Initial state and transition state solvation effects in the cobaltitungstate oxidation of iodide in binary aqueous solvent mixtures期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

Initial state and transition state solvation effects in the cobaltitungstate oxidation of iodide in binary aqueous solvent mixtures

Authors:	Michael J. Blandamer John Burgess Philip P. Duce Robert I. Haines Alexander McAuley

Affiliation:	(1) Chemistry Department, University of Leicester, LE1 7RH Leicester, UK;(2) Department of Chemistry, Lash Miller Chemical Laboratories, University of Toronto, M5S 1A1 Toronto, Ontario, Canada;(3) Department of Chemistry, University of Victoria, V8W 2Y2 Victoria, B.C., Canada;(4) Present address: Whiteshell Nuclear Research Establishment, RCE 1LO Pinaua, Manitoba, Canada

Abstract:	Summary Rate constants are reported for 12-tungstocobaltate(III) [CoW₁₂O₄₀]^5– oxidation of iodide in water and in binary aqueous solvent mixtures containing up to 40% methanol, 40% acetonitrile, or 60% dimethyl sulphoxide. From these kinetic results, solubility measurements on potassium 12-tungstocobaltate(III), and published data on Gibbs free energies of transfer of appropriate ions, it has been deduced that the dominant factor in determining the marked decrease in rate observed on going from water into the binary aqueous solvent mixtures is destabilisation of the transition state for the electron-transfer reaction.

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