DIRECT MEASUREMENT OF THE REACTION CH3+OH AT AMBIENT-TEMPERATURE IN THE PRESSURE RANGE 0.3-6.2 MBAR

被引:38
作者
OSER, H [1 ]
STOTHARD, ND [1 ]
HUMPFER, R [1 ]
GROTHEER, HH [1 ]
机构
[1] DLR,INST PHYS CHEM COMBUST,PFAFFENWALDRING 38,W-7000 STUTTGART 80,GERMANY
关键词
D O I
10.1021/j100192a034
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 falloff behavior of the CH3 + OH recombination reaction CH3 + OH --> CH3OH (1a) has been quantitatively investigated for the first time. Methyl decay profiles were measured in a flow reactor at 300 K and in a pressure range between 0.3 and 6.2 mbar. The experimental conditions were such that a possible channel to (CH2)-C-1 + H2O did not contribute strongly to the CH3 profiles. Rate coefficients were extracted from the data by comparison of the experimental profiles with computer simulations. The results are in accord with the limiting rate coefficient suggested by Hochanadel et al., k1a(infinity)(298 K) = 9.3 X 10(-11) cm3 molecule-1 s-1.1 The experimental falloff curve is described by use of this value for k(infinity), together with an interpolation formula given by Troe,2 from which an approximate value for the low-pressure limit k1a0 = (2.54 +/- 1.0) X 10(-27) cm6 molecule-2 s-1 has been derived (bath gas helium). For a quantitative assessment of the possible channel to (CH2)-C-1 + H2O, reaction 1d, measurements of H20 were carried out, yielding an estimated upper limit for the rate coefficient of k1d(300 K) less-than-or-equal-to 5 X 10(-12) cm3 molecule-1 s-1.
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收藏
页码:5359 / 5363
页数:5
相关论文
共 21 条
[1]   REACTION OF CH3 RADICALS WITH OH AT ROOM-TEMPERATURE AND PRESSURE [J].
ANASTASI, C ;
BEVERTON, S ;
ELLERMANN, T ;
PAGSBERG, P .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1991, 87 (15) :2325-2329
[2]  
BAULCH DL, IN PRESS J PHYS CHEM
[3]  
BHASKARAN KA, 1979, 12TH P INT S SHOCK T, P503
[4]  
BOHLAND T, 1987, J PHYS CHEM-US, V91, P1205
[5]  
BROTHEER HH, 1985, BER BUNSEN PHYS CHEM, V89, P325
[6]   EXPERIMENTAL AND RRKM MODELING STUDY OF THE CH3+H AND CH3+D REACTIONS [J].
BROUARD, M ;
MACPHERSON, MT ;
PILLING, MJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (10) :4047-4059
[7]   BIMOLECULAR QRRK ANALYSIS OF METHYL RADICAL REACTIONS [J].
DEAN, AM ;
WESTMORELAND, PR .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1987, 19 (03) :207-228
[8]  
GREEN NJ, 1990, 23RD S INT COMB
[9]   DIRECT STUDY OF THE REACTIONS OF CH2OH AND CH3CHOH RADICALS WITH O(P-3) ATOMS [J].
GROTHEER, HH ;
RIEKERT, G ;
WALTER, D ;
JUST, T .
CHEMICAL PHYSICS LETTERS, 1988, 148 (06) :530-536
[10]  
GROTHEER HH, IN PRESS