Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF2ClC(O)OCH2CH3 with OH Radicals†

doi:10.7503/cjcu20150568

Abstract

Abstract:

The mechanism of the hydrogen abstraction reaction of CF₂Cl(O)OCH₂CH₃+OH was studied theoretically via a dual-level direct dynamics method at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. Five stable conformers(RC1—RC5) of the reactant CF₂Cl(O)OCH₂CH₃ were located, and for each conformer, the possible H-abstraction channels from —CH₃ and —CH₂— groups were taken into account. The rate constants were calculated using the improved canonical variational transition-state theory(ICVT) with the small-curvature tunneling correction(SCT) and the selectivity of the reaction sites of CF₂Cl(O)OCH₂CH₃ was evaluated. The results show that for the conformers RC1 and RC2, the H-abstraction reactions mainly take place at the —CH₂— group at low temperature, while for the conformers RC3, RC4 and RC5, the hydrogen abstraction from the —CH₃group is the major channel in the whole considered temperature range. The overall rate constant is obtained by considering the weight factors of the five conformers calculated from the Boltzmannn distribution function. It is found, that the calculated k_overall at 298 K is in good agreement with the available experimental data. The three parameter expression for the overall reaction within 200—1000 K is fitted to k_overall=5.45×10^-25 T^4.54 exp(-685/T).

Key words: Direct dynamics method, Rate constant, Variational transition-state theory, Density functional theory, Reaction mechanism

CLC Number:

O641
O643

TrendMD:

ZHU Peng, DUAN Xuemei, LIU Jingyao. Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF₂ClC(O)OCH₂CH₃ with OH Radicals^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 79.

Figures/Tables 9

Fig.1 Optimized geometries parameters of conformers RC1—RC5 at the M06-2X/aug-cc-pVDZ level^Bond lengths are in nm and bond angles are in degree.

Fig.2 Torsional potential profiles for torsion angle Cl—C—C—O for RC1(A), torsion angle C—O—C—C for RC1(B) and torsion angle Cl—C—C—O for RC3(C)

Fig.3 Optimized geometry parameters of reactants, products, transition-states, and hydrogen-bond complexes for the H-abstraction channels of R4 at the M06-2X/aug-cc-Pvdz^Bond lengths are in nm and angles are in degree.

Table 1 Standard enthalpies of formation() at 298 K calculated at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level

Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)
RC1	-838.47	RC2	-843.49	RC3	-837.22	RC4	-843.08	RC5	-842.24
P1a	-625.09	P2a	-630.53	P3a	-626.76	P4a	-631.78	P5a	-631.37
P1b	-628.02	P2b	-633.04	P3b	-649.78	P4b	-640.99	P5b	-654.38
P1c	-649.78	P2c	-654.13	P3c	-636.80	P4c	-653.54	P5c	-640.99

Fig.4 Schematic potential energy profiles for the RC1+OH reaction(A), the RC2+OH reaction(B), the RC3+OH reaction(C), the RC4+OH reaction(D) and the RC5 + OH reaction(E)^Relative energies with ZPE atthe MCG3-MPWB//M06-2X/aug-cc-pVDZ level are in kJ/mol.

Fig.5 TST, ICVT and ICVT/SCT rate constants calculated at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level versus 1000/T between 200 and 1000 K for path (R4c)(A) and for path (R4e)(B)

Fig.6 Plots of the calculated branching ratios versus 1000/T between 200 and 1000 K for the reaction RC1+OH→products(A) and the reaction RC4+OH→products(B)

Table 2 Rate constants for each conformer and the overall rate constant[koverall/(cm3·molecule-1·s-1)] in the temperature range 200—1000 K at the MCG3-MPWB//M06-2X level

T/K	10¹² k₁	10¹² k₂	10¹² k₃	10¹² k₄	10¹² k₅	10¹² k_overall
200	0.355	0.464	0.471	0.551	0.360	0.464
250	0.425	0.756	0.614	0.695	0.516	0.645
296	0.529	1.12	0.803	0.877	0.796	0.898
298	0.536	1.14	0.813	0.888	0.812	0.912(0.54±0.15)^[3]
350	0.705	1.67	1.11	0.161	1.40	1.34
400	0.926	2.31	1.50	0.149	2.35	1.92
500	1.56	4.06	2.64	0.236	6.12	3.80
600	2.53	6.51	4.40	3.60	13.7	7.03
800	5.88	14.1	10.4	7.33	47.5	19.4
1000	11.8	26.1	20.7	13.2	121	43.5

Fig.7 Plot of the contributions of RC1, RC2, RC3, RC3 and RC4 to the reaction versus 1000/T between 200 and 1000 K

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Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF₂ClC(O)OCH₂CH₃ with OH Radicals^†

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