D/H kinetic isotope effect in the reaction CH4+Cl
- 1 December 1996
- journal article
- Published by American Geophysical Union (AGU) in Geophysical Research Letters
- Vol. 23 (24) , 3619-3622
- https://doi.org/10.1029/96gl03292
Abstract
The D/H kinetic isotope effect (KIEClD) in the reaction of CH4 with Cl has been investigated using a tunable diode laser absorption spectrometer (TDLAS) to measure 12CH3D/12CH4 ratios. A KIEClD of 1.508±0.041 was obtained at room temperature (296 K). Experiments employing Fourier transform infrared measurements of 12CH3D/12CH4 ratios confirmed this result. An investigation of the temperature dependence showed an increase of KIEClD (1.592±0.057 at 223 K) with decreasing temperature. This very large D/H fractionation effect affects the overall isotope fractionation in the middle and upper stratosphere, where Cl contributes substantially to the total removal of CH4.This publication has 14 references indexed in Scilit:
- Stratospheric observations of CH3D and HDO from ATMOS infrared solar spectra: Enrichments of deuterium in methane and implications for HDGeophysical Research Letters, 1996
- Implications of the large carbon kinetic isotope effect in the reaction CH4 + Cl for the 13C/12C ratio of stratospheric CH4Geophysical Research Letters, 1996
- High-precision direct measurements of ^13CH_4/^12CH_4 and ^12CH_3D/^12CH_4 ratios in atmospheric methane sources by means of a long-path tunable diode laser absorption spectrometerApplied Optics, 1994
- Concentration and 13C records of atmospheric methane in New Zealand and Antarctica: Evidence for changes in methane sourcesJournal of Geophysical Research: Atmospheres, 1994
- Climate effects of atmospheric methaneChemosphere, 1993
- The HITRAN molecular database: Editions of 1991 and 1992Journal of Quantitative Spectroscopy and Radiative Transfer, 1992
- Carbon isotopic composition of atmospheric CH4: Fossil and biomass burning source strengthsGlobal Biogeochemical Cycles, 1991
- Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radicalJournal of Geophysical Research: Atmospheres, 1990
- Carbon kinetic isotope effect in the reaction of CH4 with HOJournal of Geophysical Research: Atmospheres, 1987
- Chemical budgets of the stratospherePlanetary and Space Science, 1983