International Journal of Chemical Kinetics p. 503 - 509 (1994)
Update date:2022-08-24
Topics:
Cafferata
Lombardo
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 ln k1/(s-1) = (31.8 ± 2.5) - [39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O - O 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.
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