Decomposition of cyclic acetone peroxides in acid media |
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Authors: | Yu. B. Tsaplev |
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Affiliation: | 1. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, 119334, Russia
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Abstract: | The kinetics and stoichiometry of the formation of active oxygen (AO) in the acidic decomposition of trimeric (TATP) and dimeric (DADP) cyclic acetone peroxides are considered. Fe(III) produced as a result of Fe(II) oxidation with active oxygen has been determined using rhodanide procedure. The kinetics of the formation of active oxygen is described by a first order equation. The effective rate constant of TATP decomposition depends on the Hammett acidity function H 0: log k eff = ?H 0 ? 2.6 (k eff is in s?1). Consequently, the decomposition rate of TATP is limited by protonation. In the HCl and H2SO4 concentration range from 0.006 to 2.9 mol/L, the decomposition of DADP occurs with k eff = 0.0010 ± 0003 s?1 at a Fe(II) concentration of 3.5 mmol/L and k eff depends linearly on the concentration of Fe(II). |
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