Density and excess molar volumes of binary mixtures of sulfolane with methanol,n -propanol,n -butanol,and n -pentanol at 298.15–323.15 K and atmospheric pressure

Densities, ρ and excess molar volumes, V?^E of the binary mixtures of sulfolane, +methanol, +n-propanol,?+n-butanol, and +n-pentanol were measured at temperatures 298.15, 303.15, 308.15, 313.15, and 318.15?K, respectively, covering the whole composition range except methanol at 303.15–323.15?K. The V ^E for the systems were found to be negative and large in magnitude. The values of V ^E of the sulfolane, +n-butanol and sulfolane, +n-pentanol mixtures are being positive at lower and higher mole fractions of the alkanols (x ₂). The magnitudes of the V ^E values of the mixtures are in the order sulfolane?+?methanol?>?sulfolane?+?n-propanol?>?sulfolane?+?n-butanol?>?sulfolane?+?n-pentanol. The observed values of V ^E for the mixtures have been explained in terms of (i) effects due to the differences in chain length of the alcohols, (ii) dipole–dipole interactions between the polar molecules, and (iii) geometric effect due to the differences in molar volume of the component molecules. These are more noticeable in the case of lower alcohols. All these properties have been expressed satisfactorily by appropriate polynomials.     

Excess thermodynamic parameters of binary mixtures of methanol,ethanol, 1-propanol,and 2-butanol + chloroform at (288.15–323.15 K) and comparison with the Flory theory

In this work we used the experimental result for calculating the thermal expansion coefficients α, and their excess values α ^E , and isothermal coefficient of pressure excess molar enthalpy and comparison the obtain results with Flory theory of liquid mixtures for the binary mixtures {methanol, ethanol, 1-propanol and 2-butanol-chloroform} at 288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, and 323.15 K. The excess thermal expansion coefficients α ^E and the isothermal coefficient of pressure excess molar enthalpy ((∂H _m^E/∂P) _T,x for binary mixtures of {methanol and ethanol + chloroform} are S-shaped and for binary mixtures of {1-propanol and 2-butanol + chloroform} are positive over the mole fraction. The isothermal coefficient of pressure excess molar enthalpy (∂H _m^E/∂P) _T,x , are negative over the mole fraction range for binary mixture of {1-propanol and 2-butanol + chloroform}. The calculated values by using the Flory theory of liquid mixtures show a good agreement between the theory and experimental.     

Vapor–liquid equilibrium of binary mixtures of trichloroethylene with 1-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol at 100 kPa

Isobaric vapor–liquid equilibria (VLE) have been obtained for the systems trichloroethylene+1-pentanol, trichloroethylene+2-methyl-1-butanol and trichloroethylene+3-methyl-1-butanol at 100 kPa using a dynamic still. The experimental error in temperature is ±0.1 K, in pressure ±0.1 kPa, and in the liquid and vapor mole fraction ±0.001. The three systems satisfy the point-to-point thermodynamic consistency test. All the systems show positive deviations from ideality. The data have been correlated with the Margules, van Laar, Wilson, NRTL and UNIQUAC equations.     

Thermodynamic properties of binary mixtures: Hexamethylphosphoric triamide + a polar liquid at 25°C

Excess enthalpies H _m ^E excess isobaric heat capacities C _p,m ^E , densities, and speeds of sound of hexamethylphosphoric triamide (HMPA)+acetonitrile (AN), + N,N-dimethylformamide (DMF), and + dimethylsulfoxide (DMSO) were measured at 25degrC. H _m ^E =–1200 J-mol^–1 for HMPA + AN, –180 J-mol^–1 for HMPA + DMF, and 75 J-mol^–1 for HMPA + DMSO C _p,m ^E is positive and considerably larger than C _v,m ^E . V _m ^E for HMPA + DMSO was small and changed sign from negative to positive around HMPA mole fraction x=0.6. V _m ^E for the other two mixtures were negative. The excess compressibilities, K _m ^E for the other two mixtures were negative. The excess compressibilities, K _S ^E and K _T ^E were similar to V _m ^E Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30-June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Thermodynamic properties of binary mixtures: Hexamethylphosphoric triamide (HMPA) with a non-polar liquid at 25°C

Excess isobaric heat capacities C _p ^E , densities and speeds of sound u of HMPA+heptane and+benzene were measured at 25°C. C _p ^E of both mixtures were positive in the range of small x and negative in the other region. The mixture containing benzene showed higher C _p ^E than the heptane mixture. They both exhibited considerably smaller C _V ^E than C _p ^E . V^E was positive for HMPA+heptane and negative for HMPA+benzene. The compressibilities K _s ^E and K _p ^E of both mixtures were negative. In both mixtures, non-random mixing is expected and [(CH₃)₂N]₃PO molecules are inhomogeneously distributed.     

Densities,viscosities, and excess properties for binary mixtures of ethylene glycol with amides at 308.15 K

The densities, ρ, and viscosities, η, of binary mixtures of ethylene glycol with formamide, N,N-dimethyl formamide and N,N-dimethyl acetamide, have been measured over the entire composition range at 308.15 K. From this experimental data, excess molar volume, \( V_{\text{m}}^{\text{E}} \) , deviation in viscosity, Δη, and excess Gibbs free energy of activation of viscous flow, \( \Delta G^{{ * {\text{E}}}}, \) have been determined. Negative values of \( V_{\text{m}}^{\text{E}} \) , Δη, and \( \Delta G^{{ * {\text{E}}}} \) are observed over the entire composition range in the mixtures studied. The observed negative values of various excess and deviation parameters are attributed to the existence of strong interactions, like dipole–dipole interactions, H-bonding between the carbonyl group of amide molecules, and hydroxyl group of glycol molecules, geometrical fitting of smaller molecules into the voids created by larger molecules in the liquid mixtures. The excess properties have been fitted to Redlich–Kister-type polynomial, and the corresponding standard deviations have been calculated. The derived partial molar volumes and excess partial molar volumes also support the \( V_{\text{m}}^{\text{E}} \) results. The experimental viscosity data of all of these liquid mixtures have been correlated with four viscosity models.     

Thermodynamic and transport properties for binary and ternary mixtures of 2-methyltetrahydrofuran?+?chlorobenzene?+?cyclopentanone at T?=?298.15?K

Abstract  

Experimental densities ρ, viscosities η, and refractive indices n _D of the ternary mixtures consisting of 2-methyltetrahydrofuran + chlorobenzene + cyclopentanone and constituted binary mixtures were measured at T = 298.15 K for the liquid region and at ambient pressure for the whole composition range. Excess molar volumes V_\textm^\textEV_{\text{m}}^{\text{E}}, deviations in the viscosity Δη, and deviations in the refractive index Δn _D from the mole fraction average for the mixtures were derived from the experimental data. The excess partial molar volumes V_\textm,i^\textEV_{{\text{m}},i}^{\text{E}} were also calculated. The binary and ternary data of V_\textm^\textEV_{\text{m}}^{\text{E}}, Δη, and Δn _D were correlated as a function of the mole fraction by using the Redlich–Kister and the Cibulka equations, respectively. McAllister’s three-body interaction model is used for correlating the kinematic viscosity of binary mixtures with the mole fraction.     

Thermo-physical properties of the binary mixture of benzaldehyde with bromobenzene at 303.15, 308.15, and 313.15?K

The values of density, viscosity, and ultrasonic velocity for the binary liquid mixture of benzaldehyde with bromobenzene have been measured over the entire range of composition at 303.15, 308.15, and 313.15?K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (????), deviation in velocity (?U), deviation in isentropic compressibility (??? _s), excess internal pressure (???), excess intermolecular free length (?L _f), and excess acoustic impedance (?Z). McAllister??s three-body-interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich?CKister polynomial equation to obtain their coefficients and standard deviations. The thermo-physical properties (density, viscosity, and ultrasonic velocity) under the study were fitted to the Jouyban?CAcree model.     

Thermodynamic and spectroscopic properties of 2-pyrrolidinones. 7. ΔE T N for binary solvent mixtures of 2-pyrrolidinone andN-methylbenzenesulfonamide at 30 and 50°C

ΔE _T ^N values for 2-pyrrolidinone and N-methylbenzenesulfonamide solvent systems, in which the solvents were benzyl alcohol, 1,4-dioxane and hexamethylphosphoric triamide, were determined over the whole mole fraction range. The study was carried out at 30 and 50°C. The ΔE _T ^N values were positive for all of these systems, with the exception of the 2-pyrrolidinone-hexamethylphosphoric triamide system, which was slightly negative. The results are discussed in terms of intermolecular interactions and preferential solvation.     

Thermodynamic and spectroscopic properties of 2-pyrrolidinones. 6. Normalized ET(30) parameters for binary solvent mixtures of 2-pyrrolidinone at 30 and 50°C

E _T (30) and E _T ^N values of 2-pyrrolidinone-solvent systems, where the solvent was acetone, dimethyl sulfoxide, 2-propanol, dichloromethane and water, were measured over the whole mole fraction range at 30 and 50°C. The excess E _T ^N values were positive for all except the 2-pyrrolidinone-water system. Deviations from additivity are discussed in terms of intermolecular interactions.     

Hetero-molecular association in binary mixtures of solvent extractants and diluents at temperature 303.15 K

Ultrasonic velocity and viscosity measurements have been made for binary liquid mixtures of solvent extractants, LIX reagents such as LIX 84 and LIX 984 in benzene, amyl alcohol and tri-n-butyl phosphate (TBP) at temperature 303.15?K and at atmospheric pressure. The measured values of ultrasonic velocity, density and viscosity have been utilised to compute various thermo-acoustic parameters and their excess functions, which provide information about the nature and strength of intermolecular interactions present in the systems.     

Excess molar volume measurements of ternary mixtures [2-propanol+ethyl acetate+n-hexane] and their binary constituents at 298.15, 308.15 and 313.15 K

The excess molar volume of the ternary mixture [2-propanol?+?ethyl acetate?+?n-hexane], and its binary constituents; [2-propanol?+?ethyl acetate], [2-propanol?+?n-hexane] and [ethyl acetate?+?n-hexane] were evaluated by the mixtures density measurements over the whole concentration range at three temperatures 298.15, 308.15 and 313.15?K. The excess molar volumes data were fitted to the Redlich–Kister (RK) type equation and the parameters of this equation have been calculated and presented for the studied mixtures.     

Excess properties and spectroscopic studies of binary system of 1-methoxy-2-propanol + dimethyl sulfoxide at T = (298.15–318.15) K

Thermophysical property data for the binary system of 1-methoxy-2-propanol (PGME) + dimethyl sulfoxide (DMSO), a potential candidate for use as the scrubbing liquid for the absorption of SO₂, are lacking in the literature. This paper presents experimental data at 0.1 MPa on the density and viscosity for this binary system measured over the whole composition range at T = (298.15, 303.15, 308.15, 313.15 and 318.15) K. The extended combined uncertainty U_c with a 0.95 level of confidence for the pycnometer method and Ubbelohde viscometer used in this study is 0.002 g·cm^?3 and 0.028 cm²·s^?1, respectively. The PGME + DMSO system shows negative values of the excess molar volume at all temperatures and compositions. Based on UV-Vis and FTIR, the intermolecular interaction of PGME with DMSO was confirmed as hydrogen bonding between the hydroxyl hydrogen atom in PGME and the oxygen atom in DMSO.     

Is there any sense to investigate volumetric and acoustic properties of more binary mixtures containing Ionic Liquids?

The excess speed of sound, excess molar volume and excess molar isentropic compressibility of 52 binary mixtures containing Ionic Liquids at T = 298.15 K were calculated using selected literature speed of sound and density data. The second components were alcohols: methanol, or ethanol, or 1-propanol, or 2-propanol, or 1-butanol or other solvents: acetone, acetonitrile, tetrahydrofuran, dichloromethane and dimethylsulfoxide. The Balankina’s relative excesses, X_bal, i.e. the ratios between excess and ideal quantities X^E/X^id were also determined to reduce the structural impact of pure components to absolute excesses. Analysis of quantities determined shows some patterns for concentration dependences of large groups of mixtures; thus, the scheme for influence of anion or cation of Ionic Liquids and solvent on Balankina’s relative excesses was proposed. It seems that presented analysis provide the knowledge about absolute and relative excess quantities for other mixtures without doing the experimental work. It is also visible that analysis of excess molar quantities and X_bal parameters can support the interpretation of interactions which occur between Ionic Liquids and solvent.     

Measurement of Some Thermodynamic and Acoustic Properties of Binary Solutions of N,N-Dimethylformamide with 1-Alkanols at 30°C and Comparison with Theories

Densities, and ultrasonic velocities, uof binary mixtures of N,N-dimethylformamide (DMF) + methanol, + ethanol, + 1-propanol, + 1-butanol, + 1-pentanol, and + 1-hexanol have been measured at 30°C. The ultrasonic velocities have been compared with values calculated from the free-length theory ( FLT) due to Jacobson and collision-factor theory ( CFT) due to Schaaffs. The measured data are used to compute adiabatic compressibility (k _s), deviation in adiabatic compressibility (k _s), intermolecular free length (L _f), molar volume (V _m), and available volume (V _a). The excess molar volume ( V _m ^E) and excess free length (L _f ^E) are also evaluated. For all systems, these results were satisfactorily correlated by the Redlich–Kister polynomial. These parameters are used to discuss dissociation of the self-associated 1-alkanol molecules and the formation of aggregates between unlike molecules through C=O...H–O hydrogen bonding.     

Thermodynamic properties of o-phthalic acid and its products of dissociation at 0–200°C and 1–5000 bar

Values of the pH for four solutions in a KHPh-HCl-KOH system, where Ph denoting C₈O₄H₄, are measured at 25–70°C depending on pressure (1–1000 bar). The experimental results and the available literature data are processed on the base of Helgeson-Kirkham-Flowers (HKF) equation of state [1] and the GIBBS, OptimA, and OptimB programs from the HCh software package [2]. The obtained standard thermodynamic properties and HKF parameters of H₂Ph_aq, HPh^?, and Ph^2? aqueous species, provides calculation of the pH of phthalate buffers in a wide range of temperatures (up to 200°C) and pressures (up to 5 kbar). The calculated values for the biphthalate buffer (0.05m KHPh) correspond to the IUPAC recommendations (at 0–50°C and 1 bar) with an accuracy of 0.005 pH units, and to the values of pH measured in this study at elevated Tp parameters (25–70°C and pressures of up to 1 kbar) within the limits of ±0.02 pH units.