Column chromatographic separation of uranium(VI) and other elements using poly(dibenzo-18-crown-6) and ascorbic acid medium

A selective and very effective separation method for uranium(VI) has been developed by using poly(dibenzo-18-crown-6) and column chromatography. The separations are carried out from ascorbic acid medium. The adsorption of uranium(VI) was quantitative from 0.00002 to 0.006 M ascorbic acid. The elution of uranium(VI) was quantitative with 2.0-8.0 M HCl and 2.0-5.0 M H2SO4. The capacity of poly(dibenzo-18-crown-6) for uranium(VI) was found to be 0.92 +/- 0.01 mmol g(-1) of crown polymer. Uranium(VI) was separated from a number of cations in binary as well as in multicomponent mixtures. The method was extended to the determination of uranium in geological samples. It is possible to separate and determine 5 ppm of uranium(VI) by this method. The method is very simple, rapid, selective and has good reproducibility (approximately +/- 2%).     

Analytical application of poly [dibenzo-18-crown-6] for chromatographic separation of thorium(IV) from uranium(VI) and other elements in glycine medium

A selective and effective chromatographic separation method for thorium(IV) has been developed by using poly [dibenzo-18-crown-6] as stationary phase. The separations are carried out from glycine medium. The sorption of thorium(IV) was quantitative from 1 × 10^?2 to 1 × 10^?4 M glycine. The elution of thorium(IV) was quantitative with 2.0–8.0 M HCl, 4.0–7.0 M HBr, 1.0–2.0 M HClO₄ and 5.0 M H₂SO₄. The capacity of poly [dibenzo-18-crown-6] for thorium(IV) was found to be 0.215 ± 0.01 mmol/g of crown polymer. The effect of concentration of glycine, metal ion, foreign ion and eluents has been studied. Thorium(IV) was separated from a number of cations in ternary as well as in multicomponent mixtures. The applicability of the proposed method was checked for the determination of thorium(IV) in real as well as geological sample. The method is simple, rapid, and selective with good reproducibility (approximately ±2 %).     

Analytical application of poly[dibenzo-18-crown-6] for column chromatographic separation of Nd(III) from Ce(III), U(VI) and other elements

This research is dedicated to the study of analytical application of poly[dibenzo-18-crown-6] for separation of Nd(III) from possible lanthanides, actinides and other metal ions. A simple and efficient column chromatographic method has been developed using poly [dibenzo-18-crown-6] as stationary phase and hippuric acid as a counter ion. The capacity of crown polymer for Nd(III) was found to be 0.55 ± 0.01 mmol/g. Nd(III) was quantitatively separated from Ce(III), U(VI) and other elements in binary as well as multicomponent mixtures. Separation yields were good and reproducible (±2 %). This method has important application for separation of Nd(III) from Ce(III) rapidly and selectively.     

Column chromatographic separation of Ce(III) from U(VI) and other elements in hippuric acid medium as an analytical application of poly[dibenzo-18-crown-6]

A simple and efficient column chromatographic method has been developed for the separation of Ce(III) from U(VI) and Ni(II)/Zn(II)/Cd(II)/Co(II)/Ba(II) etc. using poly[dibenzo-18-crown-6] as stationary phase and hippuric acid as a counter ion. HCl and H₂SO₄ were most efficient eluting agents for Ce(III). The capacity of crown polymer for Ce(III) was found to be 0.285 ± 0.01 mmol/g. The tolerance limits of various cations and anions for Ce(III) were determined. Ce(III) was quantitatively separated from U(VI) and Ni(II)/Zn(II)/Cd(II)/Co(II)/Ba(II) in binary as well as multicomponent mixtures. The good separation yields were obtained and had good reproducibility (±2 %). The method incorporated the determination of Ce(III) in real sample. The method was simple, rapid and selective.     

Solvent extraction of uranium(VI) using dibenzo-18-crown-6 in nitrobenzene from ammonium thiocyanate medium

Solvent extraction of uranium(VI) from aqueous solutions of ammoniumthiocyanate has been investigated in the presence of dibenzo-18-crown-6. Uranium(VI)was quantitatively extracted from 1.0M ammonium thiocyanate using 0.01M dibenzo-18-crown-6in nitrobenzene. Back extraction of U(VI) was quantitative with various strippingagents. Separation of U(VI) from other elements was achieved from binary aswell as multicomponent mixtures. Uranium was determined in monazite sand andsyenite rock samples. The method is very simple, rapid and highly reproducible(approximately ±2%).     

Liquid-liquid extraction separation of uranium(VI) from associated elements using dibenzo-24-crown-8 from hydrobromic acid medium

Liquid-liquid extraction of uranium (VI) from hydrobromic acid solutions with dibenzo-24-crown-8 in nitrobenzene have been investigated. Uranium(VI) was quantitatively extracted from 6.0–8.0M hydrobromic acid with 0.001–0.01M dibenzo-24-crown-8 and was quantitatively stripped from the organic phase with 0.1–1.0M hydrochloric acid, 0.5–10M nitric acid, 2–10M perchloric acid, 3.0–10M sulfuric acid or 3.0–10M acetic acid. It was possible to separate uranium(VI) from a number of elements in binary mixtures. Most of the elements showed very high tolerance limit Uranium(VI) was also separated from a number of associated elements in multicomponent mixtures. The method is very simple, selective, rapid and highly reproducible (approximately±2%) and was applied to the analysis of uranium in geological samples.     

Separation of molybdenum(VI) from other elements by solvent extraction with dibenzo-18-crown-6 from hydrochloric acid medium

DB-18-C6 was used for the extractive separation analysis of molybdenum(VI) from a range of other elements. Molybdenum(VI) was quantitatively extracted from 8M hydrochloric acid with 0.01M DB-18-C6 in nitrobenzene. It was stripped from the organic phase with 2M nitric acid and determined spectrophotometrically with Tiron at 390 nm. Molybdenum was separated from a large number of elements in binary mixtures, the tolerance limit for most elements being very high. Selective extraction of molybdenum permits its separation from barium, thorium, cesium, rubidium, strontium, lanthanum, chromium(III) and cerium(III). The method was extended for the analysis of molybdenum in a soil sample.     

Solvent extraction separation of uranium(VI) with dibenzo-24-crown-8

Uranium(VI) was quantitatively extracted with 0.01M DB-24-crown-8 in nitrobenzene from 6 to 10M hydrochloric acid. From the organic phase uranium was stripped with 2M nitric acid and determined spectrophotometrically with PAR at 530 nm. Uranium(VI) was separated from a large number of elements in binary mixtures as well as from multicomponent mixtures. The method was extended to the analysis of uranium in geological samples and animal bone.     

Column chromatographic separation of thorium (IV) from associated elements using poly-(dibenzo-18-crown-6) from sodium nitrate medium

A simple column chromatographic method has been developed for the separation of thorium from associated elements using poly-(dibenzo-18-crown-6). The separations are carried out from sodium nitrate medium. The adsorption of thorium was quantitative from 0.1-0.5M sodium nitrate. Amongst the various eluents tested, 1.0-8.0M HCl, HBr, H₂SO₄ and 3.0-8.0M HClO₄ were found to be particularly efficient for e elution of thorium. The capacity of poly-(dibenzo-18-crown-6) for thorium was found to be 1.034 mmole/g of crown polymer. Thorium was arated from number of elements in binary mixtures in which most of the elements showed a very high tolerance limit. It was possible to separate tium from a number of elements in multicomponent mixtures. The method was extended to the determination of thorium in monazite sand and ga: artles. The method is very simple, rapid, selective and has good reproducibility (approximately±2%).     

Column chromatographic separation of molybdenum (VI) from alloys with poly-(dibenzo-18-crown-6) from a hydrochloric acid medium

A very simple column chromatographic separation method has been developed for molybdenum (VI) using poly-(dibenzo-18-crown-6). The separations are carried out from hydrochloric acid medium. The adsorption of molybdenum (VI) on a poly-(DB-18-C-6) was quantitative from 2.5 to 10.0M HCl. Amongst the various eluents tested, 0.5M ammonium hydroxide was found to be an efficient eluent. Molybdenum (VI) was separated from a large number of elements in binary form, as well as from multicomponent mixtures. The method was applied for the analysis of molybdenum from various alloy samples. The method is very simple, rapid, selective and reproducible. The reproducibility of the procedure is +/-2%.     

Extraction of rare-earth elements by alkylated dibenzo-18-crown-6 and dicyclohexano-18-crown-6 from acid solutions

The extraction of rare-earth elements (REE) by alkylated crown ethers (dibenzo-and dicyclohexano-18-crown 6; DB18C6 and DCH18C6) from acid solutions in the chloroform-water system is studied. The extraction of the REE with DCH18C6 and its alkylated derivatives in the presence of trichloroacetic acid (TCA) is far more efficient than the extraction with DB18C6 and its alkylated derivatives or when nitric or acetic acid is used instead of TCA. The distribution coefficients for the cerium metals are far higher than for the yttrium metals. The metal: crown ether ratio in the extracted complex in all cases is 1:1.     

Column chromatographic separation of thorium(IV) from ascorbic acid medium using poly-(dibenzo-18-crown-6)

A simple separation method has been developed for thorium(IV) using poly-(dibenzo-18-crown-6) and column chromatography. The separation was carried out from ascorbic acid medium. The adsorption of thorium(IV) was quantitative from 0.001-0.01M ascorbic acid. The elution of thorium(IV) was quantitative with 4.0-8.0M HCl, 3.0-6.0M HClO₄, 4.0-8.0M H₂SO₄ and 1.0-8.0M HBr. The capacity of poly-(dibenzo-18-crown-6) for thorium(IV) was found to be 1.379±0.01 m^.mol/g of crown polymer. Thorium(IV) was separated from a number of cations in binary as well as in multicomponent mixtures. The method was extended to the determination of thorium in monazite sand. It is possible to separate and determine 5 ppm of thorium(IV) by this method. The method is very simple, rapid, selective and has good reproducibility (approximately ±2%).     

Synthesis and crystal structure of aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(perchlorato-O)potassium perchlorate

A new compound, aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(perchlorato-O)potassium perchlorate ([K(DB18C6)(H₂O)]⁺ · [K(ClO₄)(DB18C6)] · ClO ₄ ^? ; compound I) is synthesized and studied by X-ray crystallography. The crystals are triclinic: a = 9.050 Å, b = 9.848 Å, c = 26.484 Å, α = 82.87°, β = 84.16°, γ = 77.93°, Z = 2, space group P $\bar 1$ . The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.058 for 5960 independent reflections (CAD4 diffractometer, λMoK _α radiation). A complex cation [K(DB18C6)(H₂O)]⁺ and a complex molecule [K(ClO₄)(DB18C6)] are of the host-guest type; they are linked into a dimer through two K⁺ → π(C) bonds formed by one of the two K⁺ cations with two C atoms of the benzene ring of the DB18C6 ligand from the adjacent complex. Both DB18C6 ligands in I have a butterfly conformation with approximate symmetry C _2v .     

Synthesis and crystal structure of aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)-(tetrachlorocuprato(II)-Cl)potassium

New mixed complex compound aqua(dibenzo-18-crown-6)potassium (dibenzo-18-crown-6)(tetrachlorocuprato(II)-Cl)potassium, [K(CuCl₄)(Db18C6)]^? · [K(Db18C6)(H₂O)]⁺, is synthesized and its crystal structure is studied by the method of x-ray structural analysis. The structure includes two independent complex ions, both of guest-host type: two cations K⁺ are located in the respective cavities of the Db18C6 crown-ligand (one in each) and each is coordinated by all its six O atoms and one Cl atom of the anion-ligand [CuCl₄]^2? or O atom of the ligand water molecule. Coordination of these two K⁺ cations is completed to hexagonal pyramidal one by formation by each of unusually weak coordination bond K⁺ → π(\(C\dddot - C\)) with two C atoms of respective benzene ring in the neighboring Db18C6 ligand. In this crystal structure the complex anions and cations form dual infinite chains via these coordination bonds and interionic O-H?Cl hydrogen bonds.     

Copper(II) thiocyanide complexes extractable with [dibenzo-18-crown-6-K] + in chloroform

Summary Cu^II can be extracted from aqueous KSCN solutions using 2,3,11,12-dibenzo-1,7,10,13,16-hexaoxacyclooctadiene (di-benzo-18-crown-6) in CHCl₃. Raman and i.r. spectroscopies establish that the species present in the organic phase after extraction corresponds to [Cu₂OH(SCN)₅]-[dibenzo-18-crown-6-K ⁺]₂, where the Cu^II thiocyanide complex and the K⁺ crown complex are ionically associated.     

Dibenzo-18-crown-6 diaqua(dibenzo-18-crown-6)potassium triiodide: Synthesis and crystal structure

A new compound, dibenzo-18-crown-6 diaqua(dibenzo-18-crown-6)potassium triiodide [K(Db18C6)(H₂O)₂)⁺ · I₃⁻ · Db18C6 (I), is synthesized and studied by X-ray crystallography. The crystals of compound I are orthorhombic: a = 22.065 ?, b = 22.140 ?, c = 9.433 ?, Z = 4, space group Pccn. Structure I is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 for all 5974 unique reflections. Structure I contains the following asymmetric units: a half of the I₃⁻ centrosymmetric anion and two halves of the mixed equally average [K(Db18C6)(H₂O)₂]⁺ host—guest complex cation (a) and a free Db18C6 molecule, each stacked on the axes 2 of the perpendicularly averaged plane of the eighteen-membered macroheterocycle. In complex I, both Db18C6 molecules (a and b) have a “butterfly” conformation with approximate symmetry C _2v . Original Russian Text ? A.N. Chekhlov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 3, pp. 516–520.     

Synthesis of Bis(2,2-benzimidazolyl)dibenzo-18-crown-6

A method has been developed for the introduction of benzimidazole substituents into the dibenzo-18-crown-6 molecule by condensation of its 4′,4″(5″)-diacetyl derivative with ortho-phenylenediamine. Increasing the length of the hydrocarbon chain of the acyl substituent or replacing Ac by CSNH₂ led to a decrease in the yield of the desired product. No product was formed when Ac was replaced by COOH or CN. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, 1388–1390, September, 2005.     

Crystal Structure of Bis(dibenzo-18-crown-6)rubidium Triiodide

Crystalline bis(dibenzo-18-crown-6)rubidium triiodide complex [Rb(DB18C6)₂]⁺ · I₃ ^– (I) is synthesized and its structure is studied by X-ray diffraction analysis. The structure of I (space group Pnma, a = 23.854 Å, b = 23.612 Å, c = 7.863 Å, Z = 4) is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 against 3990 independent reflections (CAD4 automated diffractometer, MoK ). Structural units of crystal I are the I₃ ^– anions and [Rb(DB18C6)₂]⁺ cations. The crystal has the structure intermediate between that of a standard host–guest complex and a sandwich complex. In the structure of complex I, the crystallographic plane with symmetry m passes through the I₃ ^– anion (perpendicularly to its axis) and complex cation. The coordination polyhedron of the Rb⁺ cation is a strongly distorted hexagonal pyramid with the O atom of one crown ligand at the axial vertex and a base of six O atoms of another DB18C6 crown ligand.     

Synthesis and crystal structure of ammonium (picrate) (dibenzo-18-crown-6)

NH₄(Pic)(DB18C6) (Pic=picrate and DB18C6=dibenzo-18-crown-6), (C₂₆H₃₀N₄O₁₃) FW 606.56, arthorhombic,Pmn2₁,a=26.045(5),b=12.055(3),c=8.982(3) Å,V=2820(1) ų,Z=4,D _c =1.429 g/cm³, CuK, =1.54184 Å, (CuK)=9.5 cm^–1,F(000)=1272,T=298 K. The structure has been refined toR=0.0475 for 2617 unique observed reflections. In the lattice the 1:1 complex exists as a 2:2 dimer in which the crown are coupled through the Pic anions and NH₄ ⁺ cations. The asymmetric unit consists of two independent half crown ethers of which two opposite O atoms are on the mirror plane, two half ammonium cations of which the N and two H atoms are also on the mirror plane while the Pic anion is in a general position. Relative to each other, the corwn ethers are shifted by about 7.3 Å alongb and 1 Å alongc. The 1:1 sandwich of NH₄ with DB18C6 and Pic on dimerisation becomes a club pseudo-sandwich with three phenyl rings on either side of the mirror plane, thus forming a nearly parallel stack with a 3.6 Å inter-ring distance. The NH₄ ions hold the structure; two H atoms on the mirror plane are hydrogen-bonded to the opposite oxygens of the crown located on the purely aliphatic part of the ring (2.10(1), 2.06(3) and 2.26(3), 2.05(1) Å) for the two independent crowns, respectively, while the other two H atoms form mirror-related bifurcated hydrogen bonds with the phenoxide oxygen (1.99(1) and 2.01(1) Å) and theo-nitrogen oxygen (2.44(2) and 2.34(1) Å) of the picrates. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82037 (29 pages)     

Solvent extraction of uranium(VI) into toluene by dicyclohexano-18-crown-6 from mixed aqueous-organic solutions

Extraction behaviour of uranium(VI) from mixed organo-aqueous solutions containing water-miscible protic aliphatic alcohols and several aprotic solvents was investigated by using dicyclohexano-18-crown-6(DC18C6) as an extractant. The organic phase was a binary solution of DC18C6 and toluene while the polar phase was a three component solution of uranyl nitrate, polar additive and aqueous nitric acid. Methanol, ethanol, isobutanol, dioxane, acetone, propylene carbonate and acetonitrile were used as the organic components of the mixed (polar) phase. Propylene carbonate, acetone, acetonitrile and dioxane increased the extractability of U(VI), whereas alcoholic additives showed only an antagonistic effect. The relative increase in extraction was found to be more at lower nitric acid concentrations. Possible reasons for such behaviour are briefly discussed. Recovery of U(VI) from loaded organic phase was easily accomplished using dilute perchloric acid and sulphuric acid. A sample method was standardized for the separation of plutonium(IV) from uranium(VI) based on its reductive stripping.