Binary Liquid Research Articles

Preferential Solvation in Binary Liquid Mixtures with Norbornadiene

Norbornadiene has been found useful in organic and polymer synthesis and recently its mixtures have been found useful in solar energy storage. Structure factors S(0) help to identify structure and binding at microscopic level and also play a significant role in understanding and characterizing exchanges in liquid systems. Preferential solvation Parameter δij provides information about deviation from ideal behavior for the solvent. In this work structure factors S(0) and preferential solvation Parameter δij were evaluated of binary Liquid Mixtures of Norbornadiene with Benzene, Cyclohexane, Decane, and Carbon Tetrachloride using Kirkwood Buff formalism. For the said binary mixtures experimental data pertaining to the calculations were taken from literature. Obtained results indicate that molecules which tend to form dipole interactions or hydrogen bonds form favorable interactions as seen in Norbornadiene + carbon tetrachloride where the small molecule of CCl4 is not sterically hindered to approach the polar Norbornadiene molecule. Long chain and ring structure of carbon have a negative influence on hetero interactions. Studying these parameters will develop predictive techniques to determine the right composition for optimum performance of the liquid mixture.

Thermodynamic Study of Properties in Certain Binary Liquid Mixtures Containing Anisole with 2-Butoxyethanol at Different Temperatures (303.15K to 318.15K)

Comprehensive experimental investigations were carried out on density (ρ), viscosity (η), and ultrasonic velocity (u) for binary mixtures comprising Anisole and 2-Butoxyethanol within the temperature range of 303.15K to 318.15K, covering the complete range of mole fractions. These parameters were measured at intervals of 5K. Derived excess parameters, including acoustic impedance (ZE), intermolecular free length (LEf), molar volume (VEm), excess ultrasonic velocity (uE), and excess viscosity (ηE), were calculated to probe the molecular interactions present in the mixture. These excess parameters were correlated with temperature and mole fraction, revealing the complexity and nature of intermolecular interactions. Notably, the Arrhenius, Bingham, Eyring, Grunberg, Kurata, Nissan, and Tamura models were utilized to theoretically validate the acquired empirical data. This study aims to offer invaluable insights into the thermodynamics and molecular dynamics that govern these binary liquid mixtures.

Effect of electric field on the wetting behavior of GaInSnBiZn high-entropy alloy in NaOH aqueous solution

The GaInSnBiZn low-melting-point high-entropy alloy exhibits promising prospects for utilization in the realm of flexible electronic devices, offering a promising alternative to common binary or ternary room-temperature liquid metals. By utilizing the sessile drop method, the wetting behavior of GaInSnBiZn/SiO2 was investigated, focusing on the effects of applied voltage and NaOH solution concentration. It was revealed that the alloy's electro-wetting is primarily influenced by the generation and dissolution of the surface oxide layer, as well as the interaction of the electric double-layer effect. The optimal response voltages for achieving the fastest wetting rate were found to be 16 V, 10 V, 18 V, and 8 V in 0.5 mol/L, 1.0 mol/L, 1.5 mol/L, and 2.0 mol/L concentrations, respectively, with 18 V at 1.5 mol/L concentration identified as the optimal process selection. The spreading behavior of the alloy in low-concentration NaOH solutions followed Tanner's Law, while in the 2.0 mol/L concentration, significant repellence and wetting angle saturation were observed. The wetting process of the alloy at various stages was described using the power-law equation R = atc, while the wetting mechanism of the alloy was elucidated through the application of the Lippmann equation and the electric double-layer effect equation.

Controlling liquid-liquid phase behaviour with an active fluid.

Demixing binary liquids is a ubiquitous transition explained using a well-established thermodynamic formalism that requires the equality of intensive thermodynamics parameters across phase boundaries. Demixing transitions also occur when binary fluid mixtures are driven away from equilibrium, but predicting and designing such out-of-equilibrium transitions remains a challenge. Here we study the liquid-liquid phase separation of attractive DNA nanostars driven away from equilibrium using a microtubule-based active fluid. We find that activity lowers the critical temperature and narrows the range of coexistence concentrations, but only in the presence of mechanical bonds between the liquid droplets and reconfiguring active fluid. Similar behaviours are observed in numerical simulations, suggesting that the activity suppression of the critical point is a generic feature of active liquid-liquid phase separation. Our work describes a versatile platform for building soft active materials with feedback control and providing an insight into self-organization in cell biology.

Thermophysical Studies on Binary Liquid Mixtures of Benzyl Alcohol and Alkylamines at 298.15–308.15 K

Thermophysical Studies on Binary Liquid Mixtures of Benzyl Alcohol and Alkylamines at 298.15–308.15 K

Studying of Acoustical Parameters of Some Binary Liquid Mixture at 303.15 K and 3 M. Hz

The ultrasonic velocity, density and viscosity of 1,4- dioxane with alkanols systems have been measured experimentally at 303.15 K over the frequency 3 M. Hz. From these three values, we have calculated thermodynamic and excess thermodynamic parameters such as adiabatic compressibility, deviation in adiabatic compressibility, molar volume excess molar volume, free length, excess free length, Viscosity, deviation in viscosity, internal pressure ,excess internal pressure, acoustic impedance, excess acoustic impedance, excess sound velocity, Rao,s constant, Wada constant, relaxation time and relaxation strength of binary liquid mixture to interpret the nature of the interactions taking place in the binary liquid mixtures. The results analyzed in the sight of molecular interaction between the components. The interaction resulting in the interstitial accommodation of 1, 4- dioxane into alkanols are the predominant factor over dipole-dipole interaction.

Refractive Index Measurements of Ethanol–Water Binary Liquid Solutions Using a Graded-Index Fiber Tip Sensor

Refractive Index Measurements of Ethanol–Water Binary Liquid Solutions Using a Graded-Index Fiber Tip Sensor

Starving Free Solvents: Toward Immiscible Binary Liquid Electrolytes for Li‐Metal Full Cells

AbstractCurrent state‐of‐the‐art Li batteries use single‐phase electrolytes; however, these electrolytes often encounter difficulty in simultaneously fulfilling the nonidentical electrochemical requirements of cathodes and anodes. Here, a class of immiscible binary liquid electrolyte (BLE) is designed by starving free solvent molecules. Based on their electrochemical stability window, 1,2‐dimethoxyethane (DME) and succinonitrile (SN) are selected as model solvents for Li‐metal anodes and LiNi0.8Co0.1Mn0.1 (NCM811) cathodes, respectively. Li bis(fluorosulfonyl)imide (LiFSI), which promotes Li+ solvation (i.e., reduces free solvents), enables the phase separation of the miscible solvent mixture (SN−DME), and an increase in its concentration strengthens the coordination of Li+−FSI− in the solvation sheath, thus yielding (anion‐derived) fluorine‐rich electrode–electrolyte interphases. The resulting BLE allows 4.4 V Li‐metal full cells to exhibit a stable capacity retention under a constrained cell condition (Li (20 µm, 4.1 mAh cm−2)||NCM811 (3.8 mAh cm−2), N (negative)/P (positive) capacity ratio = 1.08), which exceed those of previously reported binary liquid electrolytes.

Selective Chirality Transfer to the Bis(trifluoromethylsulfonyl)imide Anion of an Ionic Liquid.

Chirality transfer from the chiral molecule (R)-1,2-propylene oxide to the achiral anion of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid is observed. The chiral probe selectively affects one part of the binary ionic liquid, i. e., it has previously been shown experimentally and theoretically that this particular imidazolium cation can be affected by chirality transfer, but in the present system chirality is almost exclusively transferred to the anion and not to both parts of the solvent (anion and cation). This observation is of high relevance because of its selectivity and because anion effects are usually much more important in ionic liquid research than cation effects. From ab initio molecular dynamics simulations, a conformational analysis and dissected vibrational circular dichroism spectra are obtained to study the chirality transfer. While in the neat ionic liquid two mirror imaged trans conformers of the anion occur almost equally, we observe an excess of one of these conformers in the presence of the chiral solute, causing optical activity of the anion. Although the cis conformers are not tremendously affected by the chirality transfer, they gain in total population when (R)-1,2-propylene oxide is dissolved in the ionic liquid.

Studying Different Thermodynamic Properties of Binary Liquid Mixture of Ethyl Acetate with 1-Alkanols at 303.15K

Abstract: Experimental values of ultrasonic velocity (u), density (ρ) and viscosity (η) for the binary mixtures of ethyl acetate with 1-alkanols have been measured at 303.15 K over the entire mole fraction range. Using these data, the excess isentropic compressibility (βES), excess intermolecular free length (LEF), excess molar volume (VEM), excess free volume (VEF) and excess available volume (VEa) have been calculated. These parameters were used to study the nature and extent of intermolecular interaction between component molecules present in the binary mixtures. Excess values of isentropic compressibility, intermolecular free length, molar volume, free volume and available volume were plotted against the mole fraction of ethyl acetate over the whole composition range. From the properties of these excess parameters, the nature and strength of the interactions in these binary systems are discussed.

Thermodynamic properties of {glycerol (1) + tert-butanol (2)} mixtures at temperatures from 278 K to 323 K and pressures up to 100 MPa

In the present study the densities at atmospheric pressure and the compression coefficients of a binary liquid mixture {glycerol (1) + tert-butanol (2)} were measured within the temperature range from 278.15 K to 323.15 K (278.15, 288.15, 288.15, 308.15 and 323.15) and pressures up to 100 MPa (10, 25, 50, 75 and 100). Due to the limited solubility of tert-butanol in glycerol and the transition of the mixture to the solid phase the measurements at 278.15 K and 100 MPa were carried out up tox2 = 0.45 (x2 is the mole fraction of tert–butanol). The excess molar volumes, molar isothermal compression, molar isobaric thermal expansion, isochoric coefficient of thermal pressure mixtures, as well as the partial molar volumes of the mixture components, including their limit values, were calculated. The excess molar volume values at 323.15 K (the only temperature at which the compression was measured over the entire composition range) were found to be negative. The partial molar volume of glycerol (GL) at 323.15 K was characterized by the presence of a baric inversion region. The limiting partial molar volume of GL was shown to decrease in its own environment as the pressure rose and to increase in the TBA environment. The molar isothermal compression of the mixture varied depending on the composition without extremes, and the partial molar isothermal compression of GL had negative values. The molar isobaric thermal expansion of the mixture in the area of small tert-butanol (TBA) additives changed slightly at low temperatures and pressures and the increase in both the pressure and the temperature led to dispersion of their concentration dependences. The isochoric coefficient of thermal pressure decreased with an increase in x2, forming a small plateau at small TBA additions. The results obtained were discussed from the perspective of solute–solvent and solute–solute interactions.

All-Optical Rapid Formation, Transport, and Sustenance of a Sessile Droplet in a Two-Dimensional Slit with Few-Micrometer Separation.

We present a sessile droplet manipulation platform that enables the formation and transport of a droplet on a light-absorbing surface via local laser-beam irradiation. The mechanism relies on solutocapillary Marangoni flow arising from a concentration gradient in a binary mixture liquid. Because the mixture is strongly confined in a two-dimensional slit with a spacing of a few micrometers, the wetting film is stably sustained, enabling the rapid formation, deformation, and transport of a sessile droplet. In addition, to sustain the droplet in the absence of laser irradiation, we developed a method to bridge the droplet between the top and bottom walls of the slit. The bridge is stably sustained because of the hydrophilicity of the slit wall. Splitting and merging of the droplet bridges are also demonstrated.

Transport and optical properties of the binary liquid mixture containing 1,3-diaminopropane and alkyl acetates (C1-C4) at T= (303.15-318.15) K: experimental investigations and theoretical modelling

ABSTRACT Physicochemical properties of pure liquids and their liquid mixtures at different compositions and at different temperatures have a significant role in the optimisation of chemical processes. Present report involves the analysis of the physicochemical properties of 1,3-diaminopropane and alkyl acetate. The viscosity () and refractive index () of 1,3-Diaminopropane, 1,3-DAP (1), with alkyl acetates, AAc, (C1-C4) (2) were measured at different temperatures (T = 303.15 to 318.15 K) under the atmospheric pressure 0.1 MPa. Deviation in viscosity, , deviation in refractive index, , and excess Gibbs free energy of activation, for these binary mixtures were calculated from measured viscosity and refractive index data and fitted to Redlich-Kister polynomial equation (R.K.). The data were analysed in terms of the Graph theoretical approach (GTA) to study the interactions in binary mixtures. The values were also correlated by using Bloomfield and Dewan (BFD) model and various correlations. data were correlated by various relevant correlations.

Repeated Microphase Separation and Heating-free Distillation-like Behavior of Miscible Binary Liquid Mixtures Using Nanoconfined Grafted Polymer Layers.

Nanoconfinement is known to drive phase separation (often denoted as microphase separation) of two highly miscible liquids by subjecting the two liquids to disparate influences. Here, we propose a paradigm shift to this problem: we introduce the idea of "repeatability" in nanoconfinement-driven microphase separation. A drop consisting of two highly miscible liquids (A and B) is made to pass through a nanochannel grafted with a collapsed layer of polymer that is philic to A but phobic to B. Subsequently, a significant number of molecules of liquid A get imbibed into the polymer layer and the polymer layer partially swells, while the molecules of liquid B mostly remain out of the polymeric layer and are carried away, emerging as a drop on the other side of the polymer bilayer. This passage of drop (of liquids A and B) is continued, and each time liquids A and B get separated with liquid A imbibing into the polymer layer and liquid B being carried away with the drop. This scenario, therefore, points to the repeated occurrence of the microphase separation of miscible binary liquid mixtures, enabling the processing of a much larger volume of liquid, given the fact that the presence of a grafted polymer layer continues to provide a dynamically increasing space where liquid A can get localized after being separated from liquid B. We quantify such repeated microphase separation by noting the extent of separation (of liquid A) and extent of recovery (of liquid B) as functions of nanochannel height and number of passes. Interestingly, we establish that this process also leads to a distillation-like behavior (without any heat addition), where the concentration of liquid B (equivalent to the "less volatile" liquid in a standard distillation process) progressively increases inside the drop after its passage through the nanochannel.

Surface tension and viscosity of binary ionic liquid mixtures from high vacuum up to pressures of 10 MPa

In the present study, we investigated the surface tension and viscosity of binary ionic liquid (IL) mixtures at or close to saturation conditions from high vacuum conditions up to elevated pressures. We studied four different mixtures of 1,3-bis(2-(2-methoxyethoxy)ethyl)imida-zolium iodide ([(mPEG2)2Im]I) and 1-methyl-3-octylimidazolium hexafluorophosphate ([C8C1Im][PF6]) with [C8C1Im][PF6] mole contents between (4.6 and 49.8) mol%. Argon (Ar) gas of relatively low solubility was used to vary the applied pressure between (0.1 and 10) MPa. For temperatures from (303 to 363) K, the surface tension obtained by the pendant-drop (PD) method was used to determine the saturated liquid viscosity from surface light scattering (SLS). These studies are complemented by additional PD measurements under ultraclean high vacuum (HV) conditions in a second setup. At about 0.1 MPa, the surface tension and viscosity of the IL mixtures show negative deviations from a linear mixing rule based on the molar bulk composition, which is more pronounced at lower temperatures. The surface tension values at 0.1 MPa and under HV agree with each other and lie closer to the values of [C8C1Im][PF6] that has a distinctly lower surface tension than [(mPEG2)2Im]I and is surface-active. For the equimolar IL mixture at 303 K, an increase in the pressure up to 10 MPa has a negligible influence on the viscosity, while it causes a distinct reduction in the surface tension compared to the value at 0.1 MPa. The pressure-dependent relative change for the viscosity of the ternary mixtures of the two ILs and Ar corresponds well to the mean values of the positive and negative relative changes observed for the two binary [(mPEG2)2Im]I-Ar and [C8C1Im][PF6]-Ar subsystems, respectively. For the surface tension, the absolute changes at a given pressure are very similar regardless of the IL bulk composition, suggesting a similar weak Ar enrichment at the gas–liquid interface.

A new approach to analysing the adsorption of non-electrolyte binary liquid solutions by solid adsorbents. Prediction of absolute adsorption from excess adsorption data only

A new approach to analysing the adsorption of non-electrolyte binary liquid solutions by solid adsorbents. Prediction of absolute adsorption from excess adsorption data only

Liquid Crystal-Templated Porous Microparticles via Photopolymerization of Temperature-Induced Droplets in a Binary Liquid Mixture.

Porous polymeric microspheres are an emerging class of materials, offering stimuli-responsive cargo uptake and release. Herein, we describe a new approach to fabricate porous microspheres based on temperature-induced droplet formation and light-induced polymerization. Microparticles were prepared by exploiting the partial miscibility of a thermotropic liquid crystal (LC) mixture composed of 4-cyano-4'-pentylbiphenyl (5CB, unreactive mesogens) with 2-methyl-1,4-phenylene bis4-[3-(acryloyloxy)propoxy] benzoate (RM257, reactive mesogens) in methanol (MeOH). Isotropic 5CB/RM257-rich droplets were generated by cooling below the binodal curve (20 °C), and the isotropic-to-nematic transition occurred after cooling below 0 °C. The resulting 5CB/RM257-rich droplets with radial configuration were subsequently polymerized under UV light, resulting in nematic microparticles. Upon heating the mixture, the 5CB mesogens underwent a nematic-isotropic transition and eventually became homogeneous with MeOH, while the polymerized RM257 preserved its radial configuration. Repeated cycles of cooling and heating resulted in swelling and shrinking of the porous microparticles. The use of a reversible materials templating approach to obtain porous microparticles provides new insights into binary liquid manipulation and potential for microparticle production.

Nanoscale liquid-vapor phase change characteristics of binary mixtures from molecular dynamics perspective

Nanoscale thin liquid film boiling of a binary liquid mixture subjected to extremely rapid heating within molecular dynamics framework is the focus of our study. A three-phase MD simulation domain is considered where liquid argon-krypton (Ar-Kr) binary mixture rests over a solid Platinum (Pt) like substrate. The molecular system starting from freezing state is subjected to non-equilibrium boundary heating following a sufficient equilibration period to induce liquid–vapor phase change process. Depending on the mixture composition and boundary heating rate, four distinct phase change scenarios have been observed. Characteristics of different phase change scenarios have been studied in terms of important system parameters such as transient atomistic distribution, temperature, pressure, evaporation history, onset of liquid cluster splashing from the wall along with atomic kinetics parameters like COM (Center of Mass), and MSD (Mean Square Displacement). Addition of Kr with Ar that is less volatile compared to Ar, has been found to result in a delay in the evaporation onset and decrease in interaction energy. As a consequence, with the increase of Kr fraction in the binary mixture, the mobility of the evaporated atoms is hindered and the onset temperature of liquid splashing from the wall that resembles generation of “Leidenfrost Film” changes. Also, the near wall atomistic energetics is significantly influenced by mixture composition. Finally, a contour of various phase change modes for Ar-Kr binary mixtures has been presented as a function of mixture composition and boundary heating rate. Present work has been found to be aligned with contemporary works in the context of the derived heat transfer properties.

Binary liquid film condensation from water-ammonia vapors mixture flowing downward along a parallel plate condenser

The ammonia-water film condensation is used as an efficient working fluid in industrial applications such as refrigeration, plate condenser and evaporator, absorber/generator heat exchange, air-conditioning, heat pumps and separation processes. The present work focuses on a numerical investigation of water-ammonia condensation on a falling binary liquid film inside a parallel plate condenser by mixed convection. The parallel plate condenser is composed by two parallel vertical plates. One of the plates is wetted by liquidfilm and cooled by the thermal flux cooling while the other plate is isothermal and dry. Parametric computations were performed to investigate the effects of the inlet parameters of gas, the properties of the binary liquid film as well as the thermal flux cooling on the combined mass and heat transfer and on the efficiency of the parallel plate condenser. The results show that an increase in the inlet vapor of ammonia as well as of vapor water enhances the efficiency of the parallel plate condenser. It is shown also that an enhancement of efficiency of the parallel plate condenser has been recorded when the thermal flux cooling and inlet liquid flow rate is elevated. Whereas the increase of the inlet liquid concentration of ammonia inhibits the efficiency of the parallel plate condenser.

Estimation of Component Activities and Molar Excess Gibbs Energy of 19 Binary Liquid Alloys from Partial Pair Distribution Functions in Literature

This work proposes a new method for estimating the molar excess Gibbs energy and activity of liquid alloy based on recent research. The local composition theory provides a connection between the structures of liquid alloys and the thermodynamic models. The partial pair distribution function (PPDF) was utilized to calculate the parameters of the MIVM, RSM, Wilson, and NRTL. The statistics of the number of molecular pairs of MIVM and RSM were rewritten, which resulted in new forms of the two models. To enhance the NRTL’s estimation performance, the coordination number was incorporated into it (M-NRTL). The aforementioned model and Quasi-chemical model (QCM) were utilized to estimate the excess Gibbs energy and activity of 19 alloys. The alloys contained multiple sets of PPDFs, which enabled the calculation of multiple sets of model parameters. The work examined the impact of expressing the model parameters as first-order linear functions of the components or as constants on the accuracy of the estimation. The parameters were treated as constants. MIVM, RSM, and M-NRTL provided an average relative deviation (ARD) of activity of less than ±20% for 15, 10, and 9 alloys by estimation. When model parameters were expressed as a function of components, QCM showed the best estimation performance, having nine alloys with an ARD of less than ±20%. The number of alloys with an ARD of less than ±20% corresponding to MIVM, RSM, Wilson, NRTL, and M-NRTL was six, five, three, five, and two, respectively. This new method offers simplicity, numerical calculation stability, and excellent reproducibility.