Liquid structure of trihexyltetradecylphosphonium chloride at ambient temperature: an X-ray scattering and simulation study.

We report on an experimental and simulation study done on a representative room temperature ionic liquid, namely tetradecyltrihexylphosphonium chloride, at ambient conditions. The study was conducted using small and wide angle X-ray scattering and molecular dynamics simulations. Both approaches converge in indicating that this material is characterized by the existence of strong P-Cl interactions (with characteristic distances between 3.5 and 5.0 A) and by the occurrence of nanoscale segregation, despite the symmetric nature of the cation and similarly to other room temperature ionic liquids. A good agreement is found between the structure factor and pair correlation functions obtained from MD simulations and the corresponding experimental observables, thus strongly validating the interaction potential used in the simulations.

Transport properties in ionic liquids and ionic liquid mixtures: the challenges of NMR pulsed field gradient diffusion measurements.

Pulsed field gradient NMR is a powerful method for the measurement of diffusion coefficients in liquids and solids and has begun to attract much attention in the ionic liquids field. However, aspects of the methodology as traditionally applied to solutions may not be uniformly applicable in these more viscous and chemically complex systems. In this paper we present data which shows that the Pulsed Gradient Spin Echo (PGSE) method in particular suffers from intrinsic internal gradients and can produce apparent diffusion coefficients which vary by as much as 20% for different 1H nuclei within a given molecule--an obvious anomaly. In contrast, we show that the Pulsed Gradient Stimulated Echo method does not suffer from this problem to the same extent and produces self-consistent data to a high degree of accuracy (better than 1%). This level of significance has allowed the detection, in this work, of subtle mixing effects in [C(3)mpyr][NTf(2)] and [C(4)mpyr][NTf(2)] mixtures.

Broadband dielectric response of the ionic liquid N-methyl-N-ethylpyrrolidinium dicyanamide.

Dielectric relaxation measurements as a function of temperature, and of concentration in a non-coordinating solvent, the first reported for an ionic liquid, indicate a crossover in the relaxation mechanism due to varying levels of ion aggregation and the interplay of formation kinetics and relaxation dynamics of associates.

Ionic liquid mixtures-variations in physical properties and their origins in molecular structure.

In order to explore the various possible property trends in ionic liquid mixtures, five different ionic liquids were mixed with N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([C3mpyr][NTf2]), and the viscosities, excess molar volumes, ionic conductivities, and phase diagrams of the mixtures were determined over a range of temperatures. In a number of the mixtures the crystallization of both components was completely suppressed and no melting point was observable. Such mixtures of similar ionic liquids thus have potential for use in low-temperature applications by extending the liquid range to T(g). The molar conductivities and viscosities are described as approximating predictable or "simple" mixing behaviors, while excess molar volumes were found to show a variety of mixing and nonideal mixing effects. Mixture equations for viscosity and conductivity are discussed and analyzed. An immiscibility window was observed in the trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P(6,6,6,14)][NTf2]) in the [C3mpyr][NTf2] system in the [C3mpyr][NTf2]-rich region. Unusual physical properties are exhibited by miscible compositions near the demixing line. These compositions are described as [P(6,6,6,14)][NTf2]-like, even up to 0.5 mol fraction of [C3mpyr][NTf2].

On the concept of ionicity in ionic liquids.

Ionic liquids are liquids comprised totally of ions. However, not all of the ions present appear to be available to participate in conduction processes, to a degree that is dependent on the nature of the ionic liquid and its structure. There is much interest in quantifying and understanding this 'degree of ionicity' phenomenon. In this paper we present transport data for a range of ionic liquids and evaluate the data firstly in terms of the Walden plot as an approximate and readily accessible approach to estimating ionicity. An adjusted Walden plot that makes explicit allowance for differences in ion sizes is shown to be an improvement to this approach for the series of ionic liquids described. In some cases, where diffusion measurements are possible, it is feasible to directly quantify ionicity via the Nernst-Einstein equation, confirming the validity of the adjusted Walden plot approach. Some of the ionic liquids studied exhibit ionicity values very close to ideal; this is discussed in terms of a model of a highly associated liquid in which the ion correlations have similar impact on both the diffusive and conductive motions. Ionicity, as defined, is thus a useful measure of adherence to the Nernst-Einstein equation, but is not necessarily a measure of ion availability in the chemical sense.

Ionic liquids in electrochemical devices and processes: managing interfacial electrochemistry.

Many ionic liquids offer a range of properties that make them attractive to the field of electrochemistry; indeed it was electrochemical research and applications that ushered in the modern era of interest in ionic liquids. In parallel with this, a variety of electrochemical devices including solar cells, high energy density batteries, fuel cells, and supercapacitors have become of intense interest as part of various proposed solutions to improve sustainability of energy supply in our societies. Much of our work over the last ten years has been motivated by such applications. Here we summarize the role of ionic liquids in these devices and the insights that the research provides for the broader field of interest of these fascinating liquids.