2.

3: Electrode Potential, Standard Electrode

Potential and Electromotive force (e.m.f.) of a cell

In this section, you will learn the following:

(A) Electrode potential, standard electrode potential
(Eθ) and electromotive force of a cell (cell e.m.f. =
Ecell)
(B) Standard reduction potential (Eθred )
(C) Calculation of the values of e.m.f. of a standard
cell (Eθcell ) from given values of Eθred
(D) Determine the oxidizing agent and reducing agent
from given values of Eθred
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(A) Electrode potential (Eθ)
• What happens if a piece of metal, M is immersed in an aqueous
solution containing the Mn+ ions?
• Metals are reducing agents, so M has the tendency to lose
electrons and goes into the solution as Mn+ aqueous ions,
leaving behind the electrons. This makes the metal rod
negatively charged with respect to its aqueous solution.
M(s)  Mn+ (aq) + ne

Figure 1: dissolution of metal M

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• Conversely the Mn+ ions in the solution can ‘snatch’ electrons
from the metal atoms on the metal rod and get reduced and
deposit as M atoms. This makes the metal rod positively
charged with respect to its aqueous solution.
Mn+ (aq) + ne  M (s)

Figure 2: Deposition of M

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• At equilibrium, the rate of dissolution of M is
equal to the rate of deposition of Mn+ .
M(s) Mn+(aq) + ne
• This sets up a potential difference between
the metal and its aqueous ions. This potential
difference Is called the electrode potential.
• The position of equilibrium depends on the
nature of the metal.

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• For a very reactive metal such as magnesium, the
equilibrium lies more to the right-hand side. As a
result the magnesium rod acquires a nett negative
charge with respect to the solution.
• Mg(s) Mg2+ (aq) + 2e
• The Mg2+/Mg half-cell is said to have a negative
electrode potential.
• For less reactive metal such as silver, the equilibrium
lies more to the left-hand side. As a result, the silver
rod acquires a nett positive charge with respect to
the solution.
• Ag(s) Ag+ (aq) + e
• The Ag+/Ag half-cell is said to have a positive
electrode potential.
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• The electrode potential is a measure of the
ease of loss of electrons by a metal.
• The more negative the electrode potential of
a half-cell, the easier it is for the metal to lose
electrons (oxidation).
• The more positive the electrode potential of a
half-cell, the easier it is for its ion to accept
electrons (reduction).

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Reflect
Compare the electrode potential of the half-cells in the
Daniell cell.
Which half-cell has a more negative electrode potential?
Which half-cell has a more positive electrode potential?

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Electromotive force (e.m.f.)
• The potential energy of the electron at the
negative electrode (anode) is higher than at the
positive electrode (cathode). Hence the electron
is able to move spontaneously from anode to
cathode.
• It is the difference in the electrode potential of
the two half-cells that provides the driving force
that drives electrons through the connecting
wires from the negative electrode to the positive
electrode.
• The potential difference between two half-cells is
called the cell potential, Ecell , also known as
electromotive force (e.m.f.) of a cell.
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• Since Ecell is measured in volts, Ecell is also
known as cell voltage.
• The value of e.m.f. of a chemical cell depends
on the concentration of reactant and product
as well as the temperature at which the
reaction takes place.

Ecell = Electromotive force (e.m.f.) = cell potential

= cell voltage = the difference in the electrode
potential between two half-cells

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Standard electrode potential
• The following sets of conditions are the standard
conditions for measuring electrode potentials of half-
cells:
– Temperature is fixed at 250C (298K)
– Pressure is fixed at 101 kPa or 1 atm
– Concentration of ions in the electrolytes is fixed at 1.00
mol dm-3
• Under such conditions, the electrode potential of a
half-cell is called the standard electrode potential, SEP,
and given a symbol of Eθ with a unit of volt.
• The Eθ value depends on the concentration,
temperature and pressure of reactants and products at
the electrode.
Standard electrode potential (Eθ) refers to the potential difference for a
reaction that happens at an electrode. 10
• In standard conditions, the cell e.m.f. is known as
standard electromotive force and is represented by
the symbol Eθcell . Eθcell is also known as the standard
cell potential.
Note:
• The electromotive force is measured in volt (V).
• One volt is the potential difference between two points
that will impart one joule (1J) of energy per coulomb (C)
of charge that passes through it.
• Example:
The standard e.m.f. of the Daniell cell (Zn-Cu cell) is 1.10
V. The method to obtain this value is discussed in Section
(D)
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Standard Electrode Potential of Non-Metals
Example: Hydrogen gas
• When hydrogen gas is passed through a tube
containing an inert electrode in contact with a
dilute acid, the following equilibrium is achieved.

H2 (g) 2H+ (aq) + 2e

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Figure 3: Hydrogen electrode

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• This situation also results in a potential
difference between the hydrogen gas and the
acid solution which contains hydrogen ions.
This potential difference is the electrode
potential of hydrogen.
• If the concentration, temperature and
pressure of the gas is at standard conditions,
then, the half-cell is known as the standard
hydrogen electrode, and the electrode
potential is known as standard hydrogen
electrode potential.
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Measuring standard electrode potential
• The absolute value of the standard electrode potential of
a half-cell cannot be measured because we need another
half-cell to complete the circuit. So, what is measured is
always the difference between the two half-cells.
• However, if a particular half-cell is chosen as reference
and arbitrarily assigned its standard electrode potential
as zero, then, the e.m.f. of a cell consisting of the half-cell
and the reference half-cell would give the standard
electrode potential of the half-cell under investigation.
• The half-cell chosen as reference is the standard
hydrogen electrode.
• Hence, when the electrode of a half-cell under
investigation is connected to the standard hydrogen
electrode, the reading of the voltmeter connected to the
two electrodes is the value of the standard electrode
potential of the half-cell.
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Measuring standard electrode potential
(Refer to reading material in Google Classroom)
• The half-cell which standard electrode potential is to be
measured is connected to the standard hydrogen
electrode to form an electrochemical cell.
• The cell e.m.f. (measured using a high resistant
voltmeter) and the direction of flow of current are then
noted.
• The standard electrode potential of the half-cell under
investigation can then be calculated.
• The set-up of apparatus depends on the state of the half-
cell under investigation:
– Half-cells consisting of a solid electrode and its aqueous ions
– Half-cells consisting of a gas and its aqueous ions
– Half-cells consisting of aqueous ions
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Example:
Apparatus to measure the standard electrode potential of zink

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• A negative value is given to the electrode that
acts as a negative electrode (anode) when it is
connected to the hydrogen electrode.
• A positive value is given to electrodes that acts
as the positive electrode (cathode) when it is
connected to the hydrogen electrode.
(Refer to the table of standard electrode
potentials provided.)

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The Electrochemical Series (Refer to the table of Standard Electrode Potential) 19
 (B) Standard reduction potential (Eθred )
• In the standard electrode potential
series, the reactions for the half-cells are
written as reduction with a reversible
sign. The standard electrode potential is
also known as standard reduction
potential (Eθred ).
• It is the potential difference for the half-
equation that occurs at the cathode or
the anode.
(Refer to the list of standard reduction
potential, Eθred provided to you.) 20
Example 1
• With reference to the table of standard
electrode potential and standard reduction
potential, the standard reduction potential of
zinc electrode can be written in short as
EθZn2+/Zn = - 0.76 V.
• This means that, if the zinc electrode is
connected to the hydrogen electrode to form
a complete circuit, the zinc electrode is the
negative electrode, ie. the anode.

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The Electrochemical Series (Refer to the table of Standard Electrode Potential) 22
Example 2
• The standard reduction potential of copper
electrode can be written in short as
EθCu2+/Cu = + 0.34 V.
• This means that when the copper electrode is
connected to the hydrogen electrode to form
a complete circuit, the copper electrode is the
positive electrode (cathode)

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The Electrochemical Series (Refer to the table of Standard Electrode Potential) 24
Activity 1
Using the standard reduction potential table,
state
(a) EθFe2+/Fe
(b) EθPb2+/Pb

Which of the two metals, iron or lead more

readily forms positive ions in solution?

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(C) Calculation of standard e.m.f. Eθcell from the
values of Eθred
Case 1: If two values of Eθred are provided
The value of the standard e.m.f. Is calculated using the
following formula
Eθθ = Eθθ (cathode) – Eθθ (anode)
E cell
cell = E red
red (cathode) – E red
red(anode)

Example 1: for the Zn-Cu chemical cell,

Eθcell = Eθred (cathode) – Eθred(anode)

= 0.34 V - (- 0.76 V)
= 1.10 V
Hint: Electrode with a more negative value is the anode
and electrode with the more positive value is the cathode
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Examples:

27
 Eθcell = Eθred (cathode) – Eθred(anode)
Examples

28
Example

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Case 2: If a redox reaction is given
• If a redox reaction is given, to determine Eθcell,
the first step is to write the half-equation for
oxidation and reduction from the given
equation.
• Next, determine the anode dan cathode.
• Then, determine Eθcell using the same method
as the example in Case 1.
Anode is the negative electrode where electrons are released
and oxidation occurs.
Cathode is the positive electrode where electrons are received
and reduction occurs
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Example: The redox equation for the Zn-Cu chemical cell is:

Zn (s) + Cu2+ (aq) → Zn2+(aq) + Cu (s).

The half-equations are:

Anode: Zn(s) → Zn2+(aq) + 2e- Oxidation

Cathode: Cu2+(aq) + 2 e- → Cu(s) Reduction

Hence, Eθcell = Eθred (cathode) – Eθred(anode)

= 0.34 V - (- 0.76 V)
= 1.10 V

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Example
A fuel cell is an electrochemical
cell that converts the chemical
energy of a continuous supply of
reactants into electrical energy.

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Example
Answer

33
Activity 2

34
Tutorial 2.3
Answer the following questions.

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(D) Determining the oxidizing agent and
reducing agent from the Eθred value
A negative Eθred value
• The standard reduction potential for zinc
electrode can be written in short as
EθZn2+/Zn = - 0.76 V.
• This means that when the zinc electrode is
connected to the hydrogen electrode to form
a complete circuit, the zinc electrode is the
negative electrode (anode)

36
• The reaction that occurs at the anode is
oxidation. Hence, the half-equation at the
anode is:
Zn(s) → Zn2+(aq) + 2e- Eθ = + 0.76 V
• Since zinc is oxidized, zinc is a reducing agent.
Note:
With reference to the table of standard reduction potential,
Zn2+(aq) + 2e- → Zn(s) Eθ = - 0.76 V
If the above equation is written backwards, the negative
value becomes positive.
Zn(s) → Zn2+(aq) + 2e- Eθ = + 0.76 V

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• In conclusion, the more negative the value of
Eθred for a metal, the higher the reducing
power (strength as reducing agent) of the
metal.
• For example, lithium is a stronger reducing
agent compared to zinc.
• Example:
Arrange the following metals according to
increasing strength as reducing agent:
Mg, Al, Ba
Answer: Al, Mg, Ba
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A positive Eθred value
• The standard reduction potential for copper
electrode can be written in short as
EθCu2+/Cu = + 0.34 V.
• This means that when the copper electrode is
connected to the hydrogen electrode to form a
complete circuit, the copper electrode is the
positive electrode (cathode).

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• The half reaction that occurs at the cathode is
reduction. Hence, the equation at the cathode is:
Cu2+(ak) + 2 e- → Cu(p) Eθ = + 0.34 V
• Since the Cu2+ ion is reduced, the Cu2+ ion is an
oxidizing agent.
• In conclusion, the more positive the value of Eθred
for a metal ion, the higher the oxidizing power
(strength as oxidizing agent) of the metal ion.
• For example, silver ions are stronger oxidizing
agent compared to copper(II) ions.

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Example:
The Eθ values for three elements, x, y, and Z are given below:

Arrange the ions of the elements in ascending order of their

oxidizing strengths.
Solution
Notice that the half-equations are written as oxidation process.
We need to reverse them to become reduction processes for
easy comparison.

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THE END

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