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In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or full cell reaction) from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities (often approximated by concentrations) of the chemical species undergoing ...
The above equation is a modern statement of the theorem. Nernst often used a form that avoided the concept of entropy. [1] Graph of energies at low temperatures. Another way of looking at the theorem is to start with the definition of the Gibbs free energy (G), G = H - TS, where H stands for enthalpy.
However, the Nernst equation is limited, as it is modeled without a time component and voltammetric experiments vary applied potential as a function of time. Other mathematical models, primarily the Butler-Volmer equation, the Tafel equation, and Fick's law address the time dependence.
For a cell reaction characterized by the chemical equation: O x + n e − ↔ R e d {\displaystyle Ox+ne^{-}\leftrightarrow Red} at constant temperature and pressure, the thermodynamic voltage (minimum voltage required to drive the reaction) is given by the Nernst equation :
Some commercially available reference electrodes have an internal junction which minimizes the liquid junction potential between the sample solution and the electrolyte in the reference electrode (KCl). The internal electrolyte is at fixed composition and the electrode response is given by the Nernst equation: E = E 0 − RT/F ln a F −, where:
The upper graph shows the current density as function of the overpotential η . The anodic and cathodic current densities are shown as j a and j c, respectively for α=α a =α c =0.5 and j 0 =1mAcm −2 (close to values for platinum and palladium).
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.
Liquid junction potential (shortly LJP) occurs when two solutions of electrolytes of different concentrations are in contact with each other. The more concentrated solution will have a tendency to diffuse into the comparatively less concentrated one.