A new model for the activity coefficients of individual ions in aqueous electrolyte solutions

In this study, the individual ion activity coefficient in an aqueous solution is modeled with a new model. This model contains two physical significant ionic parameters regarding the ionic solvation and the closest distance of approach between ions in a solution. The present model was evaluated by the estimation of the individual activity coefficients of the ions of thirty electrolytes in aqueous solutions. The results showed that this model suitably predicts the individual ion activity coefficients in aqueous two-electrolyte solutions consisting of the binary pairs of electrolytes of NaCl, KCl, KBr and CaCl₂ in a temperature range from 298.15 to 243.15 K. The results by this model were compared to the literature values. The average absolute relative deviations of vapor pressures showed acceptable agreement between experimental data and the results of this model.     

Modeling aqueous electrolyte solutions. Part 2. Weak electrolytes

In this work the ePC-SAFT model is applied to weak electrolytes, such as weak acids or salts that do form ion pairs. Considering an association/dissociation equilibrium accounts for the fact that the electrolytes are not fully dissociated. Applying this approach, modeling the mean ionic activity coefficients (MIAC) as well as the water activity coefficients (WAC) is in very good agreement with experimental data for the aqueous HF system as well as for solutions of cadmium halides or alkali acetates. Experimental MIACs of ZnBr₂ and ZnI₂ reveal the formation of more than one complex in aqueous solutions. Implementing a simultaneous two-step ion-pairing mechanism also allows the modeling of the MIAC of these zinc salts in water.     

Correlation and prediction the activity coefficients and solubility of amino acids and simple peptide in aqueous solution using the modified local composition model

In this work, the modified Wilson model was used to obtain the activity coefficients of amino acids and simple peptides in non-electrolyte aqueous solutions. The Wilson model was modified using the new local mole fraction proposed by Zhao et al. and non-random case for the reference state. The binary interaction parameters (BIP) of the modified Wilson model for amino acid–water pairs were obtained using the experimental data of the activity coefficients for amino acids available in the literature. The modified Wilson model was also used to correlate the solubility of amino acids in water and the values of Δh/R, Δs/R, and Δg/R of the solutions studied were reported. The results obtained showed that the modified Wilson model can accurately correlate the activity coefficients as well as the solubility of amino acids and simple peptides in aqueous solutions. Also the modified Wilson model was coupled with the Pazuki–Rohani model to correlate the mean ionic activity coefficients of electrolytes in aqueous amino acid solutions. The results showed that the proposed model can accurately correlate the activity coefficients of the electrolytes in aqueous amino acid solution.     

Activities and osmotic coefficients of tropospheric aerosols: (NH4)2SO4(aq) and NaCl(aq)

The theory of multilayer adsorption for concentrated aqueous electrolytes developed by Ally and Braunstein (1998) is used to calculate the thermodynamic activities and osmotic coefficients of supersaturated solutions of (NH₄)₂SO₄(aq) and NaCl (aq) which are among man-made aerosols of atmospheric importance. The basis of the model is the postulate of Stokes and Robinson that concentrated aqueous electrolytes may be viewed as an irregular ionic lattice structure. Application to the electrolytes mentioned above is a special case of the generalized results which are proven (Ally and Braunstein, Braunstein and Ally) to be consistent with the Gibbs–Duhem equation. Calculated thermodynamic properties are compared against experimental data from isopiestic and electrodynamic balance (EDB) measurements.     

Does the low optical band gap of yellow Bi<Subscript>3</Subscript>YO<Subscript>6</Subscript> guarantee the photocatalytical activity under visible light illumination?

Bi₃YO₆, which is known as an ionic conductor, was tested here as an electrode and photoanode in contact with aqueous electrolytes. Bi₃YO₆ was deposited onto the Pt substrate and the such prepared electrode was polarized in various aqueous electrolytes. The optical energy band gap of the material equal to 1.89 eV was determined using the Kubelka-Munk function resulting from the UV-Vis spectrum (allowed indirect transition) and also was calculated using the semi-empirical PM7 method (3.38 eV of HOMO-LUMO energy gap). Despite the yellow color of Bi₃YO₆, the tested material exhibits photoelectroactivity only in the UV range of electromagnetic radiation. The anodic photocurrent characteristic for n-type metal oxide semiconductors was recorded. The electrode exhibits diffusion-controlled cathodic activity while polarized in chloride-free aqueous electrolytes.     

Temperature and Concentration Dependence of the Electrical Conductance,Diffusion, and Kinetics Parameters of the Ions in Aqueous Solutions of Sulfuric Acid,Selenic Acid,and Potassium Tellurate

The temperature and concentration dependences of the electrical conductance of aqueous solutions of sulfuric acid, selenic acid, and potassium tellurate were studied. The coefficients of the corresponding empirical equations were determined, and the values of equivalent conductances of the anions were evaluated at infinite dilution at the experimental temperatures. The values of the coefficients in the Fuoss and Onsager equation were evaluated for the three electrolytes at 298 K. The values of the molecular and ionic coefficients of self-diffusion at infinite dilution were calculated in the temperature range 288–318 K. The change of the translational energy Δ E∘_tr. of water molecules in the ionic hydration sphere was determined. The number of water molecules participating in the ionic hydration sphere at 298 K and the changes of Gibbs free energy, enthalpy, and entropy of activation of ionic conductance were calculated. The results obtained were interpreted according to the Samoylov’s theory of positive and negative hydration of ions. The differences observed in the temperature dependences of the mentioned parameters were explained in terms of the different radii and hydration numbers of the ions.     

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.     

Mutual diffusion coefficients of aqueous MnCl2 and CdCl2, and osmotic coefficients of aqueous CdCl2 at 25°C

Volume-fixed mutual diffusion coefficients have been measured for aqueous MnCl₂ and CdCl₂ solutions from 0.004 to 4.93–5.00 mol-dm^–3 (M) at 25°C. Diffusion coefficients for MnCl₂ decrease to a minimum, rise to a maximum, and then decrease rapidly; such behavior is typical for strong electrolytes. In contrast CdCl₂ diffusion coefficients decrease continuously with concentration; similar behavior is known for certain other associated electrolytes. Since thermodynamic diffusion coefficients for both salts are qualitatively similar, diffusion differences may be primarily due to thermodynamic rather than mobility factors. Isopiestic data were measured for CdCl₂ from 1.79 to 7.29 mol- (kg H₂O)^–1, and critically compared to other isopiestic and emf data for CdCl₂. Higher quality emf data are completely consistent with isopiestic data. Recommended smoothed values of activity coefficients, osmotic coefficients, water activities, and activity derivatives are given for CdCl₂ at 25°C.Work performed under the auspices of the Office of Basic Energy Sciences (Geosciences) of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract number W-7405-ENG-48.     

Study of the reaction Fe(CN)5(4‐CNpy)3− + S2O82− in aqueous salt and micellar solutions

The reaction Fe(CN)₅(4‐CNpy)³⁻ + S₂O₈²⁻ (4‐CNpy=4‐cyanopyridine) was studied in aqueous salt solutions in the presence of several electrolytes as well as in anionic, cationic, and nonionic surfactant solutions. In aqueous salt solutions the noncoulombic interactions seem to be important in determining the positive salt effects observed. The salting effects are influencing the activity coefficients of any participant in the reaction, including those ion pairs which can be formed between the anionic reagents and the cations which come from the added salts. The changes in surfactant concentration in anionic and nonionic surfactant solutions do not affect the reaction rate, which is similar to that in pure water at the same ionic strength. In cationic micellar solutions an increase in the rate constant compared to that in pure water is found; the reaction rate decreasing when the surfactant concentration increases. The kinetic trends can be explained assuming that the reagents are totally bound to the micelles and, therefore, an increase in the surfactant concentration results in a decrease in the reagent concentrations at the micellar phase and thus in a decrease in the observed rate constant. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet: 31: 229–235, 1999     

Correlation of the extraction constant values of Cu(II) by 5-dodecylsalicylaldoxime from phosphoric acid media

The equilibrium constant values of copper(II) extraction from phosphoric acid media by LIX 622 (67.7% 5-dodecylsalicylaldoxime, Cognis Ireland) taking into account the formation in the organic phase of the complex CuL₂, HL being 5-dodecylsalicylaldoxime, at different ionic strengths have been calculated. Elmore's model has been considered for the speciation of the aqueous phase. A new approach for the calculation of the activity coefficient of H₂PO₄⁻ has also been proposed. The extraction equilibrium constant values obtained at the different ionic strengths have been successfully correlated considering the activity coefficients of the species in solution as well as the release of water molecules in the extraction process. The extraction constant value at infinite dilution of the complex CuL₂ is also reported.     

Mean activity coefficients at 25°C for NaBr−Ca(NO3)2−H2O mixtures,a ternary system without a common ion

The mean ionic activity coefficients of NaBr in aqueous mixtures of NaBr and Ca(NO₃)₂ were determined at 25°C at a total ionic strenghth of 3, 4.5 and 6 molal. The measurements were made using an electrochemical cell with the ion-selective electrodes (ISE), Na-ISE against Br-ISE as a reference electrode. The experimental mean activity coefficients of NaBr obey Harned's Rule. The mean activity coefficients of Ca(NO₃)₂ were calculated using the cross differentiation of the mean activity coefficients.     

Mean Ionic Activity Coefficients and Dissociation Constant of HCl in the System HCl-H2SO4-H2O at 298 K

The mean ionic activity coefficients of HCl (_1±) in the system HCl-H₂SO₄-H₂O at 298 K were calculated by the Mikulin and MacKay-Perring methods and were then used for calculating the mixed thermo- dynamic dissociation constant of HCl (K _m). The mean value of the constant proved to be equal to that found previously for aqueous solution of HCl, and deviations from the mean value are most likely due to the fact that, when calculating K _m, incompleteness of dissociation of both electrolytes was neglected. The _1± values calculated by the MacKay-Perring and Mikulin methods virtually coincide, within the determination and calculation errors, with the published data. This result confirms the suitability of the previously suggested procedure for determining the strictly thermodynamic mixed dissociation constants from the experimental data on the vapor pressure in combination with the mean ionic activity coefficients.     

Theoretical calculations of the ionic strength dependence of the ionic product of water based on a mean spherical approximation

A modified version of the restricted primitive model for electrolyte solutions based on the mean spherical approximation (MSA) is applied to estimate the ionic strength dependence of the ionic product of water in aqueous solutions containing different salts, which are commonly used as background electrolytes (NaCl, KCl, KNO₃, and NaC10₄). The modification involves the use of permittivity of the solvent as concentration-dependent parameter and a single average effective diameter. This is a way of including effects originated from the solvent which do not exist in the primitive model. In the case of potassium nitrate and sodium perchlorate, a complete methodology to calculate the effective diameter and density dependence of the dielectric constant has been proposed and developed. Fits between calculated and experimental pK_w values are possible over wide concentration ranges using a single adjustable parameter, namely, the average hard core diameter of water.     

The solubility of oxygen in sea water and solutions of electrolytes according to the pulse proton NMR data

The possibility of determining the content of dissolved oxygen (O₂) in distilled water, sea water, and aqueous solutions of electrolytes with errors of ～2% without preliminary instrument calibration was demonstrated. The reasons for different relaxation efficiency coefficients reported by various authors were analyzed. The results of the determination of the content of O₂ from the rate of spin-lattice relaxation in sea water and separate solutions of sea water components at 25°C depending on water salinity (S) up to 180‰ inclusive are presented. Noticeable changes in the steepness of the dependence of the content of O₂ on S at 80–90‰ were observed; these changes were related to the attainment of the boundaries of the complete solvation of the main sea water ions. The main reasons for the discrepancies between the oxygen salting out coefficients K _S found by various authors were explained, and the interrelation between the solubility of O₂ and ion hydration characteristics was revealed. The O₂ salting out constants for sea water and solutions of slats contained in sea water obtained from relaxation measurement data are given. The filling of “ice-like formation” voids was shown to be the main mechanism of the solution of O₂ in water and aqueous solutions of electrolytes.     

Viscosity B Coefficients for Alkali–Metal Bromides in 3-Hydroxypropionitrile–Acetonitrile Mixtures at 25°C

The viscosity B coefficients were measured for LiBr, NaBr, KBr, RbBr, CsBr, Bu₄NBPh₄ and Bu₄NBr in 3-hydroxypropionitrile–acetonitrile mixtures over the entire composition range at 25°C. The B coefficients of these electrolytes were large and positive and were split into their respective ionic values using the method of Gill and Sharma. The ionic B coefficients were positive for all the electrolytes.     

Hygrometric Determination of Water Activities, Osmotic and Activity Coefficients, and Excess Gibbs Energy of the System MgSO4–K2SO4–H2O

Ternary aqueous solutions of MgSO₄ and K₂SO₄ have been studied by the hygrometric method at 25°C. The relative humidity of this system is measured at total molalities from 0.35 mol-kg^–1 to about saturation for three ionic-strength fractions (y = 0.25, 0.50, and 0.80 of MgSO₄. The data allow calculation of water activities and osmotic coefficients. From these measurements, the Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results are used to calculate the excess Gibbs energy at total molalities for ionic-strength fraction y.     

Variations of activity coefficients in concentrated electrolyte solutions at constant lonic strength

Measurements of different types on various (trace) electrolytes in HClO₄–Na(Li)ClO₄ solutions at several (constant) values of the ionic strength have been used to determine the variation of their activity coefficients with changing amount of perchloric acid in the solution. These variations (with respect to the hydrogen ion) differ considerably among different cations and anions. The results for the alkali metal ions and the anions are interpreted in the light of the recent work of Pitzer on short-range ionic interactions. The results for the cations with outerd-electrons and the alkaline earth metal ions are interpreted in terms of ion-solvent interactions. It is concluded that the use of HClO₄–NaClO₄ solutions of high ionic strength (rather than the use of HClO₄–LiClO₄ solutions) is advisable in studies where the variation in activity coefficients must be accounted for. Finally, it is shown that the usual interpretation of the influence of the salt medium in studies of complex equilibria and reaction kinetics is sometimes questionable.     

Dissolution enthalpy of glycine in aqueous solutions of bivalent metal electrolytes

Measurement of the dissolution enthalpies of glycine in aqueous solutions of MgCl₂, CaCl₂, SrCl₂, BaCl₂, Mg(NO₃)₂ and Ca(NO₃)₂ at 298.15 K have been undertaken. The enthalpic heterogeneous interaction coefficients of the glycine zwitterion with the dissociated electrolyte have been calculated using the standard enthalpies of solution of amino acid in water and in aqueous solution of electrolytes. The effect of the ion type and of the structure of glycine on the magnitude of the enthalpic interaction coefficients are discussed.     

Correlation of the Extraction Constant Values of Zn2+ and Cd2+ from Phosphoric Acid Media by Bis(2,4,4-trimethylpentyl)dithiophosphinic Acid Dissolved in Toluene

Values of the extraction constants of Zn²⁺ and Cd²⁺ from aqueous phosphoric acid solutions (0.36 to 7.31 mol?L^?1) by Cyanex 301 in toluene, involving formation of the complexes ZnR₂ and CdR₂ with R being bis(2,4,4-trimethylpentyl)dithiophosphinate, have been correlated at T=298 K as a function of the ionic strength. For this purpose the activity coefficients of all of the aqueous species have been calculated taking into account both the protolytic equilibria of concentrated phosphoric acid and complexation reactions between the cations and the phosphoric acid species. Good correlations have been obtained for the extraction constant values with the ionic strength, provided the release of water molecules during the extraction processes is considered. Finally, extraction constant values are reported at infinite dilution.     

A pitzer mixed electrolyte solution theory approach to assignment of pH to standard buffer solutions

The IUPAC recommendations for the pH scale for aqueous solutions are based on the Bates-Guggenheim (B-G) convention (1961) for the single ion activity coefficient of the chloride ion in the standard buffer(s). This convention was adopted as a reasonable estimate based on the Debye-Huckel theory and is limited in its application to ionic strengths less than 0.1 mol-kg^–1. This approach ignores the results of many workers over the years on the properties of mixed electrolyte solutions and their prediction on the basis of the theories of Harned, Scatchard, Guggenheim and more recently of Pitzer. The literature data of EMF measurements on appropriate weak acid systems have been reexamined to determine both the pK_a values and values of appropriate Pitzer interaction coefficients. The latter are used to calculate single chloride ion activity coefficients for the chosen compositions of pH standard buffers, and compared with the B-G convention values. Calculations were made to check the consistency of the pH values with determined pK_a values using the Pitzer treatment for all the required single ion activity coefficients. The overall aim was to remove the ionic strength restriction of the B-G convention and rationalize the approach to pH standardization for such diverse aqueous media as sea water, blood and acid-rain water.An account of this work was presented at the 12^th International Conference on Chemical Thermodynamics, Snowbird, Utah, August 1992.