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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:   Ethane, 1-chloro-2-fluoro-C2H4 + ClF
Reaction order:   1
Temperature:   600 - 1800 K
Rate expression:   3.87x1014 [s-1] e-607000 [J/mole]/RT
Category:  Theory
Data type:   Ab initio
Pressure dependence:   Rate constant is high pressure limit
Comments:   Calculated at HF/6-311++G(d,p) level. Very large barrier of 600 kJ/mol means this channel essentially doesnt happen

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.

View full bibliographic record.


Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
600 5.56E-39
700 1.97E-31
800 9.03E-26
900 2.29E-21
1000 7.62E-18
1100 5.81E-15
1200 1.47E-12
1300 1.58E-10
1400 8.72E-9
1500 2.82E-7
1600 5.91E-6
1700 8.65E-5
1800 9.41E-4