Influence of specific reactant-solvent interactions on intrinsic activation entropies for outer-sphere electron-transfer reactions

Joseph T Hupp, Michael J. Weaver

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

The physical basis of the solvent contribution to the intrinsic activation entropy, ΔS*int, for outer-sphere electron-transfer reactions in homogeneous solution is examined in terms of the entropic parameters for the constituent electrochemical half-reactions. A relationship for calculating ΔS*int is derived which takes into account specific reactant-solvent interactions for the isolated redox centers by employing electrochemical reaction entropy data. This relation yields rather larger and more structure-sensitive values of ΔS*int, than those deduced on the basis of the usual dielectric continuum treatment. These considerations indicate that the more negative values of ΔS*int typically extracted from experimental kinetic data arise largely from the modification to the specific reactant-solvent interactions within the precursor complex caused by the proximity of the other redox center.

Original languageEnglish
Pages (from-to)1860-1864
Number of pages5
JournalJournal of Physical Chemistry
Volume88
Issue number9
Publication statusPublished - 1984

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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