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In electrochemistry, electrode potential is the voltage of a galvanic cell built from a standard reference electrode and another electrode to be characterized. [1] By convention, the reference electrode is the standard hydrogen electrode (SHE). It is defined to have a potential of zero volts. It may also be defined as the potential difference ...
The reaction coordinate is roughly a measure of distance, with the body of the electrode being on the left, the bulk solution being on the right. The blue energy curve shows the increase in Gibbs energy for an oxidized molecule as it moves closer to the surface of the electrode when no potential is applied.
The electric potential also varies with temperature, concentration and pressure. Since the oxidation potential of a half-reaction is the negative of the reduction potential in a redox reaction, it is sufficient to calculate either one of the potentials. Therefore, standard electrode potential is commonly written as standard reduction potential.
The data below tabulates standard electrode potentials (E°), in volts relative to the standard hydrogen electrode (SHE), at: Temperature 298.15 K (25.00 °C; 77.00 °F); Effective concentration (activity) 1 mol/L for each aqueous or amalgamated (mercury-alloyed) species; Unit activity for each solvent and pure solid or liquid species; and
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 ...
During the early development of electrochemistry, researchers used the normal hydrogen electrode as their standard for zero potential. This was convenient because it could actually be constructed by "[immersing] a platinum electrode into a solution of 1 N strong acid and [bubbling] hydrogen gas through the solution at about 1 atm pressure".
The absolute electrode potential is then defined as the Gibbs free energy for the absolute electrode process. To express this in volts one divides the Gibbs free energy by the negative of Faraday's constant. Rockwood's approach to absolute-electrode thermodynamics is easily expendable to other thermodynamic functions.
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.