ALKALINITY

The alkalinity of water is measure of its capacity to neutralize acids. The alkalinity of
natural water is due to the salts of carbonate, bicarbonate, borates, silicates and
phosphates along with the hydroxyl ions in free state. However the major portion of
the alkalinity in natural water is caused by hydroxide, carbonate and bicarbonate,
which may be ranked in order of their association with high pH values. Alkalinity
values provide guidance in applying proper doses of chemicals in water and
wastewater treatment processes, particularly in coagulation and softening.

Principle

Alkalinity of a sample can be estimated by titration with standard sulphuric acid.
Titration to pH 8.3 or decolourisation of phenolphthalein indicator will indicate
complete neutralization of pH and of CO3 while to pH 4.5 or sharp change from
yellow to pink or methyl orange indicator will indicate total alkalinity (complete
neutralization of OH, CO3, HCO3).

Reagents

1. Standard H2SO4 (0.02 N): - Prepare 0.1 N H2SO4 by diluting 3.0 ml conc. H2SO4 to
1000 ml. Standard it against standard Na2CO3 0.1 N. Dilute appropriate volume of
H2SO4 (approx. 0.1 N) to 1000 ml to obtain standard 0.02 N H2SO4.

2. Phenolphthalein Indicator: - Dissolve 5 gm in 500 ml 95% ethyl alcohol. Add 500 ml
distilled water. Add drop-wise 0.02 N NaOH till faint colour appears.

3. Methyl Orange Indicator: - Dissolve 0.5 gm and dilute to 1000 ml with CO2 free
distilled water.

Procedure

1. Take 25 or 50-ml sample in a conical flask and add 2-3 drops of phenolphthalein
indicator.


2. If pink colour develops titrate with 0.02 N H2SO4 till it disappears or pH is 8.3. Note the
volume of H2SO4 required.

3. Add 2-3 drops methyl orange to the same flask and continue titration till pH down to 4-
5 or orange colour changes to pink.

Note the volume of H2SO4 added

4. In case pink colour does not appear after addition or phenolphthalein continue as in 3
above.

5. Calculate Total (T) phenolphthalein (P) and methyl orange alkalinity as follows and
express in mg/l as CaCO3.

P - Alkalinity, mg/l as CaCO3 = A x 1000/ml sample
MO - Alkalinity, mg/l as CaCO3 = B x 1000/ml sample
T - Alkalinity, mg/l as CaCO3 = (A + B) x 1000/ml sample
In case H2SO4 is not 0.02 N apply the following formula:-

Alkalinity, mg/l as CaCO3 = A x N x 50,000 / ml sample

Where,

N = Normality of H2SO4 used.

Once the phenolphthalein and total alkalinity is determined, then three types of alkalinities
i.e. hydroxide, carbonate and bicarbonate are easily, calculated from the table below: -

Values of P &
T
OH CO3 HCO3
P = 0 0 0 T
P < T 0 2p T-2p
P = T 0 2p 0
P > T 2p-T 2(T-p) 0
P = T T 0 0



ACIDITY

Method - Titration

Principle

Hydrogen Ions present in a sample as a result of dissociation or hydrolois of solute react
with additions of standard alkali.

Procedure

1. ml of sample
2. If the pH is above 4.0 then add 0.02 N sulfuric acid (H2SO4) to reduce pH to 4 or less.
3. Add 5 drops (30%) H2O2
4. Then boil for 2 to 5 minutes
5. Cool to room temperature
6. Add phenolphthalein indicator
7. Titrate with standard alkali solution of0.02 N NaOH solution

Calculation

Acidity, as mg CaCO3/l = [(AxB)-(CxD) x 50,000 / ml of sample

Where,

A = ml NaOH titrant used
B = Normality of NaOH
C = ml H2SO4 used and
D = Normality of H2SO4