Theoretical study of hydrogen abstraction by small radicals from cyclohexane-carbonyl-hydroperoxide
- 85 Downloads
Hydrogen abstraction from carbonyl-hydroperoxide is a new reaction class in the low-temperature oxidation of hydrocarbons. In this work, a comprehensive study to the kinetics for the hydrogen abstraction from cyclohexane-carbonyl-hydroperoxide (CCHP) is investigated using the CBS-QB3 composite method. Five small active radicals (H, CH3, O (3P), OH and HO2) are selected as the extracting agents, and the corresponding barrier heights are computed. Guided by the reaction barriers, the preferable path on hydrogen abstraction from CCHP is identified. The two-transition-state model is employed to obtain the overall rate constant when HO2 and OH act as the extracting agents due to the formation of reactant and product complexes. High-pressure-limit rate constants for 25 elementary reactions are reported in the modified Arrhenius form. Branching ratios for the site-specific hydrogen abstraction reactions ranging from 300 to 2500 K are illustrated to show the temperature dependence of preferable path. Compared with the theoretical rate constants obtained in this work, the values estimated by using analogy rules have obvious deviations at low temperature. The obtained hydrogen abstraction reactions are added to the JetSurF2.0 mechanism, thereby improving its kinetic modeling results for cyclohexane oxidation. Present work provides accurate kinetic parameters for this new type of reaction class which can be helpful to improve the predictive capability for hydrocarbon mechanism.
KeywordsHydrogen abstraction Cyclohexane-carbonyl-hydroperoxide Low temperature Rate constant
This work is supported by the National Science Foundation of China (Nos. 91741201, 91641120).
- 5.Zhou CW, Li Y, O’Connor E, Somers KP, Thion S, Keesee C, Mathieu O, Petersen EL, DeVerter TA, Oehlschlaeger MA, Kukkadapu G, Sung C-J, Alrefae M, Khaled F, Farooq A, Dirrenberger P, Glaude PA, Battin-Leclerc F, Santner J, Ju Y, Held T, Haas FM, Dryer FL, Curran HJ (2016) Combust Flame 167:353CrossRefGoogle Scholar
- 13.Rossi M (2017) Atmos Chem Phys 13(15):7359Google Scholar
- 18.B Sirjean, E Dames, DA Sheen, FN Egolfopoulos, H.Wang, DF Davidson, RK Hanson, H Pitsch, CT Bowman, CK Law, W Tsang, NP Cernan-sky, DL Miller, A Violi, RP Lindstedt (2010) JetSurF version2.0, Septem-ber19, http://melchior.usc.edu/JetSurF/JetSurF2.0
- 20.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,Cheeseman JR, Scalmani G, Barone V, Mennucci B, PeterssonGA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF,Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, KitaoO, Nakai H, Vreven T, Montgomery Jr. JA, Peralta JE, OgliaroF, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, GompertsR, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkaso, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian09 Revision B.01. Gaussian Inc, WallingfordGoogle Scholar
- 27.Mokrushin V, Tsang W (2009) ChemRate v158, National Institue of Standards and Technology: Gaithersburg M 2009, Chemrate 2009Google Scholar
- 31.Pechukas P (1981) Annu Rev Phys Chem 32(32):59Google Scholar
- 41.CHEMKIN-PRO 15092 Reaction Design: San Diego 2009Google Scholar