Electrochemistry describes how chemical reactions can produce electricity or how electricity can be

used to produce chemical reactions (how is that for symmetry?). This should not be so surprising as
electricity is simply the flow of electrons. As we have learned, electrons are the sweet candy of
chemistry. It seems like a lot of reactions happen so that one substance can capture the electrons from
another substance. Well, at least in redox reactions!
There are two basic electrochemical environments the galvanic cell and the electrolytic cell.
1.

The Galvanic (Voltaic) Cell

a. Galvanic Cell Basics
Galvanic cells produce electrical energy through spontaneous chemical reactions. The proper
term for what we call a battery is really a cell. An actual battery is several galvanic cells linked
together (the term battery implies the linking together of like objects). A car battery is an actual
battery; if you have ever seen water added to a car battery, you will note that there are many
caps to open in which to pore the water. Each one of these openings leads to a different cell.
A typical galvanic cell is composed of two compartments (half-cells). Each half-cell contains a
metal electrode and a solution that is made of ions of the metal. One half cell is designed to
supply electrons and the other pulls-on/accepts these electrons. If the electrodes in the two halfcells are connected together by wire, electrons are transferred from the half-cell where
(oxidation/reduction) takes place to the half-cell where (oxidation/reduction) takes place. This
would simply serve to heat the wire, so normally the wire is connected to a device (such as a
motor) to supply it with energy from the electrons
so that it can do work.
Say a zinc electrode is immersed in zinc sulfate and a copper electrode is immersed in cupric
sulfate. If the two half cells are properly connected, electrical current will result from the
spontaneous chemical reactions in each half cell. In this case, electrons are supplied by the zinc
half-cell and accepted by the copper half-cell. Whether a chemical gains or loses electrons
depends on with what it is paired. The two reactions are as follows:

What draws the electrons away from the zinc electrode is electromotive force (also called cell
potential). It is measured in volts (V) which is 1 joule of energy per coulomb of charge. There
is 1.602 x 10 -19 C of charge per electron. The voltage of a cell depends on what chemicals are
involved.
To complete the flow of charge, a ____________________ is used to connect the two half cells.
This allows ions to flow without the solutions in the two half-cells mixing. What causes the
flow of ions through the salt bridge is the maintenance of electrical neutrality of each half-cell.
As electrons leave the side where oxidation takes place, ________ enter to maintain the neutral
charge. Likewise, where reduction takes place, __________ enters to maintain the neutral

charge.
As each electrode is quite different, they are given different names. The anode is another name
for the electrode where ____________ takes place. It is given a _____________ sign because
of the build-up of excess electrons on its surface. The cathode is the name for the electrode
where ___________ takes place. It is given a _____________ sign because it constantly
undergoes the loss of electrons. How can you associate these names with the process that is
associated with it?
Electrodes can be directly involved in the reaction or just a place where the reaction occurs. In
this type of reaction, platinum is often used as the inert electrode.
b. The Flow of Charge in a Galvanic Cell
Diagram a simple galvanic cell, such as the one on page _______.

Label the above for the direction of the flow of electrons, flow of ions, anode, cathode (with the
sign on each), the salt bridge and the chemical process at each electrode (use the two chemical
processes you specified on the previous page).
If the cell is constructed of reactants and products in their thermodynamic standard states, the
cell is called a standard cell. What are the standard thermodynamic states? More about this
later.

c. The Overall Chemical Reaction in a Galvanic Cell

Well, this is a chemistry class! Anyhow, add the two half-cell reactions together to produce one
overall reaction:

You should note that the zinc electrode is (losing/gaining) mass while the copper electrode is
(losing/gaining) mass. All electrons should balance-out so that none is shown in the overall
reaction.
As the reaction proceeds, the cell voltage decreases. At some point, the reaction ceases as it
reaches equilibrium and no more voltage is produced (there is no flow of electrons). Ah, you
killed the darn thing, so sad!

d. Shorthand Notation for a Galvanic Cell

Here is an example of notation for a galvanic cell:
Zn|Zn 2+ (1.0M)||Cu 2+ (1.0M)|Cu
The anode is always written first. The single line shows the separation between an electrode
and the solution it contacts. The double line represents the salt bridge.
If a platinum electrode is used, for instance, with the following reaction:
Fe 3+ + e- Fe 2+
It would be shown in the standard notation as

e. Standard Potentials and the Electromotive Series

As stated earlier, the voltage that a cell can deliver depends on the chemicals that are involved.
The voltage of a cell is determined by comparing the potentials of each electrode and adding
them so that at one oxidization occurs and at the other reduction occurs.
To do what is suggested above (subtracting potential values to determine the potential of a cell),
each electrode needs a standard potential value. This is done by pairing it with hydrogen (the
so-called standard hydrogen electrode, SHE). The SHE is arbitrarily assigned a value of zero
so that any voltage produced by a standard cell is assigned to the other electrode.
For example, say the SHE is in a cell set-up with zinc. A 1.0 M solution of zinc chloride is in
contact with the zinc and a 1.0 M solution of hydrochloric acid is in contact with the SHE. A
salt bridge connects the two and a voltage meter is connected between the electrodes. We
notice that the zinc is losing mass so that we know that _________________ is taking place.
The zinc electrode is therefore the (anode/cathode). At the hydrogen electrode, __________
gas is bubbling out so that we know that __________________ is taking place. It is the
(anode/cathode). A voltage of 0.763 should result. This value is given to the zinc as its
standard potential. This can be verified by looking at an Electromotive Series. The
Electromotive Series is a list of half reactions, arranged by reduction potential for convenience.

If one wants to determine the standard potential at an anode, one would just flip the sign of the
potential and reverse the stated reaction. So this series gives all the standard potentials,
regardless of whether you are looking at the anode or cathode.
As to the signs, if the standard reduction potential is positive, then it is more readily reduced
when paired with the SHE; conversely, if the sign is negative, the reaction is more readily
____________ if paired with the SHE.
Instead of zinc, pair a copper electrode with the SHE. When copper is connected to a SHE, we
notice that the copper increases in mass. Is it undergoing oxidation or reduction? Now find the
proper equation for copper in the electromotive series. Does it need to be flipped? Add it to the
SHE equation to determine the cell potential.

f. Potentials for a Cell

Okay, so now that we know how the standard reduction potentials were established, we can use
them to determine the potential of an entire cell by following the following these guidelines.
When looking at the reaction at each electrode, the more positive standard potential is left as
written (it is the cathode, where reduction takes place). The equation at the other electrode is
reversed and the sign is flipped for its standard electrode potential. If you are asked for the
standard potential for the cell, just add the two values together (one of which has been flipped
in sign). The overall reaction is just the sum of the two half-reactions (one of which has been
flipped). If the reaction is spontaneous (and it should be if this is a voltaic cell!) then the cell
potential is positive. A negative cell potential would mean that electricity is needed to produce
the reaction.
Practice: At standard conditions, chromium (III) ions are put into a cell with a chromium
electrode in one half cell connected to another half-cell with a copper electrode and copper (II)
ions. What is its standard cell potential? What is the overall reaction? Is copper plated onto
the copper electrode or is chromium plated onto the chromium electrode? Write the cell
shorthand notation for this reaction.

2.

Electrolytic Cells
a. Some Basics
Electrolytic cells use energy to make chemicals react. Specifically, non-spontaneous reactions
occur by the input of electrical energy. Often inert electrodes, such as
____________________, are used that do not react with the solutions but simply supply or
attract electrons in the solution.
b. Electrolysis of Molten Sodium Chloride.
Carbon electrodes, connected to a battery, are immersed in molten sodium chloride. Why is it
necessary for it to be molten? Remember, to conduct electricity, the charges must be free to
move. In a crystal, the ions cannot move but they can in the molten state. Anyhow, it is
observed that a greenish gas is produced at one electrode and a silvery white metal is produced
at the other. What are these two products?
From the previous information, deduce the two reactions. Write the overall reaction. Which
reaction happens at the anode? Which reaction happens at the cathode?

c. Electrolysis of Aqueous Sodium Chloride

In this reaction, hydrogen gas is liberated at one electrode while chlorine gas is liberated at the
other electrode while the solution becomes basic. In other words, water is reduced in preference
to sodium. Write the half reactions and the overall reaction for this process.

d. Electrolysis of Aqueous Sodium Sulfate

In this process, hydrogen gas (where the solution becomes basic) and oxygen gas (where the
solution becomes acidic) is produced. Oh, water is again being reduced and in this case, also
oxidized. The sodium and sulfate ions help to conduct the current through the solution but they
do not react. Write the two half reactions and the overall reaction.

e. Faraday's Law of Electrolysis

Michael Faraday observed that the amount of substance that undergoes oxidization or reduction
is proportional to the electrical current running through the cell. In his honor, a Faraday is
defined as
This is equal to ___________________ coulombs.
An ampere (a rate of electrical flow) is defined as 1 coulomb per second.
These equalities can be used in stoichiometry to convert from current to mass
amps-->coulombs-->mol of electrons-->mass substance
Here is a practice problem: What mass of copper is produced through electrolysis if 2.50 amps
of electrical current is passed through a copper(II)sulfate solution for 50.0 minutes.

3.

Practical uses of the Galvanic and Electrolytic Cells

a. Electrolytic Refining and Electroplating
Electrolysis is used to produce metals from impure metals. For instance, impure copper can be
refined to pure copper if the impure copper (connected to the positive dc terminal) acts as an
anode and pure copper as a cathode (as it is connected to the negative dc terminal). The flow
of electrons is from the __________ to the ___________. The electrodes are typically in a
sulfuric acid solution. In the solution, copper ions are formed at the _________ and are
attracted to the ____________, as it is negative. Here, copper atoms are reformed. In the
solution, other cations are present, but the copper is much more concentrated and the copper is
much less active (more likely to accept electrons than to release them). This purification
process can be used to plate copper onto other substances ( like shoes or other metals) if the
cathode is replaced by the other substance. Draw this set-up and the chemical reactions at each
electrode.

Corrosion Protection
Corrosion happens for many reasons, but one common method is the oxidation of a metal by
oxygen gas in the presence of water. This is basically a redox reaction. For instance, iron can
act as an anode:

the electrons migrate through the water to an area where the metal is exposed to oxygen so that
a reduction process occurs:

Several ways to protect a metal against corrosion include:

1.
2.
3.
4.
5.

Protective coating such as paint

Galvanizing (coating steel with the more active metal zinc)
Plating the metal with a less easily oxidized metals
Connect the metal with a sacrificial anode, a piece of metal that is more active and
therefore preferentially oxidized
Allow a metallic oxide to naturally form (acid rain often interferes with this an statues)

Be sure to know the details of these, especially the sacrificial anode.