Binodal Research Articles

Using COSMO-RS to design organic biphasic systems containing deep eutectic solvents for the separation of natural compounds

This study is aimed at evaluating the potential of the conductor-like screening model for real solvents (COSMO-RS) in designing biphasic systems for the separation of natural compounds. This model was used to predict binodal curves and phases composition of organic biphasic systems containing deep eutectic solvents. The results obtained demonstrate that COSMO-RS in most cases predict the binodal curves of the biphasic systems with a good precision. Moreover, the partition coefficients of six natural compounds, namely quercetin, apigenin, coumarin, β-ionone, retinol, and α-tocopherol, were evaluated, with COSMO-RS predictions showing excellent agreement with experimental data when the compound partition significantly in both phases. Furthermore, COSMO-RS was able to effectively capture the influence of changes in the system composition on partition coefficients. Thus, these results indicate that COSMO-RS can be a powerful tool in the design of separation and purification systems.

Estimation of solid-liquid coexistence curve for coarse-grained water models through reliable free energy method

The anomalies properties of water have been interpreted theoretically using several all-atom and coarse-grained water models. Here we use a robust and traditional free energy approach to develop the solid-liquid coexistence curve for water using coarse-grained monatomic mW and machine-learned bond order potential (ML-BOP) water models. We employ the pseudo-supercritical thermodynamic path in combining multiple histogram reweighting (MHR) and Gibbs-Duhem integration. The ML-BOP model has a broad density-temperature hysteresis loop and shows lower maximum and minimum densities as compared to the mW model. The computed excess Helmholtz free energy and the Gibbs free energy at the approximate melting temperature are higher for the ML-BOP model in comparison with the mW model. The pressure dependence fusion curve for both water models aligns with the literature. This analysis indicates that the free energy method accurately captures the solid-liquid transformation and the thermodynamic melting point of water.

Design of novel aqueous two-phase systems to be coupled in biological remediation processes

The ability of a biodegradable Deep Eutectic Solvent (DES) reline to induce phase segregation in aqueous solutions of polymeric non-ionic surfactants (Tween 20 and Tween 80) has been demonstrated as a preliminary step to be employed for assisting a biological degradation process of a model contaminant. The binodal curves for systems composed of (surfactants + reline + Water) have been determined at several temperatures, and the experimental data have been correlated using well-known equations. The equilibrium data have been analysed in the light of the operating temperature and the hydrophobicity of surfactants. Tie-lines of these systems have been determined, together with useful parameters such as tie-line length and tie-line slopes. Othmer-Tobias and Bancroft equations have been applied to provide an adequate description of the equilibrium data. Finally, the application of this new approach for the remediation of aqueous polluted effluent has proven to be highly efficient, with extraction percentages exceeding 99% for two model persistent contaminants (Acid Black 48 and Crystal Violet). Consequently, this ATPS is proposed as an extra-stage to enhance the remediation percentages achieved through biological methods. Furthermore, the process has been simulated using commercial software.

A Comparative Azeotropic Research on Combustion of Common Ternary Systems

Methyl Tertiary Butyl Ether (MTBE) and Methanol are effective fuel oxygenate that boost octane number, improve fuel performance, combustion behavior and minimize environmental pollutant emissions. In the petroleum business, however, their high-water solubility restricts their use in terms of fuel homogeneity loss. This work presents a full investigation map for the status of the phase diagram for the tertiary system of MTBE-methanol-water at different temperatures; 0, 40, and 70oC, and different pressures; 1.0 and 3.0 atm, based on different compositions. Furthermore, the thermodynamic coefficient, UNIFAC-LL, was linked to the Aspen plus Version 9. After validation of the software by the real experimental data, the software was used to complete the full map at all missing conditions. Pressure does not influence the occurrence of phase transitions, but the temperature has a minor effect on the LLE. The methanol concentration at which phase separation occurred dropped from 43% to 31.2% when the temperature was lowered from 70 to 40°C. With the use of simulation, the compositions at which phase separation occurs were also discovered. Last but not least, it was observed that the thermodynamic model (UNIFAC-LL) properly predicted the behavior of the methanol-water–MTBE ternary system with less than 3% inaccuracy in the binodal curve points. Consequently, a validated phase diagram is developed to accurately predict the physical state of the MTBE-methanol-water system at ant temperature, pressure, and mole fraction of each component. Hence, it guarantees the feasibility of using this tertiary system, as an effective octane booster additive, under severe working conditions.

Measurements, correlations and thermodynamic modeling of aqueous two-phase systems of polyvinylpyrrolidone (PVP) + sulfate/citrate salts

Aqueous two-phase systems (ATPS) can be described as an alternative to traditional liquid-liquid extraction systems, typically consisting of a polymer and a salt solution. An alternative polymer called polyvinylpyrrolidone (PVP) has emerged as a viable option for ATPS due to its low cost, stability, and potential. This study aimed to investigate the effect of the molecular weight of poly (vinylpyrrolidone) (PVP) (K17, K25, and K30) and the temperature (298.15, 303.15, and 308.15 K) in the system ATPSs composed of PVPs and sodium sulfate/potassium sulfate/tri sodium citrate. The tie-line data were determined by measuring the density (ρ) and refractive index (nD). Moreover, the phase compositions and plait point are investigated for different PVPs molecular weight, temperature, and salt type. In addition, the effect of these parameters on the binodal curve, tie-line length (TLL), and slope of tie line (STL) are analyzed in detail by comparing them with the literature data. The impact of the parameters on the binodal curves was investigated by utilizing the values of the effective excluded volume parameter (EEV) that were calculated from the LLE data. Furthermore, the binodal curves and the tie-line compositions were well-fitted by using some semi-empirical equations. The phase separation ability is enhanced with temperature and PVPs molecular weight. The modified UNIFAC-NRF is used to correlate the liquid-liquid equilibrium data of the studied systems and the optimized binary group interaction parameters were determined.

Improved accuracy in pentraxin-3 quantification assisted by aqueous biphasic systems as serum pretreatment strategies

Although pentraxin-3 holds promise as a diagnosis/prognosis biomarker of microbial infections and lung cancer, its analysis in human serum can be constrained by matrix effects caused by high abundance proteins – human serum albumin and immunoglobulin G. Aqueous biphasic systems composed of polymers and citrate buffer are here proposed as a serum pretreatment step to improve the accuracy of pentraxin-3 analysis. Binodal curves were determined to identify the compositions required to form two phases and to correlate the polymers' properties and performance in serum pretreatment and biomarker extraction. Aqueous biphasic systems were evaluated regarding their ability to deplete human serum albumin and immunoglobulin G at the interphase. Polymers of relatively high to intermediate hydrophobicity were unveiled as efficient components to deplete high abundance serum proteins. Considering the possibility to extract pentraxin-3 from human serum into the polymer-rich phase, the system composed of polyethylene glycol with a molecular weight of 1000 g·mol−1 simultaneously achieved >93 % of human serum albumin and immunoglobulin G depletion and complete biomarker extraction. The accuracy of analysis of pretreated human serum by enzyme-linked immunosorbent assays outperformed that of a non-pretreated sample, with a relative error of 0.8 % compared to 14.6 %, contributing to boost pentraxin-3 usefulness as a biomarker.

Assessment of the pseudopotential lattice-Boltzmann method for modeling multiphase fuel droplets

An improved pseudopotential lattice–Boltzmann model was proposed for simulating multiphase flow dynamics to describe fuel droplets, and its thermodynamic consistency was tested against the Peng–Robinson equation of state. The studied liquid fuels included paraffinic hydrocarbons with a different number of carbon atoms (C[Formula: see text]–C[Formula: see text]), methanol (CH[Formula: see text]OH), hydrogen (H[Formula: see text]), ammonia (NH[Formula: see text]), and water (H[Formula: see text]O). To improve accuracy and reduce the magnitude of the spurious currents, the multi-relaxation times collision operator was implemented and the forcing term was computed using the hybrid pseudopotential interaction force with an eighth-order isotropic degree. The pseudopotential lattice–Boltzmann model accurately predicted the equilibrium densities and captured satisfactorily the thermodynamic vapor-liquid coexistence curve given by the analytical solution of the Peng–Robinson equation of state for acentric factors ranging from [Formula: see text]0.22 to 0.56, keeping the maximum average error for the liquid and vapor branches below 0.8% and 3.7%, respectively. Nevertheless, Peng–Robinson was found to be insufficiently accurate to replicate the actual thermodynamic state, especially for H[Formula: see text]O and CH[Formula: see text]OH, for which the results strongly deviated from the experimental vapor-liquid equilibrium densities and reached average errors for the vapor phase of nearly 28%. Furthermore, the surface tension ([Formula: see text]) was retrieved using the multiphase pseudopotential lattice–Boltzmann results and served to verify the thermodynamic consistency of the pseudopotential lattice–Boltzmann with respect to the parachor model. Lastly, the pseudopotential lattice–Boltzmann model was also shown to predict accurately the transient behavior of oscillating droplets. Overall, the enhanced model satisfactorily predicted the properties and behavior of the substances for a wide range of conditions.

Characterization of choline chloride‐based deep eutectic solvent for anthocyanin extraction via aqueous two‐phase system: Physicochemical properties and liquid–liquid equilibrium phase diagram

AbstractThe purpose of this research is to characterize and explore the feasibility of deep eutectic solvent‐based aqueous two‐phase system (DES‐ATPS) for its potential application in the extraction and purification of anthocyanins. Various combinations and molar ratios of DES using choline chloride as hydrogen bond acceptor (HBA) and butanediol (BDO), ethylene glycol (EG), and lactic acid (LA) as hydrogen bond donor (HBD) were synthesized, screened, and investigated on its physicochemical properties. The binodal phase diagrams were developed as basis for the ATPS development. It was noted that LA‐based natural deep eutectic solvents (NADES) were highly polar and likely to enhance the solubility of anthocyanin in DES. Regardless, the simple molecular structure and low viscosity of EG‐ and BDO‐based DES enhanced the solubility of anthocyanin and recorded a monomeric anthocyanin content ranging from 10.52 ± 0.78 mg cyanidin‐3‐glucoside/g at 40°C and 10.78 ± 0.84 mg cyanidin‐3‐glucoside/g at 30°C, respectively. Lastly, the liquid–liquid equilibrium binodal curves were developed and ChCl:1,3‐BDO (1:4) and ChCl:1,4‐BDO (1:4) exhibited excellent phase‐forming ability, thus concluding its excellent potential for anthocyanin extraction through ATPS.

Equilibrium phase behavior of ternary systems formed by polyethylene glycol + choline salts + water

The economic and environmental potentialities of the application of choline salts in aqueous two-phase systems (ATPS), as well as the incipiency of works of these ionic liquids (ILs) combined with polyethylene glycol (PEG), are the reasons for the characterization of new “green” ATPS formed by PEG (400 and 1500 g.mol−1) combined with choline-based ILs (choline chloride, choline bitartrate, and choline dihydrogen citrate). Choline chloride was preferentially concentrated in the top phase, while the lower phase was rich in PEG. The opposite behavior was observed for bitartrate and dihydrogen citrate. ATPS formed by PEG1500 exhibits a significant increase in the biphasic area as the temperature increases; while for systems formed by PEG400, this same trend is slight, demonstrating that phase segregation has an endothermic character. The salting-out effect and the hydrophobicity of the polymer explain the increase of the biphasic area with increasing the charge density of the anion and increasing polymer molar mass, respectively. The data were fitted with good correlation using the Merchuk equation for the binodal curves and Guan equation for the tie-lines.

Liquid−vapor order parameter and coexistence-curve diameter of nitrogen, ethylene, and sulfur hexafluoride: From the triple point to the critical scaling regime

Analytic closed-form expressions are obtained for the liquid and vapor saturation densities defining the coexistence curve. The densities are modeled with broken power laws and Weibull distributions. Specifically, the coexistence curves of nitrogen, ethene and sulfur hexafluoride are derived, without the use of perturbative expansions, based on high-precision data extending from the triple point into the critical regime. The analytic continuation of the vapor branch below the triple point decays exponentially at low temperature. The order parameter and coexistence-curve diameter of the fluids are assembled from the regressed liquid and vapor branches of the coexistence curve, and the critical power-law scaling of these quantities is examined. The scaling exponents of the order parameter and the reduced diameter are regressed and compared with the calculated critical exponents of the 3D Ising universality class. Index functions representing the Log−Log slopes (temperature-dependent effective exponents) of the liquid and vapor densities, order parameter and diameter are used to determine the onset of the ideal power-law scaling regime and to illustrate the slope evolution of these quantities in the subcritical regime.

Molecular dynamics study of diffusionless phase transformations in HMX: β-HMX twinning and β-ɛ phase transition

We use molecular dynamics to study the mechanism of deformation twinning of β-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (β-HMX) in the P21/n space group setting for the twin system specified by K1=(101), η1=[101¯], K2=(101¯), and η2=[101] at T=1 and 300 K. Twinning of a single perfect crystal was induced by imposing increasing stress. The following three forms of stress were considered: uniaxial compression along [001], shear stress in the K1 plane along the η1 direction, and shear stress in the K2 plane along the η2 direction. In all cases, the crystal transforms to its twin by the same mechanism: as the stress increases, the a and c lattice parameters become, respectively, longer and shorter; soon after the magnitude of a exceeds that of c the system undergoes a quick phase-transition-like transformation. This transformation can be approximately separated into two stages: glide of the essentially intact {101} crystal planes along ⟨101¯⟩ crystal directions followed by rotations of all HMX molecules accompanied by N-NO2 and CH2 group rearrangements. The overall process corresponds to a military transformation. If uniaxial compression along [001] is applied to a β-HMX crystal which is already subject to a hydrostatic pressure ≳10 GPa, the transformation described above proceeds through the crystal-plane gliding stage but only minor molecular rearrangements occurs. This results in a high-pressure phase of HMX which belongs to the P21/n space group. The coexistence curve for this high-pressure phase and β-HMX is constructed using the harmonic approximation for the crystal Hamiltonians.

Parameters of the Liquid-Gas-State Triangle for Hard-Core Attractive Yukawa Fluids.

We discuss the triangle of the liquid-gas concept within the fluid-lattice gas isomorphism approach and the Zeno-element, taking the hard-core Yukawa fluid (HCAYF) as an example. The applicability of such an isomorphism is demonstrated by the symmetrization of binodals with mapping onto the Ising model coexistence curve. We show that the parameters of the isomorphism transformation reflect the liquid-phase instability for hard-core Yukawa potential and its generalization. We also provide a simple mean-field estimate for the parameter z of the fluid-lattice gas transformation and use it to obtain the locus of the critical point.

Using the Intrinsic Geometry of Binodal Curves to Simplify the Computation of Ternary Liquid-Liquid Phase Diagrams.

Phase diagrams are powerful tools to understand the multi-scale behaviour of complex systems. Yet, their determination requires in practice both experiments and computations, which quickly becomes a daunting task. Here, we propose a geometrical approach to simplify the numerical computation of liquid-liquid ternary phase diagrams. We show that using the intrinsic geometry of the binodal curve, it is possible to formulate the problem as a simple set of ordinary differential equations in an extended 4D space. Consequently, if the thermodynamic potential, such as Gibbs free energy, is known from an experimental data set, the whole phase diagram, including the spinodal curve, can be easily computed. We showcase this approach on four ternary liquid-liquid diagrams, with different topological properties, using a modified Flory-Huggins model. We demonstrate that our method leads to similar or better results comparing those obtained with other methods, but with a much simpler procedure. Acknowledging and using the intrinsic geometry of phase diagrams thus appears as a promising way to further develop the computation of multiphase diagrams.

Thermodynamics and microstructures of Euler–Heisenberg black hole in a cavity

Euler–Heisenberg black holes with quantum electrodynamics (QED) correction are embraced by a cavity in this paper, which serves as a boundary of the black hole spacetime and contributes to the equilibrium of the system. We explore the thermodynamic properties of the black hole, including the phase transitions and phase structures. The small/large black hole phase transition occurs for a negative QED parameter, while the reentrant phase transition can be observed for a small positive QED parameter. Then the thermodynamic geometry is investigated to diagnose microscopic interactions of black hole thermodynamic systems. For the reentrant phase transition, the small black holes are dominated by repulsion for the first-order coexistence curve, while the interaction between the small black hole molecules could be attractive or repulsive for the small/large black hole phase transition.

High-order modeling of multiphase flows: Based on discrete Boltzmann method

The high-order kinetic model for compressible multiphase flow is presented within the framework of the discrete Boltzmann method (DBM). Based on the Carnahan–Starling state equation, this model can describe the phase transition by introducing a source term of molecular interaction on the right-hand side of the Boltzmann equation. Meanwhile, the force term is incorporated to describe the external force. Through Hermite polynomial expansion, the equilibrium distribution function is expressed. Compared to the Navier–Stokes equations, the DBM provides more detailed and accurate information on both hydrodynamic and thermodynamic non-equilibrium effects. Finally, the model is verified through several typical benchmarks, including the liquid–vapor coexistence curve, free-falling process, shock wave, sound wave, thermal phase separation, and two-bubble oblique collision.

Molecular simulations of the vapour-liquid coexistence curve of square-well dimer fluids

In this work, we evaluate the liquid-vapour coexistence diagram and the critical point for two different ranges, and of the square-well dimer fluid, using two different simulation methods: (1) In the critical point vicinity, we use a new algorithm, based on transition rates, that can obtain the chemical potential as a function of the density at a given temperature and (2) Molecular Dynamics simulations using the direct coexistence technique for temperatures far below the critical region. The transition rate method has been proposed by Sastre and was used for the evaluation of the critical temperature of square-well monomers with high accuracy. The simulations in the low-temperature region were carried out using molecular dynamics simulations with the direct coexistence method and a continuous version of the square-well potential proposed recently by Zerón et al.

Nanoprecipitation through solvent-shifting using rapid mixing: Dispelling the Ouzo boundary to reach large solute concentrations

HypothesisThe addition of a non-solvent to a solute in good solvent solution leads to nanoprecipitation, which is the spontaneous formation of nanodomains. Yet, increasing solute concentration usually leads to the formation of macrodomains that quickly separate into a bulk phase, which is a severe process limitation. The corresponding concentration threshold, often termed as the Ouzo boundary, remains a mystery that could find its origin in the complex interplay between nanoprecipitation and mixing. ExperimentsWe performed a systematic investigation of nanoprecipitation thermodynamics and kinetics as well as its interplay with mixing hydrodynamics for the hexadecane-acetone-water system, in the presence of the non-ionic C16EO8 surfactant. The binodal curve and its underlying tie-lines were obtained using Raman spectroscopy, allowing the computation of the spinodal curve. Kinetics were probed using a continuous flow setup that combines two sequential rapid mixers. The impact of mixing efficiency was probed systematically by varying the oil concentration for respectively slow and rapid mixing, while the uncoupling from mixing and nanoprecipitation was quantified by modifying systematically the flow rate in a continuous flow approach. FindingsWe elucidate the nature of the Ouzo boundary that marks the maximal solute concentration leading to nanoobjects. Rather than a thermodynamic boundary, as evidenced by its uncorrelation to the spinodal curve, it results from the coupling of nanoprecipitation and mixing when both processes occur within the same time range, leading to heterogeneous conditions and the escape of some objects to the macroscale. Increasing the solute concentration speeds up nanoprecipitation and thus requires increasingly faster mixing times to uncouple both processes. Accordingly, if the mixing efficiency is large enough, it is possible to dispel the Ouzo boundary and reach very large solute concentrations. Implementing rapid mixing strategies in continuous flow approaches is thus the solution to overcome the most stringent condition of nanoprecipitation and open the way to scale-up, while also providing efficient means to probe its fast mechanism. Overall, the simultaneous control of hydrodynamics and physical chemistry is thus key to boost up the Ouzo effect.

Behavior of the fullerene/water system under liquid and liquid–vapor conditions: A molecular dynamics approach

Classical molecular dynamics simulations were carried out to quantify the behavior of fullerenes in water, under liquid phase and liquid–vapor conditions. Different molalities of fullerene were considered in the study. Radial distribution functions, static dielectric constant and equation of state were evaluated in liquid phase. Direct liquid–vapor coexistence simulations of water with fullerene added were conducted to explore density profiles, liquid–vapor coexistence curve, pressure tensor components and surface tension variations with respect to water. An all-atom fullerene model studied by Monticelli and the SPC/ɛ description of water were used. At ambient conditions fullerene–fullerene and fullerene-water correlations decreased as molality increased. In turn, the static dielectric constant decreased due that fullerenes hinder the dipolar orientation of water molecules. As temperature increased, the static dielectric constant lowered. Part of the study was conducted at 373 K from 10 to 24 kbar, revealing that density of the system increased as molality was higher while fullerene-fullerene correlations decreased and fullerene-water correlations increased slightly. Concerning the static dielectric constant, a decrease was observed due that fullerenes and fullerene aggregates disturbed water structure as molality increased. As the system is compressed at a fixed molality, fullerenes become more uniformly distributed and the dielectric constant increases. Therefore, increasing the pressure is a mechanism to force the dipolar orientation of water molecules. On the other hand, liquid–vapor coexistence was studied from 280 to 650 K using molalities from 0.037 to 0.695 mol/kg. Liquid–vapor simulations revealed that the location of fullerenes and the formation of aggregates affect the behavior of surface tension. Fullerenes can locate at the liquid–vapor interfaces forming aggregates that obstruct the pass of water molecules to the vapor, so surface tension increases slightly with respect to water. At 0.695 mol/kg, larger clusters were observed but they located predominantly within the liquid phase and therefore acted in the opposite direction, that is, they favored the migration of water molecules to the vapor and surface tension dropped. In addition, a peculiar behavior was observed for temperatures above 500 K: surface tension increased its value as temperature increased. This behavior could be attributed to the fact that at such high molality the calculated surface tension might not longer correspond to liquid–vapor interfaces, instead it could be related to a sort of solid–liquid interface that have formed into the system. These calculations set the basis for improving the description of fullerene/water interactions as more experimental information becomes available and also serve as reference data in the design of interaction parameters to model water-soluble fullerenes.

Bitangent planes of surfaces and applications to thermodynamics

The classical van der Waals equation, applied to one or two mixing fluids, and the Helmholtz (free) energy function A yield, for fixed temperature T, a curve in the plane R2 (one fluid) or a surface in 3-space R3 (binary fluid). A line tangent to this curve in two places (bitangent line), or a set of planes tangent to this surface in two places (bitangent planes) have a thermodynamic significance which is well documented in the classical literature. Points of contact of bitangent planes trace ‘binodal curves’ on the surface in R3. The study of these bitangents is also classical, starting with D.J. Korteweg and J.D. van der Waals at the end of the 19th century, but continuing into modern times. In this paper we give a summary of the thermodynamic background and of other mathematical investigations and then present a new mathematical approach which classifies a wide range of situations in R3 where bitangents occur. In particular, we are able to justify many of the details in diagrams of binodal curves observed by Korteweg and others, using techniques from singularity theory.

Observation of Solid-Liquid Phase Transitions of Brine Using the Far-Ultraviolet Charge-Transfer-to-Solvent Band.

Although determining the chemical states of salts and ions is critical in numerous fields, such as elucidating biological functions and maintaining food quality, the current direct observation methods are insufficient. We propose a spectral analysis method of directly observing the phase transitions of NaCl solutions using the changes in the charge-transfer-to-solvent band and the absorption band representing the first electron transition (Ã ← X̃) of H2O. The intensities of these bands may be observed using attenuated total reflection far-ultraviolet spectroscopy. According to the well-known phase diagram of aqueous NaCl, we observe spectral changes during freezing-thawing and may spectroscopically detect the phase transitions from liquid to mixed liquid-solid and solid phases, including eutectic crystals, in addition to their coexistence curves.