Ternary Liquid Systems Research Articles

Enhanced energy transfer via surface plasmons in ternary liquid systems of coumarin-151, ethanol, and benzaldehyde

This investigation explores the plasmonic effect on molecular fluorescence within ternary liquid systems comprising 7-amino-4-(trifluoromethyl) coumarin (C-151) laser dye, ethanol, and benzaldehyde. A key aspect of our investigation involves examining ZrN nanosphere and ZrN nanoshell within these mixtures, marking the first instance of such an analysis in ZrN and ternary liquid compositions. Utilizing experimentally obtained refractive indices, we evaluate resonance peaks in the spectra and their shifts. Our findings reveal improved fluorescence characteristics in C-151 laser dye with the addition of ZrN nanoparticles. Theoretical results suggest that plasmonic nanoparticles play a significant role in enhancing dye fluorescence. These findings deepen our understanding of plasmonics in complex liquid environments and highlight ZrN's potential as an effective alternative plasmonic material for efficient molecular energy transfer at the nanoscale.

THERMODYNAMIC PROPERTIES OF TERNARY LIQUID MIXTURE OF TOCOPHEROL ACETATE WITH CHLOROFORM AND DIETHYL ETHER AT 293 K

The reported study, measured the ultrasonic velocity (u), density (ρ) and viscosity (η) of ternary liquid mixtures of α-Tocopherol acetate with chloroform and diethyl ether in the concentration range (0 to 0.1 M) at 293K. These experimental parameters can be used to calculate various thermodynamic parameters like free volume (Vf), internal pressure (πin), Vander-Wall Constant (b) and Gibbs free energy (∆G*) etc. to identify the strength of molecular interaction. The results so obtained support the formation of complex structure and molecular aggregation through intermolecular hydrogen bonding in the ternary liquid system of α -Tocopherol acetate with chloroform and diethyl ether.

Phase equilibrium of three-component liquid systems composed of water, alcohol, and sodium chloride studied by the reference interaction-site model integral equation theory.

A theoretical method for calculating the thermodynamic properties and phase equilibria of a binary liquid mixture using the reference interaction-site model (RISM) integral equation theory, which we had proposed recently, was extended to ternary liquid systems containing salt. A novel dielectric correction of the RISM theory for a mixture of solvents was also proposed. The theory was applied to mixtures composed of water, alcohol, and NaCl, where the alcohol was either methanol or ethanol. The decrease in NaCl solubility with increasing alcohol molar fractions in the solvent was calculated. In the ethanol system, the theory yielded salt-induced liquid-liquid phase separation, which was observed experimentally in a ternary mixture of water, 1-propanol, and NaCl. The phase diagram of the ternary system was determined theoretically.

Multicomponent diffusivities in supercritical and liquid ternary systems

A database of tracer multicomponent diffusivities (Dm,i) in sub/supercritical and liquid ternary systems was compiled, comprised of 1530 points and 153 systems. Two Dm,i hybrid free-volume equations were developed, the predictive Multicomponent Tracer Liu-Silva-Macedo (Multi-TLSM) and the 1-parameter Multi-TLSMAD correlation. Furthermore, six literature models were tested: the Wilke-Chang equation, the 2-parameters Dymond–Hildebrand–Batschinski (DHB) correlation, and four 2-parameters correlations of Magalhães et al. Their performance was assessed calculating the average absolute relative deviation (AARD) and average relative deviation (ARD), leading to the following conclusions: (i) the Multi-TLSM model is recommended for Dm,i estimation, (AARD = 10.38 % and ARD = −0.20 %), even for many polar and hydrogen-bonding systems; (ii) the Wilke-Chang equation (AARD = 12.46 % and ARD = 4.37 %) is also recommended because of its simplicity; (iii) The Multi-TLSMAD (AARD = 4.32 % and ARD = −0.29 %) and three correlations of Magalhães et al. (AARD = 2.94–3.03 % and ARD = 0.14–0.40 %) can be chosen if their parameters are known or if some data points are available for their preliminary estimation.

Numerical investigations of electric field-mediated active droplet transfer in a ternary phase system

A method of active transport of a droplet from a carrier liquid to a target liquid is proposed with the aid of an electric field. Numerical investigations shed light on the dynamics associated with the active migration of a water droplet across the interface of two weakly conducting oils via application of an electric field. With the aid of two model ternary liquid systems, two modes of droplet transfer are identified—(i) the film drainage mode and (ii) the tailing mode. In the film drainage mode obtained for the model system of silicone oil–water–oleic acid, at low electric fields, the water droplets undergo negligible distortions in shape and the film drainage and rupture occur in a quasi-steady manner. At higher fields, the droplet distorts into a prolate with unsteady drainage and the film rupture. The rate of film drainage increases with the strength of the applied electric field. The tailing mode of droplet transport is achieved for very low interfacial tension between the carrier and the target liquids. For the model system of silicone oil–water–soybean oil, in the tailing mode, the droplet entrains carrier liquid approximately equal to 4.5 times its own volume into the target liquid with the length of the tail as high as eight times the drop radius. The interfacial tensions of the liquid pairs, densities, viscosities, and dielectric constants of the liquids comprising the ternary system are the key parameters influencing the dynamics of migrations. The phenomena may find applications in liquid–liquid extraction, micro-reactions, and ultra-low tensiometry.

Ultrasonic analysis of ternary liquid mixture of riboflavin with water and methanol at 288K

In the present study, density, viscosity and ultrasonic velocity have been measured for ternary liquid system of Riboflavin with water and methanol at 288 K in the concentration range 0.00 to 0.1 M. These measured values and derived parameters were used to performed molecular interaction study at 2 MHz using ultrasonic interferometer technique. The results of reported study have been thoroughly analysed and eventually interpreted at the possible molecular interaction such as structure making, solute-solvent and hydrogen bonding effect in the liquid solution of Riboflavin with water and methanol.

Physicochemical properties of a ternary liquid system containing Tri-n-butyl phosphate, benzene and m-xylene at temperatures ranging from 298.15 to 313. 15 K

• Ultrasonic velocity ( U ), density ( ρ ) and viscosity ( η ) of ternary liquid mixtures (Tri-n‑butyl phosphate + benzene + m -xylene) were measured. • Deviation functions have been computed from experimental data and discussed graphically. • These deviation functions were fitted to Redlich-Kister type of polynomial equation to estimate coefficients and standard error. • Ultrasonic velocities of ternary system (TBP + benzene + m -xylene) were computed by using different theoretical models. • Molecular interactions between components of ternary system were discussed. Ultrasonic velocity, density and viscosity of ternary liquid system: Tri-n‑butyl phosphate + benzene + m -xylene have been measured at atmospheric pressure (0.1 MPa) and at temperature ranging from 298.15 to 313.15 K. The observed data were utilized to calculate various physicochemical properties such as relaxation time ( τ ), isentropic compressibility ( Ks ), intermolecular free length ( L f ) and free volume ( V f ). The deviation in isentropic compressibility ( ΔK s ), intermolecular free length ( ΔL f ) and free volume ( ΔV f ) were computed and fitted to the Redlich-Kister type of polynomial equation. The deviation functions were discussed in terms of molecular interactions existing between the unlike components of the system. Further, ultrasonic velocities were computed by using different theoretical models of ultrasonic velocity such as Nomoto's relation, Van Dael-Vangeel's ideal mixing relation, Impedance dependence relation and Rao's specific sound velocity relation and have been compared with the corresponding experimental data. The IDR model has shown close results to experimental observations.

Application of graduate‐level numerical tools to teach phase equilibria of liquid ternary systems

AbstractThe present paper describes a numerical technique to compute phase equilibria of ternary liquid systems. First, particle swarm optimization is used to estimate the binary interaction parameters of the NRTL (Non‐Random Two Liquid) and UNIQUAC (Universal Quasi‐Chemical) models. We show how the arc‐length continuation method allows the calculation of the liquid–liquid equilibrium diagram for any ternary system. A total of seven case studies of industrially important mixtures are described. Both Type I systems (oleic acid–water–ethanol, water–1‐propanol–toluene, DEC–ethanol–water, water–propionic acid–n‐hexane, and water–TMA–benzene) and Type II mixtures (water–1‐butanol–n‐hexane) are discussed. In addition, a system with temperature‐dependent behavior (n‐hexane–methyl cyclopentane–aniline) is studied. The numerical techniques and the thermodynamic problem involved in this paper are suitable for a first‐year graduate‐level course in chemical engineering. All computer coding is based either on Mathematica© or Matlab®. This is an ideal opportunity to introduce graduate students to advanced commands and programming syntax of state‐of‐the‐art mathematical software.

Estimation of Thermodynamic Properties and Phase Equilibria in Systems of Deep Eutectic Solvents by PC-SAFT EoS

This study examines the capabilities and shortcomings of perturbed-chain-statistical associating fluid theory equations of state (PC-SAFT EoS) applied for predicting properties and phase equilibria in systems of deep eutectic solvents. Treating deep eutectic solvents as pseudo-pure compounds and describing them as mixtures of two independent constituents are explored. Examples of choline chloride as the hydrogen bond acceptor (HBA) and levulinic acid, ethylene glycol, and phenol as hydrogen bond donors (HBDs) in a 1:2 molar ratio are considered. Excess properties of deep eutectic solvents with n-alkanols and water along with solubilities of carbon dioxide and ammonia are also considered. Besides that, liquid–liquid ternary systems of deep eutectic solvents with n-alkanes and 1-alkanols are analyzed. It has been found that although the pseudo-pure compounds approach with 2B associative scheme correctly estimates excess volumes, it exhibits poor accuracy in predicting excess enthalpies, solubility data, and liquid–liquid equilibria in ternary systems. When a temperature-dependent binary interaction between HBA and HBDs is applied, the individual approach predicts these properties in a more accurate manner.

A molecular dynamics study of the atomic-level surface structural phase diagram for the existence form of nanobubbles and its influence in a dynamic system

The nucleation of nanobubbles was studied through molecular dynamics (MD) simulations. The wettability and surface atomic-level structural features of the substrate were found to play a role in a ternary (solid, liquid, and gas) system that was composed of only simple Lennard-Jones fluids. The simulation first revealed that surface nanobubbles form only on a hydrophobic substrate, while for a hydrophilic substrate, bulk nanobubbles are formed in the liquid. Second, the existence form of nanobubbles and some behavioral characteristics strongly depend on the surface structural features. Specifically, we deduced the phase diagram of the nanobubbles with respect to the critical structural parameters and then defined a critical region for the formation of surface nanobubbles: cap-shaped surface nanobubbles can stably form above the upper critical line but not below the lower critical line; the contact angle decreases as the parameter value increases. Finally, the existence of nanobubbles was found to affect the dynamic properties of the system.

Estimation of the viscosities of melt for Sn-based ternary lead-free solder alloys

ABSTRACTThe proposed thermodynamic parameters were extended to the liquid ternary alloy system, and a prediction model of the viscosity for liquid alloy was proposed. The viscosity of the ternary liquid lead-free solder alloy was calculated using the thermodynamic parameters and the prediction model for viscosity of ternary liquid alloy. The results show that the calculated viscosity of the ternary liquid lead-free solder alloy is consistent with the reported experimental values, and the prediction model has good rationality. At the same time, compared with the complex Seetharaman model, Moelwyn-Hughes model and Kaptay model, the prediction model for viscosity of ternary liquid alloy depends only on the element's basic physical parameter (density, melting temperature, absolute atomic mass, electro-negativity, electron density, molar volume, and Pauling radius). The entire calculation process is relatively simple. Additionally, the proposed prediction model of viscosity can be applied to system calculations having similar physical and thermodynamic properties as ternary liquid Tin-based lead-free alloys.

Validation of Messaâdi equation on viscosity-temperature dependence for some ternary liquid mixtures by statistical correlation analysis

ABSTRACT The analysis of viscosity of fluid systems is in great demand by the optimisation of industrial products and processes. For this instance, numerous empirical expressions have been suggested in the literature to treat and investigate the viscosity of pure, binary and ternary solvents mixtures. In this circumstance, an interesting empirical equation correlating the two parameters related to the viscosity Arrhenius-type equation has recently proposed by Messaâdi et al. for some pure solvents and binary liquid mixtures. This work attempts to extend their equation to ternary liquid systems. Statistical analysis is made to perform this aim by utilising 113 data sets from previous works of some ternary solvents systems at different compositions. The validation of the generalised Messaâdi expression for ternary liquid systems oversimplifies the prediction of shear viscous behaviour as well as the estimation of one non-disposable parameter value when only the second one is present in literature.

Determination of surface tension of liquid ternary Ni–Cu–Fe and sub-binary alloys

ABSTRACTExperimental data in the literature are almost limited to determine the thermophysical properties of multicomponent complex alloys, especially due to the inability of laboratories to achieve the desired ideal conditions, due to the difficulty of protection from oxidation at high temperatures and other contamination at high temperatures, due to time and cost in laboratory studies. Due to these reasons, the theoretical data obtained in this subject is of great importance. In this study, a series of geometric and physical models, such as Chou’s general solution model (GSM), Muggianu’s Model, Kohler’s Model, Toop’s Model, Hillert’s Model, Guggenheim’s Model, Butler’s Model, Egry’s Model and ideal solution model for quasi-binary alloy system for Section A: Ni0.4(1 – x)CuxFe0.6(1 – x). and Section B: (NixCu0.2Fe0.8 – x) are used to calculate the surface tension-composition and surface tension-temperature curves of the Cu-Fe-Ni ternary liquid system are plotted. The data for this process is evaluated by means of an extended Redlich-Kister-Muggianu polynomial fit to the experimental values of the surface tensions of the binary liquid alloy systems. The obtained results for these models are also compared with the available data in the literature and relatively good agreements are observed. In addition, the surface segregation having important key factor in determining surface tension of the liquid alloy Ni-Fe-Cu has also been investigated in this work.

Densities, viscosities, and refractive indices of binary and ternary mixtures of methanol, acetone, and chloroform at temperatures from (298.15–318.15) K and ambient pressure

Densities, viscosities, and refractive indices of binary and ternary liquid systems of methanol, acetone, and chloroform at temperatures from)298.15–318.15(K and ambient pressure were measured. In this regard, it should be stressed that the measurements covered the whole composition range of the components in the binary and the ternary systems. In addition, the experimental data have been utilized in order to extract some derived properties like excess molar volume (VE), viscosity deviation (Δη), and refractive index deviation (ΔnD). To correlate the aforementioned derived properties, the well-known Redlich-Kister and Cibulka equations were applied on the binary and ternary mixtures, respectively. Consequently, the control parameters, as well as the corresponding standard deviations, were completely reported. Moreover, for further validation, the McAllister three-body interaction model for kinematic viscosity and Grunberg-Nissan model for dynamic viscosity were examined and the results were thoroughly compatible with the Redlich-Kister polynomial equation. By using the derived properties, the nature of the intermolecular interactions and the hydrogen bond between solvents in the binary and ternary mixtures were discussed and the results are satisfying in terms of matching to the theoretical models.

Insights for Designing the Hydrocarbon Recovery from Ionic Liquids by Distillation in the Aliphatic/aromatic Separation by Liquid-liquid Extraction

Nowadays the aliphatic/aromatic separation by liquid-liquid extraction using ionic liquids (ILs) is an interesting topic in the search of a new class of separation processes for the oil industry. The wide majority of papers published until now has focused in maximizing the IL extractive properties as can be found in a recent review by Canales and Brennecke (2016); in addition, in the recent past, this search was also oriented to find a commitment election between IL extractive and physical properties, with especial focus on reducing the viscosity to limit its impact on mass transfer and pumping (Larriba et al., 2013a). However, the challenge in the development of this new liquid-liquid extraction technology based on ILs is the selective recovery of aromatics from the solvent. Although IL non-volatile character is suggested as a clear advantage for separation purposes, this is truly a limitation in the vapor-liquid separation as was reported in last papers dealing with the vapor-liquid equilibria involving aliphatics, aromatics, and ILs due to the pretty low equilibrium pressures (Navarro et al., 2015). In addition, the thermal stability of ILs is another drawback since scarce species could be used at industrial scale over 473 K (Navarro et al., 2013). Finally, extracted aromatics have not commercial purity and further purification is mandatory before the aromatic/IL separation (Larriba et al., 2013a). In this work, the simulation of three different recovery sections based on vapor-liquid separations was performed to give some remarks that can help to design distillation processes involving large amounts of ionic liquids. Seven ionic liquids among the most promising species proved so far were selected to completely cover the transferability between liquid-liquid and vapor-liquid equilibria (LLE and VLE, respectively). Aspen Plus commercial simulator was used implementing the Non-Random Two Liquids (NRTL) models from the experimental data regressions for the corresponding n-heptane + toluene + ionic liquid ternary systems. Aromatic recoveries and purities for three different process configurations were analysed in order to stablish the impact of the ionic liquid extractive and thermal properties on the design of a suitable recovery section from an industrial point of view.

Liquid–Liquid Extraction of Alcohols from Their Azeotropic Mixtures with Hexane Using Ionic Liquid

The phase behavior of alkane/alcohol/ionic liquid ternary systems is essential for designing the separation process of alcohol from its mixture with alkane. In this work, 1-ethyl-3-metylimidazolium thiocyanate ([Emim][SCN]) has been experimentally studied as an extractive agent for this process. New experimental liquid–liquid equilibria (LLE) data for four ternary systems (hexane/ethanol/[Emim][SCN], hexane/1-propanol/[Emim][SCN], hexane/2-propanol/[Emim][SCN], and hexane/1-butanol/[Emim][SCN]) are presented under standard conditions (pressure = 101.3 kPa and temperature = 298.15 K). The selectivity (S) and solute distribution coefficient (β) are measured to investigate the effectiveness of ionic liquid as a solvent to separate alcohol from its azeotropic mixtures with hexane. Furthermore, the effect of alcohol chain length has been investigated. Finally, nonrandom two-liquid model is utilized and tuned to model the experimental LLE data.

Unravelling various types of non-covalent interactions of benzyl amine with ethers in n – hexane at 303.15K by ultrasonic and DFT methods

Physicochemical behaviour of n – hexane solutions containing benzyl amine (BA) and alicyclic ethers in the concentration range 0.02M–0.20 M is extensively studied through acoustical (experimental) and Density Functional Theory (DFT) methods and the nature of non-covalent molecular interactions existing in these ternary liquid mixtures have been investigated. Two structurally different ethers, namely, tetrahydrofuran (THF) and 1,4-dioxane (DIOX) are used. Ultrasonic velocity (u) at 2 MHz frequency, density (ρ) and viscosity (η) are measured for the ternary liquid systems at different concentrations andat 303.15 K. The existence of strong BA – ether non-covalent interaction and formation of hydrogen bonded complexes is identified in both the systems through the variations in acoustical and excess thermo-acoustical parameters with concentration. The influence of structure of ether on the strength of molecular interaction has been analysed through the calculation of formation constants of these complexes computed using Kannappan equation. An attempt has been made using meta hybrid density functional theory to confirm the existence of hydrogen bonded complexes in these two systems through the computed interaction energies and hydrogen bonding parameters. Computational investigation shows CH---π dispersive interactions in these complexes in addition to the classical hydrogen bonding.

The Development of Intelligent Models for Liquid–Liquid Equilibria (LLE) Phase Behavior of Thiophene/Alkane/Ionic Liquid Ternary System

ABSTRACT This paper develops three models based on artificial neural network (ANN), support vector machine (SVM) and least square support vector machine (LSSVM) algorithm for phase behavior of thiophene/alkane/ionic liquid ternary system. The shuffled complex evolution (SCE) was employed to acquire the optimal magnitudes of hyper parameters (σ2 and γ) which are embedded parts of SVM and LSSVM models, and the trial and error was employed to obtain the optimal numbers of neuron and layers for ANN intelligent model. Gathering and using 618 LLE data, the comparison between the optimized version of applied intelligent models in giving the LLE was also made. The findings are indicative of a prefect agreement between the estimation from intelligent models and the experimental data. The finding also reveals that the performance of SVM in prediction of solubility is somewhat better than other intelligent models (i.e., ANN and SVM) as coefficient determination (R2) and root mean squared error (RMSE) are respectively 0.9961 and 0.0447 for test sets of data. This is likely due to the existence of structural risk minimization principle of SVM which is embodied in SVM algorithm and effectively minimizes upper bound of the generalization error, rather than minimizing the training error.

On the impact of the ISS reboosting maneuvers during thermodiffusion experiments of ternary liquid systems: Pure diffusion

In the present study, the effects of reboosting maneuvers on the diffusion process during the thermodiffusion experiments known as Diffusion and thermodiffusion Coefficients Measurements in ternary liquid mIXtures (DCMIX) are analyzed. These experiments have systematically conducted in the International Space Station (ISS). Six different compositions of a 1,2,3,4-TetraHydroNaphtalene (THN), IsoButylBenzene (IBB) and n-Dodecane (nC12) mixture have been studied by means of numerical simulations. Real acceleration levels have been used to compute the unsteady buoyancy term in the momentum equation. Different gravity scenarios have been considered by changing both the intensity and the duration of the reboosting as well as its orientation, parallel or perpendicular to the concentration gradients. In these thermodiffusion experiments, the different components of the mixture separate in a parallelepipedic Soret cell, with a constant externally imposed temperature gradient between two opposite walls. When the temperature and concentration distributions reach the steady state, and consequently linear concentration profiles between hot and cold walls are achieved, the temperature difference is switched off and the components of the mixture diffuse until uniform concentration distributions are obtained. The present simulations only reproduce this last pure diffusive part of the thermodiffusion experiment. Results show that when a reboosting occurs, errors in the obtaining of the diffusion coefficients arise because of the convection generated. The lower values of the diffusion coefficient show a larger error since they are more sensitive to disturbances. The maximum error is obtained when the acceleration is acting perpendicular to the concentration gradient, which is the most harmful orientation.

Property estimation of water/alcohol/ionic liquid ternary system: Density

One of the most highly important applications of ionic liquids is for separation of the components of water/alcohol azeotropic mixture. The use of ionic liquids for this purpose creates a ternary system for which the determination of thermodynamic behavior and physical properties is highly matter of interest in design and operation of effective separation plants. In this work, the density of the aqueous ionic liquid ternary system is modelled based on three intelligent connectionist approaches. For the modelling, 1663 experimental density data points for ternary systems including 17 different ionic liquids in four aqueous alcohols (methanol, ethanol, propanol, and pentanol) solution were analyzed and taken into account at temperature range [288–343] K and pressure ranges [100–3000] kPa. The Shuffled complex evolution (SCE) algorithm was employed for optimization of the model parameters and constants. Four statistical parameters of R2, AARD, RMSE and STD were calculated for the connectionist models to compare their performance in the degree of comprehensiveness and accuracy. The highly matched results of the modelling with experimental demonstrate that the intelligent approach provides a suitable replacement for conventional thermodynamic models and equation of states which need too many fitting parameters.