The bulk properties of the water-dimethylsulfoxide system at 278–323.15 K and atmospheric pressure

The densities of water-dimethylsulfoxide (DMSO) mixtures were measured over the temperature range 278–323.15 K and over the whole range of compositions at atmospheric pressure. The partial molar volumes of water and dimethylsulfoxide, mixture volumetric thermal expansion coefficients, and partial molar volumetric thermal expansion coefficients of the components were calculated. The composition dependences of the density of the mixture passed a maximum at x ～ 0.6 at all temperatures (x is the mole fraction of dimethylsulfoxide). The composition dependences of the partial molar volumes of water and DMSO also passed extrema.     

The viscosity of the binary vapor mixture methanol-triethylamine at low densities and in the saturated vapor phase of the vapor-liquid equilibrium

For the first time, results of precision measurements of the viscosity coefficient of the binary vapor mixture methanol-triethylamine at low densities are reported. The relative measurements with an all-quartz oscillating-disk viscometer were carried out for nearly equimolar mixtures along five isochores at densities from 0.010 to 0.033 mol dm⁻³ as well as for a mixture of the mole fraction y_meth = 0.3322 at a density 0.016 mol dm⁻³ in the temperature range between 298 and 498 K. The uncertainty is estimated to be ±0.2% at ambient temperature, increasing to ±0.3% at higher temperatures. Isothermal values of a mixture with the averaged mole fraction y_meth = 0.5002 were recalculated from the original experimental data and evaluated with a first-order expansion for the viscosity, in terms of density. A so-called individual correlation on the basis of the extended theorem of corresponding states was employed to describe the interaction viscosity in the limit of zero density. Some data points at low temperatures had to be excluded from this calculation, since the measurements were performed in the saturated vapor phase. For these data points the vapor-liquid equilibrium had to be evaluated to assign the correct mole fraction in the vapor to the measured viscosity.     

Measurements and predictions of density and carbon dioxide solubility in binary mixtures of ethanol and n-decane

The solubility of carbon dioxide (CO₂) in binary mixtures of ethanol and n-decane has been measured using an in-house developed pressure-volume-temperature (PVT) apparatus at pressures up to 6 MPa and two different temperatures (303.2 and 323.2 K). Three different binary mixtures of ethanol and n-decane were prepared, and the densities of the prepared mixtures were measured over the studied pressure and temperature ranges. The experimental data of CO₂ solubility in the prepared mixtures and their saturated liquid densities were then reported at each temperature and pressure. The solubility data indicated that the gas solubility reduced as the ethanol mole fraction in the liquid mixture increased. The dissolution of CO₂ in the liquid mixtures resulted in the increase in the saturated liquid densities. The impact of gas dissolution on the saturated liquid densities was more pronounced at the lower temperature and lower ethanol compositions. The experimental solubility and density data were compared with the results of two cubic equations of state (EOSs), Soave–Redlich–Kwong (SRK) and Peng–Robinson (PR). The modeling results demonstrated that both EOSs could predict the solubility data well, while the saturated liquid densities calculated with the PR EOS were much better than those predicted with the SRK EOS.     

The densities and molar volumes of molten lead(II) dodecanoate/dodecanoic acid mixtures over their complete composition range: Evidence for non-ideal behaviour

Data are presented for the densities and molar volumes of the molten system lead(II) dodecanoate/dodecanoic acid over its complete composition range. For equimolar mixtures, plots of molar volume against temperature show curvature at high temperatures, suggesting deviations from ideal behaviour. Support for this comes from a plot of molar volume at constant temperature against acid mole fraction. Densities and molar volumes are reported for lead (II) carboxylate/carboxylic acid (0.5 mole fraction) and for pure carboxylic acid for the even chain acids C₁₀ to C₁₈. The molar volumes at constant temperature in these cases are linear functions of chain length, although the volume occupied per methylene group in equimolar mixtures is suggested to be slightly smaller than with pure soap or pure acid. An explanation for non-ideal behaviour becoming more marked at higher temperature is given in terms of acid monomer-dimer equilibria.     

High-Pressure Densities and Derived Volumetric Properties (Excess,Apparent and Partial Molar Volumes) of Binary Mixtures of Methanol + [BMIM][PF<Subscript>6</Subscript>]

The density of five (0.02297, 0.08317, 0.26147, 0.49343, 0.75255 mole fraction BMIMPF₆) binary methanol + BMIMPF₆ (1-n-butyl-3-methylimidazolium hexafluorophospate) mixtures have been measured with a vibrating-tube densimeter. Measurements were performed at temperatures from 298 to 398 K and at pressures up to 40 MPa. The total uncertainties of the density, temperature, pressure, and concentration (mole fractions) measurements were estimated to be less than 0.1 kg⋅m⁻³, 15 mK, 5 kPa, and 10⁻⁴, respectively. The uncertainties reported in this paper are expanded uncertainties at the 95% confidence level with a coverage factor of k=2. The measured densities were used to study of the effect of temperature, pressure, and concentration on the derived volumetric properties such as excess, apparent and partial molar volumes. It is shown that the values of excess molar volume for methanol + BMIMPF₆ mixtures are negative at all measured temperatures and pressures in the whole concentration range. The measured densities were used to develop Tait-type equations of state for pure components and the mixtures. The structural properties such as direct and total correlation function integrals were calculated using the derived partial molar volumes at infinite dilution.     

Transport Coefficients of High Temperature SF6–He Mixtures Used in Switching Applications as an Alternative to Pure SF6

Sulfur hexafluoride (SF₆) gas has a quite high global warming potential and hence it is required that applying any substitute for SF₆ gas. Much interest in the use of a mixture of helium and SF₆ as arc quenching medium were investigated indicating a high performance of arc interruption. The calculated values of transport coefficients of mixtures of SF₆–He mixtures, at high temperatures are presented in this paper: to the knowledge of the authors, related data have not been reported in the literature. The species composition and thermodynamic properties are determined by the method of Gibbs free energy minimization, using standard thermodynamic tables. The transport properties including electron diffusion coefficients, viscosity, thermal conductivity and electrical conductivity, are evaluated by using the Chapman–Enskog method expanded up to the third-order approximation (second-order for viscosity). Particular attention is paid to the collision integral database by the use of the most accurate and recent cross-sections or interaction potentials available in the literature. The calculations, which assume local thermodynamic equilibrium, are performed in the temperature range from 300 to 30,000 K for different pressures between 0.1 and 16 atm. An evaluation of the current interruption performance by adding He into SF₆ is discussed from a microscopic point of view. The properties with regard to SF₆–He mixtures calculated here are expected to be reliable because of the improved collision integrals employed.     

Calculation of thermodynamic properties and transport coefficients for SF6-N2 mixtures in the temperature range 1,000–30,000 K

We have computed the equilibrium composition, the transport coefficients (viscosity, electrical and thermal conductivities), the thermodynamic properties (Gibbs and Helmholtz potentials, entropy, enthalpy, specific heats), and the derived quantities (mass density, sound velocity) for SF₆-N₂ mixtures in conditions relevant to circuit-breaker arcs: temperatures between 1000 and 30,000 K, pressures in the range 1–10 atm. The validity of our computation has been checked by a detailed comparison of our results with those available in the literature concerning pure SF₆ and pure N₂. In SF₆-N₂ mixtures the chemical reactions (dissociation, ionization) have a strong influence on thermal conduction and heat capacities. The effect of SF₆ on the properties of such mixtures is elucidated: in a mixture containing 40% SF₆, the amplitude of the thermal conduction peak appearing around 7500 K is reduced by a factor of 4 relative to that of pure N₂. The influence of pressure on the properties of the plasma between 1 and 10 atm is relatively low.     

Solubility and preferential solvation of phenacetin in methanol + water mixtures at 298.15 K

The mole fraction solubility of phenacetin (PNC) in methanol + water binary solvent mixtures at 298.15 K was determined along with density of the saturated solutions. All these solubility values were correlated with the Jouyban–Acree model. Preferential solvation parameters of PNC by methanol (δx_1,3) were derived from their thermodynamic solution properties using the inverse Kirkwood–Buff integrals (IKBI) method. δx_1,3 values are negative in water-rich mixtures but positive in methanol mole fraction of >0.32. It is conjecturable that in the former case the hydrophobic hydration around non-polar groups of PNC plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behaviour of methanol.     

Densities,Excess Molar Volumes,and Thermal Expansion Coefficients of Aqueous Aminoethylethanolamine Solutions at Temperatures from 283.15 to 343.15 K

The densities of aqueous mixtures of aminoethylethanolamine (CAS #000111-41-1) were measured over the entire compositional range at temperatures of 283.15–343.15 K. The results of these measurements were used to calculate excess molar volumes and isobaric thermal expansion coefficients, and partial molar and apparent molar volumes and excess isobaric thermal expansion coefficients were subsequently derived. The excess molar volumes were correlated as a function of the mole fraction using the Redlich–Kister equation. Temperature dependences of the Redlich–Kister coefficients are also presented. The partial molar volumes at infinite dilution of AEEA in water were determined using two different methods. In addition, the solution density was correlated using a Joubian–Acree model. Aqueous solutions of AEEA exhibit similar properties to the aqueous solutions of other alkanolamines (like monoethanolamine) used in acid gas sweetening.     

Size effects in the solid phase transition of SF6 clusters

The structure of SF₆ clusters produced in a free jet expansion is studied by electron diffraction methods. A solid phase transition is known to occur when clusters are warmed up by changing several experimental conditions in the expansion of a Ne + SF₆ mixture. In the present study, the total stagnation pressure and the SF₆ mole fraction are varied in order to understand how these parameters influence the structural state of the clusters and further to observe the phase transition for different cluster sizes. When the stagnation pressurep ₀ is larger than about 10 bar, a given mole fraction results in clusters with identical structure and probably identical temperature. Whenp ₀ is decreased below 10 bar, identical structures are found for lower and lower mole fractions. This structural behaviour suggests that for small clusters, containing less than about 500 molecules, the transition steps occur at temperatures lower than those observed for larger clusters. The possibility of detecting a temperature variation in the diffraction patterns of small cubic clusters is discussed.     

Reverse nonequilibrium molecular-dynamics calculation of the Soret coefficient in liquid benzene/cyclohexane mixtures

Reverse nonequilibrium molecular dynamics is the method applied here for the investigation of thermal diffusion in realistic molecular fluids. The Soret coefficients of benzene/cyclohexane mixtures are calculated using an all-atom model. The autocorrelation functions indicate that the mole fraction gradient converges much slower than the temperature gradient. Compared to experimental data, the results show the same tendency of the Soret coefficient variation versus the mole fraction. Although a systematic error exists for the magnitude of the Soret coefficient, a meanwhile systematic error for both the mutual diffusion and thermal diffusion coefficients provides some explanation of it; and the calculation with different force field parameters indicates a possibility to annihilate the systematic error. The influences of algorithm variables such as cutoff lengths and perturbation intensities are tested. Furthermore the temperature dependence of the Soret effect is observed, yielding the same trend as previous studies.     

SPECTROPHOTOMETRIC STUDY OF THE THERMODYNAMICS OF COMPLEXATION OF LITHIUM AND SODIUM IONS WITH DIBENZO-24-CROWN-8 IN BINARY DIMETHYLFORMAMIDE-ACETONITRILE MIXTURES USING MUREXIDE AS A METALLOCHROMIC INDICATOR

Abstract

Complexation of Li⁺ and Na⁺ with dibenzo-24-crown-8 has been studied in dimethylformamide-acetonitrile mixtures by means of a competitive spectrophotometric technique using murexide as metal ion indicator. Stabilities of the resulting 1:1 complexes were investigated at various temperatures and enthalpies and entropies of complexation were determined from the temperature dependence of the formation constants. Sodium forms a more stable complex with the crown ether than lithium. There is an inverse linear relationship between log K_f and the mole fraction of DMF in the solvent mixtures. The ΔH°-TΔS° plot of all thermodynamic data, obtained for both crown complexes in different solvent mixtures, shows a fairly good linear correlation, indicating the existence of an enthalpy-entropy compensation effect in complexation.     

Thermal behaviour of diclofenac, diclofenac sodium and sodium bicarbonate compositions

This work aims to investigate the thermal behaviour of diclofenac, diclofenac sodium, and NaHCO₃ both as single components and binary mixtures. In particular, the melting point and latent heat of fusion binary diagrams of the diclofenac sodium/diclofenac mixtures at different mole fraction compositions were investigated in order to gain information about the thermal behaviour of their solid mixtures. A good agreement between liquidus curves, calculated by the Schroeder-Van Laar equation from fusion enthalpies and temperatures, and the experimental results was found. For all binary compositions, an endothermic effect at 153°C, probably due to the eutectic fusion, is present.     

(p,V,T) Behaviour and miscibility of (polysulfone+THF+carbon dioxide) at high pressures

The (p,V,T) behaviour and the miscibility of polysulfone in binary fluid mixtures of tetrahydrofuran (THF) and carbon dioxide (CO₂) have been investigated in the temperature range from (300 to 425) K at pressures up to 70 MPa. Densities of polysulfone solutions (mass fraction=0 to 0.496) in a solvent mixture of THF and CO₂ with a mass fraction of CO₂ of 0.1 were determined as a function of pressure from the homogeneous one-phase region through the phase separation point into the two-phase region at selected temperatures. The densities at the demixing pressures at these temperatures were also determined. No significant changes in density were found across the phase boundary, indicating that coexisting phases must have similar densities, which is often the case with (liquid+liquid) phase separation in high-pressure systems. The variations of density or specific volume with polymer concentration have also been investigated at selected temperatures and pressures. The data show unique features which are helpful in understanding the phase behaviour of this system which shows multiple miscibility windows. The isothermal compressibility of the polymer solutions as determined from the density data does not show any significant dependence on polymer concentrations. The compressibilities display the expected decrease with pressure and increase with temperature.     

Mutual diffusion in binary mixtures of ionic liquids and molecular liquids by dynamic light scattering (DLS)

The present study shows that dynamic light scattering (DLS) is capable of measuring mutual diffusion coefficients for binary mixtures of ionic liquids (ILs) with different molecular liquids over the complete composition range. Evidence is given that the light scattering signals are related to true molecular binary diffusion. The method stands out due to its ability to work non-invasively in macroscopic thermodynamic equilibrium with reasonable accuracy and within convenient measurement periods. Compared with other techniques, mixtures with distinctly higher viscosities can be probed. For exemplary binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO(4)]) with acetone, acetonitrile, dichloromethane, ethanol, or water as well as of 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO(3)]) with acetone, water, or methanol, mutual diffusivity data were measured over a wide range of composition at a temperature of 293.15 K. In general, the mutual diffusivity increases with increasing mole fraction of the molecular liquid and similarities to aqueous solutions of classical inorganic salts can be found. The characteristic behavior of the mutual diffusion coefficients is influenced by the nature of the chosen molecular liquid. For IL water mixtures, low light scattering intensities were observed despite the large refractive index difference of the pure components. The reason for this behavior may be the existence of water clusters in the mixtures. Additional measurements for IL acetone mixtures at temperatures ranging from 278.15 K to 323.15 K showed that the temperature dependence of the mutual diffusivity can be represented by Arrhenius functions and is increasing for decreasing mole fractions of acetone.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

Experimental excess molar properties of binary mixtures of (3-amino-1-propanol + isobutanol, 2-propanol) at T = (293.15 to 333.15) K and modelling the excess molar volume by Prigogine–Flory–Patterson theory

Density and viscosity of binary mixtures of (x₁3-amino-1-propanol + x₂isobutanol) and (x₁3-amino-1-propanol + x₂2-propanol) were measured over the entire composition range and from temperatures (293.15 to 333.15) K at ambient pressure. The excess molar volumes and viscosity deviations were calculated and correlated by the Redlich–Kister (RK) equation. The thermal expansion coefficient and its excess value, isothermal coefficient of excess molar enthalpy, and excess partial molar volumes were determined by using the experimental values of density and are described as a function of composition and temperature. The excess molar volumes are negative over the entire mole fraction range for both mixtures and increase with increasing temperature. The excess molar volumes obtained were correlated by the Prigogine–Flory–Patterson (PFP) model. The viscosity deviations of the binary mixtures are negative over the entire composition range and decrease with increasing temperature.     

Lumry's law and the quenching of anthracene fluorescence by bromide in aqueoust-butyl alcohol

The Stern-Volmer quenching constant for the quenching of anthracene fluorescence by bromide at 298.15 K shows a complex dependence on alcohol mole fraction in water plust-butyl alcohol mixtures. A similar pattern is observed at other temperatures except near 285 K, the Lumry temperature for aqueous systems.     

Physicochemical properties of (1-butyl-1-methylpyrrolydinium dicyanamide + γ-butyrolactone) binary mixtures

Experimental densities, electrical conductivities and dynamic viscosities of the pure 1-butyl-1-methylpyrrolydinium dicyanamide ionic liquid, [bmpyrr][DCA], and its binary liquid mixtures with γ-butyrolactone (GBL) were measured at temperatures from (273.15 to 323.15) K and at pressure of 0.1 MPa over the whole composition range. From the experimental density data the related excess molar volumes were calculated and fitted using Redlich–Kister’s polynomial equation. Obtained values are negative in the whole range of ionic liquid mole fraction and at all temperatures. Other volumetric properties, such as isobaric thermal expansion coefficients, partial molar volumes and partial molar volumes at infinite dilution were also calculated, in order to obtain information about the interactions between GBL and the selected ionic liquid. Negative values of these properties for both components indicate stronger interactions between GBL and IL compared to the pure components and better packing due to the differences in size and shape of the studied molecules. From the viscosity results, the Angell strength parameter was calculated and found to be 5.47 indicating that [bmpyrr][DCA] is a “fragile” liquid. All the results are compared with those obtained for binary mixtures of 1-butyl-1-methylpyrrolydinium bis(trifluoromethylsulfonyl)imide, [bmpyrr][NTf₂], with GBL.     

Solution thermodynamics and preferential solvation of hesperidin in aqueous cosolvent mixtures of ethanol,isopropanol, propylene glycol,and n-propanol

The solubility of hesperidin in some {cosolvent (1) + water (2)} mixtures expressed in mole fraction at temperatures from 293.15 K to 333.15 K reported by Xu et al. has been used to calculate the apparent thermodynamic functions, Gibbs energy, enthalpy, and entropy, of the dissolution processes by means of the van’t Hoff and Gibbs equations. Non-linear enthalpy–entropy relationships were observed for this drug in the plots of enthalpy vs. Gibbs energy of dissolution with positive or negative slopes regarding mixtures composition and/or cosolvent. Moreover, the preferential solvation of hesperidin by the cosolvents was analysed by using the inverse Kirkwood–Buff integrals observing that this drug is preferentially solvated by water in water-rich but preferentially solvated by cosolvents in mixtures 0.20 (or 0.24) ≤ x₁° ≤ 1.00. Furthermore, a new mathematical model was proposed for correlating/predicting the solubility of hesperidin in binary solvent mixtures at various temperatures.