Type of Document	Master's Thesis
Author	Hulvey, Glenn A.
URN	etd-06102009-063106
Title	Internal pressure's role in the selectivity of the bromine radical
Degree	Master of Science
Department	Chemistry
Advisory Committee	Advisor Name Title Tanko, James M. Committee Chair Marand, Hervé L. Committee Member Merola, Joseph S. Committee Member
Keywords	Toluene.
Date of Defense	1993-01-05
Availability	restricted
Abstract The results of our studies demonstrate a link between selectivity in free radical brominations and the internal pressure of solvent. The study encompassed l8 solvents and/or mixtures over which the rate constant ratio for SH2 ring opening of cyclopropylbenzene (kC) vs hydrogen abstraction from toluene (kH) by bromine atom was found to vary by nearly a factor of twenty as a function of solvent. The observed rate constant ratios correlate with the cohesive energy density of the solvent, which is approximately equal to the internal pressure (kC/kH is found to increase with increasing solvent pressure) for the solvents used in this study. A similar competition pitting cyclopropylbenzene against p-chlorotoluene shows the same solvent effect. It is suggested that the observed variation in selectivity "with solvent pressure occurs because the volume of activation with kC is more negative than for kH by about 20 cm3/mol.
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