Aplicação de Zr/Ti-PILC no processo de adsorção de Cu(II), Co(II) e Ni(II) utilizando modelos físico-químicos de adsorção e termodinâmica do processo

The aim of this investigation is to study how Zr/Ti-PILC adsorbs metals. The physico-chemical proprieties of Zr/Ti-PILC have been optimized with pillarization processes and Cu(II), Ni(II) and Co(II) adsorption from aqueous solution has been carried out, with maximum adsorption values of 8.85, 8.30 and 7.78 x10^-1 mmol g^-1, respectively. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data with a linear regression process. The energetic effect caused by metal interaction was determined through calorimetric titration at the solid-liquid interface and gave a net thermal effect that enabled the calculation of the exothermic values and the equilibrium constant.

Obtenção e caracterização de carvão ativado de caroço de buriti (Mauritia flexuosa L. f.) para a avaliação do processo de adsorção de cobre (II)

Na região amazônica, algumas indústrias despejam cobre nos corpos receptores que, em elevadas concentrações, é tóxico para os seres vivos. A remoção de cobre de efluentes industriais é realizada por diversos processos como a adsorção. Neste trabalho mostrou-se o resultado da adsorção de cobre (II) em carvão ativado de caroço de buriti carbonizado a 400 °C e ativado a 900 °C. O carvão ativado foi caracterizado em termos de área específica, tamanho dos poros, densidades aparente e real, porosidade, microscopia eletrônica de varredura, conteúdo de cinzas, pH, umidade, carbono fixo e grupos funcionais de superfície. O estudo de equilíbrio de adsorção avaliou a influência do diâmetro das partículas do carvão, do tempo de contato adsorvente/adsorbato, do pH e da concentração inicial da solução de cobre (II) sobre a remoção de cobre (II). Com base nos resultados, concluiu-se que há uma maior eficiência de remoção de cobre (II) para diâmetro < 0,595 mm, tempo de contato de 300 minutos, pH 4,0 e concentrações iniciais de cobre (II) de 50 e 80 mg L^-1. O modelo matemático de Langmuir foi o que melhor se ajustou aos dados de equilíbrio de adsorção. A partir do tempo de contato de 15 minutos todas as concentrações de equilíbrio ficaram abaixo do máximo permitido de 1,0 mg L^-1 previsto pela legislação vigente para lançamento de efluentes em corpos receptores.

Metal biosorption onto dry biomass of Arthrospira (Spirulina) platensis and Chlorella vulgaris: Multi-metal systems

Binary and ternary systems of Ni2+, Zn2+, and Pb2+ were investigated at initial metal concentrations of 0.5, 1.0 and 2.0 mM as competitive adsorbates using Arthrospira platensis and Chlorella vulgaris as biosorbents. The experimental results were evaluated in terms of equilibrium sorption capacity and metal removal efficiency and fitted to the multi-component Langmuir and Freundlich isotherms. The pseudo second order model of Ho and McKay described well the adsorption kinetics, and the FT-IR spectroscopy confirmed metal binding to both biomasses. Ni2+ and Zn2+ interference on Pb2+ sorption was lower than the contrary, likely due to biosorbent preference to Pb. In general, the higher the total initial metal concentration, the lower the adsorption capacity. The results of this study demonstrated that dry biomass of C. vulgaris behaved as better biosorbent than A. platensis and suggest its use as an effective alternative sorbent for metal removal from wastewater. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis, characterization and X-ray crystal structures of dinuclear nickel(II) complexes of a novel potentially hexadentate but functionally tetradentate binucleating ligand

A binucleating potentially hexadentate chelating agent containing oxygen, nitrogen and sulfur as potential donor atoms (H2ONNO) has been synthesized by condensing alpha,alpha-xylenebis(N-methyldithiocarbazate) with 2,4-pentanedione. An X-ray crystallographic structure determination shows that the Schiff base remains in its ketoimine tautomeric form with the protons attached to the imine nitrogen atoms. The reaction of the Schiff base with nickel(II) acetate in a 1:1 stoichiometry leads to the formation of a dinuclear nickel(II) complex [Ni(ONNO)](2) (ONNO2- = dianionic form of the Schiff base) containing N,O-chelated tetradentate ligands, the sulfur donors remaining uncoordinated. A single crystal X-ray structure determination of this dimer reveals that each ligand binds two low spin nickel(II) ions, bridged by a xylyl group. The nickel(II) atoms adopt a distorted square-planar geometry in a trans-N2O2 donor environment. Reaction of the Schiff base with nickel(II) acetate in the presence of excess pyridine leads to the formation of a similar dinuclear complex, [Ni(ONNO)(py)](2), but in this case comprises five coordinate high-spin Ni(II) ions with pyridine ligands occupying the axial coordination sites as revealed by X-ray crystallographic analysis. (c) 2005 Published by Elsevier B.V.

Synthetic, EPR spectroscopic, magnetic and X-ray crystallographic structural studies on copper(II) complexes of the tridentate N2S donor ligand formed from 6-methyl-2-formylpyridine and S-methyldithiocarbazate (Hmpsme)

New copper(II) complexes of general empirical formula, Cu(mpsme)X center dot xCH(3)COCH(3) (mpsme = anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate; X = Cl, N-3, NCS, NO3; x = 0, 0.5) have been synthesized and characterized by IR, electronic, EPR and susceptibility measurements. Room temperature mu(eff) values for the complexes are in the range 1.75-2.1 mu(beta) typical of uncoupled or weakly coupled Cu(II) centres. The EPR spectra of the [Cu(mpsme)X] (X = Cl, N-3, NO3, NCS) complexes reveal a tetragonally distorted coordination sphere around the mononuclear Cu(II) centre. We have exploited second derivative EPR spectra in conjunction with Fourier filtering (sine bell and Hamming functions) to extract all of the nitrogen hyperfine coupling matrices. While the X-ray crystallography of [Cu(mpsme)NCS] reveals a linear polymer in which the thiocyanate anion bridges the two copper(II) ions, the EPR spectra in solution are typical of a magnetically isolated monomeric Cu(II) centres indicating dissociation of the polymeric chain in solution. The structures of the free ligand, Hmpsme and the {[Cu(mpsme)NO3] center dot 0.5CH(3)COCH(3)}(2) and [Cu(mpsme)NCS](n) complexes have been determined by X-ray diffraction. The {[Cu(mpsme)NO3]0.5CH(3)COCH(3)}(2) complex is a centrosymmetric dimer in which each copper atom adopts a five-coordinate distorted square-pyramidal geometry with an N2OS2 coordination environment, the Schiff base coordinating as a uninegatively charged tridentate ligand chelating through the pyridine and azomethine nitrogen atoms and the thiolate, an oxygen atom of a unidentate nitrato ligand and a bridging sulfur atom from the second ligand completing the coordination sphere. The [Cu(mpsme)(NCS)](n) complex has a novel staircase-like one dimensional polymeric structure in which the NCS- ligands bridge two adjacent copper(II) ions asymmetrically in an end-to-end fashion providing its nitrogen atom to one copper and the sulfur atom to the other. (c) 2005 Elsevier B.V. All rights reserved.

Ligational behaviour of (E)-2-amino-N ` -1-(2-hydroxyphenyl) ethylidene]benzohydrazide towards later 3d metal ions: X-ray crystal structure of nickel(IV) complex

Ligational behaviour of (E)-2-amino-N'-1-(2-hydroxyphenyl)ethylidene]benzohydrazide (Aheb) towards later 3d metal ionscopper(II), cobalt(II), manganese(II), zinc(II), cadmium(II) and nickel(IV)] has been studied. Their structures have been elucidated on the basis of spectral (IR, H-1 NMR, UV-Vis, EPR and FAB-mass), elemental analyses, conductance measurements, magnetic moments, and thermal studies. During complexation Ni(II) ion has got oxidized to Ni(IV). The changes in the bond parameters of the ligand on complexation has been discussed by comparing the crystal structure of the ligand with that of its Ni(IV) complex. The X-ray single crystal analysis of Ni(aheb)(2)]Cl-2 center dot 4H(2)O has confirmed an octahedral geometry around the metal ion. EPR spectra of the Cu(II) complex in polycrystalline state at room (300 K) and liquid nitrogen temperature (77 K) were recorded and their salient features are reported. (C) 2014 Elsevier B.V. All rights reserved.

Topological Diversity of Coordination Polymers Containing the Rigid Terephthalate and a Flexible N,N'-Type Ligand: Interpenetration, Polyrotaxane, and Polythreading

Reactions of zinc(II) or cadmium(II) salts with terephthalic acid (H(2)tp) and 1,3-bis(4-pyridyl) propane (bpp) have afforded four coordination polymers at room temperature, [Zn(mu-tp)(mu-bpp)](n)center dot 2nH(2)O (1), [Cd-2(mu-tp)(2)(mu-bpp)(3)](n)center dot 2nH(2)O (2), [Cd(mu-tp)(mu-bpp)(H2O)](n)center dot nH(2)O (3), and [Cd-2(mu-tp)(mu-bpp)(2)(bpp)(2)Br-2](n) (4). Single-crystal X-ray diffraction has revealed interesting topological features for these compounds.

Luminescent supramolecular polymers: Cd2+-directed polymerization and properties

A family of supramolecular polymers was prepared via Cd2+-directed self-assembly polymerization of his (2,2':6',2 ''-terpyridine)-based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV-visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434-442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nn in DMAc solution. Complexation polymerization of bis(2,2':6',2 ''-terpyridine)-based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38-0.54. Single-layer light-emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8-11 V.

Structure characterization and physical properties of a complex with supramolecular architectures Co-2(2,6-DPC2Co(H2O)5 center dot 2H(2)O (DPC=2,6-pyridinedicarboxylate)

Reaction of 2,6-pyridinedicarboxylic with CoCl2 . 6H(2)O in aqueous solution give rise to a three-dimensional Complex CO2(2,6-DPC)(2)Co(H2O)(5).2H(2)O (DPC = 2,6-pyridinedicarboxylate) 1. It has been characterized by elemental analyses, infrared spectra (IR) spectrum, thermogravimetric (TG) analysis, EPR spectrum, and single crystal X-ray diffraction. The complex crystallizes in the P2(1)/c space group with a = 8.3906(3) Angstrom, b = 27.4005(8) Angstrom, c = 9.6192(4) A, alpha = 90.00degrees, beta = 98.327(2)degrees, gamma = 90.00degrees, V = 2188.20(14) Angstrom(3), Z = 4. There are two types of cobalt environments: Co(1) is coordinated by four oxygen atoms from four carboxyl groups and two nitrogen 2 atoms which are all from pdc(2). Co(2) is coordinated by six oxygen atoms, five from coordinated water molecules and one from a carboxyl of pdc(2) - of which the other oxygen atom is linked to the Co(1). The extensive intermolecular hydrogen bonds are formed in the crystal by means of the five coordinated water molecules.

Investigation on the corrosion inhibitive effect of 2H-pyrazole-triazole derivatives in acidic solution

Four research methods, such as weight loss test, electrochemical techniques, adsorption isotherm, and quantum chemical calculation, were employed in this paper to study the inhibition efficiency (IE) and inhibition mechanism of three 2H-pyrazole-triazole derivatives, BHOT, FHOT, and CHOT in 1 M HCl solution for mild steel. Using the electrochemical technique, three inhibitors were proved to show a mixed-type character for mild steel by suppressing both anodic and cathodic reactions on the steel surface. The adsorption models of three compounds were established at different temperatures according to their adsorption isotherms. The results of the quantum chemical calculation method indicated that the adsorption sites of 2H-pyrazole-triazole derivatives were strongly centralized on benzene ring, triazole ring, or other substituents. All the results showed that the three derivatives were excellent inhibitors in I M HCl solution for mild steel.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

Comparison of AGNES (absence of gradients and Nernstian equilibrium stripping) and SSCP (scanned stripping chronopotentiometry) for trace metal speciation analysis

The free metal ion concentrations obtained by SSCP (stripping chronopotentiometry at scanned deposition potential) and by AGNES (absence of gradients and Nernstian equilibrium stripping) techniques have been compared and the usefulness of the combination of both techniques in the same electrochemical cell for trace metal speciation analysis is assessed. The free metal ion concentrations and the stability constants obtained for lead(II) and cadmium(II) complexation by pyridinedicarboxylic acid, by 40 nm radius carboxylated latex nanospheres and by a humic acid extracted from an ombrotrophic peat bog were determined. Whenever possible, the free metal ion concentrations were compared with the theoretical predictions of the code MEDUSA and with the free metal ion concentrations estimated from ion selective electrodes (ISE). SSCP values were in agreement with the ones obtained by AGNES, and both of them agreed reasonably with the ISE values and the theoretical predictions. For the lead(II)-humic acid, it was not possible to obtain the stability constants by SSCP due to the heterogeneity effect. However, using AGNES it is possible to obtain, for these heterogeneous systems, the free bulk metal concentration, which allows us to retrieve the stability constant at bulk conditions.

Arsenic and germanium determination by hydride generation in the D.C. plasma optical emission spectrometer

Modifications to the commercial hydride generator, manufactured by Spectrametrics, resulted in improved operating procedure and enhancement of the arsenic and germanium signals. Experiments with arsenic(III) and arsenic(V) showed that identical reiults could be produced from both oxidation states. However, since arsenic(V) is reduced more slowly than arsenic(III), peak areas and not peak heights must be measured when the arsine is immediately stripped from the system (approximately 5 seconds reaction). When the reduction is allowed to proceed for 20 seconds before the arsine is stripped, peak heights may be used. For a 200 ng/mL solution, the relative standard deviation is 2.8% for As(III) and 3.8% for As(V). The detection limit for arsenic using the modified system is 0.50 ng/mL. Studies performed on As(V) standards show that the interferences from 1000 mg/L of nickel(II), cobalt(II), iron(III), copper(II), cadmium(II), and zinc(II) can be eliminated with the aid of 5 M Hel and 3% L-cystine. Conditions for the reduction of germanium to the corresponding hydride were investigated. The effect of different concentrations of HCl on the reduction of germanium to the covalent hydride in aqueous media by means of NaBH 4 solutions was assessed. Results show that the best response is accomplished at a pH of 1.7. The use of buffer solutions was similarly characterized. In both cases, results showed that the element is best reduced when the final pH of the solution after reaction is almost neutral. In addition, a more sensitive method, which includes the use of (NH4)2S208' has been developed. A 20% increase in the germanium signal is registered when compared to the signal achieved with Hel alone. Moreover, under these conditions, reduction of germanium could be accomplished, even when the solution's pH is neutral. For a 100 ng/mL germanium standard the rsd is 3%. The detection limit for germanium in 0.05 M Hel medium (pH 1.7) is 0.10 ng/mL and 0.09 ng/mL when ammonium persulphate is used in conjunction with Hel. Interferences from 1000 mg/L of iron(III), copper(II), cobalt(II), nickel(II), cadmium(II), lead(II), mercury(II), aluminum(III), tin(IV), arsenic(III), arsenic(V) and zinc(II) were studied and characterized. In this regard, the use of (NH4)ZS20S and Hel at a pH of 1.7 proved to be a successful mixture in the sbppression of the interferences caused by iron, copper, aluminum, tin, lead, and arsenic. The method was applied to the determination of germanium in cherts and iron ores. In addition, experiments with tin(IV) showed that a 15% increase in the tin signal can be accomplished in the presence of 1 mL of (NH4)2S20S 10% (m/V).

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.