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INTRODUCTION
Many chemical reactions in nature, particularly in living
system, occur in aqueous solutions. Reactions are often carried
out in the laboratory in aqueous solutions, since these are
generally more rapid in solution than when pure solid reactants
are mixed. A quantitative analysis is one in which the amount of
concentration of particular species in a sample is determined
accurately and precisely.
Volumetric analysis helps in the determination of composition
of solutions by allowing them to react with standard solutions.
Any solution of known concentration is called a standard
solution. The completion of a reaction in solution is referred to
as end point or equivalence point. The end point of volumetry
is indicated by substances called indicators. They undergo a
colour change at the completion of the reaction.
The reaction used in volumetric analysis must fulfill the
following conditions:
(i) The chemistry of the reaction should be known and it
should be represented by a definite chemical equation.
(ii) The reaction should be instantaneous and proceed to
completion over a fairly wide range of concentrations.
(iii) There must be means to know the exact state of its
completion.
The process of addition of the unknown solution from the
burette to the measured volume of solution of the substance to
be estimated untill the reaction between the two is just complete,
is termed as titration. Thus, a titration involves two solutions,
i.e., unknown and standard solution.
Indicators : An auxiliary substance which helps in the usual
detection of the completion of the titration or equivalence point
or end point is termed as indicator, i.e., substance which undergo
some easily detachable changes at the equivalence point are
used as indicators. They possess one colour in the presence
of an excess of the substance to be estimated and another colour
in the presence of an excess of the standard solution of the
reagent used and thus these substances indicate the exact end
point.
VOLUMETRIC ANALYSIS
Table 5.1. Range of important pH indicators
Indicator pH range Colour in acid Colour in alkaline Used in titration of a solution of
solution solution
Methyl-orange 3.0 4.4 Pink Yellow Strong acid against a weak base
Methyl red 4.4 6.3 Red Yellow Strong acid against a weak base
Litmus 6.0 8.0 Red Blue Strong acid against a strong base
Phenolphthalein 8.2 10.00 Colourless Pink Strong or weak acid against a strong base
Characteristics of a Good Indicator
(i) The colour change of the indicator must be clear and
sharp, i.e., it must be sensitive.
(ii) The pH range over which the colour change takes place
must be such as to indicate when the reaction is complete.
Indicators can be classified into several types, viz. (i)
neutralisation indicator (acid-base or pH indicators), (ii) oxidation-
reduction indicators, (iii) mixed indicators, (iv) adsorption
indicators (v) screened indicators (vi) universal indicators (vii)
metal indicators.
Exceptions :
(i) Litmus and phonolphthalein cant be used during titrations
in which carbon dioxide is liberated because when equal
amount of acid and alkali are used, the liberated CO
2
will
give the pH of the solution as 4. For these types of
titrations, methyl orange (3.0 4.4) or more satisfactorily
methyl yellow (2.9 4.0) are considered good. However,
for better results the liquid should be boiled to drive off
the carbon dioxidegas.
(ii) No indicator is suitable in titrations of a weak acid against
a weak base.
Theories of Indicators
(1) Ostwalds theory : According to this theory, indicators,
in general, are either weak acids or weak bases, with the
characteristic property of having different colours in the ionised
and unionised forms. For example, the ionisation of an acid
indicator or HIn may be represented as,
HIn H
+
+ In

weak acid colour B

colour A
The unionised molecule HIn has one colour (colour A), while
ionised ion In has another colour (colour B). The above ionisation
is characterised by,
K
In
=
[H ][In ]
HIn
+
or [H
+
] =KIn
[HIn]
[In]
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Use of Double Indicators
In the titration of alkali-mixture(NaOH +Na
2
CO
3
) or (NaCO
3
+NaHCO
3
) two indicators (phenolphthalein and methyl orange)
are used. For example, when an acid solution is added to a mixture
of NaOH and Na
2
CO
3
in presence of phenolphthalein indicator,
the pink colour of indicator is discharged. The end point
corresponds to complete neutralisation of NaOH and conversion
of Na
2
CO
3
to NaHCO
3
, i.e.,
NaOH +HCl NaCl +H
2
O ... (i)
andNa
2
CO
3
+HCl NaHCO
3
+NaCl ... (ii)
Let the titre value at this stage be equal to x ml.
Methyl orange is then added to the above solution
containing NaHCO
3
and acid is further added till a yellow to red
colour change is observed. This step corresponds to
neutralisation of NaHCO
3
, i.e.,
NaHCO
3
+HCl NaCl +H
2
O +CO
2
... (iii)
Let the titre value at this stage =y ml.
Total volume of acid used =(x + y) ml
From equations (ii) and (iii), it is evident that volume of the
acid required for complete neutralisation of
Na
2
CO
3
=2y ml
(Since 1 molecule of NaHCO
3
is produced from 1 molecule
of Na
2
CO
3
, the amount of acid required for reactions (ii) and (iii)
should be the same i.e., y ml).
Hence volume of acid required for neutralisation of NaOH
=(x + y) 2y
=(x y) ml
Using normality equation, the strength of NaOH and Na
2
CO
3
can be calculated.
When a mixture containing Na
2
CO
3
and NaHCO
3
is titrated
against an acid, the phenolphthalein indicator corresponds to
the reaction,
Na
2
CO
3
+HCl NaHCO
3
+NaCl ... (iv)
At this stage phenolphthalein changes colour from pink to
colourless. At this stage methyl orange is used and addition of
acid is continued. When NaHCO
3
originally present and formed
from reaction (iv) is neutralised, the colour changes from yellow
to red to mark the second end point corresponding to the
reaction:
NaHCO
3
+HCl NaCl +H
2
O +CO
2
... (v)
In this case let x ml of acid correspond to first end point
and y ml of acid correspond to second end point. From reactions
(iv) and (v), it is evident that x ml of acid is equivalent of half of
Na
2
CO
3
present in the mixture and y ml of acid is equivalent of
half of Na
2
CO
3
plus total NaHCO
3
present in the mixture. Hence
volume required for neutralisation of Na
2
CO
3
=2x ml ... (A)
and volume required for neutralisation of
NaHCO
3
=(y x) ml .... (B)
Where KIn is known as indicator constant.
Taking logarithms and changing the sign, we have
pH =p
KIn
+log
[In]
[HIn]
=p
KIn
+log
[Ionisedform]
[Unionisedform]
Thus colour of the indicator is determined by the ratio
[In/HIn] and is governed by the pH of the solution.
Salient features of Ostwald ionic theory of acid-base
indicators
(a) An acid-base indicator is usually a weak organic acid (e.g.,
phenolphthalein) or base (e.g., methyl orange). Its
undissociated form posseses a colour which is different
from its ions. Thus the colour change is due to ionisation.
(b) If the indicator is weak acid, the colour of its anions will
be deeper than that of unionised form. In case, it is base,
its cation is deep coloured than that anions.
(c) Although acid base indicators are weak electrolytes, their
dissociation increases on the addition of strong acid or
strong base.
The Quinonoid theory : This theory attempts to explain the
cause of colour in naturally occurring materials which contain
organic compounds. According to this theory, an indicator is an
equilibrium mixture of at least two tautomeric forms, one of which
can exist in an acid solution and the other in alkaline solution.
Sal ient features of qui nonoid theory of aci d-base
indicators
(a) Each acid-base indicator exists in two or more tautomeric
forms; one in acidic medium and the other in alkaline
solution.
(b) Colours of the two tautomeric forms are different due to
the difference in their structures. One of them has benzoid
structure which is either colourless or light coloured, while
the other has deep coloured quinonoid structure.
Approximate determination of pH of an indicator
The approximate pH of a solution can be determined by
comparing its effect on different indicators or on papers
impregnated with their solutions. Suppose that the following
colours were obtained when drops of an unknown solution were
mixed with drops of indicators solution on a spot plate.
Indicator Colour
Methyl orange Yellow or orange
Methyl red Yellow
Phenolphthalein Colourless
Phenol red Yellow
The orange colour of methyl orange indicates that pH >4.4
and the yellow colour of methyl red indicates that pH >6.2.
Since phenol red was turned yellow, the pH must be below 6.8.
Therefore, pH must be in the range 6.2 6.8 or roughly 6.5.
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To determine the amount of sodium hydroxide and sodium
carbonate in given mixture:
To determine the amount of sodium hydroxide and sodium
carbonate in a given mixture, we have to use two indicators,
phenolphthalein and methyl orange. When a mixture of sodium
hydroxide and sodium carbonate is titrated with a standard
solution of hydrochloric acid, using phenolphthalein as indicator,
the strong base is neutralised first.
NaOH +HCl NaCl +H
2
O ... (i)
After the completion of above reaction, the carbonate is
converted completely to bicarbonate.
Na
2
CO
3
+HCl NaHCO
3
+NaCl .... (ii)
At this point, phenolphthalein changes from pink to
colourless, marking the first end point. Methyl orange is added
now and orange-yellow colour is developed.
On adding acid, the bicarbonate is converted to carbonic
acid and colour changes to red, marking the second end point.
NaHCO
3
+HCl NaCl +H
2
CO
3
... (iii)
Let V
1
ml of acid be required upto first end point and V
2
ml
of acid be required from first end point to second end point.

Suppose, V ml of alkali solution is titrated with hydrochloric
acid of normality N. From the above readings, it is possible to
calculate the amounts of NaOH and Na
2
CO
3
.
Amount of NaOH in mixture =40 N
(V V )
V
1 2


g/L
Amount of Na
2
CO
3
in mixture =53 N
2V
V
2
g/L
To determine the amount of sodium carbonate and
bicarbonate in a mixture:
The method involves the successive use of two indicators,
phenolphthalein and methyl orange. When a cold mixture of
sodium carbonate and sodium bicarbonate is titrated against a
standard solution of hydrochloric acid, using phenolphthalein
as indicator, the sodium carbonate is converted into sodium
bicarbonate first and colour changes from pink to colourless,
marking the first end point.
Na
2
CO
3
+HCl NaHCO
3
+NaCl
If methyl orange is added at this stage, solution acquires
orange yellow colour. On further addition of the acid, all the
bicarbonate is neutralised and the colour changes to red. This is
the second end point.
NaHCO
3
+HCl NaCl +H
2
CO
3
Suppose V ml of mixture is titrated with a standard
hydrochloric acid of normality N. Let V
1
ml of the acid be required
upto first end point and V
2
ml of the acid be required from first
end point to second end point.

From these readings, it is possible to calculate the amounts
of sodium carbonate and sodium bicarbonate.
Amount of Na
2
CO
3
=53 N
2V
V
1
g/L
Amount of NaHCO
3
=84 N
(2V V )
V
2 1


g/L
To determi ne the amount of ni t rogen (Kj el dahl s
process) :
This method is used for the estimation of nitrogen in organic
substances. This method is based on the fact that when an
organic compound containing nitrogen is heated with
concentrated sulphuric acid, the nitrogen in it is converted
quantitatively into ammonium sulphate. The resultant liquid is
than treated with excess of sodium hydroxide and the liberated
ammonia gas is absorbed in excess of standard acid solution.
The unreacted acid is estimated by titration with standard alkali.
The difference of the two gives the volume of standard acid that
actually combines with the evolved ammonia. From this, the
percentage of nitrogen in the organic compound can be calculated.
Let the mass of organic substance be w g and V ml of N HCl
is required for complete neutralisation of evolved ammonia; then,
V ml N HCl

V ml N NH
3
17 g NH
3

14 g nitrogen
Amount of nitrogen in V ml N NH
3
=
40 N V
1000

% of nitrogen =
14 N V
w
where N stands for normality of acid used
V stands for volume of acid used
and w stands for mass of organic substance.
Various Types of Titrations
1. Acid-base titrations : The determination of acids/bases
by titration with standard base/acid e.g.
NaOH + HCl = NaCl +H
2
O
CH
3
COOH +NaOH =CH
3
COONa +H
2
O
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In these titrations H
+
ions of the acid combines with OH

ions of the alkali to form unionised molecules of water.

HA + BOH BA + H
2
O
Acid alkali salt water
With the use of organic dyes (weak acids/weak bases), the
end point in these titrations can be determined. Phenolphthalein
is used as an indicator in the titration of strong alkalies and
methyl orange is used as an indicator in the titration of strong
acids.
2. Redox titrations : The determination of strength of a
reducing agent/oxidising agent by titration with a standard
solution of oxidising/reducing agent, e.g.,
2KMnO
4
+10FeSO
4
+8H
2
SO
4
=K
2
SO
4
+2MnSO
4
+5Fe
2
(SO
4
)
3
+8H
2
O
K
2
Cr
2
O
7
+6FeSO
4
+7H
2
SO
4
=K
2
SO
4
+Cr
2
(SO
4
)
3
+3Fe
2
(SO
4
)
3
+7H
2
O
2KMnO
4
+3H
2
SO
4
+5H
2
C
2
O
4
=K
2
SO
4
+2MnSO
4
+8H
2
O +10CO
2
The chemical reaction proceed with transfer of electrons
(simultaneous loss or gain of electrons) among the reacting ions
in aqueous solution.
These titrations are named after the reagent used, as:
(i) Iodimetric titrations : The determination of reducing
agents by direct titrations with standard iodine solution is called
iodimetry. Reducing agent such as arsenite, sulphite, thiosulphate
and stannous chloride etc. are oxidised by iodine.
As
2
O
3
+2I
2
+2H
2
O =As
2
O
5
+4HI
2Na
2
S
2
O
3
+I
2
=Na
2
S
4
O
6
+2NaI
Since it is difficult to prepare the solution of iodine (volatile
and less soluble in water), it is dissolved in potasium iodide
solution.
KI + I
2
KI
3
potassium tri-iodide
(ii) Iodometric titrations : Indirect determination of oxidising
agents by titrations of liberated iodine from iodide like KI, with
standard Na
2
S
2
O
3
is called iodometric titrations. Oxidising agents
such as, K
2
Cr
2
O
7
, KMnO
4
, ferric salts, CuSO
4
etc. are reduced
quantitatively when treated with large excess of KI in acidic or
neutral medium and liberate equivalent amount of iodine.
2CuSO
4
+4KI =2CuI +2K
2
SO
4
+I
2
K
2
Cr
2
O
7
+7H
2
SO
4
+6KI =Cr
2
(SO
4
)
3
+4K
2
SO
4
+7H
2
O +3I
2
I
2
+2Na
2
S
2
O
3
=Na
2
S
4
O
6
+2NaI
In Iodimetric and iodometric titration, starch solution is used
as an indicator. Starch solution gives blue or violet colour with
free iodine. At the end point, the blue or violet colour disappears
when iodine is completely changed to iodide.
(iii) Dichromate titration : These are titrations in which,
potassium dichromate is used as an oxidising agent in acidic
medium. The chemical equation is
K
2
Cr
2
O
7
+4H
2
SO
4
K
2
SO
4
+Cr
2
(SO
4
)
3
+4H
2
O +3 [O]
or
Cr
2
O
7
2
+14H
+
+6e 2Cr
3+
+7H
2
O
It is mainly used for the titration of iodides and ferrous
sulphates. In the titration of K
2
Cr
2
O
7
versus ferrous salt, either
an external indicator (potassium ferricyanide) or an internal
indicator (diphenyl amine) can be used.
3. Precipitation titration : Determination of anions like
halide, cyanide, thiocyanate, arsenate, phosphate etc. by
precipitating with AgNO
3
provide examples of precipitation
titrations.
NaCl +AgNO
3
=AgCl +NaNO
3
KSCN +AgNO
3
=AgSCN +KNO
3
It depends on the formation of insoluble precipitates, when
the solution of two reacting substances are brought in contact
with each other.
4. Complexo metric titration : In this type of titration, an
undissociated complex is formed at the equivalence point. These
titrations are superior to precipitation titration as there is no
error due to co-operation.
Hg
2+
+2SCN

Hg (SCN)
2
Ag
+
+2CN

[Ag (CN)
2
]

EDTA is a useful reagent which forms complexes with metals.

In the form of disodium salt, it is used to estimate Ca
2+
and Mg
2+
ions in presence of erichrme black T as an indicator.
Law of Equivalence : According to this law, the chemical
substances react in the ratio of their chemical equivalent
masses.

Massof substanceA
Massof substanceB
Chemical equivalentmassof A
Chemical equivalentmassof B
=
or
Massof substanceA
Chemical equivalentmassof A
=
Massof substanceB
Chemical equivalentmassof B
Or milli-gram equivalent of A =milli-gram equivalent of B
Or gram equivalent of A =gram equivalent of B.
The point at which the amount of the reactants are just
equivalent is known as equivalence point or end point.
Methods of expressing concentration of solutions
The concentration of a solution can be expressed in various
ways :
Percent by mass : The percent by mass of a solute in a
solution is the mass of the solute divided by the total mass of
the solution times 100.
% solute =
Massof soluteingrams
Massof solutioningrams
100
Molarity (Molar concentration) : It is defined as the number
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of moles of the solute per litre of the solution.
Molarity =
Numberof molesof solute
Numberof litresof solution
Or Molarity Number of litre of solution =Number of moles
of solute
Molarity of the solution =
w
M V
Where w is weight of the solute
M is the molecular mass and V is volume of solution.
Strength of the solution (g/L) =Molarity Molecular mass
Molality : It is the number of gram moles of the solute present
in 1 kg of the solvent.
Molality =
Numberof grammolesof thesolute
Numberof kilogramsof thesolvent
Molality =
w M
W M W
/
/1000
w
1000 =

Where w is the weight of the solute
M is the molecular mass of the solute
W is the weight of the solvent.
Normality : The concentration of a substance in a given
volume of its solution is called its strength and is expressed as
(i) grams per litre or
(ii) gram-equivalent per litre (normality).
When a gram equivalent (equivalent weight in g.) of a
substance is contained in 1 litre of its solution, the solution is
described to be normal. The concentration of a solution
expressed in terms of normality represents the fraction or multiple
of a normal solution. Mathematically,
Normality (N) =
StrengthingLit
Equivalentweight
1
If w grams of the solute having equivalent mass E be present
in V litre of the solution. Normality =
w / e
V
Mole fraction : It is defined as the number of moles of the
substance divided by the total number of moles of the solution.
Take three components X, Y and Z.
Component X Y Z
Mass (grams) w
1
w
2
w
3
Molecular mass m
1
m
2
m
3
No. of gram moles
w
m
1
1
w
m
2
2
w
m
3
3
Total number of gram moles =
w
m
w
m
w
m
1
1
2
2
3
3
+ +
Mole fraction of X, (f
1
) =
w m
w
m
w
m
w
m
1 1
1
1
2
2
3
3
/
+ +
Mole fraction of Y, (f
2
) =
w m
w
m
w
m
w
m
2 2
1
1
2
2
3
3
/
+ +
Mole fraction of Z, (f
3
) =
w m
w
m
w
m
w
m
3 3
1
1
2
2
3
3
/
+ +
The sum of mole fractions of a solution is always equal, i.e.
to 1.
Relationship between normality and molarity : As we know
strength of the solution (g/L) =Normality equivalent mass
Similarly,
Strength of the solution (g/L) =Molarity Molecular mass
Thus,
Normality
Molarity
Molecularmassof thesubstance
Equivalentmassof thesubstance
=
=n
Normality =n Molarity
Normality Equation : As we know from the law of
equivalence, substances react in the ratio of their equivalent
weights. Hence equal volumes of equinormal solutions exactly
react with each other. Suppose N
1
and V
1
are the normality the
volume of one of the solution and N
2
and V
2
are the normality
and volume of the other solution, then according to the law of
equivalence
N
1
V
1
=N
2
V
2
This relation is called normality equation and is very useful
for volumetric calculations.
Equivalent Weight : For an element or compound it is defined
as the number of parts by weight of that element or compound
which combines with or displaces 1.008 parts by weight of
hydrogen or 8 parts by weight of oxygen or 35.45 parts by weight
of chlorine. The equivalent weights of different substances are
ascertained as follows :
(i) Equivalent weight of an element =
Atomicweight
Valency
(ii) Equivalent mass of an acid
=
Molecular massof the acid
Numberof replaceableHatoms
=
Molecular massof theacid
Numberof replaceableHatoms
(iii) Equivalent mass of a base
=
Molecularmassof thebase
Acidityof thebase
(iv) Equivalent mass of a salt =Mol. mass of the salt Total
no. of positive or negative valencies of the radicals.
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(v) Equivalent mass of an oxidising agent.
(a) Available oxygen concept : It is the mass of an oxidising
agent which provides 8 grams of oxygen for oxidation. For example,
K
2
Cr
2
O
7
+4H
2
SO
4
K
2
SO
4
+Cr
2
(SO
4
)
3
+4H
2
O +3 [O]
294.2 g 48 g
Eqv. mass of K
2
Cr
2
O
7
=
2942
48
8
.
=49.04
Acidic medium :
2KMnO
4
+2KOH K
2
MnO
4
+H
2
O +[O]
2 158 g 16 g
Eqv. mass of KMnO
4
=
2 158
16

8 =158
Neutral medium :
2KMnO
4
+H
2
O 2MnO
2
+2KOH +3[O]
2 158 g 3 16 =48 g
Eqv. mass of KMnO
4
=
2 158
48
8

=
158
3
=52.67
(b) Oxidation number concept : According to this concept
Equivalent mass =
Molecularmass
Total changeinoxidationnumber
e.g., KMnO
4
(acidic medium),
KMnO MnSO
+7 2
4 4
+
Change in O.N. =(7 2) =5
Equivalent mass =
Mol.mass
5
=
158
5
=31.6
(c) Electron concept : According to this concept
Eqv. mass of an oxidising agent
=
Molecularmass
No.of electronsgainedby1mole
e.g.,
in Acidified KMnO
4
MnO
4

+8H
+
+5e Mn
2+
+4H
2
O
Eqv. mass of KMnO
4
=
Molecularmass
5
=
158
5
=31.6.
Table 5.2 Equivalent weight of Acids, Bases and Salts.
Formula Mol. wt. Total positive character Eq. wt.
HCl 36.5 1 (H
+
) 36.5
H
2
SO
4
98 2 (2H
+
) 40
(COOH)
2
90 2 (2H
+
) 45
NaOH 40 1 (Na
+
) 40
KOH 56 1 (K
+
) 56
Na
2
CO
3
106 2 (Na
+
) 53
CaCO
3
100 2 (Ca
2+
) 50
Hardness of Water
The hardness of water is due to the presence of bicarbonates,
chlorides and sulphates of calcium and magnesium. The hardness
is temporary if there are bicarbonates and is permanent when
chlorides and sulphates of calcium and magnesium are present.
The extent of hardness is known as degree of hardness. It is
expressed as equivalents of calcium carbonate, though it may
actually be caused by other salts. Hence, it may be defined as
the number of parts by weight of calcium carbonate (or its
equivalent), present per million parts by weight of water. Thus
if water contains 50 parts of MgSO
4
per million parts of water, its
degree of hardness will be 50 p.p.m., i.e., 50 parts per million
because
1 g mol of MgSO
4
=1 g mol of CaCO
3
120 g =100 g
60 g =50 g
In actual determination of degree of hardness, titration is
carried out with a standard soap solution or with E.D.T.A
(ethylene diamine tetra acetic acid).
Water softener
There are various types of water softeners.
(i) Washing soda : When water is boiled with Na
2
CO
3
both
temporary and permanent hardnesses are removed.
CaCl
2
+Na
2
CO
3
CaCO
3
B
+2NaCl.
(ii) Slaked lime : Clark used slaked lime to remove hardness.
Bicarbonates of calcium and mangesium are converted into
insoluble carbonates.
Ca (HCO
3
)
2
+Ca(OH)
2
2CaCO
3
+2H
2
O
insoluble
Mg (HCO
3
)
2
+Ca (OH)
2
MgCO
3
+CaCO
3
+2H
2
O
insoluble
(iii) The hardness can also be removed by alums, ion-
exchange resins and permutit. Permutit is an artificial zeolite, i.e.,
sodium aluminium orthosilicate (Na
2
Al
2
Si
2
O
8
.x H
2
O)
CaCl
2
+Na
2
Al
2
Si
2
O
8
Ca (Al
2
Si
2
O
8
) +2NaCl
Here Ca
++
ion is replaced by Na
+
ion and is retained as calcium
zeolite. Ions present in water can be removed by means of ion
exchange resins. Water is first passed through cation exchange
resins (gaint organic molecules with SO
3
H or COOH groups),
which removes the cations like Na
+
, Ca
2+
, Mg
2+
and others by
exchange with H
+
. Resulting water is now passed through anion
exchange resins (organic molecules with NH
2
group), which
removes the anions like Cl

, SO
4
2
and NO
3

by exchange with
OH

ions.
(iv) Calgon process : Hard water is percolated over calgon
(sodium hexa meta phosphate Na
6
P
6
O
18
). Ca
2+
and Mg
2+
present
in hard water react with calgon to give complex ion, which do
not react with soap to form any ppt.
Ca
2+
+Na
2
Na
4
(PO
3
)
6
4Na
+
+Na
2
Ca (PO
3
)
6
2
EDUACHIEVERS ACADEMY Volumetric Analysis 5
www.winiit.com,www.winaieee.com,www.winbitsat.com
eduachievers 2011

7
E
D
U
A
C
H
I
E
V
E
R
S

A
C
A
D
E
M
Y
Estimation of Permanent Hardness
It is due to the presence of chloride and sulphate of calcium
and magnesium in water. For the estimation, water is treated with
Na
2
CO
3
solution, where chlorides and sulphates are converted
into carbonates (insoluble).
CaCl
2
+Na
2
CO
3
CaCO
3
+2NaCl
MgSO
4
+Na
2
CO
3
MgCO
3
+Na
2
CO
4
So the water sample is boiled with Na
2
CO
3
upto dryness
and from the amount of Na
2
CO
3
consumed, the permanent
hardness can be estimated.
Estimation of Temporary Hardness
The temorary hardness is due to bicarbonates of calcium
and magnesium, which is estimated with HCl or H
2
SO
4
as
Ca (HCO
3
)
2
+H
2
SO
4
CaSO
4
+2H
2
O +2CO
2
Mg (HCO
3
)
2
+2HCl MgCl
2
+2H
2
O +2CO
2
So, temporary hardness can be estimated by titrating water
with acids, using methyl orange as an indicator.
Formulae used in volumetric analysis
Molarity (M) =mol L
1
solution =
1000
1
1
w
m V
Normality (N) =g eqv. L
1
solution =
1000
1
1
w
m V
Molality
' M
=mol kg
1
solvent =
1000
1
1 2
w
m w
' M
=
1000
1000
1
M
M ( ) d m
where d =density (g ml
1
) of solution
In case of dilution, from one conc. to other
N
1
V
1
=N
2
V
2
M
1
V
1
=M
2
V
2
but In redox and neutralisation reaction
N
1
V
1
=N
2
V
2
Normality of an acid =molarity basicity (of acid)
Normality of a base =molarity acidity (of a base)
Normality of mixture of strong acid or base =
E
E
NV
V
Normality of mixture of strong acid and strong base
(i ) If N
1
V
1
(acid) =N
2
V
2
(base) then mixture is neutral.
(ii) If N
2
V
2
(acid) >N
2
V
2
(base) then mixture is acidic.
(iii) N (acid) =
N V N V
V V
1 1 2 2
1 2

+
(iv) If N
1
V
2
(acid) <N
2
V
2
(base) then mixture is basic.
(v) N (base) =
N V N V
V V
2 2 1 1
1 2

+
(vi) If a number of acids are mixed, the combined normality
of the mixture, N
x
is given by
N
x
V
x
=N
1
V
1
+N
2
V
2
+N
3
V
3
+.....
where V
x
is the total number of the mixture, N
1
and V
1
are the normality and volume respectively of one acid,
N
2
and V
2
of second acid and so on.