EXP NO: 01

·1• • lly in the given

Object : To determine the amount of iron (Fe ) volumetr1ca
solution, by permanganatometry method.
Materials required : (i) pipette, burette along with the stand, conical flask, etc.
• 'd
(ii) Oxalic a~id, potassium permanganate! d~J. Su1phunc aci
the given ferrous sulphate solution, d1st1l1ed water.

Indicator used : KMnO 4, as the self-indicator.

Reactions involved : (i) _Standardization o(KMn04 by Oxalic acid:-

2 KMnO4+3 H2SO4 _ __... K2SO4+ 2MnSO4 +3H2O +[O)

5H2C2Os + 5(0] 5 H2O + l0CO2

2KMnO4 +3 H2SO4+5H2C2O4 K2SO4+ 2MnSO4+8H2O + 10CO2

(ii) Reaction o[Fe2+ with KMnO,_

2 K.MnO4 +3 H1 SO4 - - - - - K2SO4 + 2MnSO4 +3H2O +5[0]

{2FeSO4 + H2SO4+ 5[0] Fe (SO4)3+H2O} x5

2 KMnO4 +3 H2SO4+l0 FeSO4 a. K2SO4+2MnSO4+5 Fe2 (SO4)3 + 8H2O

End point : Appearance of pink colour in the (colourless) solution reaction.

Method ••

(I) 0.1 N, 100ml standard solution of oxalic acid is prepared by u~ing the formula,
EVN
W=-
1000

(2) The pennanganate solution is standardized against the standard Oxalic acid
solution. For this, the 10ml pipette is washed with the distilled water and later
rinsed with the previously prepared Oxalic acid solution. 10 ml of Oxalic acid
solution is taken \Vith the pipette in a pre washed conical flask. To it about 5ml of
/

Page 1 -
 u·
•
I
'· I ; i . I I ',, - .
. . - •.I( _) I I,. .. '
:-., )!q t: ., --:.dd
•• io n ts t:~k .~dI ~nd
. '
~ •
UO \.V n t en in th the ini •· .
- . .\t ur e !S -
co lo ro rn th~ bu re hc!at~ ,., - 1·1
tt: _Pl e- nn se d 501nl buretd ~o ab ou r 10-so-c. 1t! pc [Link].n.::•J': :.irr-'..t-=
r,~ d~ r ap pe ar s in th te.
"a 1n:::-n • h ~ in t~ e co nic al fla sk wi Th e KNfnOJ sol LI ti on is the n n: n.
in t e bure•t e rer th co ns tan t sh ak ing till the
re d ox • . ict1on so lut1•on. Th is is lig ht pi nk
t3 te Is the en d po int ot• the tit • rat •
re ct· tra tio n • Tl1e . rec . ord ed as the vo lum e
of ~M nO J so lut ion requir
ion . Th.e
a 1n gs ( \,Vi •h · . t1trat1 • • ed • h
on 15 repea , . tn t e
<.;;l in t 1 1e er ro r li1nit of ±2ted at ,east th ne e to obtai.n t\vo conc
%). . or da nt

T n b I c I • Sta d \
• .. • n ar d1. sa tio n of KMnO
.c
SI N o; -T 1~ vY io ~l ~u
1
1 ·a ~m =e ~o ~f ~o -v .-~ 1~
.,.. 11 ·-c 7l -- ~~ -- ... -- -- --
\
In iti al bu re tte Fi -- -= f- i
Vo lu m e--
I ac i pi pe tte d ou t : na l bu re tte
\
1

f
!
I (m l)
,J
I re ad in g
(ml)
re ad
ml
in g KM nO
o
-'
co ns um ed (m l)
l
l
I l
'l
_,_ _;_ -- -L_ ____::~=----
-=--=-J_'-=--=--=-~-=--=--=--=--=--=--=-~
~-=--=--=--=--=--=--=--=--=-~L__ _
___ _J t
Th e str en gt h of pe nn
an ga na te solution '
SI V 1= S2 Y2 to us e it ([Link] ) is determined
lat er in the titration again 4 using the formula, \
st the giv en iron solution. \ t

t
3. Th e gi ve n iro n (F e 2 'I
...) so lu tio n is tit
rated against the pe rm an
th is, ga na te solution. Fo r \
(i) T'he gi ve n, pr ov
id ed iro n so lu tio n of fer
fiask: is fil le d vvith di rous sulphate in th e 25
st ille d wa ter up to the 0 ml vo lu me tri c
mark in the volumetric fla
sk.

(ii ) ? 5 1nl of th e di lu
te d solution of iron is tak
vvhich ar ou nd 15 rnl ( ~n. in a pre-'v:ashed coni
one sn1aJJ test tube) of cal flask to
th en titrated ag ai ns t th d1l. H2SO-' 1s added.
e permanganate solutio Th is mixtu re is
co nt in uo us ly sh ak in g n at roon1 temperature by
th~ flask in swirling n1
ap pe ar an ce of pi nk co otion till the end point,
lo ur in the solution:_ is of the
Je 3 st rh 1ic e to ob ta in t,v achi~v~d. The titrat~o~
o concordant readings is repeated at
(Vv·1th1n the en·or lun
1t of =2% ).

Pa ge 2
~ I
i
~ -.
~~~

l.!
T
,~~~• ~
"'-!
•
T:1bJc2: F··· .
-
• "'-- -
SI No y; --- __
.. stin1 at1on
()
1· 1· ~·
·r )t
t
1u tne of iron - l •--- --- --- --: --" w. := ~r i'
0

:r out ( m I)
, Initia l bure tte Fin~I bure tte 1
solu tion pipe tted i re:iding (ml) readi ng (ml) '
Volu me of
KJYlnO~
~/__ __ __j__ _ _ _~~c~on~s~u.!:m:.::e:.=-d.-!.(_m_n
1
j
/
I
;--~~- + - - -
•t
··- - · - · - - - - t - - - - - - ~ - - - -
7 I
i ---i I
I
I

Ca lcu ht tion:

( i) The stren gth of the perm anga nate solution will

be,

-
S2- (s~r1): wher e S I and V 1 belon g to oxali c acid,
:ind S.,- and V., belono to the perm anga nate.
- 0

(ii) Sinc e 1N, l 000 n1I Fe 2"" solut ion contains 55.85
g Fe2...
5_;.35 X SZ )( 250
.•. S2 N, 250m l solut ion \.Viii cont ain=
0
1000 b

Resu lt:

The given 1ron solut ion conta ined ...... ...... ...... ...
g Fe2~ m
?50 1nJ.

Page 3
 '
11
EXP. NO.: 04

Object: Verification of Beer- Lambert law with potassium permanganate and

estimation of potassium present in the given unknown solution of potassium
permanganate, spectrophotometrically.
I
I
Materials required: Spectrophotometer, 50ml volumetric flask, burette , pipette,
.l beakers, potassium dichromate, distilled water, etc.

Theory: When a beam of light is passed through an absorbing medium , a portion of

it gets absorbed and the rest is transmitted. The extend of absorption depends upon
(i) the wavelength of incident radiation (ii) thickness of absorbing medium, and (iii)
the concentration, if the absorbing medium is a solution (considering that the solvent
' part of the solution is non- absorbing or transparent by nature). Thus, by measuring
the intensities of the incident as well as emerging radiations, we can qualitatively as
well as quantitatively identify the absorbing species present in solution under study.
This technique is called photometry, whereas the technique of spectral study by
measuring the intensities of colours is known as calorimetry. In calorimetry, the
intensity of colour due to a species is compared with the intensity of colour in its
solution of definite concentrations, which are termed as standards.

Beer's Law: It is a law governing the absorption of incident light by an absorbing

species. Infact , Beer's law is the extension of Lambert's law is the extension of
Lambert's law applied to the absorbing species in solution phase of a definite
concentration . Thus Beer's law can be stated as "when a light radiation travels
through a solution of an absorbing medium, the rate of decrease of intensity of
incident radiation with the distance , x (i.e the thickness of the medium), travelled by
the light radiation , is directly proportional to the intensity of the incident radiation
1
as well as the concentration of the of the solution expressed in mol.L- .". Thus
mathematically, the law can be deduced as,

-di /d x I.c ............. ............. ........... (1)

or, -dl/d x = k' I.e .............. ............. (2)

Integrating equation (2) within proper limits of the intensity, I and the thickness, x,

r lx
..,, di= - k' c f:,-x •
_0 ax..........
x-
.......... (3) or,

2.303 log! = -k' c x .............. ....... (4)

Page 11
 I I Putting (k'/2.303) =c and log loIx= A., i.e, equation (4) can be written as:
/I\ l
A= log:= cc x ......... ......... ........(5)
I l
'
Where, A (or log~•o.. ) is called the absorbance or optical density of the absorbing
I •
I I
I.
1 l species and c is termed as the molar absorbtivity or the molar extinction
.lI coefficient of the absorbing species when the concentration, c of the absorbing solute
'! 3
in the solution is express~d as mol L- . In equation (5), the unit of c is mol dm- , tJ:iat
I
1

ii" .
't of xis cm and the unit..q[ cis dm mor cm- . Thus one should obtain a linear graph
3 1 1
I:
l' passing through ori~in ~hen plott~d between A on the coordinate and on:- the
I: abscissa , at a particular temperature· and for particular wavelength radiation of the
f
absorbing species. •. 7''
'
I •
Limitations of Beer's Law:-

1. The law is not obeyed if the radiation used is not monochromatic in nature
2. The law governs the absorption of dilute solutions only. At high concentrations, the
ions of the solute, if it is an electrolyte, are close enough to each other so as to disturb
j the charge distribution of their neighbours. Thus the interionic interaction can
drastically alter the ability of the solute to absorb a given wavelength of the incident
radiation which violates the the linear relationship between A and c in eqn (5).
3. According to eqn (5) , therefore, A C( c the law is vaid upto the experimental
concentrations of the absorbing species only, and the law cannot be generalized for
any concentration of the absorbing solute. Morever, following the limitation 1,
above, the law is valid only for dilute solutions.
Procedure:
3
yPrep are 50ml stock solution KMnO4 in distilled water of strength l.S00x 10- M.
2. Prepare 25ml solution each of KMnO4 in tablet from the stock solution
prepared in
~ step I above for five mixtures of volumes 0.5ml, 1.0ml, 1.5ml, 2.0ml & 2.5ml each.
3. Wash thoroughly the cuvettes of the spectrophotometer with distilled
water. Fill one
of theJ cuvettes upto ¾ its height with distilled water and dry it gently from outside
th

with the help of tissue [Link] the other cuvette with experimental solution of
KMnO4 of strength 9.0 x10- M of solution 3 upto the same height and dry it too
5

from its outside. Keep the water cuvette in the reference holder of the
spectrophotometer . Whereas, the cuvette carrying the experimental solution is to be
kept in the same holder. Close the lid of the cuvette chamber so that no str~y light
enter the chamber from outside. Note the values of absorbance of the absorbing
Page I 2
 l
solutions at different wavelengths (nm) , A, ranging from 850-350 nm with a
1. difference of 5- 10 nm . The value of wavelength at which absorbance is maximum
is called Amax .Draw a graph between A (nm) on the abscissa and absorbance A, on
the ordinate for the KMnO4 solution. Determine A max from this graph. A max is a
characteristic property of an absorbing species and is a constant at a particular
temperature irrespective of concentration.
4. Determine the values of absorbance, A at Amax for each mixtures of KMnO4 having
5 5
different strengths, 3.0 x 10- M(for mixture 1), 6.0 x 10- M(for mixture 2), 9.0 x
5 5
10-5M(for mixture 3), 12.0 x 10- M(for mixture 4), 15.0 x 10- M(for mixture 5)
by using Table 3.
3
5. Plot a graph between the concentrations, c (mol dm- ) of various solutions K.MnO4
on the abscissa and their corresponding absorbance value ,A on the ordinate. A
linear graph, with positive slope, passing through the origin, is the experimental
verification of Beer's law for [Link] 4 ( the absorbance for the solution at its zero
concentration is zero, when the linear graph is extrapolated to zero concentration).
6. With the help of the graph so obtained, one can find the strength of the unknown
solution of [Link] 4at the same temperature. Also the amount of potassium present in
the given unknown solution of KMnO4 can be determined after determining the
strength of the given KMnO4 solution with the help of the graph.

Observations: Room temperature= .................. 'C.

Table 2 : Absorbance value of 9.0 x

Table 1: Preparation of Five Mixtures 10-5 M KMnO4 (Mixture.03)
at varying wavelengths
Volume of
Mixture KMnO4stock
SI. No. >.. ( nm) Absorbance
No. solution to be (A)
added in 25 ml
volumetric flask
1 0.5 ml l 510
,
2 1.0 ml 2 515
3 1.5 ml 3 520
4 2.0 ml 4 525 /

5 2.5 ml 5 530
u To be supplied 6 535
7 540
8 545
9 550

Page I 3

_J
 Abs

ous KMn04 solution at>. max

Table 3 : : Absorbance values of vari
centration, M A
Mix. No. Vol. of stock solution KMn04 con
0.5 ml 3.0 X 10•:>
I 6.0 X 10·)
2 1.0 ml
I.5. ml 9.o x Io·)
3• 12.0 X 19·:>
4 2.0ml
2.5 ml )5.0 10·:>
X
5
To be supplied To be determined
Unknown (U)

Abs , rnkno11·11

Cone

Calculations :
n the quantities
ed in the procedure above, betwee
(i) Plot the two graphs, as mention K.MnO4 at
ervation, to verify the Bee r's law for
from the two tables above in the obs solute.
inite range of concentrations of the
the working temperature, for a def amount of
n solution of KMnO4 is 25 ml, the
(ii) If the amount of the given unknow
be dete1mined as :
K+ present in this solution then can
• Page I4
 39.098 g ofK +
IM, 1000 ml ofK 2Cr20 7 aq. soln. contains
39 098 X 25 XS
100 o
tain = g
25 ml of S M given KMnO4 soln. will con

orig in, between the concentrations of

Result : ( 1) A linear graph passing through the
ce values, with a positive slope, verifies
KMnO4 and the correspondence absorban
the Bee r's law for KMnO4 at ..... .... c, and
0

I n KMnO4 solution was found

(2) The amount of K + present in the give
to be ..... ..... .. g .

.... .
..... ..... ..... ... ... ... xxxx ..... ..... .. ..... ..... .....

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