Kinetic and mechanistic studies of atmospheric degradation of diethyl pyrocarbonate initiated by OH radicals and chlorine atoms

被引:3
作者
Rimondino, Guido N. [1 ]
Iriarte, Ana G. [1 ]
Grosso, Mercedes [1 ]
Malanca, Fabio E. [1 ]
机构
[1] Univ Nacl Cordoba, Fac Ciencias Quim, Dept Fisicoquim, INFIQC,CONICET,Inst Invest Fisicoquim Cordoba, Ciudad Univ X5000HUA, Cordoba, Argentina
关键词
Diethyl pyrocarbonate; Kinetics; Atmospheric lifetimes; Infrared spectra; Reaction products; GAS-PHASE REACTIONS; HYDROXYL RADICALS; CL ATOMS; RATE COEFFICIENTS; RATE CONSTANTS; SERIES; TEMPERATURE; OXIDATION; CHEMISTRY; PHOTOOXIDATION;
D O I
10.1016/j.jphotochem.2021.113409
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 atmospheric reactivity of dicarbonyl compounds is becoming an increasing environmental concern due to the growth in their emissions, tracked by their usage as solvents and industrial additives during the last decades. In this paper, the gas phase degradation of diethyl pyrocarbonate (DEPC) initiated by both hydroxyl radicals and chlorine atoms was studied. The rate coefficients for the reaction between DEPC with OH radicals (k(OH)) and chlorine atoms (k(Cl)) were determined, being k(OH) = 1.2 x 10(-)(12) cm(3) molec(-1) s(-1) and k(Cl) = 3.4 x 10(-12) cm(3) molec(-1) s(-1). The analysis of the photo-oxidation products and the reaction mechanism were both experimentally determined by infrared spectroscopy and supported by theoretical calculations. Formations of dicarbonyl compounds (CH3CH2OC(O)OC(O)CH3, CH3CH2OC(O)OC(O)H), acetic acid, formic acid, formaldehyde, carbon monoxide, and carbon dioxide were observed. Finally, environmental implications are concluded based on the atmospheric lifetime of DEPC.
引用
收藏
页数:7
相关论文
共 40 条
  • [31] KINETICS AND MECHANISM OF THE ATMOSPHERIC OXIDATION OF TERTIARY AMYL METHYL-ETHER
    SMITH, DF
    MCIVER, CD
    KLEINDIENST, TE
    [J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1995, 27 (05) : 453 - 472
  • [32] Unexpectedly high concentrations of molecular chlorine in coastal air
    Spicer, CW
    Chapman, EG
    Finlayson-Pitts, BJ
    Plastridge, RA
    Hubbe, JM
    Fast, JD
    Berkowitz, CM
    [J]. NATURE, 1998, 394 (6691) : 353 - 356
  • [33] Direct kinetic study of reactions of hydroxyl radicals with alkyl formates
    Szilágyi, I
    Dóbé, S
    Bérces, T
    Márta, F
    Viskolcz, B
    [J]. ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE-INTERNATIONAL JOURNAL OF RESEARCH IN PHYSICAL CHEMISTRY & CHEMICAL PHYSICS, 2004, 218 (04): : 479 - 492
  • [34] Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the gas-phase reactions of Cl(2P3/2) atoms with C3-C6 ketones
    Takahashi, Kenshi
    Iwasaki, Erika
    Matsumi, Yutaka
    Wallington, Timothy J.
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (07) : 1271 - 1276
  • [35] THOUKIS GEORGE, 1962, AMER J ENOL VITICULT, V13, P105
  • [36] Products of the gas-phase reaction of the OH radical with the dibasic ester CH3OC(O)CH2CH2CH2C(O)OCH3
    Tuazon, EC
    Aschmann, SM
    Atkinson, R
    [J]. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1999, 33 (17) : 2885 - 2890
  • [37] RATE COEFFICIENTS FOR THE REACTIONS OF OH RADICALS WITH METHYLGLYOXAL AND ACETALDEHYDE
    TYNDALL, GS
    STAFFELBACH, TA
    ORLANDO, JJ
    CALVERT, JG
    [J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1995, 27 (10) : 1009 - 1020
  • [38] THE GAS-PHASE REACTIONS OF HYDROXYL RADICALS WITH A SERIES OF ESTERS OVER THE TEMPERATURE-RANGE 240-440-K
    WALLINGTON, TJ
    DAGAUT, P
    LIU, RH
    KURYLO, MJ
    [J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1988, 20 (02) : 177 - 186
  • [39] Relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols
    Wu, H
    Mu, YJ
    Zhang, XS
    Jiang, GB
    [J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2003, 35 (02) : 81 - 87
  • [40] Temperature-dependent kinetics study of the gas-phase reactions of atomic chlorine with acetone, 2-butanone, and 3-pentanone
    Zhao, Z.
    Huskey, D. T.
    Nicovich, J. M.
    Wine, P. H.
    [J]. INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2008, 40 (05) : 259 - 267