Vesna Najdanovic-Visak

A detailed thermodynamic analysis of [C4mim][BF4]+ water as a case study to model ionic liquid aqueous solutions

Since determining experimentally a wide variety of thermophysical properties—even for a very small portion of the already known room temperature ionic liquids (and their mixtures and solutions)—is an impossible goal, it is imperative that reliable predictive methods be developed. In turn, these methods might offer us clues to understanding the underlying ion–ion and ion–molecule interactions. 1-Butyl-3-methylimidazolium tetrafluoroborate, one of the most thoroughly investigated ionic liquids, together with water, the greenest of the solvents, have been chosen in this work in order to use their mixtures as a case study to model other, greener, ionic liquid aqueous solutions. We focus our attention both on very simple methodologies that permit one to calculate accurately the mixtures molar volumes and heat capacities as well as more sophisticated theories to predict excess properties, pressure and isotope effects in the phase diagrams, and anomalies in some response functions to criticality, with a minimum of information. In regard to experimental work, we have determined: (a) densities as a function of temperature (278.15 < T/K < 333.15), pressure (1 < p/bar < 600), and composition (0 < xIL < 1), thus also excess molar volumes; (b) heat capacities and excess molar enthalpies as a function of temperature (278.15 < T/K < 333.15) and composition (0 < xIL < 1); and (c) liquid–liquid phase diagrams and their pressure (1 < p/bar < 700) and isotopic (H2O/D2O) dependences. The evolution of some of the aforementioned properties in their approach to the critical region has deserved particular attention.

Phase behaviour of room temperature ionic liquid solutions: an unusually large co-solvent effect in (water + ethanol)

A surprising mixed solvent effect, both in its magnitude and direction, has been found in the phase diagram of the ternary mixture of ([C4mim][PF6]+(water+ethanol)). For a molar ratio of 1∶1 of water to ethanol, the co-solvent effect in the near-critical demixing temperature can be as large as 80 K.

Liquid–liquid behaviour of ionic liquid–1-butanol–water and high pressure CO2-induced phase changes

The liquid–liquid equilibrium of the [C4mim][NTf2]–1-butanol system presents upper critical solution temperature (UCST) behaviour. We report the influence of added water as well as the effect of hydrostatic pressure on the cloud points. Similarly to previously studied systems that involved RTILs in our laboratories, water is shown to be a very good co-solvent with alcohols. If a small amount of water is present in the [C4mim][NTf2]–1-butanol system it decreases the UCST as much as 1.5 K per mol% of water added to butanol. The hydrostatic pressure effect on cloud points is rather modest (≈−3.5 × 10−3 K bar−1). As for liquid–vapour equilibria, a new apparatus which employs a high-pressure variable-volume cell, was conceived and built. The apparatus was tested for the well-known system 1-butanol–CO2. Demixing pressures of the ternary and quaternary mixtures, (1-butanol–water–CO2) and ([C4mim][NTf2]–1-butanol–water–CO2), were determined for a few compositions and temperatures. The demixing pressure is strongly controlled by the water concentration.

Synthesis of fatty acid methyl esters via direct transesterification with methanol/carbon dioxide mixtures from spent coffee grounds feedstock

The feasibility of in situextraction and transesterification of spent coffee ground oil into fatty acid methyl esters with supercritical methanol has been investigated in the temperature range 473–603 K, and in the pressure range 10.0–30.0 MPa. At 30.0 MPa and 603 K, a fatty acid methyl esters (FAME) yield of 84.9% was obtained. Carbon dioxide was added to methanol with the aim of reducing the operating temperature and pressure. It was demonstrated that at a reaction temperature of 573 K, pressure of 10.0 MPa and a CO2/MeOH molar ratio of 0.11, a FAME yield of 93.4% was obtained.

Volumetric Properties and Spectroscopic Studies of Pyridine or Nicotine Solutions in Liquid Polyethylene Glycols

Densities and molar excess volumes of the solutions of pyridine or nicotine in liquid polyethylene glycol, PEG200 and PEG400, have been determined at several temperatures. The experimental molar excess volumes are negative, thus indicating strong attractive interactions between the components, as could be expected considering their highly polar nature and good hydrogen bond abilities. For the pyridine systems, this negativity is slightly increased as the temperature rises, while the opposite tendency is observed for the nicotine mixtures. When pyridine and nicotine solutions are compared, the former-particularly those with PEG400-exhibit substantially more negative molar excess volumes than the latter. The effect of the polymer chain length on the results for the nicotine solutions is almost negligible. However, this is not the case when pyridine is one of the components: a longer chain induced considerably higher compression on mixing. The Fourier-transform infrared analysis allowed interpretation of the negative experimental molar excess volumes in terms of specific inter- and intramolecular interactions.

Two ways of looking at Prigogine and Defay's equation

In the search for understanding of several types of abnormal thermodynamic behaviour in the vicinity of critical lines of binary liquid mixtures, we have revisited an apparently forgotten relationship between the pressure dependence of the critical temperature and the second derivatives with respect to the composition of the volumetric and enthalpic properties of the mixture. We refer to an equation originally developed in the fifties by Prigogine and Defay and soon afterwards analysed by others. Under some restrictive assumptions, the T–p slope of the critical locus can simply be inferred from the ratio between vE and hE. The interest and usefulness of this approximate relation is self-evident. Values for any one of the three properties involved,(dT/dp)c, vE or hE, can be assessed based on the availability of the other two. Moreover, the amplitude of the divergence of thermodynamic response functions to criticality are intimately associated with the slope of the critical locus. A link between critical behaviour and solution excess properties is thus established. For instance, double critical points tend to occur if one of the excess properties changes its sign as the temperature or pressure is varied. In this work, we have started a detailed study of the practical limits of validity of the approximate relation. Five binary liquid mixtures were tested, all of them sharing a UCST/LCSP-type of phase transition. Although, from a theoretical perspective, the original second-derivatives approach should perform better, in practice, the direct ratio of the excess properties constitutes a superior strategy for obtaining (dT/dp)c values. The underlying reasons for this are discussed in detail. The T–p critical slope is normally found to play a secondary role in assessing the critical amplitudes of diverging thermodynamic functions.

Solubility of Mixtures Containing Soybean Oil, Ionic Liquid and Methanol

This paper presents data on mutual solubility of the binary (soybean oil + ionic liquid) and ternary (soybean oil + methanol + ionic liquid) systems, where ionic liquid stands for 1-butyl-3-methylimidazolium thiocyanate [C4MIM][SCN] or 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C4MIM][NTf2] or 1-butyl-3-methylimidazolium dicyanamide [C4MIM][DCA] or 1-butyl-3-methylimidazolium hexafluorophosphate [C4MIM][PF6] or 1-butyl-3-methyl imida zolium hydrogensulfate [C4MIM] [HSO4] or 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C10MIM][NTf2] or methyltrioctylammonium bis(trifluoromethylsulfonyl)imide [ALIQUAT][NTf2] or methyltrioctylammonium chloride [ALIQUAT][Cl]. Solubilities were determined by the cloud point titration method in the temperature range of 298 K to 343 K. Obtained results suggest that imidazolium based ionic liquids exhibit lower solubility in soybean oil than ionic liquids with the aliquat cation. Thus, aliquat based ionic liquids are good candidate to be used as co-solvents for biphasic (methanol + soybean oil) mixture.