Date of Award

3-9-1965

Document Type

Thesis

Degree Name

Master of Arts (MA)

Department

Chemistry

First Advisor

C. M. Hull

Second Advisor

B. E. Norcross

Third Advisor

B. E. Norcross

Abstract

Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.

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