ELECTROCHEMISTRY

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

ELECTROCHEMISTRY

- is the branch of chemistry that deals with the relationship between

chemical changes taking place in chemical reactions and electrical energy. It
deals with the study of electrical properties of solutions of electrolytes and
also the chemical changes brought about by electrical energy. Thus, it
enables us to elucidate how chemical energy produced in a redox reaction
can be converted into electrical energy and how electrical energy can be
used to bring about a redox reaction which is otherwise non-spontaneous.

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

ELECTRODE POTENTIAL

ORIGIN OF ELECTRODE POTENTIAL

- An electrode is a metal plate or rod dipped in a solution of its own

ions. A galvanic cell is made up of two such electrodes and current flows
from one electrode to the other. This indicates that the two electrodes of the
cell are at different potentials. Also, redox reactions occur in a galvanic cell.
It is necessary to draw a relation between all these observations to help us
to know how potential arises in an electrode.

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

 In order to understand the origin of potential of an electrode,
consider a zinc electrode which consists of a Zn strip dipped in 𝑍𝑛𝑆𝑂4 of any
concentration. Nernst proposed that in the electrode, there will appear two
tendencies – oxidation and reduction processes. If the tendency, say
oxidation occurs in the electrode, the Zn atoms on the surface of the metal
undergo oxidation, leaving behind electrons on the surface.

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −

The 𝑍𝑛2+ ions pass into the solution, hence the metal strip becomes
negatively charged. The positively charged metal ions in the solution would
accumulate around the metal in an order (Figure 1). If the other tendency –
reduction occurs in this electrode, then Zn2+ ion in the solution would
undergo reduction by grabbing electrons from the metallic surface (Figure 2).

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

 𝑍𝑛2+ + 2𝑒 − → 𝑍𝑛

With this, the metallic surface becomes positively charged. The

negatively charged ions in the solution would accumulate around the metal.
The two tendencies happen simultaneously on the same electrode. As the
two tendencies oppose each other, it can be visualized that equilibrium exists
between them:

𝑍𝑛 ⇌ 𝑍𝑛2+ + 2𝑒 −

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

 Hence, an electrical double layer called Helmholtz electrical double
layer (HED) is established at the metal–aqueous solution interface. The
actual tendency of the electrode (to gain or lose electrons) depends on which
direction the equilibrium would shift to. If the equilibrium shifts in the
forward direction, oxidation occurs. If the equilibrium shifts in the backward
direction, reduction occurs. Across the HED layer, there is movement of
charges. This results in the build up of potential called electrode potential. It
is defined as the potential that exists between the metal or a gas and its ions
in aqueous solution, at their equilibrium when they are in contact with each
other. The electrode potential of a metal is thus a measure of its tendency to
lose or gain electrons when in contact with a solution of its own salt.

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE

OXIDATION POTENTIAL

If oxidation occurs at the electrode, the potential of the electrode

can be termed as oxidation potential. For the zinc electrode, the reaction can
be represented as:

𝑍𝑛 ⇌ 𝑍𝑛2+ + 2𝑒 −

The electrode in which oxidation occurs at equilibrium is referred to as a

negative electrode. For example, the oxidation potential of zinc electrode
with 1 M 𝑍𝑛𝑆𝑂4 at 298 K is +0.76 V.

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REDUCTION POTENTIAL

If reduction occurs at the electrode, the potential of the electrode is

referred to as reduction potential. For the zinc electrode, the reaction can be
represented as:

𝑍𝑛2+ + 2𝑒 − ⇌ 𝑍𝑛

If reduction occurs at equilibrium in an electrode, it is termed as positive

electrode. The reduction potential of a zinc electrode with 1 M 𝑍𝑛𝑆𝑂4 at 298
K is -0.76 V.

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 By comparing the oxidation and reduction potential values of the
same electrode, the spontaneous reaction occurring in the electrode can be
predicted. In case of zinc electrode, the oxidation potential is more positive
than its reduction potential. Thus, oxidation is a spontaneous reaction.
However, polarity of an electrode depends on the other electrode to which it
is connected.

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STANDARD ELECTRODE POTENTIAL (𝑬°)

It is defined as the potential that exists between the metal or the gas
and its aqueous solution of unit concentration at 298 K when the sum of all
partial pressures of the gaseous reactants and products, if any, is equal to 1
atm pressure. This value is considered to compare the relative abilities of
different electrodes to undergo oxidation or reduction reaction.

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CHEMISTRY FOR ENGINEERS CEFFORTES, ECE
ASSIGNMENT NO.1

1. Explain the origin of electrode potential.

2. The standard reduction potential of zinc is -0.76V. Explain.

CHEMISTRY FOR ENGINEERS CEFFORTES, ECE