See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/225470158

Mechanism of gold dissolving in alkaline

thiourea solution

Article in Journal of Central South University of Technology · January 2007

DOI: 10.1007/s11771-007-0094-0

CITATIONS READS

4 371

2 authors, including:

Yun-yan Wang
Central South University
39 PUBLICATIONS 244 CITATIONS

SEE PROFILE

All content following this page was uploaded by Yun-yan Wang on 03 December 2014.

The user has requested enhancement of the downloaded file.

J. Cent. South Univ. Technol. (2007)04−0485−05
DOI: 10.1007/s11771−007−0094−0

Mechanism of gold dissolving in alkaline thiourea solution

CHAI Li-yuan(柴立元), WANG Yun-yan(王云燕)

(School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China)

Abstract：Reaction mechanism of gold dissolving in alkaline thiourea solution was studied by electrochemical methods, such as
cyclic voltammetry, chronopotentiometry, AC impedance, linear sweep voltammetry. Apparent activation energy of anodic process of
gold electrode dissolving in alkaline thiourea solution is 14.91 kJ/mol. Rate determining step is the process of gold thiourea complex
diffusing away from electrode surface to solution. The results of AC impedance and chronopotentiometry indicate that thiourea
adsorbs on gold electrode surface before dissolving in solution. There does not exist proceeding chemical reactions. Formamidine
disulfide, the decomposed product of thiourea, does not participate the process of gold dissolution and thiourea complex. Species
with electro-activity produced in the process of electrode reaction adsorbs on the electrode surface. In alkaline thiourea solution, gold
dissolving mechanism undergoes the following courses: adsorption of thiourea on electrode surface; charge transfer from gold atom
to thiourea molecule; Au[SC(NH2)2]ads+ receiving a thiourea molecule and forming stable Au[SC(NH2)2]2+; and then Au[SC(NH2)2]2+
diffusing away from the electrode surface to solution, the last step is the rate-determining one.

Key words: gold; alkaline thiourea; dissolution mechanism

Oxidization of thiourea into formamidine disulphide,

1 Introduction
Dissolution of gold in thiourea solution was
reported firstly in 1941[1], and then the theory and
process of gold leaching in thiourea solution have been
most widely studied throughout the world mainly
because thiourea is not detrimental to the environment,
non-toxic to humans, and the dissolution of gold in
thiourea solutions is much faster than in cyanide
solutions[2−9]. However, there is little industrial
application of gold leaching in thiourea solution, except
higher consumption of thiourea, insufficient
investigation on gold leaching in thiourea solution is also
the limitation[10−13]. Since gold leaching in the alkaline
thiourea solution is still at the developmental stage, as far
as studies of mechanism there is little report besides our
group’s research. Therefore, a better and further
understanding of the foundation will play an important
role on guiding application industrially. Firstly,
dissolution mechanism of gold electrode in alkaline
thiourea solution should be make clear, which can offer
some guidance for mechanism of gold leaching from
ores in alkaline thiourea solution.
In alkaline thiourea solution, combining the
property of thiourea, the process of gold dissolving in
alkaline medium may be expressed as: Diffusion of
thiourea to electrode surface; Adsorption of thiourea on
electrode surface, Au+SC(NH2)2→Au[SC(NH2)2]ads;
2SC(NH2)2+2OH−−2e=(SCN2H3)2+2H2O; Complex of
gold and thiourea losses an electron and is oxidized,
Au[(SC(NH2)2)]ads−e=Au[SC(NH2)2]ads+; Transformation
of formamidine disulphide into thiourea again,
(SCN2H3)2+2H2O+2e=2SC(NH2)2+2OH−; Complex
formation, Au[SC(NH2)2]+ads+ SC(NH2)2=
Au[SC(NH2)2]2+; Diffusion of Au[SC(NH2)2]2+ from
electrode surface to solution. The above characteristics
are the theoretical foundations for gold leaching in
thiourea solution. However, to describe kinetics of gold
dissolution exactly, some questions, such as whether gold
dissolution undergoes the above courses, how does
formamidine disulfide affect gold dissolution, which step
is indeed the rate-determining one, how much is the
reaction orders of reactants, and what are the kinetics
parameters of reaction process, need to be determined
through experiments[14−15]. Accordingly, in this study
gold dissolving process in alkaline thiourea solution was
investigated by electrochemical methods, such as cyclic
voltammetry, chronopotentiometry, AC impedance.
2 Experimental
Electrochemical measurements were conducted by
CHI660A electrochemical workstation monitored by
computer. Three-electrode system was applied, H style
cell with sand core glass septum served as electrobath,
working electrode was the gold electrode with the purity

Foundation item: Project(50004009) supported by the National Natural Science Foundation of China
Received date: 2006−10−20; Accepted date: 2006−12−23
Corresponding author: WANG Yun-yan, PhD, Associate professor; Tel: +86-731-8830875; E-mail: wyy@mail.csu.edu.cn
486 J. Cent. South Univ. Technol. 2007, 14(4)
of 99.99% and area of 1 cm2, a platinum piece with great
area compared to working electrode as counter electrode,
and Hg/HgO electrode dipped in 1 mol/L NaOH solution
as reference electrode[16]. Salt bridge with Luggin
capillary was used to eliminate border potential between
different solutions and to decrease Ohm resistance of
solution. The surface of specimens was polished by
13 μm abrasive paper, dipped successively in acetone
and washed by redistilled water before immersion in the
test solution. Before polarization measurements
commenced, the solution was purged by a stream of
purified N2 for at least 15 min in order to remove the
dissolved oxygen. The cell was maintained in a
thermostated water bath to keep a constant temperature
at 25 ℃, The scan rate of steady-state polarization was
controlled at 10 mV/s.
The electrolyte was composed of 0.1 mol/L
SC(NH2)2 and 0.25 mol/L stabilizing reagent. The
conditions were controlled as pH value of 12.5 adjusted
by diluent NaOH solution.
3 Overall electrode reaction
Thiourea is a complexing agent with the property of
reduction, which can form complexes with many metal
ions. For gold ions, thermodynamic data (the stability
constant of Au[SC(NH2)2]2+ is 22.1) shows that thiourea
is a strong complexing agent. Gold forms only one stable
complex with thiourea, the gold-bisthiourea complex.
During the process of gold dissolving in alkaline
thiourea solution, gold loses one electron and combines
with two thiourea molecules, which indicates that
electrode reaction gains one electron. The mainly
existing form of gold in solution is Au(SC(NH2)2)2+. So
overall electrode reaction can be written as follows:
Au+2 SC(NH2)2-e= Au(SC(NH2)2)2+ (1)
4 Electrode reaction mechanism
4.1 Determination of rate-determining step
Although the result of cyclic voltammetry indicates
that gold dissolving in alkaline thiourea solution is
irreversible, whether it is controlled by electrochemical
polarization or concentration gradient polarization should
be testified further. And here activation energy of
electrode reaction is efficient[14]. Activation energy is
12−16 kJ/mol when electrode reaction is controlled by
species diffusion; while the fact that activation energy is
more than 40 kJ/mol indicates that electrochemical
reaction is the rate-determining step. However activation
energy is similar to that of diffusion process if there exist
preceding reactions of chemical transforming, and its
value is related to the speed of the preceding reaction and
the concentration of the mainly existing ion.
η-lgJη curve is drawn according to linear sweep
curves at different temperatures, the relationship between
lgJη and 1/T at the same overpotential is made out on the
basis of the relationship between activation energy and
temperature(shown in Fig.1 where, η is over potential, V;
Jη is current density, mA/cm2, T is temperature, K). The
slope of the line in Fig.1 is −4 131.26, correlation
coefficient is 0.999 5, and the calculated apparent
activation energy is 14.91 kJ/mol, which indicates that
Au[SC(NH2)2]2+diffusing away from the electrode
surface to solution is the rate-determining step during
gold dissolving in alkaline thiourea solution.
Fig.1 Relationship between current density and temperature
4.2 Determination of thiourea adsorbing on gold
electrode surface before reaction
4.2.1 Determination of thiourea adsorption by AC
impedance
Thiourea, oxidant, alkali and H2O competitively
adsorb on the surface of gold electrode exposed to the
alkaline solution composed of thiourea and oxidant.
Thiourea molecule adsorbing on the active site of gold
surface changes electron cloud distribution of gold atom
through the action between gold atom and sulfur atom of
thiourea, which makes gold dissolve easily because of
potential decline of Au-Au(I).
Adsorption of thiourea on electrode surface,
Au+SC(NH2)2=Au[SC(NH2)2]ads, takes place firstly
during gold dissolving in alkaline thiourea solution, and
then charge transfers from gold atom in
Au[(SC(NH2)2)]ads to thiourea molecule,
Au[(SC(NH2)2)]ads−e=Au[SC(NH2)2]ads+. Electrode
surface process and AC impedance should be used to
ascertain the adsorption property of thiourea on gold
surface.
Based on AC impedance theory of electrode surface
process[15], supposing that thiourea adsorbs on gold
electrode surface, non-Faraday adsorption impedance(Z)
can be expressed as follows:
1 (2)
Z=R + sol
1
jωCdl +
1 1
Ra − j + Rw − j
ωCa ω Cw
where Rsol is solution resistance; Cdl is double layer
 CHAI Li-yuan, et al: Mechanism of gold dissolving in alkaline thiourea solution
capacitance; Ra and Ca are adsorption resistance and
adsorption capacitance caused by thiourea adsorbing on
electrode surface, respectively; Rw and Cw are Warburg
resistance and capacitance caused by thiourea diffusing
from solution to electrode surface, respectively. ω is
angle frequency, j denotes imaginary. The corresponding
equivalent circuit sketch and AC impedance diagram are
shown in Fig.2.
Fig.2 Equivalent circuit sketch(a) and AC impedance
diagram(b) of thiourea adsorption
When existing chemical adsorption, AC impedance
diagram is made up of a semicircle representing
adsorption and a beeline with angle of 45˚ to abscissa
representing diffusion. While without chemical
adsorption, AC impedance diagram is only a beeline with
angle of 45˚ to abscissa. So AC impedances of gold
dissolving in NaOH solution and alkaline thiourea
solution at pH value of 12.5 were measured respectively,
the conditions were controlled as frequency of 0.1−
10 000 Hz, potential of 0.58 V(vs SHE), sine wave with
Δφ of 5 mV. The results are shown in Fig.3.
Fig.3 AC impedance diagram of Au electrode dissolving in
NaOH solution and alkaline thiourea solution
1—NaOH solution; 2—Alkaline thiourea solution
487
It is obvious that AC impedance diagram is made up
of a semicircle representing adsorption within high
frequency range and a beeline representing diffusion in
alkaline thiourea solution, which is similar to the above
theoretical AC impedance. AC impedance diagram is
only a beeline without a semicircle in NaOH solution,
which indicates that thiourea firstly adsorbs on the
electrode surface before participating reaction. In partial
zoom figure, it can be seen that there is a semicircle with
a small diameter, which is caused by OH− adsorption on
gold surface in two different solutions[16]. Therefore,
thiourea adsorbs on gold electrode surface before
dissolving in alkaline thiourea solution.
4.2.2 Determination of thiourea adsorption by
chronopotentiometry
The total consumed quantity of electric charge can
be divided into QC which is used for diffusion of reactant
in solution and Qθ which is consumed to form cover
layer or adsorption layer when a constant current passes
through the electrode, so
πn 2 F 2 D (C0 ) 2
Q = Qθ + QC = Qθ + (3)
4i
where n is the number of electron; F is Faraday
constant; D is diffusion coefficient; C0 is the original
concentration of reactant; i is current.
Eqn.(3) indicates that there is a linear relationship
between Q(=iτ) and i, there exists adsorption when the
line does not pass through origin. Contrarily, there is not
reactant adsorption on electrode surface if the line has
not intercept.
Based on the chronopotentiometry curves measured
under different constant currents (Fig.4), transition time
and quantity of electric charge were calculated and listed
in Table 1. The relationship between Q and 1/i is shown
in Fig.5 and the fitted equation is:
Q=0.984 4+0.084 39/i (R=0.995 8) (4)
Fig.4 Effect of anodic current on transition time(τ) of Au
dissolving in 0.2 mol/L alkaline thiourea solution
1—0.06 mA; 2—0.08 mA; 3—0.12 mA; 4—0.25 mA
488 J. Cent. South Univ. Technol. 2007, 14(4)
From Fig.5 and the fitted equation it can be seen 4.4 Determination of whether formamidine
that the line does not pass through origin and Qθ is disulphide participates reaction
0.984 4 mC. Therefore, the result of chronopotent- In chronopotentiometry curves measured under
iometry also illuminates that thiourea adsorbs on gold different constant currents (Fig.5) there is only one
electrode surface before dissolving in alkaline thiourea transition time, which indicates that there is only one
solution. electron that transfers during gold dissolving in alkaline
thiourea solution. So it can be concluded that
Table 1 Transition time and charge quantity of formamidine disulfide, the decomposed product of
chronopotentiometry curves with different currents thiourea, does not participate the process of gold
Current/mA τ/s Q/mC dissolution and thiourea complex.
0.06 40.5 2.43
0.08 24.7 1.98
0.12 14.1 1.69
0.25 5.36 1.34

Fig.6 Relationship between iτ1/2 and i of chronopotentiometry

4.5 Determination of adsorption of species with

Fig.5 Relationship between Q and 1/i of chronopotentiometry
4.3 Determination of preceding chemical reaction
Whether the decomposed product of thiourea
participates the electrode reaction can be justified by the
existing of proceeding chemical reaction.
Chronopotentiometry experiment is performed at
different currents for estimating preceding chemical
transforming reaction undergoes or not before gold
dissolution.
The experimental data abide by the follow equation
if there is a preceding reaction[14]
1
nFAr πD I π
iτ 2 = − ⋅ erf ( K −1 + K1 )τ
2 K K1 + K −1 2
where K1 and K−1 are rate constants of positive and
reverse reaction, respectively, K ＝ K1/K−1, D is the
diffusion coefficient, r=aO0+aR0, a is activity, A is
electrode area, τ is transition time. The relationship
between iτ1/2 and i is linear when i is low, while iτ1/2 is
independent of i when i is high.
Fig.6 gives the relationship between iτ1/2 and i.
There is a linear relationship between iτ1/2 and i with a
positive slope. The results do not agree with the
theoretical equation, which indicates that preceding
chemical transforming reaction does not exist before
thiourea reacts with gold.
electro-activity
There is a linear relationship between peak current
density Jp and scan rate ν when species with
electro-activity adsorbs on electrode surface. There is a
linear relationship between peak current density Jp and
ν1/2 when diffusion species adsorbs on electrode surface.
Cyclic voltammetrical curves of gold electrode in
alkaline thiourea solution at different scan rates are
shown in Fig.7. The relationship between scan rate and
peak current density is shown in Fig.8, Fig.9 and Table 2.
Fig.8 indicates that the diffusion species adsorbs on
electrode surface. Approximate linear relationship in
Fig.9 indicates that there is a kind of species with
electro-activity adsorbing on electrode surface. Smaller
(5) current density is caused by great effect of passivation of
gold electrode surface on gold dissolving in alkaline
thiourea when scan rate is as slow as 10 mV/s.
4.6 Determination of electrode reaction mechanism
From the above results it can be concluded that in
alkaline thiourea solution, gold dissolution mechanism
undergoes the following courses: adsorption of thiourea
on electrode surface; charge transfer from gold atom to
thiourea molecule; Au[SC(NH2)2]ads+ receiving a thiourea
molecule and forming stable Au[CS(NH2)2]2+; and then
Au[SC(NH2)2]2+ diffusing away from the electrode
surface to solution, the last step is the rate-determining
step.
 CHAI Li-yuan, et al: Mechanism of gold dissolving in alkaline thiourea solution
Fig.7 Cyclic voltammetrical curves of gold electrode in
0.05 mol/L alkaline thiourea solution at different scan rates
Scan rate/(mV·s−1): 1—10; 2—50; 3—100; 4—200
489
14.91 kJ/mol. Rate determining step is the process of
gold thiourea complex diffusing away from electrode
surface to solution. The results of AC impedance and
chronopotentiometry indicate that thiourea adsorbs on
gold electrode surface before dissolving in alkaline
thiourea solution. There does not exist proceeding
chemical reaction. Formamidine disulfide, the
decomposed product of thiourea does not participate the
process of gold dissolution and thiourea complex.
Species with electro-activity produced in the process of
electrode reaction adsorbs on the electrode surface.
2) Mechanism of gold dissolving in alkaline
thiourea is: adsorption of thiourea on electrode surface;
charge transfer from gold atom to thiourea molecule;
Au[SC(NH2)2]ads+ receiving a thiourea molecule and
forming stable Au[SC(NH2)2]2+; and then Au-
[SC(NH2)2]2+ diffusing away from the electrode surface
to solution, the last step is the rate-determining one.

References
[1] GRONEWALD T. Potential application of thiourea in the processing
of gold[J]. J S African Inst M&M, 1977, 77(11): 217−223.
[2] ORGUL S, ALTALAY U. Reaction chemistry of gold leaching in
thiourea solution for a Turkish gold ore[J]. Hydrometallurgy, 2002,
67(1/3): 71−77.
[3] DENG T L, LIAO M X, WANG M H, et al. Enhancement of gold
extraction from biooxidation residues using an acidic sodium
sulphite-thiourea system[J]. Mineral Engineering, 2001, 14(2):
263−268.
Fig.8 Relationship between v1/2 and Jp [4] KUMAR V, MURTHY D S R, RAO K V. Extraction of gold from an
Indian low-grade refractory gold ore through physical beneficiation
and thiorea leaching[J]. Hydrometallurgy, 2003, 68(1/3): 125−130.
[5] GONEN N. Leaching of finely disseminated gold ore with cyanide
and thiourea solutions[J]. Hydrometallurgy, 2003, 69(1/3) 169−176.
[6] SENANAYAKE G.. Gold leaching in non-cyanide lixiviant systems:
Critical issues on fundamentals and applications[J]. Minerals
Engineering, 2004, 17(6): 785−801.
[7] SENANAYAKE G.. Analysis of reaction kinetics, speciation and
mechanism of gold leaching and thiosulfate oxidation by ammoniacal
copper(II) solutions[J]. Hydrometallurgy, 2004,75(1/4): 55−75.
[8] UBALDINI S, FORNARI P, Massidda R, et al. Innovative thiourea
gold leaching process[J]. Hydrometallurgy, 1998, 48(1): 113−124.
[9] NINAE M, OBOSO A. TAKENAKA Y, et al. Synergistic extraction
of gold from sulfuric acid solution containing thiourea[J]. Nippon
Kinzoku Gakkaishi/Journal of the Japan Institute of Metals, 1991,
55(8): 867−873.
[10] GASPAR V, MEJEROVICH A S, MERETUKOV M A. et al.
Practical application of potential-pH diagrams for Au-CS(NH2)2-H2O
Fig.9 Relationship between v and Jp and Ag-SC(NH2)2-H2O systems for leaching gold and silver with
acidic thiourea solution[J]. Hydrometallurgy, 1994, 34(3): 369−381.
[11] CHANDRA I, JEFFREY M I. An electrochemical study of the effect
Table 2 Relationship between scan rate and peak current of additives and electrolyte on the dissolution of gold in thiosulfate
density solutions[J]. Hydrometallurgy, 2004, 73(3/4): 305−312.
[12] HUANG Zi-qing. Theory Introduction to Electrolyte Solutions[M].
−1 v1/2/
v/ (mV·s ) Vp/V Jp/(mA·dm−2) Jp/v 1/2 Beijing: Science Press, 1983: 84−86. (in Chinese)
(mV·s−1)1/2
[13] BARD A J, PARSONS R, JORDAN J. Standard Potentials in
10 0.655 1.985 3.162 0.628 Aqueous Solution[M]. International Union of Pure and Applied
50 0.780 4.398 7.071 0.622 Chemistry. New York: Basel Press, 1985: 287−321.
[14] HU Yu-de, CHEN Bai-zhen. Investigating Methods of Metallurgical
100 0.830 6.095 10.000 0.610 Electrochemistry[M]. Changsha: Central South University of
200 0.880 9.038 14.142 0.625 Technology Press, 1990. (in Chinese)
[15] CAO Chu-nan. Electrochemical Principles of Corrosion[M]. Beijing:
Chemical Industry Press, 1985: 252−261.(in Chinese)
5 Conclusions [16] BARDER A J, FUKNA L R. Principle and Application of
Electrochemistry Technique[M]. GU Lin-ying, LÜ Ming-xiang,
SONG Shi-zhe, et al translate. Beijing: Chemical Industry Press,
1) Apparent activation energy of anodic process of 1986: 615. (in Chinese)
gold electrode dissolving in alkaline thiourea solution is (Edited by ZHAO Jun)

View publication stats