TY - JOUR

T1 - OH-initiated oxidation of benzene - Part II. Influence of elevated NOx concentrations

AU - Klotz, B

AU - Volkamer, R

AU - Hurley, MD

AU - Andersen, Mads Peter Sulbæk

AU - Nielsen, OJ

AU - Barnes, I

AU - Imamura, T

AU - Wirtz, K

AU - Becker, KH

AU - Platt, U

AU - Wallington, TJ

AU - Washida, N

PY - 2002

Y1 - 2002

N2 - The present work represents a continuation of part I of this series of papers, in which we investigated the phenol yields in the OH-initiated oxidation of benzene under conditions of low to moderate concentrations of NOx, to elevated NOx levels. The products of the OH-initiated oxidation of benzene in 700 760 Torr of N-2/O-2 diluent at 297 +/- 4 K were investigated in 3 different photochemical reaction chambers. In situ spectroscopic techniques were employed for the detection of products, and the initial concentrations of benzene, NOx, and O-2 were widely varied (by factors of 6300, 1500, and 13, respectively). In contrast to results from previous studies, a pronounced dependence of the product distribution on the NOx concentration was observed. The phenol yield decreases from approximately 50-60% in the presence of low concentrations (10 000 ppb) NOx concentrations. In the presence of high concentrations of NOx, the phenol yield increases with increasing O-2 partial pressure. The rate constant of the reaction of hydroxycyclohexadienyl peroxyl radicals with NO was determined to be (1.7 +/- 0.6) x 10(-11) cm(3) molecule(-1) s(-1). This reaction leads to the formation of E, E-2,4-hexadienedial as the main identiable product (29 +/- 16. The reaction of the hydroxycyclohexadienyl radical with NO2 gave phenol (5.9 +/- 3.4 and E,E-2,4-hexadienedial (3.4 +/- 1.9, no other products could be identified. The residual FTIR product spectra indicate the formation of unknown nitrates or other nitrogen-containing species in high yield. The results from the present work also show that experimental studies aimed at establishing/verifying chemical mechanisms for aromatic hydrocarbons must be performed using NOx levels which are representative of those found in the atmosphere.

AB - The present work represents a continuation of part I of this series of papers, in which we investigated the phenol yields in the OH-initiated oxidation of benzene under conditions of low to moderate concentrations of NOx, to elevated NOx levels. The products of the OH-initiated oxidation of benzene in 700 760 Torr of N-2/O-2 diluent at 297 +/- 4 K were investigated in 3 different photochemical reaction chambers. In situ spectroscopic techniques were employed for the detection of products, and the initial concentrations of benzene, NOx, and O-2 were widely varied (by factors of 6300, 1500, and 13, respectively). In contrast to results from previous studies, a pronounced dependence of the product distribution on the NOx concentration was observed. The phenol yield decreases from approximately 50-60% in the presence of low concentrations (10 000 ppb) NOx concentrations. In the presence of high concentrations of NOx, the phenol yield increases with increasing O-2 partial pressure. The rate constant of the reaction of hydroxycyclohexadienyl peroxyl radicals with NO was determined to be (1.7 +/- 0.6) x 10(-11) cm(3) molecule(-1) s(-1). This reaction leads to the formation of E, E-2,4-hexadienedial as the main identiable product (29 +/- 16. The reaction of the hydroxycyclohexadienyl radical with NO2 gave phenol (5.9 +/- 3.4 and E,E-2,4-hexadienedial (3.4 +/- 1.9, no other products could be identified. The residual FTIR product spectra indicate the formation of unknown nitrates or other nitrogen-containing species in high yield. The results from the present work also show that experimental studies aimed at establishing/verifying chemical mechanisms for aromatic hydrocarbons must be performed using NOx levels which are representative of those found in the atmosphere.

U2 - 10.1039/b204398j

DO - 10.1039/b204398j

M3 - Tidsskriftartikel

VL - 4

SP - 4399

EP - 4411

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 18

ER -