PRACTICBAL

CHEMISTRY
(For B.Sc. I, II & l Year Students)

O.P. PANDEY
D.N. BAJPAI
S.CHAND S. GIRI
 9
Volumetric Analysis
(Titrimetric Analysis)

Introduction
Volumetry is a subject which involves estimation of quantities of chemical species (element,
compound, radical or 1on) indirectiy by measuring the volume of the solution of that particular spe
cies in a suitabie solvent, Ttis the mass of the chemical species which takes part in the reaction but
measure the volume of the solution for calculation of the reacting mass of that very species. he
we
masses of the species react and form under volumetric conditions always in the ratio of their so
called 'chemical equivalent wetghts' This is enumerated as "Law of Equivalence which is applied
inall volumetric estimations. The technique involved in it is called titration.
The main task in titration is the standardisation of a
given solution with the heip of known stan
dard solution where a chemical species of the nature of primary standard has been used. Keeping t

viewthe precautions taken in the preparation of standard solution, we weigh out accurately almost
desired weight of the substance to dissolve in a solvent water. The solution is made homogeneous by
proper shaking. The standard solution may be pipetted and filled in rinsed burette as directed accord
ingto the convenience of the exercise. This standard solution is now titrated against the unknown
soluion using suitable indicator. Sometimes even indicator is avoided where one of the titrantS
possesses sharp colour in solution. Titration is simple mixing of two solutions to react ina beaker or
conical tlask. At the time of completion of the reaction, a visible colour may be achieved which is
regarded as the practical end point. It shows that reaction has been theoretically complete just before
addition of one of the titrants by a fraction of drop. The volumes of titrants are sufficient to calculate
the quantity of the mass of either the species dissolved in the solution if mass of the one species is
already known from Law of Equivalence (N, V=N,V).
Primary and secondary standard substances. The substance which fulfills the following req-
uIsites is called 'primary standard substance or primay standard, t must
b e easily available in highly pure state.
2. be easily soluble in the desired solvent.
S not suffer decomposition in presence of solvent
4. be stable in and unaffected by the a.

h a v e large cquivalent weight so that weighing errors are minimised.

Oliscompositionmust not changeon standing Nt nystasCo p e r 7al

Commonly used primary standards are: Anhydrous Na,Co, Oxalic acid, sucinic acid, K,Cr0,
errous ammonium sulphate, NaCI and AgO, etc.

nough the hydrated salts are not good primary standardsbut those which are not efflorescent
a s Cuso,5H,0, Na,B,O,10H,Oand H,C,O,2H,O work satisfactory. The standard solution
primarystandard substance is called "primary standard solution. This is prepared by dissolv
CEurately weighed out sampie of the dry reagent in known volume of the solvent.
hose substances which do not fulfil the above requirements and their standard solutions can not
Tpared by direct weighing. are called 'Secondary standard substoances or secondary standards'
Common secondary standards are alkali hydroxides and inorganic acids etc. An approximate
E Of the secondary standard is dissolved in a known volume and the exact strength of the solu
89
 Practical Chem
of the suitabie reagent. This process
by titrating it against standard solution ess is cile
15 Tound
Standardisation-
as the number of parts by weighnt, a chemical species c o
or displacedwelght.
with Equivalent Itis
by 1.008 defined
parts of hydrogen, 8 parts of oxYgen or 35.5 parts by weight of ch
chlonne
Mol v
Eq wt. of an acidbasicity

Eq wt. of a base
Mol w
acidity
wL of cation+ Eq. wL. of anion
Eq wt of an electrolyte Eq. =

Equivalecnt weight is not always constant. t may change trOm reacuo0 to reaction. Such w
wts. of
otten observed in ihe reaction involvingg OXIdaliotn rcductio e8- Eq copper
ous are
Phate, temous sulphate and of sodium thiosulphate are halt ot their moleulcar weights in usual
tead
uons but in redax reactions both, mol. Wt. and cq. WL. are oten cquall.
The equivalent wt. cxpressed in gm is called gm equivalent wt. ot the substance

trength of the solution. itis expressed in following ways

(9 Percentage. Number of gms of a substance dissolved in l00 gm ot its solution It is gene
ally used in dilute solutions of electrolytes in water. 1 0 Naci means that 100 gm ot its solution

contains 10 gm of NaCl.
(4) Molaliry. lt is number of gm-moles of substance dissolved in lo00 gm of solvent.

(i) Molarity. Itis number of gm-moles ofthesubstancedissolved perlitre ofthesolution.If

Dne gm-mole ot a substance is dissolved in a solvent and the solution is made up to the one litre, such
a solution is called Molar Solution.
Ifw gm of a substance is dissolved in V ml of the solution and mol. wt. of the substance is M

Molarity 1000
gm/litr
mol. Wt
(i) Normality, It is number of gm equivalents of the substance dissolved per litre of the s0l
tion. If one gm. equivalent of an acid, base or salt is dissolved in water and the solution is made up
one litre, such a solution is called "Nomal Solution.
Ifw gm ofa substance is dissolved in V mlof the solution and equivalent wt. of the substance t

NormalityE D00
ttre
Eqwt
sole
() Formaliy. Number of gram formula weights of the substance dissolved in a litre aft
tion.
gm7 itre
Formality Formula wt.
Standard solution. A solution of known strength is called standard solution. 1t prepu

either by direct weighingofthe substanceor after titrating it with another standard solution ie:
ardisatijon with the help of another standard solution.
Calculation of the normality of prepared solution:

(0 If mass of the substance taken is W gm

i) Equivalent weight of the substance E
In 250 ml measuring flask the normality of solution
Volumetnic Analysis
1

1000 w
250 xE
4x wt.of the substance taken
Eq.w
Calculationof the required weight for preparing the standard solution
Suppose equivalent wt. of the substance is E and we have to prepare a solution of N normality in
Vml measuring flask.

Substance in gm per litre NxE

Substance in gm in V mi NXExV
T000
Titration. ltis the process for standardisation of a solution. Two solutions are generally used in

every titration where strength of one is generally known. The solution to be titrated is taken in a
conical fhask tDy using a pipette of 10, 20 or 25 ml and the other solution is taken in the burette
Indicator is added at desired stage to the solution taken in the conical flask and burette solution is
generally poured into it. A sharp colour change occurs at the completion of the reaction This point
is called "End point'.
There are so many types of titrations but the most common are

1. Neutralization titrations
2. Redox titrations which also include iodine titrations
3. Precipitation titrations
4. Complexometric titrations.

Acidimetry and Alkalimetry

The determination of concentration of acid by standard alkali is known as acidimetry and the
TrEverse process is alkalimetry. Though it has a wide range in the volumetric analysis but few experi
ments are discussed below.

EXERCISE
U
To determinethe strengik of NaOH und Na,C0, present in a solution and find their
Petrceniuge composiion.
Theory. The mixture is titratied with a stand ard solution of HCl or H,S0, by the selective use of
tndicators. With
HCI, the reactions proceed in the Ioliowing ways
0
NaOH +HCl NaCl+ H,O odca-fhasep
Na,CO,+HCI NaCl+ NaHCO,Splr-itle afe
This NaHC0, further reacts wilh HCl

NaHCO, +HCI NaCl+H,0+Co

he phenolphthalein is added as first indicator which loses its colour of alkaline medium when
DH and half Na, CO, are neutralised. In fact, it does not give colour in NaHCO, solution.

ow Lse of methyf orange as second indicator is made which shows the complete neutralisation.
rocedure. Take 25 ml supplied solution and add 2 drops of phenolphthalein indicator. Now
e i t with standard solution ofHCI (prepare if not supplied) until the additional drop of HCI fades
Hcolourof solution. Note this reading. Now add two drops of methyl orange and add slowly
Ccoi util the last drop of HCI gives red colour. Note this second rending. Repeat it for the
comect readings.
h e second reading of buretie includes previous volume as well, used with phenolphthlein indicntor
ervation. 1, Volume of HCl used with phenolphthalein indicator V, mb
Volume of HCI used with methyl orange indicator ie, vol. obtained aler subtracting first
 2 Practical Chemie
reading from second reading of burette- V, ml
Caleulation. The volume used in first reading shows the compiete neutralsation of Nac
halt neutralization of Na,cO, as half of it has been converted to a i a t is alkaliney

NaOHH+ 1/2Na,Co,
V, ml
and
V ml 12 Na,CO (by latter reaction shown in the
heory of t
Hencecomplete Na,cO, required 2V,m
2. NaOH required only (V-V)ml7-7
If the normality of HCl be N, the normality of NaOH solution, N, willbe
)NVENY(Na
Lx Na Strength of NaOH Eq. wt. of NaOH x normality

-40x gm/litre
Amount of NaOH in 100 m
40 x25
N x 10 o r say x,
Similarly, it may be worked out for Na, CO
3'a
The strength of Na,cO, 53 x 2, *gm/litre
o

Amount of Na,CO, in100ml- 53x No rsay x,

4 25x 10

37 1.
Percentage of NaOH in mixture: 100

2 Percentage of Na, Co, in mixture: x 100

EXERCISE2
To determine the strength of
Na,cO, aind
NalHCO, preent in a solution and also Jind
hetr percenfage composifion.
Theory. The principle
involved in it, is just similar to
that of discussed
Na,CO, will react
in two steps and the same two indicators previously. Here a
will be used. The chemical reaction
taking place are as follows:

Na,CO, + HCI
NaCl+ NaHCO,
NaHCO,+ HCI NaCl+
Procedure. Pipette out 25 ml H,O+CO,
indicator. Add gradually a standardof the supplied solution and add two drops of ple
last drop ofit fades thephenoip
solution of HCl till the
solution Note this end point
with HCl and see the light carefuly, Now, add two drops of pink co
pink as end
point. methyl orange indicator a n
Note also this
previous volume used with first indicalor). Kepeat experiment
reading. (This reading will a l
Observations. Let to ensure the
accuracy ot your
Volume of HCIused when
2 Volume phenoiphthalein used
of HClused in all V,ml
Calculation. V, mi. 1s the volume for V,ml
reacts alkaline. Theretore, half neutralization of Na,co, as
Na,co, as NaHCO,
NaHCoy formed
total volume used to neutralise
total volume of the acid Na,CO,
used for 2V, ml
isation of complcte neutral-
Na,co, and
NaHCO, both
V, ml
 Volumetric Analysis

Hence the volume of HCI required for

Ifthe normality of HCT be N,
NaHCOD (V,-2V,) ml
and that of
Na,C0, be N
N, 2V
5
Strength Eq. wt. xnormality
Strength of Na,CO, * N X2V
25 gm/litre
Amount of Na,CO, in 100 ml = 53x N,X2
or
25x10 say

Similarly, the normality of NaHCO,=(%-2) R o

25
Strength of NaHCO, = 84
xN,V,-2V)
gm/litre
Amountof NaHCO, in 100 ml XN XG- 2V,) or say 2
25 x 10

Percentage of Na,CO,= X100 Op

Percentage of NaHC0, =
x100
t
EXERCISE3
To determine the
percentage of ammonia in an ammonium salt.
Theory. When an ammonium salt (except carbonate and
wIith an excess of sodium
bicarbonate) is decompc
hydroxide solution, ammonia is liberated according to the e
If a known
NH,CI+NaOH NaCl + H,0 + NH,
quantity of NaOH (in excess of that required to decompose the amm
uSed, and, after the
ween these
decomposition is complete, the unused NaOH is determined, the-
quantities gives the amount of NaOH equivalent to the ammonium salt tam
Procedure. Weigh accurately about I to 2 gm of the amm. salt, and transfer it
caker and dissolve in about 75 ml of water. Add 50 ml (measured) N-NaOH soluti-
1 s more than sufficient to decompose the ammonium salt and boil gently to expe-
nlervals of about five minutes, test for ammonia in the escaping steam with a pie
spaper-the test paper being held outside the beaker. Boil for about half an h-
position is complete, i.e., when no ammonia is detected in the vapours, cool t
Ster it to a 250 ml measuring flask. Dilute the solution up to the mark and shake
the
23 ill burette with N/10 HCI. Pipette out 25 ml of the above solution into a con
rops of methyl orange as an indicator. Naw add slowly HCI solution from bure
COnstanty titl a/piny colour is just(obtaingd. Note the burette reading and rep
WO
COncordant Teadings are obtained.
Calcuiat
 94 Practical Chemie
Vmlof N1OHCI
Vmlof N/1O NaOH
V/10ml of N-NaOH
Thus vol. of N-NaOH left unreacted in 250 ml of sofution

250xV or Vml
x10
25
Vol. ofN-NaOH reacted with amm. salt
(50-V) ml
Now I gm. cquivalent NaOH Igm equivalent NH,
1000 ml N-NaOH 17 gm NH,

(50-V) ml N-NaOH 50-V) NH,

O008m
Hence amount of NH, in I gm amm. salt

1750-V em
wx1000gm

Percentage (W/W) of NH, in amm. salt

17(50-V)100
wx1000

17(50
10w
Note 1. If the ammonium salts contain free acid (as an impurity), the amount of acid presient must be
determined by a separate titration.
2. The ammonium radical in salts like ferrous ammonium sulphate can not be determined by this method

aspartof sodium hydroxideis used up inthe precipitatinnof hydroxide of the heavy metal.
Oxidation-Reduction (Redox.) Titrations
Redox-titrations include all those varieties of titrations where one reactant is oxidised and the
other is reduced. The indicator is so chosen as to the colour in
give either of the conditions.
Oxidation is defined
the process of loss of one or more
as
electrons and reduction, the gain of
or more electrons by atoms or ions. Both, oxidation and
reduction are complementary to one anoui
on
and take place simultaneously, Le. one cannot take
place without the other.
The reagent undergoing reduction is called
oxidising agent (oxidant), i.e., an oxidising agcn
gains electrons and is reduced to lower valency state. The reagent which
undergoes oxidato
called reducing agent (reductant) Le. a reducing agent loses
electrons and is oxidised to higic
valency state. The reducing agents are generally sodium oxalate,
nium sulphate, oxalic acid etc. The commonly
ferrous sulphate, ferous a
employed oxidants are KMnO,, K,Cr,0, (both a c
fied), I, solutions etc.
In redox titrations, the estimations are
generally done by the following methods
[A] Potassium permanganate method
[B] Potassium dichromate method
(C) lodine method
The first two methods will be discussed in
this chapter and the third one is discussed in u
chapter.
Calculation of equivalent weights of oxidants and
The cquivalent weight of a substances tnvolved in
reductants.
lated by any one of the following methods oxidation-reduction (redox) titrations calc
VolumetrC Analysis

LAvailable oxygen method,

2 Oxidation number method and
3. lon-electron method
Out of these, oxidation number method is convenient. Few exanples folew
( ) Equivalent weight ef KMnO, in acldic medihum. The reduction of KMtnO, in acidic medius
is represented oy
the Tolowing equation
MnO, +3H,SO K,SO,+2Mnso, +H,0+s0
The oxidation of Mn in KMnO,7
inMnSO, +2
This shows the gain is ofS electrons. Therefore,

Eq. wt. ofKMnO,

The E
S

--31.6
is 31.6
Eq. wt. of KMnO, in acidic medium
Itis oxidised acconding to following equation.
) Eq. wt. of Ferrous Suiphate.
2FeSO,+H,SO, +[O] FeSO)) +H,O
there
sulphate, the loss of only one electron per ferrous ion is
Since ferrous is converted to ferric
It is, therelore,

152
Eq. wt. of FeSO,
wt. of FeSO, 7H,0 278
Eq.
ammonium salphate, (NH,),SO,FesO,6H,0
6) E4. wL. of Jerrous resistant to oxidation and so
is pertfermed over terrous
lt is a double salt and is, therefore, quite Tes equivaicnt weght is eual to
tha
same manner as does ferTOus sulphate,
Sulphate. t reacts in the
of its molecular weight ie. 392

4) Eg. wL of axalic Acid.

It is oxidised in the following way

FOOH 2H,0+0 2Co,+3H,O

COOH
*0
The oxidation state of C, in H,C,0
C inC O , + 4
+8
So for Ca this will be Therefore,
in 2 carbons is 2.
The loss of electrons
Eq. wt. ofoxalicacid

63 reacts with a
dichromate n a c i e medhm
Potassium
dichromate.
E g w. of Potassium
cuucing agent as follows
Cr,0,+6FeSO, (NH,);so, +7H,SOD +
o(NH,,SO, +
71,O
3Fe,(SO,)h+K,SO, + C,(SO,)
Here Cr, changed to Cr,
 volimefnc Analysi 103

196 solution of diphenyl amine in chemically pure conc. H,SO, (sp gravity 1.84).
The end point obtained follows:
is as

Take 25 ml of solution ot terrous tons, add about 25 ml dil. H,SO, 6-8 drops of indicator and
syrup of phosphoric acid. Now add K,Cr,0, solution from burette until the last drop C
e from green (due to tormed chromium sulphate) to blue-violet which persists even on s
the cha point.
This is
6) N-phenyl anthranilie acid (0.005 M solution) is also used as an indicator. Take 25 ml of
solution of reducing g c n conicallask, ncidify with about 25 ml H,SO, (dilute ) and then add
few drops
of the
inaicator solution. Titrat he , 0 , and when yellowish green
sharply to purple red, indicates t
solution changes
Oxidised form of this indicator is purple-red and reduced form is colourless.

EXERCISE922
To
delermine the strength ofa given solution offerrous ammonium sulphate by titrating
tagainst A 5oution and using pot.fericyanide as an externalindicator.
Theory. Acidic K,Cr,0, is a strong oxidising agent. When it is added to ferrOus
ammonium
dil
sulphate solution contaning dil. H,SO, or
unchanged hence not shown in the equation.
HCl, only FeSO, is oxidised and (NH,),SO, remains
The reactions taking place are as follows

KCr,0,+ 4H,SO, K,SO,+Cr(SO,)h +4H,O+30

6FeSO+3H,SO, +30
3Fe,(SO), +3H,O
Thecomplete reaction is:
K,Cr,O,+6FeSO4 +7H,SO 3Fe(SO)+K,S0,+Cry(SOh +7H,0
(Cr0 14H +6Fe 6Fe +2Cr+7H,0
end point, the indicator fails to produce blue
At the
mixture.
colour when treated with a drop of titration
Procedure: This involves following steps.
(a) Preparationof apprax. N/30ferrous amm, sulphate soluiion (known solution).
Equivalent wt. of it is 392-12 hence weigh accurately about 392.12/120-3-267 gm and transfer
toa250 mi measuring flask. Dissolve it in distilled water, add S ml of cone. H,SO, and then make up
the volume. Shake well. Nomality of this solution will be :
4 xw
392-12
where w is mass of ferr.
sulphate dissolved
amm. in 250 ml of water
0) Standardisation of K,Cr0,solution with known ferrous ammonium sulphate solution.
Rinse and fill burette with K_Cr,0, solution. Note the initial reading. Pipette out 25 ml of
ndard ferrous amm. sulphate solution in a clean conical flask and add to it about equal volume of
NSO, Puta series ofdrops of indicator (pot. ferricyanide solution) with the help of glass rod, on
t e tile or a plate. Run in solution from the burette and when nearly 15 ml. is added, take out from
lask, a drop of titration mixture and mix it with one of the drops of indicator. A strong blue colour
De produced. Continue the titrations and repeat the process at diferent intervals and when the
h r o indicator-drop does not give blue colour, the end point is reached. Note the reading of the
CE. Repeat the titration to get the exact end point.
Titration with unknown ferr. amm sulphate solution
For this, proceed exactly in the same way as above
Observations
This is recorded in tabular fon.
 volumetric Analysis

(B) TItration with unknown solutionofoxalic acid.

Sd
SNo of Cuiic arid Burette reading Hil.of KAMnO, used

Initial Final
mi
00 mi
mi 00 ml
3 mi 00 mi

Say V
Calculations : , 1s thie volume of KMnO, solution used with 25 ml of standard oxalic acid
soluion.
Vol x normality of KMnO, solution= volx normality of standard
oxalicacidsolution
Nomalityof KMnO, solution
Equivalent wt. of oxalic acid is 63
IVis the vol, of KMnO, solution used with 25 ml of supplied oxalic acid solution
Vol. x normality of supplied oxalic acid solution
=Vol. x normality of KMnO, solution

Normaltyof supplied acid solution xX

5x V,x 63
Strength of supplied oxalic acid solution in gm/litre
25x4xwx63
25 xV, x63

Strength of supplied oxalic acid solution=

4xwx gm lit
Result. The strength of given oxalic acid solution is gm lit
Precautions
Mn0, solution atacks rubber hence it shoulid always be taken inaglass stoppered burete
f sulphuric acid is not added in sufficient quantity, a bruwn ppt. of hydrated manganese dioxide is
omed and end point is not properly detected and also the readings are not reliable
Due to intense colour of KMnO, solution. its lower meniscus is not properly read hence note the
puretie reading at the upper mcniscus.

A t the end point, the pink tinge musr ersist for 30 seconds. Beyond this time, the pink colour may
p e a r due 1o reduction brought about by certain substances prcscnt in air.
a k e chemically pure KMnO, because ordinary KMnO, contains oxides of nitrogen which reduce
KMn0
Athe end paint, we get a light pink colour, Adda drop of osalic acid to it. if pink colour disappears
e h d point is corect

EXERCISE5
o dertermine the strength in gmilitre of a given solution offerrous ammonium sulphate
or' salt) being provided with approx. N30 KMnO, solution.
eory. The acidified KMnO, beingan oxidising agent converts terrous ions to ferric ions
ording to the following cqualbon
2KMnO,+3H,SO- K,SO,+2MnSO,+3H,0+50
1oFeSO,(NH,),SO,6H,O1+50+SH,So
SFe5O+10NH),SO, + 65H,O
 98

2MnO, +16H 10c 2Mn +8H,0

PracticalChemi
1OFe 1OFe10e
2MnO,+ 16H 10Fe 2Mn 10Fe+8H,0
in the
This titration is done in cold because o n heating,
ferrous sulphate present Mohr's sek
Oxidised by air. salt g
Procedure. It involves
three steps
(a) Preparation of standard N/30ferrous ammonium suiphate soluiion (nown solution
Since equivalent wt. of ferrous ammonium sulphate is 392, hence weigh accurately about 9 2

3.266 gm of the ferrous amm. sulphate for 250 ml. solution ofN50 strength. ransfer it to a 250
measuring fask, add first S-10 ml of dil. H,so, and dissolve it Add distiled water to make upthe
volume to 250 ml.
(6) Stamdardisation of KMnO,solution by knownferroS ammonim suiphate solution
(0 Rinse and fill the glass stoppered burette with KMnO, solution. Kead the upper level ef
solution.
( n Pipette out 25 ml of known ferrous ammonium sulphate in a clean conical flask and add
about 25 ml dil. H,SO
(Note. Do not heat the contents of titration flask).
i n Add the solution of KMnO, from burette very slowly and shake the tlask after each addition

until a light pink colour justappears. Note the reading of the buretie. 1he comectness ofend poit
15Judged by adding a drop of ferT. amm. sulphate solution to the litration mixture. if the pink colour
disappears, the end point is corect
( ) Repeat the titration until two concordant readings are obtained.
)Determination of strength of ghven ferrous ammonium suilphate (unknown) solution
Rinse and fill the burette with standardised KMnO, solution.
) Pipette out 25 ml of unknown ferrous amm. sulphate solution inatitration flask and proceed
for titration exactly in the same way as you have done with known ferrous amm. sulphate.
Observations
A) Titration with known solution of ferous ammonium sulphate (F.A.S.)
SNo Vol ofFAS
Burette reading Vol. of KMnO uaed
aitial Final
25 m 0-0 ml mi mi
25 ml 0-0 ml mi
25 ml 0-0 ml

Say V
(B) Titration with given solution of FA.S.
S No Vol. ofFASs
Burettereading Vol. of KMnO, used
nitial tnal
25 ml 00 ml
25 ml 0-0 ml
mi
25 ml 00 ml

Caleulations. Let

w mass of ferrous amm. sulphate dissoived in 250 mi solution.

p
 olumeli0 Analysi

V Vol, of KMnO, used with 25 ml. known solution

ol of KMnO, used with 25 ml. of given solution.

Nomality of known soln. 4Xw

392
Vol.x normality of KMnO, soln. w Vol.X normality of known soln.

soln.25X4Xw
Nornality of KMnO, 392 *V
Vol. xnormality of known soln.Vol. x normality of KMn0, known soln
V, x 25x4 xw
Normality of known soln. 25x 392xV,
Eqwt.offemous amm. sulphate is 392.
Strength = Normalityx Eq. wt

Strength of given ferrous amm. sulphate solution in gn/litre

4xwxV
V,
Result. The strength of given ferrous ammonium sulphate soution is. gm it

EXERCISE6
Toextimateferrous (Fe")andferrie (Fe)ionsgiven inthemicture.
Theory. Finst of all, the ferous ions are estimated by KMnO, solution. After this, we reduce ferrie
lonsin the sameamount of fresh solution to ferous state and this time titration against KMnO
estimates total ions present in the solution.
Procedure. Pipette out 10 mi of supplied solution and add nearly 10 ml of dil. H,SO, in it an
irate it against standard KMnO, taken in burctte, The apperance of light pink colour shows en

Now, take again 10 ml of supplied solution and boil it with zinc and sulphuric acid for 10 minute
s0 as to convert all ferric ions to ferrous state. Now this is titrated as above with KMnO, Note th
cnd point of this also. This shows the ferous ions originally present and ferrous ions obtained t
reduction of ferric ions.
Observation. () Volume of KMnO, Used first time = V, ml

(4) Volume of KMnO, used with reduced solution = Vml

Calculation. V, volume used to oxidise ferrous ions already present, to feric ions in 10 m
solution
Let N, be normality of KMnO, (say 1/10) and N, nomality of ferous ions.
N=0V
10
Nowstrength of ferrous ionsin gm/litre
Eq. wt x Normality

-56x010
S6xV
100
Similarly for Fe ions
Volume of KM0, required for ferric ions only
= (V-V) ml.
 Thus amount of calcum in the Su
250 x0-0 -gm
10x0.02004xxVgm
=
0.02004 Vgm
xxx

0.055i gm
anhydrous CaCl
=
of solution.
ImlofN-KMnO, present in the supplicd
volume

Also
CaCl
anhydrous
of anhydrous
Hence amount of
ience amount
10x 0.0551xxxV gm
= 0.55 xrx Vgm.
POTASSIUMDICHROMATE METHODS
In presence of an acid (dil. HCI or dil H,S0,) K,Cr,O7, acts as an oxidising agent
ent
and
available tor
oxidaton ot reducing agent as shov
up three
atoms of oxygen
molecule of it gives
+ 4H,0+30
below KSO, +Cr,(SO),
K,Cr,0, +4H,SO, 2KCI+ 2CrCl+ 4H,O+30
K,CrO,+8HCI 2 C + 4H,O+ 30D
Cr,0,1+ 8H
by gaining
3 eiectrons (provided by reducinp s

That is in presence of H ions, each Cratom from +o tO+ 3). Hence in acidic me
valency of Cr changes medin
to trivalent C r ion (i.e.,
15reduced as
the half reaction is represented
ICr0,1+14H+6e 2CP+7H,0

detection
dicators and end point temieyanide acis as external india
0 External indicator. About 0.1%
solution of potassium it becomes contan
indicator because the old solutton of
tor Use ferricyanide
freshly prepared pot.
nated with pot. ferrocyanide. or a plate and te
series of drops of the indicator on a white tile
By means of a glass rod, place
a

of titration mixture and put it on one

of these drops the colo
on tile and see
end point, take a drop blue colour will be developed due
to formation of abl
If ferrous ions (Fe) are present, a strong
the following equation:
complex according to

2K,Fe(CN),+3FeSO, Fe,Fe(CN)lh+3K,SO,
ferrous fernmicyanide

(Dark blue complex)

colour becomes fainter. When a drop of solution first failk
Repeating the process, the blue ie. all Fe ions are oxidiel
produce blue colour on the indicator's drop, of the indicator's pointbecomes
this will be the end
ones. Usually at the end point, the colour drop light brownish yel
Fe ferric ferricyanide complet
due to reaction of indicator with Fe ions to produce brown coloured

Fe(S0),+2,FCN)J) 3K,S0,+2F<|Fe(CN)J Brown

(n Internal indicators. The most comonly used internal indicators are:

 c ayss 105

nse ut 2S mi of prepuared FAS solution and add to it equal volume of dilute H,SO, and o to 8
Nphenyl anthranilie acid indicatoe Add slowly dichromate solution from the ou
h e colour of the titration mixture just turms to violet red This is end point of the titration Note
aelulyRepeat the experiment until two concondant readings are obtained. This reading will be

Taion withspplied EAS, solutio

Rris prceed exactly in the same away as above. This reading will be V
Obsernatios and Calkulations

Whic observatons and calculations as in exercise 9

Result. The strength of supplicd! FA. S. solution will be

4wXm lit
EXERCISE 1u
Todetermine the stremgth in gms/itre of a given solution of K,Cr,0, provided with
ermoas amm. tulphate solution and N-phenyl anthranilic acid solution as an internal
Theory The same as in previous exercise. At the end point the green solution changes to lhgnt

purpie-ed
Procedure
(a Prpuratrioe of K,Cr0, (opprax. N/30) solution.
O-41 gm of
Eguivalent WL. of ,Cr,0, is 4903, hence weigh aceurately about
49 03/120 =

KO0ransferto a 250 mi measuring flask, dissolve in distilled water and then make up to 250 ml,
Shake well

Normality of known K,Cr,0, Ssolution 49.03

ahere w = mass of K,Cr0, dissolved in 250 ml water

(b) Sandardisation of ferous amm. sulpihate solutionwith known &,Cr,0,solution.

Rinse and fill the burette with prepared K,Cr,O, solution. Note the inital reading pipete out
5 mlof
femrous amm. sulphate soln. in a conical flask. add 25 ml of 2N-H,SO, and then 6-8 dropsof
N-phenyl anthranilic acid indicator. Add K,Cr,0, solution from burette very slowly and shake the
flaskafter esch addition until the solution becomes green (due to formation of chromiumsulphate)
Nowadd the dichromate solution drop by drop slowly until the addition of one drop of K,Cr,0
sluion suddenly changes the green colour to light purple-red. This is end point. The change of
colour is very sharp when end point reaches. Repeat the titration using cach tüme the same drops of
indicator until two concordant readings are obtained
() Titratiom with unknown A,Cr,0, 30olution.
Proceed exactly as
above
Observations. As in previous exercise.

Calculation
w=mass of K,Cr,O, dissolved in 250 ml water

V= Vol of known K,Cr0, solution used with 25 mi solution

of ferrous ammonium sulphate
V,Vol.of given K,Cr,0, solution used with 25 ml solution of
Terrous ammonium suiphate

Normality of K,Cr,0, solution

4XW
49-03
 104
Pracical Chem
(A) titration with known solution of FA.S.
ol of
S.No ll. of FAS. used Buretle
eading K,C 0, ud
Tnitial Final
25 ml 00ml
mi 00 mi
25 mi 00 ml m

Say V, mi
(8) Titration with unknown solution of E.A.
Vol. of
S.No Vol of FAS Blurete Teuung
K,Cr0, wed
Initial

25 ml 00 ml
00 mi
00 ml
Suy V, ml

Calculations
Let VVolume of K,Cr,0, used against known solution.
V = Volume of K,Cr,O, used against unknown solution.
N, Normality of K,Cr,0, solution.
According to normality cquation
Vol x normality of known soln. = Vol. x normality of K,Cr,0, solution

25x212
392-12 V, xN$-Nt
Hence, N, V392-12 N x2
In the titration against
unknown solution
25 XN = V,xN
where N is the normality of unknown solution.

N= 252 v,392-12
4*W

i A l Y 312-
Strength of unknown solution. 392-12xx4XW
4xWXV
gm/litre
Result. The strength of unknown ferrous ammonium sulphate solution is.. gm t

EXERCISE10
To determine the strength of a given solution
of ferrous ammonium sulphate (E.ASjly
titrating it against polassium dichromate solution using N-phenyl anthranilic acid a
internal indicator. 10 slandardise A,Cr0, 50lution, pule
prepare N/30 ferrous amm. 3u
solution.
Theory. Same as in exercise 9.
Procedure

(a) Preparation of N50 .A.S. solution. Same as in exercise 9

(b) Standardisation of A,Cr50, solution. Rinse and fill the burette with
K,Cr,0
oluis
 6

practical Cheniy
Iq w w
49,01

EXERCISE 4
lo determine the strength of supplied oxalie acid solufion by filraling it
N/30 KMnO, solutio against 8p
Theory. The KMnO presence of dil
in
H,SO, oxidises the oxalic acid to
CO, and H,0
2KMnO,+ 3H,SO,+5H,C,O K,SO,+2MnSO, +10CO, +8H,0
Since
21MnO,+SIC,0,+ 16H -Mn+8H,0+ 10CO
the above reaction
proceeds very slowly at room temperature, the solution in the
adding KMnO, from burette, KMnO, 4cts as a selftitration
s heated to about 60-80C before t
Procedure. It involves three stages. indicator
(a) Preparation of standard (approx. N/30) axalic acid sofation.
is 63 hence weigh accurately about 63/120=0.525 Equivalent wt. of H,C.0,2H
250 ml gmof
measuring flask and then make up the volume by oxalic
acid crystals and dissolve in
wateris
If
adding distilled water
is mass of oxalic acid
w
dissolved in 250 ml of distilled water, the
solution = 4wi63. normality of oxalic
acid
(b) Standardisation of KMnO, solution with the
fill the burette with help of known oxalic acid solution. Rinse and
KMnO,
acid solution in a clean
solution and note the initial
reading, Pipette out 25 mi of standard oxabic
titrating flask and add to it 25 ml of dil.
about 60-80C (GLe., just unbearable to H,SO4. Heat the contents gentdy t
touch by hand), Now run in
slowly (about 10-15 mi per minute) and shake the flask after KMnO, from burette ver
each addition, Avoid addition of large
amounts of KMnO, at a time otherwise a brown
ppt. of
During titration temperature of flask decreases heat ithydated
if the
again.
manganese dioxide is formed
Continue the addition of KMn
solution until a light pink colour just
appecars and persists for about 30 seconds. It is the
Note the burette reading. Repeat the titration to end poin
get at least two concordant
(c) Determination of the strength of readings.
supplied oxalic acid solution (unknown solutton)
Fill the burette with the same
in a conical flask, add 25 KMnO, solution. Pipette out 25 ml of supplied oxalic acid
ml of dil.
H,so, and heat to about 60-80°C and then solu
titration just as above. proceed wiln
Observations
It is recorded here in tabular form as
follows
(A) Titration with known solution of
oxalic acid
S.No. Vol. of oxalic acid
Burette reading Vol, of KMn0, used
Inifial inal
25 ml
0-0 ml
25 ml ml
25 ml 00 ml

ay
 Practioal Ghen
of ferrous
oxNImality
anm.sulphate solutn solution
Vol. xnormuality of known K,Cr,0,
Novmality of Ferr amm sulphate sofution
VXAXW
25 x 490 3

Simlrty
sofution
N nonality of given K,CiO,
25 xnormality of fer. ann. sulphate
solution
V, xnomality of given K,Cr0,
23 x4XwxV
25 x 49 03

4XWXM
or nomality of given K,C,0, soutnon V, x49.03
wt. (ie, 49.03)
for detertmination of strength multiply it by eq.
Strength in gm/litre of given K,Cr,O0,
4XWXY
V
ie. Strength in gm/litre of given K,Cr,0, solution.
4x wt. of K,Cr,0, dissolved in 250 ml wt.
x Vol. of
known &Cr,0,

h Vol. of given K,Cr,0, solution

Note. When the end point has been obtained, add a drop of ferrous ammonium sulphiate to the titra
misture 1f the purpie-red tinge changes to groen, the end point is correct. In this way, the correctness of the e n

point can be judgod|

lodine Titration
lodimetric and lodometric Titrations
The redox-titration using iodine directly or indirectly as an oxidising agent are called l o

Titrations. These are of two types :

1. lodimetric titrations. Iodimetric titrations are defined as those iodine titrations in wn

standard iodine solution is used as an Oxidant and iodine is directly titrated against a reducing
lodimetric procedures are used for the deterination of reducing agents like thiosulphates, sulp
en in
rsenites and stannous chloride etc. by utrating them against standard solution of iodine taken
bureite. Some cases of oxidanon-reduction reactions are given as under:
2Na,S,O,+ h Na,S,O, +2Nal
(4) Na,SO, +l, +H,0 Na,SO, +2HT
(tit) Na,AsO,+ ,+H,0 Na,AsO,+2H1
whicd
2 lodometric titrations. lodometric titrations are defined as those iodine titrations
c dw i

some oxidising agent iiberales 1ouine

trom an 10dine solution and then liberated iodine is tit
a standard solution of areducing agent added from a burette. In such titrations, a neutral or C
KI
solution of oxidising sgent empioyeu.
is The
amount of 10dine liberated
from an iodiae, dete
(ie

cqurvalent to thequantity ot the oxIdising agent present. lodometric titrations are uscu
mination of CuSO, ,CrgOs. KMnO4, Tetnc10ns, antim0nate ions, H,0,, MnO,, bromine d dhl
rine ete. The equations or s 0 e O1 tne reactions are as follows:

2Cus0+4KI Cul+2K,50, +h