Kinetics of Thermal Decomposition of Aqueous Perchloric Acid

Canadian Science Publishing - Tập 49 Số 2 - Trang 317-324 - 1971
M. Patricia Henderson1, Viola I. Miasek1, Thomas W. Swaddle1
1Department of Clzemistry, The University of Calgary, Calgary 44, Alberta

Tóm tắt

Thermal decomposition of 1.1–6.6 m aqueous perchloric acid at 295–322° yields oxygen, chlorine, and a small quantity of hydrochloric acid. The initial rates of decomposition have been measured, using a perchlorate ion activity electrode, and show 3.5 order dependence on the stoichiometric perchloric acid concentration; the corresponding rate coefficient and activation energy at 300.0° are 3.1 × 10-7 m −2.5 s−1 and 84 kcal mole−1, respectively. The order of reaction with respect to time is less than 3.5 and depends upon the initial perchloric acid concentration; this effect is due to acceleration of the decomposition by the reaction products, notably chloride ion. It is suggested that the rate-determining step in the decomposition of aqueous perchloric acid is the reaction of two undissociated HClO4 molecules to give H2O, ClO3, and ClO4.

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