oxygen in the water.
If acid isnt added the
Chapter 15 Volumetric analysis
(Redox titrations)
To prepare a standard solution of ammonium
iron sulphate and use this solution to
standardise a solution of potassium
permanganate.
Potassium permanganate (KMnO 4 ) is a powerful
oxidizing agent and is a deep purple colour. It
cannot be obtained in sufficiently pure form to
weigh it out accurately and make up a standard
solution directly. We must titrate an
approximate solution of potassium
permanganate (0.02 M) against a primary
standard solution, ammonium iron sulphate (0.1
M).
Prepare the ammonium iron sulphate solution.
The molecular formula of ammonium iron
sulphate is NH 4 2 SO4 .FeSO4 .6H 2 O and
its molecular mass is 392. The advantage
of using a substance with such a large
relative molecular mass is that a high
degree of accuracy is assured when
weighing it.
Place a clean dry beaker on an electronic
balance. Press the zero button to bring
the reading on the balance back to 0.00g.
Weigh out 9.8 g of ammonium iron
sulphate crystals as accurately as
possible, into the beaker.
Dissolve the crystals by adding 20 ml of
dilute sulphuric acid. Add some deionised
water to the beaker. Mix the contents
well.
Transfer the contents of the beaker to a
250 ml volumetric flask and make up the
volume to the graduation mark, observing
all of the usual procedures.
The addition of sulphuric acid is vital as it
prevents the Fe 2 ions from reacting with
solution will quickly start to turn yellow due
to formation of MnO2. If this happens
anyway, add some more sulphuric acid to
reverse the process. The solution should be
clear with a slight green tinge.
Prepare the potassium permanganate solution.
Weigh out an approximate amount of
KMnO 4 , in a beaker, enough to make an
approximately 0.02 M solution.
Dissolve in dilute sulphuric acid, transfer
and make up the solution in the usual
manner with deionised water. (see before)
Titration procedure
Fill the burette with potassium
permanganate solution following the usual
steps.
Place 20 mls of ammonium iron sulphate in
a conical flask using a pipette.
The reaction which occurs during the
titration can be summarized as follows,
MnO 4 8H 5Fe 2 Mn 2 5Fe 3 4H 2 O
If the reaction is to proceed as written,
then plenty of sulphuric acid (20 mls)
must be added to the conical flask to
supply the H+ ions.
Sulphuric acid is used instead of any of
the other common laboratory acids. It
does not get involved in the oxidation or
reduction except to donate H+ ions.
Determination of the end-point
The ammonium iron sulphate is a clear
solution. As each drop of KMnO4 solution
hits the conical flask it is reduced and
decolourised. At the end point all the
ammonium iron sulphate is used up. The
next drop of KMnO4 solution turns the
solution pink.
To determine the % of iron in iron tablets. Calculations

V1 M1 V M2
Dissolve the tablets 2
N1 N2
Crush the tablets in a mortar and pestle.
Add some conc.sulphuric acid to help it 10 M1 8.4 0.02

dissolve. 5 1
Transfer the mixture to a beaker. 8.4 0.02 5
M1
Slowly add the mixture to a beaker of 10
deionised water. M1 0.084 moles per litre
Rinse the pestle and mortar several times
and add to beaker.
grams per litre = 0.084(152)g/L
Transfer to volumetric flask
12.77
Transfer the mixture from the beaker to = 12.77g = g in 250ml
the volumetric flask using a funnel. 4
Rinse the beaker several times and add to = 3.19g in 8 tablets.
the flask. = 0.399g in 1 tablet
Top up to 250 ml with deionised water in = 399mg per tablet
the usual manner.

Titration To standardise a solution of sodium

Fill the burette with 0.02 M KMnO4
solution.
Place 10 ml of the iron tablet solution into a
conical flask, using a pipette.
Titrate in the usual manner, swirling the
flask, washing the sides regularly, adding
slowly, drop by drop at the end point, read
meniscus at eye level from the top(hard to
see bottom.).
Determination of the end-point
The iron sulphate is a clear solution
(almost). As each drop of KMnO4 solution
hits the conical flask it is reduced and
decolourised. At the end point all the iron
sulphate is used. The next drop of KMnO4
solution turns the solution pink.
Results
Volume of permanganate = 8.4ml
Concentration of permanganate= 0.02M
Factor for permanganate = 1
Volume of iron sulphate = 10ml
Concentration of iron sulphate = ?
Factor for iron sulphate = 5
thiosulphate using standard potassium
permanganate.
Sodium thiosulphate is an important reducing
agent but it cannot be made up as a primary
standard because it cannot be obtained in
sufficiently pure form. For this reason a
standard solution (accurately known) is made by
titrating a solution of approximately the
correct concentration with an iodine solution of
accurately known concentration.
However, iodine cannot be made up accurately
in a direct manner either. To get around this
we react a standard solution of acidified
potassium permanganate with excess potassium
iodide solution. (See below for reactions).
Procedure
Place 10ml of 0.02M KMnO4 into a conical
flask.
Add 10ml of dilute sulphuric acid.
Add 10 ml of 0.5M KI
A deep red colour is produced due to
liberation of iodine.
 The KMnO4 reacted with the KI in the Calculations
presence of sulphuric acid as follows,
V1 M1 V M2
2MnO4 10I 16H 2Mn 2 5I 2 8H 2 O 2
n1 n2
9.95 M1 10 0.02

The red colour is due to the presence of 5 1
iodine. 10 0.02 5
M1
9.95
0.1Molar
Titrate with sodium thiosulphate.
Titrate this solution thiosulphate solution To determine the concentration of sodium
until the red colour has faded to pale hypochlorite in bleach.
yellow.
Add starch indicator. Make up your bleach solution
The solution goes black. Put 25ml of bleach, with pipette, into
Resume titration. 250ml volumetric flask.
The end point will occur suddenly as the Add deionised water and make up to
iodine is finally used up. mark.
The black colour will suddenly disappear and Stopper and invert 20 times to mix well.
go clear. Prepare the burette

What happened? Prepare the burette

The iodine, produced by the initial reaction, Rinse the burette with the standard
reacts with the thiosulphate according to thiosulphate solution.
the following equation. Fill burette to above the zero mark with
funnel.
2 Remove funnel, adjust to zero, ensure
I 2 2S2O3 S4O6 2I
the tap connection is full.

As the iodine is used up the red fades to Prepare the conical flask
yellow. Place 10ml of the bleach solution into
Starch is introduced and the titration is conical flask.
concluded when the black colour disappears. Add 10ml dilute sulphuric acid to the
Overall, flask.
2KMnO4 = 5I2 = 10NaS2O3 Add 10ml 0.5M KI to the flask.
Carry out the calculations as if 1KMnO4 Red iodine is released.
directly with 5 NaS2O3.
Titrate with sodium thiosulphate solution
Results Titrate in the usual manner, swirling,
Volume KMnO4 =10ml rinsing regularly, add solution drop by
Molarity KMnO4= 0.02M drop.
Factor for KMnO4 = 1 When red fades to pale yellow add 4
Volume of Thiosulphate = 9.95ml drops of starch.
Molarity of thiosulphate = ? Resume titrating until black colour
Factor for thiosulphate = 5 clears.
Results
molarity thiosulphate = 0.1M
volume thiosulphate = 11.2ml
factor thiosulphate = 2
molarity hypochlorite = ?
volume hypochlorite = 10ml
factor hypochlorite = 1

Calculations
V1 M1 V2 M 2 10 M1 11.2 0.1
=
n1 n2 1 2
11.2 0.1
M1 0.056moles per l
2 10
= 0.056 74.5 = 4.175g per l
41.75g per l for the real soln.
= 4.175g per 100ml = 4.175% (w/v)