Rates of alkyl radical-radical, alkyl radical-iodine, and iodine atom-atom reactions in normal alkanes and cycloalkanes

Jay A. LaVerne, L. Wojnárovits

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Pulse radiolysis techniques have been used to determine the second order rate constants for radical-radical reactions of the parenr alkyl radicals produced in neat liquid cycloalkanes of C5 to C10 and normal alkanes of Ce to Cn. Iodine solutions of these compounds were used to determine the radical scavenging rate constants, the extinction coefficients of the iodine atom produced from this reaction, and the second-order rate constants for the subsequent reactions of the iodine atoms. None of the three sets of rate constants were found to be completely proportional to the inverse of the viscosity of the media, indicating that they are not solely diffusion rate-controlled. However, it was possible to describe the observed rate constants for the alkyl radical-iodine and iodine atom-atom reactions with a combination of a diffusion-controlled rate constant which scales inversely with the viscosity of the media and an activation-controlled rate constant which is the same for all media. The same procedure also worked for the alkyl radical-radical reactions except that the diffusion-controlled rate constant was further modified by a spin-steric factor. No significant differences were observed in all three sets of rale constants for the normal alkanes or the cycloalkanes at the same viscosity.

Original languageEnglish
Pages (from-to)12635-12640
Number of pages6
JournalJournal of Physical Chemistry
Volume98
Issue number48
Publication statusPublished - 1994

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Cycloparaffins
Alkanes
Iodine
Paraffins
alkanes
iodine
Rate constants
Atoms
atoms
Viscosity
viscosity
Radiolysis
Scavenging
scavenging
radiolysis
Chemical activation
extinction
activation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Rates of alkyl radical-radical, alkyl radical-iodine, and iodine atom-atom reactions in normal alkanes and cycloalkanes. / LaVerne, Jay A.; Wojnárovits, L.

In: Journal of Physical Chemistry, Vol. 98, No. 48, 1994, p. 12635-12640.

Research output: Contribution to journalArticle

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N2 - Pulse radiolysis techniques have been used to determine the second order rate constants for radical-radical reactions of the parenr alkyl radicals produced in neat liquid cycloalkanes of C5 to C10 and normal alkanes of Ce to Cn. Iodine solutions of these compounds were used to determine the radical scavenging rate constants, the extinction coefficients of the iodine atom produced from this reaction, and the second-order rate constants for the subsequent reactions of the iodine atoms. None of the three sets of rate constants were found to be completely proportional to the inverse of the viscosity of the media, indicating that they are not solely diffusion rate-controlled. However, it was possible to describe the observed rate constants for the alkyl radical-iodine and iodine atom-atom reactions with a combination of a diffusion-controlled rate constant which scales inversely with the viscosity of the media and an activation-controlled rate constant which is the same for all media. The same procedure also worked for the alkyl radical-radical reactions except that the diffusion-controlled rate constant was further modified by a spin-steric factor. No significant differences were observed in all three sets of rale constants for the normal alkanes or the cycloalkanes at the same viscosity.

AB - Pulse radiolysis techniques have been used to determine the second order rate constants for radical-radical reactions of the parenr alkyl radicals produced in neat liquid cycloalkanes of C5 to C10 and normal alkanes of Ce to Cn. Iodine solutions of these compounds were used to determine the radical scavenging rate constants, the extinction coefficients of the iodine atom produced from this reaction, and the second-order rate constants for the subsequent reactions of the iodine atoms. None of the three sets of rate constants were found to be completely proportional to the inverse of the viscosity of the media, indicating that they are not solely diffusion rate-controlled. However, it was possible to describe the observed rate constants for the alkyl radical-iodine and iodine atom-atom reactions with a combination of a diffusion-controlled rate constant which scales inversely with the viscosity of the media and an activation-controlled rate constant which is the same for all media. The same procedure also worked for the alkyl radical-radical reactions except that the diffusion-controlled rate constant was further modified by a spin-steric factor. No significant differences were observed in all three sets of rale constants for the normal alkanes or the cycloalkanes at the same viscosity.

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