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Rapid Gas-Phase Reactions. Amines and Boron Trifluoride. II. Pressure Dependence of Rate Constant

Glicker, Sol and Marcus, R. A. (1969) Rapid Gas-Phase Reactions. Amines and Boron Trifluoride. II. Pressure Dependence of Rate Constant. Journal of the American Chemical Society, 91 (27). pp. 7607-7610. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20150810-161259699

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Abstract

Relative rate constants for reaction of monomethylamine and trimethylamine with boron trifluoride are reported for the pressure range 0.04-600 Torr. The limiting ratio at low pressure is about 0.836, and the extrapolated high-pressure ratio is of the order 4. The half-pressure for quasi-bimolecular behavior of the monomethylamine-boron trifluoride system is in the vicinity of 70 Torr. When the data are combined with those of Kistiakowsky, et al., individual pressure-dependent rate constants can be estimated. The amine-BF_3 series has loose activated complexes and low energy for redistribution among internal modes, making it an unusual candidate for theoretical unimolecular study.


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http://dx.doi.org/10.1021/ja50001a013DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja50001a013PublisherArticle
ORCID:
AuthorORCID
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1969 American Chemical Society. Received June 4, 1969. Supported in part by a grant from the National Science Foundation; abstracted in part from a thesis submitted by S. Glicker in partial fulfillment of the requirements for the degree of Doctor of Philosophy, June 1966.
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Issue or Number:27
Record Number:CaltechAUTHORS:20150810-161259699
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150810-161259699
Official Citation:Rapid Gas-Phase Reactions. Amines and Boron Trifluoride. II. Pressure Dependence of Rate Constant Sol Glicker and R. A. Marcus Journal of the American Chemical Society 1969 91 (27), 7607-7610 DOI: 10.1021/ja50001a013
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59373
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:11 Aug 2015 15:17
Last Modified:22 Nov 2019 09:58

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