Tiago Luiz Ferreira

An analytical application of the electrocatalysis of the iodate reduction at tungsten oxide films.

Films of non-stoichiometric tungsten oxides have been deposited onto glassy carbon surfaces by electrodeposition from acidic W(VI) solutions and the chemical stability of these oxides was investigated by using the electrochemical quartz crystal microbalance. At these modified surfaces, rotating disc electrode voltammetric experiments indicated that iodate is electrocatalytically reduced in a mass-transport controlled process. The influence of the film thickness on the response to iodate was investigated and the results indicated a linear relationship between catalytic current and film thickness for relatively thin oxide layers. The modified electrode was employed successfully as an amperometric sensor for iodate in a flow injection apparatus. The linear response of the developed method is extended from 5 micromol L(-1) to 5 mmol L(-1) iodate with a limit of detection (signal-to-noise=3) of 1.2 micromol L(-1). The repeatability of the method for 41 injections of a 1 mmol L(-1) iodate solution was 0.8% and the throughput was determined as 123 h(-1). Interference from other oxidant anions such as nitrate and nitrite was not noticeable, whereas bromate and chlorate interfere at slight levels. The method was used in the determination of the iodate content in table salt samples.

Application of Microelectrode Voltammetry to Study the Properties of Surfactant Solutions: Alkyltrimethylammonium Bromides

Microelectrode cyclic voltammetry (MV) has been employed to investigate the micellar properties of solutions of homologous alkyltrimethylammonium bromides, RMe(3)ABr, R = C(10), C(12), and C(14), in water and in the presence of added NaBr. The micellar self-diffusion coefficient was calculated from the limiting current for the reversible electron transfer of micelle-bound ferrocene. From the values of this property, other parameters were calculated, including the micellar hydrodynamic radius, R(H), and aggregation number, N(agg); the latter was also theoretically calculated. We determined the values of the diffusion coefficient as a function of various experimental variables and observed the following trends: The diffusion coefficient decreases as a function of increasing surfactant concentration (no additional electrolyte added); it decreases as a function of increasing surfactant concentration at fixed NaBr concentration; and it shows a complex dependence (increase then decrease) on the NaBr concentration at a fixed RMe(3)ABr concentration. The value of the intermicellar interaction parameter decreases and then increases as a function of increasing NaBr concentration. These results are discussed in terms of intermicellar interactions and the effect of NaBr on the micellar surface charge density and sphere-to-rod geometry change. The NaBr concentration required to induce the latter change increases rapidly as a function of decreasing the length of R: no geometry change was detected for C(10)Me(3)ABr. Values of N(agg) increase as a function of increasing the length of R and are in good agreement with both literature values and values that were calculated theoretically. Thus, MV is a convenient and simple technique for obtaining fundamental properties of surfactant solutions, including additive-induced changes of micellar parameters (N(agg)) and morphology changes.

Scanning Electrochemical Microscopy as a Tool for the Characterization of Dental Erosion

When the tooth is exposed to acidic environments, an irreversible loss of dental hard tissue occurs in a process called dental erosion. In this work, the scanning electrochemical microscopy (SECM) was used to probe the consumption of protons at the vicinity of a tooth surface with a platinum microelectrode fixed at −0.5 (V) versus Ag/AgCl/KCl(sat). SECM approach curves were recorded to assess the extent of diffusion in the solution close to the tooth substrate. SECM images clearly demonstrated that the acid erosion process is very fast at solution pH values in the range between 3 and 4.

Information Extraction Techniques in Chemical Sensing

In order to produce an analytically useful signal, as mentioned in the previous chapter, we need to transduce chemical information using an instrumental technique. Numerous analytical chemistry techniques exist for the extraction of chemical information, e.g. spectrometry, separation techniques coupled with spectroscopic detection, or electrochemical and other methods. However, mainly due to the cost and necessity of portability, electrochemical and colorimetric techniques are frequently used to translate chemical information into a readable output for the analysts and users in in-field applications of chemical sensors. This chapter will introduce the concepts involved in these techniques, which are mainly used to extract information for fabricating chemical sensors.