Supporting Electrolytes
In electrolyte solutions, a salt can be added to provide a high electrolyte conductivity and decrease the ohmic losses in a cell. These solutions are often called supporting electrolytes, buffer solutions, or carrier electrolytes. The added species, a negative and a positive ion pair, predominates over all other species. Therefore, the supporting electrolyte species can be assumed to dominate the current transport in the solution. In addition, the predominant supporting ions are usually selected so that they do not react at the electrode surfaces since the high conductivity should be kept through the process, that is, they should not be electro-active species. This also means that the concentration gradients of the predominant species in a supporting electrolyte are usually negligible.
Modeling and solving for a supporting electrolyte in the Electrostatics or Secondary Current Distribution interfaces will give a potential distribution that drives the migration in the Transport of Diluted Species Interface.
The current density vector is proportional to the sum of all species fluxes as expressed by Faraday’s law:
The electroneutrality condition ensures that there is always a zero net charge at any position in a dilute solution. Intuitively, this means that it is impossible to create a current by manually pumping positive ions in one direction and negative ions in the other. Therefore, the convective term is canceled out to yield the following expression for the electrolyte current density, where j denotes the supporting species:
(6-20)
Equation 6-20 is simply Ohm’s law for ionic current transport and can be simplified to
(6-21)
where κ is the conductivity of the supporting electrolyte. A current balance gives the current and potential density in the cell
which, in combination with Equation 6-21, yields:
(6-22)
Equation 6-22 can be easily solved using the Electrostatics or Secondary Current Distribution interface and, when coupled to the Transport in Diluted Species interface, the potential distribution shows up in the migration term.