Compressibility of ethylene glycol-dimethyl sulfoxide mixtures over the pressure range 0.1–100 MPa at 308.15 K

Compressibility coefficients k were measured for binary ethylene glycol (EG)-dimethyl sulfoxide (DMSO) mixtures over the whole composition range at pressures of 0.1–100 MPa and temperature 308.15 K. Excess molar volumes of mixtures, partial molar volumes of EG and DMSO, and changes in the excess molar Gibbs energy were calculated. The concentration dependences of compressibility factors k passed a minimum at pressures of ∼10 MPa. The k coefficient increased as the pressure grew, and the dependence became linear. The composition dependences of the specific volumes of mixtures passed minima at x ∼ 0.5 as the pressure increased (x is the mole fraction of dimethyl sulfoxide). The excess molar volumes were negative (EG-DMSO mixtures formed with compression). Changes in the excess molar Gibbs energy characterized the stabilizing action of pressure on the EG-DMSO system.     

The influence of pressure (0.1–160 MPa) on the isothermal compressibility and bulk viscosity of solutions of tetrahydrofuran in ethylene glycol at 298 K

The isothermal compressibility and bulk viscosity of solutions of tetrahydrofuran (THF) in ethylene glycol were measured on a unique Micro PVT Systems unit over the concentration and pressure ranges 0–20 mol % THF and 0.1–160 MPa, respectively, at 298 K. The results were interpreted from the point of view of structural changes in the ethylene glycol-THF system.     

The thermal properties of water-n,n-dimethylformamide solutions at 278–323.15 K and 0.1–100 MPa

The isothermal compressibility coefficients κ _T , volumetric thermal expansion coefficients α, and pressure coefficients (?p/?T) _v were calculated for water-N,N-dimethylformamide (DMFA) mixtures of 12 compositions over the temperature and pressure ranges 278–323.15 K and 0.1–100 MPa. The composition dependences of κ _T passed minima, and the corresponding α and (?p/?T) _v dependences passed maxima. The structural features of water and hydrophobic hydration effects were found to play a determining role in changes in the thermodynamic properties of water-DMFA solutions.     

Thermodynamic characteristics of acid–base equilibria of glycyl-glycyl-glycine in water–ethanol solutions at 298 K

The enthalpies of the acid dissociation of glycyl-glycyl-glycine zwitterions and triglycinium ions are determined calorimetrically in water–ethanol solvents containing 0.0, 0.10, 0.30, and 0.50 molar fractions of ethanol at ionic strengths of 0.1 (maintained by sodium perchlorate) and Т = 298.15 K. It is found that increasing the ethanol content in the solvent enhances the endothermic effect of triglycinium ion dissociation and reduces the endothermic effect of glycyl-glycyl-glycine dissociation. The results are discussed in terms of the solvation thermodynamics.     

Influence of inorganic salts on the liquid–liquid equilibrium of water + furfuryl alcohol + cyclopentanone system at 298.15 K

Influence of inorganic salts on the system of liquid phase equilibrium of water + furfuryl alcohol + cyclopentanone at 298.2 K was studied. Different salt concentrations (0, 1 and 2 wt%) and the type of salt (LiCl, NaCl, KCl, and RbCl) were investigated. The results showed that the two-phase region of the ternary system enlarged by addition of salt. NRTL model was applied, and good correlation between the experimental data and the model was achieved as confirmed by the low rmsd values.     

Molecular interactions in substituted pyrimidines-acetonitrile solutions at 298.15–318.15 K

Density, ultrasonic speed in pure solvent acetonitrile (AN) and ligand solution of substituted pyrimidine in pure AN were measured at different temperatures (298.15, 303.15, 308.15, 313.15, and 318.15 K). Acoustical parameters such as adiabatic compressibility, intermolecular free length, acoustical impedance and relative association were determined from the experimental data of density and ultrasonic speed. The effect of temperature variations on the strength of molecular interaction has been studied. An excellent correlation represents in terms of solute-solvent interaction at all temperatures.     

Enthalpy characteristics of L-proline dissolution in certain water–organic mixtures at 298.15 K

A thermochemical study of the processes of L-proline dissolution in aqueous solutions of acetonitrile, 1,4-dioxane, acetone, dimethyl sulfoxide, nitromethane and tetrahydrofuran at Т = 298.15 K in the range of organic solvent concentrations x₂ = 0–0.25 mole fractions is performed. Standard values of the enthalpies of solution and transfer of L-proline from water to mixed solvent, and the enthalpy coefficients of pairwise interactions between L-proline and molecules of organic solvents, are calculated. The effect the composition of a water–organic mixture and the structure of organic solvents have on the enthalpy characteristics of L-proline dissolution and transfer is examined. The effect the energy properties of intermolecular interactions between components of a mixed solvent has on the intermolecular interactions between L-proline and molecules of cosolvent is estimated. The correlation between the enthalpy characteristics of L-proline dissolution and electron-donor properties of organic cosolvent in aqueous solutions is determined.     

Solubility and thermodynamics of dissolution of helium in water at gas partial pressures of 0.1–100 MPa within a temperature range of 278–353 K

The tables of recommended numerical values for the water solubility of helium at gas partial pressures of 0.1–100 MPa within a temperature range of 278.15–353.15 K are given. The thermodynamic characteristics of dissolution of helium in water at the mentioned parameters of state have been calculated. The independence of the dissolution enthalpy on the pressure has been recognized and explained.     

Thermochemistry of the dissolution of DL-α-alanyl-DL-norleucine in aqueous solutions of amides at 298.15 K

Enthalpies of the dissolution of DL-α-alanyl-DL-norleucine are determined by calorimetry in aqueous solutions of formamide (FA), N-methylformamide (MFA), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA) at a concentration of amides of x ₂ = 0–0.4 molar parts and T = 298.15 K. Standard values of enthalpies of dissolution Δ_sol H ^o and Δ_tr H ^o of DL-α-alanyl-DL-norleucine transfer from water to binary solvent are calculated, along with the enthalpy coefficients of pair interactions h _xy of DL-α-alanyl-DL-norleucine with amide molecules. The effect of the composition of water-organic mixtures and the structure of amides on the enthalpy characteristics of dissolution and transition of DL-α-alanyl-DL-norleucine is considered. Quantitative estimates of the contributions to energy from DL-α-alanyl-DL-norleucine-amides pair interactions determined by the polarity, polarizability, and electron acceptor and electron donor ability of organic cosolvents are given using the Kamlet-Taft correlation equation.     

Solubility of benzilic acid in select organic solvents at 298.15 K

Experimental solubilities are reported for benzilic acid dissolved in ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-propanol, 2-butanol, 2-methyl-1-propanol, diethyl ether and methyl tert-butyl ether at 298.15?K. Results of these measurements reveal that the observed solubilities in the nine alcohol solvents fall within a fairly narrow mole fraction range of each other. Benzilic acid is also very soluble in the two ether solvents studied.     

Thermodynamics of the formation of Sm3+-ethylenediamine-N,N′-disuccinic acid complexes in aqueous solutions at 298.15 K

The thermodynamic parameters of the formation of the complexes of ethylenediamine-N,N′-disuccinic acid (H₄Y) with Sm³⁺ ion are determined by means of calorimetry and measuring pH at 298.15 K and ionic strengths of 0.5, 1.0, and 1.5 (KNO₃). The values of logK, Δ _r G, Δ _r H, and Δ _r S are calculated for the formation of SmY^? and SmHY complexes at fixed and zero values of ionic strength. The resulting values are interpreted.     

Effect of pressure on the solubility of naphthalene in water at 25°C

Solubility of naphthalene in water was measured at 25°C and pressures up to 200 MPa. The solubility decreased with increasing pressure. From the pressure coefficient of the solubility, the volume change V accompanying the dissolution was estimated as 13.8±0.4 cm ³ -mol ^–1 . Further we estimated the volume change V _CH accompanying hydrophobic hydration as –0.1±0.6 cm ³ -mol ^–1 using the V value, the molar volume of crystalline naphthalene, and the partial molar volume of naphthalene in n-heptane. This V _CH is much larger (i.e., less negative) than that for hydrophobic hydration of alkyl-chain compounds and suggests that the hydration structure of naphthalene differs from that of alkyl-chain compounds.     

Viscometric studies of divalent transition metal sulphates in mixtures of water–diethylene glycol at 298.15–318.15 K

Relative viscosities of divalent transition metal sulphates solutions, viz. manganese, cobalt, nickel, copper, zinc and magnesium sulphate has been determined in water–diethylene glycol mixtures. Effect of temperature on the viscosities at 298.15–318.15 K has been studied and B coefficients of Jones–Dole equation are determined for these solutions. The obtained parameters have been interpreted in terms of ion–ion and ion–solvent interactions. Magnesium sulphate is taken as the reference electrolyte to see the change in the behavior of divalent ions when we shift from divalent transition metal ions to some other divalent ions in these solutions. Here these transition metal and magnesium sulphates behave in the same manner i.e structure makers in both water and in DEG + water mixtures.     

Effects of acrylic acid incorporation on the pressure–temperature behavior and the calorimetric properties of poly(N-isopropylacrylamide) in aqueous solutions

 We studied the effects of pH on the pressure–temperature dependence of coil–collapse transition for aqueous solutions of copolymers of N-isopropylacrylamide and acrylic acid (Ac). At low pressures, the transition temperature (T _tr) increased with pressure, but T _tr decrease with increasing pressure at pressures higher than 50–100 MPa. By increasing the pH, the transition contour shifted to a higher temperature. When the Ac content was increased, the effects of pH became more evident. From a calorimetric study at atmospheric pressure, ΔH _tr was found to become smaller by increasing the portion of the ionized residues in the copolymer. The ratio to the van't Hoff enthalpy changes became larger with an increase in pH, which indicated that the production of charge decreased the cooperative domain size. Received: 19 July 1999 /Accepted in revised form: 7 September 1999     

Potentiometric determination of the ionization constants of ethylenediamine-N,N′-diglutaric acid at 298.15 K

Step ionization constants of ethylenediamine-N,N′-diglutaric acid at 298.15 K and ionic strength values of 0.1, 0.5, and 1.0 (KNO₃) are determined by means of potentiometry. The resulting data are extrapolated to zero ionic strength using an equation with one individual parameter, and the thermodynamic ionization constants are calculated. A correlation is made between the obtained results and the corresponding data for related compounds.     

Volumetric Properties of the Nucleoside Thymidine in Aqueous Solution at T = 298.15 K and p = (10 to 100) MPa

Sound speeds have been measured for aqueous solutions of the nucleoside thymidine at T = 298.15 K and at the pressures p = (10, 20, 40, 60, 80, and 100) MPa. The partial molar volumes at infinite dilution, $ V_{2}^{\text{o}} $ , the partial molar isentropic compressions at infinite dilution, $ K_{S,2}^{\text{o}} $ , and the partial molar isothermal compressions at infinite dilution, $ K_{T,2}^{\text{o}} $ $ \{ K_{T,2}^{\text{o}} = - (\partial V_{2}^{\text{o}} /\partial p)_{T} \} $ , have been derived from the sound speeds at elevated pressures using methods described in our previous work. The $ V_{2}^{\text{o}} $ and $ K_{T,2}^{\text{o}} $ results were rationalized in terms of the likely interactions between thymidine and the aqueous solvent. The $ V_{2}^{\text{o}} $ results were also compared with those calculated using the revised Helgeson–Kirkham–Flowers (HKF) equation of state.