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Hydrogen/deuterium abstraction by chlorine atoms from gaseous ethyl chlorides. Secondary kinetic isotope effects in the system CH3CH2Cl, CH3CHDCl, CH3CD2Cl

✍ Scribed by J. Niedzielski; E. Tschuikow-Roux; T. Yano

Publisher: John Wiley and Sons
Year: 1984
Tongue: English
Weight: 543 KB
Volume: 16
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550160602

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✦ Synopsis

The abstraction of hydrogen/deuterium from CH3CH2C1, CH,CHDCl, and CH,CD,Cl by photochemically generated ground-state chlorine atoms has been investigated over the temperature range of 8-94°C using methane as a competitor. Rate constant data for the following reactions have been obtained: (1) CH,C&Cl + C1-+ CH,CHCl + HCl (21 CH,CH,Cl + C1+ CH,CH,Cl + HCI (3) C€J,CHDCl + C1+ CH,CHDCl + HCl (4) C~,CD,Cl + C1 4 CH,CD,Cl + HCI (5) CH,CQ,Cl + C1+ CH,CDCl + DCl The temperature dependence of the relative rate constants k,/k, was found to conform to the Arrhenius rate law, where the stated error limits are one standard deviation: k , / k , = (1.099 2 0.015) exp[(429 ? 2)/77 k , / k , = (1.422 ? 0.026) exp[(lll3 ? 31/q k , / k , = (1.295 t 0.029)exp[(684 2 31/27 k , / k , = (1.177 0.025) exp[(717 ? 41/77 k , / k , = (1.115 t 0.023) exp[(732 ? 21/77 k , / k , = (0.978 t 0.020) exp[(985 ? 21/77 and k , is the rate constant for the reference reaction (CH, + C1 + CH, + HCl).

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