Determination of Residual

Chlorine and Chlorine demand:

Break Point Chlorination
 Introduction
Chlorination is done in public water supplies and polluted
waters primarily to destroy or deactivate disease-producing
microorganisms.

Or to prevent spread of water borne diseases like

Cholara, typhoid etc.

Chlorination forms Trihalomethanes (THMs) and other organics

of health concern.

Thuse use of alternative disinfectants, such as chlorine dioxide

and ozone that do not cause this particular problem, is
increasing.
 Background

When chlorine is added to water, some of the chlorine

reacts first with organic materials and metals in the
water and is not available for disinfection (this is called
the chlorine demand of the water).

The remaining chlorine concentration after the chlorine

demand is accounted for is called total chlorine.
 Background
Total chlorine is further divided into:

1. The amount of chlorine that has reacted with

nitrates and other minerals are unavailable for
disinfection which is called combined chlorine and

2. The free chlorine, which is the chlorine available

to inactivate disease-causing organisms, and thus a
measure to determine the portability of water.

Total chlorine = combined chlorine + free chlorine

 Chlorine Chemistry
When Cl combines with water it produces
hypochlorous acid (HOCl) and hydrochloric acid
(HCl).

Cl2 + H2O HOCl + HCl

Both HOCl and HCl are good disinfecting agents, but

hypochlorous acid (HOCl) is 100 times more effective than
hypochlorite (OCl-)

HOCL is stable below pH 6

http://ewr.cee.vt.edu/environmental/teach/wtprimer/chlorine/chlorine.html
 Chlorine Chemistry in Water
1. Start with chlorine gas Cl2 + H2O HOCl + HCl

2. If the pH of the water is greater than 8, the hypochlorus

acid (HOCl-) will dissociate (break) to yield hypochlorite
ion.

HOCl H+ + OCl @pH>8

3. pH is less than 7, HOCl will not dissociate.

HOCl HOCl @pH<7

 Cl:NH3 and pH Impact in Water
1. If ammonia (NH3) is present in water, the
hypochlorus acid (HOCL) will react to form one
kind of chloramine depending on the pH,
temperature, and reaction time.
2. Monochloramine and dichloramine are formed at pH 4.5 -
8.5

3. Monochloramine is most common @pH>7.5; Cl2:NH3 <5:1

4. At pH 6.0, Cl2:NH3 > 5:1 -Monochloramine converts to

dichloramines

5. pH < 4.5, Cl2:NH3 ~15:1 Produces Trichloramine which is

very foul in odor.
 Chlorine-Ammonia (chloramines)
Chlorine- Ammonia reactions are governed by:

1. Rates of formation
2. pH
3. Temperature
4. Time
5. Cl:NH3 ratio

Fact: High Cl:NH3 ratio, low temp & pH favor dichloramine

 Chloramines in Water
Chloramines
1. pH 4.5-8.5
Monochloramine: NH3 + HOCl NH2Cl + H2O

2. pH 6.0
Dichloramine: NH2Cl + 2HOCl NHCl2 + 2H2O

3. pH <4.5
Trichloramine: NHCl2 + 3HOCl NHCl3 + 3H2O

Chloramines are an effective disinfectant against bacteria

but not against viruses.
 Add the Extra Free Chlorine
(HOCL)
4. Additional free chlorine (HOCL or OCL-) reacts with
chloramine to produce hydrogen ion, water , and nitrogen gas
which will come out of solution.

In the case of the monochloramine, the following reaction

occurs:
2NH2Cl + HOCl N2 + 6HCl + H2O
 Breakpoint Chlorination
Breakpoint chlorination: The point at which near complete oxidation
of nitrogen compounds are reached . Any point beyond
breakpoint is mostly free chlorine are available(HOCL and OCL -)

A. Amount of chlorine required

Theory: 7.6 to 15 times the ammonia nitrogen content of the water
Practice: up to 25 times the ammonia nitrogen content

B. Beyond breakpoint
90% free residual chlorine (HOCL and OCL -)
10% combined chlorine
 Breakpoint Chlorination
Zone I: Chlorine is destroyed by reducing agents such as Organic
matters, non organic matters, clay and silt etc.

Zone II: Chlorine comes into contact with organics and ammonia to
form Chloroorganics and chloramines.

Zone III: Chloroorganics and chloramines are partially destroyed.

Chloramines are broken down and converted to nitrogen gas
which leaves the system

Zone IV: Breakpoint. Beyond this point, free available residual is

formed. Some chloroorganics still remain as combined residual.
Break Point Chlorination
 Chlorine Effectiveness
These are all important:
1. pH
2. Temperature
3. Chlorine Demand
4. suspended solids/nitrite/organics/
reduced chemicals
5. Contact time
6. Concentration
7. Mixing Intensity
8. Type of residual
 Chlorine Effectiveness
1. pH (low pH =better disinfection)
want pH < 7.5=more hypochlorus acid
2. Temperature (warm temp=better disinfect)
chlorine disinfection power doubles every 10 degrees
3. Chlorine Demand (Low Chlorine demand=bette
disinfect)
4. Suspended solids/nitrite/organics/
reduced chemicals
 Chlorine Effectiveness
5. Contact time (longer contact = better disinfection)
Varies depending on tank dimensions
6. Concentration (higher concentration=better disinfection
Optimize the disinfection process
7. Mixing Intensity (Rapid Mixing=better disinfection)
Rapidly disperse chlorine better kill rate
8. Disinfection CT (higher actual CT=better disinfection)
As disinfection CT increases by 50, effective kill
increases 10 times
 Key Words
Chlorine Residual- Measurable chlorine remaining after the demand is
satisfied.
Chlorine Demand- The amount of chlorine destroyed by reaction with Fe,
Mn, turbidity, organics, and microorganisms in the water.

Free Chlorine Residual- point past breakpoint where

HOCl (hypochlorous acid) and OCL - (hypochlorite ion) form.
25 times more powerful than combined chlorine for disinfection
Combined residual chlorine: chlorine combined with organics or
ammonia.
NH2Cl (monochloramine) and
NH(Cl)2 (dichloramine)
N(Cl)3 (nitrogen trichloride)
 Key Words
Breakpoint chlorination: The point at which near complete
oxidation of nitrogen compounds are reached . Any point
beyond breakpoint is mostly free chlorine (HOCL and OCL -)

CT (concentration and contact time): Effectiveness of

chlorination is dependant on chlorine concentration and
contact time.

Sterilization: The destruction of all living things in a sample

Disinfection: The removal or inactivation of disease causing

(pathogenic) organisms

Chlorine Demand= Chlorine Dose- Chlorine Residual

Table
 CALCULATION

Residual chlorine (mg/L) = mL of 0.001N Sodium

thiosulfate used Multiplying Factor (MF)

where, MF = normality of Na2S2O3 equivalent wt.

of Cl2 1000 / (ml of sample taken)
= 0.001 35.45 1000/200 = 0.1773