RESUMO
In this work, a new open hardware interface based on Arduino to read electromotive force (emf) from potentiometric detectors is presented. The interface has been fully designed with the open code philosophy and all documentation will be accessible on web. The paper describes a comprehensive project including the electronic design, the firmware loaded on Arduino, and the Java-coded graphical user interface to load data in a computer (PC or Mac) for processing. The prototype was tested by measuring the calibration curve of a detector. As detection element, an active poly(vinyl chloride)-based membrane was used, doped with cetyltrimethylammonium dodecylsulphate (CTA(+)-DS(-)). The experimental measures of emf indicate Nernstian behaviour with the CTA(+) content of test solutions, as it was described in the literature, proving the validity of the developed prototype. A comparative analysis of performance was made by using the same chemical detector but changing the measurement instrumentation.
RESUMO
A new design for a true-linear generator suitable for electrochemical measures is presented. The main component of generation system is an MAX038 chip, a high-frequency relaxation-type oscillator. The design is completed with a digital interface for computer control and an output stage to make signal suitable for cyclic voltammetry experiments. A digital circuit is also included to obtain single sweep signals by isolating one period or a half-period from continuous original output. Performance of presented generator is tested up to 1 MV s(-1) obtaining good stability and linearity.
RESUMO
Cyclic voltammetry (CV) is a very useful electrochemical tool used to study reaction systems that include chemical steps that are coupled to electron transfers. This type of system generally involves the chemical reaction of an electrochemically generated free radical. Published methods exist that are used to determine the kinetics of electrochemically initiated chemical reactions from the measurements of the peak current ratio (i(pa)/i(pc)) of a cyclic voltammogram. The published method requires working curves to relate a kinetic parameter to the peak current ratio. In the presented work, a digital simulation package was used to obtain improved working curves for specific working conditions. The curves were compared with the published results for the first- and second-order chemical reactions following the charge transfer step mechanisms. According to the presented results, the previously published working curve is reliable for a mechanism with a first-order chemical reaction; however, a change in the switching potential requires a recalculation of the curve. In the case of mechanisms with a second-order step (dimerisation and disproportionation), several different views exist on how the second-order chemical term should be expressed so that different values of the constant are obtained. Parameters such as electrode type, electrode area, electroactive species concentration, switching potential, scan rate and method for peak current ratio calculation modify the working curves and must always be specified. We propose a standardised method to obtain the most reliable kinetic constant values. The results of this work will permit researchers who handle simulation software to construct their own working curves. Additionally, those who do not have the simulation software could use the working curves described here. The revelations of the presented experiments may be useful to a broad chemistry audience because this study presents a simple and low-cost procedure for the study of free radicals that otherwise should be studied with more sophisticated and expensive techniques, such as ESR or pulse radiolysis.