Abstract
THE mechanism of the thermolysis of diethyl peroxide is uncertain. Harris and Egerton believed the reaction to be a straightforward, unimolecular decomposition, although they observed short induction periods with some samples and generally much longer ones in the presence of nitric oxide1. The products suggest the occurrence of reactions involving free radicals, and in the opinion of Neumann2 the decomposition is a chain reaction. It is, however, difficult to reconcile a significant participation of free radicals in the decomposition with the first-order kinetics and the low activation energy (c. 31 k.cal.), compared with accepted dissociation energies of O—O bonds (HO—OH, 54 k.cal.3, t.BuO—Ot.Bu. 39 k.cal. 4).
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References
Proc. Roy. Soc., A, 168, 1 (1938).
Blat, Gerber and Neumann, Acta Physicochim., U.R.S.S., 10, 273 (1939). Neumann and Tutakin, Acta Physicochim., U.R.S.S., 9, 861 (1938).
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Mortlock and Style (see preceding communication).
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JENKINS, A., STYLE, D. Inhibition of the Thermal Decomposition of Diethyl Peroxide. Nature 170, 706 (1952). https://doi.org/10.1038/170706b0
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DOI: https://doi.org/10.1038/170706b0
