Analysis of the structure of acetonitrile aqueous solutions based on study of their volumetric elastic properties

The evolution of the structure of acetonitrile aqueous solutions is investigated by analyzing the concentration and temperature dependences of density, ultrasound velocity, adiabatic compressibility, excess molar volume, and excess adiabatic compressibility. It is shown that, the region in which solutions exist can be divided into five intervals that differ by solution structure. The structural features are described for each of them. It is found that in the 0.1 ≤ x ≤ 0.9 range of acetonitrile mole fractions, excess adiabatic compressibility isotherms behave abnormally: its absolute value increases with temperature, testifying to the important role played by the CH₃ group of the amide residue of acetonitrile in molecular interactions.     

Apparent molar volume and apparent molar adiabatic compressibility of 2-hydroxy-5-methyl acetophenone in <Emphasis Type="Italic">N,N</Emphasis>-dimethylformamide at different temperatures

The speed of sound and density of 2-hydroxy-5-methyl acetophenone in dimethylformamide have been measured over the range of temperatures 25–40 °C. From the experimentally determined data, values of apparent molar volume (V _ϕ), adiabatic compressibility (β_s), apparent molar adiabatic compressibility (K _s,ϕ) and their limiting values have been computed. Values at infinite dilution provide information regarding solute–solvent interaction. The density and velocity increases with increase in concentration and decreases with increase in temperature. These results have been analyzed in terms of molecular interactions between acetophenone and dimethylformamide.     

Ultrasonic and IR study of molecular association process through hydrogen bonding in ternary liquid mixtures

Complex formation in ternary liquid mixtures of heterocyclic compounds, viz. pyridine and quinoline with phenol in benzene has been studied through ultrasonic velocity measurements (at 2 MHz) in the concentration range of 0.010–0.090 at varying temperatures of 35, 45 and 55 °C. The ultrasonic velocity and density data are used to estimate adiabatic compressibility, intermolecular free length, molar sound velocity, molar compressibility and specific acoustic impedance. These acoustical parameters, in turn, are used to study the solute–solute interactions in these systems. The ultrasonic velocity shows a maxima and adiabatic compressibility a corresponding minima as a function of concentration for these mixtures. The results indicate the possible occurrence of complex formation between unlike molecules through intermolecular hydrogen bonding between the nitrogen atom of pyridine and quinoline molecules and the hydrogen atom of phenol molecule. Further, the excess values of adiabatic compressibility and intermolecular free length have also been evaluated and discussed in relation to complex formation. The infrared spectra of both the systems, pyridine–phenol and quinoline–phenol, have been also recorded for various concentrations at room temperature (35 °C) and found to be useful for understanding the presence of N⋯HO bond complexes and the strength of molecular association at specific concentrations.     

Apparent molar volumes and adiabatic compressibilities of aqueous solutions of amphiphilic drugs

The apparent molar volumes and adiabatic compressibilities of aqueous solutions of the amphiphilic tricyclic drugs, chlorpromazine, promethazine, promazine and imipramine have been determined from measurements of density and ultrasound velocity. Positive deviations of the apparent molar volume from the Debye-Hückel limiting law in dilute solution indicate possible premicellar association. The changes of molar volume and compressibility accompanying aggregate formation were appreciably smaller than those of typical surfactants, suggesting a more tightly packed aggregate. The magnitude of the increase in molar compressibility on micellisation of imipramine decreased with temperature rise between 20 and 35°C. The results are discussed in terms of the structure and hydration of the drug aggregates.     

Partial molar volumes and partial molar adiabatic compressibilities of a short chain perfluorosurfactant: Sodium heptafluorobutyrate in aqueous solutions at different temperatures

Density and ultrasound measurements of sodium heptafluorobutyrate in aqueous solutions at T = (283.15, 288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, and 323.15) K have been obtained. From these results partial molar volumes and isentropic partial molar adiabatic compressibilities were calculated. Deviations from the Debye-Hückel limiting law provide evidence for limited association at lower concentrations. The change of the partial molar volume and isentropic partial molar adiabatic compressibility upon aggregation was calculated. Variations of the change of partial molar volumes and isentropic partial molar adiabatic compressibility upon aggregation are discussed in terms of temperature.     

A volumetric study of two related amphiphilic beta-blockers as a function of temperature and electrolyte concentration

The effects of electrolyte concentration and temperature on aqueous solutions of propranolol and acebutolol hydrochlorides have been investigated using density and ultrasound velocity measurements. The electrolyte range was 0.0–0.5 and 0.4–1.0 m for propranolol and acebutolol, respectively. For each electrolyte concentration the temperature range was 288.15–313.15 K. Critical concentrations were obtained from plots of ultrasound velocity against drug concentration. Experimental results yielded the apparent molar volume and the apparent molar adiabatic compressibility for both beta-blockers, measured over a wide concentration range. Negative deviations of the apparent molar volume from the Debye–Hückel limiting law in dilute solutions indicate the absence of premicellar aggregation. A negative slope was found for ΔV_m against temperature for both drugs. This negative value suggests that the expansibility of the surfactant in the micellar state is less than that in the aqueous phase. Changes in molar volume and adiabatic compressibility accompanying aggregate formation were smaller than those of typical surfactants, suggesting a more tightly packed aggregate.     

Solvation of ionic liquids based on N-methyl-N-alkyl morpholinium cations in dimethylsulfoxide – volumetric and compressibility studies

The density and sound velocity of the solutions of ionic liquids based on N-alkyl-N-methyl-morpholinium cations, N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, N-methyl-N-octyl-morpholinium bis(trifluoromethanesulfonyl)imide and N-decyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide in dimethylsulfoxide were measured at T = (298.15 to 318.15) K and at atmospheric pressure. The apparent molar volume and apparent molar compressibility values were evaluated from density and sound velocity values and fitted to the Masson equation from which the partial molar volume and partial molar isentropic compressibility of the ILs at infinite dilution were also calculated at working temperatures. By using the density values, the limiting apparent molar expansibilities were estimated. The effect of the alkyl chain length of the ILs and experimental temperature on these thermodynamic properties is discussed. In addition, molecular dynamics simulations were used to interpret the measured properties in terms of interactions of ILs with solvent molecules. Both, volumetric measurements results and molecular dynamics simulations for ionic liquids in dimethylsulfoxide were compared and discussed with results obtained for the same IL in acetonitrile.     

Ultrasound velocity and density studies in some refined and unrefined edible oils

Density and ultrasonic velocity at a frequency of 3?MHz and in the temperature range 298–333?K are measured in some of the refined and unrefined edible oils, namely coconut oil, castor oil, sunflower oil, kardi (safflower oil) and groundnut oil, which are predominantly used in south India. Velocity has been observed to be decreasing with temperature nonlinearly in some oils in the temperature range studied. This is in agreement with others' observations made in different oils and fats. Velocity change with temperature is attributed to change in intermolecular distance with temperature and the nature of variation depends on the internal molecular dynamics. Density of all the oils has been found to be decreasing with temperature. Various physical parameters such as specific volume, molar sound velocity, adiabatic compressibility, molar compressibility and intermolecular free length have been estimated using measured data on velocity and density.     

Ultrasonic study on binary mixture containing dimethylformamide and methanol over the entire miscibility range (0 < x < 1) at temperatures 303–323 K

The experimental density and speed of ultrasound measurements in connection with literature data have been measured for pure N,N-dimethylformamide (DMF), methanol and their binary mixtures over the whole miscibility range at different temperatures 303, 308, 313, 318 and 323 K. These parameters were used to determine the adiabatic compressibility, intermolecular free length, molar compressibility, molar sound velocity, acoustic impedance, relaxation strength and their excess values. The variation of these parameters with composition of mixture indicates the nature and extent of interaction between unlike molecules. The non-ideal behavior of the system studied was explained on the basis of the dipole-induced dipole interactions and hydrogen bonding. The complex formation through intermolecular hydrogen bonding was confirmed from the recorded FTIR spectra. Available thermal energy breaks the bonds between the associated molecules into their respective monomers on increasing the temperature.     

On the applicability of the law of corresponding states to liquid methyl heptyl ketone

Methyl heptyl ketone was shown to obey the law of corresponding states as concerns the velocity of sound and adiabatic compressibility. An equation for the determination of the inversion temperature depending on the number of carbon and hydrogen atoms in molecules of liquids of this group was obtained. The inversion temperatures of 11 liquid ketones were found and used to calculate their critical temperatures. The paper presents the adiabatic compressibilities of these liquids over the temperature (273–473 K) and pressure ranges (from 0.1 to 160 MPa) studied.     

Studies of some acoustical properties in binary solutions

Various acoustical properties such as isentropic compressibility, specific impedance, molar sound velocity, molar compressibility, van der Waals constant, intermolecular free length, excess molar volume (V^E), excess viscosity, excess adiabatic compressibility, Gibb’s free energy of activation for viscous flow etc. have been calculated in three binary systems: anisole+methanol, anisole+chloroform and anisole+dimethyl foramide from sound velocity (2 MHz), density and viscosity measurements at 30°C. The results are interpreted in terms of molecular interactions occurring in the solutions.     

Hydration of Aliphatic <Emphasis Type="Italic">N</Emphasis>-Acetyl Amino Acid Amides in Solution

The temperature and concentration dependences of the ultrasound speed and density of aqueous solutions of aliphatic N-acetyl α-amino acid amides were studied using the adiabatic compression method. Parameters of the hydrate complexes formed therein were estimated on a quantitative level. The hydration number and molar compressibility of the complexes were shown to be almost independent of temperature in the range from 5 to 35°C.     

Thermodynamics of micellization of tetraethylammonium perfluorooctylsulfonate in water

Conductivity, density, and sound velocity measurements as functions of temperature were made on tetraethylammonium perfluorooctylsulfonate solutions to determine the Krafft point, the dependence on temperature of the critical micelle concentration, the micellar ionization degree, and several thermodynamic properties: Gibbs free energy, enthalpy and entropy of micellization, apparent molar partial volume, thermal expansion coefficient, and the adiabatic compressibility factor of both micellized and unmicellized surfactants. Important changes occur at about 30 degrees C. Results are interpreted on the basis of dehydration of surfactant on micellization and on temperature increase.     

A comparative study of the thermodynamic properties at the air–water interface and in the bulk of structurally related phenothiazine drugs aqueous solutions

Surface tension, conductivity, density, and ultrasound velocity measurements have been performed in order to determine in a systematic manner some of the aggregation properties of the phenothiazine drugs promazine and triflupromazine hydrochlorides. Both drugs are structurally related, differing in an extra CF₃ group in the triflupromazine molecular structure. Surface tension data showed that the presence of an extra CF₃ in the molecular structure of triflupromazine involves a higher hydrophobicity of this drug and a restriction in the number of conformations molecules can adopt due to the presence of this bulkier atomic group. This involves a larger surface area in order to accommodate triflupromazine molecules at the interface. From conductivity measurements at different temperatures, the thermodynamic quantities of the micellization process of these drugs indicate that the aggregation is a spontaneous process, mainly enthalpic, where the London-dispersion forces play an active role. Using density and ultrasound velocity measurements, apparent molar volume and adiabatic compressibility of aqueous solutions of the amphiphilic cationic drugs have been determined. Positive deviations from the Debye–Hückel limiting law of the apparent molar volume were obtained from both drugs over the whole temperature range, which provides evidence of possible pre-association at concentrations below the critical concentration. Apparent molar adiabatic compressibility of the aggregates formed by these drugs was typical of those corresponding for an aggregate formed by a stacking process.     

Adiabatic and isothermal compressibility of aqueous solutions of sodium chloride

By the example of aqueous solutions of sodium chloride an approach is developed to obtain the hydration number, molar volume and compressibility of hydrate complexes using the data on adiabatic and isothermal compressibility. It is shown that the results of calculations based on isothermal and adiabatic compressibility are consistent with each other     

A study of the hydration of potassium halides by adiabatic compression

A strict approach to determine the adiabatic compressibility of a solvent at constant entropy of the solution is developed. It is shown that the apparent adiabatic compressibility of a solute is not strictly equal to the pressure derivative of the apparent molar volume of a solute at constant entropy of a solution in the general case. With this approach, the equation for hydration numbers and adiabatic compressibility of hydrate complexes is obtained thermodynamically correctly. Parameters of the hydration of potassium chloride, bromide, and iodide are found.     

Effect of dipotassium hydrogen phosphate on thermodynamic properties of glycine and l-alanine in aqueous solutions at different temperatures

Densities, ρ, speed of sound, u for glycine, l-alanine have been measured in aqueous solutions of dipotassium hydrogen phosphate (DKHP) ranging from 0.2, 0.4, 0.6 and 0.8 mol·kg⁻¹ at temperatures T = (288.15, 298.15, 308.15 and 318.15) K. The different parameters such as apparent molar volume, limiting apparent molar volume, transfer volume, partial molar expansibility have been derived from density data. Experimental speeds of sound data were used to estimate apparent molar adiabatic compressibility, limiting apparent molar adiabatic compressibility, transfer parameter and hydration number. These parameters have been discussed in the light of ion-ion and ion-solvent interactions.     

Ultrasonic measurements and other allied parameters of praseodymium and neodymium palmitates in mixed organic solvents

Ultrasonic measurements on praseodymium and neodymium palmitates were made in a mixture of 60% benzene and 40% dimethyl sulfoxide (V/V), to determine the critical micelle concentration (CMC), soap-solvent interaction, and various acoustic and thermodynamic parameters. The values of the CMC increase with the increase in the size of the cation in the soap molecules. The ultrasonic velocity, specific acoustic impedance, apparent molar compressibility, apparent molar volume and relative association increase while the adiabatic compressibility, intermolecular free length, solvation number, molar sound velocity and available volume decrease with increasing soap concentration.     

Acoustical study on ternary mixture of dimethyl acetamide (DMAC) in diethyl ether and isobutyl methyl ketone at different frequencies

The experimental density (ρ) and the velocity (U) for ternary mixture of dimethyl acetamide diethyl ether and isobutyl methyl ketone at different frequencies (2, 4, 6 and 8 MH_Z) have been measured at a constant temperature of 308 K. These data have been used to compute acoustic impedance (Z), adiabatic compressibility (K _s), intermolecular free length (L_f ), molar volume (V_m ), molar sound velocity (R), molar compressibility (B), available volume (V _a), Lennard-Jones potential repulsive term exponent (n), relative association (R _A), interaction parameter (X) and excess values of some of the above parameters for entire range of mole fraction and are interpreted to explain molecular interaction occurring in the liquid mixture.     

Acoustical parameters of toluene + chloroform + cyclohexane mixtures at 303.15, 308.15, and 313.15 K

Ultrasonic velocity, density and viscosity of the ternary mixture of toluene + chloroform + cyclohexane, were measured at 303.15, 308.15, and 313.15 K. The thermodynamically parameters such as adiabatic compressibility (??), intermolecular free length (L _f), free volume (V _f), internal pressure (?? _i ), acoustic impedance (Z), molar sound velocity (R), and molar compressibility (W) have been obtained from the experimental data for all the mixtures, with a view to investigate the exact nature of molecular interaction. Adiabatic compressibility and intermolecular free length decrease with increase in concentration and temperature. The other parameters show almost increasing concentration of solutes. These parameters have been further used to interpret the molecular interaction part of the solute and solvent in the mixtures.