RECOMBINATION AND DECOMPOSITION OF METHYLENE RADICALS AT HIGH-TEMPERATURES

被引:32
作者
BAUERLE, S
KLATT, M
WAGNER, HG
机构
来源
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 1995年 / 99卷 / 06期
关键词
CHEMICALS KINETICS; ELEMENTARY REACTIONS; RADICALS; SHOCK WAVES; SPECTROSCOPY; ULTRAVIOLET;
D O I
10.1002/bbpc.19950990612
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
Recombination and decomposition of methylene radicals have been investigated over a wide range of experimental conditions. It has been found that H atom forming channels play only a minor role in the reactions investigated. The rate constants for the recombination channels CH2 + CH2 --> C2H2 + H-2 (1a) and C2H2 + 2H (1b) have been determined to be k(1a) = 10(15.2) (+/-) (0.2.)exp (-(50 +/- 5) kJ mol(-1)/RT) cm(3) mol(-1) s(-1) k(1b) = 10(14.3) (+/-) (0.2.)exp (-(46 +/- 5) kJ mol(-1)/RT) cm(3) mol(-1) s(-1) in the temperature range from 1100-2700 K. The H atom channel in the decomposition of methylene in argon leading to CH+H (2b) has been found to be k(2b) = 10(15.75+/-0.15.)exp((-375 +/- 15) kJ mol(-1)/RT) cm(3) mol(-1) s(-1) at temperatures between 1900-2700 K. A comparison with literature data available for channel (2a) leading to C+H-2 shows that the contribution of the H atom channel (2b) in the decomposition reaction of CH2 is around 10-15%. The energy of activation is in good agreement with the theoretically calculated value.
引用
收藏
页码:870 / 879
页数:10
相关论文
共 25 条
[1]   EVALUATED KINETIC DATA FOR COMBUSTION MODELING [J].
BAULCH, DL ;
COBOS, CJ ;
COX, RA ;
ESSER, C ;
FRANK, P ;
JUST, T ;
KERR, JA ;
PILLING, MJ ;
TROE, J ;
WALKER, RW ;
WARNATZ, J .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1992, 21 (03) :411-734
[2]   FORMATION AND DISSOCIATION OF C2 FROM HIGH-TEMPERATURE PYROLYSIS OF ACETYLENE [J].
BECK, WH ;
MACKIE, JC .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1975, 71 (06) :1363-1371
[3]  
BERMAN MR, 1983, CHEM PHYS, V73, P27
[4]   COLLISION-INDUCED INTERSYSTEM CROSSING OF CH-2 FROM (A)OVER-TILDE (1)A(1) TO (X)OVER-TILDE (3)B(1) - A CASE-STUDY OF THE MIXED-STATE MODEL [J].
BLEY, U ;
TEMPS, F .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (02) :1058-1072
[5]  
BOHLAND T, 1985, BER BUNSEN PHYS CHEM, V89, P1110
[6]   FLASH PHOTOLYSIS OF KETENE AND DIAZOMETHANE - PRODUCTION AND REACTION KINETICS OF TRIPLET AND SINGLE METHYLENE [J].
BRAUN, W ;
BASS, AM ;
PILLING, M .
JOURNAL OF CHEMICAL PHYSICS, 1970, 52 (10) :5131-&
[7]  
CARSTENSEN HH, 1994, THESIS U GOTTINGEN
[8]   RATE CONSTANTS FOR CH2(X3B1) REMOVAL BY O-2, NO, AND C2H2 FROM INFRARED DIODE-LASER FLASH KINETIC SPECTROSCOPY [J].
DARWIN, DC ;
YOUNG, AT ;
JOHNSTON, HS ;
MOORE, CB .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (03) :1074-1078
[9]   CH-ATOM AND C-ATOM TIME HISTORIES IN DILUTE HYDROCARBON PYROLYSIS - MEASUREMENTS AND KINETICS CALCULATIONS [J].
DEAN, AJ ;
HANSON, RK .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1992, 24 (06) :517-532
[10]   A SHOCK-TUBE STUDY OF REACTIONS OF C ATOMS WITH H-2 AND O2 USING EXCIMER PHOTOLYSIS OF C3O2 AND C ATOM ATOMIC RESONANCE-ABSORPTION SPECTROSCOPY [J].
DEAN, AJ ;
DAVIDSON, DF ;
HANSON, RK .
JOURNAL OF PHYSICAL CHEMISTRY, 1991, 95 (01) :183-191