Reference electrode
The saturated calomel electrode (SCE) is a
reference electrode based on the reaction between elemental
mercury and
mercury(I) chloride. It has been widely replaced by the
silver chloride electrode, however the calomel electrode has a reputation of being more robust. The aqueous phase in contact with the mercury and the mercury(I) chloride (Hg2Cl2, "
calomel") is a saturated solution of
potassium chloride in water. The electrode is normally linked via a
porous frit (sometimes coupled to a
salt bridge) to the solution in which the other electrode is immersed.
In
cell notation the electrode is written as:
Theory of electrolysis
Solubility product
The electrode is based on the redox reactions
The half reactions can be balanced to the following reaction
- .
Which can be simplified to the precipitation reaction, with the equilibrium constant of the
solubility product.
The
Nernst equations for these half reactions are:
The
Nernst equation for the balanced reaction is:
where E0 is the
standard electrode potential for the reaction and aHg is the
activity for the mercury cation.
At equilibrium,
- , or equivalently .
This equality allows us to find the solubility product.
Due to the high concentration of chloride ions, the concentration of mercury ions () is low. This reduces risk of
mercury poisoning for users and other mercury problems.
SCE potential
The only variable in this equation is the activity (or concentration) of the chloride anion. But since the inner solution is saturated with potassium chloride, this activity is fixed by the solubility of potassium chloride, which is: 342 g/L/74.5513 g/mol = 4.587 M @ 20 °C. This gives the SCE a potential of +0.248 V vs.
SHE at 20 °C and +0.244 V vs.
SHE at 25 °C,
[1] but slightly higher when the chloride solution is less than saturated. For example, a 3.5M KCl electrolyte solution has an increased reference potential of +0.250 V vs.
SHE at 25°C while a 1 M solution has a +0.283 V potential at the same temperature.
Application
The SCE is used in
pH measurement,
cyclic voltammetry and general aqueous
electrochemistry.
This electrode and the
silver/silver chloride reference electrode work in the same way. In both electrodes, the activity of the metal ion is fixed by the solubility of the metal salt.
The calomel electrode contains mercury, which poses much greater health hazards than the silver metal used in the Ag/AgCl electrode.
See also
References
-
^ Sawyer, Donald T.; Sobkowiak, Andrzej; Roberts, Julian L. (1995). Electrochemistry for Chemists (2nd ed.). Wiley. p. 192.
ISBN
978-0-471-59468-0.