Study of surface tension and surface properties of binary alcohol/n-alkyl acetate mixtures

The Butler equation is employed to describe quantitatively the nature, properties, and compositions of surface layers in binary liquid mixtures. Bulk mole fraction, surface molar area, and surface tension of pure components are necessary inputs for this equation. In addition, the UNIFAC group contribution method is applied to account for the nonideality of the bulk liquid as well as that of the surface layer. The average relative error obtained from the comparison of experimental and calculated surface tension values for 12 binary systems is less than 1%. Therefore, the model has good accuracy in comparison with other predictive equations. In addition to finding more information about the surface structure of binary mixtures, surface mole fraction was calculated using relative Gibbs adsorption values and an extended Langmuir model (EL). The obtained results show a good consistency between two models employed, i.e., the Gibbs adsorption model and EL model, based on the UNIFAC method.     

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.     

Vapour pressures and osmotic coefficients of binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate and 1-ethyl-3-methylpyridinium ethylsulfate with alcohols at T = 323.15 K

Osmotic coefficients of binary mixtures containing alcohols (ethanol, 1-propanol, and 2-propanol) and the ionic liquids 1-ethyl-3-methylimidazolium ethylsulfate and 1-ethyl-3-methylpyridinium ethylsulfate were determined at T = 323.15 K. Vapour pressure and activity coefficients of the studied systems were calculated from experimental data. The extended Pitzer model modified by Archer, and the modified NRTL model (MNRTL) were used to correlate the experimental data, obtaining standard deviations lower than 0.012 and 0.031, respectively. The mean molal activity coefficients and the excess Gibbs free energy of the studied binary mixtures were calculated from the parameters obtained with the extended Pitzer model of Archer.     

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.     

Measurement and modeling of osmotic coefficients of binary mixtures (alcohol + 1,3-dimethylpyridinium methylsulfate) at T = 323.15 K

Measurement of osmotic coefficients of binary mixtures containing several primary and secondary alcohols (1-propanol, 2-propanol, 1-butanol, 2-butanol, and 1-pentanol) and the pyridinium-based ionic liquid 1,3-dimethylpyridinium methylsulfate were performed at T = 323.15 K using the vapor pressure osmometry technique, and from experimental data, vapor pressure, and activity coefficients were determined. The extended Pitzer model modified by Archer, and the NRTL model modified by Jaretun and Aly (MNRTL) were used to correlate the experimental osmotic coefficients, obtaining standard deviations lower than 0.017 and 0.054, respectively. From the parameters obtained with the extended Pitzer model modified by Archer, the mean molal activity coefficients and the excess Gibbs free energy for the studied binary mixtures were calculated. The effect of the cation is studied comparing the experimental results with those obtained for the ionic liquid 1,3-dimethylimidazolium methylsulfate.     

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.     

Estimation of infinite dilution activity coefficients in aqueous mixtures via molecular simulation

Molecular dynamics simulations are employed to calculate infinite dilution activity coefficients of water and methanol-like species in binary mixtures using a variant of the Kirkwood coupling parameter method. Differences in residual Gibbs free energies are obtained as integrals over ensemble averages of the derivatives of total potential energy with respect to simple functions of the intramolecular potential energy parameters. The calculated limiting activity coefficients are compared with the experimental values at the same temperature obtained by direct measurement of the water/methanol binary and via extrapolation from vapor–liquid equilibria data.     

高比表面活性碳微球分离H2中少量CO2

以实验数据为依据, 结合双Langmuir模型研究了用高比表面活性碳微球材料分离H2中少量CO2的行为. 在实验中, 用高精度的IGA-003重力吸附仪测定了温度为298、273 和268 K, 压力在0-1.8 MPa范围内CO2、H2及n(CO2):n(H2)=1:9混合物在活性碳微球中的吸附等温线. 比较不同吸附模型的计算结果与实验数据, 结果表明, 双Langmuir模型与实验结果拟合得较好; 而且通过结合理想吸附溶液理论, 该模型可以准确地计算不同的混合物体系(包括H2-CO2体系)的吸附量和吸附选择性. 利用该模型求解了不同温度下各组分的分吸附量, 得到了CO2的吸附选择性;在268 K和1.7 MPa下, CO2的吸附选择性可达到73.4, 表明活性碳微球是一种优秀的吸附H2中少量CO2的材料.     

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.     

A Corresponding-state Model for Predicting Surface Tension

A generalized corresponding-state model based on two reference fluids was developed for the prediction of surface tensions for non-polar and weakly polar pure fluids and their binary mixtures. Four parameters,po, Tc, Vc and ω, were used in this model, and the acentric factor ω was used as a scaling parameter. This model has been tested for 69 pure substances and 20 binary mixtures; the average absolute deviations are 0. 28 and 0. 20 mN/m, respectively. The results indicate that the predictions by means of this model were in good agreement with experimental data. In addition, the calculated deviation would increase with the excess surface tension rising, and if the excess surface tension is less than 3 mN/m, the prediction will be good and credible.     

Solubility of budesonide in {ethanol + water} mixtures from T = (293.2 to 313.2) K: Experimental measurement and mathematical modelling

The solubility of budesonide (BDS) in binary mixtures of ethanol and water at T = (293.2–313.2) K is determined and mathematically represented using two cosolvency models, i.e. Jouyban–Acree model and Jouyban–Acree–van’t Hoff model. The mean relative deviations for fitting the solubility data of BDS in binary mixtures of ethanol + water are 6.6% and 6.5%, respectively. Furthermore, the apparent thermodynamic properties, dissolution enthalpy, dissolution entropy, and Gibbs free energy change of dissolution process of BDS in all the mixed solvents were calculated according to van’t Hoff and Gibbs equations. Dissolution of BDS in these mixed solvents is an endothermic process.     

Adsorption and Aggregation Properties of Some Polysorbates at Different Temperatures

Measurements of the surface tension of aqueous solutions of polysorbates (Tween 20, Tween 60 and Tween 80) at 293, 303 and 313 K were made. On the basis of the obtained results the Gibbs surface excess concentration of the Tweens at the water–air interface and critical micelle concentrations were determined. Knowing the Gibbs surface excess concentration and taking into account the difference between the limiting area occupied by water and Tween molecules at the water–air interface, the fraction occupied by Tween molecules was established. The limiting area occupied by the Tween molecule was calculated by applying the Joos equation. The area determined in such a way was confirmed by the calculations of cross section of Tween molecules based on the bond lengths and the angles between them as well as the average distance between the molecules, taking into account their different conformations. This area was used for calculation of the standard Gibbs energy of adsorption using the Langmuir equation. The standard Gibbs energy of Tweens adsorption at the water–air interface was also calculated from the hydrophobic part of Tween molecule–water interface tension and that of hydrophobic part. Using the determined values of standard Gibbs energy of adsorption at different temperatures, the standard enthalpy and entropy values were deduced. The standard thermodynamic functions of micellization were also determined and compared to the Gibbs energy of Tween molecules interactions through the water phase.     

Adsorption of alkyl trimethylammonium bromides at the air/water interface

A number of features of the adsorption of alkyl trimethylammonium bromides with nc=10,12,14, and 16 at the air/water interface were studied. First, the adsorption isotherms were calculated from experimental surface tension vs concentration curves by means of the Gibbs equation. Second, a novel method was used to estimate the adsorption free energy change. From the analysis of these data it was concluded that the hydrophobic driving force for the adsorption first increases with increasing adsorbed amount and then levels off in a plateau, which holds true for all four homologues. This peculiar behavior was interpreted by the formation of a thin liquid-like alkane film at the air/water interface once a certain adsorbed amount is exceeded. The hydrophobic contribution to the standard free energy change of adsorption was compared with those values previously determined for alkyl sulfate homologues. This comparison suggests that the alkyl trimethylammonium type surfactants behave as if their alkyl chain was approximately one methylene group shorter than those of the corresponding alkyl sulfates.     

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 negative adsorption of chromium atoms on alloy-oxide film boundaries during oxidation in air and anodic passivation of Fe-Cr and Ni-Cr alloys

Equilibrium of Cr atoms between the surface layer and bulk of a binary alloy was analyzed. The Gibbs adsorption equation was used to obtain the dependence of the adsorption activity of atoms in the surface layer on their activity in the bulk. An approximate thermodynamic method was used to calculate the adsorption of Fe (Ni) and Cr atoms in the surface layers of Fe-Cr and Ni-Cr alloys. According to calculations, there was negative adsorption, X _Cr ≪ 1, in the surface layer of the alloys caused by a large difference between the Gibbs surface energies of Cr and Fe (or Ni). The negative adsorption of Cr shifted chemical reaction equilibria on the alloy-oxide film boundary both in oxidation in air and in anodic passivation, 3FeO (NiO) + 2Cr = Cr₂O₃ + 3Fe(Ni), toward oxide film enrichment in the FeO (or NiO) oxide. A unified method for calculating the composition of oxide films on alloys was used for both processes. The method was based on the use of the initial data on the Gibbs surface energy of metals constituting alloys. The calculated oxide film compositions were close to the experimental X-ray photoelectron spectroscopy data.     

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 of binary and two ternary mixtures containing water–acetonitrile–methanol/ethanol at 298.15 K: experimental data,correlation and prediction by various models

Surface tension of two ternary mixtures of water/acetonitrile/methanol and water/acetonitrile/ethanol, and their constituent binaries, were measured over the whole range of composition at 298.15 K and ambient pressure. The experimental data were used to calculate in the surface tension deviations (Δσ). The negative values of Δσ for the binary and ternary systems indicate the strong hydrogen bonding between unlike molecules of mixtures (particularly in the high concentration of water). Surface tension data of the binary systems were correlated with Fu et al., Wang–Chen, Redlich–Kister and Myers–Scott models. The mean standard deviation obtained from the comparison of experimental and calculated surface tension values for binary systems with four models is less than 0.42. Finally, the concentration dependence of the surface tension deviation of the ternary mixtures at 298.15 K was correlated using Pando et al. and Ku et al. models, with satisfactory results.