The pyrolysis of CCl4 and C2Cl6 in the gas phase. Mechanistic modeling by thermodynamic and kinetic parameter estimation

Abstract

A detailed radical reaction mechanism is proposed to describe the thermal reactions of CCl4 and C2Cl6 in the gas phase quantitatively. A consistent set of activation energies and preexponential factors for all elementary reactions, in combination with enthalpies of formation and entropies for all species involved, is computer optimized to fit experimental pressure‐rise curves and concentration profiles. For this purpose new experimental results on the pyrolysis of CCl4 are used, together with published kinetic data on the pyrolysis of C2Cl6 (in the absence and in the presence of Cl2). © 1996 John Wiley & Sons, Inc.

Kinetics and mechanism of the thermal chlorination of chloroform in the gas phase

“…d Optimized [16,17], not optimized in [8]. e From simply described by a classical empirical rate equation.…”

“…It was obtained using a combined simulationoptimization-reduction procedure from OPTKIN, starting from a larger model comprising all the known steps of the pyrolyses of CCl 4 and C 2 Cl 6 [8] together with Steps 2 and Ϫ2. Indeed, for the homogeneous thermal chlorination of CHCl 3 to CCl 4 under the experimental conditions of this work, CCl 4 is not stable.…”

“…The simulated and optimized Cl 2 -pressuretime curves were obtained using OPTKIN, a userfriendly PC program for mechanistic modeling of reactions by kinetic and thermodynamic parameter optimization [11]. Applications of this program and examples of the modeling strategy are to be found in [8,10,12,13]. The sensitivity analyses were also performed with OPTKIN.…”

“…It involves the reaction couple CHCl 3 ϩ Cl ϭ CCl 3 · ϩ HCl and the thermal reactions of CCl 4 . These latter have recently been modeled [8] and the values of their parameters are thus checked in this work.…”

A Kinetic Investigation of High-Temperature Mercury Oxidation by Chlorine

“…However, oxidation via HOCl and Cl 2 rival one another at high temperatures. The rate expressions for two additional reactions were plotted in Figure 4, i.e., HgCl + M T Hg + Cl + M 38 and Cl 2 + M T 2Cl + M. 39,40 Within each of these unimolecular reactions, M is the collision partner or gas bath, which does not participate chemically in the reactions, but is taken into account within the pressure-dependent kinetic predictions using RRKM theory. The depletion of HgCl as temperature decreases is faster than the three HgCl formation reactions, while (14) comparable to the formation reactions involving HOCl and Cl 2 at high temperatures.…”