While molar volume-based models for gas solubility in ionic liquids (ILs) have been proposed, free volume within the IL can be shown to be the underlying property driving gas solubility and selecitivity. Previously published observations as to the distinct differences in solubility trends for gases such as CH4 and N2 relative to CO2 in systematically varied ILs can be attributed to positive and negative effects arising from increasing free volume with increasing alkyl chain length. Through the use of COSMOtherm as a powerful and rapid tool to calculate free volumes in 165 existing and theoretical 1-n-alkyl-3-methylimidazolium ([Cnmim]­[X]) ILs, a previously unreported, yet speculated, critical underlying relationship between gas solubility in ILs is herein described. These results build upon previous assertions that Regular Solution Theory is applicable to imidazolium-based ILs, which appeared to indicate that a global maximum had already been observed for CO2 solubility in imidazolium-based ILs. However, the findings of this computational study suggest that the perceived maximum in CO2 solubility might be exceeded through rational design of ILs. We observe that although Henry’s constants in ILs are dependent on the inverse of molar volume and free volume, the volume-normalized solubility of CH4 and N2 are proportional to free volume, while CO2 is inversely proportional to the square root of free volume. Our free volume model is compared to experimental data for CO2/CH4 and CO2/N2 selectivity, and a nearly identical plot of selectivity relative to IL molar volume can be generated from the computational method alone. The overall implication is that large, highly delocalized anions paired with imidazolium cations that have minimally sized alkyl chains may hold the key to achieving greater CO2 solubility and selectivity in ILs.

Sulfur dioxide (SO 2 ) removal is a key component of many industrial processes, especially coal-fired power generation. Controlling SO 2 emissions is vital to maintaining environmental quality, as SO 2 is a contributor to acid rain, but has value as a chemical feedstock. Although a number of novel solvents/materials including ionic liquids (ILs) have recently been proposed for alternatives to limestone scrubbing for SO 2 capture/removal from point sources, the imidazole architecture presents a convenient, inexpensive and efficient class of low volatility and low viscosity solvents to accomplish this goal. On the basis of our prior work with imidazoles for CO 2 capture, we have extended our interests toward understanding the relationship between imidazole structure and SO 2 absorption. Using a series of imidazole compounds with various substituents at the 1, 2 and/or 4(5) positions of the five-membered ring, SO 2 absorption via both chemical and physical mechanisms was observed. The chemical absorption product is a relatively stable 1:1 SO 2 −imidazole complex, while physical absorption of SO 2 is dependent on pressure and temperature. Because imidazoles are relatively small molecules, they are an efficient absorption medium for SO 2 and can form adducts wherein the mass fraction of bound SO 2 is >40 wt %. The SO 2 −imidazole complexes were also observed to produce distinct color and/or phase changes that are associated with the nature of the substituents present. The chemically bound SO 2 can be released under vacuum at moderate temperature (∼100°C) and vacuum, yielding the original neat solvent, while the physically dissolved SO 2 can be readily removed at ambient temperature under vacuum. This behavior corresponds to a much smaller enthalpy of absorption for physical dissolution (−4 to −13 kJ/mol) as determined via thermodynamic relationships compared to the binding energies of chemical complexation (−35 to −42 kJ/mol) as determined via density functional theory calculations. Increasing chemical complexation energies are correlated with increased substitution on the imidazole ring. Simulations were also employed to gain insight into the structures of the SO 2 −imidazole complexes, illustrating changes in partial charge distribution before and after complexation as well as confirming a charge transfer complex is formed based on the N−S bond length.

Despite the utility of imidazoles for a wide variety of chemical and biological applications as well as the growing research in imidazolium-based ionic liquids (ILs), synthetic studies and characterization data for N-functionalized imidazole derivatives with substituents present at the C(2) and/or C(4) and/or C(5) positions are generally unreported. Here, we modify our prior method for synthesizing monofunctionalized imidazoles and apply it to the production of a library of 30 di- and trifunctionalized alkylimidazoles using only commodity chemicals and avoiding anhydrous solvents or air/water-sensitive reagents. For all products, purities of >98% could be readily achieved, although yields were lower than in our prior work with imidazole, which may be due to mass transfer limitations and/or increased nucleophilicity of substituted imidazole products. Interestingly, we also observe that, when 4-methylimidazole or 2-ethyl-4-methylimidazole is used as a starting material, two regioisomers are inevitably formed. We employed electronic structural calculations to aid in identifying the chemical shifts and quantifying the relative presence of the regioisomers. In both series of compounds where regioisomers could be formed, the 4-methyl regioisomer was favored. Although the formation of similar regioisomers has been previously noted in the literature, it has perhaps not been fully considered in works related to imidazolium-based ILs.

The imidazole structure offers a versatile means of developing molecules with controlled/tunable physicochemical properties that have significant utility in many applications and can be further derivatized to form ionic liquids. In the literature, the vast majority of studies on structure−property relationships in these types of molecules are devoted to linear (e.g., n-alkyl) substituents. However, imidazoles with branched or cycloalkyl groups are equally accessible through convenient synthetic methods − yet there are essentially no reports on the physical properties of such compounds in the literature. Here, the absolute vapor pressures of branched and cycloalkyl derivatives of imidazole have been determined as a function of temperature by the transpiration method. The standard molar enthalpies of vaporization were derived from the temperature dependences of vapor pressures. The measured data sets were successfully checked for internal consistency by comparison with vaporization enthalpies of the parent species, and a group contribution method is put forth by which the vaporization enthalpies of imidazoles, and imidazolium-based ILs, with alkyl groups in any configuration can be rapidly predicted.

N-functionalized imidazole compounds with linear alkyl groups have been widely utilized precursors for imidazolium ionic liquids (ILs) while the effects of branched and cycloalkyl substituents on properties of imidazole compounds have not been studied; however, such compounds are just as synthetically accessible as those with linear alkyl groups. In this work, two fundamental properties, density and viscosity, of selected N-functionalized imidazoles bearing iso-propyl, iso-butyl, sec-butyl methylcyclopropyl, cyclopentyl, and methylcyclohexyl groups have been measured in the temperature range of 293.15–353.15 K for the guidance of molecular design for future applications. A linear and parabolic model were used for temperature-density correlation while temperature dependence of viscosity was summarized using the Andrade Equation and the Vogel-Fulcher-Tammann equation. In addition to experimental data, density, viscosity, vapor pressure and vaporization of enthalpies of target imidazole compounds were predicted using COSMOtherm calculations and compared with experimental data. It was found that the calculated densities were quite close to the experimental data, while viscosity data, obtained from COSMOtherm, underestimated experimental measurements and a scaling factor provided agreement with experiments. Predictions of vapor pressure were relatively reliable at low temperature, although the difference between experiment and prediction tended to expand with increasing temperature. Variances of vaporization enthalpies were small upon temperature change and a maximum error of ~12.3% was observed for all compounds studied.