Photo-Oxidation Reaction Kinetics and Mechanistics of 4-Hydroxy-2-butanone with Cl Atoms and OH Radicals in the Gas Phase

被引:5
作者
Balan, Ramya Cheramangalath [1 ]
Rajakumar, B. [1 ]
机构
[1] Indian Inst Technol Madras, Dept Chem, Chennai 600036, Tamil Nadu, India
关键词
CHEMICAL-REACTION RATES; UNSATURATED-HYDROCARBONS; ATMOSPHERIC OXIDATION; RATE CONSTANTS; PRODUCTS; SERIES; OZONE;
D O I
10.1021/acs.jpca.9b00995
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 temperaturedependent rate coefficients for the gasphase reaction of 4-hydroxy-2-butanone (4H2BN) with Cl atoms and OH radicals were explored experimentally using relative rate technique and computational methods. The concentrations of the reactants as well as products were followed using gas chromatography (GC) with the flame ionization detector, GC/mass spectrometry, and GC/infrared spectroscopy as analytical techniques. Formaldehyde was obtained as the major product during the title reaction. The kinetics of 4H2BN with Cl atoms and OH radicals were measured over the temperature range of 298-363 K at 760 Torr in the N-2 atmosphere using C3H8, C2H4, isopropanol, and n-propanol as reference compounds. The temperaturedependent rate coefficients for the reaction of 4H2BN with Cl atoms and OH radicals were obtained as k(Expt)(T) = [(1.52 +/- 0.86) X 10(-26)]T-5 exp[(2474 +/- 450)/T] cm(3) molecule(-1) s(-1) and k(expt)(T) = [(2.09 +/- 0.24) X 10(-12)] exp[-(409 +/- 15)/T] cm(3) molecule(-1) s(-1), respectively. Theoretical calculations were carried out at the M062X/6-31G(d,p) and M06-2X/6-31+G(d,p) level of theories, and the rate coefficients for H abstraction reactions were evaluated using the canonical variational transition state theory with the inclusion of smallcurvature tunneling correction over the temperature range of 200-400 K. The rate coefficients obtained over the studied temperature range were used to fit the data, and the Arrhenius expression was obtained to be k(Cl(Theory)) (200-400 K) = (6.10 x 10(-25))T-4.42 exp(2397/T) cm(3) molecule(-1) s(-1) k(OH(Theory)) (200-400 K) = (1.13 x 10(-19))T-2.27 exp(1505/T) cm(3) molecule(-1) s(-1), respectively, for the reactions of Cl atoms and OH radicals with 4H2BN. The possible reaction mechanism proposed based on the obtained products for the title reaction, thermochemistry, branching ratios, and atmospheric implications and cumulative lifetime of 4H2BN were also explored in this study.
引用
收藏
页码:4342 / 4353
页数:12
相关论文
共 39 条
[1]   Atmospheric chemistry of selected hydroxycarbonyls [J].
Aschmann, SM ;
Arey, J ;
Atkinson, R .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (17) :3998-4003
[2]   Formation of β-hydroxycarbonyls from the OH radical-initiated reactions of selected alkenes [J].
Aschmann, SM ;
Arey, J ;
Atkinson, R .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2000, 34 (09) :1702-1706
[3]   Rate constants for the gas-phase reactions of OH radicals with a series of hydroxyaldehydes at 296 ± 2 K [J].
Baker, J ;
Arey, J ;
Atkinson, R .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (34) :7032-7037
[4]   Photo Oxidation Reaction Kinetics of Ethyl Propionate with Cl Atom and Formation of Propionic Acid [J].
Balan, Ramya Cheramangalath ;
Rajakumar, B. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2018, 122 (42) :8274-8285
[5]   Cl-initiated photo-oxidation reactions of methyl propionate in atmospheric condition [J].
Balan, Ramya Cheramangalath ;
Balla, Rajakumar .
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH, 2018, 25 (21) :20999-21010
[6]   Kinetics and products of the reactions of selected diols with the OH radical [J].
Bethel, HL ;
Atkinson, R ;
Arey, J .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2001, 33 (05) :310-316
[7]   Investigation of the Gas-Phase Photolysis and Temperature-Dependent OH Reaction Kinetics of 4-Hydroxy-2-butanone [J].
Bouzidi, Hichem ;
Aslan, Lina ;
El Dib, Gisele ;
Coddeville, Patrice ;
Fittschen, Christa ;
Tomas, Alexandre .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2015, 49 (20) :12178-12186
[8]   OZONE FORMATION POTENTIAL OF ORGANIC-COMPOUNDS [J].
BUFALINI, JJ ;
WALTER, TA ;
BUFALINI, MM .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1976, 10 (09) :908-912
[9]   THEORETICAL-STUDY OF THE INITIAL PRODUCTS OF THE ATMOSPHERIC OXIDATION OF HYDROCARBONS [J].
CALVERT, JG ;
MADRONICH, S .
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1987, 92 (D2) :2211-2220
[10]   COMPUTER MODELING OF ENVIRONMENTAL CHAMBER MEASUREMENTS OF MAXIMUM INCREMENTAL REACTIVITIES OF VOLATILE ORGANIC-COMPOUNDS [J].
CARTER, WPL .
ATMOSPHERIC ENVIRONMENT, 1995, 29 (18) :2513-2527