Kinetics of the reaction between cyclopentylperoxy radicals and HO2

被引:19
作者
Crawford, MA
Szente, JJ
Maricq, MM
Francisco, JS
机构
[1] FORD MOTOR CO,RES LAB,DEARBORN,MI 48121
[2] PURDUE UNIV,DEPT CHEM,W LAFAYETTE,IN 47907
关键词
D O I
10.1021/jp9710704
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 techniques of time-resolved UV spectroscopy and transient IR absorption are used to examine the kinetics of the c-C5H9O2 + HO2 reaction over the temperature range 214-359 K. Deconvolution of the UV spectra yield time-dependent concentrations of both the cyclopentylperoxy and HO2 reactants; the transient IR experiments separately monitor HO2. Fits of these data to the appropriate reaction model yield a rate constant of k(ro2+ho2) = (3.2(-1.1)(+15)) x 10(-13)e((1150+/-200)/T) cm(3) s(-1) for the title reaction. This result is compared to the single previous study of c-C5H9O2 + HO2 kinetics, and the implications for the atmospheric chemistry of peroxy radicals are discussed. As part of the present study, a relative rate of k(cl+c5h10)/k(cl+ch3oh) = (2.3 +/- 0.3)e((300+/-200)/T) has been measured for the reaction Cl + c-C5H10 --> c-C5H9 + HCl relative to Cl + CH3OH --> CH2OH + HCl.
引用
收藏
页码:5337 / 5343
页数:7
相关论文
共 20 条
  • [1] A spectroscopic, kinetic, and product study of the (CH3)(2)C(OH)CH2O2 radical self-reaction and reaction with HO2
    Boyd, AA
    Lesclaux, R
    Jenkin, ME
    Wallington, TJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (16) : 6594 - 6603
  • [2] A DETAILED MECHANISM FOR THE GAS-PHASE ATMOSPHERIC REACTIONS OF ORGANIC-COMPOUNDS
    CARTER, WPL
    [J]. ATMOSPHERIC ENVIRONMENT PART A-GENERAL TOPICS, 1990, 24 (03): : 481 - 518
  • [3] A KINETICS STUDY OF REACTIONS OF HO2 AND C2H5O2 USING DIODE-LASER ABSORPTION-SPECTROSCOPY
    CATTELL, FC
    CAVANAGH, J
    COX, RA
    JENKIN, ME
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1986, 82 : 1999 - 2018
  • [4] TEMPERATURE-DEPENDENCE OF THE RATE-CONSTANT FOR THE HO2 + CH3O2 GAS-PHASE REACTION
    DAGAUT, P
    WALLINGTON, TJ
    KURYLO, MJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (13) : 3833 - 3836
  • [5] FLASH-PHOTOLYSIS KINETIC ABSORPTION-SPECTROSCOPY STUDY OF THE GAS-PHASE REACTION HO2 + C2H5O2 OVER THE TEMPERATURE-RANGE 228-380-K
    DAGAUT, P
    WALLINGTON, TJ
    KURYLO, MJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (13) : 3836 - 3839
  • [6] DEMORE WB, 1994, JPL PUBL, V9426
  • [7] THE ETHYLPEROXY RADICAL - ITS ULTRAVIOLET-SPECTRUM, SELF-REACTION, AND REACTION WITH HO2, EACH STUDIED AS A FUNCTION OF TEMPERATURE
    FENTER, FF
    CATOIRE, V
    LESCLAUX, R
    LIGHTFOOT, PD
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (14) : 3530 - 3538
  • [8] A PHOTOCHEMICAL KINETICS MECHANISM FOR URBAN AND REGIONAL SCALE COMPUTER MODELING
    GERY, MW
    WHITTEN, GZ
    KILLUS, JP
    DODGE, MC
    [J]. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1989, 94 (D10) : 12925 - 12956
  • [9] NONMETHANE HYDROCARBONS IN REMOTE TROPICAL, CONTINENTAL, AND MARINE ATMOSPHERES
    GREENBERG, JP
    ZIMMERMAN, PR
    [J]. JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1984, 89 (ND3) : 4767 - 4778
  • [10] ORGANIC PEROXY-RADICALS - KINETICS, SPECTROSCOPY AND TROPOSPHERIC CHEMISTRY
    LIGHTFOOT, PD
    COX, RA
    CROWLEY, JN
    DESTRIAU, M
    HAYMAN, GD
    JENKIN, ME
    MOORTGAT, GK
    ZABEL, F
    [J]. ATMOSPHERIC ENVIRONMENT PART A-GENERAL TOPICS, 1992, 26 (10): : 1805 - 1961