Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory

Zhang, Hui; Zhang, Xin; Truhlar, Donald G.; Xu, Xuefei

doi:10.1021/acs.jpca.7b09374

Cited by 16 publications

(10 citation statements)

References 84 publications

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“…Calculations using quantum methods were carried out when no data were available (See Table 2). Kinetics parameters of the reaction C6H6 + H = C6H5 + H2 (the reverse of Reaction 1 in Table 2) have already been calculated by several authors such like Zhang et al [12] or Giri et al [13].…”

Section: Kinetic Modelmentioning

confidence: 95%

A study of chlorobenzene pyrolysis

Vin

Battin‐Leclerc

Gall

et al. 2019

Proceedings of the Combustion Institute

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The pyrolysis of chlorobenzene under dilute atmosphere and quasi-atmospheric pressure was studied at temperatures from 800 to 1150 K using a fused silica jet stirred reactor (JSR) and from 800 to 1250 K in an alumina tubular reactor. Chlorobenzene was chosen as a surrogate to model the thermal decomposition of polychlorinated biphenyls (PCBs). In the jet stirred reactor, a maximum chlorobenzene conversion of 48.5 % was observed at a residence time of 2 s, a temperature of 1150 K and an inlet mole fraction of chlorobenzene of 0.005. The following species were quantified: benzene (the major product), HCl, methane, ethylene, acetylene, biphenyl, 1-, 2and 3-chlorobiphenyl, biphenylene and six isomers of dichlorobiphenyls. In the tubular reactor, a maximum chlorobenzene conversion of 95% was observed at a temperature of 1250 K under the same conditions as in the jet stirred reactor. The same reaction products were detected but with a larger formation of acetylene and methane and a smaller production of chlorinated and bicyclic compounds. The effect of two H-atom donors, methane and hydrogen, has been investigated in the JSR. Hydrogen addition has a strong inhibiting effect on the formation of chlorinated and bicyclic products. A new detailed kinetic model was developed and gave a good prediction of the global reactivity, the formation of most major products, and the effect of the addition of hydrogen and methane. Flow rate and sensitivity analyses have been made to explain the effect of H-atom donors.

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Section: Kinetic Modelmentioning

confidence: 95%

A study of chlorobenzene pyrolysis

Vin

Battin‐Leclerc

Gall

et al. 2019

Proceedings of the Combustion Institute

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“…As the first modification, the calculated CCSD(T)/cc-pVTZ vibrational frequencies were scaled by 0.975 because of the importance of anharmonicity and rovibronic coupling for vibrationally excited formaldehyde (i.e., INTc*) and the noticeable impact of anharmonicity on the frequencies and ZPE values of the triplet surfaces’ stationary points (see Table S9). The use of scale factor has been usually considered to be adequate for anharmonicity correction, for example, see refs and . In the case of 3 INTb, which possesses a torsional degree of freedom, torsional anharmonicity was included by treating the lowest vibrational frequency as a hindered rotor, while the other frequencies were treated as separable harmonic oscillators modified by a frequency scale factor .…”

Section: Results and Discussionmentioning

confidence: 99%

“…In the case of 3 INTb, which possesses a torsional degree of freedom, torsional anharmonicity was included by treating the lowest vibrational frequency as a hindered rotor, while the other frequencies were treated as separable harmonic oscillators modified by a frequency scale factor . No multistructural anharmonicity was concerned because all reactants, products, TSs, and intermediates could be described by a single structure . The applied anharmonicity corrections are expected to influence kinetics of the reaction in two ways: (i) declining the effect of dividing surface position on the rate coefficients by decreasing the effect of transitional modes and approaching the maximal Gibbs free energy change of the corresponding reaction coordinate to the saddle point and (ii) lowering the rate coefficients depending on the studied reaction and temperature.…”

Section: Results and Discussionmentioning

confidence: 99%

“…103 No multistructural anharmonicity was concerned because all reactants, products, TSs, and intermediates could be described by a single structure. 102 The applied anharmonicity corrections are expected to influence kinetics of the reaction in two ways: 104 (i) declining the effect of dividing surface position on the rate coefficients by decreasing the effect of transitional modes and approaching the maximal Gibbs free energy change of the corresponding reaction coordinate to the saddle point and (ii) lowering the rate coefficients depending on the studied reaction and temperature.…”

Section: ■ Methodsmentioning

confidence: 99%

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Chemical Kinetics Approves the Occurrence of C (³P_j) Reaction with H₂O

Keshavarz

2019

J. Phys. Chem. A

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Although both atomic carbon and water are omnipresent in human life, there is a debate about the possibility of carbon reaction with water. Some low-temperature spectroscopic investigations have rejected the reaction, whereas some room-temperature experiments and theoretical studies have accepted the possibility of the reaction by reporting rate coefficients ranging from 105 to 109 L mol–1 s–1. This study provides new lines of evidence about the reaction through exploration of the reaction mechanism using the CCSD(T) method and solving the corresponding master equation by following two main approaches. According to the results, the rate coefficient of the reaction is significantly influenced by the tunneling and hindered rotation effects, in addition to the selected total angular momentum (J). Furthermore, the total rate coefficient of the reaction increases dramatically (from 107 to 1011 L mol–1 s–1) with the rise of temperature from 100 to 4000 K, while the total rate coefficient is insensitive to pressure (0.1–10 atm). Despite some differences between the results of the two approaches, the rate coefficients of both methods are consistent with the previously reported rate coefficients. Also, in agreement with the previous studies, the major products are 2HOC + 2H and 2HCO + 2H. In general, the findings approve the occurrence of the title reaction and indicate that the mentioned conflict is due to the sensitivity of the reaction to the investigated temperature and J level. The sensitivity does not permit low-temperature spectroscopic studies to detect any products and varies the measured and calculated rate coefficients.

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“…For more details on the SS-QRRK method and its applications refer to previously published work. 24,56,[64][65][66] Here we only list the empirical or experimental parameters used in our SS-QRRK calculations: (a) hDEi was set to 75 cm À1 and 130 cm À1 based on the experimental work for bath gas He and Ar, 67 respectively; (b) The empirical L-J potential parameters were chosen as follows: s = 6.20 Å, e/k B = 494 K for o-xylene, 68 s = 2.551 Å, e/k B = 10.22 K for the bath gas He, 69 and s = 3.542 Å, e/k B = 93.3 K for the bath gas Ar. 69 The dynamics and the SS-QRRK calculations were performed by using the Polyrate 2016 70 and Gaussrate 16 71 programs.…”

Section: Dynamicsmentioning

confidence: 99%