Regularity of conductivity of concentrated aqueous solutions of strong electrolytes

Conductivity of concentrated aqueous solutions of strong electrolytes is analyzed in a wide range of temperatures and concentrations. The highest conductivity of solutions at a given temperature and the concentration corresponding to the highest conductivity are used as the generalizing parameters. It is shown that in the temperature range from 0 to 100°C and the concentration range from 0.1 to 12 M, the values of reduced conductivity (the ratio between the conductivity and its maximum value at a given temperature) for KOH aqueous solution fall on a common curve, if the reduced concentration (the ratio between the concentration of solution and the concentration corresponding to the highest conductivity) is used as the argument. The reduced conductivities of strong acids, bases, and salts of some I-I, I-II, II-I, III-I, and II-II electrolytes fall on the same curve.     

Electrical conductivity of associated electrolyte-water systems

The specific electrical conductivity (EC) of concentrated aqueous solutions of tartaric and oxalic acids was measured in the range 15–90°C. Specific electrical conductivity versus concentration and temperature relationships were analyzed for the acids studied in this work and for formic, acetic, propanoic, butanoic, chloroacetic, dichloroacetic, and trichloroacetic acids, as well as for aqueous ammonia. As the electrolyte concentration increases, the EC passes through a maximum whose position is independent of temperature. The maximal EC value of an aqueous solution of an associated electrolyte for a given temperature and the concentration corresponding to this maximal EC were used as generalizing parameters. Over the entire ranges of the temperatures and concentrations studied, normalized EC values (normalized EC is the ratio of the current EC to its maximal value for a given temperature) for all electrolytes considered fall on one curve provided that the argument is a normalized concentration (which is the ratio of the current solution concentration to its value at which specific EC has a maximal value).     

A general treatment for the conductivity of electrolytes in the whole concentration range in aqueous and nonaqueous solutions

Despite the great importance of ion transport, most of the widely accepted models and theories are valid only in the not very practical limit of low concentrations. Aiming to extend the range of applicability to moderate concentrations, a number of modified models and equations (some approximate, some fundamented on different assumptions, and some just empirical) have been reported. In this work, a general treatment for the electrical conductivity of ionic solutions has been developed, considering the electrical conductivity as a transport phenomenon governed by dissipation and feedback. A general expression for the dependence of the specific conductivity on the solution viscosity (and indirectly on concentration), from which the whole conductivity curve can be obtained, has been derived. The validity of this general approach is demonstrated with experimental results taken from the literature for aqueous and nonaqueous solutions of electrolytes.     

Electrochemistry of capillary systems with narrow pores V. Streaming potential: Donnan hindrance of electrolyte transport

The electrochemical theory of capillary systems with narrow pores outlined in Part I of this series is applied to the streaming potential and the electrical hindrance of electrolyte transport across ion selective membranes (Donnan hindrance). Both phenomena are related to the fixed ion concentration. Streaming potentials were measured while using collodion membranes of graded porosity and graded fixed ion concentration. The bulk phases consisted of aqueous KCl solutions with a concentration 2×10⁻⁴ n. The streaming potentials were calculated theoretically by using the electrical conductivity data of the membranes given in Part III of this series. The agreement between the experimental results and the predictions of the theory is good. Theory also predicts that a volume flow across the membrane caused by a hydrostatic pressure difference generates a filtration effect the concentration c_s of the electrolyte in the solution leaving the membrane on the low pressure side is lower than the concentration c on the high pressure side. The concentration ratio (c_s/c) is equal to the ratio (κ/κ_i) of the electrical conductivity of the high pressure phase κ and that of the pore fluid κ_i. The hindrance of the electrolyte transport is a transient phenomenon. It disappears slowly if the experiment is continued over a long period of time. This phenomenon, which is of importance in the understanding of ultrafiltration processes using membranes, is discussed in detail. It is compared with the observed changes in the streaming potential as a function of time. The influence of the electrical convection conductivity (electrical surface conductivity) on the streaming potential can be neglected under the chosen experimental conditions. Its influence will be discussed in Part VI of this series.     

Experimental Study on Viscosity of Colloidal Silica in Aqueous Electrolytic Solutions

The relative viscosity of colloidal silica dispersion in aqueous electrolytic solutions as the function of volume fraction of dry particles in the solutions has been experimentally determined in this work, in order to study the effects of pH and electrolytes (Na₂SO₄ and AlCl₃) on the hydration of the silica surfaces in the solutions. The results have shown that the maximum relative viscosity of the silica dispersion and the strongest hydration of the silica in aqueous solutions appeared at neutral pH, while the stronger the acidity and the alkalinity of the aqueous solution, the weaker the hydration. In the presence of the electrolytes (Na₂SO₄ and AlCl₃), the relative viscosity of the silica dispersion reduced and the hydration of the silica in aqueous solutions became weak. The higher the concentration of the electrolytes, the weaker the hydration, indicating that the destabilization of the colloidal silica dispersion in aqueous solutions might be realized through adding the high-valence electrolytes to weaken the hydration of the particle surfaces (hydration forces between the particles). Also, it has been shown that the negative zeta potentials of the colloidal silica in aqueous solutions greatly reduced in the presence of the electrolytes. Therefore, the high-valence electrolytes (Na₂SO₄ and AlCl₃) as the coagulant of colloidal silica in aqueous solutions might be originated from that the presence of the electrolytes simultaneously reduces the electrical double layer repulsive force and the hydration repulsive forces between the particles in aqueous solutions.     

Pseudolattice theory of charge transport in ionic solutions: Corresponding states law for the electric conductivity

A statistical mechanical framework for charge transport in ionic liquid–solvent mixtures based on the existence of a statistical lattice structure (pseudolattice) throughout the whole range of concentration is reported. The ion distribution is treated in a mean-field Bragg–Williams-like fashion, and the ionic motion is assumed to take place through hops between cells of two different types separated by non-random-energy barriers of different heights depending on the cell type. Assuming non-correlated ion transport, the electrical conductivity is shown to have a maximum, arising from the competition between the concentration of charge carriers in the bulk medium and their mobilities in the pseudolattice. An explicit expression for the concentration at which this maximum occurs is given in terms of microscopic parameters, and the electrical conductivity normalized by its maximum value (κ/κ_max) is shown to follow rather closely a universal corresponding states law in concentration space when represented against the ionic concentration scaled by its value at the conductivity maximum (?_α/?_max). Ion–ion and ion–solvent interactions are explicitly considered combining the path probability method for charge transport in solid electrolytes and the Bragg–Williams approximation for interparticle interactions, and their impact on the deviations of experimental data from the universal behavior of non-correlated transport analyzed. The theoretical predictions are shown to satisfactorily predict experimental values of electrical conductivity of aqueous solutions of conventional electrolytes and of mixtures of room temperature molten salts with typical solvents.     

Electrochemistry of capillary systems with narrow pores. IV. Dialysis potentials

The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes.     

Electrochemistry of capillary systems with narrow pores. IV. Dialysis potentials

The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes.     

Charging and discharging of the electrochemically swelled,aligned carbon nanotube fibers

Aligned carbon nanotube fibers are macroscopic materials with remarkable properties, such as high specific strength, stiffness, extreme flexibility as well as electrical and thermal conductivity. It is demonstrated that when subjected to negative potentials, these structures undergo the process of swelling in which the increase of their external dimension is observed. Swelling is believed to be caused by cation insertion in the process similar to intercalation. The efficiency of swelling was determined both in organic and aqueous solutions of different pH. Chronocoulometry was used as the technique to monitor the charging-discharging processes of swollen ACNT fibers in a presence of different electrolytes, i.e. LiCl, NaCl and KCl. The possibility of performing the charging-discharging cycles multiple times indicates that the swollen ACNT fibers can be considered as an advantageous material for electrodes in ion batteries and supercapacitors.     

Mobilities and ion-pairing in LiB(OH)4 and NaB(OH)4 aqueous solutions. A conductivity study

The conductivities of aqueous solutions of sodium borate at 25°C and lithium borate at various temperatures are reported. The conductivity of the B(OH) ₄ ⁻ ion is 35.3 ±0.2 S-cm²-mole⁻¹ at 25°C. The electrolytes are both associated, the lithium salt being more associated than the sodium salt. The mobilities and association constants obtained from the conductivity data agree with a model recently proposed for the H₂O−B(OH) ₄ ⁻ interactions. A discrepancy in the reported thermodynamic behavior of NaB(OH)₄ aqueous solutions has been resolved by means of the association constants obtained in the present study. Thus the usefulness of the conductivity measurements to determine excess chemical potentials of binary electrolytes in dilute solution is again shown.     

Concentration Dependence of the Activation Energy of Conductivity in Aqueous Sodium Selenite and Potassium Tellurite

The temperature and concentration dependences of conductivity have been studied for aqueous solutions of sodium selenite and potassium tellurite. The corresponding empirical equations have been derived. The activation energies of conductivity in both electrolytes are calculated for different solution concentrations. The ascertained dependence is interpreted in the light of Samoilov's theory on positive and negative hydration of ions. Analysis of the results suggests that the larger the positive hydration of ions, the higher the activation energies of conductivity for the salts.     

Electrochemistry of capillary systems with narrow pores V. Streaming potential: Donnan hindrance of electrolyte transport

The electrochemical theory of capillary systems with narrow pores outlined in Part I of this series is applied to the streaming potential and the electrical hindrance of electrolyte transport across ion selective membranes (Donnan hindrance). Both phenomena are related to the fixed ion concentration. Streaming potentials were measured while using collodion membranes of graded porosity and graded fixed ion concentration. The bulk phases consisted of aqueous KCl solutions with a concentration 2×10⁻⁴ n. The streaming potentials were calculated theoretically by using the electrical conductivity data of the membranes given in Part III of this series. The agreement between the experimental results and the predictions of the theory is good. Theory also predicts that a volume flow across the membrane caused by a hydrostatic pressure difference generates a filtration effect the concentration c_s of the electrolyte in the solution leaving the membrane on the low pressure side is lower than the concentration c on the high pressure side. The concentration ratio (c_s/c) is equal to the ratio (κ/κ_i) of the electrical conductivity of the high pressure phase κ and that of the pore fluid κ_i. The hindrance of the electrolyte transport is a transient phenomenon. It disappears slowly if the experiment is continued over a long period of time. This phenomenon, which is of importance in the understanding of ultrafiltration processes using membranes, is discussed in detail. It is compared with the observed changes in the streaming potential as a function of time. The influence of the electrical convection conductivity (electrical surface conductivity) on the streaming potential can be neglected under the chosen experimental conditions. Its influence will be discussed in Part VI of this series.     

Potassium-conducting solid electrolytes in K<Subscript>1 − 2<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>GaO<Subscript>2</Subscript> system

New solid electrolytes with a high conductivity by K⁺ ions in the K_{1 − 2x} Sr _x GaO₂ system are synthesized and studied. It is found that the introduction of Sr²⁺ ions into potassium monogallate leads to the formation of solid solutions with KGaO₂ structure in a wide range of additive concentration. These solid solutions exhibit a high conductivity; the conductivity increases monotonically with increasing concentration of strontium within the single-phase range. The electrical characteristics are related to the electrolyte structure. The results are compared with the earlier data for the gallate solid electrolytes with the additives of four-charged cations and the systems based on potassium monoferrite and monoaluminate.     

Electrical conductivity of solutions of the LiIO3-HIO3-H2O system

The electrical conductivity of aqueous LiIO₃ solutions and solutions of the LiIO₃-HIO₃-H₂O system is measured over a wide range of compositions at 25, 50, and 75°C. Isothermal surfaces of electrical conductivity are mapped, and the activation energies of conductivity are calculated. The conductivity isotherms in the LiIO₃-H₂O and HIO₃-H₂O boundary binary systems and in mixed solutions along sections with fixed electrolyte ratios each have a maximum as a function of electrolyte concentration. It is assumed that structure reorganization occurs in solutions in the concentration range corresponding to the peak conductivity. Proton migration features in the solutions in question are considered.     

Determining the radius and the apparent charge of a micelle from electrical conductivity measurements by using a transport theory: explicit equations for practical use

We propose here a procedure which combines experiments and simple analytical formulas that allows us to determine good estimations of the size and charge of ionic micelles above the critical micellar concentration (cmc). First, the conductivity of n-tetradecyltrimethylammonium bromide and chloride (TTABr and TTACl, respectively) aqueous solutions was measured at 25 degrees C, before and above their cmc. Then, an analytical expression for the concentration dependence of the conductance of an ionic mixture with three species (monomers, micelles, and counterions) was developed and applied to the analysis of the experiments. The theoretical calculations use the mean spherical approximation (MSA) to describe equilibrium properties. Here, we propose new expressions for the electrical conductivity, adapted to the case of electrolytes that are dissymmetric in size, and applicable up to a total surfactant concentration of 0.1 mol L(-1). Moreover, we show that they are good approximations of the corresponding numerical results obtained from Brownian dynamics simulations. Since the analytical formulas given in the present paper involve a small number of unknown parameters, they allow one to derive the size and charge of macroions in solution from conductivity measurements.     

Electrical conductivity of graphite suspensions in potassium chloride solutions in direct- and alternating-current electric fields

Electrical conductivity of graphite dispersions in aqueous KCl solutions has been measured. The measurements have been performed in alternating- (1000 Hz) and direct-current electric fields. In an alternating-current electric field, at electrolyte concentrations of 0.0005–0.01 М, the conductivity increases as depending on the mass fraction of the dispersed phase. In 0.1 М solutions, a decrease in the conductivity of the suspension is followed by an increase at dispersed phase contents of higher than 15 wt %. In a direct-current electric field, the conductivity of graphite suspensions (0.001–0.01 М KCl) varies slightly and increases at dispersed phase contents of higher than 15 wt %. In 0.1 М solutions, the specific conductivity of the suspension initially decreases and, then, increases at dispersed phase concentrations above 15 wt %. The unusual electrical properties of the suspensions have been explained as being results of variations in the capacitive and active components of the conductivity of graphite dispersions in electrolytes within the framework of a topological model. Particle polarization and a relatively high capacitive component of the conductivity mainly contribute to an increase in the conductivity of the suspensions in 0.0005–0.01 М electrolytes in the alternating-current electric field. A decrease in the conductivity of suspensions in 0.1 М electrolytes is due to a negative difference between the capacitive and active components of the specific conductivity. It has been assumed that the aggregation of graphite particles yields conducting structures at dispersed phase concentrations above 15 wt %.     

Electrical conductivity of aqueous acids in binary and ternary water-electrolyte systems

We analyze electrical conductivity data for aqueous solutions of strong and weak acids over a wide range of concentrations at various temperatures. Electrical conductivity isotherms in these solutions are characterized by peaks, whose parameters correlate with the molecular structure of solutions. On the basis of the concentration dependence of the activation energy of electrical conductivity, the acid solutions are divided into two groups. One includes HIO₃, H₂SO₄, and H₃PO₄; the other includes HCl, HBr, HI, HClO₄, HNO₃, and carboxylic acids. We show that anomalous proton migration is operative only in low-concentration solutions until their concentration reaches the peak on conductivity isotherms. The effect of extrinsic ions on proton mobility and on conductivity in acid-salt-water systems is considered.     

The interrelation between transfer and relaxation processes in aqueous solutions of electrolytes and hydration numbers and activation energies of molecular motions

The influence of transfer processes and activation energies on the electrical conductivity and nuclear magnetic relaxation rate of a reference aqueous solution of KCl and sea water at 15°C was studied. The closest agreement between the calculated and experimental conductivity values was obtained with the coordination numbers n _S of the K⁺ and Cl^? ions equal to 4 and 1, respectively, and the activation energy close to E _a for vapor (3.38 kcal/mol). According to nuclear magnetic relaxation rate, viscosity, diffusion, and self-diffusion measurements, the n _S values of these ions are 8 and 4, respectively, and E _a ≈ 4.6 kcal/mol. The main reasons for the difference in the n _S and E _a values for transfer processes in aqueous solutions of strong electrolytes are discussed. The temperature and concentration dependences of NMR relaxation rates and the other parameters related to molecular mobility are best described by a function which is the sum of exponential functions whose number depends on solution concentration.     

Electrophoresis of progesterone particles dispersed in carbohydrate and nonelectrolyte solutions

Electrophoretic mobilities of progesterone particles dispersed in aqueous solutions of D-glucose and urea (concentration range 0.1 to 1 mM) have been measured in order to investigate the electrical properties of the interface. Zeta potentials have been determined for this purpose. The dependence of Zeta potentials on concentration has also been examined. Theory of the electrical double layer has been used to explain the results.     

Physicochemical and electrochemical properties of sulfolane solutions of lithium salts

The physicochemical and electrochemical properties (electrical conductivity, viscosity, density, and electrochemical stability) of sulfolane solutions of various lithium salts are studied. The nature of the anion considerably affects the physicochemical and electrochemical properties of the electrolyte systems considered. Sulfolane solutions of lithium salts have moderate electrical conductivity and high electrochemical stability, and can be used as electrolytes in lithium batteries.