Predicting solvation energies of free radicals and their mixtures: A robust approach coupling the Peng-Robinson and COSMO-RS models - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Molecular Liquids Année : 2024

Predicting solvation energies of free radicals and their mixtures: A robust approach coupling the Peng-Robinson and COSMO-RS models

Résumé

Detailed kinetic models are valuable tools for a clear understanding of the dynamics of complex reacting systems based on radical-chain mechanisms, such as combustion and oxidation. Gas-phase automatic kinetic generators, such as EXGAS, RMG, MAMOX, NetGen, REACTION, and GENESYS can be used to establish a detailed network of reaction pathways and the rates associated with each reaction. The range of applications of these gas-phase kinetic generators can be extended to liquids through diffusional and solvation corrections directly applied to the gas-phase thermo-kinetic data. In this work, a flexible framework is proposed for the calculation of the solvation correction involving closed-shell (i.e., non-free radical) and open-shell (i.e., free radicals) molecules. This novel model relies on the Peng-Robinson cubic equation of state (EoS) combined with a quantum-based continuum solvation model (COSMO-RS) through an advanced mixing rule. Unlike most predictive equations of state, the proposed model requires only pure compound inputs: critical temperature (${T}$$_{c}$$_,$$_{i}$), critical pressure (${P}$$_{c}$$_,$$_{i}$), acentric factor (ω$_{i}$) and the screening charge distribution (σ-profile). These inputs were obtained for C/H/O free radicals using group corrections applied to the known values of the associated closed-shell molecules (parent molecules). The resulting EoS is able to provide fast predictions of solvation quantities of closed-shell molecules and C/H/O free radicals with a mean unsigned error of around 0.30 kcal/mol. The great advantage of this method is that it allows high-throughput computation of solvation quantities in pure solvents and mixtures at any temperature (including the supercritical domain), which could enable the simulation of complex oxidation kinetics in a wide range of applications.
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Dates et versions

hal-04541212 , version 1 (10-04-2024)

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Francisco Paes, Romain Privat, Jean-Noël Jaubert, Baptiste Sirjean. Predicting solvation energies of free radicals and their mixtures: A robust approach coupling the Peng-Robinson and COSMO-RS models. Journal of Molecular Liquids, In press, ⟨10.1016/j.molliq.2024.124641⟩. ⟨hal-04541212⟩
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