Marcus, R. A. and Winkler, C. A. (1953) Studies of RDX and related compounds: XI. The conversion of PHX to AcAn. Canadian Journal of Chemistry, 31 (6). pp. 602-614. ISSN 0008-4042. doi:10.1139/v53-083. https://resolver.caltech.edu/CaltechAUTHORS:20150422-164115124
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Abstract
The formation of AcAn from PHX, nitric acid, and acetic anhydride has been investigated at various temperatures. The effects of added acetic acid and added salts have been determined. While the reaction is first order with respect to PHX, it is of an order 2.6 with respect to nitric acid. The reaction rate is significantly decreased by small concentrations of sodium nitrate. The reaction is also characterized by a secondary salt effect and a low apparent activation energy of about 2 kcal. mole^(−1). A mechanism has been suggested in qualitative, and to some extent quantitative, agreement with the experimental data. It is postulated that the conversion of PHX involves a rate-controlling ionic reaction between PHX and nitric acid, and that this is followed by a rapid acetylation of the acidic intermediate to AcAn.
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Additional Information: | © 1953 National Research Council Canada. Manuscript received December 12, 1952. Contribution from the Physical Chemistry laboratory, McGill University, Montreal, Que., with financial assistance from the National Research Council of Canada. Graduate Student (1943-46) and holder of a National Research Council Studentship. | |||||||||
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Issue or Number: | 6 | |||||||||
DOI: | 10.1139/v53-083 | |||||||||
Record Number: | CaltechAUTHORS:20150422-164115124 | |||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150422-164115124 | |||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
ID Code: | 56896 | |||||||||
Collection: | CaltechAUTHORS | |||||||||
Deposited By: | George Porter | |||||||||
Deposited On: | 23 Apr 2015 15:10 | |||||||||
Last Modified: | 10 Nov 2021 21:05 |
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