How do residual water molecules in ionic liquids (ILs) interact with themselves, as well as with the ions? This question is crucial in understanding why the physical properties of ILs - and chemical ...reactions performed in them - are strongly affected by the residual water content. There have been three conflicting hypotheses regarding the structure and behaviour of the residual water: (i) water molecules are separated from one another, while interacting strongly with the ions, and dispersed throughout the medium; (ii) water molecules self-associate or form clusters in the ILs; (iii) residual water weakens ion-ion interactions. A satisfactory resolution of these conflicting suggestions has been hindered by the complexity and long range of the interactions in the water-IL mixture and by the often profound differences in physical structure between various different ILs. Here we present a route to resolve this question through a combination of a statistical thermodynamic theory (Kirkwood-Buff theory) with density and osmotic data from the literature. The structure of water-IL mixtures is shown to be water content dependent; at the lowest measured water concentration, strong water-IL interaction and water-water separation are observed in accordance to (i), whereas water in a more hydrophobic IL environment seems to self-associate at moderately low water concentrations, in accordance with (ii).
A rigorous statistical thermodynamic theory clarifies how residual water molecules interact in three dialkylimidazolium ionic liquids.
The ionic nature of a functionalized protic ionic liquid cannot be rationalized simply through the differences in aqueous proton dissociation constants between the acid precursor and the conjugate ...acid of the base precursor. The extent of proton transfer,
i.e.
the equilibrium ionicity, of a tertiary ammonium acetate protic ionic liquid can be significantly increased by introducing an hydroxyl functional group on the cation, compared to the alkyl or amino-functionalized analogues. This increase in apparent ionic nature correlates well with variations in solvent-solute and solvent-solvent interaction parameters, as well as with physicochemical properties such as viscosity.
Ionicity of protic ionic liquids are significantly affected by additional functionality, thereby influencing solvation properties.
It has become apparent that beer (both alcoholic and nonalcoholic) contains appreciable amounts of non-starch polysaccharides, a broad subgroup of dietary fiber. It is worth noting that the ...occurrence of non-starch polysaccharides in alcoholic beer does not imply this should be consumed as a source of nutrition. But the popularity of nonalcoholic beer is growing, and the lessons learnt from non-starch polysaccharides in brewing can be largely translated to nonalcoholic beer. For context, we briefly review the origins of dietary fiber, its importance within the human diet and the significance of water-soluble dietary fiber in beverages. We review the relationship between non-starch polysaccharides and brewing, giving focus to the techniques used to quantify non-starch polysaccharides in beer, how they affect the physicochemical properties of beer and their influence on the brewing process. The content of non-starch polysaccharides in both regular and low/nonalcoholic beer ranges between 0.5 − 4.0 g/L and are predominantly composed of arabinoxylans and β-glucans. The process of malting, wort production and filtration significantly affect the soluble non-starch polysaccharide content in the final beer. Beer viscosity and turbidity are strongly associated with the content of non-starch polysaccharides.
The solubility of cellulose has been studied as a function of composition in the binary mixture of 1,1,3,3-tetramethylguanidine and propionic acid. In amine-rich compositions, greater quantities of ...cellulose can be dissolved than in the equimolar composition, a.k.a. the protic ionic liquid TMGHOPr. By applying a methodology of a short period of heating followed by cooling, similar concentrations of cellulose can be achieved in a much shorter time period. Finally, regeneration of cellulose from solution can be achieved by altering the acid:amine molar ratio. In comparison to cellulose regenerated from these solutions using water as an antisolvent, cellulose regenerated with propionic acid exhibit a lower crystallinity as inferred from x-ray diffractometry, but a greater average molecular weight as inferred from gel permeation chromatography.
The sensitivity of ionic liquids (ILs) to water affects their physical and chemical properties, even at relatively low concentrations, yet the structural thermodynamics of protic IL– (PIL−) water ...systems at low water concentrations still remains unclear. Using the rigorous Kirkwood–Buff theory of solutions, which can quantify the interactions between species in IL–water systems solely from thermodynamic data, we have shown the following: (1) Between analogous protic and aprotic ILs (AILs), the AIL cholinium bis(trifluoromethanesulfonyl)imide (ChNTf2) shows stronger interactions with water at low water concentrations, with the analogous PIL N,N-dimethylethanolammonium bis(trifluoromethanesulfonyl)imide (DMEtANTf2) having stronger water–ion interactions at higher water contents, despite water–ion interactions weakening with increasing water content in both systems. (2) Water has little effect on the average ion–ion interactions in both protic and aprotic ILs, aside from the AIL ChNTf2, which shows a strengthening of ion–ion interactions with increasing water content. (3) Self-association of water in both PIL–water systems leading to the presence of large aggregates of water in IL-rich compositions has been inferred. Water–water interactions in DMEtANTf2 were found to be similar to those of dialkylimidazolium AILs, whereas these interactions were much larger in the PIL N,N-dimethylethanolammonium propionate (DMEtAPr), attributed to the change in anion–water interactions.
The kinetics of Diels‐Alder (DA) reactions in water has been known to be altered by salts for a long time. Yet the question how salts influence the reaction rate, either as rate‐enhancing or ...rate‐reducing additives, has so far remained unresolved. Conflicting hypotheses involve (i) indirect salt contributions through the modulation of internal pressure and (ii) making (or breaking) of the so‐called “water‐structure” by salts that strengthen (or weaken) the hydrophobic effect. In contrast to the qualitative nature of these hypotheses, here we answer this question quantitatively through a combination of transition state theory and fluctuation adsorption‐solvation theory (FAST) using the DA reaction between anthracene‐9‐carbinol and N‐ethylmaleimide as an example. We show that rate enhancement is driven by the salting out of the hydrophobic reactant, while rate‐enhancing salts exhibit stronger affinity to the transition state.
Add some salt! Diels‐Alder reactions in water are heavily influenced by the addition of salts. Statistical Thermodynamics clarifies the underlying mechanism.
We study the properties of residual water molecules at different mole fractions in dialkylimidazolium based ionic liquids (ILs), namely 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM/BF
) and ...1-butyl-3-methylimidazolium tetrafluoroborate (BMIM/BF
) by means of atomistic molecular dynamics (MD) simulations. The corresponding Kirkwood-Buff (KB) integrals for the water-ion and ion-ion correlation behavior are calculated by a direct evaluation of the radial distribution functions. The outcomes are compared to the corresponding KB integrals derived by an inverse approach based on experimental data. Our results reveal a quantitative agreement between both approaches, which paves a way towards a more reliable comparison between simulation and experimental results. The simulation outcomes further highlight that water even at intermediate mole fractions has a negligible influence on the ion distribution in the solution. More detailed analysis on the local/bulk partition coefficients and the partial structure factors reveal that water molecules at low mole fractions mainly remain in the monomeric state. A non-linear increase of higher order water clusters can be found at larger water concentrations. For both ILs, a more pronounced water coordination around the cations when compared to the anions can be observed, which points out that the IL cations are mainly responsible for water pairing mechanisms. Our simulations thus provide detailed insights in the properties of dialkylimidazolium based ILs and their effects on water binding.
How does cation functionality influence the strength of intermolecular interactions in protic ionic liquids (PILs)? Quantifying the energetics of PILs can be an invaluable tool to answer this ...fundamental question. With this in view, we have determined the standard molar enthalpy of vaporization, , and the standard molar enthalpy of formation, , of three tertiary ammonium acetate PILs with varying cation functionality, and of their corresponding precursor amines, through a combination of Calvet-drop microcalorimetry, solution calorimetry, and ab initio calculations. The obtained results suggest that these PILs vaporize as their neutral acid and base precursors. We also found a strong correlation between of the PILs and of their corresponding amines. This suggests that, within this series of PILs, the influence of cation modification on their cohesive energies follows a group additivity rule. Finally, no correlation between the of PILs and the extent of proton transfer, as estimated from the difference in aqueous pK
between the precursor acid and the conjugate acid of the precursor base, was observed.
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