Mechanistic Studies on CH3CH2O+HCHO Reaction and Rate Constants of Major Channel

被引：3

作者：

Guo Sha ^{[1
]}

Wang Weina ^{[1
]}

Jin Lingxia ^{[1
]}

Wang Shuai ^{[1
]}

Wang Wenliang ^{[1
]}

机构：

[1] Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Peoples R China

来源：

CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE | 2014年 / 35卷 / 06期

基金：

中国国家自然科学基金;

关键词：

CH3CH2O; HCHO; Density functional theory; Reaction mechanism; Rate constant; ATMOSPHERIC CHEMISTRY; FORMALDEHYDE; C2H5O; CH3O; TEMPERATURE; OXIDATION; RADICALS; RANGE; NO;

D O I：

10.7503/cjcu20131237

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of the reaction between CH3H2O and HCHO was investigated at CCSD (T) cc-pVDZ//B3LYP/6-311++ G (d, p) level. Eight possible reaction channels (five H-abstraction channels and three H-isomerization channels) for the title reaction were identified. The results indicated that channel R -> IMa(CH3CH2O center dot center dot center dot CH2O) -> TS1 -> IM1b -> P1 (CH3CH2OH+CHO) was the most favorable channel with the apparent activation energy of 14.65 kJ/mol. The rate constants of the path R1 were evaluated over a temperature range of 275-1000 K via the canonical variational transition state theory(CVT) combined with a small-curvature tunneling correction. The fitted three-parameter expression for the path R1 is k(CVT/SCT) = 2.26 x 10(-17) T-0.57 exp (-1004/T) and R1 has a positive temperature effect over a temperature range of 275-1000 K.

引用

页码：1300 / 1306

页数：7

共 24 条

[1] Mechanism for the gas-phase reaction between formaldehyde and hydroperoxyl radical. A theoretical study [J].

Anglada, JM ;

Domingo, VM .

JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (47) :10786-10794

[2]

[Anonymous], 2001, VKLAB VERSION 1 0

[3] Evaluated kinetic and photochemical data for atmospheric chemistry:: Volume I -: gas phase reactions of Ox, HOx, NOx and SOx species [J].

Atkinson, R ;

Baulch, DL ;

Cox, RA ;

Crowley, JN ;

Hampson, RF ;

Hynes, RG ;

Jenkin, ME ;

Rossi, MJ ;

Troe, J .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2004, 4 :1461-1738

[4] Experimental and theoretical study of the F, Cl and Br reactions with formaldehyde and acetaldehyde [J].

Beukes, JA ;

D'Anna, B ;

Bakken, V ;

Nielsen, CJ .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2000, 2 (18) :4049-4060

[5]

Bras G. L., 1980, CHEM PHYS LETT, V73, P357

[6] Gas-phase ultraviolet absorption cross-sections and atmospheric lifetimes of several C-2-C-5 alkyl nitrates [J].

Clemitshaw, KC ;

Williams, J ;

Rattigan, OV ;

Shallcross, DE ;

Law, KS ;

Cox, RA .

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1997, 102 (2-3) :117-126

[7] KINETIC-STUDY OF REACTIONS OF C2H5O AND C2H5O2 WITH NO AT 298K AND 0.55-2 TORR [J].

DAELE, V ;

RAY, A ;

VASSALLI, I ;

POULET, G ;

LEBRAS, G .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1995, 27 (11) :1121-1133

[8] Determination of rate coefficients for reactions of formaldehyde pyrolysis and oxidation in the gas phase [J].

Eiteneer, B ;

Yu, CL ;

Goldenberg, M ;

Frenklach, M .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (27) :5196-5205

[9]

Frisch M., 2004, GAUSSIAN 03 REVISION, DOI DOI 10.1016/J.MOLSTRUC.2017.03.014

[10]

FROST MJ, 1990, J CHEM SOC FARADAY T, V86, P1757, DOI 10.1039/ft9908601757

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