Heterogeneous Equilibria in the

Au-CN-H20 and Ag-CN-H20 Systems

T. XUE and K. OSSEO-ASARE

The equilibrium relationships in the systems Au-CN-H20 and Ag-CN-HzO have been investigated
with the aid of the DIAGRAM computer program and thermodynamic data taken from the literature.
On the basis of stability diagrams such as Eh-pH, log[Me]-pH, and log[CN]-pH, a discussion is pre-
sented of the behavior of gold and silver in cyanide solutions. It is shown that gold and silver have
similar behaviors in cyanide media; both metals exhibit wide solubility domains with di-cyanide
complexes predominating. Solid AgCN is stable only in solutions of low pH and high silver/cyanide
ratio; the species Ag(CN)~- and Ag(CN) 3- form only in concentrated cyanide solutions.

I. INTRODUCTION
THE dissolution of gold and silver in cyanide solutions
is an electrochemical process, as described by Eqs. [1]
through [3]:
Au + 2CN = Au(CN)~- + e
Ag + 2CN = Ag(CN)~ + e
02 + 4H + + 4e = 2H20
In general, the dissolution of a metal in cyanide solution
will be affected by many factors such as cyanide and metal
concentrations, pH, and the electrochemical potential. For
example, according to previous electrochemical investiga-
tions, ~-6 the rate of the anodic dissolution of gold increases
with increasing potential at low potentials, i.e., the reaction
is in an active region. However, when the potential reaches
a certain value, the dissolution rate decreases sharply, i.e.,
passivation occurs. According to passivation theory,7 such a
phenomenon is a result of the formation of an oxide or the
adsorption of a species on the surface. In order to predict the
feasibility of dissolution reactions and to determine which
species or compounds may correspond to the observed pas-
sivity, a thorough analysis of the aqueous chemistry and
thermodynamics is necessary.
In this paper, the solution chemistry of the gold- and
silver-cyanide systems is analyzed in terms of aqueous sta-
bility diagrams. Logarithmic activity-activity diagrams,
such as Eh-pH, log[Metal]-pH, and log[Ligand]-pH dia-
grams make it possible to predict on a thermodynamic basis
and for a given element, the equilibrium states of all the
possible reactions between the element, its ions, and its
solid and gaseous compounds in the presence of water.
Therefore, these diagrams have direct significance to aque-
ous chemical processes in fields such as corrosion science,
hydrometallurgy, mineral processing, geochemistry, and en-
vironmental pollution control.~
Pourbaix constructed Eh-pH diagrams for a large number
of metals, including gold and silver in aqueous medlar Sub-
sequently, in order to investigate the behavior of gold and
silver in cyanide solution, a few papers appeared which
T. XUE, Graduate Research Assistant, and K. OSSEO-ASARE. Pro-
fessor, are w~th the Metallurgy Program, Department of Materials Scmnce
and Engineering, The Pennsylvama State UmversW, Umverslty Park,
PA 16802,
Manuscnpt submitted September 29, 1983
METALLURGICALTRANSACTIONS B
dealt with the Eh-pH diagrams for Au-CN-H:O ~~and Ag-
CN_HeOt~ 12 systems. These previous results are helpful in
understanding the reactions occurring during the cyanida-
tion process. However, these earlier studies were limited in
the number of variables or species considered and in the
[1] range of activities or potentials utilized. For example, Deitz
and Halpern H considered only the lower potential region
[2] (Eh <- 0.4 volt) of the Ag-CN-H20 system.
The work presented here is an extension of the recent
[3]
paper 13 on the solution chemistry of cyanide leaching sys-
tems in which selected diagrams were presented for several
Me-CN-H20 systems (Me = Au, Ag, Cu, Ni, Co, Fe, Zn).
It involves the use of computer techniques to construct
a variety of logarithmic activity-activity diagrams over a
wide range of solution conditions for the Au-CN-H20
and Ag-CN-H,O systems. The computer program used
here. DIAGRAM, has been described by Osseo-Asare and
Brown.~4 It has been successfully used in the analysis of
the solution chemistry of ammonia 15~6and tungsten ~7hydro-
metallurgy. By using this program, not only can one
construct Eh-pH diagrams, but other diagrams such as
log[Me]-pH and log[CN]-pH can also be generated readily.
As a result, the predominance areas of the different species
and the solid/solution equilibria in the cyanide system can
be shown and analyzed completely. This study provides a
background for the electrochemical polarization studies
presented and discussed in a following paper.IS In addition,
it is hoped that the results presented here will be of interest
to those concerned with gold and silver deposition from
cyanide solutions. 19,20
II. GOLD, SILVER, AND THEIR COMPOUNDS
A. Gold and Its Compounds
Gold, the most noble of metals, is chemically unreactive
and is not easily affected by water or most acids, nor at-
tacked by oxygen and sulfur. This metal is usually found in
one of three oxidation states: native (Au~ aurous (Au(I)),
and auric (Au(III)). 2~22In its compounds, gold as Au(I) and
Au(III) has the electronic configurations of d m and d ~, re-
spectively, and exhibits mainly a covalent character because
of the high ionization potentials of the two states of oxida-
tion. Au(I) generally exhibits linear two-fold coordination
while Au(III) commonly exhibits four-fold planar coordina-
tion. Aurous oxide, Au20, the oxide AuO, and auric acid
VOLUME 16B, SEPTEMBER 1985--455
AuO(OH) are mentioned in the literature. :3 However, few and an ionic strength equal to zero except for that of the
details are available on the nature and properties of these Ag(CN) 3- complex, 3~ which in the absence of the corre-
compounds. Most of the auric compounds are powerful sponding data, is taken at 30 ~ and an ionic strength of 1.0.
oxidizing agents. Gold hydroxide, Au(OH)3, can be gen- In general, the difference between the stability constant data
erated by the addition of alkali hydroxide to solutions con- at zero and unit ionic strength tends to be very s m a l l ] 1
taining chloroaurate ion, AuC14. The hydroxide can be
dehydrated to give auric acid, AuO(OH), and ultimately
the oxide Au203. However, the peroxide AuO2 can appear III. RESULTS AND DISCUSSION
only on gold which is anodically polarized in acid or alka-
line solutions. 22'24 A, Eh-pH Diagrams
Only complex species of gold (I) and gold (III) occur in Eh-pH diagrams for the A u - H 2 0 and A g - H 2 0 systems at
aqueous solution. The ( + 3 ) valence state produces species 25 ~ are shown in Figures 1 and 2, respectively, with
which are generally more stable than those of the ( + 1) state [Au] = IAg] = 10 3 kmol m -3. Here [Au] or [Ag] denotes
except the remarkably stable cyanide complex of gold (I). the concentration of total dissolved metal ion in the system.
The hydrolysis of Au(III) leads to the formation of a se- These results are in general agreement with Pourbaix's
ries of hydroxo species: Au(OH) ~3-', from Au(OH) 2- to work. 9 For the gold system, however, the stability region of
Au(OH)~-, depending upon the pH value. 25 H , A u O y in Pourbaix's diagrams is replaced by Au(OH)~-.
G o l d d i s s o l v e s r e a d i l y in c y a n i d e s o l u t i o n , g i v i n g Both gold and silver are noble metals, as can be seen from
Au(CN)s as the only stable complex ion. Although the the diagrams. Their domains of stability cover a very large
formation of Au(CN)4 has been recognized, 26 this species
is apparently very unstable and so far no reliable thermo-
dynamic data have been presented. Solid gold cyanide,
AuCN(s), can be obtained by heating the acid H[Au(CN)2] Table I. Selected Equilibrium Constants
at 110 ~ It is a yellow powder and is sparingly soluble for the Au-CN-H20 System at 25 ~
in water, ethanol, or ether, but readily soluble in aqueous Reactions log K Ref.
cyanide solution. 26
AI1203 q'- 6H + + 6e = 2Au + 3H:O 153.43 9
AIlO2 -b 4H § + 4e = Au + 2H20 118.40 9
B. Silver and Its Compounds Au(OH)~ + 3H- + 3e = Au + 3H_,O 73.94 9
As one of the noble metals, silver has great chemical Au- + e = Au 28.62 9
AU3* 4- 3e = Au 76.03 9
stability and corrosion resistance. It is found in the native
Au(OHI z+ + H* + 3e = Au + H20 77.95 25
state in nature just as is gold. In most of its important Au(OH)~ + 2H- + 3e = Au + 2H20 78.45 25
compounds silver is univalent, i.e., Ag(I), which has the d 10 Au(OH)3(aq) + 3H- + 3e --- Au + 3H20 79.45 25
electronic configuration. As a result, A g : O , which is brown Au(OH)4 + 4H- 4- 3e = Au + 4H,O 91.22 25
in color, is the most common silver oxide. In acid or alkaline Au(OH)~- + 5H" + 3e = Au + 5H20 104.58 25
media containing powerful oxidizing agents, or at high oxi- Au(OHt 3- + 6H- + 3e = Au + 6H,O 120.55 25
dation potential, the black oxides AgO and Ag203 can be AtI(CN)2 + e = Au + 2CN- - 9.48 30
obtained by the oxidation of A g + 27 Au(CN)z + 2H * + e = Au + 2HCN 8.94 30
In aqueous solution, the ( + 1) oxidation state of silver is H + + CN- = HCN 9.21 31
stable, while the ( + 2 ) and ( + 3 ) states are powerful oxidiz- HzO = H + + OH- -14.0 31
02 + 4H" + 4e = 2H20 83.08 31
ing agents which react with water itself. The ( + 1) silver ion
forms many slightly soluble compounds and slightly ionized
complex ions. 28 The hydrolysis of silver (I) is simple, lead-
ing to only two species A g ( O H ) ( a q ) and A g ( O H ) ; . :s Table II. Selected Equilibrium Constants
Silver dissolves readily in cyanide solution. Solid AgCN. for the Ag-CN-H20 System at 25 ~
which is colorless, can be made by reacting equivalent quan- Reactions log K Ref.
tities of silver nitrate and potassium cyanide in aqueous
ammoniacal solution, followed by ammonia removal, e.g., Ag20 + 2H § + 2e = 2Ag + H2O 39.70 9
AgO + 2H § + 2e = Ag + H2 43.51 9
by bubbling air through the aqueous solution. 26 Usually, the
Ag_,O3 + 6H + + 6e = 2Ag + 3H20 140.04 9
main cyanide complex ion of silver is A g ( C N ) y . The higher Ag* + e -= Ag 13.50 9
complexes, Ag(CN)~- and Ag(CN) 3-, are stable only at Ag:- + 2e = Ag 46.98 9
high cyanide concentration. 29 Ag(OH)(aq) + H ~ + e = Ag + H20 25.50 25
Ag(OH)2 + 2H ~ + e = Ag + 2H20 37.51 25
C. Thermodynamic Data AgCN(s) + e = Ag + CN -2.16 31
Ag(CN)s + e = Ag + 2CN- -6.90 31
To construct stability diagrams, equilibrium constants are Ag(CN)~- + e = Ag + 3CN- -7.90 31
needed for the reactions of interest. Tables I and II present Ag(CN) 3 + e = Ag + 4CN -7.30 31
the thermodynamic data which were used for the calcu- Ag(OHCN)- + H- + e = Ag + CN- + H20 14.30 31
lations. As one source usually does not contain enough AgCN(s) + H § + e = Ag + HCN 7.05 31
information for all the species concerned, data used here Ag(CN)2 4- 2H* + e = Ag + 2HCN 11.52 31
come from several sources: Pourbaix, 9 Sillen and Martell, 3~ Ag(CN)~- + 3H * + e = Ag + 3HCN 19.73 31
Baes and Mesmer, 25 and Smith and Martell. 31 The log K Ag(CNh3 + 4H ~ + e = Ag + 4HCN 29.54 31
Ag(OHCN)- + 2H" + e = Ag + HCN + HzO 23.51 31
values for all the cyanide complex species are taken at 25 ~

456--VOLUME 16B, SEPTEMBER 1985 METALLURGICALTRANSACTIONSB