ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the permanganate oxidation of formic acid in aqueous perchloric acid has been studied. The results indicate that this reaction is autocatalyzed by both manganese(II) ion (formed as a reaction product) and colloidal manganese dioxide (formed as an intermediate). The apparent rate constants corresponding to the noncatalytic and autocatalytic reaction pathways are given, respectively, by the following equations \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} k_1 = (k_1^{bc} /[{\rm H}^{\rm +}] + k_1^{nc} + k_1^{ac} [{\rm H}^{\rm +}]^3)[{\rm HCOOH]} \\ k_2 = (k_2^{bc} /[{\rm H}^{\rm +}] + k_2^{nc} + k_2^{ac} [{\rm H}^{\rm +}]^3)[{\rm HCOOH]} \\ \end{array} $$\end{document} The activation energies associated with the true rate constants, k1bc, k1nc, k1ac, k2bc, k2nc, and k2ac are 37.2, 62.5, 70.9, 52.5, 40.8, and 59.9 kJ mol-1, respectively. The percentage of the total reaction corresponding to each pathway is given for typical experimental conditions. Mechanisms in agreement with the kinetic data are proposed for the six different reaction pathways observed.
Additional Material:
12 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550220306
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