R. Yu. Bek

Microbalance study of gold dissolution in alkaline sulfite-thiocarbamide electrolytes

It is shown that gold does not virtually dissolve in alkaline (pH 12.5) solutions containing either thiocarbamide or sodium sulfite. Gold dissolves in alkaline solutions simultaneously containing thiocarbamide (0.1 M) and sodium sulfite (0.5 M). The gold dissolution rate increases with the increase in the contents of thiocarbamide and sodium sulfite. The methods of microbalance and voltammetry are used in studying the mechanism of gold dissolution in a solution containing 0.5 M sodium sulfite, 0.1 M thiocarbamide, and 0.03 M KOH. The found relationships are explained based on the assumption that the gold dissolution in alkaline sulfite-thiocarbamide electrolytes affords gold sulfite complexes.

The effect of thallium ions on the gold dissolution rate in thiosulfate electrolytes

The effect of TlNO3 additions in the concentration (c1) range from 5 × 10−6 to 1 × 10−4 M on the anodic dissolution of gold in sodium thiosulfate solutions with the concentration (c2) from 0.005 to 0.2 M is studied by voltammetry on the electrode surface renewed by cutting off a thin metal layer immediately in solution and also by the quartz-crystal microbalance method. For c2 = 0.2 M, as c1 increases from 5 × 10−6 to 1 × 10−4 M, the gold anodic dissolution rate is observed to increase from 0.02 (in the absence of TlNO3) to 0.75 mA/cm2 for c1 = 7.5 × 10−5 M according to a nearly linear law. The dissolution accelerates because the effective values of the transfer coefficient and the exchange current density increase from 0.2 and 4 μA/cm2 (in the absence of TlNO3 admixtures) to 0.47 and 35 μA/cm2 (for c1 = 1 × 10−4), respectively. Experiments with the renewal of the electrode surface in the course of electrolysis suggest that the gold dissolution is catalyzed in the presence of thallium ions by the adsorption mechanism and also as the result of the mixed kinetics of their adsorption on the electrode surface.

Peculiarities of cathodic reduction of gold from sulfite-thiocarbamide electrolytes

The cathodic reduction of gold from mixed sulfite-thiocarbamide electrolytes is studied as a function of the electrolyte composition. In the absence of thiocarbamide in the gold-plating sulfite solutions, gold is deposited at the cathode at high overpotentials. The equilibrium composition of the electrolyte is calculated at various ratios between the amounts of sulfite and thiocarbamide; it is shown that an addition of 10−5 to 0.5 M thiocarbamide does not change considerably the solution composition, and gold ions are present, predominantly, in the form of the complex with sulfite ions. However, an addition of thiocarbamide to the solution leads to a decrease in the overpotential of metal deposition by approximately 0.5 V. A possible mechanism of the catalytic effect of thiocarbamide on the cathodic reduction of gold from mixed sulfite-thiocarbamide electrolytes is proposed. It is shown that sulfite ions have a stabilizing effect on the decomposition of thiocarbamide in the alkaline solutions.

Anodic behavior of gold in acid thiourea solutions: A cyclic voltammetry and quartz microgravimetry study

It is shown that at potentials E < 0.5 V (NHE) gold undergoes practically no dissolution in thiourea solutions containing no catalytically active species. The dissolution at a perceptible rate (> 100 μA cm−2) starts at E ≥ 0.65 V, with the primary process being the oxidation of thiourea, which gives rise a current peak at E ≃ 1.0 V. The thiourea oxidation at E ≥ 1.1 produces the appearance of catalytically active species, which drastically accelerate the gold dissolution process in the potential region extending from a steady-state value to 0.6 V, where the current efficiency for gold approaches 100% and a peak emerges at E ≃ 0.55 V. The peak’s height is commensurate with the value of the limiting diffusion current associated with the ligand supply. The species in question make no discernible impact on the thiourea oxidation process. Formamidine disulfide, which forms during the anodic oxidation of thiourea or which is added in solution on purpose, exerts no noticeable catalytic influence on the anodic gold dissolution. The catalytically active species is presumably the S2− ion, product of decomposition and deep oxidation of thiourea and formamidine disulfide. Indeed, adding sulfide ions in solution has a strong catalytic effect on the gold dissolution, whose character is identical to that of the effect exerted by products of anodic oxidation of thiourea at E ≥ 1.1 V μA cm−2.

Kinetics of silver anodic dissolution in thiosulfate electrolytes

AbstractThe regularities of silver anodic dissolution are studied by using the voltammetry (at the potential scan rates from 5 to 1000 mV/s) on the electrode, which was renewed immediately in the solution by cutting-off a thin surface metal layer, and quartz microgravimetry, for various concentrations of sodium thiosulfate (0.05–0.2 M). It is shown that, in the potential range from 0 to 0.4 V (normal hydrogen electrode), the polarization curves reflect the silver dissolution, whereas the contribution of oxidation of S2O32− ions is insignificant. At low potential scan rates, the process kinetics is of mixed nature. The kinetics and mechanism of anodic process are studied by using the measurements at high potential scan rates (100–200 mV/s) and the calculations of equilibrium composition of near-electrode layer. It is found that the exchange current in the electrolytes studied is 5 × 10−5 A/cm2, the transfer coefficient α is approximately 0.5, and both parameters are virtually independent of the concentration of S2O32− ions. The reaction order of silver dissolution with respect to the ligand

Effect of Thallium Adatoms on Electrode Processes in the System Gold–Cyanide Solutions

\left. {\frac{{\partial logi}} {{\partial logc}}} \right|_E

Comparison of catalytic activity of thallium and lead adatoms at the gold electrodeposition and dissolution in cyanide solutions

is close to unity and is independent of potential. With regard for the literature data on the adsorption of thiosulfate ions on silver, this result is interpreted as the evidence for the involvement of one S2O32− ion from bulk solution, along with adsorbed ligands, in the elementary act of metal dissolution.

Kinetics of gold electrodeposition from alkali-cyanide solutions: The effect of infinitesimal quantities of thallium(I) nitrate

The peculiarities of the effects of upd thallium, lead, bismuth, and mercury on the dissolution rates of gold and silver in cyanide electrolytes are compared. In general, they feature the abrupt acceleration of the dissolution of gold and, to a lesser extend, silver in the chemisorption range of mentioned ions. As the potential increases, the gold dissolution rates passes through a maximum the height of which is comparable with the limiting current of this process associated with limitations in the delivery of cyanide ions to the electrode surface. The current decay after the maximum is due to desorption of catalytically active adatoms. The chemisorption rate of thallium, lead, and bismuth ions at potentials more negative than the current peak is controlled by their diffusion to the gold surface, whereas the chemisorption rate of mercury is controlled by the adsorption kinetics. With the increase in the surface coverage with adatoms θ, the catalytic activity of all considered adatoms passes through a maximum. The sharp increase in the effective transfer coefficient in the presence of these adatoms makes the main contribution into the acceleration of the gold dissolution, while the increase in the exchange current has a smaller effect. The chemisorption of mentioned atoms on gold not only accelerates the dissolution but also changes its mechanism. For gold dissolution, the catalytic activity of upd thallium, lead, and bismuth increases in the following sequence: Tl ≪ Pb < Bi and the effect is additive in their simultaneous presence. For silver, the increase in the exchange current makes the main contribution into the acceleration of dissolution, whereas the transfer coefficient and the reaction order with respect to the ligand change insignificantly. Explanation of the observed peculiarities is given.