Skeletal chemical mechanism of high-temperature TEOS oxidation in hydrogen–oxygen environment

Abstract

This paper improves the tetraethoxysilane (TEOS) oxidation mechanism proposed by Nurkowski et al. (2015) [17] by refining the rate parameters of the key reaction channels in the mechanism. A skeletal version of the mechanism is proposed for hydrogen–oxygen environment. The rates of ethylene-loss from (tetra-, tri-, di- and dimethyldi-) ethoxysilane are computed using transition state theory. The energetics of the main pathways are refined by performing detailed ab initio calculations using the CBS-Q technique. An analysis of ethanol formation via silicates is also performed resulting in the addition of 27 new silica species to the model. Thermodynamic properties for these species are calculated via the balanced reactions method. Reasonably good agreement between the improved model and available experimental data is observed. The subsequent elimination of unimportant species and reactions is achieved via a three-stage reduction procedure. The first and second stages involve the Direct Relation Graph with Error Propagation (DRGEP) method, whereas the third stage analyses rate of progress of each reaction. The investigated conditions are taken from the experimental studies of TEOS oxidation in oxygen–hydrogen flames. The final skeletal mechanism comprises 70 species and 457 reactions and retains good reproduction of the key model properties across the chosen operating conditions as compared to the full mechanism.