Iodine value is an important quality parameter for evaluation of the oxidative stability of biodiesel and vegetable oils, but the official methods are time-consuming and demand large amounts of reagents and solvents. The present work describes a novel procedure for determination of iodine value based on the discoloration of a triiodide aqueous solution due to halogenation of the unsaturated compounds in the samples. Iodine is extracted to the organic phase and consumed proportionally to the amount of unsaturated compounds in the samples. Thus, the remaining fraction of I3- quantified by spectrophotometry in the aqueous phase is inversely proportional to the concentration of unsaturated compounds. For biodiesel samples, responses were linear from 10 to 106 g I2 per 100 g, with coefficient of variation and limit of detection estimated at 5.0% (n = 8) and 2.5 g I2 per 100 g, respectively. The corresponding values for vegetable oils were 20 to 140 g I2 per 100 g, 3.0% (n = 10), and 7 g I2 per 100 g, respectively. The procedure consumed only 1.2 mL of sample, 365 µg of I2, and 42 mg of KI with ca. 2.4 mL of waste generated per determination. The results agreed with those obtained by the official methods at the 95% confidence level.

Flow analysis changed significantly the way of performing chemical analysis by (i) mechanization of analytical procedures in a continuous flowing stream with minimal sample intercontamination; (ii) analytical measurements without attaining chemical equilibria, thus increasing the applicability of kinetic methods and allowing the exploitation of non-quantitative processes; (iii) exploitation of concentration gradients and (iv) use of unstable reagents or measurement of unstable products. Flow-based procedures are generally characterized by high sample throughput, improved precision, minimized waste generation, and often better selectivity. The performance of detection systems is usually improved because of the in-line sample conditioning and measurements under reproductive dynamic conditions and timing. However, after achieving several innovations, perspectives for further developments have been questioned mainly because of the recent decrease in the number of publications on flow analysis. The aim of this review is then to discuss the impact of flow-based methods on chemical analysis, emphasizing recent applications and developments, including miniaturization, bioanalysis, microextractions, green analytical chemistry and synergic hyphenation with other techniques and processes. The author's personal view about research perspectives in the field is also presented.

Understanding instrumental analysis is essential for obtaining reliable analytical results required by chemists in a variety of research areas and industrial activities. All instrumental techniques involve undesirable background (BG) signals originated either from concomitants in the sample or by spurious (e.g. electrical or optical) effects intrinsically related to the measurement process. BG signals may affect accuracy, precision and detection limits. Techniques characterized by low BG stands out by high detectability even when they are based on processes with low efficiency (e.g. low quantum yields and low efficiency of thermal excitation). However, minor attention has been given to this topic in analytical chemistry courses hindering students' understanding of the BG concept and its impact on the analytical performance. Although in some analytical techniques BG is well-defined and successfully compensated, some of them still need further elucidation. Sources of BG and strategies for its minimization and correction are didactically discussed for a variety of analytical techniques, including molecular and atomic spectrometry, electroanalytical methods, and separation techniques. Historical aspects and recent approaches are also addressed.

AbstractA device comprising a lab-made chamber with mechanical stirring and computer-controlled solenoid valves is proposed for the mechanization of liquid-liquid extractions. The performance was demonstrated by the extraction of ethanol from biodiesel as a model of the extraction of analytes from organic immiscible samples to an aqueous medium. The volumes of the sample and extractant were precisely defined by the flow-rates and switching times of the valves, while the mechanic stirring increased interaction between the phases. Stirring was stopped for phase separation, and a precise time-control also allowed a successful phase separation (i.e., the absence of the organic phase in the aqueous extract). In the model system, a linear response between the analytical response and the number of extractions was observed, indicating the potential for analyte preconcentration in the extract. The efficiency and reproducibility of the extractions were demonstrated by recoveries of ethanol spiked to biodiesel samples within 96% and 100% with coefficients of variation lower than 3.0%.

O reagente 1-(2-tiazolilazo)-2-naftol (TAN) tem sido extensamente usado em extração em fase sólida (EFS) sem avaliação crítica do processo de adsorção. Neste trabalho, a adsorção de TAN em XAD-7 e sílica-gel foi investigada e os dados experimentais foram ajustados aos modelos de Langmuir, Freundlich e Dubinin-Radushkevich. Estes modelos forneceram bons ajustes para ambos adsorventes e seus respectivos parâmetros K L, K F and K D-R foram calculados. O tempo mínimo de contato de adsorção de TAN e a quantidade máxima de TAN adsorvido foram menores em XAD-7 (35 min e 4,05 × 10-3 g g-1) em relação à sílica-gel (210 min e 1,81 × 10-2 g g-1). A avaliação da energia de adsorção média caracterizou a adsorção como física e as superfícies para ambos os adsorventes como energeticamente heterogêneas. Os dados experimentais para ambos os sistemas mostraram excelentes ajustes ao modelo de pseudo-segunda ordem. Concordâncias entre q max,calc e q max,exp foram encontradas em todos os casos e a constante cinética confirmou o tempo mínimo diferente para alcançar adsorção máxima de TAN em XAD-7 e sílica-gel. Sílica gel pode ser apontada como o melhor adsorvente, considerando a capacidade de adsorção e a força de interação para adsorção de TAN.

The reagent 1-(2-thiazolylazo)-2-naphtol (TAN) has been extensively used in solid-phase extraction without a critical evaluation of the adsorption process. In this work, the adsorption of TAN onto XAD-7 and silica gel has been investigated and the experimental equilibrium data were fitted to the Langmuir, Freundlich and Dubinin-Radushkevich models. These models provided good fits for both adsorbents and their respective parameters K L, K F and K D-R were calculated. For the same TAN concentration range, the minimum time of contact for adsorption and the maximum amount of TAN adsorbed per gram were lower in XAD-7 (35 min and 4.05 × 10-3 g g-1) than in silica gel (210 min and 1.81 × 10-2 g g-1). The evaluation of the mean sorption energy characterized the adsorption as physical and the surfaces for both adsorbents as energetically heterogeneous. The experimental data for both systems showed an excellent adjustment to the pseudo-second order model. Excellent agreements between q max,calc and q max,exp were found in all cases and the kinetic constant value confirmed the different minimum time to reach maximum adsorption of TAN onto XAD-7 and silica gel. By considering the adsorption capacity and the force of the interaction, silica gel can be pointed out as the best support for adsorption of TAN.

Um procedimento simples e de baixo custo, baseado na elevada diferença de solubilidade de cloreto de sódio em etanol e em água, é proposto para a estimativa do teor de água em etanol combustível. A concentração iônica de soluções saturadas com o sal é monitorada por medidas de condutividade com resposta linear até 16% de água em meio alcoólico e limite de detecção de 0,05% (v/v). O procedimento é preciso (coeficiente de variação de 0,6%, n = 10) e exato (resultados concordantes com os obtidos por titulação amperométrica de Karl Fischer com 95% de confiança). Um dispositivo eletrônico que explora o mesmo princípio foi proposto para monitoramento in situ de etanol combustível visando à detecção rápida de não conformidades. O dispositivo pode ser operado por não especialistas, gerando uma resposta binária indicada por LEDs coloridos e foi usado com sucesso na classificação de amostras comerciais adulteradas com diferentes quantidades de água.

A simple and inexpensive procedure, based on the high difference in solubility of sodium chloride in ethanol and water, is proposed to estimate the water content in ethanol fuel. The ionic concentration of solutions saturated with the salt is monitored by conductometric measurements with a linear response up to 16% water in an alcoholic medium and a limit of detection of 0.05% (v/v). The procedure is precise (coefficient of variation of 0.6%, n = 10) and accurate (results in agreement with those obtained by Karl Fischer amperometric titration at the 95% confidence level). An indicating electronic device exploiting the same principle was proposed for in situ monitoring of ethanol fuel samples aiming at the fast detection of unconformities. The device can be operated by nonexperts, generating a binary response indicated by coloured LEDs, and it successfully classified commercial samples spiked with different amounts of water.

Um procedimento analítico em sistema de análises em fluxo com multicomutação é proposto para a determinação de captopril e construção de curvas de dissolução de medicamentos. O método é baseado na reação do fármaco com Cu(II), com posterior complexação de Cu(I) com 4,4'-dicarboxi-2,2'-biquinolina (BQA) e detecção espectrofotométrica. Foi observada resposta linear entre 25 e 300 µmol L-1 captopril, com limite de detecção de 7 µmol L-1 (99,7% de confiança). O coeficiente de variação (n = 20) e a frequência de amostragem foram 2,2% e 47 determinações por hora, respectivamente, com consumo de 290 µg de BQA e geração de 3,6 mL de resíduo por determinação. Os resultados para 7 amostras de preparações farmacêuticas concordaram com os obtidos pelo procedimento volumétrico de referência com 95% de confiança. Perfis de dissolução obtidos com um aparato construído no laboratório foram concordantes com os relatados na literatura, com coeficiente de variação de 1,8% para três replicatas do produto de referência

A flow-based analytical procedure exploiting multicommutation is proposed for captopril determination and the construction of dissolution curves. The procedure is based on the redox reaction between Cu(II) and the drug with the subsequent complexation of Cu(I) with 4,4'-dicarboxy-2,2'-bichinoline (BCA) and spectrophotometric detection. A linear response was observed between 25 and 300 µmol L-1 captopril and the detection limit was estimated as 7 µmol L-1 (99.7% confidence level). The coefficient of variation (n = 20) and sampling rate were 2.2% and 47 determinations per hour, respectively, consuming 290 µg of BCA and generating 3.6 mL of waste per determination. The results for seven pharmaceutical samples agreed with those obtained by the reference volumetric procedure at the 95% confidence level. The dissolution profiles attained with a lab-made dissolution apparatus agreed with those reported in the literature, with a coefficient of variation of 1.8% for three replicates of the reference product

A flow system based on the sandwich technique is proposed for the sequential determination of ascorbic acid, dipyrone, acetylcysteine, captopril and paracetamol. The procedure is based on the reduction of Cu(II) by the analytes followed by the spectrophotometric measurement of the complex of Cu(I) with 2,2'-biquinoline 4,4'-dicarboxylic acid. Linear responses were achieved in the µmol L-1 range, with coefficients of variation better than 1.7%. Sampling rate was estimated as 60 determinations per hour, consuming 230 µg of BQA and generating 2.5 mL of waste per determination. Results for commercial samples agreed with those obtained by procedures recommended by the American and European pharmacopeias at the 95% confidence level.

Um sistema de análises em fluxo com multicomutação com detecção por quimiluminescência foi desenvolvido para a determinação de colesterol livre e total sem alterações no módulo de análises. Colesterol estearase e colesterol oxidase foram imobilizadas em esferas de vidro via glutaraldeído/3-aminopropiletoxisilano e mini-colunas contendo as enzimas foram usadas para tratamento das amostras em linha. Ésteres de colesterol foram clivados a colesterol e ácidos graxos na coluna empacotada com colesterol estearase. No reator contendo colesterol oxidase, o analito foi convertido a 4-colesten-3-ona e peróxido de hidrogênio. A detecção foi baseada na quimiluminescência produzida por H2O2 no sistema hexacianoferrato(III)-luminol. Os efeitos de variáveis químicas e hidrodinâmicas sobre o sinal de quimiluminescência foram avaliados. As curvas analíticas foram lineares entre 250 e 2500 mg L-1 e 500 e 4000 mg L-1, para colesterol livre e total, respectivamente. Limites de detecção para ambos os analitos foram estimados em 60 mg L-1 (99,7% de confiança). A frequência de amostragem foi de 55 h-1 e o consumo de reagentes foi de 350 µg de luminol e 2,6 mg de hexacianoferrato(III) de potássio por determinação. O procedimento desenvolvido foi aplicado à determinação de colesterol em ovos e soro sanguíneo humano gerando resultados concordantes com o procedimento espectrofotométrico de referência com nível de confiança de 95%.

A multicommuted flow-based procedure with detection by chemiluminescence for the determination of total and free cholesterol without changes in the flow manifold is proposed. Cholesterol esterase and cholesterol oxidase were both immobilized on glass beads via glutaraldehyde/(3-aminopropyl)-triethoxysilane and mini-columns containing the enzymes were used for online sample treatment. Cholesterol esters were cleaved to cholesterol and fatty acids at the packed reactor containing cholesterol esterase. The reactor containing cholesterol oxidase converted cholesterol to cholest-4-en-3-one also yielding hydrogen peroxide. Detection was based on the chemiluminescence produced by H2O2 in the hexacyanoferrate(III)-luminol system. Influence of both chemical and hydrodynamic variables on the chemiluminescence signals were investigated. The analytical curves were linear from 250 to 2500 mg L-1 and from 500 to 4000 mg L-1, for free and total cholesterol, respectively. Detection limits for both analytes were estimated as 60 mg L-1 at 99.7% confidence level. The sampling rate was 55 h-1 and reagent consumption was 350 µg of luminol and 2.6 mg of potassium hexacyanoferrate(III) per determination. The procedure developed was successfully applied for determination of cholesterol in eggs and in human blood serum with results in agreement with the reference spectrophotometric method at the 95% confidence level.

It is here discussed the development of a low cost analytical instrument with capacity for metals determination using atomic emission measurements in an electrothermal atomization system with a tungsten coil atomizer. The main goal was to show a new frontier for using this atomizer and to demonstrate that the simple instrumental arrangement here proposed has potential for portability and for solving analytical tasks related to metals determination. Atomic emission of calcium was selected for the adjustment of instrumental parameters and to evaluate the main characteristics of the lab-built instrument. Cobalt was determined in medicines and one alloy to demonstrate its feasibility.

Um procedimento analítico limpo baseado em extração em ponto nuvem é descrito para a determinação de cobre e ferro em materiais vegetais. Após a digestão da amostra em frascos fechados em forno de microondas, empregando mistura oxidante diluída (HNO3 + H2O2), os íons metálicos foram simultaneamente extraídos como complexos hidrofóbicos formados com 1,2-tiazolilazo-2-naftol (TAN) usando Triton X-114 como agente extrator. Íons cobre e ferro foram determinados por espectrometria de absorção atômica com chama (FAAS) e ferro também por espectrofotometria de absorção molecular UV-Vis. Nas medidas por FAAS, os limites de detecção (99,7% de confiança) foram estimados em 1 e 10 μg L-1 para cobre e ferro, respectivamente. Respostas lineares para ambos os analitos foram observadas no intervalo de 25-200 μg L-1. O fator de enriquecimento foi estimado em 30, com extração quantitativa dos complexos avaliada por medidas na solução sobrenadante remanescente após extração. Para a determinação de ferro por espectrofotometria UV-Vis, o limite de detecção (99,7% de confiança) foi estimado em 1 μg L-1, com resposta linear entre 6 e 60 μg L-1. A exatidão do procedimento foi avaliada pela determinação dos metais em materiais de referência certificados e os resultados foram concordantes com os valores certificados no nível de confiança de 95%. O consumo de reagentes foi de 1 mL HNO3, 1,1 mL H2O2, 50 mg Triton X-114 e 150 μg TAN por determinação.

A green analytical procedure exploiting cloud point extraction for determination of copper and iron in plant materials is presented. After sample digestion with a diluted oxidant mixture (HNO3 + H2O2) in a closed vessel microwave oven, metal ions were simultaneously extracted as hydrophobic complexes formed with 1,2-tiazolylazo-2-naphthol (TAN) using Triton X-114 as extracting agent. Copper and iron were determined by flame atomic absorption spectrometry (FAAS) and iron also by UV-Vis spectrophotometry. For FAAS, the detection limits (99.7% confidence level) were estimated as 1 and 10 μg L-1 for copper and iron, respectively. Linear responses for both analytes were observed in the 25-200 μg L-1 range. The enrichment factors were estimated as 30 for both analytes and the extraction was quantitative, as evaluated by measurements in the supernatant solution remaining after extraction. For iron determination by UV-Vis spectrophotometry, the detection limit was estimated as 1 μg L-1, with linear response within 6 and 60 μg L-1. The accuracy of the procedure was evaluated by determination of the metals in certified reference materials and the results agreed with the certified values at the 95% confidence level. In the whole procedure, the reagent consumption was 1 mL HNO3, 1.1 mL H2O2, 50 mg Triton X-114 and 150 μg TAN per determination.

A química brasileira está crescendo rapidamente, sendo um dos principais alicerces para o contínuo desenvolvimento do país. Inspirados no 15º Encontro Nacional de Química Analítica, ENQA, com um número recorde de participantes e comunicações, decidiu-se revisar os recentes desenvolvimentos em química analítica no Brasil. Foram escolhidas as mesmas áreas de aplicação adotadas para a organização temática do ENQA e selecionados artigos publicados por autores brasileiros em 7 periódicos de ampla penetração na área. Os dois periódicos científicos editados pela Sociedade Brasileira de Química também foram pesquisados. Esta revisão não é exaustiva, porém os trabalhos selecionados após 2008 mostram uma significativa visão geral da área. Pode-se concluir que a química analítica brasileira está saudável, em crescimento e certamente atenderá as demandas do país como uma potência emergida.

Chemical sciences in Brazil are growing fast and being one of the main supports for the continuous development of the country. Inspired on the 15th Brazilian Meeting on Analytical Chemistry, ENQA, with a record number of participants and communications, we have decided to review recent developments in analytical chemistry in Brazil. We have chosen the same application areas used for the thematic organization of the ENQA and have searched papers published by Brazilian authors in 7 major and general journals in analytical chemistry. The two scientific journals published by the Brazilian Chemical Society were also searched. This review is not comprehensive, but the selected papers published after 2008 shown an impressive overview of the area. We may conclude that analytical chemistry is healthy and growing in Brazilian scenario and certainly will attend the demands of Brazil as an emerged power.

Um procedimento simples, rápido e de baixo custo é descrito para a determinação de captopril em preparações farmacêuticas. O procedimento é baseado em um sistema de análises por injeção em fluxo explorando a formação em linha de triiodeto, o qual é consumido na presença do analito gerando um sinal transiente. Resposta linear foi observada até 200 µmol L-1 com limite de detecção de 1,0 µmol L-1 (99,7% de confiança). O coeficiente de variação (n = 20) e a freqüência de amostragem foram estimados em 1,2% e 72 determinações por hora, respectivamente. Os principais excipientes encontrados em preparações farmacêuticas não afetaram a determinação de captopril. Reamostragem na zona dispersa foi explorada para implementar diluições em linha, visando a análise direta de suspensões das amostras. Resultados da análise de amostras comerciais foram concordantes com os obtidos pelo procedimento volumétrico de referência descrito na Farmacopéia americana com nível de confiança de 95%. O consumo de reagente foi estimado em 18 µg KMnO4 e 10 mg KI por determinação, com custo de US$ 2,50 por 1000 determinações.

A simple, fast and low cost procedure for spectrophotometric determination of captopril in pharmaceutical preparations is described. The procedure is based on a flow-injection system exploiting the on-line formation of the triiodide reagent, which is consumed in the presence of the analyte generating a transient signal. Linear response was observed up to 200 µmol L-1 with a detection limit of 1.0 µmol L-1 (99.7% confidence level). The coefficient of variation (n = 20) and the sampling rate were estimated as 1.2% and 72 determinations per hour, respectively. The main excipients found in pharmaceutical preparations did not affect the captopril determination. The zone sampling approach was exploited to implement on-line dilutions, aiming direct analysis of sample extracts. Results of the analysis of commercial samples agreed with the obtained by the titrimetric reference procedure described in the US-Pharmacopeia at the 95% confidence level. The reagent consumption was estimated as 18 µg of KMnO4 and 10 mg of KI per determination, with a cost of US$ 2.50 per 1000 determinations.

A simple and low-cost flow cell with 30 cm optical path for spectrophotometric measurements is described. It presents desirable characteristics such as low attenuation of the radiation beam and internal volume (75 µL) comparable to that of a 1-cm conventional cell (80 µL). Despite the increase in optical path, the effect on sample dispersion was also similar to that attained in the commercial cell. The performance of the cell was assessed by the determination of phosphate based on the molybdenum blue method, yielding a linear response range between 0.05 and 0.8 mg L-1 phosphorus (r=0.999). The increase in sensitivity (30.4-fold) in comparison with that obtained with a conventional 1-cm flow cell agreed with that estimated by the Lambert-Beer law.

Simple experiments are proposed for measuring molecular absorption of chromate and dichromate ions using an atomic absorption spectrometer. The experiments can help undergraduate students in instrumental analysis courses understand important aspects involving conceptual and instrumental similarities and differences between frequently used analytical techniques. Hollow cathode lamps were selected with wavelengths in the region of molecular absorption of chromate and dichromate. Calibration curves were obtained and the linear dynamic range was evaluated. Results were compared with those obtained in a molecular absorption spectrometer. The molar absorptivities obtained were also compared.