Statement
8.2.32∗. When a capacitor with a charge of
Solution
Let the capacitance of the capacitor be
According to Faraday's law of electrolysis, the mass of a substance produced at an electrode is proportional to the total charge that passes through the electrolyte:
where
At first sight, one might argue that if
For sufficiently large
The flaw in this argument is the implicit assumption that the capacitor can discharge completely through an arbitrarily large number of electrolytic cells.
During electrolysis, each cell develops a chemical back electromotive force directed against the discharge current. Let the effective back EMF of one cell be denoted by
For
At the same time, the voltage across the capacitor decreases as it discharges.
If a charge
and the capacitor voltage is
The discharge and the electrolysis can continue only while the capacitor voltage exceeds the total chemical back EMF:
As the capacitor discharges,
At this point the current vanishes and the electrolysis stops.
Therefore, the total charge that actually passes through the cells is
Thus, the charge passing through each cell is not equal to the initial capacitor charge
By Faraday's law, the mass of gas produced in one cell is
Hence the total mass produced in all
Substituting the expression for
Thus,
Therefore, the total mass of gas does not increase linearly with the number of cells
In other words, increasing the number of cells simultaneously increases the number of cells producing gas and decreases the charge passing through each of them.
Moreover, if the number of cells is so large that
then the initial capacitor voltage is not sufficient to drive electrolysis at all.
Since
this condition may also be written as
In this case,
and no gas is produced.
Therefore, there is no contradiction with energy conservation. Faraday's law itself remains valid: the amount of substance produced is indeed determined by the charge that actually passes through the electrolyte. The error lies in assuming that the entire initial charge
As the number of cells increases, their total chemical back EMF increases, and the capacitor ceases to discharge before its charge reaches zero.
Answer
The capacitor does not discharge completely because electrolysis produces a chemical back EMF. For
Therefore, the charge passing through the cells is smaller than the initial charge