Name: Reg.

No:

Alkalinity measurement
Experiment: Measurement of alkalinity of given samples of water and determination of concentrations of
alkalinity constituents.

Apparatus Required: Burette, Pipette, Conical flask, Measuring cylinder, pH meter with electrodes, Beaker.

Reagents Required: Phenolphthalein indicator, Methyl orange Indicator, 0.02N H2SO4 solution.

Theory: Alkalinity of a water sample is operationally defined as its acid or H+ ion neutralizing capacity. The
ions which commonly contribute to alkalinity are OH−, CO32− and HCO3−. Out of these, HCO3− represents the
major form of alkalinity in natural waters. Bicarbonates are formed when water containing carbon dioxide
dissolves calcium and magnesium carbonates from soil and rocks. Other sources of alkalinity in natural waters,
which may by present in small amounts, are borates, silicates, phosphates and salts of organic acids.

When acid or H+ ions are added to water in a titration, the following equilibrium reactions are affected:

H+ + OH− ↔ H2O (1)

H+ + CO32− ↔ HCO3− (2)
H+ + HCO3− ↔ H2CO3 (3)

With the addition of H+ ions, in each of the reactions, the equilibrium shifts towards right; the added H+ ion
combines with the alkalinity producing ion to form the specie on the right of the equilibrium expression. Thus
there is only a marginal increase of H+ ions or decrease in pH. The titration is said to be complete when the pH
is reduced to 4.5. At this pH greater than 99% of the CO32− and HCO3− specie are converted to H2CO3. The
concentration of OH− ions, or the hydroxide alkalinity, is considered to be negligible if the pH is less than 10.

If the pH of the sample is greater than 8.3, the alkalinity titration is conducted in two steps. First it is titrated to
pH 8.3, using phenolphthalein as an indicator, which gives a pink colour at pH values higher than 8.3 and
becomes colourless at lower values. At this pH, 50% of the CO32− ions originally present in the sample are
converted to HCO3−. This portion of the alkalinity is called phenolphthalein alkalinity. Titration of the same
aliquot of the sample is then continued using methyl orange as an indicator, which turn from orange to red at pH
4.5. The total amount of the acid used represents the total alkalinity. The alkalinity of water is conventionally
expressed in terms of an equivalent amount of mg CaCO3/L.

Alkalinity is an important characteristics of water and wastewater. It influence the equilibrium among chemical
species of importance in environmental processes, effectiveness of coagulation and precipitation reactions in
water treatment, potential of water to be corrosive, suitability of aqueous environment to support organisms, etc.
Alkalinity in natural waters provides a buffering system against sharp changes in pH, which otherwise would
occur due to production or consumption of carbon dioxide and organic acids by normal aquatic flora or addition
of acidic or alkaline wastes from anthropogenic sources.

Procedure:
1. Take 50 mL water sample in a 150 mL beaker and add two drops of phenolphthalein indicator; if a slight
pink color appears it means phenolphthalein alkalinity is present in the water sample.
2. Put the beaker over a magnetic stirrer and put a clean magnetic needle in the beaker. Turn on the magnetic
stirrer at a lower speed so as to mix the liquid content gently.
3. Lower the pH electrode carefully in the beaker without touching (a) the bottom of the beaker and (b) the
rotating magnetic needle.
4. Fix the burette (filled with 0.02 N H2SO4 solution) in vertical position over the beaker keeping the outlet tip
within beaker perimeter.
5. Add a few drops of 0.02 N H2SO4 solution in the beaker and record the stable pH reading. Continue the
titration till the solution becomes colourless or reaches pH near to 8.3.
6. Thereafter add two drops of methyl orange indicator and continue the titration till the colour becomes red or
pH reading of 4.5.

Record Your Observations:

When 0.02 N H2SO4 is used in the titration, then 1 mL of the acid neutralizes 1 mg of alkalinity as CaCO3.

River Water Sample Wastewater Sample Synthetic Sample

Sample Vol. = mL Sample Vol. = mL Sample Vol. = mL
mL of 0.02N mL of 0.02N mL of 0.02N
pH pH pH
H2SO4 used H2SO4 used H2SO4 used

Signature of Teaching Assistant

Analysis of the Recorded Data/Observations:

Plot pH on y-axis vs mL 0.02 N H2SO4 on x-axis on a simple log paper. Find out the two inflection points and
calculate the concentrations of alkalinity species (see Example 2-7 of Environmental Engineering by Peavy,
Rowe and Tchobanoglous).

Further Reading:

1. Chapter 2320 dealing with Alkalinity from Standard Methods for Examination of Water and Wastewater by
APHA, AWWA & WEF from Water Environment Federation, USA
2. Chapter 17 dealing with Alkalinity from Chemistry for Environmental Engineering and Science by Clair
Sawyer, Perry McCarty & Gene Parkin from Tata McGraw Hill India.