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.     

Determination of activation energy and the obstruction effect for tracer-diffusion of Co2+ ions in agar gel medium containing transition metal nitrates

Variation of activation energy for tracer-diffusion of Co²⁺ ions in Ni(NO₃)₂, Co(NO₃)₂ and Mn(NO₃)₂ is investigated using 1% agar gel over the temperature range of 25 to 45 °C. The activation energies are obtained by the least square fitting of the diffusion coefficient data obtained at various temperatures through the Arrhenius plots. Further, the extent of obstruction effect by gel macromolecules for Co²⁺ ions in Ni(NO₃)₂, Co(NO₃)₂ and Mn(NO₃)₂ systems at various concentrations of the electrolyte have been determined. The decrease in activation energy is explained by considering the changes in the physical properties of the solution with concentration at microscopic level, while the decrease in obstruction effect expressed in terms of a is accounted for on the basis of competitive hydration between ions and agar molecule.     

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.     

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.     

Tracer-diffusion of cobalt ions in sodium and potassium nitrates in agar gel

Tracer-diffusion of Co²⁺ ions is studied in agar gel in the presence of sodium and potassium nitrates at 25°C. The diffusion coefficient values at various electrolyte concentrations are compared with the corresponding theoretical values computed on the basis of Onsager's theory. The deviations from the theory are attributed to the various co-occurring effects in the diffusion medium. The activation energy for the process of diffusion of Co²⁺ ions in presence of above electrolytes is also reported.     

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.     

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.     

Tracer diffusion of131I− ions in a few 1–2 electrolytes in agar gel

Tracer diffusion of¹³¹I^– ions is studied at different temperatures /20°C–50°C/ in 2.5% agar gel containing sodium and potassium sulphate solutions over a wide range of concentrations. The results are in qualitative agreement with the theoretical values in the concentration range 10^–6–10^–1M. Agar gel shows an obstruction effect to diffusional flow. The activation energy for tracer diffusion was found to be of the order of 16.3 kJ mol^–1.     

Electrolyte diffusion of ZnCl2 and self-diffusion of Cd2+ ions in agar gel medium at different temperatures

The values of activation energy required for the diffusion of ZnCl₂ and for Cd²⁺ ions in Cd/Ac/₂ are reported in agar gel medium at 5×10^–5 and 0.001M concentration, respectively. These values are compared with the previously reported values in the same systems at different concentrations. The decrease in activation energy with concentration of electrolyte is in agreement with the Wang's model.     

The effect of rotational and translational energy exchange on tracer diffusion in rough hard sphere fluids

A study is presented of tracer diffusion in a rough hard sphere fluid. Unlike smooth hard spheres, collisions between rough hard spheres can exchange rotational and translational energy and momentum. It is expected that as tracer particles become larger, their diffusion constants will tend toward the Stokes-Einstein hydrodynamic result. It has already been shown that in this limit, smooth hard spheres adopt "slip" boundary conditions. The current results show that rough hard spheres adopt boundary conditions proportional to the degree of translational-rotational energy exchange. Spheres for which this exchange is the largest adopt "stick" boundary conditions while those with more intermediate exchange adopt values between the "slip" and "stick" limits. This dependence is found to be almost linear. As well, changes in the diffusion constants as a function of this exchange are examined and it is found that the dependence is stronger than that suggested by the low-density, Boltzmann result. Compared with smooth hard spheres, real molecules undergo inelastic collisions and have attractive wells. Rough hard spheres model the effect of inelasticity and show that even without the presence of attractive forces, the boundary conditions for large particles can deviate from "slip" and approach "stick."     

Electrolyte-diffusion of cobalt sulphate in agar gel medium at 25 °C

The diffusion of cobalt sulphate is studied in 1% agar gel over a concentration range of 10^–5 to 0.2M at 25 °C. The experimental values of the diffusion coefficient at various concentrations determined by the zone-diffusion technique are compared with the theoretical values of diffusion coefficinets computed on the basis of Onsager-Fuoss theory. The observed deviations are interpreted in terms of relative contributions of diffusion-enhancing and diffusion-retarding interactions occurring in the water-gel-electrolyte system.     

Electrochemical behavior of electrode modified with a cobalt hexacyanoferrate film: Effect of the supporting electrolyte cation

Cobalt hexacyanoferrate films are synthesized on a glassy carbon electrode with sodium, potassium, and ammonium salts in the supporting electrolyte. The electrochemical behavior of the modified electrode is studied in individual solutions of the salts and in their mixtures. The change in electrochemical properties of cobalt hexacyanoferrate agrees with an increase in the interaction of cations with the film in the series Li⁺, Na⁺, K⁺, NH ₄ ⁺ , Cs⁺. The effect of the energy of interaction between the modify ing-substance crystal lattice and counter-ions on the electrochemical processes is discussed     

Activation energy for electrolyte diffusion of some zinc salts

Activation energies for electrolyte diffusion of Zn(NO₃)₂, ZnBr₂ and ZnI₂ in 1% agar gel at different concentrations are determined by the least-squares fitting of the diffusion coefficient data obtained at various temperatures through the Arrhenius plots. Energy of activation is found to decrease with an increase in electrolyte concentration. This trend is explained by considering the changes in the physical properties of the solution with concentration at microscopic level, as envisaged in Wang's model.     

Influence of the interaction between adsorbed organic ions and supporting electrolyte ions on the kinetic current of protonation reaction

The paper presents an ionite model of a mercury electrode covered with adsorbed organic ions, and points out that the kinetic current of protonation in the presence of ionic surfactants depends on the process of ion exchange with the participation of the so-called ionite layer formed during the adsorption of organic ions, which have long carbon chains (C10).     

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.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.     

Solvation effect of the cation of the supporting electrolyte in hexamethylphosphoramide

Polarographic reductions of sodium and potassium ions in hexamethylphosphoramide (HMPA) have been examined in various supporting electrolytes. The supporting electrolytes, which have much the same solvated radii and much the same electrocapillary curves, sometimes have a significantly different influence on the polarographic reductions of metal ions. The Li⁺ and Hex₄N⁺ ions provide a typical example. Their effective radii are seen to have much the same characteristics. However, the polarographic reduction of the sodium ion shows a difference in shape between that occurring in Li⁺ solution and that in Hex₄N⁺ solution. Another example is found in the case of Et₄N⁺, Me₄N⁺ and 5N6⁺, whose r_eff and the electrocapillary curves are much the same. However, the polarographic reductions of the sodium and potassium ions are different in these solutions. The solvation number of the solvent molecule of the supporting electrolyte cation seems to exert a great influence on these reductions. The electrocapillary curves were also examined with the tetradodecylammonium ion, tetradecylammonium ion and tetraphenylphosphonium ion used as the supporting electrolytes. The inhibition of the reduction of metal ion for these cations is evidence for their lack of solvation. The effects of the solvated asymmetrical tetraalkylammonium ions on the polarographic behaviour were also examined. When some methyl groups cooperate with the tetraalkylammonium ion, the chemical character is between that of the Et₄N⁺ ion and that of the Me₄N⁺ ion.     

Periodic precipitation of cobalt(II) oxinate in agar gel: factors influencing the flocculation

The influence of concentration, ageing and pH of the gel medium on the periodic precipitation of cobalt oxinate in agar gel is reported. The results are explained on the basis of Shinohara’s revised flocculation theory. The flocculation value (F) increases with increase in the gel concentration whereas it decreases with increase in ageing and pH of the gel. The raise in temperature of the gel increases the solubility of the sparingly soluble substance and hence theF value. The effect of additives on the periodic precipitation of cobalt (II) oxinate is reported.     

Tracer-diffusion of Mn2+ ions in agar gel containing alkali metal chlorides

Prompt gamma-neutron activation analysis, PGNAA, has been used to determine major and minor elements of bituminous coals. Calibration curves for H, C, N, Cl, Si, Ti, Al, Fe, Ca, Na, K, and S were obtained using six coals of different origin. The correlation coefficients are, in general, greater than 0.9 with the exception of C, N, and K. The -peak intensities were corrected for volume hydrogen content and normalised to the source intensity by using the 2615 keV -line from the (n, n) reaction induced in the lead container of the Cf source. Elemental compositions of new coal samples were determined. In spite of the weak neutron source intensity, the comparison between the elemental concentrations measured by PGNAA and by conventional analysis show good agreement except for N, K, S and Ca.