Kinetics of the reduction of platinum(IV) by tin(II) and copper(I) in aqueous chloride solutions
Moodley, K.G. and Nicol, M.J. (1977) Kinetics of the reduction of platinum(IV) by tin(II) and copper(I) in aqueous chloride solutions. Journal of the Chemical Society, Dalton Transactions (3). pp. 239-243.
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Rate constants for the PtIV+ SnII and the PtIV+ CuI redox reactions have been measured under various conditions using spectrophotometric and amperometric methods respectively. Rate equations (i) and (ii) describe the data for –d[PtIV]/dt=kobs.[PtIV][SnII](i), –d[CuI]//dt=2k1k2[PtIV][CuI]2//k–1[CuII]+K2[CuI](ii) the two reactions. The rate of reduction of PtIV by SnII is much faster than the rate of formation of the 1 : 1 complex between PtII and SnII. The rate of reduction by SnII varies linearlywith increasing chloride concentration in nitrate and sulphate solutions. A possible explanation is offered for the higher rates in perchlorate solutions. The data for the PtIV+ CuI system indicate that the reaction proceeds via an intermediate containing PtIII, but there is no evidence for the formation of PtIII in the reduction of PtIV by SnII. The mechanisms for both reactions are discussed in terms of complementary and non-complementary processes.
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|Publisher:||Royal Society of Chemistry|
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