Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method †

doi:10.7503/cjcu20190567

Abstract

Abstract:

The Arrhenius equation with two parameters, activation energy(E) and pre-exponential factor(A), was proposed to describe the temperature dependence of reaction rate constant in developing combustion mechanisms. As a test, the UCSD core mechanism has been re-parameterized using the two-parameter Arrhenius equation and applied to the kinetic simulation of some small molecule systems, without changing the numbers of species and elemental reactions. The results showed that although the overall mechanism optimization is not performed, the results are basically comparable with the three-parameter mechanism. The advantage of the two-parameterization is the physics of the activation energy in Arrhenius equation, and in this way one can carry out the comparison and migration of the rate constants between different mechanisms. Furthermore, the number of the variable in the global optimization of mechanism aimed at such as ignition delay time of a fuel, can be reduced considerably.

Key words: Combustion reaction mechanism, Rate constant, Two-parameterization, Numerical simulation

CLC Number:

O641
O643

TrendMD:

LI Xiangyuan,YAO Xiaoxia,SHENTU Jiangtao,SUN Xiaohui,LI Juanqin,LIU Mingxia,XU Shimin. Combustion Reaction Mechanism Construction by Two-parameter Rate Constant Method ^†[J]. Chem. J. Chinese Universities, 2020, 41(3): 512.

Figures/Tables 7

Differential form	Expression for k	Author and publication date^[1]
$dln k d t$ = $B + CT + D T 2 T 2$	k=AT^C $e - (B - D T 2) / T$	Van’t Hoff, 1898; Bodenstein,1899
$dln k d t$ = $B + CT T 2$	k=AT^Ce^-^B/T	Kooij,1893; Trautz, 1909
$dln k d t$ = $B + D T 2 T 2$	k=A $e - (B - D T 2) / T$	Schwab,1883; van’tHoff,1884; Spohr,1888
$dln k d t$ = $CT + D T 2 T 2$	k=AT^Ce^DT	…
$dln k d t$ = $B T 2$	k=Ae^-^B/T	Van’t Hoff,1884; Arrhenius,1889; Kooij, 1893
$dln k d t$ = $C T$	k=AT^C	Harcurt and Esson,1895; Veley, 1908

Differential form	Expression for k	Author and publication date^[1]
$dln k d t$ = $B + CT + D T 2 T 2$	k=AT^C $e - (B - D T 2) / T$	Van’t Hoff, 1898; Bodenstein,1899
$dln k d t$ = $B + CT T 2$	k=AT^Ce^-^B/T	Kooij,1893; Trautz, 1909
$dln k d t$ = $B + D T 2 T 2$	k=A $e - (B - D T 2) / T$	Schwab,1883; van’tHoff,1884; Spohr,1888
$dln k d t$ = $CT + D T 2 T 2$	k=AT^Ce^DT	…
$dln k d t$ = $B T 2$	k=Ae^-^B/T	Van’t Hoff,1884; Arrhenius,1889; Kooij, 1893
$dln k d t$ = $C T$	k=AT^C	Harcurt and Esson,1895; Veley, 1908

Reaction	GRI-Mech 3.0^[4]			UCSD^[5]			AramcoMech 2.0^[6]
Reaction	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)	A/(cm³· mol^-1·s^-1)	n	E/ (J·mol^-1)
O+C₂H₂=H+HCCO	1.35×10⁷	2.00	7949	4.00×10¹⁴	0	44600	2.96×10⁹	1.28	10342
O+C₂H₂=CO+CH₂	6.94×10⁶	2.00	7949	1.60×10¹⁴	0	41400	7.40×10⁸	1.28	10342
C₂H₃+O₂=HCO+CH₂O	4.58×10¹⁶	-1.39	4246	1.70×10²⁹	-5.31	27209	1.16×10¹⁶	-1.13	15861
CH₂CHO=CH₂CO+H	4.87×10¹¹	0.42	-7342	1.05×10³⁷	-7.19	185519	1.43×10¹⁵	-0.15	190790
CH₂CHO=CH₃+CO				1.17×10⁴³	-9.80	183080	2.93×10¹²	0.29	168454
H+CH₃CHO=CH₂CHO+H₂	2.05×10⁹	1.16	10062	1.85×10¹²	0.40	22425	2.72×10³	3.10	21798
C₂H₅+O₂=HO₂+C₂H₄	8.40×10¹¹	0	16213	7.50×10¹⁴	-1.00	20082	2.09×10⁹	0.49	-1637
CH₃O+O₂=HO₂+CH₂O	4.28×10^-13	7.60	-14769	4.28×10^-13	7.60	-14799	4.38×10^-19	9.50	-23016
CH₃+CH₂O=HCO+CH₄	3.32×10³	2.81	24518				3.83×10¹	3.36	18024
H+CH₄=CH₃+H₂	6.60×10⁸	1.62	45354	1.30×10⁴	3.00	33629	6.14×10⁵	2.50	40112
OH+CH₂O=HCO+H₂O	3.43×10⁹	1.18	-1870	3.90×10¹⁰	0.89	1700	7.82×10⁷	1.63	-4414
OH+C₂H₂=H+CH₂CO	2.18×10^-4	4.50	-4184	1.90×10⁷	1.70	4179	1.58×10³	2.56	-3533
OH+C₂H₆=C₂H₅+H₂O	3.54×10⁶	2.12	3640	2.20×10⁷	1.90	4700	1.48×10⁷	1.90	3974
HO₂+CH₂O=HCO+H₂O₂	5.60×10⁶	2.00	50207	4.11×10⁴	2.50	42720	1.88×10⁴	2.70	48199
2CH₃(+M)=C₂H₆(+M)	6.77×10¹⁶	-1.18	2736	1.81×10¹³	0	0	2.28×10¹⁵	-0.69	731
CH+H₂O=H+CH₂O	5.71×10¹²	0	-3158	1.17×10¹⁵	-0.75	0	1.77×10¹⁶	-1.22	99
CH+CO₂=HCO+CO				4.80×10¹	3.22	-13500	1.70×10¹²	0	2863
H+CH₃OH=CH₂OH+H₂	1.70×10⁷	2.10	20376	1.35×10³	3.20	14605	3.07×10⁵	2.55	22760
H+CH₃OH=CH₃O+H₂	4.20×10⁶	2.10	20376	6.83×10¹	3.40	30291	1.99×10⁵	2.56	43095

Fig.1 Temperature dependence of reaction rate constants for HO2+H=H2+O2(A) and C2H3+O2=CHO+CH2O(B) by three-parameter fitting and two-parameter fitting

Fig.2 Flash photolysis-resonance fluorescence(504—923 K) and flash photolysis-shock tube(880—2495 K) rate constants of O(3P)+H2=OH+H

Fig.3 Ignition delay time by UCSD, UCSD-R, UCSD-SC and the experimental data (A) 100% CH4, p=1.09 MPa; (B) 80%/20% CH4/H2, p=2.14 MPa; (C) 60%/40% CH4/H2, p=2.36 MPa.

Fig.4 Ignition delay time by UCSD, UCSD-R and the experimental data (A) 6.25%C2H4/18.75%O2/75%N2, p=0.6—0.83 MPa; (B) 6.25%C2H4/18.75%O2/75%N2, p=1.12—1.61 MPa; (C) 11.76%C2H4/17.65%O2/70.59%N2, p=0.64—0.82 MPa.

Fig.5 Ignition delay time by UCSD, UCSD-R and the experimental data (A) 30%C2H6/70%H2, p=0.12 MPa; (B) 30%C2H6/70%H2, p=0.41 MPa; (C) 30%C2H6/70%H2, p=1.62 MPa.

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