ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal gas-phase decomposition of vinyl chloride has been studied behind shock waves over the temperature range of 1350-1900°K and the density range of 7 × 10-7-1.5 × 10-3 mol/cm3 (at 1600°K) in mixtures of C2H3Cl highly diluted with argon. The ultraviolet absorption of C2H3C was recorded at 230 nm as a function of time. The decomposition proceeds via molecular elimination of HCl. The unimolecular dissociation rate is pressure dependent at all but the highest pressures applied. Application of modified HKRR theory results in the rate expression \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\infty = 10^{14.0 \pm 0.2}\, {\rm exp}[= (290 \pm 12){\rm kJ}/{\rm mol}/RT]\,{\rm s}^{- 1},\,\quad 1400^ \circ {\rm K} \le T \le 1800^ \circ {\rm K} $$\end{document} for the limiting high pressure rate constant, and in a collision efficiency of \documentclass{article}\pagestyle{empty}\begin{document}$$ \beta _c = \frac{{k_0 ({\rm experiment})}}{{k_{\rm 0} {\rm (theoretical, strong collisions})}} \cong 0.04,\quad {\rm for M} = {\rm Ar},T = 1600^ \circ {\rm K} $$\end{document} derived from the limiting low-pressure rate constant.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550090413
