The gas-phase reaction of SiH2 with dimethylether:: kinetic evidence for direct formation of a donor-acceptor adduct

被引:22
作者
Becerra, R
Carpenter, IW
Gutsche, GJ
King, KD
Lawrance, WD
Staker, WS
Walsh, R
机构
[1] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England
[2] CSIC, Inst Quim Fis Rocasolano, Madrid 28006, Spain
[3] Flinders Univ S Australia, Sch Chem Phys & Earth Sci, Adelaide, SA 5001, Australia
[4] Univ Adelaide, Dept Chem Engn, Adelaide, SA 5005, Australia
基金
澳大利亚研究理事会;
关键词
D O I
10.1016/S0009-2614(00)01352-X
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 kinetics of the title reaction have been investigated at 296 K (3-400 Torr in Ar and 3-50 Torr in SF6), and between 298 and 434 K (5 Torr in Ar). The second-order rate constants increase by ca. x 20 between 3 and 400 Torr (Ar) and ca. x 6 between 3 and 50 Torr (SF6). At 5 Torr Ar, an Arrhenius plot gives log(A/cm(3) molecule(-1) s(-1)) = -13.71 +/- 0.13 and E-a -15.3 +/- 0.9 kJ mol(-1). The data are consistent with the formation of an H2Si . . . OMe2 donor-acceptor adduct. RRKM/master equation modelling of the rate constants at 296 K gives a high pressure limiting value (k(proportional to)) of 6.6 x 10(-10) cm(3) molecule(-1) s(-1) and a binding energy of 96 kJ mol(-1) for the adduct. (C) 2001 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:83 / 90
页数:8
相关论文
共 31 条
[1]  
ALEXANDER UN, UNPUB
[2]  
ALEXANDER UN, 2000, THESIS FLINDERS U S
[3]   GAS-PHASE KINETIC-STUDY OF THE PROTOTYPE SILYLENE ADDITION-REACTION SIH2+C2H4 OVER THE TEMPERATURE-RANGE 298-595-K - AN EXAMPLE OF A 3RD-BODY MEDIATED ASSOCIATION [J].
ALRUBAIEY, N ;
WALSH, R .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (20) :5303-5309
[4]  
[Anonymous], 1993, UNIMOL PROGRAM SUITE
[5]   TIME RESOLVED KINETIC-STUDIES OF THE GAS-PHASE REACTIONS OF DIMETHYLSILYLENE WITH SOME O-DONOR MOLECULES .1. ROOM-TEMPERATURE STUDIES [J].
BAGGOTT, JE ;
BLITZ, MA ;
FREY, HM ;
LIGHTFOOT, PD ;
WALSH, R .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1992, 24 (02) :127-143
[6]   TEMPERATURE-DEPENDENCE OF THE REACTION OF SIH2 WITH D2 [J].
BAGGOTT, JE ;
FREY, HM ;
KING, KD ;
LIGHTFOOT, PD ;
WALSH, R ;
WATTS, IM .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (14) :4025-4027
[7]   THE REACTION OF GAS-PHASE DIMETHYLSILYLENE WITH DIMETHYL ETHER [J].
BAGGOTT, JE ;
BLITZ, MA ;
LIGHTFOOT, PD .
CHEMICAL PHYSICS LETTERS, 1989, 154 (04) :330-334
[8]   PROTOTYPE SI-H INSERTION REACTION OF SILYLENE WITH SILANE - ABSOLUTE RATE CONSTANTS, TEMPERATURE-DEPENDENCE, RRKM MODELING AND THE POTENTIAL-ENERGY SURFACE [J].
BECERRA, R ;
FREY, HM ;
MASON, BP ;
WALSH, R ;
GORDON, MS .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1995, 91 (17) :2723-2732
[9]   Gas-phase reaction of silylene with acetone: Direct rate studies, RRKM modeling, and ab initio studies of the potential energy surface [J].
Becerra, R ;
Cannady, JP ;
Walsh, R .
JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (23) :4457-4464
[10]  
Becerra R., 1995, RES CHEM KINET SER, V3, P263