Atmospheric chemistry of a model biodiesel fuel, CH₃C(O) O(CH₂)₂OC(O)CH₃: Kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NO_x

TY - JOUR

T1 - Atmospheric chemistry of a model biodiesel fuel, CH3C(O) O(CH2)2OC(O)CH3

T2 - Kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOx

AU - Hurley, M. D.

AU - Ball, J. C.

AU - Wallington, T. J.

AU - Toft, A.

AU - Nielsen, O. J.

AU - Bertman, S.

AU - Perkovic, M.

PY - 2007

Y1 - 2007

N2 - Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with ethylene glycol diacetate, CH 3C(O)O(CH2)2OC(O)CH3, in 700 Torr of N2/O2 diluent at 296 K. The rate constants measured were k(Cl + CH3C(O)O(CH2)2OC(O)CH3) = (5.7 ± 1.1) × 10-12 and k(OH + CH3C(O) O(CH2)2OC(O)CH3) = (2.36 ± 0.34) × 10-12 cm3 molecule-1 s-1. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the absence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)CH2OC(O)CH 3, CH3C(O)OC(O)H, and CH3C(O)OH. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the presence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)H and CH3C(O)OH. The CH3C-(O)OCH2O radical is formed during the Cl atom initiated oxidation of ethylene glycol diacetate, and two loss mechanisms were identified: reaction with O2 to give CH3C(O)OC(O)H and α-ester rearrangement to give CH3C(O)OH and HC(O) radicals. The reaction of CH3C(O)OCH2O2 with NO gives chemically activated CH3C(O)OCH2O radicals which are more likely to undergo decomposition via the α-ester rearrangement than CH 3C(O)OCH2O radicals produced in the peroxy radical self-reaction.

AB - Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with ethylene glycol diacetate, CH 3C(O)O(CH2)2OC(O)CH3, in 700 Torr of N2/O2 diluent at 296 K. The rate constants measured were k(Cl + CH3C(O)O(CH2)2OC(O)CH3) = (5.7 ± 1.1) × 10-12 and k(OH + CH3C(O) O(CH2)2OC(O)CH3) = (2.36 ± 0.34) × 10-12 cm3 molecule-1 s-1. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the absence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)CH2OC(O)CH 3, CH3C(O)OC(O)H, and CH3C(O)OH. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the presence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)H and CH3C(O)OH. The CH3C-(O)OCH2O radical is formed during the Cl atom initiated oxidation of ethylene glycol diacetate, and two loss mechanisms were identified: reaction with O2 to give CH3C(O)OC(O)H and α-ester rearrangement to give CH3C(O)OH and HC(O) radicals. The reaction of CH3C(O)OCH2O2 with NO gives chemically activated CH3C(O)OCH2O radicals which are more likely to undergo decomposition via the α-ester rearrangement than CH 3C(O)OCH2O radicals produced in the peroxy radical self-reaction.

U2 - 10.1021/jp0667341

DO - 10.1021/jp0667341

M3 - Journal article

C2 - 17388358

AN - SCOPUS:34247375251

SN - 1089-5639

VL - 111

SP - 2547

EP - 2554

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 13

ER -