Selectivity study of strongly acidic cation exchange resin Amberlite IR-120

The thermodynamic measurements was carried out to study the selectivity of cation exchange resin Amberlite IR-120 in protonated form with respect to Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ ions in solution. The equilibrium constant K was calculated using the activity coefficients of ions in solution as well as in the resin. The K values calculated for the reacting systems increase with temperature that suggests the endothermic exchange reactions with estimated enthalpy values of 38.8, 20.6, 8.45, and 7.24 kJ mol⁻¹, respectively. On the basis of calculated parameters, the selectivity of ion exchange resin with respect to various bivalent ions in the solution was predicted. The method used in our experimental work provides a basis for characterization of ion exchange resins, which can be promising materials for efficient separation of ions from industrial waste effluents.     

Study on ion exchange equilibrium for some uni-univalent and uni-divalent reaction systems using strongly basic anion-exchange resin Duolite A-113

The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl⁻/I⁻, Cl⁻/Br⁻, and uni-divalent Cl⁻/SO₄²⁻, Cl⁻/C₂O₄²⁻ reaction systems was carried out using ion-exchange resin Duolite A-113. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems were observed to increase with rise in temperature, indicating the endothermic exchange reactions having enthalpy values of 17.21, 36.60, 19.50, 18.43 kJ/mol respectively.     

A study of ion exchange equilibrium for some uni-univalent and uni-divalent reaction systems using strongly basic anion exchange resin Indion-830 (Type 1)

A study of the thermodynamics of ion exchange equilibrium for uni-univalent Cl⁻/I⁻, Cl⁻/Br⁻ and uni-divalent Cl⁻/SO ₄ ²⁻ , Cl⁻/C₂O ₄ ²⁻ reaction systems was carried out using ion exchange resin Indion-830 (Type 1). The equilibrium constant K was calculated by taking into account the activity coefficients of ions both in solution and in the resin phase. For uni-univalent ion exchange reaction systems, the equilibrium constants K′ were also calculated from the mole fraction of ions in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems increased as the temperature grew, indicating the endothermic character of the exchange reactions with enthalpies of 38.2, 32.3, 7.6, and 11.4 kJ/mol, respectively. The article is published in the original.     

Ion-isotopic exchange reaction kinetics using organic base anion exchange resins Indion-102 and Indion GS-400

The present study deals with the kinetic study of iodide and bromide ion-isotopic exchange reactions in organic based anion exchange resins Indion-102 (nuclear grade) and Indion GS-400 (non-nuclear grade) using radiotracer isotopes. The resins in iodide and bromide form were equilibrated respectively with iodide and bromide ion solutions which were previously spiked with ¹³¹I and ⁸²Br radiotracer isotopes. For both bromide and iodide ion-isotopic exchange reactions, it was observed that the values of specific reaction rate increase with increase in ion concentration from 0.001 to 0.004 M at a constant temperature of 40.0°C. However, at constant ion concentration of 0.003 M, the specific reaction rate was observed to decrease with rise in temperature from 30.0 to 45.0°C. Also it was observed that for iodide ion-isotopic exchange reaction by using Indion-102 resin, the values of specific reaction rate, amount of iodide ion exchanged, initial rate of iodide ion exchange and logK _d were 0.258 min^?1, 0.492 mmol, 0.127 mmol/min and 19.2, respectively, which were higher than 0.208 min^?1, 0.416 mmol, 0.087 mmol/min and 17.6, respectively, obtained by using Indion GS-400 resin under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resin and 0.003M labeled iodide ion solution. The same trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that, under identical experimental conditions, Indion-102 resin shows higher performance than Indion GS-400 resin.     

Comparative study on uni-univalent and uni-bivalent ion-exchange reaction on Doulite A-116

Determination of ion-exchange equilibrium constant (K) for Cl⁻/I⁻ and Cl⁻/C₂O₄²⁻ system was studied at different temperatures from 25 to 45°C and by varying concentration of iodide and oxalate ion solution. For both uni-univalent and uni-bivalent exchange systems, using 0.5 g of ion-exchange resin DUOLITE A-116 (in chloride form), the value of K increases with rise in temperature i.e., from 13.0 at 25°C to 19.05 at 45°C for Cl⁻/I⁻ system and 33.0 at 25°C to 63.0 at 45°C for Cl⁻/C₂O₄²⁻ system indicating the endothermic ion-exchange reaction. The difference in K values at the same temperature for the two was related to the ionic charge of exchangeable ions in the solution.     

Observations on the effect of temperature on performance and stability of anion exchange columns in ion chromatography

Summary The influence of column temperature on elution behaviour of several ions on anion-exchange resin beds of the Dionex Ion Pac type was investigated. Iodate, bromate, bromide and iodide ions were separated on Ion Pac AS9SC column in the temperature range of 10°C–55°C, using NaHCO₃/Na₂CO₃ and NaHCO₃ eluents. Free energy, enthalpy and entropy changes for respective ion exchange reactions were calculated and compared with literature data for classical gel type exchangers. In most cases the enthalpy change was a function of temperature. The work at elevated temperatures caused progressing resin degradation i.e. loss of strongly basic groups, accompanied by formation of weakly basic groups and also some weakly acidic groups. Similar resin degradation was observed for Ion Pac AS5 column. Observations on the changes of the plate height with the retention factor and temperature lead to conclusion that in some circumstances longitudinal diffusion in the resin phase also contributes to the total plate height.     

Evaluation of anion exchange resins Tulsion A-30 and Indion-930A by application of radioanalytical technique

Radioanalytical technique using ¹³¹I and ⁸²Br was employed to evaluate organic based anion exchange resins Tulsion A-30 and Indion-930A. The evaluation was based on performance of these resins during iodide and bromide ion-isotopic exchange reactions. It was observed that for iodide ion-isotopic exchange reaction by using Tulsion A-30 resin, the values of specific reaction rate (min^?1), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and logK _d were 0.238, 0.477, 0.114, and 11.0, respectively, which was higher than 0.155, 0.360, 0.056, and 7.3, respectively as that obtained by using Indion-930A resins under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resins and 0.003 M labeled iodide ion solution. Also at a constant temperature of 40.0°C, as the concentration of labeled iodide ion solution increases 0.001 to 0.004 M, for Tulsion A-30 resins the percentage of iodide ions exchanged increases from 59.0 to 65.1%, and from 46.4 to 48.8% for Indion-930A resins under identical experimental conditions. The identical trend was observed for both the resins during bromide ion-isotopic exchange reactions. The overall results indicate that under identical experimental conditions, Tulsion A-30 show superior performance over Indion-930A resins. The results of present experimental work have demonstrated that the radioanalytical technique used here can be successfully applied for characterization of different ion exchange resins so as to evaluate their performance under various process parameters.     

Radiotracers in kinetics of ion-isotopic exchange reactions using anion exchange resins indion-103 and indion-870

The kinetics of iodide and bromide ion-isotopic exchange reactions was studied by radio analytical technique using ¹³¹I and ⁸²Br as tracer isotopes. The parameters like specific reaction rate (min^?1), amount of ions exchanged (mmol), initial rate of ion exchange (mmol/min) and logK _d were studied to evaluate the performance of nuclear and non-nuclear grade anion exchange resins Indion-103 and Indion-870. For iodide ion-isotopic exchange reactions under experimental conditions of 35.0°C, 1.000 g of ion exchange resins and 0.002 M labeled iodide ion solution, the parameters were 0.223 min^?1, 0.300 mmol, 0.067 mmol/min and 18.7, respectively, for Indion-103, and those of 0.165 min^?1, 0.251 mmol, 0.041 /min and 16.2, respectively, for Indion-870. The similar tendency was observed during bromide ion-isotopic exchange reactions. The results suggest that Indion-103 shows greater performance than Indion-870 resin under similar experimental conditions.     

Study of temperature effect on uni-univalent and uni-bivalent ion exchange reaction

Ion exchange equilibrium constant (K) for Cl⁻/Br⁻ and Cl⁻/C₂O₄²⁻ system was studied at different temperatures from 30 to 45°C. For both uni-univalent and uni-bivalent exchange systems, the value of K increases with rise in temperature i.e., from 1.16 at 30°C to 2.95 at 45°C for Cl⁻/Br⁻ system and 19.5 at 30°C to 30.0 at 45°C for Cl⁻/C₂O₄²⁻ system indicating the endothermic ion exchange reaction. The difference in K values at the same temperature for the two was related to the ionic charge of exchangeable ions in the solution. The article is published in the original.     

Calculation on ion exchange capacity for an ion exchanger using the potentiometric titration

We calculated the characteristics of a phosphoric cation exchanger and studied an accurately computable method for ion exchange capacity for a type of potentiometric titration curve. The ion exchanger was prepared by phosphorylation of a styrene‐divinylbenzene copolymer. The ion exchange capacity was 5.7 meq/g. The experimental pK values versus χ in a phosphoric cation exchanger can explain a linear equation. The ΔpK values were obtained from the slope of a linear equation. The ΔpK values were the differences of pK values between the apparent equilibrium constant at complete and zeroth neutralization of the ion exchanger. The experimental pK values at χ = 0.5 (χ:degree of neutralization of ion exchanger) showed good agreement with the theoretical data. When it was titrated with NaOH and Ba(OH)₂ solutions, a good agreement between experimental and theoretical pK values for various χ was found in all potentiometric titration curves. The potentiometric titration curve near the inflection point in the case of divalent ions was changed more sharply than that for monovalent ions. The plot of ∂pH/∂g versus g (number of moles of alkali to 1 g of ion exchanger) was fitted to the Lorenzian distribution, from which ion exchange capacity was accurately evaluated. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3181–3188, 2000     

Isotope exchange of strontium and molybdate ions in strontium polymolybdates

The heterogeneous isotopic exchange reactions in strontium polymolybdates of Sr²⁺ and MoO₄ ^2- ions in the strontium nitrate and sodium molybdate solutions have been studied using ⁹⁰Sr and ⁹⁹Mo as tracers. Electrometric methods have been used to study the compositions of strontium molybdates obtained by adding strontium chloride to a progressively acidified solution of sodium molybdate. It has been found that the exchange fraction increases with increasing chain length of strontium polymolybdate. The exchange equilibrium constant (K _ex) has been calculated between 298 and 348 K as well as DG°, DH° and DS°. The results indicate that Sr²⁺ cations have a much higher affinity for exchangers than MoO₄ ^2- anions. By fitting the data to the Dubinin-Radushkevich (D-R) isotherm it has been shown that the exchange capacity (X _m ) for both ions is affected by the ion adsorption process at low temperatures and by the ion exchange process at high temperatures. At high concentrations, the recrystallization process contributes to on the cation exchange but is ineffective on the anion exchange mechanism.     

The thermodynamic characteristics of ion exchange in a sulfonated polymer based on <Emphasis Type="Italic">cis</Emphasis>-tetraphenylcalix[4]resorcinarene

The selectivity and thermodynamic characteristics of exchange of protons in SO₃H groups of a sulfonated network polymer based on cis-tetraphenylcalix[4]resorcinarene for Na⁺, Cu²⁺, and In³⁺ cations from aqueous solutions are considered. Semiempirical quantum-chemical calculations of molecular ensembles modeling the structure of the elementary polymer unit in the H and Na forms were performed. The experimental data on the equilibrium phase compositions and the heat of exchange were used to calculate the thermodynamic equilibrium constants, Gibbs energy, enthalpy, and entropy of ion exchange.     

Non-destructive radioanalytical technique in characterization of anion exchangers Amberlite IRN78 and Indion H-IP

The present study deals with characterization of industrial grade anion exchange resins Amberlite IRN78 and Indion H-IP for which non-destructive radiotracer technique using ¹³¹I and ⁸²Br was used. The radioisotopes were used to trace the kinetics of iodide and bromide ion-isotopic exchange reactions taking place in the two resins. It was observed that under identical experimental conditions of 40.0 °C, 1.000 g of ion exchange resins and 0.003 M labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min^?1), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol min^?1) and log K _d were 0.285, 0.544, 0.155 and 12.6 respectively for Amberlite IRN78 resin, which was higher than 0.093, 0.315, 0.029 and 4.9 respectively as that obtained by using Indion H-IP resins. Also at a constant temperature of 40.0 °C, as the concentration of labeled iodide ion solution increases 0.001–0.004 M, the percentage of iodide ions exchanged increases from 68.10 to 74.00 % for Amberlite IRN78 resin, which was higher than the increase of 40.20–42.80 % as observed for Indion H-IP resins. The identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that that under identical experimental conditions Amberlite IRN78 resins shows superior performance over Indion H-IP resins.     

A study of ion exchange selectivity coefficient by cyclic voltammetric measurement

An equation to express ion exchange selectivity coefficient was derived and used for calculating that of PPY film with the results obtained by cyclic voltammetric measurement. PPY film was synthesized by electrochemical method in aqueous solution using K₄Fe(CN)₆ as supporting electrolyte, and the anions were doped into the film. Ion exchange behaviour of doped Fe (CN)₆^3-/4- in the PPY film with Cl^?, NO₃^? or F^? ions in solution has been studied, and the corresponding ion exchange selectivity coefficients were determined.     

Study on distribution coefficient of bromine ions from aqueous solution on ion exchange resins Duolite A-161 and Duolite A-162

The ion exchange resins Duolite A-161 and Duolite A-162 in bromide form were equilibrated separately with the labeled radioactive bromide ion solution of different concentrations varied from 0.005 to 0.100 M in the temperature range 25.0–45.0°C. The K _d values of bromide ions for Duolite A-162 were found to be higher than that for Duolite A-161 under similar experimental conditions. The difference in K _d values of bromide ions for these two resins is produced by a swelling pressure depending on the water holding capacities.     

聚二烯丙基二甲基氯化铵在质子交换膜表面静电自组装过程的热力学研究

本文通过热化学方法设计了PDDA滴定质子交换膜,并研究了高分子的静电自组装过程。通过非线性拟合数据分析,求出了自组装过程的焓变（ ）和结合常数（K）。根据该反应过程中的热力学参数,可知自组装过程是“焓驱动”反应。热量的放出代表着能量的降低,有利于反应的发生;而自由度的减小不利于反应的发生。对于每个离子键的形成,单分子DDA的焓变超过了PDDA,这是因为小分子能够更加自由地结合到膜上,而高分子PDDA有一定的位阻效应。     

Treatment of triple ion formation

It is shown that the full Fuoss-Hsia equation can be extended to fit conductivity data for electrolyte solutions in which ion pairs and triple ions exist at comparable concentrations. The treatment is a three parameter fit of °, K _a , and K _t (the limiting molar conductivity, the thermodynamic ion association constant, and the thermodynamic triple ion formation constant, respectively). Using literature conductivity data for 1:1 electrolytes in solvents of low permittivity, it is demonstrated that an excellent fit can be achieved over a wide concentration range. Limitations of the treatment are discussed.     

Ion Association Between Hexaamminecobalt (III) Ion and Monovalent Anions in Methanol-Water Mixtures from 10 to 50°C

The conductivities of chloride, bromide, iodide, nitrate, and perchlorate of hexaamminecobalt(III) complex were measured in 10-80 wt.% methanol-water mixtures at varying temperatures from 10 to 50°C. The ion association constants were estimated by analyzing conductivity data in terms of the Robinson-Stokes equations. Ion-association constants calculated for all complex salts in methanol-water mixtures increased, depending on the percentage of methanol. This was equivalent to the ion-association constants increasing with a decrease in the the dielectric constant of the mixtures. K _A values increased with increasing temperature for the chloride, bromide, and iodide of [Co(NH₃)₆]³⁺. It was observed that these values indicated some disorder, dependent on the temperature, for nitrate and perchlorate. Thermodynamic parameters (Gibbs' free energy, entropy and enthalpy of ion association) were estimated from the temperature dependence of the ion-association constant. The limiting molar conductivities of complex ion and monovalent anions in the mixed solvents were determined from our experimental data by using the Kohlraush equation.     

L'influence de la temperature sur l'echange anionique

The influence of temperature on the distribution coefficients of Zn ions in systems ethanol or acetone, hydrochloric acid and Dowex 1×8 ion exchange resin (100–200 mesh) was studied. TheK _d-values increase a little with the temperature. The thermodynamic constants for some systems were calculated.