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The recombination of CF3 and CHF2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF3CHF2* molecules with 101 kcal mol-1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF3, CF3(F)C: and C2F4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF3(F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 104, 4.7 × 104, and 1.1 × 104 s-1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E0) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol-1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF3(F)C: and HF in the exit channel with a dissociation energy of ~5 kcal mol-1. Hydrogen-bonded complexes between HF and the H atom migration transition state of CH3(F)C: and the F atom migration transition state of CF3(F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed. [ABSTRACT FROM AUTHOR]

Chemical activation experiments and computational methods have been used to study the unimolecular reactions of C 2 H 5 CH 2 Br and C 2 D 5 CHFBr with 90 and 93 kcal mol -1 of vibrational energy, respectively. The four-centered elimination reactions of HBr and DBr are the dominant reactions; however, 2,1-DF, 1,1-HBr, and 1,1-HF reactions are also observed from C 2 D 5 CHFBr. The main focus was to search for the role of the C 2 D 5 (F)C:HBr adduct in the 1,1-HBr elimination for comparison with carbene adducts in 1,1-HX(Y) elimination from RCHXY (X,Y = Cl and F) molecules. Models of transition states and molecules from electronic structure calculations were used in statistical calculations of the rate constants to assign threshold energies for each reaction based on the experimental rate constants. The threshold energy for 2,1-HBr elimination from 1-bromopropane is 50 kcal mol -1 , which is in basic agreement with thermal activation experiments. Comparison of the 2,1-DBr and 2,1-HBr rate constants permits discussion of the kinetic isotope effects and the effect of F atom substitution on the threshold energy for 2,1-HBr elimination. Although CD 3 CD═CDF from 1,1-HBr elimination of C 2 D 5 CHFBr followed by D atom migration is an experimentally observed product, dissociation of the C 2 D 5 (F)C:HBr adduct may be the rate-limiting step rather than crossing the barrier associated with the transition state for 1,1-HBr elimination. The calculated dissociation energies of C 2 H 5 (X)C:HF adducts are 9.9, 9.3, and 9.0 kcal mol -1 for X = F, Cl, and Br, and the values for C 2 H 5 (F)C:HX are 9.9, 6.4, and ∼4.9 kcal mol -1 .

The gas-phase unimolecular reactions of C 2 D 5 CHFCl molecules with 94 kcal mol -1 of vibrational energy have been studied by the chemical-activation experimental technique and by electronic-structure computations. Products from the reaction of C 2 D 5 CHFCl molecules, formed by the recombination of C 2 D 5 and CHFCl radicals in a room temperature bath gas, were measured by gas chromatography-mass spectrometry. The 2,1-DCl (81%) and 1,1-HCl (17%) elimination reactions are the principal processes, but 2,1-DF and 1,1-HF elimination reactions also are observed. Comparison of experimental rate constants to calculated statistical rate constants provides threshold energies. The potential surfaces associated with C 2 D 5 (F)C: + HCl and C 2 D 5 (Cl)C: + HF reactions are of special interest because hydrogen-bonded adducts with HCl and HF with dissociation energies of 6.4 and 9.3 kcal mol -1 , respectively, are predicted by calculations. The relationship between the geometries and threshold energies of transition states for 1,1-HCl elimination and carbene:HCl adducts is complex, and previous studies of related molecules, such as CD 3 CHFCl, CD 2 ClCHFCl, C 2 D 5 CHCl 2 , and halogenated methanes are included in the computational analysis. Extensive calculations for CH 3 CHFCl as a model for 1,1-HCl reactions illustrate properties of the exit-channel potential energy surface. Since the 1,1-HCl transition state is submerged relative to dissociation of the adduct, inner and outer transition states should be considered for analysis of rate constants describing 1,1-HCl elimination and addition reactions of carbenes to HCl.

The five unimolecular HX and DX (X = F, Cl) elimination pathways of CD 2 ClCHFCl* were examined using a chemical activation technique; the molecules were generated with 92 kcal mol -1 of vibrational energy in a room-temperature bath gas by a combination of CD 2 Cl and CHFCl radicals. The total unimolecular rate constant was 9.7 × 10 7 s -1 , and branching fractions for each channel were 0.52 (2,1-DCl), 0.29 (1,1-HCl), 0.10 (2,1-DF), 0.07 (1,1-HF), and 0.02 (1,2-HCl). Comparison of the individual experimental rate constants to calculated statistical rate constants gave threshold energies for each process as 63, 72, 66, 73, and 70 kcal mol -1 , listed in the same order as the branching fractions. The 1,1-HCl and 1,1-HF reactions gave carbenes, CD 2 Cl(F)C: and CD 2 Cl(Cl)C:, respectively, as products, which have hydrogen-bonded complexes with HCl or HF in the exit channel of the potential energy surface. These carbenes have energy in excess of the threshold energy for D atom migration to give CDCl═CDF and CDCl═CDCl, and the subsequent cis-trans isomerization rates of the dihaloethenes can provide information about energy disposal by the 1,1-HX elimination reactions. Electronic structure calculations provide information for transition states of CD 2 ClCHFCl and hydrogen-bonded complexes of carbenes with HF and HCl. In addition, D atom migration in both free carbenes and in complexes formed by the carbene hydrogen bonding to HCl or HF is explored.

The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.