Direct kinetics study of the temperature dependence of the CH2O branching channel for the CH3O2+HO2 reaction

被引:46
作者
Elrod, MJ [1 ]
Ranschaert, DL [1 ]
Schneider, NJ [1 ]
机构
[1] Hope Coll, Dept Chem, Holland, MI 49423 USA
关键词
D O I
10.1002/kin.1030
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
A direct kinetics study of the temperature dependence of the CH2O branching channel for the CH3O2 + HO2 reaction has been performed using the turbulent Flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the CH2O-producing channel rate constant was investigated between 298 and 218 K at a pressure of 100 Torr, and the data were Fitted to the following Arrhenius expression: 1.6(-0.7)(+1.0) X 10(15) X exp[(1730 +/- 130)/T] cm(3) molecule(-1) s(-1). Using the Arrhenius expression for the overall rate of the CH3O2 + HO2 reaction and this result, the 298 K branching ratio for the CH2O producing channel is measured to be 0.11 and the branching ratio is calculated to increase to a value of 0.31 at 218 K, the lowest temperature accessed in this study. The results are compared to the analogous CH3O2 + CH3O2 reaction and the potential atmospheric ramifications of significant CH2O production from the CH3O2 + HO2 reaction are discussed. (C) 2001 John Wiley & Sons. Inc.
引用
收藏
页码:363 / 376
页数:14
相关论文
共 29 条
[1]   Formaldehyde production in clean marine air [J].
Ayers, GP ;
Gillett, RW ;
Granek, H ;
deServes, C ;
Cox, RA .
GEOPHYSICAL RESEARCH LETTERS, 1997, 24 (04) :401-404
[2]   EVOLUTION OF ALKYL NITRATES WITH AIR-MASS AGE [J].
BERTMAN, SB ;
ROBERTS, JM ;
PARRISH, DD ;
BUHR, MP ;
GOLDAN, PD ;
KUSTER, WC ;
FEHSENFELD, FC ;
MONTZKA, SA ;
WESTBERG, H .
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1995, 100 (D11) :22805-22813
[3]   RATE CONSTANTS FOR THE REACTIONS OF CH3O2 WITH HO2 NO AND NO2 USING MOLECULAR MODULATION SPECTROMETRY [J].
COX, RA ;
TYNDALL, GS .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1980, 76 :153-163
[4]   RATE CONSTANTS FOR REACTIONS OF CH3O2 IN THE GAS-PHASE [J].
COX, RA ;
TYNDALL, GS .
CHEMICAL PHYSICS LETTERS, 1979, 65 (02) :357-360
[5]   TEMPERATURE-DEPENDENCE OF THE RATE-CONSTANT FOR THE HO2 + CH3O2 GAS-PHASE REACTION [J].
DAGAUT, P ;
WALLINGTON, TJ ;
KURYLO, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (13) :3833-3836
[6]  
DeMore W.B., 1997, JPL PUBLICATION, P97
[7]   Temperature dependence of the rate constant for the HO2+BrO reaction [J].
Elrod, MJ ;
Meads, RF ;
Lipson, JB ;
Seeley, JV ;
Molina, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (14) :5808-5812
[8]  
Finlayson-Pitts B. J., 1999, CHEM UPPER LOWER ATM
[9]   Observations of methyl nitrate in the lower stratosphere during STRAT: Implications for its gas phase production mechanisms [J].
Flocke, F ;
Atlas, E ;
Madronich, S ;
Schauffler, SM ;
Aikin, K ;
Margitan, JJ ;
Bui, TP .
GEOPHYSICAL RESEARCH LETTERS, 1998, 25 (11) :1891-1894
[10]   REACTIONS OF SF6- AND I- WITH ATMOSPHERIC TRACE GASES [J].
HUEY, LG ;
HANSON, DR ;
HOWARD, CJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (14) :5001-5008