Electrochemical potential (${\tilde{\mu }}_{\mathrm{m}}={\mu }_{\mathrm{m}}+z{F}_{\mathrm{Far}}\psi$)

The molar electrochemical potential combines the molar chemical potential ${\mu }_{\mathrm{m}}$ with the electrical contribution $z{F}_{\mathrm{Far}}\psi$, where $z$ is the signed charge number of an ion, $F_{\mathrm{Far}}=N_{\mathrm{A}}e$ is the Faraday constant and $\psi$ is electric potential. Both terms have units $\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}$. In the particle convention the corresponding expression is ${\tilde{\mu }}_{\mathrm{particle}}={\mu }_{\mathrm{particle}}+ze\psi$, with elementary charge $e$; multiplying it by the Avogadro constant gives the molar form. Transfer between locations at the same temperature and pressure is driven by differences in electrochemical potential. The membrane transport examples use it to distinguish neutral solute transfer from ion transfer.

Define the displayed quantity as the free energy available per unit positive charge for sodium entry, with $V_m={\psi }_i-{\psi }_o$. Its negative is the signed inward electrochemical cost per charge. A reversal of the transport direction reverses the sign. At equilibrium it vanishes without requiring equal concentrations.

Start at sodium electrochemical equilibrium with $n_0$ internal ions. Exporting $n$ ions changes the membrane potential by $-ne/C$ and the internal number density to $(n_0-n)/V$. Subtracting the initially balanced chemical and electrical contributions gives the displayed incremental cost. An initial zero potential further implies $n_0=c_{o}V$ for an ideal fixed external reservoir. Nonzero initial equilibrium potential permits unequal concentrations, so that latter equality is an additional assumption.

An electrochemical gradient combines spatial changes in chemical potential and electric potential for a charged species. Passive transport proceeds downhill in electrochemical potential when an appropriate route is available; a concentration difference alone does not determine the direction for an ion.

A proton-motive force is a proton electrochemical potential difference per unit electric charge. It combines the electric potential difference and the chemical potential difference across a cell membrane; the direction and sign convention must be specified.