Geração sonoquímica de oxidantes em solução aquosa saturada de tetracloreto de carbono

In this work the CCl4 degradation in aqueous solution by sonication with 40 kHz commercial ultrasonic bath was investigated. Sonochemical degradation of CCl4 occur by the cleavage of C-Cl bond into the cavitation bubbles. Oxidation reactions and the pH decreasing in the bulk solution during sonication were attributed to chlorine radicals produced by CCl4 sonolysis, leading to increase the chloride concentration. The formation of oxidizing agents was evaluated employing I- and Fe2+ ion solutions, converted to I2 and HIO, and Fe3+, respectively. The amount of chloride and hydronium ions produced after 3 min of irradiation was 11.52 and 12.19 mmol, respectively, suggesting that the same reaction was involved to produce these ions. Fe2+ oxidation and the pH variation were monitored to estimate chlorine radical formation rate in the presence (0.107 mumol s-1) and absence (0.092 mumol s-1) of metallic ion during the first minute of sonication.

Synthesis and characterization of manganese-glycine and copper-glycine adducts

This work reports the synthesis and characterization of adducts of general formula MCl2.ngly, where M= Mn and Cu; n= 2 and 4, and gly= glycine. The manganese adducts were synthesized by dissolution of both, manganese chloride and glycine in water, whereas the copper adducts were obtained by using an alternative solid state synthesis approach. For all adducts, the obtained infrared data shows that the coordination involves the amine nitrogen atom, as well as an oxygen atom of the COO- group. The TG curves for the synthesized adducts exhibit only one mass loss step associated with the release of glycine molecules.

Oxochloroalkoxide of the Cerium (IV) and Titanium (IV) as oxides precursor

The Cerium (IV) and Titanium (IV) oxides mixture (CeO2-3TiO2) was prepared by thermal treatment of the oxochloroisopropoxide of Cerium (IV) and Titanium (IV). The chemical route utilizing the Cerium (III) chloride alcoholic complex and Titanium (IV) isopropoxide is presented. The compound Ce5Ti15Cl16O30 (iOPr)4(OH-Et)15 was characterized by elemental analysis, FTIR and TG/DTG. The X-ray diffraction patterns of the oxides resulting from the thermal decomposition of the precursor at 1000 °C for 36 h indicated the formation of cubic cerianite (a = 5.417Å) and tetragonal rutile (a = 4.592Å) and (c = 2.962 Å), with apparent crystallite sizes around 38 and 55nm, respectively.

Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

Determinação espectrofotométrica de alumínio em concentrados salinos utilizados em hemodiálise empregando pré-concentração em fluxo

An automatic flow injection procedure for spectrophotometric aluminium determination in purified water and solutions containing high salts concentrations used for hemodyalisis treatment was developed. The method was base on reaction of Al3+ with cianine eriochrome R (ECR) after preconcentration using the AG50W-X8 cationic-exchange resin. Elution was carried out using a 1 % (m/v) calcium chloride solution. The manifold comprised an automatic proporcional injector controlled by a computer equipped with an eletronic interface and software written in QuicBASIC 4.5 with facilities to control the injector and perform data acquisition. Samples with concentration ranging from 4.96 to 19.90 µg L-1 Al were analyzed and recoveries between 88 and 113% were obtained by using the standard addition method. Other profitable analytical characteristics such as a relative standard deviation 1.3 % (n = 10) for a typical sample 14.5 µg L-1 Al, a linear response ranging up to 60.0 µg L-1Al, and a sampling throughput of 10 determinations per hour were achieved. A detection limit of 4.2 µg L-1 Al was estimated as suggested by IUPAC.

Construção e aplicação de eletrodo de aço inoxidável UNS S31254 como eletrodo indicador em titulações condutimétricas

UNS S31254 SS electrodes have been built to substitute platinum in conductimetric titrations. The electrodes were tested in both acid-basic titration (chloridric acid and sodium hydroxide) and precipitation titration (sodium chloride and argentum nitrate as titrant). The practical application was exemplified from conductimetric tritations of HF mbol>¾ HNO3 mixtures used in metalurgical industry to passivate stainless steels. The results were compared with those obtained using commercial platinum electrodes. The equivalent volumes obtained were comparable within 3% experimental error. Its application depends on the nature of electrolyte. These results have shown that stainless steel, less expensive than platinum (about three order of magnitude), can substitute platinum electrodes in routine analyses and didactic laboratories.

Determinação potenciométrica em fluxo de cloreto de cetilpiridinio em desinfectantes bucais

The work describes a new procedure for cetylpyridinium chloride determination in oral disinfectants, based on a flow-injection system with potentiometric detection. The determination was based on the measurement of picrate concentration decrease as result of ion-pair reaction with the analyte present in the injected sample. In the optimised set-up the sample injection volume was kept at 400 µL and merged downstream with the reagent solution containing 1,0 x10-5 mol/L of picrate adjusted to pH 5.0 with citrate/citric acid buffer. The flow rate was fixed at 8 mL/min and the reactor length at 40 cm. The proposed procedure enables the determination of cetylpyridinium in the analytical range of 5,0x10-6 - 7,5x10-5 mol/L at a sampling rate of 60/h. The results for real samples had a precision better than 3% and were comparable to the labelled values.

Aplicações eletroanalíticas com eletrodos de prata confeccionados a partir de CDs graváveis

This paper presents a new way for the construction of silver electrodes utilizing recordable CDs. The new electrodes were explored for the quantification of chloride (by potentiometry/FIA), cyanide (by amperometry/FIA) and for lead analysis (by square wave voltammetry). For the flowing measurements, a digital multimeter, connected to a microcomputer (via RS 232 interface) was used to collect directly the potential signal (for Cl- measurements) or to take the output signal from a potentiostat (for CN- measurements). The square wave voltammetry analysis was performed in a commercial instrument. The results shown good performance of the new electrodes and the detection limit (s/n = 3) attained for these three analytes were: 0.2, 50, and 200 µg L-1 for Pb2+, Cl-, and CN- respectively.

Emprego de óxidos tipo perovskita nas oxidações do propano e CO

Simultaneous oxidation/co-precipitation of an equimolar mixture of La(III) and Co(II) nitrates and La(III) nitrate and Mn(II) chloride afforded a hydroxide gel, which was converted to LaCoO3 and LaMnO3 on calcination at 600 °C. After calcination, the obtained perovskites have been characterised by X-ray diffraction (XRD), X- ray photoelectron spectroscopy (XPS), thermogravimetric analysis (DTA - TGA) and BET specific surface determination. Specific surface areas of perovskites were 12 - 60 m²/g. XRD analysis showed that LaCoO3 and LaMnO3 are simple phase perovskite - type oxides. Traces of LaOCl, in addition to the perovskite were detected in the LaMnO3. The catalytic behavior was examined in the propane and CO oxidation. The LaCoO3 catalyst was more active to CO2 than the LaMnO3 catalyst.

Irradiação de polímeros com feixe de elétrons: caracterização de íons positivos através da técnica de tempo-de-vôo

With the aim of studying the interaction of fast electrons with solid surfaces we have developed an experimental set-up based on electron stimulated desorption (ESD) coupled to time-of-flight (TOF) mass spectrometry. Poly(methyl methacrylate) and poly(vynil chloride) samples have been irradiated by a pulsed electron beam of 1.2 keV and 0.18 µs FWHM. The results show that H+ is the main ionic species to desorb after electron bombardment. In addition, other ionic fragments were also observed and assigned. These results show the potentiality of this technique in the study of ESD of polymers.

Síntese de novos herbicidas derivados do 1,2alfa,4alfa,5-tetrametil-8-oxabiciclo[3.2.1]oct-6-en-3-ona

In this paper we report the synthesis of biologically active compounds through a [3+4] cycloaddition reaction to produce the main frame structure, followed by several conventional transformations. The 1,2alpha,4alpha,5-tetramethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (11) obtained from a [3+4] cycloaddition reaction was converted into 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8 -oxabicyclo[3.2.1]octan-3-one (13) in 46% yield. This was further converted into the alcohols 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (14), 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylidenedioxi-8 -oxabicyclo[3.2.1]octan-3beta-ol (15), 1,2alpha,4alpha,5-tetramethyl-3-butyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (17), 1,2alpha,4alpha,5-tetramethyl-3-hexyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (18) and 1,2alpha,4alpha,5-tetramethyl-3-decyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3 alpha-ol (19). Dehydration of 17, 18 and 19 with thionyl chloride in pyridine resulted in the alkenes 20, 21 and 22 in ca. 82% - 89% yields from starting alcohols. The herbicidal activity of the compounds synthesized was evaluated at a concentration of 100 µg g-1. The most active compound was 21 causing 42,7% inhibition against Cucumis sativus L.

Estudo de efeito dos sais precursores sobre as propriedades eletrocatalíticas de eletrodos de Ti-SnO2/Sb preparados por decomposição térmica

The physical and electrochemical properties of Ti-SnO2/Sb electrodes obtained by the thermal decomposition of solutions of the precursor salts SnCl2×2H2O/SbCl3 and SnSO4/Sb2(SO4)3 were investigated. The reversibility of the cyclic voltammetric response of the Fe(CN)6(4-)/Fe(CN)6(3-) redox couple was assessed using the obtained electrodes. Their catalytic activity for the oxygen-evolving reaction and maximum capacity for electronic transfer were also evaluated by potential and current linear scans in 0.5 mol L-1 H2SO4. Additionally, scanning electron microscopy analyses allowed the visualization of the morphology of the oxide films obtained. The best results were presented by the electrodes obtained from the chloride salt precursors.

Factors affecting Hg (II) adsorption in soils from the Rio Negro basin (Amazon)

Mercury (II) adsorption studies in top soils (top 10 cm) from the Rio Negro basin show this process depends strongly on some selected parameters of the aqueous phase in contact with the soils. Maximum adsorption occurred in the pH range 3.0-5.0 (>90%). Dissolved organic matter shows an inhibitory effect on the availability of Hg (II) to be adsorbed by the soils, whereas a higher chloride content of the solution resulted in a lower adsorption of Hg (II) at pH 5.0. Soils with higher organic matter content were less affected by changes in the salinity. An increase in the initial Hg (II) concentration increased the amount of Hg (II) adsorbed by the soil and decreased the time needed to reach equilibrium. A Freundlich isotherm provided a good model for Hg (II) adsorption in the two types of soil studied. The kinetics of Hg (II) adsorption on Amazonian soils showed to be very fast and followed pseudo-second order kinetics. An environmental implication of these results is discussed under the real scenario present in the Negro River basin, where acidic waters are in contact with a soil naturally rich in mercury.

Síntese de novas fitotoxinas derivadas do 8-oxabiciclo[3.2.1]oct-6-en-3-ona

The [4+3] cycloaddition was utilized in order to prepare 8-oxabicyclo[3.2.1]oct-6-en-3-one (1) derivatives. The correspondent acetonide 6 was converted into several alcohols (11-16). Addition of aryllithium reagents to 6 resulted in 3-(2-fluorophenyl)-6,7-exo-isopropylidenedioxy -8-oxabicyclo[3.2.1]octan-3alpha-ol (11, 72%) and 3-(2,4-dimethoxyphenyl)-6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan -3alpha-ol (16, 20%). The 3-butyl-6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 alpha-ol (15, 56%) was obtained through a Grignard reaction. Reduction of 6 resulted in 6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 beta-ol (7, 62%) and 6,7-exo-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3 alpha-ol (8, 20%). The alcohols were treated with thionyl chloride in pyridine, and the corresponding alkenes were obtained with 31-80% yield. The effect of these compounds on the development of radicle and aerial parts of Sorghum bicolor was evaluated.

Determinação de bromato em melhoradores de farinha por cromatografia de troca iônica com detecção espectrofotométrica

KBrO3 is registered by the FAO/OMS as a genotoxic and carcinogenic compound. In spite of this, KBrO3 is still employed by Brazilian bakeries. Nowadays ion exchange chromatography (IEC) is the most rapid and trustful method for BrO3- analysis. When at high concentrations, chloride ions can interfere in the BrO3- analysis, if the detection is performed by electrical conductivity. On the other hand, spectrophotometric detection, presented here is based on the absorption of BrO3- in the ultraviolet region (210 - 230 nm) where the absortion of chloride ions is very low, thus making possible the qualitative and quantitative analysis of BrO3- in flour improver samples.