Kinetic Modeling of Jet Propellant-10 Pyrolysis

A detailed kinetic model for the thermal decomposition of the advanced fuel Jet-Propellant 10 (JP-10) was constructed using a combination of automated mechanism generation techniques and <i>ab initio</i> calculations. Rate coefficients for important unimolecular initiation routes of <i>exo</i>-TCD were calculated using the multireference method CAS-PT2, while rate coefficients for the various primary decompositions of the <i>exo</i>-TCD-derived monoradicals were obtained using CBS-QB3. Rate-of-production analysis showed the importance of four dominating JP-10 decomposition channels. The model predictions agree well with five independent experimental data sets for JP-10 pyrolysis that cover a wide range of operating conditions (<i>T</i> = 300–1500 K, <i>P</i> = 300 Pa–1.7 × 10⁵ Pa, dilution = 0.7–100 mol% JP-10, conversion = 0–100%) without any adjustment of the model parameters. A significant part of the model comprises secondary conversion routes to aromatic and polyaromatic hydrocarbons and could thus be used to assess the tendency for deposit formation in fuel-rich zones of endothermic fuel applications