Diffusion of Cesium Ions Labeled with 134 Cs in Agar Gel Containing Alkali Metal Iodides: Obstruction Effect and Activation Energy

The effect of some alkali metal iodides on the obstruction effect and activation energy for tracer-diffusion of cesium ions in an agar gel medium was studied using the zone-diffusion technique. It to be observed that both the extent of obstruction (α) and the activation energy (E) decrease with the increasing charge density of the cation of the supporting electrolyte. These trends are explained on the basis of competitive hydration between ions and agar molecules and the relative distortion in the water structure that is brought about by these different ions and agar molecules, respectively.     

Tracer diffusion of Co2+ ions in agar gel containing multi-electrolyte systems

Tracer diffusion coefficients of cobalt ions have been measured in the supporting medium containing multi-electrolyte systems of alkali bromides. The electrolyte concentration was varied between 10^–6-0.1M at 25°C and the diffusion coefficients were determined by zone-diffusion technique using agar gel medium. The trend in the theoretical values of diffusion coefficients is accounted for by considering the relative contribution of mobility function, ionic strength as well as ion size parameter to the theoretical value in different systems. While the deviations between theoretical and experimental values of diffusion coefficients are explained on the basis of various co-occurring effects in ion-gel-water system.     

Tracer diffusion of Co2+ ions in multielectrolyte systems: Activation energy and obstruction effect

The activation energy for the tracer diffusion of Co²⁺ ions in multielectrolyte systems containing alkali bromides has been determined in agar gel medium over the temperature range of 25–45°C. The decrease in the value of the Arrhenius parameters, E and D_o, with gel percentage is explained on the basis of the transition state theory. Further, studies of the influence of electrolyte concentration on activation energy and obstruction effect reveal that both parameters decrease with the former. The decrease in activation energy is explained by considering the changes in physical properties of the solution with concentration at microscopic level, while the decrease in the extent of obstruction effect is attributed to competitive hydration between ions and agar molecules in a diffusion system.     

Determination of Activation Energy for the Diffusion of Fe<Superscript>3+</Superscript> Ions in Agar Gel Medium Containing Various Transition Metal Sulfates

The study of the diffusion of ferric ions in agar gel containing transition metal sulfates was carried out. The effect of gel concentration, electrolyte concentration and temperature on the diffusion of Fe³⁺ ions in various transition metal sulfates was studied with a view to verify Wang’s model of diffusion and the applicability of transition state theory to diffusion in a gel medium. The diffusion coefficients were measured using the zone diffusion technique. For a given concentration of electrolyte the activation energy (E) is found to decrease with an increase in the charge density of the cation of the supporting electrolyte and for a given system it is found to decrease with increasing electrolyte concentration in agreement with Wang’s model. This observation is explained on the basis of the distortion in the water structure caused by ions and agar molecules. At a given electrolyte concentration the magnitude of the Arrhenius parameters, E and D _o, is found to decrease with increasing gel concentration in agreement with the transition state theory of diffusion.     

The nature of ion exchange selectivity of phenol-formaldehyde sorbents with respect to cesium and rubidium ions

The structure of aqua complexes of alkali metal ions Me⁺(H₂O) _n , n = 1−6, where Me is Li, Na, K, Rb, and Cs, and complexes of 2,6-dimethylphenolate anion (CH₃)₂PhO⁻ selected as a model of the elementary unit of phenol-formaldehyde ion exchanger with hydrated alkali metal cations Me⁺(H₂O) _n , n = 0−5, was studied by the density functional method. The energies of successive hydration of the cations and the energies of binding of alkali metal hydrated cations with (CH₃)₂PhO⁻ depending on the number of water molecules n were calculated. It was shown that the dimethylphenolate ion did not have specific selectivity with respect to cesium and rubidium ions. The energies of hydration and the energies of binding of alkali metal cations with (CH₃)₂PhO⁻ decreased in the series Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺ as n increased. The conclusion was drawn that the reason for selectivity of phenol-formaldehyde and other phenol compounds with respect to cesium and rubidium ions was the predomination of the ion dehydration stage in the transfer from an aqueous solution to the phenol phase compared with the stage of binding with ion exchange groups.     

Activation Energy of Tracer-Diffusion of Manganese Ions (Mn2+) in Alkali Metal Chloride Solutions

The activation energy of the tracer diffusion of Mn²⁺ ions in alkali chlorid solutions (0.1M) has been determined in agar gel medium (1–2.5%) over the temperature range of 25–45 °C. The decrease in the value of the Arrhenius parameters, E and D ₀, with gel percentage is explained on the basis of the transition state theory. Further, the activation energy as a function of electrolyte concentration is also investigated using 1% agar gel in the temperature range of 25–45 °C. In both the cases, the activation energies are determined by the least square fitting of the diffusion coefficient data obtained at various temperatures through the Arrhenius plots.     

Self-Diffusion of Co2+ Ions in CoBr2, CoI2 and Electrolyte-Diffusion of ZnSO4 in Agar Gel Medium

Self-diffusion of Co²⁺ ions in CoBr₂ and CoI₂ is reported in the concentration range of 10^–5 to 0.25M in 1% agar gel at 25 °C. The deviations observed between the experimental and theoretical values of diffusion coefficients are explained by considering different types of interactions occurring in the ion-gel water system. The applicability of the transition state theory to the diffusion of ZnSO₄ in agar gel medium is tested by varying the temperature as well as the gel concentration at high concentration of the electrolyte. The activation energy E and D ₀ value decrease with increasing gel concentration in agreement with the theory.     

Tracer-diffusion of Zn2+ ions in cobalt sulphate

Tracer-diffusion of Zn²⁺ ions in the presence of CoSO₄ is studied at 25°C in 1% agar gel over a concentration range of 10^–5 to 0.25M using a zone-diffusion technique. The deviations observed between experimental and theoretical values of diffusion coefficients are explained by considering different types of interactions occurring in the ion-gel-water system. Further, study of the obstruction, effect in the diffusion of Zn²⁺ ions at different concentrations of CoSO₄ reveals that the -value decreases with increasing concentration of the electrolyte. This observation is accounted on the basis of competitive hydration between ions and agar molecules.     

Tracer diffusion of Co2+ ions in some transition metal sulphates in agar gel

Tracer diffusion of Co²⁺ ions is studied in agar gel medium in the presence of some transition metal sulphates using the zone diffusion technique. A comparison between the experimental and theoretical values of diffusion coefficients computed on the basis of Onsager's theory shows a divergence between them. These deviations are explained on the basis of various effects in the iongel-water system.     

Effect of supporting electrolyte on obstruction effect and activation energy for the tracer diffusion of cobalt ions in agar gel

The effect of some alkali metal chlorides on obstruction effect // and activation energy /E/ for the tracer-diffusion of cobalt ions is studied in agar gel medium using the zone-diffusion technique. It is observed that both the parameters, and E, decrease with increasing charge density of cation of the supporting electrolyte. This trend is explained on the basis of competitive hydration between ions and agar molecules and the relative distortion in the water structure brought about by these different ions and agar molecules, respectively.     

Self-diffusion of Co2+ ions in CoSO4 in agar gel medium: Concentration dependence of obstruction effect and activation energy

The obstruction effect and activation enerqy for the self-diffusion of Co²⁺ ions in CoSO₄ have been computed using the zone-diffusion technique in agar gel medium at five different concentrations of the electrolyte. Both parameters are found to decrease with an increase in electrolyte concentration. The decrease in obstruction effect expressed in terms of is attributed to the competitive hydration between ions and agar molecules in a diffusion system while the decrease in activation energy is explained by considering the changes in the physical properties of the solution with concentration at microscopic level.     

Tracer-diffusion of Zn2+ ions in some transition metal sulphates

Tracer-diffusion of Zn²⁺ ions is studied in zinc, manganese and copper sulphates over a concentration range of 10^–4 to 0.25M using 1% agar gel medium at 25 °C. A comparison of the experimental and theoretical values of tracer-diffusion coefficients shows a deviation from the theory. This is explained in the light of different types of interactions occurring in the ion-gel-water system. The effect of supporting electrolytes and its concentration on the obstruction effect in the tracer-diffusion of zinc ions is also examined. The obstruction effect decreases with increasing charge density of the cation of the electrolytes at a given concentration and for a particular elecrolyte it decreases with its concentration. These observations are accounted on the basis of competitive hydration between ions and agar macromolecules.     

Tracer diffusion of cobalt ions in some alkali metal chlorides

The concentration dependence of experimental diffusion coefficients of cobalt ions in presence of some alkali metal chlorides is examined in the light of the Onsager theory. The diffusion coefficients are measured in 1% agar gel using the zone-diffusion technique. The positive and negative deviations observed at higher and lower concentrations, respectively, are explained in terms of relative contributions of various types of effects occurring in the diffusion medium.     

Adsorption of Cu(II), Cd(II), Pb(II), Cr(VI) by double hydroxides on the basis of Al oxide and Zr, Sn, and Ti oxides

It was studied the equilibrium adsorption and adsorption kinetics of Cu(II), Cd(II), Pb(II), and Cr(VI) by composite hydroxides formed by Me _x O _y · nH₂O and Me_0.4–0.7Al_0.6–0.3O _y · nH₂O, where Me = Zr, Sn and Ti. It was estimated the values of the diffusion coefficients of adsorbed ions Cu(II) and Cr(VI) from kinetic values. It was established that the estimated diffusion coefficients of adsorbed ions Cu(II) are in the range 0.4 × 10⁻¹²–2.5 × 10⁻¹² m²/s for individual hydroxides and 1.2 × 10⁻¹²–2.8 × 10⁻¹² m²/s for double hydroxides. The obtained values of diffusion coefficients Cr (VI) for double hydroxides are 0.1 × 10⁻¹⁰–0.4 × 10⁻¹⁰ m²/s.     

Formation enthalpies of molecules and negative ions of ytterbium bromides

A procedure for determining the formation enthalpies of LnX _n (n = 1–3) molecules of thermally unstable lanthanide di- and trihalides that is based on measuring the equilibrium constants of reactions in Ln-X systems of various content and solving a system of thermochemical equations is suggested. The procedure is used to determine the enthalpies of formation Δ_f H ₂₉₈^o of molecules and negative ions found in the vapors of ytterbium bromides: YbBr (20 ± 3), YbBr₂ (−135 ± 10), YbBr₃ (−233 ± 12), YbBr₃⁻ (−615 ± 31), and YbBr₄⁻ (−766 ± 23) kJ/mol.     

Effect of supporting electrolyte on the activation energy for diffusion of some monovalent ions

The effect of some alkali metal bromides, iodides and sulphates on the diffusion of bromide, iodide and thallium ions, respectively, is studied at various temperatures. The activation energy required for the process of diffusion of these three ions in different supporting electrolytes have been calculated. It is found that activation energy for a given ion decreases in the reverse order of the charge density of alkali metal ions of the supporting electrolyte. This observed trend in activation energy is explained qualitatively by considering the distortion in the water structure caused by these ions and agar molecules.     

Diffusion studies of cobalt ions and their salts in agar gel medium: Obstruction effect and gel hydration

The obstruction effect in the electrolyte diffusion of cobalt halides and in tracer diffusion of Co²⁺ ions in the presence of different supporting electrolytes at various concentrations has been studied at 25 °C using the zone diffusion technique. It has been observed that obstruction effect expressed in terms of increases with concentration and is higher for electrolyte diffusion than in tracer diffusion. Further, for a given concentration it is found to decrease with increasing charge density of an anion. These observations are explained on the basis of competitive hydration between ions and agar molecules.     

Self-diffusion of lithium cations and ionic conductivity in polymer electrolytes based on polyesterdiacrylate

The processes of ionic conductivity are studied in a polymer gel electrolyte synthesized based on polyesterdiacrylate and a low-molecular solvent ethylene carbonate. The self-diffusion coefficients of solvent molecules and Li⁺ cations are measured by the NMR with the pulsed magnetic field gradient. The Li⁺ self-diffusion coefficients increase with the increase in the solvent content and are independent of the diffusion time in the interval from 10 to 1600 ms. The latter values imply the absence of limitations for the translational mobility of lithium ions in the spatial range from 10⁻⁷ to 10⁻⁵ m. Based on the Nernst-Einstein equation, the ionic conductivities are calculated and compared with the experimental conductivities measured by the impedance method. These values coincide for high contents of solvent; for low ethylene carbonate concentrations, the calculated conductivities much exceed the experimental values.     

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.     

Adsorption studies of cesium on a new inorganic exchanger ammonium molybdophosphate-alumina (AMP-Al2O3)

The applicability of ammonium molybdophosphate-alumina (AMP-Al₂O₃) for the efficient removal of Cs from aqueous solution by adsorption has been investigated. The kinetics of adsorption of cesium ions has been studied by using radioanalytical procedure over a concentration range of 10⁻⁴−10⁻² mol.dm⁻³ and in the temperature range of 303–318 K. The results showed that the uptake follows the first order rate law with respect to cesium concentration and obeys Langmuir and modified Freundlich adsorption isotherm in the concentration range studied. Equilibrium adsorption values at different temperatures have been utilised to evaluate change in standard thermodynamic parameters (ΔH ⁰, ΔG ⁰ and ΔS ⁰). From the thermodynamic parameters it is found that the process is exothermic in nature.