Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

Wang, Quan‐De; Sun, Mao-Mao; Liang, Jinhu

doi:10.1016/j.comptc.2020.113120

Cited by 8 publications

(4 citation statements)

References 57 publications

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“…The main problems, in this case, are a deficit of thermochemical data and kinetic parameters for the elementary chemical reactions, related to the mechanism and energetic of decomposition/oxidation of the components of these bio‐oil mixtures. Moreover, a deficit of data is observed not only for the whole bio‐oil mixtures, but also for the simplified compositions (surrogate), contained 6–11 components 2–8 . However, in this case, the determination of thermochemical properties and kinetic parameters of the most important reactions using the molecular modeling seems feasible.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, a deficit of data is observed not only for the whole bio-oil mixtures, but also for the simplified compositions (surrogate), contained 6-11 components. [2][3][4][5][6][7][8] However, in this case, the determination of thermochemical properties and kinetic parameters of the most important reactions using the molecular modeling seems feasible.…”

Section: Introductionmentioning

confidence: 99%

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The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

Poskrebyshev

2022

Int J of Chemical Kinetics

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In the present work, the thermochemical properties of the radicals (Y j ), formed by abstraction of H atom from Dimethyl Phthalate (o-Ph(C(O)OCH 3 ) 2 ) and p-Benzylphenol (p-PhCH 2 PhOH), are determined at the B3LYP/6-311++G(d,p) (j = 1), M06-2X/6-311++G(d,p) (j = 2), and RO/CBS-4 M (j = 3 and 4) levels of theory. Their calculated values of H o 298.15 (Y j , CALC) are used for the determination of thermochemistry of atomization (Δ r H o 298.15 (Y j ,CALC) atom ) and homodesmotic (Δ r H o 298.15 ((R Yi ) j ,CALC) REAC ) reactions of considered radicals. The reported calibration dependencies are used for the correction of calculated values and determination of the most consistent and accurate values of Δ f H o 298.15 and Δ f G o 298.15 . It is found that o-CH 3 OC(O)PhC(O)OCH 2 • (1C), p-PhC • HPhOH (1D) and p-PhCH 2 PhO • (3D) are the most thermochemically stable structures. The intersection of reported 3SE j (= 3σ j ) intervals of Δ f H o 298.15 (1C j ,CORR) atom of atomization results the value of Δ f H o 298.15 (1C,CORR) MEAN = −405.1 ± 1.3 kJ/mol (±3SE Y = 3σ Y ), while, the most accurate values of Δ f H o 298.15 (1D and 3D,CORR) REACMEAN = 114.7 ± 0.4 and 135.8 ± 5 kJ/mol (± 3SE YREAC = 3σ YREAC ) are determined using the values Δ f H o 298.15 ((R Yi ) j ,CORR) REAC of homodesmotic reactions. The values of Δ f G o 298.15 , determined using the values of Δ f H o 298.15 and S o 298.15 of these radicals, demonstrate that the exothermic reaction (17) HO 2 • + p-PhCH 2 PhOH → H 2 O 2 + p-PhC • HPhOH (-22.9 kJ/mol) is thermochemically more favorable than the reaction (19) HO 2 • + p-PhCH 2 PhOH → H 2 O 2 + p-PhCH 2 PhO • (-1.8 kJ/mol).However, the value of k T (17) = 1.63 × 10 -14 (T/298.15) 3.6 e (-6282/T) , calculated using the VTST, is kinetically more favorable at elevated temperatures, while, the reaction (19) (k T (19) = 1.04×10 -16 (T/298.15) 2.17 e (-5207/T) ) is more important at T < 200 K. The thermochemical properties of these radicals, as well as the calculated rate constants of their formation in reactions of HO 2 • radicals with p-Benzylphenol, are reported for the first time.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

Poskrebyshev

2022

Int J of Chemical Kinetics

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“…CH 3 , C 5 H 5 , and phenoxy radicals, which were found to be important intermediates, can recombine with an H radical or with themselves, leading to many different products. These include light compounds, such as CH 4 and C 2 H 6 , and heavier products, such as cyclopentadiene, methylcyclopentadiene, phenol, naphthalene, benzene, and cresol. ,,− Anisole can also participate in the bimolecular reaction with H and CH 3 radicals, forming benzene, toluene, and benzaldehyde at low temperature. ,, Pecullan et al studied the first step of anisole oxidation in an atmospheric pressure flow reactor, showing that the differences between the types of pyrolysis and oxidation products are small. Nowakowska et al and Wagnon et al further studied anisole oxidation in a jet-stirred reactor and developed a more complex mechanism of anisole pyrolysis.…”

Section: Introductionmentioning

confidence: 99%

“…13,30,36−42 Anisole can also participate in the bimolecular reaction with H and CH 3 radicals, forming benzene, toluene, and benzaldehyde at low temperature. 13,41, 43 Pecullan et al 36 studied the first step of anisole oxidation in an atmospheric pressure flow reactor, showing that the differences between the types of pyrolysis and oxidation products are small. Nowakowska et al 41 and Wagnon et al 1 further studied anisole oxidation in a jet-stirred reactor and developed a more complex mechanism of anisole pyrolysis.…”

Section: Introductionmentioning

confidence: 99%

Reaction Mechanisms of Anisole Pyrolysis at Different Temperatures: Experimental and Theoretical Studies

et al. 2021

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Pyrolysis of tar compounds plays an important role in designing optimal thermochemical processes for the conversion of biomass into globally important commodities. Therefore, it is crucial to understand the relevant reaction mechanisms and be able to predict the decomposition products of these compounds at different temperatures. In this study, the pyrolysis of anisole, which serves as an important model compound for lignin, a major component of biomass tar, was studied in a laminar-flow reactor system of N 2 gas at temperatures of 300−650 °C and a residence time of 1 s. The decomposition products were analyzed using a gas chromatograph with mass spectrometric and flame ionization detectors. To gain insights into the reaction mechanisms, detailed studies of the unimolecular and bimolecular decomposition pathways were carried out using the density functional theory and high-level coupled cluster methods. Anisole was found to decompose at temperature as low as 400 °C, which is the lowest reported temperature for anisole decomposition. Formation of benzene and toluene at low temperatures (400−450 °C) is explained by the low-energy barrier ipso-addition of CH 3 and H radicals at the methoxy moiety of anisole. At 500−550 °C, multiple reaction mechanisms lead to the formation of benzofuran, methylcyclopentadiene, benzaldehyde, cyclopentadiene, ethylbenzene, styrene, and o-xylene. Finally, at 600−650 °C, indene, phenol, and cresol were detected. The obtained results are expected to contribute to the development of predictive kinetic models for the decomposition of anisole and other similar compounds.

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Density functional theory investigation of interactions between phenolic compounds and water or hydrophobic deep eutectic solvent

2023

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Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

Cited by 8 publications

References 57 publications

The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

Reaction Mechanisms of Anisole Pyrolysis at Different Temperatures: Experimental and Theoretical Studies

Density functional theory investigation of interactions between phenolic compounds and water or hydrophobic deep eutectic solvent

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Theoretical study of the hydrogen abstraction reactions from substituted phenolic species

Cited by 8 publications

References 57 publications

The values of ΔfHo298.15 and So298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

The values of ΔfHo298.15 and So298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

Reaction Mechanisms of Anisole Pyrolysis at Different Temperatures: Experimental and Theoretical Studies

Density functional theory investigation of interactions between phenolic compounds and water or hydrophobic deep eutectic solvent

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Product

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The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate

The values of Δ_fH^o_298.15 and S^o_298.15 of the radicals formed by the abstraction of H atom from the p‐Benzylphenol and Dimethyl Phthalate