Kinetic Mechanism Study on Low Temperature for Decalin Combustion†

doi:10.7503/cjcu20180160

Abstract

Abstract:

The kinetic mechanism of low-temperature decalin combustion was studied, including reaction types such as dehydrogenation reaction, radical oxygenation reaction and 1,5 H-shift reaction. The thermodynamic parameters of species were obtained at CBS-QB3 level. The high pressure limit rate constants for reactions with transition state were obtained by transition state theory calculations, while the rate constants for barrierless reactions were obtained by variational transition state theory. Based on this mechanism, the kinetic and thermodynamic behavior of decalin oxidation reactions at low temperature were analyzed. Compared with the corresponding results from linear alkanes and monocycloalkane, the rate constants of O₂-addition to decalin radical change more fast with temperature and the energy barriers of 1,5 H-shift reactions are higher, which reveal the influence of reactant structure on kinetics. The analysis result of thermodynamic equilibrium constants showed that the O₂-addition reaction to decalin radical plays a leading role at low temperature. The rate constants of Arrhenius form for all reactions were fitted and these parameters can be used in the construction and optimization of low temperature combustion mechanism of bicycloalkane.

Key words: Decalin, Low-temperature mechanism, Rate constant, Combustion reaction, Kinetic mechanism

CLC Number:

O641

TrendMD:

LI Yingli, WANG Jingbo, LI Xiangyuan. Kinetic Mechanism Study on Low Temperature for Decalin Combustion^†[J]. Chem. J. Chinese Universities, 2018, 39(6): 1212.

Figures/Tables 12

Fig.1 Negative temperature coefficient effect of low temperature ignition delay(A), the disproportionation reaction of radical oxidation(B) and the barrierless reaction for O2 addition(C)

Fig.2 Structure and atomic sites of decalin

Fig.3 Low temperature oxidation reactions of decalin starting from C—H bond breaking at the α position(A) and β position(B)Species designation is also given.

Fig.4 Potential energy surface for the low temperature oxidation reactions starting from the α position and β position of decalin

Fig.5 Potential energy profile at the UB3LYP/CBSB7 level for the barrierless reactions of R=R1+H(A), R1+O2=R1-P1-OO(B) and R1-P2-OO+O2=R1-P3O4(C)

Table 1 High-pressure limit rate parameters for low temperature oxidation reactions of decalin in the temperature range of 500—1500 K*

Number of reaction	Reaction	lgA^*	E_a/(kJ·mol^-1)
r1	R=R1+H	14.91	300.33
r2	R1+O₂=R1-P1-OO	-0.62	63.79
r3	R1-P1-OO→R1-P2-OO	10.23	186.90
r4	R1-P2-OO+O₂=R1-P3O4	-8.17	-114.99
r5	R1-P3O4→R1-P4O4	5.82	181.46
r6	R1-P4O4→R1-P5O4	10.51	72.12
r7	R1-P5O4→R1-P6O3H+OH	12.39	65.93
r8	R1-P6O3H→R1-P7O2+OH	11.22	40.56
r9	R1-P7O2→R1-P8	13.28	221.98
r10	R=R2+H	12.39	376.02
r11	R2+O₂=R2-P1-OO	-15.59	-4.77
r12	R2-P1-OO→R2-P2-OO	13.04	214.23
r13	R2-P2-OO+O₂=R2-P3O4	-13.58	-126.50
r14	R2-P3O4→R2-P4O4	8.25	177.35
r15	R2-P4O4→R2-P5O4	8.48	63.67
r16	R2-P5O4→R2-P6O3H+OH	13.84	46.17
r17	R2-P6O3H→R2-P7O2+OH	22.58	28.05
r18	R2-P7O2→R2-P8	11.26	214.78

Fig.6 Temperature dependence of rate constants for reactions starting from α position of decalin with transition states

Fig.7 Rate constants comparison for one-step O2 addition reactions between this work and those calculated by cited literature

Table 2 Results of one-step O2 addition to ethylcyclohexane radicals in the literature

Name of reaction	lg[A/(mol^-1·cm³·s^-1)]	E_a/(kJ·mol^-1)
JetSurF 2.0^[29]	12.06	-6.36
r1^[28]	10.52	-1.09
r2^[28]	10.36	-11.09
r3^[28]	12.28	-4.35
r4^[28]	11.28	-17.62

Table 3 Kinetic parameters of 1,5 H-shift reactions from the literature

Name of reaction	lg(A/s^-1)	E_a/(kJ·mol^-1)
r1^[31]	11.51	100.75
r2^[31]	11.77	97.28
r^[30]	11.42	85.10
r3^[31]	11.78	85.35

Fig.8 Rate constants comparison for 1,5 H-shift reaction and those calculated by the literature

Fig.9 Temperature dependence of equilibrium constants for O2 addition to decalin radicals

References 31

[1]	Hilpert M., Mora B. A., Ni J., Rule A. M., Nachman K. E., Curr. Environ. Health Rep., 2015, 2(4), 412—422
[2]	Ogawa H., Ibuki T., Takayuki M. A., Miyamoto N., Energy Fuels, 2007, 21(3), 1517—1521
[3]	Ranzi E., Energy & Fuels, 2006, 20(3), 1024—1032
[4]	He J. N., Li Y. L., Zhang C. H., Li P., Li X. Y., Acta Phys. Chim. Sinica, 2015, 31(5), 836—842
	(何九宁, 李有亮, 张昌华, 李萍, 李象远. 物理化学学报, 2015, 31(5), 836—842)
[5]	Battin-Leclerc F., Prog. Energ. Combust.Sci., 2008, 34(4), 440—498
[6]	Kyungchan C., Violi A., J. Org. Chem., 2007, 72(9), 3179—85
[7]	Dagaut P., Ristori A., Frassoldati A., Faravelli T., Dayma G., Ranzi E., Proc. Combust. Inst., 2013, 34(1), 289—296
[8]	Zámostný P., Bělohlav Z., Starkbaumová L., Patera J., J. Anal. Appl. Pyrol., 2010, 87(2), 207—216
[9]	Ondruschka B., Zimmermann G., Remmler M., Sedlackova M., Pola J., J. Anal. Appl. Pyrol., 1990, 18(1), 19—32
[10]	Yang Y., Boehman A. L., Combust. Flame, 2010, 157(3), 495—505
[11]	Zeng M., Li Y., Yuan W., Zhou Z., Wang Y., Zhang L., Qi F., Combust. Flame, 2016, 167(5), 228—237
[12]	Zhu Y., Davidson D. F., Hanson R. K., Zhu Y., Davidson D. F., Hanson R. K., Combust. Flame, 2014, 161(2), 371—383
[13]	Zhang W. F., Xian L. Y., Yong K. L., Acta Phys. Chim. Sin., 2016, 32(9), 2216—2222
	(张巍峰, 鲜雷勇, 雍康乐. 物理化学学报, 2016, 32(9), 2216—2222)
[14]	Ranzi E., Frassoldati A., Grana R., Prog. Energ. Combust.Sci., 2012, 38(4), 468—501
[15]	Tan N. X., Wang F., Liu A. K., Guo J. J., Xu J. Q., Li S. H., Li X. Y., The 29th Annual Meeting of the Chinese Chemical Societ., Beijing, 2014
	(谈宁馨, 王繁, 刘爱科, 郭俊江, 徐佳琪, 李树豪, 李象远. 中国化学会第29届学术年会摘要集, 北京, 2014)
[16]	Zhang K., Banyon C., Bugler J., Curran H. J., Rodriguez A., Herbinet O., Battin-Leclerc F., B’Chirc C., Heuferc K. A., Combust. Flame, 2016, 172(10), 116—135
[17]	Rashidi M. J. A., Mehl M., Pitz W. J., Mohamed S., Sarathy S. M., Combust. Flame, 2017, 183, 358—371
[18]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.01, Gaussian Inc., Wallingford CT, 2009
[19]	Becke A. D., J. Chem. Phys., 1998, 98(7), 5648—5652
[20]	Lee C., Yang W., Parr R. G., Phys. Rev. B: Condens. Matter., 1988, 37(2), 785—789
[21]	Gonzalez C., Schlegel H. B., J. Chem. Phys., 1989, 90(4), 2154—2161
[22]	Montgomery J. A., Frisch M. J., Ochterski J. W., Petersson G. A., J. Chem. Phys., 1999, 110(6), 2822—2827
[23]	Altarawneh M. K., Dlugogorski B. Z., Kennedy E. M., Mackie J. C., Combust. Flame, 2013, 160(1), 9—16
[24]	NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 19, April 2018, Editor, Russell D. Johnson III,
[25]	Mokrushin V. T. W., Zachariah M., Knyazev V., Chem.Rate, Version 1.5.., National Institute of Standards and Technolog., Gaithersburg, MD, 2009
[26]	Zádor J., Taatjes C. A., Fernandes R. X., Prog. Energ. Combust. Sci., 2011, 37(4), 371—421
[27]	Li S. J., Tan N. X., Yao Q., Li Z. R., Li X. Y., Acta Phys. Chim. Sinica, 2015, 31(5), 859—865
	(李尚俊, 谈宁馨, 姚倩, 李泽荣, 李象远. 物理化学学报, 2015, 31(5), 859—865)
[28]	Ning H. B., Gong C. M., Tan N. X., Li Z. R., Li X. Y., Combust. Flame, 2015, 162(11), 4167—4182
[29]	Wang H., Dames E., Sirjean B., Sheen D.A., Tangko R., Violi A., Lai J. Y. W., Egolfopoulos F. N., Davidson D. F., Hanson R. K., Bowman C. T., Law C. K., Tsang W., Cernansky N. P., Miller D. L., Lindstedt R. P.,A High-temperature Chemical Kinetic Model of n-alkane(up to n-dodecane), Cyclohexane, and Methyl-, Ethyl-, n-Propyl and n-Butyl-cyclohexane Oxidation at High Temperatures, JetSurF Version 2.0, September 19, 2010()
[30]	Xing L., Zhang L., Zhang F., Jiang J., Combust. Flame, 2017, 182(8), 216—224
[31]	Miyoshi A., J. Phys. Chem. A, 2011, 115(15), 3301—3325