Abstract
The reduction of Ag(OH) 4 − by sulphite ion to give silver(I) and sulphate in strong base has been studied by stopped-flow spectrophotometry. The reaction was found to fit a second-order rate law with a rate constant k = (9.1 ± 0.1) x 10 2M −1s −1 ( T = 25°C, μ = 1.2 M). The estimated enthalpy and entropy of activation are 27 kJ mol−1 and − 153 J K−1 mol−1 respectively. Variation of rate with ionic strength is consistent with the interaction between mononegative Ag(OH) 4 − and dinegative SO 3 2−. The redox reaction appears to proceed by a one-step oxygen atom transfer. Two kinetically indistinguishable pathways are discussed. The first involves initial attack of a sulphite oxygen at an axial silver(III) site. The second pathway involves initial interaction between sulphur(IV) and a bound hydroxyl. Sulphite oxidation by silver(III) is about 10 4 times faster than that of phosphite, while no reaction is observed with NO 2 −.
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