On the Potential of a Poly(vinylidenefluoride-co-hexafluoropropylene) Polymer Inclusion Membrane Containing Aliquat® 336 and Dibutyl Phthalate for V(V) Extraction from Sulfate Solutions.

A polymer inclusion membrane (PIM) composed of 50 wt% base polymer poly(vinylidenefluoride-co-hexafluoropropylene), 40 wt% extractant Aliquat® 336, and 10 wt% dibutyl phthalate as plasticizer/modifier provided the efficient extraction of vanadium(V) (initial concentration 50 mg L-1) from 0.1 M sulfate solutions (pH 2.5). The average mass and thickness of the PIMs (diameter 3.5 cm) were 0.057 g and 46 µm, respectively. It was suggested that V(V) was extracted as VO2SO4- via an anion exchange mechanism. The maximum PIM capacity was estimated to be ~56 mg of V(V)/g for the PIM. Quantitative back-extraction was achieved with a 50 mL solution of 6 M H2SO4/1 v/v% of H2O2. It was assumed that the back-extraction process involved the oxidation of VO2+ to VO(O2)+ by H2O2. The newly developed PIM, with the optimized composition mentioned above, exhibited an excellent selectivity for V(V) in the presence of metallic species present in digests of spent alumina hydrodesulfurization catalysts. Co-extraction of Mo(VI) with V(V) was eliminated by its selective extraction at pH 1.1. Characterization of the optimized PIM was performed by contact angle measurements, atomic-force microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis/derivatives thermogravimetric analysis and stress-strain measurements. Replacement of dibutyl phthalate with 2-nitrophenyloctyl ether improved the stability of the studied PIMs.

Multivariate Optimization of a Functionalized SBA-15 Mesoporous Based Solid-Phase Extraction for U(VI) Determination in Water Samples.

A solid-phase extraction based on a functionalized SBA-15, with the Schiff base ligand, ethylenediaminepropylesalicylaldimine (SBA/EnSA), was developed for the recovery and preconcentration of trace amounts of uranium(VI) in water samples, prior to its determination spectrophotometrically using ArsenazoIII. For optimizing the parameters affecting the adsorption step (pH, adsorbent dose and adsorption time) and those influencing the desorption process (concentration and volume of eluent and desorption time), a statistical technique response surface methodology (RSM) was employed. The limit of detection and the linear dynamic range for the proposed method were 10 µg L-1, and 33.5 - 500 µg L-1, respectively. The adsorbent showed a high capacity (110.2 mg g-1) and the method allowed obtaining a preconcentration factor of 67. The inter- and intra-day relative standard deviations for a solution of 100 µg L-1 (n = 5) were found to be 4.8 - 6.2%. The developed method was successfully applied for the determination of U(VI) in water samples.

Removal of uranium(VI) ions from aqueous solutions using Schiff base functionalized SBA-15 mesoporous silica materials.

Functionalized SBA-15 mesoporous silica particles, bearing N-propylsalicylaldimine and ethylenediaminepropylesalicylaldimine Schiff base ligands, abbreviated as SBA/SA and SBA/EnSA respectively, were prepared and characterized by FT-IR, elemental analysis, TGA, XRD, TEM and SEM techniques. The potentials of these adsorbents were examined by using them in solid phase extraction of U(VI) ions from water samples. It is shown that 20 mg of SBA/SA or SBA/EnSA can remove rapidly (∼15 min) and quantitatively uranium(VI) ions from 10 to 200 mL of water solutions (pH 4) containing 0.2 mg of the ions, at 25 °C. The adsorbed ions were stripped by 1 mL of dilute nitric acid solution (0.1 mol L(-1)). It means that the studied adsorbents are able to be used for removal and concentration of uranyl ions. This allowed achieving to a concentration factor of 200 for uranyl ions. The variation in the ionic strength in the range 0-1 mol L(-1) did not affect the extraction efficiencies of the adsorbents. The adsorbents showed selective separation of uranyl ions from Cd(2+), Co(2+), Ni(2+), Mn(2+), Cr(3+), Ba(2+), Fe(3+) and Eu(3+) ions. Thermodynamic investigations revealed that the adsorption of uranyl ions by the adsorbents was spontaneous and endothermic. The Langmuir model described suitably the adsorption isotherms. This model determined the maximum adsorption capacity of the adsorbents SBA/SA and SBA/EnSA as 54 and 105.3 mg uranyl/g adsorbent, respectively. The kinetics of the processes was interpreted by using Pseudo-second-order model.

Tetra-methyl-ammonium hydrogen terephthalate.

The asymmetric unit of the title salt, C(4)H(12)N(+)·C(8)H(5)O(4) (-), contains one half of a tetra-methyl-ammonium cation and one half of a hydrogen terephthalate monoanion. The N atom of the ammonium cation lies on a twofold rotation axis and the centre of mass of the terephthalate anion is on a centre of inversion. In the crystal, the centrosymmetric terephthalate ions are linked by a very short symmetric O-H⋯O hydrogen bond [O⋯O = 2.4610 (19) Å] into a one-dimensional polymeric chain along [1-12]. The tetra-methyl-ammonium cations and terephthalate anions are then connected through a pair of bifurcated acceptor C-H⋯O hydrogen bonds, generating a three-dimensional supra-molecular network. The carboxyl-ate groups at both ends of the terephthalate anion are charge-shared with an equal probability of 0.5.