Gas/gas and gas/wall average energy transfer from very low-pressure pyrolysis

Gilbert, Robert G. and King, Keith D. (1980) Gas/gas and gas/wall average energy transfer from very low-pressure pyrolysis. Chemical Physics, 49 3: 367-375. doi:10.1016/0301-0104(80)85055-5

Author Gilbert, Robert G.
King, Keith D.
Title Gas/gas and gas/wall average energy transfer from very low-pressure pyrolysis
Journal name Chemical Physics   Check publisher's open access policy
ISSN 0301-0104
Publication date 1980-07
Sub-type Article (original research)
DOI 10.1016/0301-0104(80)85055-5
Volume 49
Issue 3
Start page 367
End page 375
Total pages 9
Place of publication Amsterdam, Netherlands
Publisher Elsevier
Language eng
Formatted abstract
The two-channel decomposition of chloroethane-2-d 1 (elimination of HCl and of DCl) has been studied using very low-pressure pyrolysis over the temperature range 975-1200 K (gas/wall collisions only) and over the range 1049-1130 K using Kr, Ne and He as bath gases. Fitting the data by solution of the integrodifferential reaction-diffusion master equation gives CH 2DCH 2Cl gas/wall downward energy collision transfer values of 6000-3500 cm -1 (975-1200 K) corresponding to collision efficiencies of 0.9-0.5; the wall is seasoned quartz. These collision efficiencies when applied to data obtained under the same conditions for the one-channel decomposition of CH 3CH 2Cl give extrapolated high-pressure Arrhenius parameters in excellent agreement with those obtained from conventional kinetic studies. The pressure-dependent data give gas/gas average downward collision energy transfer values of =600 cm -1 (Kr and Ne) and =700 cm -1 (He) over the observed temperature range (the values increasing slightly with increasing temperatures). The gas/gas energy transfer probability function, rather than being exponential in energy difference, is found to vary approximately as the exponential of the cube of the energy difference between initial and final states; the data are sensitive to this functional form since there is only a small difference between critical energies of each channel. Extrapolated high pressure rate coefficients for CH 2DCH 2Cl decomposition are 10 13.2 exp (-237 kJ mol -1/RT) s -1 (HCl elimination) and 10 13.1 exp (-244 kJ mol -1/RT) s -1 (DCl elimination). Unusual behaviour observed in the pressure dependence is interpreted as being caused by highly quantized structure in the microscopic reaction rate coefficients caused by the lack of low frequency (<400 cm -1) modes in the activated complexes.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

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: Mon, 07 Mar 2011, 15:44:54 EST