Environmental coordination chemistry: Binary systems comprising some bivalent cations and monocarboxylates in aqueous solution. Ionic medium effects on equilibrium constants

The molar single activity coefficients associated with propionate ion (Pr) have been determined at 25 degrees C and ionic strengths comprised between 0.300 and 3.00 M, adjusted with NaClO4, as background electrolyte. The investigation was carried out potentiometrically by using a second class Hg/Hg2Pr2 electrode. It was found that the dependence of propionate activity coefficients as a function of ionic strength (I) can be assessed through the following empirical equation: log y(Pr) = -0.185 I-3/2 + 0.104 I-2. Next, simple equations relating stoichiometric protonation constants of several monocarboxylates and formation constants associated with 1:1 complexes involving some bivalent cations and selected monocarboxylates, in aqueous solution, at 25 degrees C, as a function of ionic strength were derived, allowing the interconversion of parameters from one ionic strength to another, up to I = 3.00 M. In addition, thermodynamic formation constants as well as parameters associated with activity coefficients of the complex species in the equilibria are estimated. The body of results shows that the proposed calculation procedure is very consistent with critically selected experimental data.

The IFUSP race-track microtron booster accelerator end magnets antisymmetric perturbations

We will present measurements and calculations related to the antisymmetric perturbations, and comparisons with the symmetric ones, of the IFUSP race-track microtron booster accelerator end magnets. These perturbations were measured in planes situated at +/-12 mm of the middle plane, in a gap height of 4 cm, for a field distribution of about 0.1 T. The measurements were done in 1170 points, separated by a distance of 8 mm, using an automated system with a +/-1.5 mu T differential Hall probe. The race-track microtron booster is the second stage of the 30.0 MeV electron accelerator under construction at the Linear Accelerator Laboratory in which the required uniformity for the magnetic field is of about 10(-3). The method of correction employed to homogenize the IFUSP race-track microtron booster accelerator magnets assures uniformity of 10(-5) in an average field of 0.1 T, over an area of 700 cm(2). This method uses the principle of attaching to the pole pieces correction coils produced by etching techniques, with copper leads shaped like the isofield lines of the normal component of the magnetic field measured. The ideal planes, in which these measurements are done, are calculated and depend on the behavior of the magnetic field perturbations: symmetric or antisymmetric with reference to the middle plane of the magnet gap. These calculations are presented in this work and show that for antisymmetric perturbations there is no ideal plane for the correction of the magnetic field; for the symmetric one, these planes are at +/-60% of the half gap height, from the middle plane. So this method of correction is not feasible for antisymmetric perturbations, as will be shown. Besides, the correction of the symmetric portion of the field distribution does not influence the antisymmetric one, which almost does not change, and corroborates the theoretical predictions. We found antisymmetric perturbations of small intensity only in one of the two end magnets. However, they are not detected at +/- 1 mm of the middle plane and will not damage the electron beam.

Kinetics and mechanism of the induced redox reaction of [Ni(cyclam)](2+) promoted by SO5 center dot-

Oxidation of [Ni(cyclam)](2+), cyclam = 1,4,8,11-tetraazacyclotetradecane, accelerated by sulfur dioxide, was studied spectrophotometrically by following the formation of [Ni(cyclam)](3+) under the conditions: [Ni(cyclam)](2+) = 6.0 x 10(-3) M; initial [Ni(cyclam)](3+) = 8.0 x 10(-6) M; [cyclam] = 6.0 x 10(-3) M; [SO2] = (1.0-5.0) x 10(-4) M and 1.0 M perchloric acid in oxygen saturated solutions at 25.0 degrees C and ionic strength = 1.0 M. The oxidation reaction exhibits autocatalytic behavior in which the induction period depends on the initial Ni(III) concentration. A kinetic study of the reduction of Ni(III) by SO2 under anaerobic conditions, and the oxidation of Ni(II), showed that the rate-determining step involves reduction of Ni(III) by SO2 to produce the SO3.- radical, which rapidly reacts with dissolved oxygen to produce SO5.- and rapidly oxidizes Ni(II). The results clearly show a redox cycling process which depends on the balance of SO2 and oxygen concentrations in solution.

Synthesis and structural characterization of dichlorobis (1-phenyl-3-methylpyrazole) palladium(II) and diazidobis (1-phenyl-3-methylpyrazole) palladiium(II)

Mononuclear pyrazolyl Pd(II) complexes of the type [PdX2(phmPz)(2)] (X = Cl-, N-3(-)) have been prepared. The 1-phenyl-3-methylpyrazole displaces acetonitrile from [PdCl2(CH3CN)(2)] to form [PdCl2(PhMPz)(2)] (phmPz = 1-phenyl-3-methylpyrazole) (1). [Pd(N-3)(2)(PhmPz)(2)] (2) could be obtained by metathesis from [PdCl2(CH3CN)(2)] or by substitution of the chloride in (1) by the azide ion. Both complexes were characterized by elemental analysis, infrared spectroscopy, H-1 and C-13 NMR and by single crystal X-ray diffraction. The coordination geometry around Pd(II) in these complexes is nearly square-planar, with the ligands in a trans configuration.

SOLIDS COATED WITH SODIUM TETRACHLOROPALLADATE - SORBENTS FOR REDUCED SULFUR-COMPOUNDS IN AIR

A study of the preconcentration of tioethers in air by means of the passage of gas flow on solid sorbents coated with sodium tetrachloropalladate was undertaken with the aim of achieving chemical fixation. This fixation presented high specificity and blocked the migration of the sorbed compound through the other active sites. The species obtained were selectively dissolved in organic solvents, resulting in the sulfur reduced compound concentration in the organic phase, which could be determined spectrophotometrically.

A THEORETICAL RESULT ON PHASE-LAG

We prove a Theoretical result which relates phase-lag to the error constant of a numerical method for periodic problem y'' = f(x, y).

Influence of preparation methods and thermal treatment in melt-solidified and cast films of poly(vinylidene fluoride-trifluorethylene) copolymers

This paper is aimed at addressing the differences observed in film properties when poly(vinylidene fluoride-trifluorethylene) P(VDF-TrFE) films are fabricated using distinct methods. Samples were obtained either from casting a solution or by compression molding from a molten phase and characterized by differential scanning calorimetry (DSC). It is shown that the main differences between melt-solidified and cast films arise from the thermal treatment inherent in the former samples.

Measurement of atmospheric formaldehyde using a drop collector and in-situ colorimetry

A sensitive and affordable approach is described for the in-situ measurement of ambient formaldehyde. Air is sampled around a 100 microliter aqueous drop containing 3-methyl-2-benzothiazoline hydrazone. After a desired period of sampling (typ. 5 min) and a waiting period of 10 min for the reaction to be completed, a second reagent (FeCl3) is added to the drop by means of a conjoined conduit. A blue product is formed and is read after an additional 10 min of reaction by a fiber-optic/light emitting diode based photodetector. A fresh drop is then formed and the process begins anew. As demonstrated here, the limit of detection is similar to 6.25 mu g m(-3) HCHO but can be significantly improved by using longer sampling times and a sampling rate higher than 100 mi min(-1) used in most of this work. This is the first example of a chromogenic drop sensor that utilizes sequential reagent addition.

MONTE-CARLO SIMULATION OF POLYAMPHOLYTE CHAINS

Polyampholyte copolymers containing both positive and negative monomers regularly dispersed along the chain were studied. The Monte Carlo method was used to simulate chains with charged monomers interacting by screened Coulomb potential. The neutral polyampholyte chains collapse due to the attractive electrostatic interactions. The nonneutral chains are in extended conformations due to the repulsive polyelectrolyte effects that dominate the attractive polyampholyte interactions. The results are in good agreement with experiment.

Synthesis and structural studies of (1,10-phenanthroline)(thiocyanate-N)-(triphenylphosphine)copper(I)

The compound (1,10-phenanthroline)(thiocyanate-N)(triphenylphosphine)copper(I), was synthesized and studied by IR spectroscopy and X-ray diffraction techniques. It is monomeric with the thiocyanate acting as a N-donor ligand. The copper atom shows a distorted tetrahedral coordination geometry.

Multiresidue analysis of pesticides in water from rice cultures by on-line solid phase extraction followed by LC-DAD

An automated on-line solid phase extraction procedure followed by liquid chromatography with diode array detection was investigated for the determination of different classes of pesticides in water samples containing varied amount of humic substances. The different pesticides used were: carbendazin, carbofuran, atrazine, diuron, propanil, molinate, alachlor, parathion-ethyl, diazinon, trifluralin and the degradation products deisopropylatrazine and deethylatrazine. Humic substances extracted from a Brazilian sediment were used from 5 to 80 mg/l and their influence on recoveries was evaluated in neutral and acidic media. Recoveries higher than 70% were obtained for all the pesticides, from the preconcentration of 75 mi of aqueous sample fortified at 2 ng/ml using precolumns packed with PLRP-S. Good recoveries were obtained at neutral pH for most of the analytes up to 40 mg/l of humic acid. Only at 80 mg/l the recoveries were significantly affected, both at acidic and neutral pH. The method was applied to the determination of pesticides in river water spiked at 0.1 to 1 ng/ml. Detection limits obtained for water containing 10 mg/l of humic acid were between 0.05 and 0.3 ng/ml.

Analysis of the ethical aspects of professional confidentiality in dental practice

From the point of view of deontological ethics, privacy is a moral right that patients are entitled to and it is bound to professional confidentiality. Otherwise, the information given by patients to health professionals would not be reliable and a trustable relationship could not be established. The aim of the present study was to assess, by means of questionnaires with open and closed questions, the awareness and attitudes of 100 dentists working in the city of Andradina, São Paulo State, Brazil, with respect to professional confidentiality in dental practice. Most dentists (91.43%) reported to have instructed their assistants on professional confidentiality. However, 44.29% of the interviewees showed to act contradictorily as reported talking about the clinical cases of their patients to their friends or spouses. The great majority of professionals (98.57%) believed that it is important to have classes on Ethics and Bioethics during graduation and, when asked about their knowledge of the penalties imposed for breach of professional confidentiality, only 48.57% of them declared to be aware of it. Only 28.57% of the interviewees affirmed to have exclusive access to the files; 67.14% reported that that files were also accessed by their secretary; 1.43% answered that their spouses also had access, and 2.86% did not answer. From the results of the present survey, it could be observed that, although dentists affirmed to be aware of professional confidentiality, their attitudes did not adhere to ethical and legal requirements. This stand of health professionals has contributed to violate professional ethics and the law itself, bringing problems both to the professional and to the patient.

Oxygen related defects excitation and photoconductivity dependence of SnO2 sol-gel films with several light sources

Since oxygen vacancies act as donors in SnO2, the electrical properties are related to deviation from stoichiometric composition. Depending on stoichiometry SnO2 can be highly insulating or may exhibit fairly high n-type conductivity. Since bandgap transitions are in the ultraviolet range, its photoconductivity is strongly dependent on the excitation source. We have measured variation of photoconductivity excitation with wavelength for tin dioxide grown by dip-coating sol-gel technique using several light sources: tungsten lamp, xenon, mercury and deuterium, and present selected results. The main band is obtained in the range 3-4eV according to light source spectrum in the ultraviolet range. The presence of oxygen in the cryostat also affects the spectrum since electron-hole pairs react with adsorbed oxygen specimens. © 1999 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

Invex nonsmooth alternative theorem and applications

An invex constrained nonsmooth optimization problem is considered, in which the presence of an abstract constraint set is possibly allowed. Necessary and sufficient conditions of optimality are provided and weak and strong duality results established. Following Geoffrion's approach an invex nonsmooth alternative theorem of Gordan type is then derived. Subsequently, some applications on multiobjective programming are then pursued. © 2000 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.