ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal decomposition reactions of dihydro-3,6-diphenyl-5-benzyl-1,2,4,5-trioxazine (DHT) in the initial concentrations and temperature ranges of 0.004-0.013 M and 353-393 K, respectively, have been investigated in benzene, toluene, and methanol solutions. In these solvents the reaction follows a first-order kinetic law up to ca. 50% DHT conversions. However, at the higher temperatures and higher initial concentrations, an induced decomposition reaction of the DHT molecule is observed, which is suppresed by the addition of a free radical scavenger. The pseudo-first-order rate constant values for the reactions of the trioxazine in acetic acid solution (0.004 M) in the temperature range of 313-323 K, lead to activation parameters significantly different from those of the unimolecular thermolysis in other media. This supports a marked effect of the solvent on that reaction. The kinetics and the nature of the products observed in the DHT thermolysis favors a general stepwise mechanism of decomposition which resembles the type of reaction already postulated for other cyclic peroxides in solution. © 1996 John Wiley & Sons, Inc.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.3
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