Primary Atmospheric Oxidation Mechanism for Toluene

被引:76
作者
Baltaretu, Cristian O. [1 ]
Lichtman, Eben I. [1 ]
Hadler, Amelia B. [1 ]
Elrod, Matthew J. [1 ]
机构
[1] Oberlin Coll, Dept Chem & Biochem, Oberlin, OH 44074 USA
基金
美国国家科学基金会;
关键词
RATE-CONSTANT MEASUREMENTS; SECONDARY ORGANIC AEROSOL; RING-RETAINING PRODUCTS; NOX-AIR PHOTOOXIDATIONS; GAS-PHASE REACTION; ION FLOW TUBE; AROMATIC-HYDROCARBONS; HYDROXYL RADICALS; TEMPERATURE-DEPENDENCE; BRANCHING CHANNEL;
D O I
10.1021/jp806841t
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 products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique at temperatures ranging from 228 to 298 K. A major dienedial-producing pathway was detected for the first time for toluene oxidation, and glyoxal and methylglyoxal were found to be minor primary oxidation products. The results suggest that secondary oxidation processes involving dienedial and epoxide primary products are likely responsible for previous observations of glyoxal and methylglyoxal products from toluene oxidation. Because the dienedial-producing pathway is a null cycle for tropospheric ozone production and glyoxal and methylglyoxal are important secondary organic aerosol precursors, these new findings have important implications for the modeling of toluene oxidation in the atmosphere.
引用
收藏
页码:221 / 230
页数:10
相关论文
共 42 条
[1]   EFFECTS OF PRESSURE ON PRODUCT YIELDS IN THE NOX PHOTOOXIDATIONS OF SELECTED AROMATIC-HYDROCARBONS [J].
ATKINSON, R ;
CARTER, WPL ;
WINER, AM .
JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (09) :1605-1610
[2]   FORMATION OF RING-RETAINING PRODUCTS FROM THE OH RADICAL-INITIATED REACTIONS OF BENZENE AND TOLUENE [J].
ATKINSON, R ;
ASCHMANN, SM ;
AREY, J ;
CARTER, WPL .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1989, 21 (09) :801-827
[3]  
ATKINSON R, 1994, ARBR94550 CAL U STAT
[4]   RING-CLEAVAGE REACTIONS OF AROMATIC-HYDROCARBONS STUDIED BY FT-IR SPECTROSCOPY .1. PHOTOOXIDATION OF TOLUENE AND BENZENE IN THE NOX-AIR SYSTEM [J].
BANDOW, H ;
WASHIDA, N ;
AKIMOTO, H .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1985, 58 (09) :2531-2540
[5]  
Becker K.H., 1997, Chemical Processes in Atmospheric Oxidation, P79
[6]   Gas-phase reaction of OH radicals with benzene:: products and mechanism [J].
Berndt, T ;
Böge, O .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2001, 3 (22) :4946-4956
[7]   Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons [J].
Bloss, C ;
Wagner, V ;
Jenkin, ME ;
Volkamer, R ;
Bloss, WJ ;
Lee, JD ;
Heard, DE ;
Wirtz, K ;
Martin-Reviejo, M ;
Rea, G ;
Wenger, JC ;
Pilling, MJ .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2005, 5 :641-664
[8]   Formation of peroxy radicals from OH-toluene adducts and O2 [J].
Bohn, B .
JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (25) :6092-6101
[9]  
Calvert J.G., 2002, The mechanism of atmospheric oxidation of aromatics hydrocarbons
[10]   Kinetics of the C3H7O2+NO reaction:: Temperature dependence of the overall rate constant and the i-C3H7ONO2 branching channel [J].
Chow, JM ;
Miller, AM ;
Elrod, MJ .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (17) :3040-3047