Determinação da demanda química de oxigênio em águas por espectrofotometria simultânea dos íons crômio(III) e dicromato

Propõe-se metodologia analítica para a determinação da demanda química de oxigênio(DQO) em águas e efluentes pouco poluídos, pela espectrofotometria simultânea dos íons crômio(III) e dicromato, após a clássica oxidação sulfocrômica das amostras, à quente e catalisada por íons Ag+. Demonstra-se que a inter-relação entre as concentrações de DQO, de crômio(III) formado e de dicromato residual permite simplificar a resolução numérica do sistema - de multicomponente, envolvendo as concentrações desses dois íons, e medidas de absorbância em pelo menos dois comprimentos de onda para monocomponente, envolvendo diretamente a concentração em DQO, e medida de absorbância num único comprimento de onda.

Preparation and thermal behavior of mixture of basic carbonate and 4-dimethylaminocinnamylidenepyruvate with lanthanides (III) and yttrium (III) in the solid state

Solid Ln-OHCO3-DMCP compounds, where Ln represents lanthanides (III) and yttrium (III) ions and DMCP is the anion 4-dimethylaminocinnamylidenepyruvate, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), x-Ray diffraction powder patterns and elemental analysis have been used to characterize the compounds. The thermal stability as well as the thermal decomposition of these compounds were studied using an alumina crucible in an air atmosphere.

Microeletrodos: III. arranjos de microeletrodos, construção e caracterização

Neste trabalho procurou-se descrever detalhadamente o procedimento de preparo de um arranjo de eletrodos com geometria em forma de microdiscos (20,2 < r e < 25,7 mim) e estudar o comportamento eletroquímico desse conjunto de microeletrodos. Foram aplicadas diferentes equações descritas na literatura para a condição de estado estacionário e quase-estacionário e equações para a simulação de voltamogramas em regime estacionário. Para baixas velocidades, v <= 0,1 mV s-1, observou-se uma excelente sobreposição dos voltamogramas cíclicos experimental e simulado, entretanto, velocidades desta ordem de grandeza são pouco práticas do ponto de vista experimental. Observou-se, também para todos os microeletrodos estudados, uma transição da condição de corrente estacionária para quase-estacionária, com o aumento dos valores de v. Equações que permitem avaliar a contribuição das correntes radial e difusional, para a corrente total, ajustam-se perfeitamente as curvas I/E em todo o intervalo de raios dos eletrodos e valores de v empregados. Os voltamogramas obtidos para o arranjo de eletrodos operando na condição de curto circuito apresentou um fator de amplificação de 19 vezes, referente ao sinal obtido a partir de um único microeletrodo. Tal fator confirma a condição de ausência de sobreposição das camadas de difusão dos eletrodos e, portanto, reflete a contribuição individual de cada eletrodo para a corrente total.

Thermal behaviour studies of solid state compounds of cinnamylidenepyruvate with trivalent lanthanides and yttrium (III) in an atmosphere of CO2

Solid state cinnamylidenepyruvate of trivalent lanthanides (except for promethium) and yttrium, were prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), X-ray diffraction powder patterns and complexometry were used to characterize and to study the thermal behavior of these compounds in a dynamic CO2 atmosphere. The results obtained showed significative differences on the thermal stability and thermal decomposition of these compounds, with regard to the thermal behavior study in a dynamic air atmosphere.

Estudo da decomposição térmica de oxalato de estrôncio dopado com cério(III) como precursor de materiais luminescentes

Este trabalho trata da obtenção de SrC2O4, Ce2(C2O4)3, e SrC2O4 dopado com diferentes porcentagens de Ce3+ como precursores do luminóforo azul Sr2CeO4. Os precursores preparados foram estudados por TG e DTA. Uma mistura contendo SrC2O4 e Ce2(C2O4)3 na relação 4:1 respectivamente e SrC2O4 dopado com diferentes porcentagens de Ce3+, foram tratadas termicamente à 1100ºC, 12 horas. Os produtos foram analisados por XRD e espectroscopia de luminescência e apresentam mistura das fases SrCeO3, Sr2CeO4 e SrCO3. Os produtos contendo a fase Sr2CeO4 apresentam luminescência azul de banda larga, com exceção daquele obtido a partir de SrC2O4 dopado com 50% de Ce3+. Neste caso a fase predominante é SrCeO3. Pela curva DTA observa-se um pico endotérmico em torno de 1000ºC para todas as amostras, com exceção da amostra dopada em 50%, evidenciando a temperatura de formação da fase Sr2CeO4. A fase luminescente Sr2CeO4 é preferencialmente obtida partindo-se de SrC2O4:Ce3+ 25% e de misturas mecânicas na proporção de 4:1 de oxalatos de estrôncio e de oxalato de cério.

Synthesis and thermal studies of solid state 2-chloro-benzylidenepyruvic acid and its compounds with sodium, aluminium (III), gallium (III) and indium (III) cations

The synthesis of sodium 2-chlorobenzylidenepyruvate and its corresponding acid as well as binary, binary together with it's acid or hydroxo-2-chorobenzylidenepyruvate of aluminium (III), gallium (III) and indium (III), were isolated. Chemical analysis, thermogravimetry, derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and X-ray powder diffractometry have been employed to characterize and to study the thermal behaviour of these compounds. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition.

Synthesis, characterization and thermal behaviour of solid-state compounds of 4-methoxybenzoate with lanthanum (III) and trivalent lighter lanthanides

Solid-state M-4-MeO-Bz compounds, where M stands for trivalent La, Ce, Pr, Nd and Sm and 4-MeO-Bz is 4-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), X-ray powder diffractometry, infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, polymorphic transformation, ligand's denticity, thermal behaviour and thermal decomposition of the isolated compounds.

Kinetic evaluation of the dehydration of Yb(III) Lu(III) and Y(III) 4-chlorobenzylidenepyruvate by thermogravimetry (TG)

The dehydration kinetic of Yb, Lu and Y 4-chlorobenzylidenepyruvate was studied by using thermogravimetry and the kinetics parameters obtained by Flynn and Wall method suggest that the dehydration step follows a first order mechanism. The activation energies calculated were 103.6, 96.6 and 97.2 kJ/mol and the lifetime considering the temperature of 31 and 101 º C for the dehydration of these compounds were 23, 26, 31 minutes and 0.6, 1.3 and 1.4 seconds, respectively. The results have similar values and suggest that the water is attached in the same way.

Sorption kinetics and intrapaticulate diffusivity of As(III) bioremediation from aqueous solution, using modified and unmodified coconut fiber

The pollution and toxicity problems posed by arsenic in the environment have long been established. Hence, the removal and recovery remedies have been sought, bearing in mind the efficiency, cost effectiveness and environmental friendliness of the methods employed. The sorption kinetics and intraparticulate diffusivity of As (III) bioremediation from aqueous solution using modified and unmodified coconut fiber was investigated. The amount adsorbed increased as time increased, reaching equilibrium at about 60 minutes. The kinetic studies showed that the sorption rates could be described by both pseudo-first order and pseudo-second order process with the later showing a better fit with a value of rate constant of 1.16 x 10-4 min-1 for the three adsorbent types. The mechanism of sorption was found to be particle diffusion controlled. The diffusion and boundary layer effects were also investigation. Therefore, the results show that coconut fiber, both modified and unmodified is an efficient sorbent for the removal of As (III) from industrial effluents with particle diffusion as the predominant mechanism.

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.

Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Argentimetric assay of ranitidine in bulk drug and in dosage forms

Two simple, rapid and cost-effective methods based on titrimetric and spectrophotometric techniques are described for the assay of RNH in bulk drug and in dosage forms using silver nitrate, mercury(II)thiocyanate and iron(III)nitrate as reagents. In titrimetry, an aqueous solution of RNH is treated with measured excess of silver nitrate in HNO3 medium, followed by determination of unreacted silver nitrate by Volhard method using iron(III) alum indicator. Spectrophotometric method involve the addition a known excess of mercury(II)thiocyanate and iron(III)nitrate to RNH, followed by the measurement of the absorbance of iron(III)thiocyante complex at 470 nm. Titrimetric method is applicable over 4-30 mg range and the reaction stoichiometry is found to be 1:1 (RNH: AgNO3). In the spectrophotometric method, the absorbance is found to increase linearly with concentration of RNH which is corroborated by the correlation coefficient of 0.9959. The system obey Beer's law for 5-70 µg mL-1. The calculated apparent molar absorptivity and sandell sensitivity values are found to be 3.27 ´ 10³ L mol-1 cm-1, 0.107 µg cm-2 respectively. The limits of detection and quantification are also reported for the spectrophotometric method. Intra-day and inter-day precision and accuracy of the methods were evaluated as per ICH guidelines. The methods were successfully applied to the assay of RNH in formulations and the results were compared with those of a reference method by applying Student's t and F-tests. No interference was observed from common pharmaceutical excipients. The accuracy of the methods was further ascertained by performing recovery tests by standard addition method.

Complexes of 3,4-dimethoxybenzoic acid anion with Cu(II), Co(II), La(III), and Nd(III)

Physico-chemical properties of 3,4-dimethoxybenzoates of Co(II), Cu(II), La(III) and Nd(III) were studied. The complexes were obtained as hydrated or anhydrous polycrystalline solids with a metal ion-ligand mole ratio of 1 : 2 for divalent ions and of 1 : 3 in the case of trivalent cations. Their colours depend on the kind of central ion: pink for Co(II) complex, blue for Cu(II), white for La(III) and violet for Nd(III) complexes. The carboxylate groups in these compounds are monodentate, bidentate bridging or chelating and tridentate ligands. Their thermal decomposition was studied in the range of 293-1173 K. Hydrated complexes lose crystallization water molecules in one step and form anhydrous compounds, that next decompose to the oxides of respective metals. 3,4 - Dimethoxybenzoates of Co(II) is directly decomposed to the appropriate oxide and that of Nd(III) is also ultimately decomposed to its oxide but with the intemediate formation of Nd2O2CO3.. The magnetic moment values of 3,4-dimethoxybenzoates determined in the range of 76-303 K change from 4.22 µB to 4.61 µB for Co(II) complex , from 0.49 µB to 1.17 µB for Cu(II) complex , and from 2.69 µB to 3.15 µB for Nd(III) complex.

Spectroscopic analysis of C80 doping with group III and group V elements using semiempirical PM3 molecular modelling technique

Semiempirical calculations at the level of PM3 of theory were carried out to study the structural and electronic properties of C80 and some of its doped derivatives with the elements of group III and V at the level of PM3 of theory. We have selected these elements to be substituted in the fullerene-C80 cage in order to show the effect of such structural change on the electronic properties of the molecules studied. The theoretical IR spectra, some of physical and chemical properties of the molecules studied are obtained and discussed.