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Indian Journal of Chemistry -Section A (IJC-A) >
IJC-A Vol.48A [2009] >
IJC-A Vol.48A(08) [August 2009] >
| Title: | Thermal decomposition of CF3CFClO radical – A computational study |
| Authors: | Singh, Hari Ji
Mishra, B K
Gour, N K |
| Keywords: | Theoretical chemistry
Chlorofluorocarbons
Haloalkoxy radicals
Decompositions
Transition state theory |
| Issue Date: | Aug-2009 |
| Publisher: | CSIR |
| Abstract: | A theoretical study on the decomposition pathways of haloalkoxy radical formed from 2-chloro-1,1,1,2-tetrafluoroethane has been reported. Structures of all the reactants, products and transition states involved in the decomposition pathways have been optimized and characterized at MP2(full)/6-31G(d,p) level of theory. Single point energy calculations have been performed using MP4, QCISD(T) and CCSD(T) levels of theory. Critical energy barriers have been calculated for C-C bond scission and Cl elimination, the two prominent decomposition channels considered in the present investigation, and found to be 8.4 and 1.5 kcal mol-1 respectively. Results show that Cl elimination is the dominant path involving a lower barrier height. Using transition state theory, rate constants for the decomposition pathways, viz., Cl-elimination and C-C bond scission, calculated at 298 K and 1 atm pressure are found to be 4.6×105 and 5.1×104 s-1, respectively. The existence of transition states on the corresponding potential energy surface has been ascertained by performing Intrinsic Reaction Coordinate calculations. |
| Page(s): | 1096-1101 |
| ISSN: | 0975-0975 (Online); 0376-4710 (Print) |
| Source: | IJC-A Vol.48A(08) [August 2009]
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