Single-Pulse Shock-Tube Study of the Thermal Decomposition of Ethyl Fluoride and n-Propyl Chloride

Article abstract of DOI:10.1021/j100442a001

The thermal decomposition kinetics of dilute mixtures of ethyl fluoride and n-propyl chloride in argon have been investigated in a single-pulse shock tube in the temperature range 990-1140 K by the absolute and the comparative rate method.Under the experimental conditions used the decompositions proceed almost exclusively via the concerted elimination of hydrogen halide to yield the corresponding olefins.With the absolute rate method the following rate constants are obtained: for C2H5F -> C2H4 + HF (R1), k₁^<*>/s^-1 = 1E13.65+/-0.20 exp<-(59.5+/-1.0 kcal mol^-1)/RT> and for n-C3H7Cl -> CH3CHCH2 + HCl (R2), k₂^<*>/s^-1 = 1E13.44+/-0.28 exp<-(54.8+/-1.3 kcal mol^-1)/RT>.The comparative rate method, using a 0.125percent C2H5F-0.125percent n-C3H7Cl-99.75percent Ar mixture yielded a compatible result: log(k₁^<*>/s^-1) = (1.101+/-0.016)log(k₂^<*>/s^-1) - (0.960+/-0.031).The results are discussed and compared with other data in the literature.