Structure dependence of the rate coefficients of hydroxyl radical+aromatic molecule reaction

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Abstract

The rate coefficients of hydroxyl radical addition to the rings of simple aromatic molecules (kOH) were evaluated based on the literature data. By analyzing the methods of kOH determination and the data obtained the most probable values were selected for the kOH's of individual compounds and thereby the most reliable dataset was created for monosubstituted aromatics and p-substituted phenols. For these compounds the rate coefficients fall in a narrow range between 2×109mol-1dm3s-1 and 1×1010mol-1dm3s-1. Although the values show some regular trend with the electron donating/withdrawing nature of the substituent, the log kOHp Hammett substituent constant plots do not give straight lines because these high kOH's are controlled by both, the chemical reactivity and the diffusion. However, the logarithms of the rate coefficients of the chemical reactivity controlled reactions (kchem), are calculated by the equation 1/kOH=1/kchem+1/kdiff, and accepting for the diffusion controlled rate coefficient kdiff=1.1×1010mol-1dm3s-1, show good linear correlation with σp.

Original languageEnglish
Pages (from-to)82-87
Number of pages6
JournalRadiation Physics and Chemistry
Volume87
DOIs
Publication statusPublished - Jun 2013

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hydroxyl radicals
coefficients
molecules
reactivity
logarithms
phenols
plots
trends
rings
electrons

Keywords

  • Aromatic molecule
  • Hammett plot
  • Hydroxyl radical
  • Phenol
  • Rate coefficient

ASJC Scopus subject areas

  • Radiation

Cite this

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title = "Structure dependence of the rate coefficients of hydroxyl radical+aromatic molecule reaction",
abstract = "The rate coefficients of hydroxyl radical addition to the rings of simple aromatic molecules (kOH) were evaluated based on the literature data. By analyzing the methods of kOH determination and the data obtained the most probable values were selected for the kOH's of individual compounds and thereby the most reliable dataset was created for monosubstituted aromatics and p-substituted phenols. For these compounds the rate coefficients fall in a narrow range between 2×109mol-1dm3s-1 and 1×1010mol-1dm3s-1. Although the values show some regular trend with the electron donating/withdrawing nature of the substituent, the log kOH-σp Hammett substituent constant plots do not give straight lines because these high kOH's are controlled by both, the chemical reactivity and the diffusion. However, the logarithms of the rate coefficients of the chemical reactivity controlled reactions (kchem), are calculated by the equation 1/kOH=1/kchem+1/kdiff, and accepting for the diffusion controlled rate coefficient kdiff=1.1×1010mol-1dm3s-1, show good linear correlation with σp.",
keywords = "Aromatic molecule, Hammett plot, Hydroxyl radical, Phenol, Rate coefficient",
author = "L. Wojn{\'a}rovits and E. Tak{\'a}cs",
year = "2013",
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AU - Wojnárovits, L.

AU - Takács, E.

PY - 2013/6

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N2 - The rate coefficients of hydroxyl radical addition to the rings of simple aromatic molecules (kOH) were evaluated based on the literature data. By analyzing the methods of kOH determination and the data obtained the most probable values were selected for the kOH's of individual compounds and thereby the most reliable dataset was created for monosubstituted aromatics and p-substituted phenols. For these compounds the rate coefficients fall in a narrow range between 2×109mol-1dm3s-1 and 1×1010mol-1dm3s-1. Although the values show some regular trend with the electron donating/withdrawing nature of the substituent, the log kOH-σp Hammett substituent constant plots do not give straight lines because these high kOH's are controlled by both, the chemical reactivity and the diffusion. However, the logarithms of the rate coefficients of the chemical reactivity controlled reactions (kchem), are calculated by the equation 1/kOH=1/kchem+1/kdiff, and accepting for the diffusion controlled rate coefficient kdiff=1.1×1010mol-1dm3s-1, show good linear correlation with σp.

AB - The rate coefficients of hydroxyl radical addition to the rings of simple aromatic molecules (kOH) were evaluated based on the literature data. By analyzing the methods of kOH determination and the data obtained the most probable values were selected for the kOH's of individual compounds and thereby the most reliable dataset was created for monosubstituted aromatics and p-substituted phenols. For these compounds the rate coefficients fall in a narrow range between 2×109mol-1dm3s-1 and 1×1010mol-1dm3s-1. Although the values show some regular trend with the electron donating/withdrawing nature of the substituent, the log kOH-σp Hammett substituent constant plots do not give straight lines because these high kOH's are controlled by both, the chemical reactivity and the diffusion. However, the logarithms of the rate coefficients of the chemical reactivity controlled reactions (kchem), are calculated by the equation 1/kOH=1/kchem+1/kdiff, and accepting for the diffusion controlled rate coefficient kdiff=1.1×1010mol-1dm3s-1, show good linear correlation with σp.

KW - Aromatic molecule

KW - Hammett plot

KW - Hydroxyl radical

KW - Phenol

KW - Rate coefficient

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