Introduction

• It has been reported that microbial hazards are the single major cause
of nearly 80% of human mortality in India.
• Children are the worst affected, especially in rural areas and urban
slums and one third of all deaths of all children below five years of
age in India are attributed to diarrhea and pneumonia (Srikanth,
2009).
• The major enteric pathogens that account for most of the diarrheal
death, particularly in developing countries, are enterotoxigenic E. coli,
rotavirus, Vibrio cholera, and species of shigella, which are spread
through contaminated water and food or from person to person (Qadri
et al., 2005).
1 1
 Introduction
• It is reported that many states in India still have outbreaks of
cholera. During 1996-2006, at least 222,038 were affected by
cholera (Kanugo et al., 2010).
• A study on hepatitis E infections conducted in India revealed
that 70% of the cases are due to contaminated water and 20%
due to food (Gerba and Rose, 2003).
• According to UNICEF ~ 9% of global child deaths are due to
diarrhoea.
• WHO claims that gastroenteritis infection is responsible for
760,000 child deaths annually. Unfortunately, India accounts
for the highest number of deaths (24%)- around 100,000
child deaths per year. (WHO media centre, Diarrhoeal
disease. http://www.who.int/mediacentre/factsheets/fs330/en
(2013).

1 2
 Disinfection and Sterilization

• Disinfection – does not provide complete destruction of all

microorganism – not even all pathogenic organism

– Hepatitis virus and polio virus are, for example are not
completely deactivated by most disinfectants

• Sterilization: complete destruction of all organisms,

including bacteria, amebic cysts, algae, spores, and viruses.

3
 Disinfectants
• Several disinfectants are available – No disinfectant is perfect
• Characteristics of good disinfectant
– ability to kill or neutralise all pathogenic organisms and reduce the
contamination to below the minimum prescribed standards under
normal operating conditions;
– lack of characteristics that results in risks to people and the
environment;
– not results in risks to human health and environment due to
handling, shipping, and storage
– not results in toxic disinfection by-products that may harm human
health and environment;
– be reliable; and affordable capital and operation and maintenance
(O&M) costs.

1 4
 Disinfectants

• Types of disinfection

– Chemical

• Examples: Chlorine, chlorine dioxides, ozone, noble metals,

KMnO4, excess lime, bromine, iodine

– Physical

• UV radiation, x-ray, microwave irradiation, ultrasonic

disruption, heating

1 5
 Nanosilver based products in market

cartridge

Silver nanoparticles Silver impregnated carbon

1 6
1 7
1 8
 Mechanism of disinfection

• Damage to cell wall – penicillin

• Alteration of cell permeability – detergents, phenolic
compounds
• Alteration of the colloidal nature of the protoplasm- heat,
radiation, alkaline and acidic agents
• Alteration of the organism DNA or RNA - UV
• Inhibition of the enzyme activity -chlorination

1 9
 Rate of disinfection
• Factors influencing disinfectant –
– Contact time; concentration of the disinfectant; intensity of
physical agents; temperature; types of organism and nature
of the suspending liquid
• Involves many step and not simple
• Contact time – for a given conc. of disinfectant, longer
the contact time, greater the kill (Chicks, 1908)
– The rate of bacterial kill is directly proportional to the
number of living organism remaining at specified time

dN t
= −kN t .............................(1)
dt
1 10
 Rate of disinfection

0
CD=Chlorine dose
-log (Nt/No)

CD1

CD3 CD2

CD1< CD2<CD3
6

0.1 Time, min 15

1
 Rate of disinfection
• Concentration of disinfectant – the inactivation rate constant is α
concentration (Watson, 1908)
k = k ' C n − − − − − − − − − − − − − − − −(2)
– k– inactivation rate constant
– k’ – die off constant; n- coefficient of dilution; C-
concentration of disinfectant
• Combined the equation 1 and 2 (Hass and Kara, 1984)
dN t
= −k 'C n N t
dt n = 1 – both conc. and
time are equally
Nt important
ln = − k ' C n t − − − − − − − −(3) n >1 – conc. is more
N0 important than time
n<1 – time is more
1 1 1  N 
ln C = − ln t + ln  '  − ln t  important than conc.
n n k  NO 
1
 Departure from rate law

lag
-log (Nt/No)

Lag and
tailing
tailing

Time, min Time, min Time, min

-Assignment – find out the reasons for the departure from

rate law
1 13
• Problem. Estimate the time required for a 99.9%
kill for a chlorine dosage of 0.05 mg/L at a
temperature of 20 0C and a pH of 8.5 using the
expression given below. The expression was
developed base on the laboratory experiment
conducted at 5oC using a batch reactor.
Nt
ln = −10.48C 1.2 t
N0
Hint
t t E (T2 − T1 )
E = 26,000 J/mole
ln =
R = 8.3144 J/mole.K
t2 RT1T2
1
 Chlorination
• 1810: Discovery of
chlorine as a disinfectant
(H. Davy)
• 1879: Formulation of
Germ Theory (L. Pasteur)
• 1902: Use of chlorine as
a disinfectant in drinking
water supply (calcium
hypochlorite, Belgium)
• 1908 Use of chlorine as a
disinfectant in municipal
supply, New Jersey

1 15
 Chlorination
• The use of chlorine as disinfecting agents
• Merits
• cheap compared to other disinfecting agents
• readily available in various forms including gaseous
form (Cl2, ClO2), liquid or solid (sodium hypochlorite,
calcium hypochlorite).
• effective against wide spectrum of microorganisms.
[Chlorine dioxide is preferred over other chlorine
compounds when virus disinfection is needed]
• easy to apply and has relatively high solubility.
• stable and hence maintaining residual chlorine to take
care of future contamination is easy.
1 16
• Demerits
• chlorine gas is very toxic and corrosive and requires
careful handling
• can cause odour problems especially in the presence
of phenols
• free and combined chlorine residues are toxic to
aquatic organism
• formation of persistent, toxic and bio-accumulative
disinfection by products (DBPs) (eg. trihalometahnes,
haloacetic acids)
• Concern exist over the discharge of chloro-organic
compounds to the environment – long-term toxicity
effect is not known
1 17
 Chlorination

• Cl2 + H2O HOCl + H+ + Cl- (R1)

• NaOCl + H2O HOCl + NaOH (R2)
• Ca(OCl)2 + 2H2O 2HOCl +Ca(OH)2 (R3)
• HOCl OCl- + H+ (R4)

• Free available chlorine - The total quantity of HOCl and OCl- present
in water- the relative conc. of these species in water is highly
dependent on pH
1
HOCl/[HOCl + OCl-] = 1 + K i 10 pH

Ki = [H+][OCl-]/[HOCl] = 3X 10-8 mole/L at 250C

18
 Chlorine reaction with ammonia

• NH+4 + HOCl NH2Cl + H2O

• NH2Cl + HOCl NHCl2 + H2O

• NHCl2 + HOCl NCl3 + H2O

( function of temp., pH, chlorine to ammonia ratio,

contact time)

- Chlorine in these compounds is called combined

chlorine
1 19
 Break-point Chlorine
Destruction of Formation of chloro- Destruction of Formation of free
chlorine residual by organic and chloramines and chlorine and presence of
reducing compounds chloramine chloro-organic chloro-organic
compounds compounds compounds not destroyed

FCR

BP CCR

1 20
 Actual and Available chlorine

• Actual chlorine:
– (Cl2) actual, % = (weight of chlorine in compound/
molecular weight of compound) x 100

• Available chlorine
– Term used to compare the oxidizing power of the
chlorine compound – this is based on the no. of
electrons involved in the oxidation reduction process

– HOCl+ H ++ 2e- Cl-+ H2O

1 21
 Problem for practice

• Estimate the actual and available chlorine in the following

compound containing chlorine. Identify most powerful
oxidizing agent form the list.

• Cl2
• Cl2O
• ClO2
• HOCl
• NaOCl
• NHCl2
• NH2Cl
• Ca(OCl2)
1 22
 Operation and Maintenance
• Operation and Maintenance
• The Standard operating procedure (SOP) should list all major equipment of
the system together with a general description of each component and all
system controls, including local manual, remote manual or automatic
controls. Local manual controls are defined as controls located at local
control panels in the field. Remote manual controls are defined as controls
operators can change, located at the human/machine interface. Remote
automatic control is defined as control by plants control system t adjust for
either flow rate thrugh the plant or chlorine residual in the process water.
• 2. Start up and shut down procedure apply only to normal operation and
should include a detailed step-bystep approach to starting or stopping all
equipment associated with th gaseous chlorine system.
• 3. Emergency operating practices procedures that should be identified
include emergency response measures and emr=ergency contact
information. Basic safety and chemical handling information should be
included as well.
1 23
 Operation and Maintenance
• Maintenance:
• The equipment name, designation and function
provide the information needed for scheduling
preventive maintenance, and should be followed
strictly to ensure propoer operation and long
equipment life.
• The maintenance plan should include a list of the
lubricants required to be used for each system
component together with the type of lubricant,
manufacturer and the quantity required, as well as the
plant lockout/ tagout procedure, the appropriate afety
and chemical handling information, and emergency
procedure and contact information.
1 24
 Dechlorination

1. SO2 + HOCl + H2O Cl- + SO42- + 3H+ (R5)

2. SO2 + NH2Cl + 2H2O Cl- + SO42- + 2H+ + NH4+ (R6)

3. Na2SO3 + Cl2 + H2O Na2SO4 + HCl (R7)

4. Na2SO3 + NH2Cl + H2O Na2SO4 + Cl- + NH4+ (R8)

5. NaHSO3 + Cl2 + H2O NaHSO4 + 2HCl (R9)

6. NaHSO3 + NH2Cl + H2O Na2HSO4 + Cl- + NH4+ (R10)

7. Na2S2O5 + Cl2 + 3H2O 2NaHSO4 + 4HCl (R11)

8. Na2S2O5 + NH2Cl + 3H2O Na2SO4 + H2SO4 + 2Cl- + 2NH4+ (R12)

9. C + 2Cl2 + 2H2O 4 HCl + CO2 (R13)

10. C + NH2Cl + 2H2O CO2 + 2Cl- + 2NH4+ (R14)

1 25
• Design Example: Design a chlorine contact basin and
estimate the chlorine dose required for disinfect a
secondary effluent.

• Design conditions:
• Coliform count in the secondary effluent = 107/100 mL
• Required coliform count after disinfection = 10/100 mL
• Demand due to decay during chlorine contact = 2 mg/L
• Intial chlorine demand = 3.5 mg/L
• Required chlorine contact time = 60 min
• Free residual chlorine required = 0.5 mg/L
• Chlorinating agent = NaOCl (assume chlorine content is
10%)
• Peaking factor = 2.0
• Average flow = 600 m3/day
• Dispersion number at peak flow
1
= 0.015 26
Solution:
(A) Estimate the chlorine dose required
ln N t / N 0 = (C R t / b) − n
Where
• Nt = bacterial density remaining after exposure to
chlorinating agent, numbers per unit volume of
liquid
• No = Initial bacterial concentration, numbers per unit
volume of liquid
• Typical value of the coefficient b = 4 and n = 2.8
(Metcalf and Eddy, 2003)
• ln10/107 =(C R t / 4) −2 .8

• CR = 21.1 mg/L 1 27
 (B) Estimation of NaOCl requirement
(a) Total chlorine dose required =3.5 + 2 + 0.5 + 21.1 = 27.1 mg/L
(b) NaOCl + H2O HOCl + NaOH (R2)
(Note: For effective disinfection, pH needs to be adjusted to acidic range)
(c) The actual chorine present in NaOCl, % = w.t of chlorine in compound/mol.
w.t of compound
= 35.5/74.5 = 47.6 %
(d) Available chlorine = Cl equivalent* chlorine actual
= 2 x 47.6 = 95.2 %
(e) NaOCl dose required = (27.1/0.952)*(100/10)
= 284. 7 mg/L Total quantity of NaOCl required at peak flow
= peaking factor x avg. flow x chlorine dose
= 2 x 600 m3/d x1000 L/d x 284.7 mg/L= 340 Kg/d

Provide 3 units of chlorinator of size of 200 kg/day with one unit serving as
standby

28
• Design of chlorine contact basin
Assume dimensions
Depth = 2 m
Assume width = 0.5 m
Area = 1 m2
Volume of chlorination tank= Avg. flow x time x peaking factor
= (600 m3/d) x ((60 min) (1/60 h) (1/24 d)) *2
= 50 m3
Length (L) = (50 m3 /1 m2) = 50 m
• Check the velocity at peak flow = (2 x 600 m3/d) /(2 x 0.5) = 1200
m/d = 0.014 m/s

• (Refer the doc file titled “Design example – CCB” for more
details)
1 29
Chlorine contact basin

Cl2
1 30