THE HYDROLYSIS OF GOLD(I) IN AQUEOUS SOLUTIONS TO 600°C AND 1500 BAR

Abstract

The solubility of gold has been measured in aqueous solutions at temperatures between 300 and 600°C and pressures from 500 to 1500 bar to determine the stability and stoichiometry of the hydroxy complexes of gold(I) in hydrothermal solutions. The experiments were carried out using a flow-through autoclave system. The solubilities, measured as total dissolved gold, were in the range 1.2 × 10−8 to 2.0 × 10−6 mol kg−1 (0.002 to 0.40 mg kg−1), in solutions of total dissolved sodium between 0.0 and 0.5 mol kg−1, and total dissolved hydrogen between 4.0 × 10−6 and 4.0 × 10−4 mol kg−1. At constant hydrogen molality, the solubility of gold increases with increasing temperature and decreases with increasing pressure. The solubilities were found to be independent of pH but increased with decreasing hydrogen molality at constant temperature and pressure. Consequently, gold dissolves in aqueous solutions of acidic to alkaline pH according to the reactionAu(s)+H2O(l)=AuOH(aq)+0.5H2(g) Ks,1The solubility constant, logKs,1, increases with increasing temperature from a minimum of −8.76 (±0.18) at 300°C and 500 bar to a maximum of −7.50 (±0.11) at 500°C and 1500 bar and decreases to −7.61 (±0.08) at 600°C and 1500 bar. From the equilibrium solubility constant and the redox potential of gold, the formation constant to form AuOH(aq) was calculated. At 25°C the complex formation is characterised by an exothermic enthalpy and a positive entropy. With increasing temperature and decreasing pressure, the formation reaction becomes endothermic and is accompanied by a large positive entropy, indicating a greater electrostatic interaction between Au+ and OH−.