Search Results (29)

The limited understanding of intermolecular interactions in deep eutectic solvents (DESs) has restricted their rational design and broader application. In this study, a series of hydrophobic DESs (HDESs) were prepared using lidocaine as the hydrogen bond acceptor and various carboxylic acids as hydrogen bond donors. Their physicochemical properties, including density, viscosity, and thermal stability, were systematically characterized. Interactions between components were evaluated through excess molar volume, viscosity deviation, and Grunberg–Nissan parameters. Strong hydrogen bonding between lidocaine and carboxylic acids was confirmed, which weakened with increasing alkyl chain length of the acids. Furthermore, as the acid content in the mixture increased, lidocaine’s ability to disrupt the intrinsic hydrogen-bonding network of the carboxylic acids decreased, thereby weakening the hydrogen bonding interactions between the components. The extraction capability of the HDESs for cobalt ions was evaluated in aqueous systems. Cobalt, a key material in lithium-ion batteries and advanced alloys, is in rising demand due to clean energy development. The lidocaine/decanoic acid (1:2) system exhibited nearly 100% extraction efficiency, surpassing conventional extractants. The hydrophobic nature of the HDESs facilitated effective phase separation and reduced solvent loss. These findings provide theoretical insights and design principles for developing high performance HDESs tailored for environmentally friendly metal recovery, particularly in battery recycling and treatment of industrial wastewater. Full article

The gas-liquid sulfonation of α-olefin sulfonate (AOS) in falling film reactors faces significant limitations, primarily due to poor mass transfer efficiency and excessive byproduct formation. To overcome these challenges, a novel cross-shaped microchannel reactor was developed for the continuous gas-liquid sulfonation of α-olefin (AO) with gaseous sulfur trioxide (SO₃). The influence of key process parameters, including gas-phase flow rate, reaction temperature, SO₃/AO molar ratio, and SO₃ volume fraction, on product characteristics and their interactions was systematically investigated using the single-factor experiment and response surface methodology (RSM). A high-precision empirical model (coefficient of determination, R² = 0.9882) to predict product content was successfully constructed. To achieve multi-objective optimization considering product active substance content and energy efficiency, a strategy combining a two-population genetic algorithm with the entropy-weighted TOPSIS (Technique for Order of Preference by Similarity to Ideal Solution) method was implemented. Optimal conditions were determined as follows: gas-phase flow rate of 228 mL/min, reaction temperature of 52 °C, SO₃/AO molar ratio of 1.27, and SO₃ volume fraction of 4%. Compared to conditions optimized solely by RSM, this multi-objective approach achieved a significant 10% reduction in energy efficiency, with only a marginal 3.8% decrease in active substance content. This study demonstrates the feasibility and advantages of microreactors for the efficient and green synthesis of AOS. Full article

The objective of this work was to study the volumetric and transport properties of mixtures made up of biodiesel and diesel, in order to meet the desirable properties of these formulations for their practical applications. The volumetric and transport properties were analyzed for two pseudobinary mixtures constituted of diesel + beef tallow butyl ester biodiesel and diesel + waste cooking oil methyl ester biodiesel in the whole range of composition at 0.078 MPa. The study of butyl ester biodiesel was motivated by the scarcity of these properties’ data for butyl esters and the improvement of some of its physicochemical properties. The biofuels were previously transesterified from waste materials and alcohols, beef tallow with 1-butanol and cooking oil with methanol. Density measurements were performed in a vibrating tube densimeter from 293.15 to 363.15 K; the kinematic viscosity experiments were carried out in Cannon-Fenske viscometers from 293.15 to 343.15 K. The derived thermophysical properties evaluated were the excess molar volume, the partial molar volume, the thermal expansion coefficient, the dynamic viscosity and the viscosity deviation. The excess molar volumes presented positive and negative values. The Redlich–Kister correlation and the theoretical ERAS (Extended Real Association Solution) model were applied for modelling the excess molar volume. Both approaches resulted in good agreement. For viscosity, the McAllister model was implemented and yielded lower deviations for the butyl ester biodiesel. Full article

In this study, densities and viscosities of the binary solutions of monoethanolamine with diethylene glycol monoethyl ether or methyldiethanolamine were determined at 293.15, 298.15, and 303.15 K and p = 100.5 kPa. The experimental density data were tested with different equations as a function of composition (Belda and Herraez equations) and as a function of temperature and composition (Emmerling et al. and Gonzalez-Olmos–Iglesias equations). The results show that the Herraez and Emmerling et al. equations best correlate the experimental data. The experimental values of viscosity were tested with different models based on one, two, three, or four parameters. The values of excess molar volume (V^E), viscosity deviation (Δη), and excess Gibbs energy (ΔG*^E) were calculated from the experimental values and were fitted to the polynomial equations. The values of the excess molar volume are negative for both systems, while positive values were obtained for the viscosity deviation and excess Gibbs activation energy. The values of thermodynamic functions of activation of viscous flow were determined and discussed. The Fourier transform infrared spectroscopy (FT-IR) spectra of the binary solutions analyzed in this study enabled the understanding of the interactions among the molecules in these solutions. In addition, the CO₂ absorption capacity of the binary solutions of monoethanolamine with diethylene glycol monoethyl ether or methyldiethanolamine was determined experimentally. Full article

In this paper, the thermodynamic properties of terpene mixtures were investigated because they represent a promising group of compounds, usually extracted from biomass, with their most notable application as fuel performance enhancers. The densities, viscosities, refractive indices, and ultrasonic speeds of sound were measured for three binary mixtures, citral + chloroform, limonene + chloroform, and linalool + chloroform, across the full composition range at temperatures between 288.15 K and 323.15 K under atmospheric pressure. Using experimental data, excess molar volumes, viscosity deviations, refractive index deviations, and isentropic compressibility, deviations were calculated. Additionally, properties such as partial molar volumes, excess partial molar volumes, partial molar volumes at infinite dilution, and apparent molar volumes were derived. The excess and deviation properties were analyzed using the Redlich–Kister equation. A single mathematical model, the Heric–Brewer–Jouyban–Acree model, was used to represent densities, viscosities, refractive indices, and ultrasonic speeds of sound. The results obtained in this work suggest that dispersive interactions dominate in the limonene and linalool binary mixtures, while hydrogen bonding plays a significant role in the citral + chloroform system. In summary, dispersive interactions are dominant in nonpolar systems like limonene and linalool, while hydrogen bonding significantly affects the citral-chloroform mixture, where the polar groups in citral interact with chloroform molecules. These differences in intermolecular forces help explain the distinct behavior of each mixture. The modeling outcomes demonstrated that the Heric–Brewer–Jouyban–Acree model accurately correlated the experimental thermodynamic properties, with average percent deviations below 1% for all three systems. Full article

Understanding the density of CO₂ + n-decane is crucial for designing and operating CO₂ capture, transport, and storage. The safety and effectiveness of CO₂ burial is directly affected by the density of CO₂ + n-decane mixtures. The liquid densities of CO₂(1) + n-decane(2) mixtures with mole fractions of CO₂ x₁ = 0, 0.2032, 0.4434, 0.7589, and 0.8947 were measured using a vibrating tube densimeter. The combined expanded uncertainties of density with a level of confidence of 0.95 are estimated to be 0.6 kg·m⁻³. A total of 221 compressed liquid densities of CO₂(1) + n-decane(2) mixtures along the five isotherms between T = (283 and 363) K with pressures up to 100 MPa were presented. The densities of mixtures were correlated by the modified Tait equation, resulting in absolute average deviations between the experimental and calculated values of 0.028%, 0.013%, 0.017%, 0.044%, and 0.042%. In addition, the isothermal compressibility, isobaric thermal expansivity, and excess molar volume were derived from the modified Tait equation. Full article

Physical properties of the binary solutions, toluene with 2-propanol and 2-methyl-1-propanol, were measured at T = 293.15, 298.15, 303.15, 308.15, and 313.15 K and P = 100 kPa. The experimental density values were tested with the Emmerling et al. and Gonzalez-Olmos–Iglesias equations. The results indicate that the equation by Emmerling et al. is the best to correlate the density for toluene + 2-methyl-1-propanol system, while for toluene + 2-propanol, both proposed equations are proper to correlate the density with composition and temperature. The viscosity results were verified with different models containing two adjustable parameters. The values of viscosity deviation ($∆\eta$), excess molar volume (V^E), excess Gibbs energy (ΔG^*E), partial molar volumes ($\overline{V_1}$ and $\overline{V_2}$), and apparent molar volume ($V_{\phi ,1}$ and $V_{\phi ,2}$) were calculated. The values of the excess molar volume were positive for both systems, while negative values were obtained for the viscosity deviation and the excess Gibbs energy. The excess properties of the mixtures were adjusted to the Redlich–Kister equation. The values of thermodynamic functions of activation of viscous flow were computed and analyzed. Additionally, the Prigogine–Flory–Patterson (PFP) theory was applied to calculate V^E and then compared with experimental values. The values of the percentage absolute average deviation obtained suggest the validity of this theory. The Fourier transform infrared spectroscopy (FTIR) spectra of the binary solutions studied in this work allowed for the understanding of the interactions between the molecules of these systems. Full article

Density, viscosity, refractive index, and ultrasonic velocity were measured for the pure materials anisole, methanol, and toluene, and for the binary mixtures: methanol—anisole and methanol—toluene. Excess molar volume V^E, isobaric thermal compressibility α, excess Gibbs activation energy for fluid flow ΔG^E*, and excess isentropic compressibility κ_S^E were calculated from the measured quantities. For both binary mixtures V^E and κ_S^E were <0 while Δn > 0 and ΔG^E* > 0 over the entire mole fraction composition range. Anisole mixtures exhibited more negative values for V^E and κ_S^E while more positive values were displayed for Δn and ΔG^E* compared to toluene mixtures. For Δη, negative values were observed at low alcohol concentrations but positive values at high alcohol concentrations for both systems. Full article

For the present, it is difficult to obtain thermodynamic data for binary liquid alloys by experimental measurements. In this study, the molecular dynamics processes of the binary liquid alloys Pb50-Sn50, Al50-Sn50, and In50-Zn50 were simulated by using the ab initio molecular dynamics (AIMD) principle, and their partial radial distribution functions (PRDF) were obtained at different simulation steps. Combined with the relevant binary parameters of the Molecular Interaction Volume Model (MIVM), Regular Solution Model (RSM), Wilson Model, and Non-Random Two-Liquid (NRTL) models. The integral terms containing the PRDF were computed using the graphical integration method to obtain the parameters of these models, thus estimating their activity and molar excess Gibbs energy. The total average relative deviations (ARD) of the activity and molar excess Gibbs energy estimates of the four models for the binary liquid alloys Pb50-Sn50, Al50-Sn50, and In50-Zn50 at full concentration when the PRDF is obtained by the symmetry method are MIVM: 21.59% and 59.35%; RSM: 21.63% and 60.27%; Wilson: 24.27% and 86.7%; NRTL: 23.9% and 83.24%. When the PRDF is obtained by the asymmetric method: MIVM: 22.86% and 68.08%; RSM: 32.84% and 68.66%; Wilson: 25.14% and 82.75%; NRTL: 24.49% and 85.74%. This indicates that the estimation performance of the MIVM model is superior to the other three models, and the symmetric method performs better than the asymmetric method. The present study also derives and verifies the feasibility of Sommer’s equation for estimating the molar excess Gibbs energy and activity of binary liquid alloy systems in the Miedema model by using different equations of enthalpy of mixing versus excess entropy given by Tanaka, Ding, and Sommer. The total ARD of Tanaka, Ding, and Sommer’s relational equations in the Miedema model for estimating the activities and molar excess Gibbs energies of the binary liquid alloys Pb-Sn, Al-Sn, and In-Zn are 3.07% and 8.92%, 6.09% and 17.1%, and 4.1% and 14.77%. The results indicate that the estimation performance of the Miedema model is superior to the other four models. Full article

To accurately and conveniently obtain the thermodynamic data of binary liquid alloys, a new method is proposed in this study. It combines ab initio molecular dynamics (AIMD) simulation with a thermodynamic model to estimate the activity and molar excess Gibbs energy of binary liquid alloys. Additionally, two methods of grouping the partial radial distribution function (PRDF) of 5000 steps obtained by simulation are proposed for the first time. The PRDF of Al50Cu50, Al50Ni50, and Al50Fe50 is obtained by AIMD simulation. These PRDF are combined with four thermodynamic models to estimate the activity and molar excess Gibbs energy. Furthermore, the estimation results of the four models are compared with those of the Miedema model. The results show that when the first peak of the PRDF is obtained by the symmetric method, the average relative deviation (ARD) of the activity and molar excess Gibbs energy of the four models are, respectively: 28% and 32% for Molecular Interaction Volume Model (MIVM); 162% and 38% for Regular Solution Model (RSM); 508% and 65% for Wilson model; 562% and 67% for Non-Random Two-Liquid (NRTL). When the first peak of PRDF is obtained by non-symmetric method, the average ARD of the activity and molar excess Gibbs energy of the four models are, respectively: 64% and 20% for MIVM; 115% and 26% for RSM; 661% and 70% for Wilson; 727% and 72% for NRTL. In addition, the average ARD of the activity and molar excess Gibbs energy of the Miedema model are 113% and 33%. These data indicate that the estimation performance of the MIVM model is superior to the other four models, and the symmetric method performs better than the non-symmetric method. The grouping treatment of PRDF data effectively improves estimation performance. Full article

New physicochemical data for trans-perfluorodecalin (trans-PDF) and cis-perfluorodecalin (cis-PFD) are presented. Based on the differential scanning calorimetry, the temperature and heat of the solid−liquid phase transition are determined. The coefficients of Antoine’s equation are calculated based on the experimental temperature–pressure dependence data. This article also presents data on the rheological properties («zero» shear viscosity and apparent activation energy for the viscous flow) of the studied compounds. The dependencies of refractive index and excess volume (density) on temperature are studied. Gas chromatography–mass spectrometry data and FTIR, ¹³C NMR, and ¹⁹F NMR spectra are provided. The dependencies are given for the perfluoro(butylcyclohexane) (BCH)–trans-PFD, BCH–cis-PFD, and trans-PFD–cis-PFD binary systems and BCH–trans-PFD–cis-PFD ternary system: refractive index and density (liquid molar volume and excess molar volume) of composition and temperature. The dependences of the excess molar volume on the composition and temperature of the mixtures are correlated with Redlich-Kister and Kohler equations. Full article

This study was aimed at establishing the interactions prevailing in an anionic surfactant, sodium dodecyl sulfate, and dopamine hydrochloride in an alcoholic (ethanol) media by using volumetric, conductometric, and tensiometric techniques. Various methods were utilized to estimate the critical micelle concentration (cmc) values at different temperatures. The entire methods yielded the same cmc values. The corresponding thermodynamic parameters viz. the standard free energy of micellization ($G_{mic}^o$), enthalpy of micellization ($H_{mic}^o$), and entropy of micellization ($S_{mic}^o$) were predicted by applying the pseudo-phase separation model. The experimental density data at different temperatures (298.15 K, 303.15 K, 308.15 K, and 313.15 K) were utilized to estimate the apparent molar volumes ($V_{\varphi }^o$) at an infinite dilution, apparent molar volumes ($V_{\phi }^{cmc}$) at the critical micelle concentration, and apparent molar volumes ($\mathsf{\Delta }{V}_{\phi }^m$) upon micellization. Various micellar and interfacial parameters, for example, the surface excess concentration (${\mathsf{\Gamma }}_{\max }$), standard Gibbs free energy of adsorption at the interface ($\mathsf{\Delta }{G}^o{}_{ad}$), and the minimum surface area per molecule ($A_{\min }$), were appraised using the surface tension data. The results were used to interpret the intermolecular interactions prevailing in the mixed systems under the specified experimental conditions. Full article

Twelve crude oil blends prepared from seven individual crude oils and an imported atmospheric residue were characterized through a true boiling point (TBP) distillation analysis and their density. When comparing the measured TBP fraction yields with those estimated through the application of the additive blending rule, it was found that, for four crude oil blends, the additive blending rule was valid, while for the remaining eight crude oil blends, deviations of the measured TBP yields from the estimated ones were bigger than the TBP analysis’s repeatability limits. By the use of intercriteria analysis evaluation of the data for the deviation of the TBP yields from the additive blending rule and the molar excess volume of the crude oil blends, statistically meaningful relations between the delta TBP yields of light and heavy naphtha, as well as vacuum residue with the molar excess volume, were found. The higher the magnitude of the crude oil blend’s molar excess volume, the bigger the deviations of the TBP yields of naphtha and vacuum residue are. The bigger the deviation of the crude oil blend’s behavior from that of the regular solution, as quantified by the molar excess volume, the bigger the deviations of the TBP yields of naphtha and vacuum residue are. Full article

Vapor pressures and other thermodynamic properties of liquids, such as density and enthalpy of mixtures, are the key parameters in chemical engineering for designing new process units, and are also essential for understanding the physical chemistry, macroscopic and molecular behavior of fluid systems. In this work, vapor pressures between 278.15 and 323.15 K, densities and enthalpies of mixtures between 288.15 and 318.15 K for the binary mixture (2-propanol + 1,8-cineole) have been measured. From the vapor pressure data, activity coefficients and excess Gibbs energies were calculated via the Barker’s method and the Wilson equation. Excess molar volumes and excess molar enthalpies were also obtained from the density and calorimetric measurements. Thermodynamic consistency test between excess molar Gibbs energies and excess molar enthalpies has been carried out using the Gibbs–Helmholtz equation. Robinson–Mathias, and Peng–Robinson–Stryjek–Vera together with volume translation of Peneloux equations of state (EoS) are considered, as well as the statistical associating fluid theory that offers a molecular vision quite suitable for systems having highly non-spherical or associated molecules. Of these three models, the first two fit the experimental vapor pressure results quite adequately; in contrast, only the last one approaches the volumetric behavior of the system. A brief comparison of the thermodynamic excess molar functions for binary mixtures of short-chain alcohol + 1,8-cineole (cyclic ether), or +di-n-propylether (lineal ether) is also included. Full article

Vapor–liquid equilibrium (VLE) and density data for binary systems of branched alkanes + ethyl acetate are scarce in the literature. In this study, the binary mixtures 3-methylpentane + ethyl acetate and 2,3-dimethylbutane + ethyl acetate were investigated. Density measurements at atmospheric pressure were performed using a vibrating tube density meter at 293.15, 298.15 and 303.15 K. Large and positive excess molar volumes were calculated and correlated using a Redlich–Kister-type equation. Isobaric VLE data at 101.3 kPa were obtained using a Gillespie-type recirculation ebulliometer. Equilibrium compositions were determined indirectly from density measurements. The experimental data were checked for consistency by means of the Fredenslund test and the Wisniak (L-W) test and were then successfully correlated using the NRTL model. The newly studied binary systems display high deviations from ideality and minimum boiling azeotropes, the coordinates of which are reported in this work. Full article