Electrochemistry Basics – II

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 Electrodes
• Different types of electrodes
• Reference electrodes - SHE (Primary
Electrode)
• Calomel electrode (Secondary Electrode)
• Glass Electrode
• Single electrode potential -

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 Different types of electrodes
Depending on the nature of materials or its components, Cells are mainly
classified into

1. Metal – Metal Ion electrode

2. Metal – Insoluble Metal Ion Electrode

3. Gas Electrode

4. Ion Selective Electrode (Glass Electrode etc.)

Its descriptions are following,

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 (1) Metal –Metal Ion Electrode
• Eg. Daniell cell, there a metal (eg. Cu) is
immersed in its own ion (CuSO4)
• It is represented by: M/Mn+

• Generally its chemical reaction is represented

by:
M ⇌ Mn+ + ne, and its Nernst equation is:

E = E0 – (RT/nF) ln [Mn+]

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 (2) Metal –Insoluble Metal salt
Electrode
• Eg. Calomel electrode
• Here a metal M, is covered by a layer of sparingly
soluble salt (MX) solution and is dipped into a salt
solution
• Its Cell Representation: M/MX/X-

• Generally its chemical reaction is represented by:

M + X- ⇌ MX + e, and its Nernst equation is:

E = E0 – (RT/nF) ln [ 1/X- ]
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 Diagram of Calomel Electrode

Description: In Calomel electrode liquid mercury is kept in a bottle which is covered

by Calomel (Hg2Cl2). On the top of it saturated solution of KCl is used. This will
produce an EMF of +0.2422 (if we use a saturated solution of KCl) V with respect to 6
Standard Hydrogen Electrode.
 Reactions
• When it acts as Anode Cell 2Hg + 2Cl- → Hg2Cl2 + 2e-
( oxidation; Mercury is consumed)

• When it acts as Cathode Cell Hg2Cl2 + 2e- → 2Hg + 2Cl--

( reduction; Hg is produced )

Its Nernst Equation is:

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 (3) Gas Electrode
• Eg. Standard Hydrogen Electrode (SHE)
• In SHE the H2 gas (1 atm pressure) is bubbled
through a Pt foil which is immersed in a 1M
HCl solution.
• It is used as a Primary Reference Electrode
• Arbitrarily its EMF is assumed to be ZERO
E0SHE = 0.0 Volt (by definition)

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Diagram of SHE

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 (4) Glass Electrode
• It is widely used to measure pH
• It consists of thin walled glass (a doped glass
so it conducts current) which contain Ag metal
covered by AgCl salt (a precipitate).
• Cell Representation:
Ag/AgCl/0.1 M HCl/Glass/H+

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 0.1 M HCl

Its Nernst Equation is:

E G = E0G - 0.0591 [ pH ]
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 Disadvantages of SHE
• In SHE Hydrogen gas is used, which is highly
inflammable
• Experimental set up is difficult
• Maintaining 1 M HCl and 1 atmospheric
pressure of H gas is difficult
• If HCl is not very pure it will poison (catalytic
poison) the Pt surface. It may affect cell
voltage
• Not transportable
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 Advantages of Calomel Electrode
• It is widely used as a secondary standard
electrode
• It will produce a constant voltage of +0.2422V
if we use a saturated solution of KCl and at
standard Temperature
• Easy to set up and easily transportable

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