The effects of ionic strength and of ethylenediamin et etraacetic acid (EDTA) on the sorption of uranyl ion, UO22+, to SiO2·xH2O (silica gel) were investigated. It was observed that pH and the ions present in the supporting electrolytes influence the
ionic strength effects. The presence of different sodium salts in the concentration range (0.20 to 1.40M) suppressed the sorption
of UO22+ in the order: NaNO3 < NaClO4 < NaCl < NaOCOCH3 < Na2SO4 [pH 2.75(±0.05)], while the presence of perchlorate salts of Li+, Na+ and Ca2+ (0.20 to 1.40M) promoted the sorption of UO22+ on silica gel in the order: LiClO4∼NaClO4<Ca(ClO4)2 at pH 2.80(±0.05). The ionic strength effect on UO22+ sorption was studied in presence of EDTA (0–1.00·10−3M) in the pH range 2.90 to 5.57. The sorption data and speciation calculation suggest negligible complexation of UO22+ with EDTA at I≥1.00M NaClO4.
Complexation behavior of NpO2+ with ortho-silicic acid (o-SA) has been studied using solvent extraction at ionic strengths varying from 0.10 to 1.00M (NaClO4) at pcH 3.68±0.08 and 25 °C with bis-(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stability constant value
(log β1) for the 1:1 complex, NpO2(OSi(OH)3), was found to decrease with increase in ionic strength of the aqueous phase [6.83±0.01 at I=0.10M to 6.51±0.02 at I = 1.00M]. These values have been fitted in the SIT model expression and compared with similar values of complexation of the
metal ions Am3+, Eu3+, UO22+, PuO22+, Np4+, Ni2+ and Co2+. The speciation of NpO2+-o-silicate/carbonate system has been calculated as a function of pcH under ground water conditions.
Sorption of tracer Am3+ to silicate particles was studied as a function of pcH (4 to 9) and of ionic strength [0.20M to 1.50M (NaClO4)] at 298 K. The sorption increased with increased pcH from 4 to 6 above which saturation was observed. The insensitivity
of Am3+ sorption to increased ionic strength indicates inner-sphere complexation with the surface silicate sites. The effects of
different complexing anions such as carbonate, acetate, oxalate, phosphate, citrate, EDTA and humic acid, on Am3+ sorption were investigated. Synergistic enhancement in Am3+ sorption was observed in the presence of phosphate (4≤pcH≤7) and acetate (4≤pcH≤5) ligands at 0.20M NaClO4. The presence of the other ligands inhibited Am3+ sorption in the order: EDTA > citrate > oxalate > carbonate. Am3+ sorption in the presence of HA (25.00 mg/l) increased in the pcH range of 4.0 to 5.5, then decreased. Increased ionic strength
enhanced Am3+ sorption in the presence of 25.00 mg/l HA for 4≤pcH≤9. The sorption increased in the presence of a mixture of HA (25.00 mg/l)
and phosphate (1.00·10−3M) as compared to that of HA (25.00 mg/l) alone. The presence of Fe3+ (1.00·10−4M) enhanced Am3+ sorption at pcH∼4 but suppressed it from pcH of 5 to 9; 1.00·10−4M of Ca2+ and of UO22+ ions had no effect on the sorption profile.
Sorption of NpO2+ on silicate (10.00 g/l) particles dispersed in sodium perchlorate media was studied as a function of pcH and ionic strength
at 298 K. The sorption increased with increased pcH in the range of ∼6.5 to 9.2, above which saturation was observed. An increase
in ionic strength from 0.20M to 1.00M (NaClO4), increased the NpO2+ sorption, which then decreased at 1.50M (NaClO4) for 7<pcH<8.5. The effects of different types of ligands on the sorption of NpO2+ to suspended silicate were investigated. The types of ligands included: (i) inorganic anions (fluoride, carbonate, phosphate
(ii) N-donors (ethylenediamine, 1,10 phenanthroline (iii) carboxylic acids (oxalic acid, citric acid, iminodiacetic acid,
ethylenediaminetetraacetic acid) and (iv) humic acid. A synergistic enhancement in sorption to the suspended silicate was
observed for phosphate, oxalate, ethylenediaminetetraacetic acid, ethylenediamine, 1,10 phenanthroline (5<pcH<8) and humic
acid (6.5<pcH<8.8). This behavior was attributed to the formation of ternary NpO2+/silicate/ligand complexes. The effects of Ca(II) (1.00·10−3M) and Eu(III) (1.00·10−4 and 1.00·10−3M) ions on NpO2+ sorption to suspended silicate were also investigated.
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.
Authors:P. N. Pathak, P. N. Pathak, P. N. Pathak, G. R. Choppin, G. R. Choppin, and G. R. Choppin
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.
Authors:P. Pathak, R. Veeraraghavan, and V. Manchanda
The distribution behavior of uranium and thorium has been investigated in a biphasic system of different aqueous nitric acid
concentrations and a solution of tris(2-ethylhexyl) phosphate (TEHP) inn-dodecane at 25°C. The effect of different uranium and thorium concentrations in the aqueous phase on the extraction of these
metal ions is evaluated. These results indicate that TEHP is a better choice than tri-n-butyl phosphate (TBP) for the separation of233U from the irradiated thorium matrix.
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.
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.
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.