Determining the Concentration of an Analyte

As with acid-base titrations, a redox titration (also called an oxidation-reduction titration)

can accurately determine the concentration of an unknown analyte by measuring it
against a standardized titrant. A common example is the redox titration of a
standardized solution of potassium permanganate (KMnO4) against an analyte
containing an unknown concentration of iron (II) ions (Fe2+). The balanced reaction in
acidic solution is as follows:

[latex]MnO_4^-(aq)+5Fe^{2+}(aq)+8H^+(aq) \rightarrow
5Fe^{3+}(aq)+Mn^{2+}(aq)+4H_2O(l)[/latex]

In this case, the use of KMnO4 as a titrant is particularly useful, because it can act as its
own indicator; this is due to the fact that the KMnO4 solution is bright purple, while the
Fe2+ solution is colorless. It is therefore possible to see when the titration has reached
its endpoint, because the solution will remain slightly purple from the unreacted KMnO 4.

Permanganate Titration EndpointA redox titration using potassium permanganate as the titrant.
Because of its bright purple color, KMnO4 serves as its own indicator. Note how the endpoint is reached
when the solution remains just slightly purple.

Sample Calculation from Experimental Data

A standardized 4 M solution of KMnO4 is titrated against a 100 mL sample of an

unknown analyte containing Fe2+. A student conducts the redox titration and reaches the
endpoint after adding 25 mL of the titrant. What is the concentration of the analyte?

We know from our balanced equation above that permanganate and iron react in a 1:5
mole ratio. We can therefore perform the following calculation:

Stoichiometric calculation to determine moles of Fe2+From the balanced equation,

Fe and KMnO4 react in a 5:1 mole ratio.
2+

Now that we know the number of moles of iron present in the sample, we can calculate
the concentration of the analyte:

[latex]M=\frac {mol}L= \frac {0.5 mol}{0.100 L}=5 M[/latex]

Other Types of Redox Titrations

There are various other types of redox titrations that can be very useful. For example,
wines can be analyzed for sulfur dioxide using a standardized iodine solution as the
titrant. In this case, starch is used as an indicator; a blue starch-iodine complex is
formed in the presence of excess iodine, signaling the endpoint.

Another example is the reduction of iodine (I2) to iodide (I−) by thiosulphate (S2O32−),
again using starch as the indicator. This is essentially the reverse titration of what was
just described; here, when all the iodine has been reduced, the blue color disappears.
This is called an iodometric titration.

Most often, the reduction of iodine to iodide is the last step in a series of reactions in
which the initial reactions are used to convert an unknown amount of the analyte to an
equivalent amount of iodine, which can then be titrated. Sometimes halogens (or
organic compounds containing halogens) other than iodine are used in the intermediate
reactions because they are available in better-measurable standard solutions or they
react more readily with the analyte. While these extra steps make an iodometric titration
much more involved, they are often worthwhile, because the equivalence point involving
the bright blue iodine-starch complex is more precise than various other analytical
methods.