Estimation of Normal Boiling Temperatures, Critical Properties, and Acentric Factors of Deep Eutectic Solvents

Abstract

Deep eutectic solvents (DESs) are novel solvents that have shown the ability to capture carbon dioxide from flue gases. Thermodynamic modeling is needed to validate the experimental vapor–liquid equilibria (VLE) of the CO2–DES systems. To establish thermodynamic models of these solvents, their critical properties must be estimated. In the present study, a combination of the modified Lydersen–Joback–Reid (LJR) method and the Lee–Kesler mixing rules has been applied to estimate the critical properties of 39 different DESs. Normal boiling temperatures and acentric factors have also been determined. The accuracy of this method has been tested by comparison of theoretical densities determined from the estimated critical properties with experimental values. Absolute deviations ranging from 0 % to 17.4 % were observed for the estimated density values. An overall average absolute deviation of 4.9 % was observed for the studied DESs. Absolute deviations for DESs consisting of aliphatic precursors ranged from 0 % to 9.5 %, whereas for DESs consisting of at least one aromatic precursor, these ranged from 5.8 % to 17.4 %. The accuracy fell as the percentage of hydrogen-bond donors (HBD) increased. The method was also found to accurately take into account the variation in density due to a temperature change.

Palmitic‐Acid‐Based Hydrophobic Deep Eutectic Solvents for the Extraction of Lower Alcohols from Aqueous Media: Liquid–Liquid Equilibria Measurements, Validation and Process Economics

“…For this we require the molecular weight, density, boiling point, viscosity, COSMO cavity volume term, and sigma profiles. For boiling point, the Lydersen−Joback−Reid method is used to calculate the normal boiling point of DES as given below …”

Estimation of the Critical Temperatures of Some More Deep Eutectic Solvents from Their Surface Tensions

“…erefore, the critical temperatures T c , which are on the average about 4/3(T b /K) [1], are not the quantities that are relevant to their applications but have found use for the estimation of other properties that have not been measured as functions of the temperature [1,4]. Still, the critical temperatures are physical properties that ought to be known; hence, the present estimates for two dozens of deep eutectic solvents of which only eight had their T c estimated previously make sense.…”

“…ese mixtures are liquid at room temperature and freeze at a temperature considerably below the freezing points of the components, and hence, they are eutectics. Mirza et al [1] reported a group additivity method for the estimation of the critical temperatures T c (also the boiling points and densities) of deep eutectic solvents. An alternative path for the estimation of the critical temperatures is described here for deep eutectic solvents that for most of them no previous estimates were reported.…”

“…erefore, extrapolation to the nominal temperature T � 0 yields according to (1) and (2), respectively, A 0 � σ(0)V(0) 2/3 and σ 0 � σ(0). us, the critical temperature T E c according to (1) is…”

“…and T G c according to (2) is according to the group contribution estimates; the first entries are from Mirza et al [1] and the second ones are from Mjalli et al [4]. e following abbreviations are used for the HBA components of the solvents: ChCl � choline chloride; DEANCl � diethylethanolammonium chloride; Pr 4 NBr � tetrapropylammonium bromide; Bu 4 NCl � tetrabutylammonium chloride; MePh 3 PBr � methyltriphenylphosphonium bromide; BzPh 3 PBr � benzyltriphenylphosphonium bromide; and AllPh 3 PBr � allyltriphenylphosphonium bromide.…”