Synthesis, characterization, and investigation of the thermal behavior of Cu(II) pyrazolyl complexes

This work reports the synthesis, characterization, and thermal behavior of three complexes of copper (II): [CuCl(2)(HPz)(4)] (1), [CuCl(2)(HdmPz)(4)] (2), and [CuCl(2)(HIPz)(4)] (3) (HPz = pyrazole; HdmPz = 3,5-dimethylpyrazole; HIPz = 4-iodopyrazole). The compounds were characterized by elemental analysis, infrared spectroscopy, and UV-Vis measurements. The thermal study of the compounds showed that the ligands are eliminated in 2-4 stages, yielding CuO as final residue.

Reatividade do [Fe(CO)2(eta2-CS2)(PPh 3)2] frente a compostos de Cu(I): síntese de espécies binucleares heterometálicas contendo CS2 em ponte entre Fe(0) e Cu(I)

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

Distribuição de Cr, Ni, Cu, Cd e Pb em frações húmicas de diferentes tamanhos moleculares extraídas de amostras de água e de sedimentos do reservatório de captação de água superficial Anhumas - Araraquara-SP

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

Reação de precipitação de Ag na liga Cu-8%Al-6%Ag

A reação de precipitação de prata na liga Cu-8%Al-6%Ag foi estudada usando medidas de variação da microdureza com a temperatura e o tempo de envelhecimento, difratometria de raios X (DRX), calorimetria exploratória diferencial (DSC), microscopia eletrônica de varredura (MEV). Os resultados obtidos indicaram que o mecanismo da reação de precipitação da prata é um processo controlado pela difusão da prata e a velocidade desta reação atinge um máximo em torno de 500°C.

The Ni-Cu-PGE sulfide ores of the komatiite-hosted Fortaleza de Minas deposit, Brazil: Evidence of hydrothermal remobilization

The Fortaleza de Minas Ni-Cu-PGE sulfide deposit is hosted by Archean komatiitic rocks of the Morro do Ferro greenstone belt, near the southwestern margin of the Sa (aFrancisco) over tildeo Francisco craton, Minas Gerais state, Brazil. The deposit contains 6 million tonnes of ore with an average grade of 2.2 wt% Ni, 0.4% Cu, 0.05% Co and 1.2 ppm PGE+Au, and comprises (i) a main orebody, which is metamorphosed, deformed and transposed along a regional shear zone, consisting mainly of disseminated, brecciated and stringer sulfide ores that are interpreted to be of early magmatic origin, and (ii) PGE-rich discordant veins that are hosted in N-S- and NE-SW-trending late faults that cross-cut the main orebody. The discordant PGE-rich ore (up to 4 ppm total PGE) is characterized by thin, discontinuous and irregular veins and lenses of massive sulfides hosted by serpentinite and talc schist, and is relatively undeformed if compared with the early types of ore. It is composed mainly of pyrrhotite, pentlandite, chalcopyrite, magnetite, carbonates, and amphiboles, with minor cobaltite-gersdorffite, sphalerite, ilmenite, and quartz, and rarely maucherite (Ni11Asg), tellurides and platinum-group minerals (PGM). Omeeite, irarsite, sperrylite, and Ni-bearing merenskyite are the main PGM, followed by minor amounts of testibiopalladite and an unknown phase containing Ru, Te, and As. The PGM occur either included in, or at the margins of, sulfides, sulfarsenides, silicates and oxides, or filling fractures in pyrrhotite, pentlandite, and chalcopyrite, suggesting that they started to precipitate with these minerals and continued to precipitate after the sulfides were formed. The mantle-normalized metal distribution of the two samples of discordant veins shows distinct patterns: one richer in Ni-Pd-Ir-Rh-Ru-Os and another with higher amounts of Cu-Pt-Bi. Both are strongly depleted in Cr if compared with the metamorphosed magmatic ore of this deposit, which follows the general Kambalda-type magmatic trend. on the basis of structural, mineralogical and geochemical evidence, we propose that the PGE-rich discordant ore may have formed by remobilization of metals from the deformed, metamorphosed magmatic orebody (which shows a depleted pattern in these elements) by reduced (pyrrhotite - pentlandite - pyrite are stable), neutral to alkaline and carbonic fluids (carbonate-stable). The PGE may have been transported as bisulfide complexes, and precipitated as tellurides (mainly Pd) and arsenides (Pt, Rh, Ru, Os, Ir) in the late N-S and NE-SW-trending faults owing to a decrease in the activity of S caused by the precipitation of sulfides in the veins.

AC impedance study of Ni, Fe, Cu, Mn doped ceria stabilized zirconia ceramics

Doped zirconia has been used in electronic applications in the cubic crystalline phase. Ceria-stabilized tetragonal zirconia presents high toughness and can also be applied as solid electrolytes. The tetragonal phase of zirconia can be stabilized at room temperature with ceria in a broad range of composition. However, CeO2-ZrO2 has low sinterability. so it is important to investigate the effect of sintering dopants. In this study the effect of iron, copper. manganese and nickel was investigated. The dopants such as iron and copper lowered the sintering temperature from 1600 degreesC down to 1450 degreesC, with a percentage of tetragonal phase retained at room temperature higher than 98% and also with an increase of the electrical conductivity. The electrical conductivity was measured using impedance spectroscopy. The grain boundary contribution was determined and the activation energy associated with the ionic conduction was 1.04 eV. The dopants can also promote a grain boundary cleanliness verified by blocking effect measurement. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Comparative procedures for the sample decomposition of rocks used in organic agriculture and the determination of Cu, Fe, Mn, and Zn by FAAS

The aim of this work was to develop an appropriate sample preparation procedure for the flame atomic absorption spectrometry determination of Cu, Fe, Mn, and, Zn in rocks used in organic agriculture as a source of macro- and micronutrients.Six different procedures were evaluated and are classified into three groups: (a) pressure digestion system with Teflon bombs, (b) conventional wet digestion in a digester heating block, and (c) closed microwave system with pressure and temperature control.Two standard reference materials and two commercial samples were analyzed. It was found that the closed microwave system required low reagent consumption, less time, and resulted in low contamination.

Thermal behavior of the Cu-10 mass%Al and Cu-10 mass%Al-4 mass%Ag alloys

The thermal behavior of the Cu-10 mass%Al and Cu-10 mass% Al-4 mass%Ag alloys was studied using classical differential thermal analysis (DTA), optical microscopy (OM) and X-ray diffractometry (XRD). The DTA curves were obtained for annealed and quenched samples. The results indicated that the presence of silver introduces new thermal events, associated to the formation of a silver-rich phase, to the shift of the equilibrium concentration to higher A1 contents and to the decomposition of the silver-rich phase in the same temperature range of the beta(1) phase decomposition.

EFFECT OF THE ADDITION OF CR AND NB ON THE MICROSTRUCTURE AND ELECTROCHEMICAL CORROSION OF HEAT-TREATABLE AL-ZN-MG ALLOYS

The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn-1.67%Mg-0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E(cor)) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O-2 or H2O2, the present alloys were polarized up to the pitting attack. It was shown that the E(cor) measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A approximate to ST < B < C (for a given alloy). The MgZn2 precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in the E(cor) shift or in the increase in the pitting corrosion resistance.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GRAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect back- ground correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier, With 5 mug Pd + 3 mug Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400degreesC and 2100degreesC, respectively, and 20 muL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 - 50.0 mug L-1 for As, Sb, Se; 10.0 - 100 mug L-1 for Cu; and 20.0 - 200 mug L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 mug L-1 As, 0.2 mug L-1 Cu, 0.6 mug L-1 Mn, 0.3 mug L-1 Sb, 0.9 mug L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 mug L-1, 1000 mug L-1, 2000 mug L-1, 5 mug L-1, and 50 mug L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mu Sb and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by GFAAS

A method has been developed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by graphite furnace atomic absorption spectrometry (GFAAS) using a transversely heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages using the mixture Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3, and diluted ethanol (1 + 1, v/v) containing different nitric acid concentrations. With 5 rhog Pd + 3 mug Mg as the modifiers, pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1200 C and 2200degreesC respectively. For 20 muL of diluted sample (10 muL ethanol + 10 muL of 0.28 mol L-1 HNO3) dispensed into the graphite tube, analytical curves in the 2.0 - 50 mug L-1 Al, As, Cu, Fe, Mn, Ni ranges were established. The calculated characteristic masses were - 37 pg Al, 73 pg As, 31 pg Cu, 16 pg Fe, 9 pg Mn, and 44 pg Ni, and the lifetime of the tube was around 2 50 firings. The limits of detection (LOD) based on integrated absorbance were 1.2 mug L-1 Al, 2.5 mug L-1 As. 0.22 mug L-1 Cu, 1.6 L-1 Fe 0.20 mug L-1 Mn 1.1 mug L-1 Ni. The relatively standard deviations (n = 12) were less than or equal to 3%, less than or equal to 6%, less than or equal to 2%, less than or equal to 3.4%, less than or equal to 1.3%, and less than or equal to 2% for Al, As, Cu, Fe, Mn, and Ni, respectively, the recoveries of Al, As, Cu, Fe, Mn and Ni added to fuel ethanol samples varied from 77% to 112%, 92% to 114%, 104% to 113%, 73% to 116%, 91% to 122% and 93% to 116%, respectively. Accuracy was checked for Al, As, Cu, Fe, Mn, and Ni determination in 20 samples purchased at local gas stations in Araraquara city, Brazil. A paired t-test showed that the results were in agreement at the 95% confidence level with those obtained by single-element GFAAS.

Distribution profile and availability of Cr, Ni, Cu, Cd and Pb in different sediments from anhumas surface water collection reservoir, Araraquara-São Paulo State, Brazil

In this work the influence of the anhtropogenic activities in the uptake of metals at a reservoir for public water supply in Araraquara City, São Paulo State, Brazil was studied. For this, the distribution of Cr, Ni, Cu, Cd and Pb in sediments collected from Anhumas reservoir, at seven sampling points and at three depths for each point was investigated. The pseudo-total and available metals contained in the different sediment samples were assessed using an ICP-AES technique. Among the five metals studied, cadmium possesses the largest relative potential availability, with percentages of 20 to 98% for the three different sediment types. In addition, the following decreasing availability order was characterized: Cd > Cu > Pb > Ni > Cr.

Characterization of humic-rich hydrocolloids and their metal species by means of competing ligand and metal exchange - an on-site approach

An improved on-site characterization of humic-rich hydrocolloids and their metal species in aquatic environments was the goal of the present approach. Both ligand exchange with extreme chelators ( diethylenetetraaminepentaacetic acid ( DTPA), ethylendiaminetetraacetic acid ( EDTA)) and metal exchange with strongly competitive cations (Cu(II)) were used on-site to characterize the conditional stability and availability of colloidal metal species in a humic-rich German bogwater lake ( Venner Moor, Munsterland). A mobile time-controlled tangential-flow ultrafiltration technique (cut-off: 1 kDa) was applied to differentiate operationally between colloidal metal species and free metal ions, respectively. DOC ( dissolved organic carbon) and metal determinations were carried out off-site using a home-built carbon analyzer and conventional ICP-OES ( inductively-coupled plasma-optical emission spectrometry), respectively. From the metal exchange equilibria obtained on-site the kinetic and thermodynamic stability of the original metal species ( Fe, Mn, Zn) could be characterized. Conditional exchange constants K ex obtained from aquatic metal species and competitive Cu(II) ions follow the order Mn > Zn >> Fe. Obviously, Mn and Zn bound to humic-rich hydrocolloids are very strongly competed by Cu( II) ions, in contrast to Fe which is scarcely exchangeable. The exchange of aquatic metal species (e.g. Fe) by DTPA/EDTA exhibited relatively slow kinetics but rather high metal availabilities, in contrast to their Cu(II) exchange.

Distribution of Cr, Ni, Cu, Cd and Pb in different molecular size of humic fractions extracted from water and sediment samples collected at Anhumas reservoir - Araraquara/SP

In this work was studied the distribution of Cr, Ni, Cu, Cd and Pb in humic fractions with different molecular size. The HS were extracted from waters (AHS), surface sediments (HESS), interface water sediment (HSIS) and bottom sediment (HSBS) collected in the Anhumas surface water collection reservoir, located in the district of Araraquara - São Paulo State Brazil. The humic substances were extracted by procedures recommended by International Humic Substances Society (IHSS). After purification by dialysis, the humic substances were fractionated using a multistage tangential flow ultrafiltration system. The fractionation patterns of HS characterized a mass distribution relatively uniform among the fractions with different molecular sizes, with larger values in the fractions F-2 (20.8%) and F-4 (23.8%), Except for the ions Pb(II) and Cu(II), which presented relatively higher concentrations in the fractions F-2 and F-4, respectively. In general, chromium, nickel, cadmium and lead have similar distributions in the five fractions with larger and medium molecular sizes (F-1 to F-5). With relation to the mass distributions in the different humic substances fractions extracted from sediment samples collected at three depth, they presented 42-48% of HS in the fractions with larger molecular sizes (F-1 and F-2), 29-31% in the middle fractions (F-3 and F-4) and 13-20% in the fractions with smaller molecular sizes (F-5 and F-6). In general, the metallic ions presented distributions similar among the respective fractions F-1 to F-6, Exceptions for Pb(II) and M(II) in surface sediment with concentrations relatively smaller in the fractions F-2 and F-4, respectively,

Biological leaching of Mn, Al, Zn, Cu and Ti in an anaerobic sewage sludge effectuated by Thiobacillus ferrooxidans and its effect on metal partitioning

The chemical fractionation and bioleaching of Mn, At, Zn, Cu and Ti in municipal sewage sludge were investigated using Thiobacillus ferrooxidans as leaching microorganism. As a result of the bacterial activity, ORP increase and pH reduction were observed. Metal solubilization was accomplished only in experimental systems supplemented with energy source (Fe(II)). The solubilization efficiency approached similar to80% for Mn and Zn, 24% for Cu, 10% for At and 0.2% for Ti. The chemical fractionation of Mn, At, Zn, Cu and Ti was investigated using a five-step sequential extraction procedure employing KNO3. KF, Na4P2O7, EDTA and HNO3. The results show that the bioleaching process affected the partitioning of Mn and Zn, increasing its percentage of elution in the KNO3 fraction while reducing it in the KF, Na4P2O7 and EDTA fractions. No significant effect was detected on the partitioning of Cu and Al. However, quantitatively the metals Mn, Zn, Cu and At were extracted with higher efficiency after the bacterial activity. Titanium was unaffected by the bioleaching process in both qualitative and quantitative aspects. (C) 2002 Elsevier B.V. Ltd. All rights reserved.