727 -0.026 -0.85 1.346
-0.63 -0.944 -0.808 1.433 -0.768 -0.026 -0.808 1.433
-0.796 -0.937 -0.707 1.599 -0.81 -0.025 -0.707 1.599
-0.878 -0.924 -0.604 1.72 -0.893 -0.02 -0.604 1.72
-0.918 -0.891 -0.502 1.817 -1.016 0.001 -0.502 1.817
-0.961 -0.819 -1.099 0.039
-1.002 -0.764 -1.18 0.092
-1.125 -0.502 -1.304 0.193
-1.209 -0.274 -1.388 0.235
-1.292 0.064 -1.43 0.268
-1.417 0.221 -1.595 0.499
-1.468 0.333
335
Appendix (8-5.1) Calculation of diffusion coefficient.
The diffusion coefficient of Au(III) bromo complex was calculated using the
Levich's equation (4-3.5):
idA = 0.62nFD213y-116ro112cb
where the terms are as explained in appendix (8-4.1).
The slope obtained in figure (8-5.1) for pH:5.00, was 6.036xlo-3. The slope is
given by:
Slope= idA/ro 112 = 0.62nFD 213 v- 116Cb (i)
and
D213 = Slope/0.62nFv- 116Cb (ii)
Thus, using v = 0.01002 crn 2/s for 0.05 M NaBr (Weast, 1986), n = 3, Cb = 100
mg/I= 5.08x 10-4 M:
D213 = 6.036xl0-3/196.376 crn 2/s
D = 0.17xlo- 6 crn 2/s

336
Appendix (8-5.2) The prediction of cementation rate constant (kp).
The cementation reaction rate constant was predicted using equation (4-3.13):
kp = 0.62D2t3y-1t6ro112
where
kp = cementation rate constant, cm/s

D = diffusion coefficient, cm2/s
V = kinematic viscosity, cm2/s
0) = rotation speed, (rad/s)l/2
For the reduction of 100 mg/I Au(III) bromide ions in 0.05 M NaBr solution at
20°C, pH:5.00 and 1000 rpm, the diffusion coefficient calculated (refer
appendix (8-5.1)) is D = 0.l 7x 10-6 cm2/s (ie., D 213 = 3.07x 10-5 cm2/s). Using
kinematic viscosity of 0.01002 cm 2/s for 0.05 M NaBr (Weast, 1986), v- 116 =
2.15372 cm2/s. Hence,
kp = 0.62x3.07x 10-5x2.15372x 10.233

kp = 4.2x 10-4 cm/s.
337
Appendix (8-5.3) Variation of limiting current densities with rotation speed

for the reduction of 100 mg/I Au(ID) bromide ions in 0.05 M
NaBr, (90 mg/I Br2 (aq)) at 20°C, (a) pH:S.00, (b) pH:6.00,
(c) pH:7.00.
RDE Limiting current density, mA/cm2

Rotation
speed
(rad/sec) 112 pH:S.00 pH:6.00 pH:7.00
4.576 0.029 0.022 0.016
7.927 0.048 0.039 0.026
10.233 0.062 0.052 0.035
12.944 0.078 0.065 0.044
14.472 0.088 0.07 0.052

338
Appendix (9-2.1) Surface area measurements (BET methods).
Instrument: Micromeritics Instrument

(Micromeritics Instrument Coroporation)
(A) Sample ID: Zinc powder; -106+63 µm

Analysis Gas: Nitrogen
Temperature: 77K
Sample Weight: 18.1493 g
Free Space: 43.9954 cc
Equil. In trvl. 8 sec.
BET Surface Area Report: BET surface area: 0.0340 ± 0.0011 m2/g
Slope: 127.8299 ± 4.151472
Y-Intercept: 0.21704 ± 0.632756
Corr. coefficient: 9.98422E-0l
(B) Sample ID: Zinc powder; -63+45 µm

Analysis Gas Nitrogen
Temperature: 77K
Sample Weight: 10.8916 g
Equil. lntrvl: 7 sec.
BET Surface Area Report: BET surface area: 0.0547 ±0.0018 m2/g
Slope: 78.73225 ± 2.62963
Y-Intercept: 0.801644 ± 0.383844
Corr. coefficient 9.98331E-0l
339
(C) Sample ID: Zinc powder; -45+38 µm

Analysis Gas: Nitrogen
Temperature 77K
Sample Weight 12.8952 g
Equil. Intrvl. 8 sec
BET Surface Area Report: BET surface area: 0.0906 ± 0.0025 m2/g
Slope: 47.50563 ± 1.31887
Y-Intercept: 0.54359 ± 0.198766
Corr. coefficient: 9.98846E-01
340
Appendix (9-2.2) Measurement of mean particle size.
(1) -106+63 µm
Nuooer in Lower UnderlUpper 1n Lower Under!Upper 1n Lower Under~ Soan ~.:

!. 38
I 124 17. 101 42.21 11.i=, u. ~.48 0.9~- ---
101 14. 83. 3 27.4 '3. 46 v. 7.7~ 0.7M D[4,3J ~
I &8.3
~
B3.3 11.
E,,
E,8.3
5E..1
7. 76
E..39
(I,
0.
E..39
5.24
0.5ff 127.b':lµttt
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Particle size (un).
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~ 4'32 0. 39. '3 I 4S.O" 7. 37.8 ::i,c:I 4. 30 ,), 3. 5.:. 0. (i~ b'+, E,4~111~
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Particl e size (m:1).
342
(3) -45 +3 8 µm
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ij 4(;4 0.0 332 100 37.B 14.2 31.(1 29.&I 3.53 ,.). 2.38 0.(,A. Dlv ,(d jfl
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Resid1ial ~);.p32 0,:g 40; S4uer.
ff
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"fo cal lepgth stnd S.r-1
ij1-·resentat1on = vo1u11e d1striou.1on l~o. !
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Particle size (un).
343
Appendix (9-3.1) Variation of log([Ault/[Au] 0 ) ratio with time for 10 mg/I

9.8 mg/I Br2 (aq)); 20°C; pH:5.00; at different rotational
speed.
Cementation log([Au]t/[Au]o)
time, (mins)
200RPM 500RPM 1000 RPM 1500 RPM
0 0 0 0 0
5 0 -2.18E-04 -4.34E-05 -3.04E-04
10 -4.34E-06 -0.001 -0.002 -0.002
20 -0.001 -0.009 -0.013 -0.032
30 -0.007 -0.018 -0.034 -0.056
45 -0.018 -0.04 - -0.1
60 -0.026 -0.067 -0.103 -0.144
80 -0.041 -0.097 -0.155 -0.201
100 -0.056 -0.129 -0.201 -0.273
120 -0.07 -0.167 -0.249 -0.337

344
Appendix (9-3.2) Variation of log([Au1t/[Au] 0 ) ratio with time for 10 mg/I

9.8 mg/I Br2 (aq)); at pH:5.00; 1000 rpm and (i) 10°C (ii)
20°c (iii) 30°C (iv) 40°C.
Cementation log([Au1t/[Au] 0 )
time, (ruins)
10°c 20°c 3o0 c 40°c
0 0 0 0 0
5 -4.34E-06 -4.34E-05 -4.34E-04 -0.001
10 -0.001 -0.002 -0.002 -0.007
20 -0.009 -0.013 -0.022 -0.039
30 -0.021 -0.034 -0.049 -0.07
45 -0.046 - -0.089 -0.116
60 -0.076 -0.103 -0.131 -0.164
80 -0.113 -0.155 -0.194 -0.228
100 -0.156 -0.201 -0.249 -0.291
120 -0.199 -0.249 -0.31 -0.369

345
Appendix (9-3.3) Variation of log([Au]tf[Au] 0 ) ratio with time for (i) 10 mg/I
(ii) 20 mg/I (iii) 50 mg/I (iv) 100 mg/I Au(ID) bromide/Zn
cementation in 0.10 M NaBr at 20°C, pH:5.00; and 1000
rpm.
Cementation log([Au1t/[Au] 0 )
time, (mins)
Au(III): 10 Au(III): 20 Au(III): 50 Au(III): 100

mg/I mg/I mg/I mg/I
0 0 0 0 0
5 -4.34E-05 -8.69E-05 -9.35E-04 -0.001
10 -0.002 -0.002 -0.003 -0.004
20 -0.013 -0.02 -0.03 -0.055
30 -0.034 -0.041 -0.05 -0.114
45 - -0.084 -0.111 -0.239
60 -0.103 -0.12 -0.211 -0.440
80 -0.155 -0.175 -0.379 -0.680
100 -0.201 -0.233 -0.561 -0.979
120 -0.249 -0.288 -0.780 -1.398

346
Appendix (9-3.4a) Variation of log([Au]tf[Au] 0 ) ratio with time for 10 mg/I

Au(ID) bromide/Zn cementation in (i) 0.001 M (ii) 0.010 M
(iii) 0.050 M (iv) 0.100 M (v) 0.500 M NaBr (Br2 (aq): 9.8
mg/I); at 20°C; pH:5.00; and 1000 rpm.
Cementation log([Au]tf[Au] 0 )
time, (mins)
0.001 M 0.010 M 0.050M 0.100 M 0.500 M

NaBr NaBr NaBr NaBr NaBr
0 0 0 0 0 0
5 -8.69E-04 -8.35E-04 -2.17E-04 -4.34E-05 -2.17E-05
10 -0.010 -0.005 -0.002 -0.002 -0.001
20 -0.029 -0.021 -0.018 -0.013 -0.009
30 -0.050 -0.044 -0.036 -0.034 -0.025
60 -0.117 -0.111 -0.109 -0.103 -0.089
80 -0.158 -0.158 -0.156 -0.155 -0.138
100 -0.201 -0.204 -0.204 -0.201 -0.18
120 -0.246 -0.252 -0.253 -0.249 -0.229

347
Appendix (9-3.4b) Variation of log([Au]t/[Au] 0 ) ratio with time for 100 mg/I
Au(ID) bromide/Zn cementation in (i) 0.01 M (ii) 0.05 M (iii)
0.10 M (iv) 0.50 M NaBr (Br2 (aq): 98 mg/I); at 20°C;
pH:5.00; and 1000 rpm.
time, (mins)
0.01 M NaBr 0.05 M NaBr 0.10 M NaBr 0.50 MN aBr
0 0 0 0 0
5 -6.52E-04 -9.13E-04 -0.001 -4.34E-06
10 -0.009 -0.005 -0.004 -5.65E-04
20 -0.069 -0.056 -0.055 -0.027
30 -0.152 -0.129 -0.114 -0.064
45 -0.294 -0.255 -0.239 -0.180
60 -0.495 -0.460 -0.440 -0.316
80 -0.729 -0.710 -0.680 -0.523
100 -1.105 -1.046 -0.979 -0.801
120 -1.503 -1.456 -1.398 -1.174

348
Appendix (9-3.5) Variation of log([Au]tf[Au] 0 ) ratio with time for 10 mg/I

Au(ill) bromide/Zn cementation in 0.10 M NaBr (Br2 (aq):
9.8 mg/I); at 20°C; pH:5.00; 1000 rpm. and (i) pH:2.00 (ii)
pH:3.00 (iii) pH:4.00 (iv) pH:5.00 (v) pH:7.00.
Cementatio log([Au]tf[Au] 0 )
n time,
(ruins)
pH:2.00 pH:3.00 pH:4.00 pH:5.00 pH:7.00
0 0 0 0 0 0
5 -0.003 -0.002 -8.69E-04 -4.34E-05 -4.34E-06
10 -0.012 -0.009 -0.005 -0.002 -5.22E-04
20 -0.036 -0.03 -0.022 -0.013 -0.006
30 -0.059 -0.056 -0.045 -0.034 -0.027
45 -0.098 -0.091 -0.085 - -
60 -0.134 -0.129 -0.122 -0.103 -0.092
80 -0.181 -0.180 -0.177 -0.155 -0.125
100 -0.238 -0.242 -0.232 -0.201 -0.170
120 -0.284 -0.298 -0.290 -0.249 -0.203

349
Appendix (9-3.6) A typical EDAX chart.
L__ l •.•
..::,,
- ·=· .- . . -. ,- ·.. ,:.,,;,(~.
_-
'
I •
~
,,
.;
,,
i\
''
!• 1;
,, l[
I 1(
,,r II
i-l
'I
;-I
"!'-
I "ji Li ' :I·!\ (i
I I
Il
!i fa
' II ,.
1 I I } ;
I! ,1
I,-; I
; ill
I
I
i; ._...._,~-
'~'------
..-. ,-.I_;
.-,--::-11}
---~----. _, __ _
-=-~ '· ..
--, - . - ! : • .::
: !,,~·r,i 1 .. 1::0:,-,c:-,
11 ,...._1 I,
Appendix (9-3.7) A typical XRD chart.
1 .~ Cul<a1+2
C HJ .000 x: 2theta y :
4-0831 • Zn Zinc s~n
4 ~/:.J~ 1 ::1.., {.';, ;:·
350
Appendix (9-4.la) Variation of log([Ault/[Au] 0 ) ratio with time for 10 mg/I

0.10 M NaBr (Br2 (aq): 9.8 mg/I); at 20°C; pH:5.00; 500
rpm. and (i) 38X45 µm (ii) 45X63 µm (iii) 63X106 µm zinc
particle size ranges.
Cementation time, log ([Au]tf[Au] 0 )

(mins)
38X45 µm 45X63 µm 63X106 µm
0 0 0 0
1 -0.015 -0.005 -8.69E-04
2 -0.051 -0.025 -0.010
3 -0.100 -0.044 -0.014
5 -0.167 -0.087 -0.040
7 -0.238 -0.12 -0.060
10 -0.359 -0.182 -0.087
15 -0.539 -0.284 -0.143
20 -0.733 -0.387 -0.195
30 -1.097 -0.572 -0.297

351
Appendix (9-4.lb) Variation of log([Au1t/[Au] 0 ) ratio with time for 100 mg/I
0.10 M NaBr (Br2 (aq): 98 mg/I); at 20°C; pH:5.00; 500 rpm.
and (i) 38X45 µm (ii) 45X63 µm (iii) 63Xl06 µm zinc
particle size ranges.
Cementation time, log ([Au]tf[Au] 0 )

(mins)
38X45 µm 45X63 µm 63X106 µm
0 0 0 0
1 -0.068 -0.032 -0.009
2 -0.134 -0.060 -0.021
3 -0.202 -0.090 -0.035
5 -0.305 -0.140 -0.063
7 -0.489 -0.201 -0.114
10 -0.870 -0.347 -0.204
15 -1.569 -0.635 -0.359
20 -2.301 -0.924 -0.495

352
Appendix (9-4.2) Variation of log([Au]i/[Au] 0 ) ratio with time for 100 mg/I
0.10 M NaBr (Br2 (aq): 98 mg/I); 20°C; pH:5.00; and SOO
rpm at different zinc amounts.
time, (mins)
0.0604g Zn 0.1250g Zn 0.2500g Zn 0.5000g Zn
0 0 0 0 0
1 -0.045 -0.068 -0.103 -0.222
2 -0.084 -0.134 -0.218 -0.427
3 -0.118 -0.202 -0.391 -0.678
5 -0.198 -0.305 -0.690 -1.167
7 -0.269 -0.489 -1.046 -1.658
10 -0.446 -0.870 -1.585 -2.523
15 -0.796 -1.569 -2.523 -
20 -1.222 -2.301 - -
353
0.10 M NaBr (Br2 (aq): 98 mg/I); 20°C; pH:5.00; at (i) 100
(ii) 300 (iii) 500 (iv) 700 rpm.
Cementation log([Au]tl[Au] 0 )
time, (mins)
100RPM 300 RPM 500 RPM 700RPM
0 0 0 0 0
1 -0.003 -0.040 -0.068 -0.09
2 -0.015 -0.074 -0.134 -0.172
3 -0.023 -0.132 -0.202 -0.234
5 -0.034 -0.208 -0.305 -0.417
7 -0.046 -0.261 -0.489 -0.602
10 -0.068 -0.387 -0.870 -0.987
15 -0.081 -0.815 -1.569 -1.824
20 -0.086 -1.403 -2.301 -2.699

354
Appendix (9-4.4a) Variation of log{[Au]tf[Au] 0 ) ratio with time for 10 mg/I

0.10 M NaBr (Br2 (aq): 9.8 mg/I); at pH:5.00; 500 rpm and
(i) 10°c (ii) 20°c (iii) 30°C (iv) 40°C.
Cementation log{(Au]tf[Au] 0 )
time, (mins)
10°c 20°c 3o0 c 40°c
0 0 0 0 0
1 -0.012 -0.015 -0.027 -0.038
2 -0.042 -0.051 -0.066 -0.078
3 -0.075 -0.100 -0.117 -0.125
5 -0.143 -0.167 -0.190 -0.202
7 -0.201 -0.238 -0.271 -0.294
10 -0.294 -0.359 -0.420 -0.450
15 -0.450 -0.539 -0.629 -0.703
20 -0.602 -0.733 -0.839 -0.967
30 -0.928 -1.097 -1.284 -1.481

355
Appendix (9-4.4b) Variation of log([Au]tf[Au] 0 ) ratio with time for 100 mg/I
0.10 M NaBr (Br2 (aq): 98 mg/I); at pH:S.00; SOO rpm and
(i) 10°c (ii) 20°c (iii) 30°c (iv) 40°c.
time, (mins)
10°c 20°c 30°c 4o0 c
0 0 0 0 0
1 -0.054 -0.068 -0.074 -0.079
2 -0.093 -0.134 - -0.158
3 -0.153 -0.202 -0.215 -0.257
5 -0.252 -0.305 -0.377 -0.516
7 -0.334 -0.489 -0.658 -0.889
10 -0.478 -0.870 -1.222 -1.602
15 -0.921 -1.569 -2.301 -3.071
20 -1.398 -2.301 -3.523 -4.569

356
Appendix (9-4.5) Variation of log([Au]tf[Au] 0 ) ratio with time for (i) 10 mg/I
(ii) 20 mg/I (iii) 50 mg/I (iii) 100 mg/I Au(ID) bromide/Zn
(suspended particles) cementation in 0.10 M NaBr at
pH:5.00;and 500 rpm.
Cementation log([Au]1/[Au] 0 )
time, (mins)
Au(III): 10 Au(III): 20 Au(III):50 Au(III):100

mg/I mg/I mg/I mg/I
0 0 0 0 0
1 -0.015 -0.052 -0.062 -0.068
2 -0.051 -0.100 -0.119 -0.134
3 -0.100 -0.148 -0.194 -0.202
5 -0.167 -0.231 -0.294 -0.305
7 -0.238 -0.325 -0.458 -0.489
10 -0.359 -0.449 -0.672 -0.870
15 -0.539 -0.674 -1.071 -1.569
20 -0.733 -0.870 -1.481 -2.301
30 -1.097 -1.409 -2.523 -3.830

357
Appendix (9-4.6a) Variation of log([Au]tf[Au] 0 ) ratio with time for 10 mg/I

Au(ill) bromide/Zn (suspended particles) cementation in (i)
0.001 M (ii) 0.010 M (iii) 0.050 M (iv) 0.100 M (v) 0.500 M
NaBr (Br2 (aq): 9.8 mg/I); at 20°C; pH:5.00; and 500 rpm.
time, (mins)
0.001 M 0.010 M 0.050 M 0.100 M 0.500 M

0 0 0 0 0 0
1 -0.036 -0.030 -0.02 -0.015 -0.011
2 -0.095 -0.072 -0.056 -0.051 -0.023
3 -0.143 -0.123 -0.114 -0.100 -0.042
5 -0.215 -0.199 -0.188 -0.167 -0.074
7 -0.282 -0.257 -0.256 -0.238 -0.102
10 -0.374 -0.364 -0.359 -0.359 -0.157
15 -0.484 -0.533 -0.548 -0.539 -0.242
20 -0.577 -0.672 -0.750 0.733 -0.339
30 -0.757 -0.860 -1.125 -1.097 -0.551

358
Appendix (9-4.6b) Variation of log([Ault/[Au] 0 ) ratio with time for 100 mg/I
Au(III) bromide/Zn (suspended particles) cementation in (i)
0.01 M (ii) 0.05 M (iii) 0.10 M (iv) 0.20 M (v) 0.50 M NaBr
(Br2 (aq): 98 mg/I); at 20°C; pH:S.00; and SOO rpm.
Cementation log([Ault/[Au] 0 )
time, (mins)
0.01 M O.OSM 0.10 M 0.20 M O.SOM

0 0 0 0 0 0
1 -0.055 -0.060 -0.068 -0.048 -0.044
2 -0.111 -0.120 -0.134 -0.102 -0.097
3 -0.173 -0.1850 -0.202 -0.164 -0.156
5 -0.298 -0.303 -0.305 -0.268 -0.252
7 -0.516 -0.458 -0.489 -0.396 -0.359
10 -1.051 -0.845 -0.870 -0.648 -0.519
15 -2.097 -1.824 -1.569 -1.081 -0.783
20 -3.155 -2.699 -2.301 -1.538 -1.056

359
Appendix (9-4.7) The solution potential of 10 mg/I Au(ID) bromide/Zn

(suspended particles) cementation in (i) 0.001 M (ii) 0.010 M
(iii) 0.050 M (iv) 0.100 M (v) 0.500 M NaBr (containing 9.8
mg/I Br2 (aq)) at 20°C, pH:5.00, SOO rpm.
Cementatio Solution Solution Solution Solution Solution

n time, potential at potential at potential at potential at potential
(mins) 0.001 M, 0.010 M 0.050 M 0.100 M at 0.500 M
V (vs SCE) V (vs SCE) V (vs SCE) V (vs SCE) V (vs SCE)
1 -0.636 -0.727 -0.742 -0.75 -0.576
2 -0.54 -0.713 -0.761 -0.833 -0.876
3 -0.436 -0.703 -0.78 -0.856 -0.9
5 -0.334 -0.696 -0.814 -0.863 -0.902
7 -0.191 -0.625 -0.818 -0.874 -0.862
10 -0.184 -0.61 -0.782 -0.895 -0.858
15 -0.18 -0.552 -0.769 -0.885 -0.848
20 -0.142 -0.532 -0.764 -0.88 -0.843

360
Appendix (9-4.8) The solution potential of 100 mg/I Au(ill) bromide/Zn

(suspended particles) cementation in (i) 0.01 M (ii) 0.05 M
(iii) 0.10 M (iv) 0.20 M (v) 0.50 M NaBr (containing 98 mg/I
Br2 (aq)) at 20°C, pH:5.00, 500 rpm.
Cementatio Solution Solution Solution Solution Solution

n time, potential at potential at potential at potential at potential at
(mins) 0.01 M 0.05M 0.l0M 0.20M 0.50M
NaBr NaBr V (vs NaBr NaBr NaBr
V (vs SCE) SCE) V (vs SCE) V (vs SCE) V (vs SCE)
1 -0.797 -0.875 -0.883 -0.88 -0.862
2 -0.87 -0.934 -0.926 -0.915 -0.915
1. -0.89 -0.958 -0.942 -0.925 -0.928
5 -0.826 -0.97 -0.952 -0.936 -0.93
7 -0.814 -0.977 -0.969 -0.944 -0.946
10 -0.79 -0.993 -0.969 -0.952 -0.954
15 -0.789 -0.975 -0.931 -0.915 -0.955
20 -0.78 -0.888 -0.876 -0.9 -0.96

361
0.10 M NaBr (Br2 (aq): 98 mg/I); at 20°C, 500 rpm and (i)
pH:2.00 (ii) pH:3.00 (iii) 4.00 (iv) pH:5.00 (v) pH:7.00
Cementation log([Au]i/(Au] 0 )
time, (mins)
pH:2.00 pH:3.00 pH:4.00 pH:5.00 pH:7.00
0 0 0 0 0 0
1 -0.037 -0.041 -0.054 -0.068 -0.059
2 -0.073 -0.086 -0.102 -0.134 -0.117
3 -0.109 -0.125 -0.149 -0.202 -0.173
5 -0.172 -0.187 -0.244 -0.305 -0.291
7 -0.241 -0.268 -0.406 -0.489 -0.471
10 -0.325 -0.403 -0.801 -0.870 -0.740
15 -0.384 -0.775 -1.638 -1.569 -1.180
20 -0.409 -1.420 -2.523 -2.301 -1.620

362
Appendix (9-4.l0a) Variation of 1-(r/r0 ) 3 with time for 10 mg/I Au(ID)

NaBr (Br2 (aq): 9.8 mg/I); at 20°C; pH:5.00; 500 rpm. and
(i) 38X45 µm (ii) 45X63 µm (iii) 63X106 µm zinc particle
size ranges.
Cementation time, 1-(r/r0 ) 3

(mins)
38X45 µm 45X63 µm 63X106 µm
0 0 0 0
1 0.010 0.005 0.003
2 0.019 0.007 0.006
3 0.026 0.012 0.008
5 0.036 0.019 0.012
7 0.045 0.026 0.016
10 0.054 0.036 0.022
15 0.061 0.045 0.029
20 0.066 0.052 0.035
30 0.075 0.061 0.045

363
Appendix (9-4.l0b) Variation of 1-(r/r0 ) 3 with time for 100 mg/I Au(ID)
NaBr (Br2 (aq): 98 mg/I); at 20°C; pH:5.00; 500 rpm. and (i)
38X45 µm (ii) 45X63 µm (iii) 63X106 µm zinc particle size
ranges.
Cementation time, 1-(r/ro)3

(mins)
38X45 µm 45X63 µm 63X106 µm
0 0 0 0
1 0.084 0.033 0.021
2 0.151 0.063 0.038
3 0.217 0.113 0.054
5 0.297 0.157 0.095
7 0.367 0.235 0.152
10 0.464 0.315 0.213
15 0.482 0.417 0.324
20 0.496 0.463 0.385
30 0.503 0.493 0.449

364
Appendix (9-4.lla) Variation of 1-(2/3)a-(1-a)213 with time for 10 mg/I Au(ID)

NaBr (Br2 (aq): 9.8 mg/I); at 20°C; pH:5.00; 500 rpm. and
(i) 38X45 µm (ii) 45X63 µm (iii) 63X106 µm zinc particle
size ranges.
Cementation time, 1-(2/3)a-(1-a)213

(mins)
38X45 µm 45X63 µm 63X106 µm

(Xl0- 4) (Xl0- 4) (x10- 4 )
0 0 0 0
1 0.100 0.02 0.01
2 0.400 0.05 0.03
3 0.76 0.15 0.06
5 1.420 0.40 0.17
7 2.280 0.76 0.28
10 3.340 1.42 0.54
15 4.260 2.28 0.93
20 - 3.06 1.34
365
Appendix (9-4.llb) Variation of 1-(2/3)a-(1-a)213 with time for 100 mg/I Au(ID)
NaBr (Br2 (aq): 98 mg/I); at 20°C; pH:5.00; 500 rpm. and (i)
38X45 µm (ii) 45X63 µm (iii) 63x106 µm zinc particle size
ranges.
Cementation time, 1-(2/3)a-(1-a )213

(mins)
38X45 µm 45X63 µm 63X106 µm
0 0 0 0
1 8.09E-04 1.24E-04 5.lOE-05
2 0.003 4.59E-04 1.62E-04
3 0.006 0.001 3.34E-04
5 0.011 0.003 0.001
7 0.018 0.007 0.003
10 0.031 0.013 0.006
15 0.034 0.024 0.014
20 0.036 0.031 0.020
30 0.037 0.035 0.029

(Austral) Cementation of Gold From Bromide Solutions

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(Austral) Cementation of Gold From Bromide Solutions

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Cementation of gold from bromide solutions

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CEMENTATION OF GOLD FROM BROMIDE SOLUTIONS

Kwesi Buah-Mensah Armoo, BSc (Hons)

KWESI BUAH-MENSAH ARMOO

l hereb y declare that this

I gratefully acknowledge the award of a Special Commonwealth African

I wish to express my profound gratitude to Professor R.G. Robins, formerly of

Recent research efforts have developed several and improved bromine-bromide

A fundamental study has been conducted on zinc cementation of gold from

Electrochemical measurements (scanning voltammetry) usmg rotating-disc

Various computer packages/programs (DIAST AB, SYSTEM, CHEMIX) were

Increasing initial Au(ill) bromide concentration from 10 mg/I to 100 mg/I

At 0.10 M bromide concentration, shrinking core kinetics confirmed a film

2. Armoo, K. and Tran, T., Cementation of gold from bromine-bromide liquors,

3. Armoo, K., Puvvada, G. and Tran, T., Recovery of precious metals by

LIST OF FIGURES XIV

LIST OF TABLES xxxm

2-3-2-1 Aqueous gold complexes/solution chemistry 23

3-1 Introduction/Review of historical development 34

3-2 Gold Minerals/Ore deposits 38

3-3 Extraction/Leaching of Gold 41

3-4 Separation/Recovery of Gold from Aqueous solutions 66

4-1 General theory 88

4-2 Electrochemical techniques 98

4-3 Electrode systems 100

4-4 Current - potential relationships 106

4-5 Evans diagram 110

5-1 Introduction/Definition 114

5-2 Theory/fhermodynamics 115

5-3 Electrochemistry 118

5-4 Deposit/Morphology 130

5-5 Suspended particles/Shrinking-Core model 133

7-1 Introduction 140

7-2 Thermodynamic data and computational methods 140

7-3 Equilibrium solution chemistry 148

8-1 Introduction 172

8-2 Experimental 172

8-2-5-1-2 Determine of bromide 178

8-3 Scanning (Linear sweep) Voltammetry 181

8-4 Evans diagrams 191

8-5 Rate measurements/kinetics 203

9-1 Introduction 205

9-2 Experimental 205

9-2-3-4 Smface area determination 210

9-3 Cementation onto zinc rotating discs 211

9-4 Cementation onto suspended zinc particles 246

10-1 Conclusion 280

10-2 Recommendation/Suggestion for future work 285

Figure (2-1.1) The potential-pH diagram for the bromine - water

Figure 2-1.2 The potential - pH equilibrium diagram for the

Figure (2-2.1) The potential-pH diagram for the Zn-H2O at

Figure (2-3. I) The potential - pH equilibrium diagram for the

Figure (2-3.2) The potential - pH diagram for the Au-Br-H2O

Figure (2-3.3) Eh-pH diagram for the Au-Br-H2O system at 25°C

Figure (3-3.1) A schematic gold recovery process flowsheet 42

Figure (3-4.1) A general flowsheet for Merrill-Crowe

Figure (4-1.1) Flow of electrons and ions between electrode and

Figure (4-4.1) Current density-potential electrochemical reaction

Figure (4-5.1) Typical polarization curves for an arbitrary metal

Figure (4-5.2) Idealized Evans diagram showing the transition from

Figure (5-2.la) Schematic diagram showing anodic and cathodic

Figure (5-2.lb) Cementation reaction mechanism (Strickland and