Study of the surface properties and surface concentration of ionic liquid–alcohol mixtures

Surface properties for three binary mixtures containing a 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) and a long-chain alcohol (1-butanol, 1-pentanol and 1-hexanol) were determined by surface tension data at the following temperatures: (298.15, 308.15, 318.15, 328.15 and 338.15) K. The surface tension data over the entire mole fraction range are correlated by the Fu et al.(FLW) and Myers-Scott (MS) models. There is good agreement between the experimental data and the results of correlations for 15 binary systems (the three systems at five temperatures) with an average relative error below 1.5%. In addition, the UNIFAC group contribution method is applied for calculation of activity coefficients of components in solution. Moreover, the relative adsorptions of alcohol at the air/liquid interface are determined using Gibbs adsorption isotherm. The obtained results show that the values of adsorption for mixtures of alcohols/[BMIM][SCN] increase with increasing the alkyl chain length of alcohol and decreasing temperature.     

The Prediction of Surface Tension and Thermodynamic Analysis of the Surface in Mixtures of Cryogenic Liquids

The surface tensions of 42 binary cryogenic mixtures at low temperature are correlated using the Shereshefsky model and excellent results are obtained. The average percent deviation is about ～ 1.08%. The Gibbs energy change in the surface region is calculated and is used to obtain the excess number of molecular layers in the surface region. Furthermore, the model is used to derive an equation for the standard Gibbs energy of adsorption. The experimental standard Gibbs energy of adsorption is obtained from surface tension data and compared with calculated data. The agreement between experimental and calculated data is found to be very good. The magnitude of the Gibbs energy change in the surface region and the standard Gibbs energy of adsorption are discussed in terms of nature and type of intermolecular interactions in binary mixtures.     

Use of the Wilson equation to calculate solid-liquid phase equilibria in binary and ternary systems

Generalized formulation is presented for calculating simple eutectic type solid-liquid phase diagrams for binary and ternary systems by using the Wilson equation for molar excess Gibbs energy in the liquid phase. The liquidus surface and eutectic points of molten salt mixtures with a common ion were calculated and compared with experimental values. The average error in the estimation of ternary eutectic composition was ± 0.013 (mole fraction) for the two ternary systems tested. The agreement was generally better than that obtained with the regular solution approximation.     

Surface Tension Measurements for Binary Mixtures of Chlorobenzene or Chlorocyclohexane + Tetrahydrofuran at 298.15 K

Surface tensions (σ) for the binary mixtures chlorocyclohexane + tetrahydrofuran and chlorobenzene + tetrahydrofuran at 298.15 K and 1.013 bar have been determined as a function of the mole fraction. In order to analyze the surface tension behavior, the extended Langmuir (EL) and Shereshefsky models were used and parameters of the models were obtained for these mixtures. The standard Gibbs energy of adsorption (\( - \Delta G^{\circ} \)) was calculated using both models. The Gibbs energy change for replacing 1 mol of solute with 1 mol of solvent in the surface region (?G _S), and the excess number of molecular layers of solute in the surface region, were calculated using Shereshefsky’s model. The magnitudes of ?G _S and \( - \Delta G^{\circ} \) are discussed in terms of the nature and type of intermolecular interactions in the binary mixtures.     

The properties of a binary mixture of nonionic surfactants in water at the water/air interface

The behavior of mixed nonionic/nonionic surfactant solutions, that is, p-(1,1,3,3-tetramethylbutyl)phenoxy poly(ethylene glycol)s Triton X-100 (TX100) and Triton X-165 (TX165) have been studied by surface tension and density measurements. The obtained results of the surface tension measurements were compared with those calculated from the relations derived by Joos, Miller, and co-workers. From the comparison, it appeared that by using these two approaches the adsorption behavior of TX100 and TX165 mixtures at different mole fractions can be predicted. The negative deviation from the linear relationship between the surface tension and composition of TX100 and TX165 mixtures in the concentration range corresponding to that of the saturated monolayer at the interface, the values of the parameters of molecular interaction, the activity coefficients, as well as the excess Gibbs energy of mixed monolayer formation calculated on the basis of Rosen and Motomura approaches proved that there is synergism in the reduction of the surface tension of aqueous solutions of TX100 and TX165 mixture when saturation of the monolayer is achieved. The negative parameters of intermolecular interaction in the mixed micelle and calculations based on MT theory of Blankschtein indicate that there is also synergism in the micelle formation for TX100 and TX165 mixture. It was also found that the values of the standard Gibbs energy of adsorption and micellization for the mixture of these two surfactants, which confirm the synergetic effect, can be predicted on the basis of the proposed equations, which include the values of the mole fraction of surfactant and excess Gibbs energy TX100 and TX165 in the monolayer and micelle.     

Modelling interfacial properties of binary and ternary liquid mixtures of tetrahydrofuran, 2-propanol and 2,2,4-trimethylpentane

The present modelling study has been dedicated to determining the interfacial properties of binary and ternary liquid mixtures made up of tetrahydrofuran, 2-propanol and 2,2,4-trimethylpentane. The variation of the temperature is from 288 to 308 K. By using both UNIFAC activity model and the fugacity model based on the cubic plus association (CPA) equation of state (EOS), a model based on the equality of chemical potentials in the liquid and the surface layer is utilised to describe the liquid–vapour interface of these liquid mixtures. The surface tension, composition and density are simultaneously predicted. The results of this model show that experimental surface tension data are in a good agreement with the predicted ones. The model using CPA EOS and molar volume has a better performance than the one uses the UNIFAC activity model.     

Evaluation of surface composition of surface active water-alcohol type mixtures: a comparison of semiempirical models

We study adsorption at planar liquid-vapor interface of surface active binary mixtures and test three well-known models for the composition of surface phase. The models were originally presented by Guggenheim. These are compared to results for model fluids from density functional theory (DFT). The model of Laaksonen and Kulmala is in best agreement with DFT calculations. Surface mole fraction of the solute component from the Guggenheim model exceeds one for a mixture with high surface activity. The failure of the Guggenheim model is also evident in our calculations for water-methanol, water-ethanol, and water-n-propanol mixtures.     

Surface tension and density of binary mixtures of monoalcohols,water and acetonitrile: equation of correlation of the surface tension

Measurements of the surface tension (σ) and density (ρ) of binary mixtures of monoalcohols, water and acetonitrile at 298.15 K and at atmospheric pressure, as a function of mole fraction (x) have been made. The experimental values of the deviation of surface tension and the excess of molar volume (Δσ, V ^E) have been correlated by the Redlich–Kister equation. An empirical correlation equation is presented for the study of the surface tension of these mixtures, and comparisons are made of the experimental values of surface tension versus those obtained with the correlation equation and with other models of correlation. Finally, with the purpose of corroborating the validity of the correlation equation, the latter is applied to other reference binary mixtures.     

Prediction of multicomponent liquid adsorption using excess quantities I. Statistical thermodynamic derivation of the basic equation of excess formalism

The utilization of excess quantities as the basis of a thermodynamic approach can simplify the prediction of multicomponent liquid adsorption from binary data. From statistical thermodynamics, the fundamental equation is derived for the prediction of ternary or higher order data from adsorption data for the constituent binary mixtures. An additive expression is obtained for the double Gibbs free excess energies, valid for adsorption on liquid mixture/air interfaces as well as liquid mixture/solid interfaces.     

Adsorption of the Ternary Liquid Mixture Ethanol/n-Octane/n-Hexadecane onto Activated Carbon: I. The Adsorption Excess of the Ternary Mixture and of Its Binary Combinations

The adsorption isotherms of the binary mixtures of ethanol/n-Octane, ethanol/n-hexadecane and n-octane/n-hexadecane onto the activated carbon TA 95 were measured at 278 K, 288 K, 298 K and 308 K and described with mathematical functions. About 300 experimental values of the adsorption excess of the ternary mixture ethanol/n-octane/n-hexadecane onto activated carbon TA 95 at 298 K were measured by gas chromatography inside the ternary triangle. The ternary miscibility gap was determined at three temperatures. A good representation of the ternary data and the calculated activity coefficients (using the UNIFAC model) in three-dimensional space was possible with the help of transformation of coordinates. It was possible, too, by utilization of the conception of the quasi two-component representation of the mole fractions with and without miscibility gap. Several influencing factors on ternary adsorption isotherms were discussed for the system ethanol/n-octane/n-hexadecane/TA 95.     

Adsorption equilibria of binary gas mixtures on graphitized carbon black

Adsorption equilibria for binary gas mixtures (methane-carbon dioxide, methane-ethane, and carbon dioxide-ethane) on the graphitized carbon black STH-2 were measured by the open flow method at 293.2 K. The experimental pressure range was (0 to 1.6) MPa. The extended Langmuir (EL) model and the ideal adsorption solution theory (IAST) have been adopted to predict the equilibria of binary gas mixtures. The results indicate that gas mixtures adsorbed on the homogeneous surface of STH-2 exhibit the nonideal behavior, which is mainly induced by adsorbate-adsorbate interactions. The real adsorption solution theory (RAST) has been used to analyze the property of the adsorbed mixtures. The activity coefficients have been correlated with the Wilson equation. The investigation demonstrates that the nonideality of adsorbed phase is completely dissimilar with the bulk liquid phase. The adsorption of the heavier component would benefit the adsorption of the lighter component.     

Surface properties of mixtures of surface-active sugar derivatives with ionic surfactants: theoretical and experimental investigations

Surface properties of systems that are mixtures of ionic surfactants and sugar derivatives-anionic surfactant sodium dodecyl sulfate and n-dodecyl-beta-D-maltoside (SDS/DM) and cationic surfactant dodecyltrimethylammonium bromide and n-dodecyl-beta-D-glucoside (DTABr/DG)-were investigated. The experimental results obtained from measurements of surface tension of mixtures with various ratio of ionic to nonionic components were analyzed by two independent theories. First is Motomura theory, derived from the Gibbs-Duhem equation, allowing for indirect evaluation of the composition of mixed monolayers and the Gibbs energies of adsorption, corresponding to mutual interaction between surfactants in mixed adsorbed film. As second theory we used our newly developed theoretical model of adsorption of ionic-nonionic surfactant mixtures. Using this approach, we were able to describe the experimental surface tension isotherms for mixtures of surface-active sugar derivatives and ionic surfactants. We obtained a good agreement with experimental data using the same set of model parameters for a whole range of studied compositions of a given surfactant mixture. The values of surface excess calculated from both theories agreed with each other with a reasonable accuracy. However, the newly developed model of adsorption of ionic-nonionic surfactant mixtures has the advantage of straightforward determination of surface layer composition. By the solution of equations of adsorption, one can obtain directly the values of surface excess of all components (surfactant ions, counterions, and nonionic surfactants molecules), which are present in the investigated system.     

Study of viscometric properties of L-ascorbic acid in binary aqueous mixtures of D-glucose and D-fructose

The relative viscosities and activation parameters of L-ascorbic acid have been determined in water and binary aqueous mixtures of D-glucose and D-fructose at different temperatures. A and B-coefficients of Jones–Dole equation are determined using density and viscosity data. Gibbs energy of activation of viscous flow per mole of solvent as well as per mole of solute along with activation enthalpy and entropy is also determined using Feakin’s transition-state theory. The obtained results are explained in terms of intermolecular interactions and in this study L-ascorbic acid has been found as structure breaker in binary aqueous mixtures of D-glucose and D-fructose.     

Effects of solute-solvent and solvent-solvent association in liquid adsorption chromatography with binary mobile phase

Analytical equations for the capacity ratio in liquid adsorption chromatography with a binary mobile phase, involving solute-solvent and solvent-solvent association in the mobile and surface phases, have been derived. Very simple equations have been obtained for higher values of mole fraction of the more efficient eluting solvent.     

Correlation between surface and bulk structures of alcohol-water mixtures

Adsorption isotherms of binary aqueous solutions of methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, and 1-butanol are demonstrated, being calculated by using the Gibbs adsorption equation with experimental data of surface tension and vapor pressure found in the literature. For all of the alcohol-water mixtures, the maximum value in the adsorption isotherm, namely, the maximum surface excess is about that expected for the formation of a monolayer. Furthermore, the composition of the mixture for the maximum surface excess coincides with that corresponding to the minimum in the excess partial molar volume of the solutes. These results indicate that the hydrophobic hydration in bulk induces the surface excess of the alcohols and after a monolayer is formed, the hydrophobic hydration itself is no longer retained.     

Calculation of Adsorption Isotherms on Hard Solid Surfaces Using Measurements of Surface Tensions and Contact Angles

The adsorption excess isotherms of binary mixtures adsorbed on hard solids were calculated by means of surface tension and contact angle measurements using the Gibbs adsorption isotherm equation. The calculation procedure is described in detail using the authors' own measurements of mixtures containing ethylene glycol(1)/water(2) on Teflon and poly(vinyl chloride), and water(1)/n-propanol(2) on Teflon. On the basis of these results and also from surface tensions and contact angles on hard solids published by other authors, all types of isotherms were found as given for porous adsorbents in the classification of Schay and Nagy. In addition to those, new isotherm types are proposed.     

Surface thermodynamics of binary mixtures of ethylene glycol + cyclohexanol or cyclopentanol

Surface tension data of binary mixtures of ethylene glycol + cyclohexanol and ethylene glycol + cyclopentanol was measured over the entire concentration range at various temperatures. The experimental values were correlated with temperature and with mole fraction. The values of the surface entropy, surface enthalpy and excess surface tension for these mixtures were also calculated.