Low-pressure study of the reactions of Cl atoms with acrylic acid and allyl alcohol

被引:14
作者
Aranda, A [1 ]
Martínez, E [1 ]
de Mera, YD [1 ]
Rodríguez, A [1 ]
Rodríguez, D [1 ]
Cuartero, J [1 ]
机构
[1] Univ Castilla La Mancha, Fac Quim, E-13071 Ciudad Real, Spain
关键词
gas-phase reactions; rate constants; temperature; discharge-flow; mechanism;
D O I
10.1016/S1352-2310(03)00573-9
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
The kinetics of the gas-phase reactions of chlorine atoms with acrylic acid (1) and allyl alcohol (2) have been investigated at low pressure (0.5-3 Tort) in the temperature range 260-333 K using the mass spectrometric discharge-flow method. The temperature dependence of the reaction rate constants at 1 Torr have been determined under pseudo-first-order conditions in excess of organic compound over Cl atoms, giving: k(1) = (1.3+/-0.9) x 10(-13) exp(1600+/-200)/T cm(3) molecule(-1) s(-1) and k(2) = (1.1+/-0.5) x 10(-11) exp(470+/-135)/T cm(3) molecule(-1) s(-1). At room temperature and I Tort, products of abstraction and addition channels have been detected for reactions (1) and (2). By mass spectrometric quantification, the branching ratio for channels giving HCl, was determined as 0.13+/-0.05 for reaction (1) and 0.57+/-0.06 for reaction (2). The results obtained are related to previous studies, and the atmospheric implications are also discussed in relation to the homogeneous sinks of acrylic acid and allyl alcohol. (C) 2003 Elsevier Ltd. All rights reserved.
引用
收藏
页码:4361 / 4369
页数:9
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