O uso de sílica gel organofuncionalizada como agente sequestrante para metais

An overview about the homogeneous and heterogeneous methods of synthesizing silylating agents and applications of the organofunctionalized silica-gel samples was explored. The pendant molecules attached covalently to the inorganic surface displayed important properties to act as sequestrating agents for metals in aqueous and non-aqueous solutions. The large variety of basic centres anchored on organic molecules improve the capacity in adsorbing cations. The increase in adsorption is dependent on the number of basic atoms disposed on the pendant molecules on the surface. The combination of acidic and basicity properties favours the selectivity, such is exemplified by the thiol modified silicas towards mercury (II) cations.

Sobre a aplicabilidade da termogravimetria para a estimativa de parâmetros termoquímicos de compostos de coordenação: os elementos lantanídicos

By using thermochemical data reported for a series of chelates of the type [Ln(thd)3], thd = 2, 2, 6, 6 ­ tetramethyl- 3,5-heptanedione and Ln = La, Pr, Nd, Sm, Gd, Tb, Ho, Er, Tm and Yb, empirical correlations were found involving thermochemical parameters (e.g. dissociation enthalpy) and the thermodynamic temperatures of the beginning of thermal degradation of the chelates, t i. It is shown that t i values are of capital importance in the study of this all class of coordination compounds. Among others, the empirical equation is obtained: r3+ = (-0,013.Z + 1,36)/0,005, that relates the lanthanide cation radius (pm) with the atomic number of the element. The remarkable fact is that this equation is achieved by using thermogravimetric and calorimetric parameters. Is also shown that t i values are related with the P(M) function values, which are very close related with the energy difference, deltaE, between the lowest electronic energy level of the f n s²d¹ configuration and the lowest energy level of the f n+1s² configuration in the neutral gaseous atoms.

Gota suspensa para avaliação de aldeído total no ar interno e externo do ambiente

A sensitive and simple system was proposed for the in situ measurement of total aldehyde in outdoor or indoor ambient. The method is based on the use of a reagent drop as an useful interface to preconcentrate the sample prior to determination of total aldehyde as formaldehyde. The drop is formed at the tip of a cylindrical tube that contains two optical fibers placed on opposite sides and in contact with the reagent solution. One optical fiber carries the red light to the drop form a light emitting diode (LED). The transmitted light is measured by a second optical fiber/photodiode system. The analytical signal is read and converted into absorbance. The reagent solution of 3-methyl-2-benzothiazoline hydrazone (MBTH) forms a blue cation during reaction with formaldehyde that can be measured at 660 nm. Some aspects of kinetics reaction formation of dye were reevaluated. The formaldehyde reacts with MBTH and forms the azine in about 12 min. The oxidation of MBTH by Fe (III) and the formation of dye requires 3 min. The absorbance of the reagent drop is proportional to the sampling time and to the analyte concentration. The absorbance signal increases with increased sample gas flow until a maximum is reached then decreases until it forms a plateau. The proposed method was evaluated using both outdoor and indoor samples, and it was shown to viable provide an accurate measure of total aldehyde.

Líquidos iônicos contendo o cátion dialquilimidazólio: estrutura, propriedades físico-químicas e comportamento em solução

Ionic liquids, in specially those based on the 1,3-dialkylimidazolium cation, have been receiving special attention in differents areas due to their interesting physical-chemical properties. In this work, some aspects of their structure (in both solid and liquid state) and its relationships with their properties are reviewed.

Emprego de reagente em suspensão em sistema de injeção em fluxo: determinação espectrofotométrica de sulfato em águas naturais

This paper presents an automatic procedure employing a reagent in the form of a slurry in a flow-injection system. The feasibility of the proposal is demonstrated by sulphate determination in water using the Barium Chloranilate method, which is based on the precipitation of barium sulphate. The release of a stoichiometric amount of highly colored chloranilic ions is monitored at 528 nm. The reaction is carried out in alcoholic medium in order to reduce the solubility of the reagent. A considerable improvement in the sensitivity is attained by adding ferric ions to the released chloranilic ions. An on-line filtration step to separate the excess reagent from the released chloranilic ions was necessary. In addition, a column containing a cation exchange resin was included in the manifold to remove potentially interfering ions. The proposed procedure is suitable for 30 determinations per hour and the relative standard deviation is less than 2%. The analytical curve is linear between 0.0 and 40 mg L-1 and the determination limit is about 2.0 mg L-1SO4(2-). Accuracy was confirmed by running several samples already analysed by a standard turbidimetric procedure.

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.

Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane

The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates.

Determinação de Mn, Cu e Zn em matrizes salinas após separação e pré-concentração usando Amberlite XAD-7 impregnada com Vermelho de Alizarina S

The aim of this work was to explore the possibility of the application of a non-ionic resin obtained by impregnation of Alizarin Red S (VAS) in Amberlite XAD-7 for manganese, copper and zinc separation and preconcentration in saline matrices. For these system, the metals were quantitatively retained, in the pH range 8.5-10.0, by using 0.50 g of solid phase, stirring time of five minutes and a total mass up to 200 mug of each cation. The sorbed elements were subsequently eluted and a fifty-fold, ten-fold and ten-fold preconcentration factor for to Zn, Cu and Mn were obtained, respectively.

Estabilização de solo contaminado com zinco usando zeólitas sintetizadas a partir de cinzas de carvão

The effect of synthetic zeolites on stabilizing Zn-contaminated soil using 0.01 mol L-1 CaCl2 leaching solution in batch experiments was investigated. The zeolites were synthesized from coal ash by hydrothermal treatment with alkaline solution. The additive enhanced the sorption capacity of the soil and reduced leaching. Zinc leaching was reduced by more than 80% using a minimum of 10% additive. The higher cation exchange capacity of the zeolite/soil mixtures and higher pH were responsible for stabilizing Zn in soil. The poly(2-aminobenzenesulfonic acid)-coated mercury thin-film electrode was used for the determination of zinc.

Remoção de metais pesados de efluentes aquosos pela zeólita natural escolecita - influência da temperatura e do pH na adsorção em sistemas monoelementares

Cation exchange capabilities of a Brazilian natural zeolite, identified as scolecite, were evaluated for application in wastewater control. We investigated the process of sorption of chromium(III), nickel(II), cadmium(II) and manganese(II) in synthetic aqueous effluents, including adsorption isotherms of single-metal solutions. The natural zeolite showed the ability to take up the tested heavy metals in the order Cr(III) > Cd(II) > Ni(II) > Mn(II), and this could be related to the valence and the hydration radius of the metal cations. The influence of temperature (25, 40 and 60 ºC) and initial pH value (from 4 to 6) was also evaluated. It was found that the adsorption increased substantially when the temperature was raised to 60 ºC and that maximum adsorption capacity was observed at pH 6. These results demonstrate that scolecite can be used for removal of heavy metals from aqueous effluents, under optimized conditions.

Eletrodo íon-seletivo para determinação potenciométrica de alumínio(III) em meio de fluoreto

The construction and analytical evaluation of a coated graphite Al(III) ion-selective electrode, based on the ionic pair formed between the Al(F)n3-n anion and tricaprylylmethylammonium cation (Aliquat 336S) incorporated on a poly(vinylchloride) (PVC) matrix membrane are described. A thin membrane film of this ionic pair and dibutylphthalate (DBPh) in PVC was deposited directly on a cylindric graphite rod (2 cm length x 0.5 cm diameter) attached to the end of a glass tube using epoxy resin. The membrane solution was prepared by dissolving 40% (m/m) of PVC in 10 mL of tetrahydrofuran following addition of 45% (m/m) of DBPh and 15% (m/m) of the ionic pair. The effect of membrane composition, fluoride concentration, and several concomitants as potential interferences on the electrode response were investigated. The aluminium(III) ion-selective electrode showed a linear response ranging from 1.4 x 10-4 to 1.0 x 10-2 mol L-1, a detection limit of 4.0 x 10-5 mol L-1, aslope of -54.3±0.2mV dec-1 and a lifetime of more than 1 year (over 3000 determinations for each membrane). The slope indicates that the ion-selective electrode responds preferentially to the Al(F)4- species. Application of this electrode for the aluminium(III) determination in stomach anti-acid samples is reported.

Remediação de drenagem ácida de mina usando zeólitas sintetizadas a partir de cinzas leves de carvão

Zeolitic material was synthesized from coal fly ashes (baghouse filter fly ash and cyclone filter fly ash) by hydrothermal alkaline activation. The potential application of the zeolitic product for decontamination of waters from acid mine drainage was evaluated. The results showed that a dose of 30 g L-1 of zeolitic material allowed the water to reach acceptable quality levels after treatment. Both precipitation and cation-exchange processes accounted for the reduction in the pollutant concentration in the treated waters.

Myoglobins: the link between discoloration and lipid oxidation in muscle and meat

Aerobic metabolism changes rapidly to glycolysis post-mortem resulting in a pH-decrease during the transformation of muscle in to meat affecting ligand binding and redox potential of the heme iron in myoglobin, the meat pigment. The "inorganic chemistry" of meat involves (i) redox-cycling between iron(II), iron(III), and iron(IV)/protein radicals; (ii) ligand exchange processes; and (iii) spin-equilibra with a change in coordination number for the heme iron. In addition to the function of myoglobin for oxygen storage, new physiological roles of myoglobin are currently being discovered, which notably find close parallels in the processes in fresh meat and nitrite-cured meat products. Myoglobin may be characterized as a bioreactor for small molecules like O2, NO, CO, CO2, H2O, and HNO with importance in bio-regulation and in protection against oxidative stress in vivo otherwise affecting lipids in membranes. Many of these processes may be recognised as colour changes in fresh meat and cured meat products under different atmospheric conditions, and could also be instructive for teaching purposes.

Anéis aromáticos condensados e relação E4/E6: estudo de ácidos húmicos de gleissolos por RMN de 13C no estado sólido utilizando a técnica CP/MAS desacoplamento defasado

In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures.

Distribuição de mercúrio em diferentes solos da Bacia do médio Rio Negro-AM: influência da matéria orgânica no ciclo biogeoquímico do mercúrio

Soils play an important role in the biogeochemical cycle of mercury as a sink for and source of this metallic species to atmospheric and hydrological compartments. In the study reported here, various types of soil were evaluated to ascertain the influence of parameters such as pH, organic matter content, Fe, Al, sand, silt, clay, C/H, C/N, C/O atomic ratios, and cation exchange capacity on the distribution of Hg in Amazonia's mid-Negro River basin. The data obtained were interpreted by multivariate exploratory analyses (hierarchical cluster analysis and principal component analysis), which indicated that organic matter plays an important role in mercury uptake in the various soils studied. The soils in floodable areas were found to contain 1.5 to 2.8-fold higher Hg concentrations than those in non-floodable areas. Since these soils are flooded almost year-round, they are less available to participate in redox processes at the soil/atmosphere interface. Hence, floodable areas, which comprise humic-rich soils, accumulate more mercury than non-floodable soils, thus playing an important role in the biogeochemical cycle of Hg in Amazonia's mid-Negro River basin.