ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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/dm3 by the stopped-flow technique and in H2SO4—MHSO4 (M+ = Li+, Na+, K+) and H2SO4—MClO4 (M+ = H+, Li+, Na+) mixtures at constant total electrolyte concentrations of 1.00 and 2.00 mol/dm3 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.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550130205
