ENE-304: Env Engg Lab Techniques

Practical
Determination of Residual Chlorine in Water

Institute of Environmental Sciences and Engineering (IESE)

School of Civil and Environmental Engineering (SCEE) NUST,
Islamabad
 Theory
• Chlorine and uses
• Types of chlorine
• Chlorine Demand
• Breakthrough chlorination
• Significance
• Difference b/w Disinfection and Sterilization?
• Effectiveness of Chlorination & WHO Guidelines?
• DBP’s ?
• Method of Disinfection?
• Classification of Disinfections?
• Factors Effecting Disinfection ?
• Idometric Method
 Introduction
• Chlorine is highly reactive greenish-yellow gas that
combines readily with nearly all other elements. Chlorine
is widely as an important Disinfectant and
Oxidant/Oxidizing Agent in water and wastewater
treatment.
• The word "residual" means "remainder" or "that which is
left", and as the name suggests the chlorine residual test is
used to measure the amount of chlorine (at a final
consumer) that is left behind after application.
Cl2 + H2O → HOCl + HCl
HOCl → HCl + [O]
• Idometric Method
Types:
1. Free available chlorine:
Chlorine existing in water as hypochlorous acid, hypochlorite ion and Elemental
chlorine (gas) is defined as free available chlorine.
2. Combined Chlorine:
When chlorine chemically combine with organic group such as Ammonia or alkyl
etc. referred as combined chlorine. Chloramines formed are very toxic that can kill
bacteria and oxidizing organic matter.
Total Chlorine:
The sum of free and combined available chlorine.
Chlorine Demand:
The chlorine demand of water is the difference between the amount of chlorine
applied and the amount of free, combined or total available chlorine remaining at
the contact period.
Chlorine Dose = Chlorine Demand + Residual Chlorine
Breakpoint Chlorination:
It is the chlorination of water to the extent that all Ammonia present in water is
converted into trichloraamines or oxidizes to free nitrogen.
 Principle
Chlorine will liberate free iodine from potassium iodide (KI) solutions at pH 8
or less. The liberated iodine is titrated with a standard solution of sodium
thiosulphate (Na2S2O3) with starch as the indicator. This method is based on
reaction with thiosulfate solution. The end point of the titration is indicated by
the disappearance of the blue-colored, starch-iodide complex.
 Environmental Significance
• Chlorine residuals determination is used to control chlorination of
domestic and industrial wastewaters.
• Active chlorine (free and combined) should be determined at each stage in
the treatment process of drinking water .
• Chlorine determination is important to avoid bad odor ,taste and color of
water.
• It is determined in the swimming pools to avoid ill effects due to excess
chlorination.
 Apparatus & Reagents
• Erlenmeyer Flask
• Pipette
• Graduated Cylinder
• Burette
• Volumetric flask
• Acetic acid
• Potassium iodide, KI, crystals.
• Standard sodium thiosulfate
• Starch indicator solution
 Procedure
• Mix 5mL Acetic Acid and 1g KI in beaker and then add it to 100 mL water
sample.
• If chlorine is present, its color change to orange or yellow. If orange color
appears, it means chlorine is present in excess. If yellow color appears, it
means chlorine is present in less amount.
• Now titrate it against 0.01 N Sodium thiosulphate till pale yellow color
appears.
• Add 1 ml of starch solution in it. Color will change to violet.
• Again titrate it against sodium thiosulphate till violet color disappears.
• Note the volume of Na2SO3. Suppose that volume is “A”.
• Calculate residual chlorine by following equation:

mg Ax0.025x35.5x1000
Chlorine =
L Vol of sample mL
 Observation

Initial Burette Final Burette

Sr No Difference (ml)
Reading (ml) Reading (ml)
1
2
3

Volume Used = ---- mL

 Calculations/Results
ÆX 0.025 X 35.5 X 1000
Chlorine (mg/L) =
VoS o f ca np Se( nL)
Conclusion & References
 Problems
 The chlorine demand of a secondary effluent is 8.7 mg/L and the desired
chlorine residual is 0.8 mg/L. If the daily plant flow is 7000 m3/day and
the calcium hypochlorite dose is 200 Kg, what is the % available chlorine
of the calcium hypochlorite solution?

 A chlorinator is set to feed 140 Kg/day of chlorine. If the average daily

flow is 18,000 m3/day and the chlorine residual is 0.6 mg/L, what is the
mg/L of chlorine demand?

 The chlorine demand of a water under given conditions is 7 mg/L as Cl2

after a contact period of 30 minutes. Calculate the amount of Ca(OCl)2
treat 30,000 m3/day of water so that the free residual chlorine is 0.2 mg/L?
 Chlorination
• Chlorine
– discovered in 1774 by Karl W. Scheele
– identified as an element in 1810 by Humphrey Davy
• Properties
– Greenish yellow
– Diatomic gas molecule
– Suffocating Odor
– Extremely Poisonous
• Chlorination
– when chlorine and its compounds are used as disinfectants
– Powerful Oxidizing, Bleaching and Disinfecting agent
– Cheap and Reliable
 …Chlorination

Classification of Chlorine
Chlorination is classified according to its
• Point of application
• End results
– Plain Chlorination
– Pre‐Chlorination
– Post Chlorination
– Super Chlorination
– Dechlorination
 …Chlorination

Chlorine Demand and Residual

• Cl demand = Cl applied ‐ Cl residual
Sr. Dosage Residual
Type
No (mg/L) (mg/L)

1 Free Chlorine 1‐6 4

Combined
2 2‐6 4
Chlorine

Chlorine
3 0.5‐2.5 0.8
Dioxide

17
 …Chlorination

Methods of Disinfection
• Different Forms of Chlorine
– Free Available Chlorine
• Chlorine gas
• Calcium Hypochlorite Ca(OCl)2
• Sodium hypochlorite NaOCl
– Combined Available Chlorine
• Chloramines
– Chlorine Dioxide
• Vulnerable microbes
– Bacteria, viruses, protozoa
• Byproducts
– THMs
 …Chlorination

Process Chemistry
• Process Reaction:
Cl2 + H2O HOCL + HCl
HOCl H+ + OCl‐
• HOCl is 80‐100 times more effective as compared to OCl‐ in killing pathogens
• Cl2 added to water is in the form of HOCl or OCl‐ is a function of pH of water
pH HOCl (%) OCl‐1 (%)
4 100 0
5 99.7 0.3
6 97.4 2.6
7 79 21
8 27 73
9 4 96

(Brahmi Mounaouer et al. 2012)

 …Chlorination

Chlorination ‐ Generation Techniques

• Free Chlorine
– Cathode: 2 H+ (aq) + 2 e− → H2 (g)
– Anode: 2 Cl− (aq) → Cl2 (g) + 2 e−
– Overall process: 2 NaCl + 2 H2O → Cl2 + H2 + 2 NaOH
 …Chlorination

Continued
• Combined Chlorine
– Chloramine formation
HOCl + NH3  NH2Cl + H2O
NH2Cl + HOCl  NHCl2 + H2O
Sr. No NHCl2 + HOCl  NCl3 +pHH2O
Specie Cl2:N
1 Monochloramine 3‐7 5:1
2 Dichloramine >7 7:1
3 Trichloramine <3 10:1

• Chlorine Dioxide
2NaC lO2 + Cl2  2 ClO + 2 NaCl
‐ ‐ ‐
2ClO2 + 2OH  H2O+ ClO3 (Chlorate) + ClO2 (Chlorite) (in alkaline pH)

Strong Oxidant; high oxidative potentials 2.63 times greater than free chlorine, but
only 20 % available at neutral pH
 …Chlorination
Chlorine Generators and Contact
Facility
• Chlorinators are devices which introduce
chlorine gas to water using liquid chlorine
supplied in steel containers
 …Chlorination

Factors affecting Process

• Time of Contact
• Type of Residual
• Turbidity
• pH
• Temperature
• Amount of Organic Matter
• WHO Guidelines

Sr. No Parameter Value

1 pH <8

2 Turbidity < 5NTU

3 Residual Chlorine 0.5mg/L for Free Cl2

4 Contact Time 30mins

 …Chlorination

Process Scope
• Residential Usage
– Most common technology worldwide
• Wastewater
– Usually undesirable
– DBPs production
• Scope in Pakistan
– Clean Drinking Water Initiative
– Sang‐Jani Water treatment s
– Rawal Treatment Plant
– Water treatment and bottling plants like NESTLE and
Gourmet
– Small household water treatment plants: Lahore
– Wastewater treatment of ENI Pakistan Ltd.