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  • Author or Editor: P. N. Pathak x
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Summary  

Batch sorption experiments of cesium, Cs+, on SiO2 . xH2O (silica gel) have been conducted with variable times of equilibration, amounts of silica gel (0.10-1.00 g), cesium concentrations (5.00 . 10-5-2.40 . 10-3M), ionic strengths (0.20-1.40M NaClO4), pH (2.50-7.70), and temperatures (273-333 K). The diffusion coefficient of Cs+ ion was calculated to be (9.19±0.86) . 10-11 m2 . s-1 under particle diffusion-controlled conditions. The sorption rate was (3.94±0.65) . 10-3 s-1 at 298 K, pH 7.70±0.05 in 0.20M NaClO4. The sorption data fits the Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Cesium sorption on 0.20 g silica gel decreased with ionic strength from (40.42±0.34)% in 0.20M NaClO4 to (6.35±0.40)% in 1.40M NaClO4, at pH(initial) 8.20±0.05. A gradual decrease in pH with increased ionic strength is consistent with a cation-exchange mechanism. Sorption of Cs+ on silica gel decreased with increased temperature, indicating an exothermic enthalpy. The presence of anions such as fluoride, carbonate, phosphate and oxalate in the aqueous medium did not influence the cesium sorption profile.

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The complexation behavior of Ni2+with ortho-silicic acid (o-SA) has been studied as a function of ionic strength (I) from 0.20 to 1.00M (NaClO4) at pcH 4.55±0.05 and 25 °C by a solvent extraction technique with bis(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stoichiometry of the extracted species was determined to be Ni(DEHP)2(HDEHP)2. Ni2+forms a 1:1 complex, Ni(OSi(OH)3)+, as the predominant species withconcentrations of 1.00. 10-3to 1.00. 10-2M o-SA. The stability constant (logb1) values for Ni(OSi(OH)3)+complex formation decrease with increased ionic strength. These values have been fitted with the extended Debye-Huckel expression to obtain the value of logb1=6.34±0.03 at I=0.00M. The data allowed the calculation of speciation of the Ni2+- silicate system as a function of ionic strength.

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Summary  

Sorption of nickel, Ni2+, on SiO2 . xH2O (silica gel) has been studied as a function of time conditions: amount of silica gel: 0.10-1.00 g, nickel concentration: 5.00 . 10-5-1.20 . 10-3M, ionic strength: 0.20-1.40M NaClO4, pH 6.50 to 8.50, and temperature 273-318 K. From the kinetic data, the diffusion coefficient of Ni2+ ion was calculated to be 1.28(±0.07) . 10-11 m2 . s-1 under particle diffusion-controlled conditions. The sorption rate was determined as 3.79(±0.35) . 10-3 s-1 at 298 K, pH 8.40 in 0.20M (NaClO4). The sorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. Nickel sorption on 0.20 g silica gel decreased with ionic strength from 77.70±0.70% (0.20M NaClO4) to 16.12±0.37% (1.40M NaClO4) at intial pH of 8.50±0.05. A gradual decrease in pH with increasing ionic strength suggests an ion exchange mechanism and the sorption of Ni2+ on silica gel increasing with temperature indicates an endothermic enthalpy. The effect of different ligands such as fluoride, carbonate, phosphate and oxalate on Ni2+ sorption on silica gel was studied.

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The complexation behavior of Co2+with ortho-silicic acid (o-SA) has been studied as a function of ionic strength (I) from 0.20 to 1.00M (NaClO4) at pH 4.96±0.03 and 25 °C by solvent extraction with bis(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stoichiometry of the extracted species was determined to be Co(DEHP)2(HDEHP)2. Co2+forms a 1:1 complex, CoOSi(OH)3 +, as the predominant species witho-SA concentrations of 3.00. 10-4to 4.00. 10-3M. The stability constant (logb1) values for CoOSi(OH)3 +complex decrease with the increase in ionic strength. These values were fitted with the extended Debye-Huckel expression to obtain the value of logb1at I=0.00M. The effect of aging time of the o-SA solution on logb1values for CoOSi(OH)3 +complex was investigated and compared with those of the UO2OSi(OH)3 +complex.

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Sorption behavior of europium, Eu3+, on SiO2 . xH2O (silica gel) has been investigated as a function of time, the amount of silica gel, Eu3+ concentration, the ionic strength, and pH (in absence and in presence of carbonate). The sorption data were fitted to Freundlich, Langmuir and Dubinin-Radushkevich (D-R) isotherms. The sorption capacity of silica gel was determined to be in the range of (2.62-8.00) . 10-7 mol/g at pH 5.30±0.05 and 0.20M NaClO4. The mean energy of sorption was calculated to be 13.50±0.05 kJ/mol from the D-R isotherm, suggesting the involvement of ion-exchange reactions in the sorption process. Sorption of Eu3+ decreased with increased ionic strength. A gradual decrease in pH with increased ionic strength supports the involvement of an ion-exchange mechanism in the sorption process. The diffusion coefficient of Eu3+ ion on silica gel was calculated as (3.98±0.12) . 10-13 m2 . s-1 under the particle diffusion-controlled conditions.

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Sorption behavior of Th and U on cation-exchange resins was investigated from nitric acid medium by both batch and column methods. The cation-exchange studies involved the sorption of UO2 2+ and Th4+ and their cationic complexes onto Dowex 50Wx8 and Dowex 50Wx4 resins (50-100 mesh). The batch data yielded a separation factor (K d ,Th/K d, U) value of >100 for the cation-exchanger, Dowex 50Wx4 at 1-2M HNO3. Separation of uranium from thorium was also carried out by column method in nitric acid medium using cation-exchangers, Dowex 50Wx4 as well as Dowex 50Wx8. While uranium elution was possible at 1M HNO3, Th could be eluted only at higher concentration of nitric acid (>6M). The stripped solution emanating from a mixer settler employing di-2-ethyl hexyl isobutyramide as extractant and feed solution similar to THOREX process comprising 350 mg/l U and 380 mg/l Th in 0.75M HNO3 was loaded on the column and the decontamination factor value for U in the product was >1000.

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