TITLE:
Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution
AUTHORS:
Alexander G. Bordon, Andrea N. Pila, Mariela I. Profeta, María J. Jorge, Lilian C. Jorge, Jorge M. Romero, Nelly L. Jorge
KEYWORDS:
DFT, Thermal Decomposition, Chlorobenzene, Mechanism
JOURNAL NAME:
International Journal of Organic Chemistry,
Vol.9 No.1,
January
14,
2019
ABSTRACT: The thermal decomposition
of Cyclic Diperoxide of Benzaldehyde 3,6-diphenyl-1,2,4,5-tetroxane, (DFT) in chlorobenzene solution in the studied
temperature range (130°C - 166°C) satisfactorily satisfies a first order law up
to 60% conversions of diperoxide. DFT would decompose through a mechanism in
stages and initiated by the homolytic breakdown of one of the peroxidic bonds
of the molecule, with the formation of the corresponding intermediate
biradical. The concentration studied was very low, so that the effects of
secondary reactions of decomposition induced by free radicals originated in the
reaction medium can be considered minimal or negligible. The activation
parameters for the unimolecular thermal decomposition reaction of the DFT are
ΔH# = 30.52 ± 0.3 kcal·mol-1 and ΔS# = -6.38 ± 0.6 cal·mol-1 K-1. The support for a step-by-step mechanism instead of a process
concerted is made by comparison with the theoretically calculated activation
energy for the thermal decomposition of 1,2,4,5-tetroxane.