LESSON 1

INTRODUCTION TO
ELECTROCHEMISTRY
INTENDED LEARNING OUTCOMES:

1. Distinguish the different types of electrochemical cells.

2. Write the half reactions that occur at each electrode of a cell.
3. Identify which electrode is the cathode and which is the anode.
4. Draw the cell diagram for each redox reaction.
5. Calculate the standard cell potential of redox reactions.
6. Calculate standard Gibbs free energy of redox reactions.

1.1 DEFINITION OF ELECTROCHEMISTRY

Electrochemistry is the study of production of electricity from the energy released

during a spontaneous chemical reaction and the use of electrical energy to bring about non-
spontaneous chemical transformations.

1.2 ELECTROCHEMICAL CELLS

In any electrochemical process, electrons flow from one chemical substance to

another, driven by an oxidation–reduction (redox) reaction. A redox reaction occurs when
electrons are transferred from a substance that is oxidized to one that is being reduced.
The reductant is the substance that loses electrons and is oxidized in the process;
the oxidant is the species that gains electrons and is reduced in the process. The associated
potential energy is determined by the potential difference between the valence electrons in
atoms of different elements.

A redox reaction can be described as two half-reactions, one representing the

oxidation process and one the reduction process. For the reaction of zinc with bromine, the
overall chemical reaction is as follows:

Zn(s) + Br2 (aq) → Zn2+ (aq) + 2Br − (aq)

The half-reactions are as follows:

Reduction half-reaction:
Br2 (aq) + 2e− → 2Br − (aq)
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 Oxidation half-reaction:
Zn(s) → Zn2+ (aq) + 2e−

In any redox reaction, the number of electrons lost by the reductant equals the
number of electrons gained by the oxidant.

An apparatus that is used to generate electricity from a spontaneous redox reaction

or, conversely, that uses electricity to drive a nonspontaneous redox reaction is called
an electrochemical cell.

There are two types of electrochemical cell.

1. Galvanic (voltaic) cell – uses the energy released during a spontaneous redox
reaction (ΔG<0ΔG<0) to generate electricity.
2. Electrolytic cell – consumes electrical energy from an external source, using it to
cause a nonspontaneous redox reaction to occur (ΔG > 0).

Figure 1.1: Difference between a galvanic cell from an electrolytic cell.

Both types contain two electrodes, which are solid metals connected to an external
circuit that provides an electrical connection between the two parts of the system. The
oxidation half-reaction occurs at one electrode (the anode), and the reduction half-reaction

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occurs at the other (the cathode). When the circuit is closed, electrons flow from the anode
to the cathode. The electrodes are also connected by an electrolyte, an ionic substance or
solution that allows ions to transfer between the electrode compartments, thereby
maintaining the system’s electrical neutrality.

1.2.1 Voltaic (Galvanic) Cells

Consider the reaction of metallic zinc with cupric ion (Cu2+) to give copper metal and
Zn2+ ion. The balanced chemical equation is as follows:

Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)

The two metal strips, which serve as electrodes, are connected by a wire, and the
compartments are connected by a salt bridge, a U-shaped tube inserted into both solutions
that contains a concentrated liquid or gelled electrolyte. The electrolyte in the salt bridge
serves two purposes: it completes the circuit by carrying electrical charge and maintains
electrical neutrality in both solutions by allowing ions to migrate between them. Without
such a connection, the total positive charge in the Zn2+ solution would increase as the zinc
metal dissolves, and the total positive charge in the Cu2+ solution would decrease.

Figure 1.2 Salt bridge in a Zn-Cu voltaic cell.

The salt bridge allows charges to be neutralized by a flow of anions into the
Zn2+ solution and a flow of cations into the Cu2+ solution. In the absence of a salt bridge or
some other similar connection, the reaction would rapidly cease because electrical neutrality
could not be maintained.

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 The potential (𝐸cell ) of the cell, measured in volts, is the difference in electrical
potential between the two half-reactions and is related to the energy needed to move a
charged particle in an electric field. Because electrons from the oxidation half-reaction are
released at the anode, the anode in a galvanic cell is negatively charged. The cathode, which
attracts electrons, is positively charged.

A galvanic (voltaic) cell converts the energy released by a spontaneous chemical

reaction to electrical energy. An electrolytic cell consumes electrical energy from an
external source to drive a nonspontaneous chemical reaction.

Example 1.1: A chemist has constructed a galvanic cell consisting of two beakers. One
beaker contains a strip of tin immersed in aqueous sulfuric acid, and the other
contains a platinum electrode immersed in aqueous nitric acid. The two solutions are
connected by a salt bridge, and the electrodes are connected by a wire. Current begins
to flow, and bubbles of a gas appear at the platinum electrode. The spontaneous redox
reaction that occurs is described by the following balanced chemical equation:
3Sn(s) + 2NO3 − (aq) + 8H + (aq) → 3Sn2+ (aq) + 2NO(g) + 4H2 O(l)
For this galvanic cell,
(a) write the half-reaction that occurs at each electrode.
(b) indicate which electrode is the cathode and which is the anode.

Solution:
(a) reduction:
NO3 − (aq) + 4H + (aq) + 3e− → NO(g) + 2H2 O(l)
oxidation:
Sn(s) → Sn2+ (aq) + 2e−
(b) Cathode: platinum
Anode: tin

Example 1.2: Consider a simple galvanic cell consisting of two beakers connected by
a salt bridge. One beaker contains a solution of MnO4 − in dilute sulfuric acid and has
a Pt electrode. The other beaker contains a solution of Sn2+ in dilute sulfuric acid,
also with a Pt electrode. When the two electrodes are connected by a wire, current
flows and a spontaneous reaction occurs that is described by the following balanced
chemical equation:
2MnO4 − (aq) + 5Sn2+ (aq) + 16H + (aq) → 2Mn2+ (aq) + 5Sn4+ (aq) + 8H2 O(l)
For this galvanic cell,
(a) write the half-reaction that occurs at each electrode.
(b) indicate which electrode is the cathode and which is the anode.

Solution:
(a) reduction:
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 MnO4 − (aq) + 8H + (aq) + 5e− → Mn2+ (aq) + 4H2 O(l)
oxidation:
Sn2+ (aq) → Sn4+ (aq) + 2e−
(b) Cathode: platinum in the MnO4 −
Anode: platinum in the Sn solution.

1.2.2 Constructing Cell Diagrams (Cell Notation)

In a cell diagram, the identity of the electrodes and the chemical contents of the
compartments are indicated by their chemical formulas, with the anode written on the far
left and the cathode on the far right. Phase boundaries are shown by single vertical lines, and
the salt bridge, which has two phase boundaries, by a double vertical line. So for example the
cell diagram for the Zn/Cu cell is written as follows.

Zn(s)|Zn2+ (aq, +M)||Cu2+ (aq, +M)|Cu(s)

Example 1.3: Draw the cell diagram for the following reaction, assuming the
concentration of Ag + and Mg 2+ are each 1 M:
Mg(s) + 2Ag + (aq) → Mg 2+ (aq) + 2Ag(s)

Solution:
Mg(s)|Mg 2+ (aq, 1 M)||Ag + (aq, 1 M)|Ag(s)

Example 1.4: Draw a cell diagram for the galvanic cell described in Example 1.1. The
balanced chemical reaction is as follows:
3Sn(s) + 2NO3 − (aq) + 8H + (aq) → 3Sn2+ (aq) + 2NO(g) + 4H2 O(l)

Solution:
Sn(s)|Sn2+ (aq)||HNO3 (aq)|NO(g)|Pt(s)

1.3 THE GIBBS FREE ENERGY AND CELL VOLTAGE

Electrochemical cells convert chemical energy to electrical energy and vice versa. The
total amount of energy produced by an electrochemical cell, and thus the amount of energy
available to do electrical work, depends on both the cell potential and the total number of
electrons that are transferred from the reductant to the oxidant during the course of a
reaction. The total charge transferred from the reductant to the oxidant is therefore 𝑛𝐹,
where 𝑛 is the number of moles of electrons and 𝐹 = 96,483 C/mol ∙ e− (constant).
The maximum amount of work that can be produced by an electrochemical cell
(𝑤max) is equal to the product of the cell potential (𝐸cell ) and the total charge transferred
during the reaction (𝑛𝐹):

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 𝑤max = −𝑛𝐹𝐸cell

The change in Gibbs free energy (∆𝐺) is also a measure of the maximum amount of
work that can be performed during a chemical process (∆𝐺 = 𝑤𝑚𝑎𝑥 ).

∆𝐺 = −𝑛𝐹𝐸cell

In standard conditions, the value of 𝐸 0 cell is the difference of the electrode potentials
of the cathode and the anode.

𝐸 0 cell = 𝐸 0 cathode − 𝐸 0 anode

Example 1.5: Suppose you want to prepare elemental bromine from bromide using
the dichromate ion as an oxidant. Using the values in Annex-A, calculate the free-
energy change (ΔG°) for this redox reaction under standard conditions. Is the reaction
spontaneous?

Solution:
First step is to write the half-reactions.
Reduction half (cathode):
Cr2 O7 2− (aq) + 14H + (aq) + 6e− → 2Cr 3+ (aq) + 7H2 O(l)
Oxidation half (anode):
2Br − (aq) → Br2 (aq) + 2e−
To balance the resulting chemical equations, the oxidation half should be multiplied
by 3 so that the electrons in the oxidation is equal to that in the reduction.
Oxidation half (anode) × 3:
6Br − (aq) → 3Br2 (aq) + 6e−
Reduction half + Oxidation half:
Cr2 O7 2− (aq) + 6Br − (aq) + 14H + (aq) → 2Cr 3+ (aq) + 3Br2 (aq) + 7H2 O(l)
Note that the electrons from both side of the equation got cancelled. From Annex A,
𝐸 0 cathode = 1.33 V
𝐸 0 anode = 1.09 V
𝐸 0 cell = 𝐸 0 cathode − 𝐸 0 anode = 1.33 − 1.09 = 0.24 V
Because there are 6 electrons that are transferred, 𝑛 = 6.
∆𝐺 0 = −𝑛𝐹𝐸 0 cell = −6(96,483)(0.24) = −𝟏𝟑𝟖, 𝟗𝟑𝟓. 𝟓𝟐 𝐉
Since ∆𝐺 0 is negative while 𝐸 0 cell is positive, the reactions is spontaneous.

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LEARNING ACTIVITIES

Given the following redox reactions, (a) write the reactions that occur at each electrode, (b)
indicate which electrode is the cathode and which is the anode, (c) draw the cell diagram for
each, (d) calculate the 𝐸 0 cell, and (e) calculate ∆𝐺 0 .
1. 2AgBr(aq) + Ca(s) → 2Ag(s) + 2Br − (aq) + Ca2+ (aq)
2. 2Al3+ (aq) + 3Cd(s) + 6OH − (aq) → 2Al(s) + 3Cd(OH)2(aq)
3. 2Au3+ (s) + 3Cl− (aq) + 6OH − (aq) → 2Au(s) + 3ClO− (aq) + 3H2 O(l)
4. Ba2+ (aq) + Co(s) → Ba(s) + Co2+ (aq)
5. 2Bi3+ (aq) + 3MnO2 (aq) + 12OH − (aq) → 2Bi(s) + 3MnO4 − (aq) + 6H2 O(l)
6. BrO− (aq) + H2 O(l) + 2Na(s) → Br − (aq) + 2OH − (aq) + 2Na+ (aq)
7. Cs + (s) + NO2 (g) + H2 O(l) → Cs(s) + NO3 − (aq) + 2H + (aq)
8. 3Cu2+ (aq) + 2NO(g) + 4H2 O(l) → 3Cu(s) + 2NO3 − (aq) + 8H + (aq)
9. 4Fe3+ (aq) + 12OH − (aq) → 4Fe(s) + 3O2 (g) + 6H2 O(l)
10. 2K + (aq) + Sn(s) → 2K(s) + Sn2+ (aq)