Determination and correlation of liquid–liquid equilibria for four binary N,N-dimethylformamide + hydrocarbon systems

Liquid–liquid equilibrium measurements for four binary N,N-dimethylformamide + hydrocarbon (hexane, heptane, octane, and cyclohexane) systems were performed using a laser scattering technique. The experimentally determined cloud points were satisfactorily correlated with two local composition models (NRTL, and Tsuboka–Katayama's modification of the Wilson equation). In addition, the prediction of LLE by means of the modified UNIFAC (Dortmund) model was also tested.     

Vapour–liquid equilibrium for the systems diethyl sulphide + 1-butene, +cis-2-butene, +2-methylpropane, +2-methylpropene, +n-butane, +trans-2-butene

Isothermal vapour–liquid equilibrium was measured for the systems of diethyl sulphide + 1-butene, +cis-2-butene, and +2-methylpropene at 312.6 K, diethyl sulphide + n-butane was measured at 317.6 K, diethyl sulphide + trans-2-butene at 317.5 K, and diethyl sulphide + 2-methylpropane at 308.0 K. The pressure–temperature–total composition data were converted into pressure–temperature–liquid–vapour composition data using the method of Barker. Error estimates are provided for each variable. The isothermal parameters for the Wilson, NRTL and UNIQUAC activity coefficient models were regressed. The measurements were compared with the predictions by COSMO segment activity coefficient (COSMO-SAC) and UNIFAC.     

Liquid–liquid equilibria for the quaternary system methyl isobutyl ketone–water–phenol–hydroquinone

Liquid–liquid equilibria data of the quaternary system methyl isobutyl ketone (MIBK)–water–phenol–hydroquinone were measured at 25 °C under atmosphere pressure. The experimental data were correlated with the UNIQUAC and NRTL activity coefficient models on the base of the fixed binary interaction parameters that were obtained from two sub-ternary systems MIBK–water–phenol and MIBK–water–hydroquinone. The root mean square deviations (RMSD) show that the regressed results for the quaternary system were in good agreement with the experimental data for both UNIQUAC and NRTL models. The comparison between experimental and calculated distribution coefficient values of phenol and hydroquinone shows that a relative deviation of less than 5% is obtained.     

Solubility of pyrene in simple and mixed solvent systems

The solubility of pyrene was experimentally determined in simple and complex solvent systems (single, binary, ternary, quaternary and pentinary solvent systems) composed of benzene, ethylbenzene, hexane, hexanol and methylcyclohexane over a temperature range from 293 to 318 K. In addition, six models were used in this study to represent pyrene solubility in the different solvent systems. The interaction parameters for modified Wilson, NIBS/Redlich-Kister, UNIQUAC and NRTL models were estimated using the solubility data generated for pyrene in single, binary and ternary solvent systems. By re-adjusting the interaction parameters reported for Dortmund UNIFAC and ASOG models, a better representation of the solubility of pyrene was obtained compared to using reported values. Furthermore, a correction term is introduced for the ASOG model in this study to better improve pyrene solubility prediction in simple and mixed solvent systems. These estimated or re-adjusted interaction parameters for the different models, along with the reported parameters for Dortmund UNIFAC and ASOG models, were tested on complex solvent systems (quaternary and pentinary solvent mixtures), in order to check their validity and accuracy for such predictions.     

Liquid phase equilibria for mixtures of (an aliphatic hydrocarbon + toluene + γ-butyrolactone) at 298.2 K and atmospheric pressure

Liquid–liquid equilibrium (LLE) data for three ternary systems consisting of {n-heptane or n-hexane or cyclohexane (1) + toluene (2) + γ-butyrolactone (3)} were measured at 298.2 K and atmospheric pressure. The reliability of the experimental tie-line data was verified by using the Othmer–Tobias correlation. Distribution coefficients, separation factors and selectivity were evaluated for the immiscibility region. The experimental tie-line data were correlated by the UNIQUAC equation and also predicted with the UNIFAC model. The calculated results were compared with the experimental data. Better agreement with the experimental data was obtained by the UNIQUAC equation. The UNIFAC model does not provide reasonable correlations.     

Isobaric vapor–liquid equilibria for binary and ternary mixtures with cyclohexane,cyclohexene, and morpholine at 100 kPa

Vapor–liquid equilibria (VLE) data at 100 kPa have been determinated for the ternary system cyclohexane + cyclohexene + morpholine and two constituent binary systems cyclohexane + morpholine and cyclohexene + morpholine. The thermodynamic consistency of experimental data has been verified. Both binary systems deviate moderately from ideality without the presence of an azeotrope. The VLE data have been well correlated using local composition models (Wilson, NRTL and UNIQUAC) and have been also predicted with the original UNIFAC.     

Isobaric (vapour + liquid) equilibria for sulfolane with toluene, ethylbenzene, and isopropylbenzene at 101.33 kPa

Isobaric (vapour + liquid) equilibrium data have been measured for the (toluene + sulfolane), (ethylbenzene + sulfolane), and (isopropylbenzene + sulfolane) binary systems with a modified Rose-Williams still at 101.33 kPa. The experimental data of binary systems were well correlated by the non-random two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) activity coefficient models for the liquid phase. All the experimental results passed the thermodynamic consistency test by the Herington method. Furthermore, the model UNIFAC (Do) group contribution method was used. Sulfolane is treated as a group (TMS), the new group interaction parameters for CH₂–TMS, ACH–TMS and ACCH₂–TMS were regressed from the VLE data of (toluene + sulfolane) and (ethylbenzene + sulfolane) binary systems. Then these group interaction parameters were used to estimate phase equilibrium data of the (isopropylbenzene + sulfolane) binary system. The results showed that the estimated data were in good agreement with the experimental values. The maximum and average absolute deviations of the temperature were 4.50 K and 2.39 K, respectively. The maximum and average absolute deviations for the vapour phase compositions of isopropylbenzene were 0.0237 and 0.0137, respectively.     

Liquid phase equilibria of (water + propionic acid + oleyl alcohol) ternary system at several temperatures

(Liquid–liquid) equilibrium (LLE) data are investigated for mixtures of (water + propionic acid + oleyl alcohol) at 298.15, 308.15 and 318.15 K and atmospheric pressure. The solubility curves and the tie-line end compositions of liquid phases at equilibrium were determined, and the tie-line results were compared with the data predicted by the UNIFAC method. The phase diagrams for the ternary mixtures including both the experimental and correlated tie-lines are presented. The distribution coefficients and the selectivity factors for the immiscibility region are calculated to evaluate the effect of temperature change. The reliability of the experimental tie-lines was confirmed by using Othmer–Tobias correlation. It is concluded that oleyl alcohol may serve as an adequate solvent to extract propionic acid from its dilute aqueous solutions. The UNIFAC model correlates the LLE data for 298.15, 308.15 and 318.15 K with a root mean square deviation of 5.89, 6.46, and 6.69%, respectively, between the observed and calculated mole concentrations.     

“Polymeromics”: Mass spectrometry based strategies in polymer science toward complete sequencing approaches: A review

Mass spectrometry (MS) is the most versatile and comprehensive method in “OMICS” sciences (i.e. in proteomics, genomics, metabolomics and lipidomics). The applications of MS and tandem MS (MS/MS or MSⁿ) provide sequence information of the full complement of biological samples in order to understand the importance of the sequences on their precise and specific functions. Nowadays, the control of polymer sequences and their accurate characterization is one of the significant challenges of current polymer science. Therefore, a similar approach can be very beneficial for characterizing and understanding the complex structures of synthetic macromolecules. MS-based strategies allow a relatively precise examination of polymeric structures (e.g. their molar mass distributions, monomer units, side chain substituents, end-group functionalities, and copolymer compositions). Moreover, tandem MS offer accurate structural information from intricate macromolecular structures; however, it produces vast amount of data to interpret. In “OMICS” sciences, the software application to interpret the obtained data has developed satisfyingly (e.g. in proteomics), because it is not possible to handle the amount of data acquired via (tandem) MS studies on the biological samples manually. It can be expected that special software tools will improve the interpretation of (tandem) MS output from the investigations of synthetic polymers as well. Eventually, the MS/MS field will also open up for polymer scientists who are not MS-specialists. In this review, we dissect the overall framework of the MS and MS/MS analysis of synthetic polymers into its key components. We discuss the fundamentals of polymer analyses as well as recent advances in the areas of tandem mass spectrometry, software developments, and the overall future perspectives on the way to polymer sequencing, one of the last Holy Grail in polymer science.     

Interaction parameters for multi-component aromatic extraction with sulfolane

Aromatic extraction is an important operation in petrochemical processing. Design of an aromatic extractor requires the knowledge of multi-component liquid–liquid equilibrium (LLE) data. Such experimental LLE data are usually not available and therefore can be predicted using various activity coefficient models. These models require proper binary interaction parameters, which are not yet available for all aromatic extraction systems. Furthermore, the parameters available for most of the ternary systems are specific to that system only and cannot be used for other ternary or multi-component systems. An attempt has been made to obtain these parameters that are globally applicable. For this purpose, the parameter estimation procedure has been modified to estimate the parameters simultaneously for different systems involving common pairs. UINQUAC and UNIFAC models have been used for parameter estimation. The regressed parameters are shown to be applicable for the ternary as well as for the multi-component systems. It is observed that UNIQUAC parameters provide a better fit for ternary LLE data, whereas, as one moves towards the higher component systems (quaternary and quinary) the UNIFAC parameters, which are a measure of the group contributions, predict the LLE better. Effect of temperature on UNIQUAC binary interaction parameters has been studied and a linear dependence has been observed.     

Removal of heavy metal ions from aqueous solutions by filtration with a novel complexing membrane containing poly(ethyleneimine) in a poly(vinyl alcohol) matrix

A novel complexing membrane was used for the removal of heavy metal ions such as Pb(II), Cd(II) and Cu(II) from aqueous solutions. The membrane consists in a semi-interpenetrating polymer network of crosslinked poly(vinyl alcohol) as the matrix and poly(ethyleneimine) as the complexing polymer. The absorption reactions followed pseudo-first-order kinetics with similar rate constants for the three cations. A model is proposed for the absorption–desorption process in order to rationalize the data obtained for the retention ratio and the retention efficiency ratio. The corresponding equilibrium constants were determined for the three metal ions, showing that the affinity order of the membrane is Pb > Cu > Cd. This sequence is consistent with the order of maximum uptake of the ions per gram of membrane: 0.59, 0.47 and 0.33 mmol g⁻¹, respectively. On the other hand, the uptake order is different on a mass basis: 123, 30 and 37 mg g⁻¹, respectively. Regeneration of the membrane and metal recovery were studied with HCl and HNO₃ at different concentrations. Filtration of solutions of each metal ion showed large elimination ratios (96–99.5%) with a retention sequence Cd > Cu > Pb. The membrane remained efficient until complete saturation of its sites. Moreover, Cu retention is larger than expected, indicating possible additional chelation by the PVA matrix. Better retention ratios were observed when the concentration of the feed solution was kept constant. Filtration of a mixture of the three cations (all at 100 ppm concentration) resulted in the same retention sequence, but the elimination ratios were smaller and Pb was eventually displaced by Cu and Cd that were present in larger molar concentrations.     

Phase equilibria of (water + levulinic acid + dibasic esters) ternary systems

Liquid–liquid equilibrium (LLE) data of the solubility (binodal) curves and tie-line end compositions were examined for mixtures of {(water (1) + levulinic acid (2) + dimethyl succinate or dimethyl glutarate or dimethyl adipate (3)} at 298.15 K and 101.3 ± 0.7 kPa. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE data of the ternary systems were predicted by UNIFAC method. The LLE data were correlated fairly well with UNIQUAC and NRTL models, indicating the reliability of the UNIQUAC and NRTL equations for these ternary systems. The best results were achieved with the NRTL equation, using non-randomness parameter (α = 0.3) for the correlation. Distribution coefficients and separation factors were measured to evaluate the extracting capability of the solvents.     

Vapor–liquid equilibria of binary tri-potassium citrate + water and ternary polypropylene oxide 400 + tri-potassium citrate + water systems from isopiestic measurements over a range of temperatures

Water activity measurements have been carried out on the aqueous solutions of both tri-potassium citrate (K₃Cit) and polypropylene oxide (PPO) 400 + K₃Cit over a range of temperatures at atmospheric pressure. The data obtained is used to calculate the vapor pressure as a function of temperature and concentration. The effect of temperature on the constant water activity lines of aqueous PPO + K₃Cit systems has been studied and it was found that, at higher temperatures the higher concentration of polymer is in equilibrium with a certain concentration of the salt. Also it was found that the vapor pressure depression for an aqueous PPO + K₃Cit system is more than the sum of those for the corresponding binary solutions. The experimental water activities have been correlated successfully with the segment-based local composition Wilson model. The agreement between the correlation and the experimental data is good.     

Thermodynamics of aqueous solutions of methyldiethanolamine and diisopropanolamine

The vapour–liquid equilibrium (VLE) of the systems of water + methyldiethanolamine (MDEA) and water + diisopropanolamine (DIPA) was measured at several temperatures with a static total pressure apparatus. The solid–liquid equilibrium (SLE) of the same systems was measured at low amine concentrations by means of two experimental methods: a visual method and a Differential Scanning Calorimeter (DSC). The activity coefficients of water + MDEA were modelled with the NRTL equations. The model parameters were regressed from VLE, SLE and excess enthalpy data from this work and from the literature. The model developed in this work was compared with models found in the literature. The NRTL equations were also used to model the activity coefficients of the system of water + DIPA. The model parameters were fitted from the VLE and SLE data measured in this work.     

Equation of state for square-well chain molecules with variable range II. Extension to mixtures

An equation of state (EOS) developed in our previous work for square-well chain molecules with variable range is further extended to the mixtures of non-associating fluids. The volumetric properties of binary mixtures for small molecules as well as polymer blends can well be predicted without using adjustable parameter. With one temperature-independent binary interaction parameter, satisfactory correlations for experimental vapor–liquid equilibria (VLE) data of binary normal fluid mixtures at low and elevated pressures are obtained. In addition, VLE of n-alkane mixtures and nitrogen + n-alkane mixtures at high pressures are well predicted using this EOS. The phase behavior calculations on polymer mixture solutions are also investigated using one-fluid mixing rule. The equilibrium pressure and solubility of gas in polymer are evaluated with a single adjustable parameter and good results are obtained. The calculated results for gas + polymer systems are compared with those from other equations of state.     

Measurement of vapor–liquid equilibria (VLE) and excess enthalpies (H) of binary systems with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and prediction of these properties and γ using modified UNIFAC (Dortmund)

Vapor–liquid equilibria (VLE) and excess enthalpies (H^E) were measured for a variety of alkanes, alkenes, aromatics, alcohols, ketones and water in several ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM]⁺[BTI]⁻, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [BMIM]⁺[BTI]⁻, 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [HMIM]⁺[BTI]⁻ and 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [OMIM]⁺[BTI]⁻, covering the temperature range from 323.15 to 413.15 K. The new data were used together with the already available experimental data for imidazolium compounds to fit the required group interaction parameters for modified UNIFAC (Dortmund). The results show that in the future modified UNIFAC (Dortmund) can be applied successfully also for systems with ionic liquids.     

Isobaric vapor–liquid equilibrium for binary mixtures of 1-hexene + n-hexane and cyclohexane + cyclohexene at 30, 60 and 101.3 kPa

Consistent vapor–liquid equilibria (VLE) data were determined for the binary systems 1-hexene + n-hexane and cyclohexane + cyclohexene at 30, 60 and 101.3 kPa, with the purpose of studying the influence of the pressure in the separation of these binary mixtures. The two systems show a small positive deviation from ideality and do not present an azeotrope. VLE data for the binary systems have been correlated by the Wilson, UNIQUAC and NRTL equations with good results and have been predicted by the UNIFAC group contribution method.     

Modeling of thermodynamic behavior of PVT properties and cloud point temperatures of polymer blends and polymer blend + carbon dioxide systems using non-cubic equations of state

In recent years, many factors influencing phase behavior of polymer blends have been studied because of their widely technological importance, as a simple method of formulating new materials with tailored properties which make them suitable for a variety of applications. This work has three main goals which were reached by using the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) and the Sanchez–Lacombe (SL) non-cubic equations of state (EoS), which in previous works have shown their ability to handle long chain and associating interactions. First, both equations of state were tested with the correlation of the specific volumes of pure blends (PBD/PS, PPO/PS, PVME/PS, PEO/PES) and the prediction of the specific volumes for blends; second, the modeling of blend miscibilities in the liquid–liquid equilibria (LLE) of PBD/PS, PPG/PEGE, PVME/PS, PEO/PES, and PnPMA/PS blends; third, the modeling of the phase behavior of PS/PVME blends at various compositions in the presence of CO₂. PC-SAFT and SL pure-component parameters were regressed by fitting pure-component data of real substances (liquid pressure–volume–temperature, PVT, data for polymers and vapor pressure and saturated liquid molar volume for CO₂) and the fluid phase behavior of blend systems were simulated fitting one binary interaction parameter (k_ij) by regression of experimental data using the modified likelihood maximum method. Results were compared with experimental data obtained from literature and an excellent agreement was obtained with both EoS, which were also capable of predicting the fluid phase behavior corresponding to the critical solution temperatures (LCST: lower critical solution temperature, UCST: upper critical solution temperature) of blends.     

Modeling of the three-phase equilibrium in systems of the type water + nonionic surfactant + alkane

Liquid–liquid equilibria of systems water (A) + C_iE_j surfactant (B) + n-alkane (C) have been modeled by a mass-action law model previously developed and so far successfully applied to a series of binary water + C_iE_j systems and to the ternary system water + C₄E₁ + n-dodecane. These calculations provide the basis for the presented modeling. The aqueous systems give information about the association constants and the χ_AB-parameter of the Flory–Huggins theory and the ternary C₄E₁-system provides universal temperature functions for the χ_AC- and the χ_BC-parameter. The three-phase equilibrium for seven ternary C_iE_j systems (i = 6–12, j = 3–6) has been calculated by fitting one additional parameter for each of both temperature functions to the characteristic “fish-tail” point. The agreement with the experimental data is reasonably well. For systems with very small three-phase areas the results can considerably be improved by individual temperature functions that incorporate the experimental temperature maximum of the “fish” into the parameter fit. Based on the parameters of the system water + C₈E₄ + n-C₈H₁₈ the “fish-shaped” phase diagram of the system water + C₈E₄ + n-C₁₄H₃₀ was predicted reasonably well.