Influence of initial CaO/SiO2 ratio on the hydration of rice husk ash-Ca(OH)2 and sugar cane bagasse ash-Ca(OH)2 pastes

This work presents the results of a study on the hydration of pastes containing calcium hydroxide and either rice husk ash (RHA) or sugar cane bagasse ash (SCBA) in various initial CaO/SiO2 molar ratios. The products of the reactions were characterized by thermal analyses X-ray diffraction, and scanning electron microscopy. In the case of the RHA pastes, the product was composed of CaO-SiO2-H2O (type I C-S-H) or CaO-SiO2-H2O (type II C-S-H) according to the CaO/SiO2 ratio of the mixture. In contrast, in the case of the SBCA pastes, the product was composed primarily of CaO-SiO2-H2O that differed from both the previous types; the product also contained inclusions of calcium aluminate hydrates.

ESTERIFICAÇÃO E TRANSESTERIFICAÇÃO SIMULTÂNEAS DE ÓLEOS ÁCIDOS UTILIZANDO CARBOXILATOS LAMELARES DE ZINCO COMO CATALISADORES BIFUNCIONAIS

Palm oil containing 40% fatty acids was converted to methyl esters using zinc carboxylates as the esterification/transesterification catalyst. The reaction was optimized using a factorial design in which the effects of the alcohol:fatty acids molar ratio (MRAG) and the catalyst concentration (CAT) were assessed. The best conversion was achieved with CAT at 4 wt% and MRAG at 4:1. However, the solid catalyst presented significant structural changes after use. For instance, laurate anions were replaced by carboxylates of higher molecular mass, leading to the formation of a new catalytically active layered structure. Also, the glycerin obtained as a co-product contained 86 wt% glycerol.

MICROWAVE ACTIVATION OF IMMOBILIZED LIPASE FOR TRANSESTERIFICATION OF VEGETABLE OILS

This work investigated the effect of microwave irradiation (MW) on the ethanolysis rate of soybean and sunflower oils catalyzed by supported Novozyme 435 (Candida antarctica). The effects of tert-butanol, water addition and oil:ethanol molar ratio on transesterification were evaluated under conventional heating (CH), and under optimum reaction conditions (with no added water in the system, 10% tert-butanol and 3:1 ethanol-to-oil molar ratio). The reactions were monitored up to 24 h to determine the conditions of initial reaction velocity. The investigated variables under MW (50 W) were: reaction time (5.0-180 min) and mode of reactor operation (fixed power, dynamic and cycles) in the absence and presence of tert-butanol (10% (w/w). The measured response was the reaction conversion in ethyl esters, which was linked to the enzyme catalytic activity. The results indicated that the use of microwave improved the activity at fixed power mode. A positive effect of the association of tert-butanol and MW irradiation on the catalytic activity was observed. The reaction rate improved in the order of approximately 1.5 fold compared to that under CH with soybean oil. Using soybean oil, the enzymatic transesterification under MW for conversion to FAEE (fatty acid ethyl esters) reached >99% in 3h, while with the use of CH the conversions were about 57% under similar conditions.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

Ajuste de parâmetros de interação em modelos termodinâmicos

Para misturas nas quais existem interações entre moléculas diferentes aparece um parâmetro energético de interação ajustável na relação das variáveis. As grandezas termodinâmicas de excesso dão informação qualitativa dos possíveis tipos de interação. Duas grandezas importantes neste sentido são o volume de excesso e a entalpia de excesso. Neste artigo se estudam diferentes métodos, regressão com mínimos quadrados e por minimização do valor absoluto e relativo dos resíduos, para determinar a possibilidade de aplicação dos mesmos no cálculo de parâmetros de interação molecular em modelos termodinâmicos de soluções. Usam-se dados experimentais de volume molar de excesso para todo o intervalo de frações molares de 10 sistemas binários formados por acetonitrila + um álcool primário (do metanol ao n-decanol). Comparam-se os valores calculados e os dados experimentais das grandezas, e são feitas análises dos resultados.

Parâmetros cinéticos da degradação térmica de complexos entre percloratos de terras raras com lactama

Complexos de percloratos à base de terras raras com a 2-azaciclononanona (AZA) foram obtidos a partir da reação entre os respectivos sais hidratados com a AZA (proporção molar 1:8) pelo método de difusão de vapor e caracterizados por titulação complexiométrica com EDTA, microanálise (CHN), espectroscopia vibracional na região do IV, termogravimetria em atmosfera de ar e N2 e calorimetria exploratória diferencial (DSC) em atmosfera de N2. O estudo cinético desse trabalho foi realizado utilizando um software em QBASIC que faz a simulação dos dados termogravimétricos a partir de um conjunto dado de parâmetros cinéticos.

Análise química inorgânica de leite esimulação do reagente CFA-C

Na análise de leite por espectrometria de emissão ótica com plasma induzido (ICP-OES) o produto comercial CFA-C, constituído por aminas terciárias, vêm sendo usado com sucesso como diluente em fase única. Devido ao custo do produto e possibilidades de contaminação durante o armazenamento, decidiu-se desenvolver um outro reagente de propriedades equivalentes ao referido produto. Testes qualitativos mostraram que o produto não contém ácido bórico nem EDTA. Em uma titulação potenciométrica de uma solução aquosa 10% v/v CFA-C com HCl obtiveram-se dois picos potenciométricos e deduziu-se que 90% do ácido foi consumido para neutralização da amina livre e 10% foi gasto para protonar um ânion de ácido fraco usado para formar um tampão de razão molar 10:1, do tipo R3N/R3NH+. Em uma simulação desse reagente preparou-se uma solução 6,06 mol L-1 de monoetanolamina (MEA) e 0,20 mol L-1 ácido cítrico, triprótico, para formar um tampão do mesmo tipo, 10:1, baseado na propriedade do íon citrato em complexar Ca(II). Outro tampão citrato mais diluído (1,52 mol L-1) foi preparado usando trishidroximetilaminometano (TRIS), que é uma amina menos solúvel. Essas misturas foram caracterizadas por análise potenciométrica e termoanalítica. O comportamento desses novos tampões amina/citrato foi adequado e comparável ao produto comercial.

Fotoquímica e fotofísica do ácido 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno

Este trabalho versa sobre a caracterização espectroscópica do ácido 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno, substância com potencialidade em complexação de íons metálicos. Para isto foram obtidos espectros de UV/VIS do composto em meio aquoso na presença e ausência de irradiação no ultra-violeta. Foram obtidos um coeficiente de extinção molar de 36.457 L mol-1 cm-1 e uma taxa de degradação de 5,2.10-7 mol L-1 min-1, quando se irradiou uma solução do composto cuja concentração era de 3,2.10-5 mol L-1 em uma cubeta de quartzo de 10mm de caminho ótico a 7,0cm de uma lâmpada de mercúrio de 80W.

Spectrophotometric determination of diclofenac in pharmaceutical preparations assisted by microwave oven

In this work, an effective and low-cost method for the determination of sodium or potassium diclofenac is proposed in its pure form and in their pharmaceutical preparations. The method is based on the reaction between diclofenac and tetrachloro-p-benzoquinone (p-chloranil), in methanol medium. This reaction was accelerated by irradiating of reactional mixture with microwave energy (1100 W) during 27 seconds, producing a charge transfer complex with a maximum absorption at 535 nm. The optimal reaction conditions values such as reagent concentration, heating time and stability of the reaction product were determined. Beer's law is obeyed in a concentration range from of 1.25x10-4 to 2.00x10-3 mol l-1 with a correlation coefficient of 0.9993 and molar absorptivity of 0.49 x10³ l mol-1 cm-1. The limit of detection (LOD) was 1.35x10-5 mol l-1 and the limit of quantification (LOQ) was 4.49x10-5 mol l-1. In the presence of the common excipients, such as glucose, lactose, talc, starch, magnesium stearate, sodium sulphite, titanium dioxide, polyethyleneglycol, polyvinylpirrolidone, mannitol and benzilic alcohol no interferences were observed. The analytical results obtained by applying the proposed method compare very favorably with those given by the United States Pharmacopeia standard procedure. Recoveries of diclofenac from various pharmaceutical preparations were within 95.9% to 103.3%, with standard deviations ranging from 0.2% to 1.8%.

Spectrophotometric study of iron oxidation in the iron(II)/thiocyanate/acetone system and some analytical applications

The possibility of using thiocyanate to determine iron(II) and/or iron(III) in water-acetone mixture has been re-examined as part of a systematic and comparative study involving metallic complexes of pseudohalide ligands. Some parameters that affect the complete oxidation of the ferrous cations, their subsequent complexation and the system stability have been studied to optimize the experimental conditions. Our results show the viability and potentiality of this simply methodology as an alternative analytical procedure to determine iron cations with high sensitivity, precision and accuracy. Studies on the calibration, stability, precision, and effect of various different ions have been carried out by using absorbance values measured at 480 nm. The analytical curve for the total iron determination obeys Beer's law (r = 0.9993), showing a higher sensitivity (molar absorptivity of 2.10x10(4) L cm-1 mol-1) when compared with other traditional systems (ligands) or even with the "similar" azide ion [1.53x10(4) L cm-1 mol-1, for iron-III/azide complexes, in 70% (v/v) tetrahydrofuran/water, at 396 nm]. Under such optimized experimental conditions, it is possible to determine iron in the concentration range from 0.5 to 2 ppm (15-65% T for older equipments, quartz cells of 1.00 cm). Analytical applications have been tested for some different materials (iron ores), also including pharmaceutical products for anemia, and results were compared with atomic absorption determinations. Very good agreement was obtained with these two different techniques, showing the potential of the present experimental conditions for the total iron spectrophotometric determinations (errors < 5%). The possibility of iron speciation was made evident by using another specific and auxiliary method for iron(II) or (III).

Influência da temperatura de formação do íon de Keggin no processo de pilarização de esmectitas

As amostras de esmectita do estado do Pará, Amazônia, Brasil foram caracterizados utilizando XRD, FTIR e análise textural por curvas isotérmicas adsorpition-desorption nitrogênio. Na produção das argilas pilarizadas foi usado o íon Al13 (o íon de keggin), este íon foi obtido pela reação das soluções AlC(l3)6H2O / NaOH, com razão molar OH/Al=2, com intercalação em temperatura ambiente, durante as 3 horas e calcinada em 450ºC (temperatura adequada da calcinação). O material foi preparado utilizando soluções produzidas na faixa de temperatura de 25, 45, 65, 85, 105ºC, o Resultado mostrou que o processo de pilarização aumenta o espaçamento basal da argila natural de 14,02 para 19,74 Å e a área superficial de 44,30 para 198,03m²/g. a estabilidade térmica da argila natural foi melhorada pelo procedimento de pilarização.

Sensitive bromatometric assay methods for finasteride in pharmaceuticals

Three sensitive spectrophotometric methods are presented for the determination of finasteride in bulk and in tablets. The methods rely on the use of bromate-bromide reagent and three dyes namely, methyl orange, indigocarmine and thymol blue as reagents. They involve the addition of a measured excess of bromate-bromide reagent to finasteride in acid medium, and after the bromination reaction is judged to be complete, the unreacted bromine is determined by reacting with a fixed amount of either methylorange and measuring the absorbance at 520 nm (method A) or indigocarmine and measuring the absorbance at 610 nm (method B) or thymol blue and measuring the absorbance at 550 nm (method C). In all the methods, the amount of insitu generated bromine reacted corresponds to the amount of finasteride. The absorbance measured at the respective wavelength is found increase linearly with the concentration of finasteride. Beer's law is obeyed in the ranges 0.25- 2.0, 0.5-6.0 and 1-12 µg mL-1 for method A, method B and method C, respectively. The calculated molar absorptivity values are 5.7x10(4), 3.12x10(4) and 1.77x10(4) L mol-1 cm-1 respectively, for method A, method B and method C, and the corresponding Sandell sensitivity values are 0.0065, 0.012 and 0.021 µg cm-2. The limits of detection (LOD) and quantification (LOQ) are also reported for all the methods. Accuracy and, intra-day and inter-day precisions of the methods were established according to the current ICH guidelines. The methods were successfully applied to the determination of finasteride in commercially available tablets and the results were found to closely agree with the label claim. The results of the methods were statistically compared with those of a reference method by applying Student's t-test and F-test. The accuracy and reliability of the methods were further confirmed by performing recovery tests via standard addition procedure.

Sensitive spectrophotometric determination of lansoprazole in pharmaceuticals using ceric ammonium sulphate based on redox and complex formation reactions

Two simple sensitive and cost-effective spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsules using ceric ammonium sulphate (CAS), iron (II), orthophenanthroline and thiocyanate as reagents. In both methods, an acidic solution of lansoprazole is treated with a measured excess of CAS followed by the determination of unreacted oxidant by two procedures involving different reaction schemes. The first method involves the reduction of residual oxidant by a known amount of iron(II), and the unreacted iron(II) is complexed with orthophenanthroline at a raised pH, and the absorbance of the resulting complex measured at 510 nm (method A). In the second method, the unreacted CAS is reduced by excess of iron (II), and the resulting iron (III) is complexed with thiocyanate in the acid medium and the absorbance of the complex measured at 470 nm (method B). In both methods, the amount CAS reacted corresponds to the amount of LPZ. In method A, the absorbance is found to increase linearly with the concentration of LPZ where as in method B a linear decrease in absorbance occurs. The systems obey Beer's law for 2.5-30 and 2.5-25 µg mL-1 for method A and method B, respectively, and the corresponding molar absorptivity values are 8.1×10³ and 1.5×10(4) L mol-1cm-1 . The methods were successfully applied to the determination of LPZ in capsules and the results tallied well with the label claim. No interference was observed from the concomitant substances normally added to capsules.

Spectrophotometric study of the chromium(III)/azide system in the ultraviolet region and its analytical application

A sensitive and alternative method for the spectrophotometric determination of chromium(III) based on the formation of chromium(III)/azide complexes was established by investigating a new band in the ultraviolet region. The best experimental conditions for the analytical determination of this metallic ion were: ligand and perchloric acid analytical concentration = 493 and 12.0 mmol L-1, respectively; aqueous medium; T = 25.0 ºC; contact time = 1 hour. The maximum molar absorptivity coefficient occurred at 287 nm (average 1.481 ± 0.008 ´ 10(4) L mol-1 cm-1), leading to the determination of metal ion concentrations one hundred times lower than the ones formerly determined in the visible region. The system obeys Beer's Law and is suitable for chromium determination in the 0.702-2.81 mg L-1 concentration range (15-65% T, 1.00 cm-width quartz cells). Analytical applications of the current method were tested with a nutritional supplement containing chromium. Results were compared with those obtained with atomic absorption spectrometry.