Rate constants and kinetic isotope effects for hydrogen/deuterium abstraction by chlorine atoms from the chloromethyl group in CH2ClCH2Cl, CD2ClCD2Cl, CH2ClCHCl2, and CH2ClCDCl2

✍ Scribed by E. Tschuikow-Roux; F. Faraji; Jan Niedzielski

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 804 KB
• Volume: 18
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550180502

✦ Synopsis

The abstraction of hydrogen and deuterium from 1,2-dichIoroethane, 1,1,2trichloroethane, and two of their deuterated analogs by photochemically generated ground state chlorine atoms has been investigated in the temperature range 0-95°C using methane as a competitor. Rate constants and their temperature coefficients are reported for the following reactions

Over the temperature range of this investigation an Arrhenius law temperature dependence was observed in all cases. Based on the adopted rate coefficient for the chlorination of methane [L. F. Keyser, J. Chem. Phys., 69, 214 (197811 k,/cm3 s-' = (1.65 ? 0.32) x lo-" exp[-(1530 2 68)/T] which is commensurate with the present temperature range, the following rate constant values (cm3 s-*) are obtained: k, = (4.93 2 0.96) X lo-" exp[-(1087 ? 68)/T] It2 = (2.92 ? 0.57) x lo-" exp[-(1362 t 68)/T] 4 = (2.03 2 0.39) x lo-" exp[-(1705 ? 68)/T] k, = (1.68 2 0.33) x lo-" exp[-(1965 2 68)/T] ks = (1.22 2 0.24) x lo-'' exp[-(1948 2 68)/T] k6 = (1.47 ? 0.28) x lo-'' exp[-(1910 68)/T]