Abraham Model Expressions for Describing Water-to-Diethylene Glycol and Gas-to-Diethylene Glycol Solute Transfer Processes at 298.15 K

A gas chromatographic headspace analysis method was used to experimentally determine gas-to-liquid partition coefficients and infinite dilution activity dilution for 14 different aliphatic and cyclic hydrocarbons (alkanes, cycloalkanes, alkenes, alkynes), eight different aromatic compounds (benzene, alkylbenzenes, halobenzenes), five different chloroalkanes (dichloromethane, trichloromethane, 1-chlorobutane, 1,2-dichloropropane, isopropylbromide), tetrahydrofuran, butyl acetate, and acetonitrile dissolved in diethylene glycol at 298.15 K. Solubilities were also measured at 298.15 K for 31 crystalline nonelectrolyte organic solutes including several polycyclic aromatic hydrocarbons and substituted benzoic acid derivatives. The experimental results of the headspace chromatographic and spectroscopic solubility measurements were converted to gas-to-diethylene glycol and water-to-diethylene glycol partition coefficients, and molar solubility ratios using standard thermodynamic relationships. Expressions were derived for solute transfer into diethylene glycol from the calculated partition coefficients and solubility ratios. Mathematical correlations based on the Abraham model describe the observed partition coefficient and solubility data to within 0.14 log₁₀ units (or less).     

Densities,viscosities, and excess properties for binary mixtures of ethylene glycol with amides at 308.15 K

The densities, ρ, and viscosities, η, of binary mixtures of ethylene glycol with formamide, N,N-dimethyl formamide and N,N-dimethyl acetamide, have been measured over the entire composition range at 308.15 K. From this experimental data, excess molar volume, \( V_{\text{m}}^{\text{E}} \) , deviation in viscosity, Δη, and excess Gibbs free energy of activation of viscous flow, \( \Delta G^{{ * {\text{E}}}}, \) have been determined. Negative values of \( V_{\text{m}}^{\text{E}} \) , Δη, and \( \Delta G^{{ * {\text{E}}}} \) are observed over the entire composition range in the mixtures studied. The observed negative values of various excess and deviation parameters are attributed to the existence of strong interactions, like dipole–dipole interactions, H-bonding between the carbonyl group of amide molecules, and hydroxyl group of glycol molecules, geometrical fitting of smaller molecules into the voids created by larger molecules in the liquid mixtures. The excess properties have been fitted to Redlich–Kister-type polynomial, and the corresponding standard deviations have been calculated. The derived partial molar volumes and excess partial molar volumes also support the \( V_{\text{m}}^{\text{E}} \) results. The experimental viscosity data of all of these liquid mixtures have been correlated with four viscosity models.     

Densities,Refractive Indices,Ultrasonic Speeds and Excess Properties of Acetonitrile + Poly(ethylene glycol) Binary Mixtures at Temperatures from 298.15 to 313.15 K

The densities, ρ, refractive indices, n _D, and ultrasonic speeds, u, of binary mixtures of acetonitrile (AN) with poly(ethylene glycol) 200 (PEG200), poly(ethylene glycol) 300 (PEG300) and poly(ethylene glycol) 400 (PEG400) were measured over the entire composition range at temperatures (298.15, 303.15, 308.15 and 313.15) K and at atmospheric pressure. From the experimental data, the excess molar volumes, \( V_{\text{m}}^{\text{E}} \) , deviations in refractive indices, \( \Delta n_{\text{D}} \) , excess molar isentropic compressibility, \( K_{{s , {\text{m}}}}^{\text{E}} \) , excess intermolecular free length, \( L_{\text{f}}^{\text{E}} \) , and excess acoustic impedance, Z ^E, have been evaluated. The partial molar volumes, \( \overline{V}_{\text{m,1}} \) and \( \overline{V}_{\text{m,2}} \) , partial molar isentropic compressibilities, \( \overline{K}_{{s , {\text{m,1}}}} \) and \( \overline{K}_{{s , {\text{m,2}}}} \) , and their excess values over whole composition range and at infinite dilution have also been calculated. The variations of these properties with composition and temperature are discussed in terms of intermolecular interactions in these mixtures. The results indicate the presence of specific interactions among the AN and PEG molecules, which follow the order PEG200 < PEG300 < PEG400.     

Solubility of high-value compounds in environmentally friendly solvents–liquid poly(ethylene glycol) and ionic liquids: Experimental study and thermodynamic analysis

In this work the (solid + liquid) equilibria (SLE) of the solution of sustainable solvents with five high-value compounds, thymol, ferulic acid, vanillic acid, caffeic acid and caffeine, was investigated. The sustainable solvents studied were liquid poly(ethylene glycol) of average molecular mass 200 and 400 – (PEG200 and PEG400), respectively as well as imidazolium ionic liquids with bistriflamide and triflate anions ([C₄mim][NTf₂] and [C₄mim][OTf]). The obtained SLE data were correlated using the semi-empirical equation proposed by Grant. The activity coefficients of the studied solutes were calculated. Based on these correlations and calculations as well as on the thermo-physical properties of the pure constituents, the SLE behavior of the studied solutions was analyzed and discussed.     

Abraham Model Correlations for Triethylene Glycol Solvent Derived from Infinite Dilution Activity Coefficient,Partition Coefficient and Solubility Data Measured at 298.15 K

A gas chromatographic headspace analysis method was used to experimentally determine gas-to-liquid partition coefficients and infinite dilution activity coefficients for 29 liquid organic solutes dissolved in triethylene glycol at 298.15 K. Solubilities were also determined at 298.15 K for 23 crystalline nonelectrolyte organic compounds in triethylene glycol based on spectroscopic absorbance measurements. The experimental results of the headspace chromatographic and spectroscopic solubility measurements were converted to gas-to-triethylene glycol and water-to-triethylene glycol partition coefficients, and molar solubility ratios using standard thermodynamic relationships. Expressions were derived for solute transfer into triethylene glycol by combining our measured experimental values with published literature data. Mathematical correlations based on the Abraham model describe the observed partition coefficient and solubility data to within 0.16 log₁₀ units (or less).     

Densities and Viscosities for Binary and Ternary Mixtures of 2-Methylbutan-2-ol (1) + Trichloroethylene (2) + Acetonitrile (3) at 298.15 K and at Ambient Pressure (81.5 kPa)

Densities (ρ) and viscosities (η) of ternary mixtures of 2-methylbutan-2-ol (1) + trichloroethylene (2) + acetonitrile (3) and the related binary mixtures of {2-methylbutan-2-ol (1) + trichloroethylene (2)}, {2-methylbutan-2-ol (1) + acetonitrile (3)}, and {trichloroethylene (2) + acetonitrile (3)} have been measured over the whole composition range at 298.15 K and at ambient pressure (81.5 kPa). Excess molar volumes $ V_{\text{m}}^{\text{E}} $ , viscosity deviations Δη, and excess Gibbs energies of activation ΔG ^*E were derived from the experimental data. The binary and ternary data of $ V_{\text{m}}^{\text{E}} $ , Δη, and ΔG ^*E for the binary and ternary mixtures were correlated as functions of the mole fraction by using the Redlich–Kister and the Cibulka equations. Kinematic viscosities of the binary mixtures were correlated by means of several semi-empirical equations to determine the fitting parameters and the SDs. The experimental results are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Block ionomer complex micelles based on the self-assembly of poly(ethylene glycol)-block-poly(acrylic acid) and CdCl₂ for anti-tumor drug delivery

A novel block ionomer complex micelles as drug carrier is developed utilizing self-assemble of poly(ethylene glycol)-block-poly(acrylic acid) (PEG-b-PAA) and cadmium chloride. This micelles are characterized to be have good bio-compatibility, hydrophilicity, passive targeting and sustained slow release property which shows great potential for liver cancer therapy. Block ionomer complex micelles based on PEG-b-PAA and cadmium chloride can self-assemble in distilled water, and Cd(2+) agent is entrapped into the core stabilized by PEG shells. Results showed the block ionomer complex micelles to be spherically shaped. Cadmium was incorporated easily into the ionic core with remarkably high efficiency (34.25% weight (wt)/wt). The cadmium-loaded polymeric micelles exhibited sustained and slow release behavior of cadmium and a potent cytotoxicity against SMMC-7721 in vitro. This novel block ionomer complex micelles with cores of metal antitumor drug indicates to be potential carriers for effective drug delivery.     

Measurement and correlation of liquid–liquid equilibria for water + ethanol + mixed solvents (dichloromethane or chloroform + diethyl ether) at T = 293.15 K

Liquid–liquid equilibrium (LLE) data for the quaternary systems (water + ethanol + dichloromethane (DCM) or chloroform (CHCl₃) + diethyl ether (DEE)) were experimentally investigated at 293.15 K. The thermodynamic consistency of the data was performed using the Othmer–Tobias and Hand plots. The experimental tie-line data were correlated using the non-random, two-liquid (NRTL) model. As a result, the comparison of the extracting capabilities of the mixed solvents with respect to the distribution coefficients and separation factors showed that the (50% DCM +50% DEE) system had a higher separation factor for the (water + ethanol + DCM + DEE) system. On the other hand, the (50% CHCl₃ +50% DEE) system had a higher separation factor for the (water + ethanol + CHCl₃ + DEE) system. The last solvent (50% CHCl₃ +50% DEE) was found to be the best solvent, with a positive synergistic effect on DEE, high separation factor, and very low solubility in water.     

Salicylaldoxime-functionalized poly(ethylene glycol)-grafted dicationic ionic liquid as a water-soluble and recyclable ligand for palladium-catalyzed Mizoroki–Heck reactions in aqueous phase

A water-soluble salicylaldoxime-functionalized poly(ethylene glycol)-grafted dicationic ionic liquid was successfully developed as an efficient ligand for palladium acetate-catalyzed Mizoroki–Heck reactions in water. A series of aryl bromides and terminal olefin were applied to this catalytic system and the corresponding coupling products were produced in high yields. The reusability tests demonstrated that the catalyst system could be recycled for six runs with only a slightly decreased activity.     

Densities and apparent molar volumes for aqueous solutions of HNO3−UO2(NO3)2 at 298.15 K

In order to obtain the exact information of atomic number density in the ternary system of HNO₃−UO₂(NO₃)₂−H₂O, the densities were measured with an Anton-Paar DMA60/602 digital density meter thermostated at 298.15±0.01 K. The apparent molal volumes for the systems were calculated from the experimental data. The present measured apparent molar volumes have been fitted to the Pitzer ion-interaction model, which provides an adequate representation of the experimental data for mixed aqueous electrolyte solutions up to 6.2 mol/kg ionic strength. This fit yields θ ^V , and ψ ^V , which are the first derivatives with respect to pressure of the mixing interaction parameters for the excess free energy. With the mixing parameters θ ^V , and ψ ^V , the densities and apparent molar volumes of the ternary system studied in this work can be calculated with good accuracy, as shown by the standard deviations.     

The influence of pressure (0.1–160 MPa) on the isothermal compressibility and bulk viscosity of solutions of tetrahydrofuran in ethylene glycol at 298 K

The isothermal compressibility and bulk viscosity of solutions of tetrahydrofuran (THF) in ethylene glycol were measured on a unique Micro PVT Systems unit over the concentration and pressure ranges 0–20 mol % THF and 0.1–160 MPa, respectively, at 298 K. The results were interpreted from the point of view of structural changes in the ethylene glycol-THF system.     

Activity Coefficients of Electrolytes from Liquid Membrane Cells. XII. Magnesium,Lanthanum, and Tris(ethylenediamine)cobalt(III) Salts of the 1,5-Naphthalenedisulfonate Anion at 298.15 K

Activity coefficients of the highly charged electrolytes Mgds, La₂ds₃, and [Co(en)₃]₂ds₃ (en = ethylenediamine, ds²⁻=1,5-naphthalenedisulfonate anion), were determined at 298.15 K using liquid-membrane cells. These salts are found not to display large negative deviations from the Debye-Hückel limiting slope in the dilute regions, which characterize the corresponding sulfate salts. Theoretical calculations based on the primitive model (charged hard spheres in an unstructured dielectric medium) reproduce the behavior of these salts correctly up to concentrations of 0.01 mol⋅kg⁻¹ or more (0.1 mol⋅kg⁻¹ for Mgds), although ds²⁻, far from resembling a charged sphere, is a planar ion with charges distant from one another. The Pitzer model parameter values are reported for the activity and osmotic coefficients.     

Volumetric properties and volumetric interaction parameters for the CsCl–monosaccharide (d-galactose,d-xylose and d-arabinose)–water systems at T=298.15 K

Density measurements have been carried out at T=298.15 K for the CsCl–monosaccharide (d-galactose, d-xylose and d-arabinose)–water systems. The apparent molar volume of saccharides V_φ,S in the ternary solutions, the corresponding infinite dilution apparent molar volume V_φ,S^∘, and the standard transfer volume Δ_tV_φ,S^∘ of saccharides from water to aqueous CsCl solutions have been determined. The McMillan–Mayer theory was employed to relate the excess thermodynamic functions to a series of interaction parameters to obtain the volumetric interaction parameters of CsCl with monosaccharide in water. These parameters are interpreted by the group additivity principle and the stereochemistry of these monosaccharide molecules.     

Osmotic coefficient data for NaOH–NaCl–NaAl(OH)4–H2O system measured by an isopiestic method and modeled using Pitzer's model at 298.15 K

Osmotic coefficient data were obtained for the aqueous solutions of NaOH–NaCl–NaAl(OH)₄. The solutions were prepared by dissolving AlCl₃·6H₂O in aqueous NaOH solutions. The osmotic coefficients of the solutions were measured by an isopiestic method at 25°C. The osmotic coefficient data were used to evaluate the unknown binary and mixing parameters of Pitzer's model for the aqueous NaOH–NaCl–NaAl(OH)₄–H₂O system. The binary Pitzer's parameters, β⁽⁰⁾, β⁽¹⁾, and C^φ, for NaAl(OH)₄ were found to be −0.0083, 0.0710, and 0.00184 respectively. These binary parameters were obtained from the data on the ternary system. This was necessary since it was not possible to prepare a single (NaAl(OH)₄) solution. The mixing parameters, Θ_{OH⁻Al(OH)⁻4}, Θ_{Cl⁻Al(OH)⁻4}, Ψ_{Na⁺OH⁻Al(OH)⁻4}, and Ψ_{Na⁺Cl⁻Al(OH)⁻4} were found to be −0.2255, −0.2430, −0.0388, and 0.2377 respectively. The experimental osmotic coefficient data were correlated well with Pitzer's model using the parameters obtained.     

Isopiestic Investigation of the Osmotic and Activity Coefficients of {yMgCl2+(1−y)MgSO4}(aq) and the Osmotic Coefficients of Na2SO4⋅MgSO4(aq) at 298.15 K

Isopiestic vapor-pressure measurements were made for {yMgCl₂+(1−y)MgSO₄}(aq) solutions with MgCl₂ ionic strength fractions of y=(0,0.1997,0.3989,0.5992,0.8008, and 1) at the temperature 298.15 K, using KCl(aq) as the reference standard. These measurements for the mixtures cover the ionic strength range I=0.9794 to 9.4318 mol⋅kg⁻¹. In addition, isopiestic measurements were made with NaCl(aq) as reference standard for mixtures of {xNa₂SO₄+(1−x)MgSO₄}(aq) with the molality fraction x=0.5000 that correspond to solutions of the evaporite mineral bloedite (astrakanite), Na₂Mg(SO₄)₂⋅4H₂O(cr). The total molalities, m _T=m(Na₂SO₄)+m(MgSO₄), range from m _T=1.4479 to 4.4312 mol⋅kg⁻¹ (I=5.0677 to 15.509 mol⋅kg⁻¹), where the uppermost concentration is the highest oversaturation molality that could be achieved by isothermal evaporation of the solvent at 298.15 K. The parameters of an extended ion-interaction (Pitzer) model for MgCl₂(aq) at 298.15 K, which were required for an analysis of the {yMgCl₂+(1−y)MgSO₄}(aq) mixture results, were evaluated up to I=12.075 mol⋅kg⁻¹ from published isopiestic data together with the six new osmotic coefficients obtained in this study. Osmotic coefficients of {yMgCl₂+(1−y)MgSO₄}(aq) solutions from the present study, along with critically-assessed values from previous studies, were used to evaluate the mixing parameters of the extended ion-interaction model.     

Physico-chemical Properties of Binary and Ternary Mixtures of Ethyl Acetate + Ethanol + 1-Butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide at 298.15 K and Atmospheric Pressure

Densities, viscosities and refractive indices have been measured at 298.15 K and atmospheric pressure for binary and ternary mixtures of ethanol, ethyl acetate and 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl) imide [C₄mim][NTF₂]. From these experimental properties, the corresponding excess properties have been calculated and adequately fitted with the Redlich-Kister polynomial equation. The adjustable parameters and standard deviations between experimental and calculated values are reported. Interest of this mixture is due to the possibility of using [C₄mim][NTF₂] as an entrainer in the extractive distillation of ethanol + ethyl acetate. These results are compared with previously determined experimental data for mixtures of ethyl acetate and/or ethanol with the ionic liquid 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, [C₈mim][NTF₂].     

Measurement and Correlation of Excess Molar Enthalpy of Binary Mixtures Containing Butyl Acetate + 1-Alkanols (C1–C6) at 298.15 K

Excess molar enthalpies, ?H _m ^E , for the binary mixtures of butyl acetate + 1-alkanols, namely (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and 1-hexanol), were measured over the whole range of composition at 298.15 K using a Parr 1455 solution calorimeter. The excess partial molar enthalpies, ?H _m,i ^E , were calculated from the experimental excess molar enthalpies using the Redlich–Kister polynomial equation. The sign of ?H _m ^E for all systems are positive because of the disruption of hydrogen bonding and dipole–dipole interactions in the alkanols and esters, respectively. The magnitude of the ?H _m ^E values increases with increasing alkyl chain length. The behavior of ?H _m ^E was analyzed in terms of the length of the alkanol chain, the nature and type of intermolecular interactions and the balance between positive and negative effects on deviations from ideality. The experimental excess molar enthalpy data have also been correlated using the Redlich–Kister and SSF equations and two local composition models (UNIQUAC and NRTL).     

Excess molar volume and viscosity deviation for binary mixtures of polyethylene glycol dimethyl ether 250 with 1,2-alkanediols (C3–C6) at T = (293.15 to 323.15) K

In this work, density and viscosity have been determined for (polyethylene glycol dimethyl ether 250 + 1,2-propanediol, or 1,2-butanediol, or 1,2-pentanediol, or 1,2-hexanediol) binary systems over the whole concentration range at temperatures of (293.15, 303.15, 313.15, 323.15) K and atmospheric pressure. Experimental data of mixtures were used to calculate the excess molar volumes V^E, and viscosity deviations Δη. These results were fitted by the Redlich–Kister polynomial relation to obtain the coefficients and standard deviations.     

Excess thermodynamic properties of the ethylene carbonate–trifluoroethyl methyl carbonate and propylene carbonate–trifluoroethyl methyl carbonate systems at T = (298.15 or 315.15) K

The deviation in excess thermodynamic parameters such as molar volume (V^E ), viscosity ( η^E), dielectric constant (ϵ^E ), Gibbs energy of activation of the viscous flow (G ^* E ) and surface tension ( γ^E) have been determined for propylene carbonate and 2,2,2-trifluoroethyl methyl carbonate (TFMC) mixtures atT =  298.15 K and for ethylene carbonate and TEMC mixtures at T =  313.15 K. All quantities were plotted against mole fraction over the whole concentration range. Polynomial regressions have been fitted with the results. The strength and the nature of the interactions between like and unlike components have been discussed.     

Densities and Viscosities of the Regular Quinary System: Benzene (1) + Toluene (2) + Ethylbenzene (3) + Heptane (4) + Cyclooctane (5) and Its Quaternary Sub-Systems at 293.15 and 298.15 K

The densities and viscosities of the regular quinary system: benzene (1) + toluene (2) + ethylbenzene (3) + heptane (4) + cyclooctane (5), and all its corresponding quaternary sub-systems were measured over the entire composition range at 293.15 and 298.15 K. Kinematic viscosity–composition data reported in the present study were utilized to test the predictive capability of some well-known viscosity models. The models subjected to testing were: the predictive version of the McAllister’s three-body model, a generalized corresponding states principle, the group contribution GC-UNIMOD method, and the Allan and Teja correlation. Results of testing these models led to an overall AAD (%) of 1.20 for the one quaternary system that did not contain cyclooctane, and an overall AAD (%) of 8.59 for the remaining cyclooctane-containing systems. For the quinary system, the overall AAD (%) was found to be 2.92; the last two values were calculated using the value of cyclooctane of 10.595.