Theoretical study on the reaction of the phenoxy radical with O 2, OH, and NO 2

Marwan Batiha, Ala'A H. Al-Muhtaseb, Mohammednoor Altarawneh

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Unlike the chemistry underlying the self-coupling of phenoxy (C 6H 5O) radicals, there are very limited kinetics data at elevated temperatures for the reaction of the phenoxy radical with other species. In this study, we investigate the addition reactions of O 2, OH, and NO 2 to the phenoxy radical. The formation of a phenoxy-peroxy is found to be very slow with a rate constant fitted to k = 1.31 × 10 -20T 2.49 exp (-9300/T) cm 3/mol/s in the temperature range of (298-2,000 K) where the addition occurs predominantly at the ortho site. Our rate constant is in line with the consensus of opinions in the literature pointing to the observation of no discernible reaction between the oxygen molecule and the resonance-stabilized phenoxy radical. Addition of OH at the ortho and para sites of the phenoxy radical is found to afford adducts with sizable well depths of 59.8 and 56.0 kcal/mol, respectively. The phenoxy-NO 2 bonds are found to be among the weakest known phenoxy-radical bonds (1.7-8.7 kcal/mol). OH- and O 2-initiated mechanisms for the degradation of atmospheric phenoxy appear to be negligible and the fate of atmospheric phenoxy is found to be controlled by its reaction with NO 2.

Original languageEnglish
Pages (from-to)848-857
Number of pages10
JournalInternational Journal of Quantum Chemistry
Volume112
Issue number3
DOIs
Publication statusPublished - Feb 5 2012

Fingerprint

Rate constants
Addition reactions
adducts
phenoxy radical
Oxygen
Degradation
Temperature
Molecules
Kinetics
chemistry
degradation
temperature
kinetics
oxygen
molecules
hydroxide ion

Keywords

  • atmospheric life time
  • DFT
  • NO
  • O
  • OH
  • phenoxy radicals
  • rate constant

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

Theoretical study on the reaction of the phenoxy radical with O 2, OH, and NO 2 . / Batiha, Marwan; Al-Muhtaseb, Ala'A H.; Altarawneh, Mohammednoor.

In: International Journal of Quantum Chemistry, Vol. 112, No. 3, 05.02.2012, p. 848-857.

Research output: Contribution to journalArticle

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AB - Unlike the chemistry underlying the self-coupling of phenoxy (C 6H 5O) radicals, there are very limited kinetics data at elevated temperatures for the reaction of the phenoxy radical with other species. In this study, we investigate the addition reactions of O 2, OH, and NO 2 to the phenoxy radical. The formation of a phenoxy-peroxy is found to be very slow with a rate constant fitted to k = 1.31 × 10 -20T 2.49 exp (-9300/T) cm 3/mol/s in the temperature range of (298-2,000 K) where the addition occurs predominantly at the ortho site. Our rate constant is in line with the consensus of opinions in the literature pointing to the observation of no discernible reaction between the oxygen molecule and the resonance-stabilized phenoxy radical. Addition of OH at the ortho and para sites of the phenoxy radical is found to afford adducts with sizable well depths of 59.8 and 56.0 kcal/mol, respectively. The phenoxy-NO 2 bonds are found to be among the weakest known phenoxy-radical bonds (1.7-8.7 kcal/mol). OH- and O 2-initiated mechanisms for the degradation of atmospheric phenoxy appear to be negligible and the fate of atmospheric phenoxy is found to be controlled by its reaction with NO 2.

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