Thermal decomposition of benzotrifluoride. The CC bond strength and the heat of formation of the phenyl radical

I. Szilágyi, T. Bérces

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15 Citations (Scopus)

Abstract

The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first‐order rate constant of the CC bond fission, log k (sec−1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH 298°(C6H5CF3) = 103.6 ± 2.5 kcal/mole and ΔH f298°(C6H5) = 77.1 ± 3.0 kcal/mole. Applicability of the simple first‐order formula to calculation of the rate constant has been also dealt with.

Original languageEnglish
Pages (from-to)199-213
Number of pages15
JournalInternational Journal of Chemical Kinetics
Volume2
Issue number3
DOIs
Publication statusPublished - Jan 1 1970

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heat of formation
thermal decomposition
Rate constants
Pyrolysis
Hot Temperature
Gases
Decomposition
Thermodynamics
decomposition
Activation energy
gases
Pressure
Kinetics
fission
activation energy
thermodynamics
kinetics
products
benzotrifluoride

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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abstract = "The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first‐order rate constant of the CC bond fission, log k (sec−1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH 298°(C6H5CF3) = 103.6 ± 2.5 kcal/mole and ΔH f298°(C6H5) = 77.1 ± 3.0 kcal/mole. Applicability of the simple first‐order formula to calculation of the rate constant has been also dealt with.",
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AU - Bérces, T.

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N2 - The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first‐order rate constant of the CC bond fission, log k (sec−1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH 298°(C6H5CF3) = 103.6 ± 2.5 kcal/mole and ΔH f298°(C6H5) = 77.1 ± 3.0 kcal/mole. Applicability of the simple first‐order formula to calculation of the rate constant has been also dealt with.

AB - The kinetics of the decomposition of benzotrifluoride was studied from 720°c to 859°c in a flow system with and without carrier gas. Consideration of the product distribution made possible the study of the decomposition into CF3 and C6H5 radicals, which appeared to be truly homogeneous in character. The first‐order rate constant of the CC bond fission, log k (sec−1) = (17.9 ± 0.5) (99.7 ± 2.5)/θ, did not change with change of initial concentration, pressure of the carrier gas, or contact time. The Arrhenius parameters have been related to the appropriate thermodynamic data. Assumption of 0 kcal/mole for the activation energy of the reverse combination reaction yielded DH 298°(C6H5CF3) = 103.6 ± 2.5 kcal/mole and ΔH f298°(C6H5) = 77.1 ± 3.0 kcal/mole. Applicability of the simple first‐order formula to calculation of the rate constant has been also dealt with.

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