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Kinetics of cerium (IV) oxidation of mandelic acid. Ionic strength and specific cation effects

✍ Scribed by Gioacchina Arcoleo; Giuseppe Calvaruso; F. Paolo Cavasino; Emanuele Di Dio

Publisher
John Wiley and Sons
Year
1979
Tongue
English
Weight
455 KB
Volume
11
Category
Article
ISSN
0538-8066

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✦ Synopsis

The kinetics of the redox reaction between mandelic acid (MA) and ceric sulfate have been studied in aqueous sulfuric acid solutions and in HzSO4-MC104 (M+ = H+, Li+, Na+) and HzS04-MHS04 (M+ = Li+, Na+, K+) mixtures under various experimental conditions of total electrolyte concentration (that is, ionic strength) and temperature. The oxidation reaction has been found to occur via two paths according to the following rate law: rate

where

The cations considered exhibit negative specific effects upon the overall oxidation rate following the order H+ < Li+ < Na+ < K+. The observed negative cation effects on the rate constant k l are in the order Na+ < Li+ < H+, whereas the order is in reverse for kz, namely, H+ 6 Li+ < Na+. Lithium and hydrogen ions exhibit similar medium effects only when relatively small amounts of electrolytes are replaced. The type of the cation used does not affect significantly the activation parameters.

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