Experimentally determined kinetic isotope effects in the reaction of CH4 with Cl:: Implications for atmospheric CH4

被引：53

作者：

Tyler, SC ^{[1
]}

Ajie, HO

Rice, AL

Cicerone, RJ

Tuazon, EC

机构：

[1] Univ Calif Irvine, Dept Earth Syst Sci, Irvine, CA 92697 USA

[2] Univ Calif Riverside, Air Pollut Res Ctr, Riverside, CA 92521 USA

来源：

GEOPHYSICAL RESEARCH LETTERS | 2000年 / 27卷 / 12期

关键词：

D O I：

10.1029/1999GL011168

中图分类号：

P [天文学、地球科学];

学科分类号：

07 ;

摘要：

We report experimental values for the carbon and hydrogen kinetic isotope effects (KIEs) in the reaction of CH4 with Cl at temperatures between 273 and 350 K. Isotope ratio mass spectrometry was utilized to measure (CH4)-C-13/(CH4)-C-12 and CH3D/CH4 ratios on samples taken from a 5870- L reaction chamber. At 299 K, k(c12)/k(c13) = 1.0621+/-0.0001 (2 sigma) and k(h)/k(d) = 1.474+/-0.020 (2 sigma). For both KIEs, the ratio decreased with increasing temperature over the range studied. These results agree well with experimental studies using tunable diode laser absorption spectroscopy and FTIR absorption spectroscopy and with a recent theoretically-calculated set of values.

引用

页码：1715 / 1718

页数：4

共 26 条

[1]

[Anonymous], ADV ENV SCI TECHNOL

[2] Evaluated kinetic and photochemical data for atmospheric chemistry, organic species: Supplement VII [J].

Atkinson, R ;

Baulch, DL ;

Cox, RA ;

Hampson, RF ;

Kerr, JA ;

Rossi, MJ ;

Troe, J .

JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1999, 28 (02) :191-393

[3] Implications of the large carbon kinetic isotope effect in the reaction CH4+Cl for the C-13/C-12 ratio of stratospheric CH4 [J].

Bergamaschi, P ;

Bruhl, C ;

Brenninkmeijer, CAM ;

Saueressig, G ;

Crowley, JN ;

Grooss, JU ;

Fischer, H ;

Crutzen, PJ .

GEOPHYSICAL RESEARCH LETTERS, 1996, 23 (17) :2227-2230

[4] The C-13, C-14 and O-18 isotopic composition of CO, CH4, and CO2 in the higher southern latitudes lower stratosphere [J].

Brenninkmeijer, CAM ;

Lowe, DC ;

Manning, MR ;

Sparks, RJ ;

vanVelthoven, PFJ .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1995, 100 (D12) :26163-26172

[5] CARBON KINETIC ISOTOPE EFFECT IN THE OXIDATION OF METHANE BY THE HYDROXYL RADICAL [J].

CANTRELL, CA ;

SHETTER, RE ;

MCDANIEL, AH ;

CALVERT, JG ;

DAVIDSON, JA ;

LOWE, DC ;

TYLER, SC ;

CICERONE, RJ ;

GREENBERG, JP .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1990, 95 (D13) :22455-22462

[6] BIOGEOCHEMICAL ASPECTS OF ATMOSPHERIC METHANE [J].

Cicerone, R. ;

Oremland, R. .

GLOBAL BIOGEOCHEMICAL CYCLES, 1988, 2 (04) :299-327

[7] Carbon kinetic isotope effect in the reaction CH4+Cl:: a relative rate study using FTIR spectroscopy [J].

Crowley, JN ;

Saueressig, G ;

Bergamaschi, P ;

Fischer, H ;

Harris, GW .

CHEMICAL PHYSICS LETTERS, 1999, 303 (3-4) :268-274

[8] Continuing decline in the growth rate of the atmospheric methane burden [J].

Dlugokencky, EJ ;

Masarie, KA ;

Lang, PM ;

Tans, PP .

NATURE, 1998, 393 (6684) :447-450

[9]

DONNER L, 1980, J ATMOS SCI, V37, P119, DOI 10.1175/1520-0469(1980)037<0119:MANOTE>2.0.CO

[10]

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