Analytical chemistry LD

Acids, bases and salts Chemistry

Salts and ionic compounds
Leaflets C3.5.3.2

Manganometric titration of
iron(II) ions

Aims of the experiment

 To learn that a titration that does not depend on a neutralisation reaction.
 To learn potentiometry as an analytical measurement method.
 To track the potential change as a function of the addition of a reagent solution.
 To determine the iron(II) concentration through titration with a KMnO 4 solution.
 To understand manganometry as a sub-type of potentiometry.

equivalence point, is determined by the ions of the substance

Principles to be analysed. After the equivalence point, ions from the titrant
Titration in general is a method of quantitative analysis. In ti- are present in excess and determine the voltage. Then, the
tration, the concentration of a substance in a solution is deter- concentration of the substance to be determined can be calcu-
mined through the addition of a titrant. The titrant has a known lated via the equivalence point.
concentration and enters into a specific reaction with the sub- Strictly speaking, pH titrations are also potentiometric titra-
stance to be investigated. Titrations are based on a variety of tions. Calibration converts the voltage to a pH in this case.
reactions. There is acid-base titration, complexometric titration,
redox titration or precipitation titration. Potentiometric titration In this experiment, iron(II) is determined potentiometrically
is also a titration method. Manganometric titration in this exper- through titration with potassium permanganate. Mangano-
iment is a sub-type of potentiometric titration. metry is a redox titration that proceeds without the use of an
additional indicator. In this case, the property being utilised is
Potentiometry is an electroanalytic method in quantitative ana- the fact that MnO4- ions are very red-violet in colour, and turn
lytical chemistry. In this method, the concentration depend- colourless when they are reduced to Mn2+. In this experiment,
ence of the electrical potential is utilised. As described above, the reaction is as follows:
a substance is titrated using a titrant. During titration, an imme- -
diate reaction results in a measurable change in potential. The MnO4 + 5 Fe2+ + 8 H+ →
← Mn
2+
+ 5 Fe3+ + 4 H2 O
titration is tracked using an indicator electrode. For example, In the reaction, a measurable change in voltage U occurs
this can be a pH electrode or a redox electrode. which can be tracked, and the equivalence point can be deter-
At the equivalence point of the reaction, the potential suddenly mined using it. The tracking of the voltage change is deter-
increases until it continues on in a plateau. This strong change mined more precisely than the equivalence point simply be-
in potential is the result of the fact that the voltage, prior to the cause of the colour change.
MS-2016-08

Fig. 1: Setup of the Experiment.

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C3.5.3.2 LD Chemistry Leaflets

Risk assessment Equipment and chemicals

When working with potassium permanganate, make sure that 1 Pocket-CASSY 2 Bluetooth .............................. 524 018
it does not come into contact with skin or surfaces since this 1 CASSY Lab 2 ................................................... 524 220
will lead to unsightly brown spots. Using sulphuric acid requires 1 pH adapter S .................................................... 524 0672
personal protective equipment to be worn. 1 Single-rod Redox probe, BNC .......................... 667 416
1 Electronic Balance 440-3N, 200 g : 0.01 g ....... 667 7977
Potassium permanganate 1 Mini magnetic stirrer ......................................... 607 105
1 Beaker, DURAN, 250 ml, squat ........................ 664 103
Hazard statements
1 Volumetric flask Boro 3.3, 25 ml ....................... 665 791
H272 May intensify fire; oxidiser agent. 1 Volumetric flask Boro 3.3, 50 ml ....................... 665 792
H302 Harmful if swallowed. 1 Stand rod 47 cm, 12 mm diam. ........................ 300 42
1 Stand base, V-shaped, small ........................... 300 02
H410 Very toxic to aquatic life with long- 1 Graduated pipette 10 mL .................................. 665 997
lasting effects. 1 Pipetting ball ..................................................... 666 003
Safety statements 1 Burette, clear glass, 25 ml ................................ 665 845
P210 Keep away from heat/sparks 1 Burette filling funnel, plastic, 25 mm diam. ....... 665 816
1 Burette clamp, simple ....................................... 666 559
/open flames/hot surfaces. No smoking. 1 Bosshead S ...................................................... 301 09
P273 Avoid release to the environment. 1 Universal clamp 0...80 mm ............................... 666 555
1 Iron(II) sulphate-7-hydrate, 100 g ..................... 671 9100
1 Potassium permanganate, 100 g ..................... 672 7000
1 Sulphuric acid, dilute, approx. 2 N, 500 ml ....... 674 7920
1 Glucose, 100 g ................................................. 672 1100
Also necessary for wireless measurement:
1 Rechargeable battery for Pocket-CASSY 2 BT 524 019
1 Bluetooth dongle .............................................. 524 0031

Signal word: Set-up and preparation of the experiment

Hazard Set-up of the apparatus
Sulphuric acid, dilute, approx. 2N 1. The apparatus is set up as can be seen in Fig. 1.
2. Fix the stand rod in the stand base.
Hazard statements
3. Clamp the single-rod redox probe to the stand rod using a
H290 Can corrode metals. bosshead S clamp and a universal clamp.
H315 Causes skin irritation. 4. Connect the single-rod redox probe to the Pocket CASSY 2
H319 Causes serious eye irritation. using the pH adapter S.
Safety statements 5. Connect the Pocket CASSY 2 Bluetooth to a computer us-
ing a USB cable.
Signal word: P280 Wear protective gloves / eye pro-
Note: For wireless measurement, connect the battery to the
Caution tection.
Pocket CASSY 2 and connect to the PC using the Bluetooth
P302+P352 IF ON SKIN: Wash with Dongle, which connects to one of the USB ports of a PC.
plenty of water and soap. 6. Also attach the burette clamp to the stand rod and place the
P305+P351+P338 IF IN EYES: burette into the holder.
Rinse carefully with water for several 7. Position an empty beaker with a stirring magnetic onto the
minutes. Remove contact lenses if pre- magnetic stirrer.
sent and easy to do so. Continue rinsing. Preparation of the experiment
P337+P313 If eye irritation persists: Get 1. Two solutions are needed for the experiment. First of all a
medical advice/attention. 0.1 molar solution of iron(II) sulphate • 7 H2O and secondly a
0.02 molar KMnO4 solution.
Calculating the weight for Fe(II) sulphate • 7 H2O
Iron(II) sulphate ∙ 7 H2O c(FeSO4•7 H2O) = 0.1 mol/l
Hazard statements M(FeSO4•7 H2O) = 278 g/mol
H302 Harmful if swallowed. V(FeSO4•7 H2O) = 25 ml
H315 Causes skin irritation. m(FeSO4 ) = c(FeSO4 ) ∙ M(FeSO4 ) ∙ V(FeSO4 )
H319 Causes serious eye irritation. m(FeSO4 ) = 0,1 mol/l ∙ 278 g/mol ∙ 0.025 l
Safety statements m(FeSO4 ) = 0.70 g
Signal word: P302+P352 IF ON SKIN: Calculating the weight for KMnO4
Caution Wash with plenty of water and soap. c(KMnO4) = 0.2 mol/l
M(KMnO4) = 158.03 g/mol
P305+P351+P338 IF IN EYES: Rinse
carefully with water for several minutes. V(KMnO4) = 25 ml
Remove contact lenses if present and m(KMNO4 ) = c(KMnO4 ) ∙ M(KMnO4 ) ∙ V(KMnO4 )
easy to do so. Continue rinsing. m(KMnO4 )= 0.2 mol/l ∙ 158,03 g/mol ∙ 0.025 l

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LD Chemistry Leaflets C3.5.3.2

m(KMnO4 )= 0.08 g 5 ∙ c(KMnO4 ) ∙ V(KMnO4 )

c(Fe2 SO4 )=
2. Weigh in both substances and dissolve in a volumetric flask V(Fe2 SO4 )
of suitable size. Add enough water to the flask until the bottom The following applies:
of the meniscus of the water surface lines up with the calibra-
tion mark. c(KMnO4) = 0.2 mol/l
3. Place the potassium permanganate solution in the burette. V(KMnO4) = 10.2 ml
Use a small funnel to help do this. As with the volumetric flask, V(Fe2SO4) = 10 ml
fill the burette until the bottom of the meniscus of the liquid level
5 ∙ 0.02 mol/l ∙ 10.2 ml
lines up with the 25 ml mark. c(Fe2 SO4 )=
10 ml
Note: If too much solution is added to the burette, simply drain
the excess back into the volumetric flask by opening the bu- c(Fe2 SO4 ) = 0.102 mol/l
rette. Before filling the burette, test to make sure that the stop-
cock opens and closes freely. If not, apply a bit of stopcock
Since 10 ml were used, the deviation between the determined
grease.
and the theoretical value is negligibly small.
4. Pipette 10 ml of the Fe2SO4 solution into the beaker using a
graduated pipette and a pipetting ball and acidify with a small
bit of diluted sulphuric acid.
Performing the experiment
1. Load the settings in CASSY Lab 2.
2. Dip the redox electrode into the beaker and fill it with water
until the electrode dips just below the small lateral opening.
Note: Make sure that the stirring magnet cannot hit the redox
electrode.
3. Turn on the magnetic stirrer to mix the liquid.
4. The measurements are recorded manually. This means that
after a first stable measurement has established itself, the first
measurement is recorded by clicking the button on the Pocket
CASSY. Alternatively, the measurement can also be recorded
by clicking the Measurement symbol in the CASSY Lab 2
software.
5. Now add 0.5 ml of potassium permanganate solution at a
time to the Fe2SO4 solution and record a new measurement
after each addition by clicking the Pocket CASSY.
6. Continue adding until a steep increase in the measurement
curve occurs and a plateau forms thereafter. Fig. 2 Measurement curve for manganometric titration of iron(II) ions.
Observation
Results
At the beginning of the experiment, a clear Fe2SO4 solution is
present in the beaker. When the potassium permanganate so- In this experiment, a manganometric titration is carried out and
lution is added, a brief discolouration of the liquid will be ob- the concentration of iron(II) ions in a solution is determined. An
served initially at the drop point; this will disappear again al- Fe2SO4 solution is titrated with a potassium permanganate so-
most instantaneously. The further the measurement proceeds, lution of known concentration for this purpose. First, the colour
the more the solution assumes a red-violet colour. After reach- of the permanganate solution always disappears since the
ing the equivalence point, the solution will be nearly as strong added permanganate ions reduce to Mn2+ ions and Fe2+ re-
in colour as the potassium permanganate in the burette. duces to Fe3+ ions. As soon as nearly all the iron(II) has re-
acted, the solution slowly changes colour until all iron(II) ions
The titration diagram is shown in Figure 2. have been oxidised at the equivalence point, and the red-violet
Evaluation permanganate ions are in excess.

Evaluation of the experiment is done using CASSY Lab 2. To The slight deviation of about 2% shows that the titration is a
determine the exact point of equivalence using CASSY Lab, very precise measurement method.
click the right mouse button in the diagram and select the
Cleaning and disposal
Determine equivalence point sub-item in the Other eval-
uations in the context menu. Mark the curve range and the To dispose of the potassium permanganate, add glucose to the
equivalence point is provided by CASSy Lab. The value of the remaining solution. Potassium permanganate reduces to man-
equivalence point can be added to the diagram by making an- ganese dioxide through oxidation of the glucose and can then
other right click in the diagram and selecting Text under the be disposed of as heavy metal waste. This should also be done
Set mark point (see Fig. 2). to the solution in the beaker.
The concentration of the iron solution can be evaluated through The remaining iron(II) sulphate solution can be disposed of as
calculation from the volume of potassium permanganate deter- inorganic salt solution with heavy metals.
mined. In the process, be aware that a MnO4- ion can oxidise
5 Fe2+ ions.
Therefore, to determine the concentration of the Fe 2SO4 solu-
tion, use the following formula: