Complexation and ion removal studies of a polystyrene anchored Schiff base

This paper reports the synthesis of a series of six new polystyrene anchored metal complexes of Co(II), Fe(III), Ni(II), Cu(II), Zn(II), and dioxouanium(VI) using the polystyrene anchored Schiff base of 2-nitrobenzaldehyde and the corresponding metal salts. The metal salts used were anhydrous FeCl3, CoCl2 Æ 6H2O, Ni(CH3COO)2 Æ 4H2O, Cu(CH3- COO)2 Æ H2O, Zn(CH3COO)2 Æ 2H2O, and UO2(CH3COO) Æ 2H2O. Physico chemical characterizations have been made from diffuse reflectance and vibrational spectra, elemental analysis, magnetic measurements, and TG studies. The elemental analysis suggest a 1:2 metal:ligand ratio when the complexation has carried out at 70 C for about 12 h reflux. The ligand is monodentate and coordinates through the azomethine nitrogen. The Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic whereas Zn(II) and U(VI) are diamagnetic. Zn(II) is assigned a tetrahedral structure, Cu(II) and Co(II) are assigned a square planar structure and Fe(III), Ni(II), and U(VI) are all assigned an octahedral structure. The polystyrene anchored ligand has been developed as an excellent reagent for the removal of Cu(II). Optimum conditions have been developed for the removal of metal ion from solutions by studying the effect of change of concentration of metal ion, ligand, effect of pH, time of reflux, and interference effect of other ions. It was found that within a span of 20 min it is possible to remove 90% of the metal ion from a 30 ppm metal ion solution in the pH range 4–5.5.

Synthesis,characterization and application studies of some polymer supported metal complexes

Polymer supports are efficient reagents,substrates and catalysts and they are extensively used for carrying out reactions at controlled rates.Tailor-made polymer supports are highly versatile which have opened an excellent area of research.Now polymer supported chemistry is being exploited at an amazing rate and it seems to join the routine world of organic synthesis.Polymer supported ligands are found to be efficient complexing agents whose high selectivity enables the analysis and removal of heavy metal ions which are toxic to all the living organisms of land and sea.polymer supported membranes function as ion selective potentiometric sensors which allow the exchange of specific ions among other ions of the same charge.In this investigation three series of polymeric schiff bases and three series of metal complexes have been prepared.An attempt is done to develop optimum conditions for the removal of heavy metal ions using polymeric schiff bases.A novel copper sensor electrode have also been prepared from polymer supported metal complex.

Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)

The research work which was carried out to Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)Estuaries are considered as sink or source for terrestrial and various anthropogenically generated materials. These include naturally occurring elements Al, Si, Fe or trace inorganics or industrial pollutants of different types. There have been reports on both positive and negative impacts by the introduction of above materials into the ecosystem.This thesis deals with the trace metal Aluminium (Al) whose average concentration (about 8%) in the earths crust is surpassed only by that of Oxygen and Silicon. There can be no doubt that most of the land derived materials reaches the ocean through rivers via estuaries. An important aspect noticed here is that the concentration of dissolved Al is much lower in sea water than in river water.On critically analysing Cochin estuary, for the entire cycles, covering monsoon, postmonsoon and premonsoon, the following salient features are documented as hereunder. Dissolved Al exhibits high and variable trends in Cochin estuary, the influencing parameters being salinity, SPM, pH and dissolved Si. A general profile showed removal in upper/mid estuary followed by regeneration in the mid/lower estuary and further decrease seawards in the southern/northem arms.Distribution appears to be a function of freshwater input, the monsoon season exhibiting very high concentrations throughout the estuary. As the river discharge decreased with the progress of seasons, dissolved Al concentration also decreased, the metal limiting itself to the upper and mid estuary.

Synthesis, Characterization and Application Studies of Some Polymer Supported Metal Complexes

Polymer supports and polymeric complexes are highly versatile and they are successfully employed as efficient reagents, substrates and catalysts. Recently there observed a growing interest in the synthesis of tailor-made polymer supports and functionalized polymers for the preparation of metal complexes for various applications. They have the combination of properties due to the macromolecular structure as well as due to the reactivity of the functional group. An interesting feature of functional polymers is their affinity towards metal ions. Therefore the synthesis, characterization and application of such polymeric complexes have great scientific and analytical importance. In this investigation three series of polymeric complexes of transition metal ions are prepared from three schiff bases. All the complexes and polymeric schiff bases were characterized by analytical, spectral and thermal methods The thesis consist of six chapters. The first chapter contains an introduction and a brief review on application of polymer supports, polymer supported ligands and complexes. The second chapter gives the details of reagents and instruments used and the procedure adopted for the preparation of ligands and complexes. The third chapter explains the methods employed for characterization and the results are also discussed. The fourth chapter gives a detailed study of metal ion removal using ligands whereas the fifth chapter describes the development of the Cu” ion sensor electrode. The sixth chapter is the summary of the thesis and references are presented at the end.

Valorisation of industrial wastes for the removal of metals and arsenic from aqueous effluents

En la presente tesis se han realizado estudios de eliminación de metales pesados y arsénico de aguas contaminadas mediante procesos de adsorción sobre materiales de bajo coste. Dichos materiales son, en todos los casos, subproductos de industrias agroalimentarias o metalúrgicas.La tesis consta de diferentes capítulos enmarcados en tres secciones: (i) Eliminación de cromo hexavalente y trivalente (ii) Eliminación de cationes divalentes de metales pesados en presencia de complejantes y en mezclas multimetálicas y (iii) Eliminación de arsénico utilizando un subproducto de la industria de cromados metálicos como adsorbente. Los resultados obtenidos ponen de manifiesto que ciertos residuos industriales pueden ser utilizados como adsorbentes en la detoxificación de efluentes contaminados con metales pesados. La tecnología propuesta representa una alternativa sostenible y de bajo coste frente a los tratamientos actuales más costosos y dependientes, en muchas ocasiones, de productos derivados del petróleo.

Peroxydisulfate in MCM-48 silicas: powerful and clean materials for the removal of toxic gases

Sodium persulfate introduced into ordered MCM-48 silicas is described. The resulting materials are compared with existing activated carbon-based systems and MCM-48 containing transition metals such as Cu(II) and Cr(VI) for the decomposition of hydrogen cyanide and cyanogen. MCM-48 materials containing sodium persulfate alone improve on the protection offered by benchmark activated carbon systems and MCM-48 materials containing Cu(II) and Cr(VI), without the health risks associated with these metal ions.

Deprotection, tethering, and activation of a catalytically active metalloporphyrin to a chemically active metal surface: [SAc](4)P-Mn(III)Cl on Ag(100)

The adsorption and subsequent thermal chemistry of the acetyl-protected manganese porphyrin, [SA(C)](4)P-Mn(III)Cl on Ag(100) have been studied by high resolution XPS and temperature-programmed desorption. The deprotection event, leading to formation of the covalently bound thioporphyrin, has been characterized and the conditions necessary for removal of the axial chlorine ligand have been determined, thus establishing a methodology for creating tethered activated species that could serve as catalytic sites for delicate oxidation reactions. Surface-mediated acetyl deprotection occurs at 298 K, at which temperature porphyrin diffusion is limited. At temperatures above similar to 425 K porphyrin desorption, diffusion and deprotection occur and at >470 K the axial chlorine is removed.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Development of a heavy metal sorption system through the P=S functionalization of coconut (Cocos nucifera) fibers

Lignocellulosic residues are interesting materials for the production of heavy metal adsorbents for aquatic systems. Whole fibers taken from coconut (Cocos nucifera) husks were functionalized with the thiophosphoryl (P=S) group by means of the direct reaction with CI(3)P=S, (CH(3)O)(2)CIP=S or (CH(3)CH(2)O)(2)CIP=S in order to obtain an adsorptive system for `soft` metal ions, particularly Cd(2+). These functionalized fibers (FFs) were characterized by means of elemental analysis, infrared spectroscopy, thermal analysis and acid-base titration. Adsorption isotherms for Cd(2+) fitted the Langmuir model, with binding capacities of 0.2-5 mmol g(-1) of FF at 25 degrees C. (C) 2009 Elsevier Ltd. All rights reserved.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

Characterization of Post-Consumer PET after Removal of the Original Surface: Influence of Raw Material

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, characterization, and application of modified silica in the removal and preconcentration of lead ions from natural river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dependence of divalent metal ions on phosphotransferase activity of osseous plate alkaline phosphatase

Kinetic evidence for the role of divalent metal ions in the phosphotransferase activity of polidocanol-solubilized alkaline phosphatase from osseous plate is reported. Ethylenediamine tetreacetate, 1,10-phenanthrolin, and Chelex-100 were used to prepare metal-depleted alkaline phosphatase. Except for Chelex-100, either irreversible inactivation of the enzyme or incomplete removal of metal ions occurred. After Chelex-100 treatment, full hydrolase activity of alkaline phosphatase was recovered upon addition of metal ions. on the other hand, only 20% of transferase activity was restored with 0.1 mu M ZnCl2, in the presence of 1.0 M diethanolamine as phosphate acceptor. In the presence of 0.1 mM MgCl2, the recovery of transferase activity increased to 63%. Independently of the phosphate acceptor used, the transferase activity of the metal-depleted alkaline phosphatase was fully restored by 8 mu M ZnCl2 plus 5 mM MgCl2. In the presence of diethanolamine as phosphate acceptor, manganese, cobalt, and calcium ions did nor stimulate the transferase activity. However, manganese and cobalt-enzyme catalyzed the transfer of phosphate to glycerol and glucose. (C) 1997 Elsevier B.V.

An evaluation into the potential of biological processing for the removal of metals from sewage sludges

The use of sewage sludge in agricultural land as a means of sludge disposal and recycling has been shown to be economical and suitable because of the presence of nutrients such as nitrogen and phosphorus. However, municipal sludges often contain high quantities of toxic metals and other compounds that must be removed for its safe use in agricultural soils. The biological leaching of metals from sewage sludges has been shown to be a promising technique for metal detoxifying in such complex matrix. The process efficiency is dependent on several physico-chemical parameters, such as total solids concentration, metal forms, pH-ORP, and temperature. Scale-up of the process has not yet been defined and is still pursuing the correct operational design. Current research involving the bioleaching of metals from sewage sludge and its application to land, which affects soil physical properties, are presented and discussed.

Incorporation of dithiooxamide as a complexing agent into cellulose for the removal and pre-concentration of Cu(II) and Cd(II) ions from natural water samples

The present study describes the incorporation of a complexing agent, dithiooxamide, into microcrystalline cellulose for use in the pre-concentration of Cu(II) and Cd(II) ions from aqueous samples. The FTIR spectrum of the adsorbent exhibited an absorption band in the region of 800 cm-1, which confirmed the binding of the silylating agent to the matrix. Elemental analysis indicated the amount of 0.150 mmol g-1 of the complexing agent. The adsorption data were fit to the modified Langmuir equation, and the maximum amount of metal species extracted from the solution, Ns, was determined to be 0.058 and 0.072 mmol g-1 for Cu(II) and Cd(II), respectively. The covering fraction φ, which was 0.39 and 0.48 for Cu(II) and Cd(II), respectively, was used to estimate a 1:2 (metal:ligand) ratio in the formed complex, and a binding model was proposed based on this information. The adsorbent was applied in the pre-concentration of natural water samples and exhibited an enrichment factor of approximately 50-fold for the species studied, which enabled its use in the analysis of trace metals in aqueous samples. The system was validated by the analysis of certified standard (1643e), and the adsorbent was stable for more than 20 cycles, thus enabling its safe reutilization. © 2012 Elsevier B.V. All rights reserved.