Kinetics and Thermochemistry of the Addition of Atomic Chlorine to Acetylene

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Article on the kinetics and thermochemistry of the addition of atomic chlorine to acetylene.

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26 p.

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Gao, Yide; Alecu, I. M.; Hsieh, P-C; McLeod, A.; McLeod, Chris; Jones, Maxwell et al. January 1, 2007.

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Article on the kinetics and thermochemistry of the addition of atomic chlorine to acetylene.

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26 p.

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Abstract: Atomic Cl was generated by pulsed laser photolysis at 193 nm of CCl4, and was monitored by time resolved resonance fluorescence in the course of reaction with excess C2H2, diluted in Ar bath gas at pressures from 13 to 800 mbar. At 288 K simple pseudo first order kinetics were observed. Over 365–430 K bi-exponential decays were obtained, because of equilibration between the β-chlorovinyl adduct and the reactants. The ratios of forward and reverse rate constants yield ΔfH298(radical dotCHdouble bond; length as m-dashCHCl) = 274.0 ± 1.0 kJ mol−1 via a Third-Law analysis of the carbon–chlorine bond strength. The thermochemistry compares well with that predicted by an initio theory. The effective second-order rate constant was pressure dependent and was analyzed using Troe’s unimolecular formalism. Over the whole temperature range the low-pressure limiting value for addition, with Ar bath gas, is given by k0 = 4.1 × 10−30 (T/300 K)−2.47 cm6 molecule−2 s−1.

This is the accepted manuscript version of the article. Reprinted with permission from Elsevier Science Ltd., all rights reserved. The final definitive version is available here: http://www.sciencedirect.com/science/article/pii/S154074890600112X

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  • Proceedings of the Combustion Institute, 2007, Amsterdam: Elsevier Science Ltd., pp. 193-200

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  • Publication Title: Proceedings of the Combustion Institute
  • Volume: 31
  • Issue: 1
  • Page Start: 193
  • Page End: 200
  • Peer Reviewed: Yes

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  • January 1, 2007

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  • Oct. 2, 2015, 9:40 a.m.

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Gao, Yide; Alecu, I. M.; Hsieh, P-C; McLeod, A.; McLeod, Chris; Jones, Maxwell et al. Kinetics and Thermochemistry of the Addition of Atomic Chlorine to Acetylene, article, January 1, 2007; [Amsterdam, Netherlands]. (digital.library.unt.edu/ark:/67531/metadc725849/: accessed November 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.