Theoretical study of mechanism and kinetics for the addition of hydroxyl radical to phenol

The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometri...

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Bibliographic Details
Published inScience China. Chemistry Vol. 55; no. 2; pp. 270 - 276
Main Authors Wu, PengZhen, Li, Jian, Li, ShuJin, Tao, Fu-Ming
Format Journal Article
LanguageEnglish
Published Heidelberg SP Science China Press 01.02.2012
Springer Nature B.V
Subjects
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Hydroxyl radicals
Kinetics
Mathematical analysis
Rate constants
Reaction mechanisms
Thermodynamic equilibrium
Troposphere
加成反应
动力学
平衡几何结构
机制
温度范围
羟基自由基
苯酚
速率常数
phenol
hydroxyl radical
addition reaction
quantum chemistry calculation
transition state theory
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Summary:The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometries, energies, and thermodynamics properties of all the stationary points along the addition reaction pathway are calculated. The rate constants and the branching ratios of each channel are evaluated using classical transition state theory （TST） in the temperature range of 210 to 360 K, to simulate temperatures in all parts of the troposphere. The ortho addition pathway is dominant and accounts for 99.8%-96.7% of the overall adduct products from 210 to 360 K. The calculated rate constants are in good agreement with existing experimental values. The addition reaction is irreversible.
Bibliography:phenol, hydroxyl radical, addition reaction, quantum chemistry calculation, transition state theory
The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometries, energies, and thermodynamics properties of all the stationary points along the addition reaction pathway are calculated. The rate constants and the branching ratios of each channel are evaluated using classical transition state theory （TST） in the temperature range of 210 to 360 K, to simulate temperatures in all parts of the troposphere. The ortho addition pathway is dominant and accounts for 99.8%-96.7% of the overall adduct products from 210 to 360 K. The calculated rate constants are in good agreement with existing experimental values. The addition reaction is irreversible.
11-5839/O6
ISSN:1674-7291
1869-1870
DOI:10.1007/s11426-011-4380-1