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Quantum Chemical and Kinetics Study of the Thermal Gas Phase Decomposition of 2‑Chloropropene
A detailed
theoretical study of the kinetics of the thermal decomposition
of 2-chloropropene over the 600–1400 K temperature range has
been done. The reaction takes place through the elimination of HCl
with the concomitant formation of propyne or allene products. Relevant
molecular properties of the reactant and transition states were calculated
for each reaction channel at 14 levels of theory. From information
provided by the BMK, MPWB1K, BB1K, M05-2X, and M06-2X functionals,
specific for chemical kinetics studies, high-pressure limit rate coefficients
of (5.8 ± 1.0) × 10<sup>14</sup> exp[−(67.8 ±
0.4 kcal mol<sup>–1</sup>)/<i>RT</i>] s<sup>–1</sup> and (1.1 ± 0.2) × 10<sup>14</sup> exp[−(66.8 ±
0.5 kcal mol<sup>–1</sup>)/<i>RT</i>] s<sup>–1</sup> were obtained for the propyne and allene channels, respectively.
The pressure effect over the reaction was analyzed through the calculation
of the low-pressure limit rate coefficients and falloff curves. An
analysis of the branching ratio between the two channels as a function
of pressure and temperature, based on these results and on computed
specific rate coefficients, show that the propyne forming channel
is predominant