Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5376141 | Chemical Physics | 2007 | 7 Pages |
Abstract
The equilibrium reaction of CD4 + Cl â CD3 + DCl has been studied by ab initio methods. Kinetic parameters of the reaction were calculated at the MP2(fc)/cc-pVQZ//MP2(fc)/cc-pVQZ level of theory in conjunction with the thermodynamic transition state theory. The Arrhenius expression obtained for the forward reaction is k(CD4 + Cl) = 1.16 Ã 10â11exp(â16.54 kJ molâ1/RT) cm3 moleculeâ1 sâ1 (Arrhenius parameters were calculated for T = 298 K). The rate constants of the forward reaction were combined with the experimentally measured rate constants of the reverse reaction for thermodynamic studies. A third-law determination for the CD3 radical heat of formation yielded a value of 139.6 ± 2.9 kJ molâ1 and a second-law determination a value of 139.2 ± 2.5 kJ molâ1 at 298 K after a heat capacity correction. A mean value from these determinations, 139.4 molâ1, was used as the reference value in the calculations of thermodynamic properties of the CD3 radical by statistical thermodynamic methods over the temperature range, 100-1500 K.
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Authors
Jorma A. Seetula,