Preprint 85 published
Preprint 85, "First-principles thermochemistry for the combustion of TiCl4 in a methane flame", has been published on the CoMo Group website.
This work presents thermochemical data for many of the intermediates in the
early stages of the combustion of titanium tetrachloride (TiCl4) in the presence of
residual species from a methane flame. An algorithm developed for previous work is
employed to ensure that all possible species are considered, reducing the probability
of neglecting important species. Thermochemical data and enthalpies of formation
are calculated for 141 new species using density functional theory (DFT) and statistical
mechanics. Equilibrium calculations are performed to try to identify which
intermediates are likely to be most prevalent in the high temperature industrial process.
The ten species with the highest equilibrium compositions are identified and
presented in the paper. These species, TiCl3OH, Ti2O2Cl3OH, Ti2OCl4(OH)2,
TiCl2OH, TiOClOH, TiCl2(OH)2, TiOCl2OH, Ti2O3ClOH, Ti2O2Cl2(OH)2,
and TiCl(OH)2, along with the original TixOyClz species are likely to be the most
important species involved in the kinetic model. Data for the remaining species is
provided as Supplemental Material. The abundance of TiiOjClkHl species is high
considering the low amount of hydrogen present in the simulation and they are likely
to have a
significant impact on the process, something that has not been
recognized in previous publications.