Activity coefficients of DL-valine in aqueous solutions of KCl at 25°C. Measurement with ion selective electrodes and modelling

Electrochemical cells with two ion selective electrodes, a cation and an anion ion selective electrode, versus a double junction reference electrode were used to measure the activity coefficients of DL-valine at 298.15 K, up to 0.5 molality, in aqueous solutions of KCl up to 1.0 molality. The results obtained in this work are compared with those reported before for the activity coefficients of DL-valine in aqueous solutions of NaCl. The experimental data were correlated using the model proposed previously by Khoshkbarchi and Vera for the activity coefficients of amino acids in aqueous electrolytes solutions.     

From water clustering to osmotic coefficients

Water activity is an important macroscopic property of aerosol particles and droplets in the atmosphere as well as aqueous solutions in many other fields of physical chemistry. This study focuses on relating water activity, described using osmotic coefficients, to the microscopic water structure in systems of atmospheric relevance, namely, aqueous solutions of each of the four electrolytes: NaCl, (NH(4))(2)SO(4), NH(4)Cl, and Na(2)SO(4). The osmotic coefficients of these compounds, as reported in literature based on thermodynamic measurements, decrease as a function of molality for dilute solutions and increase as a function of molality for concentrated solutions. At an intermediate molality, a minimum value of the osmotic coefficient is observed. We explain this behavior by describing osmotic coefficients as the product of two concentration-dependent effects: incomplete electrolyte dissociation and variations in the microphysical water structure. The degree of dissociation in electrolyte solutions can be obtained directly from literature or derived from reported pK values, and in this work the water structure is quantified using low-wavenumber Raman spectroscopy. We use the band at 180 cm(-1) in Raman spectra of aqueous electrolyte solutions, which has been assigned to the displacement of the central oxygen atom in a tetrahedral hydrogen bonding environment composed of five H(2)O units. The abundance of such translationally restricted water molecules is essential in describing the local microphysical structure of water, and the height of the band is used to estimate the amount of such translationally restricted water molecules in solution. We were able to qualitatively reproduce and explain literature values of osmotic coefficients for the four studied electrolytes. Our results indicate that the effect of electrolyte dissociation, which decreases as a function of molality, dominates in dilute solutions, whereas changes in water structure are more significant at higher concentrations.     

Activity coefficients of electrolyte and amino acid in the systems (water + potassium chloride + dl -valine) at T = 298.15 K and (water + sodium chloride + l -valine) at T = 308.15 K

The activity coefficient data were reported for (water  +  potassium chloride  + dl -valine) at T =  298.15 K and (water  +  sodium chloride  + l -valine) at T =  308.15 K. The measurements were performed in an electrochemical cell using ion-selective electrodes. The maximum concentrations of the electrolytes and the amino acids studied were 1.0 molality and 0.4 molality, respectively. The results of the activity coefficients of dl -valine are compared with the activity coefficients of dl -valine in (water  +  sodium chloride  + dl -valine) system obtained from the previous study. The results show that the presence of an electrolyte and the nature of its cation have a significant effect on the activity coefficient of dl -valine in aqueous electrolyte solutions.     

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.     

Correlations of Thermodynamic Properties of Aqueous Amino Acid-Electrolyte Mixtures

Suitable equations have been proposed to correlate thermodynamic properties, like mean ion activity coefficients, volumes and compressibilities, of amino acids in electrolyte solutions. An amino acid–electrolyte–water interaction parameter is extracted from the regression of the amino acid property values in aqueous electrolyte solution that is then transferred to an expression to correlate the properties of the electrolyte in mixtures. The single interaction parameter can successfully correlate the published data on mean ion activity coefficients, apparent molar volumes and compressibilities of amino acids as well as of electrolytes in their aqueous mixtures. The equations are tested against the large number of experimental data sets available in the literature.     

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.     

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO₃ and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO₃). Standard thermodynamic characteristics (Δ_r H ^o, Δ_r G ^o, Δ_r S ^o, ΔC _p ^o) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.     

Measurement of activity coefficients of amino acids in aqueous electrolyte solutions: experimental data for the systems (H2O + NaBr + glycine) and (H2O + NaBr + l-valine) at T=298.15 K

Electrochemical cells with two ion-selective electrodes, a cation ion-selective electrode against an anion ion-selective electrode, were used to measure the activity coefficient of amino acids in aqueous electrolyte solutions. Activity coefficient data were measured for (H₂O + NaBr + glycine) and (H₂O + NaBr + l-valine) at T=298.15 K. The maximum concentrations of sodium bromide, glycine, and l-valine were (1.0, 2.4, and 0.4) mol · kg⁻¹, respectively. The results show that the presence of an electrolyte and the nature of both the cation and the anion of the electrolyte have significant effects on the activity coefficients of amino acid in aqueous electrolyte solutions.     

Application of the GV-MSA model to the electrolyte solutions containing mixed salts and mixed solvents

In this work the Ghotbi–Vera mean spherical approximation (GV-MSA) model, coupled with two different expressions for the cation-hydrated diameters, was used in predicting the mean ionic activity coefficients (MIAC) of electrolytes for a number of the mixed-solvent and mixed-salt electrolyte solutions at 25 °C. In all cases the cation diameters in solutions changed with concentration of electrolyte while the anion diameters were considered to be constant and equal to the corresponding Pauling diameters. In application of the GV-MSA model to the electrolyte systems, two different expressions were used for concentration dependency of cation-hydrated diameters, i.e., the GV-MSA1 and GV-MSA2 models. In case of the electrolyte solutions containing the mixed-solvent of water and alcohol, the dielectric constants of the mixed solvents were obtained by simple regression of polynomial equations in terms of weight fraction of alcohol to the pertinent experimental data available in the literature. For the mixed-salt and mixed-solvent electrolyte solutions, in order to directly calculate the MIAC of electrolytes without introducing any new adjustable parameter, the values obtained in this work for the cation-hydrated diameters in the single aqueous electrolyte solutions were used. The results obtained in this work showed that the GV-MSA2 could more accurately correlate the MIAC of electrolytes in the single aqueous electrolyte solutions in comparison to those of the GV-MSA1 and Pitzer models. Also, the results showed that the GV-MSA-based models could accurately predict the MIAC of electrolytes in the mixed-solvent electrolyte solutions in comparison to those obtained from the model of Pitzer. In case of the mixed-salt electrolyte solutions the results of the two GV-MSA-based models studied in this work reasonably predict the MIAC of electrolytes in the mixed-salt electrolyte solutions without introducing any additional adjustable parameters compared to those obtained from the model of Pitzer with two adjustable parameters.     

Expressions for the Activity Coefficients and Osmotic Coefficients of Solutions of Electrolytes and Nonelectrolytes Based on the Hydration Model of Zavitsas

In two papers Zavitsas described a model for the thermodynamic properties of aqueous solutions of a single electrolyte or nonelectrolyte (Zavitsas, J Phys Chem B 105:7805–7817, 2001; J Solution Chem 39:301–317, 2010) in which he assumed that part of the water is so strongly bound to the solute that it can be considered as part of it, and thus only the remaining unbound water is considered to be the solvent. He showed that when the usual water mole fraction was replaced by the resulting mole fraction of unbound water, obtained by optimizing an effective hydration number, basically linear relations were obtained to fairly high molalities for the freezing temperature lowering, boiling temperature elevation, and the water activity/vapor pressure of water. However, Zavitsas only considered the properties of the solvent, not the solute. In this paper we derive the corresponding expressions for the activity coefficient of the solute for the usual molality scale based on 1 kg of water, for the modified molality scale based on 1 kg of unbound water, for the mole fraction scale based on the total number of moles of water, and for the modified mole fraction scale based on the number of moles of unbound water. These equations show that if the hydration number is larger than the stoichiometric ionization number of the electrolyte, then all four types of mean activity coefficients are predicted to always be >1 (nearly all hydration numbers reported by Zavitsas for electrolyte solutions are greater than the corresponding ionization numbers), which directly conflicts with extensive experimental and theoretical evidence that the mean activity coefficients of electrolytes in aqueous solutions always initially decrease below unity. In contrast, for nonelectrolyte solutions, the hydration model of Zavitsas gives more realistic values of the activity coefficients.     

Correlation of the mean ionic activity coefficients of electrolytes in aqueous amino acid and peptide systems

The activity coefficients of electrolytes in amino acid (peptide) aqueous systems were predicted using an expression for the excess Gibbs free energy of the solution. The model combines the contribution of long-range interactions given by the Khoshkbarchi–Vera model and the contribution of short-range interactions by the local composition based models such as the Wilson, the NRTL and the NRTL–NRF. The local composition models accurately correlate the activity coefficients of 30 amino acid (peptide)–water–electrolyte systems. The results show that the Wilson model can accurately correlate the activity coefficient of the electrolyte in amino acid (peptide) aqueous systems.     

Determination of the Glass Electrode Parameters by Means of Potentiometric Titration of Acetic Acid in Aqueous Sodium or Potassium Chloride Solutions at 25°C

Single-ion activity coefficient equations are presented for the calculation of stoichiometric (molality scale) dissociation constants K _m for acetic acid in aqueous NaCl or KCl solutions at 25°C. These equations are of the Pitzer or Hückel type and apply to the case where the inert electrolyte alone determines the ionic strength of the acetic acid solution considered. K _m for a certain ionic strength can be calculated from the thermodynamic dissociation constant K _a by means of the equations for ionic activity coefficients. The data used in the estimation of the parameters for the activity coefficient equations were taken from the literature. In these data were included results of measurements on galvanic cells without a liquid junction (i.e., on cells of the Harned type). Despite the theoretical difficulties associated with the single-ion activity coefficients, K _m can be calculated for acetic acid in NaCl or KCl solutions by the Pitzer or Hückel method (the two methods give practically identical K _m values) almost within experimental error at least up to ionic strengths of about 1 mol-kg^–1. Potentiometric acetic acid titrations with base solutions (NaOH or KOH) were performed in a glass electrode cell at constant ionic strengths adjusted by NaCl or KCl. These titrations were analyzed by equation E = E _o + k(RT/F) ln[m(H⁺)], where m(H⁺) is the molality of protons, and E is the electromotive force measured. m(H⁺) was calculated for each titration point from the volume of the base solution added by using the stoichiometric dissociation constant K _m obtained by the Pitzer or Hückel method. During each base titration at a constant ionic strength, E _o and k in this equation were observed to be constants and were determined by linear regression analysis. The use of this equation in the analysis of potentiometric glass electrode data represents an improvement when compared to the common methods in use for two reasons. No activity coefficients are needed and problems associated with liquid junction potentials have been eliminated.     

Heterogeneous interaction between zwitterions of amino acids and glycerol in aqueous solutions at 298.15 K

The enthalpies of mixing of six kinds of amino acid (glycine, L-alanine, L-valine, L-serine, L-threonine, and L-proline) with glycerol in aqueous solutions and the enthalpies of diluting of amino acid and glycerol aqueous solutions have been determined by flow microcalorimetry at 298.15 K. Employing McMillan–Mayer theory, the enthalpies of mixing and diluting have been used to calculate heterogeneous enthalpic pairwise interaction coefficients (h _xy ) between amino acids and glycerol in aqueous solutions. Combining h _xy values of amino acids with glycol in the previous study, the variations of the h _xy values between amino acids and glycerol have been interpreted from the point of view of solute–solute interactions.     

Prediction of solubilities of salts,osmotic coefficients and vapor–liquid equilibria for single and mixed solvent electrolyte systems using the LIQUAC model

The electrolyte model LIQUAC has been used up till now to predict osmotic coefficients, mean ion activity coefficients, the vapor–liquid equilibrium (VLE) behavior, the solubility of gases in single and mixed solvent electrolyte systems, and solubilities of salts in aqueous solutions. In this paper, the required expressions for the calculation of salt solubilities not only in aqueous systems, but also in organic solvents and water–solvent electrolyte systems were deduced in detail based on the LIQUAC model with a fixed reference state and thermodynamic relations. Four salts (NaCl, KCl, NH₄Cl and NaF) and two solvent (water and methanol) were selected to test the derived expressions. The results show that the LIQUAC model with a fixed reference state can be used to predict osmotic coefficients, solubilities of salts in aqueous solutions, vapor–liquid equilibria, and the solubilities of salts in water–organic solvent systems with strong electrolytes.     

Enthalpic Interaction of Amino Acids with Ethanol in Aqueous Solutions at 25°C

The enthalpies of mixing aqueous ethanol solutions and with aqueous amino acid solutions (glycine, L-alanine, L-serine, L-threonine, and L-proline) and their respective enthalpies of dilution have been determined at 25^°C by a flow microcalorimetric system. The experimental data have been analyzed in terms of McMillan-Mayer formalism to obtain the enthalpic virial coefficients for heterotactic interaction. The results have been interpreted from the point of view of solute-solute interactions.     

Application of Restrictive Primitive SAFT Coupled with Different Hard-Sphere Equations to Model Mean Ionic Activity Coefficients of Electrolyte Solutions

In this work, the primitive SAFT equation of state along with three different hard-sphere equations was used to correlate and predict mean ionic activity coefficients of aqueous electrolyte solutions. The mean ionic activity coefficient of aqueous electrolyte solutions was considered as the contribution of hard-sphere and dispersion effects. The Mansoori (M), Wang-Khoshkbarchi-Vera (WKV) and Ghotbi-Vera (GV) hard-sphere equations were applied in correlating the mean ionic activity coefficient of electrolyte solutions. The comparison among above indicated equations was shown. First, vapor pressure and densities of water in the temperature range of 373.15 to 423.15 K was regressed by SAFT equation of state. In the restrictive primitive mean spherical model, ions were hard spheres without any chain structure. Neither association effects were considered in this study. Clearly, in common used five SAFT parameters were decreased to three, which were calculated by using the experimental mean ionic activity coefficients of electrolyte solutions. The comparison among three hard-sphere equations of state approved that Ghotbi-Vera hard-sphere model (GV) correlated the experimental data accurately than the others; two hard-sphere models. The mean ionic activity coefficients of some electrolyte solutions were being predicted by taking the advantage of the regressed values surely, in a wide range of molality.     

Prediction of activity coefficients of electrolytes in aqueous mixed electrolyte solutions

A method is proposed for calculating the activity coefficient of constituent electrolytes in aqueous mixed electrolyte solutions. The equations derived from the knowledge of Λ^*, the overall reduced ionic activity coefficient in a mixture, are found to predict activity coefficients accurately up to an ionic strength of 12 mol kg⁻¹ and a temperature of 473 K.     

Osmotic and Activity Coefficients of the {<Emphasis Type="Italic">x</Emphasis>ZnCl<Subscript>2</Subscript>+(1−<Emphasis Type="Italic">x</Emphasis>)ZnSO<Subscript>4</Subscript>}(aq) System at 298.15 K

Isopiestic vapor pressure measurements were made for {xZnCl₂+(1−x)ZnSO₄}(aq) solutions with ZnCl₂ molality fractions of x=(0,0.3062,0.5730,0.7969, and 1) at the temperature 298.15 K, using KCl(aq) as the reference standard. These measurements cover the water activity range 0.901–0.919≤a _w≤0.978. The experimental osmotic coefficients were used to evaluate the parameters of an extended ion-interaction (Pitzer) model for these mixed electrolyte solutions. A similar analysis was made of the available activity data for ZnCl₂(aq) at 298.15 K, while assuming the presence of equilibrium amounts of ZnCl⁺(aq) ion-pairs, to derive the ion-interaction parameters for the hypothetical pure binary electrolytes (Zn²⁺,2Cl⁻) and (ZnCl⁺,Cl⁻). These parameters are required for the analysis of the mixture results. Although significant concentrations of higher-order zinc chloride complexes may also be present in these solutions, it was possible to represent the osmotic coefficients accurately by explicitly including only the predominant complex ZnCl⁺(aq) and the completely dissociated ions. The ionic activity coefficients and osmotic coefficients were calculated over the investigated molality range using the evaluated extended Pitzer model parameters.     

The effect of ammonium sulfate on the solubility of amino acids in water at (298.15 and 323.15) K

Using the analytical gravimetric method the solubility of glycine, dl-alanine, l-isoleucine, l-threonine, and l-serine in aqueous systems of (NH₄)₂SO₄, at (298.15 and 323.15) K, were measured for salt concentrations ranging up to 2.0 molal.In the electrolyte molality range studied the experimental observations showed that ammonium sulfate is a salting-in agent for most of the amino acids studied. Furthermore, the change of the relative solubility with electrolyte concentration shows a maximum, which makes the representation of the data by a simple empirical correlation such as the Setschenow equation difficult. For the development and evaluation of a robust thermodynamic framework that makes it possible to more profoundly understand aqueous amino acid solutions with ammonium sulfate additional experimental information is needed.     

Physical chemistry of the zinc-bromine battery: I. Activity coefficients of aqueous zinc bromide

The potential of the cell Zn–Hg(2 phase)|ZnBr₂(m)|AgBr|Ag was measured from 0 to 35.9°C and for molalities from 0.125 to 4.0. From these results and values of the standard cell potential, activity coefficients of aqueous zinc bromide were calculated. Good agreement was found with the emf and isopiestic results of Stokes and Stokes, where the ranges of temperature and molality overlap. The activity coefficients of solutions more concentrated that 1.0m are much lower than those of strong 1–2 electrolytes, and this anomaly becomes more pronounced with increasing temperature.