Ternary Solutions Research Articles

An insight into the thermodynamic investigation of important metabolite(KCl)-methyl nicotinate in aqueous solution at various temperatures

We report in this communication, the data on density and speed of sound measurements for methyl nicotinate in aqueous and in 0.1 mol.kg−1 aqueous potassium chloride solutions and potassium chloride (KCl) in water and in mixture containing fixed concentration (0.1 mol.kg−1) of Methyl nicotinate (MN) solution and varying the concentration (0.01 mol.kg−1 to 0.16 mol.kg−1) at 288.15, 293.15, 298.15, 303.15, 308.15, 313.15 and 318.15 K and atmospheric pressure. The density data are used to measure apparent molar volume of solute at finite concentrations(Vϕ) and apparent molar volume of solute at infinitely dilute solutions (Vϕ0) in binary and ternary mixtures. The speed of sound data are used to measure isentropic compressibility (κS), apparent molar isentropic compressibility of solute at finite concentrations (KS,ϕ) and apparent molar compressibility of solute at infinitely dilute solutions (KS,ϕ0) for binary and ternary mixtures . The coefficient of thermal expansion (α), apparent molar expansivity of solute (Eϕ) and limiting apparent molar expansivity (Eϕ0) of solute for binary and ternary solutions at 293.15, 298.15, 303.15, 308.15 and 313.15 K have also been measured. These parameters are being used to assist in the exploration of feasible intermolecular interactions in studied binary and ternary mixtures. The structure making/breaking ability of solute in binary and ternary solutions were also examined using Hepler's constant. All these results are analyzed and discussed on the basis of solute–solute and solute–solvent interactions.

Evaluation of the activity coefficients of ternary molecular solutions from osmotic coefficient data

A method is proposed for the evaluation of the activity coefficients of a solution constituted by a solvent (1) and two non-volatile molecular solutes (2,3) from the experimental dependence of the osmotic coefficient of the ternary solution (1,2,3) on composition. A generalized analytical expression is derived to describe such dependence, based on the sum of the weighted contributions of both binary systems and the contribution due to the mixing effect. With the resulting expression and using the solution of the Gibbs-Duhem differential equation for ternary systems, the equations that allows the evaluation of the corresponding experimental activity coefficients of both solutes in ideal dilute solution reference state (molality scale) are derived. From the comparative analysis and discussion of the results obtained for three ternary systems, it was possible to verify that the proposed methodology provides a rigorous alternative to evaluate suitable values ​​of activity coefficients from experimental data of osmotic coefficients. Finally, in order to facilitate the correlation of these values with equations originated in molecular solution modelling (NRTL, UNIQUAC, etc.), the relationships between the corresponding reference states and concentration scales were established.

Long-wavelength optical properties of the Ca0.33Sr0.33Ba0.33F2 solid solution single crystals

The optical characteristics of Ca0.33Sr0.33Ba0.33F2 (CSBF) single crystal of a ternary solid solution of calcium, strontium and barium fluorides were studied in order to create disordered optical media. Characteristics of the single crystals of individual fluorides CaF2, SrF2, BaF2 and binary solid solutions Ca0.6Sr0.4F2 and Ba0.67Sr0.33F2 were obtained. Broadband reflection and transmission spectra of the said crystals were recorded in the frequency range of 3–5000 cm−1, and the values of the complex refractive indexes and dielectric constants were calculated. The generalized four parameter model were used for calculation of absorption band parameters. For the CSBF crystal, a significant broadening of the band was observed in the absorption region at optical phonon modes along with an increased absorption in the region below the optical phonon frequencies, which is typical for disordered dielectric media.

Strain Engineering of Energy Storage Performance in Relaxor Ferroelectric Thin Film Capacitors

AbstractDielectric energy storage capacitors are receiving a great deal of attention owing to their high energy density and fast charging–discharging speed. The current energy storage density of dielectrics is relatively low and cannot meet the requirements of miniaturization of pulsed power equipment. Therefore, increasing the energy storage density of dielectrics has become a research hotspot. Herein, using phase‐field simulations to design polymorphic nanodomains, the strain engineering of energy storage performance of binary and ternary solid solution relaxor ferroelectric films is investigated. The results show that the energy storage performance of the ternary film is better than that of the binary film due to the polymorphic nanodomains. In addition, as the film in‐plane strain is modified from −2% to 2%, the energy density is improved by 80%, and the efficiency also increases from 52% to 77%. This work proves the remarkable energy storage performance of polymorphic films and provides a theoretical basis to optimize the energy‐storage performance of ferroelectric thin‐film capacitors by adjusting the misfit strain.

The simulation of a green room-temperature ternary solution of water, methanol and 1-ethyl-3-methyl imidazolium chloride by all-atom Monte Carlo and DFT computational approaches

A highly dense ternary solution of water, methanol and 1-ethyl-3-methyl imidazolium chloride [emim][Cl] was investigated by a Monte Carlo (MC) program written in C language, Density Functional Theory (DFT) and Atoms-In-Molecules (AIM) theory. The all-atom approach in MC calculations of a ternary solution, the use of nonzero LJ parameters for all hydrogen atoms in simulation box and the creation of a new strategy for filling simulation box with many molecules were adopted in this research to yield a comprehensive, accurate and different work. The radial distribution function, the molar heat capacities in constant volume and pressure, the thermal expansivity, and the isothermal compressibility of the ternary system were calculated. The chemical potentials were calculated at different temperatures through Widom insertion method and the behaviors of both ideal and excess parts of chemical potentials were analyzed versus temperature. The value of electric permittivity of solution, the change of number of methanol and water molecules and the replacement of chloride anion with iodide in ionic liquid were also explored through separate simulations. The solvation structure and coordination number were investigated for various systems. The optimized sites for water and methanol around [emim]+ recognized by DFT and the HOMO and LUMO isosurfaces were discussed. Also, the hydrogen bonds between components of ternary solution were determined by AIM theory. It was shown that the results of quantum mechanics calculations confirm those of MC simulations.

High Piezoelectric Performance in Pb(Ni1/3Nb2/3)O3-Pb(Sc1/2Nb1/2)O3-PbTiO3 Ternary System Featuring Small Structural Distortion and Heterogeneous Domain Configuration.

Ternary/polynary perovskite solid solutions based on binary systems are well-known for their high piezoelectric performance. In this work, a series of Pb(Ni1/3Nb2/3)O3-Pb(Sc1/2Nb1/2)O3-PbTiO3 compositions with the particularly high piezoelectric coefficient of d33* > 1000 pm/V and d33 > 700 pC/N have been developed. The optimal performance was achieved in the 0.52PNN-0.14PSN-0.34PT composition (d33* = 1120 pm/V, d33 = 804 pC/N, and Tm = 109 °C). The high piezoelectric performance of this system is reported and is superior to those of most lead-based ternary/polynary ceramics. By a combination of in situ high-energy synchrotron diffraction with transmission electron microscopy (TEM), the origin of the high piezoelectric response has been unambiguously revealed. Upon application of an external electric field, synchrotron diffraction profiles show no splitting but prominent shifting, indicating that the large intrinsic lattice strain arising from the reduced crystal anisotropy and facilitated polarization variation is associated with the high piezoelectric response. Furthermore, microscopic studies by TEM highlight a heterogeneous ferroelectric domain configuration generated by a small local structural distortion, which is also beneficial for the high piezoelectric performance in the proposed ternary piezoelectric systems. The design process of ternary perovskite solid solutions with a wide morphotropic phase boundary region and small structural distortion may be enlightening for the exploration of other high-performance polynary piezoelectrics.

Additive-assisted preferential crystallization of racemic component: A case of norvaline

Herein, we report a successful resolution of L-norvaline, a racemic compound system, performed near the eutectic composition by coupling preferential crystallization with tailor-made additives. The structures of enantiomer and racemate were characterized by PXRD, DSC, and the enantiomeric purity were measured by Chiral HPLC. The preferential crystallization process was designed and established from binary melting phase diagram and ternary solution phase diagram. The effects of supersaturation, solution enantiomer composition, and seed quantity on the preferential crystallization process were investigated. However, the significant improvements of enantiomeric purity and product yield were demonstrated by additive-assisted preferential crystallization approach using tailor-made additives. These additives bearing similar structure motifs to norvaline a highly selective binding to the racemate rather than enantiomer and remarkably suppress nucleation of DL-norvaline, the key factor determining the resultant enantiomer purity and separation efficiency. The underly inhibition principle was revealed due to the centrosymmetric packing of the racemate while the polarity of enantiomer leads to only partial or slight crystallization suppression. The interesting inhibition mode by tailor-made additives is also believed to be applicable for other racemic crystallization systems. Our established additive-assisted preferential crystallization has showed great potential in the development of separation technology and resolution of enantiomer from racemic compounds.

Experimental study of the mass transfer behavior of carbon dioxide absorption into ternary phase change solution in a packed tower

Phase change absorbents for CO 2 are of great interest because they are expected to greatly reduce the heat energy consumption during the regeneration process. Compared with other phase change absorbents, monoethanolamine (MEA)-sulfolane-water is inexpensive and has a fast absorption rate. It is one of the most promising solvents for large-scale industrial applications. Therefore, this study investigates the mass transfer performance of this phase change system in the process of CO 2 absorption in a packed tower. By comparing the phase change absorbent and the ordinary absorbent, it is concluded that the use of MEA/sulfolane phase change absorbent has significantly improved mass transfer efficiency compared to a single MEA absorbent at the same concentration. In the 4 mol⋅L −1 MEA/5 mol⋅L −1 sulfolane system, the CO 2 loading of the upper liquid phase after phase separation is almost zero, while the volume of the lower liquid phase sent to the desorption operation is about half of the total volume of the absorbent, which greatly reduces the energy consumption. This study also investigates the influence of operating parameters such as lean CO 2 loading, gas and liquid flow rates, CO 2 partial pressure, and temperature on the volumetric mass transfer coefficient ( K G a V ). The research shows that K G a V increases with increasing liquid flow rate and decreases with the increase of lean CO 2 loading and CO 2 partial pressure, while the inert gas flow rate and temperature have little effect on K G a V . In addition, based on the principle of phase change absorption, a predictive equation for the K G a V of MEA-sulfolane in the packed tower was established. The K G a V obtained from the experiment is consistent with the model prediction, and the absolute average deviation (AAD) is 7.8%.

Microfluidic behavior of ternary mixed solutions of water/acetonitrile/ethyl acetate through experiments and computer simulations.

When ternary mixed solutions of water/acetonitrile/ethyl acetate are delivered into a microspace under laminar flow conditions, the solvent molecules show specific microfluidic flows, such as microfluidic inverted flow and tube radial distribution flow, which have been applied to novel analytical methods. In this paper, inverted flow was examined using various Y-type microchannels that had mixing angles of 0°, 90°, 180°, and 270°. Inverted flow was experimentally observed and the trigger phenomenon was also successfully expressed through computer simulations. Tube radial distribution flow, that is, annular flow, in a capillary tube is reported to cause exchange of the inner and outer phases based on the solvent composition of the ternary mixed solution. Tube radial distribution flow for an organic solvent-rich inner and a water-rich outer phases, as well as for a water-rich inner and an organic solvent-rich outer phases, could be well recreated by computer simulations for a ternary mixed solution. This highlights the effectiveness of computer simulations for such flow scenarios and will allow optimization of the operating conditions and design of microfluidic analytical devices.

Phase evolution, dielectric, ferroelectric, and piezoelectric properties of Bi(Mg0.5Hf0.5)O3–modified BiFeO3–BaTiO3

Bi(Mg0.5Hf0.5)O3–modified BiFeO3–BaTiO3 ternary solid solutions of (0.725-x)BiFeO3-0.275BaTiO3-xBi(Mg0.5Hf0.5)O3 (0 <x ≤ 0.05, abbreviated as BFO-BTO-xBMHO) were prepared for lead-free piezoelectrics. The addition of BMHO delivers a rhombohedral (R3c, denoted as R-phase) to tetragonal (P4mm, denoted as T-phase) phase transition at x = 0.05, giving the coexistence of R- and T-phase in intermediate compositions: R-phase dominated in x = 0.01–0.02 and T-phase dominated in x = 0.03–0.04. The increment of BMHO tunes the grain size, lowers the ferroelectric transition temperature (TC) and dielectric loss (tanδ), and drives a gradually ferroelectric to relaxor transition. The morphotropic phase boundary between the R-and T-phases, together with the homogeneous morphology, results in the best performance for x = 0.04 case with piezoelectric d33 of 130 pC/N, Kp of 0.286, Qm of 58.993, electrostrain Smax of 0.18%, and TC of 428 °C, showing potential applications for lead-free piezoelectric ceramics at considerably high temperature.

Management of Energy Conversion Processes in Membrane Systems

The internal energy (U-energy) conversion to free energy (F-energy) and energy dissipation (S-energy) is a basic process that enables the continuity of life on Earth. Here, we present a novel method of evaluating F-energy in a membrane system containing ternary solutions of non-electrolytes based on the Kr version of the Kedem–Katchalsky–Peusner (K–K–P) formalism for concentration polarization conditions. The use of this formalism allows the determination of F-energy based on the production of S-energy and coefficient of the energy conversion efficiency. The K–K–P formalism requires the calculation of the Peusner coefficients Kijr and Kdetr (i, j ∈ {1, 2, 3}, r = A, B), which are necessary to calculate S-energy, the degree of coupling and coefficients of energy conversion efficiency. In turn, the equations for S-energy and coefficients of energy conversion efficiency are used in the F-energy calculations. The Kr form of the Kedem–Katchalsky–Peusner model equations, containing the Peusner coefficients Kijr and Kdetr, enables the analysis of energy conversion in membrane systems and is a useful tool for studying the transport properties of membranes. We showed that osmotic pressure dependences of indicated Peusner coefficients, energy conversion efficiency coefficient, entropy and energy production are nonlinear. These nonlinearities were caused by pseudophase transitions from non-convective to convective states or vice versa. The method presented in the paper can be used to assess F-energy resources. The results can be adapted to various membrane systems used in chemical engineering, environmental engineering or medical applications. It can be used in designing new technologies as a part of process management.

Photoluminescence Spectroscopy of the InAsSb-Based p-i-n Heterostructure.

Photoluminescence in a double heterostructure based on a ternary InAsSb solid solution was observed in the mid-infrared range of 2.5–4 μm. A range of compositions of the InAs1−ySby ternary solid solution has been established, where the energy resonance between the band gap and the splitting-off band in the valence band of the semiconductor can be achieved. Due to the impact of nonradiative Auger recombination processes, different temperature dependence of photoluminescence intensity was found for the barrier layer and the narrow-gap active region, respectively. It was shown that efficient high-temperature photoluminescence can be achieved by suppressing the nonradiative Auger recombination (CHHS) process. Increased temperature, for which the energy gap is lower than the split-off band energy, leads to violation of the resonance condition in narrow gap antimonide compounds, which explains the observed phenomenon. This finding might influence future application of the investigated material systems in mid-infrared emitters used for, e.g., optical gas sensing.

Molecular Dynamics Insight into the Role of Water Molecules in Ionic Liquid Mixtures of 1-Butyl-3-methylimidazolium Iodide and Ethylammonium Nitrate.

Imidazolium-based ionic liquids are well known for their versatility as solvents for various applications such as dye-sensitized solar cells, fuel cells, and lithium-ion batteries; however, their complex interactions continue to be investigated to further improve upon their design. Ionic liquids (ILs) are commonly mixed with co-solvents such as water, organic solvents, or other ionic liquids to tailor their physiochemical properties. To better predict these properties and fundamentally understand the molecular interactions within the electrolyte mixtures, molecular dynamics (MD) simulations are often employed. In this study, MD simulations are performed on ternary solutions containing ionic liquids of 1-butyl-3-methylimidazolium iodide ([BMIM][I]) and ethylammonium nitrate ([EA][NO3]) with increasing concentration of water. As previously reported, these ternary solutions displayed a wide temperature window of thermal stability and electrochemical conductivity. Utilizing MD simulations, the complex intermolecular interactions are identified, and the role of water as a co-solvent is disclosed to correlate with changes in their bulk properties. The MD results, including simulation box snapshots, radial distribution functions, and self-diffusion coefficients, reveal the formation of heterogeneous regimes with increasing water concentration, hydrogen bonding between iodide-water, iodide-[EA]+, and a change in IL ordering when in mixtures containing water. The simulations also display the formation of water aggregates and networks at high water concentrations, which can contribute to the thermal behavior of the respective mixtures. As the design of IL-based electrolytes grows in demand with increasing complexity, this work demonstrates the capability of MD simulations containing multiple constituents and their necessity in material development through identification of microscopic structure-property relationships.

Intermixed Time-Dependent Self-Focusing and Defocusing Nonlinearities in Polymer Solutions.

Low-power visible light can lead to spectacular nonlinear effects in soft-matter systems. The propagation of visible light through transparent solutions of certain polymers can experience either self-focusing or defocusing nonlinearity, depending on the solvent. We show how the self-focusing and defocusing responses can be captured by a nonlinear propagation model using local spatial and time-integrating responses. We realize a remarkable pattern formation in ternary solutions and model it assuming a linear combination of the self-focusing and defocusing nonlinearities in the constituent solvents. This versatile response of solutions to light irradiation may introduce a new approach for self-written waveguides and patterns.

Cross-modal effect of capsaicin and pepper oleoresin on the enhancement of saltiness perception in a NaCl model solution

Reducing sodium scientifically and effectively without affecting the flavor and safety of food remains a challenge for food researchers. A few previous reports have shown that single capsaicin (C) and pepper oleoresin (P) modulate the saltiness perception and sodium reduction, respectively. However, there is a lack of research on whether combining the C + P has an interaction effect on saltiness enhancement. The cross-modal and interactive effect of C and P on the saltiness perception and NaCl reduction in a NaCl model solution at different concentrations (0.98 g/L ∼ 19.88 g/L) using the general labeled magnitude scale (gLMS) were investigated in this study. Results showed that single C or P had a significant saltiness enhancement effect at the low-to-medium NaCl concentration (0.98 g/L ∼ 4.44 g/L) solution. Importantly, it was confirmed for the first time that interactions of C and P can increase saltiness in a ternary water solution system with NaCl, C, and P significantly. And the combination of C and P enhanced the saltiness significantly at the moderate-to-high NaCl concentrations, and the maximum percentages of saltiness intensity enhancement and NaCl reduction reached 37.65% and 26.09%, respectively. This research not only provided valuable data regarding the modulating effect of the “má là” flavor on saltiness perception but also offer novel insights and a promising approach regarding sodium reduction strategies during the development of low-sodium food.

Density of solutions of formaldehyde in water and alcohols

AbstractFormaldehyde is an important chemical that is mostly handled in aqueous solutions, which generally also contain methanol; furthermore, also solutions of formaldehyde in other alcohols are used. The density of these solutions is an important thermophysical property. The available models of the density of formaldehyde‐containing solutions, however, all have shortcomings, such as a poor accuracy or a limited range of applicability. Therefore, in the present work, a new model of the density in systems of the type (formaldehyde + water + alcohol) was developed. The alcohols that are presently included in the new model are methanol, 1‐propanol, and isoprenol; an extension to other alcohols is straightforward. The model was developed using literature data and extensive new density data measured in this work covering binary, ternary, and quarternary solutions of formaldehyde in water, methanol, 1‐propanol, and isoprenol at temperatures of K and formaldehyde concentrations of 0.06 − 0.30 g g−1.

SANS Study of PPPO in Mixed Solvents and Impact on Polymer Nanoprecipitation.

We investigate the conformation of poly(2,6-diphenyl-p-phenylene oxide) (PPPO) in good and mixed solvents by small-angle neutron scattering (SANS) across its ternary phase diagram. Dichloromethane was selected as a “good” solvent and heptane as a “poor” solvent whose addition eventually induces demixing and polymer precipitation. Below the overlap concentration c*, the polymer conformation is found to be well described by the polymer-excluded volume model and above by the Ornstein–Zernike expression with a correlation length ξ which depends on the concentration and solvent/nonsolvent ratio. We quantify the decrease in polymer radius of gyration Rg, increase in ξ, and effective χ parameter approaching the phase boundary. Upon flash nanoprecipitation, the characteristic particle radius (estimated by scanning electron microscopy, SEM) is found to scale with polymer concentration as well as with nonsolvent content. Significantly, the solution volume per precipitated particle remains nearly constant at all polymer concentrations. Overall, our findings correlate ternary solution structure with the fabrication of polymer nanoparticles by nonsolvent-induced phase separation and precipitation.

Low-Temperature Hydrophilic Pervaporation of Lactic Acid Esterification Reaction Media.

Esterification reactions show a limited conversion due to the presence of water, which favors the opposite reaction. The removal of water from the reaction mixture increases the production of the ester. Pervaporation is an effective dehydration technique, usually applied to binary mixtures. The effect on pervaporation of a reactive multicomponent system involving water, ethanol, ethyl lactate and lactic acid with high acid concentration (13.5 wt. %) at relatively low temperatures (40–80 °C) was studied. Three hydrophilic membranes mainly fabricated for dehydration purposes from Sulzer Chemtech were used, i.e., PERVAP™ 3100, PERVAP™ 2216 and PERVAP™ 1131. The last one revealed as the most suitable for the application and it was further characterized with binary and ternary solutions. The membrane showed high affinity for the lactic acid. The acid permeation played a key role in the water/ethanol and water/ethyl lactate selectivity. Lactic acid permeates and crystalizes in the permeate side of the membrane at very low water concentration (below 2 wt. %), causing a drop in flux and membrane selectivity. Ethyl lactate is responsible of the loss of integrity of the membranes.

A Multilevel Analytical Theory for Prediction of Ferroelectric Perovskite Oxide Properties from Composition.

Prediction of properties from composition is a fundamental goal of materials science that is particularly relevant for ferroelectric perovskite oxide solid solutions where compositional variation is a primary tool for material design. Design of ferroelectric oxide solid solutions has been guided by heuristics and first-principles and Landau-Ginzburg-Devonshire theoretical methods that become increasingly difficult to apply in ternary, quaternary, and quintary solid solutions. To address this problem, a multilevel model is developed for the prediction of the ferroelectric-to-paraelectric transition temperature (Tc ), coercive field (Ec ), and polarization (P) of PbTiO3 -derived ferroelectric solid solutions from composition. The characteristics of the materials at different length scales, starting at the level of the electronic structure and chemical bonding of the constituent ions and ending at the level of collective behavior, are analytically related by using ferroelectric domain walls and cationic off-center displacements as the key links between the different levels of the model. The obtained composition-structure-property relationships provide a unified quantitatively predictive theory for understanding PbTiO3 -derived solid solutions. Such a multilevel analytical modeling approach is likely to be generally applicable to different classes of ferroelectric perovskite oxides and to other functional properties, and to materials and properties beyond the field of ferroelectrics.

Analysing the molecular interactions of ternary (lactose + water + tributylmethylammonium chloride) solutions at different temperatures via physicochemical methods

The interactions of lactose with tributylmethylammonium chloride (Bu3MeNCl) as the function of temperature have been studied by amalgamation of volumetric, acoustic and viscometric methods. Density, ultrasonic speed, and viscosity for varying concentrations of lactose in water and in (0.020, 0.039, 0.059, 0.079) mol.kg−1 aqueous solutions of Bu3MeNCl have been determined at five distinct temperatures (T = 293.15–313.15) K. These experimental values have been used to calculate apparent molar volume, Vϕ, limiting apparent molar volume, V0ϕ, apparent molar isentropic compression, Kϕ,s, limiting apparent molar isentropic compression, K0ϕ,s, viscosity B-coefficient, their transfer values, pair and triplet interaction coefficients, and hydration number nH. The Gibbs free energy of activation for solvent (Δµ01#) and Gibbs free energy of activation for lactose (Δµ02#) in water and in aqueous solutions of Bu3MeNCl have also been assessed and the obtained results support the outcome of volumetric, acoustic and viscometric parameters. These parameters provide better understanding of molecular interactions like solute-solute, solute-solvent interactions present in the systems. Further, it helps in determining structural and functional properties of studied systems and acquired results revealed that the solutions are characterized predominantly by solute-solvent interactions. Also, the values of second derivative of limiting apparent molar volume with respect to temperature indicated that the lactose monohydrate behaves as a structure maker in aqueous tributylmethylammonium chloride solutions.