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 ab initio calculations. Rate coefficients for important unimolecular initiation
routes of exo-TCD were calculated using the multireference
method CAS-PT2, while rate coefficients for the various primary decompositions
of the exo-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 (T = 300–1500 K, P = 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.