Electrode:
• An electrode is an electrical conductor used to make contact
with a non-metallic part of a circuit (e.g. a semiconductor, an
electrolyte, a vacuum or air).
• Electrodes are essential parts of batteries that can consist of a
variety of materials depending on the type of battery.
1. Galvanic Cell: -
A Galvanic cell is a device in which the
chemical energy is converted into electrical energy.
Ex: Dry cell…
2. Electrolytic Cell: - It is a device in which electrical
energy is converted into chemical energy.
Ex: Nelson’s cell, Down’s cell etc….
Construction of Galvanic Cell:-
• A Daniel cell is an example of Galvanic cell.
• It consists of two containers, one which is with a Zinc rod dipped
in Zinc Sulphate solution.
• The other hand with a Copper rod dipped in Copper Sulphate
solution and each electrode is known as half cell.
• These two electrodes are connected internally by Salt Bridge and
externally connected through a voltmeter using metallic wire.
• The Daniel cell is based on the Redox reaction.
Salt bridge
+
-_
Copper
Zinc Cathode
Anode
---------
---------
}}}}}}}}}}}}}}}}}}}}}}
ZnSO4 }}}}}}}}}}}}}}------ CuSO4
Solution Solution
Daniel cell
Working:
Anode Reaction :
Cathode Reaction :
Net Reaction :
Cell Notations and Conventions:-
• Anode is written on the LHS, while Cathode is written on
the RHS.
• The electrode on the left is written by writing the metal
first and then the electrolyte. The two are separated by
vertical line
ie, (or)
• The electrode on the right is written by writing the
electrolyte first and then the metal. The two are separated
by vertical line.
ie,
• The Salt Bridge is indicated by two vertical lines.
Electromotive Force of a cell (Emf):-
The Emf of the cell is a difference b/w the potential of the two
electrodes of a galvanic cell which cause the flow of current from one
electrode to other.
Mathematically Emf of a cell represented as,
Ecell= E Right – E Left
Ecell = ECathode – Eanode
Single Electrode Potential:
“The potential developed at interphase b/w the metal and solution,
when a metal is contact with solution of its own ions”.
Ex: -
Standard Electrode Potential:-
“The electrode potential when the electrode is in contact with a
solution of unit concentration of its ions at 298K. When an inert
electrode involves a gas then the gas at one atmosphere pressure at
298K”.
Ex:
Single & Standard electrode potentials are inter-related by
Nernst’s equation depending on concentration of metal ions at
particular temperature.
Reference Electrodes:-
Reference electrodes are electrodes whose potentials are known.
(OR)
Reference electrodes are electrodes with known potential and with
reference to these electrode we can determine the potential of other
electrodes.
• Primary Reference Electrode:- These are the electrodes used to
measure the potential of the other electrode, whose potential is
arbitrarily taken as zero at all temperatures.
Ex:- Standard Hydrogen electrode [SHE]
• Secondary Reference Electrode: - These are the electrodes used to
measure the electrode potential of other metals, whose potential with
respect to SHE are known.
Ex: Calomel e-de, Ag-AgCl e-de,
Construction and Working of Calomel
Electrode:-
• It consists of inner tube packed with mercury at the
bottom and a paste of mercury and mercurous
chloride is placed above the mercury.
• The outer tube is filled with a KCl solution of
known concentration (or) saturated KCl solution.
• A Pt-wire is kept immersed into the mercury to
obtain electrical contact.
• A porous disc act as salt bridge.
• The stopper in the outer tube may be removed when
additional sat’d KCl is needed.
Working:
The e-de potential of the Calomel electrode is given by Nernst eq.
0.0591 [Product]
𝐸 = 𝐸° + lo𝑔
𝑛 [Reactant]
0.0591 [Hg 2 Cl2 ]
𝐸 = 𝐸° + log
𝑛 [Hg]2 [Cl ]2
concentration of any solid material is considered to be unity,
[Hg]=[Hg2Cl2]=1
0.0591 1
𝐸 = 𝐸° + log − 2
2 [Cl ]
E = Eo – 0.0591 log [𝑪𝒍− ] at 298K.
The potential of the calomel electrode depends on the concentration of the KCl. For
Saturated KCl, the potential is +0.241V, for 1M KCl and 0.1M KCl the values are
+0.280V, and 0.334V respectively.
Standard Hydrogen Electrode:
• The hydrogen electrode is constructed by bubbling hydrogen
through an acid solution of known pH.
• A noble electrode (platinized platinum) is generally placed into
the solution to insure a large electrochemical surface area and
rapid equilibrium conditions.
Working:
Electrode representation: The net reversible electrode
reaction is;
2H+ + 2e− H2(g)
If the concentration of H+
ions is 1M and hydrogen gas is
bubbled at 1 atmospheric pressure
at
298K, it is called standard hydrogen
electrode (SHE). Its electrode
potential is officially assigned 0.0V
as thermodynamic reference point
for all potential measurements.
