Experiment 2
Aim: To estimate the total alkalinity of an industrial effluent water sample by titration with
standard hydrochloric acid using phenolphthalein and methyl orange indicators.
Principle: Alkalinity is the capacity of water to neutralize acids and is primarily due to the
presence of hydroxide (OH⁻), carbonate (CO₃²⁻), and bicarbonate (HCO₃⁻) ions. Industrial
effluents often contain these alkaline constituents because of the discharge of chemicals from
industries such as textiles, paper, detergents, electroplating, and food processing.
The determination of alkalinity is carried out by titrating the water sample with a standard
hydrochloric acid (HCl) solution. Phenolphthalein indicator is first used to determine
phenolphthalein alkalinity (endpoint at pH ≈ 8.3), followed by methyl orange indicator to
determine total alkalinity (endpoint at pH ≈ 4.5). The total alkalinity is expressed as mg/L of
CaCO₃, which is the standard reporting unit for water quality analysis.
Requirements:
Chemicals/Reagents: Standard Hydrochloric acid (0.02 N), Phenolphthalein indicator, Methyl
orange indicator, Distilled water
Materials Required: Industrial effluent water sample, Wash bottle, Filter paper (if sample
contains suspended solids)
Apparatus/Instrumentation: Burette (50 mL), Pipette (50 mL), Conical flask (250 mL),
Measuring cylinder, Funnel, Pipette filler, White tile
Experimental Procedure:
1. Rinse the burette thoroughly with distilled water followed by the standard 0.02 N
hydrochloric acid solution.
2. Fill the burette with 0.02 N hydrochloric acid and record the initial burette reading.
3. Pipette 50.0 mL of the industrial effluent water sample into a clean 250 mL conical
flask.
4. Add 2–3 drops of phenolphthalein indicator to the sample.
5. Observe the colour of the solution. If no pink colour develops, record the
phenolphthalein alkalinity as zero and proceed directly to Step 7.
6. If a pink colour appears, titrate with standard hydrochloric acid until the pink colour
just disappears and note the volume of acid consumed.
7. Add 2–3 drops of methyl orange indicator to the same solution.
8. Continue the titration with hydrochloric acid until the colour changes from yellow to
permanent orange-red.
9. Record the final burette reading.
10. Calculate the volume of acid required for total alkalinity.
11. Repeat the titration two more times until concordant readings (difference not exceeding
±0.1 mL) are obtained.
12. Calculate the average titre value. Determine the total alkalinity of the industrial effluent
in terms of mg/L as CaCO₃.
Observations:
Normality of HCl = 0.02 N
Volume of water sample = 50.0 mL
Trial Initial Burette Reading Final Burette Reading Acid Consumed
(mL) (mL) (mL)
1 0.00 18.60 18.60
2 0.00 18.50 18.50
3 0.00 18.70 18.70
Average Acid Consumed: (18.60+18.50+18.70)/3= 18.60 mL
Calculations:
Formula
Total Alkalinity (mg/L as CaCO3) = (A×N×50,000)/3
Where:
A = Average volume of acid used (mL)
N = Normality of HCl
V = Volume of sample taken (mL)
Calculation
Average acid consumed = 18.60 mL
Normality of HCl = 0.02 N
Sample volume = 50.0 mL
So (18.60 x 0.02 x 50,000)/50 = 18600 / 50 = 372 mg/L as CaCO₃
Result: The total alkalinity of the given industrial effluent water sample was determined by
acid-base titration and found to be 372 mg/L as CaCO₃
Precautions
1. Use freshly prepared and standardized hydrochloric acid solution.
2. Ensure that the burette and pipette are clean before use.
3. Remove all air bubbles from the burette tip before titration.
4. Read the burette at eye level to avoid parallax error.
5. Add the titrant slowly near the endpoint while continuously swirling the flask.
6. Use only 2–3 drops of indicator to avoid indicator error.
7. Record the endpoint immediately after the colour change becomes permanent.
8. Filter highly turbid samples before analysis if necessary.
9. Perform at least three concordant titrations for reliable results.
10. Use distilled water for rinsing glassware.
Viva-Voce Questions
1. What is meant by alkalinity in water?
2. Which ions are mainly responsible for alkalinity?
3. Why is alkalinity expressed as mg/L of CaCO₃?
4. Why are phenolphthalein and methyl orange both used in this experiment?
5. What is the endpoint pH for phenolphthalein alkalinity?
6. What is the endpoint pH for total alkalinity?
7. Why is hydrochloric acid used as the titrant?
8. What are the common industrial sources of alkalinity in wastewater?
9. Differentiate between alkalinity and hardness.
10. Why are concordant readings important in titration?
References
1. American Public Health Association (APHA), American Water Works Association
(AWWA), & Water Environment Federation (WEF). Standard Methods for the
Examination of Water and Wastewater, 24th Edition, APHA Press, Washington, DC,
2023. Official publication: [Link]
2. Douglas A. Skoog, Donald M. West, F. James Holler, and Stanley R. Crouch.
Fundamentals of Analytical Chemistry, 9th Edition, Cengage Learning, 2014.
Publisher: [Link]
3. ASTM D1067 – Standard Test Methods for Acidity or Alkalinity of Water. Official
ASTM Standard: [Link]
4. World Health Organization (WHO). Guidelines for Drinking-water Quality, 4th Edition
(with updates). [Link]