Kinetics and mechanism of the reaction of hydroxyl with benzene

Sandmeyer reactions. Part 5. Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics

“…(4) relating the molar ratio of normal to abnormal phenolic products [here inverted relative to eqn. (3)] to the copper concentration.…”

Kinetics of OH radical reaction with phenanthrene: New absolute rate measurements and comparison with other PAHs

“…Figure 6 shows OH rate coefficients with phenanthrene in comparison with selected measurements for benzene 30–35, naphthalene 10,11,32,36,37, and anthracene 7. This Arrhenius plot of one‐, two‐, and three‐member aromatic hydrocarbons shows a typical behavior of OH reactivity as a function of temperature.…”

“… Arrhenius plot of OH rate coefficients for benzene 30–35 (squares), naphthalene 10,11,32,36,37 (diamonds and triangles), anthracene 7 (filled circles), and phenanthrene (this work) (crosses). The curve that extends from 400 to 1500 K is Atkinson's recommendation 8 for the H‐abstraction rate coefficient for benzene + OH.…”

Global ab initio exploration of potential energy surfaces for radical generation in the initial stage of benzene oxidation

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] It is well known that hydrocarbon combustion follows a chain reaction mechanism, where free radicals play a dominant role in the destruction of reactant molecules. Free radicals such as OOH, OH, O, and H, are well known to be active in the benzene ame 10,[16][17][18] as well as in other hydrocarbon combustion. 14,[19][20][21] In near-sooting premixed lowpressure ames of benzene, Bittner and Howard 2 have observed an abundance of the free radicals OH, O, OOH, and H in the benzene ame and suggested that the activation and decomposition of benzene are initiated by the oxidation of atomic O, while that by molecular oxygen and other free radicals would be too slow to account for their experimental observations, which is consistent with the observations by Ko et al 22 While, Madronich and Felder 17 found that the hydrogen abstraction channel by OH radical plays a critical role in benzene consumption, giving an important intermediate phenyl radial.…”

“…8 These benzene destruction mechanisms by free radical species have been well proven by a large number of kinetic modeling studies, which are used to present a quantitative description of the combustion processes. [6][7][8][9][16][17][18]22 In addition to these combustion models, investigations of the reaction pathways of benzene activation by OH and H radicals have been undertaken using high-level ab initio methods, 23,24 which provide evidence that hydrogen abstractions from benzene by these radicals are favorable with a low activation energy of around 10 kcal mol À1 . All of these investigations indicated that free radicals, such as OH, O and atomic H, play crucial roles in benzene decomposition and subsequent PAH formation.…”