Competitive unimolecular reactions at low pressures. The pyrolysis of cyclobutyl chloride

King, Keith D., Gaynor, Brendan J. and Gilbert, Robert G. (1979) Competitive unimolecular reactions at low pressures. The pyrolysis of cyclobutyl chloride. International Journal of Chemical Kinetics, 11 1: 11-21. doi:10.1002/kin.550110103


Author King, Keith D.
Gaynor, Brendan J.
Gilbert, Robert G.
Title Competitive unimolecular reactions at low pressures. The pyrolysis of cyclobutyl chloride
Journal name International Journal of Chemical Kinetics   Check publisher's open access policy
ISSN 0538-8066
1097-4601
Publication date 1979-01-01
Sub-type Article (original research)
DOI 10.1002/kin.550110103
Volume 11
Issue 1
Start page 11
End page 21
Total pages 11
Place of publication Hoboken, NJ, United States
Publisher John Wiley & Sons
Language eng
Formatted abstract
The thermal decomposition of cyclobutyl chloride has been investigated over the temperature range of 892–1150 K using the technique of very low-pressure pyrolysis (VLPP). The reaction proceeds via two competitive unimolecular channels, one to yield ethylene and vinyl chloride and the other to yield 1,3-butadiene and hydrogen chloride, with the latter being the major reaction under the experimental conditions. With the usual assumption that gas-wall collisions are «strong,» RRKM calculations, generalized to take into account two competing pathways, show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters given by log k1(sec−1) = (14.8 ± 0.3) − (61.1 ± 1.0)/Θ for vinyl chloride formation and log k2(sec−1) = (13.6 ± 0.3) − (55.7 ± 1.0)/Θ for 1,3-butadiene formation, where Θ = 2.303 RT kcal/mol. The A factors were assigned from previous high-pressure low-temperature data of other workers assuming a four-center transition state for 1,2-HCl elimination and a chlorine-bridged biradical transition state for vinyl chloride formation. The activation energies are in good agreement with the high-pressure results which were obtained with a conventional static system. The difference in critical energies is 4.6 kcal/mol.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown
Additional Notes Article first published online: 19 October 2004.

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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Created: Tue, 08 Mar 2011, 01:48:32 EST