Brønsted acids in ionic liquids: How acidity depends on the liquid structure

Gutmann Acceptor Number (AN) values have been determined for Brønsted acid–ionic liquid mixtures, over a wide compositional range. Four systems of general formula [C2mim][A]–HA (A− = bistriflamide, [NTf2]−; triflate, [OTf]−; mesylate, [OMs]−; or acetate, [OAc]−, [C2mim]+ = 1-ethyl-3-methylimidazolium cation) were studied. A library of Brønsted acidic systems of varying acidity was constructed and the AN parameter was found to be a convenient approach for quantifying their acidity. HOAc, HOMs and HOTf, when dissolved in ionic liquids, were found to associate with the respective anions to form hydrogen-bonded anionic clusters, [A(HA)x]−. In contrast, HNTf2 was solubilised as a discrete, undissociated molecule. AN values were sensitive to the presence of anionic clusters; acidity could be buffered to a particular AN by binding the solubilised acid in the anionic cluster form. Overall, a simple way to manipulate and quantify the Brønsted acidity of acid–ionic liquid mixtures was demonstrated, and measured AN values were related to liquid speciation.

Enhancing Liquid-Phase Olefin-Paraffin Separations Using Novel Silver-Based Ionic Liquids

This paper describes the extraction of C5-C8 linear α-olefins from olefin/paraffin mixtures of the same carbon number using silver(I)/N,N-dimethylbenzamide bis(trifluoromethylsulfonyl)imide ([Ag(DMBA)₂][Tf₂N]) or silver(I)/propylamine bis(trifluoromethylsulfonyl)imide ([Ag(PrNH₂)₂][Tf₂N]) as the extracting agent. The separation performance of the system increased with increasing chain length. [Ag(DMBA)₂][Tf₂N] appeared to outperform [Ag(PrNH₂)₂][Tf₂N] in terms of both selectivity and distribution coefficient. The [Ag(DMBA)₂][Tf₂N] system was successfully modeled using the universal quasi-chemical activity coefficient (UNIQUAC) model. These results support the potential future development of amine/amide-based ligands for producing soluble silver complexes useful for the separation of olefins from paraffins.

Deep separation of benzene from cyclohexane by liquid extraction using ionic liquids as the solvent

Separation of benzene and cyclohexane is one of the most important and difficult processes in the petrochemical industry, especially for low benzene concentration. In this work, three ionic liquids (ILs), [Bmim][BF ₄], [Bpy][BF ₄], and [Bmim][SCN], were investigated as the solvent in the extraction of benzene from cyclohexane. The corresponding ternary liquid-liquid equilibria (LLE) were experimentally determined at T = 298.15 K and atmospheric pressure. The LLE data were correlated with the nonrandom two-liquid model, and the parameters were fitted. The separation capabilities of the ILs were evaluated in terms of the benzene distribution coefficient and solvent selectivity. The effect of the IL structure on the separation was explained based on a well-founded physical model, COSMO-RS. Finally, the extraction processes were defined, and the operation parameters were analyzed. It shows that the ILs studied are suitable solvents for the extractive separation of benzene and cyclohexane, and their separation efficiency can be generally ranked as [Bmim][BF ₄] > [Bpy][BF ₄] > [Bmim][SCN]. The extraction process for a feed with 15 mol % benzene was optimized. High product purity (cyclohexane 0.997) and high recovery efficiency (cyclohexane 96.9% and benzene 98.1%) can be reached. © 2012 American Chemical Society.

Determination of sorbate and benzoate in beverage samples by capillary electrophoresis - Optimization of the method with inspection of ionic mobilities

The aim of this study was to develop a fast capillary electrophoresis method for the determination of benzoate and sorbate ions in commercial beverages. In the method development the pH and constituents of the background electrolyte were selected using the effective mobility versus pH curves. As the high resolution obtained experimentally for sorbate and benzoate in the studies presented in the literature is not in agreement with that expected from the ionic mobility values published, a procedure to determine these values was carried out. The salicylate ion was used as the internal standard. The background electrolyte was composed of 25 mmol L(-1) tris(hydroxymethyl)aminomethane and 12.5 mmol L(-1) 2-hydroxyisobutyric acid, atpH 8.1.Separation was conducted in a fused-silica capillary(32 cm total length and 8.5 cm effective length, 50 mu m I.D.), with short-end injection configuration and direct UV detection at 200 nm for benzoate and salicylate and 254 nm for sorbate ions. The run time was only 28 s. A few figures of merit of the proposed method include: good linearity (R(2) > 0.999), limit of detection of 0.9 and 0.3 mg L(-1) for benzoate and sorbate, respectively, inter-day precision better than 2.7% (n =9) and recovery in the range 97.9-105%. Beverage samples were prepared by simple dilution with deionized water (1:11, v/v). Concentrations in the range of 197-401 mg L(-1) for benzoate and 28-144 mg L(-1) for sorbate were found in soft drinks and tea. (c) 2008 Elsevier B.V. All rights reserved.

Structural characterization and in vivo evaluation of retinyl palmitate in non-ionic lamellar liquid crystalline system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Agar-Based Gel Electrolyte for Electrochromic Device Application

Gel Polymer Electrolytes (GPE) based on agar and containing LiClO4 have been prepared, characterized and applied to electrochromic devices. The ionic conductivity revealed the best result of 6.5 x 10(-5) S/cm for the sample with 17 wt.% of LiClO4, which increased to 5.4 x 10(-4) S/cm at 72 degrees C. TheGPE have been used in electrochromic devices (ECD) with K-glass/WO3/GPE/CeO2-TiO2/K-glass configuration. The ECD changed transmittance values up to 30% between the colored and transparent states. The charge density measurements revealed an increase of 5.5 to 7.5 mC/cm(2) from the first to 500th cycles and then a decrease to 4.4 mC/cm(2) during the next 4500 cycles. Coloration efficiency (eta) of 25 cm(2)/C was obtained.

Sodium Alginate-Based Ionic Conducting Membranes

The present study investigates gel polymer electrolytes (GPEs) based on sodium alginate plasticized with glycerol containing either CH3COOH or LiClO4. The membranes showed ionic conductivity results of 3.1 x 10(-4) S/cm for the samples with LiClO4 and 8.7x10(-5) S/cm for the samples with CH3COOH at room temperature. The samples also showed thermal stability up to 160 degrees C, transparency of up to 90%, surface uniformity and adhesion to glass and steel. Moreover, Dynamic Mechanical Analysis revealed two relaxations for both samples and the Ea values were between 18 and 36 kJ/mol. All the results obtained indicate that alginate-based GPEs can be used as electrolytes in electrochemical devices.

Liquid-liquid equilibria in binary solutions formed by [Pyridinium-Derived][F4B] ionic liquids and alkanols:new experimental data and validation of a multiparametric model for correlating LLE data

[EN]Experimental solubility data are presented for a set of binary systems composed of ionic liquids (IL) derived from pyridium, with the tetrafluoroborate anion, and normal alcohols ranging from ethanol to decanol, in the temperature interval of 275 420 K, at atmospheric pressure. For each case, the miscibility curve and the upper critical solubility temperature (UCST) values are presented. The effects of the ILs on the behavior of solutions with alkanols are analyzed, paying special attention to the pyridine derivatives, and considering a series of structural characteristics of the compounds involved.

Binary liquid-liquid equilibria for systems of mono or disubstituted haloakanes (Cl,Br) and pyiridinium based ionic liquids. Advances in the experimentation and interpretation of results

[EN]This work presents the measurements made to define the temperature−composition curves for a set of binary systems composed of several pyridinium-based ionic liquids (ILs) [bpy][BF4] and [bYmpy][BF4] (Y = 2,3,4) with mono- and dihaloalkanes (Cl and Br) in the temperature interval [280−473] K and at atmospheric pressure. With the exception of the short chain dichloroalkanes (1,1- and 1,2-), all the compounds present some degree of immiscibility with the ionic liquids selected.

Real and imaginary parts of the vibrational relaxation of acetonitrile in its electrolyte solutions:new results for the dynamics of solvent molecules

Isotropic scattering Raman spectra of liquid acetonitrile (AN) solutions of LiBF4 and NaI at various temperatures and concentrations have been investigated. For the first time imaginary as well as real parts of the solvent vibrational correlation functions have been extracted from the spectra. Such imaginary parts are currently an important component of modern theories of vibrational relaxation in liquids. This investigation thus provides the first experimental data on imaginary parts of a correlation function in AN solutions. Using the fitting algorithm we recently developed, statistically confident models for the Raman spectra were deduced. The parameters of the band shapes, with an additional correction, of the ν2 AN vibration (CN stretching), together with their confidence intervals are also reported for the first time. It is shown that three distinct species, with lifetimes greater than ∼10−13 s, of the AN molecules can be detected in solutions containing Li+ and Na+. These species are attributed to AN molecules directly solvating cations; the single oriented and polarised molecules interleaving the cation and anion of a Solvent Shared Ion Pair (SShIP); and molecules solvating anions. These last are considered to be equivalent to the next layer of solvent molecules, because the CN end of the molecule is distant from the anion and thus less affected by the ionic charge compared with the anion situation. Calculations showed that at the concentrations employed, 1 and 0.3 M, there were essentially no other solvent molecules remaining that could be considered as bulk solvent. Calculations also showed that the internuclear distance in these solutions supported the proposal that the ionic entity dominating in solution was the SShIP, and other evidence was adduced that confirmed the absence of Contact Ion Pairs at these concentrations. The parameters of the shape of the vibrational correlation functions of all three species are reported. The parameters of intramolecular anharmonic coupling between the potential surfaces in AN and the dynamics of the intermolecular environment fluctuations and intermolecular energy transfer are presented. These results will assist investigations made at higher and lower concentrations, when additional species and interactions with AN molecules will be present.

Synthesis and Thermophysical Properties of Ether Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis(trifluoromethyl)sulfonylimide, [NTf2]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.

Comparing charge transport predictions for a ternary electrolyte using the Maxwell–Stefan and Nernst–Planck equations

In this work, we investigate and compare the Maxwell–Stefan and Nernst–Planck equations for modeling multicomponent charge transport in liquid electrolytes. Specifically, we consider charge transport in the Li+/I−/I3−/ACN ternary electrolyte originally found in dye-sensitized solar cells. We employ molecular dynamics simulations to obtain the Maxwell–Stefan diffusivities for this electrolyte. These simulated diffusion coefficients are used in a multicomponent charge transport model based on the Maxwell– Stefan equations, and this is compared to a Nernst–Planck based model which employs binary diffusion coefficients sourced from the literature. We show that significant differences between the electrolyte concentrations at electrode interfaces, as predicted by the Maxwell–Stefan and Nernst–Planck models, can occur. We find that these differences are driven by a pressure term that appears in the Maxwell–Stefan equations. We also investigate what effects the Maxwell–Stefan diffusivities have on the simulated charge transport. By incorporating binary diffusivities found in the literature into the Maxwell–Stefan framework, we show that the simulated transient concentration profiles depend on the diffusivities; however, the simulated equilibrium profiles remain unaffected.

Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Multicomponent charge transport in electrolyte solutions

The work presented in this thesis investigates the mathematical modelling of charge transport in electrolyte solutions, within the nanoporous structures of electrochemical devices. We compare two approaches found in the literature, by developing onedimensional transport models based on the Nernst-Planck and Maxwell-Stefan equations. The development of the Nernst-Planck equations relies on the assumption that the solution is infinitely dilute. However, this is typically not the case for the electrolyte solutions found within electrochemical devices. Furthermore, ionic concentrations much higher than those of the bulk concentrations can be obtained near the electrode/electrolyte interfaces due to the development of an electric double layer. Hence, multicomponent interactions which are neglected by the Nernst-Planck equations may become important. The Maxwell-Stefan equations account for these multicomponent interactions, and thus they should provide a more accurate representation of transport in electrolyte solutions. To allow for the effects of the electric double layer in both the Nernst-Planck and Maxwell-Stefan equations, we do not assume local electroneutrality in the solution. Instead, we model the electrostatic potential as a continuously varying function, by way of Poisson’s equation. Importantly, we show that for a ternary electrolyte solution at high interfacial concentrations, the Maxwell-Stefan equations predict behaviour that is not recovered from the Nernst-Planck equations. The main difficulty in the application of the Maxwell-Stefan equations to charge transport in electrolyte solutions is knowledge of the transport parameters. In this work, we apply molecular dynamics simulations to obtain the required diffusivities, and thus we are able to incorporate microscopic behaviour into a continuum scale model. This is important due to the small size scales we are concerned with, as we are still able to retain the computational efficiency of continuum modelling. This approach provides an avenue by which the microscopic behaviour may ultimately be incorporated into a full device-scale model. The one-dimensional Maxwell-Stefan model is extended to two dimensions, representing an important first step for developing a fully-coupled interfacial charge transport model for electrochemical devices. It allows us to begin investigation into ambipolar diffusion effects, where the motion of the ions in the electrolyte is affected by the transport of electrons in the electrode. As we do not consider modelling in the solid phase in this work, this is simulated by applying a time-varying potential to one interface of our two-dimensional computational domain, thus allowing a flow field to develop in the electrolyte. Our model facilitates the observation of the transport of ions near the electrode/electrolyte interface. For the simulations considered in this work, we show that while there is some motion in the direction parallel to the interface, the interfacial coupling is not sufficient for the ions in solution to be "dragged" along the interface for long distances.

Evidence of clustering in an aqueous electrolyte solution: a small-angle X-ray scattering study

The work reported hen was motivated by a desire to verify the existence of structure - specifically MP-rich clusters induced by sodium bromide (NaBr) in the ternary liquid mixture 3-methylpyridine (Mf) + water(W) + NaBr. We present small-angle X-ray scattering (SAXS) measurements in this mixture. These measurements were obtained at room temperature (similar to 298 K) in the one-phase region (below the relevant lower consolute points, T(L)s) at different values of X (i.e., X = 0.02 - 0.17), where X is the weight fraction of NaBr in the mixture. Cluster-size distribution, estimated on the assumption that the clusters are spherical, shows systematic behaviour in that the peak of the distribution shifts rewards larger values of cluster radius as X increases. The largest spatial extent of the clusters (similar to 4.5 nm) is seen at X = 0.17. Data analysis assuming arbitrary shapes and sizes of clusters gives a limiting value of cluster size (- 4.5 nm) that is not very sensitive to X. It is suggested that the cluster size determined may not be the same as the usual critical-point fluctuations far removed from the critical point (T-L). The influence of the additional length scale due to clustering is discussed from the standpoint of crossover from Ising to mean-field critical behaviour, when moving away from the T-L.