(Ternary liquid + liquid) equilibria for (water + acetone + α-pinene,or β-pinene,or limonene) mixtures

(Ternary liquid + liquid) equilibria (tie-lines) of (water + acetone + α-pinene) at T = (288.15, 298.15, and 308.15) K and (water + acetone + β-pinene, or limonene) at T = 298.15 K have been measured. The experimental (ternary liquid + liquid) equilibrium data have been correlated successfully by the original UNIQUAC and modified UNIQUAC models. The modified UNIQUAC model reproduced accurately the experimental results for the (water + acetone + α-pinene) system at all the temperatures but fairly agreed with the experimental data for the (water + acetone + β-pinene, or limonene) systems.     

(Vapour + liquid) equilibria for the binary mixtures (cis-pinane + α-pinene) and (cis-pinane + 1-butanol)

The isothermal and isobaric (vapour + liquid) equilibria for (cis-pinane + α-pinene) and (cis-pinane + 1-butanol) measured with an inclined ebulliometer are presented. The experimental results are analysed using the UNIQUAC equation with the temperature-dependence binary parameters with satisfactory results. Experimental vapour pressures of cis-pinane are also included.     

Ternary (liquid + liquid) equilibria for (water + 2-propanol + α-pinene,or β-pinene) mixtures at four temperatures

Ternary (liquid + liquid) equilibria date for the (water + 2-propanol + α-pinene, or β-pinene) systems were measured at T = (293.15, 298.15, 303.15, and 308.15) K under atmospheric pressure. The experimental results were correlated using the extended and modified UNIQUAC models. The calculated results obtained from the modified UNIQUAC model successfully represent the experimental tie-line data. The temperature influence on liquid-phase equilibria was studied.     

Modelling (vapour + liquid) and (vapour + liquid + liquid) equilibria of {water (H2O) + methanol (MeOH) + dimethyl ether (DME) + carbon dioxide (CO2)} quaternary system using the Peng–Robinson EoS with Wong–Sandler mixing rule

The (vapour + liquid) equilibria (VLE) and (vapour + liquid + liquid) equilibria (VLLE) binary data from literature were correlated using the Peng–Robinson (PR) equation of state (EoS) with the Wong–Sandler mixing rule (WS). Two group contribution activity models were used in the PRWS: UNIFAC–PSRK and UNIFAC–Lby. The systems were successfully extrapolated from the binary systems to ternary and quaternary systems. Results indicate that the PRWS–UNIFAC–PSRK generally displays a better performance than the PRWS–UNIFAC–Lby.     

Phase diagrams of (vapour + liquid) equilibrium for binary mixtures of α,α,α-trifluorotoluene with ethanol,or benzene,or chloroform at pressure 101.4 kPa

(Vapour + liquid) equilibrium (VLE) of binary mixtures of (ethanol + α,α,α-trifluorotoluene), (benzene + α,α,α-trifluorotoluene), and (chloroform + α,α,α-trifluorotoluene) have been investigated at the pressure 101.4 kPa using the dynamic-ebulliometry method over the whole composition range. The correlated VLE phase diagrams were adequately described by means of NRTL and UNIQUAC thermodynamic models. Fair attractive energies in the first two systems are capable to yield azeotropes, while moderate repulsive energies in the later system make it zeotrope.     

(Liquid + liquid) equilibria for (water + 1-propanol or acetone + β-citronellol) at different temperatures

On this paper, experimental (liquid + liquid) equilibrium (LLE) results are presented for systems composed of β-citronellol and aqueous 1-propanol or acetone. To evaluate the phase separation properties of β-citronellol in aqueous mixtures, LLE values for the ternary systems (water + 1-propanol + β-citronellol) and (water + acetone + β-citronellol) were determined with a tie-line method at T = (283.15, 298.15, and 313.15 ± 0.02) K and atmospheric pressure. The reliability of the experimental tie-lines was verified by the Hand and Bachman equations. Ternary phase diagrams, distribution ratios of 1-propanol and acetone in the mixtures are shown. The effect of the temperature on the ternary (liquid + liquid) equilibria was examined and discussed. The experimental LLE values were satisfactorily correlated by extended UNIQUAC and modified UNIQUAC models.     

Comment on “Isobaric (vapour + liquid) equilibria for the (1-propanol + 1-butanol) binary mixture at (53.3 and 91.3) kPa”

The (vapor + liquid) equilibrium values reported by Mohsen-Nia and Memarzadeh appear to be flawed. In particular, neither the reported experimental activity coefficients are consistent with the reported composition data nor the reported model parameters can be used to adequately represent their experimental data.     

Measurement and prediction of (solid + liquid) equilibria of gun powder’s and propellant’s stabilizers mixtures

A differential scanning calorimetry (d.s.c.) was used to determine binary (solid + liquid) phase equilibria (SLE) for four binary mixtures, viz. (n-nitrosodiphenylamine + diphenylamine), (2-nitrodiphenylamine + ethyl centralite), (2,4-dinitro-N-ethylaniline + methyl centralite), and (2,4-diphenylamine + 4,4′-dinitroethylcentralite). These compounds are used as stabilizers in gun powders and propellants. Results obtained with this technique are compared with those correlated by NRTL and ideal models. It was found out that all the systems are simple eutectic systems and deviations between experimental and predicted SLE results were observed.     

Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) III. HmEandVmE for 20 binary mixtures {xCu − 1H2u − 1CO2C4H9 + (1 − x)α,ω-ClCH2(CH2)v − 2CH2Cl}, where u = 1 to 4, α = 1 and v = ω = 2 to 6

In this article, the experimental data of excess molar enthalpies $H_{\mathrm{m}}^{\mathrm{E}}$ and excess molar volumes $V_{\mathrm{m}}^{\mathrm{E}}$ are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15 K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The $V_{\mathrm{m}}^{\mathrm{E}}$ are positive for mixtures of (butyl esters + 1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in $H_{\mathrm{m}}^{\mathrm{E}}$ with the dichloroethane chain length for a same ester is regular although the $V_{\mathrm{m}}^{\mathrm{E}}$ presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied.To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems’ behaviour.     

Ebulliometric determination and prediction of (vapor + liquid) equilibria for binary and ternary mixtures containing alcohols (C1–C4) and dimethyl carbonate

(Vapor + liquid) equilibrium (VLE) data for a ternary mixture, namely {methanol + propan-1-ol + dimethyl carbonate (DMC)}, and four binary mixtures, namely an {alcohol (C₃ or C₄) + DMC}, containing the binary constituent mixtures of the ternary mixture, were measured at p = (40.00 to 93.32) kPa using a modified Swietoslawski-type ebulliometer. The experimental data for the binary systems were correlated using the Wilson model. The Wilson model was also applied to the ternary system to predict the VLE behavior using parameters from the binary mixtures. The modified UNIFAC (Dortmund) model was also tested for the predictions of the VLE behavior of the binary and ternary mixtures. In addition, the experimental VLE data for the ternary and constituent binary mixtures were correlated using the extended Redlich–Kister (ERK) model, which can completely represent the azeotropic points. For the ternary system, a comparison of the experimental and the predicted or correlated boiling points obtained using the Wilson and ERK models showed that the ERK model is more accurate. The valley line, i.e., the curve which divides the patterns of vapor–liquid tie lines, was found in the (methanol + propan-1-ol + DMC) system. This valley line could be represented by the ERK model. Finally, the composition profile for simple distillation of this ternary mixture was obtained by analysis of the residue curves from the estimated Wilson parameters of the constituent binary mixtures.     

Ternary liquid–liquid equilibria for mixtures of 1-hexyl-3-methylimidozolium (tetrafluoroborate or hexafluorophosphate) + ethanol + an alkene at T=298.2 K

Liquid–liquid equilibrium data are presented for mixtures of {1-hexyl-3-methylimidozolium(tetrafluoroborate or hexafluorophospate) + ethanol + (1-hexene or 1-heptene)} at T=298.2 K. The data presented provides valuable insight into how variation of the anion of the environmentally friendly ionic liquid solvent can have a marked effect upon the separation power of ionic liquids. The sloping of the tie lines towards the ethanol vertex is observed for mixtures of {1-hexyl-3-methylimadozolium tetrafluoroborate + ethanol + (1-hexene or 1-heptene)}, whilst the reverse, i.e. sloping of the tie lines towards the ionic liquid vertex is observed for mixtures of {1-hexyl-3-methylimadozolium hexafluorophospate + ethanol + (1-hexene or 1-heptene)}. The tie line data have been correlated through the use of the NTRL model for statistical consistency. Selectivity values, derived from the tie line data, indicate that these two ionic liquids are suitable solvents for the liquid–liquid extraction of ethanol from olefins.     

Solid–liquid equilibria measurements for binary systems comprising (butyric acid + propionic or pentanoic acid) and (heptanoic acid + propionic or butyric or pentanoic or hexanoic acid)

Solid–liquid equilibria (SLE) measurements have been undertaken for carboxylic acid systems comprising (butyric acid + propionic or pentanoic acid) and (heptanoic acid + propionic or butyric or pentanoic or hexanoic acid) via a synthetic method using two complementary pieces of equipment. The measurements have been obtained at atmospheric pressure and over the temperature range of (225.6 to 270.7) K. All the acid mixtures exhibit a eutectic point in their respective phase diagrams, which have been determined experimentally. The estimated maximum uncertainties in the reported temperatures and compositions are ±1 K and ±0.0006 mole fraction, respectively. The experimental data have been satisfactorily correlated with the Wilson and NRTL activity coefficient models.     

(Solid + liquid) equilibria for the ternary system (CsBr + LnBr3 + H2O) (Ln = Pr,Nd, Sm) at T = 298.2 K and atmospheric pressure,thermal and fluorescent properties of Cs2LnBr5·10H2O

The (solid + liquid) phase equilibria of the ternary systems (CsBr + LnBr₃ + H₂O) (Ln = Pr, Nd, Sm) at T = 298.2 K were studied by the isothermal solubility method. The solid phases formed in the systems were determined by the Schreinemakers wet residues technique, and the corresponding phase diagrams were constructed based on the measured data. Each of the phase diagrams, with two invariant points, three univariant curves, and three crystallization regions corresponding to CsBr, Cs₂LnBr₅·10H₂O and LnBr₃·nH₂O (n = 6, 7), respectively, belongs to the same category. The new solid phase compounds Cs₂LnBr₅·10H₂O are incongruently soluble in water, and they were characterized by chemical analysis, XRD and TG-DTG techniques. The standard molar enthalpies of solution of Cs₂PrBr₅·10H₂O, Cs₂NdBr₅·10H₂O and Cs₂SmBr₅·10H₂O in water were measured to be (52.49 ± 0.48) kJ · mol⁻¹, (49.64 ± 0.49) kJ · mol⁻¹ and (50.17 ± 0.48) kJ · mol⁻¹ by microcalorimetry under the condition of infinite dilution, respectively, and their standard molar enthalpies of formation were determined as being −(4739.7 ± 1.4) kJ · mol⁻¹, −(4728.4 ± 1.4) kJ · mol⁻¹ and −(4724.4 ± 1.4) kJ · mol⁻¹, respectively. The fluorescence excitation and emission spectra of Cs₂PrBr₅·10H₂O, Cs₂NdBr₅·10H₂O and Cs₂SmBr₅·10H₂O were measured. The results show that the upconversion spectra of the three new solid phase compounds all exhibit a peak at 524 nm when excited at 785 nm.     

P, ρ, and T measurements of the (limonene + β-pinene) mixtures

The density, ρ, and two derived properties, isothermal compressibility, κ_T, and the coefficient of cubic expansion, α_P, were obtained for the mixtures of 1-methyl-4-(1-methylethenyl)-cyclohexene, known as limonene, and (1S,5S)-6,6-dimethyl-2-methylenebibyclo[3.1.1]heptane, known as β-pinene, for nine different compositions and the pure components at five pressures from 20 MPa to 40 MPa and six temperatures from 283.15 K to 358.15 K. The experimental uncertainty for ρ, κ_T, and α_P were respectively ±0.5 kg · m⁻³, ±14 TPa⁻¹, and ±0.005k K⁻¹, with k = 2 for all of them. Density behaviour with temperature and pressure was as expected. The values of α_P and κ_T increase with temperature and decrease with increasing pressure. Two different equations of state, conventional SAFT and PC-SAFT, were applied to predict the densities of the mixture. The best predictions were achieved with PC-SAFT.