Pseudo-binary Mixtures Research Articles

On the applicability of the Redlich-Kister framework for viscosity estimation of molten halide salt mixtures

For molten halide salt mixtures already being utilized or under consideration for carbon-free energy production systems, it is crucial that their viscosity is well understood so that system thermal hydraulics can be reliably assessed. Because of the difficulty in accurately measuring molten halide viscosity and the sheer size of the matrix of possible higher order salt mixtures that may be of interest to the energy industry, there are several gaps in the quantified understanding of molten halide viscosity across this matrix. As such, both first-principles and semi-empirical modeling techniques may be crucial for rapidly assessing this broad, complex compositional domain. Herein, the Redlich-Kister framework is applied to assess the feasibility of broadly interpolating and estimating the viscosity of several pseudobinary and pseudoternary molten halide salt systems that may be of key interest to the energy industry. The framework is based on the assumption that an ideal component and a nonideal component collectively describe the viscosity as a function of composition and temperature for a given molten halide system. Three different ideal models were considered for the ideal component, including Grunburg-Nissan, Katti-Chaudhri, and Gambill methods. Regarding the pseudobinary interpolations, the Redlich-Kister models with either the Grunburg-Nissan or Katti-Chaudhri models as the ideal component resulted in either highly (average error less than 5%) or reasonably (average error less than 15%) accurate interpolations of pseudobinary halide viscosity; BeF2- or UF4-bearing salts tended to result in reasonably accurate interpolations, whereas other pseudobinary mixtures tended to show high accuracy. Regarding the pseudoternary extrapolations, the Redlich-Kister framework shows reasonable success at estimating the extent to which a pseudoternary system may indicate deviations from ideal Grunburg-Nissan mixing, where discrepancies with comparative experimental data generally stay within 30%. The primary reasons identified for such discrepancies are (1) inaccuracy in the underlying experimental data, (2) different complexation behavior in the higher order systems compared to the pseudobinary subsystems, and (3) extrapolation into temperatures too far out of the domain, which is valid for the underlying experimental data feeding the Redlich-Kister model.

Chemistry Informed Machine Learning-Based Heat Capacity Prediction of Solid Mixed Oxides.

Knowing heat capacity is crucial for modeling temperature changes with the absorption and release of heat and for calculating the thermal energy storage capacity of oxide mixtures with energy applications. The current prediction methods (ab initio simulations, computational thermodynamics, and the Neumann-Kopp rule) are computationally expensive, not fully generalizable, or inaccurate. Machine learning has the potential of being fast, accurate, and generalizable, but it has been scarcely used to predict mixture properties, particularly for mixed oxides. Here, we demonstrate a method for the generalizable prediction of heat capacity of solid oxide pseudobinary mixtures using heat capacity data obtained from computational thermodynamics and descriptors from ab initio databases. Models trained through this workflow achieved an error (mean absolute error of 0.43 J mol-1 K-1) lower than the uncertainty in differential scanning calorimetry measurements, and the workflow can be extended to predict other properties derived from the Gibbs free energy and for higher-order oxide mixtures.

Excess Enthalpies Analysis of Biofuel Components: Sunflower Oil-Alcohols Systems.

This study addresses the pressing issues of energy production and consumption, in line with global sustainable development goals. Focusing on the potential of alcohols as "green" alternatives to traditional fossil fuels, especially in biofuel applications, we investigate the thermochemical properties of three alcohols (n-propanol, n-butanol, n-pentanol) blended with sunflower oil. The calorimetric analysis allows for the experimental determination of excess enthalpies in pseudo-binary mixtures at 303.15 K, revealing similarities in the trends of the curves (dependence on concentrations) but with different values for the excess enthalpies for each mixture. Despite the structural differences of the alcohols studied, the molar excess enthalpy values exhibit uniformity, suggesting consistent mixing behavior. The peak values of excess enthalpies for systems with sunflower oil and n-propanol, n-butanol and n-pentanol are, respectively, 3255.2 J/mole, 3297.4 J/mole and 3150.1 J/mole. Both the NRTL and Redlich-Kister equations show satisfactory agreement with the obtained values.

Unusual Hydration Properties of Choline Fluoride-Based Deep Eutectic Solvents.

The hydration properties of the fluoride-based deep eutectic solvent ethalineF [a solution of choline fluoride in ethylene glycol (EG) at a 1:2 molar ratio] are studied and compared to the most common deep eutectic solvent ethaline (the solution of choline chloride in EG at 1:2 molar ratio). The densities of the deep eutectic solvent (DES) based on choline fluoride in EG (ethalineF) and its mixtures with water as cosolvent are measured over the temperature range of 298-323 K. The excess properties, including excess molar volumes, excess partial molar volumes, and viscosity deviations from ideal behavior, are calculated for ethalineF/water and ethaline/water mixtures and compared. The experimental excess molar volumes and viscosity deviations of the studied pseudobinary mixtures are fitted using the Redlich-Kister (R-K) equation. The results of the R-K model successfully reproduced the experimentally calculated values with minimal standard deviations. All excess molar volumes and viscosity deviations had negative values, indicating stronger solvation interactions between the mixture components than between each pure DES or water. The excess partial molar volumes show that water molecules are preferentially solvated by the DES environment. We show that the disruption of the DES interactions (primarily OH...halide interactions) by high mole fractions of water is related to the peak ionic conductivity. The stark differences in hydration behavior between fluoride- and chloride-based ethaline are analyzed and discussed.

High-pressure phase equilibrium and volumetric properties of pseudo-binary mixtures of stock tank oil + nitrogen/carbon dioxide up to 463K

High-pressure phase equilibrium and volumetric properties of pseudo-binary mixtures of stock tank oil + nitrogen/carbon dioxide up to 463K

Solubility of mesalazine in pseudo-binary mixtures of choline chloride/ethylene glycol deep eutectic solvent and water at 293.15 K to 313.15 K

Mesalazine (5-ASA) is a medication utilized to treat inflammatory bowel diseases involving ulcerative colitis and Crohn’s disease. Mesalazine has fewer side effects but the low solubility and bioavailability of it is responsible for its delayed onset of action. Hence, the goal of this study is to determine the molar solubility of 5-ASA in aqueous pseudo-binary mixtures containing low toxic biocompatible choline chloride/ethylene glycol deep eutectic solvent (ChCl/EG DES) with DES mass fraction of 0.0–1.0 using a shake-flask technique at 293.2–313.2 K and approximately 85 kPa. The experimental results indicated that the solubility of 5-ASA enhanced by addition of DES mass fraction and also increasing temperature. The molarity values of 5-ASA were then modelled by some traditional cosolvency models, and regressed each model parameters. The back-computed molarity of 5-ASA using the selected cosolvency models presented a good consistency with the experimental data (lower mean percentage deviation than 5.14%). Moreover, the Gibbs and van’t Hoff equations were employed to compute the thermodynamic functions of 5-ASA dissolution process in ChCl/EG DES + water from the temperature dependency of solubility data. This analysis presented an endothermic and entropy-driven process of 5-ASA dissolution in ChCl/EG DES + water. Furthermore, enthalpy-entropy compensation analysis represented non-linear enthalpy dissolution vs. Gibbs free energy compensation plots with positive and negative slopes for 5-ASA whereas the positive and negative slopes were probably due to the enhance in solvation of 5-ASA by ChCl/EG DES molecules and the solvent-structure loosing, respectively.

Solubility of 2-Hydroxybenzoic Acid in Pseudo-Binary Mixtures of Choline Chloride/Propylene Glycol Deep Eutectic Solvent + Water at 293.15–313.15 K

Solubility of 2-Hydroxybenzoic Acid in Pseudo-Binary Mixtures of Choline Chloride/Propylene Glycol Deep Eutectic Solvent + Water at 293.15–313.15 K

Interactions between components of choline chloride/propylene glycol or ethylene glycol deep eutectic solvents in the presence of water by determination of amlodipine besylate solubility profile

Improving amlodipine besylate (AMB) solubility as a poorly water-soluble drug is one of the biggest limits in preparation of different formulations in the pharmaceutical industry. Aiming to increase the aqueous AMB solubility, its solubility in choline chloride/propylene glycol (ChCl/PG) or choline chloride/ethylene glycol (ChCl/EG) deep eutectic solvents (DESs)-water mixtures was determined here using a shake-flask way at 293.2 K–313.2 K and ambient pressure (≈85 kPa) and correlated by models of van't Hoff, Jouyban-Acree and Jouyban-Acree-van't Hoff. In these mixtures, the maximum molarities of AMB (0.297 and 0.150 mol L−1) were determined at 313.15 K when the mass fraction of ChCl/PG and ChCl/EG were 0.8 and 1.0. The maximum AMB solubility in water was (0.008 mol L−1) at 313.15 K and observed an increment of 36.7-fold and 18.5-fold in ChCl/PG + water and ChCl/EG + water, respectively. The water effect on the stability of ChCl-PG or EG hydrogen bonding interactions was investigated by measuring the molarity of AMB in ternary mixtures of ChCl + PG or EG + water at 298.15 K. Comparing the obtained results for the above-mentioned binary and ternary mixtures presented that there is no real binary mixtures of DES and water when the water mass fraction was between 0.9 to 0.4 for ChCl/PG and 0.9 to 0.2 for ChCl/EG DESs, respectively. From correlation of AMB solubility with the selected cosolvency models, the mean percentage deviations were obtained between 3.4 % to 12.3 % which are on the acceptable range. Moreover, the consequences of apparent thermodynamic analysis demonstrated an endothermic and entropy-driven dissolution of AMB in all portions of ChCl/PG or ChCl/EG + water pseudo-binary mixtures.

MD simulations explain the excess molar enthalpies in pseudo-binary mixtures of a choline chloride-based deep eutectic solvent with water or methanol.

The addition of molecular liquid cosolvents to choline chloride (ChCl)-based deep eutectic solvents (DESs) is increasingly investigated for reducing the inherently high bulk viscosities of the latter, which represent a major obstacle for potential industrial applications. The molar enthalpy of mixing, often referred to as excess molar enthalpy H E-a property reflecting changes in intermolecular interactions upon mixing-of the well-known ChCl/ethylene glycol (1:2 molar ratio) DES mixed with either water or methanol was recently found to be of opposite sign at 308.15K: Mixing of the DES with water is strongly exothermic, while methanol mixtures are endothermic over the entire mixture composition range. Knowledge of molecular-level liquid structural changes in the DES following cosolvent addition is expected to be important when selecting such "pseudo-binary" mixtures for specific applications, e.g., solvents. With the aim of understanding the reason for the different behavior of selected DES/water or methanol mixtures, we performed classical MD computer simulations to study the changes in intermolecular interactions thought to be responsible for the observed H E sign difference. Excess molar enthalpies computed from our simulations reproduce, for the first time, the experimental sign difference and composition dependence of the property. We performed a structural analysis of simulation configurations, revealing an intriguing difference in the interaction modes of the two cosolvents with the DES chloride anion: water molecules insert between neighboring chloride anions, forming ionic hydrogen-bonded bridges that draw the anions closer, whereas dilution of the DES with methanol results in increased interionic separation. Moreover, the simulated DES/water mixtures were found to contain extended hydrogen-bonded structures containing water-bridged chloride pair arrangements, the presence of which may have important implications for solvent applications.

Solubility of paracetamol in binary mixtures of biodegradable betaine/ethylene glycol deep eutectic solvent and water: measurement and correlation

ABSTRACT The goal of this work is determining paracetamol (PCM) equilibrium solubilities in aqueous pseudo-binary mixtures of betaine/ethylene glycol deep eutectic solvent (Bet/EG DES) through the shake-flask technique from 293.15 to 313.15 K and atmospheric pressure (≈ 85 kPa). The equilibrium solid phase crystal of PCM is characterized with X-ray powder diffraction analysis to identify no polymorphic transformation, solvate formation or crystal transition during the whole solvent crystallization process. The results indicate that addition of DES to water significantly enhances PCM solubility; so that, by adding 0.9 mass fraction of Bet/EG DES to water increases PCM solubility by more than 42.9 times. Moreover, the solubility data are successfully represented with the commonly used cosolvency models including Jouyban Acree, Jouyban-Acree-van’t Hoff and so on together with the activity coefficient models of NRTL and Wilson. The accuracy of each model is determined through calculation of average relative deviations (ARD%) and the results present that the Jouyban-Acree (ARD% = 6.3) and Wilson activity model (ARD% = 0.8) have better capabilities in PCM solubility correlation than the others. Finally, thermodynamic behavior of PCM in Bet/EG DES + water is studied by determination of apparent thermodynamic functions of dissolution obtained from the van’t Hoff and Gibbs equations.

Solid-liquid equilibrium of free form of oil contaminants (3-MCPD and glycidol) in lipidic systems

Esters of 3-monochloropropane-1,2-diol (3-MCPD) and glycidol are reported vegetable fats and oils contaminants formed during processing. During digestion, esterified forms are hydrolyzed making the free forms, with high toxicity to human health, possibly available in the digestive system, which could depend, among other factors, on the phase condition stablished in the gastrointestinal tract between contaminants and lipids. Therefore, this work was aimed at evaluating the solid–liquid equilibrium (SLE) of binary and pseudobinary mixtures of fatty acids (palmitic, oleic and stearic), triacylglycerols (tripalmitin, triolein and tristearin) and a partial acylglycerols, with 3-MCPD and glycidol, by differential scanning calorimetry (DSC) and thermodynamic modeling with Margules 2 and 3 suffixes, UNIFAC and ideal models. Melting properties of the contaminants were determined by DSC thermograms, with microstructure micrographs and compared to some predictive group contribution models (GC). 14 complete SLE phase diagrams could be determined. Results showed that the lipid compounds had high affinity with the free contaminants with probably the formation of liquid crystalline structures and/or solid solutions. The Margules 3 suffixes model showed the best fit with the lowest average relative deviations, no higher than 1%, although the parameters probably incorporated the non-ideality promoted by the crystalline phase behavior. The formation of mesophases and/or solid solutions with very high melting temperature probably means a difficulty of separating the contaminants from the lipid matrix in which, on the other hand, could avoid separation process or affect (probably decreasing) their absorption during digestion.

Thermophysical and excess properties of diesel + biodiesel with octanol isomers at different temperatures

Thermophysical properties of biodiesel mixtures are essential to design the injection system components and evaluate the spray characteristic through the combustion chamber as well as understand the type of interactions present in the mixture. In this work, densities, viscosities, and refractive indices of pseudo-ternary mixtures of diesel + biodiesel + 1-octanol, 2-octanol, and 2-ethyl-1-hexanol have been measured from (288.15 to 338.15) K at 0.1 MPa. In addition, properties of the pseudo-binary mixtures of biodiesel + octanol isomers are reported at the same temperature conditions and over the entire range of compositions. The experimental results for the pure components show agreement with data reported in literature within an average absolute percentage deviation of (0.019, 0.742, and 0.155) % for density, viscosity, and refractive index, respectively. Densities and viscosities of the mixtures have been compared with the limits set by the diesel fuel standard (EN 590). This work presents mixtures that meet these limits and can be considered as alternative fuels to conventional diesel. Excess molar volumes, viscosity deviations, and refractive index deviations are calculated from experimental data and represented through the Redlich-Kister equation. The McAllister and Nava-Ríos et al. equations have been used to correlate the kinematic viscosities of the pseudo binary and ternary mixtures as a function of the molar composition.

Study of the Dilution-Induced Deposition of Concentrated Mixtures of Polyelectrolytes and Surfactants.

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights on their behavior in concentrated formulations, less is known on their behavior under practical use conditions, e.g., under dilution and vectorization of deposits. This makes it difficult to make predictions for specific performance, as, for example, good hair manageability after a shampoo or a comfortable sensorial appreciation after a skin cleanser. This is especially important when considering the formulation of new, more eco-friendly formulations. In this work, a detailed study of the phase separation process induced by dilution is described, as well as the impact on the deposition of conditioning material on negatively charged surfaces. In order to gain a more detailed physical insight, several polyelectrolyte–surfactant pairs, formed by two different polymers and five surfactants that, although non-natural or eco-friendly, can be considered as models of classical formulations, have been studied. The results evidenced that upon dilution the behavior, and hence its deposition onto the surface, cannot be predicted in terms of the behavior of simpler pseudo-binary (mixtures of a polymer and a surfactant) or pseudo-ternary mixtures (two polymers and a surfactant). In many cases, phase separation was observed for concentrations similar to those corresponding to the components in some technological formulations, whereas the latter appeared as monophasic systems. Therefore, it may be assumed that the behavior in multicomponent formulations is the result of a complex interplay of synergistic interactions between the different components that will require revisiting when new, more eco-sustainable ingredients are considered.

Thermodynamic study of the aqueous pseudo-binary mixtures of betaine-based deep eutectic solvents at T = (293.15 to 313.15) K

ABSTRACT This work investigates physicochemical properties of betaine/propylene glycol (Bet/PG) and betaine/ethylene glycol (Bet/EG) DESs in water by measuring their densities in neat state and aqueous mixtures over the entire composition range at T = (288.15–318.15) K under atmospheric pressure (≈ 85 kPa). The obtained values of density were used to compute the excess molar volumes (), molar volume (V m), apparent molar volume (), limiting apparent molar expansibility () and the isobaric thermal expansion coefficient (). The solute-solvent interactions in the investigated solutions are evaluated on the basis of these important physicochemical properties. The results indicated that two studied DESs act as a structure-making solute in water over the whole temperature range using Hepler’s constant. Finally, the experimental densities were correlated with some models including Jouyban-Acree, Jouyban-Acree-van’t Hoff, modified Jouyban-Acree-van’t Hoff, Redlich-Kister and Emmerling. The Redlich-Kister expression and Jouyban-Acree model were also used for representation of values.

Interdigitated Electrode for Electrical Characterization of Commercial Pseudo-Binary Biodiesel-Diesel Blends.

Non-standard diesel blends can be harmful to the environment and human health. In this context, a simple analytical method to estimate the biodiesel mixture ratio in diesel was developed based on impedance spectroscopy (IS) associated with interdigitated sensors. In this article, four different interdigitated sensors with varied comb spacing (G) were simulated using the COMSOL Multiphysics software. Based on finite element simulations, four interdigitated electrode architectures were manufactured and evaluated. The best geometry was chosen according to theoretical data simulations, and its interdigitated electrodes were manufactured for the compositional evaluation of pseudo-binary biodiesel–diesel mixtures. According to the X-ray powder diffraction technique, the deposition of the conductive layer (Au0) over the surface of the dielectric substrate (SiO2) did not alter its phase composition. In the analysis of AFM and SEM, it was possible to observe irregular edges on the electrodes, possibly related to the manufacturing process of the thin layers and mechanical stability. Another characteristic observed in the AFM images was the height of the step of the gold layer of the sensor. Several cross sections were obtained, and the mean step value was 225.71 ± 0.0032 nm. Although there were differences in the roughness, the whole sensor had nanometric roughness. Based on the finite element method simulation performed, it can be assumed that the geometric parameters more suitable for the manufacturing of the electrode are W = 20 µm, L = 1000 µm, G = 50 µm, and N = 40 digits. The electrical characterization performed by impedance spectroscopy showed that we could differentiate between biodiesel and diesel fuels and their pseudo-binary mixtures in the low-frequency region.

High-pressure phase equilibrium and volumetric properties of pseudo-binary mixtures of stock tank oil + methane up to 463K

High-pressure phase equilibrium and volumetric properties of highly asymmetric mixtures related to reservoir fluids are critical to the development of high-pressure and high-temperature (HPHT) reservoirs. However, there is a lack of the relevant data and accurate modeling tools. In this work, we prepared asymmetric pseudo-binary mixtures of methane (CH4) + stock tank oil (STO) and systematically measured their phase equilibrium and densities at temperatures from (298.15 to 463.15) K and pressures up to 140 MPa. The methane mole fraction in these mixtures range from 0.20 to 0.61 for the density measurement, and from 0.20 to 0.81 for the phase equilibrium measurement. From the experimental densities, the isothermal compressibility values, as well as the pseudo-excess volumes, were determined. Moreover, phase envelopes, relative volumes, and liquid volume fractions below the saturation point were also measured. These data are valuable for evaluating and improving thermodynamic models for HPHT reservoir fluids. The experimental results were modeled by the Soave-Redlich-Kwong (SRK) equation of state (EoS), the Peng-Robinson (PR) equation of state, their volume translated versions SRK-VT and PR-VT, and the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT). For density, SRK and PR gave large deviations of ~18% and ~8%, respectively, as compared with ~3% for PC-SAFT. Inclusion of volume translation reduced their deviations to the same level as that for PC-SAFT. For isothermal compressibility, all the models gave deviations of 20-30%, with PC-SAFT, SRK-VT and PR-VT being slightly better. The excess volumes calculated by SRK, PR and PC-SAFT were similar and close to the experimental values. The deviations in the calculated excess volumes resulted in only ~1% deviations in the calculated densities if the experimentally determined STO densities were used. It was illustrated that the small deviations could be utilized in the excess volume method to accurately estimate the high-pressure live oil densities from the high-pressure STO densities. This excess volume method gave ~1% density deviation on average for all the models, with PC-SAFT giving the smallest maximum deviation. The deviations in calculated saturation pressures were ~5% for all the models with the overall deviation for PC-SAFT being slightly smaller.

Insight into structural properties and molecular interactions of maline (choline chloride + malonic acid) and 1, 4- butanediol based pseudo-binary mixture: A thermophysical, spectral, and simulation portrayal

The current study elucidate the thermophysical, spectral, and simulation depiction of the prepared deep eutectic solvent (DES) named as maline comprising of an equimolar mixture of choline chloride (ChCl) as hydrogen bond acceptor (HBA) and malonic acid (MA) as hydrogen bond donor (HBD) in the presence of 1, 4-butanediol (BTD) as other HBD (cosolvent). Various thermophysical properties viz., (densities, ρ, speeds of sound, u, viscosity, η and refractive index, nD) were comprehended for the examined pseudo-binary (maline and BTD) mixtures as a function of composition and temperature. The derived thermophysical properties viz., excess molar volume, VmE, excess isentropic compressibility, κsE, excess intermolecular free length, LfE, deviation in viscosity, Δη, and deviation in molar refraction, ΔRM were found to be negative while the excess speed of sound, uE, excess acoustic impedance, ZE, and deviation in refractive index, ΔnDwere found to be positive which signified the favourable hydrogen bonding interactions between maline and BTD. The partial molar volumes, V¯m,1, V¯m,2 and excess partial molar volumes, V¯m,1o and V¯m,2o of the components at infinite dilution exhibited the negative value due to the contraction in volume over the entire concentration thereby strengthening the presence of specific interaction. The molecular interaction in the examined pseudo-binary system conferred in terms of excess parameters with composition and temperature have also been correlated using the Redlich-Kister (R-K) equation. The significant shifting in the spectral profile as observed from FT-IR (Fourier-transform infrared) spectroscopy evidently inferred the favorable inter-molecular interaction within the maline and BTD based pseudo-binary mixture. A noteworthy change in the chemical shifts as deduced from1H- and 13C- NMR (Nuclear Magnetic Resonance) spectral peaks confirmed the hydrogen bonding networks between maline and BTD. Additionally, the 2D 1H–1H COSY (correlation spectroscopy) outcomes exposed the degree of variation in the inter-molecular interactions and structural arrangement between maline and BTD system. The spectral results were further validated employing theoretical (computational simulation) analysis which accounted the extensive hydrogen bonding from the evaluated computed descriptors Also, the 3D-molecular electrostatic potential (3D-MEP) explicated the effect of charge delocalization in the proximity of hydrogen bonding networks.

Liquid–Liquid Phase Behavior of Diesel/Biofuel Blends: Ternary Mixtures of n-Hexadecane, 2,2,4,4,6,8,8-Heptamethylnonane, and Ethanol and the Binary Subsystems

Mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethylnonane are common diesel fuel surrogates. This paper describes a systematic investigation of the liquid–liquid phase behavior of the ternary mixtures of the normal alkane n-hexadecane and its isomer 2,2,4,4,6,8,8-heptamethylnonane (both CnH2n+2; n = 16) with ethanol as a model system of surrogate fuels. By applying the cloud point method in the temperature range of T = 240–330 K at ambient pressure (p = 1013 mbar), the complete liquid–liquid phase diagram is obtained. The binary mixtures of the alcohol with both isomeric alkanes show partial miscibility with upper critical solution points. The behavior of the ternary mixtures is examined by investigating the quasi-binary subsystems of mixtures of the alcohol with mixtures of the two isomers for various fixed mole ratios. By changing the ratio of the different isomers, the region of the phase diagram of the alcohol mixture with the n-alkane is gradually shifted toward lower temperatures when adding the branched isomer toward the phase diagram of the binary mixture of the alcohol with the isomeric compound. The general shape of the phase bodies of the pseudobinaries, predefined by the ratio of the isomeric components, shows only a slight change. For the numerical analysis of the measured phase behavior of the pseudobinary mixtures, concepts are used that are applied for binary solutions presuming Ising criticality. A master curve is obtained when applying the corresponding state principle on the binary and the pseudobinary mixtures. Superposition of the different results allows for a comprehensive description of the liquid–liquid phase behavior, and it estimates the loci of critical line and tie lines. The limits of the range of validity of the descriptions are determined by the appearance of solid phases, which are also reported here. This study is expected to establish a basis for optimizing blends of petrochemical fuels and fuels from renewable sources.

Deep eutectic solvents on extraction of bisphenol A from water matrices: COnductor like Screening MOdel for Real Solvents prediction and experimental validation

AbstractDensities of pure distilled water, tetra butyl ammonium bromide glycerol{[TBAB][Gly]}, and different concentration of aqueous bisphenol A (aq. BPA) (i.e., 25, 50, 75, and 100 ppm) were measured at different temperatures from 293.15–343.15 K. Further, densities of the pseudo binary mixtures of aq. BPA and {[TBAB][Gly]} over the entire mole fraction were measured at different temperatures from 293.15–343.15 K. From these measured density data, the solution thermodynamic properties of the pseudo binary mixtures of aq. BPA and {[TBAB][Gly]} were calculated, and the excess molar volume data were correlated using the Redlich–Kister polynomial equation. Furthermore, the σ‐profiles and σ‐potentials of all the studied species were generated and analyzied in terms of H‐bond donor and/or acceptor at atom and molecular levels. Finally, based on the results of aq. BPA with {[TBAB][Gly]}, tetra butyl ammonium bromide decanoic acid {[TBAB][DA]} and tetra butyl ammonium bromide oleic acid {[TBAB][OA]} based deep eutectic solvents were used for the removal of BPA from the aqueous stream at 298.15 K and 1 atm. This process was characterized in terms of distribution coefficient (D), extraction efficiency (η), and also thermodynamic feasibility of the process at different temperatures.

Study of molecular radii of pseudobinary liquid mixtures by ultrasonic velocity and density

During recent past, ultrasonic velocity has been a very interesting subject due to its usefulness in studying molecular interactions in several types of liquid mixtures. Various attempts have been made to utilize the significance of thermodynamic properties computed by using ultrasonic velocity and related data in studying numerous acoustic relations.In the present work, an effort has been made to compare the radius of molecules of different liquids and their mixtures. In ternary liquid mixtures under study, the first component taken is polar and the other two components are non-polar in nature i.e. they are the mixture of alkanes which in turn are considered as second component. Thus, the ternary mixtures under study are being treated as pseudobinary mixtures. The associated thermodynamic properties of these liquid mixtures are being applied on different acoustic relations. Applicability and authentication of different acoustic relations for calculation of the molecular radii in liquid mixtures is likewise been done, where Rao's relation is found to be the finest.