First-Principles Thermochemistry for Gas Phase Species in an Industrial Rutile Chlorinator

Authors: Raphael Shirley, Weerapong Phadungsukanan, Markus Kraft*, Jim Downing, Nick E. Day, and Peter Murray-Rust


This work presents thermochemical data for possible gas phase intermediate species in an industrial rutile chlorinator. An algorithm developed for previous work is employed to ensure that all possible species are considered, reducing the number of important species neglected. Thermochemical data and enthalpies of formation are calculated for 22 new species using density functional theory, post Hartree-Fock coupled cluster calculations, and statistical mechanics. Equilibrium calculations are performed to identify whether any Ti/C intermediates are likely to be important to the high temperature industrial process. These new species are not present at high concentration in the exit stream. It is therefore likely that the two chemical processes do not interact. Rather, the Cl2 rapidly reacts with the solid TiO2 to form TiCl4 and O2. The latter then reacts with the solid C to form CO and CO2 and provide the heat. Data for all the new species is provided as Supporting Information. Finally, a new methodology for data collaboration is investigated in which the data is made openly accessible using the resource description framework. Example scripts are provided to demonstrate how to query and retrieve the data automatically.

Keywords: density functional theory (DFT), titanium dioxide, titanium tetrachloride,

Associated Project: Quantum Chemistry

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