TY - JOUR

T1 - Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

AU - Andersen, Mads Peter Sulbæk

AU - Nielsen, Ole John

AU - Hurley, MD

AU - Wallington, TJ

PY - 2002

Y1 - 2002

N2 - Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F radical and adduct formation to give the C6H5F-Cl adduct. At 296 K the rate constant for the abstraction channel is k(5a)(Cl+C6H5F) = (1.1 +/- 0.1) x 10(-17) cm(3) molecule(-1) s(-1). The C6H5F-Cl adduct undergoes rapid (k similar to 10(8) s(-1)) decomposition to reform C6H5F and Cl atoms and reaction with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate constant for the reaction of C6H5F with Cl atoms. The equilibrium between Cl atoms, C6H5F, and the C6H5F-Cl adduct is established rapidly and has an equilibrium constant estimated to be K-5b=[C6H5F]/[Cl]/[C6H5F][Cl] = (3.2 +/- 2.4) x 10(-1)8 cm(3) molecule(-1). An upper limit of k(9) <6 x 10(-17) cm(3) molecule(-1) s(-1) was, established for the reaction of the C6H5F-Cl adduct with O-2. The reaction of OH radicals with C6H5F was studied and a rate constant of k(OH + C6H5F) = (7.9 +/- 2.2) x 10(-13) cm(3) molecule(-1) s(-1) was determined. The results are discussed with respect to the available literature concerning reaction of Cl atoms and CH radicals with aromatic compounds. As part of this work, rate constants for reaction of OH radicals with 2-, 3-, and 4-fluorophenol of (6.3 +/- 1.3) x 10(-12), (2.3 +/- 0.5) x 10(-11), and (2.5 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) were determined.

AB - Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F radical and adduct formation to give the C6H5F-Cl adduct. At 296 K the rate constant for the abstraction channel is k(5a)(Cl+C6H5F) = (1.1 +/- 0.1) x 10(-17) cm(3) molecule(-1) s(-1). The C6H5F-Cl adduct undergoes rapid (k similar to 10(8) s(-1)) decomposition to reform C6H5F and Cl atoms and reaction with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate constant for the reaction of C6H5F with Cl atoms. The equilibrium between Cl atoms, C6H5F, and the C6H5F-Cl adduct is established rapidly and has an equilibrium constant estimated to be K-5b=[C6H5F]/[Cl]/[C6H5F][Cl] = (3.2 +/- 2.4) x 10(-1)8 cm(3) molecule(-1). An upper limit of k(9) <6 x 10(-17) cm(3) molecule(-1) s(-1) was, established for the reaction of the C6H5F-Cl adduct with O-2. The reaction of OH radicals with C6H5F was studied and a rate constant of k(OH + C6H5F) = (7.9 +/- 2.2) x 10(-13) cm(3) molecule(-1) s(-1) was determined. The results are discussed with respect to the available literature concerning reaction of Cl atoms and CH radicals with aromatic compounds. As part of this work, rate constants for reaction of OH radicals with 2-, 3-, and 4-fluorophenol of (6.3 +/- 1.3) x 10(-12), (2.3 +/- 0.5) x 10(-11), and (2.5 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) were determined.

U2 - 10.1021/jp025725z

DO - 10.1021/jp025725z

M3 - Journal article

VL - 106

SP - 7779

EP - 7787

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

SN - 1089-5639

IS - 34

ER -