Collisional Energy Transfer in Thermal Decomposition Reaction of 1,2-Dichloropropane

Article abstract of DOI:10.1021/j100331a059

The thermal decomposition reaction of 1,2-dichloropropane (1,2-DCP) was studied at temperatures from 663.2 to 703.2 K over the pressure range 0.04-10.0 Torr.The decomposition modes of 1,2-DCP were monitored via four reaction channels of unimolecular HCl eliminations and a negligible portion of a side radical chain reaction. 3-Chloropropene (3-CP), cis-1-chloropropene (cis-1-CP), trans-1-chloropropene (trans-1-CP), and 2-chloropropene (2-CP) were produced.Rate parameters for the thermal processes found in this study are k₃(3-CP)/s^-1=10^{13.61 +/- 0.30}exp<(-54960 +/- 1200) cal mol^-1/RT>, k_cis(cis-1-CP)/s^-1=10^{12.90 +/- 0.70}exp<(-54260 +/- 2000) cal mol^-1/RT>, k_trans(trans-1-CP)/s^-1=10^{13.21 +/- 0.80}exp<(-56070 +/- 2500) cal mol^-1/RT>, k₂(2-CP)/s^-1=10^{13.05 +/- 0.44}exp<(-59360 +/- 1500) cal mol^-1/RT>, and k_tot(total)/s^-1=10^{13.70 +/- 0.50}exp<(-54900 +/- 2500) cal mol^-1/RT>.The unimolecular thermal decomposition reactions of the four-channel 1,2-DCP system were carried out in the presence of a He bath gas to evaluate intermolecular-energy-transfer parameters.The average energies removed per collision from energized 1,2-DCP by bath gas are as follows: by the substrate, 1200 cm^-1 for the stepladder model; by He, 250 cm^-1 for the exponential model.The effects of active additives, CO2 and HCl, and the surface condition of the reaction vessel were also studied to ascertain the potential properties of the thermal decomposition reaction of 1,2-DCP.