Expt.

No.: Date:

Experiment Analysis of Iron in an alloy sample by potentiometry

Problem definition Mechanical properties of steel depend on its composition. Hence, it is
important to analyze the amount of Iron in steel for industrial applications.
Potentiometric method using KMnO4 (oxidizing agent) to oxidize Fe(1) in
Methodology steel to Fe(|) facilitates the estimation of Iron in steel.
Solution Estimation of iron (%) in different steel samples.
Students will learn to
Student learning a) perform potentiometric method
outcomes
b) analyze the composition of iron in different grades of steel

Principle:
Potassium permanganate (KMnO4) oxidizes ferrous ion toferric ion in the presence of
acid as per the reaction:
SFe*2 ’ 5Fe*s + 5e ...1)
MnOa+ 8H* +5e’ Mn* +4H,0...(2)
Overall, 5Fe*2+ MnO +8H* 5Fe*+ Mn*+ 4H,0

Electrode potential (oxidation potential) in the titration depends upon the concentration of
Fe2*, Fet and H* ions. To avoid the effect of the change in H* ion concentration, the titration
is usually carried out in large excess of acid. Oxidation potential of this redox system is given
by
RT Fe
E = E, + n
nF"Fe
Connecting the redox electrode (Platinum) with a saturated calomel electrode (SCE)
completes the necessary cell as indicated below:
Hg Hg2Ch (s), Saturated KCI Fe", Fe? |Pt
When KMnO4 is added, Fe2 is oxidized to Fe3t whose concentration increases with
progressive addition of KMnO4. The observed EMF gradually increases. At the end point, there
willbe a sharp increase due to the sudden removal of all Fe* ions. Plot-1: EMF measured (E)
vs Volume of KMnO, added and Plot-2: AE/AV vs Average volume of KMn04 was drawn. End
point of the titration is measured from the Plot-2 graph.

Requirements:
Reagents and solutions:100 mL of KMnO4 (0.05 N) solution, 100 mL of steel solution,2 N
H2SO4.

Apparatus: Calomel electrode, Platinum electrode, Potentiometer, Volumetric flasks,

Burette, Pipette, Beakers.

Page | 26
 Potentiometer AExel/ Iquisslence
Burette poinl
Pt Electrode SCE

equivalence
Salt bridge point
AA BB
V(titranl) V(titrant)

Fig. 1: Typical apparatus for Fig. 2: Typical Potentiometric titration curves.

potentiometric titrations: (a) Normal curve and (b) First derivative curve.

Procedure:
Calibration of Potentiometer:
Switch on the potentiometer and connect the standard cell terminals to either channel
A (move channel switch to position A) or channel B (move the channel switch to position B).
The meter should read 1.018 V. In case it is not 1.018 V, adjust the std. knob to obtain
reference value.

Estimation of Fe(|I) in steel:

Transfer the given unknown steel [containing Fe()] solution into aclean 100 mL
standard flask and make the solution up to the mark with distilled water and mix well. Pipette
out 20 mL made up steel sample solution into a clean 100 mL beaker and add one test tube
of dil. H2SO4 (2 N). Place Pt electrode in the beaker and connect to the +ve terminal of the
potentiometer. In another beaker, place 50 mL of saturated KCl solution and dip the SCE in
the solution and connect to the -ve terminal of the potentiometer. Place a salt bridge to
complete the cell. Read the EMF of the cell and note down the value. Add 1 mL of KMnO4
solution from the burette to the beaker containing steel sample solution. Stir the solution
carefully and measure the EME. Continue the addition of KMnO4 solution and record the EMF
for every 1 ml addition as per procedure till the potential shows atendency to increase
rapidly. After the abrupt change in cellEMF is observed, continue the titration to take 5 more
reading by adding 1 ml burette solution every time. Plot EMF (ordinate) vs. volume of KMnO4
added (abscissa) to get S-shaped curve which indicate the volume range of the end point.
To findout the volume of end point more precisely, carry out the 2nd titration in similar
way but by adding 1ml aliquots of KMnO, initially and then 0.1 ml aliquots between the two
volumes where the end point is detected. Continue the titration beyond the end point as done
above. The exact end point is determined by differential method i.e. by plotting AE/AV Vs
average volume of KMnO4 added. Calculate the normality strength of the Fe(l) in the given
solution.

Page 27
OBSERVATION AND CALCULATIONS

Potentiometric Titration-l:
Burette: KMnO4 solution (0.05 N)
tube) of dil. H,SO4
Beaker: 20 mL of steel solution containing Fe(0) + 20 mL (one test terminal
black
Electrodes: Indicator electrode (Pt) to red terminal and SCE to

Volume of
S. No.
Volume of EMF (volts) S. No. EMF (volts)
KMnO4 (mL) KMnO4 (mL)
1 OmL 335 V 11

2 12
I m 36V
3 13
385V
4
3ml 43414
5
4m
97o |15
16
5 ml 983V
7 17
bm
8 |18

9 19

10 20

0.900
0.800

0.700
(Volt)
EMF
0.600
0.500
0.400
0.300
0.200
0.100
0.000
2 4 6 10 12 14 16 18

Volume of KMnO, (mL)

Fig. 3: Plot of EMF vs Volume of KMnO, added (mL)

Page 28
Potentiometric
Burette:
Titration-ll:
KMnOa solution (0.05 N)
Beaker: 20 mL of steel solution containing Fe(ll) + 20 mL (one test tube) of dil. H,SO4
tlectrodes:Indicator electrode (Pt) to red terminal and SCE to black terminal

Vol. of KMnO4 EMF AE/AV Average

AE (Volt)AV(mL) (Volt/mL) Volume (m)
No. ( mL) (Volt)
1
415
2
29mL
3
426 0015
4 9"520 33ml.
5
930
944 1V 0085 35ml
6
960 0-065
91 0060 39 m

10

11

12

13

14

15

2.500

(volt/mL)
AE/AV,
2.000

1.500

1.000

0.500

0.000
7.4 7.8 8.2 8.6 9 9.4 9.8 10.2 10.6 11
7
Average Volume of KMnO,,(mL)

Fig. 4: PIot of AE/AV vs Average volume of KMnO4 added.

Page 29
Vume KMnoy em Plst2 = 3-3ml
Calculation:
(NxV) of steel sample solution =(Nx V) of KMnOa
0.05 Nx Volume of KMn04 from Plot-2 0o5 X 3.3
N of steel sample
solution = 20 mL of steel sample 20

Amount of Fe present in 1 Lof sample solution =Normality of steel sample xAt. wt. of Fe (55.85)
..Amount of Fe present in given (100 ml) sample solution
Normality of steel sample x 55S.85 x 100
&25XIoX55-5X I00 1000
=0"04607625 grams in 100 mL
oo0

be = 0*05_grams.
Result:The amount of Iron present in given steel sample is found to

No:
Sampu
240DS0306

Page | 30
HAttt

Sri Balaji Stores, Cell: 98946 61515