Supramolecular assemblies of metal ions in complex bimetallic and trimetallic salts based on hexacyanoferrate(III) ion

Two complex heterometallic salts with formulae Tl-6[Fe(CN)(6)](1) (33)(NO3)(OH) (1) and [Co(bpy)(2)(CN)(2)](2){[Ag(CN)(2)](0) (5)[Fe(CN)(6)](0) (5)} 8H(2)O (2) have been synthesized and fully characterized Single crystal X-ray analyses reveal that compound 1 is comprised of discrete Tl+ cations and [Fe(CN)(6)](3-) anions together with OH- and NO3- anions Compound 2 contains [Co(bpy)(2)(CN)(2)](+) cations and {[Ag(CN)(2)][Fe(CN)(6)]}(-) anions together with eight molecules of water of crystallization Both structures form unprecedented three-dimensional supramolecular networks via non covalent interactions Another important observation is that the stereochemically active inert (lone) pair present on Tl+ plays little role in controlling the structure of 1 The water molecules in 2 play important roles in providing stability organizing a supramolecular network through hydrogen bonding In the syntheses of 1 and 2 Fe(II) is oxidized to Fe(III) and Co(II) to Co(III) respectively facilitating the formation of the salts that are obtained Both compounds exhibit photoluminescence emission in solution near the visible region.

Thermospheric Control of the Auroral Source of O+Ions for the Magnetosphere

Linear theory, model ion-density profiles and MSIS neutral thermospheric predictions are used to investigate the stability of the auroral, topside ionosphere to oxygen cyclotron waves: variations of the critical height, above which the plasma is unstable, with field-aligned current, thermal ion density and exospheric temperature are considered. In addition, probabilities are assessed that interactions with neutral atomic gases prevent O+ ions from escaping into the magnetosphere after they have been transversely accelerated by these waves. The two studies are combined to give a rough estimate of the total O+ escape flux as a function of the field-aligned current density for an assumed rise in the perpendicular ion temperature. Charge exchange with neutral oxygen, not hydrogen, is shown to be the principle limitation to the escape of O+ ions, which occurs when the waves are driven unstable down to low altitudes. It is found that the largest observed field-aligned current densities can heat a maximum of about 5×1014 O+ ions m−2 to a threshold above which they are subsequently able to escape into the magnetosphere in the following 500s. Averaged over this period, this would constitute a flux of 1012 m−2 s−1 and in steady-state the peak outflow would then be limited to about 1013 m−2 s−1 by frictional drag on thermal O+ at lower altitudes. Maximum escape is at low plasma density unless the O+ scale height is very large. The outflow decreases with decreasing field-aligned current density and, to a lesser extent, with increasing exospheric temperature. Upward flowing ion events are evaluated as a source of O+ ions for the magnetosphere and as an explanation of the observed solar cycle variation of ring current O+ abundance.

Erbium and Ytterbium Codoped Titanoniobophosphate Glasses for Ion-Exchange-Based Planar Waveguides

This work presents the optical properties of erbium-doped and erbium/ytterbium codoped Na(2)O-Al(2)O(3)-TiO(2)-Nb(2)O(5)-P(2)O(5) glass systems and also the characterization of planar waveguides obtained by typical thermally assisted Ag+<-> Na+ ion-exchange process. The glass systems allow the preparation of single mode and multimode planar waveguides presenting a strong and relatively broad emission at 1536 nm. The emission signal in the infrared region is intensified for silver-containing samples when compared with free-silver samples. The emission signal intensification may be attributed to a nonplasmonic energy transfer from silver species to Er3+ ions as no bands related to surface plasmon resonance (SPR) of silver nanoparticles were observed.

Removal of radionuclides from acid mine waters by retention on adsorbing materials

This study proposes a method for decontamination of acid drainage water from a uranium mine, as an alternative process to lime treatment. The research embodied the recovery of uranium with an ion-exchange resin, treatment of effluent resin with lime, or with inorganic adsorbents and biosorbents. The uranium decontamination level using the resin process was 94% and allowed the recovery of this element as a commercial product. Among the inorganic adsorbents studied, phosphogypsum was effective for Ra-226, Ra-228, and Pb-210 removal. Among the biosorbents, Sargassum sp.was superior in relation to its specific capacity to accumulate and remove Ra-226.

A new approach for determining stability constants of metal ion complexes in aquatic systems based on flow injection-ion exchange-flame atomic absorption spectrometry coupling

A method based an ion exchange(IE)-atomic absorption spectrometry(AAS) coupled by flow techniques, allowing the determination of formation constants of, at least, the first species of complex systems, in aqueous solution, was developed.The IE-AAS coupling reduces significantly the number of experimental steps in comparison with IE batch methods, resulting in an important increase in analytical rate. The method is simple both from experimental and computational points of view, making possible its utilization by workers without special expertise in the field of complex equilibria in solution. on the other hand, taking into account mainly the amount of hollow cathode lamps available to date, the developed procedure may be applied, within certain limitations, to the study of many systems whose features prevent the use of traditional approaches.

Er-doped silica-based waveguides prepared by different techniques: RF-sputtering, sol-gel and ion-exchange

Erbium-activated silica-based planar waveguides were prepared by three different technological routes: RF-sputtering, sol-gel and ion exchange. Various parameters of preparation were varied in order to optimize the waveguides for operation in the NIR region. Particular attention was devoted to the minimization of the losses and the increase of the luminescence efficiency of the metastable I-4(13/2) state of the Er3+ ion. Waveguide properties were determined by m-line spectroscopy and loss measurements. Waveguide Raman and luminescence spectroscopy were used to obtain information about the structure of the prepared films and about the dynamical processes related to the luminescence of the Er3+ ions.

Er3+-doped germanate glasses for active waveguides prepared by Ag+/K+ <-> Na+ ion-exchange

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interaction of mercury(II) with humic substances from the Rio Negro (Amazonas State, Brazil) by means of an ion exchange procedure

The aquatic humic substances (HS) investigated in this study with respect to their binding capability towards mercury(II) were isolated from the river Rio Negro, Amazonas State - Brazil, by means of the adsorbent XAD 8. Labile/inert fractions of inorganic Hg(II) complexes formed with these HS were characterized using an ion-exchange batch and column technique, respectively, based on Chelite S. This collector exhibits high Hg(II) distribution coefficients, Kd, up to the order of 104 decreasing, however, in the case of small Hg(II)/HS ratios (< 0.1 μg Hg(II) / mg HS). The influence of different complexation parameters (ratio of Hg(II)/HS, pH, contact time, complexing time) relevant for Hg(II) binding in aquatic environments was assessed. The Hg(II) lability in dissolved HS is mainly influenced by the mass ratio of Hg(II)/HS and the ageing of Hg(II)-HS species formed. This is particularly obvious in the case of low Hg(II) loading of HS where slow transformation processes of freshly formed Hg(II)-HS species significantly decrease their lability, leading to incomplete recoveries (< 20%) of the total Hg(II) bound to HS.

Minimization of lead and copper interferences on spectrophotometric determination of cadmium using electrolytic deposition and ion-exchange in multi-commutation flow system

A new strategy for minimization of Cu2+ and Pb2+ interferences on the spectrophotometric determination of Cd2+ by the Malachite green (MG)-iodide reaction using electrolytic deposition of interfering species and solid phase extraction of Cd2+ in flow system is proposed. The electrolytic cell comprises two coiled Pt electrodes concentrically assembled. When the sample solution is electrolyzed in a mixed solution containing 5% (v/v) HNO3, 0.1% (v/v) H2SO4 and 0.5 M NaCl, Cu2+ is deposited as Cu on the cathode, Pb2+ is deposited as PbO2 on the anode while Cd2+ is kept in solution. After electrolysis, the remaining solution passes through an AG1-X8 resin (chloride form) packed minicolumn in which Cd2+ is extracted as CdCl4/2-. Electrolyte compositions, flow rates, timing, applied current, and electrolysis time was investigated. With 60 s electrolysis time, 0.25 A applied current, Pb2+ and Cu2+ levels up to 50 and 250 mg 1-1, respectively, can be tolerated without interference. For 90 s resin loading time, a linear relationship between absorbance and analyte concentration in the 5.00-50.0 μg Cd 1-1 range (r2 = 0.9996) is obtained. A throughput of 20 samples per h is achieved, corresponding to about 0.7 mg MG and 500 mg KI and 5 ml sample consumed per determination. The detection limit is 0.23 μg Cd 1-1. The accuracy was checked for cadmium determination in standard reference materials, vegetables and tap water. Results were in agreement with certified values of standard reference materials and with those obtained by graphite furnace atomic absorption spectrometry at 95% confidence level. The R.S.D. for plant digests and water containing 13.0 μg Cd 1-1 was 3.85% (n = 12). The recoveries of analyte spikes added to the water and vegetable samples ranged from 94 to 104%. (C) 2000 Elsevier Science B.V.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Solid-phase extraction of metal ions from fuel ethanol with a nanostructured adsorbent

This work describes the synthesis and characterization of a new octakis[3-(2,2'-dipyridylamine)propyl]octasilsesquioxane (T8-Pr-DPA), and a study of the metal ion preconcentration in fuel ethanol. Batch and column experiments were conducted to investigate for the removal of heavy metal ions from fuel ethanol. The results showed that the Langmuir allowed to describe the sorption equilibrium data of the metal ions on T8-Pr-DPA in a satisfactory way. The following maximum adsorption capacities (in mmolg-1) were determined: 3.62 for Fe (III), 3.32 for Cr (III), 2.15 for Cu (II), 1.80 for Co (II), 1.62 for Pb (II), 1.32 for Ni (II) and 0.88 for Zn (II). The thermodynamic parameters for the adsorption process such as free energy of adsorption (δG), enthalpy of adsorption (δH) and entropy of adsorption (δS) were calculated. Thermodynamic parameters showed that the system has favorable enthalpic, Gibbs free energy, and entropic values. The sorption-desorption of the metal ions has made possible the development of a preconcentration and determination method of metal ions at trace level in fuel ethanol. The method of quantitative analysis for Fe, Cu, Ni and Zn in fuel ethanol by Flame AAS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, limit of detection, limit of quantification, and the relative standard deviation and accuracy. The accuracy of the method was assessed by testing analyte recovery in the fuel ethanol samples. © 2013 Elsevier B.V.

Quantum exchange interaction of spherically symmetric plasmoids

We study nano-sized spherically symmetric plasma structures which are radial nonlinear oscillations of electrons in plasma. The effective interaction of these plasmoids via quantum exchange forces between ions is described. We calculate the energy of this interaction for the case of a dense plasma. The conditions when the exchange interaction is attractive are examined and it is shown that separate plasmoids can form a single object. The application of our results to the theoretical description of stable atmospheric plasma structures is considered. (C) 2012 Elsevier Ltd. All rights reserved.

Removal of Pb2+ from aqueous solutions using two Brazilian rocks containing zeolites

The removal of Pb2+ from aqueous solution by two Brazilian rocks that contain zeolites-amygdaloidal dacite (ZD) and sandstone (ZS)-was examined by batch experiments. ZD contains mordenite and ZS, stilbite. The effects of contact time, concentration of metal in solution and capacity of Na+ to recover the adsorbed metals were evaluated at room temperature (20A degrees C). The sorption equilibrium was reached in the 30 min of agitation time. Both materials removed 100% of Pb2+ from solutions at concentrations up to 50 mg/L, and at concentrations larger than 100 mg/L of Pb2+, the adsorption capacity of sandstone was more efficient than that of amygdaloidal dacite due to the larger quantities and the type of zeolites (stilbite) in the cement of this rock. All adsorbed Pb2+ was easily replaced by Na+ in both samples. The analysis of the adsorption models using nonlinear regression revealed that the Sips and the Freundlich isotherms provided the best fit for the ZS and ZD experimental data, respectively, indicating the heterogeneous adsorption surfaces of these zeolites.

Styrene Based Ion Exchange Resins with Oxine Functionalized Groups

Oxine ligands placed on styrene base ion exchange resins selectively remove iron and gallium from acidic solutions. After loading, the oxine resin is stripped of the loaded metals and used again for further metal removal. The resins can be used for process streams, acid rock drainages, or any other iron or gallium containing solution.