Rate and mechanism of the reactions of OH and Cl with 2-methyl-3-buten-2-ol

被引:81
作者
Ferronato, C
Orlando, JJ
Tyndall, GS
机构
[1] Univ Grenoble 1, IUT Grenoble 1, Dept Chim, Grp Rech Environm & Chim Appl, F-38000 Grenoble, France
[2] Natl Ctr Atmospher Res, Div Atmospher Chem, Boulder, CO 80303 USA
关键词
D O I
10.1029/98JD00528
中图分类号
P4 [大气科学(气象学)];
学科分类号
0706 ; 070601 ;
摘要
An environmental chamber/Fourier transform infrared system was used to determine the rate coefficient k(1) for the gas-phase reaction of OH with 2-methyl-3-buten-2-ol (MBO, (CH3)(2)C(OH)CH=CH2), relative to the rate of its reaction with ethylene (k(2)) and propylene (k(3)). Experiments performed at 295 +/- 1 K, in 700 torr total pressure of air, gave k(1) = (6.9 +/- 1.0) x 10(-11) cm(3) molecule(-1) s(-1). At 295 +/- 1 K, the reaction of OH with MBO yielded, on a per mole basis, (52 +/- 5)% acetone, (50 +/- 5)% glycolaldehyde, and (35 +/- 4)% formaldehyde. The production of acetone from the oxidation of MBO may be of significance globally. The kinetics and mechanism of the reaction of chlorine atoms with MBO (k(15)) have also been studied at 700 torr total pressure of air and 295 +/- 1 K. The rate coefficient was determined using a relative rate technique, with ethane (k(16)), ethylene (k(17)), and cyclohexane (k(18)) as reference compounds. The value of k(15) was found to be (3.3 +/- 0.4) x 10(-10) cm(3) molecule(-1) s(-1) at 295 K. The major carbon-containing products obtained in the Cl-atom oxidation of MBO were acetone (47 +/- 5)%, chloroacetaldehyde (53 +/- 5)%, HCOCl (<11%), and formaldehyde (6 +/- 2)%.
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页码:25579 / 25586
页数:8
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