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Chemical Reduction of Gold(III) Bromide Complexes Using Sodium Nitrite - Kinetic Aspects

Pacławski K.

Archives of Metallurgy and Materials

2020

Vol. 65, iss. 2

667--675

In this work, the spectrophotometric studies on the kinetics of redox reaction between gold(III) bromide complexes and sodium nitrite, were carried out. From the kinetic curves collected under different conditions of reactants concentration, addition of bromide ions, temperature, pH and ionic strength, corresponding rate constants have been determined. The obtained results suggest the complex path of the [AuBr4]- reduction consisting of two parallel, bimolecular reactions where different reductant species (HNO2 and NO2-) take place and consecutive step with the metallic gold production. The second-order rate constants at 20°C are equal to 2.948 and 0.191 M-1·s-1, respectively. The values of activation enthalpy and activation entropy for the first and the second parallel step of the reaction were found to be ΔH‡ = 29.18 kJ·mol-1 and ΔS‡ = –13.95 J·mol-1·K, and ΔH‡ = 40.75 kJ·mol-1 and ΔS‡ = –31.06 J·mol-1·K, respectively. It was found that the reaction accelerates significantly with the increase of pH and is inhibited with the increase of Br- concentration. The substitutive, inner-sphere mechanism of electron transfer in the studied system was also suggested.