Science and Technology Production
Article
Authorship
Nesprias, Rosa Karina
;
Eyler, Gladys Nora
;
Cañizo, Adriana Ines
;
BARRETO, GASTON PABLO
Date
2017
Publishing House and Editing Place
Sociedade Brasileira de Química
Magazine
QUÃMICA NOVA,
vol. 40
(pp. 388-394)
Sociedade Brasileira de Química
Summary
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The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 °C temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86% peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decompose...
The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 °C temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86% peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (kH/kD <1).
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Key Words
ISOTOPIC SECONDARY INVERSE EFFECTDEUTERATED ACETONE DIPEROXIDEACETONE DIPEROXIDETHERMOLYSIS
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