Partial molar volumes of organic solutes in water. XVIII: Selected polyethers(aq) and 3,6-dioxa-1-heptanol(aq) at T = (298 to 573) K and at pressures up to 30 MPa

Density data for dilute aqueous solutions of four aliphatic ethers (2,5-dioxahexane, 3,5-dioxaheptane, 3,6-dioxaoctane, and 2,5,8-trioxanonane) and one ether-alcohol (3,6-dioxa-1-heptanol) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at temperatures from T = 298 K up to either T = 443 K (3,5-dioxaheptane) or T = 573 K (other solutes) and at pressures close to the saturated vapour pressure of water, at pressures between 15 and 20 MPa and at 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. XIII. Butanols (aq) at temperatures T = 298 K to 573 K and at pressures up to 30 MPa

Density data for dilute aqueous solutions of 1-butanol, 2-butanol, 2-methyl-1-propanol (iso-butanol), and 2-methyl-2-propanol (tert-butanol) 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. XVI. Selected aliphatic hydroxyderivatives(aq) at T =(298 to 573) K and at pressures up to 30 MPa

Density data for dilute aqueous solutions of two diols (1,6-hexanediol, 2,2-dimethyl-1,3-propanediol) and two polyhydric alcohols (2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,3,4,5-pentanepentaol) are presented together with 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 and at pressure close to the saturated vapour pressure of water, at pressures between 15 and 20 MPa and at p = 30 MPa. While temperature dependences of partial molar volumes of both diols are monotonous, maxima are observed on the curves for polyhydric alcohols. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter.     

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.     

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.     

Measurements of the viscosity of carbon dioxide at temperatures from (253.15 to 473.15) K with pressures up to 1.2 MPa

The viscosity of carbon dioxide was measured over the temperature range T = (253.15 to 473.15) K with pressures up to 1.2 MPa utilizing a new rotating-body viscometer. The relative expanded combined uncertainty (k = 2) in viscosity (including uncertainties of temperature and pressure) was (0.20 to 0.41)%. The instrument was specifically designed for measurements at low gas densities and enables measurements of the dynamic viscosity at temperatures between T = 253.15 K and T = 473.15 K with pressures up to 2 MPa. For carbon dioxide, the fluid specific measuring range with regard to pressure was limited to 1.2 MPa due to the formation of disturbing vortices inside the measuring cell at higher pressures. The model function for the viscosity measurement was extended in such a way that the dynamic viscosity was measured relative to helium. Therefore, the influence of the geometry of the concentric cylindrical system inside the measuring cell became almost negligible. Moreover, a systematic offset resulting from a small but inevitable eccentricity of the cylindrical system was compensated for. The residual damping, usually measured in vacuum, was calibrated in the entire temperature range using viscosity values of helium, neon and argon calculated ab initio; at T = 298.15 K recommended reference values were used. A viscosity dependent offset of the measured viscosities, which was observed in previously published data, did not occur when using the calibrated residual damping. The new carbon dioxide results were compared to other experimental literature data and to the correlation, which is currently considered the reference for viscosities of carbon dioxide.     

(p, ρ, T) Properties for n-butane in the temperature range from 280 K to 380 K at pressures up to 200 MPa

The (p, ρ, T) properties for n-butane in the compressed liquid phase were measured by means of a metal-bellows variable volumometer in the temperature range from 280 K to 380 K at pressures up to 200 MPa. The mole fraction purity of the n-butane used in the measurements was 0.9997. The expanded uncertainties (k = 2) in temperature, pressure, and density measurements have been estimated to be less than ±3 mK; 1.4 kPa (p ⩽ 7 MPa), 0.06% (7 MPa < p ⩽ 50 MPa), 0.1% (50 MPa < p ⩽ 150 MPa), and 0.2% (p > 150 MPa); and 0.09%, respectively. In the region above100 MPa at T = 280 K and T = 440 K, the uncertainty in density measurements increases from 0.09% to 0.13% and 0.22%, respectively. Eight (p, ρ, T) measurements at the same temperatures and pressures as the literature values have been conducted for comparisons. In addition, comparisons of the available equations of state with the present measurements are reported.     

Salt effects on the partition coefficients of phenol in two-phase mixtures of water and carbon dioxide at pressures from (8 to 30) MPa at a temperature of 313 K

Partition coefficients K_c of phenol between an aqueous solution containing different salts and a compressed CO₂ phase have been determined at T=313 K. For NaCl and (CH₃)₄NBr a pressure range from 8 MPa to around 30 MPa was investigated, for KCl and NaBr measurements were performed at a pressure of 22 MPa. The salt concentration has been varied between (0.25 and 3.0) mol·dm⁻³. With increasing pressure a rise in K_c is observed which typically is also found in systems free of salt. Salting-out was observed for the alkali salts, salting-in has been found for the ammonium salt, both effects increased with increasing salt concentration. From the concentration dependence of the K_c values Setschenow coefficients k_S have been derived. At p>10 MPa values are obtained as found in two phase mixtures of water with other organic solvents at ambient pressure. This conclusion was confirmed with both literature and own experimental data in the case of salting-out by NaCl as well as for the salting-in by (CH₃)₄NBr from measurements with phenol in (water + cyclohexane) at T=313 K.     

Phase equilibrium measurements of (methane + benzene) and (methane + methylbenzene) at temperatures from (188 to 348) K and pressures to 13 MPa

New isothermal pTxy data are reported for (methane + benzene) and (methane + methylbenzene (toluene)) at pressures up to 13 MPa over the temperature range (188 to 313) K using a custom-built (vapor + liquid) equilibrium (VLE) apparatus. The aim of this work was to investigate literature data inconsistencies and to extend the measurements to lower temperatures. For (methane (1) + benzene (2)), measurements were made along six isotherms from (233 to 348) K at pressures to 9.6 MPa. At temperatures below 279 K there was evidence of a solid phase, and thus only vapor phase samples were analyzed at these temperatures. For the (methane (1) + methylbenzene (3)) system, measurements were made along seven isotherms from T = (188 to 313) K at pressures up to 13 MPa. Along the 198 K isotherm, a significant change in the data’s p,x slope was observed indicating (liquid + liquid) equilibria at higher pressures. The data were compared with literature data and with calculations made using the Peng–Robinson (PR) equation of state (EOS). For both binary systems our data agree with much of the literature data that also deviate from the EOS in a similar manner. However, the data of Elbishlawi and Spencer (1951) for both binary systems, which appear to have received an equal weighting to other data in the EOS development, are inconsistent with the results of our measurements and data from other literature sources.     

Measurements of (p, ρ, T) properties for isobutane in the temperature range from 280 K to 440 K at pressures up to 200 MPa

Measurements of (p, ρ, T) properties for isobutane in the compressed liquid phase have been obtained by means of a metal-bellows variable volumometer in the temperature range from 280 K to 440 K at pressures up to 200 MPa. The volume-fraction purity of isobutane used was 0.9999. The expanded uncertainties (k = 2) of temperature, pressure, and density measurements have been estimated to be less than 3 mK, 1.5 kPa (p ⩽ 7 MPa), 0.06% (7 MPa < p ⩽ 50 MPa), 0.1% (50 MPa < p ⩽ 150 MPa), and 0.2% (p > 150 MPa), and 0.11%, respectively. In region more than 100 MPa at 280 K and 440 K, the uncertainty in density measurements rise up to 0.15% and 0.23%, respectively. The differences of the present density values at the same temperature between two series of measurements, in which the sample fillings are different, are within the maximum deviation of 0.09% in density, which is enough lower than the expanded uncertainty in density. Eight (p, ρ, T) measurements at the same temperatures and pressures as the literature values have been conducted for comparison. In addition, vapour pressures were measured at T = (280, 300) K. Moreover, the comparisons of the available equations of state with the present measurements are reported.     

Density measurements of liquid 2-propanol at temperatures between (280 and 393) K and at pressures up to 10 MPa

Liquid densities for 2-propanol have been measured at T = (280, 300, 325, 350, 375, and 393) K from about atmospheric pressure up to 10 MPa using a vibrating tube densimeter. The period of vibration has been converted into density using the Forced Path Mechanical Calibration method. The R134a has been used as reference fluid for T ? 350 K and water for T > 350 K. The uncertainty of the measurements is lower than ±0.05%. The measured liquid densities have been correlated with a Starling BWR equation with an overall AAD of 0.025%. The same BWR equation agrees within an AAD lower than 0.2% with the experimental values available in the literature over the same temperature and pressure range.     

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.     

Isothermal (vapour + liquid) equilibrium for binary mixtures of (tetrahydrofuran + 1,1,2,2-tetrachloroethane or tetrachloroethene) at nine temperatures

Vapour pressures of (tetrahydrofuran + 1,1,2,2-tetrachloroethane, or tetrachloroethene) at nine temperatures between T = 283.15 K and T = 323.15 K were measured by a static method. The reduction of the vapour pressures data to obtain activity coefficients and excess molar Gibbs energies was carried out by fitting the vapour pressure data to the Redlich–Kister polynomial according to Barker’s method. Excess molar volumes were also measured at T = 298.15 K. A comparative analysis about the thermodynamic behaviour of both systems is performed, in terms of hydrogen bonding and electron-donor–acceptor interactions, as well as the resonance effect in tetrachloroethene.     

Partial molar volumes of organic solutes in water. XXI: Cyclic ethers at temperatures T = (278 to 373) K and at low pressure

Density values for dilute aqueous solutions of five cyclic ethers obtained using the Anton Paar DSA 5000 vibrating-tube densimeter and the laboratory-made flow densimeter are presented together with partial molar volumes at infinite dilution (standard partial molar volumes) calculated from the measured results. The cyclic ethers were either five-members cycles with one or two oxygen atoms (oxolane, 1,3-dioxolane) or six-members cycles with one, two, or three oxygen atoms (oxane, 1,4-dioxane, 1,3,5-trioxane). The measurements were performed at temperatures from T = 278 K up to T = 373 K and at either atmospheric pressure or at p = 0.5 MPa. The group contribution method is proposed and values of group contributions are evaluated. Standard partial molar volumes predicted for several other cyclic ethers including large cycles (crown ethers) are compared with available data from the literature.     

(p, ρ, T) properties and apparent molar volumes Vϕ of CaCl2 in methanol at T = (298.15 to 398.15) K and pressure up to 40 MPa

The (p, ρ, T) properties and apparent molar volumes V_ϕ of CaCl₂ in methanol at T = (298.15 to 398.15) K, at pressures up to 40 MPa are reported, and apparent molar volumes have been evaluated. The experimental (p, ρ, T) values were described by an equation of state. The experiments were carried out at m = (0.10819, 0.28529, 0.65879 and 2.39344) mol · kg⁻¹ of calcium chloride.     

(Liquid + liquid) equilibrium for the system {ethyl stearate(1) + ethanol(2) + glycerol(3)}

This paper reports the results of a new experimental study on the (liquid + liquid) equilibrium of the system {ethyl stearate(1) + ethanol(2) + glycerol(3)} at atmospheric pressure and at T = (313.15 and 323.15) K. The equilibrium compositions were measured by gas chromatography. Ternary diagrams were obtained for each temperature and the equilibrium data were compared to the system in the presence of salt (NaCl) at T = 323.15 K. The experimentally determined (liquid + liquid) equilibrium data were satisfactorily correlated with NRTL and UNIQUAC equations. A comparative analysis was performed using the UNIFAC-LLE group contribution method. From the results presented herein good predictions were obtained for this ternary system.     

Saturated liquid densities of propane at T = (280 to 365) K

Saturated liquid densities for propane were obtained by means of a metal-bellows variable volumometer at T = (280, 300, 320, 340, 360, and 365) K. The mol-fraction purity of the propane used in the measurements was 0.99997. The expanded uncertainties (k = 2) in temperature, pressure, and density measurements were estimated to be less than ±3 mK, 1.4 kPa (p ≦ 7 MPa), and ±0.09%, respectively. For the determination of the saturation boundary at each temperature for propane, we measured the density data at intervals of about 20 kPa very close to the saturation boundary. After such measurements had been completed, the saturated liquid density data at each temperature were determined as the intersection between the isotherm and our previously determined vapour pressure value. The discrepancies between the three series in the present measurements, in which different sample fillings were used, were also confirmed to be sufficiently lower than the experimental uncertainty. The saturated liquid density correlation was also provided for the systematic comparisons between the present measurements and the literature data.     

Isothermal (vapour + liquid) equilibrium at several temperatures of (1-chlorobutane + 1-butanol,or 2-methyl-2-propanol)

Vapour pressures of (1-chlorobutane  +  1-butanol, or 2-methyl-2-propanol) at several temperatures between T =  278.15 and T =  323.15 K were measured by a static method. Reduction of the vapour pressures to obtain activity coefficients and excess molar Gibbs energies was carried out by fitting the vapour pressure data to the Redlich–Kister equation according to Barker’s method. For (1-chlorobutane  +  2-methyl-2-propanol) azeotropic mixtures with a minimum boiling temperature were observed over the whole temperature range.     

Partial molar volumes of organic solutes in water. XV. Butanediols(aq) at temperatures from (298 K to 573 K) and at pressures up to 30 MPa

Density data for dilute aqueous solutions of three butanediols (1,3-butanediol, 2,3-butanediol, 1,4-butanediol) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at temperatures from 298.15 K up to 573.15 K and at pressures close to the saturated vapour pressure of water, at pressures close to 20 MPa and 30 MPa. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter.     

Measurements of HmE and VmE for (propane + sulphurhexafluoride) in the near critical region

A flow mixing calorimeter followed by a vibrating-tube densimeter has been used to measure excess molar enthalpies H_m^E and excess molar volumesV_m^E of {xC₃H₈ +  (1  − x)SF₆}. Measurements over a range of mole fractionsx have been made at the pressure p =  4.30 MPa at eight temperatures in the rangeT =  314.56 K to 373.91 K, in the liquid region at p =  3.75 MPa andT =  314.56 K, in the two phase region at p =  3.91 MPa andT =  328.18 K, and in the supercritical region at p =  5.0 MPa andT =  373.95 K. The measurements are compared with results from the Patel–Teja equation of state which reproduces the main features of the excess function curves as well as it does for similar measurements on{xCO₂ +  (1  − x)C₂H₆} ,{xCO₂ +  (1  − x)C₂H₄} and{xCO₂ +  (1  − x)SF₆} reported previously.