New local composition model for electrolyte solutions

A new model for representation of the excess Gibbs energy of electrolyte solutions is proposed. The excess Gibbs energy of an electrolyte solution is expressed as a sum of contributions of a long-range and a short-range excess Gibbs energy term. The Pitzer–Debye–Hückel model is used as a long-range contribution to the excess Gibbs energy. A new expression based on the local composition concept, which is the non-random factor (NRF)–Wilson model, is developed to account for the short-range contribution to the excess Gibbs energy. The main difference between this model and the electrolyte-NRF model available in the literature is the assumption that the short-range energy parameter between species in a local cell has an enthalpic rather than Gibbs energy nature. The utility of the model is demonstrated with the successful representation of the mean ionic activity coefficient of several aqueous electrolyte solutions. The results show that with only two adjustable parameters per electrolyte, the model is valid for the whole range of electrolyte concentration, from dilute solution up to saturation. The results are compared with those obtained from the NRTL, NRF and Wilson models. The model presented in this work produces better results.     

Surface tension of electrolyte solutions

A simple analytic expression is derived for the excess surface tension of electrolyte solutions, which is in good agreement with the experimental data on NaCl in the concentration range up to as high as 1 M. This expression is consistent with the following two theories: (i) The recent theory of Levin and Flores-Mena (Europhys Lett (2001) 56:187), who demonstrated the important contribution of the formation of an ion free layer at the air–electrolyte solution interface, and (ii) the Onsager–Samaras theory (J Chem Phys (1934) 2:528) modified by taking into account the ion-free layer effect. It is shown that the excess surface tension consists of three parts: the contributions of the ion-free layer, the image interaction between the electrolyte ions and the ion-free layer, and the image interaction between the electrolyte ions and air.     

An enthalpic approach to delineate the interactions of cations of imidazolium-based ionic liquids with molecular solvents

We present a systematic investigation on the enthalpic assessment of the interactions operating between the cation and anion of four imidazolium ionic liquids with aqueous and various nonaqueous solvents. Accurate experimental information gathered with the help of an isothermal titration calorimeter at 298.15 K has been analyzed for excess partial molar enthalpy of the ionic liquid, H(IL)(E), in terms of hydrophobic and solvation effects. The variations in the limiting excess partial molar enthalpy of the ionic liquid, H(IL)(E, ∞), have been correlated with solvent properties. We have quantified the enthalpic effects due to dissociation of ionic liquids in very dilute solutions and to clathrate formation with the increasing concentration of ionic liquid. A change in enthalpic behavior from endothermic to exothermic is observed on increasing the carbon chain length attached to the imidazolium ring. The solvent reorganization around the cationic species has been unraveled by employing the ionic liquid interaction parameters called as H(IL-IL)(E) deduced from the H(IL)(E) data. The apparent relative molar enthalpy, φ(L), derived from H(IL)(E) data has been examined in the light of the specific ion interaction theory as advanced by Pitzer with accurate results.     

Thermodynamics of sodium maleate and chloride adsorption at an aqueous solution-gas interface

Surface tension of solutions of sodium chloride in water and sodium maleate in aqueous alkaline solutions in a wide concentration range at 298 and 303 K are measured. It is found that the dependences of surface tension of electrolyte solutions on concentration have extreme character. The obtained dependences are discussed from the standpoint of the effect of the nature of the solute and the processes of desolvation on the composition of surface layers and the surface activity of a solution. Total electrolyte adsorption isotherms are calculated using experimental surface tension and excess adsorption isotherms.     

N,N-二甲基甲酰胺在不同浓度氯化钠水溶液中的稀释过程热力学

应用等温流动微量热法测定了298.15 K时N,N-二甲基甲酰胺(DMF)在纯水及不同浓度氯化钠水溶液中的稀释焓, 根据McMillan-Mayer理论计算得到各级同系焓相互作用系数. 结果表明, DMF在纯水及氯化钠水溶液中的焓对相互作用系数h2均为正值, 并且随着氯化钠浓度的增加, h2的值逐渐增大. 根据溶质-溶质相互作用和溶质-溶剂相互作用对结果进行了解释.     

蓖麻油酸甲酯乙氧基化物水溶液的动态表面张力

用最大气泡压力法分别测定了不同环氧乙烷(EO)加合数(10、12、14、16、20)的蓖麻油酸甲酯乙氧基化物(ECAME)水溶液的动态表面张力(DST)。考察了浓度、温度和无机电解质对DST的影响,探讨了不同浓度时DST参数(动态表面张力特性参数n,平衡时间t^*,曲线最大斜率R_1/2)的变化规律。结果表明,随着EO数由10增加到20,DST不断增大;随着浓度由0.5×10^-5 mol/L增加到10×10^-5 mol/L,n由3.02减小到1.05,t^*值由14.45减小到2.29,R_1/2由0.43增大到6.44,则动态表面活性增大,DST降低;随着温度由25 ℃升高至45 ℃,DST降低;吸附初期DST曲线随无机电解质浓度的增大而升高,吸附后期DST曲线随无机电解质浓度的增大而降低。和常规的脂肪酸甲酯乙氧基化物(FMEE)相比,ECAME的动态表面活性更加优异,这为开拓ECAME的应用指明了新的方向。     

Effects of Electrolytes on the Transport Phenomena in a Cation-Exchange Membrane

The effect of electrolyte solutions on the characteristics of the current-voltage (I-V) curve in a cation-exchange membrane (CMX membrane, Tokuyama Soda, Inc.) was studied based on the concentration polarization and electroconvection theory. The study includes the limiting current density (LCD), plateau length, and the ratio of resistance of region III to region I of the I-V curve (R(3rd)/R(1st)). Different electrolyte solutions, HCl, LiCl, NaCl, KCl, CaCl(2), MgCl(2), and AlCl(3), were used in this study. The LCD values of the electrolytes were correlated with the diffusion coefficient of the cation (D(+)) and valence of the cation and anion (z(+), z(-)). Except for the HCl solution, the LCD values of the electrolytes increased linearly with D(+)(1-z(+)/z(-)), implying that the current in this region was governed by the concentration polarization phenomena. The deviation of the HCl solution from the linearity is due to a particular transport mechanism of the proton called the Grotthuss-type transport. The differences in the plateau length and the resistance ratio, R(3rd)/R(1st), with the electrolytes were explained by the Péclet number (Pe) representing a transport pattern in the electroconvection theory. The Péclet number is proportional to the Stokes radius of an ion. An electrolyte with a large Stokes radius has a shorter plateau length and a lower ratio of R(3rd)/R(1st) than those of an electrolyte with a small Stokes radius. Water-splitting measurements for the different electrolyte solutions in the CMX membrane revealed that the contribution of water splitting to the overlimting current was insignificant regardless of the electrolytes used in this study. However, when metal hydroxides, such as Al(OH)(3), formed on the surface of the membrane, significant water splitting was observed. Copyright 2001 Academic Press.     

Entropy studies in interface science: An ageless tool

It is possible to obtain (excess) interfacial entropies from the temperature dependence of some characteristic surface parameter. Such excess entropies contain much valuable information. Their studies lead to deeper insight into the interfacial properties. In some cases, quite unexpected results are obtained. In the present paper, we shall consider three illustrations: (1) the surface excess entropy of the electrical double layer on silver iodide, (2) the surface excess entropy of the interface between air and electrolyte solutions and (3) the surface excess entropy of Langmuir polymeric monolayers. Their analysis starts with defining this characteristic parameter and measuring its temperature dependence, followed by a brief thermodynamic analysis to obtain the sought entropy.Given the generality of this methodology, its applicability is likely to be extended to a variety of other interfacial properties, in particular when competition between electric and non-electric forces plays a role as in self-assembly, hydrophobic bonding and polyelectrolytes.     

Activity Coefficient Prediction for Binary and Ternary Aqueous Electrolyte Solutions at Different Temperatures and Concentrations

The mean spherical approximation (MSA) model, coupled with two hard sphere models, was used to predict the activity coefficients of mixtures of electrolyte solutions at different temperatures and concentrations. The models, namely the Ghotbi-Vera-MSA (GV-MSA) and Mansoori et al.-MSA (BMCSL-MSA), were directly used without introducing any new adjustable parameters for mixing of electrolyte solutions. In the correlation step, the anion diameters were considered to be constant, whereas the cation diameters were considered to be concentration dependent. The adjustable parameters were determined by fitting the models to the experimental mean ionic activity coefficients for single aqueous electrolytes at fixed temperature. The results showed that the studied models predict accurately the activity coefficients for single electrolyte aqueous solutions at different temperatures. In the systems of binary aqueous electrolyte solutions with a common anion, the GV-MSA model has slightly better accuracy in predicting the activity coefficients. Also, it was observed that the GV-MSA model can more accurately predict the activity coefficients for ternary electrolyte solutions with a common anion, especially at higher concentrations.     

A Study of Surface Properties of Red Mud by Potentiometric Method

A bauxite waste of alumina manifacture, i.e., red mud (RM), is an oxide-like adsorbent capable of removing radiocesium and strontium. The adsorption behavior of these radionuclides is dominated by the surface charge of the adsorbent and the number of available adsorption sites. In this study, the surface charge densities (sigma), microscopic acidity constants (pK(s)), and site distributions of the RM in 10(-3)-1 M concentrations of NaCl, CsCl, and SrCl(2) solutions were evaluated from potentiometric titration data. The reciprocal slopes of the pH-sigma curves are higher than those predicted by double-layer theory. This suggests that surface charge and the counter charge are located in a region inside the surface because the porous and/or gel surface layer is permeable to these ions. Ionic strength dependency of sigma in CsCl solutions is similar to those found for other oxides. In SrCl(2) and NaCl solutions, at any pH the surface charge decreases as the electrolyte concentration increases. This behavior of the RM may be attributed to the existence of differently charged oxide surface sites of variable affinity for electrolyte ions. Uptake of protons on these sites could be interpreted in terms of H(+) adsorption and well described by the Freundlich equation. The empirical Freundlich parameters were used to characterize a site distribution function which provides information about the affinity ratio of the adsorption sites to H(+) and supporting electrolyte cations. Copyright 2000 Academic Press.     

Enthalpies of Dilution of N,N′-hexamethylenebisacetamide in Pure Water and Aqueous Solutions of Alkali Halide at 298.15 K

Enthalpies of dilution of N,N′-hexamethylenebisacetamide in water and aqueous alkali halide solutions at the concentration of 0.150 mol⋅kg⁻¹ (approximately the concentration of physiological saline) have been determined by isothermal titration microcalorimetry at 298.15 K. The enthalpic interaction coefficients in the solutions have been calculated according to the excess enthalpy concept based on the calorimetric data. The values of enthalpic pair-wise interaction coefficients (h ₂) of the solute in aqueous solutions of different salts were discussed in terms of the different alkali salt ions and weak interactions of the diluted component with coexistent species as well as the change in solvent structure caused by ions.     

Surface adsorption and micelle formation of surface active ionic liquids in aqueous solution

Aqueous solutions of three kinds of surface active ionic liquids composed of the 1-alkyl-3-methylimidazolium cation have been investigated by means of surface tension and electrical conductivity measurements at room temperature (298 K). The surface tension measurements provided a series of parameters, including critical micelle concentration (cmc), surface tension at the cmc (gammacmc), adsorption efficiency (pC20), and effectiveness of surface tension reduction (Picmc). In addition, with application of the Gibbs adsorption isotherm, maximum surface excess concentration (Gammamax) and minimum surface area/molecule (Amin) at the air-water interface were estimated. The effect of sodium halides, NaCl, NaBr, and NaI, on the surface activity was also investigated. It was found that both the pC20 and the Picmc were rather larger than those reported for traditional ionic surfactants and the cmc values were somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides, and comparable to typical anionic surfactants, sodium alkyl sulfates. These results demonstrate that the surface activity of long-chained imidazolium IL is somewhat superior to that of conventional ionic surfactants.     

Extension of the electrolyte NRTL and Wilson models for correlation of viscosity of strong electrolyte solutions at different temperatures

The electrolyte NRTL model [C.C. Chen, L.B. Evans, AIChE J. 32 (1986) 444–454] and electrolyte Wilson model [E. Zhao, M. Yu, R.E. Sauvé, M. Khoshkbarchi, Fluid Phase Equilibr. 173 (2000) 161–175] have been extended for the representation of the dynamic viscosity of strong electrolyte solutions. The models are based on Eyring's absolute rate theory and the electrolyte NRTL and Wilson models for calculating the excess Gibbs energy of activation of the viscous flow. The utility of the models is demonstrated with a successful representation of the viscosity of several electrolyte solutions at different temperatures. The results show that, the model is valid for the whole range of salt concentration and it is reliable for correlation of the viscosity of electrolyte solutions at different temperatures by only four adjustable parameters per binary system.     

Adsorption of cetyltrimethylammonium bromide and propanol mixtures with regard to wettability of polytetrafluoroethylene. I. Adsorption at aqueous solution-air interface

Measurements of surface tension of aqueous solutions of cetyltrimethylammonium bromide (CTAB) and propanol mixtures (gamma(L)) for 1 x1 0(-5), 1 x 10(-4), 6 x 10(-4), and 1 x 10(-3) M concentrations of CTAB as a function of propanol concentration in the range from 0 to 6.67 M at 293 K were carried out. The obtained results indicate that there is first-order exponential relationship between the surface tension and propanol concentration in the solution at constant CTAB concentration. These results were compared with those calculated from the equations derived by von Szyszkowski, Joos, Miller et al. From the comparison it resulted that the values of gamma(L) determined by the Szyszkowski equation are correlated with those measured only in a limited propanol concentration range because of changes of the constant related to the specific capillary activity in this equation as a function of propanol concentration, particularly in the range of its high concentration. In the case of the modified Joos equation there is a correlation between the calculated and measured values of gamma(L) only at a very low concentration of propanol. The values of the surface tension of aqueous solutions of CTAB and propanol mixtures determined by the relationships of Miller et al. at CTAB concentration, corresponding to unsaturated surface layer in the absence of propanol, are close to those measured, but there are bigger differences between the calculated and measured values of the surface tension for solutions at a constant value of CTAB concentration close to CMC. However, the values of the surface tension of aqueous solution of CTAB and propanol mixtures calculated from the modified Miller et al. equation, in which the aggregation process of alcohol molecules at water-air interface was taken into account, are in excellent agreement with those measured. The measured values of the surface tension and the Gibbs equations were used for determination of the surface excess of CTAB and propanol concentration at solution-air interface. The obtained results indicate that at the constant concentration of CTAB equal to 1 x 10(-5) and 1 x 10(-4) M there is a maximum of excess concentration of propanol in the surface region at its bulk concentration close to 1 M. Using the calculated values of the surface excess concentration of propanol and CTAB at solution-air interface and assuming the proper thickness of the interface region, the total values of their concentration in this region were evaluated. Next, the standard surface free energy of CTAB and propanol mixtures adsorption was calculated. The calculated values of this energy indicate that the tendency to adsorb molecules of CTAB and propanol decreases with increasing propanol concentration probably because of entropy of adsorption decrease resulting from water structure destruction by propanol molecules.     

Planar electric double layer for a restricted primitive model electrolyte at low temperatures

Monte Carlo simulation and the modified Poisson-Boltzmann theory are used to investigate the planar electric double layer for a restricted primitive model electrolyte at low temperatures. Capacitance as a function of temperature at low surface charge is determined for 1:1, 2:2, 2:1, and 3:1 electrolytes. Negative adsorption can occur for 1:1 electrolytes at low surface charge with low electrolyte concentration. The 1:1 electrolyte diffuse layer potential as a function of surface charge displays a maximum at low densities. At high densities, the diffuse layer potential is negative with a negative slope. The Gouy-Chapman-Stern theory fails in this low-temperature regime, whereas the modified Poisson-Boltzmann theory is fairly successful in this regard.     

丝氨酸在蔗糖水溶液中的稀释焓

利用LKB 2277生物活性检测仪分别测定了298.15 K时丝氨酸在不同组成的蔗糖水溶液中的稀释焓, 利用McMillan-Mayer理论,计算了丝氨酸在不同组成的蔗糖水溶液中的焓对相互作用系数,并与其在葡萄糖水溶液中的焓对相互作用系数h2进行了比较.结果表明,丝氨酸在蔗糖和葡萄糖水溶液中的焓对相互作用系数h2都是负值,并且随着糖浓度的增加,h2系数的绝对值逐渐减少.根据溶质-溶质相互作用和溶质-溶剂相互作用对结果进行了解释.     

Application of the MSA-based models in correlating the surface tension for single and mixed electrolyte solutions

Experimental values for surface tension of single and mixed electrolyte solutions were correlated using the models based on the perturbation theory. The Mean Spherical Approximation (MSA) model, coupled with the Ghotbi–Vera (GV) and the Mansoori et al. (BMCSL) equations of state, were used to correlate the experimental values of the surface tension. The results showed that the models can favourably correlate the experimental values for single electrolyte solutions. However, it was observed that the GV–MSA model can more accurately predict the surface tension for single electrolytes, especially at higher concentrations. Two different expressions for concentration dependency of cation hydrated diameters were used. Therefore, in terms of such dependency different forms of the models, i.e., GV–MSA1, GV–MSA2, BMCSL–MSA1 and BMCSL–MSA2 were introduced. It should be stated that the prediction of the surface tension for the mixed electrolyte solutions were made without introducing any new adjustable parameters. The results showed that GV–MSA2 model can predict more accurately the surface tension of electrolyte mixtures particularly at higher concentrations. Finally, the GV–MSA model was directly used to correlate the experimental results for the surface tension for both single and mixed electrolyte solutions with 2 and 4 adjustable parameters. The results showed that both of the models can accurately predict the experimental data of surface tension. These models can favourably fit and also, predict the surface tension of single electrolyte solutions with less than 1% average absolute relative deviation (AARD). The prediction capability of the proposed models is also acceptable for mixtures of electrolytes.     

Thermodynamic quantities of surface formation of aqueous electrolyte solutions VIII. Aqueous solutions of sulfates salts

In this work the surface tension of the aqueous solutions of alkali metal sulfate, magnesium sulfate, and magnesium nitrate have been measured with an expectation that the effect of sulfate salts on the air/water surface differs from that of typical electrolyte because of their peculiar results of surface potential data. The results show that the slope of surface tension-concentration curves of sulfate salts depends to some extent upon cations while that of alkali metal nitrate gives almost the same magnitude. In order to make comparison with salts of different valence types, we used the ratio of surface excess density to bulk concentration of a salt as an index of surface activity of the salt. It was shown that the surface activity of a salt largely dependent upon its valence type as well as its specific property of anion.     

Interactions between cationic starch and anionic surfactants

The surface tensions and the phase equilibria of dilute aqueous cationic starch (CS)/surfactant systems were investigated. The degree of substitution of the CS varied from 0.014 to 0.772. The surfactants investigated were sodium dodecyl sulphate (SDS), potassium octanoate (KOct), potassium dodecanoate (KDod) and sodium oleate (NaOl). The concentrations of CS were 0.001, 0.01 and 0.1 w%.Critical association concentrations (cac) occur at surfactant concentrations well below the critical micelle concentrations of the surfactants, except for KOct, KDod and NaOl at the lowest CS concentrations investigated (0.001 w%). The surface tensions of CS/surfactant solutions decrease strongly already below the cac. This is attributed to the formation of surface active associates by ion condensation. Associative phase separation of gels formed by CS and surfactant takes place at extremely low concentrations when the surfactant/polymer charge ratio is somewhat larger than 1. The gel is higly viscous and contains 40–60% water, depending on the concentration of electrolyte, the surfactant hydrocarbon chain length and the nature of the polar head of the surfactant.The concentration at which the phase separation occurs decreases with increasing surfactant chain length and the concentration of simple electrolyte, factors that promote micelle formation. This indicates that the gels are formed by association of CS to surfactant micelles. When surfactant well in excess of charge equivalence is added, the gels dissolve because the CS/surfactant complexes acquire a high charge.     

Influence of electrical double-layer interaction on coal flotation

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.