Estudo da eletrocristalização de Ni e Ni-P sobre ultramicroeletrodo de platina

This work describes a comparative study of the electrocrystallization of Ni and Ni-P on Pt ultramicroelectrodes using chronoamperometric measurements. It was possible to confirm that in all cases a progressive nucleation was the predominant mechanism. Moreover, the application of the Atomistic Theory to the experimental rate of nuclei formation showed that the number of atoms in the critical nucleus was zero, except for Ni-P on Pt at low overpotentials were a value of one was observed. Furthermore, the physical characterisation of the different deposits on Pt by atomic force microscopy allowed observing the coalescence of the hemispherical nuclei of Ni and Ni-P at t max thus confirming the results obtained from the current-time analysis.

Design and evaluation of a continuous flow, integrated nebulizer-hydride generator for flame atomic absorption spectrometry

An evaluation of the performance of a continuous flow hydride generator-nebulizer for flame atomic absorption spectrometry was carried out. Optimization of nebulizer gas flow rate, sample acid concentration, sample and tetrahydroborate uptake rates and reductant concentration, on the As and Se absorbance signals was carried out. A hydrogen-argon flame was used. An improvement of the analytical sensitivity relative to the conventional bead nebulizer used in flame AA was obtained (2 (As) and 4.8 (Se) µg L-1). Detection limits (3σb) of 1 (As) and 1.3 (Se) µg L-1 were obtained. Accuracy of the method was checked by analyzing an oyster tissue reference material.

Determination of Cd and Pb in fuel ethanol by filter furnace electrothermal atomic absorption spectrometry

A method was developed for quantification of Cd and Pb in ethanol fuel by filter furnace atomic absorption spectrometry. Filter furnace was used to eliminate the need for chemical modification, to stabilize volatile analytes and to allow the application of short pyrolysis step. The determinations in samples were carried out against calibration solutions prepared in ethanol. Recovery tests were made in seven commercial ethanol fuel samples with values between 90 and 120%. Limits of detection were 0.1 µg L-1 for Cd and 0.3 µg L-1 for Pb. Certified water samples (APS 1071, APS 1033, NIST 1643d, NIST 1640) were also used to evaluate accuracy and recoveries from 86.8% to115% were obtained.

Implementação computacional do modelo carga-fluxo de carga-fluxo de dipolo para cálculo e interpretação das intensidades do espectro infravermelho

The first computational implementation that automates the procedures involved in the calculation of infrared intensities using the charge-charge flux-dipole flux model is presented. The atomic charges and dipoles from the Quantum Theory of Atoms in Molecules (QTAIM) model was programmed for Morphy98, Gaussian98 and Gaussian03 programs outputs, but for the ChelpG parameters only the Gaussian programs are supported. Results of illustrative but new calculations for the water, ammonia and methane molecules at the MP2/6-311++G(3d,3p) theoretical level, using the ChelpG and QTAIM/Morphy charges and dipoles are presented. These results showed excellent agreement with analytical results obtained directly at the MP2/6-311++G(3d,3p) level of theory.

On-line preconcentration system using a microcolumn packed with Alizarin Red S-modified alumina for zinc determination by flame atomic absorption spectrometry

A simple and sensitive on-line flow injection system for determination of zinc with FAAS has been described. The method is based on the separation and preconcentration of zinc on a microcolumn of immobilized Alizarin Red S on alumina. The adsorbed analyte is then eluted with 250 µL of nitric acid (1 mol L-1) and is transported to flame atomic absorption spectrometer for quantification. The effect of pH, sample and eluent flow rates and presence of various cations and anions on the retention of zinc was investigated. The sorption of zinc was quantitative in the pH range of 5.5-8.5. For a sample volume of 25 mL an enrichment factor of 144 and a detection limit (3S) of 0.2 µg L-1 was obtained. The precision (RSD, n=7) was 3.0% at the 20 µg L-1 level. The developed system was successfully applied to the determination of zinc in water samples, hair, urine and saliva.

Eletrização de dielétricos: novas propostas para resolver velhos problemas

Electrostatic phenomena were discovered long ago but their interpretation according to well-established atomic-molecular theory is still lacking. As a result, electrostatic phenomena are often irreproducible and uncontrolled, causing serious practical problems. Highly reproducible recent experimental results on electrostatic charging from this and other laboratories are reviewed in this work, together with a description of the relevant but not so usual Kelvin probe and Faraday cup techniques. These results support a new model for electrostatic charging of dielectrics and insulated metals, based on the role of moist atmosphere as a charge reservoir.

Retrieval of kinetic rates in reactions with semi batch liquid phase using ill-posed inverse problem theory

A neural network procedure to solve inverse chemical kinetic problems is discussed in this work. Rate constants are calculated from the product concentration of an irreversible consecutive reaction: the hydrogenation of Citral molecule, a process with industrial interest. Simulated and experimental data are considered. Errors in the simulated data, up to 7% in the concentrations, were assumed to investigate the robustness of the inverse procedure. Also, the proposed method is compared with two common methods in nonlinear analysis; the Simplex and Levenberg-Marquardt approaches. In all situations investigated, the neural network approach was numerically stable and robust with respect to deviations in the initial conditions or experimental noises.

Ion pair-dispersive liquid-liquid microextraction of trace amount of rhodium ion in water and road dust samples prior to flame atomic absorption spectrometry determination

A simple ion pair-dispersive liquid-liquid microextraction method was proposed for preconcentration trace amounts of rhodium. An ion association complex of RhCl4- and tetradecyldimetylbenzylamonium was extracted into cholorobenzene. The volume and the type of extractive and dispersive solvents, the extraction time and the pH of the aqueous solutions were optimized. The calibration curve was linear in the range of 0.6-500 ng mL-1 of rhodium. The limit of detection was 0.10 ng mL-1 in initial solution and preconcentration factor was 40. The proposed method was successfully applied to the extraction and determination of rhodium in road dust and water samples.

Organic and total mercury determination in sediments by cold vapor atomic absorption spectrometry: methodology validation and uncertainty measurements

The purpose of the present study was to validate a method for organic Hg determination in sediment. The procedure for organic Hg was adapted from literature, where the organomercurial compounds were extracted with dichloromethane in acid medium and subsequent destruction of organic compounds by bromine chloride. Total Hg was performed according to 3051A USEPA methodology. Mercury quantification for both methodologies was then performed by CVAAS. Methodology validation was verified by analyzing certified reference materials for total Hg and methylmercury. The uncertainties for both methodologies were calculated. The quantification limit of 3.3 µg kg-1 was found for organic Hg by CVAAS.

Dispersive liquid-liquid microextraction for the simultaneous separation of trace amounts of zinc and cadmium ions in water samples prior to flame atomic absorption spectrometry determination

In the proposed method, carbon tetrachloride and ethanol were used as extraction and dispersive solvents. Several factors that may be affected on the extraction process, such as extraction solvent, disperser solvent, the volume of extraction and disperser solvent, pH of the aqueous solution and extraction time were optimized. Under the optimal conditions, linearity was maintained between 1.0 ng mL-1 to 1.5 mg mL-1 for zinc and 1.0 ng mL-1 to 0.4 mg mL-1 for cadmium. The proposed method has been applied for determination of trace amount of zinc and cadmium in standard and water samples with satisfactory results.

A brief introduction to molecular orbital theory of simple polyatomic molecules for undergraduate chemistry students

A simple, four-step method for better introducing undergraduate students to the fundamentals of molecular orbital (MO) theory of the polyatomic molecules H2O, NH3, BH3 and SiH4 using group theory is reported. These molecules serve to illustrate the concept of ligand group orbitals (LGOs) and subsequent construction of MO energy diagrams on the basis of molecular symmetry requirements.

Simultaneous preconcentration of Cu(II), Cd(II) and Mn(II) on silica-polyethylene glycol and determination by flame atomic absorption spectrometry

A simultaneous solid phase extraction procedure for enrichment of Cu(II), Cd(II) and Mn(II) has been developed. The method is based on adsorption of Cu(II), Cd(II) and Mn(II) ions on polyethylene glycol-silica gel pre-conditioned with acetate buffer (pH 5.5). The adsorbed metal ions are eluted with nitric acid (1 mol L -1) and determined by flame atomic absorption spectrometry. The calibration graph was linear in the range of 2-140 ng mL-1 for Cu(II), 1-40 ng mL-1 for Cd(II) and 4-100 ng mL-1 for Mn(II). The limits of detection were 0.66, 0.33 and 1.20 ng mL-1 for Cu(II), Cd(II) and Mn(II), respectively.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.