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Author(s):   Rajakumar, B.; Arunan, E.
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:   CH2ClCH2ClCH2=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