For an electrolytic cell, the voltage source Vs, does not contribute directly to the potential on the electrolytic electrodes. Vs determines the current and can add charges to the electrodes. This can be observed when charging supercapacitors and is discussed in these threads : https://www.physicsforums.com/threads/supercapacitor-charging-voltage.594372/ https://www.physicsforums.com/threads/ultracapacitor-charging-voltage.680719/ Question: What is the actual potential on the electrolytic electrodes for the electrolysis of water? Example: An electrolytic cell has carbon electrodes (make them identical commercially available activated carbon supercapacitor electrodes, so a charge has to build up for a few seconds) and sulfuric acid H2SO4 electrolyte. Positive charge electrode reaction: 2 H2O(l) → O2(g) + 4 H+(aq) + 4e− 1.23 V Negative charge electrode reaction: 2 H+(aq) + 2e− → H2(g) 0.00 V 1.23V is the minimum Vs should be for hydrogen and oxygen generation to start in this cell. (There are many factors that increase this value, but use 1.23V for this example.) Charge is added to each electrode in equal amounts. The actual potential on each electrode for this cell is (1.23V/2)=0.615V. The positive charge electrode is +0.615V and the negative charge electrode is -0.615V. The electrodes are is series, so the potentials add to 1.23V. Breaking the charge down further: the positive charge electrode has (+0.3075 charge and -0.3075 ionic charge from SO4-2) and the negative charge electrode has (-0.3075 charge and +0.3075 ionic charge from H+) Is this correct?