Excess Isobaric Thermal Expansion Research Articles

Density, Speed of Sound and Derived Properties of Binary Mixtures Propiophenone + Butoxyethanol at T = (303.15, 308.15, 313.15 and 318.15) K

The current study reports the experimental density (ρ) and sound speed (u) values for binary mixes of liquids propiophenone + 2-butoxyethanol at atmospheric pressure (0.1 MPa) and T = (303.15, 308.15, 313.15 and 318.15) K for the full spectrum of composition. densities and sound speed measurements from experiments have been used to estimate excess isentropic compressibility (κsE), excess molar volume (VEm), excess molar isentropic compressibility (KEs,m), excess isobaric thermal expansivity (αEp) and excess sound speed (uE). The Redlich-Kister polynomials were used to correlate excess parameters. Excess partial molar volume quantities (VEm,1 and VEm,2) at infinite dilution and their limiting values (V0Em,1 and V0Em,2) have been analytically determined using Redlich-Kister polynomials from the experimental density data. The results have been analyzed in light of strength and interactions among molecular entities scope and extent prevalent in these mixtures.

Volumetric and acoustic studies of binary mixtures of DEC with isomeric chlorobenzene at various temperatures

ABSTRACT Densities, ρ, and speeds of sound, u, of binary liquid mixtures of diethyl carbonate with 1,2-dichlorobenzene, 1,3-dichlorobenzene and 1,2,4-trichlorobenzene have been measured over the entire range of composition at 303.15 K, 308.15 K, 313.15 K and 318.15 K and at atmospheric pressure. From the experimental data of the density and speed of sound, the excess properties such as excess molar volume, V m E , excess isentropic compressibility, κ s E , excess molar isentropic compressibility, K s , m E , excess speed of sound, u E , and excess isobaric thermal expansion, α p E , have been calculated. For better knowledge of the solute and solvent interaction, excess partial molar volumes, V ˉ m , 1 E and V ˉ m , 2 E , and excess partial molar volumes, V ˉ m , 1 ∘ E and V ˉ m , 2 ∘ E of the components at infinite dilution have been measured. All the excess parameter values have been fitted using the Redlich–Kister polynomial smoothing equation. The calculated excess values have been analysed in terms of molecular interactions and structural effects.

Acoustic and volumetric study of binary mixtures containing Ethyl propionate with amides at various temperatures

The development of biofuels to replace fossil fuels has recently increased at an exponential rate. Many chemical molecules with a wide range of functional groups make up biofuels. There is a strong correlation between the interactions between these molecules and the performance of biofuels. In this paper, the authors presented the new findings related to interactions existing in ethyl propionate and Formamide(F), N-Methylformamide (NMF), and N, N-Dimethylformamide (DMF) in a pure state as well as in their mixtures. Densities and speeds of sound at various temperatures (298.15–323.15 K) and at ambient pressure 0.1 MPa have been measured for these mixtures. From experimental data, the excess properties such as excess molar volume, VmE, excess isentropic compressibility, κsE, excess molar isentropic compressibility, Ks,mE, excess speed of sound, uE, and excess isobaric thermal expansivity, αpE, of the investigated mixtures were calculated. All the excess parameter values were fitted using the Redlich-Kister polynomial smoothing equation. The results were analysed in terms of molecular interactions. The excess partial molar volume, V¯m,1E, V¯m,2E , excess partial molar isentropic compressibility, K¯s,m,1EK¯s,m,2E over the whole composition range together with partial molar volume, V¯m,10, V¯m,20, partial molar isentropic compressibility K¯s,m,10, K¯s,m,20, excess partial molar volume, V¯m,10E, V¯m,20E and excess partial molar isentropic compressibility, K¯s,m,10E,K¯s,m,20E at infinite dilution have also been calculated from the experimental density measurements and analytically obtained using Redlich-Kister polynomials. The variations of these parameters with changes in composition and temperature have been discussed in terms of intermolecular interactions prevailing in these mixtures.

Experimental density and volumetric properties of DESs based on tetrabutylammonium bromide and used for effective extraction of naphthol green B and malachite green

AbstractBACKGROUNDTo improve the quality of wastewater and thereby to meet the standards as per environmental production agency in US and UK. In the present work, Malachite green (MG) and Naphthol Green B (NGB) has been taken as model dyes in wastewater. Solvent extraction process was carried out using deep eutectic solvents (DESs) as an alternative solvent for organic and ionic liquids.RESULTSThe possible molecular interaction between DESs and selective dyes in water were analyzed and discussed in details using volumetric properties including excess molar volume , partial molar volume , excess partial molar volume , apparent molar volume , isobaric thermal expansion () and excess isobaric thermal expansion (αE). Further, the extraction of selective dyes was conducted and characterized in terms of extraction efficiency (η), effect of temperature on extraction efficiency, effect of shaking time on extraction efficiency, effect of concentration on extraction efficiency, effect of HBD on extraction efficiency, distribution coefficient (D). Finally, the thermodynamic extraction feasibility was analysed by means of Gibbs free energy , change in enthalpy , and change in entropy .CONCLUSIONThere is possible molecular interaction between hydrophilic DESs and NGB/MG in water at molecular level. 96% of extraction efficiency was obtained for NGB using hydrophobic DESs like {[TBAB][DA]} and {[TBAB][OA]} whereas {[TBAB][DA]} and {[TBAB][OA]} gave above 72% removal efficiency of MG. Finally the thermodynamic feasibility of extraction process was analyzed and discussed. © 2023 Society of Chemical Industry (SCI).

Compressed liquid densities for cyclopentane/n-heptane mixtures from 293.15 K to 363.15 K at pressures up to 70 MPa

The compressed liquid densities of pure cyclopentane, n-heptane and its binary mixtures were measured with the vibrating-tube densimeter. The temperature ranges were from 293.15 K to 363.15 K and the pressures up to 70 MPa. The density data were correlated with the Tammann-Tait equation. The excess molar volumes, isothermal compressibility and isobaric thermal expansivity were calculated and discussed. In addition, the SRK and PR equation of state and the corresponding volume-translation equations were used to predict the densities of the mixtures, and the predictive accuracy was analyzed.

Studies of solute - solvent interaction of ethyl acetate with 1-Butyl-3-methylimidazolium tetrafluoroborate at T = (298.15–323.15) K

In this work, densities and speeds of sound of binary mixtures of 1- butyl −3-methylimidazolium Tetrafluroborate ionic liquid (IL) with Ethyl acetate (EtOAc) have been measured at temperatures 298.15 – 323.15 K at atmospheric pressure. With the help of experimental results, a discussion is carried out on the molecular interactions and the effect of temperature on interactions through excess properties such as excess molar volumes, VmE, excess isentropic compressibility, κsE, excess speeds of sound, uE, excess molar isentropic compressibility, Ks,mE, excess isobaric thermal expansion,αpE. The excess properties are adequately fitted with the Redlich-Kister polynomial equation. The excess partial molar volumes, V¯m,1E and V¯m,2E; excess partial molar isentropic compressibilities, K¯s,m,1E and K¯s,m,2E; excess partial molar volumes, V¯m,1°E and V¯m,2°E; excess partial molar isentropic compressibilities, K¯s,m,1°E and K¯s,m,2°E of the components at infinite dilution also been measured.

Understanding of molecular interactions between ethyl acetate and 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide: A thermophysical study

In this work, densities, speeds of sound and refractive index of pure and binary blends of 1-butyl-3-methylimidazolium bis(trifluromethylsulfonyl)imide ionic liquid (IL) with Ethyl acetate (EtOAc) have been measured at various temperatures at atmospheric pressure 0.1 MPa. With the help of experimental results, a discussion is carried out on the molecular interactions and the effect of temperature on interactions through excess properties such as excess molar volumes, VmE, excess isentropic compressibility, κsE, excess speeds of sound, uE, excess molar isentropic compressibility, Ks,mE, excess isobaric thermal expansion, αpE. The excess properties are adequately fitted with the Redlich-Kister polynomial equation. The excess partial molar volumes, V¯m,1E and V¯m,2E and excess partial molar isentropic compressibility, K¯s,m,1E and K¯s,m,2E, excess partial molar volumes, V¯m,1°E and V¯m,2°E and excess partial molar isentropic compressibility, K¯s,m,1°E and K¯s,m,2°E of the components at infinite dilution also been measured. For a better understanding of molecular interactions, authors discussed with various cationic and anionic ILs with Ethyl acetate.

Density, speed of sound and derived thermodynamic properties of binary liquid mixtures of 1-chlorohexane with toluene and tetradecane under high pressures

The densities and speeds of sound of binary mixtures of 1-chlorohexane with toluene and tetradecane were measured at temperatures from 298.15 K to 433.15 K, and the pressures up to 100.1 MPa. The parameters of the Redlich–Kister equation were determined. The values of isentropic and isothermal compressibility, isobaric thermal expansivity, isobaric and isochoric heat capacity were calculated. Thereafter, excess molar volumes, excess speed of sounds, excess isentropic compressibilities, excess isothermal compressibilities, excess isobaric thermal expansivity, excess isobaric heat capacities, and excess isochoric heat capacities, were estimated.

Application of Prigogine–Flory–Patterson theory to correlate the thermodynamic properties of aqueous mixtures of some three-component deep eutectic solvents based on choline chloride and carboxylic acids at T = (288.15 to 318.15) K

Thermodynamic properties of some neoteric three-component deep eutectic solvents (DESs) and their mixture with water are of great practical and fundamental importance in various fields of sciences. In this work the measurements of density and speed of sound data for neat four DESs (choline chloride/lactic acid/ethylene glycol, choline chloride/lactic acid/glycerol, choline chloride/oxalic acid/ethylene glycol and choline chloride/oxalic acid/glycerol) and their aqueous mixture were carried out over the entire composition range at T = (288.15 to 318.15) K. Some of the thermodynamic properties including the excess molar volumes (VE), the apparent molar volumes (Vφ,1 and Vφ,2), excess isobaric thermal expansion (αp, mE), the isentropic compressibility deviation (Δκs) and speed of sound deviation (Δu) were computed based on these data. These main properties were evaluated according to numerous solute-solvent interactions among the various components in the mixtures for all of the investigated systems. In addition, the properties were fitted by the Redlich–Kister and Hwang equations. Finally, the capability of Prigogine–Flory–Patterson (PFP) theory for reproducing the main experimentally observed properties of the investigated systems containing DESs. The binary interaction parameter χ12 of PFP theory are negative and these represent the stronger interactions between the components (DESs + water), as compared to the self-interactions among the pure components in the systems.

Physicochemical parameters of the binary mixtures of formamide/N-methylformamide with 2-chloroethanol at different temperatures

ABSTRACT The pseudo-Gruneisen parameter , effective Debye temperature, acoustic nonlinearity parameter , internal pressure and isobaric thermal expansion coefficient have been evaluated for binary liquid mixtures of formamide (FA) and N-methylformamide (NMF) with 2-chloroethanol (2Cl-OH) at 298.15 K, 308.15 K and 318.15 K, over the entire concentration range. The excess pseudo-Gruneisen parameter , excess effective Debye temperature , excess nonlinearity parameter, excess internal pressure and excess isobaric thermal expansion coefficient were also calculated. The calculated values are reasonably satisfactory with the experimental results on sound propagation data of liquid mixtures. These physicochemical parameters play an important role in understanding of the significance of anharmonic and nonlinear behaviour with regard to intermolecular interactions in the liquid mixtures.

Densities and thermal expansions of (water + tetrahydrofuran) mixtures within the temperature range from (274.15 to 333.15) K at atmospheric pressure

The mixture {water (1) + tetrahydrofuran (2)} densities have been measured over the whole composition range at temperatures between (274.15 and 333.15 K) and atmospheric pressure using the vibration type densimeter. Values of excess molar volume and molar isobaric thermal expansion of the mixture as well as apparent/partial molar volumes (down at infinite dilution) for water and tetrahydrofuran (THF) have been calculated. It is shown that the formation of the water + THF mixture occurs with decreasing its volume under all the temperatures. Concentration dependences of partial molar volumes of water and THF are characterized by the presence of extreme regions. Standard (limiting) partial molar volumes of water and THF increase as the temperature is rising. Increase in both temperature and THF content influence on the value of molar isobaric expansion of the mixture in the same way.

Volumetric properties of n-hexadecane/ethyl octanoate mixtures from 293.15 K to 363.15 K and pressures up to 60 MPa

The densities of pure ethyl octanoate and n-hexadecane/ethyl octanoate mixtures were measured from 293.15 K to 363.15 K and up to 60 MPa using U-shape vibrating-tube densimeter. The results were correlated as Tait equation, the excess molar volumes, isothermal compressibilities, and isobaric thermal expansivities of the mixtures were calculated and analyzed. In addition, the parameters in the PC-SAFT equation for ethyl octanoate were obtained based on the high-pressure densities obtained in this work and the vapour pressure in the literatures. The densities of the mixtures were predicted by PC-SAFT equation, the absolute average deviations between the experimental results and those calculated were less than 0.52%.

Measurement and correlation of thermophysical properties in aqueous solutions of some novel bio-based deep eutectic solvents (lactic acid/amino acids) at T = (298.15 to 313.15) K

Thermodynamic properties of novel bio-based deep eutectic solvents (DESs) and their mixture with other solvents is of great importance in extraction and pharmaceutical sciences. In the present study new class of these neoteric sustainable solvents composed of amino acids and lactic acid have been prepared, density and speed of sound data for neat lactic acid/alanine, lactic acid/glycine and lactic acid/histidine and their aqueous mixture have been measured over the entire composition range at T = (298.15, 303.15, 308.15 and 313.15) K. Based on these data, some of the thermodynamic properties including the excess molar volumes (VE), apparent molar volume (Vϕ), excess isobaric thermal expansion (αp,mE), the excess molar isentropic compressibility (κEs,m) and limiting apparent molar expansibility (ϕE,10) have been calculated. For all of the studied systems above, these important properties have been analysed based on various solute-solvent interactions, occurring between the components of the mixtures. Furthermore, it has been found that all the investigated DESs act as a structure-breaker in water over the whole temperature range using Hepler’s constant. The properties have been correlated by the Redlich-Kister type equations.

Effect of temperature on molecular interaction of ethyl acetate with ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The speeds of sound, u and densities, ρ, of the pure and their mixtures of Imadazolium based Ionioc liquid having cation 1-butyl-3-methylimidazolium ([BMIM]+) with the anion hexaflurophospate [PF6]− with Ethyl acetate (EtOAc) have been determined from 0 to 1 mol fraction range of ILs with interval 0.1 at (298.15–323.15) K at pressure 0.1 MPa. We used the measured data to assess the excess molar volumes, VmE., excess isentropic compressibility, κsE, excess speeds of sound, uE, excess molar isentropic compressibility, Ks,mE, excess isobaric thermal expansion, αpE, were calculated and fitted with Redlich-Kister polynomial equation. The excess partial molar volumes, V¯m,1E and V¯m,2E and excess partial molar isentropic compressibilities, K¯s,m,1E and K¯s,m,2E, excess partial molar volumes, V¯m,1oE and V¯m,2oE and excess partial molar isentropic compressibilities, K¯s,m,1oE and K¯s,m,2oE of the components at infinite dilution also been measured. The departure of measured properties has been explored in terms of intermolecular interactions.Simultaneously, the FTIR studies exhibited qualitative analysis of ion-pair formation, interactions of ion–dipole and hydrogen bonding between IL with the EtOAc.

Volumetric and acoustic study of 1,4-butanediol with 2-ethoxyethanol/2-butoxyethanol at various temperatures

The speeds of sound, u and densities, ρ, of the blends, 1,4-butanediol (1,4-BD) with 2-ethoxy ethanol (2-EE) and 2-butoxyethanol (2-BE), including those of pure liquids, have been determined from 0 to 1 mol fraction range of 1,4-BD with interval 0.1 at 303.15 K to 318.15 K at pressure 0.1 MPa. We used the measured values to assess the excess molar volumes, VmE, excess isentropic compressibility, κsE, excess speeds of sound, uE, excess molar isentropic compressibility, Ks,mE, excess isobaric thermal expansion αpE, and the results were fitted with Redlich-Kister equation. The excess partial molar volumes and isentropic compressibilities of the components at infinite dilution have also been measured. The departure of measured properties has been explored in terms of intermolecular interactions. Moreover, the theoretical ultrasonic speeds are computed based on the scaled particle theory and compared with the experimentally measured values.

Volumetric and compressibility properties for aqueous solutions of choline chloride based deep eutectic solvents and Prigogine–Flory–Patterson theory to correlate of excess molar volumes at T = (293.15 to 308.15) K

The thermodynamic properties of deep eutectic solvents (DESs) as neoteric and green solvents are needed to develop and design processes and understand molecular interactions in these type of systems. In this regard, the density (ρ) and speed of sound (u) were measured for aqueous solutions of the DESs based on choline chloride (ChCl) as hydrogen bond acceptor (HBA) with some hydrogen bond donors (HBDs) ethylene glycol (EG), oxalic acid (OA), and malonic acid (MA). On the basis of this data, the excess and deviation molar properties were calculated. In the whole concentration range, the values obtained for excess molar volumes, VE, and isentropic compressibilites deviations, Δκs are negative and that they are increased with increasing the temperature indicating strong interactions between DESs and water. To better undestanding molecular interactions, properties such as excess isobaric thermal expansion (αp, mE), apparent molar volume (Vϕ, 1), and limiting apparent molar expansibility (ϕE, 10) were also calculated. Some equations such as Redlich-Kister and Hwang et al. were used to correlate these properties. Finally, the Prigogine–Flory–Patterson (PFP) theory was used to correlate the excess molar volumes values.

Acoustic and volumetric study of renewable oxygenated fuel additives at (298.15–323.15) K: Isomeric butanediols with ethylbutyrate

Today biofuels are emerging in an exponentially manner in order to replace the fossil fuels. Biofuels are composed of several organic compounds containing wide variety of functional groups. The interactions existing among these compounds play a significant role in the efficiency of the biofuels. In this paper, the authors presented the new findings related to interactions existing in ethylbutyrate and α, ω-alkanediols in pure state as well as in their mixtures. Densities and speeds of sound at various temperatures (298.15–323.15) K and at ambient pressure 0.1 MPa have been measured for these mixtures. From experimental data, the excess properties such as excess molar volume, VmE, excess isentropic compressibility, κsE, excess molar isentropic compressibility, Ks,mE, excess speed of sound, uE, and excess isobaric thermal expansion, αpE, of the investigated mixtures were calculated. All the excess parameter values were fitted using the Redlich-Kister polynomial smoothing equation. The results were analysed in terms of molecular interactions. The partial molar volumes, V¯m,1 and V¯m,2, partial molar isentropic compressibilities, K¯s,m,1 and K¯s,m,2, excess partial molar volumes, V¯m,1E and V¯m,2E and excess partial molar isentropic compressibilities, K¯s,m,1E and K¯s,m,2E over whole composition range; the excess partial molar quantities of the components at infinite dilution have been calculated. The variations of these parameters with change in composition and temperature have been discussed in terms of intermolecular interactions prevailing in these mixtures. The VmE values for these mixtures were also calculated by using Prigogine–Flory–Patterson (PFP) theory and the results were compared with experimental findings.

Investigation of Physico-chemical Properties for the 1-Butyl-3-methylimidazolium Tetrafluoroborate ([Bmim][BF4])–Diethylenetriamine (DETA) System for CO2 Capture

This paper presents the experimental values of densities, viscosities and refractive indices for 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4])–diethylenetriamine (DETA) mixtures over the entire composition range and temperature range 298.15–333.15 K. The physico-chemical properties such as excess molar volume, partial molar volume, partial molar volume at infinite dilution, apparent molar volume, apparent molar volume at infinite dilution, isobaric thermal expansion coefficient and excess isobaric thermal expansion coefficient were calculated from the experimental density data. The excess Gibbs energy and excess entropy of flow were determined from the viscosity data using Eyring’s theory of rate process. The specific interactions between molecules in mixtures were explained by analyzing the behavior of the thermodynamic excess/deviation properties. To determine the correlating accurately with the utilized models including the Redlich–Kister, modified Graber, Lorentz–Lorenz and McAllister equations, the adjustable parameters and standard deviations were determined. Moreover, the qualitative analysis of these properties was further legitimized with Fourier-transform infrared (FTIR) spectroscopic studies.

Physicochemical properties, 1H NMR, ab initio calculations and molecular interactions in a binary mixture of N-methylimidazole with ethyl acetate

For a binary mixture of x N-methylimidazole (hereafter abbreviated as N-mim) + (1 − x) ethyl acetate (hereafter abbreviated as EAC), the density, sound velocity, viscosity and refractive index at (288.15, 298.15, 308.15, 318.15, and 328.15) K, mixing enthalpy at 298.15 K, and 1H NMR measurements combined with the ab initio calculations were carried out over a full molar fraction range.The density, sound velocity, isentropic compressibility, refractive index, viscosity, Gibbs energy of activation of viscous flow and the isobaric thermal expansivity were correlated with a polynomial well. The excess molar volume, excess isobaric thermal expansivity, isobaric thermal expansivity deviation, excess sound velocity, sound velocity deviation, excess isentropic compressibility, isentropic compressibility deviation, excess refractive index, refractive index deviation, excess logarithm viscosity, viscosity deviation, excess Gibbs energy of activation of viscous flow and the molar mixing enthalpy, were calculated and fitted to a Redlich-Kister polynomial. The activation parameters of viscous flow of the mixture, chemical shift changes of N-mim and EAC protons, interaction energy and second-order perturbation stabilization energy of 2-CH···OC, 2-CH···N and CH···O H-bonds were calculated.The mixing process of N-mim with EAC is an endothermic process with volume contraction. The energy to break the like molecular interactions is bigger than that to form dislike molecular interactions, and the volume contraction is mainly attributed to both the free volume difference and the more effective steric accommodation of molecules in the mixture.The 2-CH···OC and 2-CH···N H-bonds are approximately equivalent in dimers, 2-CH···OC H-bond in dimer (N-mim + EAC) is stronger and more stable than the CH···O H-bonds in EAC dimer. The amount of 2-CH···OC H-bond reaches a zenith at x ≈ 0.5. The formation of 2-CH···OC H-bond leads to the electron density rearrangement of the N-mim and EAC molecules, where the electron densities of the N-mim and EAC protons decrease and increase, respectively.

Thermo physical, optical and spectroscopic perspectives of molecular interactions in binary mixtures of Ethyl Lactate and Dimethyl Adipate at T = 303.15–318.15 K and atmospheric pressure

ABSTRACTMolecular interactions are evaluated in the binaries of Ethyl Lactate and Dimethyl Adipate using experimental values of density, ultrasonic velocity and refractive index over entire composition range as a function of temperature from 303.15 to 318.15 K at atmospheric pressure. Excess thermodynamic properties: excess molar volume, excess isentropic compressibility, excess isothermal compressibility, excess free length, excess isobaric thermal expansion coefficient, excess ultrasonic velocity and refractive index deviations are computed and fitted with Redlich-Kister polynomial equation to obtain the binary coefficients and the standard deviations. The existence of specific interactions in the mixture is revealed by excess properties, and further supported by partial molar properties. FTIR analysis ascertains the dominance of packing effect in the studied mixtures. Prediction of refractive index for the mixtures and pure components is done by several mixing rules with the estimation of relative errors. In addition, data are analysed by the Prigogine–Flory–Patterson theoretical model.