Chem. J. Chinese Universities ›› 2014, Vol. 35 ›› Issue (6): 1300.doi: 10.7503/cjcu20131237
• Physical Chemistry • Previous Articles Next Articles
GUO Sha, WANG Weina*(), JIN Lingxia, WANG Shuai, WANG Wenliang
Received:
2013-12-17
Online:
2014-06-10
Published:
2014-04-21
Contact:
WANG Weina
E-mail:wangwn@snnu.edu.cn
Supported by:
CLC Number:
TrendMD:
GUO Sha, WANG Weina, JIN Lingxia, WANG Shuai, WANG Wenliang. Mechanistic Studies on CH3CH2O+HCHO Reaction and Rate Constants of Major Channel†[J]. Chem. J. Chinese Universities, 2014, 35(6): 1300.
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)]
Species | Δr | Species | Δr | Species | Δf |
---|---|---|---|---|---|
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 | Δr | Species | Δr | Species | Δf |
---|---|---|---|---|---|
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 |
T/K | kTST | kCVT | kCVT/SCT | T/K | kTST | kCVT | kCVT/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 |
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 | kTST | kCVT | kCVT/SCT | T/K | kTST | kCVT | kCVT/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 |
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