Neste trabalho, a espectroscopia no infravermelho médio foi utilizada para investigar o efeito da quantidade (25 ou 40%) e do tipo de plastificante (di-2-etilhexil ftalato (DOP), di-2-etilhexil sebacato (DOS) e 2-nitrofenil octil éter (NPOE)) na resposta analítica de uma fase sensora de poli(cloreto de vinila) (PVC) para a determinação de hidrocarbonetos clorados (clorobenzeno (ClB), tricloroetileno (TCE) e triclorobenzeno(TCB)) em água. Foi observado que os filmes com 40% de plastificante geraram maior sensibilidade e menores limites de detecção que aqueles preparados com 25%, embora esses últimos sejam de manipulação mais fácil. Um comportamento similar foi também observado para fases sensoras preparadas com os plastificantes NPOE e DOS. Com o uso da fase sensora de PVC-DOS e um tempo de extração de 60 min, foram obtidos limites de detecção de 0,3, 0,6 e 0,5 mg L-1 para clorobenzeno, tricloroetileno e triclorobenzeno, respectivamente.

In this work, mid-infrared spectroscopy has been employed to investigate the effect of amount (25 or 40%) and type of plasticiser (di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl phthalate (DOP) and 2-nitrophenyl octyl ether (NPOE)) on the analytical response of a poly(vinylchloride) (PVC) sensing phase for the determination of the chlorinated hydrocarbons (chlorobenzene (ClB), trichloroethylene (TCE) and trichlorobenzene (TCB)) in water. It was observed that films with 40% of plasticiser provided higher sensitivity and lower limits of detection than those with 25%, although the later films are easier to handle. A similar behaviour was also observed for sensing phases prepared with the plasticisers NPOE and DOS. By employing a DOS-based PVC sensing phase and extraction time of 60 min, limits of detection of 0.3, 0.6, and 0.5 mg L-1 were obtained for chlorobenzene, trichloroethylene and trichlorobenzene, respectively.

Optical chemical sensors with detection in the near and mid infrared region are reviewed. Fundamental concepts of infrared spectroscopy and optical chemical sensors are briefly described, before presenting some aspects on optical chemical sensors, such as synthesis of NIR and IR reagents, preparation of new materials as well as application in determinations of species of biological, industrial and environmental importance.

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.

The behaviour of Nafion® polymeric membranes containing acid-base dyes, bromothymol blue (BB) and methyl violet (MV), were studied aiming at constructing an optical sensor for pH measurement. BB revealed to be inadequate for developing sensing phases due to the electrostatic repulsion between negative groups of their molecules and the negative charge of the sulfonate group of the Nafion®, which causes leaching of the dye from the membrane. On the other hand, MV showed to be suitable due to the presence of positive groups in its structure. The membrane prepared from a methanolic solution whose Nafion®/dye molar ratio was 20 presented the best analytical properties, changing its color from green to violet in the pH range from 0.6 to 3.0. The membrane can be prepared with good reproducibility, presenting durability of ca. 6 months and response time of 22 s, making possible its use for pH determination in flow analysis systems.

Este trabalho descreve o uso do método de linearização de Gran em titulações em fluxo monossegmentado com detecção potenciométrica. O programa de controle pode estimar o ponto final após a adição de três ou quatro alíquotas de titulante. Alternativamente, o ponto final da titulação pode ser determinado pelo método da segunda derivada. Neste caso, alíquotas adicionais de titulante são adicionadas até a proximidade do ponto final e três pontos antes e após o ponto estequiométrico são usados para o cálculo de ponto final. O desempenho do sistema foi avaliado pela determinação de cloreto em soluções isotônicas e parenterais. O sistema emprega um eletrodo indicador tubular de Ag2S/AgCl. Uma titulação típica, realizada de acordo com a definição IUPAC, requer apenas 60 mL de amostra e aproximadamente o mesmo volume de titulante (AgNO3). Uma titulação completa pode ser realizada entre 1 e 5 min. Foram obtidas exatidão e precisão (desvio padrão relativo de 10 replicatas) de 2% e 1% para o método de Gran e 1% e 0,5% para o método de Gran associado ao método da segunda derivada, respectivamente. O sistema proposto reduz o tempo para realizar uma titulação, com baixo consumo de amostra e reagente, além de possibilitar uma amostragem automática completa e adição de titulante sem a necessidade de uma etapa de calibração.

An automatic potentiometric monosegmented flow titration procedure based on Gran linearisation approach has been developed. The controlling program can estimate the end point of the titration after the addition of three or four aliquots of titrant. Alternatively, the end point can be determined by the second derivative procedure. In this case, additional volumes of titrant are added until the vicinity of the end point and three points before and after the stoichiometric point are used for end point calculation. The performance of the system was assessed by the determination of chloride in isotonic beverages and parenteral solutions. The system employs a tubular Ag2S/AgCl indicator electrode. A typical titration, performed according to the IUPAC definition, requires only 60 mL of sample and about the same volume of titrant (AgNO3) solution. A complete titration can be carried out in 1 - 5 min. The accuracy and precision (relative standard deviation of ten replicates) are 2% and 1% for the Gran and 1% and 0.5% for the Gran/derivative end point determination procedures, respectively. The proposed system reduces the time to perform a titration, ensuring low sample and reagent consumption, and full automatic sampling and titrant addition in a calibration-free titration protocol.

Este trabalho descreve um procedimento automático em fluxo monossegmentado para titulação potenciométrica aplicado à determinação de cloreto em leite e vinho. O sistema de fluxo foi desenvolvido com base em uma válvula solenóide de 6 vias, controlada por um microcomputador através de um programa escrito em VisualBasic 3.0. Um eletrodo indicador tubular de Ag2S seletivo a Cl- e um eletrodo de referência convencional de Ag/AgCl foram empregados. Um algoritmo baseado na diferença de potencial entre duas adições subsequentes de titulante foi desenvolvido, possibilitando a determinação do ponto final da titulação em, no máximo, 10 tentativas, com uma precisão melhor que 1,0%. O sistema proposto foi avaliado pela determinação de cloreto em leite e vinho, usando uma solução padrão de AgNO3 como titulante. A exatidão foi avaliada comparando-se os resultados com aqueles obtidos pelo método da AOAC, não sendo encontradas diferenças significativas ao nível de confiança de 95%.

An automated flow potentiometric titration procedure for the determination of chloride in milk and wine exploiting the monosegmented flow approach is described. The flow network was designed based on a six-way solenoid valve, controlled by a microcomputer running software written in VisualBasic 3.0, allowing selection of the titration conditions. An Ag2S tubular electrode selective for Cl- and a conventional Ag/AgCl electrode were employed as indicator and reference, respectively. An algorithm based on the potential difference between two subsequent titrant additions was developed, allowing to reach the end point in less than 10 attempts, with a precision better than 1.0%. The proposed system was evaluated by determining chloride in milk and wine, using a standard AgNO3 solution as titrant. Accuracy was ascertained by comparing the results with those obtained using the AOAC procedure. No significant difference at a 95% confidence level was observed.

This paper describes some aspects of multichannel spectrophotometry, principles of photodiode arrays and their applications in Analytical Chemistry.