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O. Dobis, S.W. Benson

Detailed Kinetic Investigation of the C₂H₅+Cl₂ Reaction and Analysis of the Reaction of CH₃+Cl₂ Initiated by H-Atom Contamination at 298K and at Millitorr Pressures

The bimolecular reaction: C₂H₅ + Cl₂ ⁴→ C₂H₅Cl + Cl is studied in the very low pressure reactor (VLPR) system at 298K starting with Cl/C₂H₆/Cl₂ mixtures. Mass conservation is found to be 97 ± 3% for the overall chemical change in the system. From the C₂H₅Cl product formation kinetics, k₄=(1.05±0.05)·10^-12cm³/(molecule-s) is derived. Two independent estimates of the A factor gives A₄=1.3 ·10^-12cm³/(molecule-s). These parameters yield a positive activation energy of 0.13 kcal/mol in contrast with recently reported negative activation energy values. Some side reactions of small extent are initiated by H atom contamination in the system. The measurement of CH₃Cl product formed from CH₃+Cl₂¹¹→CH₃Cl+Cl gives k₁₁=(3.4±0.3) · 10^-12cm³/(molecule-s) with an estimated A factor of A₁₁=5.0×10^-12cm³/(molecules). The source of CH₃ radicals is the side reaction H+C₂H₅→2CH₃.

Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0942-9352
Volume: 215, 03/2001
Pages: 283

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