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Very low pressure reactor. A new technique for measuring rates and equilibriums of radical-molecule reactions at low temperature. Heat of formation of the methyl radical

Baghal-Vayjooee, M. H. and Colussi, A. J. and Benson, S. W. (1978) Very low pressure reactor. A new technique for measuring rates and equilibriums of radical-molecule reactions at low temperature. Heat of formation of the methyl radical. Journal of the American Chemical Society, 100 (10). pp. 3214-3215. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20150623-154815650

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Abstract

We wish to report here a new method for measuring rate constants and equilibrium constants of molecule-radical reactions near ambient temperatures. The method, using a very low pressure reactor (VLPR) is a variation of our very low pressure pyrolysis technique (VLPP) which has been described in detail elsewhere. VLPP has been restricted to high temperatures (>700 K) because of the necessity of generating radicals rapidly (< 10^(-1) s) via thermal pyrolysis. It also suffers from the difficulty of requiring extensive correction for radical reactions on the reactor walls. We have solved the first problem of generating radicals at low temperatures by dissociating diatomics in a microwave discharge and diffusing them into the reactor. The atoms as generated will react with suitably chosen substitutes to form radicals. The surface reactivity problem has been solved by using a fluorocarbon coating on our reactor walls which seems to be totally inert (< 10^5 collisions) to reactive atoms or radical. We are engaged in an extensive study of radical reactions using these technique. The present report is concerned with its application to equilibria.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00478a044DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00478a044PublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1978 American Chemical Society. Received February 1, 1978. This work was supported in part by grants from the National Science Foundation (CHE-76-16787A01) and the Army Office of Scientific Research (DAAG29-76-G-0195).
Funders:
Funding AgencyGrant Number
NSFCHE-76-16787A01
Army Research Office (ARO)DAAG29-76-G-0195
Issue or Number:10
Record Number:CaltechAUTHORS:20150623-154815650
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150623-154815650
Official Citation:Very low pressure reactor. A new technique for measuring rates and equilibriums of radical-molecule reactions at low temperature. Heat of formation of the methyl radical M. H. Baghal-Vayjooee, A. J. Colussi, and S. W. Benson Journal of the American Chemical Society 1978 100 (10), 3214-3215 DOI: 10.1021/ja00478a044
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58550
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 18:13
Last Modified:03 Oct 2019 08:37

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