THEORY OF THERMAL UNIMOLECULAR REACTIONS IN THE FALL-OFF RANGE .2. WEAK COLLISION RATE CONSTANTS

被引:568
作者
GILBERT, RG [1 ]
LUTHER, K [1 ]
TROE, J [1 ]
机构
[1] UNIV GOTTINGEN,INST PHYS CHEM,D-3400 GOTTINGEN,FED REP GER
来源
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 1983年 / 87卷 / 02期
关键词
CHEMICAL REACTIONS - Reaction Kinetics;
D O I
10.1002/bbpc.19830870218
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 master equation of thermal unimolecular reactions in the fall-off range has been solved for a number of representative molecular systems. Weak collision broadening factors F**W**C(k// /k// infinity ) are derived and represented empirically. Weak collision efficiencies beta //c for the low pressure range are calculated for very high temperatures. Combined with earlier representations (part I) of strong collision broadening factors F**S**C(k//0/k// infinity ), compact empirical expressions for the rate coefficient in the full fall-off range are proposed. These expressions are useful for data representation and modeling of complex reaction system which involve isomerization, dissociation and recombination reactions.
引用
收藏
页码:169 / 177
页数:9
相关论文
共 25 条
[1]   UNIMOLECULAR PROCESSES IN VIBRATIONALLY HIGHLY EXCITED CYCLOHEPTATRIENES .1. THERMAL-ISOMERIZATION IN SHOCK-WAVES [J].
ASTHOLZ, DC ;
TROE, J ;
WIETERS, W .
JOURNAL OF CHEMICAL PHYSICS, 1979, 70 (11) :5107-5116
[2]   EVALUATED KINETIC AND PHOTOCHEMICAL DATA FOR ATMOSPHERIC CHEMISTRY .1. CODATA TASK GROUP ON CHEMICAL-KINETICS [J].
BAULCH, DL ;
COX, RA ;
CRUTZEN, PJ ;
HAMPSON, RF ;
KERR, JA ;
TROE, J ;
WATSON, RT .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1982, 11 (02) :327-496
[3]   INTERMOLECULAR ENERGY TRANSFER IN GAS REACTIONS [J].
CHOW, N ;
WILSON, DJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1962, 66 (02) :342-&
[4]   SOLUTION OF MASTER EQUATION FOR UNIMOLECULAR REACTIONS [J].
GAYNOR, BJ ;
GILBERT, RG ;
KING, KD .
CHEMICAL PHYSICS LETTERS, 1978, 55 (01) :40-43
[5]   UNIMOLECULAR REACTIONS AS RADIATIONLESS TRANSITIONS - CALCULATION OF RATE OF DECOMPOSITION OF N2O [J].
GILBERT, RG ;
ROSS, IG .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1971, 24 (08) :1541-+
[6]   GAS-GAS AND GAS-WALL AVERAGE ENERGY-TRANSFER FROM VERY LOW-PRESSURE PYROLYSIS [J].
GILBERT, RG ;
KING, KD .
CHEMICAL PHYSICS, 1980, 49 (03) :367-375
[7]   DIRECT OBSERVATION OF COLLISIONAL DEACTIVATION OF HIGHLY EXCITED TOLUENE [J].
HIPPLER, H ;
TROE, J ;
WENDELKEN, HJ .
CHEMICAL PHYSICS LETTERS, 1981, 84 (02) :257-259
[8]  
HIPPLER H, 1983, J CHEM PHYS, V87
[9]  
LUTHER K, 1979, 17TH S INT COMB PITT, P535
[10]   ANALYSIS OF THE UNIMOLECULAR REACTION N2O5 + M REVERSIBLE NO2 + NO3 + M [J].
MALKO, MW ;
TROE, J .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1982, 14 (04) :399-416