Kinetics of the CN+CH2CO and NCO+CH2CO reactions

被引:21
作者
Edwards, MA [1 ]
Hersberger, JF [1 ]
机构
[1] N Dakota State Univ, Dept Chem, Fargo, ND 58105 USA
关键词
kinetics; ketene; radical reactions;
D O I
10.1016/S0301-0104(98)00174-8
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 CN + CH2CO and NCO + CH2CO reactions were studied over the temperature ranges 296-567 K and 296-556 K, respectively, using time-resolved infrared diode laser absorption and visible laser-induced fluorescence spectroscopy. The total rate constant data were fit to the following expressions: k(1)(CN + CH2CO) = (2.37 +/- 0.5) X 10(-11) exp[552.6 +/- 97/T] and k(2)(NCO + CH2CO) = (1.71 +/- 0.27) X 10(-12) exp[713.2 +/- 56/T] cm(3) molecule(-1) s(-1). Detection and quantification of CO product yields suggests that an addition-elimination mechanism producing CH2CN + CO or CH2NCO + CO dominates these reactions, and that hydrogen abstraction to produce HCN + HCCO or HNCO + HCCO is a minor or negligible product channel. (C) 1998 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:231 / 237
页数:7
相关论文
共 36 条
[1]   KINETIC-STUDIES OF THE GAS-PHASE REACTIONS OF CN WITH O-2 AND H-2 FROM 294-K TO 1000-K [J].
ATAKAN, B ;
JACOBS, A ;
WAHL, M ;
WELLER, R ;
WOLFRUM, J .
CHEMICAL PHYSICS LETTERS, 1989, 154 (05) :449-453
[2]   KINETIC-STUDIES OF THE REACTIONS OF CN RADICALS WITH ALKANES IN THE TEMPERATURE-RANGE BETWEEN 294-K AND 1260-K [J].
ATAKAN, B ;
WOLFRUM, J .
CHEMICAL PHYSICS LETTERS, 1991, 186 (06) :547-552
[3]   KINETIC-STUDIES OF THE REACTIONS OF NCO RADICALS WITH NO AND O2 IN THE TEMPERATURE-RANGE BETWEEN 294-K AND 1260-K [J].
ATAKAN, B ;
WOLFRUM, J .
CHEMICAL PHYSICS LETTERS, 1991, 178 (2-3) :157-162
[4]   ABSOLUTE RATE CONSTANTS FOR THE REACTION OF CN WITH CH4, C2H6, AND C3H8 FROM 292-K TO 1500-K USING HIGH-TEMPERATURE PHOTOCHEMISTRY AND DIODE-LASER ABSORPTION [J].
BALLA, RJ ;
CASLETON, KH ;
ADAMS, JS ;
PASTERNACK, L .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (22) :8694-8701
[5]   KINETIC-STUDY OF THE NCO+C2H4 REACTION [J].
BECKER, KH ;
KURTENBACH, R ;
WIESEN, P .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (16) :5986-5991
[6]   TEMPERATURE AND PRESSURE-DEPENDENCE OF THE NCO+C2H2 REACTION [J].
BECKER, KH ;
KURTENBACH, R ;
SCHMIDT, F ;
WIESEN, P .
CHEMICAL PHYSICS LETTERS, 1995, 235 (3-4) :230-234
[7]   ACUCHEM - A COMPUTER-PROGRAM FOR MODELING COMPLEX CHEMICAL-REACTION SYSTEMS [J].
BRAUN, W ;
HERRON, JT ;
KAHANER, DK .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1988, 20 (01) :51-62
[8]   TEMPERATURE-DEPENDENCE OF THE RATE OF THE REACTION BETWEEN THE OH RADICAL AND KETENE [J].
BROWN, AC ;
CANOSAMAS, CE ;
PARR, AD ;
WAYNE, RP .
CHEMICAL PHYSICS LETTERS, 1989, 161 (06) :491-496
[9]   KINETICS OF CN REACTIONS WITH ALLENE, BUTADIENE, PROPYLENE AND ACRYLONITRILE [J].
BUTTERFIELD, MT ;
YU, T ;
LIN, MC .
CHEMICAL PHYSICS, 1993, 169 (01) :129-134
[10]   REACTION OF KETENE WITH ATOMIC HYDROGEN AND OXYGEN [J].
CARR, RW ;
GAY, ID ;
GLASS, GP ;
NIKI, H .
JOURNAL OF CHEMICAL PHYSICS, 1968, 49 (02) :846-&