Kinetics Of Oxidative Dissolution Of Lead Sulfide

The kinetics of oxidative dissolution of lead sulfide in solutions of nitric acid and sodium hypochlorite was studied using the rotating disk method and the factor experiment design. The dependences of the PbS dissolution rate on concentration of oxidant (HNO3 or NaOCl), temperature, disk rotation frequency, and duration of interaction were determined. The adequate kinetic models allowing calculating the specific dissolution rate at any combination of values of the influencing factors were obtained. As a result of the complex analysis of kinetic parameters, the modes of the each process proceeding were established, their macromechanisms were determined, and the limiting stages of the oxidative dissolution processes were revealed. The dissolution kinetics of lead sulfide in solutions of nitric acid was found to have several regimes. At HNO3 concentrations below 0.5 mol/L, the process proceeds in a mixed mode close to a diffusion-controlled. It is caused by low oxidative activity of HNO3 and considerable diffusional diffuculties at this acid concentration range. At the nitric acid concentrations more than 0.5 mol/L and less than 6.0 mol/L, the process was found to be kinetically controlled. The limiting stage of the interaction is the surface chemical reaction. The observed relatively high order of the dissolution rate with respect to the concentration of HNO3 was explained by the autocatalytic action of the acid reduction products. At nitric acid concentrations exceeding 6 mol/L, the process proceeds in a mixed mode close to a diffusion-controlled, and the dissolution rate sharply decreased that was explained by a decrease in the solubility of reaction products. When lead sulfide is dissolved in sodium hypochlorite solutions, at first time the amount of PbS transferred into solution remains close to zero. Gradually, as time goes, this amount begins to increase sharply. The dissolution rate rises and reaches the maximum value, further remaining constant. At the steady-state regime, the dissolution rate is independent of the duration of interaction and disk rotation frequency. The process was found to be kinetically controlled. The limiting stage is likely to be chemical reaction on the surface of solid lead sulfide. The obtained kinetic characteristics enlarge the database on hydrochemical oxidation kinetics of sulfides and can be used for the elaboration of the recommendations for the effective comprehensive exploitation of lead-bearing ores and concentrates. Keywords: lead sulfide, nitric acid, sodium hypochlorite, hydrochemical oxidation, dissolution kinetics