Date of Award

8-1982

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Dr. D.C. Berndt

Second Advisor

Dr. R.H. Anderson

Third Advisor

Dr. R.C. Nagler

Fourth Advisor

Dr. R.C. Eisenberg

Abstract

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the rate constant in the micellar phase, K is the substrate-micelle association constant and N is the micellar aggregation number, do not exist for the para and meta compounds considered as a group. Only para derivatives alone gave the meaningful results. A multiple regression analysis indicates that log k(,m) is very well correlated by a combination of the lipophilicity substituent parameter, (pi), and the polar substituent parameter, (sigma)('+). Log K/N is correlated roughly with the (pi) and (sigma)('+) parameters. The results indicate that specific micellar effects on the reaction rates occur for the systems investigated.

Access Setting

Dissertation-Open Access

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