PVT,viscosity, and surface tension of ethanol: New measurements and literature data evaluation

In this work, the results of density, viscosity, and surface tension measurements for ethanol are presented. Ethanol with stated mass fraction purity greater than 0.998 was further purified using molecular sieves. Density was measured within the temperature and pressure ranges, respectively, T = (278.15 to 353.15) K and p = (0.1 to 35) MPa by means of a vibrating tube densimeter, model DMA 512P from Anton Paar with an estimated uncertainty of ±0.5 kg · m^?3. The experimental (p, ρ, T) results have been correlated by Tait equation. From this equation the isobaric expansivity, the isothermal compressibility, and the thermal pressure coefficient have been calculated. Viscosity was measured over the range T = (273.15 to 346.15) K using an Ubbelohde viscometer with a Schott–Geräte automatic measuring unit (Model AVS-470) with the associated uncertainty of ±0.001 mPa · s. The measured values were combined with selected values from the literature covering the range T = (223 K to 503) K, and the VTF model has been fitted to all the data. The surface tension of the liquid was measured using a tensiometer KSV Sigma 70 with a Du-Noüy ring for the range of T = (274.77 to 318.99) K with an uncertainty of ±0.01 mN · m^?1. Using these data and critically assessed data of other authors compiled from the literature, a form of the IAPWS equation was used to correlate the surface tension within the temperature range 223 K up to the critical temperature.     

The thermodynamic properties of DyBr3(s) and DyI3(s) from T=5 K to their melting temperatures

Low-temperature calorimetric measurements have been performed on DyBr₃(s) in the temperature range (5.5 to 420 K ) and on DyI₃(s) from T=4 K to T=420 K. The data reveal enhanced heat capacities below T=10 K, consisting of a magnetic and an electronic contribution. From the experimental data on DyBr₃(s) a C⁰_p,m (298.15 K) of (102.2±0.2) J·K⁻¹·mol⁻¹ and a value for {S⁰_m (298.15 K) − S⁰_m (5.5 K)} of (205.5±0.5) J·K⁻¹·mol⁻¹, have been obtained. For DyI₃(s), {S⁰_m (298.15 K) − S⁰_m (4 K)} and C⁰_p,m (298.15 K) have been determined as (226.9±0.5) J·K⁻¹·mol⁻¹ and (103.4±0.2) J·K⁻¹·mol⁻¹, respectively. The values for {S⁰_m (5.5 K) − S⁰_m (0)} for DyBr₃(s) and {S⁰_m (4 K) − S⁰_m (0)} for DyI₃(s) have been calculated, giving S⁰_m (298.15 K)=(212.3±0.9) J·K⁻¹·mol⁻¹ in case of DyBr₃(s) and S⁰_m (298.15 K) =(233.1±0.7) J·K⁻¹·mol⁻¹ for DyI₃(s). The high-temperature enthalpy increment has been measured for DyBr₃(s) in the temperature range (525 to 799 K) and for DyI₃(s) in the temperature range (525 to 627 K). From the results obtained and enthalpies of formation from the literature, thermodynamic functions for DyBr₃(s) and DyI₃(s) have been calculated from T→0 to their melting temperatures at 1151.0 K and 1251.5 K, respectively.     

The molar enthalpies of solution and vapour pressures of saturated aqueous solutions of some cesium salts

Vapour pressures of water over saturated solutions of cesium chloride, cesium bromide, cesium nitrate, cesium sulfate, cesium formate, and cesium oxalate were determined as a function of temperature. These vapour pressures were used to evaluate the water activities, osmotic coefficients and molar enthalpies of vapourization. Molar enthalpies of solution of cesium chloride, Δ_solH_m(T = 295.73 K; m = 0.0622 mol · kg⁻¹) = (17.83 ± 0.50) kJ · mol⁻¹; cesium bromide, Δ_solH_m(T = 293.99 K; m = 0.0238 mol · kg⁻¹) = (26.91 ± 0.59) kJ · mol⁻¹; cesium nitrate, Δ_solH_m(T = 294.68 K; m = 0.0258 mol · kg⁻¹) = (37.1 ± 2.3) kJ · mol⁻¹; cesium sulfate, Δ_solH_m(T = 296.43 K; m = 0.0284 mol · kg⁻¹) = (16.94 ± 0.43) kJ · mol⁻¹; cesium formate, Δ_solH_m(T = 295.64 K; m = 0.0283 mol · kg⁻¹) = (11.10 ± 0.26) kJ · mol⁻¹ and Δ_solH_m(T = 292.64 K; m = 0.0577 mol · kg⁻¹) = (11.56 ± 0.56) kJ · mol⁻¹; and cesium oxalate, Δ_solH_m(T = 291.34 K; m = 0.0143 mol · kg⁻¹) = (22.07 ± 0.16) kJ · mol⁻¹ were determined calorimetrically. The purity of the chemicals was generally greater than 0.99 mass fraction, except for HCOOCs and (COOCs)₂ where purities were approximately 0.95 and 0.97 mass fraction, respectively. The uncertainties are one standard deviations.     

Apparent molar volumes and apparent molar heat capacities of aqueous KI,HIO3, NaIO3, and KIO3 at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

We determined apparent molar volumes V_? at 298.15 ? (T/K) ? 368.15 and apparent molar heat capacities C_p,? at 298.15 ? (T/K) ? 393.15 for aqueous solutions of HIO₃ at molalities m from (0.015 to 1.0) mol · kg^?1, and of aqueous KIO₃ at molalities m from (0.01 to 0.2) mol · kg^?1 at p = 0.35 MPa. We also determined V_? at the same p and at 298.15 ? (T/K) ? 368.15 for aqueous solutions of KI at m from (0.015 to 7.5) mol · kg^?1. We determined C_p,? at the same p and at 298.15 ? (T/K) ? 393.15 for aqueous solutions of KI at m from (0.015 to 5.5) mol · kg^?1, and for aqueous solutions of NaIO₃ at m from (0.02 to 0.15) mol · kg^?1. Values of V_? were determined from densities measured with a vibrating-tube densimeter, and values of C_p,? were determined with a twin fixed-cell, differential temperature-scanning calorimeter. Empirical functions of m and T were fitted to our results for each compound. Values of K_a, Δ_rH_m, and Δ_rC_p,m for the proton ionization reaction of aqueous HIO₃ are calculated and discussed.     

Apparent molar volumes and apparent molar heat capacities of aqueous tetrahydrofuran,dimethyl sulfoxide, 1,4-dioxane,and 1,2-dimethoxyethane at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

We determined apparent molar volumes V_? at 278.15 ? (T/K) ? 368.15 and apparent molar heat capacities C_p,? at 278.15 ? (T/K) ? 393.15 at p = 0.35 MPa for aqueous solutions of tetrahydrofuran at m from (0.016 to 2.5) mol · kg^?1, dimethyl sulfoxide at m from (0.02 to 3.0) mol · kg^?1, 1,4-dioxane at m from (0.015 to 2.0) mol · kg^?1, and 1,2-dimethoxyethane at m from (0.01 to 2.0) mol · kg^?1. Values of V_? were determined from densities measured with a vibrating-tube densimeter, and values of C_p,? were determined with a twin fixed-cell, differential, temperature-scanning calorimeter. Empirical functions of m and T for each compound were fitted to our V_? and C_p,? results.     

Thermophysical properties of 1-alkylpyridinum bis(trifluoromethylsulfonyl)imide ionic liquids

The thermophysical properties of 1-alkylpyridinium bis(trifluoromethylsulfonyl)imide, [C_npy][Tf₂N] ionic liquids where n = 4, 8, 10, or 12 have been determined. Density ρ, and dynamic viscosity η, were determined at T = (293.15 to 353.15) K and refractive index n_D, was measured at T = (293.15 to 333.15) K. Empirical correlations are proposed to represent the present experimental results. The values of the coefficient of thermal expansion were calculated from the experimental density values. The thermal decomposition temperature, T_d was also determined using thermogravimetric analyzer (TGA) at a heating rate of (10 and 20) K · min^?1.     

The enthalpy of dilution and thermodynamics of Na2CO3(aq) and NaHCO3(aq) fromT = 298 K toT = 523.15 K and pressure of 40 MPa

Molar enthalpies of dilution Δ_dilH_mofNa₂CO₃(aq) were measured from molality m =  1.45 mol · kg ^− 1to m =  0.008 mol · kg ^− 1at seven temperatures from T =  298 K toT =  523 K at the pressure p =  7 MPa, and at four temperatures fromT =  371 K to T =  523 K at the pressurep =  40 MPa. Molar enthalpies of dilutionΔ_dilH_m of NaHCO₃(aq) were measured fromm =  0.98 mol · kg ^− 1tom =  0.007 mol · kg ^− 1at the same temperatures and pressures. Hydrolysis and ionization equilibria contribute substantially to the measured enthalpies under many of the conditions of this study. Explicit consideration of these reactions, using thermodynamic quantities from previous studies, facilitates a quantitative representation of apparent molar enthalpies, activity coefficients, and osmotic coefficients with the Pitzer ion-interaction treatment over the ranges of temperature, pressure, and molality of the experiments.     

Volumetric properties of aqueous solutions of glutaric acid

Densities of aqueous solutions with molalities up to 6 mol · kg⁻¹ were determined at 5 K temperature intervals, from T = 288.15 K to T = 333.15 K. Densities served to evaluate the apparent molar volumes, V_2,ϕ(m, T), the cubic expansion coefficients, α(m, T), and the changes of isobaric heat capacities with respect to pressure, (∂C_P/∂P)_T,m. They were qualitatively correlated with the changes in the structure of water when glutaric acid is dissolved in it.     

Density,viscosity, refractive index,excess molar enthalpy,viscosity, and refractive index deviations for the (1-butanol + 2-butanone) binary system at T = 303 K. A new adiabatic calorimeter for heat of mixing

Density, viscosity, refractive index, and heat of mixing measurements for {x₁ 1-butanol + (1 ? x₁) 2-butanone} at T = 303 K were made over the whole concentration range. Data of the binary mixture were further used to calculate the viscosity and refractive index deviations, and excess molar enthalpy. The excess or deviation properties were fitted with the Redlich–Kister polynomial relation to obtain their coefficients and standard deviations. The construction of an adiabatic calorimeter useful in the neighbourhood of room temperature is described. Its performance was checked by measuring the heat of mixing for {x₁ benzene + (1 ? x₁) cyclohexane} over the whole concentration range at T = 298 K. Experimental results are within a standard deviation of 9 J · mol^?1 of the accepted literature values.     

The heat capacities and thermodynamic properties of NiAl2O4 and CoAl2O4 measured by adiabatic calorimetry from T = (4 to 400) K

The low-temperature heat capacity of NiAl₂O₄ and CoAl₂O₄ was measured between T = (4 and 400) K and thermodynamic functions were derived from the results. The measured heat-capacity curves show sharp anomalies peaking at around T = 7.5 K for NiAl₂O₄ and at T = 9 K for CoAl₂O₄. The exact cause of these anomalies is unknown. From our results, we suggest a standard entropy for NiAl₂O₄ at T = 298.15 K of (97.1 ± 0.2) J · mol^?1 · K^?1 and for CoAl₂O₄ of (100.3 ± 0.2) J · mol^?1 · K^?1.     

Critical parameters for propane determined by the image analysis

The (p, ρ, T) measurements and visual observations of the meniscus for propane were carried out carefully in the critical region over the range of temperatures: ?60 mK ? (T ? T_c) ?  40 mK and of densities: ?4 kg · m^?3 ? (ρ ? ρ_c) ? 6 kg · m^?3 by a metal-bellows volumometer with an optical cell. Vapour pressures were also measured at T = (320.000, 343.132, 369.000, and 369.625) K. The critical point of T_c, ρ_c, and p_c was determined by the image analysis of the critical opalescence. Comparisons of the critical parameters with values given in the literature are presented.     

Thermodynamics of the oxidation–reduction reaction {2 glutathionered(aq) + NADPox(aq)=glutathioneox(aq) + NADPred(aq)}

Microcalorimetry, spectrophotometry, and high-performance liquid chromatography (h.p.l.c.) have been used to conduct a thermodynamic investigation of the glutathione reductase catalyzed reaction {2 glutathione_red(aq) + NADP_ox(aq)=glutathione_ox(aq) + NADP_red(aq)}. The reaction involves the breaking of a disulfide bond and is of particular importance because of the role glutathione_red plays in the repair of enzymes. The measured values of the apparent equilibrium constant K^′ for this reaction ranged from 0.5 to 69 and were measured over a range of temperature (288.15 K to 303.15 K), pH (6.58 to 8.68), and ionic strength I_m (0.091 mol · kg⁻¹ to 0.90 mol · kg⁻¹). The results of the equilibrium and calorimetric measurements were analyzed in terms of a chemical equilibrium model that accounts for the multiplicity of ionic states of the reactants and products. These calculations led to values of thermodynamic quantities at T=298.15 K and I_m=0 for a chemical reference reaction that involves specific ionic forms. Thus, for the reaction {2 glutathione_red⁻(aq) + NADP_ox³⁻(aq)=glutathione_ox²⁻(aq) + NADP_red⁴⁻(aq) + H⁺(aq)}, the equilibrium constant K=(6.5±4.4)·10⁻¹¹, the standard molar enthalpy of reaction Δ_rH^o_m=(6.9±3.0) kJ · mol⁻¹, the standard molar Gibbs free energy change Δ_rG^o_m=(58.1±1.7) kJ · mol⁻¹, and the standard molar entropy change Δ_rS^o_m=−(172±12) J · K⁻¹ · mol⁻¹. Under approximately physiological conditions (T=311.15 K, pH=7.0, and I_m=0.25 mol · kg⁻¹ the apparent equilibrium constant K^′≈0.013. The results of the several studies of this reaction from the literature have also been examined and analyzed using the chemical equilibrium model. It was found that much of the literature is in agreement with the results of this study. Use of our results together with a value from the literature for the standard electromotive force E^o for the NADP redox reaction leads to E^o=0.166 V (T=298.15 K and I=0) for the glutathione redox reaction {glutathione_ox²⁻(aq) + 2 H⁺(aq) + 2 e⁻=2 glutathione_red⁻(aq)}. The thermodynamic results obtained in this study also permit the calculation of the standard apparent electromotive force E^′o for the biochemical redox reaction {glutathione_ox(aq) + 2 e⁻=2 glutathione_red(aq)} over a wide range of temperature, pH, and ionic strength. At T=298.15 K, I=0.25 mol · kg⁻¹, and pH=7.0, the calculated value of E^′o is −0.265 V.     

The solubility measurements of sodium dicarboxylate salts; sodium oxalate,malonate, succinate,glutarate, and adipate in water from T = (279.15 to 358.15) K

The solubility measurements of sodium dicarboxylate salts; sodium oxalate, malonate, succinate, glutarate, and adipate in water at temperatures from (278.15 to 358.15 K) were determined. The molar enthalpies of solution at T = 298.15 K were derived: Δ_solH_m (m = 2.11 mol · kg^?1) = 13.86 kJ · mol^?1 for sodium oxalate; Δ_solH_m (m = 3.99 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium malonate; Δ_solH_m (m = 2.45 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium succinate; Δ_solH_m (m = 4.53 mol · kg^?1) = 16.55 kJ · mol^?1 for sodium glutarate, and Δ_solH_m (m = 3.52 mol · kg^?1) = 15.70 kJ · mol^?1 for sodium adipate. The solubility value exhibits a prominent odd–even effect with respect to terms with odd number of sodium dicarboxylate carbon numbers showing much higher solubility. This odd–even effect may have implications for the relative abundance of these compounds in industrial applications and also in the atmospheric aerosols.     

Molar heat capacity and thermodynamic properties of 1-cyclohexene-1,2-dicarboxylic anhydride [C8H8O3]

The molar heat capacity C_p,m of 1-cyclohexene-1,2-dicarboxylic anhydride was measured in the temperature range from T=(80 to 360) K with a small sample automated adiabatic calorimeter. The melting point T_m, the molar enthalpy Δ_fusH_m and the entropy Δ_fusS_m of fusion for the compound were determined to be (343.46 ± 0.24) K, (11.88 ± 0.02) kJ · mol⁻¹ and (34.60 ± 0.06) J · K⁻¹ · mol⁻¹, respectively. The thermodynamic functions [H_(T)−H_(298.15)] and [S_(T)−S_(298.15)] were derived in the temperature range from T=(80 to 360) K with temperature interval of 5 K. The mass fraction purity of the sample used in the adiabatic calorimetric study was determined to be 0.9928 by using the fractional melting technique. The thermal stability of the compound was investigated by differential scanning calorimeter (DSC) and thermogravimetric (TG) technique, and the process of the mass-loss of the sample was due to the evaporation, instead of its thermal decomposition.     

The thermodynamics of formation,molar heat capacity,and thermodynamic functions ofZrTiO4(cr)

As part of an ongoing study of titanate-based ceramic materials for the disposal of surplus weapons-grade plutonium, we report thermodynamic properties of a sample ofzirconium titanate (ZrTiO₄) quenched from a high-temperature synthesis. The standard enthalpy of formationΔ_fH_m^o was obtained by using high-temperature oxide-melt solution calorimetry. The molar heat capacity C_{p, m}was measured fromT =  13 K to T =  400 K in an adiabatic calorimeter and extrapolated toT =  1800 K by using an equation fitted to the low-temperature results. The results atT =  298.15 K areΔ_fH_m^o =  − (2024.1  ±  4.5)kJ · mol ^− 1,Δ₀^TS_m^o =  (116.71  ±  0.31 )J · K ^− 1· mol ^− 1, andΔ_fG_m^o =  − (1915.8  ±  4.5 )kJ · mol ^− 1; the molar entropy includes a contribution of 2 R ln2 to account for the random mixing of Zr^4 + and Ti^4 + on a four-fold crystallographic site. Values for the standard molar Gibbs energies and enthalpies of formation of ZrTiO_4,Δ_fG_m^oandΔ_fH_m^o , and for the free energies and enthalpies for the reaction to form ZrTiO₄(cr) from ZrO₂(cr) and TiO₂(cr), are tabulated over the temperature interval, 0 ⩽(T / K)⩽ 1800. From these results, we conclude that ZrTiO₄is not stable with respect to (ZrO₂ +  TiO₂) at T =  298.15 K, but becomes so at T =  (1250  ±  150) K.     

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T = (298.15 and 323.15) K,and representation with an extended ion-interaction (Pitzer) model

Isopiestic vapor-pressure measurements were made for Rb ₂SO ₄(aq) from molalitym =  (0.16886 to 1.5679 )mol · kg ^− 1atT =  298.15 K and from m =  (0.32902 to 1.2282 )mol · kg ^− 1at T =  323.15 K, and for Cs ₂SO₄ (aq) from m =  (0.11213 to 3.10815 )mol · kg ^− 1at T =  298.15 K and fromm =  (0.11872 to 3.5095 )mol · kg ^− 1atT =  323.15 K, with NaCl(aq) as the reference standard. Published thermodynamic information for these systems were reviewed and the isopiestic equilibrium molalities and dilution enthalpies were critically assessed and recalculated in a consistent manner. Values of the four parameters of an extended version of Pitzer`s model for osmotic and activity coefficients with an ionic-strength dependent third virial coefficient were evaluated for both systems at both temperatures, as were those of the usual three-parameter Pitzer model. Similarly, parameters of Pitzer`s model for the relative apparent molar enthalpies of dilution were evaluated at T =  298.15 K for both Rb ₂SO ₄(aq) and Cs ₂SO ₄(aq) for the more restricted range of m⩽ 0.101 mol · kg ^− 1. Values of the thermodynamic solubility product K_s(Rb₂ SO ₄, cr, 298.15 K )  =  (0.1392  ±  0.0154) and the CODATA compatible standard molar Gibbs free energy of formationΔ_fG_m^o (Rb ₂SO ₄, cr, 298.15 K )  =  − (1316.91  ±  0.59)kJ · mol ^− 1, standard molar enthalpy of formationΔ_fH_m^o (Rb ₂SO ₄, cr, 298.15 K )  =  − (1435.07  ±  0.60)kJ · mol ^− 1, and standard molar entropy S _m^o(Rb₂ SO ₄, cr, 298.15 K )  =  (199.60  ±  2.88)J · K ^− 1· mol ^− 1were derived. A sample of one of the lots of Rb ₂SO ₄(s) used for part of our isopiestic measurements was analyzed by ion chromatography, and was found to be contaminated with potassium and cesium in amounts that significantly exceeded the claims of the supplier. In contrast, analysis by ion chromatography of a lot of Cs ₂SO ₄(s) used for some of our experiments showed it was highly pure.     

Measurements of the critical parameters for {xNH3 + (1 − x)H2O} with x = (0.9098, 0.7757, 0.6808)

Measurements of the critical parameters for {xNH₃ + (1 ? x)H₂O} with x = (0.9098, 0.7757, 0.6808) were carried out by using a metal-bellows variable volumometer with an optical cell. The expanded uncertainties (k = 2) in temperature, pressure, density, and composition measurements have been estimated to be less than 3.2 mK, 3.2 kPa, 0.3 kg · m^?3, and 8.8 · 10^?4, respectively. In each mole fraction, the critical temperature T_c was first determined on the basis of the intensity of the critical opalescence. The critical pressure p_c and critical density ρ_c were then determined as the point at which the meniscus disappears on the isotherm at T = T_c. The expanded uncertainties (k = 2) in the present critical parameters have also been estimated. Comparisons of the present values with the literature data as well as the calculated values afforded using the equation of state are also presented.     

Viscometric studies on saccharides in aqueous magnesium chloride solutions at T = (288.15 to 318.15) K

The viscosity B-coefficients of mono-, di-, tri-saccharides and the derivatives (methyl glycosides) in m_B = (0.5, 1.0, 2.0, and 3.0) mol · kg⁻¹ aqueous solutions of magnesium chloride have been determined from viscosity data using the Jones–Dole equation at T = (288.15, 298.15, 308.15, and 318.15) K. The viscosity B-coefficients of transfer (Δ_tB), the temperature derivatives of B-coefficients (dB/dT), pair and triplet viscometric interaction coefficients (η_AB, η_ABB) have been determined. The viscosity B-coefficients data of systems studied in water have been reported earlier. The results have been interpreted in light of the solute–solute and solute–solvent interactions occurring in these systems. The comparison of results has been made with those reported in the presence of potassium chloride, ammonium sulphate, and sodium sulphate.