ISSN:
0538-8068
Keywords:
Chemistry
;
Physics Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reinvestigation of the gas phase thermal reaction of 1,1,2,2-tetramethylcyclopropane (699-759°K) gave for the unimolecular disappearance of reactant, k(TMC) = 1015.27-63.93/θ sec-1, in good agreement with the original results of Frey and Marshall. However, evidence for a high activation energy (E = 79 ± 5 kcal/mole), competitive unimolecular decomposition to 2,3-dimethyl-1 and -2-butenes was also obtained. It is proposed that the serious discrepancy noted [1] between the experimentally observed Arrhenius parameters for the overall reaction kinetics, and those predicted by transition state calculations assuming a biradical mechanism for the isomerization reactions (previously believed to be the only primary reaction mode) can be explained in terms of the increasing importance of the decomposition reactions at higher reaction temperatures.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550020102
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