Kinetics of thermal decomposition of dimethyldioxirane in oxygen atmosphere

Abstract

Dimethyldioxirane decomposition in oxygen atmosphere follows a first-order kinetic law. Decomposition rate constant (k, s "t) in acetone in the temperature range from 30 to 50~ has been determined as lgk = (7.1 + 0.9)-(16.0 + 1.4)/0, 0 = 2.303KT kcal/moL

Dioxiranes: from oxidative transformations to chemiluminescence

“…124 It comes as no surprise that the dioxirane decomposition under an atmosphere of O 2 , which inhibits the radical chain process, strictly follows first-order kinetics irrespective of the initial dioxirane concentration or temperature (30 ± 49.5 8C). 132 e. Isomerisation of dimethyldioxirane to methyl acetate Although arguments in favour of the radical mechanism of decomposition of the dioxirane 1a are quite forcible, the existence of a parallel channel of the decomposition of 1a, namely, its isomerisation to MA via a biradical intermediate, can also be considered to be proven.…”

“…For example, this concerns MA, small amounts of which get into solutions of 1a in exactly this way. 112,119 Impurities that have got into a dioxirane solution via this route can be involved in the radical decomposition of dioxirane; hence, the different lifetimes of the dioxirane 1a synthesised by various researchers and the non-reproducibility of the kinetic data 15,109,112,118,119,123,132 can be due to different natures and amounts of non-controllable impurities able to accelerate decomposition of the dioxirane 1a and promote the formation of different decomposition products (see Table 2). This resembles the situation observed in the study of the kinetic and activation parameters of decomposition of tetramethyldioxetane (TMD).…”