Small angle X-ray studies of short-range order in non-stoichiometric pseudoprotic ionic liquids: the influence of chemical structure.

Mixtures of organic acids and amines have been studied extensively owing to their unusual physicochemical properties and applications as solvents for extraction. In equimolar ratios they represent pseudoprotic ionic liquids, and in other, "nonstoichiometric" ratios they display a range of odd physicochemical behaviors. We report the results of small-angle X-ray scattering studies of a series of such systems with a range of chemical structures chosen to explore the link between molecular geometry and the character of the emergent nanoscale local liquid structure. We find that while the details vary, structure can emerge even when the hydrogen-bonding character of the components is changed significantly and the character of their hydrocarbon substituents is altered. The consistent emergence of local order in the face of varying chemical structures indicates that the process is robust. This implies that the emergence of such structure may in fact be far more common in liquid mixtures than is currently recognized, and a great many structures may be suitable for the synthesis of pseudoprotic ionic liquids.

Relationship between liquid nanoscale structure in solvents and the strength of the Hofmeister effect in extraction experiments.

In this study, we used mixtures of carboxylic acids and amines as solvents for the liquid-liquid extraction of copper salts with various anions from aqueous phase, and systematically varied the acid/amine ratio to determine its influence on extraction efficiency. The organic phases resulting from these extraction experiments were studied using small-angle X-ray scattering (SAXS), establishing a connection between the extraction process and the liquid structure. A relationship is found between the extent of extraction for the metal salt, the strength of the Hofmeister effect of the anions of the salt, and the characteristic lengthscale of the observed liquid nanoscale structure before and after extraction.

Extraction of Acids and Bases from Aqueous Phase to a Pseudoprotic Ionic Liquid.

We report experiments on the extraction of acids and bases from an aqueous phase to a pseudoprotic ionic liquid phase consisting of an equimolar mixture of trihexylamine and octanoic acid. We observed the extraction of a wide range of acids and bases, and investigated the mechanism of extraction in detail. Our results confirmed the observation of the Hofmeister effect in these systems reported in our previous work, where the extent of the extraction of copper salts was significantly influenced by the interactions between extracted inorganic anions and the organic phase. Our results further demonstrated that the organic layer served as a "floating buffer" capable of stabilizing the pH of an acidic or alkaline aqueous phase. The results tie current interest in protic and pseudoprotic ionic liquids to earlier work on the extraction of acids using amine and acid⁻base couples as extraction agents in an inert organic solvent.

Nanoscale viscosity of confined polyethylene oxide.

Complex fluids near interfaces or confined within nanoscale volumes can exhibit substantial shifts in physical properties compared to bulk, including glass transition temperature, phase separation, and crystallization. Because studies of these effects typically use thin film samples with one dimension of confinement, it is generally unclear how more extreme spatial confinement may influence these properties. In this work, we used x-ray photon correlation spectroscopy and gold nanoprobes to characterize polyethylene oxide confined by nanostructured gratings (<100nm width) and measured the viscosity in this nanoconfinement regime to be ∼500 times the bulk viscosity. This enhanced viscosity occurs even when the scale of confinement is several times the polymer's radius of gyration, consistent with previous reports of polymer viscosity near flat interfaces.

X-Ray scattering and physicochemical studies of trialkylamine/carboxylic acid mixtures: nanoscale structure in pseudoprotic ionic liquids and related solutions.

We report the results of X-ray scattering, physical, and spectroscopic measurements on a series of water-saturated trialkylamine/carboxylic acid mixtures. The results demonstrate the existence of well-defined nanoscale structures in bulk liquid mixtures at specific acid : amine ratios. These structures are analogous to those observed in ionic liquids but are driven by the formation of a hydrogen-bonded network rather than via inter-ion Coulomb forces. The results of the physical components of this study are closely analogous to prior observations on anhydrous, low molecular weight acid/amine mixtures, but this is to our knowledge the first time these observations have been augmented by the use of X-ray scattering. The results therefore bridge the gap between early work on amine/acid mixtures and recent studies of protic and pseudoprotic ionic liquids.

Selective extraction of metal ions from aqueous phase to ionic liquids: a novel thermodynamic approach to separations.

The selective extraction of metals from aqueous mixtures has generally relied on the use of selective ionophores. We present an alternative strategy that exploits a recently developed approach to extraction into an ionic liquid phase, and show that a high degree of control over selectivity can be obtained by tuning the relative concentrations of extraction agents. A thermodynamic model for the approach is presented, and an experimental separation of strontium and potassium ions is performed. It is shown that tuning the concentrations of the species involved can shift the ratio of potassium to strontium in the ionic liquid phase from 4:1 to 3:4. This extraction is performed under mild conditions with relatively common reagents. The result is a proof-of-concept for a novel separations scheme that could have great importance in a wide range of technological applications.

A proposed voltage dependence of the ionic strength of a confined electrolyte based on a grand canonical ensemble model.

Electrodes with highly porous morphologies are of great technological interest, as their exceptionally high specific surface areas make them ideal for use in capacitors, battery electrodes and electrochemical sensors. There is a large body of research focusing on the structure of confined electrolytes in these systems, but the majority of these studies focus on cases where the length scale of the porous domain is equal to or less than the Debye screening length of the electrolyte. In this work, we use a thermodynamic model to consider the structure of electrolytes in mesoscale domains, where the pore dimensions are significantly larger than the Debye screening length. In this limit, the interface is screened by the electrochemical double layer and the enclosed volume primarily consists of an electroneutral 'bulk liquid' domain. Despite the absence of direct interactions between ions in the bulk domain and the charged interface, we show that minimization of the free energy of the system leads to a reduction in the ionic strength of the electrolyte within the bulk liquid domain of the pore. Based on our model studies, we anticipate that this depletion will apply for porous domains with widths of the order of 50-200 nm even under mild experimental conditions and low applied voltages. The results imply relationships between electrolyte strength, surface morphology and applied voltage that may be important in device design.

A novel mechanism for the extraction of metals from water to ionic liquids.

We present a novel mechanism for the extraction of metals from aqueous phases to room-temperature ionic liquids (ILs) by use of a high-temperature salt as an extraction agent. The mechanism capitalizes on the fact that charged metal complexes are soluble in ILs; this allows for extraction of charged complexes rather than the neutral species, which are formed by conventional approaches. The use of a well-chosen extraction agent also suppresses the competing ion-exchange mechanism, thus preventing degradation of the ionic liquid. The approach permits the use of excess extractant to drive the recovery of metals in high yield. This work presents both a thermodynamic framework for understanding the approach and experimental verification of the process in a range of different ILs. The method has great potential value in the recovery of metals, water purification and nuclear materials processing.

Instantaneous normal mode analysis of a series of model molten salts.

A combination of analytical theory and molecular dynamics simulation was previously used to investigate how the dynamics of a fused salt are affected by the distributions of mass and charge in its component ions. These studies are now extended by using instantaneous normal mode analysis to explore how changes in ionic structure affect translational and rotational dynamics at different frequencies. The results indicate that the details of the charge distribution are important in coupling translational and rotational motion in ionic liquids. The observations are broadly consistent with the predictions of the charge lever moment formalism, and provide insight on the nature of dynamics in fused salts.

Electrostatic interactions in ionic liquids: the dangers of dipole and dielectric descriptions.

Ionic liquids have attracted a great deal of attention as media for chemical processes, but many fundamental questions about their behavior remain unanswered. Their electrostatic character remains particularly mysterious, and a number of theoretical studies have attempted to address it using various models. These models often make use of a dipolar description of the charge distribution of an ion, or the dielectric continuum model for the medium. In this work, we review these approaches and show that their application to ionic liquids is questionable on fundamental physical grounds. While not formally incorrect, the descriptions are prone to certain conceptual or numerical errors when applied to molecular ionic systems. We highlight these problems, and discuss some alternative approaches currently in the literature.

A molecular dynamics study of the influence of ionic charge distribution on the dynamics of a molten salt.

The distribution of charge in an ion of a fused salt is known to be an important determinant of liquid dynamics. However, the details of this relationship remain poorly understood. We present the results of molecular dynamics simulations on a model molten salt system and show that changes in the distribution of ionic charge can have a profound effect on liquid dynamics. In particular, we observe complex relationships between the distribution of charge, the rate of ionic rotation, and the translational diffusion of ions in the liquid.

The relationship between ionic structure and viscosity in room-temperature ionic liquids.

We investigate the relationship between ionic structure and viscosity in room-temperature ionic liquids. We build on an earlier theoretical work and derive an ionic property we call the charge lever moment (CLM) that provides insight on ionic liquid dynamics. We use electronic structure calculations to determine the CLM for ions in typical ionic liquids and demonstrate a correlation between this property and the experimental viscosities of ionic liquids. The relationship provides insight into the role of librational motion in ionic liquids in general, and the interpretation of Kerr effect experiments is discussed.

A comparative study of solvation dynamics in room-temperature ionic liquids.

The solvation dynamics of ionic liquids have been the subject of many experimental and theoretical studies but remain poorly understood. We analyze these dynamics by modeling the time-resolved fluorescence response of coumarin 153 in two room-temperature ionic liquids: 1-butyl-1-methylpyrrolidinium bromide and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. Our results demonstrate that phenomena such as electrostatic screening operate significantly differently in the two liquids, and the relative importance of translational and rovibrational components of the ionic response depends significantly on the character of the ions involved. However, collective motion dominates the response of both ionic liquids, and the qualitative features of this collective behavior are strikingly similar in both cases.

Electrostatic interactions of a neutral dipolar solute with a fused salt: a new model for solvation in ionic liquids.

Ionic liquids represent a novel and poorly understood class of solvents, and one challenge in understanding these systems is how one should view the electrostatic character of solute-solvent interactions. The highly structured nature of a fused salt makes a dielectric continuum approximation difficult to implement, and there is no obvious connection between the structure of an individual ion and the polarization character of the medium. We address this problem by making the ansatz that rather than polarizing the medium, the solute may be viewed as intercalating in the charge distribution of the neat liquid such that the solvent screens the electric field of the solute. This approach allows derivation of an analytical expression for the distribution of solvent charge about the solute, and this distribution is found to be a close match to simulation data. The theory also predicts that the electrostatic character of solute-solvent interactions should be determined primarily by the number density of solvent ions, a prediction proven correct by analysis of existing experimental data. The approach represents a new model for the interpretation of solvation phenomena in ionic liquids.

Characterization of the solvation dynamics of an ionic liquid via molecular dynamics simulation.

The solvation dynamics of ionic liquids have been the subject of intense experimental study but remain poorly understood. We present the results of molecular dynamics simulations of the solvation dynamics of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate in response to photoexcitation of the fluorescent dye coumarin-153. We reproduce the time-resolved fluorescence Stokes shift using linear response theory, then use novel statistical techniques to analyze cation and anion contributions to the signal. We find that the solvation dynamics are dominated by collective ionic motion and characterize the time scale for various features of the collective response. Further, we use the Steele analysis [Mol. Phys. 61, 1031 (1987)] to characterize the contributions to the observed Stokes shift made by translational and rovibrational degrees of freedom. Our results indicate that in contrast to molecular liquids, the rovibrational response is trivial and the observed fluorescence response arises almost entirely from ionic translation. Our results resolve previously open questions in the literature about the nature of the rapid dynamics in room-temperature ionic liquids and offer insight into the physical principles governing ionic liquid behavior on longer time scales.

Systematic and statistical error in histogram-based free energy calculations.

A common technique for the numerical calculation of free energies involves estimation of the probability density along a given coordinate from a set of configurations generated via simulation. The process requires discretization of one or more reaction coordinates to generate a histogram from which the continuous probability density is inferred. We show that the finite size of the intervals used to construct the histogram leads to quantifiable systematic error. The width of these intervals also determines the statistical error in the free energy, and the choice of the appropriate interval is therefore driven by the need to balance the two sources of error. We present a method for the construction of the optimal histogram for a given system, and show that the use of this technique requires little additional computational expense. We demonstrate the efficacy of the technique for a model system, and discuss how the principles governing the choice of discretization interval could be used to improve extended sampling techniques.