Assignment Topic

Disinfection by Chlorine (Chlorination)

Submitted to:

Dr. RafiaRehman Submitted by:

Yumna Malik 9936

BS 7th (Morning) Supervisor:

Dr. Muhammad Jawad Saif

Department of Applied Chemistry

Government College University

Faisalabad
Disinfection By chlorine (Chlorination)

Basic Principles
Disinfection:

Itis the process of destroying the pathogenic bacteria and microorganisms is known as
disinfection or sterilization.

Pathogenic organisms:

Theseare bacteria or viruses which cause diseases.

Disinfectants:

The chemicals and the substances used for disinfecting are known as disinfectants.

Importance of Purification:
This process is most important because pathogenic bacteria which are present may cause
various diseases, which are disastrous for public life.
There are many methods of disinfection. We discuss here only disinfection by chlorine also
called chlorination.
Other Disinfection Treatment Processes:

■ Ultraviolet Light
■ Ozonation

Reference:

• 1 John Brady, William Garber and James F. Stahl, "Chapter 10: Disinfection and
Chlorination," in Operation of Wastewater Treatment Plants, Volume I, (Sacramento, CA:
California State University, Sacramento Foundation, 2001), p. 422.

Chlorination
Chlorine and its forms are strong oxidants which kill the microorganisms and bacteria which
cause diseases in humans. Chlorine is universally used for disinfection because it is,
 ■ It is cheap
■ It is reliable

■ It is easy to handle

Chlorine give disinfecting effects for long periods so water does not recontaminate.

Chlorination chemicals are relatively,

■ Easy to obtain
■ Economical
■ Effective
■ Easy to apply

Disinfecting Action of Chlorine:

Chlorine make hypochlorite ions and hypochlorous acid when we dissolve chlorine in water.
Hypochlorous acid or hypochlorite ions have a disastrous effect on many living microscopic
organisms.

Cl2+H2OpH>5 HOCL+HCl Dissociation of Hypochlorous Acid:

It is unstable and partially dissociate into hypochlorite ions.

HOCl ^ClO- + H+(pH>8 and pH<7)

ClO-are hypochlorite ions. Salts of hypochlorous acid are hypochlorites.

Dependence on pH:
These reactions depends on pH. HOCL is more effectively dissociate if pH is high and it dissociate
less if pH is low.
1- If pH is less than 7, then HOCl does not dissociate. At this pH, HOCl is present.
2- If pH is les than 5, then chlorine does not react with water and chlorine is present as
elemental chlorine.
3- If pH is greater than 10 then hypochlorite ions are dominant specie.
 pH Dominant
Specie
<5 Cl2
>5<7 HOCL
>10 OCI

Free Chlorine:

If all the three forms which are HOCL (hypochlorous acid) , OCL (hypochlorite ions) , Cl2(Chlorine)
-

present in water sample then it is called free chlorine.

Enzymatic Hypothesis:

According to this hypothesis ,hypochlorous is most destructive one.

Due to this reason, pH of water is maintained slightly less than 7 to prevent HOCL dissociation.

Destructive Nature of HOCL is due to:

According to enzymatic hypothesis, these ions react with enzymes which are present in the cells
of bacteria. These enzymes are necessary for their growth or other process. As a result, enzymes
deactivate which are in the cells of organisms and deactivate by HOCL. They kill bacteria and
micro-organisms which further not divide.
HOCL is 80 more destructive for bacteria as compare to OCL- ions.

Formation of chloramines:

HOCL (hypochlorous acid) immediately react with ammonia which are present in water. They
form various chloramines.
Chemistry:

The reactions which are taken place are:

NH3+HOCL -> NH2G+H2O

This reaction occur when pH is greater than 7.5.

NH2G+HOCL -> NHG2+H2O

This reaction takes place when pH is 5 to 6.5.

NHCl2+HOCL > NG3+H2O

This reaction takes place when pH is less than 4.5.

Predominant specie:

In the process of chlorination, we keep pH less than 7, around 6.7. As a result, dichloramine is

the dominant one.

Chlorine reserves:

The chloramines which are formed by the reaction of HOCL with ammonia are,

1- Stable

2- Disinfecting properties.

So chloramines are act as chlorine reserve.

Combined chlorine:

1- Chlorine in the form of chloramines called combined chlorine.

2- Combined Chlorine is less effective than free chlorine.

References:

• DWI (2010) Advice for Applicants and water suppliers - Advice Sheet 9 - Emergencies -
Use of equipment and disinfectants Feb 2010
• USEPA (2004) Response Protocol Toolbox: Planning for and Responding to Drinking
Water Contamination Threats and Incidents Module 5: Public Health Response Guide
April 2004
• WHO (2004) Guide to promotion of Drinking-Water disinfection in emergencies
• EPA (2010) European Communities (Drinking Water) (No. 2) Regulations 2007 A
handbook on the Implementation of the Regulations for Water Service Authorities for
Public Water Supplies

Break Point Chlorination

Definition:

The breakpoint chlorination of water defined as the chlorination to such an extent that
microorganisms as well as bad tastes and odours present in water are also destroyed.
To disinfect water, amount of chlorine is added accordingly to the organic and inorganic
impurities which are present in water. When we add chlorine in water then it seems that
chlorine which is available is not equal to the chlorine which is added.
The relationship between the amount of chlorine added and free residual chlorine which is
proved by experiments.

Diagram:

Oxidation of Formation of Destruction Free

reducing chloro-organic of chloro- residual
compounds compounds and organic and chlorine
by chlorine chloramines ◄- - chloramines
►

Break-poinl

Applied chlorine dose

Breakpoint chlorination curve

Curve is divided into four stages.

Stage 1:

From step 1, it seems that we add lower amount of chlorine then the chlorine which added is
consumed and no residual chlorine present.
Reason:

1- At the start, chlorine reacts with the inorganic impurities which are present in water and
forms chlorides.
2- These chlorides does not have residual oxidizing power.
Stage 2: At This stage, the amount of chlorine is increased and as result respective amount of
residualchlorine is also increased. At this stage chloramines are formed. Chloramines are formed
when
chlorine is used by ammonia.

Formation of chloramines gives us the test for finding estimation of chlorine like free chlorine
which we estimate in stage 1.
■ Monochloramine, dichloramine and trichloramine are influenced by,
1- pH
2- Relative concentrations of ammonia and chlorine
3- Temperature
4- Reaction time
If pH range is less than 7, molar ratio of chlorine:ammonia is increased above 1:1 then further
reactions occur due to which further monochloramine convert into dichloramine and
decomposition of dichloramine occur.

Overall Reaction:

2NHs+HOa2N^-+HCl +H2O

This process is used to eliminate ammonia by water treatment.

Step 3:
When we increased amount of chlorine then chloramines andchloro-organic compounds are
completely oxidizedbecause they use chlorine. As a result, free residual chlorine decrease. So
residual chlorine decreases so much and it reaches a dip where destruction by oxidation is
complete.
This dip is known as break point. Organic compounds completely destroy when chlorination
occur upto breakpoint. Because of their destruction unpleasant taste and smell of water.

Stage 4:

The chlorine added is not used in any reaction after breakpoint and residual chlorine quantity is

same of added chlorine.

References:
• DWI (2010) Advice for Applicants and water suppliers - Advice Sheet 9 - Emergencies -
Use of equipment and disinfectants Feb 2010
• USEPA (2004) Response Protocol Toolbox: Planning for and Responding to Drinking Water
Contamination Threats and Incidents Module 5: Public Health Response Guide April
2004
 Chlorine demand
Free chlorine is only available if chlorine demand is match with other reacting species. Chlorine
reacts with components of wastewater. The components which are present in wastewater react
and attach with chlorine before the reaction of chlorine with pathogens.
Chlorine demand is defined as the demand by inorganic and organic materials. It is the
difference between chlorine amount which is added and residual chlorine.

■ There are inorganic compounds which firstly react with chlorine are,
1- Hydrogen sulfide
2- Ferrous iron
3- Manganese
4- Nitrite
■ Ammonia(NHs) present in all wastewaters and it secondly react with chlorine. When
their reaction occur then chloramines formed. These chloramines act as disinfectants.
Three forms of chloramines are,
1- Monochloramine
2- Dichloramine
3- Trichloramine
■ Organic compounds react with chlorine at last and as a result chloro-organic compounds
formed. Thy slightly cause disinfection.
Chlorine Residual
Chlorine residual include combine chlorine (eg. Monochloramine) these chloramines have
disinfectant properties plus free chlorine. Chlorine residual is component of chlorine which is
applied, that is used for disinfection.
 ★ Chloramines: It is a form of combined chlorine.
★ Chloro-organic compounds: It is a weak form of combined chlorine.
★ Free chlorine: It is a form of residual and is the strongest form used for
disinfection.
The sum of chlorine demand and residual chlorine is chlorine dosage.

★ Chlorine Dose = Chlorine Demand + Chlorine Residual

★ Chlorine Residual = Combined Chlorine Forms + Free Chlorine
★ Chlorine Demand = Chlorine Dose - Chlorine Residual
Chlorine Chlorine Chlorine
D ose Demand + Residual

Chlorination after Breakpoint

■ Chlorination after breakpoint increases free residual chlorine (Ch, HOCl, O-Cl)
■ There is a germicidal action on micro-organisms by free chlorine and combined chlorine
(chloramines)
■ Free chlorine instantaneously kill pathogens
■ Combine chlorine give germicidal effect for long time
Reference:

• 1 John Brady, William Garber and James F. Stahl, "Chapter 10: Disinfection and
Chlorination," in Operation of Wastewater Treatment Plants, Volume I, (Sacramento, CA:
California State University, Sacramento Foundation, 2001), p. 422
Use of Chlorine as an Effective Disinfectant

For use of chlorine as an effective disinfectant, the dose of chlorine is slightly greater than
breakpoint.
■ Water is disinfected if free residual chlorine is about 0.2ppm. It means added chlorine in
the dose upto breakpoint +0.2ppm.
■ If amount of free residual chlorine is greater than 0.2ppm cause,
1- Bad taste in water
2- Harmful because it irritates the membrane of intestine

Forms of Chorine
There are various forms of chlorine which can be applied are,

O Chlorine gas/ liquid :

Molecular chlorine is applied in liquid or gas form into the water. Liquid form is used these days.
Chlorinator:

Liquid chlorine is one and half times havier as compared to water. Liquid chlorine is kept in
cylinder called chlorinator. Chlorinator use liquid chlorine and take chlorine from container and
mix it with small amount of water and form strong chlorine solution. We use water injector to
fed chlorine solution into the distribution system.
Diagram:

Advantages:

Liquid chlorine is widely usedbecause of the following advantages,

1- It can be stored easily for long time and cannot deteriorate

2- It is cheap
3- It is easily available
4- Take less space for storage
5- On applying it, no sludge is formed
6- It is very powerful disinfectant and remain in water for long period, specially when
ammonia is also present.
© Bleaching powder/Hypochlorites:
Ca or Mg hypochlorites are used for chlorination. These are used for chlorination of small public
supplies. When hypochlorite dissolved in H2O, it make hypochlorite ions.

Ca(OClh^Ca2+ +2OCl_ (H2O)

(Calcium hypochlorite)

When OCl- ions combine with water following reaction would take place.

OCl_ + H+HQCl(pH<7>and PH>8)

(Germicide)

HOCl and OCl_ are used for disinfection.

Hig test chlorite and perchloron:

Commercially available calcium hypochlorite called hig test chlorite. It contains 60% to 70% of
chlorine which is available.

Bleaching Powder:

It is also used for chlorination. When it is freshly prepared, it contains 30% of available chlorine.

CaOCl2 + H2O -> Ca(OH)2 + Ch

(Bleaching powder)

Cl 2 + H2O _> HOCl + HCl

(Germicide)

Bleaching powder is unstable and when exposed to light or air they lose their chlorine content.

Disadvantages:
Bleaching powder and hypochlorites are not used in modern days for the treatment of water
because of the following reasons,
1- Due to presence of lime, pH of water is increased and it become hard.
2- Chlorine present in low amount.
3- If we store bleaching powder for long time, it deteriorates.
These are used to treat small public supplies for,

■ Swimming pools
■ Storage reservoirs
 ■ Emergency disinfectants
© Use of chlorine tablets:
They are used sometimes for the disinfection of small amount of water.

■ They are expensive

■ Available as halazone tablets
© Use of chloramines:
These are stable. Chloramines are formed the reaction of chlorine and ammonia when they are
mixed in 2:1 by volume.
Cl + NH3 -> ClNH2 + HCl
2

They remain in water as residuals for enough time because of their stability as compared to
chlorine which evaporates after some time.
■ They act as greater safeguard against recontamination

■ They are weak disinfectant as compared to free chlorine

Advantages:

■ Do not cause bad taste and smell even these are used in excess
■ These are very useful when phenols present

When reaction of free chlorine and phenol takes place, chlorophenols are formed which cause
unpleasant taste to water. In the presence of phenols, the chloramines do not form
chlorophenols. As a result, no bad taste developed.
© Use of CIO2 Gas:
■ It is strong and powerful disinfectant
■ It is 2 and half (2 1/2) times stronger than chlorine
■ It is produced when chlorine gas pass through NaClO2(sodium chlorite)

Reaction:

2NaClO2+ Cl22NaCl + 2ClO2

■ It is costly and unstable
■ It is used immediately after its production
■ It can be used for highly alkaline waters because action of ClO2 is unaffected at high pH
(6 to 10)

References:
 • WHO (2004) Guide to promotion of Drinking-Water disinfection in emergencies
• Buchanan, R.E., editor; , and N.E. Gibbons, editor. , eds. 1974. Bergey's Manual of
Determinative Bacteriology, 8 th ed. Williams & Wilkins, Inc., Baltimore, Md. 1246 pp.
• Antonelli, M.; Rossi, S.; Mezzanotte, V.; Nurizzo, C. (2006) Secondary Effluent
Disinfection: PAA Long Term Efficiency. Environ. Sci. Technol., 40 (15), 4771-4775.

Dechlorination
■ Overchlorinationis the amount greater than 0.2ppm after the breakpoint. It cause bad
odour and taste in water.
■ Dechlorinationis the removal of chlorine from water
■ Process of dechlorination is done to such an extent that sufficient residual chlorine
remain in water(0.1 to 0.2 ppm )
■ To maintain residues, chlorine will be added

Dechlorinating agents:

These dechlorinating agents are used for dechlorination.

1- SO2 gas
2- Na2S2O3

3- Na2 SO3

Reactions:

SO2 + Cl 2 + 2 H2 O -> H2 SO4 + 2HCl

Na2SO3+ Cl2 +H2 O _^la2SO4 + 2HCl

Other ways of dechlorination:

1- detention ponds
2- aeration
3- sunlight
4- activated carbon
5- addition of sulfur compounds.
Water which is treated is passed through bed of molecular carbon.It can also be done by adding
activated carbon into H2 O and carbon absorb chlorine. These carbon then removed by process
of filteration.
References:

• 1 John Brady, William Garber and James F. Stahl, "Chapter 10: Disinfection and
Chlorination," in Operation of Wastewater Treatment Plants, Volume I, (Sacramento,
CA: California State University, Sacramento Foundation, 2001), p. 422.
• EPA (2010) European Communities (Drinking Water) (No. 2) Regulations 2007 A
handbook on the Implementation of the Regulations for Water Service Authorities for
Public Water Supplies
• DoEHLG (2009) Circular L04/09 - Drinking Water Incident Response Plans
• DWI (2010) Advice for Applicants and Water Suppliers - Advice Sheet 5 - Approval of
products made from recognised materials and from metals May 201
• DWI (2010) Advice for Applicants and water suppliers - Advice Sheet 9 - Emergencies -
Use of equipment and disinfectants Feb 2010
• USEPA (2004) Response Protocol Toolbox: Planning for and Responding to Drinking
Water Contamination Threats and Incidents Module 5: Public Health Response Guide
April 2004
• WHO (2004) Guide to promotion of Drinking-Water disinfection in emergencies
• Buchanan, R.E., editor; , and N.E. Gibbons, editor. , eds. 1974. Bergey's Manual of
Determinative Bacteriology, 8th ed. Williams & Wilkins, Inc., Baltimore, Md. 1246 pp.
• Antonelli, M.; Rossi, S.; Mezzanotte, V.; Nurizzo, C. (2006) Secondary Effluent
Disinfection: PAA Long Term Efficiency. Environ. Sci. Technol., 40 (15), 4771-4775.
• Cochran, W. G. and Cox, G. M. (1957) Methods for increasing accuracy. In: Experimental
Designs, pp. 29-31 (Bradly, R. B., Kendall. D. G., Hunter, J. S. and Watson, G. S., Eds).
New York: Wiley. Dixon, W. J. and Mood, A. M. (1948) A method for obtaining and
analyzing sensitivity data. J. Am. statist. Ass. 43, 109-126.