‫بسم هللا الرحمن الرحيم‬

Albaha University
Faculty of Science
Chemistry Department

Water treatment

Major elective I (CHEM10707)

Chapter 1
Chemical and physical properties of water
1
 Water is a polar molecule
(‫)ا لماء جزىء ق طبى‬
• In each water molecule, the oxygen atom
attracts more than its "fair share" of
electrons
• The oxygen end “acts” negative
• The hydrogen end “acts” positive
• Causes the water to be POLAR
• However, Water is neutral (equal number of
e- and p+) --- Zero Net Charge

2
 Water molecules
slightly positive
charge

hydrogen bond between

(+) and (-) areas of
different water molecules

slightly negative charge

3
Hydrogen Bonds exist between water molecules

• Formed between a highly electronegative atom of

a polar molecule and a hydrogen
• One hydrogen bond is weak , but many hydrogen
bonds are strong

Negative oxygen end of one water molecule is

attracted to the positive hydrogen end of another
water molecule to form a HYDROGEN BOND
 Water’s Properties
(‫)خصائصا لماء‬
• Cohesion – Adhesion - Capillarity
• High Specific Heat
• High Heat of Vaporization
• Density
• Solvent
• Salinity – Hardness
• pH
• Dissolved gases
• Transparency - Turbidity
• Conductivity
• Taste and odor

5
 Cohesion
• Water clings to polar molecules through
hydrogen bonding
– Cohesion : Attraction between particles
of the same substance (water is
attracted to itself)
• Results in surface tension : a measure of
the strength of water’s surface : a measure
of the force necessary to stretch or break
the surface of a liquid
• Produces a surface film on water that
allows insects to walk on the surface of
water

6
 Adhesion

• Attraction between two different

substances.
• Water will make hydrogen bonds with
other surfaces such as glass, soil, plant
tissues, and cotton.
• Capillary action-water molecules will “tow”
each other along when in a thin glass tube.
• Example: transpiration process which
plants and trees remove water from the
soil, and paper towels soak up water.

7
 High Specific Heat
• Amount of heat needed to raise or lower 1g
of a substance 1° C.

• Water resists temperature change, both for

heating and cooling.

• Water can absorb or release large amounts

of heat energy with little change in actual
temperature.
 High Heat of Vaporization

• Amount of energy to convert 1g or a

substance from a liquid to a gas

• In order for water to evaporate, hydrogen

bonds must be broken.

• As water evaporates, it removes a lot of

heat with it.
 High Heat of Vaporization
• Water's heat of vaporization is 540 cal/g.
• In order for water to evaporate, each gram
must gain540 calories (temperature doesn’t
change --- 100oC).
• As water evaporates, it removes a lot of heat
with it (cooling effect).
• Water vapor forms a kind of global ‘‘blanket”
which helps to keep the Earth warm.
• Heat radiated from the sun warmed surface of
the earth is absorbed and held by the vapor.
 Water is less dense as a solid

• Ice is less dense as a solid than as a liquid (ice

floats)
• Liquid water has hydrogen bonds that are
constantly being broken and reformed.
• Frozen water forms a crystal-like lattice
whereby molecules are set at fixed distances.
 Water is less dense as a solid

Which is ice and which is water?

 Solutions & Suspensions
• Water is usually part of a mixture.
• There are two types of mixtures:
– Solutions
– Suspensions
 Solution
• SOLUTE
– Substance that is being dissolved
• SOLVENT
– Substance into which the solute dissolves

Suspension
• Substances that don’t dissolve but separate into tiny
pieces.
• Water keeps the pieces suspended so they don’t settle
out.
 Salinity
• The amount of dissolved solids in water
– Includes ions of chloride (Cl-), sodium (Na+),
sulfate (SO42-), magnesium (Mg2+), calcium (Ca2+)
and potassium (K+)
• Measured using a hydrometer to calculate specific
gravity, or by conductivity. Units would be
measured in ppt.
• Surface salinity is greatly influenced by
temperature.
– High temps cause increased evaporation rates
and increased salinity.
15
16
 Hardness
• Hard water is water that has high mineral content,
mainly salts of calcium and magnesium.
• Calcium in water mainly due to the presence of
limestone, gypsum, dolomite.
• Magnesium salts occur in natural waters, sea
waters (130ppm).
• These salts are estimated as CaCO3

17
 Dissolved gases
Dissolved nitrogen
• Dissolved nitrogen is the most common gas N2 in the ocean.
Dissolves from the atmosphere where it is 78%.
– Nitrogen gas can’t be used by organisms until it is attached to
oxygen in a process called nitrogen fixation.
– Nitrogen fixation occurs because blue-green algae convert N 2 gas to
a useable form that animals need for building proteins and amino
acids.
• N can be present in water as NH3, NH4+ , NO3-, NO2-

18
 Dissolved oxygen
• Primarily comes from photosynthesis of marine
plants and algae. They produce over 50% of the total
atmospheric oxygen O2.
• Dissolved oxygen indicates health of an aquatic
system.
• Can range from 0 to18 ppm.
• Most natural water systems require 5-6 ppm to
support a diverse population.

Solubility of dissolved
oxygen in fresh water

19
Dissolved carbon dioxide (CO2)
• Carbon dioxide is highly soluble in sea water
which contains about 50 times more CO2 than the
atmosphere.
– Enters the water from air as well as through
respiration.
• Can be depleted at surface by plants.
• Necessary for shell formation.
• Oceans remove and store CO2 which remain
relatively constant at 45-54 ml/liter of sea water.

20
 pH

• In sea water, pH is between 7.5 –8.5

– Closely associated to dissolved CO2
• CO2 is a reactant in photosynthesis and a product of
respiration.
– Dissolves easily in sea water and is stored in marine shells
and sediments.
• H2O + CO2 = H2CO3, Lowers pH
• H2CO3 = HCO3-+ H+, raises pH
• Both reactions change the pH of the water.
• pH is expressed on a scale from 0 -14 21
The pH scale

22
 Carbon Forms and pH of Water Bodies
• Carbonic acid (H2CO3), Bicarbonate (HCO3- ), and Carbonate
(CO32-).
• H2CO3 = H+ + HCO3- = CO32- + 2H+
1
Fraction of each carbonate species

H2CO3 HCO -
0.8 3 2-
CO3
e
or
M 2

te

e
CO

na

at
0.6

on
rb

rb
ca

Ca
Bi

0.4

0.2

0
4 5 6 7 8 9 10 11
Seawater pH
 Transmission of light

• light in the sea comes from two sources: sun and organisms
• a large portion of the electromagnetic radiation from sun
(or moon) is reflected back into atmosphere -- so only the
upper kilometers of the water column are illuminated
• light below the surface differs from that above in both
quality and quantity because a major change occurs at the
air-sea surface interface 

24
 Light control

• Marine plants (autotrophs) make their own food

by photosynthesis. Heterotrophs can’t make food
so they eat plants.
• The cycle depends on light entering the water
which may be absorbed or reflected.
– About 65% of light energy is absorbed in the first 5 feet
and can’t be used by autotrophs.

25
 Light penetration
• Water absorption preferentially removes both long
(red) and short (ultraviolet) wavelengths, rapidly
resulting in near-monochromatic blue light, which is
then reduced by 90% for every 70 m of depth 
– in coastal waters material from plant decay can absorb
additional short wavelengths, resulting in a greenish hue to
the water
– turbidity allows green wavelengths to penetrate

• Blue is transmitted best

• Light is inversely proportional to depth. As you descend, it
gets darker.
26
27
 Turbidity

•Turbidity is a measure of the suspended sediments.

•More sediments results in less light penetration and

poor visibility. Photosynthesis is reduced.
•The compensation zone is the depth where the rate
of photosynthesis = rate of respiration.
–Oxygen production = rate of respiration

28
 Turbidity
• Indicates “Total suspended solids” (TSS) in water
• High turbidity in e.g. monsoon period

“Turbidimeter”: measures light scattered at 900

Turbidity unit: JTU = FTU= NTU: Nephelometric

turbidity units.

WHO guideline 5 NTU.

In some (tropical) rivers during monsoon:1000 NTU!

29
Turbidity

• Turbidity can be measured

with a Secchi Disk as visibility.
• Divide the depth of the Secchi
line by the water’s depth.
• Turbidity is lower in areas of
high productivity.

30
 Pressure
• Pressure at sea level is the weight of air
(14.7 Psi)
• As you descend, pressure results from the
weight of the water above you (hydrostatic
pressure) as well as air pressure.

31
 Pressure going down
• For every 33 feet = 1 atm of pressure
• At 100 feet = 4 atm of pressure or 58.8 psi
• Increased pressure lowers water’s freezing point
without affecting the volume.

• When ascending, the air volume in your lungs

expands. The lungs could be ruptured if you do not
continuously exhale.

• There is a limit to how much pressure a person can

with stand. It varies due to experience but safe,
recreational diving stops at 130 feet.
32
Clausius–Clapeyron diagram

33
 ELECTRICAL CONDUCTIVITY (EC)
• EC is reciprocal of electrical resistance; it indicates
presence of cations (K+; Na+,Ca2+….) and anions (Cl- ; HCO3- ;
SO42- …)
• Unit: μS/cm or mS/m (S=Siemens). Values in most natural
waters: 10-1000 μS/cm
• Measure electrical current in the solution by using
electrical circuit with two platinum plates.
• EC is often used as (fully automated) water quality check
for TDS (total dissolved solids), e.g. for drinking water.
In agriculture for quality of the irrigation/drainage water.
34
 REDOX POTENTIAL (Eh)
• Connected with “aerobic” vs “anaerobic” conditions of
surface/groundwaters
• Expressed in (milli)Volts.
- At low redox potential (e.g. : -200 mV), we can
expect presence of “reduced” components: S2- ; CH4;
Fe2+ ; NH4+, …
- At high redox potential (e.g.: +500 mV), we can
expect presence of “oxidized” components: O2 ; NO3- ;
Fe3+ ; SO42- ..
• Measurement: with Eh electrode

35
 Taste and Odor
• There are several possible causes of taste and odor
problems in drinking water.
• Many taste and odor compounds have very low
thresholds
• Most taste and odor compounds are not a health
concern, but some can be.
• Taste and odor problems may create the
perception that water is not safe to drink.

36
 Overview
Taste/Odor Chemical Source
Chlorine taste & odor Chlorine (Cl) Too much chlorine
Chlorine odor Chloramines (R-NHCl) Chlorine below breakpoint
Fruity odor Aldehydes Ozonation
Rusty or metallic Iron (Fe) Naturally occurring,
taste corroded pipes
Rusty or metallic Manganese (Mn) Naturally occurring
taste
Sulfur taste and odor Hydrogen Sulfide Naturally occurring
(H2S)
Musty taste and odor Geosmin Blue-Green Algae
Musty taste and odor 2-Methylisoborneol Blue-Green Algae
(MIB)
Fishy, grassy Various Algae
 2-methylisoborneol (MIB)

Aldehyde

38
 Water age
• Water quality can change over time:
– Lower chlorine residual
– Increased bacterial growth (biofilms)
– Changes in temperature, pH, dissolved O2
– Precipitation of minerals
– Increased disinfection byproducts
– Taste & odor problems

39
 Relationships of parameters
• Properties of water are interconnected. Their
relationship to each other demonstrates how
easily the delicate balance can be disturbed.
– Direct relationship = Two parameters both
increase or decrease at the same time
– Inverse relationship = one parameter increase,
while the other decreases.

40
 Water treatment

Major elective I (CHEM10707)

Chapter 2

Basic physical-chemical processes in water

treatment
41
 Technologies
• Chemical methods
Coagulation, flocculation, combined with flotation and
filtration, precipitation, ion exchange, electroflotation,
electrokinetic.
• Physical methods
Membrane-filtration processes (nanofiltration, reverse
osmosis, electrodialysis, . . .) and adsorption techniques.
• Biological treatments
Biodegradation methods such as fungal decolorization,
microbial degradation, adsorption by (living or dead)
microbial biomass and bioremediation systems

42
 Advantages and disadvantages
Chemical methods
Advantages :
• Rapid and efficient process
• Removes all pollutants types, produce a high-quality
treated effluent
• No loss of sorbent on regeneration and effective
Disadvantages :
• Expensive, and although the pollutants are removed,
accumulation of concentrated sludge creates a
disposal problem
• High energy cost, chemicals required.
43
 Advantages and disadvantages
Physical methods
Advantages :
• The most effective adsorbent, great, capacity,
produce a high-quality treated effluent
• No sludge production, little or no consumption of
chemicals.
Disadvantages :
• Economically unfeasible, formation of by-products,
technical contraints
44
 Advantages and disadvantages
Biological treatments
Advantages :
• Economically attractive, publicly acceptable
treatment
Disadvantages :
• Slow process, necessary to create an optimal
favorable environment, maintenance and
nutrition requirements

45
 Coagulation
• Definition
destabilisation of colloid particles by the
addition of chemicals (coagulant)
• Applications
Industrial waste containing colloidal and
suspended solids (e.g. pulp and paper, textile)

46
47
 Coagulant type
• Metal coagulants :aluminium-based
coagulants, Fero-based coagulants magnesium
chloride (MgCl2)
• Organic polymer coagulants : Polyacrylamide,
Chitosan, Moringa olifeira Alginates (brown
seaweed extracts)

48
 Coagulant agent

Alum
Magnesium chloride

Polyacrylamide

Moringa oleifera
Chitosan
49
 Coagulant - Reaction
• Some of the coagulants used include:
· Aluminium sulphate
· Ferric chloride
· Ferric sulphate
· Lime (not true coagulant)
· Polymer as coagulant aid eg cationic, anionic, non-ionic.
· PAC – new types

Al2(SO4)3.18H2O+ 3Ca(HCO3)
2Al(OH)3+ 3CaSO4+ 6CO2 + 18H2O
Al(OH)3 or Al2O3 ( form as floc is the key element causing
destabilisation of charge).
50
 Flocculation
• is a process of forming aggregate of flocs to
form larger settleable particle. The process
can be described as follows:
· Mutual collision of small floc resulting in bigger
size.
· Usually slow speed or gentle mixing is used so
as not to break the large flocs due to shear.
· Polymer or large molecular weight compound
is added to enhance floc build up. Most of
them are proprietary chemicals.
51
Flocculation mechanism

52
Flocculation mechanism

53
Flocculation mechanism

54
Raw waste Floc Formation Settle floc

55
 Flocculation

• The benefits of flocculation are:

· To improve settling of particles in

sedimentation tank
· To increase removal of suspended
solids and Biological Oxygen Demand
· To improve performance of settling
tanks

56
 Differences
• Coagulation: is a chemical
technique which is directed
towards the destabilisation
of the charged colloidal
particals.

• Flocculation: is the slow

mixing technique which
promotes the
agglomeration of the
stabilised particles.

57
58
59
 CHEMICAL PRECIPITATION
• Definition:
Removal of metal ions from
solution by changing the
solution composition, thus
causing the metal ions to
form insoluble metal
complexes.
chemical
solution with insoluble “clean
reaction +
soluble ions complexes Water”

Cu2+ + 2 OH- = Cu(OH)2

Fe3+ + 3 OH- = Fe(OH)3
Fe2+ + 2 OH- = Fe(OH)2 60
Natural methods of precipitation include settling or sedimentation,
where a solid forms over a period of time due to ambient forces like
gravity or centrifugation

61
 CHEMICAL PRECIPITATION
(Applications)
• Removal of metals from waste stream
– e.g. plating and polishing operations, mining, steel manufacturing,
electronics manufacturing
– include arsenic, barium, chromium, cadmium, lead, mercury, silver

• Treatment of “hard” water – removal of

Mg2+ and Ca2+
• Phosphorus removal
• Making pigments
• Removing salts from water in water
treatment
62
 CHEMICAL PRECIPITATION
(Theoretical Background)
• Solubility equilibria
A chemical reaction is said to have reached equilibrium
when the rate of forward reaction is equal to the rate of
the reverse reaction

ABs  A+ + B-

where ABs : solid; A+, B- - ionic species

63
 CHEMICAL PRECIPITATION
(Theoretical Background)
Due to dilute concentration,
Ksp = [A+] [B-]
= solubility product constant
where [ ] refer to molar
concentration

A+ + B- Solubility
Compound (mg/L) Ksp

CaCO3 18 5 x 10-9

ABs CaCl2 745000 159 x 106

CaCO3 = Ca2+ + CO32-

64
 Solubility Equilibria
molar solubility = [S]

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp is the solubility product constant
Ksp = [Ag+][Cl-]

MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2

Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]

Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2

Dissolution of an ionic solid in aqueous solution:

Q < Ksp Unsaturated solution No precipitate

Q = Ksp Saturated solution

Q > Ksp Supersaturated solution Precipitate will form

 What is the solubility of calcium carbonate in g/L ?
(Ksp = 5 x 10-9)

2- Ksp = 5 x 10-9
CaCO3 (s) Ca (aq) + CO3 (aq)
2+

Initial (M) 0.00 0.00

Ksp = [Ca2+][CO32-]
Change (M) +s +s Ksp = s2

Equilibrium (M) s s 
s = Ksp

s = 7,07 x 10-5

[Ca2+] = 7,07 x 10-5 M

[CO32-] = 7,07 x 10-5 M

7,07 x 10-5 mol CaCO3 100 g CaCO3

Solubility of CaCO3 = x = 7,07 x 10-3 g/L
1 L soln 1 mol CaCO3
 Exercise :
Solubility of CaSO4 is 0,67 g/L. Calculate Ksp
m (gm ) 0.67 g
n   4.9  10 3 mol
M.wt. 136 .2g / mol

CaSO4 (s) ⇋ SO42-(aq) + Ca2+(aq)

Solubility S S

Ksp = [Ca2+(aq)] [SO42-] (aq)

Ksp = [S] [S]

Ksp = s2 = [4.9 x 10-3]2 = 2.4 x 10-5

 CHEMICAL PRECIPITATION
(Basic Principles)
A. Add chemical
precipitants to
waste stream
B. Mix thoroughly
C. Allow solid
precipitates to
form floc by slow
mixing
D. Allow floc to settle
in clarifier

68
 CHEMICAL PRECIPITATION
(Types of Precipitation)

Heavy metals are removed with

• Hydroxide precipitation (OH-)
• Sulphide precipitation (S2-)
• Carbonate precipitation (CO32-)

Phosphorus removal
• Phosphate precipitation (PO43-)

69
 CHEMICAL PRECIPITATION
(Hydroxide Precipitation)
• Add lime (CaO) or sodium hydroxide (NaOH) to waste
stream to precipitate heavy metals in the form of metal
hydroxides.

Cd2+ + Ca(OH)2  Cd (OH)2  + Ca2+

• CaO in the form of slurry (Ca(OH)2) while NaOH in the

form of solution.
• NaOH is easier to handle but is very corrosive.
• Will form floc and settle in clarifier

70
 CHEMICAL PRECIPITATION
(Sulphide Precipitation)
• Use of sulphide in the form of FeS, Na2S or NaHS
• Better metal removal as sulphide salt has low solubility
limit
Cu2+ + FeS  CuS  + Fe2+
• Limitation : can produce H2S (g) at low pH
2 H+ + FeS  H2S + Fe2+
• At low pH, reaction will proceed to the right. Thus,
require pH > 8 for safe sulphide precipitation.

71
 Water Softening
– Hard water : is usually defined as water which contains a
high concentration of Ca2+ and Mg2+ ions.
– Water Softening : is the removal of hardness from water.
– Types of Hardness
• Carbonate hardness (Temporary Hardness)
– Calcium bicarbonate Ca(HCO3)2
– Magnesium bicarbonate Mg(HCO3)2
• Non-carbonate hardness (Permanent Hardness)
– Calcium sulfate CaSO4 and chloride CaCl2
– Magnesium sulfate MgSO4 and chloride MgCl2
 Water Softening
• Classification of water according to its hardness:

Soft < 50 mg/L as CaCO3

Moderately Soft 50 – 150 mg/L as CaCO3
Hard > 150 – 300 mg/L as CaCO3
Very Hard >300 mg/L as CaCO3

73
 Water Softening
• Hardness Impact
– Case water to form scales and resist to soap.
– Clog pipes
– Causes excessive use of soaps and detergents.
– Hard water harms many industrial processes.
– Ruin water heaters and boilers.
– Reduce heating efficiency.
 Water Treatment
Softening (Chemical Precipitation)
• Water Softening Methods
– Chemical precipitation: [lime – soda ash
softening]. By using lime Ca(OH)2 and soda ash
Na2CO3
– Advantages:
• Aids in coagulation
• Aids in disinfection
• Help precipitates heavy metals.
– Disadvantages
• Large quantities of sludge
 Water Softening (Chemical
Precipitation)
• Chemistry of Precipitation Softening
– Lime is added to remove carbonate hardness
– Soda ash is added to remove non-carbonate
hardness
– CO2 is applied after lime treatment to lower pH (re-
carbonation).
– Lime softening consists of raising the waters pH to
produce calcium carbonate and magnesium
hydroxide which settle out of the water.
 Water Softening (Chemical
Precipitation)

– Lime Softening
Ca(HCO3)2 + Ca(OH)2  2 CaCO3 ↓ + 2 H2O (pH=9.25)
Mg(HCO3)2 + Ca(OH)2  CaCO3 ↓ + MgCO3 ↓ + 2 H2O
– Ca (OH)2 Ca2+ + 2 OH-
– Soda Ash Softening
CaSO4 + Na2CO3  CaCO3 ↓ + Na2SO4
CaCl2 + Na2CO3  CaCO3 ↓ + 2 NaCl

77
Water Softening (Chemical Precipitation)

– Lime-Soda Ash Softening

MgSO4 + Ca(OH)2 + Na2CO3  CaCO3 ↓ + Mg(OH)2
↓ + NaCO3

– Re-carbonation
Ca(OH)2 + CO2  CaCO3 ↓ + H2O
CaCO3 + CO2 +H2O  Ca(HCO3)2

78
 ION EXCHANGE
• Definition
Ion exchange is basically a reversible chemical process
wherein an ion from solution is exchanged for a similarly
charged ion attached to an immobile solid particle.
Removal of undesirable anions and cations from solution
through the use of ion exchange resin
• Applications
– Water softening
– Removal of non-metal inorganic
– Removal or recovery of metal

79
 ION EXCHANGE
(Medium - resin)
• Consists of an organic or inorganic
network structure with attached
functional group
• Synthetic resin made by the
polymerisation of organic compounds
into a porous three dimensional
structure
• Exchange capacity is determined by
the number of functional groups per
unit mass of resin

80
 ION EXCHANGE
(Type of Resin)
a. Cationic resin - exchange positive ions
b. Anionic resin – exchange negative ions

(a) (b)

81
 ION EXCHANGE
(Exchange Reactions)
• Cation exchange on the sodium cycle :

Na2 · R + Ca2+  Ca · R + 2Na+

where R represents the exchange resin. When all exchange sites are
substantially replaced with calcium, resin is regenerated by passing a
concentrated solution of sodium ions (5-10%) through the bed:

2Na+ + Ca · R  Na2 · R + Ca2+

82
 ION EXCHANGE
(Exchange Reactions)
Softening : Anion exchange replaces anions with hydroxyl ions:

SO42- + R · (OH)2  R · SO4 + 2OH-

where R represents the exchange resin.
Regeneration : when all exchange sites are substantially replaced with
sulphate, resin is regenerated by passing a concentrated solution of
hydroxide ions (5-10%) through the bed:

R · SO4 + 2OH-  SO42- + R · (OH)2

83
 ION EXCHANGE
(Basic Principles)
H+, CN- H+, OH- Clean
water

Anion
Cation
Resin
Resin

Cr3+, CN-

84
 ION EXCHANGE
(Selectivity)
• Cations:
Ra2+ > Ba2+ > Sr2+ > Ca2+ > Ni2+ > Cu2+ > Co2+ > Zn2+ > Mn2+ > Ag+
>Cs+ > K+ > NH4+ > Na+ > H+ > Li+

• Anions:
HCRO4- > CrO42- > ClO4- > SeO42- > SO42- > NO3- > Br- > HPO4- >
HAsO4- > SeO32- > CO32- > CN- > NO2- > Cl- > H2PO4-, H2AsO4-,
HCO3- > OH- > CH3COO- > F-

Note: The least preferred has the shortest retention time, and
appears first in the effluent and vice versa for the most
preferred.

85
 ION EXCHANGE
(Selectivity)
Some contaminants are not easy to remove by
conventional ion exchange resins. In many cases, very
specific resins have been developed for these
contaminants. Selective resins are available today for the
removal of :
•Boron
•Nitrate
•Perchlorate
•Nickel
•Chromate

86
ION EXCHANGE
.

87
 Reaction rate

• Reaction rate is a measure of how fast a reaction occurs, or

how something changes during a given time period.
• A common measure of reaction rate is to express how the
concentration of a reaction participant changes over time.
• It could be how the concentration of a reactant decreases, or
how the concentration of a product increases. This is the
standard method we will be using.
• Rate is a measure of how something changes over time.
Rate = Change in concentration
Change in time

88
• Let's try an example of calculating a reaction rate. Consider
the following reaction:
A→B
• The following data were obtained for how the concentration
of these substances changed during the experiment.

Time A B
(min) mol/L mol/L
0.0 1.000 0.000
3.0 0.400 0.600
6.0 0.250 0.750

89
We could measure the rate of the reaction either by measuring how the concentration of
reactant A changes or how the concentration of product B changes. Let's measure A's
average rate of change first:

the delta symbol, Δ is used to indicate a change. ΔT, for example, means "the change in
temperature."

Compare this rate to the rate of just the first three minutes of the reaction:

If we calculate the average rate based on the production of product B:

90
 Factors that Affect the Chemical Reaction
Rate
• Concentration of Reactants
A higher concentration of reactants leads to more effective
collisions per unit time, which leads to an increasing reaction
rate (except for zero order reactions).
• Temperature
Usually, an increase in temperature is accompanied by an
increase in the reaction rate. Temperature is a measure of the
kinetic energy of a system

91
 Factors that Affect the Chemical Reaction
Rate
• Medium
The rate of a chemical reaction depends on the medium in which
the reaction occurs. It may make a difference whether a medium
is aqueous or organic; polar or nonpolar; or liquid, solid, or
gaseous.
• Presence of Catalysts and Competitors
Catalysts (e.g., enzymes) lower the activation energy of a chemical
reaction and increase the rate of a chemical reaction without
being consumed in the process.
Catalysts work by increasing the frequency of collisions between
reactants, altering the orientation of reactants so that more
collisions are effective, reducing intramolecular bonding within
reactant molecules.
92
 Water treatment

Major elective I (CHEM10707)

Chapter 3

Oxidation and Chlorination

93
 Oxidation
a method by which wastewater is treated by using oxidizing
agents.
Generally, two forms :
• Chemical oxidation
• UV assisted oxidation using chlorine, hydrogen peroxide,
ozone, or potassium permanganate are used for treating
the effluents, especially those obtained from primary
treatment (sedimentation)
94
 CHEMICAL OXIDATION
(Oxidants)

• Rapid and efficient process

• High energy cost, chemicals required

REDOX
Oxidation and reduction in terms of oxygen transfer

Definitions
Oxidation is gain of oxygen.
Reduction is loss of oxygen.

• Fe2O3 + 3CO  2Fe + 3CO2

95
 Another definition
Oxidation and reduction in terms of hydrogen transfer
– These are old definitions which aren't used very much
nowadays. The most likely place you will come across
them is in organic chemistry.
Definitions
•Oxidation is loss of hydrogen.
•Reduction is gain of hydrogen.

CH3CH2OH CH3CHO
Oxidation by loses of hydrogen

96
 Another definition
Oxidation and reduction in terms of electron
transfer
• This is easily the most important use of the
terms oxidation and reduction at A' level.
Advanced level

Definitions
• Oxidation is loss of electrons. OIL
• Reduction is gain of electrons. RIG
OIL RIG  oxidation is loss, reduction is gain
CuO + Mg  Cu + MgO
Cu2+ + Mg  Cu + Mg2+
97
 Oxidation States (Oxidation Numbers)

• Oxidation state shows the total number of

electrons which have been removed from an
element (a positive oxidation state) or added
to an element (a negative oxidation state) to
get to its present state.
– Oxidation involves an increase in oxidation state
– Reduction involves a decrease in oxidation state

98
 Some elements almost always have the
same oxidation states in their compounds:
• Group 1 metals : always +1
• Group 2 metals : always +2
• Oxygen : usually -2 except in peroxides and F2O
• Hydrogen : usually +1 except in metal hydrides where it
is -1
• Fluorine : always -1
• Chlorine : usually -1 except in compounds with O or F

99
100
 Example 1:
• This is the reaction between magnesium and hydrochloric
acid or hydrogen chloride gas:
Mg + 2HCl MgCl2 + H2
0 +1 -1 +2 -1 0
• The magnesium's oxidation state has increased - it has been
oxidised. The hydrogen's oxidation state has fallen - it has
been reduced. The chlorine is in the same oxidation state on
both sides of the equation - it hasn't been oxidised or
reduced.

101
 Example 2:
• The reaction between sodium hydroxide and
hydrochloric acid is:
NaOH + HCl  NaCl + H2O
+1 -2 +1 +1 -1 +1 -1 +1 -2

• Nothing has changed. This isn't a redox

reaction.

102
 Example 3:
• The reaction between chlorine and cold dilute
sodium hydroxide solution is:
2NaOH + Cl2  NaCl + NaClO + H2O
+1 -2 +1 0 +1 -1 +1 +1 -2 +1 -2

• One atom has been reduced because its

oxidation state has fallen. The other has been
oxidised.

103
 Common oxidizing agents

• Hydrogen peroxide (H2O2) and other inorganic peroxides

• Nitric acid (HNO3) and Nitrates (NO3-)
• Chlorites (ClO2-), chlorate (ClO3-), perchlorate (ClO4-), and
other analogous halogen compounds
• Hypochlorite (ClO-) and other hypohalite compounds such as
bleach
• Fluorine and other halogens
• Ozone (O3)
• Nitrous oxide(N2O)
• Silver oxide (AgO)
• Permanganate salts (MnO4-)

104
 Hydrogen peroxide
• In acidic solutions H2O2 is one of the most powerful
oxidizers known—stronger than chlorine, chlorine dioxide,
and potassium permanganate.
• Also, through catalysis, H2O2 can be converted into
hydroxyl radicals (.OH), which are highly reactive.
• H2 + O2 → H2O2
• It is used as a disinfectant, antiseptic, oxidizer, propellant
in rocket. Hydrogen peroxide is naturally produced in
organisms as a by-product of oxidative metabolism. Nearly
all living things (specifically, all obligate and facultative
aerobes) possess enzymes known as peroxidase.

105
 Iron and Manganese Removal
• Aeration, Chemical Oxidation, Sedimentation and
filtration.
– The common method for the removal of Fe and Mn
from well water without softening.
– Aeration: to initiate oxidation of Fe++ and Mn++.
– Aeration oxidize the soluble ferrous iron (Fe2+) to
insoluble ferric iron (Fe3+)
– High removal of Mn2+ is not possible by this
technique because manganese cannot be oxidized
as easily as iron with plain aeration.
 Oxidation of Fe and Mn 2+ 2+

– Chemical oxidation (e.g. potassium permanganate KMnO4,

chlorine): to oxide Fe++ and Mn++:

Fe(HCO3)2 + KMnO4  Fe(OH)3 ↓ + MnO2 ↓

Ferrous bicarbonate Ferric hydroxid Manganese dioxide
Mn(HCO3)2 + KMnO4  MnO2 ↓
Manganous bicarbonate Manganese dioxide

– Theoretically, 1 mg/L of potassium permanganate oxidizes

1.06 mg/L of iron and 0.52 mg/L of manganese
• Example
– A well water supply contains 3.2 mg/L of iron and
0.8 mg/L of manganese. Estimate the dosage of
potassium permanganate required for the iron
and manganese oxidation.

KMnO4 required = 3.2 x (1.0/1.06) + 0.8 x (1.0/0.52)

= 3.02 + 1.54 = 4.6 mg/L
 Electrochemical treatment
• During redox reactions, electrons pass from one substance to
another. Electrochemistry is the branch of chemistry that deals with
the conversion between chemical and electrical energy.
• The fact that different substances are oxidized more readily than
others is the driving force behind electrochemical cells, and it is this
force that forces electrons through the external circuit from the
anode (site of oxidation) to the cathode (site of reduction). This
force is known as the potential difference or electromotive force
(emf or E). Potential difference is measured in volts (V), and thus is
also referred to as the voltage of the cell. Voltage is a measure of
the tendency of electrons to flow. The higher the voltage, the
greater the tendency for electrons to flow from the anode to the
cathode.
109
Chlorine Chemicals Used for Water Disinfection
• Chlorine chemicals are very effective against bacteria,
viruses and fungi that contaminate water.
Four types of chlorine chemicals are commonly used in
agriculture:
• Sodium Hypochlorite
• Calcium hypochlorite
• Gaseous chlorine
• Chlorine dioxide.
Sodium hypochlorite - NaOCl
Sodium hypochlorite is a yellowish liquid with an active
chlorine concentration of 10-15% pH around 13.
It is not very stable, and when it comes in contact with air,
light or high temperatures, the chlorine evaporates and
therefore its concentration in water decreases. The
chemical reaction with water is:
NaOCl + H2O  HOCl + Na+ + OH-
Due to its high pH,  sodium hypochlorite increases water pH. the
reaction of sodium hypochlorite with water results in two forms:
HOCl (hypochlorous acid) and OCl-.

The ratio between HOCl and OCl- depends on the pH. HOCl is a
much more effective disinfectant than OCl (100 time more
effective), and since this form is predominant in a pH range of
3.0-6.7, the treated water should be acidified. 
• It is possible to acidify the water using sulfuric acid, and it
is recommended to maintain the pH in the range of 5.8-6.5
in order to ensure effective disinfection while keeping the
pH in a favorable range for irrigation.
• The amount of sodium added to water using sodium
hypochlorite, generally does not significantly affect water
quality, since disinfection is achieved at relatively at low
concentrations of chlorine (usually <10 ppm).
• Advantages - Easy transport and storage, highly effective
when correctly used.
• Disadvantages - Corrosive, precautions should be taken in
handling, evaporates/disintegrates upon contact with air,
light and high temperatures, Short shelf-life.
Sodium hypochlorite disinfection system
• Calcium hypochlorite - Ca(ClO)2
• Calcium hypochlorite is more stable than sodium
hypochlorite, and contains a higher chlorine
concentration (30-75%).The chemical reaction with
water is:

Ca(OCl)2 + 2 H2O 2 HOCl + Ca2+ + 2OH-

• Like sodium hypochlorite, calcium hypochlorite also

increases water pH, so it is advised to acidify the water
during the disinfection process.
• Calcium hypochlorite is available as white powder or
tablets, therefore it should first be dissolved in water,
and only then it is injected into the treated water.
Calcium hypochlorite isn't highly soluble, so it dissolves
better in soft or medium-hard water. It is
recommended to dissolve it in warm water, in order to
improve its solubility.

• In any case, all forms of calcium hypochlorite contain

insoluble residues that form sediments in the solution.
It is important to eliminate the sediment before
injecting the calcium hypochlorite solution into the
treated water tank to avoid clogging.
• Advantages - Easy transport and storage, more
stable than sodium hypochlorite, does not add
sodium to the water, highly effective when
correctly used.

• Disadvantages - low solubility, might cause

clogging, the final chlorine concentration in
water is dependent on the extent of dissolution
achieved.
• Gaseous Chlorine - Cl2
• This is chlorine in its pure form, which is a very strong
oxidizing and disinfecting agent. It is stored and
transported in cylinders, as pressure-liquefied gas. The
chemical reaction with water is:
Cl2(g) + H2O  HOCl + H+ + Cl-
• Unlike sodium or calcium hypochlorite, gaseous
chlorine decreases water pH.  
• Advantages - highly effective disinfectant. Reduces
water pH so additional acidification is not necessary,
uniform and rapid dissolution in water.
• Disadvantages - Requires skill and strictest precautions
in handling.
• Chlorine dioxide - ClO2
• Chlorine dioxide is very different from the other forms
of chlorine described above. It cannot be compressed
or commercially stored, because it becomes volatile
under pressure. Therefore it is always produced on site
as part of the disinfection process.
Sodium chlorite NaClO2 and hypochlorous acid HClO
are stored in separate containers and are injected into
a chlorine dioxide generator where they react and
produce chlorine dioxide.
• The concentrations of chlorine dioxide needed to
achieve effective disinfection are lower than the
concentrations needed when using other chlorine
forms.
• Advantages - A powerful oxidant,
effectiveness of disinfection does not depend
on pH or organic load in the water, no
byproducts (such as chloramines) are formed,
rapid and uniform dissolution in water.

• Disadvantages - Requires skill, very strict

precautions in handling.
Chlorine dioxide generator
Zone 1: Chlorine
consumed by Chlorine
reducing
compounds (e.g.
H2S)
Zone 2: Formation
of chloramines and
chlorinated
organics. Chlorine
odor.
Zone 3:
Chloramines and
organics partly
destroyed.
Zone 4: Residual
formed. Too much
residual → chlorine
taste & odor
 Exercises
Chlorine usage in the treatment of 21000 m3/day is 8
kg/day. The residual chlorine after 15 minutes contact
time is 0.15 mg/L. Calculate the dosage in milligrams per
litre and the chlorine demand of the water.
Name Hypochloric ion Perchlorate ion Hydrogen Ozone
peroxide

Formula

Name Nitrous oxide Permenganate Nitrate

salt

Formula
 Water treatment
Major elective I (CHEM10707)

Chapter 4

Wastewater Treatment

124
 What is Wastewater Treatment?
• Wastewater treatment is also referred to as
sewage treatment
• Process of removing physical, chemical, and
biological contaminants from wastewater and
household sewage
• Goal is to separate wastewater into:
– Environmentally-safe fluid waste stream
– Solid waste to be disposed or reused
Wastewater Sources
• Wastewater comes from:
– Homes
• Sinks, showers, toilets,
washing machines,
dishwashers
– Businesses
– Industrial facilities
– Storm runoff
• From roads, parking lots,
roofs

Image: http://www.acumen.com.my/content/chemical-testing?q=node/6
 What Needs to be Removed?
• Wastewater may contain a variety of
substances:
– trash and debris
– human waste
– food scraps
– oils
– grease
– soaps
– chemicals (cleaning, pesticides, industrial)
– pharmaceuticals and personal care products

http://www.westfield.ma.edu/personalpages/draker/edcom/final/webprojects/sp11/triparoundworld/Marine.html
 What Needs to be Removed?
• Wastewater from both domestic and industrial sources
may contain a variety of potentially harmful
contaminants, including:
– Bacteria
• E. coli (right), Giardia, Hepatatis A
– Viruses
– Nitrates
– Metals
• mercury, lead, cadmium, chromium, arsenic
– Toxic materials
– Salts

http://www.anh-usa.org/the-european-e-coli-outbreak-the-real-story/
 Example 1: Concentration
• A 4.2 mL wastewater sample was tested and
found to contain 7.6 ng of lead (II) ions. What
is the molarity of lead (II) ions in this solution?
 Example 1 Solution
7.6 ng Pb x 10-9 g x 1 mol Pb x 1 mL soln
4.2 mL 1 ng 207.2 g Pb 10-3 L

= 8.73 x 10-9 mol/L

= 8.73 x 10-9 M Pb
 Why Treat it?
• The environment is able to naturally dilute and
degrade water contaminants, but only in small
amounts
• Wastewater
treatment
reduces pollutants
to levels that the
environment can
safely handle and
process
 Why Treat it?
• Decaying solid matter left in water consumes
dissolved oxygen from the water
– Known as Biochemical Oxygen Demand (BOD): the
amount of dissolved oxygen needed by aerobic
organisms to break down organic matter
– Lack of oxygen can kill plants and aquatic life
• Excessive nutrients (nitrogen and phosphorous)
can also lead to deoxygenation
– Increased plant and algae growth, which eventually
die and decompose, lead to an increased BOD
Steps of the Wastewater Treatment Process

• 1. Pretreatment
• 2. Primary Treatment
• 3. Secondary Treatment
• 4. Tertiary Treatment
• 5. Sludge Processing
 Treatment Process
Step 1: Pretreatment
• Prepares waste water for entering
the treatment plant
• Removal of larger debris by
screening (shown right)
– Trash
– Tree limbs
• Removal of grit and gravel by
screening and settling
– Gravel must be removed early as it
can damage machinery and
equipment in the treatment plant
http://www.alard-equipment.com/wastewater/index.htm
 Treatment Process
Step 2: Primary Treatment
• In Primary Treatment, as much solid material is
removed as possible by relying on gravity
• Removes most of the sludge and scum
• Sludge: Organic and inorganic materials which will
naturally settle
– removed by sedimentation
• Scum: Materials which will float (oil, grease, soap)
– removed by skimming
• This step successfully removes 50 to 70% of
suspended solids and up to 65% of oil and grease
• Colloidal and dissolved materials are not affected by
this step
 Separation of Oil and Grease
• Oil and grease will naturally separate from water due to
differences in polarity
• This is also known as the hydrophobic effect
• Water is considered a polar substance
• Oil and grease are typically long chains of hydrocarbons,
making them nonpolar, hydrophobic substances
• Oils and grease rise to the top of water due to a difference in
density

http://novocreamseparators.com/blog/clean-separation/
 Primary Treatment: Physical Separation

• Sewage flows through large tanks known as primary

clarifiers or primary sedimentation tanks
– Round or rectangular basins, 3 to 5 meters deep
– Water retained here for 2 to 3 hours
• Sludge will settle toward the bottom of tanks, while
scum will rise to the top. Both are removed and
pumped to sludge treatment tanks
• Mechanical scrapers continuously drive sludge into a
well at the bottom of the tanks to be removed
• Mechanical skimmers or rakes remove oils and
grease from the surface.
– May be recovered to use in saponification
 Saponification
• Saponification is the base hydrolysis of fats and
oils to produce glycerol and a crude soap

triglyceride (fat) glycerol

 Primary Treatment: Aeration
• Another process during primary treatment is
aeration
• Water is agitated and exposed to air, which
serves two purposes:
– Allows some dissolved gases to escape, such as
foul smelling hydrogen sulfide gas
– Allows more oxygen to be dissolved into the
water. Oxygen may be bubbled into water at this
point.
• Increasing dissolved oxygen in water
compensates for the increased BOD and
helps with the sludge settling process
 Example 2: Concentration
• 9 ppm is considered a healthy dissolved
oxygen concentration in water. What is this
concentration expressed in molarity?

Example 2 Solution
9 g O2 x 1000 g H2O x 1 mol O2
1000000g H2O 1 L H2O 32 g O2

= 3 x 10-4 M O2
 Treatment Process Step 3:
Secondary Treatment
• Secondary treatment is designed to remove
residual organic materials and suspended
solids that were not removed during primary
treatment
• Works to degrade the biological content of
the sewage that comes from human waste,
food waste, soaps and detergent.
• Removal of biodegradable dissolved and
colloidal organic matter using aerobic
biological treatment and flocculation
 Secondary Treatment:
Aerobic Biological Treatment
• performed in the presence of oxygen by
aerobic microorganisms
– Aerobic = in presence of oxygen
• principally bacteria and protozoa
• metabolize the organic matter in the
wastewater, including sugars, fats, and short-
chain hydrocarbons
• Results in production of several inorganic
products, including CO2, NH3, and H2O, as well
as reproduction of more microorganisms
 Secondary Treatment:
Flocculation
• Process in which colloids
come out of suspension
to form flakes, or floc
• Differs from
precipitation!

– Precipitation involves particles which are

dissolved in a solution
– Flocculation involves particles that are suspended
within a liquid, not dissolved
http://www.tech-faq.com/flocculation.html
 Colloids and Flocculation
• Particles finer than 0.1 µm in water remain in constant
motion because they often carry an electrostatic
charge which causes them to repel each other.
• If the electrostatic charge of colloid particles is
neutralized, the finer particles start to collide and
combine together into larger groups of particles
– Due to the influence of Van der Waals forces:
• These larger and heavier particles are called flocs
• Floc can either be filtered out of wastewater or left to
settle out as sludge
 Treatment Process
Step 4: Tertiary Treatment
• Tertiary treatment (also known as advanced
treatment) includes the remaining processes
necessary to remove the following from wastewater:
– Nitrogen
– Phosphorus
– additional suspended solids
– remaining organics
– heavy metals
– dissolved solids
• Final treatment stage before water is released into
rivers, lakes, or groundwater
 Tertiary Treatment
• Depending on the types of contamination and
the desired end use, one or more processes
may be used in tertiary treatment:
– Sand filtration
– Nutrient removal (nitrogen and phosphorous)
– Odor removal
– Disinfection (via chlorination, ozone, or UV
radiation)
 Tertiary Treatment
• Sand filtration
– Removes any remaining suspended solids not
removed by sedimentation and flocculation
– May be combined with filtering over activated
carbon to remove toxins and odors

http://water.me.vccs.edu/concepts/filters.html
 Tertiary Treatment
• Nutrient Removal
– Excessive release of nitrogen and phosphorous
leads to a condition known as eutrophication
(presence of excessive nutrients)
– Eutrophication
encourages excessive
algae and weed
growth
• Leads to
deoxygenation of
water
• Some algae can
release toxins into
water http://05lovesgeography.blogspot.com/2011/02/eutrophication.html
 Tertiary Treatment
• Nutrient removal may be accomplished through
biological processes by passing wastewater through
5 different chambers:
1. Anaerobic fermentation zone
very low dissolved oxygen levels and the absence of
nitrates
2. Anoxic zone
low dissolved oxygen levels but nitrates present
3. Aerobic zone
4. Secondary anoxic zone
5. Final aeration zone
Biological Nutrient Removal Zones

http://www.wedotanks.com/anaerobic-aerobic-wastewater-treatment-plant.asp
 Example 3: Dilution and Concentration

• Nitrogen is usually present in wastewater as

ammonia. 3.5 million L of wastewater
entering a treatment plant have an initial
ammonia concentration of 0.75 mM. By the
time the wastewater reaches the tertiary
treatment phase, the volume has been
reduced to 2.9 million L. What is the
concentration of ammonia at this point?
 Example 3 Solution
(M1)(V1) = (M2)(V2)

(0.75 mM NH3)(3.5 million L)=(M2)(2.9 million L)

M2 = 0.91 mM
 Nutrient Removal: Nitrogen
• Nitrogen removal takes place in two parts:
– Nitrification: oxidation of ammonia to nitrate
– Denitirication: reduction of nitrate to nitrogen gas
• Nitrogen gas is then released into the
atmosphere
 Nutrient Removal: Nitrogen
Nitrification
• Nitrification occurs in the 3rd zone (aerobic zone)
• Two step process
– Each step carried out by a unique bacteria
• Step 1: oxidation of ammonia to nitrite (NO2 -)
NH3  NO2 -
• Step 2: oxidation of nitrite to nitrate (NO3 - )
NO2 -  NO3 -
 Nutrient Removal: Nitrogen
Denitrification
• After nitirification in the 3rd zone, wastewater rich in
nitrates is recycled back to the 2nd zone (first anoxic
zone)
• The recycled nitrates, in the absence of dissolved
oxygen, are reduced by bacteria to nitrogen gas
NO3 -  N2
– Incoming organic carbon compounds present in this
zone act as hydrogen donors
 Nutrient Removal: Nitrogen
• Denitrification
• In zone 4, the second anoxic zone, any nitrates
not reduced in zone 2 are reduced by the
respiration of bacteria present
• In zone 5, the re-aeration zone, oxygen levels
are increased to stop the denitirication
process
– Stopping denitirification prevents problems with
settling
 Example 4: Redox Reactions

• Redox Reactions: Balance the three redox half reactions associated with nitrogen removal:
– Nitrification Step 1
– Nitrification Step 2
– Denitrification

Nitrification Step 1
Example 4 Solution NH3  NO2-
NH3 + 2H2O  NO2- + 7 H+
NH3 + 2H2O  NO2- + 7 H+ + 6 e-

Nitrification Step 2
NO2-  NO3-
NO2- + H2O NO3- + 2 H+
NO2- + H2O NO3- +2H+ + 2e-

Denitrification
NO3-  N2
2 NO3-  N2
2 NO3- + 12 H+  N2 + 6H2O
2 NO3- + 12H+ + 10e-  N2 + 6H2O
 Nutrient Removal: Phosphorous
• Phosphorous may occur as organic or inorganic forms
– Of the 5 to 20 mg/L total phosphorous content in
wastewater, 1 to 5 mg/L is organic
• Phosphorous is typically present in the form of
phosphates
• Typical forms include:
– Orthophosphates: easily used in biological metabolism
– Polyphosphates: contain two or more phosphorous
atoms in a complex molecule. Can slowly undergo
hydrolysis to orthophosphates
• Phosphorous may be removed biologically or
chemically
 Chemical Removal of Phosphorous
Using Calcium
• Usually added in the form of lime, Ca(OH)2.
• Reacts with the natural alkalinity in the wastewater to
produce calcium carbonate
Ca(HCO3)2 + Ca(OH)2  2CaCO3 + 2H2O
• As the pH value of the wastewater increases past 10,
excess calcium ions will then react with the phosphate,
to precipitate in hydroxylapatite:
10 Ca2+ + 6 PO43- + 2 OH- ↔ Ca10(PO4) + 6(OH)2 (s)
• Amount of lime required depends on pH of water
rather than amount of phosphate present
• Neutralization may be required to lower the pH before
further treatment or disposal, typically by
recarbonation with carbon dioxide
 Example 5: Acids, Bases, and pH
• The pH of domestic wastewater is about 7.2.
– What are the concentrations of hydronium and
hydroxide ions in water at this point?
– Lime is only effective in removing phosphorous at
a pH higher than 10. What is the pH of 9800 L of
water treated with 50 g Ca(OH)2?
 Example 5 Solution
Part 1: Part 2:
[H3O+] = 10 -pH 50.0 g x 1 mol Ca(OH)2 x 2 mol OH
= 10 -7.2 9800 L 74.1 g 1 mol Ca(OH)2
= 6.3 x 10-8 M = 1.38 x 10 -4 M OH-

[H3O+] [OH-] = 1 x 10-14 [H3O+] = 1 x 10-14

[OH-] = 1 x 10-14 1.38 x 10 -4
6.3 x 10-8 = 7.25 x 10 -11 M H3O+]

= 1.6 x 10-7M pH = -log[H3O+]

= -log (7.25 x 10 -11 M)
= 10.1
 Chemical Removal of Phosphorous
Using Aluminum
• Typically use alum or hydrated aluminum sulfate
to precipitate aluminum phosphates (AlPO4).
Al3+ + HnPO43-n ↔ AlPO4 + nH+
• Reaction affected by pH, equilibrium of
competing reactions, and presence of trace
elements in wastewater
• Aluminum may adversely affect some of the
bacteria used in sludge and digestion and should
be used carefully
 Chemical Removal of Phosphorous
Using Iron
• Iron (III) chloride or sulfate or iron (II) sulfate
can be used to form iron phosphate
precipitates
Fe3+ + HnPO4 3-n ↔ FePO4 + nH+
• Lime is usually added to raise the pH to
enhance the reaction
 Example 6: Solubility and Net Ionic
• Write the full balanced equation (including
states) and the net ionic equation for the
reaction of iron (III) sulfate with sodium
phosphate.
 Example 6 Solution
Balanced Reaction:
Fe2(SO4)3(aq) + 2Na3PO4(aq)  2FePO4(s) + 3Na2SO4(aq)

Net:
Fe3+(aq) + PO43-(aq)  FePO4 (s)
 Tertiary Treatment: Disinfection
• Disinfection of wastewater reduces the number of
microorganisms in water that may lead to disease
before discharging back into the environment
• Usually the very last step before discharge
• Effectiveness depends upon conditions of treated
water at this point, including cloudiness and pH
• Three major strategies: chlorination, ozone, and UV
radiation

http://www.purewater2000.com/Ultraviolet.html
 Disinfection: Chlorination
• Most commonly used form • Drawbacks:
of disinfection due to low – may create chlorinated organic
cost and high effectiveness compounds that may be carcinogenic
• The exact mechanism by – Residual chlorine is toxic to aquatic life
which chlorine disinfects is • May be necessary to dechlorinate
not fully understood. It water before release
likely involves oxidative
damage to microbial cell
membranes and vital
protein systems
• Chlorination also helps to
reduce any odors in the
water

http://chlorination.us/chlorination/chlorination/
 Disinfection: UV Radiation
• Ultraviolet radiation damages the genetic structure of
bacteria and viruses which makes them incapable of
reproduction
• Since no chemicals are used, UV disinfection poses no risk to
organisms which will later encounter the treated water
• Requires highly treated water
with little cloudiness.
Suspended solids in the water
may block out the UV rays
• Maintaining UV lamps can be
costly
 Disinfection: Ozone
• Ozone (O3) is generated by passing oxygen gas
(O2) through a high voltage potential. Voltage
breaks O2 into oxygen atoms which will
recombine as O3 gas
O2 + electricity  O3
• Ozone is very unstable. Generated as needed
rather than stored
• Produces fewer by-products than chlorination,
but much more costly
 Example 7: Reaction Stoichiometry
• Write the balanced equation for the synthesis
of ozone from oxygen

• If 56.8 g of ozone must be synthesized, how

many moles of oxygen gas are required?
 Example 7 Solution
3 O2  2 O 3

56.8 g O3 x 1 mol O3 x 3 mol O2

48 g O3 2 mol O3

= 1.78 mol O2
 Disinfection: Ozone
• Ozone is very effective in destroying viruses and
bacteria and may act by several mechanisms:
– Direct oxidation and destruction of the cell wall with
leakage of cellular components
– Reactions with radical by-products of ozone
decomposition
– Damage to the constituents of the nucleic acids (purines
and pyrimidines)
– Breakage of carbon-nitrogen bonds leading to
depolymerization
 Tertiary Treatment: Odor Removal
• Odor in waste water typically form as a result of
anaerobic conditions
• Most common odor is hydrogen sulfide gas
• Odor is eliminated along the way by aeration,
chlorination, biological degradation, and circulation
of fluids
• Other methods to eliminate hydrogen sulfide are by
adding iron salts, hydrogen peroxide, or calcium
nitrate
 Treatment Process
Step 5: Sludge Treatment
• Sludge consists of all the solid material removed from
wastewater during the water treatment process
• While the water in treatment is ready for release into
streams and groundwater, sludge requires further
treatment before it can be disposed or used
– Must reduce the amount of organic matter
– Must reduce the number of disease causing microbes
– Remove as much remaining liquid as possible
• Sludge treatment options include:
– Aerobic digestion
– Anearobic digestion
– Composting
– Incineration
 Sludge Treatment
• Sludge is most often processed by biological
anaerobic digestion
• Bacteria metabolize the organic material in the
sludge
– Occurs over a period of 10 to 60 days, depending on
the capabilities of the digesting tanks
– Reduces the volume of sludge that requires disposal
– Makes the sludge more stable
– Improves the dewatering characteristics of the sludge
• Shorter retention time and smaller tanks required
• Requires higher temperatures, resulting in a
higher energy cost
Sludge Treatment
• One byproduct of
anaerobic sludge
digestion is the
production of biogas
• Biogas contains about 60
to 65% methane (CH4)
and can be recovered as
an energy source.
• Methane is a
combustible, renewable
fuel
CH4 +http://home.comcast.net/~hollywastewater/Process.htm
O2  CO2 + H2O
 Sludge Treatment
• In small sewage treatment plants, sludge is
processed using aerobic digestion
• Under aerobic conditions, bacteria will
consume organic material and convert it into
carbon dioxide
• Energy cost associated with adding oxygen to
process and blowers to remove CO2
 Sludge Treatment
• Composting of sludge is similar to aerobic digestion,
except other organic materials such as sawdust are
mixed in with the sludge
• Incineration is the least used method of sludge
treatment.
– Sludge burns poorly due to low calorific value, so extra
fuels must be added
– Worries of emissions associated with sludge
– High energy cost to vaporize residual water present in
sludge
 Sludge Treatment
• Sludge that does not originate
from highly industrialized areas • Water is removed
and is for the most part free of from sludge by
toxic chemicals can be used as centrifugation and
fertilizer addition of
chemicals that aid in
polymer formation
• Dried sludge can be
converted into
fertilizer pellets
which are usually
rich in phosphorous

http://www.thewatertreatmentplant.com/sludge-treatment-equipment.htm
 Water Treatment
Feed wastewater
stream
 View the entire process in action
PRETREATMENT

PRIMARY
TREATMENT

SECONDARY
TREATMENT

TERTIARY
TREATMENT

To discharge or
reuse/recycling

http://photomynthesis.wordpress.com/2010/09/16/wetland-services/water-treatment-plant/
 Water treatment

Major elective I (CHEM10707)

Chapter 5

Technologies for seawater desalination

182
 Introduction
• Desalination is a process of removing dissolved salts from
seawater to produce fresh water for consumption.
• There are two major types of desalination technologies
around the world, namely :
• Membrane desalination : special filter (membrane) to
produce desalinated water
• Thermal desalination : involves the boiling/evaporation of
seawater to give off water vapor which, on condensation,
yields salt-free liquid water
 Introduction
• Reverse osmosis ("RO") is a predominant form of
membrane desalination. For thermal desalination, the
most commonly adopted technologies are multi-stage
flash evaporation ("MSF") and multi-effect distillation
("MED") . RO is currently the most widely used method
for desalination. In 2012, it accounted for 63% of the
desalination production capacity worldwide, followed
by MSF (23%) and MED (8%)
 1- Reverse osmosis
‫لعكسي‬DD‫ ا‬D‫لتناضح‬DD‫ا‬
• RO is a desalination process with the use of semi-
permeable membranes which allow the passage of
water molecules but not the dissolved salts.
• In an RO process, seawater is firstly pre-treated to
remove suspended solids. Sufficient pressure is then
applied with the use of high pressure pumps to force
water passing through the semi-permeable
membranes, leaving the dissolved salts behind.
• Desalinated water then undergoes post-treatment,
such as pH adjustment and disinfection, to make it
suitable for drinking.
Basic process of reverse osmosis
Osmosis versus reverse osmosis
Reverse osmosis efficiency
 Calculations in reverse osmosis
• Salt rejection % :
• The higher the salt rejection, the better the system is
performing. A low salt rejection can mean that the
membranes require cleaning or replacement.

• Sal t Passage %
• This is simply the inverse of salt rejection described in
the previous equation. The lower the salt passage, the
better the system is performing.
 Calculations in reverse osmosis
• Recovery %
• Percent recovery is the amount of water that is being
‘recovered’ as good permeate water.

• For example, if the recovery rate is 75% then this

means that for every 100 gallons of feed water that
enter the RO system, you are recovering 75 gallons as
usable permeate water and 25 gallons are going
to drain as concentrate.
• Concentration Factor
The concentration factor is related to the RO system
recovery. The more water you recover as permeate
(the higher the % recovery), the more concentrated
salts and contaminants you collect in the concentrate
stream.

For example, if your feed flow is 100 gpm and your

permeate flow is 75 gpm, then the recovery is
(75/100) x 100 = 75%. To find the concentration factor,
the formula would be : 1 ÷ (1-75%) = 4.
• A concentration factor of 4 means that the water going
to the concentrate stream will be 4 times more
concentrated than the feed water is. If the feed water
in this example was 500 ppm, then the concentrate
stream would be :
500 x 4 = 2000 ppm.
 2- Multi-stage flash evaporation
‫ا لتبخير ا لوميضيا لمتع دد ا لمراحل‬
• MSF is a type of thermal desalination which has already
been in use since around 1960s.
• MSF facilities consist of a number of chambers
connected to one another, with each successive
chamber operating at a progressively lower pressure.
• Source water/pre-treated water (i.e. feed water) first
passes from back to front through a tubing system to the
brine heater, where water is heated under a high
pressure.
• The heated water then enters the first chamber at
reduced pressure, causing it to boil rapidly with a
portion evaporating into vapor.
 Multi-stage flash evaporation
• In each successive chamber which operates at
a reducing pressure, the same process
repeats.
• The vapor generated by evaporation is
converted into fresh water by condensation.
Basic process of multi-stage flash
evaporation
 3- Multi-effect distillation
‫ا لتقطير ب طريقة ا لتأثير متع دد ا لمراحل‬
• Similar to MSF, MED is an evaporation process going
through a series of chambers (also known as "effects"),
with each successive chamber operating at a
progressively lower pressure.
• Yet MED differs from MSF in that the vapor formed in
one chamber condenses in the next chamber with the
heat released acting as a heating source.
• In addition, feed water is sprayed over the tube bundle
on top of each chamber in a typical MED process.
 Multi-effect distillation
• As shown in the figure , external steam is introduced in
the first chamber and feed water evaporates as it
absorbs heat from the steam.
• The resulting vapor enters through the tube to the
second chamber at a reduced pressure. The heat
released by condensation causes the feed water in the
second chamber to evaporate partly. The process
repeats in the third chamber and so on. In each
chamber, the vapor condensing into fresh water inside
the tube is then pumped out.
 Multi-effect distillation
• The efficiency of MED can be raised with the addition of a
vapor thermo-compressor. As indicated, the thermo-
compressor extracts part of the steam generated in the
final chamber for recycling use.

• The extracted steam will be mixed with the external

steam for compression
under a high pressure, which then acts as a heating
source in the first chamber.
Basic process of multi-effect distillation
Comparison of the three major desalination
technologies