Abstract
The kinetics of oxidation of malonic acid, studied in aqueous acid perchlorate, conform to the rate law $$\begin{gathered} - d[Cr^{VI} ]/dt = (k_2 K_1 [H^ + ] + k_3 K_1 K_2 [H^ + ]^2 )1 \hfill \\ + K_1 [H^ + ][Cr^{VI} ]_T [H_2 ma]_T \hfill \\ \end{gathered} $$ where [CrVI]T and [H2ma]T are the gross analytical concentrations of CrVI and malonic acid respectively. The stoichiometry of the reaction is variable as the initial oxidation product of the organic acid undergoes further partial oxidation. The rate is also inhibited by anions and the quantitative effect of Cl− in particular has been analysed, suggesting a chloro-chromium(VI) complex. A reaction mechanism is suggested.
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