Binary Liquid Mixture Research Articles

Intra- and Inter-molecular Interactions between 1-Alkanol and Benzonitrile: Computational and Thermodynamic Study

This study presents an investigation on the intra- and inter-molecular interactions of binary systems composed of benzonitrile (BN) and 1-alkanols, namely, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, and 1-heptanol. For this purpose, from the experimental density (ρ) and speed of sound (u) data, excess volume (VE), isentropic compressibility (κs), and excess isentropic compressibility (ksE) were calculated for all binary liquid mixtures at different temperatures from (293.15 to 323.15) K with an interval of 5 K and at 0.1 MPa. Then, the calculated excess properties data have been correlated with the Redlich–Kister polynomial equation satisfactorily. Moreover, the interaction energies, bond characteristics, optimized geometries, and natural bond orbital (NBO) were theoretically calculated using the DFT-B3LYP method with 6-31G (d,p) basis sets for pure components and their complexes.

Demonstration of Solute-specific Synergism in Binary Solvents.

The structure and solvation behavior of binary liquid mixtures of Methanol (MeOH) and N, N-Dimethylformamide (DMF) are explored by ascertaining their intermolecular interactions with either Rhodamine-B (RhB) or Rhodamine101 (Rh101) dye through steady-state absorption, emission, and two-photon induced fluorescence. Specifically, in the present investigation, we examine the strong synergistic solvation observed for the combinations of hydrogen bond donating (MeOH) and accepting (DMF) solvent pairs. Solvatochromism causes the solvatochromic probe molecules to sense increased polarity compared to their bulk counterparts. The origin of synergism was explained in terms of solute-solvent and solvent-solvent interactions in binary solvent mixtures interactions, as evidenced by probe dependence. The solvation behavior of the Methanol and DMF binary solvent mixture shows strong probe dependence, with Rh101 showing synergism while RhB does not.

Estimation of thermal conductivity of Na–K liquid metal alloy

For the first time the thermal conductivity of Na–K alloy has been computed using eight theoretical equations, already developed for binary liquid mixtures. The thermal conductivity values of Na–K alloy were obtained at three different temperatures (308,348,423) K, and at four different compositions of alloy. We have employed density and sound speed data for calculating λ alloy with the help of recently developed correlation. Density-Sound speed-thermal conductivity correlation gave excellent results.

Mechanical and surface properties of corona‐treated titanium dioxide‐embedded opaque white low‐density/Linear low‐density polyethylene film

AbstractThis study encompasses the characterization of corona‐treated milky white co‐extruded polyethylene films. The surface energies developed at various applied voltages were investigated by standard wetting (dyne) solutions of binary liquid mixtures. A maximum treatment of 40 dynes/cm was achieved at 3.0 kW of the applied load. Maximum heat seal joint strength of 1.05 kN/m was achieved only when an untreated/untreated surface combination was sealed, while a treated/treated surface combination exhibited the minimum heat seal joint strength of 0.98 kN/m. Standard Scotch tape method was employed for testing peel adhesion. An applied load of more than 3.0 kW shows a decreasing trend in surface energy. The coefficient of friction on the treated surface was also investigated. Aging under different environmental conditions had hardly any impact on the treatment levels within the time period under study. A sufficiently opaque (Opacity—99%) white film at Titanium dioxide (TiO2) loading of 7.5% resulted in a very good barrier film.

Thermodynamic and spectral studies of molecular interactions in binary liquid mixtures of 1-butoxy-2-propanol with amines at different temperatures

ABSTRACT Binary liquid mixtures of 1-butoxy-2-propanol with amines namely diethylamine, dipropylamine and triethylamine have been discussed in the present discussion. Measurements of density and speed of sound of pure liquids and their binary mixtures have been carried out over the entire composition range and temperatures (298.15, 303.15 and 308.15) K. To study the thermodynamic behaviour of these liquid mixtures, various parameters were calculated using the experimentally measured data. Strong intermolecular interactions among the components of binary liquid mixtures were confirmed by calculated parameters. Various excess and deviation properties were correlated to composition using the Redlich–Kister polynomial. Further, density and speed of sound data were correlated with composition using Jouyban–Acree model. The experimental results have been analysed by using Prigogine–Flory–Patterson (PFP) theory. 1H-NMR spectra of binary mixtures at equimolar composition has also been studied.

Extraction of chitin from white shrimp (Penaeus vannamei) shells using binary ionic liquid mixtures

Binary ionic liquid mixtures (IL) were used for the first time to extract chitin from shrimp shells. Two ionic liquids, 1-ethyl-3-methylimidazole acetate ([EMIM][Ac]) and 1-butyl-3-methylimidazole bromide salt ([BMIM][Br]), were mixed at ratios of 0:1, 1:1, 3:2, 4:1, and 1:0 and the properties of the IL and the characteristics of extracted chitin were investigated. With an increase in proportion of [EMIM][Ac], the viscosity, dielectric constant, and dielectric loss of IL gradually decreased (p < 0.05), whereas the conductivity, radius of gyration increased (p < 0.05). The best quality of chitin using IL (3:2) was achieved when the viscosity, conductivity, and radius of gyration were 0.16 ± 0.00 Pa‧s, 0.30 ± 0.01 S/m, and 0.10 ± 0.00 nm, respectively. The yield of chitin extraction using IL was 35.72 ± 0.31 %, and this was approximately 2.04 times higher than that using the acid-base method (17.50 ± 0.16 %). The Whiteness index (WI) of chitin extracted using IL (3:2) (94.93 ± 0.09) was better than commercial chitin (93.31 ± 0.11), and the secondary structure, surface morphology and thermal stability were similar to commercial chitin. Therefore, the binary ionic liquid mixture can be used as an effective green solvent to extract chitin from shrimp shells.

Thermodynamic study of triacetin or ethyl levulinate and alcohol binary mixtures

The subject of presented research is the study of liquid binary mixtures consisting of ester and alcohol combination; triacetin or ethyl levulinate, as one component, and ethanol or isobutanol, as second component. Thermodynamic and transport data were measured in the broad temperature range, T=(288.15/298.15–323.15/333.15) K, and at atmospheric pressure, p = 0.1 MPa. All corresponding excess and deviation properties were calculated including the excess molar volume, viscosity deviation, refractive index deviation, isentropic compressibility deviation and excess molar Gibbs energy of activation of viscous flow, and correlated with the basic Redlich-Kister equation. The analysis of possible chemical interactions and structural effects taking place in the mixtures was led in the terms of ester structure, complexity of ester molecule and chain length and branching of the alcohol molecule. The thermodynamic analyses showed change of the sign of the excess molar volume depending on the alcohol present in the mixture. FT-IR spectra were recorded for all four systems for the compositions where maximum excess molar volumes are obtained to support the conclusions derived from the mixtures’ nonideal behaviour. In addition, modelling of viscosity is performed with the two- and three-parameter correlative models, as well as excess molar volume correlation with the Peng-Robinson equation of state and three-parameter van der Waals mixing rule.

Diverse wetting behavior of a binary mixture of antagonist liquids: Nanodroplet with finite precursor film and leak-out phenomenon

The binary mixtures containing the partial and total wetting liquids corresponding to a specified substrate are commonly seen. However, studies of their wetting behavior, particularly the leak-out phenomenon, are very scarce. The wetting state of a nanodroplet of the binary mixture on a smooth substrate is investigated by Many-body dissipative particle dynamics. The influences of the molecular size of the partial wetting liquid and the affinity between the two liquids on the leak-out phenomenon are examined. Dependent on the mixture composition (ϕp), three wetting regimes of the nanodroplet can be identified: (I) total wetting, (II) partial wetting with precursor film, and (III) partial wetting. The binary droplet always spreads spontaneously in regime (I), while its contact angle (CA) changes with the composition monotonously in regime (III). However, in regime (II), the CA remains constant regardless of the composition. The droplet morphology exhibits the fried-egg shape, a spherical cap surrounded by a precursor film. The compositions in both egg yolk and egg white regions remain unaltered for varying ϕp in the plateau regime (II). Although the affinity between the two liquids is strong, some of the total wetting liquid always escape from the spherical cap to precursor film in regime (II), the so-called leak-out phenomenon. The outcome can be beneficial to the application of nanotechnologies such as lithography and microfluidics.

Evaluation of the Polarity in Binary Liquid Mixtures as a Function of Volume Fraction

The variation of solvatochromic polarity parameters as a function of mole fraction data may not represent the realistic environment of the solvatochromic probe molecule. This is because of the fact that the solvation environment of the solvatochromic probe molecules is not only determined by the number of individual solvent molecules around it but also by the size of those individual solvent molecules. In this regard we wish to understand the variation of ET N polarity parameter of binary liquid mixtures as a fuction of volume fractions. Representation of the ET N parameter as a function of volume fraction data leads to a completely different dataset for binary liquid mixtures where water is used as one of the solvents. These mixtures usually display negative deviations from linearity for the ET N values, when ET N values are plotted as a function of mole fraction values of the solvents. On the other hand, if the ET N values are plotted as a function of volume fraction values of the solvents in binary liquid mixtures containing water, these deviations are minimized to a large extent and even reversed to the positive deviations in some of these mixtures. This study gives an insight into a long lasting problem of understanding the negative deviations of the ET N values from linearity observed in binary liquid mixtures of water, as these deviations are either minimized or reversed into positive deviations when ET N values are plotted versus volume fraction of solvents. This study opens up a whole new discussion about the solvatochromic data of the solvent mixtures, whether this data must be represented as a function of mole fraction values or as a function of volume fraction of the solvents. The representation of the solvatochromic data as a function of volume fraction of solvents might lead to new insights in studying the solute-solvent interactions in binary solvent mixtures.

Experimental investigation on the thermophysical properties of the ionic liquid-based binary system for heat transfer applications

Based on the innovation in the development of ionic liquids, the aim of the present work is to investigate the thermophysical properties of novel hydrophilic ionic liquid 1-Ethyl-3-Methyl Imidazolium Tetra FluoroBorate (EMIMBF4) and water as binary systems experimentally at various mass fraction and at various temperatures. A room-temperature ionic liquid blended with deionized water in four different mass fractions as 20%, 15%, 10%, and 5% to prepare an ionic liquid and water binary mixture at room temperature. Thermal stability and the thermophysical characteristics of EMIMBF4 such as thermal conductivity, specific heat capacity, viscosity, and density, were measured in the temperature range of 25?C to 90?C. The results reveal that the specific heat capacity increased by 13%, and thermal conductivity enhanced 9%, at 5 wt.% mass fraction. The overall mass drop is reached 75.1% at 20 wt.% mass fractions.

Volumetric properties of binary liquid mixture of cyclopentyl methyl ether with 1-pentanol at 298.15 k temperature

The densities (ρ) and ultrasonic speeds (u) of Cyclopentyl methyl ether, 1- Pentanol and their binary mixture with the whole composition range have been measured at 298.15 K. From the experimental data the excess molar volume (VE), deviations in isentropic compressibility (∆ks), deviations in ultrasonic speed (∆u), deviations in acoustic impedance (∆Z) have been determined. The sign and magnitude of these parameters were found to be sensitive towards interactions prevailing in the studied system. Moreover, VE values were theoretically predicted by using Flory’s statistical theory. The variations of derived parameters mentioned above with composition offer a convenient method to study the nature and extent of interactions between the component molecules of the liquid mixture not easily obtained by other means.

On the microscopic origin of Soret coefficient minima in liquid mixtures.

Temperature gradients induce mass separation in mixtures in a process called thermodiffusion and quantified by the Soret coefficient. The existence of minima in the Soret coefficient of aqueous solutions at specific salt concentrations was controversial until fairly recently, where a combination of experiments and simulations provided evidence for the existence of this physical phenomenon. However, the physical origin of the minima and more importantly its generality, e.g. in non-aqueous liquid mixtures, is still an outstanding question. Here, we report the existence of a minimum in liquid mixtures of non-polar liquids modelled as Lennard-Jones mixtures, demonstrating the generality of minima in the Soret coefficient. The minimum originates from a coincident minimum in the thermodynamic factor, and hence denotes a maximization of non-ideality mixing conditions. We rationalize the microscopic origin of this effect in terms of the atomic coordination structure of the mixtures.

Thermodynamic properties of binary liquid mixtures of benzyl alcohol with 2-Alkoxyethanols at varying temperatures

In the present research, density (ρ) and speed of sound (u) for binary liquid mixtures of the benzyl alcohol (BA) with three 2-alkoxyalcohols {2-methoxyethanol (2-ME), 2-ethoxyethanol (2-EE), and 2-butoxyethanol (2-BE)} at temperatures of 298.15, 303,15 and 308.15 K have been measured over complete concentration of benzyl alcohol under 0.1 MPa pressure. According to measured results, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs) were computed and these observed results were correlated to Redlich−Kister (R-K) polynomial expansion. Further, molar volume (Vm), apparent molar volumes (Vm,∅,1 and Vm,∅,2), acoustic impedance (Z), isentropic compressibility (ks), intermolecular free length (Lf), deviation in intermolecular free length (ΔLf) were calculated at all worked temperatures. For all studied systems, excess molar volume (VmE) and deviation in isentropic compressibility (Δκs), and deviation in intermolecular free length (ΔLf) were negative over the entire mole fraction range of benzyl alcohol at all measured temperatures. Among the three systems, benzyl alcohol with 2-ethoxyethanol containing system showed more negative. By using the obtained results, intermolecular interactions were discussed between benzyl alcohol and 2-alkoxyethanols. Moreover, the influence of temperature on intermolecular interactions was analyzed using above said parameters.

Thermophysical modelling of transport and optical properties of 1-propanol+1,3-diaminopropane or 1,2-diaminopropane or 1-amino-2-propanol binary liquid mixture at T=298.15-318.15 K: Molecular interaction analysis by density functional theory (DFT) and graph theoretical approach (GTA)

BackgroundPure liquid properties cannot always satisfy the need of chemical processes. Therefore, liquid mixtures are preferred in different compositions, and the thermo-physical properties of liquid mixtures are highly significant for different processes. The present report involves thermo-physical of amines and 1-propanol. Amines are utilized for CO2 absorption processes. MethodsThe viscosity (η) and refractive index (nD) of 1P (1-propanol) (1) + Amines (1,3-DAP(1,3-diaminopropane), 1,2-DAP(1,2-diaminopropane) and 1A2P(1-amino-2-propanol)) (2) binary mixture were measured at T = 298.15-318.15 K under the atmospheric pressure 0.1 MPa. Experimental data of η and nD were further used to determine deviation in viscosity (Δη), excess Gibbs free energy of activation (G*E) and deviation in refractive index (ΔnD). Δη were analyzed by Bloomfield and Dewan model (BFD) and also examined in term of Graph theoretical approach (GTA). The η and nD data were further correlated by various relevant correlations Significant findingsThe derived thermo-physical properties were well correlated with Redlich-Kister polynomial equation. DFT studies indicated the strength of molecular interactions and supported the graph theory in predicting probable associative molecular species in the liquid mixtures. Further, in 1P + amines binary liquid mixtures, the dominant interaction is OH—–NH.

Experimental evidence and computational results in the investigation of thermodynamic properties and molecular structure of hydrogen-bonded cyclohexylamine and ethyl methyl ketone system

Combining experimental and computational study is a fundamental and attractive method for analyzing intermolecular hydrogen bonds and specific interactions in binary mixtures of different liquids. An experimental and computational investigation of the structural interactions between the molecules of cyclohexylamine and ethyl methyl ketone (EMK) is presented. In the experimental part of the work, the density of mixtures of cyclohexylamine and EMK in the specific mole fractions is reported at 298.15, 303.15, 308.15, and 313.15 K and at an absolute pressure of 86.7 kPa. Densities data have been used to evaluate the excess molar volumes, the thermal expansion coefficients, and the isothermal coefficient of pressure excess molar enthalpy. The Jouyban–Acree model has been used for mathematical correlation of the densities. Using the Redlich-Kister equation, the results of excess molar volumes were fitted. Through computational technics such as density functional theory (DFT), quantum theory of atoms in molecules (QTAIM), and also molecular dynamics (MD) simulations, the analysis of intermolecular hydrogen-bonded associations has been accomplished. MD simulations computed density and radial distribution functions (RDFs) in the liquid phase at 298.15 K and at 1 atm.

General Adsorption Model to Describe Sigmoidal Surface Tension Isotherms of Binary Liquid Mixtures

Surface tension (σ) isotherms of liquid mixtures can be divided into Langmuir-type (L-type, including LI- and LII-type) and sigmoid-type (S-type, including SI- and SII-type). Many models have been developed to describe the σ-isotherms. However, the existing models can well describe the L-type isotherms, but not the S-type ones. In the current work, a thermodynamic model, called the general adsorption model, was developed based on the assumption of surface aggregation occurring in the surface layers, to relate the surface composition with the bulk one. By coupling the general adsorption model with the modified Eberhart model, a two-parameter equation was developed to relate the σ with the bulk composition. Its rationality was examined using the σ data of 10 binary mixtures. The results indicate that the new model can accurately describe the S- and L-type isotherms of binary liquid mixtures, showing a good universality. One advantage of the model is that its two parameters, i.e., the adsorption equilibrium constant (K) and the average aggregation number (n), can be estimated by linear fitting experimental σ data, thereby obtaining unique values. This model suggests that the S- and LII-type isotherms arise from the surface aggregation (n ≠ 1). In addition, the standard molar Gibbs free energy of surface adsorption (ΔG̃ad0) and the apparent surface layer thickness (τ) were analyzed for 10 binary mixtures. The ΔG̃ad0 data suggest that the order of adsorption tendency is LI-type ≫ SI-type ≈ SII-type > LII-type, and the strong adsorption usually corresponds to large τ. This work provides a feasible model for describing the S-type isotherms and a better understanding of the surface properties of liquid mixtures.

Thermodynamic, transport and spectral studies (FTIR) for some binary liquid mixtures of morpholine with isopropyl acetate, N-methylformamide and 2-propanol at various temperatures

ABSTRACT Densities, speeds of sound and viscosities of binary mixtures of morpholine with isopropylacetate, N-methylformamide and 2-propanol including those of pure liquids, over the entire composition range were measured at various temperatures (303.15, 308.15 and 313.15) K and 0.1MPa. Using the experimental data, the excess volume, excess isentropic compressibility, deviation in viscosity, excess partial properties of the components at infinite dilution were calculated. Finally, the Prigogine-Flory-Patterson (PFP) Theory is applied to identify the most predominant molecular interaction. Jouyban Acree model was used to correlate the experimental values of density, speed of sound and viscosity. Further binary mixing and FT-IR spectra were studied at equimolar concentration. From these results, the nature of interaction has been discussed in terms of intermolecular interaction between the mixing components

Thermoacoustical study of intermolecular interactions in binary liquid mixtures of benzaldehyde with methanol and ethanol

Density (ρ) and ultrasonic velocity (u) for the binary mixtures of benzaldehyde with methanol and ethanol have been observed experimentally at 293, 303 and 313 K over the different compositions. The data so obtained was employed for the computation of specific heat ratio (γ), heat capacity (CP), effective Debye temperature (θD) and pseudo-Grüneisen parameter (Γ) excess pseudo-Grüneisen parameter (ΓE), excess molar volume (VmE) and excess isentropic compressibility (Δks) which were further endorsed to the Redlich-Kister polynomial equation. Excess parameters were graphed with the varying mole fraction of benzaldehyde and further considered for examining the nature and extent of molecular interaction in these two types of binary mixtures. The excess parameters with negative values in the observations were elaborated in terms of interaction between molecules of the constituents of the mixtures. The observed ultrasonic velocity and density were also fitted in first order polynomial equation. This research proves that the interaction between benzaldehyde and methanol is stronger than benzaldehyde and ethanol.

Correlation analysis of the relationship between Arrhenius viscosity parameters in Binary Liquid Mixtures

Recent linear model for pure fluids was developed by our research team. Extending and validating this model for binary fluid mixtures is the aim of this work. To achieve this, a statistical analysis of experimental data sets of 300 observations for 16 binary liquid mixtures in accordance with the families of organic liquid solvents over different temperature ranges, at atmospheric pressure, and at different molar fraction. It was found that the extended model for binary liquid mixtures facilitates the calculation of viscous behavior and engineering manipulations. In the 16 subgroups, it is possible to estimate a missing Arrhenius viscosity parameter if the second one is known. Furthermore, using statistical comparison techniques, one can accurately determine this missing parameter in specific subgroups. Those objectives help engineers to gain an in-depth understanding of pure liquids or mixtures of binary liquids to address their challenges in fluidization technology.

Density and Refractive Index of Binary Ionic Liquid Mixtures with Common Cations/Anions, along with ANFIS Modelling

Ionic liquids have many interesting properties as they share the properties of molten salts as well as organic liquids, such as low volatility, thermal stability, electrical conductivity, non-flammability, and much more. Ionic liquids are known to be good solvents for many polar and nonpolar solutes. Combined with their special properties, ionic liquids are good replacements for the conventional toxic and volatile organic solvents. Each ionic liquid has different properties than others. In order to alter, tune, and enhance the properties of ionic liquids, sometimes, it is necessary to mix different ionic liquids to achieve the desired properties. However, using mixtures of ionic liquids in chemical processes requires reliable estimations of the mixtures’ physical properties such as refractive index and density. The ionic liquids used in this work are 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]), 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]), and 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM][PF6]). These ionic liquids were supplied by Io-li-tec and used as received. However, new measurements for the density and refractive index were taken for the pure ionic liquids to be used as reference. In the present work, the densities and refractive indices of four different binary mixtures of ionic liquids with common cations and/or anions have been measured at various compositions and room conditions. The accuracy of different empirical mixing rules for calculation of the mixtures refractive indices was also studied. It was found that the overall absolute average percentage deviation from the ideal solution in the calculation of the molar volume of the examined binary mixtures was 0.78%. Furthermore, all of the examined mixing rules for the calculation of the refractive indices of the mixtures were found to be accurate. However, the most accurate empirical formula was found to be Heller’s relation, with an average percentage error of 0.24%. Furthermore, an artificial intelligence model, an adaptive neuro-fuzzy inference system (ANFIS), was developed to predict the density and refractive index of the different mixtures studied in this work as well as the published literature data. The predictions of the developed model were analyzed by various methods including both statistical and graphical approaches. The obtained results show that the developed model accurately predicts the density and refractive index with overall R2, RMSE, and AARD% values of 0.968, 7.274, 0.368% and 0.948, 7.32 × 10−3 and 0.319%, respectively, for the external validation dataset. Finally, a variance-based global sensitivity analysis was formed using extended the Fourier amplitude sensitivity test (EFAST). Our modelling showed that the ANFIS model outperforms the best available empirical models in the literature for predicting the refractive index of the different mixtures of ionic liquids.