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Mechanistic and Kinetic Study of the Gas-Phase Reaction of Atomic Chlorine with Cyclohexanone using an Absolute and a Relative Technique; Influence of Temperature

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Abstract

The reaction of Cl with cyclohexanone (1) was investigated, for the first time, as a function of temperature (273–333 K) and at a low total pressure (1 Torr) with helium as a carrier gas using a discharge flow-mass spectrometry technique (DF-MS). The resulting Arrhenius expression is proposed, k 1= (7.7 ± 4.1) × 10−10 exp[–(540 ± 169)/T]. We also report a mechanistic study with the quantitative determination of the products of the reaction of Cl with cyclohexanone. The absolute rate constant derived from this study at 1 Torr of total pressure and room temperature is (1.3 ± 0.2) × 10−10 cm3 molecule−1 s−1. A yield of 0.94 ± 0.10 was found for the H-abstraction channel giving HCl. In relative studies, using a newly constructed relative rate system, the decay of cyclohexanone was followed by gas chromatography coupled with flame-ionisation detection. These relative measurements were performed at atmospheric pressure with synthetic air and room temperature. Rate constant measured using the relative method for reaction (1) is: (1.7 ± 0.3) × 10−10 cm3 molecule−1 s−1. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH radicals.

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Authors and Affiliations

  1. Departamento de Química Física, Facultad de CC Químicas, Universidad de Castilla-La Mancha, Avenida Camilo José Cela, N° 10, 13071 -, Ciudad Real, Spain

    Ernesto Martínez, Alfonso Aranda, Yolanda Díaz-De-Mera & Ana Rodríguez

  2. Departamento de Química Física, Facultad de CC Medio Ambiente, Universidad de Castilla-La Mancha, Avenida Carlos III, S/N, 45071-, Toledo, Spain

    Diana Rodríguez & Alberto Notario

Authors
  1. Ernesto Martínez
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  2. Alfonso Aranda
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  3. Yolanda Díaz-De-Mera
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  4. Ana Rodríguez
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  5. Diana Rodríguez
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  6. Alberto Notario
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Martínez, E., Aranda, A., Díaz-De-Mera, Y. et al. Mechanistic and Kinetic Study of the Gas-Phase Reaction of Atomic Chlorine with Cyclohexanone using an Absolute and a Relative Technique; Influence of Temperature. Journal of Atmospheric Chemistry 48, 283–299 (2004). https://doi.org/10.1023/B:JOCH.0000044424.22309.d8

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