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Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.

Recently, it has been reported that addition of a cosolvent significantly influences solubility of cellulose in ionic liquids (ILs), but little is known about the influence mechanism of the cosolvent on the molecular level. In this work, four kinds of typical molecular solvents (dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), CH₃OH, and H₂O) were used to investigate the effect of cosolvents on cellulose dissolution in [C₄mim][CH₃COO] by molecular dynamics simulations and quantum chemistry calculations. It was found that dissolution of cellulose in IL/cosolvent systems is mainly determined by the hydrogen bond interactions between [CH₃COO](-) anions and the hydroxyl protons of cellulose. The effect of cosolvents on the solubility of cellulose is indirectly achieved by influencing such hydrogen bond interactions. The strong preferential solvation of [CH₃COO](-) by the protic solvents (CH₃OH and H₂O) can compete with the cellulose-[CH₃COO](-) interaction in the dissolution process, resulting in decreased cellulose solubility. On the other hand, the aprotic solvents (DMSO and DMF) can partially break down the ionic association of [C₄mim][CH₃COO] by solvation of the cation and anion, but no preferential solvation was observed. The dissociated [CH₃COO](-) would readily interact with cellulose to improve the dissolution of cellulose. Furthermore, the effect of the aprotic solvent-to-IL molar ratio on the dissolution of cellulose in [C₄mim][CH₃COO]/DMSO systems was investigated, and a possible mechanism is proposed. These simulation results provide insight into how a cosolvent affects the dissolution of cellulose in ILs and may motivate further experimental studies in related fields.

Aqueous solutions of five ionic liquids (ILs) of the 1-n-alkyl-3-methylimidazolium bromide family, [C(n)mim]Br (n = 4, 6, 8, 10, 12), were investigated by NMR measurements at 298.2 K as a function of IL concentrations. Critical aggregation concentrations and aggregation numbers of these ILs were determined by 1H NMR except for [C4mim]Br in D2O. The effects of the alkyl chain length of the cations were examined on the aggregation behavior of the ILs. 1H NMR data of the solvent D2O were used to investigate the hydration of the ILs in D2O, and it was found that the ionic hydration and the cation-anion association or aggregation of the ILs offset each other. The microenvironment of different protons of cations of the ILs in the aggregates was probed by determining the spin-lattice relaxation rate (1/T1). It is suggested that the imidazolium rings in the aggregates are exposed to water and that the molecular motion of the aggregates is more restricted than that of the monomers of the ILs. Furthermore, a stair-like microscopic aggregation structure is suggested for the [C(n)mim]Br/D2O (n = 6, 8, 10) systems from 2-D 1H-1H NOESY measurements.

Carboxylate-anion-based imidazolium ionic liquids (ILs)are powerfulsolvents for cellulose and lignin. However, little is known abouttheir fundamental physicochemical properties. In this work, 1-butyl-3-methylimidazoliumcarboxylate ILs 1-butyl-3-methylimidazolium formate ([C4mim][HCOO]), acetate ([C4mim][CH3COO]), propionate([C4mim][CH3CH2COO]), and butyrate([C4mim][CH3(CH2)2COO]),in which the alkyl chain length in the anions is being varied in contrastto the more usual studies where alkyl chain length in the cationsis varied, have been synthesized and their densities and surface tensionshave been determined experimentally at different temperatures. Byusing these data, the molar volume, isobaric expansivity, standardentropy, lattice energy, surface excess entropy, vaporization enthalpy,and Hildebrand solubility parameter have been estimated for theseILs. From the analysis of structure–property relationship,the effect of alkyl chain length in the anions on these physicochemicalproperties of the ILs has been assessed and the dissolution of celluloseand lignin in these ILs has been discussed. Such knowledge is expectedto be useful for understanding the nature of this class of solventfor the dissolution of biomacromolecules. [ABSTRACT FROM AUTHOR]

Material preparation in ionic liquids and environmental pollution control by ionic liquids are often closely dependent on the aggregation behavior of ionic liquids in solution. In the present work, conductivity, fluorescence probe, and dynamic light scattering techniques have been used to study the effect of organic solvents on the aggregation behavior of 1-dodecyl-3-methylimidazolium bromide in water. It was shown that the critical aggregation concentration (CAC), the ionization degree of the aggregates (α), and the standard Gibbs energy of aggregation (ΔGm°) of the ionic liquid increase, while its aggregation number (Nagg) and aggregates’ size decrease with increasing concentration of organic additives in water. These results have been discussed from the favorable interactions of alkyl chain of the ionic liquid with the mixed solvents. It is suggested that the solvophobic parameter, characterized quantitatively by Gibbs energy of transfer of hydrocarbon from gas into a given solvent, can be used to account for the effect of organic additives on the formation and growth of the ionic liquid aggregates in water. Aggregation behavior of ionic liquids in aqueous organic solutions can be modulated simply by the solvophobic parameters of hydrocarbon in the mixed solvents. [ABSTRACT FROM AUTHOR]