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Electroanalytical chemistry


Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The three main categories are potentiometry (the difference in electrode potentials is measured), coulometry (the cell's current is measured over time), and voltammetry (the cell's current is measured while actively altering the cell's potential).

Potentiometry passively measures the potential of a solution between two electrodes, affecting the solution very little in the process. One electrode is called the reference electrode and has a constant potential, while the other one is an indicator electrode whose potential changes with the composition of the sample. Therefore, the difference of potential between the two electrodes gives an assessment of the composition of the sample. In fact, since potentiometric measurements in a non-destructive measurement, assuming that the electrode is in equilibrium with the solution we are measuring the potential of the solution. Potentiometry usually uses indicator electrodes made selectively sensitive to the ion of interest, such as fluoride in fluoride selective electrodes, so that the potential solely depends on the activity of this ion of interest. The time that takes the electrode to establish equilibrium with the solution will affect the sensitivity or accuracy of the measurement. In aquatic environments Platinum due to its high electron transfer kinetics is often used, although an electrode made from several metals can be used in order to enhance to electron transfer kinetics. The most common potentiometric electrode, by far is the glass-membrane electrode used in a pH meter.


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