Despite the widespread acknowledgment that deep eutectic solvents (DESs) have negligible vapor pressures, very few studies in which the vapor pressures of these solvents are measured or computed are available. Similarly, the vapor phase composition is known for only a few DESs. In this study, for the first time, the vapor pressures and vapor phase compositions of choline chloride urea (ChClU) and choline chloride ethylene glycol (ChClEg) DESs are computed using Monte Carlo simulations. The partial pressures of the DES components were obtained from liquid and vapor phase excess Gibbs energies, computed using thermodynamic integration. The enthalpies of vaporization were computed from the obtained vapor pressures, and the results were in reasonable agreement with the few available experimental data in the literature. It was found that the vapor phases of both DESs were dominated by the most volatile component (hydrogen bond donor, HBD, i.e., urea or ethylene glycol), i.e., 100% HBD in ChClEg and 88%–93% HBD in ChClU. Higher vapor pressures were observed for ChClEg compared to ChClU due to the higher volatility of ethylene glycol compared to urea. The influence of the liquid composition of the DESs on the computed properties was studied by considering different mole fractions (i.e., 0.6, 0.67, and 0.75) of the HBD. Except for the partial pressure of ethylene glycol in ChClEg, all the computed partial pressures and enthalpies of vaporization showed insensitivity toward the liquid composition. The activity coefficient of ethylene glycol in ChClEg was computed at different liquid phase mole fractions, showing negative deviations from Raoult’s law.
Vapor pressures and vapor phase compositions of choline chloride urea and choline chloride ethylene glycol deep eutectic solvents from molecular simulation
Note: This paper is part of the 2021 JCP Emerging Investigators Special Collection.
Hirad S. Salehi, H. Mert Polat, Frédérick de Meyer, Céline Houriez, Christophe Coquelet, Thijs J. H. Vlugt, Othonas A. Moultos; Vapor pressures and vapor phase compositions of choline chloride urea and choline chloride ethylene glycol deep eutectic solvents from molecular simulation. J. Chem. Phys. 21 September 2021; 155 (11): 114504. https://doi.org/10.1063/5.0062408
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