Isomerization and decomposition of chloromethylacetylene

Article abstract of DOI:10.1002/ijch.199600032

The isomerization and thermal decomposition of chloromethylacetylene (CMA) has been studied with two shock tube techniques. The first experiment (Jerusalem) utilizes single-pulse shock tube methods to measure the isomerization rate of CMA to chloroallene. In addition, equilibrium constants can be estimated at ～1200 K. The second experiment (Argonne) monitors Cl-atom formation at temperatures above ～1150 K. Absolute yield measurements have been performed over the 1200-1700 K range and indicate that two decomposition channels contribute to CMA destruction, namely, Cl fission and HCl elimination. The results show that the branching fraction between processes is temperature dependent. Therefore, direct Cl-atom fission is accompanied by molecular elimination, undoubtedly giving HCl and one or more isomers of C₃H₂. MP2 6-31G(d,p) ab initio electronic structure calculations have been used to determine vibration frequencies and moments of inertia for three C₃H₃Cl isomers. Using these quantities, the experimental equilibrium constants required that ΔH⁰₀(CH₂Cl-C≡CH ? CHCl=C=CH₂) = -0.24 kcal mole^-1. A potential energy surface pertinent to the present system has been constructed, and RRKM calculations have been carried out in order to explain the isomerization rates. The isomerization data can be explained with E₀ = 52.3 kcal mole^-1 and 〈ΔE_down〉 = 225 cm^-1. Subsequent semi-empirical Troe and RRKM-Gorin modeling of the Cl atom rate data require E₀ = (67.5 ± 0.5) kcal mole^-1 with a (ΔE_down) = (365 ± 90) cm^-1. This suggests a heat of formation for propargyl radicals of (79.0 ± 2 5) kcal mole^-1.