EXPERIMENT NO.

– 1

Aim:- Measurement of alkalinity in the a given water sample.

Chemical Rrquired:- N/30 HCl, phenolphthalein, methyl orange, water sample.
Apparatus Required:- Conical flasks, burette, pipette, reagent droppers.
Theory:- Determination of alkalinity due to different ions is based on the titration of the water
sample against a standard acid making selective use of indicators. The indicators used are
phenolphthalein and methyl orange. The reactions taking place may be represented by the
following equations:
(a) OH– + H+ → H2O
(b) CO32– + H+ → HCO3- P
(c) HCO3– + H+ → CO2 + H2O M
The volume of the acid used upto phenolphthalein end point corresponds to the reaction (a) and
(b) i.e. complete neutralization of OH- ions and half neutralization of CO32– ions upto HCO3-
stage.
The volume of the acid used upto methyl orange end point corresponds to the reaction (a), (b)
and (c) i.e. complete neutralisation of OH¯, CO32– and HCO3– ions.
Thus from the respective volume of the acid used, the respective strengths of various ions can be
determined.
A known volume of the sample is titrated against a standard acid using phenolphthalein as
indicator and alkalinity is found out in terms of CaCO3 equivalents by using normality equation.
This alkalinity is called phenolphthalein alkalinity (P). Similarly the sample is titrated against a
standard acid using methyl orange as indicator and alkalinity is calculated in terms of CaCO3
equivalents. This alkalinity is called methyl orange alkalinity (M) or total alkalinity of water
sample.
From the measurement of phenolphthalein alkalinity and methyl orange alkalinity, it is possible
to calculate the magnitude of various forms of alkalinity present in water sample,
1. Alkalinity due to HCO3– only.
2. Alkalinity due to CO32– only.
3. Alkalinity due to CO32– and HCO3– .
4. Alkalinity due to CO32– and OH–.
5. Alkalinity due to OH– only.
Discussion:- Case I When phenolphthlein alkanity = 0 this implies that volume of the acid used
till the phenolphthlein end point is 0.This can only happen if CO32- and OH- both are absent.
Whatever alkanity is present is due to HCO3- ions and can be detected using methyl orange as
indicator.
Case II When P = 1/2M this implies that only CO32- ions are present. Neutralization using
phenolphthlaein as indicator reaches upto HCO-3 .Same amount of acid will be further used when
methyl orange is used as indicator to neutralize HCO -3 to water and CO2 as represented. The
strength of carbonate will be given by M or 2P.
Figure: Relative amounts of acid used, using phenolphthalein and methyl orange as indicator.

Case III when P < 1/2 M ,this implies that besides carbonate ions,HCO32- ions are also present.
The acid used uptil phenolphthlein end point corresponds to half neutrlisation of carbonate ions.
Further titrations using methyl orange as indicator corresponds to neutralization of HCO 32-
obtained from carbonate ions and HCO3 - originally present in the reaction.
Alkalinity due to CO32– = 2P
Alkalinity due to HCO32 = ( M – 2 P)
Case IV when P > 1/2M .This implies that besides CO32- ,OH will be completely neutralized by
the acid whereas CO32- will be neutralized upto HCO -3 stage using phenolphthlein as indicator.
On further titration with the acid using methyl orange as indicator, the neutralization of
carbonate takes place.
Alkalinity due to CO32– = 2 ( M – P )
Alkalinity due to OH¯ = M – 2 ( M – P ) = ( 2P – M )
Case (V) When P = M implies that only OH¯ ions are present.
Alkalinity due to OH¯ = P = M

Thus on the basis of the analysis of water with respect to phenolphthalein alkalinity and methyl
orange alkalinity, the alkalinity due to different ions can be calculated. The results are
summarized in the following table;
 Alkanity OH- CO2-3 HCO3-
P=0 NIL NIL M
P=½M NIL 2P NIL
P<½M NIL 2P ( M – 2P )
P>½M ( 2P – M ) 2(M–P) NIL
P=M P=M NIL NIL

Indicator:- Phenolphthalein and methyl orange.

End point:- pink to colourless, yellow to red.
Procedure:-
(i) Rinse and fill the burette with 1/30 N HCl. Note the initial burette reading.
(ii) Pipette out 20 ml of water sample into a conical flask. Add 1-2 drops of phenolphthalein.
Pink colour may or may not appear.
(iii) If pink colour in conical flask appears then titrate the water sample with 1/30 N HCL till
the pink color disappears.
(iv) Note down the burette reading upto phenolphthalein end point.
(v) Now add 1-2 drops of methyl orange indicator into the same water sample. Yellow colour
appears.
(vi) Titrate it with 1/30 N HCl till a red color is obtained.
(vii) Record the observation and repeat the experiment to get three concordant readings.

Observations:-
a) Water sample I
Normality of HCl used = 1/30 N
Volume of solution taken in titration flask (V w) = _____ml
Burette Reading upto Burette Reading upto methyl orange
S.No.
phenolphthalein end point end point
Initial Final Vol used Initial Final Vol used
Reading Reading (ml) (V1) Reading Reading (ml) (V2)
1.

2.

3.

4.

Concordant Volume = ml Concordant Volume = ml

Volume of the acid used upto phenolphthalein end point (V 1) = _____ml

 Volume of the acid used upto methyl orange end point (V 1 + V2) = _____ml

b) Water sample II
Normality of HCl used = 1/30 N
Volume of solution taken in titration flask (V w) = _____ml
Burette Reading upto Burette Reading upto methyl orange
S.No.
phenolphthalein end point end point
Initial Final Vol used Initial Final Vol used
Reading Reading (V1´) Reading Reading (V2´)
1.

2.

3.

4.

Concordant Volume = ml Concordant Volume = ml

Volume of the acid used upto phenolphthalein end point (V 1´) = _____ml
Volume of the acid used upto methyl orange end point (V 1´ + V2´) = _____ml

c). Water sample III

Normality of HCl used = 1/30 N
Volume of solution taken in titration flask (Vw) = _____ml
Burette Reading upto Burette Reading upto methyl orange
S.No.
phenolphthalein end point end point
Initial Final Vol used Initial Final Vol used
Reading Reading (V1´) Reading Reading (V2´)
1.

2.

3.

4.

Concordant Volume = ml Concordant Volume = ml

Volume of the acid used upto phenolphthalein end point (V 1´) = _____ml
 Volume of the acid used upto methyl orange end point (V 1´ + V2´) = _____ml

Calculations:-
a) Water sample I

i) Phenolphtalein alkalinity in terms of CaCO3 equivalents

NPVw = N1V1
Water sample Acid

NP = ______

Strength in terms of CaCO3 equivalents = NP x Equivalent weight of CaCO3 (50)

= X = ________g / L
Therefore, Phenolphthlein alkalinity = X x 1000 mg / L

= _________mg / L = ________ppm

ii) Methyl orange alkalinity in terms of CaCO3 equivalents

NM (Vw) = N1 (V1 + V2)
Water sample Acid

NM = ______N
Strength in terms of CaCO3 equivalents = NM x Equivalent weight of CaCO3

= Y = ________g / L
Therefore, Phenolphthlein alkanity = Y x 1000 mg / L

= _________mg / L = ________ppm

b) Water sample II

i) Phenolphtalein alkalinity in terms of CaCO3 equivalents

NP´ Vw = N1V1´
Water sample Acid

NP´ = ______N
Strength in terms of CaCO3 equivalents = NP´ x Equivalent weight of CaCO3 (50)

= X´ = ________g / L
Therefore, Phenolphthlein alkalinity = X´ x 1000 mg / L

= _________mg / L = ________ppm
ii) Methyl orange alkalinity in terms of CaCO3 equivalents
NM´ (Vw) = N1 (V1´ + V2´)
Water sample Acid
 NM´ = ______N
Strength in terms of CaCO3 equivalents = NM´ x Equivalent weight of CaCO3 (50)

= Y´ = ________g/L
Therefore, Phenolphthlein alkanity = Y´ x 1000 mg/L

= _________mg/L = ________ppm

c) Water sample III

iii) Phenolphtalein alkalinity in terms of CaCO3 equivalents

NP´ Vw = N1V1´
Water sample Acid

NP´ = ______N
Strength in terms of CaCO3 equivalents = NP´ x Equivalent weight of CaCO3 (50)

= X´ = ________g / L
Therefore, Phenolphthlein alkalinity = X´ x 1000 mg / L

= _________mg / L = ________ppm
iv) Methyl orange alkalinity in terms of CaCO3 equivalents
NM´ (Vw) = N1 (V1´ + V2´)
 Water sample Acid

NM´ = ______N
Strength in terms of CaCO3 equivalents = NM´ x Equivalent weight of CaCO3 (50)

= Y´ = ________g/L
Therefore, Phenolphthlein alkanity = Y´ x 1000 mg/L

= _________mg/L = ________ppm

d) Ions causing the alkalinity:

To find out the alkalinity in terms of individual ions, we find out to which case the value of
P and M falls and from table we calculate the amount of individual ions

Results:-
a) Water sample I
Phenolphthalein alkalinity = ______ ppm of CaCO3.
Methyl orange alkalinity = ________ ppm of CaCO3.
Ions causing alkalinity =
b) Water sample II
Phenolphthalein alkalinity = ______ ppm of CaCO3.
Methyl orange alkalinity = ________ ppm of CaCO3
Ions causing alkalinity =
c) Water sample III
Phenolphthalein alkalinity = ______ ppm of CaCO3.
Methyl orange alkalinity = ________ ppm of CaCO3
Ions causing alkalinity

Precautions:-
1. End point must be noted carefully.
2. Initial and final reading must be noted cautiously.
3. While observing the end point for methyl orange, always compare with colour of sample
having methyl orange indicator before titration.

Viva-Voce Question
1. Define Alkalinity of water.
2. What do you mean by phenolphthalein and methyl orange alkalinity?
3. What is the principle of EDTA titration?
4. What will be observed is methyl orange indicator is added first in the titration?
5. Explain the various trends observed with phenolphthalein and methyl orange alkalinity
values.
6. What are the disadvantages of hard water?
7. What is standard hard water (SHW)? Why titration with (SHW) is carried out?
8. How does the behavior of indicator changes with pH?