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Title of Thesis

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

Author(s)

Mukhtiar Ali

Institute/University/Department Details
National Centre for Excellence in Physical Chemistry / University of Peshawar, Peshawar
Session
1996
Subject
Physical Chemistry
Number of Pages
130
Keywords (Extracted from title, table of contents and abstract of thesis)
Kinetics, Mechanism, Gas Phase, Thermal, Decomposition, Substituted, Cyclopropanes, Arrhenius

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.

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S. No. Chapter Title of the Chapters Page Size (KB)
1 0 CONTENTS

 

 
57 KB
2

1

INTRODUCTION 1
2,007 KB
3 2 EXPERIMENTAL 38
525 KB
4 3 RESULTS OF THERMAL ACTIVATION STUDIES 49
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5 4 DISCUSSION OF THERMAL ACTIVATION STUDIES 91
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6 5 APPENDICES & REFERENCES 108
498 KB