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In other words, the exchange current density is the rate of reaction at the reversible potential (when the overpotential is zero by definition). At the reversible potential, the reaction is in equilibrium meaning that the forward and reverse reactions progress at the same rates. This rate is the exchange current density.
Reversible potentials can be sometimes converted to the standard electrode potential for a given electroactive species by extrapolation of the measured values to the standard state. The value of the electrode potential under non-equilibrium depends on the nature and composition of the contacting phases, and on the kinetics of electrode ...
[1] [2] At chemical equilibrium or in phase equilibrium, the total sum of the product of chemical potentials and stoichiometric coefficients is zero, as the free energy is at a minimum. [3] [4] [5] In a system in diffusion equilibrium, the chemical potential of any chemical species is uniformly the same everywhere throughout the system. [6]
For example, from Fe 2+ + 2 e − ⇌ Fe(s) (–0.44 V), the energy to form one neutral atom of Fe(s) from one Fe 2+ ion and two electrons is 2 × 0.44 eV = 0.88 eV, or 84 907 J/(mol e −). That value is also the standard formation energy (∆ G f °) for an Fe 2+ ion, since e − and Fe( s ) both have zero formation energy.
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 ...
This is represented by the green curve in the above figure. The equilibrium rate constants will be written as k fe and k be, and the equilibrium concentrations will be written c oe and c re. The equilibrium currents (j ce and j ae) will be equal and are written as j o, which is known as the exchange current density.
The electric potential outside each material is controlled by its work function, and so dissimilar metals can show an electric potential difference even at equilibrium. The Volta potential is not an intrinsic property of the two bulk metals under consideration, but rather is determined by work function differences between the metals' surfaces ...
The natural variables are important not only to specify the potential value at the equilibrium, but also because if a thermodynamic potential can be determined as a function of its natural variables, all of the thermodynamic properties of the system can be found by taking partial derivatives of that potential with respect to its natural ...