INFORMATION TO USERS

The most advanced technology has been used to photograph and reproduce this manuscript from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order.

University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road, Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600

Order Number 1341473

Leaching and electrochemical behavior of gold in iodide solutions Qi, Peihao, M.S.
The University of Arizona, 1990

UMI

300 N. Zeeb Rd. Ann Arbor, MI 48106

LEACHING & ELECTROCHEMICAL BEHAVIOR OF GOLD IN IODIDE SOLUTIONS

by Peihao Qi

A Thesis Submitted to the Faculty of DEPARTMENT OF MATERIALS SCIENCE AND ENGINEERING In Partial Fulfillment of the Requirements For the Degree of MASTER OF SCIENCE In the Graduate College The UNIVERSITY OF ARIZONA

19 9 0

STATEMENT BY AUTHOR

This thesis has been submitted in partial fulfillment of requirements for an advanced degree at the University of Arizona and.is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author.

SIGNED

APPROVAL BY THESIS DIRECTOR This thesis has been approved on the date shown below:

u,mo
(f xofessor of Materials Science & Engineering cfete '

ACKNOWLEDGEMENTS

I wish to express my heartfelt thanks to Dr. J. Brent Hiskey, my thesis and research supervisor, for his great assistance, constant guidance and encouragement during my study for M.S. degree. I am also grateful to the Arizona Mining and Mineral Resources Research Institute under U. S. Bureau of Mines for their financial support. I would like to acknowledge Drs. W. G. Davenport and S. Raghavan for serving in my defense committee. I also wish to thank all of our group members for their beneficial discussions and assistance. I also wish to take this opportunity to appreciate my wife, Siying Chen, for her constant and useful discussion, inspiration and support.

TABLE OF CONTENTS LIST OF ILLUSTRATIONS . . LIST OF TABLES ABSTRACT CHAPTER 1. INTRODUCTION 2. LITERATURE REVIEW 2.1 Leaching Aspects of Gold 2.1.1 Dissolution Chemistry of Gold 2.1.2 Polyiodide Species 2.1.3 Bromide Leaching 2.1.4 Iodide Leaching 2.2 Potential-pH Equilibrium Diagrams 2.2.1 Au-HpO System 2.2.2 Au-Cl"-H20 System 2.2.3 Au-Br"-H20 System 2.2.4 Au-I'-HjO System 2.3 Electrochemical Behavior of Gold in Halides . 2.3.1 Electrochemical Behavior of Gold in Chloride Solutions 2.3.2 Electrochemical Behavior of Gold in Bromide Solutions 2.3.3 Electrochemical Behavior of Gold in Iodide Solutions 2.3.4 Adsorption of Halides on the Gold Surface 2.4 Rotating Disk Electrode 3. EXPERIMENTAL PROCEDURE 3.1 Experimental Preparation 3.2 Leaching Tests 3.2.1 Apparatus 3.2.2 Conditions 11 14 14 14 17 18 19 20 20 22 .22 22 26 27 33 33 35 36 37 37 39 39 41 6 9 10

TABLE OF CONTENTS (Continued) 3.3 Electrochemical Tests 3.3.1 Apparatus 3.3.2 Conditions 4. RESULTS AND DISCUSSION 4.1 Leaching Kinetics 4.1.1 I2/Ij Solution Chemistry 4.1.2 Effect of Disk Rotating Speed 4.1.3 Effect of Iodine Concentration 4.1.4 Effect of Iodide Concentration 4.1.5 Effect of Electrolytes 4.1.6 Effect of Temperature 4.1.7 Effect of pH 4.1.8 Comparison with Cyanidation 4.1.9 Kinetic Considerations 4.2 Electrochemistry 4.2.1 Cyclic Voltammetry of Gold in Halides . 4.2.2 Cyclic Voltammetry of Gold in Various [Nal] 4.2.3 Anodic Polarization of Gold in Different [Nal] 4.2.4 Effect of Disk Rotating Speed 4.2.5 Reduction of Iodine Species on Gold . . 4.2.6 Mixed Halide System 4.2.7 Effect of Sweep Rate 5. CONCLUSIONS 5.1 Leaching of Gold 5.2 Electrochemistry Behavior REFERENCES 41 41 43 44 44 44 47 50 56 56 62 66 66 70 74 74 79 81 85 92 95 95 100 100 101 104

LIST OF ILLUSTRATIONS Figure 1. Potential-pH equilibrium diagram for the goldwater system for dissolved gold species of 10"4 M (after ref. 5) Potential-pH equilibrium diagram for the gold chloride system for [Au] = io"5 and [CI] = 10~2 M (after ref. 5) Potential-pH equilibrium diagram for the gold bromide system for [Au] = 10^ and [Br] = 10"2 M (after ref. 5) Potential-pH equilibrium diagram for the gold iodide system for [Au] = 10"5 and [I] = 10"2 M (after ref. 5) Current density and potential curves for gold in unstirred NaCl solutions (after ref. 28) ... . Cyclic voltammograms at a sweep rate of 20 mV/s and at a rotaint gold-disk electrode of 600 rpm in various solutions (after ref. 32) Schematic illustration of the gold rotating disk . Schematic representation of reaction apparatus for leaching cell

21

2.

23

3.

24

4.

25 30

5. 6.

32 38 40

7. 8. 9.

Schematic representation of three electrode cell . 42 46 48 49 51

10. Solubility of iodine at 25C as a function of sodium iodide concentration 11. Distribution of I?(aq) and Ij as a function of iodide concentration 12. Gold dissolution at various disk rotation speeds using 10~2 M I" and 5x10 M I2 13. Gold dissolution rate plotted against the squareroot of disk rotation speed

LIST OF ILLUSTRATIONS (CONTINUED) Figure 14. Effect of I, concentration on the dissolution of gold in 10"^ M Nal 15. Reaction order plot for Ij 16. Effect of I2 concentration on the dissolution of gold from a stationary disk using a stirring bar for agitation 17. Effect of I" on the dissolution of gold in the presence of 10~3 M I2 18. Reaction order plot for I" 19. Effect of temperature on the dissolution of gold in 10"2 M Nal and 5xio~3 M I2 20. Effect of temperature on the dissolution of gold in 10"2 M Nal and lxio-3 M I2 21. Arrhenius plots for the leaching of gold in 10"2 M Nal solution containing 5xio~3 and lxio-3 M I2, respectively 22. Solubility of iodine at 10"2 M Nal as a function of temperature 23. Effect of pH on the dissolution of gold in 10~2 M Nal, 10 M I2 and 10"1 M Na2S04 24. Comparison of iodide and cyanide leaching of gold for different I2 concentrations 25. Cyclic voltammograms of gold in solutions contai ning 10~2 M NaCl, NaBr, and Nal respectively and 1 M HC104 with a scan rate of 20 mV/s and a static electrode . . . . . . . . . . . . . . . . . . . . . 52 55

57 58 60 63 64

67 68 69 71

76

26. Cyclic voltammograms of gold in 1 M HC10, with a scan rate of 20 mV/s and a static electrode ... 78

LIST OF ILLUSTRATIONS (CONTINUED) Figure 27. Cyclic voltammograms of gold in various concen trations of Nal and 1 M HC10A with 20 mV/s and a stirring bar for agitation

80

28. Anodic polarization curves of gold in different concentrations of sodium iodide and 4xio_1 M Na2S04 using a scan rate of 1 mV/s and a RDE at 500 rpm ...................... 82 29. Comparison of anodic polarization curves of gold at 10"2 M Nal with and without disk rotation ... 84 30. Schematic diagrams of electrochemical processes for gold with rotation 31. Schematic diagram of electrochemical processes for gold without rotation 32. Effect of disk rotating speed on the anodic oxidation of gold at 2xl0 -3 M Nal 33. Effect of disk rotating speed on the anodic oxidation of gold at 10"2 M Nal 34. Plot of limiting current densities for the first (0.65 V) and the second (0.95 V) plateau regions as a function of o1/2 86 87 .88 89

91

35. Effect of iodine concentration on its reduction on gold at 10"2 M Nal and a RDE at 500 rpm .... 94 36. Anodic polarization curves of gold in mixed halide systems 37. Effect of sweep rate on the anodic oxidation of gold at 10"2 M Nal and a RDE at 500 rpm 97 98

LIST OF TABLES Table 1. Distribution of iodine species as a function of I2 2. Distribution of iodine species as a function of Nal 54 59

3. Gold dissolution rate in the presence of salts ... 61 4. Dissolution rate of gold as a function of tempe rature 65

5. Comparison of predicted & experimental rates .... 75 6. Limiting current densities taken from the infle ction point to the plateau region as a function of disk rotating speed 7. Limiting current densities for the reduction of iodine species on gold as a function of Nal concentration using 10' 3 M I 2

93

.96

10

ABSTRACT

Of the halogens, the gold iodide complexes are the most stable in aqueous solutions. A series of experiments was performed to investigate the kinetics and mechanism of the leaching reaction between gold and iodide. Using a rotation disk technique, the most important kinetic parameters were measured. The reaction rate was found to be first order with respect to Ij and half order with respect to I". A gold leaching rate of about 2.6xio-9 mol/cm2sec for 10"2 M I" and 5xio-3 M I2 was obtained. This value is close to that for typical cyanidation. The reaction rate appears to be

controlled mainly by diffusion of reactants through the boundary layer of solution to the gold electrode under the conditions studied. The electrochemical study of gold in different halide solutions, with emphasis on iodide, was also carried out. The electrochemical techniques used in this investigation include cyclic voltammetry and linear sweep voltammetry. The results displayed the sequential oxidation for gold dissolution in iodide solution and confirmed that iodide has the strongest oxidation capability of dissolving gold of the halides.

11

CHAPTER ONE INTRODUCTION

Gold undoubtedly is the most noble of metals. Its noblity is exhibited by the fact that it is the only metal that cannot be oxidized by dissolved oxygen at any temperature and is also not attacked by strong acids and alkalis. Fortunately, gold can dissolve in aqueous solution containing both an

appropriate complexing ligand and an oxidizing agent [1]. Cyanidation of gold, a typical example, was invented as early as 1880's [2,3], in which CN~ was used as a complexing ligand and 02 as an oxidant according to the reaction

4AU + 8CN" + 02 + 2H20

4Au(CN)2 + 40H"

(1)

Although traditional cyanidation remains the overwhelming choice for treating free milling gold and silver ores because of its economy and process simplicity, there are certain classes of ores and concentrates that are considered

refractory. The inability of conventional cyanidation to treat effectively these materials has prompted the search for more powerful lixiviants. In addition, because of its toxicity and the problems of waste disposal management, the use of cyanide has been of some environmental concern.

12

Over the last few years there has been an intense effort to identify lixiviants other than cyanide for gold and silver leaching. These include thiourea (CS(NH2)2), thiosulfate (S20~ ), halides (CI", Br" and I"), malononitrile (CH(CN)2),

acetonitrile (CH3CN) and polysulfides. Iodide/iodine were employed in this investigation. Here I" served as a complexing ligand and I2 as an oxidant for gold dissolution according to the reaction

2Au

I" +

IJ

2AUI2

(2)

The resulting Aulj can be further oxidized to give Aul^ and Au can also be oxidized directly to Aul^ conditions. This research work includes two parts. In the first part, the fundamental kinetics and mechanism of leaching gold in iodide solution were investigated by using a rotating disk technique. The effects of disk rotating speed, iodine and iodide concentration, temperature, pH and in the presence of different electrolytes were measured to find put the reaction orders, activation energy and rate controlling process so that a rate equation could be predicted. Oxygen and hydrogen peroxide were also examined as oxidants in the iodide system. The electrochemical behavior of gold in halides was examined in the second part. Focus, however, was put on goldunder certain

13

iodide system. Cyclic voltammetry measurements were used to distinguish and determine the oxidation capability and the oxidation potentials for gold in iodide solutions. Linear sweep voltammetry methods were employed to determine the electrochemical nature of oxidation and reduction processes for gold. The effects of disk rotating speed, sweep rate and iodide concentration were the fundamental parameters

considered in this investigation. In addition, reduction of iodine species at the gold electrode and aspect of mixed halide systems were also studied.

14

CHAPTER TWO LITERATURE REVIEW

2.1 Leaching Aspects of Gold

2.1.1 Dissolution Chemistry of Gold Even though traditional cyanidation is still widely practiced in commercial operations, its ineffectiveness in treating some refractory ores and concentrates, the high toxicity of cyanide and the problems of waste disposal management have provoked the search for more powerful and nonoxic ligands. Gold is generally realized to be oxidized to gold(I) and/or gold(III) complexes in the presence of a coordinating ligand (X) [1]:

Au Au

+ +

2X 4X

= =

AuX+ AuX;j+

+ +

e3e"

(3) (4)

It is also possible to oxidize Au(I) to Au(III) in the presence of these complexing ligands:

AuXj

2X

AuXf

2e~

(5)

15

It is easy to find that the standard potential for reaction (4) is equal to the combination of the standard potentials for reactions (3) and (5) . Thus, whether the disproportionation reaction (6) for Au(I) complex occurs or not will depend on its equilibrium constants (K6)

3AuX*

- 2Au

AuXf

2X

(6)

Solid aurous iodide (Aul(s)) exists in aqueous solution merely as an intermediate or a bridging species [4]. It forms Aulj with I" in iodide solution

Aul(s) +

I" =

Aul"

(K7 0.124)

(7)

When the solution contains Ij , an alternative to reaction (7) is possible

Aul(s) +

Ij

Aul"

(K8 0.039)

(8)

Their investigations also show that Aul(s) slowly decomposes according to the following reaction

2AuI(s) +

I"

2Au(s) +

Ij

(9)

Hiskey and Atluri [5] recently reviewed the dissolution

16

chemistry of gold and silver in different lixiviants. The halides were shown to have special properties for the

processing of gold and silver ores and concentrates. Gold forms both Au(I) and Au(III) complex ions with chloride, bromide and iodide depending on solution chemistry conditions. In aqueous solution, the stability of the gold-halide

complexes increases in the order CI" < Br" < I" which shows a preference for gold to bond with large polarizable ligands. They concluded that there are two important reasons to use halides as lixiviants for gold; one is their extreme stability in aqueous solution, and the other is that all are to some extent soluble in water and can also serve as oxidants for gold. Finkelstein and Hancock [6] have analyzed the stability of various gold complexes in terms of standard potential diagrams for aurous and auric complexes. They demonstrated that with CI", the stable species is the AuCl^ complex. On the other hand, with I", the preferred species is the Aulj complex. A borderline situation appears to exist with Br". This behavior reflects that Au(I) has a greater affinity of soft polarizable ligand than does Au(III) . They put both Au(I) and Au(III) into B-type metal ions which means that the stability of their complexes tends to decrease with increasing electronegativity of the ligand donor atom. Thus, for halides, the stability order follows CI" < Br" < I".

17

Bromide and iodide also exhibit the ability to form polyhalide complexes [7, 8]. This characteristic promotes the dissolution of Br2(liq) and I2(s) in aqueous solution. Iodine reacts with iodide ion as follows:

^(s)
12<aq>

I2(aq)

(10) I3 (11)

The triiodide ion can serve as an oxidant for gold leaching according to the following electrochemical reactions:

Au Ij 2Au

+ + +

21" 2e"

- -

Aulj 31" Ij ->

e"

anodic

(12)

cathodic (13) 2AuIj overall (2)

I" +

2.1.2 Polyiodide Species Iodine is generally viewed as dissolving in an aqueous solution by the formation studies of polyiodide suggested the complexes. following

Spectrophotometric

have

iodine/iodide complexation equilibria [9]:

2(aq)

+ I3

I"
r2-

(11)

I" + *2 2i;
+

(14) (15)

r2-

(16)

18

In addition to these, Sillen and Martell [7] report the possible presence of 1^ and l|~ . Among these reactions,

equilibrium constants of Kn = 7.14xio2 for reaction (11) and K16 = 1.21 for reaction (16) have been reported by Latimer [8] and estimated from the data provided by Sillen and Martell [7], respectively. Sano et al. [9] also indicated that reaction (14) occurs predominantly at very high ionic strength and can be discared at low ionic strength. Reaction (15) can be neglected from the possible origin of the relaxation since the positive value of the enthalpy change results in the decrease of iodine concentration with the increase of

temperature.

2.1.3 Bromide Leaching Although the leaching of gold in bromide solution can be traced back to 1882 [10], it has not been used widely because of the problems of handling, high vapor pressure and corrosion nature of liquid bromine. Other leaching processes using halogens, halides or other halogen-bearing compounds [11-14] were also reported to extract and recover precious metals from ores. Recently, Dadgar [15] developed a liquid bromine carrier of considerably lower vapor pressure than liquid bromine and used the bottle-roll-leach technique and agitation of the slurry for cyanide and bromide leaching tests. The same gold

19

extractions (94-96%) were achieved for 24-48 hour cyanide leaching (Ixi0"2-4xi0"2 M NaCN) and 6 hour bromide leaching (2.5xl0-2 M Br2 and 0-l.6xl0~1 M NaBr) on two samples of Canadian flotation concentrate. In addition, 99.9% or more gold recoveries were obtained from bromide pregnant solutions using carbon absorption, ion exchange and zinc precipitation methods respectively. Furthermore, almost the same cost for chemicals was estimated for cyanidation and bromine leaching.

2.1.4 Iodide Leaching McGrew and Murphy [16] proposed the use of an I"

containing electrolyte to leach gold ores. An iodine lixiviant is added to an ore containing iodine reducing components. As iodide ion increases in the lixiviant, it is possible with continued addition of iodide to achieve the desired

concentration for leaching gold. This is made possible by the complexation of I2 with I" to form the polyiodide species. They report that the initial solubility of iodine is about 1.2xio-3 M and that the desired concentration of about 1.2xio"2 M could be attained by solution recycle. In a column experiment, 80% of the gold in a marcasite ore was recovered by iodine leaching. It should be noted that gold did not start to dissolve until a sufficient concentration of iodine species remained in solution. Murphy [17] further reported treatment of the loaded

20

solution in an electrolytic cell to deposit gold at a cathode, and then convert the iodide to iodine at an anode to regenerate the leaching solution after leaching of gold ores with an iodide-iodine solution.

2.2 Potential-pH Equilibrium Diagrams

Oxidation

potential-pH (Eh-pH)

equilibrium

diagrams

provide a starting point for the study and interpretation of electrochemical reactions, although whether real reactions take place readily or not will depend on kinetic factors. These diagrams for gold in different lixiviant system have been systematically summarized [5].

2.2.1 AU-H20 System The extremely noble nature of gold in the absence of coordinating ligands is illustrated by the Eh-pH relationships for AU-H20 system shown in Figure 1. The dashed lines delineate the stability limits of water. Metallic gold covers a very large area of predominance, including the entire domain of water stability. The oxidized forms of gold only occur at potentials above the upper-stability limit of water. Thus, in the absence of complexing ligands, gold cannot be oxidized in strong acids or strong alkalis. Gold is the only metal with this property and is truly the most noble metal.

21

Au(OH),

HAuO

Figure 1

Potential-pH equilibrium diagram for the gold-water system for dissolved gold species of 10"4 M (after ref. 5).

22

2.2.2 AU-C1~-H20 System In the presence of coordinating ligands, the Eh-pH diagrams for gold are very different. Figure 2 depicts the effect of the additional 10~2 M CI" to the Au-H20 system. The shaded area shows the region of the water domain occupied by dissolved gold species. Hence, gold can exist in an oxidized form (AuCl^ complex) in chloride solution under highly acid conditions. On the other hand, there thermodynamic stability for AuClj is no region of

at this concentration.

Increasing the chloride concentration to 0.1 M, a region for AuClj would appear in the Eh-pH diagram.

2.2.3 Au-Br"-H20 System The Eh-pH behavior for gold in 10~2 M Br" is presented in Figure 3. This diagram expresses the existence of both AuBrj and AuBr^ complexes. In addition, a larger region of stability for AuBr^ is evident compared with that for AuCl^ .

2.2.4 AU-I"-H20 System The Eh-pH behavior of the AU-I"-H20 system is given in Figure 4 for 10~2 M I". This diagram illustrates that metallic gold is oxidized in the presence of iodide to yield both Aulj and Aul^ complexes. By comparison, it is not difficult to find that the gold iodide system has the largest stability region for both Au(I) and Au(III) complexes, and the stability area

23

2.0

AuO:

1.5

AuCl

Au(OH)

1.0

0.5

0.0

0.5 2

10

12

14 16

Figure 2

Potential-pH equilibrium diagram for the gold chloride system for [Au] = 10"5 and [CI] = 10"2 M (after ref. 5).

24

2.0

AUO;

Au(OH)J
1.5

AuBr
1.0

HAuO

AuBr
0.5

0.0

0.5 2

10

12

14

16

Figure 3.

Potential-pH equilibrium diagram for the gold bromide system for [Aul = io-5 and TBrl = 10"2 M (after ref. 5).

25

2.0

,Au02,

1.5
1.0

HAuO*"

0.5
Aui;

0.0

-0.5 ~2

1
0

1 2

1 4

I 6

I i I 10 12 14 16

Figure 4

Potential-pH equilibrium diagram for the gold iodide system for [Au] = 10"5 and [I] = 10"2 M (after ref. 5).

26

for Aulj extends upto about pH 12. Therefore, of the halogens, the gold iodide complexes are the most stable in aqueous environments.

2.3 Electrochemical Behavior of Gold

There

are

two

important

characteristics One is

to that

study the

electrochemical

electrode

processes.

activation energy of the reaction step with regard to charge transfer depends on the potential difference between the electrode and the solution, which was first recognized by Ergey-Gruz and Volmer [18]. The other is that the rate of an electrochemical reaction is dependent on the structure of the double layer at the electrode surface since it affects the distribution of ion concentration and electric potential near the electrode. This was stated by Frumkin [19]. To discuss current density-potential (i-E) curves, Kiss [20] described two cases often seen for anodic dissolution of metals; after a current density reaches a certain extent, it then drops because of passivation on the electrode surface or hits the limiting current density in which the dissolution rate is controlled by diffusion. A number of investigators have studied the fundamental electrochemistry of gold using chloride and sometimes bromide as complexing lixiviants [21-31]. However, only limited work

27

has been devoted to the basic electrochemistry of gold oxidation in iodide solution. In addition, the results for anodic dissolution and the explanation offered are somewhat inconsistent.

2.3.1 Electrochemical Behavior of Gold in Chloride Solutions As summarized by Nicol [21-22], cyclic voltammograms for gold in the presence of only acidic and alkaline electrolyte media are generally similar and voltammograms for gold in chloride solution indicate a rise in anodic current density at about 1.0 V followed by passivation which is believed to be caused by the formation of an oxide film on the electrode. Oxygen and chlorine evolution take place at potentials higher than 1.6 V. Just and Landsberg [23] studied the anodic passivation of gold in hydrochloric acid using galvanostatic and

potentiostatic methods and a rotating disk electrode, and showed that the passivation time for gold was determined by transport processes. Heumann and Panesar [24] determined analytically the gold species resulting from electrochemical oxidation in sodium chloride to be both Au(I) and Au(III) species for potentials below 1.2 V. At potentials between 1.2 and 1.4 V, a plateau region was found where the reaction is controlled by diffusion of chloride ions to the gold surface. Then at approximately

28

1.5 V, passivation was observed due to the formation of an oxide layer. Oxygen evolution started at about 1.6 V. Gaur and Schmid [25] produced cyclic voltammograms of gold in 2X10"4 to lxio-2 M KC1 solutions containing 10"1 M HCIO^. A current peak at about 1.2 V was attributed to the oxidation of Au to Au(III). Its height was dependent on the chloride concentration and its position was independent of chloride concentration indicating that it was the formation of

"adsorbed oxygen" on the electrode surface, which prevented further dissolution of gold as Au(III). On the reverse scan, this film was removed at about 0.9 V. In addition, this passive film was stable for 13 hours at 10"2 M KCl and at 1.1 V. Gallego et al. [26] defined the anodic current peak for cyclic voltammograms of gold in concentrated HCl solutions as the electro-dissolution of gold to Au(I) and the cathodic current peak as the electro-deposition of the dissolved Au(I). The proposed mechanism did not involve the direct oxidation of Au(I) to Au(III), but incorporated an improbable

disproportionation step for adsorbed Au(I). Podesta and co-workers [27] found that AuClj was the electro-dissolution species of gold. Its reaction was

diffusion controlled and an oxide layer formed when the solution was depleted of CI" ion. This oxide layer caused the anodic current drop and the passivation of electrode. As Cl"

29

diffused backwards, the oxide layer dissolved. Frankenthal and Siconolfi [28] discussed the normal shape of the steady-state i-E curves for gold in chloride solutions as shown in Figure 5 and divided them into five potential regions: active, prepassive, prepassive-to-passive transition, passive and transpassive. The gold dissolution rate was independent of pH at pH > 1.5 and increased remarkably with the decrease of pH at pH < 0. In the active region, gold anodically dissolved to Au(I) and then to Au(III) . Diffusional limiting current densities caused by chloride ion depletion at the anode surface were observed only at [Cl~] > 0.1 M. In the prepassive region, a film of an oxide or hydroxide of gold was found. In the prepassive-to-passive transition region, an oxide or adsorbed oxygen film was formed. In the passive and transpassive region, the gases Cl2 and 02 were evolved. Benari and co-authors [29] showed that the current increased almost linearly with potential and no passivation existed for linear sweep voltammetry for gold in

chloride/dimethylsulfoxide solution, which differed from that observed in water/chloride solution. Nicol and Schalch [21, 30-34] reviewed and made a detailed study of the dissolution and passivation of gold in, chloride solutions. They [30] found that the dissolved Au(III) species increased with potential, and decreased with the increase of chloride concentration and with the decrease of

30

O SAI'O NOtt 1M NOCi O CUM NOCI Qt 10 12 It II

POTENTIAL, VOLTS Vt SCC.

Figure 5

Current density and potential curves for gold in unstirred NaCl solutions (after ref. 28).

31

rotating speed at all potentials. The Au(I) appeared as an intermediate species which could be further oxidized to Au(III) or could diffuse away from the electrode into the bulk solution. The dissolution rate for Au(I) also increased with the increase of chloride concentration and the

disproportionation rate for Au(I) was negligible. They [31-32] also found that cyclic voltammograms of gold (at 20 mV/s) in 10"3 M NaCl resulted in an anodic oxidation peak followed by passivation and a cathodic reduction peak on the reverse scan. In 10"2 M NaCl, however, reactivation instead of cathodic peak was obtained, which indicated that no oxide existed, as shown in Figure 6. The reactivation of the electrode, which occurred at potentials close to those at which passivation occurred during the reverse scan, was possibly caused by quick

dissolution of the oxide film in high concentration of chloride. Furthermore, cyclic voltammograms of gold (at 5 mV/s) at lower concentrations of hydrochloric acid exhibited typical diffusion-controlled behavior at high potentials. The height of this diffusional region was dependent on the agitation, and was about proportional to the concentration of HC1, which indicated that diffusion of chloride ions to the electrode surface limited the dissolution rate. The height of this diffusional region was not affected notably by

temperature. There was no big difference between cyclic voltammograms using sodium chloride and hydrochloric acid.

32

1M HOO. 1M HCKfc AND V'MNaa 1M HCKfc ANO ' M NtCI /' .-""'x 1*1

1.2

POTENTIAL V

Figure 6

Cyclic voltairnnograms at a sweep rate of 20 mV/s and at a rotaint gold-disk electrode of 600 rpm in various solutions (after ref. 32).

33

They [34] also showed, after studying the cathodic deposition of gold, that the deposition of gold from Au(I) in chloride solutions was favored both thermodynamically and kinetically over that from Au(III), and passivation caused by the

formation of oxides on the electrode could be prevented by low anodic current density, high temperature and high chloride concentration.

2.3.2 Electrochemical Behavior of Gold in Bromide Solutions Gaur and Schmid [25] reported a cyclic voltammogram for gold in 4xio-4 M KBr containing 10"1 M HC104 and using a relatively fast scan rate (40 mV/s). This scan showed a rise in current density indicating the oxidation of Au to AuBr^ and no passivation on the gold electrode up to 1.4 V. Nicol [21] conducted some experiments using a gold diskplatinum ring electrode in bromide solution. The results showed that the general shape of curves for gold oxidation in bromide was similar to that in chloride solution and that Au(I), Au(III) and bromine were all produced during anodic oxidation.

2.3.3 Electrochemical Behavior of Gold in Iodide Solutions Nicol [21] predicted that the electrochemical behavior of gold in iodide solution would be similar to that in bromide solution with possible passivation by insoluble Aul.

34

Gold-iodide complexes on the surface of a gold electrode were analyzed using Surface-Enhanced Raman Spectroscopy (SERS) during anodic oxidation [35-36]. Loo [35] concluded that Aulj was the predominant species at potentials < 0.5 V and Aul^ prevailed at potentials > 0.7 V. The similar phenomena were also detected in chloride and bromide solutions. Based on these results, the following mechanism for the

electrochemistry dissolution of gold in aqueous solutions containing halide ions was proposed:

Au

X" + = + =

(AuX~)ad X" = (AuX")ad + e"

(17) (18) (19) 2e" (20) (21)

(AuX")ad (AuXj )ad (AuX")ad (AuX^ )ad

AuXj (dissolution) 2X" = (AuX')ad +

AuX^ (dissolution)

where X represents CI, Br or I. Tadayyoni et al. [36] pointed out that iodide formed an irreversibly adsorbed and electro-inactive layer on gold in dilute iodide concentration (10~3 M) . They also pointed out that thick insoluble iodine films (>10-100 nm) were formed on the gold electrode at higher iodide concentrations where the iodine generated exceeded its solubility. Thus, the solid iodine rather than triiodide is the main surface product at the electrode surface.

35

Qureshi [37] indicated that the oxidation of I- on a gold wire rotating electrode followed two steps. The I~ was initially oxidized to adsorbed I and the latter was further oxidized to iodate. Davis and Tran [38] recently studied electrochemical dissolution of gold in iodide, bromide and chloride solutions using a rotating disk electrode system and explained the kinetics and mechanisms of the leaching process in terms of the Evans diagrams. Optimum leaching conditions were

determined for each reagent.

2.3.4 Adsorption of Halides on the Gold Surface Takamura and co-authors [39] demonstrated that the

adsorption of CI", Br" and I" anions on gold was diffusion controlled. The adsorption extent followed an order I" > Br" > CI" and I" adsorbed at the lowest potential. Clavilier and Huong [40] also studied the double layer structure on gold and also concluded that the adsorption increased in the order I" > Br" > CI". Cadle and Bruckenstein [41] confirmed the adsorption of chloride on gold electrodes in the disk potential range of 0.2 to 1.8 V using the ring-disk electrode technique. They also found that adsorbed chloride ions existed in two different states on a gold electrode.

36

2. 4 Rotating Disk Electrode

The rotating disk electrode theory which was first described by Levich in 1942 [42-43] has been discussed at length by several literature [44-47], It is quite easy to construct and compose a disk of the electrode material imbedded in a rod of an insulating materials. It is also easy to clean the electrode surface by polishing without changing its geometry, and also simple to change the experimental conditions by variations in the rotating rate. The liquid flow and the mass transport in solution are the two principal factors affecting the performance of the electrodes [44]. Riddiford [45] discussed as many as twelve types of the experimental electrodes. However, in practice the shape of electrodes is usually not bothersome except perhaps at high rotating rates which may cause turbulence and vortex formation [46]. Some of the papers [44-45] also discussed the

applications of disk electrodes. These involve the measurement of diffusion coefficients, the studies of electrode volume reaction kinetics (including preceding, parallel and follow-up chemical reactions). Others include electro-deposition, the dissolution of metals in corroding media and the molten salt system and so on.

37

CHAPTER THREE EXPERIMENTAL PROCEDURE

3.1 Experimental Preparations

The rotating disk technique was employed as a fundamental method for the leaching and electrochemical tests. Two grams of gold high purity powder which was obtained from D.F. Goldsmith Chemical & Metal Corp. was used to make the gold pellet. The flat pellet was formed in a 1.27 cm diameter pressure mold at a total pressure of 20,000 pounds per square inch. The calculated density of pellet was approximately 17.6 g/cm3 compared with the theoretical density for gold of 19.3 g/cm3. The pellet was then sealed in a Teflon holder which could be screwed on the Analytical Rotator (Model ASR2 of Pine Instrument Co.) so that only one surface of the pellet was exposed to solution. Conducting silver paste was used to connect the gold pellet and the holder. The total resistance of the assembly was measured to approach to zero. Figure 7 is a schematic illustration of the gold rotating disk used in this study. The surface of gold pellet was carefully polished on 600grit silicon carbide paper and thoroughly rinsed prior to each test. All chemicals used in this research were of reagent-

38

metallic rod

Ag paste

Au pellet

.teflon shroud

Figure 7

Schematic illustration of the gold rotating disk.

39

grade quality. Distilled-deionized water was used to prepare the required solution. Leaching solutions were made up by adding sodium iodide into small amount of the distilled-deionized water first and solid iodine was then added into the solution. After the solution was filled to the required amount, a stirring bar was used to aid the dissolution of solid iodine which is difficult to dissolve in aqueous solutions. Pure oxygen was used in the test requiring oxygen sparge. For those tests examining the effect of pH, solution pH adjustments were made with additions of sulfuric acid and sodium hydroxide.

3.2 Leaching Test

3.2.1 Apparatus Leaching reaction was carried out in a 500-ml roundbottom reaction flask with three angled necks. Samples were withdrawn at regular intervals for analysis. These samples were analyzed using a Perkin-Elmer (model 273) Atomic

Absorption Spectrophotometer. To study the effect of temperature, was a constant which

temperature

water

bath/circulator

employed

circulated water through a jacketed reaction flask. Figure 8 is the schematic diagram of the reaction

40

Analytical Rotator

11

rJacket, Reactor L J f Water

/(r=6.35mm)/
/ Solution / //,Wafer///

f. Au Pellet

Constant Temperature Bath Circulator

Figure 8

Schematic representation of reaction apparatus for leaching cell.

41

apparatus.

3.2.2 Conditions The leaching experiments were carried out under the following conditions, which were maintained constant except for the studied or indicated parameters:

Solution: Temperature: Rotating Speed: Time: pH:

lxlO"2 M Nal & 5xl0"3 M I2 room temperature (23C) 500 rpm 6 hours 46 (natural pH)

3.3 Electrochemical Tests

3.3.1 Apparatus A conventional three-compartment cell was employed for electrochemical measurement during this study as shown in Figure 9. The cell consisted of a gold-rotating disk working electrode (RDE), two graphite rods as the counter-electrodes, and a saturated calomel electrode (SCE) as a reference electrode with the end of the Luggin capillary tube positioned directly below the surface of the gold disk. A potentiostat (PAR Model 273) was used to set and control the

electrochemical conditions and current-potential curves were

42

Counter Electrode

Working Electrode

Reference Electrode

Au Pellet Probe Solution

Figure 9

Schematic representation of three electrode cell.

43

recorded on an X-Y recorder (Houston Instrument Model 200).

3.3.2 Conditions All potentials reported in this paper are with respect to the SCE scale. Sodium sulfate or perchloric acid was added to the halide solutions to establish the ionic strength of these solutions. All scans were started at the corresponding rest potentials. All of the electrochemical experiments were carried out at room temperature (23C) and at natural pH (6.2-6.5 for Na2S04 containing solutions and < 0 for HC104 containing solutions) . A disk rotating speed of 500 rpm was used for most of the experiments and disk rotating speeds from 200 to 700 rpm were used for the tests of the anodic oxidation of gold as a function of disk rotating speed. A stirring bar was also employed to perform some early tests. The tests for cyclic voltammetry and for linear sweep voltammetry were conducted at sweep rates of 20 and 1 mV/s, respectively. Sweep rates ranging from 1 to 200 mV/s were used to investigate the tests of the anodic polarization of gold as a function of sweep rate.

44

CHAPTER FOUR RESULTS AND DISCUSSION

4.1 Leaching Kinetics

Dissolution of gold in iodide proceeds by the following reaction:

2AU

I" +

Ij

2AuI"

(2)

As shown iodide and iodine are consumed during the course of this reaction. The dissolution experiments were carried out with negligible changes in the bulk concentration of iodide and iodine. As predicated from the general reaction, the amount of gold dissolved from a rotating disk of constant area should vary as a linear function of time. Linear rate constants having the units (/xmol/cm2 hr) were determined from the slopes of these plots.

4.1.1 Xg/Xj Solution Chemistry A series of polyiodide complexes exist in iodine/iodide solutions as discussed in 2.1.2. Unfortunately, thermodynamic data are extremely scarce for the polyiodide complexes. Latimer [8] gives an equilibrium constant of = 7.14xio2 for

45

reaction (11) and it is possible to calculate a value of K16 = 1.21 from the data provided by Sillen and Martell [7].

I" +
21;

I2 -

Ij

(K = 7.14X102) (K.. <K16 - 1.21)

(11)
(16)

l!" <6~

From these considerations, the solubility of iodine should depend on the aqueous concentration of iodide. The solubility of iodine at 25C as a function of Nal

concentration is given in Figure 10 [48]. It is clear that iodine solubility is directly related to iodide concentration. The highest concentration of iodide used in this investigation was lxio-2 M. At this level, the maximum solubility of iodine is approximately

6xio-3

M I2.

The distribution of iodine species plays an important role in this system. As shown above there are a number of

polyiodides that may exist in aqueous solution of iodine. The formation of these follows the general equilibria:

*2<aq)

" K

<22>

where x is an odd number or

+ IxM

**

Ixi

(23)

10
\ o E E
ii i i

10

12

14

16

18

20

[ Nal ] (mmol/l)

Figure 10

Solubility of iodine at 25C as a function of sodium iodide concentration.

47

where x* is an even number. It can be seen that the formation of the monovalent polyiodide complexes (I~ ) involves reactions with I2(aq) while formation of the divalent polyiodide (1*7) complexes requires I". With available thermodynamic data, it is possible to calculate distribution of species relationship for I", I2<aq)'
a n d

*6

o t h e r

species can be considered

negligible according to mass action consideration and the fact that in our study dilute concentration of both I" and I2 were utilized. The distribution of I2(aq) and Ij as a function of iodide concentration is provided in Figure 11. At lxio-2 M I", the triiodide species is the predominant form in aqueous solution.

4.1.2 Effect of Disk Rotating Speed Gold dissolution rate was determined as a function of disk rotating speed in solution containing lxio-2 M I" and 5xio~3 M I2> Linear dissolution rates were observed for

rotating speeds from 400 to 1800 rpm as shown in Figure 12. Levich derived the following mass flux expression for

hydrodynamic convective diffusion in liquids [49]:

j = 0.62 Dz/3 (<>1/2 V'1/6 C0

(24)

where j is the mass flux (mol/cm2 sec), D is the diffusion coefficient (cm2/sec), v is the kinematic viscosity (cm2/sec),

48

.0

0.8

0.6
0.4

0.2

0.0 -5

-4

-3

-2

-1

log [ I ]

Figure 11

Distribution of I2(aq) iodide concentration.

a n d

I3

a s

function of

49

1800 rpm 1200 a 1000 A 800 600 o 400

Time (hrs)

Figure 12

Gold dissolution at various disk rotation speeds using 10"2 M I" and 5x10 M I2.

50

o) is the rotating speed (rad/sec) and C0 is the concentration of bulk solution (mol/cm3) . The above equation shows that the diffusional flux to the surface of the disk is proportional to the 2/3 power of the diffusion coefficient D, to the (-1/6) power of the kinematic viscosity, and to the 1/2 power of the disk rotating speed. Figure 13 represents a plot of the dissolution rate (R) versus the square root of disk-rotating speed (o). The linear relationship shown in Figure 13 agrees favorably with the diffusion theory of Levich and suggests that the rate is controlled by a diffusional process. However, at the concentrations of iodine and iodide employed, the rate is significantly lower than predicted by equation (24) for typical values for D. This indicates that the reaction may contain mixed kinetics involving both diffusion and charge transfer.

4.1.3 Effect of Iodine Concentration The effect of iodine concentration on gold dissolution in solutions containing lxio-2 M I" was examined for I2 additions ranging from lxio-4 to 5xio~3 M. Gold dissolution as a function of I2 concentration is depicted in Figure 14. These data display excellent first order kinetics and indicate increasing rate with increasing iodine. As explained earlier, the

concentration of iodine was limited by its solubility in sodium iodide. Furthermore, the complexation equilibrium must

51

20 1x10 2 M Nal 5x10" 3 M lo

16
CN

E o E
3
0)

12

a a:

10

12

14

16

CJ1/2 (s"1/2)

Figure 13

Gold dissolution rate plotted against the square root of disk rotation speed.

52

70
N

60
50

1x10~2 M Nal

<N

E
\

40
2.5x10

30 20
5x10~4

0m

Time (hrs)

Figure 14

Effect of I2 concentration on the dissolution of gold in 10"2 M Nal.

53

be considered in determining the distribution of oxidant species. The concentration of iodide/iodine species is given in Table 1 for various concentration of I2(s) added to a solution containing 10"2 M Nal. Also provided in Table 1 are dissolution rates as a function of I2 concentration. The concentration of Ij is approximately 5 times greater than I2(s) for these conditions. A reaction order plot was determined for Ij for I2(aq) concentrations of lxio"3, 5xio~4 and
lxio"4

M.

Iodide concentration remains essentially constant in this range. This plot is shown in Figure 15 and yields a slope of 0.96. A first order dependence on Ij is indicated by these results. It should be noted that a first order dependence on
1 2<aq>

a lso

obtained for the reaction at these conditions.

In some early experiments, the effect of oxidants other than iodine was investigated using a stationary disk and a stirring bar for agitation. Oxygen and hydrogen peroxide are compared in Figure 16 with different iodine concentrations in solutions containing lxio-2 M Nal. These results show that almost no gold was dissolved using either a 1 atm P02 sparge or 2xio-2 M hydrogen peroxide solution. Unlike conventional cyanidation, which is characterized by relatively low

oxidation potentials and the use of air in the oxidation process, leaching gold in iodide requires more aggressive oxidants. Even at low concentrations of iodine, measurable levels of gold are found to dissolve. It should be noted that

54

Table 1: Distribution of Iodine Species as a Function of l2

Nal (M)

^(s)

Rate* (R)

m]
(M)
4 02X10"3 2.13xl0"3 8.73x10"* 4.42X10"4 9.35X10"5

[I"] (M)

[I2] (M)

ciS"] (M)

(M)

10"2 10"2 10"2 10-2 10"2

5X10"3 2.5X10"3 1X10"3 5X10"4 lxlO"4

8.71 5.58 4.04 2.10 0.47

5.94X10-3 7.86X10"3 9.13X10"3 9.56X10"3 9.91X10"3

-4 9.48X10'

1.96X10 -5

3.80x10"-4
1.34X10 -4

5.49x10"-6 9.22X10 -7
-7 2.36X10"

-5 6.48X10'

1.32X10 -5

-8 1.06X10"

* Dissolution rate (nmol/cm2 hr).

55

0.7

0.1
-0.2
i

slope = 0.96

-0.5 -4.5

-4.0

-3.5
log[ I3]

-3.0

-2.5

Figure 15

Reaction order plot for Ij.

56

the experiments employing lxio-2 and 2xio~2 M I2 were above the solubility limit of iodine at lxio"2 M Nal. The lower rate observed for 5xio-3 M I2 in Figure 16 as compared to that in Figure 14 is attributed to the decreased hydrodynamic

efficiency of the system using the stirring bar.

4.1.4 Effect of Iodide Concentration The effect of iodide concentration on gold dissolution was investigated for a fixed iodine concentration. In this series of experiments, Nal additions ranging from 10~3 to 10~2 M were used. Gold dissolution as a function of Nal

concentration is provided in Figure 17. The rate was observed to increase with increasing Nal concentration. The

concentration of iodide/iodine species is given in Table 2 for the conditions employed in this series of tests. A reaction order plot is shown for I" in Figure 18. The slope of this line is 0.52 which indicates a half-order dependence on I" for the leaching reaction. This suggests that an electrochemical process other than just diffusion may involve in the reaction.

4.1.5 Effect of Electrolytes Gold dissolution using lxio-2 Nal and 5xi0"3 M I2 was examined with different concentrations of sodium sulfate and sodium chloride. These results are summarized in Table 3. The rate of gold dissolution is relatively insensitive to sodium

57

2x10~"2 M I,

a 1x10-2

5x10-3 O2x10~3
o r Q2 m HP2

10 11

Time (hrs)

Figure 16

Effect of I2 concentration on the dissolution of gold from a stationary disk using a stirring bar for agitation.

58

40
1x10~3
CM

Nal
M I,
A

1x102 M

30
5x10-3

20
2x10-3 1x10-3

10

1 0

1 1

Time (hrs)

Figure 17

Effect of I" on the dissolution of gold in the presence of 10"3 M I2.

59

Table 2: Distribution of Iodine Species as a Function of Nal

Nal (M)

-^(s)

Rate*
(R)

3 (M)

[i"] (M)

[I2]

CI|- 3

(M)

(M)

(M)

lxicr2

10"3 10"3 10"3 10"3

3.94 2.86 1.51 1.02

8.73x10"* 7.62x10"* 5.35x10"* 3.48x10"*

9.13X10"3

1.34X10-4

9.22X10"7 7.03X10"7 3.46xl0"7 1.47X10"7

5X10"3 2X10"3 lxlO"3

4.24X10"3
1.46X10"3

-4 2.52X10'

5.13X10 -4 7.48X10"-4

6 52x10"*

* Dissolution rate (/xmol/cm2 hr) .

60

1.0

0.5
01

u 0

u* _o
0.0

slope = 0.52

-0.5 -3.5

-3.0

-2.5
log [ r ]

-2.0

-1.5

Figure 18

Reaction order plot for I".

61

Table 3: Gold Dissolution Rate in the Presence of Salts

(M)

(/mol/cm2 hr)

(M)

(/xmol/cm2 hr)

1X10"3 5xl0"3 1X10"2 5X10"2 lxlO"1 5X10"1

10.68 10.85 9.85 9.09

lxlO"3 5X10"3 1X10"2 5xl0"2 1X10"1 5xl0"1

10.02 11.05 9.80 9.93

9.31 7.14

11.11 7.06

62

sulfate concentration in the range of lxio-3 to lxio-1 M. However, there is a noticeable decrease in the rate when the sodium sulfate concentration is increased to 5xio~1. The data for sodium chloride indicate similar behavior. The decrease in gold dissolution rate at the high concentration of both sodium sulfate and sodium chloride can be explained in terms of possible activity coefficient effects and the fact that iodine solubility decreases in the presence of these salts [48]. Solubility data [48] show that iodine solubility in lxio"2 M Nal drops from 6.0xl0~3 M to 2.5xl0~3 M in the presence of 1.63 M Na2S04 and in lxio"3 M Nal from 1.8X10"3 to 5.0xi0"4 at the same Na2S04 concentration.

4.1.6 Effect of Temperature Two sets of tests were performed to determine the influence of temperature on the gold dissolution rate. One set was carried out using 5xio-3 M I2 and the other using lxio-3 M I2. The concentration of Nal was fixed at lxio"2 M.

Temperatures ranging from 10 to 35C were investigated. Owning to volatility and thermal instability of iodide, experiments at temperature higher than 35C were not performed. The results are summarized in Figures 19 & 20 for 5xio"3 and lxio-3, respectively for the initial kinetic region. The initial kinetic data obtained at two hours and less resulted in well behaved first order rate plots as shown in Table 4.

63

1.0

1.5

Time (hrs)

Figure 19

Effect of temperature on the dissolution of gold in 10-2 M Nal and 5xio-3 M I2.

64

30

1.0

1.5

Time (hrs)

Figure 20

Effect of temperature on the dissolution of gold in 10~* M Nal and lxlO-3 M I2.

65

Table 4: Dissolution Rate of Gold as a Function of Temperature (iimol/cm2 hr)

[I2]
(M) 10 15

Temperature, C
20 25 30 35

5X10"3 1X10"3

6.41 3.31

8.10 5.04

8.75 6.41

11.40 7.97

15.26 9.28

18.49 11.04

66

The rate constants for the initial stages of reaction are higher than those previously reported for extended reaction time. Their values are plotted according to the Arrhenius1 law in Figure 21. The activation energies under these conditions are 31.6 kJ/mol for 5xl0"3 M I2 and 34.4 kJ/mol for lxlO"3 M I2. The high activation energy supports the possibility of an electrochemical process controlling the reaction rate. Iodine solubility as a function of temperature at 10"2 M Nal was extrapolated from the data provided by [48], as shown in Figure 22. Obviously, iodine solubility decreases linearly with the decrease of temperature from 7.4xi0"3 M at 60C to 5.3xio"3 M at 10C. However, the system studied remained within these solubility limits.

4.1.7 Effect of pH The effect of pH on gold dissolution using lxio-2 M Nal and lxio-3 M I2 with lxio-1 M Na2S04 was examined in the pH range from 2 to 10. The initial pH of this solution was

approximately 8.20. Sodium hydroxide and sulfuric acid were used to adjust the pH. As shown in Figure 23, the rate of dissolution of gold with I'/I2 is relatively insensitive to pH over this range.

4.1.8 Comparison with Cyanidation The comparison of gold leaching between iodide and

67

3.5

"D 3.0
CM

E <2.5
o ^ 2 .0

Ea = 31.6 kJ/mol

o tx
+>

- 1.5

Ea = 34.4 kJ/mol

1.0
3.2 3.3 3.4 3.5 3.6 3.7 1/f. * 10 -3 (K~1)

Figure 21

Arrhenius plots for the leaching of gold in 10"2 M Nal solution containing 5xio-3 and lxio-3 M I2, respectively.

68

8
10 ^ M

6 -

10

20

30

40

50

60

Temperature (C)

Figure 22

Solubility of iodine at 10"2 M Nal as a function of temperature.

69

6 -

1x10
CM

M Na2S04

E o o E =L

5 -

v_^ <Z> +-> a

4 -

a:

3 -

6
pH

10 11 12

Figure 23

Effect of pH on the dissolution of gold in 10"2 M Nal, 10"3 M I2 and 10"1 M Na2S04.

70

cyanide is presented in Figure 24, in which the leaching conditions are listed separately and the data for cyanide leaching is selected from [50]. Nearly the same level of gold dissolution rate was achieved in the solutions containing lxio-2 M Nal and 5xio-3 M I2 (R = 2.6xio"9 mol/cm2 sec) as in alkaline cyanide solution containing >2.7xio-3 M KCN (R = 2.8xio'9 mol/cm2 sec) and air as an oxidant. This suggests that iodide may adequately serve as a substitute for cyanide in the leaching of gold.

4.1.9 Kinetic Considerations The rate controlling step for the dissolution of gold in iodide solution is postulated to involve a mixed kinetic regime similar to that involved in the cyanidation of gold and silver [51]. Gold dissolution rate follows a linear

relationship with the square root of the disk rotation speed which may indicate that diffusion of reactants through the liquid boundary layer to the gold surface may control the rate. However, by the observation alone it is not possible to eliminate mixed kinetics (i.e. diffusion plus charge transfer) from being rate controlling. As demonstrated by the

fundamental electrochemical studies by kudryk and Kellogg [50] for the cyanidation of gold and by Hiskey and Sanchez [52] for the cyanidation of silver, the mixed kinetic region exhibits anodic dissolution rates that yield a linear relationships

71

CN

o \

>2.7x10""3 M KCN 5x10~3 M l2

o E

3 -O o >

to

tn

1x10

MI

b 3 <

Time (hrs)

Figure 24

Comparison of iodide and cyanide leaching of gold for different I2 concentrations.

72

against the square root of rotation speed. The effect of temperature reported in this study reflects a complex process possibly involving a diffusion control mechanism. At lower I2 concentrations, the experimental activation energy was determined to be 34.4 kJ/mol. While at higher I2 concentrations, a value of 31.6 kJ/mol was obtained for the leaching reaction. As pointed out by Levich [49], activation energies for aqueous diffusion in the viscous hydrodynamic boundary layer are usually in the range of 8.4 to 12.6 kJ/mol. Furthermore, it has been reported that cathodic iodine reduction

Ij

2e =

31"

(14)

in a solution of lxio-1 M I2 and 1 M KI is characterized by an activation energy of about 10.5 kJ/mol for limiting currents under laminar flow conditions [49]. The Ea values that characterize the leaching of gold in iodide/iodine solutions in this study suggest that the leaching mechanism may involve mixed kinetics. Iodine solubility was considered in determining the effects of iodine and iodide on the dissolution of gold. Iodine remained soluble for all the data at various I2 concentrations, the rate of gold dissolution increased with increasing I2 under these conditions such that

73

<*

[i- ]

The triiodide complex had the highest concentration of iodine specific capable of oxidizing gold and the rate was found to have a first order dependence on this species. A first order dependence was also observed for aqueous iodine (I2(aq>) For constant total iodine concentration, the rate increased uniformly with increasing iodide concentration according to the following relationship.

[I~]1/2

The half-order dependence on iodide suggests that a process other than strictly diffusion is controlling the rate of gold dissolution. As shown in Table 2, the predominant iodine species shifts from the triiodide to aqueous iodine as the Nal increases from lxlO"3 M. However, if the reaction order with respect to [I"] is determined for narrow range of Nal where [Ij] predominants and is essentially constant (i.e. Nal at lxio-2 and 5xi0"3), the reaction order is 0.42 with respect to [I"]. On the other hand, if [I2<aq)] predominants (i.e. Nal at 2xio~3 and lxio-3 M) the reaction order is 0.49 with respect to [I"]. Under conditions where the triiodide complex prevails (i.e. high [I"]) then the rate should vary according to

74 R = k e"Ea/RT [I3 ] [!"]1/2

(26)

If the following conditions are chosen, [Nal] = 10"2 M and [I2] = 10"3 M where Ea = 34.4 kJ/mol, it is found that the predicted rates are very close to the experimental ones as shown in Table 5. The results from this leaching work suggest that a rate controlling process other than just diffusion may control the dissolution of gold in I"/I2 solutions.

4.2 Electrochemistry

4.2.1 Cyclic Voltammetry of Gold in Halides Cyclic voltammograms of gold in halide solutions with 1 M HCIO^ using a sweep rate of 20 mV/s are shown in Figure 25. In the presence of 10"2 M NaCl, an anodic peak, corresponding to the oxidation of Au to AuCl^ is observed at about 1.0 V, followed by passivation due to the formation of an oxide film on the gold surface. After the direction of the scan was changed at 1.5 V, the current returns to zero and then shows a cathodic peak at 0.85 V. In the presence of 10"2 M NaBr, a similar shape of curve, representing the oxidation of Au to AuBr^ was observed at about 1.0 V. During the reverse scan, reactivation is observed at about 1.1 V and a cathodic peak is also obtained at about 0.75 V. Other experiments (which are

75

Table 5: Comparison of Predicted & Experimental Rates (ixmol/cm2 hr)

Predicted Nal(M) I2(M)

Experimental

10~2 10"2
M < 1

1X10"3 5X10"4 1X10"4

4.02 2.08 0.45

4.04/3.94 2.10 0.47

76

100
cm'

100
cm'

300

cm'

L_l I I I I I I I I I I I I 1I I II III 1I 1
0.4 0.6 0.8 1.0 1.2 1.4 0.4 06 0.B 1.0 1.2 1.4 0.4 0.6 0.0 1.0 1.2 1.4
E(VviSCE) E(VvSCE) E(VvtSCE)

Figure 25

Cyclic voltammograms of gold in solutions containing 10"2 M NaCl, NaBr, and Nal respectively and 1 M HC104 with a scan rate of 20 mV/s and a static electrode.

77

not presented here) show that the reverse scan almost traced the forward scan and no cathodic peak was found when a stirring bar was used to agitate the solution under the same conditions. This indicates strong reactivation. Thus,

reactivation is believed to be caused by rapid dissolution of the oxide film. It should be noted that the anodic peak for the oxidation of Au to AuClj or AuBrj might be merged into the one for AuCl^ or AuBr^ , respectively, because the

difference of reduction potential between Au(I) and Au(III) species is very small (< 60 mV) [46]. In the presence of 10"2 M Nal, the anodic scan records a peak at about 0.4 which clearly represents the oxidation of Au to Aulj The peak current density is 1.2 mA/cm2. This value is greater than that for oxidation of Au to Au(III) in either chloride or bromide at 10"2 M. A region of passivation appears up to 0.9 V, afterwhich a large anodic peak is obtained at 1.1 V for Au to Aul^ . Peak current density of the AuI^T is 4.2

mA/cm2 (ip of this wave was measured using the decaying current of first wave as the baseline [46]) . This indicates the strong oxidation capability of iodide and this phenomenon is

consistent with the discussion of the Eh-pH diagram for goldiodide system. The electrode was then passivated again due to the formation of an oxide film on the gold surface. During the reverse scan, a cathodic peak was also observed at

approximately 0.85 V.

Figure 26

Cyclic voltammograms of gold in 1 M HC10A with a scan rate of 20 mV/s and a static electrode.

79

4.2.2 Cyclic Voltammetry of Gold in Various [Nal] Figure 26 shows the cyclic voltammogram of gold in pure water where 1 M HC104 is added for conductivity. The anodic peak at 1.3 V represents the formation of Au203 and the subsequent peak represents oxygen evolution. On the reverse scan, a relatively large cathodic peak is produced at 0.9 V, indicating that the oxide film on the surface of the electrode is easily reduced. This is similar to that discovered by Nicol and Schalch [32]. Cyclic voltammograms of gold in various concentrations of Nal with 1 M HC104 and a stirring bar for agitation are shown in Figure 27. The anodic oxidation of gold in 10~3 and 10~2 M Nal are shown in Figure 27a and 27b, respectively, and indicate initial oxidation of gold at about 0.5 V followed by a plateau region where diffusion is controlling. The general shape of the voltammogram was essentially the same at 5xio"3 M Nal. Limiting current density values in this region are 0.51, 2.92 and 3.99 mA/cm2 for lxlO"3, and 5X10"3 and lxio-2 M Nal, respectively. Further oxidation to the Au(III) species takes place above 1.0 V. Increasing the concentration to 10"1 M Nal resulted in the scan shown in Figure 27c. It should be noted that nearly identical shape was obtained for a scan at 5xio-2 M Nal. The position of the anodic peak for Au(I) occurs at about 0.45 V for both concentrations. The peak current densities are 31.57

80

10 M Nol

10 M Nol

04

oe

oa to 1 .2 E (Vvt SCEI

1.4

04 06 08 10 1.2 14
E (Vvt SCE)

>2 04 06 06 10 12 14
E
(Vi

SCE)

(a)

(b)

(c)

Figure 27

Cyclic voltammograms of gold in various concentrations of Nal and 1 M HC104 with 20 mV/s and a stirring bar for agitation.

81

and 57.62 mA/cm2 for 5xi0'z and lxio-2 M Nal, respectively. The electrode at these concentrations indicates prepassive

behavior followed by passivation and a small rise in current density at above 1.1 V for formation of Au(III) species. Passivation was only observed at the higher concentrations of Nal. It is believed that passivation of the gold electrode is caused by formation of solid iodine on the electrode surface. It should be noted that the oxidation of iodide to solid iodine occurs at a standard half cell potential of 0.54 V (SHE). The region between 0.6 and 1.0 V where current density is independent of potential is a region where the reaction is controlled by diffusion through the solid iodine film.

4.2.3 Anodic Polarization of Gold in Different [Nal] Anodic polarization curves of gold in different

concentrations of sodium iodide in 4xio~1 M Na2S04 using a scan rate of 1 mV/s and a rotating speed of 500 rpm are shown in Figure 28. Natural pH is approximately 6.2 to 6.5 in these solutions. At concentrations up to 3xio-3 M Nal, two plateaus and no passivation were found. Above 0.5 V, where Au(I) was formed as discussed earlier, the current density is relatively insensitive to increase in potential until about 0.8 V. This is believed to be a region controlled by boundary layer diffusion. At above 0.8 V, the current density starts to rise as Au(I) is oxidized to Au(III). Finally, a second plateau is

82

5r

5XI0"2M

3 X I0~3 M 2X I0~3 M 5XIO"3M

IXIO"3M

0.5

0.6 0.7 E (VvsSCE)

0.8

Figure 28

Anodic polarization curves of gold in different concentrations of sodium iodide and 4xio"1 M Na2S04 using a scan rate of 1 mV/s and a RDE at 500 rpm.

83

reached. At higher concentrations of Nal (i.e. 10~2 M Nal), one anodic peak appears at 0.55 V followed by passivation and diffusion through a solid layer. This transition takes place at about 4xio-3 M Nal. The voltammogram at this concentration indicates a broad diffusion region followed by passivation at higher potentials. The peak becomes sharper and moves to lower potentials indicates as that Nal the concentration oxidation of increases. gold at Again the this

higher

concentrations of Nal resulted in the formation of a passive film on the gold surface. It is interesting to compare the electrochemical results at 10"2 M Nal with and without disk rotation as shown in Figure 29. The initial oxidation of gold at 500 rpm yields a higher Au(I) peak current density, prepassive behavior, and a broad diffusion region. With rotation, the rate of I" transported to the surface is relatively high and oxidation to solid iodine can result in film formation at the electrode. Furthermore, Aulj is transported away from the electrode at a relatively fast rate and subsequent oxidation to Aul^ is not detected when the surface film is present. The oxidation of gold without rotation first produces a Au(I) peak with very low current density because of the locally depleted I". The depletion of iodide also prevents strong passivation by solid iodine. A noticeably higher Au(III) peak is found at about 0.95 V. This indicates the accumulation of Aulj at the surface and

84

<5

500 rpm z
UJ
3

o2

without disk rotation

3 01-

o 0.3

0.4

0.5

0.6 0.7 E (VvsSCE)

0.8

0.9

Figure 29

Comparison of anodic polarization curves of gold at 10~2 M Nal with and without disk rotation.

85

subsequent oxidation to Aul^. Similar experiments were performed using 1 M HC104 instead of 4xio_1 M Na2S04 as electrolyte. Essentially the same results were observed with the higher iodide concentrations. However, only one plateau representing the oxidation of Au to Au(I) was found at lower concentrations. Under these

conditions, the oxidation to Au(III) probably occurs at higher potentials. Schematic and general with and diagrams of electrochemical

processes for gold

without disk rotation are

summarized in Figures 30 and 31. In general, at low iodide concentration and with rotation the oxidation of gold occurs sequentially. However, at the high iodide concentration and with rotation a passive film of solid iodine forms. Without rotation, passive film does not occur because of the low degree of iodide transported to the surface, and the oxidation of gold occurs by a sequential process with the second wave higher than that with rotation because of the accumulation of Aulj at the surface.

4.2.4 Effect of Disk Rotating Speed Results for the anodic oxidation of gold as a function of disk rotating speed are shown in Figures 32 and 33 for 2xi0~3 and lxio"2 M Nal, respectively. In general, the plateau regimes and the oxidation peaks increase with increasing disk rotating

86

WITH ROTATION

Au + 21" - Aulj + e"

Low [I"] Low Potential (1st plateau)

AuII

Au + 21* - Aulj + e" Aulj + 21" - Aul^ + 2e"

Low [I"] High Potential (2nd plateau)

Au + 21" - Aulj + e"

High [I"]

^2(5) Figure 30 Schematic diagrams of electrochemical processes for gold without rotation

WITHOUT ROTATION

I~ conc. small at the surface

Au + 21" - Aui: +
Au

Aui; + 21" - Aui; + 2e" iUlT

AuIT

Figure 31 Schematic diagram of of electrochemical processes for gold without rotation.

88

2X10

MNal 700 rpm

600
500 400 300

200

0.6 0.7 E (VvsSCE)

Figure 32

Effect of disk rotating speed on the anodic oxidation of gold at 2xio~3 M Nal.

89

I0"2 M Nal inflection point

700rpm 600 >500 400 300 200

0.6 0.7 E (VvsSCE)

Figure 33

Effect of disk rotating speed oxidation of gold at 10"2 M Nal.

on the anodic

90

speed from 200 to 700 rpm. According to the Levich equation [49] the limiting current density (it, A/cm2) is proportional to the one half power of the rotating speed (o1/2, rad/sec)

it = 0.62nF D2/3 0)1/2 V_1/6 C0

(27)

where n is the number of electrons per molecule oxidized or reduced; F is the Faraday constant (coulomb/mol), D is the diffusion coefficient (cm2/sec), v is the kinematic viscosity (cm2/sec) and C0 is the bulk solution concentration (mol/cm3) . As shown in Figure 34, a plot of limiting current densities for the first plateau region taken at 0.65 V (almost the same slope can be obtained at 0.60 or 0.63 V) using 2xio-3 M Nal yields an excellent correlation with o1/2. The diffusion coefficient can be calculated for a one electron process using the slope of this line. Its value of D as determined from these data is 1.35xio-5 cm2/s. This value is quite close to the diffusion coefficient reported for sodium iodide at 25C [53]. In the first plateau region, the reaction is controlled by a boundary layer diffusion process. Limiting current density values for the second plateau were determined by the procedure described by Bard and Faulkner [46]. Here values at 0.95 V are plotted versus o1/2 also presented in Figure 34. A fairly good correlation is obtained for these data. The noticeably low slope of this plot reflects the low concentration of the

91

CM

^ 1.5
o >

2x10"3 M Nal

E
<3 1.0
c o O -+-< c <D L_ L. 0.5 3 o D C

CJV2( S-V*)

Figure 34

Plot of limiting current densities for the first (0.65 V) and the second (0.95 V) plateau regions as a function of <i>1/2.

92

species that is being oxidized in the second wave. Data for lxio-2 M Nal (Figure 33) show that the limiting current densities (as determined from the inflection point to the plateau region) are relatively insensitive to rotating speed. This confirms that the electrode reaction is controlled by diffusion through a solid iodine film at these potentials for high Nal concentrations as discussed in the previous section. Table 6 lists those limiting current densities taken from two different tests.

4.2.5 Reduction of Iodine Species on Gold The effect of iodine concentration on its reduction on gold is depicted in Figure 35. Cathodic current densities attain well defined limiting values for the iodine

concentration between lxio-3 and 5xio~3 M with 10"2 M Nal at a rotating speed of 500 and a scan rate of 1 mV/s. From these results, it is possible to calculate the reaction order with respect to Ij concentration. At both large cathodic

overpotentials in the limiting current region and small overpotentials (i.e. 0.35 V), the reaction was found to follow a first order dependence on Ij. These results confirm the first order effect for Ij observed during the kinetic study. Furthermore, the diffusion coefficient for reduction of Ij as calculated from these results ranged from 0.9xi0~5 to 1.18xi0"5 cm2/s.

93

Table 6: Limiting Current Densities Taken from the Inflection Point to the Plateau Region as a function of Rotating Speed (im, mA/cm2)

Rotating Speed, rpm 200 300 400 500 600 700

iUn) (mA/cm2) iUin(mA/cm2)

1.15 0.80

1.28 1.10

1.03 1.10

1.17 1.46

1.48 1.43

1.58 1.25

94

2
(/)

0L

0.0

0.2 0.3 E (VvsSCE)

0.4

Figure 35

Effect of iodine concentration on its reduction on gold at 10"2 M Nal and a RDE at 500 rpm.

95

Additional scans of reduction on gold at constant I2 concentration of 10"3 M and different Nal concentrations were also carried out. However, the reduction of iodine species on gold is relatively insensitive to iodide concentration in the range lxio-3 to 3xio-3 M Nal as shown in Table 7.

4.2.6 Mixed Halide System Anodic polarization curves of gold were obtained using mixed halide solutions. Figure 36 depicts scans using 10~2 M NaI/10"2 M NaBr, 10-2 M NaI/10"2 M NaCl, and 10"2 M NaBr/10"2 M NaCl at 500 rpm and 1 mV/s. It is apparent that iodide plays the major role in the mixed halide solutions. In fact, there is very little difference between the curves for Nal/NaBr and Nal/NaCl as compared with the system containing only 10"2 M Nal. With the addition of NaBr or NaCl in the Nal solution, the gold oxidation peak shifts to slightly lower potentials. The mixed NaBr/NaCl system appears to be the same as the single halide system shown in the scan in Figure 25.

4.2.7 Effect of Sweep Rate The effect of sweep rate on the anodic polarization of gold is displayed in Figure 37. Here the scan rate ranged from 1 to 50 mV/s using 10"2 M Nal concentration and 500 rpm rotating speed. As the scan rate increases., the oxidation potential shifts to higher values indicating an irreversible

96

Table 7: Limiting Current Densities (mA/cm2) for the Reduction of Iodine Species on Gold as a Function of Nal Concentration Using 10~3 M l2

Limiting Current Density, iUm (mA/cm2) E,, V Nal, M 0 E2, V 0.5 E3, V 1

0 lxlO"3 3X10-3 lxlO-2

0.592 0.683 0.742 0.722

0.588 0.683 0.742 0.714

0.580 0.683 0.730 0.702

97

IO"2M Nal/NaCI 5r IO"2M Nal/NaBr

> 3

UJ

10

M NaBr/NaCI

0.2

0.3

0.4

0.5 0.6 0.7 E (VvsSCE)

0.8

0.9

Figure 36

Anodic polarization curves of gold in mixed halide systems.

98

IO~2MNaI
CVJ

50 mV/s

20

Qr 2

0.2 E (VvsSCE)

Figure 37

Effect of sweep rate on the anodic oxidation of gold at 10~2 M Nal and a RDE at 500 rpm.

99

reaction. At the slower scan rates, up to 10 mV/s, only one gold oxidation peak is observed followed by passivation as discussed previously. At faster scan rates, Au is first oxidized to Au(I) and then a region where boundary layer diffusion occurs is developed. After that, Au(I) is further oxidized to Au(III). This indicates that if the scan rate is fast enough, the solid iodine film does not form at the electrode surface and this results in the sequential oxidation of Au to Au(I) to Au(III).

100

CHAPTER FIVE CONCLUSIONS

5.1 Leaching of Gold

1. Gold dissolution in the presence of iodide using iodine as an oxidant proceeds by the following reaction: 2Au + I" + Ij = 2AuIj

2. Dissolution of gold in I~/I2 solutions follows the first order kinetics.

3. The first order rate is proportional to square root of the disk rotation speed.

4. The reaction is first order with respect to the triiodide complex and half-order with respect to iodide.

5. Oxidants such as oxygen and hydrogen peroxide have almost no effect on the gold dissolution with iodide.

6. Gold dissolution is insensitive to the presence of Na2S04 and NaCl and is also insensitive to pH over the range pH 2 to
10.

101

7. Of the halogens, iodide has the strongest capability of dissolving gold in aqueous solutions. Its dissolution rate has the same level comparing with that of gold cyanide system.

8. At low I2 concentrations, the experimental activation energy was determined to be 34.4 kJ/mol. While at higher I2 concentrations, a value of 31.6 kJ/mol was obtained for the leaching reaction.

9. Gold dissolution rate in 5xi0"3 M I2 and lxio-2 M I" is 2.6xi0"9 mol/cm2 sec which is comparable to that in 2.7xio-3 M KCN with air as an oxidant (i. e. typical cyanidation conditions).

5.2 Electrochemical Behavior

1.

Cyclic

and

linear

sweep

voltammograms

indicate

the

sequential oxidation of gold in iodide solutions where both Au(I) and Au(III) iodide species form. This phenomenon is in agreement with the Eh-pH diagram of the gold-iodide system. On the other hand, only anodic oxidation of gold to Au(III) species was found in either bromide or chloride solution at 1CT2 M NaBr or NaCl.

2. The anodic oxidation of gold occurs at noticeably higher

102

current densities in iodide than that in either bromide or chloride. This observation confirms the strong complexing ability of iodide with gold.

3. At low concentrations of Nal, it was found that gold is initially oxidized to Au(I) and then attains a plateau region where boundary layer diffusion controls the reaction.

Afterwhich, Au(I) is further oxidized to Au(III). The reaction sequence is also observed at faster scan rates using higher sodium iodide concentrations. While at low scan rates and higher concentrations of Nal, only one oxidation peak is observed followed by passivation resulting from the formation of a solid iodine film on the electrode surface. In this region, the reaction is controlled by diffusion through the surface film.

4. Results for the anodic polarization of gold as a function of disk rotating speed clearly show that limiting current densities for both oxidation steps are proportional to half power of disk rotating speed in 2xio~3 M Nal. For oxidation of gold to Aulj i a diffusion coefficient of 1.35X10"5 cm2/s was determined for iodide.

5. Reduction of iodine species on the gold surface follows a first order dependence on Ij which confirms the first order

103

effect observed during the kinetic study.

6. The polarization behavior of mixed halides indicates little difference between Nal/NaBr and Nal/NaCl and is essentially equivalent to the behavior of a NaT system.

104

REFERENCES

1.

R. J. Puddephatt, The Chemistry of Gold (Elsevier Scientific Publishing Co., New York, 1962).

2.

J. S. MacArthur, (1887).

R. W. Forrest and W. Forrest,

British Patent

14,

174

3.

J. S. MacArthur, R. W. Forrest and W. Forrest, U. S. Patents 403, 202, and 418, 137 (1889).

4. 5.

A. Hakansson and L. Johansson, Chem. Scr., 1975, 7, 201-203. J. B. Hiskey and V. P. Atluri, Mineral Processing and Extractive Metallurgy

Review, 1988,
6. 7.

4,

95-134.

N. P. Finkelstein and R. D. Hancock, Gold Bull., 1974, 7, 72-77. L. G. Sillen and A. E. Martell, Stability Constants of Metal Ion Complexes (The Chemical Society, London, 1964).

8.

W. M. Latimer, The Oxidation States of the Elements and Their Potentials in

Aqueous Solution (Prentice-Hall, Englewood Cliffs, New Jersey, 1952), 2nd

Ed. 9. T. Sano, H. Hori, M. Yamamoto, and T. Yasunaga, Bull. Chem. Soc. Jpn., 1984, 2, 575-576. 10. C. A. Schaeffer, U. S. Patent 267,723 (1882). 11. C. G. Fink and G. L. Putnam, U. S. Patent 2,283,198 (1940).

105
12. R. P. Homick and H. Sloan, U. S. Patent 3,957,505 (1976). 13. S. K. Bahl and G. L. Leach, U. S. Patent 4,190,489 (1980). 14. R. H, Sergent and K. N. Thanstrom, U. S. Patent 4,637,865 (1987). 15. A. Dadgar, J. Metals, 1989, 41(12), 37-41. 16. K. J. McGrew and J. W. Murphy, U.S. Patent 4,557,759 (1985). 17. J. W. Murphy, U. S. Patent 4,734, 171 (1988). 18. T. Erdey-Gruz and M. Volmer, Z. Phys. Chem. A, 1930, 150, 203-213. 19. A. N. Frumkin, Z. Phys. Chem. A, 1933, 164, 121-133. 20. L. Kiss,

Kinetics of Electrochemical Metal Dissolution

(Elsevier Science

Publishing Co. Inc., New York, 1988). 21. M. J. Nicol, Gold Bull., 1980, 13, 46-55. 22. M.J. Nicol, Gold Bull., 1980, 13, 105-111. 23. G. Just and R. landsberg, Electrochin. Acta, 1964,

9,

817-826.

24. T. Heumann and H. S. Panesar, Z. Phys. Chem., 1966,

229,

84-97. 279-291.

25. J. N. Gaur and G. M. Schmid, J. Electroanal. Chem., 1970, 26. J. H. Gailego, C. E. Castellano, A. J. Callandra and

24,

A. J. Arvia,

J.

Electroanal. Chem., 1975, 66, 207-230.

27. J. J. Podesta, R. C. V. Piatti and A. J. Arvia, Electrochim. Acta, 1979, 24, 633-638. 28. R. P. Frankenthal and D. J. Siconolfi, 1192-1196.

J. Electrochem. Soc.,

1982,

129,

106
29. M. D. Benari, G. T. Hefter and A. J. Parker, Hydrometallurgy, 1983, 367-389. 30. E. Schalch and M. J. Nicol, Gold Bull., 1978, 11, 117-123. 31. E. Schalch, M. J. Nicol and B. D. Charlton,

10,

Chloride Hydrometallurgy,

Proceedings, Brussels, 1977, 336-356.

32. M. J. Nicol, 1844, 1981. 33. M. J. Nicol, 1846, 1981. 34. E. Schalch, M. J. Nicol, J. W. Diggle, B. D. Charlton and J. P. H. Vaessen,

National Institute for Metallurgy, Johannesburg,

Report No.

National Institute for Metallurgy, Johannesburg, Report No.

National Institute for Metallurge, Johannesburg, Report No. 1848, 1981.

35. B. H. Loo, J. Phys. Chem., 1982, 86, 433-437. 36. M. A. Tadayyoni, P. Gao and M. J. Weaver, J. Electroanal. Chem., 1986,

198,

125-136.

37. M. M. Qureshi, Pak. J. Sci., 1984, 33, 31-33. 38. A. Davis and T. Tran, Presentation at the 118th SME Annual Meeting, Vegas, Nevada, 1989. 39. T. Takamura, K. Takamura and E. Yeager, J. Electroanal. Chem., 1971, 279-291. 40. J. Clavilier and N. V. Huong, J. Electroanal. Chem., 1973, Las

29,

41,

193-199. 325-331.

41. S. H. Cadle and S. Bruckenstein, J. Electroanal. Chem., 1973,

48,

107
42. V. G. Levich, Acta Physicochim. URSS, 1942, 17, 257-302. 43. V. G. Levich, J. Phys. Chem. (U.S.S.R.), 1944, 18, 335-355. 44. F. Opekar and P. Beran, J. Electro anal. Chem., 1976, 45. A. C. Riddiford,

69,

1-105.

Advances in Electrochemistry and Electrochemical

Engineering, Interscience, New York, 1966, 4, 47-116.

46. A. J. Bard and L. R. Faulkner, Electrochemical Methods Sons, New York, N. Y., 1980). 47. R. N. Adams, Electrochemistry at Solid Electrodes York, 1969). 48. H. L. Silcock, Solubilities of Inorganic and Organic Compounds (Pergamon Press, 1979), Vol. 3, Part 1. 49. V. G. Levich, Physicochemical Hydrodynamics Cliffs, New Jersey, 1962). 50. V. Kudryk and H. H. Kellogg, J. Metals, 1954, 5, 541-548. (Prentice-Hall, Englewood (Marcel Dekker, New (Jhon Wiley and

51. M. E. Wadsworth, Mining Engineering, 1985, 6,557-562. 52. J. B. Hiskey and V. M. Sanchez, J. Appl. Electrochem., in press. 53. T. W. Chapman, PhD Thesis, University of California-Berkeley, 1967, p. 56.