Metal carbonyls with zinciron bond: synthesis and vibrational spectra

The compounds of the type LZnFe(CO)4 (L = dien, trien, tn, s-diMeen, Meen) not yet reported and (NH3)3ZnFe(CO)4, already known, were prepared and studied by IR and Raman spectroscopy. The data obtained suggest that LZnFe(CO)4, for L = (NH3)3, dien and trien are monomers with a bipyramidal trigonal configuration around the iron atom, while for L = tn, s-diMeen and Meen the complexes are probably polymers having a center of symmetry with iron atoms octahedrally co-ordinated. © 1979.

Studies on double selenates. I. Thermal decomposition of lanthanum and alkali metal double selenates

Thermogravimetry, differential thermal analysis and other methods of analysis have been used to study the decomposition of hydrated lanthanum and alkali metal double selenates up to 1300°C. The results showed slight variations in the initial temperature of the various intermediate decomposition stages of the double selenates, as compared with the initial temperature of the corresponding decomposition of the simple selenates. The results also permitted the suggestion of mechanisms of thermal decomposition of these compounds. © 1980.

Optical transition probabilities and compositional dependence of Judd-Ofelt parameters of Er3+ ions in fluoroindate glass

Fluoroindate glasses containing 1, 2, 3, and 4 mol% ErF3 were prepared in a dry box under an argon atmosphere. Absorption spectra of these glasses at room temperature were obtained. The Judd-Ofelt parameters Ωλ (λ = 2, 4, 6) for f-f transitions of Er3+ ions as well as transition probabilities, branching ratios, radiative lifetimes, and peak cross-sections for stimulated emission of each band were determined. The concentration effect on the intensities is analyzed. The optical properties of the fluoroindate glasses doped with Er3+ ions are compared with those of other glasses described in the literature. © 1995.

Magneto-optical rotation of heavy-metal oxide glasses

Magneto-optical rotation was measured at room temperature for glasses containing Bi2O3-CdO-GeO2 (BCG), and Bi2O3-PbO-GeO2-B2O3 (BPGP). A pulsed magnetic field between 50 and 80 KG was used to measure Faraday rotation at 632.8 nm as a function of the concentration of Bi and Cd for BCG and Bi and Pb for BPGB. Verdet constant as high as 0.162 min G-1 cm-1 at 632.8 nm for the BPGB sample with the highest concentrations of Bi and Cd was found. Verdet constant increases linearly with the heavy-metal concentration for the BPGB whereas it reaches some saturation for the BCG system. Measurements of the magneto-optical rotation at other wavelengths in the visible and the refractive index at 632.8 nm are also reported. © 1998 Elsevier Science B.V. All rights reserved.

Filmes de metal-hexacianoferrato: Uma ferramenta em química analítica

Chemically modified electrodes based on hexacyanometalate films are presented as a tool in analytical chemistry. Use of amperometric sensors and/or biosensors based on the metal-hexacyanoferrate films is a tendency. This article reviews some applications of these films for analytical determination of both inorganic (e.g. As3+, S2O3 2-) and organic (e.g. cysteine, hydrazine, ascorbic acid, gluthatione, glucose, etc.) compounds.

fac-[RuCl3(no)(dppb)] (I) and mer-[RuCl3(NO)(diop)] (II) complexes: Syntheses, characterization and x-ray structures

The fac-[RuCl3(NO)(dppb)] complex I has been prepared from solution of the correspondent mer isomer in refluxing methanol (dppb = 1,4-bis(diphenylphosphino)butane). The mer-[RuCl3(NO)(diop)] (II) has been obtained from the mer-[RuCl3(diop)(H2O)] by bubbling NO for 1 h in dichloromethane (diop = 2S,3S-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane). The complexes have been characterized by microanalysis, cyclic voltammetry (CV), IR and 31P{1H} NMR spectroscopies. The crystal and molecular structures of these two compounds have been determined from X-ray studies. The mer-[RuCl3(NO)(dppb)] isomer III was characterized in solution by NMR spectra (31P{1H}, 1H{31P}, 31P-1H HETCORR, COSY 1H-1H, HMQC 1H-13C and HMBC 1H-13C). © 2002 Elsevier Science Ltd. All rights reserved.

Ceramic Crucible Corrosion by Heavy Metal Oxide Glasses, Part II: Diffusion Study

Due to their low cost and high resistance to corrosion, ceramic crucibles can be used for the melting of PBG glasses (PbO-BiO 1.5GaO 1.5). These glasses present good window transmission from ultra-violet to infrared, making their use as optical fibres promising. However, their disadvantage is the high reactivity, leading to the corrosion of different crucibles, including gold and platinum ones. In this work, the corrosion of Al 2O 3, SnO 2 and ZrO 2 crucibles after melting at temperatures varying from 850 to 1000°C, was evaluated by Scanning Electronic Microscopy (SEM) in conjunction with microanalysis by EDS. The lead diffusion profile in the crucible material was obtained. Diffusion coefficients were calculated according to the Fick and Fisher theories. Results indicated that the different crucibles presented similar behaviour: in the region near the interface, diffusion occurs in the volumetric way and in regions away from the interface, diffusion occurs through grain boundary.

Quantitative structural analysis of the transition from LT-Li xCoO2 to HT-LixCoO2 using the rietveld method: Correlation between structure and electrochemical performance

A quantitative phase analysis was made of LixCoO2 powders obtained by two distinct chemical methodologies at different temperatures (from 400 to 700°C). A phase analysis was made using Rietveld refinements based on X-ray diffraction data, considering the Li xCoO2 powders as a multiphase system that simultaneously contained two main phases with distinct, layered and spinel-type structures. The results showed the coexistence of both structures in LixCoO 2 obtained at low temperature (400 and 500°C), although only the layered structure was detected at higher temperatures (600 and 700°C), regardless of the chemical powder process employed. The electrochemical performance, evaluated mainly by the cycling reversibility of Li xCoO2 in the form of cathode insertion electrodes, revealed that there is a close correlation between structural features and the electrochemical response, with one of the redox processes (3.3 v/3.9 v) associated only with the presence of the spinel-type structure. © 2003 Elsevier B.V. All rights reserved.

Thermal study of nickel(II) pyrazolyl complexes

The thermal behavior of the pyrazolyl complexes [NiCl2(HPz) 4] (1), [Ni(NCS)2(HPz)4] (2), [NiCl 2(HdmPz)4]·2H2O (3) and [Ni(NCS) 2(HdmPz)4]·2H2O (4) (HPz=pyrazole, HdmPz=3,5-dimethylpyrazole) has been studied by thermogravimetry (TG) and differential thermal analysis (DTA). The TG data indicated that the thermal stability of [NiX2(HL)4] (X=Cl, NCS) compounds varies depending on the pyrazolyl ligand in the following order HL=HPz>HdmPz. From the thermal decomposition of 3 and 4 it was possible to isolate the intermediate compounds [Ni(μ-Cl)2(HdmPz)2] (3a) and [Ni(μ-1,3-NCS) 2(HdmPz)2] (4a), respectively. The final products of the thermal decompositions of 1-4 were identified as NiO by X-ray powder diffraction. © 2005 Akadémiai Kiadó, Budapest.

Thermal decomposition of palladium(ii) pyrazolyl complexes: Part II

Thermal behavior of pyrazolyl complexes [PdCl2(HPz)2] (1), [PdCl2(HdmPz)2] (2), [Pd(SCN)2(HPz) 2] (3), [Pd(SCN)2(HdmPz)2] (4), [Pd(N 3)2(HdmPz)2] (5), [Pd(PzNHCO)2] (6) and [Pd(dmPzNHCO)2] (7) (HPz=pyrazole, HdmPz=3,5-dimethylpyrazole) has been studied by TG and DTA. In general, the thermal stability of [PdX 2(HL)2] (HL=HPz, HdmPz) compounds varies in the following order: HdmPz>HPz as well, according to the trends X=Cl ->SOT->NNN-. Except for 5, the [PdX 2(HL)2] complexes showed higher thermal stability than the 6 and 7 chelates. No stable intermediates were isolated during the thermal decompositions because of the overlapping degradation processes. The final products of the thermal decompositions were identified as metallic palladium by X-ray powder diffraction. © 2005 Akadémiai Kiadó, Budapest.

Four new metal complexes with the amino acid deoxyalliin

The solid complexes [Co(C6H10NO2S) 2], [Ni(C6H10NO2S)2], [Cu(C6H10NO2S)2] and [Fe(C 6H10NO2S)2] were obtained from the reaction of cobalt(II), nickel(II), copper(II) and iron(II) salts with the potassium salt of the amino acid deoxyalliin (S-allyl-L-cysteine). Electronic absorption spectra of the complexes are typical of octahedral structures. Infrared spectroscopy confirms the ligand coordination to the metal ions through (COO-) and (NH2) groups. EPR spectrum of the Cu(II) complex indicates a slight distortion of its octahedral symmetry. Mössbauer parameters permitted to identify the presence of iron(II) and iron(III) species in the same sample, both of octahedral geometry. Thermal decomposition of the complexes lead to the formation of CoO, NiO, CuO and Fe2O3 as final products. The compounds show poor solubility in water and in the common organic solvents. ©2005 Sociedade Brasileira de Química.

Tetragonal to monoclinic phase transition observed during Zr anodisation

Plasma electrolytic oxidation (PEO) is a coating procedure that utilises anodic oxidation in aqueous electrolytes above the dielectric breakdown voltage to produce oxide coatings that have specific properties. These conditions facilitate oxide formation under localised high temperatures and pressures that originate from short-lived microdischarges at sites over the metal surface and have fast oxide volume expansion. Anodic ZrO2 films were prepared by subjecting metallic zirconium to PEO in acid solutions (H2C 2O4 and H3PO4) using a galvanostatic DC regime. The ZrO2 microstructure was investigated in films that were prepared at different charge densities. During the anodic breakdown, an important change in the amplitude of the voltage oscillations at a specific charge density was observed (i.e., the transition charge density (Q T)). We verified that this transition charge is a monotonic function of both the current density and temperature applied during the anodisation, which indicated that Q T is an intrinsic response of this system. The oxide morphology and microstructure were characterised using SEM and X-ray diffraction experiments (XRD) techniques. X-ray diffraction analysis revealed that the change in voltage oscillation was correlated with oxide microstructure changes during the breakdown process. © 2012 Springer-Verlag Berlin Heidelberg.

Strongly luminescent, highly ionic europium in a lanthanum diphenylphosphinate matrix

A series of insoluble, chemically inert and thermally stable compounds La1-xEux(DPP)3 (x = 0.50, 0.20, 0.10, and 0.050; DPP = diphenylphosphinate) was synthesized and characterized by elemental and thermogravimetric analysis, FT Infrared spectroscopy and X-ray powder diffraction. Luminescence spectroscopy at both 77 and 298 K showed changes in the intensity of the hypersensitive transition 5D 0 → 7F2 of Eu3+ which are dependent of the excitation wavelength, suggesting that the europium occupies two different sites in the compounds. The large quantum efficiency and quantum yield, as well as the long radiative lifetime of the 5D0 Eu3+ level of the series of compounds, which are desirable qualities for light-conversion molecular devices, are discussed in terms of the interactions and the energy transfer process between the ligands and the metal ion. © 2012 Elsevier B.V. All rights reserved.

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.

XAS/WAXS time-resolved phase speciation of chlorine LDH thermal transformation: Emerging roles of isovalent metal substitution

The XAS/WAXS time-resolved method was applied for unraveling the complex mechanisms arising from the evolution of several metastable intermediates during the degradation of chlorine layered double hydroxide (LDH) upon heating to 450 °C, i.e., Zn2Al(OH)6·nH2O, ZnCuAl(OH)6·nH2O, Zn2Al 0.75Fe0.25(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O. After a contraction of the interlamellar distance, attributed to the loss of intracrystalline water molecules, this distance experiences an expansion (T > 175-225 °C) before the breakdown of the lamellar framework around 275-295 °C. Amorphous prenucleus clusters with crystallo-chemical local order of zinc-based oxide and zinc-based spinel phases, and if any of copper-based oxide, are formed at T > 175-225 °C well before the loss of stacking of LDH layers. This distance expansion has been ascribed to the migration of Zn II from octahedral layers to tetrahedral sites in the interlayer space, nucleating the nano-ZnO or nano-ZnM2O4 (M = Al or Fe) amorphous prenuclei. The transformation of these nano-ZnO clusters toward ZnO crystallites proceeds through an agglomeration process occurring before the complete loss of layer stacking for Zn2Al(OH)6· nH2O and Zn2Al0.75Fe0.25(OH) 6·nH2O. For ZnCuAl(OH)6·nH 2O and ZnCuAl0.5Fe0.5(OH)6· nH2O, a cooperative effect between the formation of nano-CuO and nano-ZnAl2O4 amorphous clusters facilitates the topochemical transformation of LDH to spinel due to the contribution of octahedral CuII vacancy to ZnII diffusion. © 2013 American Chemical Society.