Hidrólise parcial da superfície do polyethylene terephthalate (PET): transformando um rejeito em um material de troca catiônica para aplicação ambiental

In this work it is proposed a simple and versatile undergraduate chemical experiment in polymer and environmental technology based on the process of polyethylene terephthalate (PET) hydrolysis. Polyethylene terephthalate from post-consume bottles is submitted to a controlled partial hydrolysis which allows the students to follow the reaction by a simple procedure. The students can explore the reaction kinetics, the effect of catalysts and the exposed polyethylene terephthalate surface area on the hydrolysis reaction. The second and innovative part of this experiment is the technological and environmental application of the hydrolyzed polyethylene terephthalate as a material with cation exchange properties. The surface hydrolyzed polyethylene terephthalate can be used as adsorbent for cationic contaminants.

Mecanismos químicos e mineralógicos de transformação da magnesioferrita de solo derivado de tufito, da região do Alto Paranaíba, MG

Magnetic soils forming on tuffite of the region of Alto Paranaíba, Minas Gerais, Brazil, usually contain iron-rich spinels exceptionally rich in magnesium and titanium. In this work, samples of the magnetically separated portion from the sand fraction of a Brunizém (Chernossolo) and from its mother-rock material were analyzed with synchrotron X-ray diffraction and 57Fe-Mössbauer spectroscopy. Magnesioferite (MgFe2O4) and maghemite (its pure non-stoichiometric spinel structure, Fe8/3 ⊕ 1/3 O4, where ⊕ = cation vacancy, corresponds to γFe2O3) were the magnetic iron oxides so identified. Basing on these data, a consistent chemical-mineralogical model is proposed for the main transformation steps involving these iron oxides in the pedosystem, starting on magnesioferrite to finally render hematite (αFe2O3), passing through maghemite as an intermediate specie.

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.

Efecto del catión, del anión y del co-ión sobre la agregación de líquidos iónicos en solución acuosa

The aggregation behavior of thirteen 1-alkyl-3-methylimidazolium based ionic liquids in aqueous solution is presented, considering variations of the alkyl side chain length as well as the anionic moiety. Cation and anion molecular volumes are selected as appropriate molecular descriptors. Additionally, the existing relationship between critical micelle concentration (CMC) and electrolyte concentration in solution is established, aiming to clarify ion effects. CMC values were obtained by measuring electrical conductivity and surface tension. It was confirmed that aggregation of ionic liquids in aqueous solution and in presence of inorganic salts is affected by the factors developed in this study.

Gas-phase solvolysis type reactions of SiCl3+ cations

Gas-phase SiCl3+ ions undergo sequential solvolysis type reactions with water, methanol, ammonia, methylamine and propylene. Studies carried out in a Fourier Transform mass spectrometer reveal that these reactions are facile at 10-8 Torr and give rise to substituted chlorosilyl cations. Ab initio and DFT calculations reveal that these reactions proceed by addition of the silyl cation to the oxygen or nitrogen lone pair followed by a 1,3-H migration in the transition state. These transition states are calculated to lie below the energy of the reactants. By comparison, hydrolysis of gaseous CCl3+ is calculated to involve a substantial positive energy barrier.

Application of ftir in the determination of acrylate content in poly(sodium acrylate-co-acrylamide) superabsorbent hydrogels

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

Processo de estabilização de resíduos orgânicos: vermicompostagem versus compostagem

Two processes are used to stabilize organic wastes: composting and vermicomposting.There are no studies in the literature showing which process is most effective over the short term. In this study, 3 organic wastes were composted and vermicomposted for 90 days, and the parameters pH, effective cation exchange capacity, total organic carbon, total Kjeldahl nitrogen, Ptotal, E4/E6 ratio, hydrophobicity and aromaticity indexes were determined. In all experiments, vermicomposted materials showed higher stability, proving a superior tool for stabilization of these organic wastes.

Syntheses, characterization and antifungal activity of tris(1,10-phenanthroline)iron(ii) bis(n-r-sulfonyldithiocarbimate)zincate(ii)

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.

Preparation and immobilization of diNOsarcobalt(III) complex in zeolite y for the catalyzed production of hydrogen peroxide

A complex cation, diNOsarcobalt(III), [Co(diNOsar)]3+, (diNOsar = 1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo-[6.6.6]eicosane), was synthesized and immobilized in the cavities of a Y zeolite by the reaction of precursor species in the pores of the zeolite. The encapsulated material was compared to the compound diNOsarcobalt(III) chloride, [Co(diNOsar)]Cl3. Both diNOsarcobalt(III) chloride and the zeolite-encapsulated complex, [Co(diNOsar)]3+/zeolite, were obtained in high yield and characterized by ultraviolet-visible and infrared spectroscopy. X-ray diffraction demonstrated the incorporation of the complex cation into the pores of the zeolite. The catalytic production of hydrogen peroxide from oxygenated water confirmed the successful synthesis of the complex diNOsarcobalt(III) immobilized in the zeolite.

Líquidos iônicos como plastificantes em blendas de borracha nitrílica/polianilina

Two imidazolium-based ionic liquids (C4MIMTf2N and C4MIMBF4) were used to verify their influence on polyaniline (PANI) and nitrile rubber (NBR)/PANI blend properties and the vulcanization process. High conductivity values were observed for PANI-C4MIMTf2N samples and no interference was found for the C4MIMBF4 samples. These materials were added to NBR by mechanical mixing. Based on the torque results, the presence of C4MIMBF4 does not protect the vulcanization reaction of NBR with PANI as performed by C4MIMTf2N. The highest conductivity value was obtained with 7 wt. % of PANI-DSBA-C4MIMTf2N (10-6 S/cm). This result is attributed to the more effective interaction of PANI and NBR phases promoted by the ionic liquid.

Modificação do polímero condutor polianilina para uso como trocador catiônico

This article reports the use of polyaniline (PAni), chemically and electrochemically synthesized, for copper removal from aqueous solutions. PAni films were electrodeposited on reticulated vitreous carbon (RVC). In all cases, p-toluenesulfonate anion (PTS-) was used as the dopant to obtain cation exchange properties. RVC/PAni showed no expressive copper removal due to the small amount of polymer in the film. Chemically synthesized PAni-PTS- was obtained in its reduced form (leucoesmeraldine). PAni degraded at neutral pH but remained stable at low pH, showing a very high ion-exchange capacity, which is superior to those observed for commercial resins.

SYNTHESIS AND CHARACTERIZATION OF HDTMA-ORGANOCLAYS: INSIGHTS INTO THEIR STRUCTURAL PROPERTIES

This study aims to synthesize and characterize organoclays developed from an Argentinian montmorillonite (Bent) using hexadecyltrimethylammonium bromide (HDTMA-Br) as the intercalation agent. Subsequently, an adsorption mechanism is proposed. The obtained organoclays were more hydrophobic than the starting clay. Surfactant molecules were adsorbed initially through cation exchange in sites placed in the interlayer space of the clay. Adsorption in such sites continued until the interlayer space was saturated. Depending on the surfactant loading introduced during the intercalation process, different organizations of surfactant in the interlayer were obtained. Further adsorption of surfactant occurred in the mesopores generated by tactoids in the "house of cards" organization. This process kept surfactant molecules relatively free and out of the interlayer space.

AVALIAÇÃO DO RADICAL N,N-DIETIL-1,4-FENILENODIAMINO (DEPD•+) COMO SONDA ESPECTROFOTOMÉTRICA PARA DETERMINAÇÃO DA CAPACIDADE ANTIOXIDANTE EM BEBIDAS

AbstractMany well-established methods for determining the antioxidant capacities in several samples have been described in literature. However, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)) are the main two methods that utilize radicals as spectrophotometric probes for analysis. Nevertheless, these methods have certain limitations because of their slower kinetics, solvent polarity effects, the hydrophilicity and lipophilicity of the compounds, chemical costs, etc. In this study, a spectrophotometric method for determining the antioxidant capacity in beverages was developed based on an exploration of the cation radical derived from DEPD. This method was based on the oxidation of aromatic amines with Fe(III) ions at pH 4.0, which leads to their corresponding purple cation radicals (DEPD•+) with λmax values at 500 and 540 nm. The addition of an antioxidant after the formation of the radical leads to a reduction in color intensity that is proportional to the antioxidant concentration in the medium. Results obtained using this method were compared with the Folin-Ciocalteau, ABTS and DPPH methods in terms of applications in wines, teas, and infusions samples. Linear correlation analysis at a 95% confidence level was employed to compare the results, which were in good agreement with a correlation coefficient of r > 0.9000. Thus, the developed method was simple, accurate, and consistent with other assays for the determination of the total amount of phenolic compounds and antioxidant capacity.

FASES ESTACIONÁRIAS DE LÍQUIDOS IÔNICOS EM CROMATOGRAFIA GASOSA: FUNDAMENTOS, AVANÇOS RECENTES E PERSPECTIVAS

Since their original discovery in 1914, ionic liquids (IL) have been widely examined and explored in chemistry due to their unique physical and chemical properties. Ionic liquids are collectively known as organic salts and have melting points of 100 °C or under. The molten salts most employed in analytical chemistry, including gas chromatography (GC), consist of an organic cation paired with an organic or inorganic anion. This class of materials exhibits negligible vapor pressure and may have their properties (e.g.thermal stability and selectivity) structurally tuned by imparting different moieties to the cation/anion. Currently, there are an estimated 1018possible combinations of IL. In this context, the prospection of highly selective IL-based stationary phases for gas-liquid chromatography has enabled high peak capacity and efficient separations of many critical pairs in complex samples. In this review, we present and discuss fundamental characteristics of ionic liquids and introduce important solvation models for gas-liquid systems. In addition, recent advances and applications of IL in conventional and multidimensional gas chromatography are outlined.

Influence of vinasse application in hydraulic conductivity of three soils

The potassium ion, present in great amount in the vinasse because it is a monovalent cation, has the characteristic of promoting the dispersion of clay particles, in the same way as the sodium, causing a reduction in the pore space of the soil and, in its turn, reducing its permeability. To evaluate this effect of reduction by application of vinasse to the soil, an experiment was conducted for three different soils, with the objective of evaluating the effect of the application of different doses of vinasse on hydraulic conductivity of saturated soil and verifying its possible chemical changes of these soils. For that, it was used PVC columns (in a scheme of constant head permeameter to obtain the values of hydraulic conductivity of saturated soil), filled with three soils - Dark Red Latosol (DRL), Purple Latosol (PL) and Eutrophic Red Nitossol (ERN) - , in which were applied four doses of vinasse (0, 150, 300 and 450m³ ha-1), distributed in a completely randomized design with a 3x4 factorial scheme with three replications. The results evidenced that only the Dark Red Latosol (DRL) showed a reduction in the values of hydraulic conductivity of saturated soil, and in front of the application of vinasse, up to 300m³ ha-1, it was observed an increase in the concentrations of potassium, calcium and cation exchange capacity (CEC) ions.