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Title: Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl
Journal: Phys. Chem. Chem. Phys.
Volume: 5
Page(s): 3897 - 3904
Year: 2003
Reference type: Journal article
Squib: 2003RAJ/ARU3897-3904
Reaction:
CH2ClCH2Cl → CH2=CHCl + HCl
Reaction order:
1
Temperature:
600 - 1800
K
Rate expression:
4.79x1013 [s-1] e-244100 [J/mole]/RT
Category: Theory
Data type:
Ab initio
Pressure dependence:
Rate constant is high pressure limit
Comments:
Using B3LYP/6-311++G(d,p) barrier and hindered rotor partition function.
Ab initio and density functional theory (DFT) study of 1,2 Elimination channels from chloro, fluoro, and chlorofluoroethanes. Used mainly B3LYP/6-311++G(d,p) and CCSD(T)/6-311++G(d,p) energies. Rate expressions from TST. Hindered rotor included in partition functions.
DFT barriers agreed relatively well (5-10 kJ/mol) with experimental values. CCSD(T) barriers were somewhat high (about 30-40 kJ/mol). A factors were accordingly higher.
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Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [s-1] |
|---|---|
| 600 | 2.69E-8 |
| 700 | 2.92E-5 |
| 800 | 5.53E-3 |
| 900 | 3.26E-1 |
| 1000 | 8.51E0 |
| 1100 | 1.23E2 |
| 1200 | 1.14E3 |
| 1300 | 7.46E3 |
| 1400 | 3.74E4 |
| 1500 | 1.51E5 |
| 1600 | 5.15E5 |
| 1700 | 1.51E6 |
| 1800 | 3.95E6 |