Chemistry 111 Lab: Redox Titration

AN OXIDATION-REDUCTION
TITRATION
Experiment Done Using Equivalents and Normality

itration is a very general way of using the reaction between two compounds to determine the amount of one of them. You have already used
titrations to determine the amount of acid present in an unknown sample and,
from this, the equivalent weight of the acid. Now you will use the reaction
between an oxidizing agent (KMnO4) and a reducing agent (Na2C2O4) to
determine the amount of sodium oxalate, Na2C2O4, in an unknown sample.
This titration is particularly convenient since it provides its own endpoint: as
long as reducing agent is present, the purple KMnO4 will be reduced to nearly colorless Mn2+; when all of the reducing agent has been used, the next purple drop will remain in solution to signal completion of the titration, that is,
the endpoint.
To determine the number of equivalents of Na2C2O4 present in a sample,
we need to know the exact normality of the KMnO4 used in the titration, as
well as the volume of the oxidizing agent used to reach the endpoint. That is,
we will need to standardize the KMnO4 solution first. The KMnO4 (of
unknown normality) is titrated against a known weight of pure ferrous ammonium sulfate [Fe(NH4)2(SO4)2 6H2O], a source of the Fe2+ ion. Once you
have determined the normality of the KMnO4 solution you can use it as the
standard in your titration of Na2C2O4 in your unknown.
While the process of titration seems straightforward enough, sources of
error are common enough to make it a challenge (as you may have already
found in the acid-base titration experiment). Your first thoughts about sources
of error probably center on the accuracy of the endpoint. In practice, you are
not likely to overshoot the endpoint by more than a few drops, so we must
look for other sources of error as well. More likely chances for error include:
Incomplete mixing of the KMnO4 solution initially. This will mean that
each buret full will have a different concentration.
Weighing errors, simple misreading of the balance and/or loss of sample
when transferring it to the flask.
Buret reading errors such as air bubbles in the tip, unrecorded initial readings, careless or incorrect readings, and buret leakage during titration.
Loss of sample in titration through splashing, incomplete dissolution of
sample, or neglecting to wash down the sides of the flask occasionally.

Consistency of results, while no guarantee of accuracy, is an encouraging

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Chemistry 111 Lab: Redox Titration

sign. A consistency check is given in the procedure to allow you to evaluate

your results (and carry out more titrations if needed).

EXPERIMENTAL PROCEDURE
A. Standardization of a Potassium Permanganate Solution
1. Clean and rinse your graduated cylinder and Erlenmeyer flasks. Clean a
buret and rinse with distilled water until the water drains cleanly from the
inverted buret.
The dilution procedure can
be carried out fairly
roughly, since you will standardize the solution later.

The exact amount of water

is not important. The
H 2SO4 is needed for proper acidity control.

2. Prepare a dilute solution of KMnO4 by placing about 60 mL of the concentrated solution in your 500 mL Erlenmeyer flask and dilute with distilled water to a total volume of 300 mL. Stopper the flask and shake thoroughly to mix the solution. You can now determine the exact concentration of this solution by titrating it against a known quantity of ferrous ion,
Fe2+.
3. In your Pre - L a b o r a t o ry Assignment you calculated the mass of
Fe(NH4)2(SO4)2 6H2O required in the titration. Weigh out this mass on
a piece of weighing paper on the analytical balance; weigh to the nearest
0.001 g and be sure that you record your balance readings. Place the sample in a 125 or 250 mL flask, dissolve it in roughly 30 mL of distilled water,
and add 10 mL of 3 M H2SO4.
4. Titrate your sample of Fe(NH4)2(SO4)2 6H2O with the KMnO4 solution using the following procedure: (You may want to do a preliminary
titration to see how the end point comes out.)
(a) Place a piece of white paper under the flask so that the color at the endpoint can be seen clearly.
(b) Fill the buret and be sure the solution completely fills the tip. Record
the initial buret reading on the Report Form.
(c) Add KMnO4 solution from the buret, swirling the flask constantly.
(d) Occasionally rinse down the walls of the flask with distilled water
from your wash bottle. Titrate until the last drop of KMnO4 added
leaves a lasting pink color. The first appearance of a permanent pink
color occurs when the KMnO4 that is added becomes equivalent to the
amount of Fe2+ present.
(e) Record the final buret reading on the report form.
5. Titrate another sample of Fe(NH4)2(SO4)2 6H2O, adding the first 20
mL of KMnO4 rapidly and then approaching the endpoint with care.
Record your data and then check for consistency (using the same method
outlined in the Acid-Base Titration).

Chemistry 111 Lab: Redox Titration

Consistency Check =

volume KMnO4 used (mL)

mass of sample (g)

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= volume KMnO4 per gram

These values from successive titrations should agree within 0.5 mL. If not,
you will need to carry out more titrations until satisfactory agreement is
reached.

B. Analysis of Sodium Oxalate in an Unknown Solid Mixture

Obtain an unknown from your instructor. Be sure to record the unknown
number on your report form. Weigh out a sample of approximately 1 gram
(but weigh it accurately to the nearest 0.001 g) and transfer to a clean 125 or
250 mL Erlenmeyer flask. Dissolve your sample in approximately 50 mL of
distilled water and 25 mL 3 M H2SO4. Swirl to dissolve.
Heat the solution to between 55 and 60 C. Titrate the sample with standardized KMnO4 in the usual manner, maintaining the temperature in the 5560 C range. Record your data on the Report Form. Repeat the titration with
another sample of the unknown. Check your results for consistency as outlined above in the standardization section. Do further titrations if necessary.

Add the acid cautiously;

your unknown contains
Na 2 CO3 and foaming may
occur.
Your instructor will demonstrate ways to maintain the
temperature. Temperature
control is important here.