FTIR gas-phase kinetic study on the reactions of OH radicals and Cl atoms with unsaturated esters: Methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate

JUAN P. COLOMER , MARÍA B. BLANCO, ALICIA B. PEÑÉÑORY , IAN BARNES , PETER WIESEN , MARIANO A. TERUEL *

ATMOSPHERIC ENVIRONMENT

PERGAMON-ELSEVIER SCIENCE LTD

Lugar: Amsterdam; Año: 2013 vol. 79 p. 546 - 552

1352-2310

The relative-rate technique has been used to obtain rates coefficients for the reactions of the unsaturated esters methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate withOHradicals and chlorine atoms at (2982) K in synthetic air at a total pressure of (76010) Torr. The experimentswere performed in an environmental chamber using in situ FTIR detection tomonitor the decay of the esters relative to different reference compounds. The following room temperature rate coefficients (in units of cm3 molecule1 s1) were obtained: k1(OH þ (CH3)2C]CHC(O)OCH3) ¼ (4.46  1.05)  1011, k2(Cl þ (CH3)2C]CHC(O) OCH3) ¼ (2.78  0.46)  1010, k3(OH þ CH3CH]C(CH3)C(O)OCH2CH3) ¼ (8.32  1.93)  1011, k4(Cl þ CH3CH]C(CH3)C(O)OCH2CH3) ¼ (2.53  0.35)  1010, k5(OH þ CH2]CHCH2C(O)OCH3) ¼ (3.16  0.57)  1011, k4(Cl þ CH2]CHCH2C(O)OCH3) ¼ (2.10  0.35)  1010. With the exception of the reaction of Cl with methyl-3,3-dimethyl acrylate (k2), for which one determination exists in the literature, this study is the first kinetic study for these reactions under atmospheric pressure. Reactivity trends are discussed in terms of the effect of the alkyl and ester groups attached to the double bond on the overall rate coefficients towards OH radicals. The atmospheric implications of the reactions were assessed by the estimation of the tropospheric lifetimes of the title reactions.