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Cerium (IV) oxidation rate of p ‐chloromandelic acid in perchlorate and sulfate media
Author(s) -
Calvaruso Giuseppe,
Cavasino F. Paolo,
Sbriziolo Carmelo
Publication year - 1981
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550130205
Subject(s) - chemistry , cerium , perchlorate , inorganic chemistry , redox , ionic strength , sulfate , supporting electrolyte , reaction rate , sodium perchlorate , intramolecular force , reaction rate constant , electron transfer , electrolyte , kinetics , catalysis , ion , photochemistry , electrochemistry , stereochemistry , electrode , organic chemistry , physics , quantum mechanics , aqueous solution
The rate of the cerium (IV) oxidation of p ‐chloromandelic acid has been studied in perchlorate media at an ionic strength of 1.50 mol/dm 3 by the stopped‐flow technique and in H 2 SO 4 MHSO 4 (M + = Li + , Na + , K + ) and H 2 SO 4 MClO 4 (M + = H + , Li + , Na + ) mixtures at constant total electrolyte concentrations of 1.00 and 2.00 mol/dm 3 using the conventional spectrophotometric method. In perchlorate media the kinetic data indicate the formation of two intermediate complexes between cerium (IV) and the organic substrate, but only one is significantly involved in the intramolecular electron‐transfer process. The oxidation rate is markedly lower in sulfate media, where two reaction paths have been found to contribute to the overall redox reaction. The univalent cations examined exhibit negative specific effects upon the overall oxidation rate increasing in the order H + < Li + < Na + < K + . Activation parameters have been also estimated.