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Central South University
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All content following this page was uploaded by Yun-yan Wang on 03 December 2014.
(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.
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 η-lgJη curve is drawn according to linear sweep
area compared to working electrode as counter electrode, curves at different temperatures, the relationship between
and Hg/HgO electrode dipped in 1 mol/L NaOH solution lgJη and 1/T at the same overpotential is made out on the
as reference electrode[16]. Salt bridge with Luggin basis of the relationship between activation energy and
capillary was used to eliminate border potential between temperature(shown in Fig.1 where, η is over potential, V;
different solutions and to decrease Ohm resistance of Jη is current density, mA/cm2, T is temperature, K). The
solution. The surface of specimens was polished by slope of the line in Fig.1 is −4 131.26, correlation
13 μm abrasive paper, dipped successively in acetone coefficient is 0.999 5, and the calculated apparent
and washed by redistilled water before immersion in the activation energy is 14.91 kJ/mol, which indicates that
test solution. Before polarization measurements Au[SC(NH2)2]2+diffusing away from the electrode
surface to solution is the rate-determining step during
commenced, the solution was purged by a stream of
gold dissolving in alkaline thiourea solution.
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.
Fig.3 AC impedance diagram of Au electrode dissolving in Fig.4 Effect of anodic current on transition time(τ) of Au
NaOH solution and alkaline thiourea solution dissolving in 0.2 mol/L alkaline thiourea solution
1—NaOH solution; 2—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
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gold electrode dissolving in alkaline thiourea solution is (Edited by ZHAO Jun)