Types of electrodes.

1. Metal-metal ion electrode:

This type of electrode consists of a metal in contact with a solution of its own ions. At the surface of the electrode, a
potential arises.

For example: 1. Zinc in a solution of zinc sulphate.

2. Copper in a solution of copper sulphate.

3. Metal-metal salt ion electrode:

This type of electrode consists of a metal in contact with one of its sparingly soluble salts and a solution of a soluble salt
having a common anion with the sparingly soluble salt.

For example: 1. Calomel electrode Hg / Hg2Cl2 / Cl-

2. Silver-Silver chloride electrode Ag / AgCl (s) / Cl-

3. Gas electrode:
Electrode system in which one of the electrode material is a gas, bubbled over inert metal((Pt)) in contact with solution
containing ions / electrodes at which gases are reversible. Inert metal is used to make electrical contact because gases cannot
conduct electricity. The electrode potential value depends on the pressure of the gas and activity of the solution.

For example: 1. Hydrogen electrodes Pt / H2 (1atm) / H+ (1M) or Pt/H2/HCl

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4. Redox Electrode:
This type of electrode consists of an inert electrode (Pt or Au) develops potential due to the presence of oxidized and
reduced forms of the same substances in solution.

For example: 1. Pt / Fe2+, Fe3+ 2. Pt / Sn2+ Sn4+

,

5. Ion Selective Electrode:

Electrodes which have the ability to respond to certain specific ions in a mixture of ions in a solution are called ion
selective electrodes. This electrode contains suitable non-porous membrane separates two solutions, containing similar ions of
different concentrations and acts as an electrochemical membrane.

The potential developed at the electrode depends on the concentration of that particular ionic species.

Ex: Glass electrode(Ag/AgCl/HCl/HCl/Glass), crystalline membrane electrode, Solid state membrane electrode.

6. Amalgam electrode:
Amalgam is the alloy of any metal with mercury. An amalgam electrode is a modification of metal-metal ion electrode. It
is formed by placing the metal-amalgam in contact with a solution of metal ion. In place of a metal, its solution in mercury is
used.

For example: 1. Zinc amalgam electrode [Zn2+/Zn(Hg)] 2. Ag-amalgam electrode.

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 Reference Electrode:
Reference electrodes is an electrode which has a stable and known electrode potential with reference to which
the electrode potential of any other electrode can be determined.
By knowing the potential of one electrode and EMF of a galvanic cell, potential of other electrode can be
determined using the formula: Ecell = Ecathode – Eanode
Criteria:
i. Potential should be known under the conditions of utility.
ii. It should show minimum variation with respect to temperature.

Types:
I. Primary reference electrode:
Standard hydrogen electrode (SHE) is the only primary reference electrode (gas
electrode).
Represented as Pt/H2(g)(1 atm) / HCl(1M)
The potential of SHE is taken as zero by convention. Therefore, potential values
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electrode.
 Advantages of SHE:
a) It can be used over the entire range of pH
b) It exhibits no salt error and highly accurate.
c) It has negligible electric leakage errors.

Limita Construction and maintenance is difficult since it’s a gas

electrode.
ti ons Pt metal used in the electrode is easily poisoned by
any impurity present in the system.
of Cannot be used in the presence of oxidizing agents like
SHE: nitrates, H2S, chlorides, etc. as they poison Pt.
Difficulty in maintaining pressure at 1 atm under normal
laboratory condition.

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II. Secondary reference electrode
These are the electrodes whose potential is measured w.r.t. SHE and then can be used as reference electrode for
measuring potentials of other electrodes.
Eg: Calomel electrode, silver-silver chloride electrode

Construction:
• Calomel electrode is a metal-metal salt ion electrode.
• The electrode consists of a narrow glass tube with two side tubes.
• A little Hg is placed at the bottom of the glass tube followed by a layer of

Hg2Cl2 (Mercurous chloride or calomel) and paste of Hg.

• The remaining part of the glass tube is filled with KCl solution of definite
concentration.
• The thin glass tube with a platinum wire is then inserted, taking care that
the platinum wire dips into mercury.

Representation:
Hg|Hg2Cl2|KCl(sat)
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Working Principle:
The calomel electrode can act as anode or cathode depending on the nature of another electrode of the cell.

As anode: As cathode:
2Hg Hg2Cl2 Hg2+ + 2Cl-
+ -
Hg2+ + 2e-
+ 2Cl
Hg2Cl2
Hg2 Hg2+ + 2e- 2Hg

2Hg + 2Cl- Hg2Cl2 + 2e-

Hg2Cl2 + 2e- 2Hg + 2Cl-

Electrode Potential of calomel electrode is given by:

ECE = EoCE -0.0598 log [Cl-] at 298 K

• Calomel electrode is reversible with respect to Cl- ions

• Potential value of calomel electrode decreases with increase in concentration of KCl as
fallows.
Name Decinormal CE Normal CE Saturated CE
Conc of KCl 0.1 N 1.0 N Saturated
Potential of 0.3335 0.281 0.242
CE in V
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 Example: Measurement of electrode potential(Zinc) using Calomel electrode:

Ecell is measured using a potentiometer:

Ecell = Ecathode – Eanode

2+
= ESCE – EZn /Zn
2+
EZn /Zn = ESCE – Ecell

ESCE = 0.2422 V
2+
Therefor, EZn /Zn = 0.2422
V – Ecell

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Advantages: Disadvantages:
a) Easy to set up and operate. a) Calomel electrode should not be used at above 50
b) Potential values do not vary much with variation in C because the mercurous chloride breaks down
o

temperature. yielding unstable readings.

c) Not poisoned by oxidizing impurities. b) Since mercury is toxic, this electrode losing its
d) They are calibrated with respect to SHE. popularity.

Application:
• Used as a reference electrode in PH meter.
• Used to measure the potential of any other electrode.

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