2P Determination of alkalinity and acidity in water
Mohammad Ali
Chemist
The alkalinity is the quantitative capacity of aqueous media to react with hydrogen ions. The
alkalinity of natural or treated water is normally due to the presence of calcium, magnesium,
sodium and potassium. Borates, phosphates and silicates also contribute to alkalinity.
Most waters contain bicarbonate and carbonates only. The occurrence of hydroxide ions in
natural waters is very rare, unless artificial contamination has occurred. In surface waters
where algae are flourishing the waters may contain appreciable amounts of carbonate and
hydroxide alkalinities. Boiler water usually contains carbonate and hydroxide alkalinities.
Chemically treated waters, particularly softened waters (by lime or lime soda process)
contain carbonates and hydroxide.
Phenolphthalein / Methyl orange are the indicators commonly used for alkalinity titrations.
Phenolphthalein gives a pink color in presence of hydroxide or normal carbonate. The
change from pink to colorless occurs of pH 8.3. Methyl orange gives yellow color in presence
of all three types of alkalinities and is orange in presence of acid. The color change occurs at
a pH value of about 4.5.
The volume of acid required for the first end point (P-
alkalinity) is due to the OH- neutralization and 8 8.3
convention of CO32- to HCO3-
The second end point represents the complete
conversion of HCO3- to H2CO3
4 4.5
1
ml of 0.02N H2SO4
Fig: Electronic end point
If there is phenolphthalein(P-alkalinity) alkalinity it is due to hydroxide or carbonate or both. If
there is methyl orange alkalinity it is due to any one of the alkalinities or hydroxides and
carbonate together. It is to be stated that hydroxide and bicarbonate alkalinities can not co-
exist together. Methyl orange alkalinity after termed as M-alkalinity or total alkalinity.
Calculation of three forms of alkalinity:
The titre values obtained from phenolphthalein and total alkalinity determines are used to
estimate the three forms of alkalinity as shown in the following table:
Hydroxide alkalinity as Carbonate alkalinity as Bicarbonate alkalinity
If
CaCO3 CaCO3 as CaCO3
P=0 0 0 T
P<½T 0 2P T – 2P
P=½T 0 2P 0
P>½T 2P – T 2 (T-P) 0
P=T T 0 0
Where P is phenolphthalein alkalinity and T is total alkalinity (It is assumed that the entire
alkalinity is due to the presence of bicarbonate, carbonate and hydroxide only and other ions
contributing to alkalinity are absent.)
Interpretation of the result:
Is really an expression of buffering capacity, if essentially absorbs the excess of H + ions and
protects the water body from the fluctuation in pH. In most natural water bodies, the buffering
system is carbonate- bicarbonate.
Alkalinity is important for fish and aquatic life because it protects or buffers against rapid pH
changes. Living organisms’ especially aquatic life; function best in pH range of 6.0 to 9.0.
Alkalinity is a measure of how much acid can be added to a liquid without causing a large
change in pH. Higher alkalinity levels in surface waters will buffer acid rain and other acids
wastes and prevent pH changes that are harmful to aquatic life.
The determination of alkalinity of provides an idea of the nature of salts present.
If the alkalinity is equal to hardness calcium and magnesium salts are only present.
If the alkalinity is greater than hardness, it indicates the presence of basic salts; sodium
and potassium in addition to those of calcium and magnesium.
If alkalinity is less than hardness neutral salts of calcium or magnesium must be present
that are not carbonates; usually these are sulphates.
Alkalinity is an important parameter involved in corrosion control. It must be known in
order to calculate the Langelier Saturation Index.
Alkalinity measurements are used as the means of evaluating the buffering capacity of
waste waters and sludges.
Alkalinity and pH are the factors in determining the amenability of waste waters to
biological treatment.
Name: . . . . . . . . . . . S.N. . . . . . . . . .
Determination of Alkalinity
01. Principle: Alkalinity of water is normally due to presence of hydroxide, carbonate
bicarbonate ions and is directly determined by titration with standard acid solution.
02. Reagents: (a) Standard 0.01M HCl solution, (b) methyl orange indicator (c)
phenolphthalein indicator.
03. Apparatus & Instruments: a) Conical Flask, b) burette, c) pipette, etc.
04. Procedure:
(1) Take 50 ml sample in a conical flask
(2) Add 3 drops phenolphthalein indicator if no pink coloration occurs there is no
phenolphthalein alkalinity
(3) Titrate with 0.01M HCl solution
(4) Add 2 drops of methyl orange indicator
(5) Titrate with0. 0.01M HCl solution
[Link] for P-Alkalinity:
S.N Vol. of Burette reading Average
sample
Initial Final Difference
[Link] for Total or M-Alkalinity
S.N Vol. of Burette reading Average
sample
Initial Final Difference
BR x Molarity xDf x MW of CaCO3 x106
06. Calculation: = Sample Volume×1000×Ef
Sample weight x 1000