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Tri-ethyl phosphate (TEP) is an organophosphorous compound (OPC) used as a simulant for highly toxic nerve agents such as Sarin GB. High temperature decomposition pathway during TEP pyrolysis has been proposed previously and takes place via seven concerted elimination reactions. Computational study to investigate the kinetics of these seven reactions is carried out at CBS-QB3 level of theory. The transition state optimization is done at B3LYP/6-311G(2d,d,p) theory level and CanTherm is used to derive the Arrhenius coefficients. The pre-exponential factors of the rate constant of these reactions are found to be up to 50 times lower than the estimated values from the literature. In addition, kinetics of reaction of trioxidophosphorus radical (PO¬3) with H2 (H2+PO3=HOPO2+H); which is one of the important reactions in predicting CO formation during TEP decomposition, is also investigated computationally at the same theory level. The new kinetic parameters derived from the computational study is used with TEP kinetic model proposed recently by our group. In addition, an alternative decomposition pathway for TEP decomposition via H-abstraction, radical decomposition and recombination reactions are added. The proposed mechanism was validated with literature's experimental data i.e. intermediate CO time-history data from pyrolysis and oxidation experiments and ignition delay times. Fairly good agreement with experiments was obtained for pyrolysis and oxidation CO yield within 1400-1700K. The model was able to predict the ignition times of rich TEP mixture (phi=2) within 25% of the experimental results while the discrepancies for stoichiometric and rich mixtures were larger. Discussion on results of sensitivity and reaction pathway analysis is presented to identify the important phosphorous reactions and to understand the effect of addition of the alternative TEP decomposition pathway.
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Name: The journal of physical chemistry. A
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