Issue 15, 2010

Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part I: reactions with alkanes (CH4, C2H6, C3H8, C4H10)

Abstract

The kinetics of the reactions of the linear butadiynyl radical, C4H (CCCCH), with methane, ethane, propane and butane have been studied over the temperature range of 39–300 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis—laser induced fluorescence technique. The rate coefficients, except for the reaction with methane, show a negative temperature dependence and can be fitted with the following expressions over the temperature range of this study: kC2H6 = 0.289 × 10−10 (T/298 K)−1.23 exp(−24.8 K/T) cm3 molecule−1 s−1;kC3H8 = 1.06 × 10−10 (T/298 K)−1.36 exp(−56.9 K/T) cm3 molecule−1 s−1;kC4H10 = 2.93 × 10−10 (T/298 K)−1.30 exp(−90.1 K/T) cm3 molecule−1 s−1.The rate coefficients for the reaction with methane were measured only at 200 K and 300 K yielding a positive temperature dependence: kCH4 = 1.63 × 10−11 exp(−610 K/T) cm3 molecule−1 s−1.Possible reaction mechanisms and product channels are discussed in detail for each of these reactions. Potential implications of these results for models of low temperature chemical environments, in particular cold interstellar clouds and planetary atmospheres such as that of Titan, are considered.

Graphical abstract: Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part I: reactions with alkanes (CH4, C2H6, C3H8, C4H10)

Article information

Article type
Paper
Submitted
08 Apr 2009
Accepted
04 Aug 2009
First published
25 Sep 2009

Phys. Chem. Chem. Phys., 2010,12, 3666-3676

Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part I: reactions with alkanes (CH4, C2H6, C3H8, C4H10)

C. Berteloite, S. D. Le Picard, N. Balucani, A. Canosa and I. R. Sims, Phys. Chem. Chem. Phys., 2010, 12, 3666 DOI: 10.1039/B907154G

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