WATER SHED MANAGEMENT

STRUCTURES
Rain water harvesting
Course overview
• Total Course Credit: 3
• Midterm Examination 30 Marks
• Class Assessment (Assignments, interaction, tutorials, viva etc.)
10 Marks
• Major Examination 60 Marks
• Suggested Reading:-
• Integrated Watershed Management: Principles and Practice by Isobel W.
Heathcote
• Das, Ganshyam.Hydrology and Soil Conservation Engineering, Prentice Hall
of India. .
Lecture outline and outcomes
• Introduction
• Importance of Water Shed Development for improvement in
Environment.
• Status of Watershed Development in India,
• Watershed Concepts
 What is a Watershed?
• A watershed is simply the geographic area through which water
flows across the land and drains into a common body of water,
whether a stream, river, lake, or ocean.
• The watershed boundary will more or less follow the highest
ridgeline around the stream channels and meet at the bottom or
lowest point of the land where water flows out of the watershed,
the mouth of the waterway.
• Much of the water comes from rainfall and stormwater runoff.
• The quality and quantity of stormwater is affected by all the
alterations to the land--mining, agriculture, roadways, urban
development, and the activities of people within a watershed.
• Watersheds are usually separated from other watersheds by
naturally elevated areas.
• A watershed may be only a few hectares as in small ponds or
hundreds of square kilometres as in rivers.
Objectives of watershed management
• Main goal - sustainable management of water resources.
Sub targets
• supply and securing of clean and sufficient drinking water
• provision and securing of access to sanitation;
• improvement and restoration of soil quality;
• improvement of infrastructure (supported by clean drinking
water, access to sanitation);
• Environmental education, to sustain the interventions.
Why watershed management?
• Management of the environment has been primarily focussed on
specific issues such as air, land, and water.
• Point sources of pollution have been addressed very well- improved
landfills, remediation of waste sites and contaminated groundwater,
Wastewater treatment plants.
Challenge
• A continuing problem for our waters are nonpoint source pollution.
• Typically complex problems that are difficult to manage.
How watershed approach helps?
• To allow a clear geographical and hydrological definition of an area to
be managed.
• The watershed approach directly address upstream‐downstream water
user conflicts.
• Management and modelling water resources can only be conducted,
when a hydrological watershed is defined.
Scope of engineering interventions?
• Land management – For example, restricting the sediment flow into a
water body.
• Water quality – For example, restrict the pollution from the
stormwater / wastewater into a water body.
• Water quantity – Collect the water that pours down into the catchment.
• Water scarcity – Ground water recharge structures.
Let’s listen to some stories to understand!
Case study – Dal Lake (Source:- Vision document by IITR)

DAL LAKE- FACTS & FIGURES

• Highly regarded by tourists for its serene beauty
• Among the centres of Kashmiri civilization.
• Location:- 34°6’N and 34°10’N latitude and 74°50’E and 74°54’E
longitude.
• Total catchment is 337.17 sq km
• Fed by Telbal nallah, a stream which comes from the Marsar Lake high up
in the mountains which drains the largest sub-catchment area of about 145
km2 and contributes to about 60-70% of the total inflow to the lake.
• Other smaller streams viz., Boutkal, Peshpaw nallah, Merakhsha nallah,
etc., around the shore line besides some contribution from groundwater
THREATS & ISSUES

• Water quality deterioration: discharge of untreated and treated

wastewater.
• SOURCES: inshore areas such as Houseboats, dwelling areas is much
worse compare to offshore areas.
• Dal Dwellers- Hamlets in Dal Lake:
• Houseboats
• Un-sewered Areas in Shalimar, Botpora
• Existing Sewage Treatment Plants
Sewage treatment plants along Dal Lake
 Sludge Dumping Area in Shalimar at the bank of Dal Lake

Solution is an INTEGRATED SLUDGE MANAGEMENT FACILITY FOR WASTEWATER

TREATMENT PLANTS
Grey water discharge and solid waste dumping in
the Telbal Nallah
• The control of Nutrients and silt from four major inlet drains for
limiting excessive weed growth and siltation.
• IMPLEMENTATION OF ONL-LINE ALUM TREATMENT AND
SILT CONTROL MEASURES IN LAKE CATCHMENT

A Typical on-line alum dosing system for any of the

inflow drains of Dal Lake
Restoration of aquatic Habitat
• Schizothracines, (also called trouts), inhibits the lentic as well lotic
water bodies of Kashmir. These are highly valued fishes, preferred to
most other fish species.
• Goal:- Restoring the Schizothorax population back to normal by
improving the water quality

Demarcating no fishing zone Putting up the Hatcheries

• Sewage inflow from inhabitants

Houses of Dal Dwellers Houseboats

Propose low cost and affordable solutions

Boulder Creek, Colorado USA Watershed Project

• Ammonia toxicity problem in Boulder Creek.

• Local wastewater treatment plant was targeted for an
expensive upgrade to reduce nitrate levels believed to
be responsible.
• Monitoring showed it is from non-point sources in the
watershed, agricultural runoff.
• Create buffer strips to reduce agricultural and grazing
runoff.
• Rebuilding diversion and return flow structures (to
block agricultural irrigation return flow) minimized the
impact.
Source: Principles of Watershed Management. US EPA
Lack of proper housing degrades water resources
Management of Water Quantity - Rainwater harvesting

• The water is free; the only cost is for collection and use.
• The end use of harvested water is located close to the source, eliminating the need
for complex and costly distribution systems.
• Rainwater provides a water source when groundwater is unacceptable or
unavailable, or it can augment limited groundwater supplies.
• The zero hardness of rainwater helps prevent scale on appliances, extending their
use; rainwater eliminates the need for a water softener and the salts added during
the softening process.
• Rainwater harvesting reduces flow to stormwater drains and also reduces non-
point source pollution.
• Rainwater harvesting helps utilities reduce the summer demand peak and delay
expansion of existing water treatment plants.
• Rainwater harvesting reduces consumers’ utility bills.
Basic Components – Roof top rainwater harvesting
• Roof top RWH is technique for capturing of rain from roofs and stored in
tanks / reservoirs / groundwater aquifers.
• 06 basic components:
• Catchment surface: the collection surface from which rainfall runs off
• Gutters and downspouts: channel water from the roof to the tank
• Leaf screens, first-flush diverters, and roof washers: components which
remove debris and dust from the captured rainwater before it goes to the
tank
• One or more storage tanks, also called cisterns
• Delivery system: gravity-fed or pumped to the end use
• Treatment/purification: for potable systems, filters and other methods to
make the water safe to drink
RWH system in buildings
Source:-Texas water board
The catchment surface – the roof
• Water quality from different roof catchments is a function of the type
of roof material and climatic conditions.
• Clay/concrete tile
• Clay and concrete tiles are both porous.
• Good for maintaining water quality and sealants can decrease the
water loss.
• Composite material
• Care should be taken to avoid leaching of the toxins from the roof
material.
• Those materials can be used for the irrigation water.
 Gutters and Downspouts
• Gutters are installed to capture rainwater running off the eaves of a
building.
• For potable water systems, lead cannot be used as gutter solder, as is
sometimes the case in older metal gutters.
• The slightly acidic quality of rain could dissolve lead and thus
contaminate the water supply.
• Screens
• To remove debris that gathers on the catchment surface, and ensure
high quality water for either potable use or to work well without
clogging irrigation.
• The defense in keeping debris out of a rainwater harvesting system is
some type of leaf screen along the gutter or in the downspout.
First-Flush Diverters
• A roof can be a natural collection surface for dust, leaves, blooms, twigs,
insect bodies, animal feces, pesticides, and other airborne residues.
• The first flush diverter routes the first flow of water from the catchment
surface away from the storage tank.
• The flushed water can be routed to a planted area.
• The first-flush diverter gives the system a chance to rid itself of the
smaller contaminants, such as dust, pollen, and bird and rodent feces.
• simplest first-flush diverter is a PVC standpipe
• The volume of rainwater to divert depends on the number of dry days,
amount of debris, and area of roof surface.
 Roof Washers

• The roof washer, placed just ahead of the storage

tank, filters small debris for potable systems and also
for systems using drip irrigation.
• Roof washers consist of a tank, usually between 120-
and 200 litres capacity, with a filter (30 micron filter).
• Without proper maintenance they not only become
clogged and restrict the flow of rainwater, but may
themselves become breeding grounds for pathogens.
Storage tank
• The size of storage tank or cistern is dictated by several variables: the
rainwater supply (local precipitation), the demand, the projected length
of dry spells without rain, the catchment surface area, aesthetics,
personal preference, and budget.
• Material can be polypropylene, fiber glass, concrete.
Design of storage tanks – Simple approach
• Quantity of water stored depends on size of catchment and size of the
storage tanks.
• Basic data for designing drinking water requirements:
• Average annual rainfall
• Size of catchment
• Drinking water requirement
• How much water can be harvested?
• Rainwater harvesting potential = Rainfall volume x collection efficiency
= Area x height of rainfall x roof runoff coefficient x loss coefficient
• Loss coefficient = For evaporation, spillage, first flush wastage (0.8 for all
situations)
• Example :-
• 60cm rainfall in monsoon period, 100 square meter roof top, tile finish
roof with runoff coefficient as 0.85: Assume drinking water
requirement is 10 liters per capita per day. Add a safety factor of 20%
for losses etc. How many members of a family it will sustain drinking
water supply?
• Answer ## members
Water balance approach
• Catchment area and rainfall determine supply, and
• Demand dictates required storage capacity.
• Monthly Rainfall
• Two different estimators of monthly rainfall are commonly used: average
rainfall and median rainfall.
• Median rainfall is the amount of rainfall that occurs in the midpoint of all
historic rainfall totals for any given month.
• half of the time the rainfall was less than the median and half of the time
rainfall was more than the median.
• Median rainfall provides for a more conservative calculation of system
sizing than average rainfall.
Procedure
• Basic monthly water balance calculation is
Water available (gallons or m3) = Initial volume in storage (gallons) +
gallons captured – gallons used.
• A table like below
Month Water Average Rainfall End-of month
Demand Rainfall Collected Storage
A B C D

Add
1 B x Area x C-A previous
Runoff coeff x storage in
Collection the tank to
system the
efficiency collected
2 C2+D1-A2 water
• If the calculated storage amount is zero or less, use zero for the next
month.
• Rainfall exceeding storage capacity is ignored (water lost).
• Column D should be always more than zero, if not the collection area
needs to be increased or the monthly demand should be reduced).
Treatment of stored water
Method Location Result
Screening Gutters and Downspouts Prevent leaves and other debris
Leaf screens and strainers from entering the tank
Settling
Sedimentation Within tank Settles out particulate matter
Activated carbon Before tap Removes chlorine for taste
Filtering
Roof washer Before tank Eliminated Suspended solids
Inline/multi cartridge After pump Sieves sediment
Slow sand Separate tank Traps particulate matter
Disinfection
Boiling / distilling Before use Kills microorganisms
Chemical (Chlorination) Within tank or at pump (liquid, Kills microorganisms
tablet or granular)
Ultraviolet light Before tap Kills microorganisms
Ozonation Before tap Kills microorganisms
Nano filtration Before tap Removes molecules
Reverse Osmosis Before tap Removes contaminants
Yang et al., 2019
Disinfection process - Chlorination
• Disease causing organisms in water are: Bacteria, protozoan oocystes, viruses and helminth ova.
• Bacteria
• Harmless Bacteria colonize in the intestinal tract of human beings and are routinely shed with
feces. When infected individual the pathogenic bacteria are released in the wastewater. This is the
case of animals as well.
• Some common bacterial pathogens in wastewater are:
• Genus Salmonella – Many species of this group cause disease in humans, such as, Typhoid fever –
caused by Salmonella Typhi (Most sever and serious) & Food poisoning caused by Salmonella is
known as Salmonellosis.
• Shigella – Intestinal diseases Shigellosis (Inflammation of the intestines accompanied by bloody
diarrhoea)
• Vibrio cholerea – Disease agent for Cholera. Humans are the only host for this bacteria and mode
of transmission is water.
• Myobacterium tuberculosis – Disease is TB.
• Escherchia Coli (E.Coli) and some strains of Pseudomonas - Waterborne Gastroenteritis (an
inflammation of the lining of the stomach and intestines. The main symptoms include vomiting and
diarrhea.Most common in newborns.
Protozoa
• Cryptospardium Parvum – Disease is Cryptosporidiosis – Symptom is
diarrhea
• Giardia lamblia – Disease is Giardiasis – Symptom is diarrhea and
Nausea.
• Both of these protozoa are present in the environment and can
contaminant the water.
• Cryptospardium Parvum is present as oocyst and Giardia lamblia as
cyst.
• The cyst is a dormant stage of protozoa which facilitates the survival
during unfavourable environmental conditions. Forms a protective
membrane or thickened wall.
• Oocyst is a a thick-walled cell type that is present in the life cycle of
protozoa which contains a zygote. The oocyst breaks in the stomach
and intestine of the host and the parasite's life cycle goes on again.
• After entering infected humans, they multiply and get infected and
released as infected oocysts /cysts. Afterwards get transmitted to
others.
• These organisms are of concern because of their presence in all
wastewaters and ineffectiveness of chlorine for their inactivation or
destruction.
• UV disinfection has been effective.
Life cycle of Cryptospardium parvum
and Giardia Lamblia
Helminths
• Helminths mean all parasitic worms.
• Helminths fall under 3 major phyla; Nematoda (Roundworms), Platyhelminths
(flatworms) and Annelida (segmented worms). Human infection is with first two types
and third is useful such as leaches.
• Ascaris lumbricoides (large roundworm and a nematode)– Disease is Ascariasis –
Symptom is Roundworm infestation. This disease is most prevalent parasitic infection.
• Taenia saginata (beef tapeworm, a platyhelminth)- Disease is Taeniasis- Symptom is
Tapeworm presence.
• The infectious eggs of parasitic worms (Helminth ova) are present in wastewater which
are harmful to human beings.
• Some species of helminths are present as adult organism or larvae, but mostly eggs are
present in wastewater.
• Helminth eggs of size more than 10um are removed in sedimentation, filtration.
• Eggs of Ascaris (a helminth species) can survive for up to 10 years in biosolids, making it
an important species to manage.
Viruses

• More than 100 types of disease-causing viruses excreted by humans.

• Most important viruses and relevant to water are Enteroviruses which
are named by their transmission-route through the intestine.
• Enteric Viruses multiply in the intestinal tract and are released in the
fecal matter of infected persons. Important Enteroviruses are
• Poliovirus – Disease is Meningitis, paralysing
• Hepatitis A virus – Disease in hepatitis- Symptoms are Jaundice and
fever
• Norovirsuses and Rotavirus – Disease is Gastroenteritis – Symptoms
are diarrhea and Vomiting
Disinfection process

• Disease causing organisms in water are: Bacteria, protozoan oocystes

and cysts, helminth ova and viruses
• Most important in Rainwater harvesting systems because of relation to
human health.
• The objective of disinfection is to achieve the given level of
destruction or inactivation of disease causing organisms.
• Not all organisms are killed by Disinfection so it is different from
sterilization (that means destruction of all organisms).
Water disinfectant properties
Disinfection methods and agents

• Most common are use of chemical agents and non-ionizing radiation.

• Chemical agents – 1. Chlorine and its compounds and 2. Ozone. Others are
bromine and iodine but not common.
• Radiation (Non-ionizing- that do not ionize atoms)– In general energy in the
form of electro magnetic waves, heat and acoustic waves that can be
transmitted over large distance without conductors are termed as radiation.
E waves include visible light, infra red light, microwaves and radio waves.
UV is the most common form of E waves used for disinfection.
• Heating:- Processes are boiling (Destroys some bacteria) and pasteurization
(heating treatment for some amount of time. Used for sludge before
applying for land use).
• Removal by mechanical means:- Incident removal occurs by screening,
sedimentation. Membrane filtration (microfiltration and ultrafiltration) can
reduce pathogenic organisms.
Mechanisms of Disinfection
• Principal mechanisms define action of a disinfectant.
• Damage to cell wall – Chlorine and Ozone- Cell lysis and death
• Alteration of cell permeability- Chlorine and Ozone damage cell wall and
hence cell permeability.
• Alteration of organisms DNA or RNA – UV radiation causes rupturing of
DNA strands or forms double bonds in the DNA. This causes disruption in
replication process and no longer reproduction.
• Inhibition of enzyme activity – In pasteurization, Heating alters the structure
of enzymes making them inoperative
Physical infrastructure used for disinfection
• The main purpose of disinfection reactors is to maximize contact between
the disinfecting agent and the liquid to be disinfected.
• For Chlorine and related compounds
• Reactor types are baffled contact chambers
• Long pipelines.
• Both of these two types are plug flow reactor (In plug flow, the
concentration of reactant decreases progressively along the direction of flow
through the system; in mixed flow, the concentration drops immediately to a
low value and is constant through the reactor).
• For ozone
• Applied by bubbling ozone gas through the liquid in contact chamber.
• For UV
• Both open and closed type contact chambers are used.
Disinfection design parameters / factors
• Contact time – depends on the hydraulic efficiency of contact chambers
• Concentration of the disinfectant
• Temperature
• Type of organism
• Nature of liquid (unfiltered, filtered, organic matter present or not)
• The type of upstream treatment process
Contact time
• After disinfectant is added, time of contact is the time before effluent is
discharges or reused.
• Governed by Chick’s law
• For a given concentration of disinfectant , the longer the contact time, the
greater the kill.
• In differential form, it means
𝑑𝑁𝑡
= −𝐾𝑁𝑡
𝑑𝑡
Where LHS is rate of change in the number (concentration) of organisms with
time
K= inactivation rate constant (T-1) ;
𝑁𝑡 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑜𝑟𝑔𝑎𝑛𝑖𝑠𝑚𝑠 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡;
t=time
• 𝑊𝑖𝑡ℎ 𝑡 = 0, 𝑁𝑡 = 𝑁0 ;
𝐼𝑛𝑡𝑒𝑟𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑤𝑖𝑙𝑙 𝑔𝑖𝑣𝑒 Inactivation in a batch reactor
𝑁𝑡
𝑙𝑛 = −𝐾𝑡
𝑁0
𝑁
• To obtain value of K, plot -𝑙𝑛 𝑁𝑡 LHS versus contact time (t), where K is the
0
slope of the resulting line of best fit.
 Concentration of chemical disinfectant
• Inactivation rate constant is related to concentration of disinfectant as well by Chick Watson Expression
𝐾 = ⋀𝐶 𝑛 (⋀ is kaeret)
𝑊ℎ𝑒𝑟𝑒 𝐾 = 𝑖𝑛𝑎𝑐𝑡𝑖𝑣𝑎𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑇 −1 , 𝑏𝑎𝑠𝑒 𝑒,
⋀ = 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑒𝑛𝑡 𝑜𝑓 𝑠𝑒𝑝𝑐𝑖𝑓𝑖𝑐 𝑙𝑒𝑡ℎ𝑎𝑙𝑖𝑡𝑦,
𝐶 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑑𝑖𝑠𝑛𝑓𝑒𝑐𝑡𝑎𝑛𝑡 𝑚𝑔𝐿−1 ,
𝑛 = 𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑟𝑒𝑙𝑎𝑡𝑒𝑑 𝑡𝑜 𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛 𝑜𝑓 𝑑𝑖𝑠𝑓𝑒𝑐𝑡𝑎𝑛𝑡
• Combining previous expression proposed for contact time.
𝑑𝑁𝑡
= −⋀𝐶 𝑛 𝑁𝑡
𝑑𝑡
𝑁𝑡
𝐼𝑛𝑡𝑒𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑔𝑖𝑣𝑒𝑠 𝑙𝑛 = −⋀𝐶 𝑛 𝑡
𝑁0
𝑙𝑜𝑔𝑁𝑡
Or = − ⋀𝑏𝑎𝑠𝑒10 𝐶 𝑛 𝑡
𝑁0
𝑁𝑡
• 𝐴𝑠𝑠𝑢𝑚𝑖𝑛𝑔 𝑛 = 1, 𝑤𝑒 𝑔𝑒𝑡 𝑙𝑜𝑔 = − ⋀𝑏𝑎𝑠𝑒10(𝐶𝑇) = − ⋀𝑏𝑎𝑠𝑒10(𝐷)
𝑁0

Where, C=residual concentration of disinfectant ,mg/L

T=contact time in the reactor (min)
D= Germicidal dose for given degree of inactivation, mg.min/L
• This concept of dose (CxT) is important to determine performance of disinfectants.
• The concept is adopted for establishing guidelines for disinfection of water supplies.
• The CT values can be designed accordingly for the required reduction of microorganisms i.e. CT can be derived for a particular value
of Nt
The CT values can be designed accordingly for the required reduction of microorganisms i.e.
CT can be derived for a particular value of Nt
Temperature and disinfection
• More temperature results in rapid kill.
• Decided by the van’t Hoff-Arrhenius relationship.
• In terms of specific lethality, the effect of temperature is given by

Where ⋀1 and ⋀2 are coefficients of specific lethality at temperatures T1

and T2.
E is activation energy (J/mol)
R= universal gas constant, 8.3144 J/mol.K
Nature of suspending solid
• Chick and Watson derived coefficeints are derived at lab scale with distill
water.
• In practice, the nature of water must be evaluated carefully.
• 03 constituents present in wastewater are important
• Inorganic constituents that can react with disinfectant, such as ammonia.
• Organic matter including both natural organic matter (NOM) and other
organic compounds. NOM is derived from humic material, algae and reacts
with oxidizing disinfectant and leaves less for disinfection
• Suspended material – Adsorption of disinfectant on suspended material and
shields the entrapped bacteria.
 Deviation from Chick’s law due to nature of liquid.

Ideal chicks law, time or dose on X-axis (first

order kinetics)
a) If reacting constituents are present:- Lag effect in which disinfectant reacts first
with constituents in liquid after which the response is log linear (first order
kinetics).
b) If suspended particles are present:- Log linear response followed by tailing effect
in which large particles shield the organisms to be disinfected.
c) Both a and b are present:- (Actual case) Combining lag, log linear and tailing
effect.
Effect of upstream treatment process
• The extent to which upstream process removes NOM, organic matter
and suspended solids, will make disinfection effective.
• It is normally impossible to achieve complete disinfection without
adopting any method such as filtration, sedimentation for the removal
of large suspended solids. This reduces the shielding of disease-
causing microorganisms.
 Application of CT concept in disinfection

• Use of CT concept is popular in the design of

disinfection systems.
• A CT value with contact time is normally specified
depending on type of water and end use.
• Since water constituents effect curve linearity so site
specific testing is required to establish CT dose value
because CT curves established in literature may be
developed in distilled water or different type of water.
Since
• Normally 450mg.min/L with 90-minute contact time at
peak flow is recommended.
• However, CT has its own restrictions, which need to be
avoided.
• Higher contact time may result in shielding of bacteria by
solids. So, water should be devoid of suspended particles. Disinfection dose versus
response curve with water
containing suspended solids
1 log means 90% removal
2 log means 99% removal
3 log means 99.9% removal
4 log means 99.99% removal
𝑁𝑡
1 log 𝑚𝑒𝑎𝑛𝑠; − log =1
𝑁0
𝑁𝑡
𝑂𝑟 = 10−1
𝑁0
𝐴𝑠𝑠𝑢𝑚𝑒 𝑁0 = 100; 𝑁𝑡 = 10
Disinfection with chlorine
• Chlorine (Cl2), and chlorine dioxide (ClO2), sodium hypochlorite (NaOCl, liquid bleach) calcium hypochlorite (Ca(OCl2).
Chlorine
• can be present as gas or pressurized liquid.
• Unconfined liquid chlorine vaporizes rapidly to gas at standard temperature and pressure.
• Solubility of chlorine is 1% at 10oC.
• Concerns are toxic substance transported by rail and truck that are prone to accidents, plant operators and aquatic life.
• Reaction of chlorine to organic compounds for disinfection by products that are carcinogenic.
Sodium Hypochlorite
• Available as aqueous solution with 12.5 – 17% available chlorine.
• Can be manufactured on site as well.
• Disadvantage is chemical cost – 150 – 200% of the cost of chlorine.
• Handling – Require conditions to avoid corrosiveness, fumes and caking in chemical feed lines.
• Onsite manufacturing is expensive and preferred for only big plants.
Calcium Hypochlorite
• Available commercially as dry (white powder, granules, tablets)
• Handling – Cool, dry place and away from chemicals in corrosion resistant containers.
• Expensive than chlorine.
Chemistry of chlorine compounds
• When Cl2 in the form of gas is added to water, hydrolysis and
ionization takes place.
• Hydrolysis – Chlorine forms hypochlorous acid (HOCl)
𝐶𝑙2 + 𝐻2 𝑂 → 𝐻𝑂𝐶𝑙 + 𝐻 + + 𝐶𝑙 −
𝐻𝑂𝐶𝑙 𝐻 + 𝐶𝑙 −
• Equilibrium constant 𝐾ℎ = = 4.5 𝑥 10−4 𝑎𝑡 25𝑜 𝐶
𝐶𝑙2
• Ionization – Ionization of hypochlorous acid to hypochlorite ion
(OCl-)
𝐻𝑂𝐶𝑙 → 𝐻 + + 𝑂𝐶𝑙 −
𝐻 + 𝑂𝐶𝑙 −
• 𝐼𝑜𝑛𝑖𝑧𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡 𝐾𝑖 = = 3𝑥10−8 𝑎𝑡 25𝑜 𝐶
𝐻𝑂𝐶𝑙
Because HOCl has no charge and it is better
• Total quantity of HOCl and OCl- is called free chlorine. able than other chlorine-based disinfectants
• Their distribution is important because HOCl is more effective in (i.e., hypochlorite ions) to penetrate the cell
killing. walls. Conversely negatively-charged ion OCl
is repelled as microbes have a negatively
charged wall (e.g., cell wall of bacteria).
 Chemistry of chlorine compounds
• Percentage distribution of HOCl at various
temperatures can be computed as below equation and
using pH of solution and K values from the table.

Ki values at different temperatures.

pH = -log [H+]
Percentage distribution of HOCl

Distribution of HOCl and OCl- at 0

and 20 oC at different pH. Lower
pH = HOCl is dominant.
Hypochlorite reactions in water
• Hypochlorite salts (sodium and calcium) also hydrolyse to form HOCl
as below.
• Then ionization of HOCl proceeds as discussed previously.
Chlorine and ammonia
• In water especially in wastewater, ammonia and other forms or nitrogen are
present.
• Hypochlorous acid being active oxidizing agent reacts readily with
ammonia to form chloroamines.
• 𝑁𝐻3 + 𝐻𝑂𝐶𝑙 → 𝑁𝐻2 𝐶𝑙 𝑚𝑜𝑛𝑜𝑐ℎ𝑙𝑜𝑟𝑜𝑎𝑚𝑖𝑛𝑒 + 𝐻2 𝑂
• 𝑁𝐻2 𝐶𝑙 + 𝐻𝑂𝐶𝑙 → 𝑁𝐻𝐶𝑙2 𝐷𝑖𝑐ℎ𝑙𝑜𝑟𝑜𝑎𝑚𝑖𝑛𝑒 + 𝐻2 𝑂
• 𝑁𝐻𝐶𝑙2 + 𝐻𝑂𝐶𝑙 → 𝑁𝐶𝑙3 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑡𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒 + 𝐻2 𝑂
• These combined forms (chloroamines) are called combined chlorine
residual as opposed to free chlorine.
• Dominant is monochloroamine and dichloroamine and formation depends
on chlorine to nitrogen ratios.
Breakpoint chlorination
• This terms means a point whereby enough chlorine is added to react with all
oxidizable substances such that if additional chlorine is added, it will remain
as free chlorine.
• Free chlorine reacts with other substances such ammonium ions and organic
matter because it forms a strong oxidizing agent in water i.e. hypochlorous
acid (HOCl)
• 𝐶𝑙2 + 𝐻2 𝑂 −→ 𝐻𝑂𝐶𝑙 + 𝐻+ + 𝐶𝑙 −
• First readily oxidizable substances are oxidized by chlorine such
as hydrogen sulphide, Fe etc.
• Then with ammonia to form chloroamines between point A and
peak of the curve.
• Mole ratio of chlorine to ammonia less than 1,
monochloroamines, dichloroamines are formed.
• At peak, mole ratio of chlorine to ammonium (as N) is equal to 1
and corresponding weight ratio is 5.06.
• Between peak and breakpoint some chloroamines are converted
to nitrogen trichloride and remaining are oxidized to nitrous
oxide and nitrogen and the chlorine is reduced to chloride ion.
• Continue chlorination after breakpoint will result in proportional
increase in the free chlorine.
• The chlorine demand is the amount of chlorine that must be
added to reach a desired level of residual

Overall reaction
Acid generation in chlorination
• Addition of chlorine gas produces
acid (HCl) due to hydrolysis reaction.
• Reaction is previously described
𝐶𝑙2 + 𝐻2 𝑂 → 𝐻𝑂𝐶𝑙 + 𝐻 + + 𝐶𝑙 −
• Reaction of HOCl as described in
breakpoint chlorination also produces
acid.

• Combining these two equations will

give how many H+ moles we need to
neutralise to avoid reducing pH.

• The alkalinity in water balances and

there is slight pH drop.
Increase in Total dissolved solids

• Check the above final reaction of breakpoint chlorination

• With chlorination, dissolved solids also get added.
• For example, this reaction; 6 moles of HCl, 2 moles of H+ are formed.
2 moles of NH4+ are removed.
• Incase of water reuse, increase in TDS should be checked before
supplying.
Example - Analysis of disinfection process
Step 1

Overall breakpoint chlorination reaction

Step 2

2mg/L is the ammonia concentration

Step 3
• Overall breakpoint chlorination reaction divided by 2, to
get value in per mole of ammonium ion.
• One mole produces 4 moles of H+
• To produce 4 moles of OH-, 2 moles of lime CaO are consumed or
56.08.
• Expressing CaO as CaCO3 factor is 100 because molecular weight
of CaCO3 is 100
Step 4
Modelling and Example 12-4