The gas-phase oxidation of acetic acid by nitrogen dioxide

Pandey, Raj N. (1967) The gas-phase oxidation of acetic acid by nitrogen dioxide. Masters thesis, Memorial University of Newfoundland.

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    Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.
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Abstract

This thesis presents the results of a preliminary investigation of the gas-phase oxidation of acetic acid by nitrogen dioxide and is an example of a chemical process in which nitration competes with destructive oxidation of an organic molecule. The products of the reaction are CO, CO ₂, CH₃NO₂, NO, H₂O and possibly small quantities of N₂O and N₂. Carbon and nitrogen balances within 95% were obtained, about as expected when the analytical errors are considered. Small quantities of other products cannot be excluded. An induction period of ~900 seconds was observed at low temperature (~190°C) but no induction period was observable at 253.5°C. The induction period at low temperature indicates a complicated reaction mechanism. The rate using CH₃COOD indicated that carboxyl hydrogen abstraction reactions were kinetically important. For the same initial pressure of acetic acid and NO₂ the total pressure rise is not greatly changed by adding NO, or by using D- acid as the reactant. The reaction is auto catalysed by NO. With the techniques used the reaction rate was found to depend on the CH₃COOH and NO₂ concentrations but accurate orders could not be determined. As will be seen in the result section the method used is not suitable due to concurrent decomposition of NO₂. Although a final complete mechanism cannot be written at this time, the partial one discussed in this thesis has been suggested because it explains the formation of products and stimulates further study.

Item Type: Thesis (Masters)
URI: http://research.library.mun.ca/id/eprint/7284
Item ID: 7284
Additional Information: Includes bibliographical references.
Department(s): Science, Faculty of > Chemistry
Date: 1967
Date Type: Submission
Library of Congress Subject Heading: Oxidation-reduction reaction; Acetic acid

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