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

Abstract

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 6-311++G(2dp, 2df) 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. phenol, hydroxyl radical, addition reaction, quantum chemistry calculation, transition state theory

Benchmarking of DFT functionals for the kinetics and mechanisms of atmospheric addition reactions of OH radicals with phenyl and substituted phenyl‐based organic pollutants

“…For the reaction with C 6 H 5 OH, the Δ E ‡ and Δ G ‡ values for • OH addition to one of the ortho positions are at least 1.9 and 3.7 kcal mol −1 lower, respectively, compared to the addition to the other positions. A similar conclusion was obtained in previous theoretical studies . The formation of inter‐molecular hydrogen bonds (Figure ) between the incoming • OH and the OH of C 6 H 5 OH in the TS for • OH addition to the ortho position may be the reason for its low Δ E ‡ and Δ G ‡ values.…”

Secondary organic aerosol in residences: predicting its fraction of fine particle mass and determinants of formation strength

“… 2. Temperature‐dependent reaction rate constants were from Master Chemical Mechanism, MCM v3.2 (Bloss et al., ; Jenkin et al., , ; Saunders et al., ), except those for phenol (Wu et al., ), p‐dichlorobenzene (Arnts et al., ), glyoxal and methylglyoxal (Plum et al., ), acetone (Gierczak et al., ), and carbon tetrachloride (Cupitt, ). The alkanes n‐tridecane, n‐tetradecane, and n‐pentadecane were assumed as the same as n‐dodecane.…”

Dimethyl Phthalate Degradation by UV/H2O2: Combination of Experimental Methods and Quantum Chemical Calculation

“…Similar C‐C bonding characteristics have been observed for OH addition to C1, C2, C3, C5, and C6 positions of DMP. The distance of the newly formed C‐O bond in the six adducts ranges from 1.415 to 1.449 Å. C‐C bonding characteristics have also been reported for OH‐phenol adducts .…”