Excess Partial Molar Isentropic Compressibilities Research Articles

Insight into molecular interactions prevailing in N,N-dimethylformamide + alkyl acrylates mixtures at different temperatures: An experimental and theoretical investigation

The excess isentropic compressibility, excess speed of sound, excess molar isentropic compressibility and deviation in viscosity were evaluated from the experimental values of speeds of sound and viscosities of N,N-dimethylformamide + methyl acrylate/ethyl acrylate/n-butyl acrylate binary mixtures over the entire composition range at temperatures (288.15–318.15) K and pressure (101 kPa). Further, the partial molar isentropic compressibility; excess partial molar isentropic compressibility of the components over the entire composition range and also at infinite dilution have been calculated. These evaluated parameters have been interpreted in relations to prevailing interactions in these mixtures. These interactions were found dependent on the size of alkyl group in acrylate molecules and the amide-acrylate interactions decline with increase in size of the alkyl group. Moreover, the speeds of sound for the mixtures were calculated by scaled particle theory and the results compared well with the experimental results. Also, the viscosities of these mixtures were correlated by means of various empirical relations and the results were found in good agreement with the experimental results.

Thermodynamic and transport properties of binary mixtures containing 1,2-propanediol with 2-methoxyethanol and 2-ethoxyethanol at different temperatures

In the present investigation density, speed of sound, and viscosity have been reported for binary liquid mixtures of 1,2-propanediol (1,2-PD) with 2-methoxyethanol (2-ME) and 2-ethoxyethanol (2-EE) over the entire composition range at T= (298.15–323.15) K. From the experimental data, excess molar volume, (VmE), excess isentropic compressibility, (κsE), excess molar isentropic compressibility, (κs,mE), excess speed of sound, (uE), excess isobaric thermal expansion,αpE, and deviation in viscosity (Δη) of liquid mixtures have been calculated. 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. All excess properties have been correlated using the Redlich-Kister smoothing polynomial equation. The VmE results are analysed in the light of Prigogine-Flory-Patterson theory. Analysis of each of the three contributions viz. interactional, free volume, and P* to VmE has shown that interactional contribution and free volume effect are negative for all the mixtures, and P* contribution is positive for the mixtures of 2-ME. The variations of these parameters with changes in composition and temperature have been discussed in terms of intermolecular interactions prevailing in these mixtures. Further, the viscosities of these binary mixtures were correlated theoretically by using various empirical and semi-empirical models and the results were compared with the experimental findings.

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.

Study of molecular interactions in binary mixtures of 2-ethyl-1-hexanol with primary alcohols (propan-1-ol, 2- propen-1-ol and 2- propyn-1-ol) at various temperatures

ABSTRACT The densities (ρ), viscosities (η), and speeds of sound (u) were reported for binary mixtures of 2-ethyl-1-hexanol with aliphatic primary alcohols (propan-1-ol, 2-propen-1-ol, 2-propyn-1-ol) over the entire composition range from 303.15 K to 313.15 K and at atmospheric pressure 0.1 MPa. The excess parameters (VE,κs E), deviation in viscosity, excess partial molar volumes, ( and ) excess partial molar isentropic compressibility’s ( and ) of the components at infinite dilution were calculated from the densities, speeds of sound, and viscosities at experimental temperatures. The variation of these properties with composition of the mixtures suggests hydrogen bond and charge-transfer complex formation between 2-ethyl-1-hexanol and self-associated primary alcohols. The VE results have been analysed in the light of Prigogine-Flory-Patterson theory. An analysis of each of the three contributions, namely, interactional, free volume and P* to VE shows that interactional contribution was positive for all binary systems. The free volume effect and P* contribution were negative for all the mixtures. Furthermore, the FTIR spectra have been recorded at 298.15 K and found to be useful for understanding the presence of hydrogen bonding between dissimilar molecules in the liquid mixtures. A good agreement was obtained between excess quantities and spectroscopic data.

Study of intermolecular interactions in binary mixtures of methyl acrylate with benzene and methyl substituted benzenes at different temperatures: An experimental and theoretical approach

• Reports new u and η data of methyl acrylate + aromatic hydrocarbons mixtures. • The study provides estimation of excess properties of these mixtures. • Provides information on nature and relative strength of interactions in these media. • Various empirical and semi-empirical models are used to correlate viscosity data. • The scaled particle theory (SPT) is used to predict ultrasonic speed theoretically. The ultrasonic speeds, u and viscosities, η of the binary mixtures of methyl acrylate with benzene, toluene, o -xylene, m -xylene, p -xylene, and mesitylene over the whole mole fraction range were measured at six different temperatures and at atmospheric pressure. From the experimental data, the excess isentropic compressibility, κ s E , excess ultrasonic speed, u E , excess molar isentropic compressibility, K s,m E , excess specific impedance, Z E and deviations in viscosity, Δ η have been calculated. The partial molar isentropic compressions, K ¯ s,m,1 and K ¯ s,m,2 , and excess partial molar isentropic compressions, K ¯ s,m,1 E and K ¯ s,m,2 E over the whole composition range, partial molar isentropic compressions, K ¯ s,m,1 ̂ and K ¯ s,m,2 ̂ , and excess partial molar isentropic compressions, K ¯ s,m,1 ̂ E and K ¯ s,m,2 ̂ E of the components at infinite dilution have also been calculated. The results specified the existence of weak interactions between unlike molecules, and these interactions follow the order: benzene > toluene > p -xylene > m -xylene > o -xylene > mesitylene. The magnitude of interactions was found to be dependent on the number and position of the methyl groups in these aromatic hydrocarbons.

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.

FTIR spectra of pure components and their binary liquid components (Binary mixtures of formamide with aniline, N-methyl aniline and N,N-dimethyl aniline)

Densities (ρ) speeds of sound (u) and viscosities (η) of binary mixtures of formamide (F) with aniline (A), N-methylaniline (NMA)and N,N-dimethylaniline (DMA), including those of pure liquids, over the entire composition range were measured at temperatures (303.15, 308.15 and 313.15) K and 0.1 MPa. Using the experimental data, the excess parameters (VE , κs E ), deviation in viscosity (Δη), excess partial molar volumes, and , and excess partial molar isentropic compressibilities, and of the components at infinite dilution were calculated. The VE results have been analyzed in terms of Prigogine-Flory-Patterson theory. An analysis of each of the three contributions viz. interactional, free volume and P* to VE shows that free volume effects are negative for all the binary mixtures. FT-IR properties have been carried out to study the specific interaction, such as the formation of a hydrogen bond between unlike molecules in the binary liquid mixtures. A good agreement is observed among the excess parameters and FT-IR spectroscopic properties

Insight into intermolecular interactions in benzonitrile + methyl acrylate/ethyl acrylate/n-butyl acrylate/t-butyl acrylate binary mixtures at temperatures from 293.15 to 318.15 K: Ultrasonic and viscometric study

The ultrasonic speeds, u and viscosities, η of binary mixtures of benzonitrile with alkyl acrylate (methyl acrylate, ethyl acrylate, n-butyl acrylate and t-butyl acrylate) over the entire composition range, including the pure liquids, were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and at pressure, p = 101 kPa. From the experimental data, the excess isentropic compression, κsE, excess ultrasonic speed, uE, excess molar isentropic compression, Ks, mE and deviations in viscosity, Δη have been calculated. The excess properties were correlated by the Redlich-Kister polynomial equation. The partial molar isentropic compressions and excess partial molar isentropic compressions over the whole composition range; and partial molar isentropic compressions and excess partial molar isentropic compressions of the components at infinite dilution have also been calculated. The variations of these parameters with composition and temperature have been discussed in terms of intermolecular interaction prevailing in these mixtures. Further, the η data of these mixtures were theoretically correlated with various empirical and semi-empirical models and the results were compared with the experimental data.

Physicochemical study of intermolecular interactions in binary mixtures of acetonitrile with alkyl acrylate monomers at temperatures from 293.15 K to 318.15 K by using ultrasonic speed and viscosity data

The ultrasonic speeds, u and viscosities, η of binary mixtures of acetonitrile with alkyl acrylate (methyl acrylate, ethyl acrylate, n-butyl acrylate and t-butyl acrylate) over the entire composition range were measured at temperatures (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K and at atmospheric pressure. From the experimental data, the excess isentropic compressibility, κsE, excess ultrasonic speed, uE, excess molar isentropic compressibility, Ks,mE and deviations in viscosity, Δη have been calculated. The partial molar isentropic compressibilities and excess partial molar isentropic compressibilities over whole composition range, partial molar isentropic compressibilities and excess partial molar isentropic compressibilities of the components at infinite dilution are calculated. The variation of these parameters is discussed in terms of molecular interactions in these mixtures. The viscosities of these mixtures were correlated using various models and the ultrasonic speeds of these mixtures were theoretically calculated using scaled particle theory and the results are compared with experimental values.

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.

Elucidation of molecular interactions in the mixtures of 2-methoxyaniline with alkyl acetates through transport and thermodynamic properties at T = (303.15, 308.15 and 313.15) K

Abstract Densities, viscosities and speeds of sound of binary mixtures of 2‑methoxy aniline with aliphatic alkyl acetate (methyl acetate, ethyl acetate and butyl acetate) including those of pure liquids, over the entire composition range were measured at various temperatures and atmospheric pressure 0.1 MPa. Using these data, the excess volume, and deviation in viscosity, excess isentropic compressibility, excess partial molar volumes and excess partial molar isentropic compressibilities of the components at infinite dilution were calculated. The excess volume results have been analyzed in the light Prigogine-Flory-Patterson theory. The free volume effect and P* contribution are negative for all the mixtures.

Ultrasound speed study of the ternary liquid mixture (water + ethanol + 1-propanol) at T = 293.15 K and P = 0.1 MPa

Sound speed measurements in 42 ternary aqueous mixtures of ethanol plus 1-propanol and new measurements in the three binary mixtures, composed by the three same components, were made at T = 293.15 K and P = 0.1 MPa. Following the volumetric study recently published, a compressibility analysis is now presented in order to complement our previous work, mainly based on derived properties such as excess partial molar isentropic compressions of the three components and their limiting values. As far as we know curves for limiting excess partial molar isentropic compressions of the i component in the ternary mixture were derived for the first time. Transfer functions of these limiting values when water and alcohol molecules are transferred from the aqueous binary to the ternary mixture, are presented and interpreted in terms of hydrophobic hydration and H-bonding effect.

Thermal analysis of molecular interactions in binary mixtures of propipohenone with isomeric cresols at various temperatures through thermophysical properties

ABSTRACT Densities (ρ), viscosities (η) and speeds of sound (u) of binary mixtures of propiophenone with isomeric cresols (ortho-cresol, meta-cresol and para-cresol) including those of pure liquids, over the entire composition range, were measured at temperatures T = (303.15 K, 308.15 K and 313.15 K) and atmospheric pressure 0.1 MPa. Using these data, the excess volume and deviation in viscosity, excess isentropic compressibility, excess partial molar volumes and excess partial molar isentropic compressibilities of the components at infinite dilution were calculated. The variation of these excess properties with the composition of the mixtures suggests hydrogen bond interactions, acid–base interactions, π–π interactions and n–π interactions between unlike molecules. The VE results have been analysed in the light Prigogine–Flory–Patterson theory. An analysis of each of the three contributions, namely, interactional, free volume and characteristic pressure P* to VE shows that free volume contribution is negative for all binary systems.

Investigation of ketonic effect in molecular interactions of 2-methylcyclohexanone with aniline, N-methyl aniline and N,N-dimethyl aniline at various temperatures

Densities (ρ) and speeds of sound (u) and viscosities (η) of binary mixtures of 2-methoxy aniline with aniline, N-methyl aniline and N, N-dimethyl aniline including those of pure liquids, over the entire composition range were measured at temperatures (303.15, 308.15 and 313.15) K and 101.3 kPa. Using the experimental data, the excess volume (VE ) and excess isentropic compressibility (κs E ), deviation in viscosity (Δη), excess partial molar volumes, and and excess partial molar isentropic compressibilities, and of the components at infinite dilution were calculated. These values indicate the formation of intermolecular hydrogen bonding (N-H·····O = C) between the hydrogen atom of amine group of aniline /N-methyl aniline /N, N-dimethyl aniline and the oxygen atom of carbonyl group of 2-methylcyclohexanone in the binary liquid mixtures.

Influence of chlorine atom on thermodynamic and transport properties of binary liquid mixtures at various temperatures (halo-hydrocarbons and 2-methoxyaniline)

The densities (ρ), ultrasonic speeds (u), and viscosities (η) are reported for binary mixtures of o-chlorotoluene, m-chlorotoluene and p-chlorotoluene with 2-methoxy aniline at temperature range from (303.15–318.15) K and at a pressure p = 0.1 MPa. In addition, excess functions such as excess molar volume, excess isentropic compressibility and deviation in viscosity are calculated from the density, speed of sound and viscosity and the Redlich–Kister equation, correlates these properties. The excess partial molar volumes, and , and excess partial molar isentropic compressibilities, and of the components at infinite dilution are calculated. As well, the calculated excess properties were discussed in terms of the influence of chlorine atom on interactions between halo hydrocarbons and 2-methoxy aniline. Moreover, the VE values have been analysed with Prigogine-Flory-Patterson theory and shown that the free volume contribution is the supporting factor for negative values of excess molar quantities.

Study of Intermolecular Interactions in Binary Mixtures of 2-Methoxyaniline with Chlorinated Ethanes at Various Temperatures

Densities (ρ), speeds of sound (u), and viscosities (η) are reported for binary mixtures of 2-methoxyaniline with chlorinated ethane components (1,2-dichloroethane, 1,1,2-trichloroethane and 1,1,2,2-tetrachloroethane) over the entire composition range of mole fraction at T = (303.15–313.15) K and at atmospheric pressure (0.1 MPa). The excess properties: excess molar volume, excess isentropic compressibility and deviation in viscosity are calculated from the experimental density, speed of sound and viscosity. Excess properties are correlated using the Redlich–Kister polynomial equation. The excess partial molar volumes and excess partial molar isentropic compressibilities are calculated for all the binary systems throughout the composition range and at infinite dilutions. The results are analyzed in terms of electron donor–acceptor interactions leading to the formation of intermolecular complexes and hydrogen bonding between 2-methoxyaniline and chlorinated ethane molecules. The VE results are analyzed in light of the Prigogine–Flory–Patterson theory. Analysis of each of the three contributions viz. interactional, free volume and P* to VE has shown that the interactional contribution are positive for all studied systems, the free volume and P* contributions are negative for all the binary mixtures.

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.

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.

Volumetric and sound speed study of aqueous 1-butanol liquid mixtures at different temperatures

Simultaneous measurements of density and sound speed, at five temperatures, T = (283.15–303.15) K and pressure, P = 0.1 MPa within the miscible composition range were performed in 24 aqueous liquid mixtures of 1-butanol. Composition and temperature effects on different excess molar, and excess partial molar properties such as volume, isobaric expansion and isentropic compression are analysed, in terms of different changes in the hydration and association patterns, across the composition ranges studied. Comparison of the different thermodynamic properties, derived for this system, with those for two aqueous system of smaller number of carbon atoms is made. Limiting excess partial molar volumes, isobaric expansions and isentropic compressions at both ends of the composition range are presented. Limiting partial molar isentropic compression values for 1-butanol, infinitely diluted in water, compare very well with values calculated by the group contribution scheme previously presented by some of us.