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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 sample's composition. Therefore, the difference in ...
Reference electrodes generally used are hydrogen electrodes, calomel electrodes, and silver chloride electrodes. The indicator electrode forms an electrochemical half-cell with the interested ions in the test solution. The reference electrode forms the other half-cell. The overall electric potential is calculated as
A second electrode acts as the other half of the cell. This second electrode must have a known potential to gauge the potential of the working electrode from; furthermore it must balance the charge added or removed by the working electrode. While this is a viable setup, it has a number of shortcomings.
Most electrodes work over a limited range of conditions, such as pH or temperature, outside of this range the electrodes behavior becomes unpredictable. The advantage of a pseudo-reference electrode is that the resulting variation is factored into the system allowing researchers to accurately study systems over a wide range of conditions.
An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is a simple membrane-based potentiometric device which measures the activity of ions in solution. [1] It is a transducer (or sensor ) that converts the change in the concentration of a specific ion dissolved in a solution into an electrical potential .
A redox indicator (also called an oxidation-reduction indicator) is an indicator which undergoes a definite color change at a specific electrode potential. The requirement for fast and reversible color change means that the oxidation-reduction equilibrium for an indicator redox system needs to be established very quickly. Therefore, only a few ...
The design of the electrodes is the key part: These are rod-like structures usually made of glass, with a bulb containing the sensor at the bottom. The glass electrode for measuring the pH has a glass bulb specifically designed to be selective to hydrogen-ion concentration.
The auxiliary electrode may be isolated from the working electrode using a glass frit. Such isolation prevents any byproducts generated at the auxiliary electrode from contaminating the main test solution: for example, if a reduction is being performed at the working electrode in aqueous solution, oxygen may be evolved from the auxiliary electrode.