A review of effects of silver,lead, sulfide and carbonaceous matter on gold cyanidation and mechanistic interpretation

Despite the wealth of published data on the beneficial or detrimental effects of silver, lead, sulfide, and carbonaceous matter on the rate of gold cyanidation at an anode or by dissolved oxygen, the lack of comparative studies on relative effects has hampered rationalisation of the role of these activators or passivators of gold. In the present study, the published rate data per unit surface area of gold, silver, and gold–silver alloys based on electrochemical or chemical dissolution of rotating discs or foils of constant surface area in aerated cyanide solutions at ambient temperatures are analysed on the basis of the Levich equation. The current status of the reaction mechanism is also reviewed and updated on the basis of species distribution and potential–pH diagrams, stoichiometric factors, and interim chemical species of gold(I), silver(I), and lead(II). The anodic peak potentials of reported voltammograms closely follow the potential–pH lines of Au(I)/Au(0) and Pb(II)/Pb(0) couples. Despite the formation of stable complexes between lead(II), nitrate, and hydroxide ions, the total calculated soluble lead(II) in alkaline solutions of pH range 10–11 saturated with lead hydroxide is shown to be < 0.1 g/m³. A comparison of the reported diffusion coefficients of cyanide ions and dissolved oxygen with the values based on the Levich plots of reported rates reveals the rate-controlling stoichiometric M/CN or M/O₂ molar ratios. The difference between some of these ratios and the generally accepted ratios of M/CN = 1/2 and M/O₂ = 1/0.5 or 1/0.25 based on the formation of M(CN)₂⁻, H₂O₂ or OH⁻ in the overall cyanidation reaction is attributed to the oxidation of cyanide to cyanate and passivation due to the formation of gold hydroxides/oxides. The alloyed or dissolved silver and lead eliminate passivation due to the involvement of mixed hydroxo–cyano complexes of silver and lead ions in the surface reaction. Gold dissolution by oxygen in cyanide-rich solutions is limited by oxygen diffusion, but enhanced by the presence of a low concentration of sodium sulfide due to the involvement of hydrosulfide ion in the surface reaction. However, excess lead or sulfide retards gold cyanidation due to surface blockage by metallic lead, lead hydroxide, or due to passivation by Au₂S/S. Even low concentrations of hydrosulfide passivate gold–silver alloys due to the formation of Ag₂S. This can be eliminated by adding stoichiometric quantities of lead(II) to precipitate sulfide as PbS. Large stoichiometric ratios of O₂/M for the cyanidation of graphite coated gold appears to be a result of the enhanced oxidation of cyanide by oxygen or hydrogen peroxide, leading to a cyanide deficiency at the surface and passivation of gold by hydroxide/oxide. The presence of excess cyanide or lead(II) does not override this effect.