Technical Report 97, c4e-Preprint Series, Cambridge

First-principles thermochemistry for gas phase species in an industrial rutile chlorinator

ref: Technical Report 97, c4e-Preprint Series, Cambridge

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

Associated Theme: Quantum Chemistry

Abstract

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 forming TiCl4 and O2. The latter then reacts with the solid C forming CO and CO2 and providing the heat. Data for all the new species is provided as Supplemental Material. 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.

Supplementary material is available here. An overview of which is given here.

Material from this preprint has been published in: Journal of Physical Chemistry A 114, 11825-11832, (2010)

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