Thermodynamic and Kinetic of Iodine Iodide Leaching in Gold Hydrometallurgy
Thermodynamic and Kinetic of Iodine Iodide Leaching in Gold Hydrometallurgy
Thermodynamic and Kinetic of Iodine Iodide Leaching in Gold Hydrometallurgy
Abstract: The thermodynamic equilibria and kinetic aspect of gold dissolution in iodine−iodide leaching were studied with emphasis
on the effects of pH value and temperature on the system. The results of thermodynamic analysis of iodine in aqueous solution were
given and numerous forms of iodine exist mainly in the acid region of pH values. An increase of the potential of the system results in
an increase of iodine speciation. The oxidizing potential of the system will increase by the addition of element iodine. The IO3−
anions are stable in the potential range from −2.0 to −0.75 V and at рН value greater than 12.1. An increase of the temperature shifts
boundaries of existence of various iodine species in the acid region of pH values. Some of them become unstable. The determined
values of the diffusion coefficients and the thickness of the diffusion boundary layer, as well as the solvent concentration on the disc
surface (14 mg/L) indicate that the process proceeds in the external diffusion region. Thus, while choosing the conditions of leaching
from gold-containing materials of different origins of iodide solvents, it is necessary to carry out the process within the acidic region
of pH values, where I−, I3− and IO4− ions are capable to form complex compounds with metals.
Key words: gold; hydrometallurgy; iodine−iodide leaching; non-cyanide lixiviants
Table 2 Isobaric-isothermal potentials of gold dissolution reactions with different complex-forming reagents and oxidants
273 K 293 K 313 K 333 K 353 K
Chemical reaction ΔGо/ ΔGо/ ΔGо/ ΔGо/ ΔGо/
lg K lg K lg K lg K lg K
( kJ·mol−1) ( kJ·mol−1) ( kJ·mol−1) ( kJ·mol−1) ( kJ·mol−1)
2Au+3Cl2+2HCl→2HAuCl4 (4) 840.5 −160.7 861.3 −153.5 882.7 −147.3 904.7 −141.8 927.1 −137.1
2Au+4NaCN+O2+2H2O→
(5) −99.1 18.9 −92.1 16.4 −84.9 14.2 −77.3 12.1 −69.2 10.3
2NaAu(CN)2+2NaOH+H2O2
5Au+20KBr+3KMnO4+29H→
(6) −943.4 180.4 −938.8 167.3 −913.4 155.4 −920.8 144.4 −907.3 134.2
5H[AuBr4]+3MnCl2+23KCl+12H2O
Au+HNO3+3HCl→
(7) 51.4 −9.8 46.2 −8.3 41.3 −6.9 36.5 −5.8 32.4 −4.8
AuCl3+NO↑+2H2O
2Au+2KI+I2+2HCl→
(8) −34.3 6.7 −33.8 6.1 −32.4 5.4 −30.5 4.8 −28.4 4.2
2H[AuI2]+2KCl
2NH2SO2OH+6KI+H2SO4+2Au→
(9) −349.8 66.9 −348.7 62.2 −348.9 58.2 −351.1 55.1 −355.2 52.5
2K[AuI2]+I2+2K2SO3+(NH4)2SO4
2NH2SO2OH+3KI+H2SO4→
(10) −245.5 46.6 −247.7 44.4 −251.4 42.0 −257.9 40.5 −266.2 39.4
K[I·I2]+K2SO4+(NH4)2SO4+SO2
2KI+I2+Au+H2SO4→
(11) −104.3 19.9 −101.1 18.0 −97.2 16.2 −93.2 14.6 −88.9 13.2
2H[AuI2]+K2SO4
5Au+5KI+KMnO4+8HCl→
(12) −510.9 88.8 −490.1 82.5 −493.3 76.9 −496.6 71.9 −500.7 67.5
5AuI++MnCl2+6KCl+4H2O
5Au+5KBr+KMnO4+8HCl→
(13) −231.6 44.3 −264.7 40.7 −266.8 37.7 −269.6 35.5 −272.9 32.6
5AuBr+ MnCl2+6KCl+4H2O
2Au+2KBr+Br2+2HCl→
(14) −30.9 5.9 −28.4 5.1 −25.5 4.3 −22.1 3.5 −18.2 2.3
2H[AuBr2]+ 2KCl
2Au+2KCl+Cl2+2HCl→
(15) −59.3 11.4 −60.5 10.8 −60.9 10.2 −60.8 9.3 −60.1 8.8
2H[AuCl2]+ 2KCl
4Au+8S2O32−+O2+2H2O→
(16) −34.3 6.7 −33.8 6.1 −32.4 5.4 −30.5 4.8 −28.4 4.2
4Au(S2O3)23−+4OH−
S. S. KONYRATBEKOVA, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3774−3783 3777
The use of oxidants (Cl2, Br2, I2 and KMnO4), along potential sufficient for gold dissolution (Table 3).
with iodide ion, increases significantly the probability of To summarize, an iodine−iodide system has a
dissolution (Reactions (11)−(15) in Table 2) of both gold number of advantages: lower toxicity, higher stability of
and metals sulfides, in particular iron sulfide. The results formed complexes and lower redox potential as
are in good agreement with the literature data [42,43], in compared with other non-cyanide leaching systems.
which the authors demonstrated the feasibility of gold The Gibbs energy of Reactions (9) and (12) is
dissolution with potassium iodide solutions in the significantly lower than zero, which indicates a
presence of an oxidant (H2О2, I2, OCI−). In a thermodynamic probability of these reactions even at
thermodynamic study of DAVIS et al [28], I3− was shown room temperature.
as the predominant oxidants species in both systems. The feasibility of the gold leaching process with
However, if the concentrations of OCl− and I− equal, the iodine-containing solutions at low temperatures can be
solid iodine forms. In these systems, iodide (I−) is used to confirmed in an indirect way with the aid of Pourbaix
form I3− which is responsible for the gold oxidation and diagrams showing the thermodynamically stable states of
more free iodide needed for the gold complexation is iodine in aqueous solutions within the iodine
destroyed in the I−−OCl− system than that in the I−−I2 concentrations studies, as well as the potentials and pH
system. The formation of solid AuI also explains the values of the medium. The phase diagrams of φ−pH
lower rate of gold dissolution determined for certain (Pourbaix diagrams) are given in Figs. 1, 2 and 3 for
conditions in the kinetic study. iodine-containing systems at 25, 50 and 80 °C,
BONDARENKO and KULIKOV [44] pointed out respectively.
good prospects for application of iodine−iodide leaching The Pourbaix diagrams of I−H2O system are plotted
of gold. It was demonstrated that it was feasible to form with the aid of the above mentioned software for
complex haloid anions in the process of treatment of thermodynamic calculations of initial iodine
gold-containing materials with aqueous solutions of concentration of c(I)initial=1×10−2 mol/L within the pH
cyclic type with alkyl or haloid radicals [42]. The value interval of 0−14 and the potential range from −2.0
thermodynamic calculations presented in Table 2 to 2.0 V (vs SHE).
(Reactions (8)−(11)) confirm the probability of
At the potential range from −2.0 to −0.6 V and pH
iodine−iodide leaching of gold from gold-containing
value interval of 0−12.1 and 25 °C, iodine is in the form
materials. Iodide is required in this case as a
of iodide ion I− (Figs. 1(a), 2(a) and 3(a)). Along with
complex-forming agent ensuring the formation of a
this ion, it is possible that IO3− ion is also present in the
stable complex with gold, and iodine is needed as an
solution, which at the given potential and pH values is
oxidant preventing disproportioning of the formed gold
less stable (Figs. 1(b), 2(b) and 3(b)) and becomes stable
complex and gold precipitation [45].
in the potential range from −2.0 to −0.75 V at pH value
The gold dissolution reaction in an iodine−iodide
of 12.1 and higher value.
system is expressed with Reaction (17).
At the potential range from −0.5 to −1.0 V, iodine
2Au+I¯+I3¯→2AuI2¯ (17) exists predominantly in the form of hypoiodous acid
As shown in Table 3, chloride and thiocyanate (Figs. 1(a), 2(a) and 3(a)). Under the same conditions,
leaching of gold-containing minerals does not result in the formation of unstable iodine ions such as H2IO+, I–,
the formation of insoluble metal compounds, which is H3IO62−, I3– and IO3– is possible (Figs. 1(b), 2(b) and
confirmed by the values of the isobaric−isothermal 3(b)).
potentials (ΔGо>>0) and equilibrium constant of With increasing the potential above 0.25 V, IO4–
Reaction (4). The thermodynamic probability of gold ions become stable at the pH value interval of 0−8.5, and
dissolution in aqua regia (Reaction (7)) increases H3IO62− ions become stable at the pH value greater than
substantially in comparison with the previous solvents. 8.5, and the formation of IO3– and I3– ions is possible.
In a poly-iodide solution, the formation of complex AuI4− An increase of the temperature causes a shift of
is also possible [46]. MURPHY [47] pointed out that regions of existence of both stable and unstable iodine
by selecting proper concentrations of iodide ion ions. With an increase of the temperature, the region
and molecular iodine, it was possible to obtain a redox of IO3− existence shifts to a more acidic region at 50 °C
Table 3 Standard oxidation potential and formation heat of haloid gold complexes
Parameter Cl3¯ Cl¯ Br3¯ Br¯ I3¯ I¯ (SCN)3¯ CN¯
Standard reduction potential/V −1.00 −1.15 −0.86 −0.96 −0.57 −0.56 −0.64 −0.57
Formation heat/ (kJ·mol−1) 48.55 17.58 24.7 15.49 0.84 3.18 – –
3778 S. S. KONYRATBEKOVA, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3774−3783
Fig. 1 Pourbaix diagrams of I–H2O system at 25 °C: (a) Region of existence of stable iodine ions; (b) Region of existence of unstable
forms of iodine
Fig. 2 Pourbaix diagrams of I–H2O system at 50 °C: (a) Region of existence of stable iodine ions; (b) Region of existence of unstable
forms of iodine
Fig. 3 Pourbaix diagrams of I–H2O system at 80 °C: (a) Region of existence of stable iodine ions; (b) Region of existence of unstable
forms of iodine
with the pH value down to about 11.3 (Fig. 2(a)) and at to about 9.0.
80 °C with the pH value down to 10.5 (Fig. 3(a)). At the An increase of the temperature results in not only a
same time, the region of H3IO62− existence moves shift of the boundaries regions of existence of various
slightly toward the alkaline region at 50 °C with the pH iodine forms, but also a disturbance of their stability,
value up to about 8.75 and at 80 °C with the pH value up e.g., the formation of H2IO+ cation becomes
S. S. KONYRATBEKOVA, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3774−3783 3779
thermodynamically impossible. Thus, a thermodynamic preset mixing time, the gold-containing disc was
analysis of the I−H2O system suggests a conclusion that removed from the solution, washed with distilled water,
numerous iodine forms (I−, H3IO62−, IO3–, I3– and IO4–) dried and weighed. The mass loss of the disc was
exist mainly in the acidic region of pH values. An determined to assess the gold dissolution in time, and
increase of the potential of the system (more than accordingly the rate of metal transition to the solvent
–0.5 V) results in an increase of the number of iodine from a unit surface of the specimen.
forms of the aquatic medium. An increase of the The study of gold dissolution versus time was
temperature causes a shift of the boundaries of the iodine conducted using iodide solutions with a concentration of
form existence region towards the acidic region of the 40 mg/L and at a rotational speed of not more than
pH values. At the same time, some of them become 80 r/min to prevent the dissolution of the base material.
unstable, in particular H2IO+ ion. The effect of stirring speed and iodide solution
On the basis of the conducted studies, it can be concentrations on the gold dissolution was performed at
concluded that the gold leaching process should be approximately 30 min.
carried out within the acidic region of pH values, where In all cases, the copper content of the solution was
I−, I3– and IO4– ions are present, which are capable to monitored to make sure that the disc material did not
form complex compounds with gold. The oxidizing dissolve and the test results obtained were within the
potential of the system will increase in this case by the permissible error.
addition of element iodine. Since the system was closed, the condition of the
stationarity of the diffusion stream made it possible to
3.2 Kinetics of gold dissolution in iodide solutions solve the differential equations of the 1st and 2nd Fick
The determined values of the diffusion coefficients laws and obtain an integral expression, which is used for
using the rotating disc method and the thickness of the calculating heterogeneous diffusion processes.
diffusion boundary layer, as well as the solvent In accordance with the 1st Fick law, the mass of a
concentration on the disc surface indicate that the substance (dmi), diffusing through a flat surface with an
process proceeds in the external diffusion region. area S and perpendicular to the diffusion flow density
QI and HISKEY [26] used a glassy carbon rotating during a time (dτ), is proportional to S·dτ and the
disk electrode to investigate the electrochemistry of concentration gradient dρi/dx:
iodide and a gold rotating disk electrode to explore the dmi=−DiSdτ(dρi/dx) (18)
oxidation behavior of gold in iodide solutions. The
where Di is the diffusion coefficient.
effects of iodide concentration, electrode rotation and
The minus sign indicates the diffusion process
sweep rate on the electrochemical behavior of gold were
toward a decreasing concentration gradient. If the
examined. In addition, the reduction of iodine species on
diffusion process rate is assumed to be J=Ji=dmi/(dτ·S),
the gold electrode was also investigated. Two oxidation
called the diffusion flow density, then the equation of the
peaks, which represented the oxidations of Au to Au(I)
1st Fick law has a simple form:
and Au(III), were observed. It was confirmed that iodide
was oxidized sequentially to tri-iodide and then to iodine J=−Di(dρi/dx) (19)
and both of these reactions were reversible. At high The reaction equation was recreated with the
concentrations of iodide and/or a slow scan rate, boundary conditions for any t on the reaction surface x=0
passivation, which was caused by the formation of solid and ρi=ρn, within the solution volume x=δ, ρi=ρо.
iodine on the gold electrode surface, was found. Equation (2.3) has the following form:
The rotating disc method was used to study the
Ji=Δmi/(60τS) (20)
kinetics of gold dissolution from gold-containing
material [48]. The test was carried out under The calculation results are given in Table 4.
hydrodynamic conditions at an installation comprising a The repeatability of the dissolution rate in the case
reaction vessel with a capacity of 0.5 L, a magnetic of different reaction time is very good as the points only
mixer and a support stand with a disc fixed on it. A disk slightly deviate from a straight line. A deviation from a
having a diameter of 20 mm had a copper base plated straight line becomes noticeable at τ>150 min, therefore,
with gold (the mass of gold on the disc was 0.0711 g). further kinetics studies were conducted at τ=150 min
The disc was installed at the vessel center, without (Fig. 4).
touching its bottom. Then the vessel was filled with The dissolution rate is dependent on the mixing
iodide-containing solution and the mixing was started. intensity, which is the main feature of the diffusion
Gold dissolution from the disc was conducted at room regime. The preliminary studies (Fig. 5) indicate that
temperature (18−22 °C). The iodine concentration of the with increasing the mixing intensity above 100 r/min,
solvent varied from 40 to 250 mg/L. After the end of a the kinetics of the process changes (the slope angles of
3780 S. S. KONYRATBEKOVA, et al/Trans. Nonferrous Met. Soc. China 25(2015) 3774−3783
Table 4 Test conditions and calculation results
ρо/(mg·L−1) n/(r·min−1) mo/g mi/g Δm/g J/(10−7 g·сm−2·s−1) Di/(10−9 сm2·s−1) δn/10−7 сm
40 1.3230 1.3220 0.0010 0.18
60 1.3230 1.3218 0.0012 0.22
40 1.12 1.27
80 1.3230 1.3216 0.0014 0.25
100 1.3230 1.3214 0.0016 0.28
40 1.3280 1.3248 0.0032 0.56
60 1.3280 1.3241 0.0039 0.69
100 1.53 1.74
80 1.3280 1.3236 0.0044 0.78
100 1.3280 1.3230 0.0050 0.88
40 1.3338 1.3278 0.0060 1.06
60 1.3338 1.3264 0.0074 1.31
200 1.60 1.81
80 1.3338 1.3254 0.0084 1.48
100 1.3338 1.3243 0.0095 1.68
40 1.3477 1.3399 0.0078 1.38
60 1.3477 1.3381 0.0096 1.70
250 2.02 2.29
80 1.3477 1.3367 0.0110 1.94
100 1.3477 1.3353 0.0124 2.19
τ: 150 min; ν: 0.015 сm2/s; S: 6.28 сm2; t: 18−22 °С
Acknowledgement
This collaborative research was based on the results
of bilateral contacts of Mineral-Metal Recovery and
Recycling (MMR&R) Research Group, Mineral
Processing Division, Department of Mining Engineering,
Suleyman Demirel University, Isparta, Turkey, and
Mining and Smelting Institute after O.A. Baikonurov,
Kazakh National Technical University named after K.I.
Satpaev, Almaty, Kazakhstan.
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碘−碘化物浸金湿法冶金的热力学和动力学
S. S. KONYRATBEKOVA1, A. BAIKONUROVA1, G. A. USSOLTSEVA1, C. ERUST2, A. AKCIL2
1. Mining and Smelting Institute after O.A. Baikonurov, Kazakh National Technical University named after K.I. Satpaev,
Satpaev Street, 22, Almaty 050013, Republic of Kazakhstan;
2. Mineral−Metal Recovery and Recycling Research Group, Mineral Processing Division,
Department of Mining Engineering, Suleyman Demirel University, Isparta TR32260, Turkey
摘 要:研究金在碘−碘化物浸出液中的溶解热力学平衡和动力学,着重研究 pH 值和温度对体系的影响。水溶液
中碘的热力学分析结果表明,多种形式的碘化物主要存在于 pH 值为酸性的区间。体系电势的增加导致碘化物种
类的增加,碘元素的添加能提高体系的氧化电位。IO3−离子能稳定存在于电势范围为–2.0 至–0.75 V 和 pH 值大于
12.1 的区间。提高温度会使各种碘化物在酸性 pH 区间存在的边界线发生移动,其中一些碘化物变得不稳定。扩
散系数和扩散边界层厚度的测量值以及圆盘表面的溶剂质量浓度(14 mg/L)分析表明,浸出过程在外层扩散区域进
行。因此,当选择碘化物浸出含金物料时,浸出过程必须在 pH 值为酸性区间内进行,在这些区间 I−、I3–和 IO4–
离子能和金属形成配合物。
关键词:金;湿法冶金;碘−碘化物浸出;无氰浸出剂
(Edited by Mu-lan QIN)