Kinetics of vibrationally hot propane produced by methylene insertion into ethane

F. B. Growcock; W. L. Hase; J. W. Simons

doi:10.1021/j100648a029

Kinetics of vibrationally hot propane produced by methylene insertion into ethane

F. B. Growcock, W. L. Hase, J. W. Simons

Chemistry and Biochemistry

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Abstract

The reaction of ethane with excited singlet state methylene radicals produced via the photolysis of diazo-methane at 4358 Å, yields chemically activated propane with an average energy of 119.4 ± 2.0 kcal/mol. The measured decomposition rate coefficient for the energized propane is (4.7 ± 1.2) × 10⁸ sec^-1. This rate is correlated by RRKM and absolute rate theory calculations with thermal A factors in the range 10^16.7-10^17.2 sec^-1 and radical recombination rate coefficients in the range 2.2 × 10⁹-5.8 × 10⁹ l. mol^-1 sec^-1, which are substantially lower than estimates of experimental recombination rates for CH₃ + C₂H₅. A dilemma of possible theoretical significance exists.

Original language	English
Pages (from-to)	607-614
Number of pages	8
Journal	Journal of physical chemistry
Volume	76
Issue number	4
DOIs	https://doi.org/10.1021/j100648a029
State	Published - 1972

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title = "Kinetics of vibrationally hot propane produced by methylene insertion into ethane",

abstract = "The reaction of ethane with excited singlet state methylene radicals produced via the photolysis of diazo-methane at 4358 {\AA}, yields chemically activated propane with an average energy of 119.4 ± 2.0 kcal/mol. The measured decomposition rate coefficient for the energized propane is (4.7 ± 1.2) × 108 sec-1. This rate is correlated by RRKM and absolute rate theory calculations with thermal A factors in the range 1016.7-1017.2 sec-1 and radical recombination rate coefficients in the range 2.2 × 109-5.8 × 109 l. mol-1 sec-1, which are substantially lower than estimates of experimental recombination rates for CH3 + C2H5. A dilemma of possible theoretical significance exists.",

author = "Growcock, {F. B.} and Hase, {W. L.} and Simons, {J. W.}",

year = "1972",

doi = "10.1021/j100648a029",

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volume = "76",

pages = "607--614",

journal = "Journal of physical chemistry",

issn = "0022-3654",

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T1 - Kinetics of vibrationally hot propane produced by methylene insertion into ethane

AU - Growcock, F. B.

AU - Hase, W. L.

AU - Simons, J. W.

PY - 1972

Y1 - 1972

N2 - The reaction of ethane with excited singlet state methylene radicals produced via the photolysis of diazo-methane at 4358 Å, yields chemically activated propane with an average energy of 119.4 ± 2.0 kcal/mol. The measured decomposition rate coefficient for the energized propane is (4.7 ± 1.2) × 108 sec-1. This rate is correlated by RRKM and absolute rate theory calculations with thermal A factors in the range 1016.7-1017.2 sec-1 and radical recombination rate coefficients in the range 2.2 × 109-5.8 × 109 l. mol-1 sec-1, which are substantially lower than estimates of experimental recombination rates for CH3 + C2H5. A dilemma of possible theoretical significance exists.

AB - The reaction of ethane with excited singlet state methylene radicals produced via the photolysis of diazo-methane at 4358 Å, yields chemically activated propane with an average energy of 119.4 ± 2.0 kcal/mol. The measured decomposition rate coefficient for the energized propane is (4.7 ± 1.2) × 108 sec-1. This rate is correlated by RRKM and absolute rate theory calculations with thermal A factors in the range 1016.7-1017.2 sec-1 and radical recombination rate coefficients in the range 2.2 × 109-5.8 × 109 l. mol-1 sec-1, which are substantially lower than estimates of experimental recombination rates for CH3 + C2H5. A dilemma of possible theoretical significance exists.

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U2 - 10.1021/j100648a029

DO - 10.1021/j100648a029

M3 - Article

AN - SCOPUS:33947090958

SN - 0022-3654

VL - 76

SP - 607

EP - 614

JO - Journal of physical chemistry

JF - Journal of physical chemistry

IS - 4

ER -

Kinetics of vibrationally hot propane produced by methylene insertion into ethane

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