Abstract
Kinetics of Br− anion oxidation by cerium(IV) species in aqueous H2SO4 solutions have been reexamined. The rate of reaction was determined spectrophotometrically based on a factor analysis of the absorbance – time data collected in the wavelength range 318–390 nm – the region characteristic for the cerium(IV) sulphato complexes. The data fit very well to a pseudo-first order dependence under a large molar excess of the reductant. The rate law of the form –d[CeIV]/dt = k[CeIV][Br–]2 has been obtained at constant H2SO4 concentration and ionic strength I = 2 m. The pseudo-first order rate constant decreases with an [H2SO4] increase from 0.1 to ca. 0.4 m range, then increases for higher [H2SO4]. The apparent activation parameters have been calculated from the third order rate constants k for different [H2SO4].
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