CH3CH2O+HCHO反应机理及主通道速率常数

doi:10.7503/cjcu20131237

摘要/Abstract

摘要：

采用CCSD(T)/cc-pVDZ//B3LYP/6-311++G(d,p)双水平计算方法研究了CH₃CH₂O+HCHO反应的微观反应机理. 结果表明, 标题反应主要存在5个抽氢和3个氢迁移异构化反应通道, 其中抽氢通道R→ IMa(CH₃CH₂O…CH₂O)→TS1→ IM1b→P1(CH₃CH₂OH+CHO)为优势通道, 其表观活化能为14.65 kJ/mol. 利用变分过渡态理论(CVT)并结合小曲率隧道效应模型计算了主通道R1在275~1000 K温度范围内的速率常数k^TST, k^CVT和k^CVT/SCT, 在此温度区间内表观反应速率常数三参数表达式为k^CVT/SCT=2.26×10^-17 T^0.57 exp(-1004/T), 显示具有正温度系数效应.

关键词: 乙氧基, 甲醛, 密度泛函理论, 反应机理, 速率常数

Abstract:

The mechanism of the reaction between CH₃CH₂O and HCHO was investigated at CCSD(T)cc-pVDZ//B3LYP/6-311++G(d,p) level. Eight possible reaction channels(five H-abstraction channels and three H-isomerization channels) for the title reaction were idenpngied. The results indicated that channel R→IMa(CH₃CH₂O…CH₂O)→TS1→IM1b→P1(CH₃CH₂OH+CHO) was the most favorable channel with the apparent activation energy of 14.65 kJ/mol. The rate constants of the path R1 were evaluated over a temperature range of 275—1000 K via the canonical variational transition state theory(CVT) combined with a small-curvature tunneling correction. The fitted three-parameter expression for the path R1 is k^CVT/SCT=2.26×10^-17T^0.57exp(-1004/T) and R1 has a positive temperature effect over a temperature range of 275—1000 K.

Key words: CH3CH2O, HCHO, Density functional theory, Reaction mechanism, Rate constant

中图分类号:

O643.1

TrendMD:

郭莎, 王渭娜, 靳玲侠, 王帅, 王文亮. CH₃CH₂O+HCHO反应机理及主通道速率常数. 高等学校化学学报, 2014, 35(6): 1300.

GUO Sha, WANG Weina, JIN Lingxia, WANG Shuai, WANG Wenliang. Mechanistic Studies on CH₃CH₂O+HCHO Reaction and Rate Constants of Major Channel^†. Chem. J. Chinese Universities, 2014, 35(6): 1300.

图/表 8

Fig.1 Optimized geometries of the reactants and products of the hydrogen abstraction, at the B3LYP/6-311++G(d,p) level Bond lengths(nm) and bond angles(°), the data in the parentheses are experimental values.

Fig.2 Optimized geometries of intermediates, transition states and the products of the hydrogen migration isomerization at the B3LYP/6-311++G(d,p) level[bond lengths(nm)]

Fig.3 Potential energy profile for the CH3CH2O+HCHO reaction at the CCSD(T)cc-pVDZ//B3LYP/6-311++G(d,p) level

Table 1 Reaction enthalpy(ΔrH298 K0—) for the title reaction, and formation enthalpies (ΔfH(g, M, 298 K)0—) for some species

Species	Δ_r $H 298 K 0 — a$ /(kJ·mol^-1)	Species	Δ_r $H 298 K 0 — a$ /(kJ·mol^-1)	Species	Δ_f $H (g, M, 298 K) 0 — b$ /(kJ·mol^-1)
R1	-57.78(-70.50±10.00)	R5	103.5(90.67±7.23)	CH₃CH₂OCH₂O	-109.9±4.00
R2	-34.40	R6	-41.48	CH₃CH₂OCHOH	-163.8±4.10
R3	-23.89(-27.40±8.10)	R7	-20.48	CH₃CHOCH₂OH	-142.8±4.00
R4	92.95	R8	-112.1	CH₂CH₂OCH₂OH	-234.4±5.00

Table 1 Reaction enthalpy(ΔrH298 K0—) for the title reaction, and formation enthalpies (ΔfH(g, M, 298 K)0—) for some species

Species	Δ_r $H 298 K 0 — a$ /(kJ·mol^-1)	Species	Δ_r $H 298 K 0 — a$ /(kJ·mol^-1)	Species	Δ_f $H (g, M, 298 K) 0 — b$ /(kJ·mol^-1)
R1	-57.78(-70.50±10.00)	R5	103.5(90.67±7.23)	CH₃CH₂OCH₂O	-109.9±4.00
R2	-34.40	R6	-41.48	CH₃CH₂OCHOH	-163.8±4.10
R3	-23.89(-27.40±8.10)	R7	-20.48	CH₃CHOCH₂OH	-142.8±4.00
R4	92.95	R8	-112.1	CH₂CH₂OCH₂OH	-234.4±5.00

Scheme 1 Eight pathways for the reactions of CH3CH2O with HCHO

Fig.4 Variation of the bond distances as a function of s at the B3LYP/6-311++G(d,p) level for the major reaction channel of CH3CH2O+HCHO(R1)

Table 2 Calculated rate constants kTST, kCVT and kCVT/SCT(cm3·molecule-1·s-1) for major channel R1 in 275—1000 K

T/K	k^TST	k^CVT	k^CVT/SCT	T/K	k^TST	k^CVT	k^CVT/SCT
275	7.41×10^-20	1.91×10^-20	1.43×10^-17	500	3.19×10^-17	4.15×10^-18	1.06×10^-16
298	2.06×10^-19	4.86×10^-20	2.02×10^-17	550	6.54×10^-17	7.56×10^-18	1.34×10^-16
325	5.66×10^-19	1.21×10^-19	2.84×10^-17	600	1.21×10^-16	1.25×10^-17	1.64×10^-16
350	1.27×10^-18	2.50×10^-19	3.73×10^-17	650	2.04×10^-16	1.92×10^-17	1.94×10^-16
375	2.57×10^-18	4.67×10^-19	4.70×10^-17	700	3.25×10^-16	2.79×10^-17	2.26×10^-16
400	4.78×10^-18	8.07×10^-19	5.76×10^-17	750	4.92×10^-16	3.87×10^-17	2.59×10^-16
425	8.3×10^-18	1.31×10^-18	6.90×10^-17	800	7.17×10^-16	5.17×10^-17	2.94×10^-16
475	2.12×10^-17	2.93×10^-18	9.34×10^-17	1000	2.36×10^-15	1.29×10^-16	4.49×10^-16

Fig.5 Fitted Arrhenius plots of the rate constant versus the reciprocal of temperature over the range of 275—1000 K for major channel R1

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CH₃CH₂O+HCHO反应机理及主通道速率常数

Mechanistic Studies on CH₃CH₂O+HCHO Reaction and Rate Constants of Major Channel^†

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