Galvanic Cell

A galvanic cell is an electrochemical cell that derives electrical

energy from chemical reactions taking place within the cell. A galvanic
cell consists of two half-cells. In its simplest form, each half-cell
consists of a metal and a solution of a salt of the metal. The salt
solution contains a cation of the metal and an anion to balance the
charge on the cation. In essence the half-cell contains the metal in two
oxidation states and the chemical reaction in the half-cell is an
oxidation-reduction (redox) reaction. The overall voltage generated by
this cells depends upon the nature of the half cells combinations. If the
movement is carried out al equilibrium, then this voltage is called
Electromotive Force (EMF) and is one of the main parameters which
characterize a galvanic cell.

The discovery of the galvanic cell was made by Luigi Galvani

(September 9, 1737 – December 4, 1798) in 1780. In 1771, he
discovered that the muscles of dead frogs legs twitched when struck
by a spark. This was one of the first forays into the study of
bioelectricity, a field that still today studies the electrical patterns and
signals of the nervous system.

Chemical reactions involving the transfer of electrons from one

reactant to another are called oxidation-reduction reactions or redox
reactions. In a redox reaction, two half-reactions occur; one reactant
undergoes oxidation and another reactant undergoes reduction. A
piece of zinc going into a solution as zinc ions, with each Zn atom
giving up 2 electrons, is an example of an oxidation half-reaction.

Zn(s) → Zn2+(aq) + 2e-

The oxidation number of Zn( s) is 0 and the oxidation number of

the Zn2+ is +2. Therefore, in this half-reaction, the oxidation number
increases.
In contrast, the reverse reaction, in which Zn2+ ions gain 2
electrons to become Zn atoms, is an example of reduction.

Zn2+(aq) + 2e- → Zn(s)

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In a reduction there is a decrease (or reduction) in oxidation number.
Chemical equation representing half-reactions must be both mass and
charge balanced.
Another example of reduction is the formation of solid copper
from copper ions in solution.

Cu2+(aq) + 2e- → Cu(s)

In this half-reaction the oxidation number of the aqueous copper

is +2, which decreases to 0 for the solid copper, and again charge and
mass are balanced. However, no half-reaction can occur by itself. A
redox reaction results when an oxidation and a reduction half-reaction
are combined to complete a transfer of electrons as in the following
example:

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

In this redox reaction, the Zn(s) is referred to as the reducing agent

because it causes the Cu2+ to be reduced to Cu. The Cu 2+ is called the
oxidizing agent because it causes the Zn(s) to be oxidized to Zn2+.

A measure of the tendency for a reduction to occur is its

reduction potential, E, measured in units of volts. At standard
conditions, 25 °C and concentrations of 1.0 M for the aqueous ions, the
measured voltage of the reduction half-reaction is defined as the
standard reduction potential, E°. Standard reduction potentials have
been measured for many half-reactions, the standard reduction
potentials are –0.76 V for zinc and +0.34 V for copper. The more
positive (or less negative) the reduction potential, the greater is the
tendency for the reduction to occur. So Cu2+ has a greater tendency to
be reduced than Zn2+. Furthermore, Zn has a greater tendency to be
oxidized than Cu. The values of E° for the oxidation half-reactions are
opposite in sign to the reduction potentials: +0.76 V for Zn and –0.34 V
for Cu.

A galvanic cell or voltaic cell is a device in which a redox

reaction, such as the one in the equation above, spontaneously occurs
and produces an electric current. In order, for the transfer of electrons
in a redox reaction, to produce an electric current, the electrons are
made to pass through an external electrically conducting wire instead
of being directly transferred between the oxidizing and reducing
agents. The design of a galvanic cell is shown below in Figure 1. In a
galvanic cell, two solutions, one containing the ions of the oxidation

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half-reaction and the other containing the ions of the reduction half-
reaction, are placed in separated compartments called half-cells. For
each half-cell, the metal, which is called an electrode, is placed in the
solution and connected to an external wire. The electrode at which
oxidation occurs is called the anode ( in our case Zn) and the electrode
at which reduction occurs is called the cathode ( Cu). The two half-cells
are connected by a salt-bridge ( KCl) that allows a “current” of ions
from one half-cell to the other to complete the circuit of electron
current in the external wires. When the two electrodes are connected
to an electric load ( voltmeter) the circuit is completed, the oxidation-
reduction reaction occurs, and electrons move from the anode (−) to
the cathode (+), producing an electric current.

Figure 1. Galvanic cell

Source: http://www.substech.com/dokuwiki/doku.php?
id=electrode_potentials

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 Rather than drawing a complete diagram like the one in Figure 1,
it is convenient to specify a galvanic cell in shorthand form. The cell
described would be written as:

Zn│Zn2+‌(1 M)║ Cu2+(1 M)│Cu

The components of the cell are written in order, starting with the
left-hand and moving across the salt bridge to the right. A single
vertical line indicates a phase boundary, such as that between the
solid Zn electrode and Zn2+(aq). The double vertical line represents a
salt bridge. By convention, the electrode written to the left of the salt
bridge in this cell notation is always taken to be the anode, and the
associated half-equation is always written as an oxidation. The right-
hand electrode is therefore always the cathode, and the half-equation
is always written as a reduction.

The cell potential, Ecell, which is a measure of the voltage that the
galvanic cell can provide, is calculated from the half-cell reduction
potentials:

Ecell = Ecathode - Eanode

At standard conditions, the standard cell potential, E°cell, is based

upon the standard reduction potentials, as shown in the equation below:

E°cell = E°cathode – E°anode

Based on the values for the standard reduction potentials for the
two half-cells (–0.76 V for Zn, anode and +0.34 V for Cu, cathode), the
standard cell potential, E°cell, for the galvanic cell in Figure 1 would be:

E°cell = +0.34 V – (–0.76 V) = +1.10 V

The positive voltage for E°cell indicates that at standard conditions

the reaction is spontaneous. It is known that ΔGo = − nFEocell, so if E°cell
is positive, then ΔGo will be negative. Thus the redox reaction in the
presented equation would produce an electric current when set up as a
galvanic cell.

When conditions are not standard, the Nernst equation, (the

equation below) is used to calculate the potential of a cell. In the
Nernst equation, R is the universal gas constant with a value of 8.314 J/
(K⋅mol), T is the temperature in K, and z is the number of electrons

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transferred in the redox reaction, in our case is 2. Q is the reaction
quotient for the ion products/ion reactants of the cell. The solid
electrodes have constant “concentrations” and so do not appear in Q.
F is the Faraday constant with a known value of 96,500 J/(V⋅mol).

In a series of galvanic cells, in which [Zn2+] is kept constant while

[Cu ] is varied, Ecell can be measured and it will be found to vary with
2+

ln[Cu2+]. A plot of the data obtained in which y is Ecell and x is ln[Cu2+]

will result in a straight line: y = mx + b.
Thus a plot such as the one shown below can be generated by
measuring the cell potential for different values of [Cu 2+], while
keeping [Zn2+] constant (at 1.0 M in this plot). The equation of the line
in this plot can then be used to determine ln [Cu2+] in a solution of
unknown concentration from its measured Ecell, as long as [Zn2+]
remains at 1.0 M and the temperature at 25oC. This is the same
principle used in a pH meter for the determination of [H+]. When the
concentration of Cu2+ ion reactant increases (or ln[Cu2+] becomes less
negative), the potential of the cell increases.

Ecelle Nernst plot: Zn(s )|Zn ||Cu |Cu(s )

ll ([Zn 2+] a t 1.0 M )

1.120

1.080

1.040

1.000

0.960

0.920

0.880

ln -14.00 -12 .00 -10.00 -8.00 -6.00 -4.00 -2.00 0.00

[Cu
]

Figure 2. Nernst plot of Ecell vs. ln [Cu2+] with [Zn2+] constant at 1.0 M.
Source : http://www.bris.ac.uk/phys-
pharm/media/plangton/ugteach/ugindex/m1_index/med_memb/file/Ne
rnst1.htm

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References:

1. http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/electrochem.html#c3
2. http://www.substech.com/dokuwiki/doku.php?id=electrode_potentials
3. Advanced Chemistry with Vernier: Experiments for AP, IB, and College General
Chemistry, Jack Randall, Vernier Software and Technology, 2004, 20-1.
4. http://en.wikipedia.org/wiki/Galvanic_cell
5. http://en.wikipedia.org/wiki/Luigi_Galvani
6. http://www.science.uwaterloo.ca/~cchieh/cact/c123/elecchem.html (review)