Faraday's laws of electrolysis


Faraday's laws of electrolysis are quantitative relationships based on the electrochemical research published by Michael Faraday in 1833.

First law

Michael Faraday reported that the mass of a substance deposited or liberated at an electrode during electrolysis is directly proportional to the charge. passed through the electrolyte.
Here, the constant of proportionality,, is called the electro-chemical equivalent of the substance. Thus, the ECE can be defined as the mass of the substance deposited or liberated per unit charge.

Second law

Faraday discovered that when the same amount of electric current is passed through different electrolytes connected in series, the masses of the substances deposited or liberated at the electrodes are directly proportional to their respective chemical equivalent/equivalent weight. This turns out to be the molar mass divided by the valence
The modern form of the second law is
where is the Faraday constant, is Avogadro's number and is the elementary charge. This form requires an understanding of chemical valence unavailable in Faraday's time.

Derivation

A monovalent ion requires one electron for discharge, a divalent ion requires two electrons for discharge and so on. Thus, if electrons flow, atoms are discharged.
Thus, the mass discharged is
where
  • is the Avogadro constant;
  • is the total charge, equal to the number of electrons times the elementary charge ;
  • is the Faraday constant.

    Mathematical form

Faraday's laws can be summarized by
where is the molar mass of the substance and is the valency of the ions.
For Faraday's first law, are constants; thus, the larger the value of, the larger will be.
For Faraday's second law, are constants; thus, the larger the value of , the larger will be.
In the simple case of constant-current electrolysis,, leading to
and then to
where:
For the case of an alloy whose constituents have different valencies, we have
where represents the mass fraction of the th element.
In the more complicated case of a variable electric current, the total charge is the electric current integrated over time :
Here is the total electrolysis time.

Applications