‫بسم هللا الرحمن الرحيم‬

Albaha University
Faculty of Science
Chemistry Department

Water treatment

Major elective I (CHEM10707)

Chapter 2

Basic physical-chemical processes in water treatment

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 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

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 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.
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 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

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 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

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 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)

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7
 Coagulant type

• Metal coagulants :aluminium-based

coagulants, Fero-based coagulants
magnesium chloride (MgCl2)
• Organic polymer coagulants :
Polyacrylamide, Chitosan, Moringa olifeira
Alginates (brown seaweed extracts)

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 Coagulant agent

Alum
Magnesium chloride

Polyacrylamide

Moringa oleifera
Chitosan
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 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). 10
 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. 11
Flocculation mechanism

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Flocculation mechanism

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Flocculation mechanism

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Raw waste Floc Formation Settle floc
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 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
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 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.

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18
19
 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 reaction insoluble + “clean
soluble ions complexes Water”

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

Fe3+ + 3 OH- = Fe(OH)3
Fe2+ + 2 OH- = Fe(OH)2 20
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

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 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
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 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

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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-

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 Solubility Equilibria
molar solubility = [S]
AgCl (s) Ag+ (aq) + Cl- (aq)
Ksp = [Ag+][Cl-] Ksp is the solubility product constant

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)

CaCO3 (s) Ca2+ (aq) + CO32- (aq) Ksp = 5 x 10-9

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

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 CHEMICAL PRECIPITATION
(Types of Precipitation)

Heavy metals are removed with

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

Phosphorus removal
• Phosphate precipitation (PO43-)

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 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

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 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.

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 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

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 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

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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

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 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

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 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

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 ION EXCHANGE
(Type of Resin)

a. Cationic resin - exchange positive ions

b. Anionic resin – exchange negative ions

(a) (b)

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 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+

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 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

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

Cation Anion
Resin Resin

Cr3+, CN-

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 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.

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 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

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ION EXCHANGE
.

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 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
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• 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

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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:

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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

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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.
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