GALVANIC CELLS

Introduction

As we know, an oxidizing agent is a substance that oxidized another substance and the
agent is reduced in the process. In other words, in the term of transfer electrons, oxidizing
agent will gain electron and this stuff is the other way around for reducing agent in which
it will loss electrons as it is undergoes oxidation.
By assimilate these facts and relate it with the definition of Redox reaction
(chemical reaction involving oxidation and reduction at the same time) we could say that
in a solution, the electrons are transferred directly from the reducing agent to the
oxidizing agent. However, if we physically separate both those agents, the transfer of
electrons can take place via an external conducting wire medium (a metal wire). As the
reaction progresses, its sets up a constant flow of electrons and hence generates electricity
(that is, it produces electric work such as driving an electric motor).
The experiment apparatus for generating electric through the use of a spontaneous
reaction is called a galvanic cell or voltaic cell, after the Italian scientists Luigi Galvani
and Alessandro Volta, who constructed early versions of the device. Galvanic cell could
be nothing more than just two different metals being immersed into an electrolyte and
connected by wire. Daniel cell or a zinc-copper cell is another example of a galvanic cell.
In this cell, zinc and copper are used as electrode. Each of the metals is immersed into a
solution of its ions. The two solutions are connected through a salt bridge or a porous pot.
The functions of a salt bridge or a porous pot are to prevent the two electrodes
from mixing and to allow the movement of the ions in order to complete the circuit. A
salt bridge is made from a piece of filter paper soaked in a saturated solution which does
not react with the two electrolytes. Examples are saturated potassium nitrate solution and
saturated sodium nitrate solution. The salt bridge can also be a U-shaped tube that
contains a saturated solution.
Principle
To understand how the redox reaction occurs in a voltaic cell, let us start with some
example simple cells that are readily made in the general chemistry laboratory.

Daniell cells (Zinc-Copper cell)

When a piece of zinc is added to a water solution containing Cu2+ ions, the following
redox reaction take place:
Cu2+ (aq) + Zn (s) → Cu (s) + Zn2+
In this reaction, copper metal plates out on the surface of the zinc. The blue color of
the aqueous Cu2+ ion fades as it is replaced by the colorless aqueous Zn2+ ion. Clearly
this redox reaction is spontaneous; it involves electron configuration transfer from a
Zn atom to a Cu2+ ion.

A zinc bar is immersed in a ZnSO4 solution, and a copper bar is immersed in a CuSO4
solution. The cell operates on the principle that the oxidation of Zn to Zn2+ and the
reduction of Cu2+ to Cu can be made to take place simultaneously in separate
locations with the transfer of electron between them occurring through an external
wire. The Zn and Cu are called electrodes. The external circuit consist a voltmeter
with the leads (red and black) to the anode and cathode.
Let us trace the flow of electric current through the cell. At the zinc anode,
electrons are produced by the oxidation half reaction:
 Zn (s) → Zn2+ (aq) + 2e-
This electrode, which “pumps” electrons into the external circuit, is ordinarily marked
as the negative pole of the cell. Then, electrons generated at the anode move through
the external circuit to the copper cathode. At the cathode, the electrons are consumed,
reducing Cu2+ ions present in the solution around the electrode. Copper atoms are
produced by the reduced half-reaction:
Cu2+ (aq) + 2e- → Cu(s)
The copper electrode, which “pulls” electrons from the external circuit, is considered
to be the positive pole of the cell. The overall cell reaction equation is:
Cu2+ (aq) + Zn (s) → Cu (s) + Zn2+
As the above half-reactions proceed, a surplus of positive ions (Zn2+) tends to build up
around the zinc electrode. The region around the copper electrode tends to become
deficient in positive ions as Cu2+ ions are consumed. To maintain electrical neutrality,
cations must move towards the copper cathode or, alternatively, anions must move
towards zinc anode. In practice, both migrations occur.

Cells similar to that shown above can be set up for many different spontaneous redox
reactions. Consider, for example, the reaction
Ni (s) + Cu2+ (aq) → Ni2+ (aq) + Cu (s)
This reaction, like that between Zn and Cu2+, can serve as a source of electrical in a
voltaic cell. The cell is similar to that shown above except that, in the anode
compartment, a nickel electrode is surrounded by a solution of a Nickel (II) salt, such as
NiCl2 or NiSO4. The cell notation is
Ni (s) | Ni2+ (aq) || Cu2+ (aq) | Cu (s)
Another spontaneous redox reaction that can serve as a source of electrical energy is that
between zinc metal and H+ ions:
Zn (s) + 2H+ (aq) → Zn2+ (aq) + H2 (g)
A voltaic cell using this reactions is similar to the Zn-Cu2+ cell; the Zn | Zn2+ half-cell and
the salt bridge are the same. Because no metal is involved in the cathode half-reaction, an
inert electrode that conducts an electric current is used. Frequently, the cathode is made
of platinum. Hydrogen gas bubbled over the cathode, which is surrounded by H + ions
from a solution of HCl. The half-cell reactions occurring in the cell are
Anode (oxidation): Zn (s) → Zn2+ (aq) + 2e-
Cathode (reduction): 2H+ (aq) + 2e → H2 (g)
Overall cell reaction: Zn (s) + 2H+ (aq) → Zn2+ (aq) + H2 (g)
The cell notation is Zn (s) | Zn2+ (aq) || H+ (g) | H2 (g) | Pt. the symbol Pt is used to
indicate the presence of an inert platinum electrode.