Carbon kinetic isotope effect in the reaction CH4+Cl:: a relative rate study using FTIR spectroscopy

被引:47
作者
Crowley, JN
Saueressig, G
Bergamaschi, P
Fischer, H
Harris, GW
机构
[1] Max Planck Inst Chem, Div Atmospher Chem, D-55020 Mainz, Germany
[2] York Univ, Ctr Atmospher Chem, N York, ON, Canada
[3] York Univ, Dept Chem, N York, ON M3J 1P3, Canada
关键词
D O I
10.1016/S0009-2614(99)00243-2
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The C-12/C-13 kinetic isotope effect in the reaction of methane with chlorine atoms (KIECl12C/13C) was investigated at 298 K using photolysis of static Cl-2/CH4/N-2 miutures, with in-situ analysis of isotopic composition by FTIR absorption spectroscopy. Least squares fitting of composite (CH4)-C-12/(CH4)-C-13 spectra to reference spectra obtained at the same temperature, pressure and resolution enabled the relative (CH4)-C-12:(CH4)-C-13 content to be measured at a high precision. The result obtained was KIECl12C/13C (298 K) = 1.066 +/- 0.002 (2 sigma), in excellent agreement with the single previous experimental determination at this temperature. This result confirms the unexpectedly high fractionation in the title reaction. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:268 / 274
页数:7
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