Dilute nitric or nitrous acid solution containing halide ions as effective media for pure gold dissolution

Abstract

The greatly enhanced oxidation ability of dilute aqueous nitric acid (0.10–2.0 mol L⁻¹) containing bromide and iodide salts as well as chloride salts has been examined based on the dissolution kinetics of pure gold at 30–60 °C. It has been found that bromide salts are more effective than chloride salts in gaining the ability of dissolving gold in dilute aqueous nitric acid solution. At 60 °C, a piece of gold-wire (ca. 20 mg) is dissolved in 20 mL of as low as 0.10 mol L⁻¹ HNO₃ solution containing 1.0–5.0 mol L⁻¹ NaBr and the dissolution rate constant, log(k/s⁻¹), increases linearly (from −5.78 to −4.52) with the increasing NaBr concentration. The addition of organic solvents, such as acetonitrile and acetic acid, causes acceleration of gold dissolution in LiBr and NaBr solutions. With increasing MeCN contents, for instance, the log(k/s⁻¹) value of 0.10 mol L⁻¹ HNO₃ solution containing 2.0 mol L⁻¹ NaBr increases linearly from −5.30 to −4.61 at 30% (v/v) MeCN. The bromide salts affect the gold dissolution rate constant in the order of KBr < NaBr < LiBr < CaBr₂. With increasing NaI concentration (0.20–3.0 mol L⁻¹), some acceleration in log(k/s⁻¹) of 0.50 or 1.0 mol L⁻¹ HNO₃ solution has been observed; however, the slope of acceleration as the function of NaI concentration is much smaller than that of NaCl or NaBr. The gold dissolution ability has been examined also for nitrous acid containing chloride and bromide ions at 35 °C. The NaNO₂ solution containing twice or more amounts of HX (X = Cl, Br) gives the maximum efficiency for gold dissolution, according to the log(k/s⁻¹) values of the mixed solutions of NaNO₂ (0.10–2.0 mol L⁻¹) and HX of various concentrations. The influence of oxidation by dilute nitric and nitrous acids on the gold dissolution is discussed from the standpoint of the redox potentials in “modified” aqueous solutions and not of the changes in the activity coefficients of ions.