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Kinetics and Mechanism of the Gas Phase Thermal Decomposition of Substituted Cyclopropanes

Ali, Mukhtiar (1996) Kinetics and Mechanism of the Gas Phase Thermal Decomposition of Substituted Cyclopropanes. PhD thesis, University of Peshawar, Peshawar.

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Abstract

The gas phase thermal decomposition of Methyl-cyclopropane carboxylate [MCC] (682-793K, 5-50 Torr), Cis-2- methylcyclopropanecarboxylic acid (cMCCA) (692-753K, 10-70 Torr) , Methylcyclopropanemethanol (MCM) (562-622K, 4-16 Torr) Cis 2-methylcyclopropanemethanol (cMCM) (483-97K, 5 -24 Torr) have been investigated in aged reactions vessels. Arrhenius parameters were determined for homogenous, unimolecular, formation of the isomeric products and for the overall loss of reactions. The formation of isomeric products and the observed Arrhenius parameters in all the above mentioned studies are consistent with a biradical mechanism in which the methanol, carboxylic groups stabilizes while carboxylate groups destabilises the transition states for If-transfer and, to a lesser extent, the transition state for geometric isomerization. cMCCA and cMCM underwent first order, reversible geometric isomerization incompetition with structural isomerization. On the basis of biradical mechanism the results provide evidence for the formation of distinguishable biradicals on opening the cMCCA and cMCM rings. The effect of the surface on the reaction was studied using the packed reaction vessel for the above mentioned substituted cyclopropane.

Item Type:Thesis (PhD)
Uncontrolled Keywords:Kinetics, Mechanism, Gas Phase, Thermal, Decomposition, Substituted, Cyclopropanes, Arrhenius
Subjects:Physical Sciences (f) > Chemistry(f2)
ID Code:6718
Deposited By:Mr. Javed Memon
Deposited On:21 Jul 2011 10:15
Last Modified:21 Jul 2011 10:15

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