Unit I Water Treatment

Part B

In the previous document, a brief description of hardness, methods to measure the hardness of
water, problems associated with the usage of hard water in boiler industries, treatment methods for the
boiler feed water were provided. In continuation, the treatment methods for the brackish water are
discussed briefly, in this document.

Type of water Freshwater Brackish water Saline water Briny water

Hardness (g/L or parts per thousand) < 0.5 0.5 – 30 30 – 50 > 50

In the scarcity of surface water and groundwater, brackish water is used in the domestic and
industrial uses. As the salt content is very high, brackish water can not be treated using the zeolite or ion-
exchange process.

Desalinization of brackish water:

1. Electrodialysis: Impurities are removed from the brackish water by applying electricity
2. Reverse Osmosis: Pure water is removed from the brackish water by filtration

Electrodialysis:

I II III

A B

The principle involved in electrodialysis is the removal of the dissolved ions by attracting them
towards the opposite terminals. In the given figure, the device is separated into three compartments (I, II,
and III) by the membranes (A & B). Membrane A contains positively charged functional groups
(ammonium group). Due to coulombic repulsion, positive ions cannot get closer to the membrane A. So
positive ions cannot pass through the membrane A. Thus, membrane A acts as an anion-selective
membrane. Similarly, membrane B contains negatively charged functional groups (carboxylate,
sulphonate). Hence membrane B will act as a cation-selective membrane and allows only the cations to
pass through it.
Upon applying voltage:
 Cations in the three compartments will try to move towards left direction
o Membrane A will not allow the cations to pass through it
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  No movement of cations from compartment I to II
 Movement of cations from compartment II to III
 The concentration of cations in compartment II will decrease
Similarly,
 Anions in the three compartments will try to move towards the right direction
o Membrane B will not allow the anions to pass through it
 No movement of anions from compartment III to II
 Movement of anions from compartment II to I
 The concentration of anions in compartment II will decrease
On whole, the concentration of cation and anion will decrease and we will get pure water in the central
compartment.
In a real electrolysis device, many cation-selective membranes (CSM) and anion-selective
membranes (ASM) will be arranged alternative to each other, as follows;

While applying voltage, the anions will move to the left side from the compartments labeled P,
and the cations will move to the right from the compartments P. In the compartments I, anions, and
cations will get into from right and left, respectively. Hence the salt content will get concentrated. The
voltage will be applied till the precipitate begins to form in the compartments I. We will get pure water
from the compartments P. Thus, in the electrodialysis, impurities are removed from the brackish water to
obtain the pure water.
The limitations are the ion-selective semi-permeable membrane can be neutralized with certain
substances such as iron oxide, manganese oxides, colloid, and large organic anions. The suspended solids
with a diameter greater than 10 mM may plug the pores of the membrane. These problems can be
prevented by using suitable pre-treatment methods, which include removal of organic matter through
carbon filtration, colloidal particles through flocculation, and larger suspended particles by filtration.
Another method to desalinate brackish water is the RO method.

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Reverse Osmosis:
 Removal of pure water from the impure
water by filtration.
 Osmosis: Movement of solvent from
dilute solution to concentrated solution
while these two solutions are separated
by semi-permeable membranes
 Osmosis is driven by osmotic pressure
 Reverse Osmosis: Movement of solvent from the concentrated side (impure water) to dilute side
(pure water) by applying pressure higher than the osmotic pressure
 Known as hyperfiltration or super filtration
 RO membranes are made of cellulose acetate, polymethacrylate, and polyamide polymers.
 RO method is capable of removing particles larger than 0.1 nm.
 Bacteria, salts, sugar molecules, dye molecules, and proteins, can be removed by the RO method.

The water treated by electrodialysis and RO process might contain infectants and pathogenic
bacteria; hence the water is not potable. The impurities present in the water can be oxidizable. To express
the amount of oxidizable impurities present in the water, two parameters are used namely, Chemical
Oxygen Demand (COD) and Biological Oxygen Demand (BOD). They are the amount of oxygen needed
for the oxidation of impurities. Impure water will have higher BOD/COD values.
BOD: Amount of oxygen needed for the biological oxidation of impurities.
COD: Amount of oxygen needed for the chemical oxidation of impurities.
BOD values of certain wastes are listed below
 Domestic sewage – 200-600 mg/L
 Vegetable processing – 200-5,000 mg/L
 Slaughterhouse waste – 1,000-4,000 mg/L
 Cattle shed effluents – 20,000 mg/L

In the measurement of COD, oxidizing agents such as KMnO4 or K2Cr2O7 will be used to oxidize
the impurities present in the water. In the measurement of BOD, the organic impurities present in the
water will be oxidized using micro-organisms. Oxidation using micro-organisms is a strategy used in the
treatment of wastewater. The micro-organisms are infectious. To remove the infectious micro-organisms
and pathogenic bacteria, the water should be sterilized. There are various methods of sterilization of water
which include ozonation, UV treatment, and chlorination.
 Ozonation: Ozone is readily absorbed by water due to its high solubility in water. Also, ozone
disinfects almost all pathogens. It is unstable and produces nascent oxygen. O3  O2 + [O]
The nascent oxygen is a powerful oxidizing agent and kills all the pathogenic bacteria.
Limitation: As ozone is unstable, onsite generation of ozone is needed. This process is more
expensive and cannot be used on a large scale.

 UV treatment: Treating the water with high energy radiations such as Ultraviolet rays kills all the
pathogenic bacteria. In general, the UV treatment method is used in the disinfection of the water
used in swimming pools.

 Chlorination: In this method, water is sterilized by treating with chlorine or chlorinating agents.
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 o Chlorine gas: While bubbling chlorine gas into water, it produces nascent oxygen and
hypochlorous acid (HOCl). Both of them are disinfectant. HOCl effectively penetrates
the negatively charged cell walls of the pathogenic bacteria, produces reactive oxygen
species (ROS), ruptures the cell wall of microorganisms, and kills the microorganisms.

Cl2 + H2O  HOCl + HCl

HOCl → HCl + [O]

Chlorine gas is toxic, hence other chlorinating agents are preferred.

o Chlorinating agents: Releases free chlorine or HOCl on treatment with water.

 Bleaching powder (Calcium oxychloride): CaOCl2 + H2O  Ca(OH)2 + Cl2

 Sodium hypochlorite (NaOCl): NaOCl + H2O  HOCl + NaOH

 Chloroamine (ClNH2): ClNH2 + H2O  HOCl + NH3

Bleaching powder introduces Ca2+ hardness. The excess chlorinating agents also produce
disagreeable odor and a bad taste in water. It also irritates the mucous membrane. The excess chlorine in
overchlorinated water can be removed by either passing the water through a bed of molecular carbon or
treating it with NH3. Small quantities of reducing substances like SO2 or Na2SO3 can be used to remove
excess chlorine. If the amount of chlorine/chlorinating agent added is less than the amount of infectious
organisms, the treated water is not free from pathogenic bacteria. Drinking such water will lead to health-
related problems. To assure complete sterilization, the Breakpoint chlorination method is adopted.

Breakpoint chlorination:
 Making a plot between the applied chlorine
and residual chlorine to assure complete
disinfection.
 Applied chlorine in the x-axis: Amount of
chlorine added to the water.
 Residual chlorine in the y-axis: Amount of
chlorine remaining in the water, after the
reaction.

The exact amount of chlorine required to kill microorganisms and to remove organic matter is
called breakpoint chlorination. In this process, the water sample is treated with chlorine and estimated for
the residual chlorine in water and plotted by taking residual chlorine as a function of applied chlorine
which gives the break-point chlorination graph. For normal water, the graph contains four stages.

 Stage I: 0 to A in the graph. Oxidation of easily oxidizable chemicals like H 2S, Fe2+, Mn2+, etc.
The added chlorine will become chloride. As all the added chlorine will be consumed fast, the
amount of residual chlorine will be close to zero. This stage continues until the complete
oxidation of easily oxidizable substances.

 Stage II: A to B in the graph. Once the easily oxidizable substances are completely oxidized,
further added chlorine reacts with organic matter/microorganism, to form chloro- organic
compounds without oxidizing them. If NH3 is present, it will also react with chlorine to form
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 chloramine. In this stage, added chlorine is not involved in any decomposition or redox reaction.
Hence, the residual chlorine increases linearly with the amount of added chlorine. The graph in
the region will be a line with a slope of around 45 °. This stage continues until the complete
chlorination of all the organic compounds.

 Stage III: B to C in the graph. Upon adding further chlorine, the oxidation of chlorine will be
initiated. As the chlorine will be consumed during the oxidation, the amount of residual chlorine
decreases and reaches a dip when the oxidative destruction is complete. The dip indicates the
complete oxidation of the infectious organisms present in the water.

 Stage IV: There are no more reactions to happen. As the addition of chlorine is continued further,
the residual chlorine keeps increasing.

Reaching the dip between stages III and IV assures the destruction of infectants in the water.

Specifications (Indian standards) for Drinking water

Parameter WHO (mg/L) ISI (mg/L) US (mg/L)

Appearance Clear Clear Clear
Smell Odorless Odorless Odorless
Taste Pleasant Pleasant Pleasant
Turbidity < 10 NTU < 10 NTU < 10 NTU
pH 6.5 – 9.2 6.5 – 8.5 6.5 – 8.5
Total hardness 500 300 -
Chlorides < 250 250 250
Sulfates < 250 150 250
Fluoride < 1.5 0.6 – 1.2 1.5
Total dissolved solids 500 500 < 500
Iron 1.0 0.3 < 0.3
Zinc - - 5.5
Lead 0.1 0.1 < 0.05
Mercury - 0.001 0.001
Arsenic 0.05 0.05 0.05
Cadmium 0.01 0.01
6+
Chromium (Cr ) - 0.05 0.05
Phenol 0.002 0.001 0.001
Polycyclic aromatic hydrocarbon (PAH) - - 0.002
Pesticides (total) - Absent 0.005
Microorganism 0 0 0
Chemical oxygen demand 10.0 4.0 4.0
Biological oxygen demand 6.0 - 5.0
Dissolved gas like H2S, CO2, and NH3 0 0 0

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Water specification for different sectors

Healthcare: Water for injection must have the highest level of chemical purity and must be
completely sterile, i.e. free from pathogens. Injection grade was prepared through distillation i.e. by
means of condensing clean steam and also obtained by high pressure reverse process osmotic
membrane process.

Electronic industry: Ultrapure water is mainly used in the electronics industry for critical
application, including semi-conductors and printed circuit board. It has been purified to very strict
specification, containing only H2O where H+ and OH- in equilibrium.

Construction industry: Quality of water for construction industry is same as potable water. The
water should be free from impurities such as suspended solids, dissolved salts, sewage, oils and
organic matter.

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