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.

Hidrogenofosfato de titânio lamelar: síntese, troca iônica e intercalação

The development associated with the research field involving crystalline inorganic lamellar titanium hydrogenphosphate, Ti(HPO4).H2O, synthesized as alpha or gamma forms, is directly linked to the huge number of reactions, that occur inside the free interlamellar space. Two distinguishable well-characterized features such as ion-exchange and intercalation reactions are explored here. From the interactive point of view, the acidic OH centres distributed on the lamella can interact with cations or with basic polar molecules to exchange or to intercalate them. These chemical reactions are normally followed by an expansion of the interlamellar space, proportional to the amount intercalated, reflecting in ion radii or organic molecule size lengths used in ion-exchange or insertion processes, respectively. The effectiveness of the exchange increased when the original matrix has the proton of OH group previously ion-exchanged by an alkaline or an alkylammonium cations. Monoalkyl-, dialkyl- and heterocyclic amines are focused in this revision as clear and elucidative examples of acid-base interactive processes, that come out inside of the well-formed infinite sequence of inorganic lamellar structure.

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.

Distribuição de metais e caracterização das constantes de troca entre espécies metálicas e frações húmicas aquáticas de diferentes tamanhos moleculares

In this work the metal distribution and exchange constants between metal species and aquatic humic fractions with different molecular sizes were studied. The aquatic humic substances (AHS) were extracted by XAD-8 resin from water sample collected from Itapitanguí river, São Paulo State, Brazil. The AHS were fractionated in six fractions with different molecular sizes (>100 - <5 kDa) and characterized by several techniques. Molar ratios H/C suggested higher aromaticity for fractions F1 and F6 whereas molar ratios C/N didn´t show any differences regarding the humification degree between the fractions. The UV-Vis absorbance a254/a436 ratio showed higher results for F4 and F5, probably by less condensed features. FTIR studies showed high similarity in the functional groups in the fractions. The highest percentage of traces of Co, Al, Fe, Mn, Cu, Zn and Ni (determined by ICP-AES) was preferably complexed by fractions F3 and F4 with a greater amount of dissolved organic carbon (DOC). In addition, the exchange constants, determined by ultrafiltration method, showed complexes AHS-Fe and AHS-Al with higher stability than complexes AHS-Co in all fractions.

Models for the estimation of thermodynamic properties of layered double hydroxides: application to the study of their anion exchange characteristics

Several models for the estimation of thermodynamic properties of layered double hydroxides (LDHs) are presented. The predicted thermodynamic quantities calculated by the proposed models agree with experimental thermodynamic data. A thermodynamic study of the anion exchange process on LDHs is also made using the described models. Tables for the prediction of monovalent anion exchange selectivities on LDHs are provided. Reasonable agreement is found between the predicted and the experimental monovalent anion exchange selectivities.

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.

Efeito de substâncias empregadas para remoção de cobre sobre o teor de compostos secundários da cachaça

High copper content is of great concern among producers of sugar-cane spirits who frequently use filters instead of cleaning the stills. This study compared the efficiency of activated carbon, ion-exchange-polymeric resin, and activated-carbon/iron-oxide magnetic composite for copper reduction without removing excessive organic compounds that are important for the beverage's quality. Resin was the most efficient copper adsorbent, removing fewer organic compounds. The composite also removed copper; however, it also removed large amounts of organic compounds. Activated carbon didn't remove sufficient copper to reduce its concentration to less than 5 g L-1, and it removed large amounts of higher alcohols and esters.

Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC). The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II)-sulfathiazole, Co(II)-ST) in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test), with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

Preparação e propriedades de zeólitas faujasita contendo cátions amônio

Sodium faujasite zeolites with Si/Al ratio of 1.4 and 2.5 were exchanged with methylammonium cations. The influence of framework aluminum and ion exchange degree in their basic properties were evaluated. These properties were assessed in the Knoevenagel catalytic condensation. The sodium ion exchange was restricted to the supercavity and the exchange degree depended on the cation volume and on the Si/Al ratio. The higher catalytic activity is achieved for the zeolite with the lower Si/Al ratio exchanged with the monomethylammonium cation. The best performance of this catalyst is attributed to the higher basicity in combination with elevated micropore volume.

Recovery of manganese and zinc from spent Zn-C and alkaline batteries in acidic medium

The anode and the internal paste of spent Zn-C and alkaline batteries were leached with 2 mol L-1 H2SO4 at 80 ºC for 2 h. Solid/liquid ratio was 1/10 (g mL-1). The leachate was treated with Na2S in order to precipitate Hg, Cd and Pb. Zn was quantitatively isolated at pH 1,5-2 by adding Na2S. Mn can be precipitated at pH close to 7. Na2S may be replaced by oxalic acid. Zn precipitated at pH around 0, whereas Mn was quantitatively recovered at pH > 4. Acidity control is a critical parameter. Na2SO4 and carbon are the end products.

Separation and preconcentration of copper in environmental samples on Amberlite XAD-8 resin after complexation with a carbothioamide derivative

A new solid phase extraction (SPE) method has been developed for the selective separation and preconcentration of Cu (II) ions in food and water samples prior to its flame atomic absorption spectrometry determination. The method is based on the adsorption of the Cu(II) - 2-{[4-Amino-3-(4-methylphenyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]acetyl}-N-phenyl hydrazinecarbothioamide complex on Amberlite XAD-8 resin. The metal complex retained on the resin was eluted with 7.5 mL of 2.0 mol L-1 HCl in acetone. The optimum conditions for the SPE of Cu(II) ions were investigated, and the method was subsequently applied to sea water, stream water, rice, tea, and tobacco samples for the determination of Cu(II) levels.

Separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography

An effective method for the rapid separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was successfully established. In the present study, a two-phase solvent system composed of chloroform-n-butanol-methanol-water (4:1:4:2, v/v/v/v) was used for HSCCC separation. A one-step separation in 4 h from 150 mg of crude extract produced 26.3 mg of trans-resveratrol-3-O-glucoside, 42.0 mg of pieceid-2"-O-gallate, and 17.9 mg of trans-resveratrol with purities of 99.1%, 97.8%, and 99.4%, respectively, as determined by high-performance liquid chromatography (HPLC). The chemical structures of these compounds were identified by nuclear magnetic resonance (NMR) spectroscopy.

FAST GC-FID METHOD FOR MONITORING ACIDIC AND BASIC CATALYTIC TRANSESTERIFICATION REACTIONS IN VEGETABLE OILS TO METHYL ESTER BIODIESEL PREPARATION

A fast gas chromatography with a flame ionisation detector (GC-FID) method for the simultaneous analysis of methyl palmitate (C16:0), stearate (C18:0), oleate (C18:1), linoleate (C18:2) and linolenate (C18:3) in biodiesel samples was proposed. The analysis was conducted in a customised ionic-liquid stationary-phase capillary, SLB-IL 111, with a length of 14 m, an internal diameter of 0.10 mm, a film thickness of 0.08 µm and operated isothermally at 160 °C using hydrogen as the carrier gas at a rate of 50 cm s-1 in run time about 3 min. Once methyl myristate (C14:0) is present lower than 0.5% m/m in real samples it was used as an internal standard. The method was successful applied to monitoring basic and acidic catalysis transesterification reactions of vegetable oils such as soybean, canola, corn, sunflower and those used in frying process.

The Li+, Na+ and K+ ion exchange reaction process on the surface of mixed oxide SiO2/TiO2/Sb2O5 surface prepared by the sol-gel processing method

The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

Lability of Cd, Cr, Cu, Mn and Pb complexed by aquatic humic substances

The lability of Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) complexed by humic substances (HSs) was investigated by means of ion exchange on cellulose modified with p-aminobenzoic groups (Cell-PAB), using a batch procedure. The HSs were extracted from water samples using adsorption in a column packed with XAD 8 resin. The metal-HS complexes were prepared by adding solutions containing all the aforementioned metal ions ( Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) ). The results indicated that the distribution coefficients (Kd) of Cell-PAB decreased with the presence of HSs, and that the lability of metal fractions complexed by HSs decreases in pH values > 4.0, complexation time > 10 h and HS concentration > 500 mg L-1. The metal exchange between HSs and Cell-PAB exhibited the following order of metal ion lability: Cd < Pb < Mn @ Cr < Cu.