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Chemistry

Electrochemistry
Reference Electrodes and Electrode Potential

What you already know

● Characteristics of anode What you will learn

● The role of the salt bridge
● Criteria for selecting the salt ● Reference electrode
bridge ● Types of electrode potential
● Electrode potential ● Cell potential
● Standard electrode potential
● Cell potential and EMF
 Reference Electrode
Ecell calculation when both the electrodes in a cell prefer reduction

Suppose, the reduction potential of an electrode is 4 V and that of another

electrode is 3 V, the electrode with a higher reduction potential (i.e., 4 V)
undergoes reduction, and the electrode with comparatively lower reduction
potential (i.e., 3 V) forcibly undergoes oxidation.
Then the overall cell potential (Ecell) is obtained as:

Reduction potential of Reduction potential of

substance reduced - substance oxidized
Ecell =

Ecell = 4 - 3 = 1 V
Thus, to calculate the overall cell potential (Ecell), it is essential to know what is
the “exact potential” of any electrode without any variation.
 Reference Electrode

Calculating the exact potential of an electrode

Consider a Zn metal strip immersed in a

solution of Zn2+ ions as shown in Figure.

Zn (s) ⇌ Zn2+ (aq) + 2e−

Dynamic equilibrium
Zn metal in a
solution of Zn2+
 Reference Electrode
The Zn2+ ions that are produced from the Zn metal strip move into the solution. At the
same time, electrons from the solution are deposited on the Zn metal strip. Thus, the
system achieves a dynamic equilibrium. This can be observed in the magnified part of
figure.

The region around the metal strip is highly concentrated with Zn2+ ions. The Zn metal
strip is negatively charged due to the electron deposition.

Due to this charge separation, a potential difference is developed. It is not possible

to measure the potential difference by connecting a voltmeter to the solution of the
electrode.

This is because of the formation of a layer of oppositely charged ions around the
wire which creates another cell (i.e., another equilibrium along with the existing one).
 Reference Electrode
The potential of an individual half-cell cannot be measured. Only the difference
between the two half-cell potentials (emf) can be measured.

If the potential of one half-cell is known, the electrode potential of the other half-cell
can be calculated using the cell potential (Ecell). From the measured emf (Ecell), the
potential of the electrode can be obtained by subtracting the potential of the
reference electrode.

If we arbitrarily choose the potential of one half-cell, then the potential of other
half-cell can be determined with respect to this. Therefore, an electrode (half-cell) of
the known electrode potential (reference electrode) is needed, with respect to which
the potential of the other electrodes are calculated.
 Reference Electrode

Reference electrode

● An electrode of a known potential can be treated as a reference

electrode.
● The most commonly used reference electrode is the hydrogen electrode.
● The potential of all other electrodes are measured with respect to
hydrogen electrode.
● Under standard conditions, the standard hydrogen electrode (SHE) acts
as the reference electrode.
 Types of Electrode Potential

Two major types of electrode potentials are given as follows:

Electrode Potential

Oxidation Reduction
Potential (OP) Potential (RP)
 Types of Electrode Potential

Oxidation Potential (OP)

● The electrode potential for the oxidation half reaction is known as

oxidation potential.
● Electrode in which the oxidation half reaction happens is termed
as a negative electrode.
● Consider the oxidation half reaction is given as follows:

M(s) Mn+ (aq) + ne-

 Types of Electrode Potential

Oxidation Potential (OP)

● The shorthand notation for the oxidation potential of the

above half reaction can be given as:
EoM(s)/Mn+ (aq)
● Oxidation potential under standard conditions is known as standard
oxidation potential (SOP). The notation for SOP is given as:
EoM(s)/Mn+ (aq)
where, o represents the standard state and M stands for the species
that undergoes oxidation.
 Types of Electrode Potential

Example H2O2 ⇌ O2 + 2H+ + 2e−

Oxidation half cell

Representation

Eo
H2O2 / O2
 Types of Electrode Potential

Example Cu (s) ⇌ Cu2+ (aq) + 2e−

Oxidation half cell

Representation

o
E Cu(s) / Cu2+(aq) = −0.34 V
 Types of Electrode Potential

Example Zn (s) ⇌ Zn2+ (aq) + 2e−

Oxidation half cell

Representation

o
E Zn(s) / Zn2+(aq) = +0.76 V
 Types of Electrode Potential

Reduction potential

● The electrode potential for the reduction half reaction is known as reduction
potential.
● Electrode in which the reduction half reaction happens is termed a positive
electrode.
● Consider the reduction half reaction is given as follows:

Mn+ (aq) + ne- M (s)

● The shorthand notation for the reduction potential of the above half reaction
can be given as: Eo
Mn+ (aq) /M (s)
● Standard reduction potential (SRP) is denoted as: Eo n+
M (aq) /M (s)
 Types of Electrode Potential

Example Cu2+ (aq) + 2e− ⇌ Cu (s)

Reduction half cell

Representation

o
E Cu2+
(aq) / Cu (s) = +0.34 V
 Types of Electrode Potential

Example Zn2+ (aq) + 2e− ⇌ Zn (s)

Reduction half cell

Representation

o
E Zn2+
(aq) / Zn(s) = −0.76 V
 Types of Electrode Potential

Example H2O2 + 2H+ + 2e− ⇌ 2H2O

Reduction half cell

Representation

o
EH O / H2O
2 2
 Types of Electrode Potential

Oxidation potential v/s reduction potential

● Oxidation and reduction potentials for an electrode are equal in value and
opposite in sign.

Oxidation potential = - Reduction potential

Standard oxidation potential (SOP) = - Standard reduction potential (SRP)

Example: EoCu2+ (aq) /Cu(s)= -0.34 V

EoCu(s)/Cu2+ (aq)= 0.34 V

 Types of Electrode Potential
Higher the reduction potential (or SRP) of a species, higher is the tendency to get
reduced and greater is the oxidising power.

Consider the reduction potentials of reactions as follows:

Cu2+ (aq) + 2e- ⇋ Cu(s) : EoCu2+ (aq) /Cu(s) = 0.34 V

Zn2+ (aq) + 2e- ⇋ Zn(s) : EoZn2+ (aq) /Zn(s) = - 0.76 V

Here, the reduction potential is highest for copper electrode and it has a greater
tendency to get reduced (i.e., forward reaction) when compared to zinc electrode.
Hence, copper is a stronger oxidising agent than zinc.
 Types of Electrode Potential
Higher the oxidation potential (or SOP) of a species, higher is the tendency to get
oxidised and greater is the reducing power.

Predicting the spontaneous reaction occurring at an electrode

By comparing the oxidation and reduction potential values of the same electrode,
the spontaneous reaction occurring at the electrode can be predicted.
Consider the case of copper electrode:

Cu2+ (aq) + 2e- ⇋ Cu(s) : EoCu2+ (aq) /Cu(s)= 0.34 V

Cu(s) ⇋ Cu2+ (aq) + 2e- : EoCu(s)/Cu2+ (aq) = -0.34 V

 Types of Electrode Potential

Here, the reduction potential is more positive (+0.34 V) than its oxidation potential
(−0.34 V). Thus, the reduction of copper is a spontaneous reaction.

Consider the case of zinc electrode:

Zn2+ (aq) + 2e- ⇋ Zn(s) : EoZn2+ (aq) /Zn(s) = -0.76 V

Zn(s) ⇋ Zn2+ (aq) + 2e- : EoZn(s)/Zn2+ (aq) = 0.76 V

In the case of zinc electrode, the oxidation potential is more positive (+0.76 V) than
its reduction potential (-0.76 V). Thus, the oxidation of zinc is a spontaneous
reaction.
 Cell Potential (EMF)

According to the IUPAC convention, the standard electrode potential is now

expressed in terms of standard reduction potential (SRP).

If the value of standard reduction potential is positive, then reduction is favoured,

and if the value of standard reduction potential is negative, then oxidation is
favoured.

When two half-cells are connected, the one with the higher standard reduction
potential acquires electrons from the one with lower standard reduction potential,
which is forced to undergo oxidation.
 Cell Potential (EMF)
Consider two reductions, half-reactions are given as follows. The second reaction
involving B (not boron) is considered hypothetically for the purpose of
understanding.

Cu2+ (aq) + 2e- ⇋ Cu(s) ; EoCu2+ (aq) /Cu(s) = 0.34 V ……(1)

B2+ (aq) + 2e- ⇋ B(s) ; EoB2+ (aq) /B(s) = 0.5 V ……(2)

Reaction (2) has a higher reduction potential than reaction (1).

Hence, it will undergo reduction by acquiring electrons from the half-cell involving
Cu and Cu2+. Also, the half-cell involving Cu and Cu2+ will undergo oxidation.
 Cell Potential (EMF)

The overall cell potential can be calculated as follows:

Cu(s) ⇋ Cu2+ (aq) + 2e-; Eo 2+ or Eooxidation = 0.34 V …(3)

Cu (s)/Cu (aq)
2+ -
B (aq) + 2e ⇋ B(s); Eo 2+ or Eoreduction = 0.5 V …...(4)
B (aq)/B (s)

Adding reactions (3) and (4) will give the overall cell reaction and cell
potential (Eocell) as:

Cu(s) + B2+ (aq) ⇋ B(s) + Cu2+(aq); Eocell = -0.34 V +0.5 V =0.16 V

 Cell Potential (EMF)
Sign of cell potential

● The sign of the cell potential tells us the direction in which the reaction must
shift to reach equilibrium.

● If the electrode potentials of both the half-cells are same (either both half-cells
have the same oxidation potential or both have the same reduction potential),
then the overall cell potential (Eocell) will become zero. Hence, the overall
reaction will remain in a state of equilibrium.

● Reactions for which Eocell is positive and have equilibrium constants that favour
the formation of the products of the reaction. Such reactions occur naturally and
are referred to as spontaneous reactions.
 Cell Potential (EMF)
For better understanding, an example is given as follows:

Zn2+ (aq) + 2e- ⇋ Zn(s) ; EoZn2+ (aq) /Zn(s) = -0.76 V

Cu(s) ⇋ Cu2+ (aq) + 2e- ; EoCu(s)/Cu2+ (aq) = -0.34 V

o
Eo
=
E 2+ - EoCu (s)/Cu2+ (aq)
cell Zn (aq) /Zn (s)

Eocell = -0.76 -(-0.34) = -0.42 V

Since the Eocell value is negative, this reaction is not favoured in the forward direction
(i.e., formation of Zn and Cu2+).
Here, the backward reaction is favoured (i.e., formation of Cu and Zn2+). In this
reaction, the oxidation of Zn to Zn2+ and the reduction of Cu2+ to Cu is favoured.
 Cell Potential (EMF)

● Eocell = 0; overall reaction at equilibrium

● Eocell > 0; spontaneous reaction (forward shifting of reaction)
● Eocell < 0; non-spontaneous reaction (backward shifting of reaction)

● The magnitude of the cell potential is a measure of

the driving force for the reaction.
● The larger the value of the cell potential, the farther
is the reaction from equilibrium.
 Cell Potential (EMF)
It is possible to calculate Eocell if the following two key points are noted:

● When the standard oxidation potential (SOP) of a species is positive, then the
species have a higher tendency to get oxidised.

● When the standard oxidation potential (SOP) is negative (that means standard
reduction potential is positive), the species have a higher tendency to get
reduced.
Formula to calculate cell potential/EMF
º
Ecell is a
SRP of substance positive
SRP of substance
º
Ecell = reduced − oxidised number
 Cell Potential (EMF)

We know that:

SRP of substance oxidized = - SOP of substance oxidized

Hence, formula for Eocell becomes:

Eocell = SRP of substance reduced - (-SOP of substance oxidized)

Eocell = SRP of substance reduced + SOP of substance oxidized

Eocell= Eoreduction + Eooxidation

 Cell Potential (EMF)

Few cases of EoCell calculation is given as follows:

Case 1:
Consider two half-cells with standard oxidation potentials (SOP) 3 V and -5 V.
The half-cell with SOP of -5 V actually prefers reduction (i.e., has an SRP of 5 V).

Eocell = Eooxidation + Eoreduction

Eocell= 3 + 5 = 8 V
 Cell Potential (EMF)

Few cases of EoCell calculation is given as follows:

Case 2:
Consider two half-cells. Half-cell 1 has a standard oxidation potential (SOP) of
-3 V and half-cell 2 has a standard reduction potential (SRP) of +5 V.

Eocell = Eooxidation + Eoreduction

Eocell= -3 + 5 = 2 V
 Cell Potential (EMF)

Few cases of EoCell calculation is given as follows:

Case 3:
Consider two half-cells. Half-cell 1 has a standard reduction potential (SRP) of
2 V and half-cell 2 has a standard oxidation potential (SOP) of -1.9 V.

Eocell = Eooxidation + Eoreduction

Eocell= -1.9 + 2 = 0.1 V