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• W2044474497 abstract "The discharge-flow kinetic technique coupled to mass-spectrometric detection has been used to determine the variable-temperature dependence of the rate constant and product branching fractions for the reaction between F(2P) and C2H4 at P = 1 Torr nominal pressure (He). The reaction was studied at T = 202 and 236 K by monitoring the decay of C2H4 in the presence of a large excess of F(2P). The overall rate coefficients were determined to be k1(202 K) = (1.7 ± 0.4) × 10-10 cm3 molecule-1 s-1 and k1(236 K) = (2.1 ± 0.5) × 10-10 cm3 molecule-1 s-1 with the quoted uncertainty representing total errors. Further, the branching fractions for the two observed reaction channels F + C2H4 → C2H3 + HF (1a) and F + C2H4 → C2H3F + H (1b) were determined by quantitatively measuring the yield of C2H3F under conditions of excess C2H4. The stabilized adduct, C2H4F, was not detected at T = 202 K. The derived branching fractions were Γ1a(202 K) = 0.25 ± 0.09, Γ1b (202 K) = 0.75 ± 0.16, and Γ1a(236 K) = 0.27 ± 0.13, and Γ1b (236 K) = 0.73 ± 0.20, where the quoted uncertainty represents total errors. By inclusion of k1(298 K) = (3.0 ± 0.8) × 10-10 cm3 molecule-1 s-1, a revised value that used data from our previous study and Γ1a(298 K) = 0.35 ± 0.04 and Γ1b (298 K) = 0.65 ± 0.04 from a laser photolysis/photoionization mass spectrometry study, we obtain the Arrhenius expressions k1a(T) = (7.5 ± 4.0) × 10-10 exp[(−1.2 ± 0.3)/(RT)] and k1b(T) = (5.2 ± 1.0) × 10-10 exp[(−0.6 ± 0.1)/(RT)] in units of cm3 molecule-1 s-1 for k and in units of kcal mol-1 for activation energy. The quoted uncertainty represents total errors at 1σ precision errors plus 15% systematic errors. RRKM calculations have shown that the critical energy for H addition to C2H3F is less than 6 kcal mol-1 larger than that for the addition of F to C2H4 and that the competitive decomposition of chemically activated C2H4F radicals favor C−H bond rupture by a factor greater than 1000 over that for C−F bond rupture." @default.
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• W2044474497 date "1999-05-22" @default.
• W2044474497 modified "2023-09-27" @default.
• W2044474497 title "Absolute Rate Constant and Product Branching Fractions for the Reaction between F and C₂H₄ at <i>T</i> = 202−298 K" @default.
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• W2044474497 doi "https://doi.org/10.1021/jp9901747" @default.
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