American Chemical Society
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Theoretical Calculation of Reaction Rates and Combustion Kinetic Modeling Study of Triethyl Phosphate (TEP)

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posted on 2019-03-29, 00:00 authored by Sneha Neupane, Ramees K. Rahman, Artëm E. Masunov, Subith S. Vasu
Triethyl phosphate (TEP) is an organophosphorus compound used as a simulant for highly toxic nerve agents such as sarin GB. A high temperature decomposition pathway during TEP pyrolysis has been proposed previously and takes place via seven concerted elimination reactions. A computational study to investigate the kinetics of these seven reactions was carried out at the CBS-QB3 level of theory. The transition state optimization was done at the B3LYP/6-311G­(2d,d,p) theory level, and CanTherm was used to derive the Arrhenius coefficients. The pre-exponential factors of the rate constant of these reactions were found to be up to 50 times lower than the estimated values from the literature. In addition, kinetics of reaction of the trioxidophosphorus radical (PO3) with H2 (H2 + PO3 → HOPO2 + H), which is one of the important reactions in predicting CO formation during TEP decomposition, was also investigated computationally at the same theory level. The new kinetic parameters derived from the computational study were used with the 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 was added. The proposed mechanism was validated with the literature’s experimental data, that is, 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 1200–1700 K. The model was able to predict the ignition times of the rich TEP mixture (φ = 2) within 25% of the experimental results, while the discrepancies for stoichiometric and rich mixtures were larger. Discussions on results of sensitivity and reaction pathway analysis are presented to identify the important phosphorus reactions and to understand the effect of addition of the alternative TEP decomposition pathway.