Excess molar volumes and ultrasonic studies of N-methyl-2-pyrrolidone with ketones at T = 303.15 K

Excess molar volumes (V^E) and ultrasonic studies at T = 303.15 K and atmospheric pressure have been measured over the whole composition range for the binary mixtures of N-methyl-2-pyrrolidone (NMP) with ketones. The ketones studied in the present investigation include methyl ethyl ketone (MEK), diethylketone (DEK), methyl propyl ketone (MPK), methyl isobutyl ketone (MIBK), and cyclohexanone (CH). The V^E values were measured using a dilatometer and were negative over the entire mole fraction range for NMP with MEK, DEK, MPK, and MIBK and were positive for NMP with CH. The ultrasonic sound velocities for the above systems were measured with a single crystal interferometer at a frequency of 3 MHz. The sound velocity (u) results have been used to calculate isentropic compressibility (K_s) and deviation in isentropic compressibility (ΔK_s) over the entire range of volume fraction. The sound velocity results have been predicted in terms of free length theory (FLT), collision factor theory (CFT), and Nomoto relation. The results reveal that all the theories gave a satisfactory estimate of the sound velocity. The deviation values of the isentropic compressibilities (ΔK_s) were negative over the entire range of volume fraction in all the binary liquid mixtures except in the binary system NMP with CH, where we observed positive ΔK_s values. The results are interpreted on possible molecular interactions between components.     

Excess molar volumes and viscosities of (1,1,2,2-tetrabromoethane + 1-alkanols) at T = (293.15 and 303.15) K

Density and viscosity measurements for binary mixtures of (1,1,2,2-tetrabromoethane + 1-pentanol, or + 1-hexanol, or + 1-heptanol, or + 1-octanol, or + 1-decanol) at T = (293.15 and 303.15) K, have been conducted at atmospheric pressure. The excess molar volumes V^E, have been calculated from the experimental measurements, and the results were fitted to Redlich–Kister equation. The viscosity data were correlated with the model of Grunberg and Nissan, and McAllister four-body model. The excess molar volumes of (1,1,2,2-tetrabromoethane + 1-pentanol, or + 1-haxanol, or + 1-heptanol, or + 1-octanol) had a sigmoidal shape and the values varied from negative to positive with the increase in the molar fraction of 1,1,2,2-tetrabromoethane. The remaining binary mixture of (1,1,2,2-tetrabromoethane + 1-decanol) was positive over the entire composition range. The effects of the 1-alkanol chain length as well as the temperature on the excess molar volume have been studied. The results have been qualitatively used to explain the molecular interaction between the components of these mixtures.     

Excess molar volumes and partial molar volumes for (propionitrile + an alkanol) at T = 298.15 K and p = 0.1 MPa

The excess molar volumes and the partial molar volumes for (propionitrile + an alkanol) at T = 298.15 K and at atmospheric pressure are reported. The hydrogen bonding between the OH⋯NC groups are discussed in terms of the chain length of the alkanol. The alkanols studied are (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol).The excess molar volume data was fitted to the Redlich–Kister equation The partial molar volumes were calculated from the Redlich–Kister coefficients.     

Excess molar volume of (linalool + an alkanol) atT = 303.15 K

In this paper, densities of (linalool  +  methanol, or ethanol, or n -propanol, or n -butanol) are determined at T =  303.15 K using a vibrating-tube densimeter. The excess molar volumes V_m^Evalues are negative in all the systems over the entire composition range and correlated by the Redlich–Kister equation. The effects of chain length of alkanols onV_m^E have been discussed.     

Ultrasonic studies on binary mixtures of some aromatic ketones with acetonitrile at T = 308.15 K

The speed of sound and density of acetophenone, propiophenone, para-methyl acetophenone, and para-chloro acetophenone with acetonitrile have been measured over the entire range of mole fraction at T = 308.15 K. From the experimentally determined data, values of deviations in speed of sound, isentropic compressibility, and intermolecular free-length have been computed. The deviation in isentropic compressibility Δκ_S is fitted to a Redlich–Kister type equation. The deviation in speed of sound is positive where as the deviations in isentropic compressibility and intermolecular free length are negative for all the systems. This trend indicates that the specific interactions are operative between unlike molecules. The reactivity order of ketones with acetonitrile is para-chloro acetophenone > para-methyl acetophenone > acetophenone > propiophenone.     

Excess molar enthalpies of binary mixtures containing 2-decanone or dipentyl ether with long-chain n-alkanes at T = 298.15 K

Excess molar enthalpies (H^E) of binary mixtures of 2-decanone or dipentyl ether with n-alkanes, including n-dodecane, n-tetradecane, and n-hexadecane, were measured with an isothermal titration calorimeter (ITC) at T = 298.15 K under atmospheric pressure. All the measured H^E values are positive over the entire range of composition, indicating that all these mixing processes are endothermic. The H^E values varying with composition are found to be nearly symmetric for each binary system. It was also shown that the H^E values follow the order of n-hexadecane > n-tetradecane > n-dodecane at a given composition in either the 2-decanone or dipentyl ether binary systems. An empirical Redlich–Kister equation correlated quantitatively these new H^E data. The Peng–Robinson and the Patel–Teja equations of state, and the NRTL model were also applied to fit the H^E results. Among these tested correlative models, the Patel–Teja equation of state with two adjustable binary interaction parameters generally yielded the best representation.     

Excess molar volumes of (an alkane + 1-chloroalkane) atT = 298.15 K

The densities of the following: (pentane  +  1-chloropropane, or 1-chlorobutane, or 1-chloropentane, or 1-chlorohexane), (hexane  +  1-chloropropane, or 1-chlorobutane, or 1-chloropentane, or 1-chlorohexane), (heptane  +  1-chloropropane, or 1-chlorobutane, or 1-chloropentane, or 1-chlorohexane), (octane  +  1-chloropropane, or 1-chlorobutane, or 1-chloropentane, or 1-chlorohexane), were measured at T =  298.15 K by means of a vibrating-tube densimeter. The excess molar volumes V_m^E, calculated from the density data, are negative for (pentane  +  1-chloropentane, or 1-chlorohexane) and (hexane  +  1-chlorohexane) over the entire range of composition. (Pentane  +  1-chlorobutane), (hexane  +  1-chloropentane) and (heptane  +  1-chlorohexane) exhibit an S-shapedV_m^E dependence. For all the other systems,V_m^E is positive. The V_m^Eresults were correlated using the fourth-order Redlich–Kister equation, with the maximum likelihood principle being applied for determining the adjustable parameters.     

Excess molar enthalpies and excess molar volumes of (an alkanol + a nitrile compound) atT = 298.15 K andp = 0.1 MPa

Excess molar enthalpies and excess molar volumes at T =  298.15 K andp =  0.1 MPa are reported for (methanol, or ethanol, or 1-propanol  +  1,4-dicyanobutane, or butanenitrile, or benzonitrile). For all the mixtures investigated in this work the excess molar enthalpy is large and positive. The excess molar enthalpy decreases as the carbon chain number of the alkanol species increases from methanol to propanol. The excess molar volumes are both positive and negative. The Extended Real Associated Solution and the Flory–Benson–Treszczanowicz models were used to represent the data. Both these models describe better the excess molar enthalpy than the excess molar volumes of (an alkanol  +  a nitrile compound).     

Partial molar volumes of organic solutes in water. XIV. Polyhydric alcohols derived from ethane and propane at temperatures T = 298 K to T = 573 K and at pressures up to 30 MPa

Density data for dilute aqueous solutions of 1,2-ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,2,3-propanetriol (glycerol) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at temperatures from T = 298.15 K up to T = 573.15 K and at pressure close to the saturated vapour pressure of water, at pressures close to p = 20 MPa and p = 30 MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter.     

Partial molar volumes of organic solutes in water. XXIII. Cyclic ketones at T = (298 to 573) K and pressures up to 30 MPa

Density data for dilute aqueous solutions of four cyclic ketones (cyclopentanone, cyclohexanone, cycloheptanone, and cyclohexane-1,4-dione) are presented together with standard molar volumes (partial molar volumes at infinite dilution) calculated from the experimental data. The measurements were performed at temperatures from T = 298 K up to T = 573 K. Experimental pressures were close to the saturated vapor pressure of water, and (15 and 30) MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter. Experimental standard molar volumes were correlated as a function of temperature and pressure using an empirical polynomial function. Contributions of the molecular structural segments (methylene and carbonyl groups) to the standard molar volume were also evaluated and analyzed.     

Density and viscosity of binary liquid systems of N-methylacetamide with aromatic ketones at T = 308.15 K

The densities and flow times of binary mixtures of N-methylacetamide with acetophenone, propiophenone, paramethyl acetophenone and parachloro acetophenone have been determined at T = 308.15 K and are employed to calculate the excess molar volumes, viscosities and deviations in viscosity over the entire range of mole fraction. All isotherms of V^E as a function of composition of ketones show negative deviations except propiophenone, whereas all isotherms of Δη as a function of composition of ketones record negative deviations except parachloro acetophenone. The V^E and Δη values are fitted to a Redlich–Kister type equation. The results are interpreted in terms of molecular interactions occurring in the solutions.     

Excess molar enthalpies of binary systems containing 2-octanone,hexanoic acid,or octanoic acid at T = 298.15 K

An isothermal titration calorimeter was used to measure the excess molar enthalpies (H^E) of six binary systems at T = 298.15 K under atmospheric pressure. The systems investigated include (1-hexanol + 2-octanone), (1-octanol + 2-octanone), (1-hexanol + octanoic acid), (1-hexanol + hexanoic acid), {N,N-dimethylformamide (DMF) + hexanoic acid}, and {dimethyl sulfoxide (DMSO) + hexanoic acid}. The values of excess molar enthalpies are all positive except for the DMSO- and the DMF-containing systems. In the 1-hexanol with hexanoic acid or octanoic acid systems, the maximum values of H^E are located around the mole fraction of 0.4 of 1-hexanol, but the H^E vary nearly symmetrically with composition for other four systems. In addition to the modified Redlich–Kister and the NRTL models, the Peng–Robinson (PR) and the Patel–Teja (PT) equations of state were used to correlate the excess molar enthalpy data. The modified Redlich–Kister equation correlates the H^E data to within about experimental uncertainty. The calculated results from the PR and the PT are comparable. It is indicated that the overall average absolute relative deviations (AARD) of the excess enthalpy calculations are reduced from 18.8% and 18.8% to 6.6% and 7.0%, respectively, as the second adjustable binary interaction parameter, k_bij, is added in the PR and the PT equations. Also, the NRTL model correlates the H^E data to an overall AARD of 10.8% by using two adjustable model parameters.     

Excess properties of the binary mixtures of methylcyclohexane + alkanes (C6 to C12) at T = 298.15 K to T = 308.15 K

Experimental values of density, viscosity, and refractive index at T = (298.15, 303.15, and 308.15) K while the speed of sound at T = 298.15 K in the binary mixtures of methylcyclohexane with n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, and iso-octane are presented over the entire mole fraction range of the binary mixtures. Using these data, excess molar volume, deviations in viscosity, molar refraction, speed of sound, and isentropic compressibility are calculated. All the computed quantities are fitted to Redlich and Kister equation to derive the coefficients and estimate the standard error values. Such a study on model calculations in addition to presentation of experimental data on binary mixtures are useful to understand the mixing behaviour of liquids in terms of molecular interactions and orientational order–disorder effects.     

Diffusion coefficients of nickel chloride in aqueous solutions of lactose at T = 298.15 K and T = 310.15 K

Binary mutual diffusion coefficients (interdiffusion coefficients) of nickel chloride in water at T = 298.15 K and T = 310.15 K, and at concentrations between (0.000 and 0.100) mol · dm^?3, using a Taylor dispersion method have been measured. These data are discussed on the basis of the Onsager–Fuoss and Pikal models. The equivalent conductance at infinitesimal concentration of the nickel ion in these solutions at T = 310.15 K has been estimated using these results. Through the same technique, ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂, and D₂₁) for aqueous solutions containing NiCl₂ and lactose, at T = 298.15 K and T = 310.15 K, and at different carrier concentrations were also measured. These data permit us to have a better understanding of the structure of these systems and the thermodynamic behaviour of NiCl₂ in different media.