Desenvolvimento de metodologias eletroanalíticas para a determinação de metais em biocombustíveis empregando a análise por injeção em batelada (BIA)

Abstract

In this thesis it is shown that the association of electroanalytical technique Square- Wave Anodic Stripping Voltammetry (SWASV) with Batch-Injection Analysis (BIA) allows the development of analytical methods for determination of metals (Cu, Cd, Pb, Hg and Zn) in ethanol fuel and biodiesel samples. Metals can be incorporated into biofuels during storage and transportation processes, which can damage engines and cause environmental problems. Therefore, it becomes necessary to develop analytical methods aiming the quality control of metals in these samples, preferably methods that are easy to operate, fast, inexpensive and robust. BIA-SWASV allowed direct determination (no dilution of the sample) of Cd, Pb, Cu and Zn in fuel ethanol employing Au and Hg film electrodes. Detection limits in the range of 0.6 to 5 pg L"1, linear range from 12.5 to 200 pg L-1 and recovery values of between 87 and 109% were obtained for analysis of 1 mL of sample and deposition time of 90 s (total time of each measurement of ~200 s). The time of sample injection by the electronic micropipette used by the BIA system was 40 s, that is, the deposition of metal occurred even after the end of injection (diffusional transport of species to the electrode). In addition, in this thesis it is presented the combination of Screen-Printed Electrodes (SPE) to the BIA system aimed to the development of analytical methods with portable characteristics. This system was combined with other components that operate using batteries as electronic pipettes, mini- potentiostat and laptop computer, and applied to the determination of metals (Pb, Cu and Hg) in biodiesel samples after acid digestion. It was used in the experiments SPE's with Au conductive ink as a working electrode (SPGE), reduced the volume of sample to 200 pL (in conventional electrodes was used 1000 pL) with injection time of 40 s (injection rate of 5 pL s-1), and in these conditions, detection limits lower than 1,0 pg L-1 (equivalent to 6 pg g-1), linear range between 20 and 280 pg L-1 and recovery values between 90 and 110% for biodiesel fortified samples were obtained. The low sample consumption extended the lifetime SPGE’s for a whole day of analysis (210 injections). BIA system associated with electroanalytical techniques allowed the development of inexpensive,simple, accurate, portable (especially with the use of SPE's) analytical methods, employing reduced sample volume, which can be applied for the routine and on-site determinations of metals in ethanol fuel and biodiesel samples.