Date of Award

6-1959

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Hilton A. Smith

Committee Members

William T. Smith, E. Cohen, M. J. Jonnich

Abstract

An improved effusiometry apparatus for analyzing hydrogen and deuterium mixtures was constructed and utilized to study the exchange reaction of deuterium with methanol over Raney nickel catalyst.

The exchange reaction was zero order with respect to deuterium pressure and pseudo-zero order with respect to methanol concentration. The apparent activation energy was found to be 3.5 kcal./mole. The specific reaction rate was 2.9 1. mm. min.-1 g.-1.

The effects of nitro compounds upon the exchange of deuterium with methanol over Raney nickel were studied. All of the compounds decreased the exchange at very low concentrations and all, except nitromesitylene, prevented the exchange at higher concentrations. Except for nitromesitylene, the effects paralleled the kinetics of catalytic hydrogenation of these nitro compounds under similar conditions.

Since Raney nickel can liberate hydrogen directly, a method for determining per cent exchange in is presence was developed. It was shown that the exchanged hydrogen did originate from the hydroxyl hydrogen of methanol.

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