Reaction of the Hydroxyl Radical with Phenol in Water Up to Supercritical Conditions
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- 作者：Julien Bonin ; Ireneusz Janik ; Dorota Janik ; David M. Bartels
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：March 15, 2007
- 年：2007
- 卷：111
- 期：10
- 页码：1869 - 1878
- 全文大小：192K
- 年卷期：v.111,no.10(March 15, 2007)
- ISSN：1520-5215
文摘
The rate constants for the reactions of phenol with the hydroxyl radical (OH
) in water have been measuredfrom room temperature to 380 
C using electron pulse radiolysis and transient absorption spectroscopy. Thereaction scheme designed to fit the data shows the importance of an equilibrium, giving back reactants (OHradical and phenol) from the dihydroxycyclohexadienyl radical formed by their reaction, and the non-negligiblecontribution of the hydroxycyclohexadienyl radical absorption from H atom addition. The accuracy of thereaction scheme and the reaction rate constants determined from it have been determined by the analysis oftwo different experiments, one under pure N2O atmosphere and the second under a mixture a N2O and O2.We report reaction rates for the H and OH radical addition to phenol, the formation of phenoxyl, the second-order recombination, the reaction of dihydroxycyclohexadienyl with O2, and the decay of the peroxyl adduct.Nearly all of the reaction rates deviate strongly from Arrhenius behavior.
) in water have been measuredfrom room temperature to 380 C using electron pulse radiolysis and transient absorption spectroscopy. Thereaction scheme designed to fit the data shows the importance of an equilibrium, giving back reactants (OHradical and phenol) from the dihydroxycyclohexadienyl radical formed by their reaction, and the non-negligiblecontribution of the hydroxycyclohexadienyl radical absorption from H atom addition. The accuracy of thereaction scheme and the reaction rate constants determined from it have been determined by the analysis oftwo different experiments, one under pure N2O atmosphere and the second under a mixture a N2O and O2.We report reaction rates for the H and OH radical addition to phenol, the formation of phenoxyl, the second-order recombination, the reaction of dihydroxycyclohexadienyl with O2, and the decay of the peroxyl adduct.Nearly all of the reaction rates deviate strongly from Arrhenius behavior.