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Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase
Author(s) -
Cafferata Lázaro F. R.,
Lombardo José D.
Publication year - 1994
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550260503
Subject(s) - chemistry , activation energy , thermal decomposition , kinetics , reaction rate constant , acetone , homolysis , decomposition , atmospheric temperature range , reaction mechanism , octane , stepwise reaction , chemical kinetics , order of reaction , catalysis , thermodynamics , radical , organic chemistry , physics , quantum mechanics
Abstract The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6‐tetramethyl‐1,2,4,5‐tetroxane (ACDP) in the presence of n ‐octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first‐order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six‐fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k 1 /(s −1 ) = (31.8 ± 2.5) − [(39.0 ± 2.5)/ RT ]. The value of the energy of activation in kcal/mol correspond to one OO bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.