A kinetic and mechanistic study of the reaction of Cl atoms with acrolein:: Temperature dependence for abstraction channel

被引：10

作者：

Aranda, A ^{[1
]}

de Mera, YD ^{[1
]}

Rodríguez, A ^{[1
]}

Rodríguez, D ^{[1
]}

Martínez, E ^{[1
]}

机构：

[1] Univ Castilla La Mancha, Fac Ciencias Quim, Dept Quim Fis, E-13071 Ciudad Real, Spain

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2003年 / 107卷 / 30期

关键词：

D O I：

10.1021/jp027767t

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：

Rate coefficients for the reaction CH2CHCHO + Cl --> P (1) at different temperatures (260-333 K) have been determined using a discharge flow-mass spectrometric technique (DF-MS) at low total pressure. k(1) was found to be pressure-independent at T = 298 K in the pressure range 0.5-3 Torr. The temperature dependence of the reaction rate constant has been determined under pseudo-first-order kinetic conditions in excess of acrolein over Cl atoms, with no significant changes in the rate constant. At room temperature and 1 Torr, products of both abstraction (1a) and addition (1b) channels have been detected. The branching ratio for abstraction channel at 298 K and 1 Torr was determined as 0.83 +/- 0.13 and led to HCl and CH2CHCO* radical. The temperature dependence of this abstraction channel has also been studied, giving the Arrhenius expression k(1a) = (5.4 +/- 2.0) x 10(-10) exp{(-748 +/- 110)/T} cm(3) molecule(-1) s(-1) in the temperature range 260-333 K. The results obtained are related to previous studies, and the mechanism of reaction is discussed.

引用

页码：5717 / 5721

页数：5

共 33 条

[1] KINETICS OF THE GAS-PHASE REACTIONS OF NO3 RADICALS WITH A SERIES OF ALKYNES, HALOALKENES, AND ALPHA,BETA-UNSATURATED ALDEHYDES [J].

ATKINSON, R ;

ASCHMANN, SM ;

GOODMAN, MA .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1987, 19 (04) :299-307

[2] KINETICS OF THE GAS-PHASE REACTIONS OF OH RADICALS WITH A SERIES OF ALPHA,BETA-UNSATURATED CARBONYLS AT 299 +/- 2 K [J].

ATKINSON, R ;

ASCHMANN, SM ;

PITTS, JN .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1983, 15 (01) :75-81

[3] Low-pressure study of the reaction of Cl atoms with isoprene [J].

Bedjanian, Y ;

Laverdet, G ;

Le Bras, G .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (06) :953-959

[4] Night-time atmospheric loss process for unsaturated aldehydes:: Reaction with NO3 radicals [J].

Cabañas, B ;

Salgado, S ;

Martín, P ;

Baeza, MT ;

Martínez, E .

JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (18) :4440-4445

[5] The reactions of atomic chlorine with acrolein, methacrolein and methyl vinyl ketone [J].

Canosa-Mas, CE ;

Cotter, ESN ;

Duffy, J ;

Thompson, KC ;

Wayne, RP .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2001, 3 (15) :3075-3084

[6] A kinetic study of the reactions of NO3 with methyl vinyl ketone, methacrolein, acrolein, methyl acrylate and methyl methacrylate [J].

Canosa-Mas, CE ;

Carr, S ;

King, MD ;

Shallcross, DE ;

Thompson, KC ;

Wayne, RP .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1999, 1 (18) :4195-4202

[7]

*CICAD 2002, 2002, CONC INT CHEM ASS DO

[8]

DEMERA YD, 2002, J PHYS CHEM A, V106, P8627

[9] ROOM-TEMPERATURE RATE CONSTANTS FOR THE REACTION OF OH WITH SELECTED CHLORINATED AND OXYGENATED HYDROCARBONS [J].

EDNEY, EO ;

KLEINDIENST, TE ;

CORSE, EW .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1986, 18 (12) :1355-1371

[10]

*ENV CAN, 1996, NAT AIR POLL SURV NA

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