Thermodynamic Properties Of Binary Mixtures Research Articles

FT-IR studies and excess thermodynamic properties of binary mixtures at various temperatures and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of 4-Hydroxy-4-methyl-pentan-2-one with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol, and 1-amino propan-2-ol were calculated at temperatures ranging from 303.15 to 313.15 K and atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and infinite dilution molar partial properties are also calculated for each binary system. Heteroassociates molecules forming complexes and chemical forces with specific interactions can be discussed from the results. The Prigogine–Flory–Patterson theory is used to identify the most important interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion. FTIR studies confirm the experimental findings of the investigated mixtures.

FT-IR studies and excess thermodynamic properties of binary mixtures of propargyl alcohol and amino alcohols at different temperatures and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of propargyl alcohol with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol, and 1-amino propan-2-ol were calculated at temperatures ranging from 303.15 to 313.15 K and atmospheric pressure over the entire composition range. Experimental measurements are used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and infinite dilution molar partial properties are also calculated for each binary system. The Prigogine-Flory-Patterson theory is used to identify the most important interaction. The results of the Jouyban-Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion. FTIR studies have also been added to confirm the experimental findings of the investigated mixtures.

Thermodynamic properties of binary mixtures of methyl acetate and some selected ketonesat varying compositions and temperatures

Density and viscosity measurements of binary mixtures of methyl acetate with propanone, butan-2-one and pentan-2-one were carried out at varying compositions (0 to 1) of methyl acetate and temperatures of 25, 30, 35 and 40◦C. The experimental data obtained were correlated with the Redlich-Kister polynomial equation from where excess molar volumes (VE ), excess viscosities (ηE), excess Gibbs free energies of activation for viscous flow (ΔG*E ), fitting coefficients and standard deviations of the mixtures were calculated. The ηE values were positive for mixtures of butan-2-one and pentan-2-one at all compositions and temperatures but gradually decrease with increasing composition and temperature. The mixtures of methyl acetate with propanone showed negative values of excess viscosity at all compositions of methyl acetate. The negative values are observed to be directly proportional to temperature. The values of VE for mixtures of methyl acetate + propanone system display positive deviations at lower compositions (0-0.4) and negative for higher mole fractions. The excess molar volumes of mixtures of butan-2-one and pentan-2-one are negative at the studied compositions and temperatures with a minimum at 0.3 composition and subsequent gradual decrease in negativity with increasing composition. The excess Gibbs free energy of activation for viscous flow (ΔG*E ) are positive at all compositions and temperatures and reaches a maximum at 0.3 composition above which it decreases. These results have been interpreted on the basis of the type and nature of interactions as well as differences in molecular architecture between the solvent mixtures.

Thermodynamic Properties of Binary Mixtures Containing Ionic Liquid 1-Butyl-3-methylimidazolium Thiocyanate and Ethanolamines at Different Temperatures: Measurement and PC-SAFT Modeling

Thermodynamic Properties of Binary Mixtures Containing Ionic Liquid 1-Butyl-3-methylimidazolium Thiocyanate and Ethanolamines at Different Temperatures: Measurement and PC-SAFT Modeling

Research on the thermodynamic properties of binary mixtures containing R1234ze(E) based on Helmholtz model

R1234ze(E) has excellent environmental protection properties, but the unsatisfactory latent heat of vaporization and volumetric cooling capacity impede its application. A mixture with excellent thermophysical properties and environmental performance can be obtained through blending R1234ze(E) with other working fluids. In this paper, the vapor-liquid equilibrium data of R1234ze(E)/R32, R1234ze(E)/R152a, R1234ze(E)/R290, and R1234ze(E)/R161 were correlated by Helmholtz equation of state combined with the mixing rule, and the calculation model of thermodynamic properties was established. On this basis, temperature glides, latent heats of vaporization, saturated vapor pressures, and other thermodynamic properties of binary mixtures containing R1234ze(E) were calculated and compared. The results indicate that the standard boiling points and critical temperatures of the four binary mixtures containing R1234ze(E) were similar to those of R22 in most mass concentration ranges. And their saturated vapor pressures at 298.15 K were all lower than that of R22 except for R1234ze(E)/R32 mixed in a few proportions. The latent heat of vaporization and specific heat capacity at a constant pressure of the four mixtures were larger than those of R1234ze(E) and adding the four pure refrigerants with excellent thermodynamic properties into R1234ze(E) helps to improve the latent heat of vaporization and specific heat capacity of the binary mixtures. Among the four mixtures, R1234ze(E)/R290 is an azeotropic mixture and R1234ze(E)/R152a is a non-azeotropic mixture. Finally, the recommended mixing ratios of R1234ze(E)/R32, R1234ze(E)/R152a, R1234ze(E)/R290, and R1234ze(E)/R161 to replace R22 were in the range of 0.56/0.44∼0.76/0.24, 0.58/0.42∼0.71/0.29, 0.27/0.73∼0.85/0.15, and 0.58/0.42∼0.84/0.16.

Predicting Temperature‐Dependent Activity Coefficients at Infinite Dilution Using Tensor Completion

AbstractKnowledge of thermodynamic properties of mixtures is essential in many fields of science and engineering. However, the experimental data is usually scarce, so prediction methods are needed. Matrix completion methods have proven to be very successful in predicting thermodynamic properties of binary mixtures. In this approach, the experimental data is organized in a matrix whose rows and columns correspond to the two components, and whose entries indicate the value of the studied thermodynamic property at fixed conditions. In the present work, we extend the concept to tensor completion methods (TCMs). This allows to account for the variation of the studied property depending on the chosen conditions. The feasibility is demonstrated by applying a TCM to predict activity coefficients at infinite dilution. The third dimension of the tensor is used to describe the influence of the temperature. The TCM is shown to yield better predictions than the well‐established UNIFAC method. Furthermore, the proposed TCM is able to learn and unveil the physical law describing the temperature dependence of activity coefficients from the scarce experimental mixture data only.

Excess Thermodynamic Properties of Binary Mixtures of Dimethyl Malonate with some Branched Alkanols

The intermolecular hydrogen bond interactions in the dimethyl malonate with some branched alkanols (2-methyl-1-propanol, 2-propanol, and 2-butanol) binary mixture have been studied experimentally and theoretically. The ultrasonic velocities U, densities ρ of binary mixtures of dimethyl malonate with 2-methyl-1-propanol, 2-propanol, 2-butanol from 303.15 K to 318.15 K were measured. Excess molar volume (VE), deviation in adiabatic compressibility (Δβad) and excess intermolecular free length ( LEf) have been calculated from the measured experimental data. It is observed that the order of interactions in dimethyl malonate – branched alkanols mixtures is 2-methyl-1-propanol > 2-propanol > 2-butanol.

Dynamical Anomaly of Aqueous Amphiphilic Solutions: Connection to Solution H-Bond Fluctuation Dynamics?

We have investigated the possible connection between “dynamical anomaly” observed in time-resolved fluorescence measurements of reactive and nonreactive solute-centered relaxation dynamics in aqueous binary mixtures of different amphiphiles and the solution intra- and interspecies H-bond fluctuation dynamics. Earlier studies have connected the anomalous thermodynamic properties of binary mixtures at very low amphiphile concentrations to the structural distortion of water. This is termed as “structural anomaly.” Interestingly, the abrupt changes in the composition-dependent average rates of solute relaxation dynamics occur at amphiphile mole fractions approximately twice as large as those where structural anomalies appear. We have investigated this anomalous solution dynamical aspect by considering (water + tertiary butanol) as a model system and performed molecular dynamics simulations at several tertiary butanol (TBA) concentrations covering the extremely dilute to the moderately concentrated regimes. The “dynamical anomaly” has been followed via monitoring the composition dependence of the intra- and interspecies H-bond fluctuations and reorientational relaxations of TBA and water molecules. Solution structural aspects have been followed via examining the tetrahedral order parameter, radial and spatial distribution functions, numbers of H bonds per water and TBA molecules, and the respective populations participating in H-bond formation. Our simulations reveal abrupt changes in the H-bond fluctuations and reorientational dynamics and tetrahedral order parameter at amphiphile concentrations differing approximately by a factor of 2 and corroborates well with the steady-state and the time-resolved spectroscopic measurements. This work therefore explains, following a uniform and cogent manner, both the experimentally observed structural and dynamical anomalies in microscopic terms.

Effect of ketonic group on thermodynamic properties of binary mixtures containing aromatic alcohol at different temperatures

Densities (ρ) and speeds of sound (u) data for the binary mixtures of benzyl alcohol (BA) with methyl ethyl ketone (MEK), diethyl ketone (DEK), methyl propyl ketone (MPK), and methyl isobutyl ketone (MIBK) have been investigated at four temperatures (T = 303.15, 308.15, 313.15 and 318.15 K) and pressure (P = 0.1 MPa) over the entire composition range. These data have been utilized to derive excess molar volume (VmE), excess isentropic compression (KSE) and excess speed of sound (uE)for all the systems. The experimentally determined values have been correlated by Redlich-Kister polynomial equation. Further, these results have been analysed by different theoretical treatment such as Prigogine–Flory–Patterson (PFP) theory, intermolecular free length theory and collision frequency theory. The different types of interaction between the component molecules could be addressed by the changes in positive and negative values of excess properties. The applications of present study can be used to build comprehensive theoretical models for designing various technological processes in chemical and biochemical industries.

Volumetric and thermodynamic properties of binary mixtures of p-cymene with α-pinene, limonene and citral at atmospheric pressure and temperatures up to 323.15 K

An experimental analysis of density, refractive index, speed of sound and the viscosity at atmospheric pressure and temperatures T = (288.15 to 323.15) K has been carried out for the three binary systems, i.e. (p-cymene + α-pinene), (p-cymene + limonene) and (p-cymene + citral). Excess molar volumes, viscosity deviations, deviations in isentropic compressibility and excess Gibbs free energy of activation of viscous flow were calculated from experimental data. The results were fitted employing Redlich-Kister polynomial equation. Also, partial molar volumes, excess partial molar volumes and partial molar volumes at infinite dilutions were calculated to elucidate the non-ideal behavior of investigated mixtures. Furthermore, Prigogine-Flory-Patterson (PFP) model was successfully applied for the correlation of excess molar volumes of examined binary mixtures. The results of excess molar volume correlations show very good agreement with experimental measurement.

Use of Nonideality Parameters for the Analysis of the Thermodynamic Properties of Binary Mixtures.

Two parameters are introduced, a nonideality index (NII) and a nonideality area (NIA), for the analysis of the variations of thermodynamic properties of binary mixtures. Their calculation is based, for the NII, on experimental plots of the variation of a given property (density, refractive index, viscosity, etc.), and for the NIA, on experimental plots of its excess value (excess enthalpies, molar volumes, viscosities, refractive indices, isentropic compressibilities, etc.) with the mixture composition. Both nonideality parameters are therefore not based on any theoretical model or on its derived parameters, being applicable with any fitting equation. The NII or NIA values for a thermodynamic property of a series of related binary mixtures reveal interesting trends, which are not evident in most analyses of such systems. Besides their predictive value, these trends provide information on the relevance of solvent characteristics of the binary mixture, thus supporting new insights or interpretations of the experimental data.

Equations of State for the Thermodynamic Properties of Binary Mixtures for Helium-4, Neon, and Argon

Based on the conceptual design reports for the Future Circular Collider cryogenic system, the need for more accurate thermodynamic property models of cryogenic mixtures of noble gases was identified. Both academic institutes and industries have identified the lack of a reliable equation of state for mixtures used at very low temperatures. Detailed cryogenic architecture modeling and design cannot be carried out without accurate fluid properties. Therefore, the helium–neon equation was the first goal of this work, and it was further extended to other fluids beneficial for scientific and industrial applications beyond the particle physics needs. The properties of the noble gas mixtures of helium–neon, neon–argon, and helium–argon are accurately modeled with the equations of state explicit in the Helmholtz energy.

Transport and Thermodynamic Properties of Binary Mixtures Formed by Acetonitrile, Cyclohexene, and Cyclohexanone

The densities of acetonitrile, cyclohexene, and cyclohexanone are measured at 298.15, 303.15, and 313.15 K. Their dynamic viscosities in the 293.15–333.15 K range of temperatures in increments of 5 K under atmospheric pressure are determined. The densities and viscosities of the binary systems formed by acetonitrile, cyclohexene, and cyclohexanone are studied at three temperatures. Using experimental data, the excess molar volumes and viscosity deviations are calculated for the binary systems. All of the systems exhibit deviations from ideal behavior.

PFG-NMR and MD Simulation Study of Self-Diffusion Coefficients of Binary and Ternary Mixtures Containing Cyclohexane, Ethanol, Acetone, and Toluene

Recently, Guevara-Carrion et al. published a comprehensive molecular dynamics (MD) study on the thermodynamic properties of binary mixtures containing methanol, ethanol, acetone, benzene, cyclohexa...

Thermodynamic properties for binary mixtures of 1-chlorohexane + some hydrocarbons at different temperatures and atmospheric pressure

The values of densities and speeds of sound for the binary mixtures of 1-chorohexane with two hydrocarbons, as toluene and tetradecane, were measured at several temperatures in the range of (298.15 to 318.15) K and atmospheric pressure. The obtained experimental data of the mixture were correlated by the Jouyban-Acree model. From the experimental data, the related excess and deviation quantities, namely the excess molar volumes, the partial molar volumes, the excess speeds of sound, the isentropic compressibilities, the excess isentropic compressibilities, the molar isentropic compressibilities and the excess molar isentropic compressibilities, were calculated and reported in this work. All these excess thermodynamic properties were correlated with the Redlich-Kister polynomial equation. The experimental results have been also used to test the applicability of the Prigogine-Flory-Patterson theory. Discussions concerning the experimental and calculated results in relation to the molecular interactions and structural effects between components of mixtures are presented.

Reply to “Comments on study of thermodynamic properties of binary mixtures of propionitrile with dimethylsulfoxide (or diethylsulfoxide) at temperatures from (298.15 to 323.15) K”

Reply to “Comments on study of thermodynamic properties of binary mixtures of propionitrile with dimethylsulfoxide (or diethylsulfoxide) at temperatures from (298.15 to 323.15) K”

Comments on “Study of thermodynamic properties of binary mixtures of propionitrile with dimethylsulfoxide (or diethylsulfoxide) at temperatures from (298.15 to 323.15) K”

The negative excess molar volumes reported by Ghazoyan and coworkers for binary propionitrile + dimethyl sulfoxide and propionitrile + diethyl sulfoxide are not thermodynamically consistent with the positive numerical values that the authors give for the partial molar excess volumes for the individual mixture components. Moreover, the authors' calculated partial molar volumes of the individual mixture components are not consistent with the molar volumes of the mixtures based on the experimental densities.

Study of thermodynamic properties of binary mixtures of propionitrile with dimethylsulfoxide (or diethylsulfoxide) at temperatures from (298.15 to 323.15)K

In this work the thermodynamic properties such as volumetric and viscosity properties of binary mixtures of propionitrile with dimethylsulfoxide (or diethylsulfoxide) have been investigated with the use of density and viscosity measurements over the full range of compositions at temperatures from (298.15 to 323.15) K. Excess molar volumes, VmE, apparent molar volumes, Vϕ, i, partial molar volumes, V¯i, partial excess molar volumes, V¯iE partial molar volumes at infinite dilution, Vi∞, and thermal expansion coefficients, αp, for binary liquid mixtures were calculated. Viscosity deviations, ηE, and excess Gibbs energy, ΔG⁎E, of activation of viscous flow were calculated too. In addition, the FTIR measurements of these mixtures have been performed as well. The results obtained confirm that intermolecular interaction between sulfoxides and propionitrile molecules is stronger in propionitrile-diethylsulfoxide rather than in propionitrile-dimethylsulfoxide mixtures.

Prediction and Correlations of Thermodynamic Properties of Binary Mixtures N-Ethyl-2-pyrrolidone (EP) + Ethanolamine (MEA), Diethanolamine (DEA) and Triethanolamine (TEA) as a Function of Temperature

Prediction and Correlations of Thermodynamic Properties of Binary Mixtures N-Ethyl-2-pyrrolidone (EP) + Ethanolamine (MEA), Diethanolamine (DEA) and Triethanolamine (TEA) as a Function of Temperature

Diagram Fase dan Sifat Termodinamik Campuran Biner Ketoprofen-Asam Suksinat

The equilibrium phase diagram and thermodynamic properties of a mixture of drugs and additives are information related to various possible interaction processes between components. Therefore, we conducted a study of the phase diagrams and thermodynamic properties of binary mixtures of ketoprofen-succinic acid to estimate the types of interactions that may occur between these materials. The solid-liquid phase diagram of ketoprofen-succinic acid binary mixtures was determined by differential scanning calorimetry and composition of eutectic system was determined accurately using a Tamman diagram. The measurement of binary mixtures of ketoprofen-succinic acid with differential scanning calorimeter obtained the value of melting temperature and heat of fusion of ketoprofen- succinic acid system. The solid-liquid phase diagram of ketoprofen- succinic acid showed the formation of eutectic type phase diagram. The Tamman diagram showed accurately composition of the eutectic system of the Kp-SA binary mixtures at the mole fraction of Kp 0.87 and temperature 96.9oC.Keywords: ketoprofen, phase diagram, eutectic system, Tamman diagram