LEC-4

Water Treatment
 Water Treatment
1. Physical treatment
a) Storage
b) Physical coagulation
c) Filtration
2. Chemical treatment
a) Chemical coagulation
b) Water softening (Removing the Hardness)
c) Using Ion- Exchange units
3. Biological Treatment
a) Physical sterilization methods (Disinfection by) :
- Heating
- Using Uv Radiation
b) Chemical sterilization methods (Disinfection by) :
- Chlorination
- Ozonation
Purification of Drinking Water
Flow diagram

Conventional water treatment

Water supply

Chemical
additions Flocculation Removal of suspended materials
Sedimentation and precipitation by gravity

Filtration Removal of unsettled hardness

precipitate and residual floc

Chlorine, to establish residual

Disinfection 0.3 mg/L preventing bacterial
growing

Drinking water
 Purification of Drinking Water

Steps in a typical water treatment plan

- Coagulation (settling and precipitation)

- Hardness removal

- Disinfection
 Coagulation
◼ Coagulation (or settling and precipitation)
◼ The finest particles, such as colloidal minerals,
bacteria, and pollen do not settle in the raw
water.
◼ Removal of this colloidal particles is necessary:

◼ to give the finished water a clear appearance

◼ because they contain viruses and bacteria that

are resistant to later disinfection.
 Coagulation
◼ The capture of the fine particles is done by
adding to the water either iron(III) sulfate,
Fe2(SO4)3, or aluminum sulfate, Al2(SO4)3.

◼ In the case of aluminum sulfate, Al(OH)3 is

formed (in the pH range 6-8):
Al 3+ (aq) + 3 HCO 3- (aq) → Al(OH) 3 (s) + 3 CO2 (aq)
◼ At this pH values, Al(OH)3 is close to its
minimum solubility and at equilibrium very little
aluminum is left dissolved in the water.
 Coagulation
◼ Aluminum hydroxide forms a very
gelatinous precipitate, which settles very
slowly and which incorporate the colloidal
particles.
◼ With iron(III) sulfate the chemistry is
analogous
◼ Fe
3+ forms gelatinous iron hydroxide

Fe(OH)3.
◼ These reactions consume hydroxide

 pH decreases (neutralize alkaline water)

 Hardness Removal
◼ Hardness is characterized by the
concentration of Ca2+ and Mg2+.
◼ Major problem caused by hard water:
formation of mineral deposits.
◼ Calcium can be removed by addition
of phosphate (see later).
◼ A more common way is by
precipitation and filtering of insoluble
CaCO3
 Hardness Removal
◼ When the calcium is present primarily as
“bicarbonate hardness” (intermediate pH), it
can be removed by direct addition of
Ca(OH)2 alone:
Ca 2+ + 2HCO 3- + Ca(OH) 2 → 2 CaCO3 (s) + 2 H 2 O

◼ When bicarbonate ion is not present at

substantial levels, a source of CO3- must be
provided at a high pH to prevent conversion
of most of the carbonate to bicarbonate.
 Hardness Removal
◼ Source of carbonate ion: sodium carbonate, Na2CO3.

◼ The precipitation of magnesium as the hydroxide

requires a higher pH than the precipitation of
calcium as Ca
the2+ carbonate
+ CO32- → CaCO3 (s)

◼ The high pH required may be provided by the basic

carbonate ion from soda ash (Na2CO3)
2+
Mg + 2 OH → Mg(OH) 2 (s)
-
 Hardness Removal
◼ There are two main problems:
◼ Supersaturation effect: Some CaCO3 and
Mg(OH)2 usually remain in solution. They need to
be removed.
◼ Use of highly basic sodium carbonate, which
gives the product water an excessively high pH,
up to pH 11.
◼ Solution: water is recarbonated by bubbling
CO2 into it.
 The carbon dioxide converts the slightly soluble
calcium carbonate and magnesium hydroxide to
their soluble bicarbonate forms
 Disinfection
◼ Disinfection is the most essential part of water
treatment
◼ Disinfectant used in water treatment:
◼ chlorine
◼ chlorine dioxide
◼ ozone
◼ ultraviolet radiation
 Disinfection/Chlorine
◼ Chlorine dissolves in water:

◼ Aqueous chlorine rapidly hydrolyzes to form

hypochlorous acid: Cl (g)  Cl (aq)
2 2

◼ Hypochlorous acid is a weak acid that dissociates

according to the reaction: Ka = 3×108 mol/ L
Cl2 (aq) + H 2O  H + + Cl- + HOCl(aq)
HOCl(aq)  H + + OCl-
Disinfection/Chlorine - 2

Speciation of active chlorine as a function of pH

 Disinfection/Chlorine
◼ Sometimes (e.g. swimming pools)
hypochlorite salts, Ca(OCl)2, are
substituted for chlorine gas as a
disinfectant.
◼ The hypochlorite salts are safer to handle
than gaseous chlorine.
◼ Sodium hypochlorite, NaOCl, can also be
used as a substitute for chlorine.
◼ The hypochlorite ions is then converted to
hypochlorous acid:
OCl- + H 2O  HOCl + OH-
 Disinfection/Chlorine
◼ The two chemical species formed by chlorine in water, HOCl
and OCl-, are known as free available chlorine.
◼ Free available chlorine is very effective in killing bacteria (in
particular HOCl).
◼ HOCl(aq) about 10× more effective than ClO -(aq) –result of
the more lipophilic HOCl crossing bacterial membranes more
easily
◼ water with pH > 7.5 requires more chlorine – or longer
disinfection time – than water with pH < 7.5
◼ In the presence of ammonia chloroamines are formed.
◼ Alkaline pH will prevent the formation of these chloroamines.
◼ The chloroamines are called combined available chlorine.
◼ Breakpoint (Cl:N (wt/wt) =8:1)
 Disinfection/Chlorine
• important terms:
➢chlorine dose = concentration originally used
➢chlorine residual = concentration in the finished
water
➢chlorine demand = concentration consumed by
oxidizable substances present in the water
➢free available chlorine = sum of concentrations of
HOCl(aq) and ClO-(aq)
➢combined available chlorine = the concentration of
chloroamines
 Disinfection/Chlorine
Problems with the use of chlorine as a disinfectant:
◼ Simultaneous production of some toxic chlorinated
organic compounds (e.g. chlorinated phenol).
◼ Production of trihalomethanes (THMs), CHX3. Of
particular concern is the formation of chloroform,
CHCl3 (carcinogen, suspected to affect
reproductive system)
◼ chlorination byproducts, notably trihalomethanes.

◼ Example: chloroform CHCl3 which is often present

at 10ppb or more. Source is natural substances
(humic acids)
◼ >C(=O)CH3 + 3HOCl —> –CO2- + CHCl3 + 2H2O
 Disinfection/Chlorine Dioxide
◼ Chlorine dioxide, ClO2, is an effective water
disinfectant
◼ In the absence of impurity Cl2, it does not
produce THMs in water treatment.
◼ Chlorine dioxide oxidize organic molecules
by extracting electrons from them.
◼ Chlorine dioxide is a gas that is violently
reactive with organic matter and explosive
when exposed to light.
 Disinfection/Chlorine Dioxide
◼ Chlorine dioxide is generated on-site, for example by the
reaction of chlorine gas with solid sodium hypochlorite:

◼ unstable, must be made in situ

2 NaClO 2 (s) + Cl2 (g)  2 ClO 2 (g) + 2 NaCl(s)
◼ an oxidizing agent, not a chlorinating agent — no taste and
odour
10 2 + 5H2SO4 → 8ClO 2 + 5Na 2SO4 + 2HCl + 4H2O
problems
NaClO
◼ no residual effect – rapidly decomposes – must add Cl2
afterward
◼ Some concern has been raised over possible health effects of
its main degradation byproducts, ClO2- and ClO3- (chlorate)
ions.
Disinfection/Chlorine Dioxide
 Disinfection/Ozone
◼ Ozone (stronger oxidizer than O2) is
sometimes used as a disinfectant instead of
chlorine, particularly in Europe.
◼ unstable, must be made in situ – by electric
discharge on dry O2 (air)
◼ Process: air is filtered, cooled, dried, and
pressurized, then subjected to an electrical
discharge of approximately 20,000 volts.
◼ 3O2 —> 2O3 formed as a dilute mixture in air
◼ The ozone produced is then pumped into a
contact chamber where water contacts the
ozone for 10-15 minutes.
 Disinfection/Ozone
• ozonation equipment is expensive, only
economic on a large scale
• an oxidizing agent, not a chlorinating agent
– no taste and odour problems, but cannot
be used like ClO2 as a temporary
replacement for chlorine
• no residual in the water, decomposition is
pH dependent (also faster at higher water
temperature)
A typical ozone water-treatment system
ozone air
air dried
generator
air
corona
filter
water discharge
desiccator
contact
chamber pump
20,000 volts

compressed air
oxygen cooled
air

purified water
refrigeration
 Disinfection/Ozone
◼ Interest in ozonation arises from the
possible production of toxic
organochlorine compounds by water
chlorination.
◼ ozone is more destructive to viruses
than is chlorine.
◼ Unfortunately, the solubility of ozone in
water is relatively low, which limits its
disinfective power.
 Disinfection/Ultraviolet light
◼ Ultraviolet radiation having wavelenghts below 300
nm is very damaging to life, including
microorganisms by photochemical cross-linking of
DNA, which absorbs strongly at this wavelength
◼ Mercury lamps (germicidal lamps) are available,
having their output radiation principally at 254 nm
(UV-C at 254 nm – major output of a low pressure)
Advantage of UV method:
- Short contact time: 1-10 s. Ozone and chlorine
both require contact of 10-50 minutes, therefore
construction of a large reaction tank. UV
disinfection can be run on a simple “flow-through”
system (no holding tank)
 Disinfection/Ultraviolet light
Advantage of UV method:
- Low installation costs. Ozone generators are complex

and expensive to install; chlorine equipment is less so.

- Not influenced by pH or temperature. Chlorination and

ozonation work best at lower pH, chlorine because

more of it is in the HOCl rather than the OCl- form,
ozone because it decomposes more rapidly at high pH.
- applicable to large and small scale installations, even

domestic use
- No toxic residues.

◼ water must be clear and free of absorbing solutes

 Disinfection/Ultraviolet light
◼ Cost comparison between the various disinfectants:

Disinfectant Plant capacitya Costb

Cl2 0.05 26.0
0.5 3.0
1.0 1.7
ClO 2 0.05 52.5
0.5 11.1
1.0 8.6
O3 0.05 72.5
0.5 9.6
1.0 6.6
UV 0.05 21.9
0.5 7.2
1.0 5.3

• small installations: UV is cheapest, then chlorine

• large installations: chlorine is cheapest by a wide margin

The Treatment of Wastewater
and Sewage
 Pollutants in Sewage
◼ Typical municipal sewage contains
oxygen-demanding materials,
sediments, grease, oil, scum,
pathogenic bacteria, viruses, salts, algal
nutrients, pesticides, refractory organic
compounds and heavy metals.
◼ Major disposal problem with sewage:
the sludge produced as a product of the
sewage treatment process.
 Pollutants in Sewage
Constituent Potential sources Effects in water
Oxygen-demanding Mostly organic materials, Consume dissolved oxygen
substances particularly human feces
Refractory organics Industrial wastes, household Toxic to aquatic life
products
Viruses Human wastes Cause disease (possibly
cancer); major deterrent to
sewage recycle through
water systems
Detergents Household detergents Esthetics, prevent grease
and oil removal, toxic to
aquatic life
Phosphates Detergents Algal nutrients
Grease and oil Cooking, food processing, Esthetics, harmful to some
industrial wastes aquatic life
Salts Human wastes, water Increase water salinity
softeners, industrial wastes
Heavy metals Industrial wastes, chemical Toxicity
laboratories
Chelating agents Some detergents, industrial Heavy metal ion
wastes solubilization and transport
Solids All sources Esthetics, harmful to
aquatic life
 Sewage Treatment
◼ Three main categories:
- primary treatment: primary settling,
mechanical treatment
- secondary treatment: biological
treatment, include the related problem
of disposal of sewage sludge
- tertiary treatment: include advanced
treatment.
 Primary Treatment
◼ Primary treatment of waste water consists
of the removal of insoluble matter such as
grit, grease, and scum from water.
- First step: screening to remove or reduce

the size of trash and large solids that get

into the sewage system. The solids are
collected on screens and scraped off for
subsequent disposal.
- Second step: Grit removal.
 Primary Treatment
◼ In the second step the sewage enters a
large lagoon and moves through slowly
enough that any solid particles settle out.
◼ Some materials float at the surface of the
sewage (Those materials are called grease).
They are removed by a skimming device.
◼ The effluent form the primary settler is
almost clear, but has a high BOD (several
hundred milligrams per liter).
 Secondary Treatment
◼ Objective of the secondary treatment: to
reduce the BOD to acceptable level
(below 100 mg/L).
◼ The basic principle consists of the action
of microorganisms provided with added
oxygen degrading organic material in
solution or in suspension.
◼ Two main systems:
◼ Trickling filter

◼ Activated sludge
 Trickling Filter
◼ The simplest biological waste treatment.
◼ The trickling filter is a large round bed of
sand and gravel.
◼ A rotating boom sprinkle sprays the
wastewater over rocks or other solid
support material covered with
microorganisms.
◼ Main threat: presence of toxic substances,
which would kill the microorganisms.
◼ Disadvantage: require large space
◼ Advantage: low energy consumption
 Activated Sludge Reactor
◼ Very effective wastewater treatment.
◼ Require less land and, being enclosed, can
be maintained at the optimum
temperatures for biological activity.
◼ The reactor is a large tank in which the
wastewater is agitated and aerated to
provide the oxygen required by the
microorganisms.
◼ A portion of the sludge of microorganisms
is removed from the exit stream of the
reactor and recycled into the influent
stream.
 Activated Sludge Reactor

◼ Schematic of activated sludge reactor:

 Activate Sludge Reactor
◼ BOD may be removed by:
◼ oxidation of organic matter to provide energy
for the metabolic process.
◼ Synthesis, incorporation of the organic matter
into cell mass.
 Activated Sludge Reactor
◼ The water content in the sludge may be
removed by some drying process and the
resulting dewatered sludge may be
incinerated or used as landfill.
◼ To a certain extent, sewage sludge may be
digested in the absence of oxygen by
methane-producing anaerobic bacteria to
produce methane and carbon dioxide
◼ A well-designed plant may produce enough
methane to provide for all of its power needs.
 Tertiary Treatment
◼ In some cases a portion of the drinking
water is actually water that has been
discharged from a municipal sewage
treatment.
◼ Tertiary waste treatment (also called
advanced waste treatment): term used
to describe a variety of processes
performed on the effluent from the
secondary waste treatment.
 Tertiary Treatment
◼ The contaminants removed by tertiary
treatment fall into three general categories:
◼ suspended solids: responsible for residual
biological oxygen demand in secondary sewage
effluent waters.
◼ dissolved organic compounds: they are
potentially the most toxic
◼ dissolved inorganic materials: the major problem:
nitrates and phosphates (nutrient for algae). Also,
potentially hazardous toxic metals may be found
among the dissolved inorganics.
 Removal of Solids
◼ Some of the colloidal particles
are removed using aluminum
salt which forms Al(OH)3.
◼ Similar to the process described

during the purification of the

drinking water.
 Removal of Dissolved Organics
◼ The standard method for removal of
dissolved organic material is by adsorption
on activated carbon.
◼ Activated carbon is characterized by a very
large surface area.
◼ The carbon is regenerated by heating it to
950C in a steam-air atmosphere.
◼ Adsorbent synthetic polymers can also be
used instead of activated carbon. They are
regenerated by using solvent such as
isopropanol and acetone.
 Removal of Dissolved Inorganics
◼ The effluent of secondary waste
treatment generally contains 300-400
mg/L more dissolved inorganic material
than does the municipal water supply.
◼ The most cost-effective methods of
removing inorganic material from water
is currently membrane processes.
◼ Methods considered: reverse osmosis,
electrodialysis, and ion exchange.
Water Desalination
 Removal of Dissolved Inorganics
◼ Methods considered: reverse osmosis,
electrodialysis, and ion exchange.

◼ These methods used for: Desalination

process which helps to remove salts
from sea water to make it drinkable
 Reverse Osmosis
◼ Basic principle: force water through a
semipermeable membrane that allows the
passage of water but not other material.
 Electrodialysis
◼ Basic principle: apply a direct current across a
body of water separated into vertical layers by
membranes alternately permeable to cations
and anions.
◼ Cations migrate toward the cathode and anions
toward the anode.
 Layers of water enriched in salts alternate with
those from which salts have been removed.
Electrodialysis
 Ion Exchange
◼ Basic principle: passing the water successively
over a solid cation exchanger and a solid anion
exchanger, which replace cations and anions by
hydrogen ion and hydroxide ion, respectively.

H + -{Cat(s)} + M + + X- → M + -{Cat(s)} + H + + X-

OH− + {An(s)} + H + + X- → X − + {An(s)} + H 2O

◼ The cation exchanger is regenerated with strong
acid and the anion exchanger with strong base.
Waste Water Treatment Methods

◼ aeration to remove volatile solutes

◼ precipitation of divalent cations
◼ coagulation and flocculation
◼ settling
◼ filtration
◼ disinfection
 A typical municipal water treatment plant

lime coagulant
Raw water

first basin:
aerator insoluble second basin: filter
Mg2+ Ca2+ flocculation
precipitate

carbon chlorine
dioxide

Clean water
sludge lagoon