Whole

Cyanide regeneration from Thiocyanate with the use of Anion
exchange resins
Author:
Lee, Kenneth Chung-Keong
Publication Date:
2005
DOI:
https://doi.org/10.26190/unsworks/22998
License:
https://creativecommons.org/licenses/by-nc-nd/3.0/au/
Link to license to see what you are allowed to do with this resource.
Downloaded from http://hdl.handle.net/1959.4/23018 in https://

unsworks.unsw.edu.au on 2023-10-27
Cyanide Regeneration from Thiocyanate
with the use of Anion Exchange Resins
A thesis submitted for the degree of
Doctor of Philosophy
By
Kenneth Chung-Keong Lee

B.E. Chemical Engineering (UNSW)
School of Chemical Engineering and Industrial Chemistry

Faculty of Engineering
The University of New South Wales
Sydney, Australia
October 2005
Abstract
It is known in many gold operations that less than 2% of the cyanide consumed
accounts for the gold and silver dissolution. The majority of the cyanide is consumed
by minerals contained in the gold ore to produce many different cyanide soluble
complexes or used in converting cyanide to other related species such as thiocyanate
and cyanate. The high costs associated with cyanide and thiocyanate detoxification
and excessive cyanide utilisation encountered when treating ores with high cyanide
consumption constitutes a significant proportion of the overall processing costs. This
study examines the possibility of recovering free cyanide from thiocyanate using a
process based on the Acidification-Volatilisation-Regeneration (AVR) circuit in
conjunction with a pre-concentration stage using commercially available ion-
exchange resin.
From thermodynamic modelling based on the STABCAL program it was found that it
was thermodynamically possible to recover cyanide from thiocyanate if the oxidation
of cyanide to cyanate can be stopped. Addition of copper to the system found that the
majority of the thiocyanate exists as copper(I) thiocyanate (CuSCN) solid.
Using ion-exchange resins can be an effective way to concentrate thiocyanate from

tailing solutions or slurries. Four different models were successfully used to model
the equilibria between thiocyanate and chloride on commercial ion-exchange resins.
By normalising the equilibria data when applying the Mass action law the equilibria
becomes independent of ionic strength within the range of concentration considered.
An advantage of this is that only one unique equilibrium constant is used to describe
the ion-exchange process.
The electrochemical and kinetic studies showed that the reaction between thiocyanate
and hydrogen peroxide is catalysed by hydrogen ions. Secondly under acidic
conditions the rate of cyanide recovery by the AVR circuit was faster than at higher
pH conditions. The overall reaction of thiocyanate with respect to the concentration
of thiocyanate and hydrogen peroxide is an overall third order reaction. The derived
i
third order rate expression is first order with respect to thiocyanate concentration and
second order with respect to hydrogen peroxide concentration. Previous studies
showed that the production of cyanide inhibits the reactions between thiocyanate and
hydrogen peroxide, but by removing cyanide from the reaction by air stripping, this
was not observed. Addition of copper to the system did not show a catalytic effect on
the reaction but it was found that copper (II) ions suppresses competing reactions that
occurred without affecting the reaction between thiocyanate and hydrogen peroxide.
ii
Table of Contents
Abstract ...........................................................................................................................i
Table of Contents......................................................................................................... iii
List of Figures ..............................................................................................................vii
List of Tables ...............................................................................................................xii
List of Publications .................................................................................................... xiii
Chapter 1 General Introduction .....................................................................................1
1.1 Introduction..............................................................................................................1
1.2 Objectives of this study........................................................................................2
1.2.1 Literature review ........................................................................................2
1.2.2 Solution equilibria of the thiocyanate-water and copper-thiocyanate-water
systems...................................................................................................................3
1.2.3 Binary ion-exchange equilibria between thiocyanate and chloride using
commercially available Purolite A500u/2788 .......................................................3
1.2.4 Recovery of cyanide by air stripping from the oxidation of thiocyanate by
hydrogen peroxide .................................................................................................4
1.2.5 Electrochemical oxidation half-cell reaction of thiocyanate ........................4
Chapter 2 Cyanide Chemistry........................................................................................5
2.1 Introduction..........................................................................................................5
2.2 Free Cyanide ........................................................................................................6
2.3 Complex cyanides................................................................................................8
2.4 Other Cyanide Related Compounds...................................................................12
2.5 The Cyanide Cycle.............................................................................................12
2.6 Degradation of Cyanide .....................................................................................14
2.6.1 Complexation..............................................................................................14
2.6.2 Cyanide Complex Precipitation ..................................................................14
2.6.3 Adsorption...................................................................................................14
2.6.4 Oxidation of cyanide to cyanate .................................................................15
2.6.5 Volatilization...............................................................................................16
2.6.6 Biodegradation............................................................................................17
2.6.7 Formation of Thiocyanate...........................................................................18
2.6.8 Hydrolysis and Saponification of HCN ......................................................18
Chapter 3 Cyanide Management Using Chemical Oxidation Processes .....................23
3.1 Introduction........................................................................................................23
3.2 Cyanide Destruction...........................................................................................25
iii
3.2.1 The INCO process.......................................................................................25
3.2.2 Peroxygens..................................................................................................27
3.2.2.1 The Efflox Process...............................................................................28
3.2.2.2 Ozone ...................................................................................................31
3.2.3 Chlorination ................................................................................................33
3.3 Cyanide Recovery of free and weak-acid dissociable cyanides ........................36
3.3.2 MNR (SART) Process ................................................................................40
3.3.3 Copper Electrowinning Process..................................................................41
3.4 Pre-concentration Processes...............................................................................44
3.4.1 Resin Technologies.....................................................................................44
3.4.1.1 AuGMENT Process .............................................................................44
3.4.1.2 Vitrokele Process .................................................................................45
3.4.1.3 Elutech Process ....................................................................................47
3.4.1.4 Cognis AURIX Resin ..........................................................................48
3.4.1.5 Dow-Mintek (Minix) Ion exchange resin ............................................49
3.4.1.6 Superhydrophilic Ion Exchange Polymers...........................................49
3.4.1.7 Elution of Thiocyanate from Strong based ion exchange resins..........51
3.4.1.7.1 Elution of Thiocyanate Using Mineral Acids ...............................51
3.4.1.7.2 Elution of thiocyanate with potassium chloride and potassium
hydroxide .....................................................................................................52
3.4.1.7.3 Elution of thiocyanate with Ferric ions.........................................52
3.4.2 Solvent Extraction.......................................................................................55
3.5 Processes for the recovery of Cyanide From Thiocyanate ................................57
3.5.1 Chemistry of Cyanide Regeneration from Thiocyanate .............................58
3.5.1.1 Ozone ...................................................................................................59
3.5.1.3 Hydrogen Peroxide ..............................................................................64
3.5.1.4 Caro’s Acid ..........................................................................................65
3.5.1.5 Chlorination .........................................................................................66
3.5.1.6 Oxygen.................................................................................................67
3.5.1.7 Sulphur Dioxide ...................................................................................67
Chapter 4 Solution Equilibria ......................................................................................76
4.1 Introduction........................................................................................................76
4.2 Chemical Reactions ...........................................................................................78
4.3 Theoretical Background on the formation of Eh-pH .........................................79
4.4 Distribution Diagrams........................................................................................85
4.4.1 Theory behind the distribution diagram......................................................85
4.5 Developments in computer aided programs to produce Pourbaix diagrams .....91
4.5.1 Point-by-point method ................................................................................91
4.5.2 Line elimination method .............................................................................92
4.5.3 Convex polygon method .............................................................................93
4.6 Pourbaix Diagrams for the Thiocyanate-Water and Copper-Thiocyanate-Water
Systems ........................................................................................................................95
4.6.1 Thiocyanate-Water System.........................................................................95
4.6.2 Copper-Thiocyanate-Water System............................................................98
4.8 Conclusion .......................................................................................................114
iv
Chapter 5 Ion Exchange Resin...................................................................................119
5.1 Introduction......................................................................................................119
5.2 Theory ..............................................................................................................120
5.2.1 Characterisation of ion-exchange equilibrium in a binary mixture ..........120
5.2.2 Adsorption Isotherm Models ....................................................................121
5.2.2.1 Langmuir Isotherm.............................................................................121
5.2.2.2 Freundlich Isotherm ...........................................................................122
5.2.2.3 Dubinin-Radushkevich Isotherm .......................................................123
5.2.2.4 Mass-Action Sorption Model.............................................................124
5.3 Experimental ....................................................................................................131
5.3.1 Reagents and Materials .............................................................................131
5.3.2 Equipment and Instrumentation................................................................132
5.3.3 Procedure for analysis of thiocyanate .......................................................133
5.3.4 Experimental Procedures ..........................................................................134
5.4 Results and Discussion ....................................................................................136
5.4.1 Equilibrium Study.....................................................................................136
5.4.2 Langmuir Model Fitting............................................................................138
5.4.3 Freundlich Model Fitting ..........................................................................141
5.4.4 Dubinin-Radushkevich Model Fitting ......................................................142
5.4.6 Mass Action Law Model Fitting ...............................................................145
5.5 Conclusions......................................................................................................148
Chapter 6 Recovery of Cyanide from Thiocyanate using Hydrogen Peroxide .........152
6.1 Introduction......................................................................................................152
6.2 Chemistry of thiocyanate oxidation using hydrogen peroxide ........................153
6.3 Decomposition of hydrogen peroxide..............................................................158
6.4 Reaction rate expressions.................................................................................159
6.4.1 Derivation of a first order integrated rate expression ...............................159
6.4.2 Derivation of a second order integrated rate expression...........................160
6.4.3 Derivation of a third order integrated rate expression ..............................161
6.5 Experimental ....................................................................................................165
6.5.3 Analytical Procedures to determine the concentration of thiocyanate, free
cyanide and hydrogen peroxide .........................................................................169
6.5.3.1 Procedure for thiocyanate determination ...........................................169
6.5.3.2 Procedure for free cyanide determination..........................................169
6.5.3.2.1 Preparation of 0.01M standard silver nitrate solution.................169
6.5.3.2.2 Preparation of silver sensitive 5-(4-
(dimethylamino)benzylidene)rhodanine indictor.......................................169
6.5.3.2.3 Analytical procedure for cyanide analysis..................................169
6.5.3.3 Procedure for hydrogen peroxide determination ...............................170
6.5.3.3.1 Preparation of standard potassium permanganate solution.........170
6.5.3.3.2 Standardisation of potassium permanganate solution.................171
6.5.3.3.3 Analytical procedure for hydrogen peroxide analysis ................171
6.5.4 Experimental Procedure............................................................................172
6.6 Results..............................................................................................................175
6.7 Conclusions......................................................................................................189
v
Chapter 7 Electrochemical Studies of Thiocyanate Oxidation ..................................193
7.1 Introduction......................................................................................................193
7.2 Voltammetry ....................................................................................................194
7.2.1 Rotating Disc Electrode ............................................................................196
7.3 Experimental ....................................................................................................199
7.3.2.1 Electrodes...........................................................................................199
7.3.2.2 Equipment ..........................................................................................200
7.3.3 Experimental Procedure............................................................................202
7.4 Results..............................................................................................................204
7.5 Conclusions......................................................................................................216
Chapter 8 Conclusions and Recommendations..........................................................218

8.1 Conclusions......................................................................................................218
8.1.1 Solution Equilibria for thiocyanate-water and copper-thiocyanate-water
systems...............................................................................................................218
8.1.2 Ion-exchange equilibria between thiocyanate and chloride......................219
hydrogen peroxide .............................................................................................220
6.1.4 Electrochemical studies of thiocyanate oxidation.....................................221
8.2 Recommendations for further work .................................................................222
Appendix A: Fortran Code for Marquardt algorithm applied to the Mass-action Law
....................................................................................................................................224
Appendix B: Experimental data for ion-exchange equilibria between thiocyanate and

chloride ......................................................................................................................236
Appendix C: Experimental for the recovery of cyanide from thiocyanate using

hydrogen peroxide .....................................................................................................239
Appendix D: Experimental for the electrochemical study of thiocyanate oxidation 243
Publications…………………………………………………………………………248
vi
List of Figures
Figure 2.1: Distribution of HCN and CN as a function of pH @25oC ..........................7
Figure 2.2: Distribution of different copper cyanide species as a function of pH.
Thermodynamic data for system used from NBS Tables (Wagman et al., 1982)..8
Figure 2.3: The cyanide cycle, (Whitlock and Mudder, 1986)...................................13
Figure 2.4: Eh-pH diagram for Cyanide-Water System at 25oC generated from Stabcal
using equilibrium data from NBS Tables (Wagman et al., 1982). ......................16
Figure 3.1: Illustration of the difference between hydrogen peroxide and Caro’s acid
treatment of weak-acid dissociable cyanides in real liquor solutions (Nugent et
al., 1991, Case study 1)........................................................................................30
Figure 3.2: Illustration of the difference between hydrogen peroxide and Caro’s acid
treatment of weak-acid dissociable cyanides in slurries (Nugent et al., 1991, Case
study 1).................................................................................................................30
Figure 3.3: Oxidation of cyanide to cyanate using ozone as an oxidant. Operating
conditions: T=27oC, Flow rate of gas =4 L/min, Vsg=2.92 cm/s, ozone addition
rate=0.11g/min. (Carrillo-Pedroza, 2000)..........................................................323
Figure 3.4: Flow diagram of the AVR Circuit............................................................39
Figure 3.5: May Day Mine’s AVR Circuit (left) and Resin Columns (right).............39
Figure 3.6: Pilot scale SART plant flow sheet. (Dreisinger, 2001). ..........................41
Figure 3.7: Schematic diagram of the electrolytic cell described by Lu et al. (2002).
..............................................................................................................................43
Figure 3.8: Process diagram to regenerate ion exchange resin which was loaded with
thiocyanate (Fleming,1986)…………………………………………………….54
Figure 3.9: Oxidation of thiocyanate using ozone as the oxidant. (Layne et al., 1984).
Operating conditions: pH=11.2, I=0.23, T=25oC, gas flow=1.60 L/min.............60
Figure 3.10: The effect of ozone oxidation on free cyanide (Soto et al., 1995).Note:
CN (f) is the total concentration of HCN and CN-...............................................61
Figure 3.11: Schematic of anodic and cathodic boundary layer formation for reactor
with parallel plate bipolar electrodes. (Byerley et al., 1984) ..............................63
Figure 3.12: Electrolytic oxidation of thiocyanate. A graph showing SCN/CN vs.
time in a bipolar flow reactor. (Process conditions: temperature 30oC (av),
current 8A (av), initial pH 9 un-buffered (0.09M Na2SO4), final pH 2.4) (Byerley
et al., 1984). .........................................................................................................64
Figure 4.1: Potential-pH equilibrium diagram for the system iron-water, at 25oC.
Equilibrium data for each species are from NBS tables (Wagman et al., 1982).
(Fe, Fe(OH)2 and Fe(OH)3 considered as the solid substances) ..........................77
Figure 4.2: Potential-pH equilibrium diagram for thiocyanate-water system at 25oC.
..............................................................................................................................97
Excluding cyanate and hydrogen cyanate from the simulation. ..........................98
Figure 4.4: Potential-pH equilibrium diagram for the copper-thiocyanate-water
system at 25oC, at a copper and thiocyanate concentration of 0.001M. ............100
system at 25oC, at a copper concentration of 0.001M and thiocyanate
concentration of 0.01M......................................................................................100
vii
concentration of 0.1M........................................................................................101
concentration of 1M...........................................................................................101
system at 25oC, at a thiocyanate concentration of 0.001M and changing copper
concentration from 0.001 to 1M. .......................................................................102
system at 25oC, the thiocyanate and copper concentrations are at the same of
either 0.001 or 0.01M.........................................................................................103
system at 25oC, the thiocyanate and copper concentrations are at the same of
either 0.1 or 1M..................................................................................................103
Figure 4.11: Distribution diagram for copper-thiocyanate and water system. The
initial concentration of thiocyanate and copper is 0.001M at 25oC with the
addition of copper (II)........................................................................................106
Figure 4.12: A comparison of free thiocyanate concentration (SCN-) at different pH
and Eh conditions as the ratio of thiocyanate to copper is changed. ..................107
Figure 4.13: A comparison of hydrogen thiocyanate concentration (HSCN) at
different pH and Eh conditions as the ratio of thiocyanate to copper is changed.
............................................................................................................................107
Figure 4.14: A comparison of copper (II) thiocyanate concentration (CuSCN+) at
............................................................................................................................108
Figure 4.15: A comparison of the amount of copper (I) thiocyanate (CuSCN) at
............................................................................................................................109
Figure 4.16: A comparison of copper (I) di-thiocyanate concentration (Cu(SCN)2) at
............................................................................................................................109
Figure 4.17: A comparison of copper (I) tetra-thiocyanate concentration (Cu(SCN)43-)
at different pH and Eh conditions as the ratio of thiocyanate to copper is changed.
............................................................................................................................110
Figure 4.18: A comparison of free thiocyanate (SCN-) at different pH and Eh
conditions as the ratio of copper(II) to thiocyanate changed.............................111
Figure 4.19: A comparison of hydrogen thiocyanate (HSCN) under different Eh
conditions at a pH 0 as the ratio of copper(II) to thiocyanate changed. ............112
Figure 4.20: A comparison of copper (II) thiocyanate (CuSCN+) at different pH and
Eh conditions as the ratio of copper(II) to thiocyanate changed. .......................113
Figure 4.21: A comparison of copper (I) thiocyanate (CuSCN) at different pH and Eh
conditions as the ratio of copper(II) to thiocyanate changed.............................113
Figure 4.22: A comparison of copper (II) di-thiocyanate (Cu(SCN)2) at different pH
and Eh conditions as the ratio of copper(II) to thiocyanate changed. ................114
Figure 5.1: Ion exchange with a solution. For example a cation exchanger containing
counter ions A is placed in a solution containing counter ions B (left). The
counter ions are redistributed by diffusion until equilibrium is attained (right).
(Helfferich, 1995). .............................................................................................120
viii
Figure 5.2: Algorithm to calculate the three parameters: KAB, ΛAB, ΛBA to describe
the ion exchange equilibria using the Mass-action law. ....................................130
Figure 5.3: Bench-Top Orbital Shaker Incubator. ....................................................132
Figure 5.4: Concentration profile of thiocyanate adsorption at an initial thiocyanate
concentration for each run of 1200ppm NaSCN, temperature 30oC at
atmospheric pressure..........................................................................................136
Figure 5.5: Equilibrium adsorption curves for the adsorption of thiocyanate at
different thiocyanate concentrations using Purolite A500u/2778 strong base ion
exchange resin....................................................................................................137
Figure 5.6: The Langmuir Isotherm. A plot of the thiocyanate concentration on the
resin versus the ratio of the thiocyanate concentration to equilibrium solution
concentration......................................................................................................139
Figure 5.7: Parameter b for the Langmuir isotherm at different solution concentration.
............................................................................................................................140
Figure 5.8: Comparison of experimental data to predicted values from the Langmuir
Isotherm. ............................................................................................................140
Figure 5.9: The Freundlich Isotherm. A plot of log (X) (resin concentration) versus
log (C) (solution concentration).........................................................................141
Figure 5.10: Comparison of experimental data to predicted values from the
Freundlich Isotherm. ..........................................................................................142
Figure 5.11: The Dubinin-Radushkevich Isotherm. A plot of the natural log of
thiocyanate concentration on the resin versus ε2 which is defined by equation 6.
............................................................................................................................143
Figure 5.12: The change in the value of constant K in the Dubinin-Radushkevich
isotherm with a change in ionic strength of solution. ........................................144
Figure 5.13: Comparison of experimental data to predicted values from the Dubinin-
Radushkevich Isotherm......................................................................................145
Figure 5.14: The Mass Action Law. A plot of resin fraction versus solution fraction
of thiocyanate.....................................................................................................147
Figure 5.15: Comparison of experimental data to predicted values by the Mass-
Action Law.........................................................................................................147
Figure 6.1: Graphical representation of bonding between copper(I) and the
thiocyanate group...............................................................................................158
Figure 6.2: Schematic diagram of equipment set-up for oxidation study of
thiocyanate using hydrogen peroxide. (1) Bubble Column (2) Caustic Trap (3)
Precision Bore Flowrator (4) Cadet Air Pump. .................................................167
Figure 6.3: Front view of equipment arrangement for oxidation study of thiocyanate
using hydrogen peroxide, showing: Bubble reactor, caustic trap, Precision bore
flowrator and air pump.......................................................................................167
Figure 6.4: Dimensions of the bubble column reactor. (A) Top view, (B) Side View,
(C) Front View...................................................................................................168
Figure 6.5: Oxidation of thiocyanate using hydrogen peroxide to recovery cyanide.
Initial thiocyanate concentration 1000ppm, stoichiometric amount of hydrogen
peroxide and 10g/l sulphuric acid at room temperature and pressure. ..............176
Figure 6.6: A comparison of thiocyanate concentration against time at different
solution pH. The initial concentration of thiocyanate is 1000 ppm (17.2 mM),
the amount of hydrogen peroxide added to the experiment is double the
stoichiometry required to oxidise the thiocyanate present. No copper was added
to solution...........................................................................................................177
ix
Figure 6.7: A comparison of cyanide recovery at different initial pH’s. The initial
concentration of thiocyanate is 1000 ppm (17.2 mM), the amount of hydrogen
peroxide added to the experiment is double the stoichiometry required to oxidise
the thiocyanate present. No copper was added to solution. ..............................177
Figure 6.8: The pH profile of hydrogen peroxide oxidation of thiocyanate with
different initial starting pH. The initial concentration of thiocyanate is 1000 ppm
(17.2 mM), the amount of hydrogen peroxide added to the experiment is double
the stoichiometry required to oxidise the thiocyanate present. No copper was
added to solution. ...............................................................................................179
Figure 6.9: The Eh profile of hydrogen peroxide oxidation of thiocyanate with
different initial starting pH. The initial concentration of thiocyanate is 1000 ppm
(17.2 mM), the amount of hydrogen peroxide added to the experiment is double
the stoichiometry required to oxidise the thiocyanate present. No copper was
added to solution. ...............................................................................................179
Figure 6.10: A comparison of thiocyanate concentration against time at different
experimental conditions outlined in Table 6.2...................................................181
Figure 6.11: A comparison of hydrogen peroxide concentration against time under
different experimental conditions outlined in Table 6.2....................................182
Figure 6.12: A comparison of cyanide recovered against time under different
experimental conditions outlined in Table 6.2...................................................183
Figure 6.13: Applying the third order kinetic model for the reaction between
thiocyanate and hydrogen peroxide under different initial pH’s. The initial
the thiocyanate present. No copper was added to solution. ..............................185
thiocyanate and hydrogen peroxide with a acid concentration of 10g/l sulphuric
acid. The initial concentration of thiocyanate is 1000 ppm (17.2 mM), the
amount of hydrogen peroxide added to the experiment is double the
to solution...........................................................................................................186
thiocyanate and hydrogen peroxide with an initail pH of 12. The initial
concentration of thiocyanate was 1000ppm (17.2mM), the amount of hydrogen
peroxide added to the experimentis double the stoichiometry required to oxidise
the thiocyanate present. No copper was added to solution ...............................186
thiocyanate and hydrogen peroxide in the presence of copper(II). Experimental
conditions outlined in Table 6.2……………………………………………….187
Figure 6.17: Applying the first order kinetic model for the reaction between
thiocyanate and hydrogen peroxide with an initial pH of 7. The initial
the thiocyanate present. No copper was added to solution …………………...188
Figure 6.18: Applying the second order kinetic model for the reaction between
thiocyanate and hydrogen peroxide with an initial pH of 7. The initial
the thiocyanate present. No copper was added to solution……………………188
Figure 7.1: Current-potential axes for voltammetric technquies. .............................195
x
Figure 7.2: Typical three electrode system for electrochemical measurements (Bard
& Faulkner, 1980)..............................................................................................196
Figure 7.3:Schematic diagram of the fluid flow for a rotating disc system (Miller,
1979). .................................................................................................................197
Figure 7.4: Schematic of equipment set-up for electrochemical half-cell studies. 1)
Rotating disc electrode, 2) Speed controller, 3) Potentiostat, 4) Data Acquisition
unit, 5) Counter electrode, 6) Reference electrode, 7) Thermometer, 8) 5 port
Pyrex flask, 9) Water bath. ................................................................................201
Figure 7.5: Front view of the equipment arrangement for electrochemical studies
showing: IBM computer with Quicklog PCTM software, TLC 548/9 Anolog to
digital converter, Pine intrument Rotating Disc Electrode rotator with 5 port
reaction cell and wath bath, MSR speed controller and CV-27 Potentiostat.....201
Figure 7.6: Cyclic voltammogram of the glassy carbon electrode in 0.1M Na2SO4 at
pH 2, rest potential 0V and a scan rate of 40mV/s at a temperature of 25oC. ...204
Figure 7.7: Cyclic voltammogram of a glassy carbon in a solution of 0.1M Na2SO4+
0.01M NaSCN, rest potential=0.5V (vs. Ag-AgCl electrode), pH 2, temperature
25oC. The scan rate was varied from 10 to 40 mV/s. (A) 10 mV/s, (B) 20 mV/s,
(C) 30 mV/s, (D) 40mV/s. .................................................................................207
Figure 7.8: Stationary cyclic voltammogram of a glassy carbon in a solution of 0.1M
Na2SO4, 0.01M NaSCN, rest potential=0V (vs. Ag-AgCl electrode), pH 12,
temperature 25oC. The scan rate was varied from 10 to 40 mV/s. (A) 10 mV/s,
(B) 20 mV/s, (C) 30 mV/s, (D) 40mV/s.………………………………………208
Figure 7.9: Peak currents versus square root of scan rate for the first peak in the
voltammograms shown in Figure 7.7 (pH 2) and Figure 7.8 (pH 12).………...209
Figure 7.10: Peak currents versus square root of scan rate for the second peak in the
voltammograms shown in Figure 7.7 (pH 2) and Figure 7.8 (pH 12).………...209
Figure 7.11: Rotation disc voltammograms of the anodic half-cell study of
thiocyanate. The solution was made from 0.1M Na2SO4+0.01M NaSCN, pH 12,
temperature 25oC and a rest potential of 0.5V vs Ag-AgCl reference. The
rotation frequency was varied from 50rpm to 500 rpm. (A) 50rpm, (B) 100rpm,
(C) 200rpm and (D) 500rpm.………………………………………………….211
Figure 7. 12: Rotation disc voltammograms of the anodic half-cell study of
thiocyanate. The solution contained 0.1M Na2SO4+0.01M NaSCN, pH 2 and 12,
temperature 25oC and a rest potential of 0.5V vs Ag-AgCl reference. The
rotation frequency was varied from 50rpm and 100 rpm at each pH. (A) 50rpm
and (B) 100rpm.……………………………………………………………….212
Figure 7.13: A plot of limiting current versus the square root electrode rotation
frequency for experiments conducted in Figure 7.11.…………………………212
Figure 7.14: A comparison of the stationary cyclic voltammogram of a glassy carbon
in a solution of 0.1M Na2SO4, 0.01M NaSCN with copper added to one
experiment (concentration of 0.005M CuSO4), rest potential=0.5V (vs. Ag-AgCl
electrode), pH 12, temperature 25oC and a voltage scanning rate of 40mV/s...214
Figure 7.15: Rotation disc voltammograms of the anodic half-cell study of
thiocyanate. The solution contained 0.1M Na2SO4+0.01M NaSCN with one set
of experiments containing 0.005M CuSO4, pH 2, temperature 25oC and a rest
potential of 0.5V vs Ag-AgCl reference. The rotation frequency was varied from
50rpm to 100 rpm. (A) 50rpm, (B) 100rpm………………………………….215
xi
List of Tables
Table 2.1: Classification of cyanide compounds ...........................................................6
Table 2.2: Dissociation constants for metal cyanides in decreasing stability in water..9
Table 2.3: Solubilities of Ferrocyanide and Ferricyanide in Water.............................11
Table 3.1: Operating cost associated with thiocyanate formation (Botz et al., 2001) 57
Table 3.2: Half-cell reactions for the oxidation of thiocyanate. .................................58
Table 3.3: Stoichiometric reagents demands for thiocyanate oxidation with chlorine
(Botz et al., 2001).................................................................................................67
Table 4.1: Gibbs Free Energies for Thiocyanate and related species at 25oC. ...........96
Table 4.2: Operating conditions for the simulations to determine the distribution
diagrams for the copper-thiocyanate-water system. ..........................................105
Table 5.1: Values for Parameters in the Debye-Huckel law (Appendix 7.1, Robinson
et. al., 1965) .......................................................................................................128
Table 5.2: Typical Chemical and Physical Characteristics for Purolite A-500 and A-
500u/2788. (Purolite 2002) ...............................................................................131
Table 5.3: Parameters in the model based on the Langmuir isotherm......................139
Table 5.4: Parameters in the model based on the Freundlich isotherm. ...................142
Table 5.5: Parameters in the model based on the Dubinin-Radushkevich isotherm.144
Table 6.1: Heat of decomposition of hydrogen peroxide .........................................159
Table 6.2: Experimental conditions for thiocyanate oxidation experiments with the
addition of copper. The initial concentration of thiocyanate for each experiment
is 1000 ppm SCN-. Experiments were carried out at room temperature and
pressure. Airflow rate 1.2 L/min.......................................................................181
Table 6.3: 3rd order reaction constants for a reaction between thiocyanate and
hydrogen peroxide. The initial concentration of thiocyanate is 1000 ppm (17.2
mM), the amount of hydrogen peroxide added to the experiment is double the
to solution...........................................................................................................185
Table 7.1: Specifications of the cyclic voltammograph............................................200
Table 7.2: Peak Currents for different scan rates for figure 7.7. ..............................207
Table 7.3: Peak Currents for different scan rates for figure 7.9. ..............................208
Table 7.4: Rotating frequency of the working electrode and the related limiting
currents for the experiments shown in Figure 7.11............................................213
xii
List of Publications
1. Use of ion exchange resin for cyanide management during the processing
of copper-gold ores.
T. Tran, K. Lee, K. Fernando and S. Rayner
In: Proceedings of Minprex 2000 International Congress on Mineral
Processing and Extractive Metallurgy, held in Melbourne, Australia, 11-13
September 2000, pp 207-215.
2. Use of ion exchange resin for the treatment of cyanide and thiocyanate
during the processing of gold ores.
T. Tran, K. Fernando, K. Lee and F. Lucien
In: Cyanide: Social, Industrial and Economic Aspects. Proceedings of a
symposium held at Annual Meeting of TMS (The Minerals, Metals and
Materials Society), held New Orleans, Louisiana. February 12-15, 2001, pp
289-302.
3. Halide as an alternative lixiviant for gold processing-an update.
T. Tran, K. Lee and K. Fernando
In: Cyanide: Social, Industrial and Economic Aspects. Proceedings of a
symposium held at Annual Meeting of TMS (The Minerals, Metals and
Materials Society), held New Orleans, Louisiana. February 12-15, 2001, pp
501-508.
4. Patent: Selective recovery of precious metal(s).
K. Lee, F. Lucien, R. Rajasingam and T. Tran
Patent Number: WO02099144, Publication date: 2002-12-12.
5. Ion-exchange equilibria for Au(CN)2-/Cl-, Au(CN)2-/SCN-, and SCN-/Cl- in
aqueous solution at 303K.
N. Jayasinghe, K. Lee, F. Lucien and T. Tran
In: Journal of Chemical and Engineering Data, American Chemical Society,
In print. Web Release Date: July 9, 2004.
xiii
Chapter 1
General Introduction
1.1 Introduction
Cyanide has been used to recover gold economically from ore for over the past one
hundred years, but only a small amount of the cyanide consumed accounts for
leaching the precious metals (gold and silver) from the gold bearing ores. It is known
in many gold operations that less than 2% of the cyanide consumed accounts for the
gold and silver dissolution. The majority of cyanide is consumed by minerals
contained in the gold ore to produce many different cyanide soluble complexes or
used in converting cyanide to other related species such as thiocyanate and cyanate.
A small amount of cyanide is lost through volatilisation of hydrogen cyanide when
cyanide is protonated. In New South Wales, Australia, the Environmental Protection
Authority limits the various metal cyanide species which constitute CNWAD (weak-
acid dissociable cyanides) for discharge into tailing dams to less than 30ppm.
Currently there are no limits to discharge thiocyanate into tailing dams in Australia
but in the future due to consumer pressure upon the government may enforce
discharge limits for thiocyanate into tailing dams.
Detoxification of cyanide is commonly used to remove CNWAD from tailing waters.

The high costs associated with cyanide and thiocyanate detoxification and excessive
cyanide utilisation encountered when treating ores with high cyanide consumption
constitutes a significant proportion of the overall processing costs. Cyanide
consumption higher than 5kg/tonne ore is generally found to be prohibitive for
processing, often preventing the development of these ore resources. This has
prompted the development of several alternative technologies that recover base metal
cyanides and other species such as thiocyanate to recycle cyanide for re-use in the
leaching stage.
1
One of the first cyanide recovery processes is based on the use of acid to regenerate
cyanide as hydrogen cyanide gas, which is then adsorbed by a caustic or lime solution
to produce sodium cyanide or calcium cyanide, respectively. The Acidification-
Volatilisation-Regeneration (AVR) circuit in its original form (such as the Cyanisorb
process) is expensive and less effective in treating dilute liquors or slurries containing
less than 500ppm cyanide due to the handling of large volumes of liquor. However, if
the AVR circuit is operated in conjunction with a pre-concentration stage such as ion-
exchange or solvent extraction the AVR technique is more useful for handling low
volumes of concentrated cyanide streams.
1.2 Objectives of this study
This study examines the possibility of recovering of free cyanide from thiocyanate
using a process based on the AVR circuit in conjunction with a pre-concentration
stage using commercially available ion exchange resin. The study will include a
review of the chemistry of cyanide in a mining operation and management processes
used to control the cyanide levels discharged to tailing ponds. Experimental work and
discussions have been focused on the stability of different thiocyanate-water and
copper-thiocyanate-water systems, binary ion-exchange equilibria between
thiocyanate and chloride using commercially available Purolite A500u/2788, recovery
of cyanide by air stripping from the oxidation of thiocyanate by hydrogen peroxide
and electrochemical oxidation half cell reaction of thiocyanate.
1.2.1 Literature review
Literature review examines the chemistry of cyanide in a gold operation, dividing the
many cyanide species formed and other related species into different classes. As a
part of the cyanide cycle the review will cover discussions on the several natural
pathways via which cyanide will degrade in the natural environment. Literature on
different cyanide management processes used to control cyanide and thiocyanate
levels discharged to tailing pond either by destruction of cyanide and thiocyanate or
recovery of free cyanide from waste cyanides or thiocyanate was also reviewed.
2
1.2.2 Solution equilibria of the thiocyanate-water and copper-thiocyanate-
water systems
Thermodynamic modelling has been successfully applied to a wide range of

metallurgical, hydrometallurgical and geochemical processes. The production of
Pourbaix and distribution diagrams is required to provide an understanding of the
distribution of the predominant species in a thiocyanate-water and copper-
thiocyanate-water system. This may give support to the understanding of the
electrochemistry and reaction mechanisms for the oxidation of thiocyanate in the
presence with or without copper. The thermodynamic modelling was established by
using a modelling program (STABCAL) to generate the Pourbaix and distribution
diagrams.
1.2.3 Binary ion-exchange equilibria between thiocyanate and chloride using

commercially available Purolite A500u/2788
Using commercially available ion exchange resin (Purolite A500/2788) ion-exchange

equilibria was examined between thiocyanate and chloride at 303 K. The
experimental data was correlated and compared using various adsorption isotherm
models to determine the apparent equilibrium constants for the binary system and to
look at the effectiveness of using ion exchange resins to concentrate and remove
thiocyanate from mine liquors. By examining different binary systems with other
species such as base and precious metal cyanides using models to predict the
equilibria for ion-exchange, a comparison of the relative affinity of different counter
ions can be determined by using the cross product rule. This can be valued in the
prediction of the loading characteristics of more complex systems found in the mining
industry.
3
hydrogen peroxide
The recovery of cyanide from thiocyanate was studied under various different
conditions using hydrogen peroxide. The experiments conducted involved oxidising
thiocyanate to cyanide where an Acidification-Volatilisation-Reneutralisation circuit
recovered the cyanide generated. The rate of reaction was observed under different
operating conditions by changing the pH and the concentration of copper and
hydrogen peroxide of the system. The aim of this study is to understand the overall
reaction mechanism between thiocyanate and hydrogen peroxide to recover cyanide
that can be re-used in the leach stage of the gold operation.
1.2.5 Electrochemical oxidation half-cell reaction of thiocyanate
Electrochemical studies were used to examine the oxidation half-cell reaction of

thiocyanate using a voltametric technique based on the Rotating Disk Electrode
(RDE) system. Many researchers have successfully used the RDE system to examine
different redox reactions. The technique involves the oxidation half-cell reaction of
thiocyanate in the absence of any chemical oxidants. The effects of various factors,
namely, solution pH, scanning rates and disc rotation speeds and addition of copper
on the current-potential relationship of the thiocyanate half-cell reaction were
evaluated.
4
Chapter 2
Cyanide Chemistry
2.1 Introduction
Over the past hundred years cyanide has been used commonly within the gold
industry to leach gold and silver from ores because it is an efficient lixiviant (or
leachant) to dissolve these precious metals. Dilute cyanide solutions can be used to
leach the precious metal and at current market prices for gold it is economical to use
cyanide for many different ores. Only a small amount of the cyanide consumed
accounts for leaching gold and silver from gold bearing ores. It is known that in
many gold operations less than 2% of the cyanide consumed accounts for the of gold
and silver dissolution (Marsden and House, 1992). Side reactions with other minerals
within the ore consume most of the free cyanide.
The majority of the cyanide that is consumed reacts with many cyanide soluble
minerals found commonly in gold bearing ores. For example copper minerals such as
azurite (Cu3(CO3)2(OH)2) malachite (Cu2CO3(OH)2), cuprite (CuO2), tenorite (CuO),
chalcocite (Cu2S) and covellite (CuS). Other less soluble minerals are bornite
(Cu5FeS4), chrysocolla (Cu2H2Si2O5(OH)4) and chalcopyrite (CuFeS2) (Tran et al,
2000). Sulphide minerals can also react with free cyanide present in leach solutions
to form thiocyanate. The loss of free cyanide is also due to its oxidation to cyanate or
hydrogen cyanate and the volatilisation in the form of hydrogen cyanide (HCN).
The chemistry of cyanide is complex and dynamic. The different species of cyanide
have been classified into 3 different categories namely free cyanide, weak-acid
dissociable and strong acid dissociable cyanides according to the relative stability of
each species. This classification can be further subdivided into 5 sub-categories as
shown in Table 2.1. Other related species such as thiocyanate and cyanate are species
related to the cyanide family but have to be considered under a different category.
5
Table 2.1: Classification of cyanide compounds
Classification Compound
Free cyanide
1. Free cyanide CN, HCN
Weak-acid dissociable cyanide

2. Simple compounds
(a) Readily soluble salts NaCN, KCN, Ca(CN)2, Hg(CN)2
(b) Neutral insoluble salts Zn(CN)2, Cd(CN)2, Cu(CN), Ni(CN)2, Ag(CN)
3. Weak complexes Zn(CN)42-, Cd(CN)3-, Cd(CN)42-
Strong-acid dissociable cyanide

4. Moderately strong complexes Cu(CN)2-1, Cu(CN)3-2, Ni(CN)4-2, Ag(CN)2-1
5. Strong complexes Fe(CN)6-4, Co(CN)6-4, Au(CN)2-1, Fe(CN)6-3
Source: Scott and Ingles (1987)
2.2 Free Cyanide
Free cyanide refers to two different species, the cyanide ion (CN-) and hydrocyanic
acid or otherwise known as hydrogen cyanide (HCN). The relationship between the
two species depends on the pH of the system. In water the free cyanide is also in
equilibrium with HCN according to equation 2.1
HCN ⇔ H + + CN - [2.1]
where the pKa for HCN is
2347.2
pK a = 1.3440 + [2.2]
T + 273.16
and T is temperature given in degrees Celsius (Izatt et al., 1962).
6
100
90
80
[HCN]/([HCN]+[CN]) (%)
70
60
50
40
30
20
10
0
6 7 8 9 10 11 12
pH
Figure 2.1: Distribution of HCN and CN as a function of pH @ 250C.
The distribution of CN- and HCN as a function of pH is shown in figure 2.1. Most
gold plants operate at a pH of 10.5 to 12 to keep the predominant species of cyanide
as CN-. If the pH drops too low as in natural and brackish waters, which have pH
below 8.3, cyanide will exist predominantly as HCN. This is important because HCN
has a relatively high vapour pressure (100 kPa at 26oC, Huiatt, 1982) and will
volatilise readily from the liquid surface under ambient conditions causing a loss of
cyanide from the solution. The rate of cyanide loss depends greatly on the formation
of HCN, which is dependent on pH.
7
2.3 Complex cyanides.
Simple cyanide complexes are salts of hydrocyanic acid. These salts will dissolve
completely in solution to produce a free alkali cation and cyanide anions (such as
sodium cyanide).
Complex cyanides include those formed between cyanide and cadmium, nickel,
copper, silver and zinc. In some cases, multi-cyanide complexes are formed in a step-
wise manner; an example of this is copper cyanide. Depending on the ratio of CN- to
Cu(I) the predominant species are CuCN(s) or Cu(CN)2-, Cu(CN)32- and Cu(CN)43- as
illustrated in Figure 2.2.
100%
Cu(CN)3 Cu(CN)4
Distribution of Copper Cyanide Species
90%
CuCN
80%
70%
60%
50%
40%
Cu(CN)2
30%
20%
10%
0%
2 3 4 5 6 7 8 9 10 11 12
pH
Figure 2.2: Distribution of different copper cyanide species as a function of pH. Thermodynamic
data for system used from NBS tables (Wagman et al., 1982).
8
Weak acid dissociable cyanides create serious problems during waste handling
especially those which exist in more than one form such as copper cyanide
complexes. As free cyanide decomposes with time by ultra-violet light, more cyanide
can be liberated from copper cyanide complexes and the equilibrium will shift from
Cu(CN)43- and Cu(CN)32- to complexes of Cu(CN)2- and finally to CuCN(s). This
maintains the high level of free cyanide within the tailing ponds. If excess cyanide
exist in the tailing waters, copper cyanide can uptake the cyanide to form stable
complexes of Cu(I) species and acts as a sink to store the free cyanide. This
equilibrium effectively buffers the free cyanide concentration within the tailing waters
and complicates the cyanide management of the tailings.
Stability of each cyanide compound is dependant on the metal associated with it, the
most stable being iron and the weakest being zinc and cadmium. The dissociation
constants of selected cyanide complexes are presented in Table 2.2. The rate of
dissociation of the complex or the release of free cyanide depends on a number of
factors. These factors include intensity of light, temperature of the water, pH, total
dissolved solids and concentration of the cyanide complex.
Table 2.2: Dissociation constants for metal cyanides in decreasing stability in water.
Complex Dissociation Constant
1.0 x 10-52
-3
Fe(CN)6
1.0 x 10-47
Fe(CN)6-4
4.0 x 10-42
Hg(CN)4-2
5.0 x 10-28
Cu(CN)3-2
1.0 x 10-22
Ni(CN)4-2
-1 1.0 x 10-21
Ag(CN)2
-2 1.4 x 10-17
Cd(CN)4
1.3 x 10-17
Zn(CN)4-2
Source: Caruso (1975)
As with weak acid dissociable cyanides, strong-acid dissociable cyanides will liberate
free cyanide by reflux, but at a much lower pH. These include cyanides of iron, gold
9
and cobalt. These cyanide compounds are very stable and therefore are classified as
non-toxic.
From environmental standpoint, the most significant strong-acid dissociable cyanides

are iron cyanides. This is because iron cyanide has very high chemical stability,
which results in extremely slow rates of dissociation and very low solubilities in
water. Secondly, iron cyanide complexes can undergo a variety of chemical
reactions, for example they can combine with other metals to form very stable double
salts without the loss or exchange of the cyanide ligand as shown in Table 2.3.
Under certain conditions iron cyanide will decompose to release cyanide into the
environment. Theses complexes resist natural degradation until the free cyanide and
more degradable metal cyanides have dissipated. Iron cyanides are capable of
breaking down and releasing cyanide when exposed to intense ultraviolet radiation as
illustrated in the following reaction (equation 2.3):
⎯⎯
UV
Fe(CN)-46 + H 2 O ←⎯⎯ ⎯
⎯→ Fe(CN)5 .H 2 O + CN -1 [2.3]
dark
This maybe a problem at mine sites across the world if iron cyanides are present in
their tailing dams. It is possible that the free cyanide can be reintroduced into the dam
sites after the removal of free and more degradable metal cyanides. It would be
unlikely that iron cyanides pose a significant problem concerning for the management
of cyanide in tailing waters but its presence introduces another variable for
consideration.
10
Table 2.3: Solubilities of Ferrocyanide and Ferricyanide in Water.
Name Solubility (g/l)
Formula
Ammonium Ferricyanide (NH4)3Fe(CN)6 Very soluble
Ammonium Ferrocyanide (NH4)3Fe(CN)6.3H2O Soluble
Barium Ferrocyanide Ba2Fe(CN)6.6H2O 1.7 (15oC)
Cadmium Ferrocyanide Cd2Fe(CN)6.XH2O Insoluble
Calcium Ferrocyanide Ca2Fe(CN)6.12H2O 868 (25oC)
Cobalt Ferrocyanide Co2Fe(CN)6.XH2O insoluble
Copper (I) Ferricyanide Cu2Fe(CN)6 insoluble
Copper (II) Ferricyanide Cu3(Fe(CN)6)2.14H2O insoluble
Copper (I) Ferrocyanide Cu2Fe(CN)6.XH2O insoluble
Iron (II) Ferricyanide Fe3(Fe(CN)6)2 insoluble
Iron (III) Ferricyanide FeFe(CN)6 -
Iron (II) Ferrocyanide Fe2Fe(CN)6 insoluble
Iron (III) Ferrocyanide Fe4(Fe(CN)6)3 insoluble
Lead Ferricyanide Pb3(Fe(CN)6)2.5H2O slightly soluble
Magnesium Ferrocyanide Mg2Fe(CN)6.12H2O 330
Manganese (II) Ferrocyanide Mn2Fe(CN)6.7H2O insoluble
Nickel Ferrocyanide Ni2Fe(CN)6.XH2O insoluble
Potassium Ferricyanide K3Fe(CN)6 330 (4oC)
Potassium Ferrocyanide K4Fe(CN)6.3H2O 278 (12oC)
Silver Ferricyanide Ag3Fe(CN)6 0.00066 (20oC)
Silver Ferrocyanide Ag4Fe(CN)6.H2O insoluble
Sodium Ferricyanide Na3Fe(CN)6.H2O 189 (0oC)
Sodium Ferrocyanide Na4Fe(CN)6.10H2O 318.5 (20oC)
Strontium Ferrocyanide Sr2Fe(CN)6.15H2O 500
Thallium Ferrocyanide Tl4Fe(CN)6.2H2O 3.7 (18oC)
Tin (II) Ferrocyanide Sn2Fe(CN)6 insoluble
Tin (IV) Ferrocyanide SnFe(CN)6 insoluble
Zinc Ferrocyanide Zn2Fe(CN)6 insoluble
Source: Huiatt et al. (1982)
11
2.4 Other Cyanide Related Compounds
A number of cyanide related compounds are produced during the cyanidation process
such as thiocyanate, cyanate and ammonia. Thiocyanate is formed by the reaction of
cyanide and liable sulphur during the leaching process. The sulphur may originate
from the attack of lime or cyanide on pyrrhotite, or be formed by air oxidation of
sulphide minerals. Sulphur ions can be introduced by the dissolution of the readily
soluble metal sulphide minerals. Thiocyanate is chemically and biologically
degradable to produce ammonium, carbonate and sulphate as final products. These
products especially ammonium ions at sufficiently high levels can become toxic to
plant and animal life.
Oxidants can be used during the leaching process to increase the rate of dissolution of
gold, but in turn also increase the oxidation of cyanide to cyanate. Common oxidants
used are oxygen, chlorine, ozone and hydrogen peroxide. In acidic conditions cyanate
will decompose to ammonia and carbonate via a hydrolysis reaction.
2.5 The Cyanide Cycle
There are several natural pathways via which cyanide will degrade in the natural
environment. The degradation is due to complexation of cyanide with metal ions or
cyanide complex precipitation to form stable precipitates. Other pathways include the
adsorption of cyanides on minerals, the breakdown of cyanide to form other related
compounds, such as cyanate and thiocyanate and then there is biodegradation of
cyanide under aerobic conditions. The last two pathways that are worth discussion
are volatilization and hydrolysis/saponification of hydrogen cyanide. This is
illustrated well in Figure 2.3 showing the different pathways that can occur to render
cyanide harmless to the environment. The following section will discuss each
pathway in more detail.
12
13
Figure 2.3 : The cyanide cycle, (Whitlock and Mudder, 1986)
2.6 Degradation of Cyanide
2.6.1 Complexation
As discussed before cyanide can form many stable complexes with many different
metals. The solubilities of these complexes range from very soluble to insoluble.
Complexes that are not very stable will decompose to release free cyanide.
The formation of metal complexes reduces the toxicity by the removal of free cyanide
in solution. Complexation of cyanide with transitional metals act as an intermediate
for the formation of more stable compounds to remove free cyanide from being
mobile in the environment; for example the iron cyanide double salts. These
complexes can be immobilized from the environment by either precipitation or
absorption onto organic or inorganic materials.
2.6.2 Cyanide Complex Precipitation
Formation of cyanide double salts as stable precipitates reduces the mobility of

cyanide within the environment. Ferrocyanide and ferricyanide form very stable
cyanide insoluble precipitates with a number transitional metals like iron, copper and
zinc (seen in Table 2.3). Formation of these precipitates can occur over a wide range
of pH from 2 to 11.
2.6.3 Adsorption
Adsorption of cyanide is another mechanism to remove cyanide from a waste stream.

Soils that possess high anion exchange capacity would attenuate cyanide freely, for
example soils that contain a high content of kaolin clay, chlorite, gibbsite clay, and/or
iron and aluminium oxides and soils that contain cation exchange minerals like
montmorillonite would have a lesser ability to uptake cyanide. Organic materials
within soils and rock will absorb cyanide from solution. It is well known that
14
carbonaceous materials will uptake cyanide. Cyanide bound with copper, zinc or
nickel has shown a higher absorption capacity on carbon.
2.6.4 Oxidation of cyanide to cyanate
The Pourbaix diagram representing the cyanide-water system (Figure 2.4) shows that
cyanate is the predominant stable species within the cyanide-water system at 25oC.
Cyanide converts to cyanate according to the simplified reaction (equation 2.4):
HCN + 1
2 O 2 → HCNO [2.4]
Under natural conditions, the oxidation of cyanide to cyanate can be slow. An

oxidant such as hydrogen peroxide, ozone or chlorine can be used to accelerate the
oxidation. Alternatively the use of ultraviolet light in conjunction with catalysts like
titanium dioxide, cadmium sulphide and zinc oxide has been shown to convert
cyanide to cyanate (Domenech et al., 1989; Marsman et al., 1995; Dabrowski et al.,
2002; Chiang et al., 2002 and 2003). It have been theorized that the ultraviolet light
activates the catalyst to convert the dissolved oxygen within solution to ozone which
then reacts with the cyanide.
15
2
1
Eh (volts)
OCN-
-1
HCN(a)
CN-
[CN]=0.001M aat 25 degrees Celcius
-2
0 2 4 6 8 10 12 14
pH
Figure 2.4: Eh-pH diagram for Cyanide-Water System at 25oC generated from Stabcal using
equilibrium data from NBS Tables (Wagman et al., 1982).
2.6.5 Volatilization
Hydrogen cyanide is produced by a hydrolysis reaction between cyanide ion and

water according to the following reaction (equation 2.5):
CN − + H 2 O → HCN + OH − [2.5]
The pKa value for the CN-/HCN equilibrium above is 9.22 at 25oC.
Most mines will operate leach solutions at a pH of 10.5 to 12. The barren solutions
after metal recovery will have free cyanide remaining. With time the solution will
absorb carbon dioxide, reducing the pH of the barren solutions and form hydrogen
cyanide, which will slowly volatilise.
16
2.6.6 Biodegradation
Certain bacteria in the environment have been found to consume cyanide for a
nitrogen source to produce ammonia and nitrates. Biodegradation has been
successfully used at Homestake Mining Company, South Dakota USA, to detoxify
cyanide waste effluents using a strain of fungus, Fusarium Lateritium (Smith and
Mudder, 1993).
Under aerobic conditions it was reported that up to 200ppm cyanide could be

converted to nitrogen in soils (Fuller, 1984), which provides an ideal source of
nutrients for plants. Under anaerobic digestion research has shown that the bacteria
will degrade cyanide to a much lower level (2ppm cyanide), but at higher cyanide
concentrations (> 200ppm) for found to be toxic to the bacteria (Fuller, 1984).
The use of biodegradation to reduce the concentration of cyanide in the effluent

during the primary treatment of tailing waters can encounter many problems. For
example, biological organism cannot tolerate low temperatures causing the biological
organisms to die and cyanide will be released into the tailing ponds. Then it will take
some time to re-establish the environment to culture enough bacteria to consume
cyanide again.
17
2.6.7 Formation of Thiocyanate
Many gold ores contain sulphide materials. In neutral or basic solutions,

polysulphides and thiosulfate are produced from the oxidation of these sulphides.
Free cyanide will react with these various polysulphides (equation 2.6) and thiosulfate
(equation 2.7) compounds to form thiocyanate, as seen in the following reactions:
S−x2 + CN − → S(x−2−1) + SCN − [2.6]
S 2 O 3−3 + CN − → SO 3−2 + SCN − [2.7]
The formation of thiocyanate from different minerals that have been associated with
gold bearing ores was studied by Smith and Mudder (1993). They concluded that the
minerals that contributed to the formation of thiocyanate at a solution pH of 10 were
chalcopyrite, chalcocite, pyrrhotite and free sulphur. Iron sulphide minerals form
thiocyanate but to a lesser extent. The sulphur contained in sphalerite and pyrites is
relatively non-reactive with cyanide at a pH of 10.
2.6.8 Hydrolysis and Saponification of HCN
HCN can undergo two different hydrolysis reactions at low pH to form ammonium
formate (equation 2.8) and formic acid (equation 2.9). The extent of each product
formed is dependent on the pH of the system. Lower pH favours the formation of
formic acid. The two reactions are represented as:
HCN + 2H 2 O → HCOONH 4 [2.8]
HCN + 2H 2O → NH 3 + HCOOH [2.9]
Cyanide degradation via the above reaction is not rapid. Hoecker and Muir (1987)
have conducted high temperature hydrolysis reaction of cyanide in autoclaves. From
these experiments they estimated the rate of cyanide hydrolysis to ammonium formate
18
of 4% per month by extrapolating the data from the high temperature experiments
performed at room temperature. Similar results were found by DuPont with the rate
of cyanide hydrolysis to ammonium formate of 2% per month (Longe and DeVries,
1988).
19
References
Caruso S.C., “The Chemistry of cyanide Compounds and their Behaviour in the
Aquatic Environment”, Carnegie Mellon Institute of Research, June 1975.
Chiang K., Amal R., Tran T. “Photocatalytic degradation of cyanide using titanium
dioxide modified with copper oxide.” Advances in Environmental Research, (2002),
Vol. 6(4), pp 471-485.
Chiang K., Amal R., Tran T. “Photocatalytic oxidation of cyanide: Kinetic and
mechanistic studies.” Journal of Molecular Catalysis A:Chemical, (2003), Vol.
193(1-2), pp 285-297.
Dabrowski B., Zaleska A., Janczarek M., Hupka J., Miller J. “Photooxidation of
dissolved cyanide using TiO2 catalyst.” Journal of Photochemistry and Photobiology
A: Chemistry, (2002), Vol. 151(1-3), pp 201-205.
Domench X., Peral J. “Cyanide photo-oxidation using a titanium(IV) oxide –coated

zeolite.” Chemistry and Industry, (1989), Vol. 18, pp 606.
Fuller W. “Cyanides in the Environment with Particular Attention to the soil.”

Cyanide and the Environment, Vol. 1, Colorado State University, Fort Collins,
Colorado, 19-46, 1984.
Hoecker W. and Muir D., “Degradation of Cyanide.” The AusIMM Adelaide Branch,
Research and development in Extractive Metallurgy, May, 1987.
Huiatt J, Kerrigan J., Olson F. and Potter G., Proceedings of a cyanide Workshop,
Cyanide from Mineral Processing, U.S. Bureau of Mines, Salt Lake City, Utah,
February 2-3, 1982
Izatt R.M. et al. “Thermodynamics of metal-cyanide coordination. I. PK, Ho, and So

values as a function of temperature for hydrocyanic acid dissociation in aqueous
solution”, Inorganic Chemistry 1: 828, 1962.
20
Longe G.K. and DeVries F.W., “Some Resent Considerations on the Natural
Disappearance of Cyanide.” Economics and Practice of Heap Leaching in Gold
Mining. Cairns Queensland, Australia, August 1988.
Marsman E., Appelman J., Tauw Milieu B., Deventer N. “Removal of complexed
cyanides by means of UV-irradation and biological mineralization.” Soil and
Environment (1995), Vol. 5 (Contaminated Soil 95, vol 2), pp 1295-1296.
Marsden J., House I. “The Chemistry of Gold Extraction”, Ellis Horwood,

Chichester, UK. 1992.
Tran T., Lee K., Fernando K. and Rayner S. “Use of Ion exchange Resin for Cyanide
Management During the Processing of Copper-Gold Ores”, Proceedings of Minprex
2000, International Congress on Mineral Processing and Extractive Metallurgy, 11-
13 September 2000.
Scott J. and Ingles J. “State-of-the-art Process for the Treatment of Gold Mill
Effluents”, Mining, Mineral and Metallurgical Processes Division, Industrial
Programs Branch, Environment Canada, Ottawa, Ontario, March 1987.
Smith A., Mudder T. “The Environmental geochemistry and fate of cyanide”,

Proceedings of the Society of Economic Geologists Meeting, Denver, Colorado,
April, 1993.
Wagman D., William E., Parker V., Schumn R., Halow I., Bailey S., Churney K.and
Nuttal R. “The NBS tables of Chemical thermodynamic properties. Selected values
for inorganic and C1 and C2 organic substances in SI units.” Journal of Physical and
Chemical Reference Data. Vol. 11, 1982, Supplement No. 2. Published by American
Chemical Society and the American Institute of Physics for the National Bureau of
Standards.
Whitlock J.L. and Mudder T.I. “The Homestake Wastewater Treatment Process:
Biological Removal of Toxic Parameters from Cyanidation Wastewaters and
21
Bioassay Effuent Evaluation”, R.W. Lawrence et al, eds., Fundamental and Applied
Biohydrometallurgy, 1986, 327-339.
Young C., “Cyanide: Just the Facts.” Proceedings of Cyanide: Social, Industrial and
Economic Aspects. 97-113. Annual Meeting of TMS (The Minerals, Metals and
Materials Society) New Orleans, Louisiana, Feburary 12-15, 2001.
22
Chapter 3
Cyanide Management Using
Chemical Oxidation
Processes
3.1 Introduction
Since the development of the cyanidation process in the late 19th century there has
been no other processes to rival its use in the industry. However, a number of
accidents involving cyanide-contaminated wastes have affected the local
environment. For example the cyanide spill at the Aural gold mine in Baia Mare,
Romania became an international incident in early 2000 (DeVries, 2001). In this
case, the dam containing cyanide-contaminated waste broke and cyanide was released
into the Tisza River (which flows into the Danube) affecting one of the major
waterways in Europe. This incident was compounded by the negative attitude toward
mining activities worldwide. Tighter regulations to reduce the effect of future
accidents have been implemented as a result. Greece, Turkey, and the state of
Montana of the United States of America have banned the use of cyanide in new
mining operations.
Environmental protection authorities in Australia have imposed strict regulations on

the level of cyanide released into tailing dams. Most gold operators have to treat their
cyanide waste prior to discharge into their tailing ponds. Within New South Wales,
the Environmental Protection Authority specifies that the weak acid dissociable
cyanide levels for discharge into tailing dams must be less than 30 ppm (Tran, 2000).
On an international stage, the International Cyanide Management Code has
established an upper limit of 50 ppm of weak acid dissociable cyanide to open pond
areas (Ciminelli, 2002).
23
The control of cyanide in gold operations can be achieved by different techniques.
The technique that can be used depends on the type of cyanide complexes present and
the total level of cyanide in solution. There are two types of cyanide control that can
be used. Either the waste cyanide is destroyed to products that are not as hazardous
(for example cyanate), or recovered to form free cyanide to be recycled to be re-used
within the operation.
The detoxification techniques that are commonly used by plant operations are based
on the use of an oxidant such as hydrogen peroxide (Interox’s Efflox or Degussa
process) or SO2/air mixture (Inco process). Earlier cyanide recovery processes used
acid to regenerate free cyanide as HCN gas, which was adsorbed by a caustic or lime
solution to produce sodium or calcium cyanide, respectively. An example of such a
process is the Acidification-Volatisation-Regeneration (AVR) circuit. Compared with
oxidation, AVR is expensive and less efficient when treating dilute tailing waters or
slurries having less than 500 ppm cyanide due to the handling of large volumes of
liquors or slurries. However, the AVR technique is more suitable for handling low
volumes of concentrate cyanide streams produced from solvent extraction (Henkel’s
SX-MNR process) or ion-exchange.
Cyanide recovery from thiocyanate has not been commercialised from lab-scale
research. This technology would be suitable to cyanidation operations that have a
high cyanide consumption that is attributed to thiocyanate formation. In Australia it is
not required for a mine to treat the thiocyanate before releasing it into tailing dams.
In the reaction to recover cyanide from thiocyanate carbon is reduced from C(IV) to
C(II) while sulphur is oxidised from S(-II) to S(VI) (Botz 2001).
This chapter reviews current chemical oxidation processes that are used to control
cyanide and cyanide related products. It examines the different management
techniques from cyanide destruction to recovery of cyanide from cyanide waste
streams with particular attention to cyanide recovery from thiocyanate.
24
3.2 Cyanide Destruction
Detoxification of tailings involves mainly the destruction of weak-acid dissociable

cyanide species from solution. This is achieved by a wide range of processes such as
oxidation to cyanate (CNO-), using chlorine, hydrogen peroxide or sulphur dioxide/air
mixtures; precipitation as copper-iron cyanide complexes and biological treatment.
Chlorine when used can form potential toxic chloro-cyanide species and its use to
destroy cyanide is unfavoured in mining operations. The commonly used oxidation
techniques practised within the industry are based on hydrogen peroxide and sulphur
dioxide/air mixture. These oxidation techniques have been used extensively around
the world to destroy cyanide-contaminated wastes because of proven process
performance, low capital and running costs and relatively simple plant design.
3.2.1 The INCO process
The INCO process (named after the International Nickel Company) uses sulphur
dioxide-air mixtures with copper (as a catalyst) to oxidise weak-acid dissociable
cyanides to cyanate. Removal of free cyanide and complex metal cyanides species
from wastewater streams is very slow with SO2 and air alone. Copper catalyses the
removal of free cyanide (equation 3.1), complex heavy metal cyanide (equation 3.2)
and thiocyanate (equation 3.3) species from the stream. Normally the SO2/air process
is configured as a single stage continuous treatment facility in which the reagents are
dispersed into solution using a well agitated vessel. The process can be applied to
pulps and clear wastewaters. The process was first patented in 1984 (Borberly et al.,
1984) and has been used successfully at many mines over the world.
CN − + SO 2 (g) + O 2 (g) + H 2 O → CNO − + H 2SO 4 [3.1]
M(CN) xy − x + x SO 2 (g) + x O 2 (g) + x H 2 O → x CNO − + x H 2SO 4 + M y + [3.2]
SCN − + 4SO 2 (g) + 4O 2 (g) + 5H 2 O → CNO − + 5H 2SO 4 [3.3]
25
One of the benefits of the INCO process is that the sulphur dioxide used can be
provided in many different forms. The least expensive is to generate sulphur dioxide
on site from roaster gas or burning elemental sulphur. Otherwise reagents such as
liquid SO2 and sodium sulfite or sodium metabisulfite can be brought into the
operation (Devuyst 1991). A typical process removes total cyanide to less than 2
mg/l, from feeds containing total cyanide in the range of 50-2000 mg/l (Robbins et al.
2001).
The preferred oxidation occurs between a pH from 5 to 10 with the introduction of

lime or caustic to neutralise the acid produced within the redox reaction. If the pH of
the system is too low the rate of oxidation of cyanide is reduced. Therefore the
theoretical consumptions for sulphur dioxide and lime are 2.5mg SO2/mg CNWAD and
2.2 g CaO/mg CNWAD. Many operations increase the level of reagents several times
higher to increase the rate of oxidation of cyanide reducing reaction time to less than
an hour.
This process is not effective for the removal of thiocyanate due to increased
consumption of SO2. It was found that with an addition of nickel (as a catalyst) with
or without copper a higher concentration of SO2 of about 4.5 mg SO2/mg SCN is
required to destroy thiocyanate (Borbely et al., 1984). Any iron cyanide present in the
wastewaters is removed by precipitation as double salts with copper, zinc or nickel as
with other oxidation processes. The presence of iron cyanide affects the level of
copper added as catalyst because copper is consumed in the formation of different
iron cyanide double salts. Copper is normally added as copper sulphate at 50 mg/l or
higher if iron cyanide is present.
26
3.2.2 Peroxygens
Peroxygens are a group of powerful oxidants that have been used to detoxify cyanide
waste streams. The most commonly used peroxygens in the mining industry for
cyanide detoxification include hydrogen peroxide (Degussa process), Caro’s acid
(Efflox process), and ozone.
The Degussa process uses hydrogen peroxide as the oxidant in the destruction of
cyanide. Hydrogen peroxide reacts with cyanide to produce cyanate (equation 3.4)
and where added in excess the products produced are carbonate and nitrite (equation
3.5). Nitrite can continue to be oxidised to form nitrate (equation 3.6). Otherwise, in
acidic conditions, cyanate will hydrolyse to produce ammonium and bicarbonate ions
(equation 3.7).
CN − + H 2 O 2 → CNO − + H 2 O [3.4]
CNO − + 3H 2 O 2 → NO −2 + CO 32− + 2H 2 O + 2H + [3.5]
NO 2− + H 2 O 2 → NO 3− + H 2 O [3.6]
CNO − + 3H 2 O → NH 4+ + HCO 3− + OH − [3.7]
This process has great success in removing most weak acid dissociable cyanides but
has no effect on thiocyanate and strong-acid dissociable cyanides. Even with this
drawback many plants use this method as the primary destruction process as well as a
stand-by process for emergencies (Young et al., 1995).
Other reagents have been used to increase the reaction rate and efficiencies of
hydrogen peroxide. The most common additive is cupric ions. The copper acts as a
catalyst for the oxidation when hydrogen peroxide is the oxidant and is normally not
consumed. However, if iron cyanide is present within the waste, the copper will be
27
consumed due to the formation of the copper-iron cyanide double salt. Degussa
technology was used at the Ok Tedi gold mine in Papua New Guinea, using 70%
hydrogen peroxide at 2.0 to 4.5 times the stoichiometric requirements and copper
sulphate catalyst added at 10-20% of the cyanide concentration at a pH of 9.0 to 9.5.
All the weak acid dissociable cyanides were oxidised to cyanate, and the metal ions
released during oxidation were precipitated as hydroxides.
Another addition to the process has been developed by Dupont to increase the
efficiencies of the oxidation of cyanide with hydrogen peroxide containing the same
starting levels of cyanide. This was the addition of formaldehyde/Kastone to the
process. Cyanide will react with formaldehyde (HOCH) (equation 3.8) in the
presence of Dupont’s Kastone reagent to form glycolnitrile (HOCH2CN). In the
presence of hydrogen peroxide glyconitrile hydrolyses to glycolic acid amide
(HOCH2CONH2) (equation 3.9) (Young et al., 1995).
CN − + HOCH(aq) + H 2 O → HOCH 2 CN(aq) + OH − [3.8]
HOCH 2 CN(aq) + H 2 O → HOCH 2 CONH 2 (aq) [3.9]
3.2.2.1 The Efflox Process
The Efflox process was developed by Interox Chemicals and has been used
extensively in Australia at mines like Kanowna Belle in Western Australia and
Beaconsfield in Tasmania. The process uses peroxymonosulphuric acid, otherwise
known as Caro’s acid. This oxidant is made by the reaction of hydrogen peroxide and
sulphuric acid (equation 3.10). An advantage of using this oxidant is that it is
stronger than hydrogen peroxide (shown in equations 3.11 and 3.12).
H 2 O 2 + H 2SO 4 → H 2SO 5 + H 2 O [3.10]
H 2 O 2 + 2H + + 2e − → 2H 2 O E o = 1.77 Volt [3.11]
28
H 2SO 5 + 2H + + 2e − → H 2SO 4 + H 2 O E o = 1.81 Volt [3.12]
With a benefit of having a higher oxidation potential, Caro’s acid has been reported to
have greater stability than hydrogen peroxide, in the presence of transition metals.
This leads to higher efficiencies in terms of oxidant consumption for particular
processes (Nugent et al., 1991).
Nugent et al. (1991) compared the rate of oxidation of cyanide using hydrogen
peroxide and Caro’s acid. The experiments were carried out in solution and slurries
containing with the same starting levels of cyanide. Each experiment was conducted
batch wise on a 250ml to 1000ml scale. The hydrogen peroxide was added as a 50%
w/w solution to a portion of cyanide liquor or to 45% w/w solid slurry. The results
are shown in Figure 3.1 and Figure 3.2, which compare the final weak-acid
dissociable cyanide concentration when using hydrogen peroxide or Caro’s acid dosed
at different levels into either the solution or slurries. For comparison, the Caro’s acid
doses are expressed in equivalent units of hydrogen peroxide. It can be seen that for
the equivalent amount of hydrogen peroxide used, Caro’s acid is more efficient in
destroying weak acid dissociable cyanides. The treatment was also applied to slurry
solution (Figure 3.2) and although the consumption of reagents was higher as
expected, Caro’s acid is still more effective than hydrogen peroxide alone. Caro’s
acid experiments showed that in either solutions or slurries the residual concentrations
of weak-acid dissociable cyanides were similar. While when using hydrogen
peroxide the concentration of residual weak-acid dissociable cyanides in the slurry
experiments were higher than with experiments conducted in solutions.
29
6
Hydrogen peroxide
Caro's acid
5
4
ln(CNWAD)
0
0 5 10 15 20 25
Dose equivalence of oxidant (Mole H2O2/Mole CNWAD)
Figure 3.1: Illustration of the difference between hydrogen peroxide and Caro’s acid treatment
of weak-acid dissociable cyanides in real liquor solutions (Nugent et al., 1991, Case study 1).
Hydrogen Peroxide
5 Caro's Acid
4
ln(CNWAD)
0
0 2 4 6 8 10 12
Dose equivalence of oxidant (Mole H2O2/Mole CNWAD)
Figure 3.2: Illustration of the difference between hydrogen peroxide and Caro’s acid treatment
of weak-acid dissociable cyanides in slurries (Nugent et al., 1991, Case study 1).
30
3.2.2.2 Ozone
Ozone is another commonly used oxidant that can be used for cyanide management
(Sondak et al., 1967; Rowley et al., 1980; Zeevalkink et al. 1980 and Carrillo-Pedroza
et al., 2000). Ozone is a superior oxidant to oxygen and has two mechanisms to
oxidise cyanide to cyanate: ozonation (equations 3.13) and catalytic ozonation
(equation 3.14).
CN − + O 3 (aq) → CNO − + O 2 (aq) [3.13]
3CN − + O 3 (aq) → 3CNO − [3.14]
Cyanate can undergo further oxidation with ozone to form carbonate and nitrogen gas
(equation 3.15 and 3.16) (Young, 1995), and because of this cyanate does not undergo
the hydrolysis reaction to produce nitrites or nitrates in the system.
2CNO − + O 3 (aq) + H 2 O → 2HCO 3− + N 2 (g) [3.15]
2CNO − + 3O 3 (aq) + H 2 O → 2HCO 3− + N 2 (g) + 3O 2 (aq) [3.16]
There is an operational limit when using ozone, as the efficiency of oxidation drops
when the pH is greater than 11 (Young, 1995). This is because hydroxide has been
found to decompose ozone. Most mine operations will operate leach solutions in
alkaline conditions, typically above 11 to prevent the loss of cyanide by volatilisation,
as seen in Figure 2.1.
The mechanism that controls the reaction is the rate of mass transfer of ozone
(Garrison et al., 1975 and Mathieu, 1977). Work reported by Zeevalkink in 1980
showed that the presence of cyanide increased the mass transfer of ozone into the
aqueous cyanide solution by 1.5 times compared to pure water alone. Carrillo-
Pedroza (2000) found that as long as cyanide was present in solution the redox
potential, pH level of the system and dissolved ozone level remained constant. When
31
cyanide was completely oxidised the pH of the system decreased and the redox
potential of the system increased to around 600mV. The change was attributed to
other reactions between ozone and other species present such as cyanate and
ammonia. Figure 3.3 shows the destruction of cyanide with respect to ozone addition
and the continued oxidation to cyanate.
1.2
0.8
CN ;CNO (mol)
-
0.6
-
0.4
Cyanide
Cyanate
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
Ozone added (g)
Figure 3.3: Oxidation of cyanide to cyanate using ozone as an oxidant. Operating conditions:
T=27oC, Flow rate of gas =4 L/min, Vsg=2.92 cm/s, ozone addition rate=0.11g/min. (Carrillo-
Pedroza, 2000).
32
3.2.3 Chlorination
One of the first techniques developed for cyanide remediation was chlorination, which
has been used in the gold mining industry since 1889 (Young, 1995). Alkaline
chlorination is economical and efficient for the removal of free and weak-acid
dissociable cyanides. The disadvantages of using chlorination to control the level of
cyanide in an operation are the high reagent cost associated with controlling the pH
for optimal oxidation and high discharge concentrations of chlorine or hypochlorite
leaving the cyanide management system, which are as toxic to the environment as
cyanide. Chlorine is no longer the preferred process due to the potential formation of
toxic chloro-cyanide species. It has been replaced by oxidation techniques which
employ hydrogen peroxide or sulphur dioxide/air.
The oxidation of cyanide to cyanate using chlorination occurs by the formation of an

intermediate species. Firstly, chlorine reacts with cyanide (equation 3.17) to form
cyanogen chloride (CNCl) and in alkaline conditions cyanogen chloride is converted
to cyanate (equation 3.18). The overall reaction from cyanide to cyanate is described
in equation 3.19.
CN − + Cl 2 (g) → CNCl(aq) + Cl − [3.17]
CNCl(aq) + 2OH − → CNO − + H 2 O + Cl − [3.18]
CN − + Cl 2 (g) + 2OH − → CNO - + H 2 O + 2Cl − [3.19]
When chlorine is in excess, cyanate continues to oxidise to produce nitrogen and

carbon dioxide (equation 3.20). This reaction consumes large amounts of chlorine
and hydroxide causing problems in the release of hydrogen cyanide and cyanogen
chloride if the pH of the system drops below pH of 10.
2CNO − + 3Cl 2 (g) + 4OH − → N 2 (g) + 2CO 2 (g) + 6Cl − + 2H 2 O [3.20]
33
Chlorine can be used to convert thiocyanate and weak acid metal cyanides to cyanate.
Thiocyanate reacts with chlorine with a higher consumption rate compared to cyanide
(equation 3.21). The sulphur forms sulphate within the oxidative environment.
SCN − + 4Cl 2 (g) + 10OH − → CNO − + SO 24− + 8Cl − + 5H 2 O [3.21]
Because of the alkaline conditions for the conversion of cyanogen chloride to cyanate,
the weak-acid dissociable metal cyanides form metal hydroxides (equation 3.22).
Strong acid dissociable cyanides are not oxidised by chlorination.
M(CN) xy − x + x Cl 2 (g) + (2x + y) OH − → x CNO − + 2x Cl − + M(OH) y + x H 2 O
where x > y [3.22]
Lancy et al. (1960) studied the rate of reaction for continuous oxidation of cyanide
wastes using chlorination. The chlorination was carried out in two reaction vessels.
The primary reactor where the majority of the oxidation took place required reaction
time of 15-30 minutes with an operational pH of 10-11 and excess active chlorine.
The size of the reactor depended on the presence of copper and nickel. Secondary
stage of oxidation required a shorter retention period of 15 minute with neutral pH.
Lancy et al. (1960) found that hypochlorite was produced during the chlorination
process (equation 3.23). They observed that hypochlorite could oxidise cyanide. The
reactions that occur with hypochlorite are very similar to chlorination. Hypochlorite
will oxidise free and weak-acid dissociable metal cyanides and thiocyanate. Other
cyanide compounds will not react readily with hypochlorite. Research done by Baden
(1973) on the use of hypochlorite in the oxidation of iron cyanides demonstrates the
reaction kinetics are very slow. Addition of silver nitrate accelerates the oxidation
rate but the rate is still slow in comparison to that for weak-acid dissociable or free
cyanides.
Cl 2 (g) + 2OH − → Cl − + OCl − + H 2 O [3.23]
34
The reaction with hypochlorite, as with chlorination, is a two-step reaction in which
there is the formation of an intermediate species cyanogen chloride, which forms
cyanate under alkaline conditions (equation 3.24 and 3.25).
CN − + OCl − + H 2 O → CNCl(aq) + 2OH − [3.24]
CNCl(aq) + 2OH − → CNO − + Cl − + H 2 O [3.25]
When in excess hypochlorite solution, as with chlorination, cyanate will react with
hypochlorite to produce nitrogen and carbon dioxide (equation 3.26).
2CNO − + 3OCl − + H 2 O → N 2 (g) + 2CO 2 (g) + 3Cl − + 2OH − [3.26]
The following reactions show the stoichiometry for the reactions of thiocyanate and
weak acid dissociable metal cyanides with hypochlorite (equations 3.27 and 3.28).
SCN − + 4OCl − + 2OH − → CNO − + SO 24− + 4Cl − + H 2 O [3.27]
M(CN) xy − x + x OCl − + y OH − → x CNO − + x Cl − + M(OH) y
where x > y [3.28]
35
3.3 Cyanide Recovery of free and weak-acid dissociable
cyanides
Although several technologies have been developed for the recovery of cyanide from
tailing solutions, only the Acidification-Volatilisation-Reneutralisation (AVR) circuit
has been commercialised successfully. Considerable efforts in recent years have been
spent in improving techniques for the recovering of cyanide producing many
promising processes to reclaim cyanide for example Cyanisorb, AuMENT, Vitrokele,
MNR(SART) and the Elutech processes.
For the long term at the mine site if cyanide were recovered from the beginning of the
mines life, rehabilitation of the site becomes fairly simple because there are no
significant amounts of cyanide related product present in the mine wastewaters. It can
be a benefit for the operation because recovery circuits, and by the sale of metals
recovered as by-products, the cost to recover cyanide can become less expensive than
cyanide. The availability of such options makes the recovery of cyanide a very
attractive proposition.
The recovery of cyanide from thiocyanates can be costly because of the higher
reagent consumption required. At present, legislation in Australia does not limit the
amount of thiocyanate that can be released into tailing waters. However, in view of
the growing practices and the possibility of more stringent legislation, the elimination
of thiocyanates from tailing waters poses a potential problem for mine operators.
3.3.1 Acidification-Volatilisation-Reneutralisation (AVR) Circuit
The AVR circuit has been known since 1929. It was first referred to as the Mille
Crows Process, but since the 1970’s, after developments by CANMET and
McNamara, it has been referred to as the AVR process (Tran et al., 2000). This
process takes advantage of the volatile nature of hydrogen cyanide at low pH. Many
other cyanide recovery techniques use a variation of the AVR circuit, either using it as
the recovery step for cyanide or to concentrate the cyanide to a useable concentration.
36
A considerable effort has been made to improve the performance of AVR since its
introduction. It has become accepted by the industry as an option for treating
moderate or strong cyanide liquors (over 500 ppm CNWAD). However, copper is
precipitated as copper cyanide (CuCN) during the acidification stage and is an
unsaleable product which binds up the available cyanide, leading to a recovery of
67% of the maximum amount of cyanide available. Equations 3.29 and 3.30 describe
the recovery of cyanide from copper cyanide and then the recovery of cyanide in
alkaline solutions.
Cu(CN) 32− + H 2 SO 4 → CuCN(s) + 2HCN(g) + SO 24− [3.29]
2HCN(g) + Ca(OH) 2 → Ca(CN) 2 (aq) + 2H 2 O [3.30]
The cyanide associated with thiocyanate cannot be recovered by acidification alone.

This becomes an issue when thiocyanate levels are too high in leach liquors. For
example, it has been reported that levels of thiocyanate in mine liquors have reached
levels in excess of 2000ppm (Soto et al., 1995). In such cases, the cyanide that has
been consumed in the formation of this by-product becomes economically significant.
The AVR circuit involves acidification of the cyanide liquors or slurries to lower the
pH of the liquor or slurry from pH ~ 10 to pH ~ 3 to convert free cyanide and weak
acid dissociable cyanides (complexes of Zn, Cd, Ni) to HCN. The HCN is then
volatilised by passing air bubbles through the liquor or pulp. The HCN/air stream is
scrubbed in a lime slurry or sodium hydroxide solution to convert HCN into free
cyanide. The process involves a series of aeration columns as illustrated in Figure
3.4. It consists of two process units, one to volatilise hydrogen cyanide using a carrier
gas and the second column is used to absorb the hydrogen cyanide gas into an
aqueous alkaline solution. The system is a closed loop circuit with respect to cyanide.
A number of carrier gases can be used with the preferred gas being air. Other gases
that have been suggested include nitrogen and carbon dioxide from other processes.
The US patent 5,254,153 (Mudder et al., 1993) suggested the stripping tower operated
under negative pressure and the air-HCN mixture being positively removed. If
37
packing is used the operating pressure drop is about 15 to 30 mm water per meter of
packing material. The flow rate of air needed to carry the cyanide from the waste
stream varies from 250 to 1000 cubic meters of air per cubic meter of solution. The
patent states a preferred operation flow rate of 300-800 m3 air/m3 solution, which
corresponds to a flux of 2.8 to7.4 cubic meters of air per square meter of pH adjusted
mixture per minute, based on a period of 3 to 4 hours.
At the May Day Mines, Cobar, N.S.W. Australia, the stripping and adsorption towers
were packed with plastic media to improve the recovery of cyanide. The preferred
packing materials have a size from 50 to 75 mm and are made from either stainless
steel, ceramic materials or plastics. The most commonly used packing materials are
Pall rings, Rashig rings, Tellerette rings, saddles and grids. This system at May Day
Mines was designed and used to effectively handle 100 tonne of cyanide per hour.
Air was used as the carrier gas with a flow rate of 10,000 m3/hour (Figure 3.5).
A similar process based on the AVR circuit has been marketed by Unifield
Engineering (USA) (called the Cyanisorb process). A number of US patents covering
the process (US 4,994,243, US 5,078,977 and US 5,254,153) have been filed. The
process is slightly different from the original AVR circuit in that clear solutions or
slurries are processed at near neutral pH.
38
Air
Acid
Caustic
Solution
Cyanide
Waste
Acidification
Tank Volatilisation Cyanide
Zone Recovery
Tower
Recovered
Cyanide
Solution
Air
Air
Blower
Figure 3.4: Flow diagram of the AVR Circuit.
Figure 3.5: May Day Mine’s AVR Circuit (left) and Resin Columns (right).
39
3.3.2 MNR (SART) Process
The MNR process was developed by Metallgesellschaft Natural Resources in

Germany. It is also known as the SART process which stands for Sulphidisation,
Acidification, Recycle and Thickening process. As implied in the name of the
process, it uses sulphidisation and acidification (to less than pH 5) of copper/cyanide
rich liquors to precipitate copper as synthetic chalcocite (Cu2S) and recover free
cyanide.
The acidification and sulphidisation steps are conducted simultaneously as follows:
2Cu(CN) 32− + 2H 2 SO 4 + H 2 S → Cu 2 S(s) + 6HCN(g) + 2SO 24− [3.31]
The main advantage of using this method over other recovery processes is that all the
cyanide from the cyanide complex can be recycled. The copper precipitate is a
marketable product which can be processed into to copper metal. The copper
sulphide can also be blended with other copper flotation concentrates produced on site
as in the Telfer mine in Western Australia (Dreisinger et al., 2001).
The SART process produces a slurry of copper sulphide precipitate and free cyanide.
This slurry is fed to a thickener where the copper sulphide is recovered in the
underflow and either added to other copper flotation concentrates or refined for sale.
The overflow from the thickener is adjusted with an alkaline solution to raise the pH
of the solution to convert the hydrogen cyanide to sodium or calcium cyanide.
Another option is to acidify the overflow further to form gaseous hydrogen cyanide
and recover cyanide via adsorption columns (Davis et al., 1998; Dreisinger, 1998).
Figure 3.6 shows a flow sheet of a pilot scale SART plant (Dreisinger, 2001).
Dreisinger (2001) conducted pilot plant trails using the SART process for the Telfer
Mine. They found that the reaction is nearly stoichiometric with respect to copper,
where the sulphur additions were able to remove 95% of the copper from solution.
The sulphuric acid consumption was 1.7-2.4 kg of 100% sulphuric acid/kg weak acid
dissociable cyanide to achieve a pH of 4-5. At this pH range the recovery of copper
40
was over 95% and the cyanide recovery was over 94%. Dreisinger (2001) also tested
H2SO3 as an alternative to sulphuric acid. The use of H2SO3 was not as successful,
leaving over 5 times more copper in solution compared to sulphuric acid. It was
proposed that H2SO3 reacted with the sulphur and formed a copper complex
preventing it from precipitating from the solution.
Figure 3.6: Pilot scale SART plant flow sheet. (Dreisinger, 2001).
Free cyanide can react with sulphur to form thiocyanate. This represents a
disadvantage of the process because of the loss of recovered cyanide and the
formation of copper thiocyanates (soluble and insoluble species), which can
contaminate the final product.
3.3.3 Copper Electrowinning Process
This process was developed to recover copper metal and cyanide from dilute copper
cyanide wastes. Fleming et al. (1995) have filed a patent (US patent 5,411,575)
which describes a process to electrowin copper from solution using a membrane-type
electrowinning cell. The cell uses a sodium permeable ion-exchange membrane
(Nafion 417) developed by Du Pont. The membrane separates the two cell
41
compartments, which prevents the oxidation of cyanide to cyanate at the anode. The
anolyte solution is made from concentrated sodium hydroxide solution. This provides
sodium ions to the cell for cation transfer through the membrane from the anolyte to
the catholyte solution. Copper is electroplated from the catholyte solution leaving the
cyanide in the catholyte. The half-cell reactions for the cell are shown below
(equations 3.32 to 3.35):
Anode : 4NaOH → O 2 (g) + 2H 2 O + 4Na + + 4e − [3.32]
Membrane : 4Na + (anolyte) → 4Na + (catholyte) [3.33]
Cathode : 4Na + + 4Na 2 Cu(CN) 3 + 4e − → 4Cu(s) + 12NaCN [3.34]
Overall : 4Na 2 Cu(CN) 3 + 4NaOH → O 2 (g) + 2H 2 O + 4Cu(s) + 12NaCN [3.35]
The consumption of sodium hydroxide has been reported to be significantly higher

than reaction stoichiometry, which can be attributed to the side reaction of hydrogen
formation at the cathode (Lu et al., 2002). To reduce the effect of these side reactions,
Lu et al. (2002) proposed a second system using sodium chloride. As a by-product
chlorine can be formed at the anode. The half-cell reaction as the anode is given be
equation 3.36 and the overall reaction shown equation 3.37:
Anode : 2NaCl → 2Na + + Cl 2 + 2e − [3.36]
Overall : 4Na 2 Cu(CN) 3 + 4NaCl → 4Cu(s) + 12NaCN + 2Cl 2 [3.37]
Lu et al. (2002) used a flow through electrolytic membrane cell to show the effect of
the cyanide to copper ratio on the recovery of copper and cyanide. The electrolytic
cell used a graphite-felt anode compressed between painted stainless steel mesh,
shown in Figure 3.7. Their main conclusion was that the current efficiency of copper
plating on the felt decreases with an increase in the cyanide to copper ratio and
42
current density. The accumulation of copper deposited on the felt increases the
specific surface area of the cathode thus increasing the conductivity of the felt, which
improves copper deposition. Lu et al. (2002) reported that 60% of the copper was
successfully removed from diluted copper cyanide solutions (~1g/l copper). The
energy requirement for the cell was 1-2 kWh/kg Cu at a current density of 30-100
A/m2.
Inlet/Outlet Inlet/Outlet
Anolyte Anolyte
Anode Anode
Cathode Thermometer
Catholyte
inlet Catholyte
outlet
Anode Anode
Chamber Chamber
Membrane Membrane
Cell Cell
Figure 3.7: Schematic diagram of the electrolytic cell described by Lu et al. (2002).
43
3.4 Pre-concentration Processes
Two types of processes that have been used to concentrate cyanide waste streams
from mine waste are solvent extraction and ion-exchange resin based technologies.
Solvent extraction is widely used in the processing of copper ores. Ion-exchange
resins have been used in the mining industry since the 1980’s to recover gold from
gold liquors at the Golden Jubilee Mine in South Africa (Fleming et al, 1984 (A);
1984 (B); 1990) and earlier in the former USSR states (Bolinski and Shirley 1996;
Marsden and House 1992).
The processes that were developed focused on the recovery of precious metals such as
gold and silver cyanides. Later studies focussed on the recovery of precious metals
and cyanide species, especially the copper cyanide species. The early resin-based
technologies have used basic eluants such as thiocyanate, chloride and hydroxide to
remove gold cyanide from the loaded resin for further processing. However, in the
presence of base metal cyanide complexes in the liquor, sulphuric acid is also used to
strip these complexes off the resin. Acid elution employed in several ion exchange
resin processes destroys the cyanide complexes loaded on the resin, regenerating
cyanide for recycling via hydrogen cyanide formation.
3.4.1 Resin Technologies
3.4.1.1 AuGMENT Process
The AuGMENT process (Fleming et al. 1998, Le Vier et al. 1997) uses commercially
available strong-base ion-exchange resin to recover and pre-concentrate free cyanide
and copper cyanide species. The resin is pre-treated by impregnating the ion-
exchange resin with CuCN(s). This has been found to promote the adsorption of
copper cyanide species and free cyanide. The affinity of the resin for copper cyanide,
in particular, the Cu(CN)2-1 species, is higher than free cyanide itself. The loading
mechanism can be described by equation 3.38:
44
2R 2 − SO 24− (CuCN (s) ) + Cu(CN) 32− + 2CN1− → 3R − Cu(CN)12− + R − CN − + 2SO 24−
where R represents the resin backbone and functional group. [3.38]
Once resin is loaded, copper cyanide can be eluted from the resin using a copper
cyanide/caustic eluant (CNTotal:Cu ratio between 3.5:1 to 4.0:1 and a copper
concentration between 10 to 70 g/l Cu and 10 g/l NaOH) (Davis et al., 1998). With
short elution times the resin is substantially eluted and the resulting eluant having a
CNTotal:Cu ratio of <4:1. Elution is described by equation 3.39:
2R − Cu(CN)12− + Cu(CN) 32− + 2CN1− → R 2 − Cu(CN) 32− + Cu(CN) 32− [3.39]
As part of the AugMENT process, copper is produced from copper cyanide using the
Du Pont membrane cell (as described earlier). Gold has to be recovered prior to
copper electrowinning and cyanide recovery. Cyanide can also be recovered via an
AVR circuit, where the copper cyanide is precipitated and re-dissolved in the loaded
catholyte ahead of the electrowinning circuit.
3.4.1.2 Vitrokele Process
The Vitrokele process uses a proprietary strong-base ion-exchange resin to recover

waste cyanides from either clear solution or slurries. The resin is based on a highly
cross-linked polystyrene structure (VitrokeleTM 911 and 912). Ligands bound to the
resin structure have not been publicly disclosed but V912 is believed to be a type 1
quaternary amine functionality (Jay W., 2000).
Once loaded, base metal cyanides are eluted using a strong cyanide eluant (equation
3.40). The precious metal cyanides and other strongly bound complexes are eluted
from the resin using a zinc tetracyanide eluant (equation 3.41). The elution step using
the zinc tetracyanide eluant is only required every second or third base metal elution
depending on the relative loadings of the precious and other strongly bound species.
The other elution step uses sulphuric acid as an eluant, which removes most cyanide
complexes. An AVR circuit is applied to recover the cyanide for recycling in the
45
leaching plant or used as an eluant in one of the stripping cycles (equation 3.40 and
3.41).
R 2 − Cu(CN) 3 + 2CN − → 2R − CN + Cu(CN) 32− [3.40]
2R − Au(CN) 2 + Zn(CN) 24− → R 2 − Zn(CN) 4 + 2Au(CN) −2 [3.41]
where R represents the resin backbone and functional group.
This process has been successfully applied at the Connemara Mine in Zimbabwe for
processing oxidised ores using heap leaching (Satalic et al., 1996). During the period
from July 1997 to June 1998, this process was tested on copper-gold ores at May Day
Mines, Cobar, N.S.W. Australia under sponsorship of an Industrial Research &
Development syndicate scheme (Paterson et al., 1997).
At the May Day Mine, the Vitrokele technology was used in a vat-leach operation to
treat 250 000 tonnes of agglomerated ore. The ore was graded at 2.2 gpt Au, 15.2 gpt
Ag and 0.12% Cu. The resultant leach solution contained 2-3ppm Au, 25ppm Ag,
50ppm Zn, 200ppm Cu and <1ppm Fe. As report earlier a strong cyanide (100g/l
NaCN, 10 g/l NaOH) eluant was used to elute copper from the resin. This step
produces a copper liquor in a strong cyanide background, which is then acidified to
precipitate the copper as copper cyanide. The hydrogen cyanide is regenerated using
an AVR circuit (as seen in Figure 3.5).
Gold was eluted from the resin and recovered from an electro-elution circuit, similar
to the operation in the former Golden Jubilee plant in South Africa. Zinc tetracyanide
at 50-60oC was used as the eluant to strip gold from the resin in a closed loop in
which gold is recovered by electrowinning immediately after elution (Marsden et al
1992). For efficient elution of gold from the resin, the gold concentration has to be
maintained <1ppm Au. Even under these conditions the gold elution has been
reported to take as long as 48 hours the Golden Jubilee (Fleming et al., 1984, 1990).
Similar elution times were used at the May Day site.
46
Several technical problems developed during the operation of the Vitrokele process
that led to the abandonment of the Vitrokele Process at the May Day Mines. One of
the major problems was that the base metal elution was not effective to remove most
of the copper from the resin. The interaction between residual copper cyanide and
sulphuric acid eluant lead to the formation of solid copper cyanide in the resin, which
passivated the resin surface and active sites. Other species such as insoluble copper-
iron or zinc-iron cyanide double salts have the same effect. These precipitates can
form at neutral or acidic conditions (Tan, 2000).
Imperial Mining concluded its Syndicate R&D project at the May Day Mines on 30
June 1998. In their June 1998 Quarterly Report to the Australian Stock Exchange,
Imperial Mining stated:
“The R&D program clearly proved that the Vitrokele technology was not able to cope
with the extraction of copper cyanides adsorbed onto the Vitrokele 912 resin. This
critical failure affected almost all other crucial unit operations from adsorption of
metals from pregnant liquor solution onto the resin to elecro-elution of the precious
metals. Above all, the removal of copper from the circuit and the recovery and
regeneration of sodium cyanide within the plant became impossible to control.”
3.4.1.3 Elutech Process
After the abandonment of the Vitrokele process at May Day Mines, another elution
technique was developed to overcome the problem of the elution of copper cyanides
from commercially available ion exchange resin (Tran et al., 2000). The improved
elution technique was developed based on an acid-oxidation technique. Using
hydrogen peroxide as the oxidant in an acidic media, copper is oxidised to cupric ions,
thus destroying the copper cyanide complex and liberating hydrogen cyanide
(equation 3.42). An AVR circuit recovers the cyanide. Once the copper cyanide is
oxidised the copper is no longer attracted to the resin.
2Cu(CN)12− + H 2 O 2 + 6H + → 2Cu 2+ + 4HCN + 2H 2 O [3.42]
47
The advantage of this elution technique was that in every cycle conducted at the May
Day operation all the adsorbed copper was eluted from the resin. However, in the
presence of iron cyanides, cupric ions will readily form stable copper-iron double
salts, which can passivate the ion exchange resin.
After its elution from the resin, copper can be recovered either by precipitation as
copper hydroxide or by solvent extraction/electrowinning. For the removal of
precious metals from the resin, May Day used conventional using zinc tetracyanide
eluant to elute the precious metals followed by electrowinning.
3.4.1.4 Cognis AURIX Resin
Gold selective resins have been developed to process gold liquors. One such resin is
Cognis Aurix resin that contains guanidine-based ligands. These resins have an
intermediate strength between weak base and strong base ion exchange resins. They
exhibit a pKa of approximately 12 and are capable of being protonated at the operating
pH of liquors from gold plants (Jay, 2000). The resin is easily deprotonated by 1M
sodium hydroxide, thus it can be stripped easily by a change in pH (Mackenzie et al.,
1995).
The chemistry of the loading and stripping can be illustrated in the following
reactions (equation 3.43 & 3.44):
Loading [3.43]
NH2 NH2
RN=〈 + H2O ⇔ RN(H)=〈⊕ + OH-
NH2 NH2
NH2 NH2
-
RN(H)=〈⊕ + OH + [Au(CN)2] -
⇔ RN(H)=〈⊕ . [Au(CN)2]- + OH-
NH2 NH2
48
Elution [3.44]
NH2 NH2
-
RN(H)=〈⊕ .[Au(CN)2] + OH -
⇔ RN(H)=〈 + H2O + [Au(CN)2]-
NH2 NH2
where R represents the resin backbone.
3.4.1.5 Dow-Mintek (Minix) Ion exchange resin
This particular resin was developed for the gold industry to be gold selective over
other base metal cyanides. To increase the selectivity of gold over copper cyanide,
the theoretical ion exchange capacity of the resin was lowered to 0.7-0.9 mmol/g,
which is 25% of the capacity of other strong base ion exchange resins (Jay, 2000).
This Minix resin does not readily absorb metal cyanides like cobalt and iron. The
eluant that is used to elute the gold from the resin is acidic thiourea, because zinc
cyanide is poorly adsorbed.
3.4.1.6 Superhydrophilic Ion Exchange Polymers
Another alternative is the use superhydrophilic polymers. These polymers are

urethane-based containing distributed urea, biuret and allophanate groups, which will
sorb anionic metal groups. It has been found that water-soluble oxide-based polymers
bind with metal cyanide complexes. If the charge density of the polymer is high
enough, the metal may be displaced from the accompanying cyanide ions. This is the
basis of a novel technique for the separation and recovery of copper and other cyanide
species. Oretek holds the patent rights for this process (Jay, 1999).
Recovery of free cyanide and metals that are associated with the cyanide complex
from slurries or solution is done without adjustment of pH. By avoiding pH
adjustment by acidification, generation of hydrogen cyanide is eliminated. The loose
macrocycle structure formation of the polymer matrix enables the copper ion to be
49
sequestered at the centre of the macrocycle cavity, thus coordinating with copper as
follows (equation 3.45):
R
N NR2
H R R
N
N N
H
N + Cu(CN)X + X (CN-)
N R Cu
R
N N N
R R
NH2
where R represents either H, -CH3, -aromatic group, -alkyl chain, -functional group, -
CH2-CH2-NH2. (Jay 2001) [3.45]
An ultrafiltration unit can separate the loaded polymer where the metal-polychelator
complex (retentate) is separated from the cyanide ions (permeate). The free cyanide
can be directly returned to the leach circuit. Copper is recovered by conventional
electrowinning directly from the polychelated copper polymer solution releasing the
polychelator for recycle. The half-cell reactions for the electrowinning cell are given
in equations 3.46-3.48:
Anode : Cu(P) + 2e - → Cu 2+ + (P) [3.46]
H 2 O → 1 2 O 2 + 2H + + 2e − [3.47]
Cathode : Cu 2+ + 2e − → Cu [3.48]
50
3.4.1.7 Elution of Thiocyanate from Strong based ion exchange resins
Thiocyanate has been used as an eluant to elute precious metals like gold cyanide
(Au(CN)2- (Davison, 1962; Fleming,1986). It was found that thiocyanate’s affinity to
strong base ion exchange resins, which lead to great difficulty in displacing the
thiocyanate anion in order to regenerate the resin. In an early case study where
thiocyanate was not eluted from the resin before exposing the resin to gold cyanide
solution found that the adsorption of gold was slower than when the resin was in a
chloride form (Fleming, 1986).
Three processes were developed to convert strong base ion exchange resin in the form
of thiocyanate (R-SCN, where R represents the resin backbone and functional group)
back into the resin original form, either chloride, hydroxide or sulphate (R-Cl, R-OH,
R2-SO4), depending which application the ion exchange resin was used.
3.4.1.7.1 Elution of Thiocyanate Using Mineral Acids
In 1962, Davison filed a patent that proposed a process involving the use of
thiocyanate eluant to strip gold from ion-exchange resins. Sulphuric acid was used to
strip the thiocyanate from the eluted resin and fresh resin is then used to recover the
thiocyanate from the acid liquor. Equation 3.49 illustrates the elution of thiocyanate
from ion-exchange resin in the form thiocyanate:
2R − SCN + H 2SO 4 → R 2 − SO 4 + 2H + + 2SCN − [3.49]
Fleming (1986) repeated Davison’s work and found that when using sulphuric acid to
elute thiocyanate from the resin. After treating the resin that was loaded with
thiocyanate with ten times its volume with acid solution only 50% of the thiocyanate
was eluted from the resin. Fleming (1986) examined other mineral acids such as
nitric and hydrochloric acid and found more satisfactory recoveries from the resin but
51
found that in these eluants thiocyanate decompose fairly rapidly to form elemental
sulphur.
3.4.1.7.2 Elution of thiocyanate with potassium chloride and potassium

hydroxide
Sapjeta et al. (1987) developed a two-stage elution technique to convert resin in the
form of thiocyanate to hydroxide. They proposed the following mechanism for
regeneration (equations 3.50 and 3.51):
R − SCN + Cl − → R − Cl + SCN − [3.50]
R − Cl + OH − → R − OH + Cl − [3.51]
From the first stage of elution, it was reported that 75% of the SCN could be removed
from the resin in 80 minutes using 2M KCl at 45oC. In the second stage it was found
that 100% of the chloride form was converted to hydroxide form using 2M KOH after
1 hour at 45oC. Upon subsequent regeneration there was no significant change in
elution rate of thiocyanate and inferred that this process had no negative effect on the
resin. The resin was checked if there would be a change in gold capacity, after one
regeneration cycle the capacity was 2.9 meqiv Au/g of wet resin. This value did not
change after subsequent regeneration cycles (Sepjeta et al., 1987).
3.4.1.7.3 Elution of thiocyanate with Ferric ions
Fleming (1986) developed an elution process to regenerate resin loaded with

thiocyanate using ferric ions. Regeneration takes place under conditions where ferric
thiocyanate complex cations (Fe(SCN)2+) are formed and then washed from the resin
by the eluant solution. Thiocyanate can be recovered by neutralising the regenerating
52
solution to precipitate iron oxide (Fe(OH)3) to leave thiocyanate ions in solution.
Figure 3.8 illustrates the flow diagram for this process.
The regeneration of ion exchange resin loaded with thiocyanate is contacted with a
eluant containing ferric ions to form Fe(SCN)2+ as shown in equation 3.52. The resin
from this stage can re recycled in the adsorption of precious metals from pregnant
solutions.
2R − SCN + Fe2 (SO)3 → R 2 − SO 4 + 2Fe(SCN)2 + + 2SO 24 − [3.52]
Thiocyanate is recovered by precipitating iron as ferric oxide; the reaction can be

described by equation 3.53. By solid liquid separation, thiocyanate solution can be
separated from iron precipitate and recycled for the elution of gold loaded ion
exchange resin.
Fe(SCN) 2 + + 3OH − → Fe(OH)3(s) + SCN − [3.53]
Iron can be reused in the process by digesting the ferric oxide using a mineral acid to
form ferric ions. This reaction is described by equation 3.54.
2Fe(OH)3 + 3H 2SO 4 → 2Fe3+ + 3SO 24 − + 6H 2O [3.54]
Fleming (1986) found if iron concentration was greater than 40g/l, the elution
efficiency dropped. This was due to the formation of anionic ferric thiocyanate
species that reabsorb onto the resin. Another way formation of anionic ferric
thiocyanate species could occur if there is an uneven flow pattern throughout the resin
bed, this could influence localised iron concentrations. The recovery of thiocyanate
was reported to be approximately 90% (Sapjeta et al., 1987).
53
Metal source
material
Leach Liquor Leaching Residue
Loaded Liquor
Loading of Resin Barren Liquor
SCN-
Loaded-Resin
Regenerated
Resin Elution Metal Recovery
Metal
-
SCN
SCN-Resin
Regeneration
Fe(SCN)2+ Ca(OH)2
Precipitation
Fe(OH)3 + SCN- FeSO4
Liquid
Solid
Fe(OH)3
H2SO4 Acid Digestion
CaSO4
Figure 3.8: Process diagram to regenerate ion exchange resin which was loaded with thiocyanate.
(Fleming, 1986)
54
3.4.2 Solvent Extraction
Solvent-extraction processes have been developed for the removal of copper cyanide
complexes from aqueous copper/gold cyanide solutions. Many different reagents
have been developed, for example XI-78 from the Henkel Corporation based on
mixtures of quaternary amine and a weak acid (Davis et al., 1998). An alternate
solvent extractant is LIX® 79 developed by COGNIS, a guanidine-based extractant
(Virnig et al., 1996; Kordosky et al., 1993). These extractants have similar extraction
properties but XI-78 is characterised by a higher loading capacity compared to LIX®
79.
Normal operation of solvent extraction process for the recovery of a metal product
and cyanide regeneration from cyanide bearing solutions comprises three main steps.
Firstly to recover the metal cyanide species from cyanide solutions solvent extraction
is used, using one of the developed extractants. This is followed by stripping the metal
cyanide species from the loaded organic phase into an aqueous phase. The third step
involves recovering the metal by electrowinning or precipitation while recovering
cyanide by electrolysis or acid volatilisation and alkali adsorption, as discussed
before.
The extractants are very good at adsorbing metal cyanide complexes but stripping the
anions from the extractant can be difficult as the metal complexes must be eluted from
the loaded organic with a second anionic species (for example chloride and
hydroxide). This can be overcome by the addition of a hydrocarbon-soluble weak
acid to the organic phase. The extraction and stripping is then controlled by adjusting
the pH of the aqueous phase. The pH range of operation can be optimised by the
selection of a weak acid having the appropriate pKa.
Davis et al. (1998) describes that the quaternary amine cation (using XI-78) must
extract an anion to maintain charge neutrality in the organic phase. Large anionic
metal complexes are therefore extracted via an ion-pair mechanism. Copper cyanide
is extracted from aqueous solution in the accordance with equation 3.55 and 3.56:
55
Q + RO − (org) + HOH → Q + (org) + ROH(org) + OH − (aq) [3.55]
2Q + (org) + Cu(CN) 32− (aq) → (Q + ) 2 Cu(CN) 32− (org) [3.56]
where ROH represents nonylphenol and Q+ is the quaternary amine cation.
Once the loaded organic phase is contacted with an aqueous strip solution having a
pH >13, the nonylphenol is converted to the highly hydrocarbon-soluble phenoxide
anion. This forms an ion pair with the quaternary amine cation stripping the loaded
anionic metal species to the aqueous phase (equation 3.57).
(Q + ) 2 Cu(CN) 32− (org) + 2ROH(org) + 2OH − (aq) →

[3.57]
2Q + RO − (org) + 2H 2 O + Cu(CN) 32− (aq)
Other existing technologies can be employed to separate the metal cation and the
cyanide. The most suitable technologies are AVR, MNR and the Du Pont processes.
56
3.5 Processes for the recovery of Cyanide From
Thiocyanate
Thiocyanate formation from cyanidation of gold bearing ores is becoming a more

common problem during gold processing. Depending on the sulphur content of the
ore that is contacted with cyanide, the level of thiocyanate that is formed as a by-
product from cyanidation may range from a few mg/l to well over 1000 mg/l. In
extreme cases it has been reported that the thiocyanate level in solution is in excess of
5000 mg/l at mine sites which use cyanidation circuits following biological sulphur-
oxidation processes (Botz et al., 2001). The high level of thiocyanate is caused by
the interaction of cyanide with oxidized and partially oxidized sulphur species.
Thiocyanate is not regulated in mine discharge waters, but it is known that

thiocyanate is toxic to many aquatic species. If mine waters are required to comply to
a toxicity test, thiocyanate may be of concern (for example US E.P.A.’s Whole
Effluent Toxicity W.E.T. test). Therefore thiocyanate detoxification may be needed
in plant operations to comply with the test. Cyanide detoxification that many mines
use may not destroy thiocyanate and other measures may be needed to reduce the
level of thiocyanate.
Another problem caused by the side reaction of cyanide with sulphide materials
within the ore is the cost of cyanide that is consumed. It has been estimated that given
that the cost of cyanide was given at USD 1.30 per kilo of cyanide. The formation of
thiocyanate can account for USD 1.10 as reported by Botz et al. (2001). Table 3.1
shows that if the level of thiocyanate is in excess of 1000 ppm, the additional cost to a
mine is in excess of USD $1 million on an annual basis.
Table 3.1: Operating cost associated with thiocyanate formation (Botz et al., 2001)
Thiocyanate Concentration (ppm) Annual Sodium Cyanide Cost Due to
Thiocyanate Formation (USD)
500 0.8 million
1000 1.5 million
5000 7 million
Note: Calculated for a solution flow of 150 m3/hr and a NaCN purchase price of USD 1.30/kg.
57
3.5.1 Chemistry of Cyanide Regeneration from Thiocyanate
The regeneration of cyanide from thiocyanate can be described by the half-cell

reaction in equation 3.58. There is potentially a continued oxidation of cyanide to
cyanate as described in other oxidation techniques for cyanide destruction to cyanate.
SCN − + 4H 2 O → CN − + H 2SO 4 + 6H + + 6e − [3.58]
Many different oxidants have been studied for the recovery of cyanide from
thiocyanate. Some examples are listed in Table 3.2.
Under acidic conditions several authors (Botz et al., 2001; Soto et al., 1995) have
noted that the oxidation of thiocyanate to cyanide does not continue to form cyanate.
This may be explained in terms of the hydrolysis of cyanide ions. Under acidic
conditions the oxidant oxidises the cyanide ion but not the acid form, hydrogen
cyanide. Thus at low pH, when the concentration of cyanide ion is very low, cyanide
destruction basically stops (Jara et al., 1996).
Table 3.2: Half-cell reactions for the oxidation of thiocyanate.

Oxidant Half-cell Reaction
Oxygen O 2 (g) + 4H + + 4e − → 2H 2 O
Chlorine Cl 2 (g) + 2e − → 2Cl −
Hydrogen Peroxide H 2 O 2 + 2H + + 2e − → 2H 2 O
Caro’s Acid H 2SO 5 + 2e − → SO 24− + H 2 O
Sulphur Dioxide SO 2 (g) + O 2 (g) + 2e − → SO 24−
Ozone O 3 + 6H + + 6e − → 3H 2 O
58
3.5.1.1 Ozone
Ozone has been widely used in many water purification processes. To date, the
majority of experimental work conducted using chemical oxidants to regenerate
cyanide from thiocyanate has been performed using ozone. In comparison to cyanide
destruction, ozone is typically used in operations with small volume and low
concentration of cyanides. Ozone operations have relatively high operation costs
compared to other oxidants such as chlorine, hydrogen peroxide and sulphur dioxide
(Botz et al., 2001).
The oxidation reaction for thiocyanate can take place via two different reactions (Soto
et al., 1995) as shown by equations 3.59 and 3.60. Further oxidation of cyanide to
cyanate can also occur (equation 3.61).
SCN − + 3O 3 (g) + 2OH − → CN − + SO 24− + 2O 2 + H 2 O [3.59]
SCN − + O 3 + H 2 O → CN − + O 2 + H 2SO 4 [3.60]
CN − + O 3 → CNO − + O 2 [3.61]
Both reactions for the oxidation of thiocyanate to cyanide and the continuation of
cyanide to cyanate are fast and are probably mass transfer controlled (Layne et al.,
1984). Representative results for ozonation of thiocyanate are shown in Figure 3.9
which show the concentration of cyanide and related compounds as a function of time
in an ozonation reactor (Layne et al., 1984).
As seen in Figure 3.9 during the first 20 minutes there is a rapid decrease in
thiocyanate concentration that corresponds to a rapid increase in cyanide
concentration. Beyond 20 minutes the concentration of cyanide decreases due the
continued oxidation of cyanide to cyanate. After 40 minutes the concentration of
cyanide approaches zero. The highest cyanide concentration occurs approximately
after 20 minutes of reaction time and this corresponds to approximately 75% of
59
cyanide being regenerated from the oxidation of thiocyanate. Similar results have
been found by Kemker et al. (1980) in which cyanide regeneration was approximately
80 to 85% conversion of thiocyanate to cyanide at a pH of 10.
1.8
Total N
1.6
1.4 CNO-
SCN-
Millimoles/litre
1.2
CN-
1
0.8
0.6
0.4 NO3
0.2
0
0 10 20 30 40 50 60
Time (min)
Figure 3.9: Oxidation of thiocyanate using ozone as the oxidant. (Layne et al., 1984). Operating
conditions: pH=11.2, I=0.23, T=25oC, gas flow=1.60 L/min.
Soto et al. (1995) studied the effect of pH on the oxidation of cyanide using ozone as
the oxidant. Their findings showed that the rate of cyanide destruction to cyanate
decreases as the pH decreases with negligible oxidation below a pH of 4, as seen in
Figure 3.9. In comparison with the work by Layne et al. (1984) it appears that with an
operational pH of 10, the cyanide formed through the oxidation of thiocyanate is
subsequently oxidised to cyanate. In Figure 3.10, the small decrease observed at pH 4
and 6 is largely due to volatilisation of HCN and confirmed by the control test with
nitrogen instead of ozone (curve A, Figure 3.10).
60
250
200
A
CN (f) (mg/L)
150 pH 4
pH 6
100
pH 8
50
pH 12 pH 10
0
0 1 2 3 4 5 6 7
Ozone addition (g)
Figure 3.10: The effect of ozone oxidation on free cyanide (Soto et al., 1995).Note: CN (f) is the
total concentration of HCN and CN-.
The effect of dissolved copper on the rate of oxidation of cyanide to cyanate using
ozone is significant when the copper level is in excess of approximately 10 – 50 ppm
at any pH. This catalytic advantage is commonly used to promote the destruction of
cyanide and forms the basis of several destruction patents (Mathre, 1971; Neville,
1980 and Borbely et al., 1984).
Pilot tests using ozone for the recovery of cyanide from thiocyanate were conducted
for TVX Hellas for their Olympias project in Greece in 1998 and 1999 (Botz, 2001).
The ore from Olympias Project is refractory and near complete oxidation of mineral
sulphides was required before cyanidation. This was accomplished by using a
bacterial leach to oxidise the sulphide ore. Upon cyanidation, significant levels of
thiocyanate were formed, ranging from 2.5 g/l to in excess of 12 g/l. This level of
thiocyanate accounted for approximately 90% of the total cyanide consumption in the
circuit. Regeneration of cyanide was conducted in a bubble column reactor. The
consumption of ozone during the tests was approximately 0.93 gram ozone per gram
of oxidised thiocyanate or about 1.12 moles of ozone per mole of oxidised thiocyanate
giving an average cyanide recovery of 85%.
61
3.5.1.2 Electrolytic Oxidation of Thiocyanate
An alternative to chemical oxidation of thiocyanate is the use of an induced electric

potential to provide the oxidising environment to regenerate free cyanide. This
technology has been successfully tested on a laboratory scale but to date there has
been no full scale testing. An inherent feature of the electro-regeneration of cyanide
from thiocyanate is that the regenerated cyanide is always present under strongly
oxidising conditions. The half-cell reaction is represented by:
CN − + 2OH − → CNO − + H 2 O + e − [3.62]
At the anode surface many different electro-chemical reactions occur involving

thiocyanate, cyanide, cyanate and various oxysulphur species. While the
identification of these reactions is difficult, some of the overall stoichiometries
representing electro-decomposition of thiocyanate are described in equations 3.63–
3.65.
SCN − + 4H 2 O → CN − + SO 24− + 8H + + 6e − [3.63]
SCN − + 5H 2 O → CNO − + SO 24− + 10H + + 8e − [3.64]
SCN − + 6H 2 O → 12 N 2 + CO 2 + 12H + + SO 24− + 11e − [3.65]
In addition to the above reactions, water and hydroxide ions are oxidised at the anode
to form oxygen gas according to equations 3.66 and 3.67. At the cathode there is the
reduction of water to form hydrogen gas (equation 3.68). If other electro-reducible
species are present in the solution for example copper cyanide complexes they will
form elemental copper at the cathode.
2H 2 O → O 2 (g) + 4H + + 4e − [3.66]
62
4OH − → O 2 + 2H 2 O + 4e − [3.67]
2H 2 O + 2e − → H 2 + 2OH − [3.68]
Byerley et al. (1984) used a bipolar flow reactor to regenerate cyanide from
thiocyanate (Figure 3.11). The electrode was made from graphite or coke, depending
on the experimental set-up. They presented data showing the electrolytic oxidation of
thiocyanate using synthetic solutions at varying pH. It was found that 80% of the
cyanide was regenerated at a pH of 2.0 – 2.5. A decrease in cyanide recovery was
observed at neutral to alkaline pH levels. This was attributed to the protonation of the
cyanide ion, which is less susceptible to oxidation to cyanate.
Bi Polar Electrode
++++++++++++++++++++++
Basic cathodic boundary layer
SCN- + 4H2O = CN- + 8H+ + SO42- + 6e-
-------------------------------
++++++++++++++++++++++
2H2O + 2e- = H2 + 2OH-
Bulk pH 9.5 – 11.5
Acidic anodic boundary layer
-------------------------------
Figure 3.11: Schematic of anodic and cathodic boundary layer formation for reactor with
parallel plate bipolar electrodes. (Byerley et al., 1984)
Representative electrolytic cyanide regeneration data presented by Byerley et al.

(1984) are shown in Figure 3.12. The initial pH of the system (pH of 9) was reduced
to a final pH of 2.4 after 200 minutes of cell operation since the oxidation of
thiocyanate is acid positive (equation 3.65). Cyanide recovery for this experiment
was 82%. Other experiments that were buffered in alkaline conditions gave a
63
maximum cyanide regeneration of 13% after 30 minutes of reaction time. After this
period, the regeneration efficiency decreased and approached zero at 120 minutes.
The power consumption of the cell during the experiment was approximately 0.03
kW.hr/g of thiocyanate oxidised.
6000
5000
4000
SCN,CN (mg/l)
3000
CN
2000
1000
SCN
0
0 50 100 150 200 250
Time (min)
Figure 3.12: Electrolytic oxidation of thiocyanate. A graph showing SCN/CN vs. time in a
bipolar flow reactor. (Process conditions: temperature 30oC (av), current 8A (av), initial pH 9
un-buffered (0.09M Na2SO4), final pH 2.4) (Byerley et al., 1984).
3.5.1.3 Hydrogen Peroxide
Hydrogen peroxide has been widely used for cyanide destruction. There have also
been studies for the study of the production of cyanide from the oxidation of
thiocyanate using hydrogen peroxide (Orban, 1986; Wilson et al., 1960(A) and 1960
(B)). The studies conducted by Wilson et al. (1960 (A) and (B)) showed continued
oxidation of cyanide to cyanate that affects the regeneration of cyanide from
thiocyanate at low pH. The reaction of thiocyanate with hydrogen peroxide to
produce cyanide is shown in equation 3.69.
SCN − + 3H 2 O 2 → HCN + SO 24− + H + + 2H 2 O [3.69]
64
Soto et al. (1995) have stated that hydrogen peroxide could not be used for the
regeneration of cyanide from thiocyanate because it is not a sufficiently strong
oxidant. They suggested using stronger oxidants for example ozone or chlorine.
Chlorine can produce toxic derivatives and its use in the mining as well as other
industries is questionable. The preferred oxidant that Soto et al. (1995) used for
cyanide regeneration from thiocyanate is ozone.
Wilson et al (1960 (A) and (B)) proposed that the reaction between thiocyanate and
hydrogen peroxide occurs by two different mechanisms, depending on the pH of the
system. At low pH the oxidation reaction forms hydrogen cyanide and sulphate and
the rate of thiocyanate destruction is much faster than in alkaline solutions. In
alkaline conditions, sulphur di-cyanide (S(CN)2) is formed as an intermediate before
decomposing to cyanate (equation 3.70):
S(CN) 2 + H 2 O → SCN − + CNO − + 2H + [3.70]
It was noted that dissolved copper resulted in rapid catalytic oxidation of cyanide to
cyanate, even at low pH, destroying any regenerated cyanide. Therefore, in using
hydrogen peroxide as an oxidant it is critical to maintain a sufficiently low copper
concentration to minimise the catalytic oxidation of cyanide to cyanate.
3.5.1.4 Caro’s Acid
At low pH, Caro’s acid is capable of regenerating cyanide from thiocyanate (Smith et
al., 1966 (A) and (B)). The chemistry is very similar to that for hydrogen peroxide as
the oxidant, under alkaline conditions in that sulphur di-cyanide is formed as an
intermediate. Equations 3.71-3.73 describe the oxidation of thiocyanate with Caro’s
acid to form free cyanide, di-cyanide and cyanate.
SCN − + 3HSO 5− + H 2 O → HCN + 4SO 24− + 4H + [3.71]
SCN − + HSO 5− + HCN → SO 24− + S(CN) 2 + H 2 O [3.72]
65
HCN + HSO 5− → CNO − + SO 24− + 2H + [3.73]
From the experiment conducted by Smith et al. (1966 (B)), no cyanate was produced
by the direct oxidation of cyanide by Caro’s acid. Cyanate was formed by the
decomposition of the intermediate sulphur di-cyanide.
3.5.1.5 Chlorination
Chlorine has been widely used in the mining industry for cyanide destruction. The
process is operated under alkaline conditions (above pH 10) and results in the
complete oxidation of thiocyanate and cyanide to cyanate (Botz et al., 2001). It has
been theorised that at low pH, chlorine partially oxidises thiocyanate to yield
hydrogen cyanide (Flynn et al., 1995) as illustrated in equation 3.74.
SCN − + 3Cl 2 (g) + 4H 2 O → HCN + SO 24− + 7H + + 6Cl − [3.74]
In addition, chlorine oxidises cyanide to cyanate according to the following reaction:
CN − + Cl 2 (g) + H 2 O → CNO − + 2H + + 2Cl − [3.75]
Botz et al. (2001) calculated the stoichiometric requirements for thiocyanate and
cyanide oxidation with chlorine and the lime needed to neutralise the acid generated
in these reactions (shown in Table 3.1)
66
Table 3.3: Stoichiometric reagents demands for thiocyanate oxidation with chlorine (Botz et al.,
2001).
Reaction Lime Addition Chlorine Addition
(g CaO/g SCN) (g Cl2/g SCN)
Cyanide Regeneration 3.86 3.67
Complete Thiocyanate 4.83 4.90
Destruction
3.5.1.6 Oxygen
The advantages in using oxygen for cyanide regeneration from thiocyanate waste
solutions are that it is relatively inexpensive and readily available. However, a study
conducted by Botz et al. (2001) suggested that the regeneration reaction is
prohibitively slow for practical application. At present, efforts are being made to use
oxygen in the presence of either zeolites or aqueous catalysts consisting of
homogeneous metal salts of copper, manganese and cobalt (Vicente et al., 2003).
Vicente et al. (2003) studied the oxidation of thiocyanate using oxygen at a pressure
of 100 atm and a temperature of 200oC. The experiments were conducted under
alkaline conditions to stabilise any cyanide formed. High temperatures were used to
ensure that the oxidation took place at an adequate rate, while a high pressure was
used to maintain a high oxygen concentration, thereby further increasing the oxidation
rate. The degree of oxidation was a function of temperature, oxygen partial pressure,
residence time and oxidizability of the pollutants.
3.5.1.7 Sulphur Dioxide
Sulphur Dioxide based processes have been used for cyanide destruction but not as of
yet for cyanide recovery. When sulphur dioxide was used for cyanide destruction it
was found that only 10% of the thiocyanate was oxidised (Botz, 2001). The use of
sulphur dioxide and oxygen for thiocyanate oxidation to regenerate cyanide has not
been thoroughly investigated. The following reaction occurs under acidic conditions
(equation 3.76):
67
SCN − + 3SO 2 (g) + 3O 2 (g) + 4H 2 O → HCN + 4SO 24− + 7H + [3.76]
As described in section 3.2.1 sulphur dioxide is used to oxidise cyanide to cyanate in

the presence of a copper catalyst and oxygen.
68
References
Bolinski L., Shirley J. “Russian Resin-In-Pulp technology, current status and resent
developments.” Proceedings from Randol Gold Forum ’96. Randol International
1996, pp 419-423.
Borberly G., Devuyst E., Ettel V., Mosoiu M., Schitka K. “Cyanide removal from
Aqueous Streams.” Canadian Patent No. 1,165,474, 10 April 1984; Covered by US
Patent 4,537,686 27 August 1985.
Baden H. “Silver catalysed oxidation complex of metal cyanides.” US patent

3,772,194. Filed November 13th 1973.
Botz M., Dimitriadis D., Polglase T., Phillips W. and Jenny R. “Processes for the
regeneration of cyanide from Thiocyanate.” Journal of Minerals and Metallurgical
Processing Vol. 18, No. 3, August 2001, pp 126-132.
Byerley J., Enns K. “ Electrochemical regeneration of cyanide from waste

thiocyanate for cyanidation.” CIM Bulletin, Vol. 77, No. 861, 1984. pp 87-93.
Carrillo-Pedroza F.R, Nava-Alonso F. and Uribe-Salas A. “Cyanide ocidation by

ozone in Cyanide Tailings: Reaction Kinetics.” Minerals Engineering, Vol. 3, No. 5,
2000, pp 541-548.
Ciminelli V. “Ion Exchange Resins in the Gold Industry.” JOM, Vol. 54, No. 10,
October 2002, pp 35-36.
Davis M., Sole K., Mackenzie J., Virnig M. “A Proposed sovent extraction route for
the treatment of copper cyanide solutions produced in leaching gold ores.” ALTA
Copper Hydrometallurgical Forum, Brisbane, Australia, October 1998.
Dreisinger D. “The MNR or SART process applied to heap leach solution arising
from cyanide treatment of copper-gold ores.” Paper presented at Metallurgical In-
House Seminar, Orange N.S.W. Australia, Feburary 2-4 1998.
69
Dreisinger D., Barter J., Lane G., Mitchell D., Kelson R., Dunne R. Trang C.
“Cyanide Management by Sart.” Proceedings from Cyanide: Social, Industrial and
Economic Aspects. Annual Meeting of TMS (The Minerals, Metals and Materials
Society) New Orleans, Louisiana, Feburary 12-15, 2001. pp549-363.
Devuyst E., Robbins G. “Cyanide Pollution Control – the INCO Process.”

Proceedings from Randol Gold Forum Cairns ’91. Cairns International Hotel, Cairns,
Queensland Australia 16-19 April, 1991. pp 145-147.
DeVries F. “Brief Overview of the Baia Mare Dam Breach”, Proceedings from
Cyanide: Social, Industrial and Economic Aspects, a symposium held at Annual
Meeting of TMS (The Minerals, Metals and Materials Society) New Orleans,
Louisiana, USA, February 12-15,2001, pp 11-14.
Fleming C. “Regeneration of thiocyanate resins.” US Patent 4,608,176, August 26,

1986.
Fleming C., Cromberge G. 1984 (A). “The elution of auro-cyanide from strong and
weak base resins.” Journal of the South African Institute of Mining and Metallurgy,
84(9), 1984, pp 269-280.
Fleming C., Cromberge G. 1984 (B). “Small scale pilot-plant tests on the resin-in-
pulp extraction of gold from cyanide media.” Journal of the South African Institute of
Mining and Metallurgy, 84(11), 1984, pp 369-378.
Fleming C., Seymore D. “Golden Jubilee RIP Plant.” Proceedings from Randol Gold
Forum, Squaw Valley ’90. Randol International, pp 237-241.
Fleming C., Grot W., Thorpe J. “Hydrometallurgical Extraction Process.” United

States. Patent 5,411,575, May 2, 1995.
Fleming C., Grot W., Thorpe J. ““Hydrometallurgical Extraction Process.” United

States. Patent 5,807,421, September 15, 1998.
70
Flynn C., McGill S. “Cyanide Chemistry: Precious Metals Processing and Waste
Treatment.” NTIS Document PB96-117841, 1995.
Garrison R., Mauk E., Prengle H. “Advanced Ozone Oxidation System for Complex
Cyanides.” Proceedings for First International Symposium on Ozone, International
Ozone Institute, Waterbury, 1975, pp 551-577.
Goldstone A., Mudder T., “Cyanide Regeneration Process.” United States Patent
4,994,243. February 1991.
Imperial Mining. “Quarterly Report to the Australian Stock Exchange, Sydney,

N.S.W., June 1998. (website: Http://www.asx.com.au).
Jara J., Soto H., Nava F. “Regeneration of cyanide by oxidation of thiocyanate.”

United States Patent 5,482,694, January 9, 1996.
Jay W. “Recovery of metal values from values from aqueous solutions and slurries.”
Australian Patent Application PQ3934/99, 1999.
Jay W. “Copper cyanidation chemistry and the application of ion exchange resins and
solvent extractants in copper-gold cyanide recovery systems.” Proceedings from
ALTA 2000 SX/IX-1, Adelaide, Australia.
Jay W. “Copper-Gold Cyanide Recovery Systems.” Proceedings from Cyanide:

Social, Industrial and Economic Aspects, a symposium held at Annual Meeting of
TMS (The Minerals, Metals and Materials Society) New Orleans, Louisiana, USA,
February 12-15,2001, pp 317-337.
Kemker G., Roadcap S., Sitchin R. “The Ozonolysis of aqueous solutions of phenol
and thiocyanate.” NTIS Document ORNL/MIT-318, 1980.
Kordosky G., Kotze M., Mackenzie J., Virnig M. “New Solid and Liquid Ion
Exchange Extractants for Gold.” Proceedings from XVIII International Minerals
Processing Congress, Sydney Australia 1993. pp 1195-1203.
71
Lancy L. and Wasser L. “Plant for continuous alkaline chlorination of waste waters
containing cyanide.” From Water Pollution Abstracts 33, No. 158 (1960).
Layne M. Singer P., Lidwin M. “Ozonation of Thiocyanate.” Conference

proceedings form Cyanide and the Environment, Tucson Arizona, U.S.A. 1984, pp
433-455.
Le Vier K., Fitzpatrick T., Brunk K., Ellett W. “AuGMENT Technologies: an

update.” Proceedings from Randol Gold Forum ’97, Monterey, CA, 1997, pp 135-
137.
Lu J., Dreisinger D., Cooper W. “Copper electrowinning from dilute cyanide solution
in a membrane cell using graphite felt.” Hydrometallurgy, vol. 64, pp 1-11 2002.
Mackenzie M., Virnig M., Johns M. “Henkel AURIX resin-an update.” Proceedings
from Randol Gold Forum Perth ’95: Gold Metallurgy and Environmental
Management. 14-17th March 1995, Perth, Western Australia, pp 425-431.
Mathre O. “Destruction of cyanide in aqueous solutions.” United States Patent

3,617,567, 2 November 1971.
Marsden I., House I. “Chemistry of Gold Extraction.” 1992, published by

Hollingsworth, London.
Mathieu G. “Ozonation for destruction of cyanide in Canadian Gold Mill Effluents-A

Pleliminary Evaluation.” CANMET report,77-11, 1977, pp 45.
Mudder T., Goldstone A., “Cyanide Recovery Process.” United States Patent
5,078,977, January 7th, 1992.
Mudder T., Goldstone A., “Cyanide Recycling Process.” United States Patent
th
5,254,153, October 19 , 1993.
72
Neville R. “Method for the removal of free and complex cyanides from water.”
United States Patent 4,312,760. January 26, 1982.
Nugent A., Oliver M. “The Efflox Process: Comparison of Hydrogen Peroxide and
Caro’s Acid (H2SO5) for Mine Effluent Treatment.” Proceedings from Randol Gold
Forum Carins ’91. Cairns International Hotel, Cairns, Queensland, Australia 16-19
April, 1991. pp 141144.
Orban M. “Oscillations and Bistability in the Cu(II)-Catalysed reaction between

H2O2 and KSCN.” Journal of the American Chemical Society, Vol. 108, 1986, pp
6893-6898.
Paterson M., Jenkins A. “Vitrokele resin technology for the recovery of complex and
free cyanide.” Proceedings from Workshop on Management of Cyanide in Mining.
14-16 April 1997, Perth W.A. Australia.
Robbins G., Devuyst E., Malevich A., Agius R., Iamarino P. Lindrall M. “Cyanide
management at boliden using the INCO SO2/air process.” Proceeding from
International Conference on Mining and the Environment (Securing the Future), Vol.
2, Skelleftea, Sweden 2001, pp 718-728.
Rowley M. and Otto F. “Ozonation of cyanide with emphasis on gold mill

wastewaters.” Canadian Journal of Chemical Engineering, Vol. 58, 1980, pp 646-
653.
Sapjeta J., Law H. and Caseboldt. “Regeneration of ion–exchange resins used for
gold Recovery.” Industrial Engineering Chemical Research, Vol. 26, 1987, pp 1716-
1719.
Satalic D., Spenser P., Paterson M. “Vitrokele: commercial application in the gold
industry.” Proceedings from AusIMM Annual Conference 1996. The Australasian
Institute of Mining and Metallurgy, Melbourne. Pp 167-172.
73
Smith R., Wilson I. “The Mechanism of the Oxidation of Thiocyanate Ion by
Peroxomonosulphate in Aqueous Solution. I. Stoichiometry of the reaction.”
Australian Journal of Chemistry, Vol 19,1966, pp 1357-1363.
Smith R., Wilson I. “The Mechanism of the Oxidation of Thiocyanate Ion by

Peroxomonosulphate in Aqueous Solution. II. Kinetics of the reaction.” Australian
Journal of Chemistry, Vol 19,1966, pp 1365-1375.
Sondak N.E. and Dodge B.F. “The Oxidation of Cyanide-Bearing Plating Wastes By
Ozone: Part 1.” Plating, Vol. 48, 1967. pp 173-180.
Sondak N.E. and Dodge B.F. “The oxidation of Cyanide-Bearing Plating Wastes By
Ozone: Part 2.” Plating, Vol. 48, 1967. pp 280-284.
Soto H., Nava F., Leal J., Jara J. “Regeneration of cyanide by ozone oxidation of
thiocyanate in cyanidation tailings.” Minerals Engineering, Vol. 8, No. 3, 1995, pp
273-281.
Tan E. “Stability of Copper/Iron cyanide double salts.” Undergraduate honours

thesis, School of Chemical Engineering and Industrial Chemistry, The University of
New South Wales 2000.
Tran T., Lee K., Fernando K. and Rayner S. “Use of Ion exchange Resin for Cyanide
Management During the Processing of Copper-Gold Ores”, Proceedings from
Minprex 2000, International Congress on Mineral Processing and Extractive
Metallurgy, 11-13 September 2000.
U.S. Environmental Protection Agency “Technical Report: Treatment of Cyanide

Heap Leaches and Tailings.” September 1994. EPA530-R-94-037, NTISPB94-
201837.
Vicente J., Diaz M. “Thiocyanate/Phenol Wet Oxidation Interactions.”

Environmental Science and Technology, Vol. 37, No. 7, 2003, pp 1452-1456.
74
Virnig M., Mackenzie J., Adamson C. “The use of guanidine-based Extractants for
the recovery of gold.” Hidden Wealth, South African Institute of Mining and
Metallurgy, Johannesburg, South Africa. 1996. pp 151-156.
Wilson I., Harris G., (1960 (A)) “The Oxidation of Thiocyanate Ion by Hydrogen
Peroxide. I. Th pH-Independent Reaction.” Journal of the American Chemical
Society, Vol. 82, 1960, pp 4515-4517.
Wilson I., Harris G. (1960(B)) “The oxidation of thiocyanate by Hydrogen Peroxide,

II. The acid catalysed reaction.” Journal of the American Chemical Society, Vol. 83,
1960, pp 286-289.
Young C., Jordan T. “Cyanide Remediation: Current and Past Technologies.”

Proceedings of the 10th Annual Conference on Hazardous Waste Research, Kansas
State University Manhattan, Kansas, USA, May 23-24, 1995, pp104-129.
Zeevalkink J. et al. “Mechanism and Kinetics of Cyanide Ozonation in Water.”

Water Research, Vol. 14, 1980, pp 1375-1385.
75
Chapter 4
Solution Equilibria
4.1 Introduction
Potential-pH equilibria shown as Pourbaix diagrams have been used extensively to

describe complex chemistry of aqueous redox systems. These diagrams have been
used to help evaluate problems in corrosion science and the stability of different
metal-water systems. The concept has been expanded to different areas in
hydrometallurgy and geochemistry. These diagrams describe regions of stability of
various species under different Eh and pH conditions, which are desired or undesired.
The species will be formed as predicted by the diagram unless some features of the
process kinetics interfere. Kinetic aspects are very important considerations, but it is
clear that they can be studied efficiently only after equilibrium aspects treated by
Pourbaix diagrams are fully understood (Guy G. et al., 1962).
Pourbaix diagrams originated from the theoretical prediction of oxidation-reduction

catalytic processes and the conditions under which these reactions take place in
aqueous solutions. The theory originated on work done by Michaelis which was
based from experimental work conducted by Travers and Thiesse for chemical
systems involving gaseous phase reactions. Pourbaix saw a correlation between
aqueous systems and the theory defined by Michaelis was applied to electrochemical
systems involving aqueous solution chemistry (Pourbaix, 1974).
The theory has been applied to problems that involve the electrochemistry of metals
and non-metals and its application spreads to different branches of electrochemistry
and related fields. Pourbaix describes the application of this theory in the study on the
corrosion of iron. For example, iron can react to form iron oxides and or iron ions
within the aqueous system depending on the aqueous environment where iron is kept,
as seen in Figure 4.1. This figure is divided into several different areas that define the
most predominant species at a particular pH and Eh and relates how the predominant
76
species change as the pH and Eh is changed. In the case iron-water system as seen in
Figure 4.1, the most predominant species at a pH of 4 and Eh of 0V is Fe2+. If it is of
interest to produce a product of Fe(OH)3 from the solution of Fe2+ at a pH of 4 and Eh
of 0V, it can be produced by either increasing the pH or Eh of the system above 6 or
0.25V. If the Eh of the Fe2+ solution is reduced to –0.25V at the same pH of 4 and
then the pH of the system is increased the predominant species changes from Fe2+ to
form Fe(OH)2 before forming the product Fe(OH)3. It maybe disadvantage in
forming Fe(OH)2 as an intermediate through the formation of Fe(OH)3 product
because a higher pH is required which increases the amount of base needed.
Secondly, contamination of the Fe(OH)3 product with Fe(OH)2 which will not happen
if the formation of Fe(OH)3 could be produced without forming Fe(OH)2 as an
intermediate product. By considering each possible reaction that can occur within the
aqueous system, Pourbaix has shown that the limiting conditions for the occurrence of
all known reactions can be represented conveniently in a single diagram.
Fe3+
Fe(OH)3
1
Eh (volts)
O2
0 Fe2+
Fe(OH)2
H2
-1
Fe
-2
0 2 4 6 8 10 12 14
pH
Figure 4.1: Potential-pH equilibrium diagram for the system iron-water, at 25oC. Equilibrium
data for each species are from NBS tables (Wagman et al., 1982). (Fe, Fe(OH)2 and Fe(OH)3
considered as the solid substances)
77
This chapter examines the theory behind the production of Pourbaix and distribution
diagrams and recent developments to automate the production of these diagrams for
different chemical systems. This theory is applied to produce Pourbaix diagrams for
thiocyanate-water and copper-thiocyanate-water systems using the modelling package
STABCAL (version W32-Stabcal). Distribution diagrams were constructed to show
how the ratio of copper to thiocyanate changes the equilibrium concentration of the
different copper thiocyanate species under different pH and Eh conditions.
4.2 Chemical Reactions
Aqueous reactions can be divided into two categories, namely chemical and
electrochemical reactions as defined by Pourbaix (1974). A chemical reaction is a
“reaction which only neutral molecules and positively or negatively charged ions take
part, with the exclusion of electrons”. The electrochemical (or electrode) reaction
shall be defined as “being a reaction involving, besides molecules and ions, negative
electrons (e-) arising from a metal or other substance by metallic conduction. Such
reactions are oxidations if they proceed in the direction corresponding to the liberation
of electrons; or reductions if they proceed in the direction corresponding to the
consumption of electrons”.
These two processes can be summarised in terms of half-cell reactions, which are
shown in generalised form by equation 4.1, written in the form of a reduction:
aA + cH+ +ne- = bB + mH2O [4.1]
By describing a chemical system using the generalised reaction formula we obtain

equilibrium relations that relate the reaction as a function of pH and the electrode
potential. pH measures the effect of the H+ ions and the electrode potential measures
the effect of the charges (e-).
78
4.3 Theoretical Background on the formation of Eh-pH
Any chemical reaction can be described with the general equation (equation 4.1). By
bringing all the terms to one side of the equation the reaction can be written in a more
concise form (equation 4.2):
∑v mγ γ − ne − = 0 [4.2]
where e- is an electron, n is the number of electrons transferred in the reaction, γ an

identification or index of the species and vγ is the stoichiometric coeffiecient of
species mγ. vγ are define as positive for product species and negative for reactants
when the equation is written in reduction form. As an example for equation 4.1:
va = -a, vH+ = -c, vb = +b and vH2O = +m
where a,b,c and m are positive integers.
It is useful to compare the electrode process to some reversible reference electrode in

which the state of equilibrium of a given reversible electrochemical reaction is
obtained. In most cases the standard hydrogen electrode is used for which the
reaction is defined by equation 4.3:
2H + + 2e − ↔ H 2 [4.3]
The standard hydrogen electrode behaves ideally, that is, the activity of H+ in solution
and the fugacity of the gas are unitary (aH+ = pH2 = 1). By applying equation 4.2, the
reference electrode and any reference electrode can be described by equation 4.4:
∑v ref m ref − ne − = 0 [4.4]
79
The overall cell reaction when comparing the reaction studied referenced to a
reference electrode would be given by combining equations 4.2 and 4.4 to give
(equation 4.5)
∑ v m −∑ v
γ γ ref m ref = 0 [4.5]
In an equilibrium situation the equilibrium potential of the cell can be described from
the relationship between Gibbs free energy of the reaction and the potential of the
cell:
ΔG + nF(E − E ref ) = 0 [4.6]
where F is Faraday’s constant (F= 96 485 coulomb/mole) and ΔG is the chemical free
energy for the overall reactions and can be calculated from the chemical potentials of
each species. Therefore ΔG can be defined as:
ΔG = ∑ v γ μ γ − ∑ v ref μ ref [4.7]
where μγ, μref are the chemical potentials of species mγ and mref respectively.
E – Eref is the electrode potential compared to a reference electrode and is defined as

chemical potential (Eh). The most commonly used reference electrode is the standard
hydrogen electrode (SHE) and by definition ESHE = 0V.
For the reaction given in equation 4.1, the relationship between Eh and pH can be
determined:
ΔG = ∑ v γ μ γ − ∑ v ref μ ref
[4.8]
= (-aμ A − cμ H + + Bμ B + mμ H 2O ) − (− nμ H + + n2 μ H 2 )
80
The chemical potential (μγ) for each species concerned can be related to its standard
potential (μγo) by the activity of the species aγ and temperature:
o
μ γ = μ γ + RTlna γ [4.9]
For the SHE reaction, μΗ+ and μH2 are the same as its standard chemical potential.
This is because each of these species are at standard state and the activity of H+ and
the fugacity of H2 is defined as unitary.
Therefore the Gibbs free energy of the reaction of interest can be written as:
o o o o o a bB .a mH 2O
ΔG = −a μ A − (c − n) μ H + − n2 μ H 2 + b μ B + m μ H 2O + RTln [4.10]
a aA .a CH +
Equation 4.10 can be simplified to:
o a bB .a mH 2O
ΔG = Δ G + RTln [4.11]
a aA .a CH +
where ΔGo is the standard free energy change for the overall reaction. Substitution of
equation 4.6 in equation 4.11 yields:
b m
ΔG RT a B .a H 2O
Eh = − − ln [4.12]
nF nF a aA .a CH +
The general relationship for the electrode potential at equilibrium can be described as:
ΔG RT
Eh = − − ∑ v γ ln a γ
nF nF γ
[4.13]
81
The ∑ v ln a
γ
γ γ term can be expressed a different way to give the following term:
∑ v ln a = ∑ ln a = ln ∏ a γ γ
vγ v
γ γ γ [4.14]
γ γ
Therefore equation 4.12 can be rewritten to give:
ΔG o RT a bB RT RT
Eh = − − ln a − 2.303 c.pH − m.ln a H 2O [4.15]
nF nF a A nF nF
From equation 4.15 it can be seen that Eh varies linearly with respect to pH. There are
special cases where there are no electrons transferred or only hydrolysis occurs
between the species of interest A and B. In the case that there is only a redox without
any hydrolysis reactions, equation 4.15 that defines the relationship between the two
species lies horizontal and parallel to the pH ordinate. The other case is when there
are only hydrolysis reactions occurring between species A and B, and then the
defining lines are vertical and parallel to the Eh ordinate. By comparing a series of
related chemical reactions at equilibrium, stable areas will be traced out, and represent
stable regions for a particular or dominant species.
The stability of water is of important consideration when constructing Pourbaix

diagrams, since most systems are aqueous. Water can be oxidised or reduced if the Eh
of the system is too high or low at the respective pH. The stability of water limits the
range of Eh for which the system can be operated. If the Eh is too high or low, water
would either breakdown to produce oxygen (an oxidative environment, high Eh
conditions) or hydrogen (a reducing environment, low Eh conditions).
Decomposition of water into its elements of hydrogen and oxygen follow the
following reaction:
2H 2 O ↔ 2H 2 + O 2 [4.16]
82
Equation 4.16 can be described by two half-cell reactions, reduction to form hydrogen
and oxidation to form oxygen. For the reduction half-cell reaction (equation 4.17):
4H + + 4e − → 2H 2 [4.17]
For the oxidation half-cell reaction (equation 4.18):
2OH − → O 2 + 2H + + 4e − [4.18]
The overall reaction when combining equation 4.17 and equation 4.18 will give the
following equation:
2H + + 2OH − → O 2 + 2H 2 [4.19]
The dissociation of water can be represented by
H 2 O ↔ H + + OH − [4.20]
and when combined with equation 4.19 will give the original equation 4.16, which
describes the decomposition of water.
For the oxidation half cell which is represented by equation 4.21:
2H 2 O → O 2 + 4H + + 4e − [4.21]
the corresponding potential at 25oC is given by
E h = 1.228 − 0.0591pH − 0.0147log p O 2 [4.22]
Similarly for the reduction half-cell the corresponding potential is given by:
83
E h = 0.000 − 0.0591pH − 0.0295log p H 2 [4.23]
For a pressure of one atmosphere for hydrogen and oxygen the logarithmic term
within the equation is equal to zero leaving the following relationships.
E h = 1.228 − 0.0591pH [4.24]
E h = 0.000 − 0.0591pH [4.25]
Between these two lines on a Pourbaix diagram the pressure of hydrogen and oxygen
is less than 1 atmosphere. Therefore at one atmosphere and a temperature of 25oC the
area between these two lines is where water is thermodynamically stable.
84
4.4 Distribution Diagrams
Distribution diagrams represent the speciation of various species in a multi-

component aqueous system. These diagrams have an added benefit over Pourbaix
diagrams as they allow an independent variable to be varied in order to see its effect
on the distribution of different species present in the system. STABCAL a program
developed Huang et al. (1989 (A) and (B)), uses the same principles as those used in
the construction of Pourbaix diagrams. The main difference between the Pourbaix
and distribution diagrams is that distribution diagrams solve calculations for a mass
balances for each component.
The mass balance for each component is defined as the mass of all the related species
to be equal to a predetermined total mass. This avoids the system becoming
supersaturated and solid species should be included for each component. The other
set of equations needed to determine the distribution of the species are defined by
chemical equilibria. The program uses thermodynamic data in the form of Gibbs free
energies of formation. From this chemical reactions, equilibrium equations and
equilibrium constants can be determined.
Two methods are used to solve the mass distribution calculations based on either free
energy minimisation and mass action (equilibrium) calculations. STABCAL uses the
mass action calculations because it does not involve sophisticated numerical methods
such as non-linear programming.
4.4.1 Theory behind the distribution diagram
Consider an aqueous system that consists of I chemical species and has J components.
There will be J mass balance equations and I - J chemical reactions, which will be
labelled as T reactions.
85
The mass balance equations are defined by equation 4.26:
∑A
i =1
ji mi = M j for j = 1 to J [4.26]
where Mj is the total concentration of jth component, mi is the concentration of the ith
species, and Aji is the number of atoms from jth component for ith species.
The equilibrium equations for the distribution diagram are similar to Pourbaix
diagrams by defining from the free energy of reaction ΔGor according to the Nernst
equation (equation 4.27). For a system with known pH and Eh, the equilibrium
equation depends on the activities of the chemical species involved. If gaseous
species are present, this can be accounted according to their reaction coefficients and
partial pressures.
(nFEh − ΔG or )
ln(K) = [4.27]
RT
Equation 4.28 describes each reaction within the system (T in total):
I I
∑ B ti ln(a i ) = ∑ B ti ln(ri m i ) = ln(K t )

i =1 i =1
for t = 1 to T [4.28]
This can be rearranged to give the following equation 4.29.
I I
∑ B ti ln(m i ) = ln(K t ) − ∑ B ti ln(ri ) = ln(K 't )

i =1 i =1
[4.29]
where ai, ri are the activity and activity coefficient of the ith species respectively, K’t
is the tth equilibrium constant that includes also the pH, Eh and activity coefficients
and gaseous pressure, and Bti stoichiometric coefficient from ith species to tth
equilibrium equation.
86
Stabcal (version W32-Stabcal) uses the Newton-Raphson method to solve the
equations for the defined chemical system. Calculations can be solved for one species
or all at once, Huang (1989(B)) uses the latter method because the system converges
faster.
Usually concentration (mi) or mole fraction (xi) are variables that are used as the
iteration variables. Another option to use is to take the logarithmic concentration as
the iteration variable. This has a benefit as it expands the concentration to a
logarithmic scale and avoids some computational problems, for example when the
concentration of mi is small. For example, in a study of the stability of different
uranium species (Huang, 1989(B)), the calculated concentration of UO2(CO3)34- was
found to be 2.3984 x 10-47 M. With results like this computations can assume that the
concentration for this species to be zero. A value of zero for a concentration or
equilibrium constant can disturb the equilibrium equations and as a result can cause
errors within a simulation. By the introducing a new variable yi = ln(mi) this problem
can be avoided. In turn with the introduction of yi, the mass balance equations are no
longer linear and the equilibrium equations to become linear equations. The mass
balance equations then become (equation 4.30):
I
f j = ∑ A ji exp(y i ) − M j = 0 [4.30]
i =1
From this the derivative of this equation with respect to y becomes (equation 4.31):
df j
= A ji exp(y i ) for j = 1 to J [4.31]
dy i
Similarly the equilibrium equations by the introduction of y become (equation 4.32):
I
g t = ∑ B ti y i − lnK 't = 0 [4.32]
i =1
and the derivative of this equation with respect to yi is (equation 4.33):
87
dg t
= B ti for t = 1 to T [4.33]
dy i
From all equations a series of matrices can be formed and solving the equations by
repeating a number of iterations till a specified tolerance is met, giving a resultant
solution (a vector of y). Haung has described the operations, which are given below:
From an initial value of yi(0), a new value of yi(0) is calculated by the following matrix
operations (equations 4.34 to 3.37).
V (0) = −(W (0) ) −1 U (0) [4.34]
where V is a I vector:
v i = y i(1) − y i(0) [4.35]
W is an I x I matrix:
(0)
⎛ df j ⎞
w ni = ⎜⎜ ⎟⎟ when n ≤ J.
⎝ dy i ⎠
[4.36]
(0)
⎛ dg ⎞
w ni = ⎜⎜ t ⎟⎟ when n > J.
⎝ dy i ⎠
U is an I vector:
u n = f j(0) when n ≤ J.
[4.37]
un = g (0)
t when n > J.
88
All calculations up to this point have only considered soluble species. When a solid is
introduced in the calculations, the calculations can be simple if the solid species are
exactly known under the systems operation conditions (Eh and pH). This sort of
information is not always available for certain conditions or if the conditions change.
The normal procedure is to calculate the distribution for the aqueous species first.
Then from the results check to see if any species are super-saturated. If saturation
occurs, search for the solid species that will precipitate. Morel and Morgan (1979)
used a trial and error method to determine the solid species.
When STABCAL introduces solid species to an aqueous system, two assumptions are
made. It assumes that all solids behave as an ideal solid solution and the solid species
have unit activity. The solid species equations are basically the same equations that
are used for aqueous species the only difference is that for solid species mole fraction
are used instead of molality to describe the species.
With all this in mind, assume a system that consists of I chemicals, of this there are Q
dissolved species, giving S solids (S = I-Q). The mass balance equations would
change to include the solid species and the equilibrium equations for the aqueous
species should remain unchanged. The new equations to describe the system are
described in equations 4.38 and 4.39 for the mass balance and equilibrium equations,
respectively.
∑B
i =1
qi ln(m i ) = ln(K 'q ) for q = 1 to Q [4.38]
I ⎛ I ⎞
∑ B si ln(m i ) = ln(K '
s ) + B ss ⎜ ∑ m s ⎟
ln ⎜ ⎟ for s = Q + 1 to I [4.39]
i =1 ⎝ s =Q +1 ⎠
The last term in equation 4.39 has been included to convert mole concentration to
mole fraction. The stoichiometric coefficient for the solid, Bss, should be one because
if all the master species are ions, there is only one solid species per solid equilibrium
equation.
89
Letting the variable ys = ln(ms) and applying the assumption that there is unit activity
for solid species, the variable ys will become zero for all solid species. The
equilibrium equations will change to give the following equation (equation 4.40):
∑B
i =1
si ln(m i ) = ln(K s' ) for s = Q + 1 to I [4.40]
From the solid solution calculations, Huang (1989(B)) has reported that some of the
solid species may be rejected because of low mole fractions or a disagreement with
the phase rule. Once a solid species is eliminated as one of the possible stable
species, iteration can start with the remaining species.
It becomes nearly impossible to reject a solid species because of negative mass since
the iteration variable is the logarithm of concentration. The program rejects the solid
species during the iteration if it causes the matrix W to become a singular determinant
or the mass is extremely small compared to the rest of the other species.
90
4.5 Developments in computer aided programs to produce
Pourbaix diagrams
Since the age of the computer, programs have been developed to aid researchers in
producing Pourbaix diagrams. The main differences between the different programs
available for producing Pourbaix diagrams differ by the approach of removing
redundant boundary lines between stable compounds. The main methods of doing
this are the point-by-point method, the line elimination method and the convex
polygon method.
4.5.1 Point-by-point method
The “point-by-point” method has been named because every point on the plane of the
Eh-pH diagram is considered separately. Duby (1963) at Colombia University
developed one of the first programs. One of the limitations of this method is the
resolution of the diagram can be limited to the number of calculations required to be
performed.
This is a foolproof method in determining the diagram since it calculates the species
with the lowest free energy of formation, which is the most stable species at each
point on the diagram. This is the basis of all equilibrium calculations in
thermodynamics. The problem that is faced by this method of calculation is that it
requires a large number of calculations for each point on the diagram and the actual
number of calculations is very dependent on the resolution of the diagram.
The output from this method is an array of symbols representing the stable species at
each point on the Eh-pH diagram. The boundaries separating the different stable
regions can be dependent on the number of points calculated. If the resolution in the
diagram is not well defined, the boundaries separating the different stable regions can
be confusing; this can be overcome by increasing the resolution of the diagram.
91
4.5.2 Line elimination method
This method focuses establishing equilibrium lines to determine relevant boundaries

between stable compounds. Brook (1971) proposed that for any chemical system can
be defined by important system characteristics:
1. The valency of stable metallic species increases as the potential increases.
2. With an increase in pH the stable ionic type changes from cationic to non-
ionic then anionic.
3. Most intersections of reaction lines are triple points.
Applying important characteristics of a system defined by Brook (1971) to group the

common species together and to order all lines generated by decreasing slope (using
the theory developed by Pourbaix). The line with the greatest slope for a given
species is defined as a phase boundary and continues to be so until it intersects with
the line with the next highest slope or plot boundary. Within the plot boundary, the
new line intersection becomes the phase boundary until it to reaches an intersection.
When the boundaries have been established for the first species (the species with the
lowest valency and least anionic), succeeding species are treated similarly except if
the line has already been considered previously. The end result is the establishment
of the phase boundary lines.
This method overcomes some of the disadvantages that occur when using the point-
by-point method by establishing line boundaries. Allowances have to be made to
allow inconsistencies in the data to make the program to accept some triple points if
the three intersections involved are less than some distance apart.
There are some deficiencies in the proposed algorithm. In some cases the algorithm
does not necessarily define a particular species uniquely, for example in the Cu-H2O
system; the following species can be defined the same, HCuO2- and CuO2-, because
they have the same oxidation number of 2+ and are both anionic (for which the ion
type parameter is –1). This can be fixed by using an alternative scheme for
92
identifying each species (Linkson, 1979). The main limitation of the method
developed by Brook (1971) is that the algorithm will not determine the correct
stability diagram if the species involved are not ultimately stable. This limits the
generality of the algorithm because before a stable system can be identified, the
program would have to be run and rerun until a consistent set of boundaries are found.
4.5.3 Convex polygon method
The convex polygon method as with the point-by-point method developed by Duby
(1977) is robust. Compared to the line elimination method the convex polygon
method has more calculations to complete increasing the computation time but has the
main advantage of eliminating the species that are not stable.
When a predominant area is found it satisfies several inequalities simultaneously and

forms a convex polygon. The line elimination method relies on the fact that the
boundaries form predominant areas; but the convex polygon method develops
procedures to form predominant areas by the formation of polygons.
The first work in defining convex polygons was studied by Froning et al. (1976).
They applied convex polygon theory to the formation of Pourbaix diagrams. Their
technique involved the use of conventional mathematical theory to determine the
convex polygon for each species from the equilibrium lines that are involved. The
equilibrium lines are considered in groups and by using a sorting algorithm
establishes possible boundaries for a species to form a convex polygon. If the
polygon is a stable area for a particular species, the convex polygon satisfies all the
equilibrium line equations for each individual species and consequently the
predominance area for that species has been determined.
STABCAL (version W32-Stabcal) was developed by Haung and used to generate the
stability diagrams for the thiocyanate-water and copper-thiocyanate-water systems.
This program uses a linear algebra method similar to the convex polygon method
developed by Verink. This model has two basic assumptions based on work done by
Garrels and Christ (1965): the total mass of each component is assigned to the
93
predominant species and the total concentration of the ligand component is assigned
to the ligand species that are not complexed to the main component. The algorithm
defines constraint equations that apply to each species. Then searches for boundary
lines and corner points of a predominant area enclosed by 2 constraints imposed to
each species, which are boundary lines of each ligand. Equilibrium constraints are
determined from equilibrium equations and chemical reactions.
94
4.6 Pourbaix Diagrams for the Thiocyanate-Water and
Copper-Thiocyanate-Water Systems
In this study stability diagrams were simulated for the thiocyanate-water system using
the Stabcal (Stability Calculation for Aqueous System) version 32-STABCAL SN 8-
19-2001. The species that were considered to determine the stability products for the
thiocyanate-water system were products related to thiocyanate and cyanide. These
species are summarised in Table 4.1 including the Gibbs free energies of formation
that were used within the simulation. A comparison between the American National
Bureau of Standards (NBS) of chemical thermodynamic properties (1982) and data
that Duby (1977) reported during studies of different copper systems showed that the
values for each species used were very similar in each reference. The values used
within the simulation were from the NBS Tables.
Other species of different sulphur compounds were included within the simulation to
balance the sulphur during the oxidation and reduction of thiocyanate. Many of the
sulphur compounds are thermodynamically unstable and tend to decompose at
standard room temperature and pressure. Pourbaix (1974) reported that the
thermodynamic instability of many sulphur compounds such as thiosulphates,
diathionites, sulphites and polythionates shows a false equilibrium between the
different sulphur species in aqueous solution. It is added that persulphates are
unstable in water. It was suggested that if the equilibria were obtained, only H2S, HS-
, S2-, S, HSO4- and SO42- would be found in solution. For this reason these 6 sulphur
compounds were the chosen species for the simulation.
4.6.1 Thiocyanate-Water System
Figure 4.2 and Figure 4.3 are potential-pH equilibrium diagrams for thiocyanate-water
system at 25oC. For Figure 4.3 the cyanate and hydrogen cyanate were removed as
stable species to show that if the oxidation of thiocyanate to produce cyanide, either
free cyanide or hydrogen cyanide would become the predominant species.
95
Table 4.1: Gibbs Free Energies for Thiocyanate and related species at 25oC.
Species Duby (1977) NBS Tables (1982)
ΔGof (kcal/mol) ΔGof (kcal/mol)
HCN (l) 27.86 29.869

HCN (aq) 28.6 28.609
CN- (aq) 41.2 41.205
-
CNO (aq) -23.3 -23.279
HCNO (aq) -28.0 -27.988
SCN- (aq) 22.15 22.158

HSCN (aq) 23.31 23.317
(SCN)2 (l) (79.9) 79.9
H2S (aq) - -6.652

-
HS (aq) - 2.887
S2- (aq) - 20.507
S (s) - 0
HSO4- (aq) - -180.667
SO42- (aq) - -177.947
CuSCN (s) 16.7 16.706

Cu(SCN)43- (aq) 87.0 87.022
CuSCN+ (aq) 34.7 34.63
Cu(SCN)2 (aq) 54.9 54.947
96
The predominant species formed in solution in the thiocyanate water system is
cyanate and its protonated form hydrogen cyanate seen in Figure 4.2. With an Eh less
than 1 V over the entire pH range, either cyanide or hydrogen cyanide is the
predominant stable species. The division between cyanide and hydrogen cyanide
occurs at the value of pKHCN at 25oC, the same applies for cyanate and hydrogen
cyanate.
The concentration of thiocyanate was varied from 0.001 to 1 M thiocyanate to see

how the areas of predominant species change with concentration. As seen in Figure
4.2, as the concentration of thiocyanate is increased the stability region for
thiocyanate increased becoming the predominant specie more stable over a wider pH
range. When cyanate and hydrogen cyanate were removed from the simulation
(Figure 4.3) the effect of concentration did not change the predominant region for
thiocyanate significantly, with thiocyanate being stable close to the water stability
hydrogen line from pH of 0 to 14.
HOCN(a)
1 OCN-
Eh (volts)
O2
0
SCN- -3
-2 -1 0
H2
-1
HCN(a)
CN-
-2
0 2 4 6 8 10 12 14
pH
97
2
1
HCN(a) CN-
Eh (volts)
O2
-3 -2 SCN-
-1 0
H2
-1 HCN(a)
CN-
-2
0 2 4 6 8 10 12 14
pH
Figure 4.3: Potential-pH equilibrium diagram for thiocyanate-water system at 25oC. Excluding
cyanate and hydrogen cyanate from the simulation.
From Figure 4.2 and Figure 4.3 it can be demonstrated that under oxidising conditions
it is thermodynamically possible for the production of free cyanide from thiocyanate
if the continued oxidation of free cyanide can be stopped. The effect of increasing the
concentration of thiocyanate from 0.001M to 1M does not introduce new predominant
species within the thiocyanate-water system.
4.6.2 Copper-Thiocyanate-Water System
In the past, copper (II) has been added as a catalyst in many cyanide destruction
processes. For the recovery of cyanide via the oxidation of thiocyanate it was
postulated that copper could give the same advantage. Therefore it is of interest to
understand the formation of different copper thiocyanate species under different
operating conditions.
98
Copper can form stable complexes with thiocyanate in an aqueous system. The four
stable complexes that can occur are solid copper (I) thiocyanate (CuSCN) and three
other soluble species complexed with either copper (I) (Cu(SCN)43- and Cu(SCN)2) or
copper (II) (Cu(SCN)+). These species were included to simulate the copper-
thiocyanate-water system.
Figure 4.4 shows the stability diagram for the copper-thiocyanate-water system at
25oC at a copper and thiocyanate concentration of 0.001M. From this diagram the
only stable species containing thiocyanate is the solid copper (I) thiocyanate with the
other species being copper and different forms of copper oxide. Increasing the
thiocyanate concentration to 0.01M with the same copper concentration of 0.001M a
new predominant region is established for copper (II) thiocyanate (CuSCN+) at a low
pH and in an oxidising environment, as seen in Figure 4.5.
The thiocyanate concentration was increased further to 0.1 and 1M as shown in Figure
4.6 and Figure 4.7, respectively. At a higher concentrations of thiocyanate the
predominant stable copper species can exist with a higher proportion of thiocyanate,
in particular Cu(SCN)2 and Cu(SCN)43-. At low pH the species that are formed are
mainly copper (I) species, either CuSCN(s), and Cu(SCN)2. At higher Eh conditions,
i.e. in an oxidising environment copper (I) thiocyanates are oxidised to copper (II)
thiocyanates to form CuSCN+. The formation of Cu(SCN)43- occurs when the
thiocyanate concentration was 1M, and is stable between the regions of CuSCN and
CuO, as seen in Figure 4.7.
As the copper concentration is increased from 0.001M to 1M, at a constant

thiocyanate concentration of 0.001M (Figure 4.8), stability regions of Cu2+, CuSCN
and CuO change. As the copper concentration is increased, CuSCN region becomes
more predominant at a higher Eh, and the CuO region extends more into the acidic
environment.
99
2
Cu2+
CuO
1
Eh (volts)
O2
CuSCN
0
Cu2O
H2
-1 Cu
-2
0 2 4 6 8 10 12 14
pH
Figure 4.4: Potential-pH equilibrium diagram for the copper-thiocyanate-water system at 25oC,
at a copper and thiocyanate concentration of 0.001M.
Cu2+
CuO
1
CuSCN+
Eh (volts)
O2
CuSCN
0
Cu2O
H2
-1 Cu
-2
0 2 4 6 8 10 12 14
pH
at a copper concentration of 0.001M and thiocyanate concentration of 0.01M.
100
2
Cu2+
CuO
1 CuSCN+
Cu(SCN)2(a)
Eh (volts)
O2
CuSCN
0
Cu2O
H2
-1 Cu
-2
0 2 4 6 8 10 12 14
pH
at a copper concentration of 0.001M and thiocyanate concentration of 0.1M.
Cu2+
1 CuSCN+ CuO
Cu(SCN)2(a)
Eh (volts)
Cu(SCN)43- O2
CuSCN
0
Cu2O
H2
-1
Cu
-2
0 2 4 6 8 10 12 14
pH
at a copper concentration of 0.001M and thiocyanate concentration of 1M.
101
As the concentration of thiocyanate and copper are changed at the same level from
0.001M to 1M (results can be seen in Figure 4.9 and Figure 4.10), similar trends
developed as observed in Figure 4.4 through to Figure 4.8. As the thiocyanate and
copper concentration is increased from 0.001 to 0.01M CuSCN+ becomes a
predominant species within the diagram above CuSCN under acidic conditions (seen
in Figure 4.9). The effect of increasing the copper and thiocyanate concentrations
above 0.01M introduces another stable region for Cu(SCN)2 between CuSCN and
CuSCN+, shown in Figure 4.10. Cu(SCN)43- is not a stable species within the Eh-pH
diagram. In this case the ratio of thiocyanate to copper does not change as with the
scenario shown in Figure 4.6. An important factor emerges in that it is important to
maintain a high thiocyanate to copper ratio for the stability of Cu(SCN)43-. However,
in practice, the concentration of thiocyanate in mine waters does not reach this level
to form Cu(SCN)43- in tailing waters.
2
0
-1
Cu2+
-2
CuO
1 -3
0 -1
-2-3
Eh (volts)
O2
CuSCN
0
Cu2O
H2
-1 Cu
-2
0 2 4 6 8 10 12 14
pH
at a thiocyanate concentration of 0.001M and changing copper concentration from 0.001 to 1M.
102
2
Cu2+ -2
-3
1 CuO
CuSCN+
Eh (volts)
O2
CuSCN -3
-2
0 -3
-2 Cu2O
H2
Cu
-1
-2
0 2 4 6 8 10 12 14
pH
the thiocyanate and copper concentrations are at the same of either 0.001 or 0.01M.
Cu2+ 0
-1
CuO
1 CuSCN+
Eh (volts)
Cu(SCN)2(a)
O2
CuSCN -1 0
0 -1
Cu2O
0
H2
-1 Cu
-2
0 2 4 6 8 10 12 14
pH
the thiocyanate and copper concentrations are at the same of either 0.1 or 1M.
103
4.7 Distribution Diagrams for the Copper-Thiocyanate-
Water System
The distribution diagrams can show which species are stable under different copper-
thiocyanate systems that are formed during the oxidation of thiocyanate in the
presence of hydrogen peroxide. From oxidation experiments using hydrogen
peroxide to oxidise thiocyanate (as seen in Chapter 6), copper was added to the
system to see if copper had any catalytic effect upon the oxidation of thiocyanate. In
these experiments the concentration of copper was constant since it was not consumed
in the reaction, while the thiocyanate concentration changed with time as it was
consumed, hence changing the ratio of thiocyanate to copper. To emulate the change
in thiocyanate to copper ratio, a base case of 0.001M thiocyanate and copper was
simulated. Then 0.1 moles of either copper or thiocyanate were added step wise to
the base case and the distribution of the different copper-thiocyanate species were
calculated.
Species that are of interest and under investigation were free thiocyanate (SCN-) and
the protonated form (HSCN) and other thiocyanate species complexed with copper
(CuSCN(s), Cu(SCN)2, CuSCN+ and Cu(SCN)43-). To keep the simulation simple and
to show the stability between the different copper-thiocyanate species the only other
species that were included in the simulation were copper (I) and copper (II) ions.
The solution chemistry of the system was changed by manipulating the pH and Eh of
the operating solution. The pH and Eh were changed to three different conditions, i.e.
the pH of the system was studied at a pH of 0, 7 and 12 and the Eh of the solution
changed from –0.25, 0 and 1 V. The conditions for each simulation are summarised
in Table 4.2.
104
Table 4.2: Operating conditions for the simulations to determine the distribution diagrams for
the copper-thiocyanate-water system.
Simulation pH Eh (V)
1 7 -0.25
2 7 0.00
3 7 1.00
4 0 -0.25
5 0 0.00
6 0 1.00
7 12 -0.25
8 12 0.00
9 12 1.00
At equilibrium, the majority of the thiocyanate exists as free thiocyanate (SCN-) or

species complexed with copper like the solid copper (I) thiocyanate (CuSCN) when
the initial concentration of thiocyanate and copper is set at 0.001M with a pH of 7 and
an Eh of 0V, seen in Figure 4.11. To this system either copper or thiocyanate were
added to change the ratio of thiocyanate to copper under different system conditions
(i.e. pH and Eh) to see how the different ratios change the distribution of species
within the system. For example in the case of Figure 4.11 additional copper was
added.
Figure 4.12 to Figure 4.17 show the individual components studied for the copper-
thiocyanate-water system when additional free thiocyanate is added to the system
changing the ratio of thiocyanate to copper ratio. Thiocyanate exists predominantly
as either free or hydrogen thiocyanate and when complexed with copper it forms
significant amounts of copper (I) and copper (II) complexes. Due to large amounts of
excess free thiocyanate, copper will form copper (I) tetra-thiocyanate (Cu(SCN)43-),
but the concentration levels are very low (in the order of magnitude of 10-7
moles/litre). Therefore the formation of Cu(SCN)43- is insignificant in the simulations
studied.
105
-3
CuSCN
CuSCN+
SCN-
-4
log(mol/L)
-5
-6 Cu(SCN)2(a)
-7
-8
0 0.2 0.4 0.6 0.8 1
Ammount of 0.1M Cu added (L)
Figure 4.11: Distribution diagram for copper-thiocyanate and water system. The initial
concentration of thiocyanate and copper is 0.001M at 25oC with the addition of copper (II).
Figure 4.12 and Figure 4.13 show the concentration of free thiocyanate and hydrogen
thiocyanate, respectively. Figure 4.12 shows that there is a drop in free thiocyanate at
a pH of 0 compared to the simulations that were at the higher pH of 7 and 12. This is
because at low pH there is an abundant amount of hydrogen ions to protonate
thiocyanate. The effect of changing Eh did not have an effect on the concentration of
free and hydrogen thiocyanate (Figure 4.12 and Figure 4.13).
106
0.06
Thiocyanate concentration (mole/litre)
0.05
0.04
0.03
0.02
0.01 Eh = -0.25, 0 or 1 at pH 7
Eh = -0.25,0 or 1 at pH 0 or 12
0
0 10 20 30 40 50 60 70 80 90 100
SCN:Cu Ratio
Figure 4.12: A comparison of free thiocyanate concentration (SCN-) at different pH and Eh

conditions as the ratio of thiocyanate to copper is changed.
Hydrogen thiocyanate Concentration (mole/litre)
0.003
Eh = -0.25,0 or 1 at pH 7 or 12
0.0025 Eh = -0.25,0 or 1 at pH 0
0.002
0.0015
0.001
0.0005
0
0 20 40 60 80 100
SCN:Cu Ratio
Figure 4.13: A comparison of hydrogen thiocyanate concentration (HSCN) at different pH and

Eh conditions as the ratio of thiocyanate to copper is changed.
107
As the thiocyanate to copper ratio approached a ratio of 15:1, the simulations that
were conducted at a pH of 7 and 12 (Figure 4.14) shows that the concentration of
CuSCN+ reached a maximum concentration of 0.005M before decreasing gradually as
the thiocyanate to copper ratio continued to be increased. As the ratio of thiocyanate
to copper ratio increased above 15:1, the concentration of CuSCN(s) was the only
species that increased (Figure 4.15), this accounts for the loss of free copper in
solution. The concentration of CuSCN+ for simulations conducted at a pH of 0 is
lower compared to simulations at a pH of 7 and 12 (Figure 4.14). At each pH level
changing the Eh of the system did not change the concentration of CuSCN+.
0.0006
Copper (II) thiocyanate concentration
Eh = -0.25, 0 or 1 at pH 0
0.0005
Eh = -0.25, 0 or 1 at pH 7 or 12
0.0004
(mole/litre)
0.0003
0.0002
0.0001
0
0 20 40 60 80 100
SCN:Cu Ratio
Figure 4.14: A comparison of copper (II) thiocyanate concentration (CuSCN+) at different pH

and Eh conditions as the ratio of thiocyanate to copper is changed.
Figure 5.15 shows that there is no difference between the nine simulations conducted
with respect to the amount of CuSCN(s) present as the concentration of thiocyanate
was increased. This species is the only species that was not affected when pH and Eh
were changed as the ratio of thiocyanate to copper was increased.
108
0.06
Copper (I) Thiocyanate concentration

0.05
0.04
(mole/litre)
0.03
0.02
0.01
Eh = -0.25, 0 or 1 at pH 0,7 or 12
0
0 20 40 60 80 100
SCN:Cu Ratio
Figure 4.15: A comparison of the amount of copper (I) thiocyanate (CuSCN) at different pH and
Eh conditions as the ratio of thiocyanate to copper is changed.
0.00025
Copper (I) di-thiocyanate Concentration
0.0002
(mole/litre)
0.00015
0.0001
0.00005 Eh = -0.25, 0 or 1 at pH 7 or 12
Eh = -0.25, 0 or 1 at pH 0
0
0 20 40 60 80 100
SCN:Cu Ratio
Figure 4.16: A comparison of copper (I) di-thiocyanate concentration (Cu(SCN)2) at different pH

and Eh conditions as the ratio of thiocyanate to copper is changed.
109
Shown by Figure 4.16, there is a lower concentration of copper (II) di-thiocyanate
(Cu(SCN)2) in very acidic conditions (pH = 0) compared to the other simulations
carried out at pH of 7 and 12. As the ratio of SCN- to copper increased to 40:1 the
concentration of Cu(SCN)2 reached a maximum concentration of 0.0002M for
solutions of pH 7 and 12 and 0.00014M at a pH of 0. Figure 4.17 shows the
concentration of copper (I) tetra-thiocyanate as the ratio of thiocyanate to copper(II)
ratio is increased. The concentration of this species maybe insignificant compared to
the other copper-thiocyanate species but there is an interesting observation. When the
ratio of SCN:Cu was lower than 15, there was no formation of Cu(SCN)43-. As the
SCN:Cu ratio increased past 15:1 the concentration of Cu(SCN)43- increased
exponentially until the ratio of SCN:Cu reached a value of 65:1 for simulations
carried out at a pH of 0 and a ratio of 90:1 at other pH levels studied. After the
SCN:Cu ratio was above 90:1 the concentration of Cu(SCN)43- was the same for all
pH levels studied.
7.0E-07
Copper (I) tetra-thiocyanate concentration
Eh = -0.25, 0 or 1 at pH 0
6.0E-07
Eh = -0.25, 0, 1 at pH 7 or 12
5.0E-07
(mole/litre)
4.0E-07
3.0E-07
2.0E-07
1.0E-07
0.0E+00
0 20 40 60 80 100
SCN:Cu Ratio
Figure 4.17: A comparison of copper (I) tetra-thiocyanate concentration (Cu(SCN)43-) at different

pH and Eh conditions as the ratio of thiocyanate to copper is changed.
110
A second set of simulations was carried out by the addition of copper (II) ions instead
of free thiocyanate increasing the ratio of copper to thiocyanate. Figure 4.18 to Figure
4.22 show the concentration of the individual species present in the different
simulations. For each simulation when copper(II) was added to the system did not
show the formation of copper(I) tetra-thiocyanate. This is because the formation of
copper(I) tetra-thiocyanate needs a high ratio of thiocyanate to copper which is not
achieved when the concentration of copper(II) is increased.
0.001
Thiocyanate concentration (mole/litre)
0.0009 Eh = -0.25, 0, 1 at pH 7 or 12
0.0008 Eh = -0.25, 0, 1 at pH 0
0.0007
0.0006
0.0005
0.0004
0.0003
0.0002
0.0001
0
0 10 20 30 40 50 60 70 80 90 100
Cu:SCN Ratio
Figure 4.18: A comparison of free thiocyanate (SCN-) at different pH and Eh conditions as the
ratio of copper(II) to thiocyanate changed.
Most of the copper added to the simulation remained as free copper (II) ions, but as
the level of copper increased the amount of thiocyanate ion (SCN-) within the
simulation decreased for all the simulations studied (Figure 4.18) due to the formation
of different complexes between copper and thiocyanate. Only in simulations
conducted with a pH of 0 showed relatively significants amounts of hydrogen
thiocyanate (Figure 4.19). In highly oxidising environments (as in simulation 6 with
an Eh of 1V, from Table 4.2) the concentration of hydrogen thiocyanate was ten times
the concentration compared to the other simulations (simulations 4 and 5) that were
conducted at a pH of 0.
111
0.001
Hydrogen Thiocyanate concentration Eh = 0.0 or 1.0V at pH 0

0.0009 Eh=-0.25V at pH 0
0.0008
0.0007
(mole/litre)
0.0006
0.0005
0.0004
0.0003
0.0002
0.0001
0
0 20 40 60 80 100
Cu:SCN Ratio
Figure 4.19: A comparison of hydrogen thiocyanate (HSCN) under different Eh conditions at a

pH 0 as the ratio of copper(II) to thiocyanate changed.
Figure 4.20 shows the concentration profile of copper (II) thiocyanate (CuSCN+).
The CuSCN+ profile is similar to results when thiocyanate (Figure 4.14) was added to
solution instead of copper (II). If the ratio of copper to thiocyanate is either too large
or small the concentration of CuSCN+ falls. The maximum CuSCN+ concentration of
0.005M occurs when the copper to thiocyanate ratio was 30:1 (Figure 4.20), a similar
result was found when the thiocyanate to copper ratio was 30:1 as seen in Figure 4.14.
As the ratio of copper to thiocyanate is increased the amount of CuSCN(s) falls from
0.001 to 0.0006M (Figure 4.21). CuSCN(s) accounts for the majority of thiocyanate
within the simulation but as the ratio of copper to thiocyanate changes, thiocyanate
forms another copper complex, which is CuSCN+. Figure 4.22 shows the
concentration profile for copper (II) di-thiocyanate (Cu(SCN)2). When the pH is 0,
the concentration of Cu(SCN)2 is lower than simulations conducted at a pH of 7 and
12. For the simulations where additional copper was added, there was no significant
concentrations of copper(I) tetra-thiocyanate (Cu(SCN)43-). Only when the ratio of
thiocyanate to copper was greater 20:1 a small amount of Cu(SCN)43- formed. The
maximum concentration of Cu(SCN)43- was found when the SCN:Cu ratio was 60:1 at
6 x 10-7M.
112
0.0006
Copper (II) thiocyanate Concentration
0.0005
0.0004
(mole/litre)
0.0003
0.0002
0.0001 Eh = -0.25, 0 or 1 at pH 0
Eh = -0.25, 0 or 1 at pH 7 or 12
0
0 10 20 30 40 50 60 70 80 90 100
Cu:SCN Ratio
Figure 4.20: A comparison of copper (II) thiocyanate (CuSCN+) at different pH and Eh conditions
as the ratio of copper(II) to thiocyanate changed.
0.0012
Copper (I) thiocyanate Concentration
0.001
0.0008
(mole/litre)
0.0006
0.0004
0.0002
Eh = -0.25, 0 or 1 at pH 0, 7 or 12
0
0 20 40 60 80 100
Cu:SCN Ratio
Figure 4.21: A comparison of copper (I) thiocyanate (CuSCN) at different pH and Eh conditions
as the ratio of copper(II) to thiocyanate changed.
113
0.000004
Copper (II) di-thiocyanate Concetration
Eh = -0.25, 0, 1 at pH 7 or 12
0.0000035
Eh = -0.25, 0 or 1 at pH 0
0.000003
0.0000025
(mole/litre)
0.000002
0.0000015
0.000001
0.0000005
0
0 10 20 30 40 50 60 70 80 90 100
Cu:SCN Ratio
Figure 4.22: A comparison of copper (II) di-thiocyanate (Cu(SCN)2) at different pH and Eh
conditions as the ratio of copper(II) to thiocyanate changed.
4.8 Conclusion
Pourbaix diagrams can be used to describe complex chemical systems showing the
thermodynamic stable species under different pH and Eh conditions. From this study
Pourbaix diagrams have been used to describe the thiocyanate-water and copper-
thiocyanate-water systems. As an extension to the Pourbaix diagram, the distribution
diagrams were created to show the equilibrium concentrations of species present in
the copper-thiocyanate-water system.
In many gold mines, the tailing waters are alkaline and have a chemical potential of
0V. If these solutions contain thiocyanate the Pourbaix diagrams developed in this
chapter (such as Figure 4.2) show that the predominant stable species formed under
these conditions at equilibrium is cyanate. The pH of the tailing waters will drop due
to changing environmental conditions, for example the adsorption of carbon dioxide.
Under extreme acidic conditions the Pourbaix diagram show that thiocyanate will
become the predominant stable species over cyanate at a neutral chemical potential or
114
a slightly reducing environment. But in the natural environment the pH level will not
drop to the level where the predominant species is thiocyanate.
Cyanide can be recovered from thiocyanate if the oxidation of cyanide to cyanate can
be stopped. This was confirmed when cyanate and hydrogen cyanate were removed
as stable species from the simulation. The resulting Pourbaix diagram (Figure 4.3)
shows that the predominant areas of cyanate and hydrogen cyanate were replaced with
cyanide and hydrogen cyanide depending on the pH of the system. The addition of
copper makes the system more complex. In comparison to the system without copper,
at equilibrium thiocyanate will form a stable complex of copper(I) thiocyanate which
is a solid under the same tailing water conditions. This reduces the mobility of a toxic
substance to the environment trapping thiocyanate within a solid, but this can also
inhibit natural processes that can convert thiocyanate to more basic compounds that
are non-toxic to the environment. In existing mines there is an opportunity of
recovering cyanide from waste species like thiocyanate that is contained in tailing
ponds from all the years of operation.
The distribution diagrams can give more information for a particular system
considered at a particular pH and Eh. The copper-thiocyanate-water system is a very
complex and the concentration of the different copper thiocyanate species is
dependent on the concentration of thiocyanate and copper as well as the solution
properties like pH and Eh. The species with the highest concentration among the
soluble species present in solution was copper (II) thiocyanate (Cu(SCN)+). When the
ratio of thiocyanate to copper was increased to 15:1 the concentration of Cu(SCN)+
increased to a maximum concentration of approximately 0.005M, as the thiocyanate
to copper ratio continued to increase, the concentration of Cu(SCN)+ decreased to
form other copper thiocyanate species that had a higher ratio of thiocyanate to copper,
for example, Cu(SCN)2 and Cu(SCN)43-. In the other case where copper
concentration was increased compared to thiocyanate, the amount of free thiocyanate
and hydrogen thiocyanate decreased, as there was more copper present in the system.
The concentration of Cu(SCN)+ approximately reached the same maximum
concentration of 0.005M, which corresponds to a copper to thiocyanate ratio of 30:1.
A copper to thiocyanate ratio above 30:1 saw all the different soluble copper-
thiocyanate concentrations decreased slightly with the production of CuSCN (s).
115
These simulations show equilibrium conditions only and when comparing these
conclusions with any kinetic experiments the results may differ since the system has
not reached equilibrium. These simulations can provide useful information about the
chemistry of the system studied and how different chemical species relate to each
other.
116
References
Brook P.A., “A computer method of Calculating Potential-pH Diagrams.” Corrosion

Science, Vol. 11, No. 6, pp 389-396, 1971.
Angus J.C and Angus C.T., “Computation of Pourbaix Diagrams Using Virtual
Species: Implementation on Personal Computers.” Electrochemical Science and
Technology, Vol. 132, No. 5, pp 1014-1019, May 1985.
Duby P., “The Thermodynamic Properties of Aqueous Inorganic Copper Systems.”

June 1977, Library of Congress Catalogue Card Number: 77-71709, National
Standard Reference Data System, National Bureau of Standards, The United States of
America.
Froning M.H., Shanley M.E. and Verink, Jr. E.D., “An improved method for
calculation of potential-pH diagrams of metal-ion-water systems by computer.”
Corrosion Science, Vol. 16, pp. 371-377, 1976.
Garrels R.M. and Christ C.L., “ Solutions, Minerals and Equilibria” 1965, Harper and
Row Publishers New York.
Guy A.G. and Rhines F.N., “Pourbaix Diagrams: A firm basis for understanding
corrosion.” Metal treatment and Drop Forging. pp 45-54, February, 1962.
Huang Hsin-Hsiung, Cuentas L., 1989(A), “Construction of Eh-pH and other stability
diagrams of Uranium in a muticomponent system with a microcomputer – 1. Domains
of Predominance Diagrams.” Canadian Metallurgical Quarterly, Vol. 28, No. 3, pp
225-234, 1989.
Huang Hsin-Hsiung, 1989(B), “Construction of Eh-pH and other stability diagrams of

Uranium in a multicomponent system with a microcomputer – II. Distribution
Diagrams.” Canadian Metallurgical Quarterly, Vol. 28, No. 3, pp 235-239, 1989.
117
Linkson P.B., Phillips B.D. and Rowles C.D., “Computer methods for the generation
of Eh-pH diagrams.” Minerals Sci. Engng, Vol. 11, No. 2., pp 65-79, April 1979.
Morel F. and Morgan J., “A numerical method for computing equilibria in aqueous
systems.” Environmental Science and Technology. Vol. 6, pp 58, 1972.
Pourbiax M., “Some applications of electrochemical Thermodynamics.” Corrosion,

Vol. 6, pp 395-404, 1950.
Pourbiax M., “Atlas of Electrochemical Equilibria in Aqueous Solutions.” Second

Edition 1974, National Association of Corrosion Engineers, Houston Texas USA.
Tran T. and Kim M.J., “Hydrometallurgy: Theory and Practice.” Channam National
University Press, ISBN 89-7598-239-4.
Townsend, Jr. H.E., “Potential-pH diagrams at elevated Temperature for the system
Fe-H2O.” Corrosion Science, Vol. 10, pp 343-358, 1970.
Verink, Jr. E.D., “A technical note: Simplified Procedure for Constructing Pourbaix
Diagrams.” Corrosion, Vol. 23, pp 371-373, 1967.
Wagman D., William E., Parker V., Schumn R., Halow I., Bailey S., Churney K.and
Nuttal R. “The NBS tables of Chemical thermodynamic properties. Selected values
for inorganic and C1 and C2 organic substances in SI units.” Journal of Physical and
Chemical Reference Data. Vol. 11, 1982, Supplement No. 2. Published by American
Chemical Society and the American Institute of Physics for the National Bureau of
Standards.
118
Chapter 5
Ion Exchange Resin
Adsorption of Thiocyanate
5.1 Introduction
Ion-exchange resins have been used in the mining industry to concentrate cyanide or
cyanide related wastes and even the precious metals such as gold and silver. In the
mining industry, ion-exchange resins have been used in two different roles, either for
the explicit recovery of the precious metals from leach liquors or the removal of
cyanide species from liquors to meet environmental requirements.
Helfferich (1995) explains the mechanism of ion exchange by considering a system of

spherical ion-exchanger beads of uniform size containing a counter ion A are placed
in a well stirred solution of an electrolyte BY, where B is another counter ion. As
equilibrium is approached, ion A diffuses out of the beads into the solution, and ion B
diffuses from the solution into the beads. This interdiffusion of counter ions is known
as ion exchange. The rate-controlling step of ion exchange is usually the diffusion of
the counter anions rather than the “chemical” exchange reaction at the fixed ionic
groups, which means that the ion-exchange process is essentially a diffusion
phenomenon. Reaction rate constants maybe defined formally, but in their physical
interpretation, have little in common with rate constants of actual chemical reactions.
Ion-exchange is inherently a stoichiometric process because each counter ion which
leaves the ion exchanger, is replaced with another counter ion to maintain the
substrate in an electrically neutral state.
This chapter examines the binary ion-exchange equilibria between thiocyanate and
chloride at 303 K using commercially available Purolite A500/2788 as the ion-
exchanger. The experimental data was correlated and compared using various
119
adsorption isotherm models to determine the apparent equilibrium constants for the
binary system and to look at the effectiveness of using ion exchange resins to
concentrate and remove thiocyanate from mine liquors.
5.2 Theory
5.2.1 Characterisation of ion-exchange equilibrium in a binary mixture
Ion exchange equilibrium is obtained when the ion exchanger is placed in an

electrolyte solution that contains a counter ion which is different from which is
already adsorbed on the ion exchanger. For example, suppose the ion exchanger is in
the A-form and the counter ion in the solution is B. Counter-ion exchange occurs,
and ion A in the ion exchanger is partially replaced by counter ion B (equation 5.1),
illustrated graphically in Figure 5.1.
A+B ↔ B+A [5.1]
B - - A - -
B B
A - B -
- A - A
- -
A - - A - -
A - A -
- - - -
A A
A B
B B
B - A -
Initial State Equilibrium
- Matrix with fixed charges A B Counter ions - Co ions
Figure 5.1: Ion exchange with a solution. For example a cation exchanger containing counter
ions A is placed in a solution containing counter ions B (left). The counter ions are redistributed
by diffusion until equilibrium is attained (right). (Helfferich, 1995).
120
5.2.2 Adsorption Isotherm Models
Many authors have used different adsorption models to describe the relationship
between equilibrium loading levels and solution concentration of different counter
ions under different operation conditions. Three adsorption isotherm models that
have been frequently used to describe adsorption processes are the Langmuir,
Freundlich and Dubinin-Radushkevich models. More recent studies have employed
the law of mass action to define the equilibrium constant for the ion-exchange
process.
5.2.2.1 Langmuir Isotherm
The Langmuir isotherm was developed to describe the adsorption of gas molecules
onto homogeneous solid surfaces (crystalline materials) that exhibit one type of
adsorption site (Langmuir, 1918). This model has been extended to describe the
adsorption of ions onto solid adsorbates including heterogeneous solids.
The Langmuir isotherm has three underlying assumptions (Atkins, 1995):
1. Adsorption cannot proceed beyond monolayer coverage.
2. All sites are equivalent and the surface is uniform (that is, the surface is
perfectly flat on a microscopic scale).
3. The ability of a molecule to adsorb at a given site is independent of the

occupation of neighbouring sites.
At equilibrium the Langmuir isotherm relates the amount of solute adsorbed per unit
weight of solid to the equilibrium solution concentration of the adsorbate, shown in
equation 5.2:
bX m C
X= [5.2]
1 + bC
121
where X is amount of solute adsorbed per unit weight of solid, b is constant related to
the energy of adsorption, Xm is the maximum adsorption capacity of solid and C is the
equilibrium solution concentration of the adsorbate.
Simplifying equation 5.2 by the substitution of B = 1/b leads to:
XmC
X= [5.3]
B+C
Taking the reciprocal of equation 5.3 and multiplying both sides by X.Xm gives a
linear relationship relating X to X/C (equation 5.4). By plotting X versus X/C, one
can determine the value for –B from the slape of the line of best-fit and the value of
Xm from the intercept.
⎛X⎞
X = −B⎜ ⎟ + X m [5.4]
⎝C⎠
5.2.2.2 Freundlich Isotherm
The Freundlich isotherm is an empirical model that relates the solute adsorbed on the
solid to the equilibrium solute solution concentration by a logarithmic change.
Freundlich (1926) defined this relationship shown in equation 5.5.
X = KC N [5.5]
where X (mmol/ml Resin) is the amount of solute adsorbed per unit weight of solid, C
(mmol/L) is the equilibrium solute solution concentration and K and N are constants.
Equation 5.5 can be transformed to a linear relationship by taking the logarithms of

both sides of the equation, shown below:
122
log X = log K + N log C [5.6]
In a plot of log X versus log C, the line of best-fit has a slope of N, and log K is its
intercept. When N = 1, the Freundlich isotherm that is represented by equation 5.5
reduces to a linear relationship, and because X/C is the ratio of the amount of solute
adsorbed to the equilibrium solution concentration (the definition of Kd), the constant
K is equivalent to the value of Kd.
At low solute concentrations the adsorption isotherms are often linear, either the
Freundlich isotherm with N = 1 or the Langmuir isotherm with bC much greater than
1 fits the adsorption data. In many cases the value of N differs from 1 showing non-
linear isotherms and the Freundlich isotherm provides a superior correlation of the
data than the Langmuir isotherm.
5.2.2.3 Dubinin-Radushkevich Isotherm
This model has been used to describe the adsorption of trace components. Should the
adsorbent surface become saturated or the solute exceeds its solubility product, the
model is inappropriate (Serne, 1992). Compared to the Langmuir isotherm, Dubinin-
Radushkevich isotherm model is more general because it does not require either
homogeneous adsorption sites or constant adsorption potential.
The model is described by equation 5.7 shown below (Dubinin et al., 1947):
X = X m e − Kε
2
[5.7]
where X is the observed amount of solute adsorbed per unit weight, Xm is the sorption
capacity of adsorbent per unit weight, K is a constant and ε is defined as
⎛ 1⎞
ε = RTln ⎜1 + ⎟ [5.8]
⎝ C⎠
123
where R is the gas constant, T is temperature (as Kelvin) and C is the solute
equilibrium solution concentration (in mM)
Equation 5.7 can be rearranged to show a linear relationship for the Dubinin-
Radushkevich isotherm (equation 5.8):
ln X = ln X m − K ε 2 [5.9]
A plot of ln X versus ε2 allow the estimation of the ln Xm as the intercept and –K as

the slope of the straight-line.
5.2.2.4 Mass-Action Sorption Model
Mass action laws and equilibrium constants have been used to described ion exchange
processes. For high concentrations of counter ions loaded on the resin and in solution,
the mass action law approach to model equilibrium is more realistic (Gomes et al.,
2001). de Lucas et al. have successfully used mass-action models to describe
different equilibrium cation ion exchange processes (de Lucas et al., 1993,1994,1998
and 2001; Valverde et al. 1999 and 2001).
Suppose that an ion exchanger (r) is initially in the form of counter ion A, and that the
counter ion in the solution is B. Counter ion exchange occurs, and the A ions in the
ion exchanger are partially replaced by B ions (equation 5.10).
βA αr − + αBβs − ⇔ βA sα − + αBβr − [5.10]
In this reversible equilibrium, both the ion exchanger and the solution contain both
competing counter ion species, A and B.
The simplest form of the mass action law, which is without activity coefficients is
defined in equation 5.11:
124
mBmA
= K AB = Constant [5.11]
mAmB
where mi is the concentration of ion i in the solution and mi is the concentration of ion
i loaded on the ion exchanger. The selectivity coefficient (KAB) is a constant and is
independent of the relative amounts of the competing species A and B.
True thermodynamic mass-action conceptual models assume that only free ion species
are adsorbed; the ion exchange capacity is constant and independent of pH and the
solution composition or total ionic strength; solutes are a true solution, which means
the species’ activities are not affected by the presence of a solid and exchange of the
counter ions is reversible and there is no hysteresis between adsorption and
desorption. Most deviations away from the mass-action law consider only one type of
adsorption site with a fixed adsorption energy (Serne, 1992).
From this basic form of the mass-action law de Lucas (de Lucas et al.,
1993,1994,1998 and 2001) expands equation 5.11 to include individual activity
coefficients for each ion on the ion exchanger and solution. Secondly de Lucas
introduces ionic fraction normalising the ion exchange equilibria data. The ionic
fraction can be defined by equation 5.12 for solution species A and B and equation
5.13 for ions adsorbed by the ion exchanger.
αC A βC B
xA = ; xB = [5.12]
N N
αq A βq B
yA = ; yB = [5.13]
qo qo
where Ci is the concentration of the ith ionic species in solution (mmol/L), N is the
total ionic concentration in the solution phase or the solution normality (mmol/L), qi
is the solute concentration of the ith species in the solid phase (mmol/L resin) and qo is
the useful capacity of the resin in the system studied (mmol/L resin)
125
de Lucas uses the mass action law to define the equilibrium constant for the ion
reaction (equation 5.10) giving a relationship to explain the exchange of two counter
ions A and B (equation 5.14). Activity coefficients for each ion (γA and γΒ) have been
included to take into account real behaviour of the ions in solution and on the ion-
exchanger. CT is defined as total concentration of all ions in solution (mmol/L).
(y B γ B ) α [(1 − x B )C T γ A ]β
K AB (T) = [5.14]
[(1 − y B ) γ A ]β (x B γ B C T ) α
Past work described by de Lucas et al. (1994) explains that there is a relative
similarity between the phenomena of adsorption and ion exchange. The activity
coefficients for the resin phase can be correlated using analogous equations proposed
by Wilson (1964) for liquid-vapour equilibria.
Wilson (1964) proposed a relationship to describe liquid-vapour equilibria using

Gibbs Excess Energy of Mixing (equation 5.15).
GE
= −∑ x i ln(1 − ∑ x j Λ ji ) [5.15]
RT i j
where xi is the mole fraction of component i, Λji are the Wilson interaction parameters
(Λii = 0, Λij ≠ Λji).
The following equation results for a binary system (equation 5.15):
GE
= − x A ln (x A + x B Λ AB ) − x B ln (x B + x A Λ BA ) [5.16]
RT
From equation 5.15, Wilson (1964) defined the activity coefficient for each
component to be defined as below:
126
x j (1 − Λ ij )
ln γ i = −ln (1 − ∑ x i Λ ji ) + 1 − ∑ [5.17]
j j 1 − ∑ x k Λ kj
k
For a binary system A and B, the activity coefficients for the resin phase can be
defined by equation 5.18 and 5.19:
yA y B Λ BA
ln γ A = 1 − ln (y A + y B Λ AB ) − − [5.18]
y A + y B Λ AB y B + y A Λ BA
yB y A Λ AB
ln γ B = 1 − ln (y B + y A Λ BA ) − − [5.19]
y B + y A Λ BA y A + y B Λ AB
The activity coefficients in the liquid phase were determined from the extended
Debye-Huckel limiting law (Robinson et al., 1965) shown by equation 5.20.
A z1 z 2 I
log10 γ i = − [5.20]
1 + Ba I
where γi is the activity coefficient for counter ion i, A and B are Debye-Huckel
parameters involving absolute temperature and the dielectric constants of the solvent,
I is the ionic strength in the bulk phase and a is the ionic diameter of the hydrated ions
i.
The extended Debye-Huckel limiting law often holds up to an ionic strength of about
I = 0.1 molar, when the ions are separated on the average by no more than about 20
angstroms (Robinson et al., 1965). Since the counter ion concentration is very dilute
and the resulting ionic strength of the solution is less than 0.1 molar, the values of A
and B for the Debye-Huckel parameters for the ion exchange system can be estimated
by A and B values for water. Table 5.1 shows values for A and B for water at various
temperatures.
127
The ionic diameters of hydrated ions were calculated from the ionic mobilities of the
respective ion by Kielland (1937). For the counter ions of chloride and thiocyanate,
Kielland estimated them as aCl = 3.0 x 10-8 cm and aSCN = 3.5 x 10-8 cm, respectively.
Table 5.1: Values for Parameters in the Debye-Huckel law (Appendix 7.1, Robinson et. al., 1965)
Temperature (oC) A [(mol/L)-1/2] 10-8B [(mol/L)-1/2cm-1]
0 0.4918 0.3248
5 0.4952 0.3256
10 0.4989 0.3264
15 0.5028 0.3273
18 0.5053 0.3278
20 0.5070 0.3282
25 0.5115 0.3291
30 0.5161 0.3301
35 0.5211 0.3312
38 0.5242 0.3318
40 0.5262 0.3323
45 0.5317 0.3334
50 0.5373 0.3346
55 0.5432 0.3358
60 0.5494 0.3371
65 0.5558 0.3384
70 0.5625 0.3397
75 0.5695 0.3411
80 0.5767 0.3426
85 0.5842 0.3440
90 0.5920 0.3456
95 0.6001 0.3471
100 0.6086 0.3488
128
Ionic strength of the solution phase in molar units can be calculated by equation 5.20:
I= 1
2 ∑z
i
2
c
i i [5.21]
where zi is the charge number of an ion i (positive for cations and negative for anions)
and ci is the molar concentration of ion i.
The mass-action equilibrium constant (KAB) and Wilson binary interaction parameters
(ΛAB and ΛBA) were determined for the system comprising counter ions of chloride
and thiocyanate using a non-linear regression method based on the Marquardt
algorithm shown in Figure 5.2. The value of these constants (KAB, ΛAB and ΛBA)
should be viewed as fitted parameters and do not represent the true thermodynamic
equilibrium constants for the ion-exchange processes of interest. The determined
values for ΛAB and ΛBA generally range from 0 to 2, which is similar for values
reported for cation-exchange systems (de Lucas et al., 1993; Valverde et al., 2001).
Note when using equation 5.14 to describe the equilibrium constant assumes that the
swelling-pressure effects are negligible (Helfferich, 1995) and the equilibrium
constant (KAB) is independent of the total concentration of ions in solution while the
binary interaction parameters (ΛAB and ΛBA) depend on the total concentration of ions
in the resin phase.
129
Start
Data
X, Y, I
Initial
KAB, ΛAB, ΛBA
Calculate
γi, Ycalc
Calculate
ε = Σ(Ycalc – Yexp)2
Yexp
ε Print
Minimum? Finish
KAB, ΛAB, ΛBA
Marquardt Subroutine
New: KAB, ΛAB, ΛBA
Figure 5.2: Algorithm to calculate the three parameters: KAB, ΛAB, ΛBA to describe the ion
exchange equilibria using the Mass-action law.
130
5.3 Experimental
5.3.1 Reagents and Materials
A commercially available anion exchange resin was used as the ion exchanger.
Purolite has developed an ion exchange resin that is suited to the gold industry
namely, Purolite A-500u/2788. This resin is based on a resin developed for water
purification Purolite A-500. The difference between A-500 and A-500u/2788 is that
A-500u/2788 has been sized to give a bead size of approximately 1mm in diameter.
Table 5.2 shows the typical chemical and physical characteristics for Purolite A-500
and A-500u/2788 anion exchange resin. Prior to usage, the resin was soaked in
distilled water for 24 hours to stabilize resin swelling.
Analytical grade sodium thiocyanate (98%) was supplied by BDH Chemical Ltd.
Hydrated ferric nitrate (98%) and nitric acid (70% wt/wt), which was used in the
determination of thiocyanate was supplied by Asia Pacific Speciality Chemicals
Limited. All solutions were prepared with distilled water.
Table 5.2: Typical Chemical and Physical Characteristics for Purolite A-500 and A-500u/2788.
(Purolite 2002)
Typical Chemical and Physical Characteristics
Polymer Structure……………………….Polystyrene crosslinked with divinylbenzene
Functional Groups…………………………………………………………..R(CH3)3N+
Physical Appearance………………………………………….Opaque Spherical Beads
Ionic form (as shipped)……………………………………………………...…Chloride
Uniformity Coefficient……………………………………………………1.7 (average)
Effective size (A-500)……………………………………………….0.50mm (average)
(A-500u/2788)…...…………………………………...1.00mm (average)
Water Retention……………………………………………………...53-58% (Cl form)
Swelling (Cl to OH)….…………………………………………………………….10%
pH Limitations…………………………………………………………………….None
Temperature Limitations (in OH from Max.)…………………………….140oF (60oC)
(in salt form Max.)……..……………………..212oC (100oC)
Chemical Resistance……… ...Unaffected by dilute acids, alkalies and most solvents
Shipping Weight…………… …………………………………….…43 lbs/ft3 (690 g/l)
Total Capacity………………………………………………..1.15 meq./ml Volumetric
3.9 meq./g min. Weight
Whole beads…...…………… ………………………………………….95 % minimum
Mechanical Strength…………………………………………..300 g minimum average
131
5.3.2 Equipment and Instrumentation
The experiment consisted of several 500 ml conical flasks where ion-exchange resin
was contacted with solutions of thiocyanate. The flasks were sealed with a rubber
stopper to minimise evaporation of the solution and placed in a temperature controlled
bench top shaker incubator made by Paton Scientific (model number 01-2116) as seen
in figure 5.3. The incubator temperature was controlled by an air heater in
conjunction with a water recirculatory loop to maintain the temperature within the
incubator to ±0.5oC of the desired temperature. A rotating platform was fixed to the
bottom of the incubator in which the conical flasks were held in place with metal
clamps. The orbital rotation speed platform can be controlled from 0 to 400 orbits per
minute.
Figure 5.3: Bench-Top Orbital Shaker Incubator.
For the analysis of thiocyanate, after addition of the ferric ions, the solutions
absorbance was measured at 460nm using a Perkin Elmer Lambda 3 ultra violet/visual
spectrophotometer.
132
5.3.3 Procedure for analysis of thiocyanate
The method used to analyse the concentration of thiocyanate was adapted from
ASTM D 4193-95, a standard test method for thiocyanate in water. Thiocyanate
reacts with ferric ions at a pH of < 2 to form a coloured complex, which is determined
colourmetrically at 460 nm and adheres to Beer’s Law.
The main influences that affect the effectiveness of this method are interferences due
to the formation of ferric ion with thiocyanate and other coloured or interfering
organic compounds that influences the colour of the solution at 460 nm. Hexavalent
chromium interferes with the analysis of thiocyanate, which can be removed by
adjusting the pH to 2 with concentrated nitric acid and adding ferrous sulphate.
Raising the pH to 8.5 to 9 with sodium hydroxide precipitates Fe(III) and Cr(III) as
the hydroxides, which are removed by filtration. Reducing agents that can reduce
Fe(III) to Fe(II) prevent the formation of ferric thiocyanate. Addition of an oxidant
such as hydrogen peroxide can remove reducing agents from solution. High
concentrations of cyanide in proportion to the concentration of thiocyanate will react
with the iron to form coloured complexes. If this problem occurs in analysis,
thiocyanate is stable in both the acid and alkaline pH range. Addition of acid to
reduce the pH and any cyanide will form hydrogen cyanide and can be stripped from
solution by air stripping.
Coloured or interfering organic compounds must be removed by adsorption on

macroreticular adsorption resin prior to analysis. Examples of interfering compounds
are fluoride, phosphate, oxalate, tartrate and borate, which all form complexes with
iron (Newman 1975). Other organic substances that form red colour solutions with
ferric ions are complexes with phenols, enols, oximes and acetates (Shriner et al.
1948). Testing method (ASTM D 4193-95) explains a procedure to remove these
interferents, but would not be needed within the analysis for these experiments
because pure systems are used that do not contain these contaminants.
The ferric nitrate solution used for the reaction between Fe3+ and SCN- to form the red
complex was made by dissolving 404 g of ferric nitrate (Fe(NO)3.9H2O) in
133
approximately 800 ml of distilled water. To this solution 80 ml of concentrated nitric
acid was added, mixed well and diluted to 1 L with distilled water.
The ASTM states that for every 50ml of thiocyanate sample 2.5ml of ferric nitrate
solution was added and mixed well. Within 5 minutes the absorbance of the solution
at 460nm in a 5.0-cm cell was determined using water as a reference. The absorbance
of known thiocyanate concentration was used to calculate a calibration graph to
determine the concentration of the thiocyanate samples. The standard solutions were
made fresh for each use to ensure the quality of the standard. Thiocyanate is a
biodegradable material; some samples may contain bacteria that can consume
thiocyanate. These samples can be preserved at a pH < 2 by the addition of a mineral
acid and refrigerated.
5.3.4 Experimental Procedures
Ion-exchange equilibria for the SCN-/Cl- binary system was determined by contacting
the Cl- form of the resin with a solution containing a fixed concentration of SCN-. A
10ml sample of Purolite A-500u/2788 that has been soaked in distilled water for 24
hours was measured and placed into 500ml conical flasks followed by the addition of
250ml of thiocyanate solution. The conical flask was sealed with a rubber stopper to
minimise the evaporation of the solution during the experiment and placed in a
temperature controlled bench top orbital shaker incubator made by Paton Scientific
(model number 01-2116) for which the temperature was set at 30± 0.5oC. The speed
of the rotating platform was set at 200 orbits per minute in all experiments.
Solution samples were taken from the conical flask at the following times during the
experiment: 0, 5, 10, 15, 30, 60, 120, 240, 360 and 480 minutes and the concentration
of thiocyanate was measured in accordance with ASTM D 4193-95 (as described in
section 5.3.3) to monitor the adsorption of thiocyanate on the resin. Duration of 480
minutes was found to be sufficient to ensure that equilibrium has been achieved
between the resin and solution. After equilibrium was established, the solution phase
was separated from the resin phase. From the knowledge of the change in
concentration of thiocyanate in the solution phase, it was possible to calculate the
composition of thiocyanate on the resin phase at equilibrium. A mass balance was
134
used to determine the equilibrium compositions of the resin and solution phases with
respect to chloride.
The partially loaded resin was then contacted with a fresh 250ml of thiocyanate
solution and allowed to reach equilibrium. The process of draining the solution phase
at equilibrium, followed by the addition of a fresh quantity of thiocyanate solution to
the same sample of resin was repeated until no further loading of thiocyanate
occurred, which was confirmed when the change in the concentration of thiocyanate
in the solution was found to be negligible. Experimental data reported represent the
average of duplicate run.
The effect of the total concentration on the ion-exchange isotherms was determined
by contacting the resin with solutions containing different concentrations of
thiocyanate. In the case of the SCN-/Cl- binary system, the SCN- concentrations of
300, 600, 900, 1200 and 1500 ppm NaSCN.
135
5.4 Results and Discussion
5.4.1 Equilibrium Study
Purolite A500u/2788 resin was contacted with five different thiocyanate solution
concentrations. To ensure the resin loading reached equilibrium, regular samples
were taken and the thiocyanate concentration measured. Figure 5.4 shows the
adsorption profile of thiocyanate onto the resin at a starting solution concentration of
1200 ppm NaSCN. After an eight-hour period it can be seen that the concentration in
solution has reached equilibrium with no change in the concentration of thiocyanate in
solution. The partially loaded resin was then contacted with a fresh 250ml of
thiocyanate solution and allowed to reach equilibrium. The process of draining the
solution phase at equilibrium, followed by the addition of a fresh quantity of
thiocyanate solution to the same sample of resin was repeated until no further loading
of thiocyanate occurred, which was confirmed when the change in the concentration
of thiocyanate in the solution was found to be negligible.
1400
1200
Concentration (ppm NaSCN)
1000 Run 1
Run 2
Run 3
800
Run 4
Run 5
600 Run 6
Run 7
Run 8
400
200
0
0 100 200 300 400
Time (min)
Figure 5.4: Concentration profile of thiocyanate adsorption at an initial thiocyanate

concentration for each run of 1200ppm NaSCN, temperature 30oC at atmospheric pressure.
136
The average loading capacity of thiocyanate over the five different concentrations was
96.26 mg NaSCN/ml resin (1.19x10-3 mol NaSCN/ml resin) with a relative standard
deviation of 2.6%. Figure 5.5 is a plot of thiocyanate loading on the resin and
concentration of thiocyanate in solution. It can be seen that there is a significant
difference in the adsorption performance of the resin at different solution
concentrations. As the ionic strength is increased the equilibrium solution
concentration is higher at a given thiocyanate resin loading.
100
90
Resin Concentration (mg NaSCN/ml
80
70
60
Resin)
50
40
30
300ppm
600ppm
20
900ppm
10 1200ppm
1500ppm
0
0 200 400 600 800 1000 1200 1400 1600
Solution Concentration (mg/l NaSCN)
Figure 5.5: Equilibrium adsorption curves for the adsorption of thiocyanate at different
thiocyanate concentrations using Purolite A500u/2778 strong base ion exchange resin.
Four different models were used to define the relationship between the loading
capacity and the solution concentration. Three of the models, based on the analogies
with the phenomenon of adsorption are the Langmuir, Freundlich and Dubinin-
Radushkevich isotherms. The other model was developed for a true ion exchange
system using the Mass Action Law.
137
5.4.2 Langmuir Model Fitting
The Langmuir model was developed to understand phenomenon of adsorption and has
been frequently used to describe the adsorption using ion exchange resins. Figure 5.6
is a plot of the thiocyanate concentration on the resin versus the ratio of the
thiocyanate concentration to equilibrium solution concentration. This describes the
Langmuir adsorption relationship of thiocyanate between the resin phase and solution
phase seen by equation 5.2.
Some outlying points can be seen for the initial thiocyanate concentration of 300 ppm
NaSCN. These points occur at the first initial adsorption runs that were carried out at
300 ppm NaSCN. For these first few runs the equilibrium thiocyanate concentrations
after 8 hours of adsorption were very low, with concentrations of less than 1 ppm
NaSCN reaching the limit of detection of the analytical technique. These points were
removed when calculating the two constants for the Langmuir isotherm.
The slope of the straight line gives the constant b, described in equation 5.4, which
relates to the energy of adsorption. At each different thiocyanate solution
concentration there was a different value for the constant b, implying that with
increasing solution concentration there is an increase in the energy of adsorption. A
plot of initial concentration of thiocyanate in solution versus the constant b (Figure
5.7) was found to give a linear relationship.
The second constant that helps describe the ion exchange process is Xm, the maximum
adsorption capacity of the solid in this case the ion exchange resin. For the different
solution concentration carried out gave very similar values for Xm with an average
value of 1.21x10-3 mol NaSCN/ ml resin with a relative standard deviation 3.3%.
This was very similar to the experimental value of 1.19x10-3 mol NaSCN/ml resin. A
summary of the different parameters that were determined based on the Langmuir
isotherm is given in Table 5.3.
138
Table 5.3: Parameters in the model based on the Langmuir isotherm.
Initial NaSCN Concentration Constants
(ppm NaSCN) (mmol/l NaSCN) b (mmol/l) Xm (mmol/ml resin)
300 3.70 0.18 1.25
600 7.40 0.20 1.14
900 11.10 0.44 1.21
1200 14.80 0.51 1.20
1500 18.50 0.64 1.25
1.4
300ppm
1.2 600ppm
900ppm
1200ppm
X (mmol SCN/ml resin)
1 1500ppm
0.8
0.6
0.4
0.2
0
0 2 4 6 8 10 12 14
(X/C) (l solution/ml resin)
Figure 5.6: The Langmuir Isotherm. A plot of the thiocyanate concentration on the resin versus
the ratio of the thiocyanate concentration to equilibrium solution concentration.
139
0.7
Constant b, for the Langmuir Isotherm

0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000 1200 1400
Initial Thiocyanate Concentration (ppm NaSCN)
Figure 5.7: Parameter b for the Langmuir isotherm at different solution concentration.
1.6
X Experimental (mmol NaSCN/ml resin)
1.4
1.2
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
X Model (mmol NaSCN/ml resin)

Figure 5.8: Comparison of experimental data to predicted values from the Langmuir Isotherm.
A comparison of the actual experimental results to the predicted values using the
Langmuir isotherm is shown in Figure 5.8. The line within Figure 5.8 shows when
the experimental and the predicted values are equal. It can be seen that the Langmuir
isotherm shows good correlation (R2 = 0.985) between the experimental results and
predicted values of the adsorption of thiocyanate onto Purolite A500u/2788 ion
140
exchange resin. There was greater agreement between the experimental and predicted
results at higher thiocyanate concentration on the resin.
5.4.3 Freundlich Model Fitting
The second model that was used to describe the adsorption of thiocyanate onto ion
exchange resin is the Freundlich Isotherm. This isotherm is an empirical model
relating the thiocyanate resin concentration and solution concentration by a log-log
relationship.
0.2
0
-2.5 -2 -1.5 -1 -0.5 0 0.5 1 1.5
-0.2
-0.4
log (X)
-0.6
300ppm
-0.8 600ppm
900ppm
1200ppm
-1
1500ppm
-1.2
log (C)
Figure 5.9: The Freundlich Isotherm. A plot of log (X) (resin concentration) versus log (C)
(solution concentration).
The Freundlich isotherm does not describe the adsorption isotherm as well as the
Langmuir isotherm. It can be seen from Figure 5.9 that the plotted results do not give
a true linear relationship (R2 = 0.766). A summary of the parameters for the
Freundlich isotherm is shown in Table 5.4. Comparing the experimental results to
predicted values as shown in Figure 5.10, it can be seen that the data exhibit a high
degree of scattering. With exception of the results for the 300 ppm NaSCN
141
adsorption experiments the constant N measured at the different concentrations of
NaSCN were very similar with values ranging from 0.230 to 0.271.
Table 5.4: Parameters in the model based on the Freundlich isotherm.

Initial NaSCN Concentration Constants
(ppm NaSCN) (mmol/l NaSCN) N K (l/ml resin)
300 3.70 0.370 0.909
600 7.40 0.230 0.787
900 11.10 0.271 0.649
1200 14.80 0.250 0.956
1500 18.50 0.239 0.641
1.6
1.4
1.2
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Figure 5.10: Comparison of experimental data to predicted values from the Freundlich
Isotherm.
5.4.4 Dubinin-Radushkevich Model Fitting
The Dubinin-Radushkevich adsorption isotherm is a correlation between the resin

loading and an inverse relationship of the equilibrium concentration. A comparison
of different equilibrium relationships between the thiocyanate in solution and
adsorbed onto the resin at the different initial thiocyanate concentration is shown in
Figure 5.11. One of the constants that are determined by the Dubinin-Radushkevich
142
isotherm is the maximum adsorption capacity for the solid Xm. As with the Langmuir
isotherm at the five different initial thiocyanate concentrations the value for Xm
converge to the same value. The average value for Xm found by this isotherm was
1.11 mmol NaSCN/ml resin, with a relative standard deviation 2.4%. This value is
very close to the calculated value of the total capacity of the resin for thiocyanate of
1.19 mmol NaSCN/ml resin. A summary of the parameters found is tabulated in
Table 5.5. As seen in Figure 5.12, for this model the value for K is dependent on the
ionic strength of the solution with K changing linearly from 2x10-8 at a concentration
of 300 ppm NaSCN to 8x10-8 at 1500 ppm NaSCN. This relationship was similar to
constant b in the Langmuir isotherm.
0.5
0.0E+00 2.0E+07 4.0E+07 6.0E+07 8.0E+07 1.0E+08 1.2E+08 1.4E+08 1.6E+08
300ppm
-0.5 600ppm
900ppm
1200ppm
ln X
-1 1500ppm
-1.5
-2
-2.5
ε
2
Figure 5.11: The Dubinin-Radushkevich Isotherm. A plot of the natural log of thiocyanate
concentration on the resin versus ε2 which is defined by equation 5.8.
143
9.00E-08
Constant K for the Dubinin-Radushkevich
8.00E-08
7.00E-08
6.00E-08
Isotherm
5.00E-08
4.00E-08
3.00E-08
2.00E-08
1.00E-08
0.00E+00
0 200 400 600 800 1000 1200 1400 1600
Initial Thiocyanate concentration (ppm NaSCN)

Figure 5.12: The change in the value of constant K in the Dubinin-Radushkevich isotherm with a
change in ionic strength of solution.
Figure 5.13 compares experimental results and the predicted values that have been
determined from the Dubinin-Radushkevich isotherm (R2 = 0.945). For a given Xexp,
Xcalc is typically higher than Xexp.
Table 5.5: Parameters in the model based on the Dubinin-Radushkevich isotherm.

Initial Solution
Concentration (ppm NaSCN) Xm (mmol/ml resin) K (1/(J2.mol2)
300 1.082 2.00E-08
600 1.094 3.00E-08
900 1.124 5.00E-08
1200 1.109 6.00E-08
1500 1.161 8.00E-08
144
1.6

1.4
1.2
0.8
0.6
0.4
0.2
0
0.000 0.200 0.400 0.600 0.800 1.000 1.200 1.400
Figure 5.13: Comparison of experimental data to predicted values from the Dubinin-
Radushkevich Isotherm.
Ion-exchange equilibria are presented in Figure 5.14 where the data are plotted in
terms of equivalent ionic fractions defined by equations 5.12 and 5.13. It was
interesting when plotting the data in the form of ionic fractions that the data at the
different ionic strengths converged to give the same relationship. This means that by
modelling the fraction of the counter ion of interest (in this case thiocyanate) in
solution and on the ion exchange resin the model becomes independent of ionic
strength of the solution within the range of concentration considered.
5.4.6 Mass Action Law Model Fitting
There are three parameters that were determined from the Mass-Action Law, KAB and
the two Wilson parameters to determine the activity coefficients for the solid phase.
An advantage of the Mass-Action Law is that the relationship is independent of
concentration. Therefore there is only one unique value of KAB to describe the ion
exchange process while for the other isotherms the relationships show the dependence
on the concentration of the solution.
145
To determine the three parameters for the Mass-Action Law, a Fortran program was
developed (appendix A). The data that was supplied to the program was the
experimental values for the fraction of thiocyanate in solution and the corresponding
fraction of thiocyanate on the ion exchange resin. At each corresponding fraction the
ionic strength was determined for the solution used. Then an initial guess was given
to the three parameters to be determined, which were KAB = 1, ΛAB = 1 and ΛBA = 1.
Each time the system looped to recalculate the three parameters, the use of the
Marquardt Subroutine was used to determine new values for KAB and the two Wilson
parameters until the error between the calculated and experimental data was
minimised. KAB was determined to be 22.20. The Wilson parameters were found to
be ΛAB = 1.805 and ΛBA = 0.265.
146
1
0.9
Thiocyanate Fraction in Resin
0.8
0.7
0.6
0.5
0.4
300ppm
0.3
600ppm
900ppm
0.2
1200ppm
0.1 1500ppm
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Thiocyanate Fraction in Solution
Figure 5.14: The Mass Action Law. A plot of resin fraction versus solution fraction of
thiocyanate.
0.9
Resin Fraction (Experimental)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Resin Fraction (Model)
Figure 5.15: Comparison of experimental data to predicted values by the Mass-Action Law.
147
It can be seen that there is good agreement between the model and experimental data
as seen in Figure 5.15. The average absolute relative deviation (AARD) was 7.20%.
From Figure 5.15, the line represents the model compared to the experimental data,
the model tends to slightly over estimates the resin fraction but is still good agreement
between the model and the experimental data.
5.5 Conclusions
From experiments using Purolite A500u/2788 the effective capacity of the ion
exchange resin for thiocyanate is 96.26 mg NaSCN/ml resin (1.19 mmol NaSCN/ml
resin). This capacity is compatible to the loading capacity for chloride of 1.15
meq/ml resin quoted by the manufacturer. Since the charge of thiocyanate is unitary
the unit is equivalent to mmol NaSCN/ml resin.
Four different relationships were used to describe the equilibrium between solution
concentration and resin loading of thiocyanate. Three isotherms have been based on
adsorption phenomenon of species onto solids, which are Langmuir, Freundlich and
Dubinin-Radushkevich isotherms. The other model has been specifically developed
for the ion exchange process, which is based on the Mass-Action Law.
From the different models based on the adsorption phenomenon the Langmuir
isotherm gave the closest approximation of the loading characteristics compared to
the experimental results. The Dubinin-Radushkevich isotherm showed good
correlation as well whereas the Freundlich isotherm showed poor correlation between
the calculated values and the experimental results. Normally the Freundlich isotherm
is used to describe adsorption equilibria with low solute concentrations and low resin
loading capacity, this usually corresponds to a linear relationship, i.e. N = 1 for this
isotherm. For this study the conditions are not ideal for the Freundlich isotherm, the
concentration of thiocyanate above trace levels and the loading capacity of the resin
has been reached, resulting with a range of N values between 0.230 – 0.370. As the
thiocyanate concentration increased the resulting N value deviated further away from
148
the value of 1, therefore showing a poor non-linear relationship for the Freundlich
isotherm.
For the Langmuir and Dubinin-Radushkevich isotherms, one of the constants

determined is the maximum effective loading capacity of the solid, in this case the ion
exchange resin. These values are 1.21 and 1.11 mmol NaSCN/ml resin respectively.
The other constant determined was b for the Langmuir isotherm and k for the
Dubinin-Radushkevich isotherm. As the solution concentration was increased these
constants increased linearly with solution concentration. Therefore these isotherms
are solution concentration dependent.
The Mass-Action law was developed to study the ion exchange process. The constant
KAB quantifies to the relationship between the counter ion loaded on the ion exchange
material and the solution concentration. In the model used to describe the adsorption
of thiocyanate on a strong base anion exchange resin assumptions were made to
account for solution and ion-exchange resin non-ideality by using activity coefficients
for the liquid phase and Wilson parameters for the resin phase respectively. The
Wilson parameters are fitting parameters for this model.
The main advantage of the Mass-Action Law over the other isotherms is that the
model is independent on the concentration of thiocyanate in solution. This means that
there is only one parameter that is needed to describe the thiocyanate adsorption
displacing chloride ions from the ion exchange resin. The parameters determined for
the Mass-Action Law at a temperature of 30oC is KAB = 22.20 and the two Wilson
parameters of ΛAB = 1.805 and ΛBA = 0.265.
By examining different binary systems with other species such as base and precious
metal cyanides using the Mass-Action Law, a comparison of the relative affinity of
different counter ions can be determined by using the cross product rule. This can be
valued in the prediction of the loading characteristics of more complex systems found
in the mining industry.
149
References
American Standard Testing Method “Standard Test Method for Thiocyanate in

Water.” Designation: D 4193-95.
Atkins P. “Physical Chemistry: 5th Edition” 1995. Published by Oxford University

Press, Oxford. ISBN 0-19-855730-2.
de Lucas Martinez A., Canizares P. Diaz J. “Binary ion exchange equilibrium for
Ca2+, Mg2+, K+, Na+ and H+ ions on Amberite IR-120.” Chemical Engineering
Technology, 1993, Vol. 16, pp 35-39.
de Lucas Martinez A., Zarca Diaz J., Canizares P. “Ion exchange equilibrium in a
binary mixture. Models for its characterisation.” International Chemical
Engineering, 1994, Vol. 34, No. 4, pp 486-497.
de Lucas A., Canizares P., Garcia M., Gomez J., Rodriguez J. “Recovery of Nicotine
from aqueous extracts of Tobacco wastes by an H+ form strong acid ion exchanger.”
Ind. Eng. Chem. Res., 1998, Vol. 37, pp 4783-4791.
de Lucas A., Valverde J., Romero M., Gomez J., Rodrigues J. “Ion exchange
equilibria in nonaqueous and mixed solvents on the cationic exchanger amberlite IR-
120.” Chemical Engineering Data, 2001, Vol. 46, pp 73-78.
Dubinin M., Radushkevich L. “Equation of the Characteristic Curve of Activated

Charcoal.” Proc. Acad. Sci. Phys.Chem. Sec. USSR, Vol. 55, 1947, pp 331-333.
Freundlich H. “Colloid and Capillary Chemistry.” 1926. Methuen, London, England.
Gomes C., Almeida M., Loureiro J. “Gold recovery with ion exchange used resins.”
Separation and Purification Technology, Vol. 24, 2001, pp 35-57.
Helfferich F. “Ion Exchange” 1995. Published by Dover Publications Incorporated,

New York. ISBN 0-486-68784-8.
150
Kielland J. “Individual Activity Coefficients of Ions in Aqueous Solutions.” Journal
of the American Chemical Society. Vol. 59, No. 9, 1937, pp 1675-1678.
Langmuir I. “The Adsorption of Gases on Plane Surfaces of Glass, Mica, and

Platinum.” Journal of the American Chemical Society, 1918, 40:1361-1403.
Newman A. “Chemistry and Biochemistry of Thiocyanic Acid and Its Derivatives.”

Publisher: Academics Press, New York, NY, 1975.
Purolite “A-500 and A500P Anion exchange resins, Type 1 Strong-Base Macroporus
Resin. Technical Data.” Purolite Product Specifications. 2002.
Robinson R., Stokes R. “Electrolyte Solutions. Second Edition (Revised)”

Publishers: Butterworths, London, 1965.
Shriner R., Fuson R. “Identification of Organic Compounds.” Publisher: John Wiley

& Sons Inc., New York, NK, 1948.
Serne R. “Conceptual Adsorption models and open issues pertaining to performance

assessment.” Radionuclide Sorption Saf. Eval. Perspect. Proc. NEA Workshop
(1992), Meeting 1991. Publisher: OECD, Paris, France.
Valverde J., de Lucus A., Rodriguez J. “Comparison between heterogeneous and

homogeneous MASS action models in the prediction of ternary ion exchange
equilibria.” Ind. Eng. Chem. Res., 1999, Vol. 38, pp 251-259.
Valverde J., de Lucas A., Gonzalez M., Rodriguez J. “Ion exchange equilibria of
Cu2+, Cd2+, Zn2+, and Na+ ions on the cationic exchanger Amberlite IR-120.” Journal
of Chemical and Engineering Data, 2001, Vol. 46, No. 6, pp 1404-1409.
Wilson G. “Vapor liquid equilibrium XI. A new expression for the excess free
energy of Mixing.” Journal of the American Chemical Society. Vol. 86, 1964, pp
127-130.
151
Chapter 6
Recovery of Cyanide from

Thiocyanate using
Hydrogen Peroxide
6.1 Introduction
Hydrogen peroxide has been used successfully in the mining industry to control the
cyanide being released to tailing ponds from leach liquors. The advantage of using
hydrogen peroxide over other strong chemical oxidants is that it will naturally
decompose into water and oxygen and does not cause secondary contamination if
used in excess. Hydrogen peroxide can also assist the rate of gold dissolution in
leaching operations by elevating the dissolved oxygen levels during its
decomposition.
The study of thiocyanate oxidation by hydrogen peroxide was first studied by Kastle
and Smith (Kastle et al., 1904) and it was determined that the reaction between
hydrogen peroxide and thiocyanate can be approximated by a third order reaction for
mixtures containing 10-2M thiocyanic acid and 3x10-2M hydrogen peroxide. Since
then further studies have found that the mechanism pathway between hydrogen
peroxide and thiocyanate is not simplistic. There has been strong debate on the
mechanism pathway with studies showing contradictory information (Figlar et al.,
2000).
152
This chapter examines the recovery of cyanide by air stripping from the oxidation of
thiocyanate by hydrogen peroxide under different conditions, where hydrogen cyanide
is recovered via a caustic trap. The rate of reaction was observed under different
operating conditions by changing the pH and the concentration of copper and
hydrogen peroxide of the system.
6.2 Chemistry of thiocyanate oxidation using hydrogen

peroxide
Wilson et al. (1960 (A) and (B)) proposed that the reaction mechanism between
hydrogen peroxide and thiocyanate occurs differently depending on the pH of the
system. In acidic media (pH<2) the overall reaction is:
[H + ]
3H 2 O 2 + SCN → HCN + HSO −4 + 2H 2 O
−
[6.1]
Deviations from ideal stoichiometry shown by equation 6.1 can occur through the
formation of intermediate products like S(CN)2 and products that come from the
hydrolysis of S(CN)2. S(CN)2 is formed when HCN reacts with another intermediate
product HOSCN. Wilson et al. (1960 (A)) proposed the following mechanism of
reaction between hydrogen peroxide and thiocyanate. The initial steps involve the
formation of the intermediates HOSCN and HOOSCN. The rate-limiting step was
thought to be the formation of HOSCN. The formation of HOSCN proceeds via two
different ways shown by equation 6.2 at pH>4 or equation 6.3 at pH<2.
H 2 O 2 + SCN − → HOSCN + OH − (pH > 4) [6.2]
H 2 O 2 + SCN − + H 3 O + → HOSCN + 2H 2 O (pH < 2) [6.3]
153
HOSCN reacts with either H2O2 (equation 6.4) or HCN (equation 6.5) to form either
HOOSCN and S(CN)2 respectively:
HOSCN + H 2 O 2 → HOOSCN + H 2 O [6.4]
HOSCN + HCN → S(CN) 2 + H 2 O [6.5]
Figlar et al (2000) stated that the reaction between HOSCN and HCN (equation 6.5)
could reduce the rate of consumption of H2O2 by as much as a factor of 2. When the
pH > 4, HOOSCN continues to react with hydrogen peroxide to produce hydrogen
cyanate (equation 6.6), otherwise when the pH < 2 HOOSCN reacts with hydrogen
peroxide to form hydrogen cyanide (equation 6.7).
HOOSCN + H 2 O 2 → H 2 SO 3 + HCNO (pH > 4) [6.6]
HOOSCN + H 3 O + → H 2 SO 3 + HCN + H + (pH < 2) [6.7]
Hydrogen cyanate will undergo hydrolysis under acidic conditions to produce

ammonium and carbonates (equation 6.8). In an oxidative environment H2SO3 will
oxidise to H2SO4 (equation 6.9).
HCNO + 2H 2 O → HCO 3− + NH +4 [6.8]
H 2 SO 3 + H 2 O 2 → H 2 SO 4 + H 2 O [6.9]
As stated previously free cyanide (CN- or HCN) in neutral or basic solutions will react
with hydrogen peroxide to form cyanate (equation 6.10). Under very acidic solutions
this reaction is very slow (Wilson et al., 1960 (B)) with little or no oxidation
occurring.
154
HCN + H 2 O 2 → HCNO + H 2 O [6.10]
The reason that HOSCN was used by Wilson et al. (1960(B)) as a proposed
intermediate product between the reaction of hydrogen peroxide and thiocyanate (seen
in equations 6.2 and 6.3) is due to the known chemical similarity between
thiocyanates and halide ions and the fact that HOX is the first product in
peroxide/halide reactions (Fortnum et al., 1960).
The production of S(CN)2 from thiocyanate with hydrogen peroxide was explained by
the reaction between cyanide with a reaction intermediate most likely HOSCN
(Wilson et al. 1960(A) and Filar et al., 2000). If the amount of hydrogen peroxide is
limited to produce relatively low concentrations of hydrogen cyanide compared to
thiocyanate, the complicating reaction between HOSCN and HCN could be avoided
(Filar et al., 2000). Therefore in acidic conditions where cyanide exists
predominantly as hydrogen cyanide, it will compete with hydrogen peroxide in
different reactions for the intermediate (HOSCN) to produce either S(CN)2 and CN-,
respectively. While at higher pH cyanide predominantly exists as CN-, which does
not compete for the intermediate HOSCN, but in the presence of hydrogen peroxide
cyanide would more likely continue to be oxidised to form cyanate.
S(CN)2 has been found to decompose to yield thiocyanate and either hydrogen
cyanide or cyanate depending on the pH of the system (Wilson et al., 1960 (B); Smith
et al., 1966). Under acidic conditions (pH<2) S(CN)2 will undergo acid hydrolysis
according to equation 6.11. Otherwise (pH>4) S(CN)2 will undergo the following
hydrolysis reaction (equation 6.12). This reaction is known to be catalysed by
nucleophiles and would be significant above a pH of 4 with the hydroxyl ion being
the main catalyst (Smith et al., 1966).
S(CN) 2 + 53 H 2 O → 56 SCN − + 23 HCN + 12 CO 2 + 12 NH 4+ + 16 HSO −4 + 12 H + [6.11]
S(CN) 2 + H 2 O → SCN − + CNO − + 2H + [6.12]
155
Figlar et al (2000) studied the reaction between ClO2 and SCN- in highly acidic
conditions and found that there exists an equilibrium HOSCN and (SCN)2 (shown in
equation 6.13). This equilibrium was expected since thiocyanate is considered as a
pseudohalide. In the presence of high concentrations of acid and thiocyanate Filar et
al. (2000) believed that (SCN)2 acts as an intermediate species to eventually form
products like cyanide and cyanate.
(SCN) 2 + H 2 O ⇔ HOSCN + SCN − + H + [6.13]
Orban (1986) reported that the addition of copper (II) ions to thiocyanate in the
presence of hydrogen peroxide leads to oscillation reactions and bistability in alkaline
solutions (Orban, 1986; Luo et al., 1989 and Orban et al., 2000). The reactions that
make the system oscillate can be described by similar chemistry seen by the
autocatalytic decomposition of hydrogen peroxide catalysed with Cu(OH)2. The
cycle can be written as follows:
2Cu 2+ + H 2 O 2 + 2OH − → 2Cu + + O 2 + 2H 2 O [6.14]
2Cu + + H 2 O 2 → 2Cu 2+ + 2OH − [6.15]
The chain carriers in equations 6.14 and 6.15 are HO2., HO., and copper(I) according
to the following reactions:
Cu 2+ + HOO − → Cu + + HO •2 [6.16]
Cu 2+ + HO •2 → Cu + + H + + O 2 [6.17]
Cu + + H 2 O 2 → Cu 2+ + OH − + OH • [6.18]
Cu + + OH • → Cu 2+ + OH − [6.19]
156
Equations 6.14 and 6.15 yields equation 6.20, the copper catalysed decomposition of
hydrogen peroxide.
2H 2 O 2 → O 2 + 2H 2 O [6.20]
Orban et al (2000) suggested that the role of thiocyanate is to transiently stabilise

copper (I) as a complex resulting in a time delay in its reoxidation to Cu2+. A
summary of the essential features of the model under alkaline conditions and its
essential features by reference to the key steps are shown by equation 6.21 to 6.27:
2H 2 O 2 + SCN − → OS(O)CN − + 2H 2 O [6.21]
2OS(O)CN − → OOS(O)CN − + OSCN − [6.22]
H 2 O + OS(O)CN − + OOS(CN) − → 2OS(O)CN • + 2OH − [6.23]
OS(O)CN • + Cu + {SCN − }n → OS(O)CN − + Cu 2+ + nSCN − [6.24]
H 2 O 2 + Cu 2+ + OH − → HOOCu(I) + H 2 O [6.25]
HOOCu(I) + nSCN − → Cu + {SCN − }n + HO •2 [6.26]
OS(O)CN − + HO •2 → SO 32− + HCNO [6.27]
The formation and consumption of the yellow intermediate species HOOCu(I) is the
species responsible for colour oscillations that occur within the solution (Orban et al.,
2000). The system oscillates due to the formation of OS(O)CN- which is generated
autocatalytically through the formation and reduction of the radical OS(O)CN. shown
by equations 6.21 to 6.24. As the concentration of HO2. radicals and copper
157
thiocyanate complexes Cu+{SCN-}n accumulate by reactions shown by equations 6.25
to 6.26 it reinitiates the cycle to form OS(O)CN-.
It was found that in the structure of Cu(I) thiocyanates there are strong π-bond
interactions between the Cu – S bonds made possible by the overlap of occupied 3dx2-
y2 and 3dz2 orbitals of copper(I) atoms with similar vacant 3dπ orbitals of the sulphur
atoms of the thiocyanate group (Kabesova et al., 1978; Kabesova et al., 1980). It also
was shown that π interactions predominate over the Cu – N bonds. This leads to a
shift of electron density from the internuclear space C-S to space C-N, therefore in
theory weakening the C-S bond. This suggests that the formation of complexes
between copper (I) and thiocyanate weakens the S-C bond in thiocyanate. A
graphical representation is shown in Figure 6.1.
π Cu
π
π
Cu N C S Cu
π
Cu
Figure 6.1: Graphical representation of bonding between copper(I) and the thiocyanate group.
6.3 Decomposition of hydrogen peroxide
Hydrogen peroxide decomposes with disproportionation in the following equation

6.28:
H 2 O 2 → H 2 O + 12 O 2 [6.28]
The reaction is highly exothermic and takes place in the presence of small amounts of
catalyst even in aqueous solution shown in Table 6.1. In the absence of a catalyst, it
occurs only in the gas phase at high temperature.
158
Table 6.1: Heat of decomposition of hydrogen peroxide
H 2 O 2 (g) → H 2 O(g) + 12 O 2 (g) -105.8 kJ/mol
H 2 O 2 (l) → H 2 O(l) + 12 O 2 (g) -98.3 kJ/mol
Source: Ullmann’s Encyclopedia of Industrial Chemistry, 5th Edition.
Decomposition can be catalysed both homogeneously by dissolved ions especially the

heavy metals iron of copper, manganese and chromium and heterogeneously by
suspended oxides and hydroxides such as manganese, iron, copper, palladium and
magnesium) and by metals such as platinum, osmium and silver. The mechanism of
decomposition in the presence of copper has been described previously in section 6.2.
Choudhary et al. (2003) found that the decomposition of hydrogen peroxide in the
presence of a metal catalyst namely palladium decreased as the concentration of
sulphuric acid was increased.
6.4 Reaction rate expressions
When studying different chemical reactions reaction rate expressions are useful tools
used to evaluate the mechanism or interaction of different components within a
reaction. Reaction rates are usually defined as the rate of change of concentration of
one or more components involved in the reaction. At a fixed temperature the reaction
rate is a function of the concentrations of some or all of the various components of the
system, and is usually expressed as a function of reactants only. In general it is not
possible to predict the rate expression for a given reaction by just knowing the
stoichiometric equation. By examining different rate expressions and experimental
data a rate expression can be determined for a particular chemical reaction, in this
case the reaction between hydrogen peroxide and thiocyanate.
6.4.1 Derivation of a first order integrated rate expression
From the two half-cell reactions the overall redox reaction for the oxidation for
thiocyanate by hydrogen peroxide is given by equation 6.1. Let A correspond to the
159
concentration of either thiocyanate or hydrogen peroxide. The following model
shown by equation 6.29, assumes that the pH of the system remains unchanged giving
an overall rate of reaction pseudo 1st order. That is that the rate of reaction is
dependent on the concentration of one reactant within the reaction.
dA
− = k.A [6.29]
dt
where k is the reaction rate constant.
Rearranging equation 6.29 gives:
dA
− = k.dt [6.30]
A
Integrating equation 6.30 yields a rate expression comparing the concentration of A

with respect to time. The limits of the integration are taken as A = Ao at t = 0 and A =
A at t = t, shown by equation 6.31. If the reaction shows first order kinetics with
respect to one reactant a plot of ln(A/Ao) against time will yield a linear relationship.
A
ln = k.t [6.31]
Ao
6.4.2 Derivation of a second order integrated rate expression
In the same manner as a first order rate reaction, let A correspond to the concentration
of either thiocyanate or hydrogen peroxide. The following model shown by equation
6.32, assumes that the pH of the system remains unchanged giving an overall rate of
reaction pseudo 2nd order with respect to one of the reactants.
dA
− = k.A 2 [6.32]
dt
160
Rearranging equation 6.32 gives:
dA
− = k.dt [6.33]
A2

A at t = t, shown by equation 6.34. If the reaction shows second order kinetics with
respect to one reactant a plot of (1/A-1/Ao) against time will yield a linear
relationship.
1 1
− = k.t [6.34]
A Ao
6.4.3 Derivation of a third order integrated rate expression
From the two half-cell reactions the overall redox reaction for the oxidation of
thiocyanate by hydrogen peroxide is given by equation 6.1. Let A and B correspond
to the concentrations of hydrogen peroxide and thiocyanate respectively. The
following model assumes that the pH of the system remains unchanged giving an
overall rate of reaction pseudo-3rd order, first order with respect to the concentration
of thiocyanate and second order with respect with the concentration of hydrogen
peroxide (equation 6.35).
dA
− = kA 2 B [6.35]
dt
From the redox reaction between thiocyanate and hydrogen peroxide (equation 6.1),
for every mole of thiocyanate consumed three moles of hydrogen peroxide is
consumed. Therefore the consumption of hydrogen peroxide compared to thiocyanate
can be defined as (equation 6.36):
161
dA = 3dB [6.36]
Integrating equation 6.36 between t = 0 and t = t gives:
A o − A = 3(B o − B) [6.36]
and rearranging equation 6.36 gives:
A Ao
B= − + Bo [6.37]
3 3
where Ao and Bo are the initial concentrations.
Substituting B from equation 6.37 into equation 6.35 to give a an equation in the two
variables A and t, therefore:
dA ⎛ A A⎞
− = kA 2 ⎜ B o − o + ⎟ [6.38]
dt ⎝ 3 3⎠
and rearranging equation 6.38 gives:
dA
− = k.dt [6.39]
2⎛ Ao A ⎞
A ⎜ Bo − + ⎟
⎝ 3 3⎠
Now by partial fractions rewrite the left hand side as a sum of 3 simpler terms. Let
1 p q r
≡ 2 + + [6.40]
2⎛ Ao A ⎞ A A ⎛ A A⎞
A ⎜ Bo − + ⎟ ⎜ Bo − o + ⎟
⎝ 3 3⎠ ⎝ 3 3⎠
162
where p, q and r are constants and the identity symbol means equality of the two sides
of equation 6.40 for all values of A. The values of p, q and r can be evaluated by
using a common denominator and equating coefficients of like powers of A in the
numerators. Equating the numerators gives (equation 6.41):
⎛ A A⎞ ⎛ A A⎞
1 ≡ p⎜ B o − o + ⎟ + qA⎜ B o − o + ⎟ + rA 2 [6.41]
⎝ 3 3⎠ ⎝ 3 3⎠
Equating constant terms when A = 0, gives (equation 6.42)
⎛ A ⎞
1 = p⎜ B o − o ⎟ [6.42]
⎝ 3 ⎠
Therefore solving for constant p (equation 6.43),
3
p= [6.43]
3B o − A o
and equating coefficients of A by setting A equal to Ao-3Bo and 1; constants q and r

can be determined as shown in equations 6.44 and 6.45, respectively.
1 3A o B o
q=− − [6.44]
(A o − 3B o ) 2
(3B o − A o + 1)(A o − 3B o )2
1
r= [6.45]
(A o − 3B o )2
Therefore equation 6.39 can be rewritten in the following:
163
⎛ ⎞
⎜ ⎟
p q r
− dA⎜ 2 + + ⎟ = k.dt [6.46]
⎜A A Ao A ⎟
⎜ Bo − + ⎟
⎝ 3 3⎠

A at t = t. After integration and substituting p, q and r gives equation 6.47.
⎡ 3 ⎡1 1 ⎤ ⎡ 1 3A o B o ⎤ A ⎤
⎢ ⎢ − ⎥+⎢ + 2 ⎥
ln ⎥
⎢ 3B o − A o ⎣ A A o ⎦ ⎢ (
⎣ oA − 3B ) 2
(3B − A + 1)( A − 3B ) ⎥
⎦ A0 ⎥
−⎢ ⎥ = kt
o o o o o
⎢ ⎡ 1 ⎤ Bo ⎥
⎢ +⎢ 2 ⎥
ln ⎥
⎣ ⎣⎢ (A o − 3B o ) ⎦⎥ B ⎦
[6.47]
If the oxidation of thiocyanate with hydrogen peroxide is a third order reaction as

described by equation 6.47, data from the experiment would yield a linear plot if the
left hand side of equation 6.47 is plotted against t.
164
6.5 Experimental
Analytical grade hydrogen peroxide (30 wt%) which was a certified ACS reagent was
supplied by Sigma-Aldrich. Two stabilising agents were added to the hydrogen
peroxide stock solution, 0.5ppm stannate and 1ppm phosphorus. This solution was
kept in the original polyethylene bottle and refrigerated to avoid decomposition. To
ensure that the concentration of hydrogen peroxide did not show signs of
decomposition it was periodically titrated against standard potassium permanganate.
Analytical grade sodium thiocyanate (98%) and hydrated copper sulphate (98%)
(CuSO4.5H2O) were used for these experiments and were supplied by BDH Chemical
Ltd and Asia Pascific Speciality Chemicals Limited. The pH adjustment was made by
the addition of either analytical grade sulphuric acid (98 wt%) or a solution made
from analytical grade sodium hydroxide (97%) and supplied by Asia Pacific
Speciality Chemicals Limited.
The following chemicals were used to determine the concentration of hydrogen

peroxide, free cyanide and thiocyanate. Analytical grade potassium permanganate
(99%) supplied by Asia pacific Speciality Chemicals Limited for the determination of
hydrogen peroxide. The analysis of free cyanide concentration used analytical grade
silver nitrate (99%) and 5-(4-(Dimethylamino)benzylidene)rhodanine (97%) and
supplied by Prolabo Ltd. and Sigma-Aldrich Ltd., respectively. Determination of
thiocyanate concentration used hydrated ferric nitrate (98%) and nitric acid (70 wt%),
which was supplied by Asia Pacific Speciality Chemicals Limited. All solutions were
prepared with distilled water.
165
The experimental set-up to recover cyanide from thiocyanate consisted of a bubble

column, a caustic trap, a small air pump, a precision bore flowrator and instruments to
measure pH and Eh. The schematic diagram of the equipment set-up is shown in
Figure 6.2, while its front view arrangement is shown in Figure 6.3. The bubble
column reactor was custom made from Perspex, dimensions of the reactor given in
Figure 6.4. It was made from three sections clamped together by three equally spaced
tie rods placed 5mm away from the edge of the head and base of the reactor. The
middle of the base was counter sunk to conceal the glass frit and a 2mm O-ring,
providing even bubble size and good aeration over the cross sectional area of the
reactor. When clamped down the O-ring provides a watertight seal. The head of the
reactor was also counter sunk to align the middle Perspex section; the rim of the top
of the cylinder was lined with vacuum grease to keep the reactor airtight.
The caustic trap consisted of a 500ml measuring cylinder fitted with a ground glass
Quickfit fitting with two arms to allow air into and out of the caustic trap. The air
was drawn through the caustic solution by extending the inlet from the Quickfit fitting
to near the base of the measuring cylinder with 6mm silicon tubing. At the end of the
tubing a stone sparger was fitted to provide small air bubbles for better mass transfer.
A small diaphragm Air Cadet air pump (model: 7530-50) from Cole-Parmer
Instrument Company was used to draw air through the reactor and the caustic trap.
The air flow rate was controlled by a needle valve precision bore flowrator made by
Fisher and Porter (Workington, London). All tubing used in the apparatus was 6mm
silicon tubing supplied made by Nalgen.
A Perkin Elmer Lambda 3 ultra violet/visual spectrophotometer was used in the

analysis of thiocyanate. After addition of the ferric ions to the thiocyanate solution,
the absorbance was measured at 460nm.
166
1 2 3 4
Figure 6.2: Schematic diagram of equipment set-up for oxidation study of thiocyanate using
hydrogen peroxide. (1) Bubble Column (2) Caustic Trap (3) Precision Bore Flowrator (4) Cadet
Air Pump.
Figure 6.3: Front view of equipment arrangement for oxidation study of thiocyanate using
hydrogen peroxide, showing: Bubble reactor, caustic trap, Precision bore flowrator and air
pump.
167
8mm
∅6mm
∅6mm
∅6mm
(A)
∅6mm ∅6mm
12mm 15mm 15mm
28mm 5mm
(B) (C)
350mm
6mm
28mm
4mm
14mm ∅6mm
12mm
Figure 6.4: Dimensions of the bubble column reactor. (A) Top view, (B) Side View, (C) Front
View.
168
6.5.3 Analytical Procedures to determine the concentration of thiocyanate,
free cyanide and hydrogen peroxide
6.5.3.1 Procedure for thiocyanate determination
The procedure that was followed to determine the concentration of thiocyanate is

described in section 5.3.3.
6.5.3.2 Procedure for free cyanide determination
6.5.3.2.1 Preparation of 0.01M standard silver nitrate solution.
Silver nitrate (AgNO3) was dried to a constant weight in an oven at 40oC. It was
allowed to cool to room temperature in a dessicator. To make the 0.01M silver nitrate
solution, 1.699g dry silver nitrate was dissolved in 1000ml of distilled water. This
stock solution was stored in a dark-coloured bottle.
6.5.3.2.2 Preparation of silver sensitive 5-(4-

(dimethylamino)benzylidene)rhodanine indictor
Dissolve 20mg of 5-(4-(dimethylamino)benzylidene)rhodanine in 100ml of acetone.
6.5.3.2.3 Analytical procedure for cyanide analysis
The titration procedure uses silver nitrate with the rhodanine indicator to measure free
cyanide concentrations greater than 1mg/l. The detection limit for this procedure is
0.3 mg/l. The main factors that can affect the effectiveness of this method to analyse
free cyanide concentration are interference that actually change the free cyanide
concentrations in solution. Sulphides can adversely affect the titration procedure.
Samples that contain hydrogen sulphide, metal sulphides or other compounds that
may produce hydrogen sulphide (this interference can be removed by distillation).
Positive errors may occur with samples that contain nitrate and/or nitrite. Nitrate and
169
nitrite can form nitrous acid which can reacts with some organic compounds to form
oximes. These compounds can decompose to generate HCN. The interference of
nitrate and nitrite can be eliminated by pre-treatment with sulfamic acid. Weak acid
dissociable cyanides present in the sample can change the concentration of free
cyanide available in solution. An example of this is copper cyanide. As the level of
free cyanide in solution drops there is an equilibrium shift to increase the level of free
cyanide and reduce the amount of cyanide associated with copper cyanide.
A 5 ml cyanide sample was added to a conical flask. To this solution four drops of
benzal-rhodanine indicator was added. If cyanide is present, the solution turns a
yellowish-brown colour. Then this solution was titrated against standard silver nitrate
solution until the first change in colour from yellowish-brown to pink.
The free cyanide concentration [CN-] expressed in mol/l, is given by the following
formula:
2 x (titre, ml) x [AgNO 3 ]standard

[CN - ] = [6.43]
(sample volume, ml)
where [CN-] is the cyanide sample concentration (M), [AgNO3]standard is the

standardised concentration (M) of silver nitrate and titre (in mls) is the amount of
silver nitrate used in the titration.
6.5.3.3 Procedure for hydrogen peroxide determination
6.5.3.3.1 Preparation of standard potassium permanganate solution
Standard potassium permanganate (KMnO4) solution was made by dissolving 1.86 g

KMnO4 in 800mls of distilled water. This solution was heated to boiling, then the
heat was lowered to keep the solution just below boiling point for 1 hour. To remove
any undissolved material from the KMnO4 solution it was passed through either glass
wool or a fritted glass funnel. Additional distilled water was added to make the final
170
volume of 1000ml. The stock solution was standardised against sodium oxalate and
stored in a dark-coloured bottle.
6.5.3.3.2 Standardisation of potassium permanganate solution
Analytical grade sodium oxalate (Na2C2O4) was dried at 105-110oC for 1 hour and
allowed to cool to room temperature in a dessicator. 0.30+0.01g of dry sodium
oxalate was measured and quantitatively transferred to a 500ml flask. To the sodium
oxalate 250ml of 5wt% H2SO4 (which has been boiled for 10-15 minutes and allowed
to cool room temperature) was added to dissolve the oxalate. This solution was
titrated with the prepared potassium permanganate solution until the appearance of a
pink colour. Once the solution turns pink it was heated to a temperature of 60oC,
upon heating the pink colour will disappear if the solution is not over-titrated. The
titration was completed when additional potassium permanganate was added until the
pink colour persists for about 30s. The normality of potassium permanganate is given
by:
(Na 2 C 2 O 4 , g)
KMnO 4 , N = [6.44]
(0.04903 x titration , ml)
6.5.3.3.3 Analytical procedure for hydrogen peroxide analysis
This method describes the determination of hydrogen peroxide concentration in an

aqueous solution. The reaction of potassium permanganate with hydrogen peroxide in
acidic medium according to the following redox reaction:
2MnO −4 + 5H 2 O 2 + 6H + → 5O 2 + 2Mn 2+ + 8H 2 O [6.45]
The concentration of hydrogen peroxide was determined by a titration using

standardised potassium permanganate. A known volume of H2O2 sample was added
to a 250 ml flask, ranging from 1 to 5mls. To this sample 10mls of 5N sulphuric acid
(H2SO4, 2.5mol/l) was added to keep the solution acidic. The hydrogen peroxide
171
sample was titrated against standardised 1.86g/l potassium permanganate solution
until the solution turned pale pink colour. The titration end point has been reached
when the pale pink colour persists for at least 30s. The standardised potassium
permanganate solutions used in the titration must be standardised regularly.
The concentration [H2O2] of hydrogen peroxide solution expressed in mol/l, is given

by the following formula:
5 x (titre, ml) x [KMnO 4 ]standard

[H 2 O 2 ] = [6.46]
2 x (sample volume, ml)
where [H2O2] is the hydrogen peroxide sample concentration, [MnO4-]standard is the

standardised concentration of potassium permanganate and titre (in mls) is the amount
of potassium permanganate used in the titration.
6.5.4 Experimental Procedure
The rate of reaction between thiocyanate and hydrogen peroxide to recover cyanide
was examined by contacting a solution of thiocyanate and a solution of hydrogen
peroxide in a bubble column. Experimental set-up is given in detail in section 6.5.2.
Various conditions were changed within this set of experiments to evaluate the effect
of initial pH of the solution, addition of copper (II) ions as a catalyst and the
concentration of hydrogen peroxide to the rate of reaction between thiocyanate and
hydrogen peroxide and the recovery of cyanide from the reaction. All experiments
were conducted at room temperature and at a constant airflow.
As shown in Figure 6.2 and 6.3, the bubble column was connected to the caustic trap
followed by a needle valve and air pump. Silicon tubing was used to join each piece
of apparatus. Air was drawn through the bubble column and caustic trap keeping a
slight negative pressure throughout the bubble column and caustic trap at all times. If
any leaks did occur the air would be drawn through the caustic trap at all times,
therefore eliminating the risk of hydrogen cyanide being released from the
experiment.
172
Two 250 ml solutions were freshly made for each experiment. The first solution
contained the desired amount of thiocyanate and copper sulphate and the second
solution contained the desired amount of hydrogen peroxide. The initial pH of the
experiment was adjusted before each experiment. Each solution was adjusted with
either 0.5M sodium hydroxide solution or concentrated sulphuric acid. Care was
taken to add the sulphuric acid slowly to keep the solution cool to avoid hydrogen
peroxide decomposition occurring before the experiment.
400ml of 0.5M sodium hydroxide was poured to the caustic trap. An initial sample
was taken from the caustic trap for a blank cyanide titration. All seals and tubing
were checked before the air pump was turned on to provide negative pressure within
the bubble column. The thiocyanate/copper solution was drawn into the column.
After the addition of the thiocyanate solution, the hydrogen peroxide solution was
drawn into the bubble column. Mixing the two solutions was achieved by continuous
air bubbling (this took less than 2 seconds). A sample from the bubble column was
taken after the two solutions were mixed and the experiment started. The amount of
air drawn through the bubble column and caustic trap was controlled by a needle
valve. Solution samples were taken from the bubble column and the caustic trap at
the following times during the experiment: 0, 20, 40, 60, 120, 240, 360, 480 and 1440
minutes. The bubble column samples were analysed for thiocyanate concentration,
hydrogen peroxide concentration, pH and Eh, the samples from the caustic trap were
analysed for free cyanide concentration. The analytical procedures followed to
determine the concentration of thiocyanate, hydrogen peroxide and cyanide are
described in section 6.5.3 (Analytical procedures) to determine the concentration of
thiocyanate, free cyanide and hydrogen peroxide.
Within this set of experiments the pH was varied from 100g/l sulphuric acid to pH 12.
The starting concentration of thiocyanate was 1000 ppm SCN- (17.22 mM). It can be
seen from equation 6.1 that for every mole of thiocyanate destroyed 3 moles of
hydrogen peroxide is consumed. Based on this relationship either stoichiometric or
twice the stoichiometric amounts of hydrogen peroxide were used this equates to a
concentration of 1.8g/l or 3.6g/l H2O2, respectively. Addition of copper was added in
173
a ratio of 1:1 or 2:1 copper to thiocyanate on a mole basis, resulting in a copper
concentration of 0.6g/l to 1.2g/l CuSO4, respectively.
174
6.6 Results
The concentration of thiocyanate in tailing waters found at gold operations could be in

excess of 5000ppm SCN- (Botz et al, 2001). These concentrations maybe considered
high at mines where thiocyanate is formed as a by-product in the cyanidation process.
As a compromise the initial thiocyanate level for the oxidation experiments were set
at 1000ppm SCN-. The effect of acid concentration, hydrogen peroxide concentration
and the addition of copper (II) ions were examined in this study. The concentration
levels of each parameter were related to the stoichiometric relationship of the initial
amount of thiocyanate present in each experiment.
Figure 6.5 is an example of typical results from the oxidation of thiocyanate with
hydrogen peroxide under acidic conditions. Thiocyanate is oxidised by hydrogen
peroxide to form cyanide ion under acidic conditions. In acidic conditions cyanide
will protonate to form hydrogen cyanide, which can be stripped from solution using
air. This air is then bubbled through the caustic trap where cyanide is effectively
removed and trapped in the caustic solution. The concentration of cyanide is
determined from samples taken from the bubble column. The advantage of using an
Acidification-Volatilisation-Reneutralisation (AVR) circuit to recover the cyanide
from solution is it removes cyanide from an oxidative environment stopping further
cyanide oxidation occurring to other species like cyanate. It can be seen from other
previous thiocyanate oxidation studies using different oxidants such as ozone,
chlorine and electrolytic oxidation (Botz et al. 2001, Byerley et al. 1984 and Soto et
al. 1995) that the cyanide concentration increases till a point in the experiment where
the rate of further oxidation of cyanide is greater than the oxidation of thiocyanate to
cyanide. By not stopping further cyanide oxidation it lowers cyanide recovery and
increases oxidant consumption, therefore increasing the chemical costs. From Figure
6.5 it can be seen that the chemical reaction between thiocyanate and hydrogen
peroxide follows very closely to stoichiometry in acidic conditions. For every mole
of thiocyanate consumed, 3.8 moles of hydrogen peroxide was used. Hydrogen
peroxide consumption was higher than the stoichiometric relationship of 1:3 (mole
basis) which can be due to consumption by other side reactions, for example cyanide
oxidation to cyanate or decomposition of hydrogen peroxide.
175
20 90
SCN or NaCN concentration (mM) 18 80
16
70
H2O2 concentration (mM)

14
60
12
Thiocyanate 50
10 Cyanide
Hydrogen peroxide 40
8
30
6
20
4
2 10
0 0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.5: Oxidation of thiocyanate using hydrogen peroxide to recovery cyanide. Initial
thiocyanate concentration 1000ppm, stoichiometric amount of hydrogen peroxide and 10g/l
sulphuric acid at room temperature and pressure.
The most significant influence in the recovery of cyanide from the oxidation of
thiocyanate using hydrogen peroxide is the pH of the solution. This has been
confirmed already by previous studies (Wilson et al,. 1960(A) and 1960(B)). The pH
of the system has a dual effect in the recovery of cyanide from thiocyanate. The
reaction between thiocyanate and hydrogen peroxide to produce cyanide is catalysed
by hydrogen ions, therefore a low pH is required for faster kinetics. In Figure 6.6 it
shows results of a set of experiments where the pH was varied under the following
process conditions at an initial thiocyanate concentration of 1000ppm (17.2mM SCN-
), the amount of hydrogen peroxide was double the stoichiometric amount needed to
oxidise all the thiocyanate present with an airflow rate of 1.2 L/min. It can be seen
that thiocyanate is destroyed at a faster rate at lower pH. In acidic conditions cyanide
ions protonate to form hydrogen cyanide, which is not readily oxidised to cyanate in
the presence of an oxidant compared to the cyanide ion (CN-) (Jara et al., 1996).
Therefore in very acidic media the hydrogen ions inhibit the oxidation of cyanide
through the forming hydrogen cyanide, maximising cyanide recovery. This
176
20
10 g/l Sulphuric Acid
initial pH 2
Initial pH 7
Initial pH 12
SCN Concentration (mM)
15
10
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.6: A comparison of thiocyanate concentration against time at different solution pH.
The initial concentration of thiocyanate is 1000 ppm (17.2 mM), the amount of hydrogen
peroxide added to the experiment is double the stoichiometry required to oxidise the thiocyanate
present. No copper was added to solution.
20
10 g/l Sulphuric Acid
pH 2
pH 7
pH 12
NaCN Concentration (mM)
15
10
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.7: A comparison of cyanide recovery at different initial pH’s. The initial concentration
of thiocyanate is 1000 ppm (17.2 mM), the amount of hydrogen peroxide added to the experiment
is double the stoichiometry required to oxidise the thiocyanate present. No copper was added to
solution.
177
can be seen in Figure 6.7 that the lower the pH of the system the higher the cyanide
recovery and it was easier to remove hydrogen cyanide from solution.
Under conditions of excess hydrogen peroxide and low pH’s, Wilson and Harris
(1960(A)) noticed that the reaction showed mild inhibition by hydrogen peroxide.
This may be due to a competing reaction between hydrogen cyanide and thiocyanate
in the formation of side products of sulphur di-cyanide (S(CN)2) and its hydrolysis
products. But by reducing the concentration of hydrogen cyanide from the system by
air stripping, concentrations of hydrogen cyanide can be low enough that the
complicating reaction between hydrogen cyanide and thiocyanate could be avoided.
Therefore the hydrogen cyanide inhibition can be neglected when studying the
reaction kinetics.
Since the reaction between thiocyanate and hydrogen peroxide produces acid the pH
of the solution decreases with time. As seen in Figure 6.8 for the experiments with an
initial pH of 12 and 7 the pH of the solution decreases over the first 200 minutes of
the experiment reaching a constant pH for the remainder of the experiment. When
comparing the cyanide recovery (Figure 6.7) and the pH of the solution (Figure 6.8)
for the experimental run with an initial pH of 7 it was only after the pH of the system
stabilised was when the rate of cyanide recovery increased. In the case with an initial
pH of 12, there may not be enough acid produced to protonate the cyanide produced
to protect it from further oxidation resulting in a very low cyanide recovery. It is
evident that the pH 2 and 10g/l sulphuric acid that the pH affects the rate at which
hydrogen cyanide is removed from the bubble column.
As the pH of the solution decreases with reaction time, the Eh of the system increases,
which is due to the additional acid formed during the reaction, as seen in Figure 6.9.
For experiments where the pH was less than 2, the amount of acid produced did not
change the pH of the system and it remained relatively constant and inturn the Eh of
the system did not change significantly. When the initial pH of the system started at
12 the initial Eh 0.071 V (vs. SCE) increasing to 0.382 V (vs. SCE) after 200 minutes.
178
12
10 g/l Sulphuric acid
Initial pH 2
10
Initial pH 7
Initial pH 12
8
pH
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.8: The pH profile of hydrogen peroxide oxidation of thiocyanate with different initial
starting pH. The initial concentration of thiocyanate is 1000 ppm (17.2 mM), the amount of
hydrogen peroxide added to the experiment is double the stoichiometry required to oxidise the
thiocyanate present. No copper was added to solution.
0.6
0.5
0.4
Eh (V vs SCE)
0.3
0.2
10 g/l sulphuric acid
initial pH 2
0.1 Initial pH 7
Initial pH 12
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.9: The Eh profile of hydrogen peroxide oxidation of thiocyanate with different initial
starting pH. The initial concentration of thiocyanate is 1000 ppm (17.2 mM), the amount of
179
Copper(II) ions was added to the system to see if the reaction between hydrogen
peroxide and thiocyanate would be affected by the copper. In alkaline systems it was
found that addition of copper(II) ions leads to oscillation reactions and bistability
(Luo et al., 1989; Orban, 1986 and Orban et al., 2000). These oscillation reactions
were only stable in alkaline conditions (pH >12), since the overall reaction between
thiocyanate and hydrogen peroxide produces acid, to maintain a pH > 12 addition of
an alkali was needed. In acidic conditions these oscillation reactions are not stable
but copper may act in a similar way outlined by Orban (1986). Copper enhances the
autocatalytic decomposition of hydrogen peroxide. In one of the steps of
decomposition of hydrogen peroxide copper (II) ions are reduced to form copper(I)
ions, which then complex with thiocyanate present in solution. From Pourbaix
diagrams (Figures 4.4-4.7) it was found that the stability zone of copper (I)
thiocyanate complexes was larger than for copper (II) thiocyanate complexes. These
are the predominant species formed in the copper-thiocyanate-water systems under
the operating conditions carried out in the experiments. By removing free thiocyanate
from the system side reactions that consume hydrogen cyanide can be avoided.
Oxidation may be aided by the addition of copper to the system because when copper
(I) complexes with thiocyanate the bond between the sulphur atom and carbon atom
weakens as electron density is rearranged and inturn strengthening the triple bond
between the carbon and nitrogen.
From the initial oxidation experiments it was found that a low pH is required for high
cyanide recovery. A set of eight experiments was conducted to understand the
oxidation of thiocyanate and hydrogen peroxide in the presence of copper. The
conditions for each experiment are tabulated in Table 6.2.
Figure 6.10 is a comparison of thiocyanate concentration against time under different

experimental conditions outlined in Table 6.2. These experiments showed faster
kinetics than experiments shown in Figure 6.6 that did not contain any copper. The
lowest residual thiocyanate concentration was 0.3ppm SCN-.
180
Table 6.2: Experimental conditions for thiocyanate oxidation experiments with the addition of
copper. The initial concentration of thiocyanate for each experiment is 1000 ppm SCN-.
Experiments were carried out at room temperature and pressure. Airflow rate 1.2 L/min.
Experiment Copper Hydrogen peroxide Sulphuric acid
concentration concentration concentration
(g/l) (g/l) (g/l)
1 0.6 1.8 10
2 1.2 1.8 10
3 1.2 3.6 10
4 0.6 3.6 10
5 0.6 3.6 10
6 0.6 3.6 100
7 0.6 1.8 100
8 1.2 3.6 100
20
Experiment 1
Experiment 2
Experiment 3
SCN concentration (mM)
Experiment 4
15
Experiment 5
Experiment 6
Experiment 7
Experiment 8
10
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.10: A comparison of thiocyanate concentration against time at different experimental

conditions outlined in Table 6.2.
181
Figure 6.11 is a plot of residual hydrogen peroxide concentration against time for each
experiment that contained copper. Four experiments contained double the
stoichiometric requirement of hydrogen peroxide (experiments 3,5,6 and 8), Figure
6.11 shows that the consumption of hydrogen peroxide was greater than half the
amount of hydrogen peroxide added to the experiments. This is due to the continued
decomposition of hydrogen peroxide in the presence of a copper catalyst. After all
the thiocyanate was consumed in the reaction the concentration of hydrogen peroxide
slowly decreased even further with time which could be due to further oxidation of
cyanide to cyanate and then even leading to the oxidation of cyanate to nitrate and
carbonates.
180
Hydrogen peroxide concentration (mM)
Experiment 1
160 Experiment 2
Experiment 3
140 Experiment 4
Experiment 5
120 Experiment 6
Experiment 7
100 Experiment 8
80
60
40
20
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.11: A comparison of hydrogen peroxide concentration against time under different
experimental conditions outlined in Table 6.2.
With the addition of copper to the oxidation of thiocyanate, cyanide recovery

continued to be high, as shown in Figure 6.12. Experiment 6 recovered 100% of the
theoretical cyanide produced if all the thiocyanate present is converted to cyanide, the
concentration of copper, hydrogen peroxide and sulphuric acid in the experiment were
[Cu2+] = 0.6 g/l, [H2O2] = 3.6 g/l and [H2SO4] = 100 g/l. For all the other experiments
cyanide recovery was greater than 80%. Since the air flowrate was set at 1.2 L/min
for each experiment the only factor that changes the overall cyanide recovery is
182
related to the operating conditions of each experiment. It can be seen in Figure 6.10
that for experiment 6 that the thiocyanate was all oxidised within the first 40 minutes,
therefore increasing the initial concentration of cyanide available to be stripped from
solution from an early stage in the experiment. It was found it took over 24 hours to
be able to strip the cyanide formed during the oxidation of thiocyanate. Experiment 6
shows that even if the cyanide was left in an oxidative acidic environment (where the
sulphuric acid concentration was 100g/l) that cyanide would not continue to oxidise to
cyanate. The recovery of cyanide using the AVR circuit occurred over a 24 hour
period because of slow mass transfer from solution to the stripping air. In this time
hydrogen cyanide was left in contact with residual thiocyanate and oxidants, which
can react with hydrogen peroxide to produce cyanate, carbonates and nitrates or their
hydrolysis products. This can lead to low in cyanide recovery for the other
experiments. At the end of these experiments cyanate was determined ranging in
concentration from 10-15 ppm in solution. Due to the hydrolysis of cyanate in acidic
condition, the concentration of cyanate will change rapidly therefore it can not be
used to close the mass balance.
120
100
Cyanide recovered (%)
80
60 Experiment 1
Experiment 2
Experiment 3
40 Experiment 4
Experiment 5
Experiment 6
20 Experiment 7
Experiment 8
0
0 200 400 600 800 1000 1200 1400 1600
Time (min)
Figure 6.12: A comparison of cyanide recovered against time under different experimental
conditions outlined in Table 6.2.
183
The 3rd order reaction kinetics based on the derived rate expression defined in section
6.4.3 was used to describe the rate of reaction between hydrogen peroxide. The
kinetic model assumes that the rate of reaction is 1st order with respect to the
thiocyanate concentration and 2nd order with respect to the hydrogen peroxide
concentration. For the experiments that did not contain any copper the validation of
the mechanism shown by equation 6.42 was determined by plotting the left hand side
of the equation 6.42 against time showing a linear relationship (shown in Figure 6.13
and Figure 6.14). As the acid concentration was increased the rate reaction increased
resulting in a larger reaction constant k, shown in table 6.3. The effect of increasing
the acid concentration from a pH of 7 to 10 g/l sulphuric acid the reaction constant k
increased an order of magnitude. Under these reaction conditions the reaction
mechanism did not show the mild inhibition by hydrogen cyanide as observed by
other authors reported by Wilson and Harris (1960(A)). This is a direct result of
removing hydrogen cyanide from the bubble column.
The experiment shown in Figure 6.15 (with an initial pH of 12) shows that under
these conditions the reaction does not follow the third order reaction as with the other
experiments carried out at lower pH. This was the only experiment were the pH level
changed significantly over the duration of the experiment. Therefore the pH level has
to remain constant for the pseudo third order expression described by equation 6.42 to
hold true.
When applying the 3rd order reaction kinetic model defined by equation 6.42 to the
experiments that contained copper it was found that these experiments did not show a
linear relationship seen in Figure 6.16. This may be due to the reactions between
copper (II) ions and hydrogen peroxide to produce free radicals which will react with
thiocyanate changing the rate limiting step within the reaction, therefore affecting the
overall 3rd reaction mechanism described by equation 4.47.
184
Table 6.3: 3rd order reaction constants for a reaction between thiocyanate and hydrogen
peroxide. The initial concentration of thiocyanate is 1000 ppm (17.2 mM), the amount of
Acid concentration k (min-1.mol-2)
(10 g/l Sulphuric acid) 15.8
pH 2 0.32
pH 7 0.19
300
250
3rd Order Kinetic Model
200
150
100
50 Initial pH 2
Initial pH 7
0
0 100 200 300 400 500 600
Time (min)
Figure 6.13: Applying the third order kinetic model for the reaction between thiocyanate and
hydrogen peroxide with an initial pH of 2 or 7. The initial concentration of thiocyanate is 1000
ppm (17.2 mM), the amount of hydrogen peroxide added to the experiment is double the
stoichiometry required to oxidise the thiocyanate present. No copper was added to solution.
185
12000
10000
3rd order kinetic model
8000
6000
4000
2000
0
0 100 200 300 400 500 600
Time (min)
hydrogen peroxide with a acid concentration of 10g/l sulphuric acid. The initial concentration of
thiocyanate is 1000 ppm (17.2 mM), the amount of hydrogen peroxide added to the experiment is
double the stoichiometry required to oxidise the thiocyanate present. No copper was added to
solution.
250
200
3rd order kinetic model
150
100
50
0
0 100 200 300 400 500 600
Time (min)
hydrogen peroxide with an initial pH of 12. The initial concentration of thiocyanate is 1000 ppm
(17.2 mM), the amount of hydrogen peroxide added to the experiment is double the stoichiometry
required to oxidise the thiocyanate present. No copper was added to solution.
186
1200
1000
3rd oder kinetic model
800
600
400
Experiment 5
200
Experiment 6
Experiment 8
0
0 100 200 300 400 500 600
time (min)
hydrogen peroxide in the presence of copper(II). Experimental conditions outlined in Table 6.2.
The same data shown in Figures 6.13 and 6.14 was used in examination if the reaction
rate was either first or second order with respect of either hydrogen peroxide or
thiocyanate concentration. Figure 6.17 shows the plot to determine if the reaction rate
is first order described by equation 6.31 at initial pH of 7. From this figure the plot is
not linear with respect to either hydrogen peroxide or thiocyanate concentration and
therefore is not a first order reaction. A similar result is seen for second order
reaction described by equation 6.34 and shown by Figure 6.18. It can be seen that the
plot is not linear with respect to either hydrogen peroxide or thiocyanate concentration
and therefore the reaction is not a second order reaction with respect to either reactant.
187
0.6 0.3
Thiocyanate
Hydrogen Peroxide
0.5 0.25
0.4 0.2
ln([H2O2]/[H2O2]o)
ln([SCN]/[SCN]o)
0.3 0.15
0.2 0.1
0.1 0.05
0 0
0 100 200 300 400 500
Time (min)
Figure 6.17: Applying the first order kinetic model for the reaction between thiocyanate and
45 2.5
Thiocyanate
40
Hydrogen Peroxide
2
35
1/[H2O2] - 1/[H2O2]o
30
1/[SCN] - 1/[SCN]o
1.5
25
20
1
15
10
0.5
0 0
0 100 200 300 400 500 600
Time (min)
Figure 6.18: Applying the second order kinetic model for the reaction between thiocyanate and
188
6.7 Conclusions
The oxidation of thiocyanate using hydrogen peroxide with or without the presence of
copper under different acid concentrations was studied to see if cyanide could be
recovered. By using an AVR circuit cyanide was stripped from solution in a bubble
column by air at a constant airflow (1.2 L/min). The air that was used to strip the
cyanide from solution was bubbled through a 0.5M caustic solution to trap the
cyanide in solution. An advantage of using the AVR circuit to recover cyanide from
solution is that it removes cyanide from solution in a form that can be added easily
back into a gold mine cyanidation circuit. Process conditions can be varied to
concentrate the cyanide recovered from the process.
Typical cyanide recovery from the oxidation of thiocyanate was greater than 80%
over a 24 hour period of the theoretical cyanide produced if all the thiocyanate present
is converted to cyanide. Figure 6.12 shows that experiment 6 gave the conditions for
100% cyanide recovery from thiocyanate. The conditions of this experiment with an
initial thiocyanate concentration of 1000 ppm SCN- were 0.6 g/l copper (II), 3.6 g/L
initial hydrogen peroxide, an acid concentration of 100 g/l sulphuric acid and an air
flowrate of 1.2 L/min. The mass transfer to remove hydrogen cyanide from the liquid
was very slow, taking over 24 hours to recover the cyanide produced in the reaction.
By ensuring that high acid concentration further oxidation of cyanide can be
minimised. The mass transfer could be increased if stripping towers were used to
increase the liquid/air contact area as with commercial projects. Increasing the
airflow rate in the bubble column caused slugging within the column reducing the
total air surface area reducing the mass transfer between the two phases.
The most significant factor for increasing the rate of reaction and recovery of cyanide
is acid concentration. As the concentration of acid was increased, the rate of
oxidation increased, by changing the pH from 7 to an acid concentration of 10g/l
sulphuric acid the reaction rate constant from 0.19 to 15.8 min-1.mol-2, respectively. If
the pH of the reaction is carried out under conditions that the acid concentration does
not change significantly the reaction rate order is independent of acid concentration.
Other than increasing the rate of reaction, the acid concentration plays an important
189
role in protonating cyanide to form hydrogen cyanide, which aids in stripping the
cyanide from solution and it has been found that hydrogen cyanide is not easily
oxidised. Therefore high acid concentrations can minimises further oxidation of the
cyanide until it is recovered from the bubble column.
The reaction between thiocyanate and hydrogen peroxide is an overall third order
reaction, 1st order with respect to thiocyanate concentration and 2nd order with respect
to hydrogen peroxide. Addition of copper to the system did not follow the same
reaction kinetic mechanism as with experiments that were carried out without copper.
This could be due to the formation of free radicals during the reaction between copper
and hydrogen peroxide can oxidize thiocyanate. The rate limiting step described by
the third order reaction described by equation 6.42 may not be the rate limiting step
therefore deviating from the third order reaction that describes the reaction between
thiocyanate and hydrogen peroxide without copper. Also addition of copper to the
experiment complicates the reaction mechanism kinetics. In the presence of hydrogen
peroxide, copper (II) ions will reduce to copper (I) as a part of the decomposition of
hydrogen peroxide. Stable complexes can form between copper (I) ions and
thiocyanate. Kabesova et al (1978) noticed the formation of copper(I) thiocyanate
complexes, weakens the sulphur-carbon bond and strengthens the triple bond between
the carbon-nitrogen bond making oxidation easier. As a result for the experiment in
the presence of copper the residual thiocyanate concentration after 24 hours is a lot
lower than experiments without copper. The lowest residual thiocyanate
concentration was 0.3 ppm. Increasing the copper concentration from 0.6 g/l to 1.2g/l
did not significantly change the rate of thiocyanate being consumed.
190
References
Botz M., Dimitriadis D., Polglase T., Phillips W. and Jenny R. “Processes for the
regeneration of cyanide from Thiocyanate.” Journal of Minerals and Metallurgical
Processing Vol. 18, No. 3, August 2001, pp 126-132.
Byerley J., Enns K. “ Electrochemical regeneration of cyanide from waste

thiocyanate for cyanidation.” CIM Bulletin, Vol. 77, No. 861, 1984. pp 87-93.
Choudhary V., Gaikwad, A. “Kinetics of hydrogen peroxide decomposition in

aqueous sulfuric acid over palladium/carbon: effect of acid concentration.” Reaction
Kinetics and Catalysis Letters. (2003), Vol. 80(1), pp27-32.
Figlar J. and Stanbury D. “Thiocyanogen as an intermediate in the oxidation of

thiocyanate by hydrogen peroxide in acidic solution.” Inorganic Chemistry, (2000),
Vol. 39, pp 5089-5094.
Fortnum D., Battagila C., Cohn S. and Edwards J. “Kinetics of the oxidation of
halide ions by monosubstituted peroxides.” Journal of the American Chemical
Society, (1960), Vol. 82, pp778.
Jara J., Soto H., Nava F. “Regeneration of cyanide by oxidation of thiocyanate.”

United States Patent 5,482,694, January 9, 1996.
Kabesova M., Kohout J., Gazo J. “Effect of the bridging mode of the thiocyanate
group in compounds on infrared spectra.” Inorganica Chimica Acta. (1978) L435.
Kabesova M., Gazo J. “Structure and classification of thiocyanates and the mutual
influence of their ligands.” Chemicke Zvesti. (1980), Vol. 34, No. 6, pp 800-841.
Kastle J., Smith C. “On the oxidation of Sulphocanic acid and its salts by hydrogen
peroxide.” Journal of American Chemistry. (1904), Vol. 32, pp 376-385.
191
Luo Y., Orban M., Kustin K. and Epstein I. “Mechanistic study of oscillations and
bistability in the Cu(II) catalyzed reaction between H2O2 and KSCN. Journal of
American Chemical Society. (1989), Vol. 111, No. 13, pp 4541-4548.
Orban M. “Oscillations and bistability in the Cu(II)-catalyzed reaction between H2O2

and KSCN. Journal of the American Chemical Society. (1986), Vol. 108, pp 6893-
6898.
Orban M., Kurin-Csorgei K., Rabai G and Epstein I. “Mechanistic studies of

oscillating copper (II) catalysed oxidation reactions of sulfur compounds.” (2000),
Vol 55, pp 267-273.
Soto H., Nava F., Leal J., Jara J. “Regeneration of cyanide by ozone oxidation of
thiocyanate in cyanidation tailings.” Minerals Engineering, Vol. 8, No. 3, 1995, pp
273-281.
Ullmann’s Encyclopedia of Industrial Chemistry, 5th Edition. (1989) Publisher: VCH

Verlagsgesellschaft mbH.
Wilson I., Harris G., (1960 (A)) “The Oxidation of Thiocyanate Ion by Hydrogen
Peroxide. I. The pH-Independent Reaction.” Journal of the American Chemical
Society, Vol. 82, 1960, pp 4515-4517.
Wilson I., Harris G. (1960(B)) “The oxidation of thiocyanate by Hydrogen Peroxide,

II. The acid catalysed reaction.” Journal of the American Chemical Society, Vol. 83,
1960, pp 286-289.
192
Chapter 7
Electrochemical Studies of
Thiocyanate Oxidation
7.1 Introduction
Voltammetry is a versatile technique for studying the mechanism of different

reduction-oxidation systems. It enables half-cell studies of the rate of electron
transfer against the applied potential. The main concerns of each half-cell reaction are
the processes and factors that are associated with the charge transfer across the
interfaces between chemical phases. There are two commonly used electrochemical
techniques, cyclic stationary electrode voltammetry where the working electrode is
stationary and hydrodynamic voltammetry where the working electrode is in motion
with respect to the solution.
This chapter examines electrochemical aspects of thiocyanate oxidation using a

voltametric technique based on the Rotating Disk Electrode (RDE) system. The
technique involves the oxidation half-cell reaction of thiocyanate in the absence of
any chemical oxidants. The effects of various factors, namely, solution pH, scanning
rates and disc rotation speeds and addition of copper on the current-potential
relationship of the thiocyanate half-cell reaction were evaluated.
193
7.2 Voltammetry
A simple electrode reaction maybe represented as:
O + ne ⇔ R [7.1]
where O and R are the oxidised and reduced forms of a species, respectively.
The applied potential controls the surface concentration of the two forms of a redox
couple (equation 7.1) as described by the Nernst equation (equation 7.2) for a
reversible couple.
RT ⎛ C OS ⎞
E = EOo ', R + ln⎜ ⎟ − E ref [7.2]
nF ⎜⎝ C RS ⎟
⎠
where E is the potential applied to the cell, volts (V), Eo’ is the formal reduction
potential of O,R couple, V vs. SHE, n is the number of electrons transferred per mole,
eq/mol, CSO,R is the surface concentration of O or R, mol/l, Eref is the half cell
potential of the reference electrode, V vs. SHE.
Thus the oxidised species (O) can be reduced to the reduced species (R) by making E
sufficiently negative (relative to EO,R – Eref) to cause the ratio of CSO/CSR to be very
small. Reversely, the reduced species (R) can be oxidised to the oxidised species (O)
by making E sufficiently positive to cause the ratio of CSO/CSR to be very large. In
other words, the reducing or oxidising strength of the working electrode is controlled
by the applied potential, E.
For equation 7.1, the following cases may be considered. When the electron transfer
rate is sufficiently fast that the ratio of the surface concentrations of the oxidised and
reduced species follow the Nernst equation throughout the entire potential sweep, the
system us then said to be reversible. If the reaction is very slow compared to the
potential sweep rate, v, so that the surface concentrations of O and R are no longer
194
maintained at Nernstian values, the system is then said to be irreversible. When the
situation lies between a reversible and irreversible system, the system is termed quasi-
reversible.
As shown in Figure 7.1, scanning the potential in the negative direction makes the
electrode a stronger reductant (causing O to be reduced to R), whereas scanning the
potential in the positive direction makes it a better oxidant (causing R to be oxidised
to O). The conversion of O to R by reduction at the electrode surface results in
cathodic current, Ic. Oxidation of R to O gives an anodic current, Ia.
ic, cathodic current
REDUCTION
As the potential is increased in a The current plotted above the line

negative direction, the electrode indicates a negative charge flow
becomes a stronger “reducing FROM the electrode.
agent”
E(+), V E(-), V
OXIDATION As the potential is increased in a

positive direction, the electrode
The current plotted above the line becomes a stronger “oxidising
indicates a negative charge flow agent”
TO the electrode.
ia, anodic current
Figure 7.1: Current-potential axes for voltammetric technquies.
The current-potential information of an electrochemical half-cell reaction under

certain condition can be obtained using a conventional three-electrode polarographic
system. This system consists of three separate electrodes, namely a reference
electrode (RE), a counter electrode (CE) and a working electrode (WE). Figure 7.2
illustrates the typical three electrode system used for electrochemical measurements.
The working electrode is where the primary electrochemical reaction occurs and
commonly made from platinum, gold, copper, zinc or glassy carbon. The opposite
side of the working electrode is referred to as the counter electrode. The
electrochemical properties of a counter electrode do not affect the behaviour of the
electrode of interest and may be any inert electrode such as a carbon rod dipping
195
directly into the test solution but normally in a separate compartment from the
working electrode (Bard and Faulkner 1980). The role of the counter electrode is to
complete the electrochemical cell and its potential is rarely of interest. The potential
of the working electrode is normally measured with respect to a reference electrode.
The standard hydrogen electrode (SHE) is almost universally accepted as a reference
electrode, however the saturated calomel electrode (SCE) or the silver-silver chloride
electrodes are usually used in experiments and practical work.
Power Supply
Working Electrode
Auxiliary Electrode
V
Reference Electrode
Figure 7.2: Typical three electrode system for electrochemical measurements (Bard & Faulkner,
1980).
7.2.1 Rotating Disc Electrode
One of the few electrode systems for which the hydrodynamic and convective-
diffusion equations have been solved rigorously for the steady state is the rotating
disk electrode (RDE). A schematic diagram is represented in Figure 7.3. Theoretical
treatment of the rotating disc system was given by Riddiford (1966), for a smooth
disc, the fluid remains laminar when the Reynolds number (refined by equation 7.3)
remains under 2x105. As the disc rotates, adjacent solution is pulled along by viscous
196
drag and is thrown away from the axis of rotation in a radial direction by the
centrifugal force. The expelled solution is replaced by flow normal (axial flow) to the
disc surface. Thus, the rotating disc acts as a pump which moves solution up from
below and then away from the electrode.
r 2ω
Re = [7.3]
v
where Re is the dimensionless parameter, r is the radial position on the disc (cm), ω is
the angular velocity (rad/s) and v is the kinematic viscosity (cm2/s).
Figure 7.3:Schematic diagram of the fluid flow for a rotating disc system (Miller, 1979).
Levich (1962) showed that for a rotating disc, under laminar flow condition the
diffusion layer thickness under the disk is given by:
−1 1
∂ o = 1.61D o 3 ω 2 v 6
1
[7.4]
197
where δο is the “diffusion” layer thickness at an electrode fed by convective transfer
(cm), Do is the diffusion coefficient of the reactive species (cm2/s), ω is the angular
frequency of rotation (1/s) and v is the kinematic viscosity of solution (cm2/s).
For a reaction controlled by a mass-transfer limited condition at the RDE, the limiting
current can be described by the Levich equation:
2 1 −1
i l = 0.620nFAD o3 ω 2 v 6 C *o [7.5]
where n is the number of moles of electrons oxidised or reduced, F is Faraday’s

constant (96 486 coulomb/mole), A is the surface area of the electrode (cm2), Do is the
diffusion coefficient of the reactive species (cm2/s), ω is the angular frequency of
rotation (1/s) and v is the kinematic viscosity of solution (cm2/s) and Co* is the bulk
concentration of the oxidising or reducing ion (mol/l).
The Levich equation predicts that ic is proportional to Co* and ω1/2. One can define
the Levich constant, ic/ω1/2Co*, which is the RDE analog of the diffusion current
constant or current function in voltammetry or the transition time constant in
chronopotentiometry (Bard and Faulkner 1980).
The rate of reaction at the electrode surface during the potential sweep can be related
to the diffusion coefficient of the reactive species, kinematic viscosity of solution and
angular frequency of rotation of the RDE (Bard and Faulkner 1980), which is shown
below:
2 −1 1
k = 0.620D o3 v 6 ω 2 [7.6]
Equating equations 7.5 and 7.6 the reaction rate constant, k, can be expressed as:
il
k= [7.7]
nFAC
198
7.3 Experimental
All chemicals reagents used in the studies in this chapter were the same as described
in Chapter 6. In addition to these chemical reagents, analytical grade anhydrous
sodium sulphate (100%) was used in these experiments and supplied by Asia Pacific
Speciality Chemicals Limited.
7.3.2.1 Electrodes
The electrochemical studies were conducted using a standard three-electrode system

(Figure 7.2), which consists of a working electrode (WE), a reference electrode (RE)
and counter electrode.
Working electrode
A glassy carbon circular polished disc was used in the study as the working electrode.
The electrode consisted of a 7mm glassy carbon disk embedded into a high-density
polyethylene holder with an outer diameter of 12mm. The working surface area of
the electrode is 0.385cm2.
Reference electrode
A standard Silver-Silver Chloride electrode was used in this study as the reference
electrode. Its cell arrangement can be represented as follows:
Ag AgCl Cl − [7.10]
199
The electrode was filled with saturated potassium chloride solution giving a potential
of 0.199V against a standard hydrogen electrode at 25oC. The measured potential
(versus the silver-silver chloride electrode) can be converted to the potential of
hydrogen at 25oC by the following equation:
E h = E measured + 0.199 V [7.11]
Counter Electrode
The counter electrode was made of a graphite rod of 14 cm in length and 6mm in
diameter.
7.3.2.2 Equipment
The equipment used for the electrochemical half-cell studies consist of a rotator,
speed controller unit, potentiostat and a data acquisition unit. The schematic diagram
of the equipment/apparatus set-up for the half cell study is shown in Figure 7.7.4,
while its front view arrangement is shown in Figure 7.7.5.
Potentiostat
A cyclic voltammograph (model:CV-27) made by Bioanalytical Systems Incorporated

was used for the voltammetry study. This unit has a built-in scanner. The
specifications of the unit are as follows:
Table 7.1: Specifications of the cyclic voltammograph

Sweep range +5.0 V
Scan rate range 0.1 mV/s to 10 V/s
Compliance voltage + 10.0 V
Maximum available current 120 mA
Current converter 2μA/V to 10.0 mA/V
200
4
1
2
3
5 6 7
Figure 7.4: Schematic of equipment set-up for electrochemical half-cell studies. 1) Rotating disc
electrode, 2) Speed controller, 3) Potentiostat, 4) Data Acquisition unit, 5) Counter electrode, 6)
Reference electrode, 7) Thermometer, 8) 5 port Pyrex flask, 9) Water bath.
Figure 7.5: Front view of the equipment arrangement for electrochemical studies showing: IBM
computer with Quicklog PCTM software, TLC 548/9 Anolog to digital converter, Pine intrument
Rotating Disc Electrode rotator with 5 port reaction cell and wath bath, MSR speed controller
and CV-27 Potentiostat.
201
Rotator and speed controller
The rotator and speed controller (model: MSR) was made by Pine Instruments. The
speed of rotation ranged from 0 to 10 000 rpm. Its accuracy is better than 1% of the
dial setting.
Data acquisition unit
To record the digital current-potential data, a data acquisition unit was made, which
consisted of a TLC584/9 LinC MOS 8-bit analog to digital converter linked to a IBM
compatible computer and Quicklog PCTM data acquisition software version 1.04
(Strawberry Tree Incorporated, 1990).
The pH of the solution was measured by Orion 520A digital pH meter. Temperature
of the solution was kept at constant temperature by immersing the reaction cell in a
water bath which was controlled by a Haake water chiller.
7.3.3 Experimental Procedure
The working solutions for the half-cell studies were made in a background solution
0.1M sodium sulphate (Na2SO4) to increase the conductivity of the solution. To the
background solution the desired amounts of thiocyanate and copper(II) as copper
sulphate were added to make the experimental concentrations. Then the solution was
adjusted to the desired pH by adding either 1M sulphuric acid or 1M sodium
hydroxide solution. To the 250ml five port spherical Pyrex flask 200ml of the
working solution was transferred. The central port of the flask contained the rotating
working electrode while the other ports contained the reference electrode, counter
electrode and thermometer to measure the temperature of the solution.
The Pyrex flask was set into the water bath and was allowed time to equilibrate to the
required temperature. The working electrode was thoroughly polished flat and
perpendicular to the electrode’s shaft using a series of polishing pads until a mirror
finish. The working electrode is secured to the shaft of the rotator and immersed
202
approximately 5 mm below the surface. Care was taken to ensure that the only
electrical contact the working electrode made with the solution was the polished
glassy carbon disc. Before each scan, the voltammograph was set at the required
potential range, appropriate scan rate and conversion factor for the anolog output for
data acquisition. The speed of the rotator was set to the required rotation rate and the
voltage was scanned over the potential range. During the scan the current-potential
relationship of the half-cell reaction was recorded using the data acquisition unit.
203
7.4 Results
The effects of various factors, namely, solution pH, scanning rates, disc rotation
speeds and addition of copper on the current-potential relationship of the thiocyanate
half-cell reaction were evaluated. All experiments were conducted at 25oC and at a
scan rate of 40mV/s unless stated otherwise.
The stationary voltametric response of the glassy carbon working electrode was
determined with respect to the Ag-AgCl reference electrode in 0.1M Na2SO4. The
cyclic voltametric response obtained for the first cycle at a scan rate of 40mV/s
(Figure 7.6), was scanned from 0 to 1.6V with respect to the Ag-AgCl electrode.
From this scan, breakdown of water became apparent above 1.0 V (vs. Ag-AgCl
electrode). The increase of current above 1.0 V (vs. Ag-AgCl electrode) was due to
the oxidation of OH- ions in solution to form oxygen gas (O2 (g)).
70
60
50
Current i (μ A)
40
30
20
Direction of scan →
10
-10
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
E (V vs. Ag-AgCl reference electrode)
Figure 7.6: Cyclic voltammogram of the glassy carbon electrode in 0.1M Na2SO4 at pH 2, rest
potential 0V and a scan rate of 40mV/s at a temperature of 25oC.
204
In aqueous solution the overall electrolysis reaction of thiocyanate predominantly
follows equation 7.10 and is believed to proceed through the formation of
thiocyanogen (S(CN)2) which is subsequently hydrolysed to sulphate and cyanide and
the electrode process is irreversible (Nicholson, 1959).
SCN − + 4H 2 O → SO 24− + HCN(aq) + 7H + + 6e − [7.10]
Wilson et al. (1960) proposed that the oxidation of thiocyanate occurred via two
different mechanisms depending on the pH of the system to form HOSCN, shown
previously by equation 6.2 when the pH >4 or equation 6.3 when the pH <2. HOSCN
will further oxidise to form S(CN)2 as described by Nicholson.
Figure 7.7 shows a stationary cyclic voltammogram of a glassy carbon electrode in a

solution of 0,1M Na2SO4 + 0.01m NaSCN, pH 2 at a different scan rates, the peak
current occurred at E = 1.35V (vs. Ag-AgCl electrode). From the reverse scan from
1.5V back to 0V there are no current peaks produced showing that the electrode
process is irreversible. This is in agreement with previous work by Nicholson (1959)
where voltammetry of thiocyanate ion in pyridine-pyridinium solutions were studied.
The scan rate was increased from 10 mV/s to 40 mV/s shown in Figure 7.7. During
the forward scan from 0V to 1.5V, two peaks that be seen. The first peak occur when
the potential reached 1.18V (vs Ag-AgCl reference electrode), with the second peak
occurring at 1.36V (vs. Ag-AgCl reference electrode) as shown in Figure 7.7. The
first peak corresponds to the oxidation of thiocyanate to cyanide; the second peak
corresponds to the further oxidation of cyanide generated at the electrode surface
when the thiocyanate was oxidised. Since Equation 7.10 may represent the sum of
perhaps seven or eight steps, some of them are slow, and deviations from
stoichiometry are easily visualised, the oxidation with species such as (SCN)2 or
SCN+ can produce broad peaks seen in Figure 7.7 instead of clearly defined peaks that
can occur with a simple oxidation, for example the oxidation of ferrous to ferric ions.
The pH of the solution was increased to 12 and the cyclic voltammogram of a glassy
carbon electrode in a solution of 0,1M Na2SO4 + 0.01m NaSCN, at a different scan
rates were repeated. The voltammograms are shown in Figure 7.8. The shape and
205
position did not change with a change in pH. The peak currents versus scan rate for
this set of experiments are tabulated in Table 7.3. At lower scan rates it can be seen
that the rate the current drop is not as pronounced in the reverse scan at higher voltage
scanning rates. This may suggest that at low scan rates the reaction is autocatalytic,
but this effect may be due to the oxidation of cyanate produced at the electrode
surface in the forward scan and not from species present in the bulk solution.
Theory predicts direct proportionality between the maximum current and the square
root of the voltage scanning rate for reversible and relatively simple irreversible
processes (Delahay, 1953), meaning that the reaction occurring at the surface of the
electrode is limited to the diffusion of the reactant to the surface of the electrode. In
the other case were the maximum current is not directly proportional to the square
root of the voltage scanning rate, the reaction rate at the electrode surface is not
limited by diffusion. Figure 7.9 shows a plot of maximum current versus the square
root of the voltage scanning rate for the first peak in the cyclic voltammogram shown
in figures 7.7 and 7.8. From the linear relationships seen in Figure 7.9 the oxidation
process at either pH is diffusion controlled, we can see that the diffusion rate constant
is higher at lower pH because the gradient of the scanning rate versus maximum
current is greater at pH 2 then when the pH was increased to 12. A simular plot was
generated for the second peak seen in Figure 7.7, shown by Figure 7.10, it shows that
the oxidation process is diffusion controlled and the diffusion rate constant is same
when the experiment is carried out at either pH 2 or 12.
206
1400
Peak 1 Peak 2
1200
D
C
1000
B
800
i (μ A)
600
A
400
Forward scan
200 Reverse
scan
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
E (V) vs Ag-AgCl
Figure 7.7: Cyclic voltammogram of a glassy carbon in a solution of 0.1M Na2SO4+ 0.01M
NaSCN, rest potential=0V (vs. Ag-AgCl electrode), pH 2, temperature 25oC. The scan rate was
varied from 10 to 40 mV/s. (A) 10 mV/s, (B) 20 mV/s, (C) 30 mV/s, (D) 40mV/s.
Table 7.2: Peak Currents for different scan rates for figure 7.7.
Scan rate (mV/s) Peak 1 Current (μA) Peak 2 Current (μA)
10 349 378
20 749 965
30 732 1165
40 965 1224
207
1600
1400 Peak 1 Peak 2
1200
D
C
1000 B
i (μ A)
800 A
600
400
Forward scan
200
Reverse scan
0
0 0.5 1 1.5 2
E (V) vs. Ag-AgCl
Figure 7.8: Stationary cyclic voltammogram of a glassy carbon in a solution of 0.1M Na2SO4,
0.01M NaSCN, rest potential=0V (vs. Ag-AgCl electrode), pH 12, temperature 25oC. The scan
rate was varied from 10 to 40 mV/s. (A) 10 mV/s, (B) 20 mV/s, (C) 30 mV/s, (D) 40mV/s.
Table 7.3: Peak Currents for different scan rates for figure 7.8.
Scan rate (mV/s) Peak 1 Current (μA) Peak 2 Current (μA)
10 - 667
20 936 880
30 1174 1000
40 1324 1267
208
1600
1400 pH 2
pH12
1200
Peak current (μ A)
1000
800
600
400
200
0
0 1 2 3 4 5 6 7
0.5 0.5
Square root of scan rate ((mV /s )
Figure 7.9: Peak currents versus square root of scan rate for the first peak in the
voltammograms shown in Figure 7.7 (pH 2) and Figure 7.8 (pH 12).
1400
pH 2
1200
pH 12
1000
Peak current (μ A)
800
600
400
200
0
0 1 2 3 4 5 6 7
0.5 0.5
Square root of scan rate ((mV /s )
Figure 7.10: Peak currents versus square root of scan rate for the second peak in the
voltammograms shown in Figure 7.7 (pH 2) and Figure 7.8 (pH 12).
209
The rotating disc electrode was used to determine the oxidation kinetics of
thiocyanate over the surface of the working electrode according to the Levich
equation. For a given set of mass transfer conditions in each experiment, such as
rotation speed of the disc electrode and solution variables (i.e. temperature,
concentration of interested species and viscosity of solution) the rate reaction of
thiocyanate is limited by how fast the thiocyanate ion can be bought to the electrode
surface. Therefore the current flowing through the circuit becomes limited. Figures
7.11 and 7.12 shows the rotating disc voltammograms of a glassy carbon working
electrode which was rotated in a solution of 0.1M Na2SO4 + 0.01M NaSCN with a
solution pH of 12 or 2, respectively. The rotation speed of the working electrode was
varied from 50 rpm to 500 rpm.
From Figure 7.12 it can be seen that by operating in different pH levels, that is, pH 12
and pH 2 that the mechanism of oxidation of thiocyanate changes with a change in
pH, the wave formation changes when the chemical potential reaches 1.1V (versus
Ag-AgCl standard electrode). This is in agreement that was proposed by Wilson et al.
(1960) that the mechanism of oxidation changes with the pH of the system. Therefore
when scanning at low pH < 2 will have a different wave formation when comparing it
to scans at high pH > 4. When looking at the overall reaction scheme, thiocyanate
will oxidise through intermediates HOSCN and HOOSCN (Wilson et al., 1960) to
form either cyanide or cyanate. Also the formation of cyanide will oxidise to produce
cyanate, therefore the oxidation process of thiocyanate will form intermediate species
such as HOSCN, HOOSCN, CN- which then will oxidise form CNO-. In both low
and high pH scans the limiting current occurred when the chemical potential reached
1.5V (vs Ag-AgCl electrode) showing that the formation of cyanate is the final
oxidation product from thiocyanate.
From Figure 7.11 the limiting current was determined for each rotating speed for the
overall reaction of thiocyanate to cyanate, which is shown in Table 7.4. From theory
defined by the Levich equation, the limiting current (iL) is proportional to the square
root of the rotation frequency of the working electrode (ω). A plot of the limiting
current versus the square root of the electrode rotation frequency shown in Figure
210
7.13 exists a linear relationship. Therefore the Levich equation is obeyed for this
system. Using equation 7.7, the rate of reaction was calculated, shown in Table 7.4.
The rate ranged from k = 0.70 to 2.54 cm/s when the electrode rotation frequency was
increased from 50 to 500 rpm, respectively.
7000
D
6000
5000
C
4000
i (μ A)
3000 B
2000 A
1000
0
0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9
E (V) vs Ag-AgCl
Figure 7.11: Rotation disc voltammograms of the anodic half-cell study of thiocyanate. The
solution was made from 0.1M Na2SO4+0.01M NaSCN, pH 12, temperature 25oC and a rest
potential of 0.5V vs Ag-AgCl reference. The rotation frequency was varied from 50rpm to 500
rpm. (A) 50rpm, (B) 100rpm, (C) 200rpm and (D) 500rpm.
211
3500
pH 2 (B)
3000
pH 12 (B)
2500
pH 2 (A)
Current (μ A)
2000
pH 12 (A)
1500
1000
500
0
0 0.5 1 1.5 2 2.5
E (V) vs. Ag-AgCl

Figure 7. 12: Rotation disc voltammograms of the anodic half-cell study of thiocyanate. The
solution contained 0.1M Na2SO4+0.01M NaSCN, pH 2 and 12, temperature 25oC and a rest
potential of 0.5V vs Ag-AgCl reference. The rotation frequency was varied from 50rpm and 100
rpm at each pH. (A) 50rpm and (B) 100rpm.
7000
6000
limiting current (μ A)
5000
4000
3000
2000
1000
0
0 1 2 3 4 5 6 7 8
ω
0.5
(s-0.5)
Figure 7.13: A plot of limiting current versus the square root electrode rotation frequency for
experiments conducted in Figure 7.11.
212
When the solution of the RDE experiment was repeated at pH of 2 with a solution
temperature was 25oC, shown by Figure 7.12, it can be seen that by reducing the pH
of 12 to 2, the limiting current is slightly higher at the lower pH. At a pH of 2 the
limiting current was 1942.86 μA and 2828.57 μA with an electrode rotation speed of
50 and 100 rpm, respectively. This corresponds to a k of 0.87 and 1.27 cm/s.
Comparing the rate constant k to the experiments that were conducted at a pH of 12,
there was a 20% increase at a rotation speed of 50 rpm, and a 6% increase when the
rotation speed was 100 rpm.
Addition of copper to the stationary voltammogram of a glassy carbon electrode in a

base solution of 0.1M Na2SO4 and 0.01M NaSCN, pH 2, temperature 25oC and a
voltage scan rate of 40mV/s is shown in Figure 7.14. It can be seen that by the
addition of copper the reaction that occurred peak 1 (at E = 1.18 V vs. Ag-AgCl
electrode) is suppressed while the oxidation products produced at peak 1 appears in its
usual position. This may be due to copper stabilising thiocyanate within solution, as
discussed in Chapter 6, but the addition copper does not change the overall rate of
reaction of thiocyanate to cyanate because the peak current is unchanged with or
without the presence of copper.
Table 7.4: Rotating frequency of the working electrode and the related limiting currents for the
experiments shown in Figure 7.11.
Rotation speed ω Limiting current (iL) K
(rpm) (s-1) (μA) (cm/s)
50 5.24 1556 0.70
100 10.47 2667 1.20
200 20.94 3722 1.67
500 52.36 5667 2.54
213
1400
Peak 1 Peak 2
1200
1000
800
i (μ A)
600
400
200
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
E (V) vs. Ag-AgCl
Figure 7.14: A comparison of the stationary cyclic voltammogram of a glassy carbon in a

solution of 0.1M Na2SO4, 0.01M NaSCN with copper added to one experiment (concentration of
0.005M CuSO4), rest potential=0.5V (vs. Ag-AgCl electrode), pH 12, temperature 25oC and a
voltage scanning rate of 40mV/s.
Figure 7.15 shows a comparison of rotating disc voltammograms between systems

that contain with or without copper. As with the stationary cyclic voltammograms
(Figure 7.14) when copper was added to the system that the addition of copper to the
system reduces the oxidation of thiocyanate as there is a reduction in limiting currents
of the RDE experiment at both rotation speeds of 50 and 100rpm in solution with a
pH of 2. Therefore addition of copper (II) ions to the system stabilizes thiocyanate
ions by the formation of stable copper thiocyanate species as discussed in previous
chapters 4 and 6, as a result reducing overall oxidation of thiocyanate in the
experiments that contained copper.
214
3500
3000 No Copper B
2500
A
2000
i (μ A)
1500
Copper
1000
500
0
0 0.5 1 1.5 2 2.5
E (V) vs. Ag-AgCl electrode
Figure 7. 15: Rotation disc voltammograms of the anodic half-cell study of thiocyanate. The
solution contained 0.1M Na2SO4+0.01M NaSCN with one set of experiments containing 0.005M
CuSO4, pH 2, temperature 25oC and a rest potential of 0.5V vs Ag-AgCl reference. The rotation
frequency was varied from 50rpm to 100 rpm. (A) 50rpm, (B) 100rpm
215
7.5 Conclusions
The electrochemical studies of thiocyanate under various conditions showed its

electrochemical behaviour. Thiocyanate oxidation is not simple and the overall
reaction to convert thiocyanate to cyanide may occur over several steps, and if some
of the individual steps as slow, deviations from this stoichiometry can be easily
visualised.
From peak current and voltage scan rate relationship of the thiocyanate oxidation
process suggests that the reaction is diffusion controlled when the pH of the solution
was either 2 or 12. Under acidic conditions the oxidation of thiocyanate is not a
relatively simple irreversible process.
By rotating disk electrode studies, the rate of reaction at the surface of the working
electrode can be determined by applying the Levich equation. The Levich equation
relates the limiting current to the square root of the frequency of rotation of the
working electrode. For the different thiocyanate systems studied the Levich equation
was obeyed. The kinetic rate constants were determined for the overall oxidation of
thiocyanate to cyanate in the presence of 0.1M sodium sulphate at pH 12 ranged from
0.70 to 2.54 cm/s.
Addition of copper sulphate to the system did not effect the oxidation of thiocyanate
at E = 1.35V (vs. Ag-AgCl reference electrode). But it did suppress competing
reactions at a lower potential. Therefore copper(II) ions do not accelerate the
oxidation of thiocyanate. Within the thiocyanate oxidation experiments using
hydrogen peroxide, copper(II) ions can accelerate the decomposition of hydrogen
peroxide. As one of the decomposition intermediate steps copper(II) ions are reduced
to copper(I). Copper(I) ions readily complex with free thiocyanate ions which can
reduce the activation energy required for the oxidation experiment with hydrogen
peroxide. Since this step was missing in the RDE experiment, this phenomenon could
not be observed.
216
References
Bard, A. and Faulkner, L.R., “Electrochemical Methods fundamentals and

Applications.” John Wiley & Sons, New York. 1980
Delahay P., “New Instrumental Methods in Electrochemistry.” Interscience, New

York. 1954.
Kabesova M., Kohout J., Gazo J. “Effect of the bridging mode of the thiocyanate
group in compounds on infrared spectra.” Inorganica Chimica Acta. (1978) L435.
Kabesova M., Gazo J. “Structure and classification of thiocyanates and the mutual
influence of their ligands.” Chemicke Zvesti. (1980), Vol. 34, No. 6, pp 800-841.
Levich V.G., “Physicochemical Hydrodynamics.” Prentice Hall, Englewood Cliffd,

New Jersey. 1962.
Miller J.D., “An analysis of concentration and temperature effects in cementation

reactions.” Mineral Science Engineering, 1979, vol. 5, no. 3, pp 242-254.
Nicholson M.M., “Voltammetry of thiocyanate ion at the stationary platinum

electrode.” Analytical Chemistry, 1959, vol. 31, no. 1, pp 128-132.
Riddiford A.C., “The rotating disk system.” Advances in electrochemistry and

electrochemical engineering, 1966, vol. 4, pp 47-116.
Wilson I. and Harris G., “The oxidation of Thiocyanate Ion by Hydrogen Peroxide. I.
The pH-Independent Reaction.” Journal of the American Chemical Society, Vol. 82,
1960, pp 4515-4517.
217
Chapter 8
Conclusions and
Recommendations
8.1 Conclusions
The first seven chapters of this thesis deal with an analysis and discussion of the
results from experiments conducted on the stability of different thiocyanate-water and
copper-thiocyanate-water systems, binary ion-exchange equilibria between
thiocyanate and chloride using commercially available Purolite A500u/2788, recovery
of cyanide by air stripping from the oxidation of thiocyanate by hydrogen peroxide,
electrochemical oxidation half cell reaction of thiocyanate and a critical review and
comparisons of the related literature. A summary of the conclusions that may be
drawn from the present work is as follows:
8.1.1 Solution Equilibria for thiocyanate-water and copper-thiocyanate-water

systems
Pourbaix and distribution diagrams of thiocyanate-water and copper-thiocyanate-

water systems were constructed using STABCAL (version 32-STABCAL SN 8-19-
2001). From the Pourbaix diagrams developed for the thiocyanate-water system that
the predominant stable species formed in solution at equilibrium is cyanate or
hydrogen cyanate depending on the pH of the solution. Under extreme acidic
conditions thiocyanate is the predominant stable species over hydrogen cyanate at
neutral chemical potential or a slightly reducing environment. When cyanate and
hydrogen cyanate were removed as stable species from the simulation, the resulting
Pourbaix diagram showed that the predominant areas of cyanate and hydrogen
218
cyanate were replaced with cyanide and hydrogen cyanide depending on the pH of the
system. Therefore cyanide can be recovered from thiocyanate if the oxidation of
cyanide to cyanate can be stopped.
Addition of copper to the thiocyanate-water system makes the system more complex.
The predominant stable species in a copper-thiocyanate-water system is copper (I)
thiocyanate which is a solid therefore reducing the mobility of thiocyanate in the
environment. As the ratio of thiocyanate to copper was increased the soluble copper
thiocyanate complexes which contained a higher ratio of thiocyanate became
predominant species at low pH as either CuSCN+, Cu(SCN)2 and Cu(SCN)43-.
The copper-thiocyanate-water distribution diagrams showed that the concentration of

the different copper thiocyanate species is dependent on the concentration of
thiocyanate and copper, as well as pH and Eh of the solution. The majority of the
copper and thiocyanate existed as copper(I) thiocyanate which is a solid. As the
concentration of thiocyanate increased compared to copper the concentration of
copper thiocyanate complexes that had a higher ratio of thiocyanate to copper
increased, i.e. Cu(SCN)2 and Cu(SCN)43-. When more copper was present in the
system by the addition of copper (II) ions, the concentration of free thiocyanate and
hydrogen thiocyanate decreased.
8.1.2 Ion-exchange equilibria between thiocyanate and chloride
Using ion exchange resins can be an effective way to concentrate thiocyanate from
tailing solutions or slurries. The effective capacity of thiocyanate on the ion-
exchange resin Purolite A500u/2788 is 1.19 mmol NaSCN/ml resin at 303 K. Four
different models were used to describe the equilibria between solution concentration
and resin loading of thiocyanate, which were the Langmuir isotherm, the Freundlich
isotherm, the Dubnin-Radushkevich isotherm and the Mass-action Law model. The
first three models showed that the equilibria between solution concentration and resin
loading are solution concentration dependent. Under the Mass-action law model the
ion-exchange equilibria are represented as equivalent ionic fraction of ions in solution
and on the ion exchanger. By normalising the ion-exchange equilibria it was found
219
that the fraction of ions in solution and on the ion exchanger becomes independent of
ionic strength (i.e. solution concentration) within the range of concentration
considered. An advantage of this is that only one unique equilibrium constant to
describe the ion-exchange process is used while other isotherms the relationships
show dependence on the concentration of the solution.

hydrogen peroxide
The oxidation of thiocyanate by hydrogen peroxide to recover cyanide is an effective

way of converting waste thiocyanate to free cyanide which can be recycled in a gold
operation. This can be an important consideration for mine rehabilitation as stricter
environmental regulations are imposed to limit the discharge of thiocyanate to tailing
dams. This could be used as a cost effective way to minimise and recycle cyanide in a
mining operation. The pH of the solution considerably affected the rate of oxidation
of thiocyanate, showing faster kinetics at lower pH’s levels. This confirmed
observations of earlier studies. It is also evident that the pH also affects the rate at
which hydrogen cyanide can be removed from the bubble column, taking over 24
hours to remove the hydrogen cyanide. With prolonged time taken to recover cyanide
from the bubble column continued oxidation of cyanide to cyanate is very slow
resulting in high recoveries in many experiments of over 80% in many cases.
The overall rate of reaction of thiocyanate with respect to the concentration of

thiocyanate and hydrogen peroxide is an overall third order reaction. The derived
third order rate expression is first order with respect to the concentration of
thiocyanate and second order with respect to the concentration of hydrogen peroxide,
shown below:
d[ H 2 O 2 ]
− = k[H 2 O 2 ] 2 [SCN − ] [8.12]
dt
where t is time, [SCN-] is the thiocyanate concentration and [H2O2] is the hydrogen
peroxide concentration.
220
Compared to previous studies it was found that the production of cyanide inhibits the
reaction between thiocyanate and hydrogen peroxide, which was taken into account
when defining the rate expression. Since cyanide was removed from the reaction by
air stripping, this study did not show the same effect that cyanide had in the previous
study.
It was proposed initially that addition of copper (II) ions would accelerate the
oxidation of thiocyanate. Previous studies found that copper(I) thiocyanate
complexes weaken the sulphur-carbon bond and strengthen the triple bond between
the carbon-nitrogen bond making oxidation easier. This was not the case as the
addition of copper(II) ions did not dramatically increase the rate of oxidation of
thiocyanate. However the residual thiocyanate concentration after a 24 hour period
was lower than experiments that were conducted without copper.
6.1.4 Electrochemical studies of thiocyanate oxidation
The anodic voltammetry of thiocyanate ion in aqueous solutions at varying pH has

been studied at the stationary and rotating glassy-carbon electrode with linear
variation of the applied potential. The oxidation of thiocyanate is not simple and the
overall reaction to convert thiocyanate to cyanide may occur over several steps
resulting in a voltammogram being a result of all of the various reactions occurring.
The reaction at the electrode surface was found to be an irreversible one. From peak
current and voltage scan rate relationship of the thiocyanate oxidation process suggest
that the reaction is diffusion controlled when the pH was 12. As the pH was reduced
to 2, the thiocyanate current deviates from this relationship, showing that under acidic
conditions the oxidation of thiocyanate is not a relatively simple irreversible process.
With the addition of copper(II) ions as copper sulphate it was found that copper (II)
ions suppress competing reactions that occurred at a lower potential without effecting
the primary oxidation of thiocyanate to cyanide. It was theorised that the formation of
by-products other than cyanide was caused by oxidation of these competing reactions.
If copper can suppress these reactions occurring without reducing the rate of reaction
higher rates of cyanide recovery can be found. It was found that the Levich equation
was obeyed for the rotating disc electrode experiments conducted. The kinetic rate
221
constants were determined for the oxidation of thiocyanate in the presence of 0.1M
sodium sulphate at pH 12 and 2 ranged from 0.70 to 2.54 cm/s, respectively.
8.2 Recommendations for further work
Due to the limited scope of this project only the overall reaction rate between
thiocyanate and hydrogen peroxide has been studied. The formation of intermediate
products formed during the reaction between thiocyanate and hydrogen peroxide and
how these products relate to the overall reaction have not been covered and studied.
Therefore, the following problems could be the objectives for further study and
clarification:
1. It has been theorised that the overall oxidation of thiocyanate to cyanide

occurs through the formation of various intermediate products. However,
detailed studies on this particular problem have not been established.
2. The effect of various additives such as iron and including copper on the rate
and extent of thiocyanate oxidation. These additives may suppress the
competing reactions that lead to products other than cyanide and the
mechanism on how these additives effect the overall reaction between
thiocyanate and hydrogen peroxide can be studied.
3. Using more effective methods to strip cyanide from solution by using AVR
stripping towers that are used commercially to remove cyanide from acidic
solutions rather than a bubble column used in this study.
4. By examining different binary ion-exchange systems with other species such

as base and precious metal cyanides using the Mass-Action Law, a comparison
of the relative affinity of different counter ions can be determined by using the
cross product rule. This can be valued in the prediction of the loading
characteristics of more complex systems found in the mining industry.
222
5. Elution studies for the elution of thiocyanate that has been adsorbed onto
anion exchange resins. Direct oxidation on ion exchange resins can affect the
ion exchange structure making the resin brittle, that is reduce the effective
lifespan of the resin. More benign elution process would overcome this
problem. Elution techniques in conjunction with the mass action model would
complete the recovery of cyanide from thiocyanate circuit within a gold
operation.
223
Appendix A: Fortran Code for Marquardt algorithm applied to
the Mass-action Law
PROGRAM IEX
IMPLICIT DOUBLE PRECISION (A-H,O-Z)
EXTERNAL RESID
DIMENSION PARM(4),X(3),F(51),XJAC(51,3),XJTJ(6),WORK(123)
DIMENSION XB(51),YB(51),SI(51),YBCALC(51)
! Program for fitting KAB and Wilson coefficients from ion exchange
! equilibrium data. Ion 'A' is initially loaded on the resin
! while ion 'B' is the counter ion.
! The program reads the experimental values of XB(I), YB(I) and SI(I)
! from the file specified in the OPEN statement (unit=2).
! The fitted values of KAB and the Wilson coefficients are obtained
! by minimising the SSRD with respect to YB(I).
! The predicted values of the loading of ion B (YBCALC(I))

! are sent to the file specified in the OPEN statement (unit=3).
! XB refers to the ionic fraction of ion B in the solution.

! YB refers to the ionic fraction of ion B on the resin.
! SI refers to the total ionic strength of the solution (cations +
anions)
OPEN(2,FILE='ascn1.dat',FORM='FORMATTED',STATUS='OLD')
OPEN(3,FILE='resultk.dat',FORM='FORMATTED',STATUS='NEW')
! Enter the number of data points (NDP) for each variable.

NDP = 51
ANDP = NDP
! Read experimental data from .dat file.

DO 5 I=1,NDP
READ(2,*) XB(I)
5 CONTINUE
DO 10 I=1,NDP
READ(2,*) YB(I)
10 CONTINUE
DO 12 I=1,NDP
READ(2,*) SI(I)
12 CONTINUE
! Initialise parameters for ZXSSQ

! Adjustable parameters: X(1)=WCAB, X(2)=WCBA, X(3)=KAB
M = NDP
N = 3
NSIG = 5
EPS = 0.0
DELTA = 0.0
MAXFN = 500
IOPT = 1
IXJAC = NDP
X(1) = 1.0D0
224
X(2) = 1.0D0
X(3) = 1.0D0
CALL ZXSSQ (RESID,M,N,NSIG,EPS,DELTA,MAXFN,IOPT,PARM,

&
X,SSQ,F,XJAC,IXJAC,XJTJ,WORK,INFER,IER)
! If ZXSSQ converges print YBCALC(I) values to .dat file

IF (INFER.GT.0) THEN
PRINT*, "Parameters regressed successfully"
PRINT*, "WCAB= ",X(1)," WCBA= ",X(2)," KAB= ",X(3)
CALL RESID (X,M,N,F)
DO 15 I=1,M
YBCALC(I) = YB(I)*(F(I) + 1.0D0)
WRITE (3,50) "YBCALC(",I,") , ",YBCALC(I)
15 CONTINUE
SUMARD = 0.0D0
DO 20 I=1,M
SUMARD = SUMARD + ABS(F(I))
20 CONTINUE
AARD = 100.0D0*SUMARD/ANDP
WRITE (3,100) "WCAB , ",X(1)

WRITE (3,100) "WCBA , ",X(2)
WRITE (3,100) "KAB , ",X(3)
WRITE (3,100) "AARD(%) , ",AARD
ELSE
PRINT *, '--------------------------------------------------
--'
PRINT *, 'INFER = 0, IER= ',IER
PRINT *, 'Convergence failed, reduce NSIG'
END IF
END FILE (UNIT=2)

END FILE (UNIT=3)
CLOSE (UNIT=2)
CLOSE (UNIT=3)
50 FORMAT (1X, A, I2, A, E12.5)

100 FORMAT (1X, A, E12.5)
STOP
END
! -------------------------------------------------------------------
---
SUBROUTINE RESID (X,M,N,F)
DIMENSION X(N),F(M)
DIMENSION XB(M),YB(M),SI(M),PHI(M),YBCALC(M), &
GAMAL(M),GAMBL(M),GAMAR(M),GAMBR(M),DENOM(M)
! A,B = debye-huckel parameters for solvent

! DA = average ionic diameter for ion A
! DB = average ionic diameter for ion B
A = 0.5161D0
B = 3.3D7
DA = 3.0D-8
DB = 3.5D-8
225
! Open file containing experimental data
OPEN(4,FILE='ascn1.dat',FORM='FORMATTED',STATUS='OLD')
DO 5 I=1,M
READ(4,*) XB(I)
5 CONTINUE
DO 10 I=1,M
READ(4,*) YB(I)
10 CONTINUE
DO 15 I=1,M
READ(4,*) SI(I)
15 CONTINUE
CLOSE (UNIT=4)
! Calculate activity coefficients for the liquid phase

! and resin phase
DO 20 I=1,M
GAMAL(I) = GAML(A,B,DA,SI(I))
GAMBL(I) = GAML(A,B,DB,SI(I))
GAMAR(I) = GAMR(1,YB(I),X(1),X(2))
GAMBR(I) = GAMR(2,YB(I),X(1),X(2))
20 CONTINUE
! Calculate values of YBCALC(I)

DO 25 I=1,M
DENOM(I) = GAMAL(I)*GAMBR(I)*(1.0D0-XB(I)) +
&
X(3)*GAMAR(I)*GAMBL(I)*XB(I)
YBCALC(I) = X(3)*GAMAR(I)*GAMBL(I)*XB(I)/DENOM(I)
F(I) = (YBCALC(I) - YB(I))/YB(I)
25 CONTINUE
RETURN
END
! -------------------------------------------------------------------
---
DOUBLE PRECISION FUNCTION GAML (A,B,D,S)
! User defined function for calculating the activity coefficient of a

! component in the liquid phase.
GAML = 10**(-1.0*A*SQRT(S)/(1.0+B*D*SQRT(S)))
RETURN
END
! -------------------------------------------------------------------
---
DOUBLE PRECISION FUNCTION GAMR (N,Y,PAB,PBA)
! User defined function for calculating the activity coefficient of a

! component in the resin phase.
! For N=1, calculate GAMR for component A.
IF (N.EQ.1) THEN
A = 1.0 - LOG((1.0 - Y) + Y * PAB)
226
B = (1.0 – Y)/((1.0 – Y) + Y * PAB)
C = Y * PBA/(Y +(1.0 – Y)*PBA)
GAMR = EXP(A – B - C)
ELSE
A = 1.0 - LOG(Y + (1.0 - Y) * PBA)
B = Y/(Y + (1.0 - Y) * PBA)
C = (1.0 - Y)*PAB/((1.0 - Y)+ Y * PAB)
GAMR = EXP(A – B - C)
END IF
RETURN
END
! -------------------------------------------------------------------
---
SUBROUTINE ZXSSQ (FUNC,M,N,NSIG,EPS,DELTA,MAXFN,IOPT,
&
PARM,X,SSQ,F,XJAC,IXJAC,XJTJ,WORK,INFER,IER)
DIMENSION X(45),F(51),PARM(4),XJAC(51),XJTJ(6),WORK(123)
INTEGER U1,U5,U4
COMMON/UNITA/U1,U5,U4
DATA SIG/9.3D0/
DATA AX/0.1D0/
DATA I0,I1,I2,I3,I4,I5/0,1,2,3,4,5/
DATA P01,TENTH,HALF,ZERO,ONE,ONEP5,TWO,
&
TEN,HUNTW,ONEP10/0.01D0,0.1D0,0.5D0,0.0D0,
&
1.D0,1.5D0,2.D0,10.0D0,1.2D2,1.D10/
! ERROR CHECKS
IER = I0
IF (M.LE.0.OR.M.GT.IXJAC.OR.N.LE.0.OR.IOPT.LT.0.OR.IOPT.GT.2)
&
GOTO 305
IMJC=IXJAC-M
IF (IOPT.NE.2) GOTO 5
IF (PARM(I2).LE.ONE.OR.PARM(I1).LE.ZERO) GOTO 305
! MACHINE DEPENDENT CONSTANTS
5 PREC = TEN**(-SIG-ONE)
REL = TEN**(-SIG*HALF)
RELCON = TEN**(-NSIG)
! WORK VECTOR IS ONCATENATION OF
! SCALED HESSIAN,GRADIENT,DELX,SCALE,
! XNEW,XBAD,F(X+DEL),F(X-DEL)
IGRAD1 = ((N+1)*N)/2
IGRADL = IGRAD1+1
IGRADU = IGRAD1+N
IDELX1 = IGRADU
IDELXL = IDELX1+1
IDELXU = IDELX1+N
ISCAL1 = IDELXU
ISCALL = ISCAL1+1
ISCALU = ISCAL1+N
IXNEW1 = ISCALU
IXNEWL = IXNEW1+1
IXBAD1 = IXNEW1+N
IFPL1 = IXBAD1+N
IFPL = IFPL1+1
IFPU = IFPL1+M
IFML1 = IFPU
227
IFML = IFML1+1
IMJC = IXJAC - M
! INITIALIZE VARIABLES
AL = ONE
CONS2 = TENTH
IF (IOPT.EQ.0) GOTO 20
AL = PARM(I1)
F0 = PARM(I2)
UP = PARM(I3)
CONS2 = PARM(I4)*HALF
GOTO 15
10 AL = P01
F0 = TWO
UP = HUNTW
15 ONESF0 = ONE/F0
F0SQ = F0*F0
F0SQS4 = F0SQ**4
20 IEVAL = 0
DELTA2 = DELTA*HALF
ERL2 = ONEP10
IBAD = -99
ISW = 1
ITER = -1
INFER = 0
IER = 0
DO 25 J=IDELXL,IDELXU
WORK(J) = ZERO
25 CONTINUE
GOTO 165
! MAIN LOOP
30 SSQOLD = SSQ
! CALCULATE JACOBIAN
IF (INFER.GT.0.OR.IJAC.GE.N.OR.IOPT.EQ.0.OR.ICOUNT.GT.0) GOTO
55
! RANK ONE UPDATE TO JACOBIAN
IJAC = IJAC+1
DSQ = ZERO
DSQ = DSQ+WORK(J)*WORK(J)
35 CONTINUE
IF (DSQ.LE.ZERO) GOTO 55
DO 50 I=1,M
II=IFML1+I
G = F(I)-WORK(II)
K = I
G = G+XJAC(K)*WORK(J)
K = K+IXJAC
40 CONTINUE
G = G/DSQ
K = I
XJAC(K) = XJAC(K)-G*WORK(J)
K = K+IXJAC
45 CONTINUE
50 CONTINUE
GOTO 80
! JACOBIAN BY INCREMENTING X
55 IJAC = 0
K = -IMJC
228
DO 75 J=1,N
K = K+IMJC
XDABS =DABS(X(J))
HH =REL*(DMAX1(XDABS,AX))
XHOLD = X(J)
X(J) = X(J)+HH
! print*, "about to call func - 1", ",",n
CALL FUNC (X,M,N,WORK(IFPL))
! print*, "call to func - 1 completed", ",",n
IEVAL = IEVAL+1
X(J) = XHOLD
! print*, "isw=",isw
IF (ISW.EQ.1) GOTO 65
! CENTRAL DIFFERENCES
X(J) = XHOLD-HH
! print*, "about to call func - 2", n
CALL FUNC (X,M,N,WORK(IFML))
IEVAL = IEVAL+1
X(J) = XHOLD
RHH = HALF/HH
DO 60 I=IFPL,IFPU
II=I+M
K = K+1
XJAC(K) = (WORK(I)-WORK(II))*RHH
60 CONTINUE
GOTO 75
! FORWARD DIFFERENCES
65 RHH = ONE/HH
DO 70 I=1,M
K = K+1
II=IFPL1+I
XJAC(K) = (WORK(II)-F(I))*RHH
! print*, "xjac(",k,")=", xjac(k)
70 CONTINUE
75 CONTINUE
! CALCULATE GRADIENT
80 ERL2X = ERL2
ERL2 = ZERO
K = -IMJC
DO 90 J=IGRADL,IGRADU
K = K+IMJC
SUM = ZERO
DO 85 I=1,M
K = K+1
SUM = SUM+XJAC(K)*F(I)
85 CONTINUE
! print*, "loop 85 completed"
WORK(J) = SUM
ERL2 = ERL2+SUM*SUM
90 CONTINUE
ERL2 = SQRT(ERL2)
! CONVERGENCE TEST FOR NORM OF
GRADIENT
! print*, "ijac=",ijac
IF(IJAC.GT.0) GOTO 95
IF (ERL2.LE.DELTA2) INFER = INFER+4
IF (ERL2.LE.CONS2) ISW = 2
! CALCULATE THE LOWER SUPER TRIANGE
OF
229
! JACOBIAN (TRANSPOSED) * JACOBIAN
95 L = 0
IS = -IXJAC
DO 110 I=1,N
IS = IS+IXJAC
JS = -IXJAC
DO 105 J=1,I
JS = JS+IXJAC
L = L+1
SUM = ZERO
DO 100 K=1,M
LI = IS+K
LJ = JS+K
SUM = SUM+XJAC(LI)*XJAC(LJ)
100 CONTINUE
XJTJ(L) = SUM
105 CONTINUE
110 CONTINUE
! ONVERGENCE CHECKs
! print*, "infer=", infer
IF (INFER.GT.0) GOTO 315
! print*, "ieval=", ieval
IF (IEVAL.GE.MAXFN) GOTO 290
! COMPUTE SCALING VECTOR
! print*, "iopt=",iopt
K = 0
DO 115 J=1,N
K = K+J
II=ISCAL1+J
WORK(II) = XJTJ(K)
115 CONTINUE
GOTO 135
! COMPUTE SCALING VECTOR AND NORM
120 DNORM = ZERO
K = 0
DO 125 J=1,N
K = K+J
II=ISCAL1+J
WORK(II) = SQRT(XJTJ(K))
DNORM = DNORM+XJTJ(K)*XJTJ(K)
125 CONTINUE
DNORM = ONE/SQRT(DNORM)
! NORMALIZE SCALING VECTOR
DO 130 J=ISCALL,ISCALU
WORK(J) = WORK(J)*DNORM*ERL2
130 CONTINUE
! ADD L-M FACTOR TO DIAGONAL
135 ICOUNT = 0
140 K = 0
DO 150 I=1,N
DO 145 J=1,I
K = K+1
WORK(K) = XJTJ(K)
145 CONTINUE
II=ISCAL1+I
IJ=IGRAD1+I
WORK(K) = WORK(K)+WORK(II)*AL
II=IDELX1+I
230
WORK(II) = WORK(IJ)
150 CONTINUE
! CHOLESKY DECOMPOSITION
! print*, "about to call leq in subr zxssq"
155 CALL LEQ (WORK,1,N,WORK(IDELXL),N,0,G,XHOLD,IER)
! print*, "call to leq done"
IF (IER.EQ.0) GOTO 160
IER = 0
IF (IJAC.GT.0) GOTO 55
IF (IBAD.LE.0) GOTO 240
IF (IBAD.GE.2) GOTO 310
GOTO 190
160 IF (IBAD.NE.-99) IBAD = 0
! CALCULATE SUM OF SQUARES
165 DO 170 J=1,N
II=IXNEW1+J
IJ=IDELX1+J
WORK(II) = X(J)-WORK(IJ)
170 CONTINUE
! print*, "about to call func - 3"
CALL FUNC (WORK(IXNEWL),M,N,WORK(IFPL))
IEVAL = IEVAL+1
SSQ = ZERO
DO 175 I=IFPL,IFPU
SSQ = SSQ+WORK(I)*WORK(I)
175 CONTINUE
IF (ITER.GE.0) GOTO 185
! SSQ FOR INITIAL ESTIMATES OF X
ITER = 0
SSQOLD = SSQ
DO 180 I=1,M
II=IFPL1+I
F(I) = WORK(II)
180 CONTINUE
GOTO 55
185 IF (IOPT.EQ.0) GOTO 215
! CHECK DESCENT PROPERTY
IF (SSQ.LE.SSQOLD) GOTO 205
! INREASE PAAMETER AND TRY AGAIN
190 ICOUNT = ICOUNT+1
AL = AL*F0SQ
IF (IJAC.EQ.0) GOTO 195
IF (ICOUNT.GE.4.OR.AL.GT.UP) GOTO 200
195 IF (AL.LE.UP) GOTO 140
IF (IBAD.EQ.1) GOTO 310
GOTO 300
200 AL = AL/F0SQS4
GOTO 55
! ADJUST MARQUARDT PARAMETER
205 IF (ICOUNT.EQ.0) AL = AL/F0
IF (ERL2X.LE.ZERO) GOTO 210
G = ERL2/ERL2X
IF (ERL2.LT.ERL2X) AL = AL*DMAX1(ONESF0,G)
IF (ERL2.GT.ERL2X) AL = AL*DMIN1(F0,G)
210 AL = DMAX1(AL,PREC)
! ONE ITERATION CYCLE COMPLETED
215 ITER = ITER+1
DO 220 J=1,N
IJ=IXNEW1+J
X(J) = WORK(IJ)
231
220 CONTINUE
DO 225 I=1,M
II=IFML1+I
WORK(II) = F(I)
II =IFPL1+I
F(I) = WORK(II)
225 CONTINUE
! RELATIVE CONVERGENCE TEST FOR X
IF (AL .GT. 5.0D0) GOTO 30
DO 230 J=1,N
IJ=IDELX1+J
XDIF =DABS(WORK(IJ))/DMAX1(DABS(X(J)),AX)
IF (XDIF.GT.RELCON) GOTO 235
230 CONTINUE
INFER = 1
! RELATIVE CONVERGENCE TEST FOR SSQ
235 SQDIF = DABS(SSQ-SSQOLD)/DMAX1(SSQOLD,AX)
IF (SQDIF.LE.EPS) INFER = INFER+2
GOTO 30
! SINGULAR DECOMPOSITION
240 IF (IBAD) 255,245,265
! CHECK TO SEE IF CURRENT
! ITERATE HAS CYCLED BACK TO
! THE LAST SINGULAR POINT
245 DO 250 J=1,N
IJ=IXBAD1+J
XHOLD = WORK(IJ)
IF (DABS(X(J)-XHOLD).GT.RELCON*DMAX1(AX,DABS(XHOLD))) GOTO
255
250 CONTINUE
GOTO 295
! UPDATE THE BAD X VALUES
255 DO 260 J=1,N
IJ=IXBAD1+J
WORK(IJ) = X(J)
260 CONTINUE
IBAD = 1
! INCREASE DIAGONAL OF HESSIAN
265 IF (IOPT.NE.0) GOTO 280
K = 0
DO 275 I=1,N
DO 270 J=1,I
K = K+1
WORK(K) = XJTJ(K)
270 CONTINUE
II=ISCAL1+I
WORK(K) = ONEP5*(XJTJ(K)+AL*ERL2*WORK(II))+REL
275 CONTINUE
IBAD = 2
GOTO 155
! REPLACE ZEROES ON HESSIAN DIAGONAL
280 IZERO = 0
DO 285 J=ISCALL,ISCALU
IF (WORK(J).GT.ZERO) GOTO 285
IZERO = IZERO+1
WORK(J) = ONE
285 CONTINUE
IF (IZERO.LT.N) GOTO 140
IER = 38
GOTO 315
! TEMINAL ERROR
232
290 IER = IER+1
295 IER = IER+1
300 IER = IER+1
305 IER = IER+1
310 IER = IER+129
! OUTPUT ERL2,IEVAL,NSIG,AL, AND ITER
315 G = SIG
DO 320 J=1,N
IJ=IDELX1+J
XHOLD = DABS(WORK(IJ))
IF (XHOLD.LE.ZERO) GOTO 320
G = DMIN1(G,-DLOG10(XHOLD/DMAX1(AX,DABS(X(J)))))
320 CONTINUE
IF(N.GT.2) GOTO 330
DO 325 J = 1,N
II=IGRAD1+J
325 WORK(J+5) = WORK(II)
330 WORK(I1) = ERL2+ERL2
WORK(I2) = IEVAL
SSQ = SSQOLD
WORK(I3) = G
WORK(I4) = AL
WORK(I5) = ITER
IS = G
IF(IS .GE. NSIG) IER=0
9000 CONTINUE
WRITE(U1,9001) IER
IF(IER.EQ.129.OR.IER.EQ.132) WRITE(U1,9129)
IF(IER.EQ.130) WRITE(U1,9130) M,N,IOPT,(PARM(I),I=1,2)
IF(IER.EQ.131) WRITE(U1,9131) WORK(I4),PARM(I3)
IF(IER.EQ.133) WRITE(U1,9133) MAXFN
IF(IER.EQ.38) WRITE(U1,9038)
WRITE(U1,9050) WORK(I1),IS,WORK(I4),ITER,IEVAL
9005 CONTINUE
!
! FORMAT STATEMENTS
!
9001 FORMAT(1H ,' ZXSSQ ERROR NO:',I3)
9038 FORMAT(1H ,'TRIVIAL SOLUTION')
9050 FORMAT(2X,'NORM.GRAD=',E10.4,2X,'NO.OF SIGNIFICANT DIGITS:',
&
I5,/,3X,'MARQUARDT PARAMETER:',E10.4,/
&
2X,I4,' ITERATIONS;',2X,I4,' FUNCTION EVALUATIONS.')
9129 FORMAT(1H ,'SINGULAR JACOBIAN')
9130 FORMAT(1H ,'INCORRECT: M=',I5,' N=',I5,' IOPT=',I5,
&
' PARM(1)=',E10.4,' PARM(2)=',E10.4)
9131 FORMAT(1H ,'MARQUARDT PARAMETER ',E10.4,
&
' EXCEED PARM(3)',E10.4)
9133 FORMAT(1H ,'FUNCTION EVALUATIONS EXCEED MAXFN',I5)
RETURN
END
SUBROUTINE LEQ (A,M,N,B,IB,IDGT,D1,D2,IER)

implicit double precision (a-h,o-z)
DIMENSION A(1),B(IB,1)
DOUBLE PRECISION A,D1,D2
233
! print*, "about to run first exec lines in leq"
! print*, "idgt=",idgt
! idgt=idgt
! print*, "past exec line 1"
! INITIALIZE IER
IER = 0
! DECOMPOSE A
! print*, "about to call dec in subr leq"
CALL DEC (A,A,N,D1,D2,IER)
IF (IER.NE.0) GOTO 9000
! PERFORM ELIMINATiON
DO 5 I = 1,M
CALL ELM (A,B(1,I),N,B(1,I))
5 CONTINUE
GOTO 9005
9000 CONTINUE
WRITE(0,9001)
9001 FORMAT(1H ,' DECOMPOSITION ERROR')
9005 RETURN
END
SUBROUTINE DEC(A,UL,N,D1,D2,IER)
DIMENSION A(1),UL(1)
DATA
ZERO,ONE,FOUR,SIXTN,SIXTH/0.0D0,1.D0,4.D0,16.D0,.0625D0/
D1=ONE
D2=ZERO
RN = ONE/(FLOAT(N)*SIXTN)
IP = 1
IER=0
DO 45 I = 1,N
IQ =IP
IR = 1
DO 40 J=1,I
X = A(IP)
IF (J .EQ. 1) GOTO 10
DO 5 K=IQ,IP1
X= X - UL(K) * UL(IR)
IR = IR+1
5 CONTINUE
10 IF (I.NE.J) GOTO 30
D1 = D1*X
IF (A(IP) + X*RN .LE. A(IP)) GOTO 50
15 IF (DABS(D1).LE.ONE) GOTO 20
D1 = D1 * SIXTH
D2 = D2 + FOUR
GOTO 15
20 IF (DABS(D1) .GE. SIXTH) GOTO 25
D1 = D1 * SIXTN
D2 = D2 - FOUR
GOTO 20
25 UL(IP) = ONE/DSQRT(X)
GOTO 35
30 UL(IP) = X * UL(IR)
35 IP1 = IP
IP = IP+1
IR = IR+1
40 CONTINUE
45 CONTINUE
GOTO 9005
50 IER = 129
234
9005 RETURN
END
SUBROUTINE ELM (A,B,N,X)
DIMENSION A(1),B(1),X(1)
DATA ZERO/0.0d0/
! SOLUTION OF LY = B
IP=1
IW = 0
DO 15 I=1,N
T=B(I)
IM1 = I-1
IF (IW .EQ. 0) GOTO 9
IP=IP+IW-1
DO 5 K=IW,IM1
T = T-A(IP)*X(K)
IP=IP+1
5 CONTINUE
GOTO 10
9 IF (T .NE. ZERO) IW = I
IP = IP+IM1
10 X(I)=T*A(IP)
IP=IP+1
15 CONTINUE
! SOLUTION OF UX = Y
N1 = N+1
DO 30 I = 1,N
II = N1-I
IP=IP-1
IS=IP
IQ=II+1
T=X(II)
IF (N.LT.IQ) GOTO 25
KK = N
DO 20 K=IQ,N
T = T - A(IS) * X(KK)
KK = KK-1
IS = IS-KK
20 CONTINUE
25 X(II)=T*A(IS)
30 CONTINUE
RETURN
END
235
Appendix B: Experimental data for ion-exchange equilibria
between thiocyanate and chloride
Appendix B reports the experimental results for ion-exchange equilibria between
thiocyanate and chloride shown in Chapter 5. All the experiments were repeated in
duplicate and the reported data is the average value between the two experiments.
Table B1: Concentration profile of thiocyanate adsorption using Purolite A500u/2778 ion-
exchange resin with an initial thiocyanate concentration of 1200ppm NaSCN. Temperature =
30oC, Pressure = 1atm. Ref: Figure 5.4. The amount of NaSCN in solution is reported in ppm
NaSCN.
Time (min) Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7 Run 8
0 1208.5 1200.2 1140.0 1158.5 1153.1 1178.3 1179.2 1151.5
5 686.2 542.7 628.8 848.7 1074.9 1157.6 1173.1 1151.5
10 432.2 286.7 421.9 760.7 1063.2 1152.2 1174.1 1155.6
15 279.4 142.2 318.5 731.1 1060.0 1155.4 1172.1 1156.6
30 64.1 89.9 243.4 709.6 1063.2 1156.5 1173.1 1153.5
60 21.1 70.8 240.4 706.5 1062.1 1153.3 1164.0 1150.4
120 18.0 70.9 242.4 709.6 1069.6 1159.8 1181.3 1158.7
240 17.9 71.1 235.3 708.6 1060.0 1153.3 1185.3 1158.7
360 17.5 71.1 239.4 707.6 1050.3 1148.9 1179.2 1148.3
480 17.5 71.6 241.4 708.6 1052.5 1135.9 1176.2 1154.6
Table B2: Equilibrium adsorption data for the adsorption of thiocyanate with an initial
thiocyanate concentration of 300ppm NaSCN (3.70 m.mol/l NaSCN) using Purolite A500u/2778
ion-exchange resin. Temperature = 30oC, Pressure = 1atm.
Solution Phase Resin Phase
Run [SCN] (m.mol/l) [Cl] (m.mol/l) Fraction [SCN] (m.mol/l) [Cl] (m.mol/l) Fraction
1 0.01 3.78 0.00 0.09 1.13 0.08
2 0.05 3.51 0.01 0.18 1.04 0.15
3 0.03 3.65 0.01 0.27 0.95 0.22
4 0.06 3.56 0.02 0.36 0.86 0.30
5 0.13 3.57 0.03 0.45 0.77 0.37
6 0.15 3.50 0.04 0.54 0.69 0.44
7 0.20 3.68 0.05 0.63 0.59 0.52
8 0.20 3.61 0.05 0.72 0.50 0.59
9 0.32 3.53 0.08 0.81 0.41 0.66
10 0.46 3.29 0.12 0.89 0.33 0.73
11 0.66 3.16 0.17 0.97 0.25 0.79
12 0.90 2.66 0.25 1.04 0.19 0.85
13 1.30 2.40 0.35 1.10 0.13 0.90
14 1.93 1.85 0.51 1.14 0.08 0.93
15 2.60 1.08 0.71 1.17 0.05 0.96
16 3.12 0.62 0.83 1.19 0.04 0.97
17 3.11 0.50 0.86 1.20 0.03 0.98
18 3.35 0.37 0.90 1.21 0.02 0.99
19 3.56 0.16 0.96 1.21 0.01 0.99
20 3.42 0.19 0.95 1.22 0.01 0.99
21 3.46 0.30 0.92 1.22 0.00 1.00
236

1 0.11 7.58 0.01 0.19 0.95 0.17
2 0.09 7.12 0.01 0.37 0.78 0.32
3 0.17 6.59 0.03 0.53 0.61 0.47
4 0.41 6.73 0.06 0.70 0.44 0.61
5 0.75 6.02 0.11 0.85 0.29 0.74
6 1.69 5.02 0.25 0.98 0.17 0.85
7 2.39 3.96 0.38 1.08 0.07 0.94
8 5.50 1.84 0.75 1.12 0.02 0.98
9 6.38 0.68 0.90 1.14 0.01 0.99
10 7.12 0.15 0.98 1.14 0.00 1.00
11 7.27 0.08 0.99 1.14 0.00 1.00
1 0.14 10.96 0.01 0.27 0.90 0.23
2 0.32 10.94 0.03 0.55 0.62 0.47
3 0.81 9.30 0.08 0.78 0.39 0.67
4 2.39 8.27 0.22 0.99 0.18 0.84
5 5.42 5.00 0.52 1.11 0.06 0.95
6 8.71 1.75 0.83 1.16 0.01 0.99
7 10.25 0.11 0.99 1.16 0.01 0.99
8 10.93 0.23 0.98 1.16 0.01 0.99
9 10.84 0.31 0.97 1.17 0.00 1.00
10 10.99 0.01 1.00 1.17 0.00 1.00
11 11.03 -0.08 1.01 1.17 0.00 1.00

1 0.22 14.69 0.01 0.37 0.81 0.31
2 0.88 13.92 0.06 0.72 0.46 0.61
3 2.98 11.08 0.21 0.99 0.18 0.84
4 8.74 5.55 0.61 1.13 0.04 0.96
5 12.98 1.24 0.91 1.16 0.01 0.99
6 14.01 0.52 0.96 1.18 0.00 1.00
7 14.51 0.04 1.00 1.18 0.00 1.00
8 14.24 -0.04 1.00 1.18 0.00 1.00
237
1 0.35 18.03 0.02 0.45 0.60 0.43
2 1.93 16.54 0.10 0.69 0.18 0.79
3 17.89 10.49 0.63 0.95 -0.08 1.09
4 13.67 3.56 0.79 1.04 -0.17 1.19
5 17.60 0.20 0.99 1.05 -0.17 1.20
6 18.29 0.07 1.00 1.05 -0.17 1.20
7 18.15 0.03 1.00 1.05 -0.17 1.20
238
Appendix C: Experimental for the recovery of cyanide from
thiocyanate using hydrogen peroxide
Appendix C reports the experimental results for the recovery of cyanide from
thiocyanate from thiocyanate using hydrogen peroxide shown in Chapter 6.
Table C1: Data for the oxidation of thiocyanate using hydrogen peroxide to recover cyanide.
Initial thiocyanate concentration 1000ppm, stoichiometric amount of hydrogen peroxide and
10g/l sulphuric acid at room temperature and pressure. Ref: Figure 6.5.
Time (min) [SCN-] (mM) [H2O2] (mM) [CN-] (mM)

0 17.21 79.46 0.00
20 12.56 67.69 0.48
40 9.39 61.80 1.22
60 7.49 55.92 2.31
120 5.22 38.26 5.81
240 3.44 26.49 10.73
360 2.19 20.60 13.44
480 1.45 17.66 14.94
1440 0.31 8.83 17.39
Table C2: Data for the comparison of thiocyanate concentration against time at different
solution pH. The initial concentration of thiocyanate is 100ppm (17.2mM), the amount of
thiocyanate present at room temperature and pressure. No copper was added to solution. Ref:
Figure 6.6.
Time 10 g/l pH 2 pH 7 pH 12
(min) [SCN-] (mM)
0 17.21 17.21 17.21 17.21
20 12.56 14.34 16.05 14.63
40 9.39 13.77 15.01 14.20
60 7.49 12.65 14.71 14.14
120 5.22 10.67 14.11 13.05
240 3.44 8.81 12.89 11.09
360 2.19 7.08 11.69 10.00
480 1.45 5.60 10.19 8.77
1440 0.31 1.40 4.70 3.77
239
Table C3: Data for the comparison of cyanide recovery against time at different solution pH.
The initial concentration of thiocyanate is 100ppm (17.2mM), the amount of hydrogen peroxide
added to the experiment is double the stoichiometry required to oxidise the thiocyanate present
at room temperature and pressure. No copper was added to solution. Ref: Figure 6.7.
Time 10 g/l pH 2 pH 7 pH 12
(min) [CN-] (mM)
0 0.00 0.00 0.00 0.00
20 0.48 0.29 0.23 0.16
40 1.22 0.70 0.36 0.16
60 2.31 0.80 0.54 0.17
120 5.81 1.28 0.79 0.29
240 10.73 3.19 1.06 0.50
360 13.44 5.02 1.74 0.55
480 14.94 6.57 2.80 0.61
1440 17.39 14.39 8.72 0.74
Table C4: Data for the pH profile of hydrogen peroxide oxidation of thiocyanate with different
initial starting pH. The initial concentration of thiocyanate is 1000ppm (17.2 mM), the amount of
thiocyanate present. No copper was added to solution. Ref: Figure 6.8.
Time PH
(min) 10 g/l 2 7 12
0 1.01 1.77 7.2 12.04
20 1.03 1.91 3.47 9.62
40 1.08 1.91 3.47 7.4
60 0.93 1.9 3.32 7.04
120 1.07 1.88 3.19 5.95
240 1.08 1.87 3.04 4.29
360 1.15 1.87 2.97 4.24
480 1.03 1.86 2.95 4.25
1440 1.02 2.47 2.63 3.98
Table C5: Data for the Eh profile of hydrogen peroxide oxidation of thiocyanate with different
initial starting pH. The initial concentration of thiocyanate is 1000ppm (17.2 mM), the amount of
thiocyanate present. No copper was added to solution. Ref: Figure 6.9.
Time Eh (V)
(min) 10 g/l 2 7 12
0 0.49 0.464 0.396 0.071
20 0.513 0.47 0.39 0.11
40 0.489 0.472 0.379 0.201
60 0.488 0.433 0.418 0.25
120 0.47 0.421 0.432 0.316
240 0.502 0.42 0.439 0.383
360 0.486 0.43 0.424 0.396
480 0.451 0.414 0.438 0.398
1440 0.464 0.509 0.472 0.386
240
Table C6: Data for the comparison of thiocyanate concentration against time at different experimental conditions outlined in table 6.2. Ref: Figure 6.10.
Time [SCN-] (mM)

(min) Experiment 1 Experiment 2 Experiment 3 Experiment 4 Experiment 5 Experiment 6 Experiment 7 Experiment 8
0 17.21 17.21 17.21 17.21 17.21 17.21 17.21 17.21
20 11.44 4.52 8.50 2.76 3.53 1.40 3.53 1.41
40 8.98 3.58 6.97 1.35 2.05 0.15 1.83 0.29
60 7.15 3.04 5.13 0.94 1.36 0.16 1.11 0.09
120 4.82 2.50 2.19 0.54 0.53 0.05 0.67 0.02
240 2.84 1.83 0.36 0.19 0.18 0.14 0.64 0.02
360 2.04 0.65 0.32 0.14 0.16 0.16 0.56 0.05
480 1.59 0.34 0.21 0.09 0.14 0.04 0.43 0.06
1440 0.50 0.21 0.02 0.07 0.01 0.01 0.21 0.01
Table C7: Data for the comparison of hydrogen peroxide concentration against time at different experimental conditions outlined in table 6.2. Ref: Figure 6.11.
Time [H2O2] (mM)

0 97.12 102.89 164.63 82.31 161.69 144.05 70.56 155.81
20 76.52 82.31 117.59 26.46 99.95 70.56 32.34 73.49
40 61.80 70.56 105.83 17.64 88.19 64.68 23.52 67.62
60 52.97 58.80 91.13 16.17 79.37 61.74 17.64 64.68
120 38.26 44.10 82.31 11.76 70.56 64.68 11.76 64.68
240 26.49 32.34 67.62 8.82 70.56 64.68 10.29 64.68
360 26.49 26.46 64.68 7.35 67.62 61.74 7.35 64.68
480 23.54 22.05 64.68 5.88 70.56 61.74 8.82 64.68
1440 11.77 11.76 55.86 2.94 61.74 55.86 7.06 61.74
241
Table C8: Data for the comparison of cyanide recovered against time at different experimental conditions outlined in table 6.2. Ref: Figure 6.12.
Time Cyanide Recovered (%)

0 2 2 2 2 2 2 2 2
20 7 6 8 12 10 16 13 11
40 10 10 14 22 19 30 22 22
60 16 12 21 30 27 41 30 31
120 30 21 41 45 48 60 47 50
240 48 37 65 63 66 80 69 69
360 60 47 78 71 74 90 79 81
480 69 55 84 77 77 94 84 86
1440 88 84 88 89 82 101 94 93
242
Appendix D: Experimental for the electrochemical study of
thiocyanate oxidation
Appendix D reports the electrochemical study of thiocyanate oxidation shown in
Chapter 7.
Table D1: Data for cyclic voltammogram of the glassy carbon electrode in 0.1M Na2SO4 at pH 2,
rest potential 0V and a scan rate of 40mV/s at a temperature of 25oC. Ref: Figure 7.6.
Potential vs Ag/AgCl Current
(V) (μA)
0.1 2.02
0.2 0.91
0.3 0.60
0.4 1.67
0.5 1.38
0.6 2.26
0.7 1.13
0.8 0.28
0.9 1.12
1 2.90
1.1 3.49
1.2 4.91
1.3 8.00
1.4 14.47
1.5 24.28
1.6 42.70
1.5 6.87
1.4 2.96
1.3 0.77
1.2 -1.37
1.1 -1.41
1 -1.70
0.9 -2.18
0.8 -1.80
0.7 -1.75
0.6 -2.34
0.5 -2.12
0.4 -2.26
0.3 -1.97
0.2 -3.60
0.1 -3.10
243
Table D2: Data for the cyclic voltammogram of a glassy carbon in a solution of 0.1M Na2SO4 +
0.01M NaSCN, rest potential=0.5V (vs. Ag-AgCl electrode), pH 2, temperature 25oC. The scan
rate was varied from 20 to 40 mV/s. Ref: Figure 7.7.
Potential vs Ag/AgCl Current (μA)
(V) 10 mV/s 20 mV/s 30 mV/s 40 mV/s
0.5 0.40 1.58 -0.39 2.29
0.6 1.00 3.98 -0.09 3.92
0.7 3.30 17.04 5.44 7.97
0.8 12.80 53.62 22.03 42.88
0.9 53.00 171.29 88.43 215.22
1 163.10 465.40 311.32 657.80
1.1 291.90 779.74 655.71 1099.06
1.2 352.60 907.77 928.65 1247.65
1.3 390.80 944.53 1132.69 1192.76
1.4 395.00 887.54 1218.09 1207.88
1.5 370.30 788.07 972.84 1029.57
1.4 324.40 645.40 708.19 761.24
1.3 223.30 456.77 445.12 468.15
1.2 127.10 295.51 258.75 278.16
1.1 78.30 193.12 151.65 164.39
1 36.20 92.32 72.57 79.61
0.9 10.60 27.17 21.11 19.37
0.8 2.50 5.37 4.96 2.65
0.7 0.80 0.76 -0.25 -1.35
0.6 0.00 -0.68 -0.10 -2.35
0.5 0.00 -0.22 -0.39 -3.04
244
Table D3: Data for the stationary cyclic voltammogram of a glassy carbon in a solution of 0.1M
Na2SO4, 0.01M NaSCN, rest potential=0.5V (vs. Ag-AgCl electrode), pH 12, temperature 25oC.
The scan rate was varied from 10 to 40 mV/s. Ref: Figure 7.9.
(V) 10 mV/s 20 mV/s 30 mV/s 40 mV/s
0.5 0.23 4.53 3.04 0.60
0.6 1.14 7.85 -0.19 3.69
0.7 0.99 16.41 14.51 8.83
0.8 3.21 55.56 98.78 26.42
0.9 9.07 154.36 264.67 100.48
1 21.53 442.22 675.74 369.72
1.1 50.33 770.84 1071.40 844.56
1.2 98.61 930.46 1172.13 1257.62
1.3 194.72 920.17 1070.00 1351.18
1.4 454.41 905.61 1010.57 1293.90
1.5 696.85 796.04 886.97 1091.47
1.6 640.97 727.97 793.72 937.15
1.7 567.65 709.66 757.03 870.01
1.8 532.66 741.63 779.16 877.23
1.9 493.35 852.04 886.54 992.91
2 847.55 1078.45 1136.15 1209.73
1.9 598.72 803.44 765.97 793.40
1.8 520.01 698.72 628.82 644.74
1.7 489.20 660.41 580.85 574.24
1.6 466.17 643.91 564.31 536.51
1.5 426.05 622.44 557.47 499.57
1.4 298.62 487.22 474.54 395.62
1.3 117.78 276.54 318.15 207.25
1.2 60.77 181.59 244.66 124.33
1.1 49.14 118.42 171.02 74.94
1 31.63 67.90 104.22 43.13
0.9 16.33 29.06 46.62 16.44
0.8 5.83 7.32 14.85 4.66
0.7 1.31 2.11 -0.29 -0.58
0.6 1.12 -0.70 -3.80 -2.18
0.5 0.04 -0.54 -0.29 -1.00
245
Table D4: Data for the Evan’s diagram. The Rotating disc electrode made from glassy carbon in
a solution of 0.1M Na2SO4+0.01M NaSCN, pH 12, temperature 25oCn and a rest potential of 0.5V
vs Ag-AgCl reference. The rotation frequency was varied from 50rpm to 500 rpm. Ref: Figure
7.11.
(V) 50 rpm 100 rpm 200 rpm 500 rpm
0.5 0.59 0.40 1.23 0.83
0.6 1.24 5.14 5.56 4.64
0.7 3.19 10.04 17.89 16.56
0.8 9.76 27.09 120.24 45.61
0.9 29.60 82.99 142.30 144.77
1 72.54 251.24 444.17 376.07
1.1 165.60 488.85 713.76 824.20
1.2 286.76 912.35 1333.15 1319.06
1.3 462.15 1323.38 1853.07 2089.08
1.4 892.50 1740.32 2302.44 2755.48
1.5 1334.66 2285.01 2916.69 3505.50
1.6 1517.11 2587.14 3474.48 4215.03
1.7 1478.69 2628.10 3728.21 5024.66
1.8 1483.22 2652.04 3832.59 5542.02
1.9 1508.98 2676.30 3825.72 5685.02
2 1538.26 2677.99 3876.60 5914.75
Table D5: Data for the Evan’s diagram. Rotating disc electrode made from glassy carbon in a
solution of 0.1M Na2SO4+0.01M NaSCN, pH 2 and 12, temperature 25oCn and a rest potential of
0.5V vs Ag-AgCl reference. The rotation frequency was varied from 50rpm and 100 rpm at each
pH. Ref: Figure 7.13.
Current (μA)
Potential vs Ag/AgCl pH 2 pH 12
(V) 50 rpm 100 rpm 50 rpm 100 rpm
0.5 0.91 0.90 0.59 0.40
0.6 0.48 15.13 1.24 5.14
0.7 12.18 87.53 3.19 10.04
0.8 58.21 296.29 9.76 27.09
0.9 196.33 740.97 29.60 82.99
1 468.85 1342.41 72.54 251.24
1.1 801.94 1836.11 165.60 488.85
1.2 1083.16 2040.99 286.76 912.35
1.3 1380.30 2184.00 462.15 1323.38
1.4 1733.13 2404.08 892.50 1740.32
1.5 1956.43 2715.39 1334.66 2285.01
1.6 1928.95 2820.59 1517.11 2587.14
1.7 1946.75 2791.71 1478.69 2628.10
1.8 1978.09 2796.19 1483.22 2652.04
1.9 2085.53 2899.22 1508.98 2676.30
2 2305.16 3034.97 1538.26 2677.99
246
Table D6: Data for the comparison of the stationary cyclic voltammogram of a glassy carbon in
a solution of 0.1M Na2SO4, 0.01M NaSCN with copper added to one experiment (concentration of
0.005M CuSO4), rest potential=0.5V (vs. Ag-AgCl electrode), pH 12, temperature 25oC and a
voltage scanning rate of 40mV/s. Ref: Figure 7.14.
Potential vs Ag/AgCl Current (μΑ)
(V) CuSO4 No CuSO4
0.5 21.68 0.60
0.6 9.41 3.69
0.7 21.20 8.83
0.8 90.62 26.42
0.9 272.31 100.48
1 556.23 369.72
1.1 746.74 844.56
1.2 850.59 1257.62
1.3 982.00 1351.18
1.4 1155.81 1293.90
1.5 986.29 1091.47
Table D7: Data for the comparison between Evan’s diagram for Rotating disc electrode made
from glassy carbon in a solution of 0.1M Na2SO4+0.01M NaSCN with one set of experiments
containing 0.005M CuSO4, pH 2, temperature 25oC and a rest potential of 0.5V vs Ag-AgCl
reference. Ref: Figure 7.15.
Current (μA)
Potential vs Ag/AgCl No Copper Copper
(V) 50 rpm 100 rpm 50 100
0.5 0.91 0.90 26.83 29.88
0.6 0.48 15.13 12.12 25.25
0.7 12.18 87.53 30.70 51.31
0.8 58.21 296.29 108.71 186.14
0.9 196.33 740.97 325.10 597.22
1 468.85 1342.41 679.61 1123.48
1.1 801.94 1836.11 914.91 1378.46
1.2 1083.16 2040.99 1041.74 1562.31
1.3 1380.30 2184.00 1286.23 1886.83
1.4 1733.13 2404.08 1677.63 2306.30
1.5 1956.43 2715.39 1726.17 2481.65
1.6 1928.95 2820.59 1714.18 2529.42
1.7 1946.75 2791.71 1746.61 2557.55
1.8 1978.09 2796.19 1807.55 2591.24
1.9 2085.53 2899.22 1929.65 2732.43
2 2305.16 3034.97 2208.16 2974.20
247

Whole

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Whole

Uploaded by

Copyright:

Available Formats

Cyanide regeneration from Thiocyanate with the use of Anion

Downloaded from http://hdl.handle.net/1959.4/23018 in https://

A thesis submitted for the degree of

Kenneth Chung-Keong Lee

School of Chemical Engineering and Industrial Chemistry

Using ion-exchange resins can be an effective way to concentrate thiocyanate from

Table of Contents......................................................................................................... iii

List of Figures ..............................................................................................................vii

List of Tables ...............................................................................................................xii

List of Publications .................................................................................................... xiii

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

Chapter 2 Cyanide Chemistry........................................................................................5

Chapter 3 Cyanide Management Using Chemical Oxidation Processes .....................23

Chapter 4 Solution Equilibria ......................................................................................76

Chapter 6 Recovery of Cyanide from Thiocyanate using Hydrogen Peroxide .........152

Chapter 8 Conclusions and Recommendations..........................................................218

Appendix B: Experimental data for ion-exchange equilibria between thiocyanate and

Appendix C: Experimental for the recovery of cyanide from thiocyanate using

Appendix D: Experimental for the electrochemical study of thiocyanate oxidation 243

Detoxification of cyanide is commonly used to remove CNWAD from tailing waters.

1.2 Objectives of this study

1.2.1 Literature review

Thermodynamic modelling has been successfully applied to a wide range of

1.2.3 Binary ion-exchange equilibria between thiocyanate and chloride using

Using commercially available ion exchange resin (Purolite A500/2788) ion-exchange

1.2.5 Electrochemical oxidation half-cell reaction of thiocyanate

Electrochemical studies were used to examine the oxidation half-cell reaction of

Weak-acid dissociable cyanide

3. Weak complexes Zn(CN)42-, Cd(CN)3-, Cd(CN)42-

Strong-acid dissociable cyanide

5. Strong complexes Fe(CN)6-4, Co(CN)6-4, Au(CN)2-1, Fe(CN)6-3

Source: Scott and Ingles (1987)

2.2 Free Cyanide

where the pKa for HCN is

and T is temperature given in degrees Celsius (Izatt et al., 1962).

Figure 2.1: Distribution of HCN and CN as a function of pH @ 250C.

From environmental standpoint, the most significant strong-acid dissociable cyanides

2.5 The Cyanide Cycle

2.6.2 Cyanide Complex Precipitation

Formation of cyanide double salts as stable precipitates reduces the mobility of

Adsorption of cyanide is another mechanism to remove cyanide from a waste stream.

2.6.4 Oxidation of cyanide to cyanate

Under natural conditions, the oxidation of cyanide to cyanate can be slow. An

Hydrogen cyanide is produced by a hydrolysis reaction between cyanide ion and

Under aerobic conditions it was reported that up to 200ppm cyanide could be

The use of biodegradation to reduce the concentration of cyanide in the effluent

Many gold ores contain sulphide materials. In neutral or basic solutions,

S−x2 + CN − → S(x−2−1) + SCN − [2.6]

S 2 O 3−3 + CN − → SO 3−2 + SCN − [2.7]

2.6.8 Hydrolysis and Saponification of HCN

HCN + 2H 2 O → HCOONH 4 [2.8]

HCN + 2H 2O → NH 3 + HCOOH [2.9]

Domench X., Peral J. “Cyanide photo-oxidation using a titanium(IV) oxide –coated

Fuller W. “Cyanides in the Environment with Particular Attention to the soil.”

Izatt R.M. et al. “Thermodynamics of metal-cyanide coordination. I. PK, Ho, and So

Marsden J., House I. “The Chemistry of Gold Extraction”, Ellis Horwood,

Smith A., Mudder T. “The Environmental geochemistry and fate of cyanide”,

Environmental protection authorities in Australia have imposed strict regulations on

Detoxification of tailings involves mainly the destruction of weak-acid dissociable

3.2.1 The INCO process

CN − + SO 2 (g) + O 2 (g) + H 2 O → CNO − + H 2SO 4 [3.1]

M(CN) xy − x + x SO 2 (g) + x O 2 (g) + x H 2 O → x CNO − + x H 2SO 4 + M y + [3.2]