Determination of

Alkalinity in Water
 Alkalinity
• Alkalinity is the water's capacity to resist changes
in pH that would make the water more acidic,
simply Acid neutralizing Capacity (ACN)
• This is an expression of buffering capacity. A buffer
is a solution to which an acid can be added
without changing the concentration of available
H+ ions (without changing the pH) appreciably
• Total alkalinity is a sum of carbonates, bi-
carbonates and Hydroxyl ions.
• Higher alkalinity provides buffer against pH
changes.
 Causes of alkalinity
• Natural causes of alkalinity are the rocks
which contain carbonate, bicarbonate, and
hydroxide compounds.
• Limestone is rich in carbonates, so waters
flowing through limestone regions or bedrock
containing carbonates generally have high
alkalinity - hence good buffering capacity.
• Brackish water or seawater typically has Total
Alkalinity of 100 to 125 mg/L.
• PEQS require for CaCO3 to be below 500 mg/l
 Significance of Alkalinity
• Rain and snow melt  acidity (dangerous for
aquatic life)
• Acidic depositions also causes the metals to
leach
• Carbonates and biocarbonates help in
mitigating metal toxicity, making them
unavailable for aquatic organisms
 Principle of Determination
• Alkalinity is expressed as phenolphthalein alkalinity or
total alkalinity (Methyl Orange)
• For samples whose initial pH is above 8.3, the
titration is conducted in two steps.
• In the first step, the titration is conducted with
phenolphthalein until the pH is lowered to 8.2,
corresponding to the conversion of carbonate to
bicarbonate ion.
• The second phase of titration is conducted until the
pH is lowered to 4.5, corresponding to methyl orange
end point, the conversion of bicarbonate ion to
carbonic acid.
 Determination of alkalinity (Titration
Method)
Apparatus
Burette
Flask
Pipette
Dropper

Reagents
• Carbon dioxide free distilled water
• Phenolphthalein indicator
• Methyl orange indicator
• 0.1 N sodium thiosulphate solution
• 0.02 N sulphuric acid.
• Phenolphthalein is used as a colorimetric
indicator of alkalinity and acidity first endpoint
• It changes color at about pH 8.3, the pH that
signifies loss of OH‐ and where all carbonates
are as HCO3 ‐
• Methyl Orange is used as a colorimetric
indicator of the final alkalinity titration
endpoint
• It changes color at about pH 4.5 where all
carbonates are as H2CO3
 Procedure
• Pipette 50 mL of sample into a clean Erlenmeyer flask
(V).
• Add one drop of sodium thiosulphate solution, if
residual chlorine is present.
• Add two drops of phenolphthalein indicator; if the pH
is above 8.3, color of solution becomes pink.
• Titrate against standard sulphuric acid in the burette,
till the color just disappears. Note down the volume
(V1).
• Then add two drops of methyl orange indicator, the
color turns yellow.
• Again titrate against acid, until the color turns to
orange yellow. Note down the total volume (V2).
 Calculations
V1 x 1000
1. Phenolphthalein alkalinity (P) as
mg/L CaCO3 =
mL of sample

V1 x 1000 V  x 1000

1. Phenolphthalein alkalinity (P) 2
2. Total alkalinity (T) as mg/L CaCO
as mg/L CaCO3 = mL
3
of sample
=
mL of sample