The vertical axis is labeled E for the voltage potential with respect to the standard hydrogen electrode (SHE) as calculated by the Nernst equation. The "H" stands for hydrogen, although other standards may be used, and they are for room temperature only.
For a reversible redox reaction described by the following chemical equilibrium: 
With the corresponding equilibrium constant : 
The Nernst equation is: 
sometimes formulated as: 
or, more simply directly expressed numerically as: 
where: 
*  volt is the thermal voltage or the "Nernst slope" at standard temperature
* λ = ln(10) ≈ 2.30, so that  volt.
The horizontal axis is labeled pH for the −log function of the H ion activity.
The lines in the Pourbaix diagram show the equilibrium conditions, that is, where the activities are equal, for the species on each side of that line. On either side of the line, one form of the species will instead be said to be predominant.
In order to draw the position of the lines with the Nernst equation, the activity of the chemical species at equilibrium must be defined. Usually, the activity of a species is approximated as equal to the concentration (for soluble species) or partial pressure (for gases). The same values should be used for all species present in the system.
For soluble species, the lines are often drawn for concentrations of 1 M or 10 M. Sometimes additional lines are drawn for other concentrations.
If the diagram involves the equilibrium between a dissolved species and a gas, the pressure is usually set to P = 1 atm = , the minimum pressure required for gas evolution from an aqueous solution at standard conditions.
In addition, changes in temperature and concentration of solvated ions in solution will shift the equilibrium lines in accordance with the Nernst equation.
The diagrams also do not take kinetic effects into account, meaning that species shown as unstable might not react to any significant degree in practice.
A simplified Pourbaix diagram indicates regions of "immunity", "corrosion" and "passivity", instead of the stable species. They thus give a guide to the stability of a particular metal in a specific environment. Immunity means that the metal is not attacked, while corrosion shows that general attack will occur. Passivation occurs when the metal forms a stable coating of an oxide or other salt on its surface, the best example being the relative stability of aluminium because of the alumina layer formed on its surface when exposed to air.