Various silica gel materials were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzod-18-crown-6 (DB18C6). The degree of functionalization of the covalently attached molecule was calculated from C, H, N analysis and ranged between 0.270 and 0.552 mmol/g (for sorbents with imidazole) and between 0.043 and 0.062 mmol/g (for sorbents with DA18C6 and DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.050 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter <40 Å was used too. Change of pore diameters of silica gel support to larger pores should have a positive influence on access of cobalt ion to sorption centers to increase of sorption capacity of sorbents. The sorption kinetics of cobalt and the influence of cobalt concentration, pH of various kinds of silica gel matrix with immobilized imidazole group in static conditions on sorption were measured. The sorption of cobalt in various conditions (pH, contact time of phases) with constant liquid-solid ratio (V/m = 50 ml/g) was studied. The distribution coefficients ranged between 200 and 50 000 ml/g (for imidazole), 85 and 120 ml/g (for DB18C6) and between 230 and 500 ml/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. Protons significantly competes to sorption of cobalt in acidic solutions. The influence of presence of other heavy or toxic metals (Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was investigated. Sorption of cobalt decreases in order Hg > Cu > Cd > Zn, Fe > Mn > Al, Cr. The presence of sodium and potassium ions at concentration 0.05 mol/l significantly influences on the sorption of cobalt with sorbent with immobilized DB18C6 functional group.
It was found that lead reacts with 18-crown-6 (L) and tungstosilicic acid (H4A) in acidic solutions and a compound with low solubility is formed what was confirmed by radiometric titration methods. Coprecipitation of complexion cation of PbL2+ with similar complexion cations of calcium, strontium and barium was studied. Formation of low soluble salts was utilized for separation of Pb from Ca, Sr and Ba from 1 mol·dm–3 HNO3. The ratio of Pb/Ca, Pb/Sr and Pb/Ba in the precipitation or separation factors Spb/M undoubted depends on the ratio of the stability constants of lead and metals with 18C6 (
M), what can be used for determination of more precise constant stability
Authors:P. Rajec, V. Švec, V. Mikulaj, and R. Hanzel
Lead as well as strontium form low solubility compounds of composition (ML2)2A·nH2O, (M=Pb2+, Sr2+), in the presence of 15-crown-5 (L) and tungstosilicic acid (H4A) in acid media as found by radiometric precipitation titration. “Sandwich” structure of crown-ether complexes of lead and
strontium could be expected due to the small size of cavity of 15-crown-5. Coprecipitation of PbL2/su2+ with crown complexes of strontium cation after adding tungstosilicic acid was studied in 0.01 mol·dm−3 HNO3. A significant influence of H+ cation in 1 mol·dm−3 HNO3 on coprecipitation of lead was observed. Formation of HL+ complexes by protonisation of 15-crown-5 competes to the formation of ML22+ complexes (approximately twenty percent of 15-crown-5 are used for creation of HL+ complexes). Formation of low solubility salts was utilised for separation of lead from strontium in 0.01 mol·dm−3 HNO3. The ratio of constant stability of lead and strontium β‘ with 15-crown-5 in 0.01 mol·dm−3 HNO3 was calculated. The separation factor S(Pb/Sr) depends on the ratio of stability constants βPbL2/βSrL2 The precipitation method can be used for separation of metals with high constant stability with crown ethers from solutions
containing other metals in the case of gradual addition of crown.