The kinetics of radiation-induced hydrogen abstraction by CCl3 and CCl3O2 radicals from cyclohexane in the liquid phase

Zeev B. Alfassi; Shlomo Mosseri

doi:10.1021/j150659a031

The kinetics of radiation-induced hydrogen abstraction by CCl₃ and CCl₃O₂ radicals from cyclohexane in the liquid phase

Zeev B. Alfassi, Shlomo Mosseri

Unit of Nuclear Engineering

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Abstract

The kinetics of the photolysis-induced free-radical reaction in carbon tetrachloride solution of cyclohexane in the absence and in the presence of oxygen were studied in the temperature range of 100-200°C. It was found that the influence of the oxygen on the chloroform formation is significant, and a new mechanism which explains the results was suggested. The rate constants for the reactions ·CCl₃ + O₂ → ·CCl₃O₂ (k₆), ·CCl₃O₂ → COCl₂ + ClO (k₇), and ·CCl₃O₂ + C₆H₁₂ → CHCl₃ + ·C₆H₁₁ + O₂ (k₈) were found as log (k₆/(M^-1 s^-1)) = 5.05 ± 0.07 and log [(k₈/k₇)/(M^-1 s^-1)] = (3.0808 ± 0.0973) - (3.7080 ± 0.1857)/θ, where θ = 2.303RT kcal/mol.

Original language	English
Pages (from-to)	3296-3300
Number of pages	5
Journal	Journal of Physical Chemistry
Volume	88
Issue number	15
DOIs	https://doi.org/10.1021/j150659a031
State	Published - 1 Jan 1984

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Engineering (all)
Physical and Theoretical Chemistry

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10.1021/j150659a031

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@article{845946e9790b44d29eaf9e292ae23986,

title = "The kinetics of radiation-induced hydrogen abstraction by CCl3 and CCl3O2 radicals from cyclohexane in the liquid phase",

abstract = "The kinetics of the photolysis-induced free-radical reaction in carbon tetrachloride solution of cyclohexane in the absence and in the presence of oxygen were studied in the temperature range of 100-200°C. It was found that the influence of the oxygen on the chloroform formation is significant, and a new mechanism which explains the results was suggested. The rate constants for the reactions ·CCl3 + O2 → ·CCl3O2 (k6), ·CCl3O2 → COCl2 + ClO (k7), and ·CCl3O2 + C6H12 → CHCl3 + ·C6H11 + O2 (k8) were found as log (k6/(M-1 s-1)) = 5.05 ± 0.07 and log [(k8/k7)/(M-1 s-1)] = (3.0808 ± 0.0973) - (3.7080 ± 0.1857)/θ, where θ = 2.303RT kcal/mol.",

author = "Alfassi, {Zeev B.} and Shlomo Mosseri",

year = "1984",

month = jan,

day = "1",

doi = "10.1021/j150659a031",

language = "English",

volume = "88",

pages = "3296--3300",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "15",

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TY - JOUR

T1 - The kinetics of radiation-induced hydrogen abstraction by CCl3 and CCl3O2 radicals from cyclohexane in the liquid phase

AU - Alfassi, Zeev B.

AU - Mosseri, Shlomo

PY - 1984/1/1

Y1 - 1984/1/1

N2 - The kinetics of the photolysis-induced free-radical reaction in carbon tetrachloride solution of cyclohexane in the absence and in the presence of oxygen were studied in the temperature range of 100-200°C. It was found that the influence of the oxygen on the chloroform formation is significant, and a new mechanism which explains the results was suggested. The rate constants for the reactions ·CCl3 + O2 → ·CCl3O2 (k6), ·CCl3O2 → COCl2 + ClO (k7), and ·CCl3O2 + C6H12 → CHCl3 + ·C6H11 + O2 (k8) were found as log (k6/(M-1 s-1)) = 5.05 ± 0.07 and log [(k8/k7)/(M-1 s-1)] = (3.0808 ± 0.0973) - (3.7080 ± 0.1857)/θ, where θ = 2.303RT kcal/mol.

AB - The kinetics of the photolysis-induced free-radical reaction in carbon tetrachloride solution of cyclohexane in the absence and in the presence of oxygen were studied in the temperature range of 100-200°C. It was found that the influence of the oxygen on the chloroform formation is significant, and a new mechanism which explains the results was suggested. The rate constants for the reactions ·CCl3 + O2 → ·CCl3O2 (k6), ·CCl3O2 → COCl2 + ClO (k7), and ·CCl3O2 + C6H12 → CHCl3 + ·C6H11 + O2 (k8) were found as log (k6/(M-1 s-1)) = 5.05 ± 0.07 and log [(k8/k7)/(M-1 s-1)] = (3.0808 ± 0.0973) - (3.7080 ± 0.1857)/θ, where θ = 2.303RT kcal/mol.

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U2 - 10.1021/j150659a031

DO - 10.1021/j150659a031

M3 - Article

AN - SCOPUS:0000871056

SN - 0022-3654

VL - 88

SP - 3296

EP - 3300

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 15

ER -

The kinetics of radiation-induced hydrogen abstraction by CCl₃ and CCl₃O₂ radicals from cyclohexane in the liquid phase

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