Reaction kinetics to low temperatures. Dicarbon plus acetylene, methylacetylene, allene and propene from 77 ≤ T ≤ 296 K

被引:75
作者
Daugey, Nicolas [1 ]
Caubet, Philippe [1 ]
Bergeat, Astrid [1 ]
Costes, Michel [1 ]
Hickson, Kevin M. [1 ]
机构
[1] Univ Bordeaux 1, Inst Mol Sci, CNRS, UMR 5255, F-33405 Talence, France
关键词
D O I
10.1039/b710796j
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 temperature dependence of the reactions of the dicarbon molecule in its ground singlet (X (1)Sigma(+)(g)) and first excited triplet (a (3)Pi(u)) states with acetylene, methylacetylene, allene and propene has been studied using a recently constructed continuous supersonic flow reactor. Four Laval nozzles have been designed to access specified temperatures over the range of 77 <= T <= 220 K and measurements have been performed at 296 K under subsonic flow conditions. C-2 was produced in its two lowest electronic states via the in situ multiphoton dissociation of C2Br4 at 266 nm. The time dependent losses of C-2 in these two states in the presence of an excess of coreagent species were simultaneously followed by laser-induced fluorescence in the Mulliken and Swan bands for the detection of singlet and triplet state C-2, respectively. The rate coefficients were measured to be very fast, with values larger than 10(-10) cm(3) molecule(-1) s(-1) and up to 5 x 10(-10) cm(3) molecule(-1) s(-1). The reactions of C-1(2) are seen to be essentially temperature independent from 77 <= T <= 296 K whereas the rate coefficients for the C-3(2) reactions are seen to increase until they are equivalent to the C-1(2) values at 77 K.
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页码:729 / 737
页数:9
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