Development of a Detailed Kinetic Model for the Oxidation of n-Butane in the Liquid Phase

The chemistry underlying liquid-phase oxidation of organic compounds, the main cause of their aging, is characterized by a free-radical chain reaction mechanism. The rigorous simulation of these phenomena requires the use of detailed kinetic models that contain thousands of species and reactions. The development of such models for the liquid phase remains a challenge as solvent-dependent thermokinetic parameters have to be provided for all the species and reactions of the model. Therefore, accurate and high-throughput methods to generate these data are required. In this work, we propose new methods to generate these data, and we apply them for the development of a detailed chemical kinetic model for n-butane autoxidation, which is then validated against literature data. Our approach for model development is based on the work of Jalan et al. [J. Phys. Chem. B 2013, 117, 2955–2970] who used Gibbs free energies of solvation [ΔsolvG(T)] to correct the data of the gas-phase kinetic model. In our approach, an equation of state (EoS) is used to compute ΔsolvG as a function of temperature for all the chemical species in the mechanism. Currently, ΔsolvG(T) of free radicals cannot be computed with an EoS and it was calculated for their parent molecule (H-atom added on the radical site). Theoretical calculations with the implicit solvent model were performed to quantify the impact of this assumption and showed that it is acceptable for radicals in n-butane and probably in all n-alkanes. New rate rules were proposed for the most important reactions of the model, based on theoretical calculations and the literature data. The developed detailed kinetic model for n-butane autoxidation is the first proposed model in the literature and was validated against the experimental data from the literature. Simulations showed that the main autoxidation products, sec-butyl hydroperoxides and 2-butanol, are produced from H-abstractions from n-butane by sec-C4H9OO radicals and the C4H9OO + C4H9OO reaction, respectively. The uncertainty of the product ratio ("butanone + 2-butanol"/"2-butoxy + 2-butoxy") of the latter reaction remains high in the literature, and our simulations suggest a 1:1 ratio in n-butane solvent.