The Chemistry of Galvanic Cells

By Alexander Hatza

Introduction:
Batteries are a constant presence in many lives today. They power our cell
phones, cars, laptops, and watches among other things. Batteries are made up of a
collection of cells (galvanic, voltaic, electrolytic, etc.) connected in series in order to
create a current that can be used to power things. These individual cells that make
up the battery have been around in some form since 1780 when Luigi Galvani
discovered that if two different metals (e.g. Copper and Zinc) are connected through
two different media a current is generated. One of the earliest cells developed after
this discovery was the aptly named galvanic cell. The galvanic cell is a device that
facilitates an oxidation-reduction reaction between two electrodes in order to
generate a current.
The purpose of this document is to describe the process by which galvanic
cells function to the reader. This process is rooted in chemistry, and basic
knowledge of chemistry will be useful in interpreting this information. However, this
description should still be understandable with only an elementary knowledge of the
subject. This process does not occur in steps but rather all at once. As such, the
author describes the process by describing the individual parts of the cell and their
respective functions in order to provide a comprehensive understanding of the
entire process for the reader.

Cathodic Half-Cell
Figure 1: Galvanic Cell with copper and zinc electrode

Anodic Half-Cell

Electrodes:
The Anode One electrode, called the anode, is the negatively charged electrode
in a galvanic cell. In this case, the anode is made of zinc. This means that electrons
will flow away from this electrode and toward the positively charged cathode
through the wire that connects them. On the anode, oxidation occurs which means
that the metal gives up electrons to create a charged metal ion; in this case, that
ion is Zn2+. The portion of the galvanic cell that contains the anode and a solution is
called the anodic half-cell. This is called a half-cell because half of the overall
oxidation-reduction reaction (namely the oxidation) occurs in this part of the cell.

The Cathode The electrode opposite the anode is called the cathode, the
positively charged electrode in a galvanic cell. In the diagram above, the cathode is
made of copper. Electrons flow from the anode toward the cathode where reduction
reactions (reactions in which a reactant gains electrons) occur to form uncharged
solid metal from ions in solution. The portion of the galvanic cell that contains the
cathode and a solution is called the cathodic half-cell.
The driving force that causes these electrons to move is a kind of potential
called an electromotive force or voltage. Voltage is the difference in electric
potential between two points. Electric potential is based on the atomic and
structural environment of a material and is essentially how disposed electrons are to
enter or leave a material. In this case, electrons are predisposed to leaving zinc and
joining with copper ions. Therefore in allowing electrons to move through the
connecting wire, an electromotive force is created and allowed to drive the current
through the cell.

Solution and Salt Bridge:

Each electrode is placed in solution that touches both the electrode and the
salt bridge. This solution contains charged metal ions (the same metal as the
electrode that is touching the solution) and a negatively charged counterpart ion
(sulfate in this case). The salt bridge contains inert ions that will help to balance the
charge in the two half-cells. As electrons leave the anode and Zn2+ begins to
accumulate in that half-cell, SO42- will enter this cell through the salt bridge in order
to maintain a neutral charge in that half-cell which will allow the reaction to
continue. As electrons enter the cathodic half-cell, they will reduce the copper ions
to form solid neutral copper. In doing this, the cell will become increasingly
negatively charged. In order to maintain neutrality, positively charged ions (in this
case Na+) will enter the half-cell from the salt bridge.

Oxidation-Reduction Reaction:
Li+ + e- Li(s)
Zn2+ + 2e- Zn(s)
Ni2+ + 2e- Ni(s)
Sn+4 +2e- Sn+2

-3.04 V
-0.76 V
-0.23 V
0.15 V

Cu2+ + 2e- Cu(s)

0.34 V
+3
+2
Fe + e- Fe
0.77 V
Figure 2: Table of common chemical reductions with associated voltage
There are two half reactions that make up the overall reaction of the galvanic
cell: Cu2+ + 2e- Cu(s) and Zn(s) Zn2+ + 2e- (the reverse of the zinc reduction
listed in the table above). The standardized voltages for each of these half reactions
are 0.34 Volts and 0.76 Volts respectively. The copper half reaction is a reduction
because the copper ion is gaining two electrons. This half reaction occurs in the
cathode. The zinc half reaction is an oxidation because the solid zinc parts with two
electrons and becomes a positively charged ion. This half reaction occurs in the
anode. These two half reactions can be combined to make the overall oxidationreduction reaction for this galvanic cell. Added together, the overall reaction is Cu 2+
+ Zn(s) Cu(s) + Zn2+. The total voltage for this overall reaction can be found by
adding together the voltages of the half reactions: 0.34 V + 0.76 V = 1.10 V. Over
time as reactants are used up and the concentration of the solutions dwindle, this
voltage will lower. However, this drop is negligible until the reactants begin to run
out completely.
As shown in the overall reaction equation above, this cell is creating solid
copper and using solid zinc. Given enough time and close attention, one observing
this cell would see that the size of the copper cathode was growing as copper ions
joined with electrons and attached to it, and the size of the zinc anode was
shrinking as electrons left the solid zinc and ions left the electrode to enter the
solution.

Commercial Use:
Disposable batteries, such as the typical A, AA, AAA, C, and D batteries are
made up of one or more galvanic cells connected in series. Connecting cells in
series (positive to negative terminal) adds the voltage of the two cells together. For
example, two of the galvanic cell above connected in series would have a voltage of
2.20 V. These commercial batteries are disposable because the products of galvanic
cells are soluble and end up as ions in the solution. In rechargeable batteries, the
products are insoluble and are attached to the electrode. In that case, when a
strong enough electromotive force is attached to the cell, the reactions run in the
opposite direction, thereby recreating the original reactants. After the electromotive
force is removed, those original reactants can then react again and act as a battery
once more.