Water treatment

Impurities in water: The water found in nature is never pure and contains a large number
of impurities.
The major types of impurities found in water are of the following types.
Impurities:

1) Water takes up the impurities when it comes in contact with soil or ground
Water becomes impure when it comes in contact with sewage or industrial
waste.
2) Organic impurities in water are generally introduced by decomposition of plants
and animals.
Nature of impurities in water:

1) Dissolved gasses: The water mainly contains carbon dioxide and oxygen. If
water contains ammonia, hydrogen sulphides and oxides of sulphur gives bad
smell and taste to water.
2) Suspended impurities: These are insoluble impurities, which can be removed by
filtration or settling. There are two types Clay, silica, oxides of iron are inorganic
impurities. Wood and disintegrated part of dead animals are organic impurities.
3) Microscopic matter: These consist mainly bacteria and other microorganisms
(algae and fungi). Generally responsible for water borne diseases
4) Dissolved mineral salts: These are the soluble impurities in water includes
carbonates, bicarbonates chlorides and sulphides of calcium and magnesium.
Oxides of iron lead etc.
5) Organic matter: It includes vegetable and animal matters i.e., decay plants and
animals.
6) colloidal impurities: They consisting of proteins, amino acids, ferric hydroxides,
clay and lumic acid etc.,

Hardness of water
Water which does not produce lather with soap solution readily is called hard water. Water
which lathers easily on shaking with soap solution is called soft water.

Hardness of water can be classified into two types

a. Temporary hardness or carbonate hardness: Temporary hardness is due to the

 presence of dissolved bicarbonates of calcium and magnesium. This hardness can be
removed by boiling of water, when bicarbonates are converted into insoluble
carbonates.
Ca(HCO3)2  CaCO3 + H2O + CO2

Mg(HCO3)2  MgCO3 + H2O + CO2

b. Permanent hardness or non-carbonate hardness: Permanent hardness is due to

the presence of chlorides and sulphates of calcium and magnesium. This hardness
can’t be removed by boiling.
The sum of temporary and permanent hardness is referred to as total hardness
of water. The units to express hardness are ppm or mg/liter of CaCO3
equivalents.

Estimation of total hardness of water: Hardness of water is determined by EDTA method,

which involves complexometric titration.
Principle: EDTA is a complexing agent, it combines with metal ions in 1:1 ratio and forms
highly soluble complexes. Thus when EDTA solution is added to hard water, Ca 2+ and Mg2+
ions combine with EDTA and form soluble complexes. Erichrome black – T is used as
indicator, the end point being indicated by the change in color from wine red to blue. When
Erichrome black – T is added to hard water at pH 10, indicator forms a wine red colored
complex with the metal ions. When the solution is titrated with EDTA, EDTA combines with
free metal ions present in the solution, when the solution doesn’t contain free Ca 2+ and Mg2+
ions. When enough EDTA is added, it is combined with Ca2+ and Mg2+ ions, which are
present in the indicator complex, at that time indicator exists as free and exhibiting blue
color. This happens at the end-point and hence color changes from wine red to blue at this
point.

Procedure: Preparation of Na2EDTA: Weigh accurately about 2.5 gm of disodium salt of

EDTA transfer into a 250 ml standard flask, add 2 to 3 ml of ammonia and distilled water,
dissolve completely, add water up to the mark, shake well for uniform concentration and
take in 50 ml burette.

Estimation of hardness of water:

Pipette out 25ml of the water sample into a conical flask. Add 2 ml of NH 4OH – NH4Cl buffer
and 2 drops of Erichrome black – T indicator. The resulting wine red colored solution is
titrated with standard EDTA solution until clear purple blue solution is obtained.

Calculation:
Volume of water sample taken = 25 ml
Concentration of EDTA =XM
Volume of EDTA consumed = V ml
Molarity of CaCO3 in water sample =XxV
25
= X x Vx 100 g/liter
25
= X x Vx 100 x 1000 mg/liter or ppm
25

BIOLOGICAL OXYGEN DEMAND: BOD is defined as “The amount of dissolved oxygen

consumed by the microorganisms to oxidize the biologically oxidizable impurities
present in 1 liter of water over the period of 5 days at 200 C”.

CHEMICAL OXYGEN DEMAND

It is defined as “the amount of oxygen consumed in the chemical oxidation of organic
and inorganic wastes present in 1 liter of waste water”.
Principle: A suitable known volume of wastewater sample is refluxed with a known excess
of K2Cr2O7 solution in H2SO4 medium and in the presence of Ag 2SO4 and HgSO4. K2Cr2O7
oxidizes all oxidisable impurities. Ag2SO4 catalyses oxidation of straight chain organic
compounds, aromatic and pyridine. HgSO4 avoids the interference of Cl ions. The amount
of unconsumed K2Cr2O7 is determined by titration with standard ferrous ammonium sulfate
solution. The amount of K2Cr2O7 solution consumed corresponds to COD of the wastewater
sample.
Procedure: Pipette out 25ml of the water sample into a conical flask. Add 1gm of HgSO 4,
1gm of Ag2SO4, 25 ml of K2Cr2O7 solution and 25 ml of 1:1 H2SO4. The conical flask is fixed
with a water condenser and the solution is refluxed for two hours. The contents are cooled
and titrated with standard ferrous ammonium sulfate solution, using ferroin as indicator,
till the color changes from blue green to reddish brown. Perform a blank titration taking
the same amount of distilled water in place of the wastewater. Let the volume required be B
ml.

Calculations:
Volume of waste water sample taken = 25 ml
Volume of standard FAS used in sample titration. = A ml
Volume of standard FAS used in blank titration. = B ml
Normality of FAS solution =XN
Amount of K2Cr2O7 consumed in satisfying the COD
in terms of FAS solution = (B-A) ml
Normality of COD N1 = X x (B-A)
V
COD of the sample = X x (B-A) x 8 gm.dm-3
V

= X x (B-A) x 8 x 1000 mg dm-3

V
PROBLEMS ON COD:
(1) In a COD experiment, 30 cm3 of an effluent sample required 9.8 cm3 of 0.001 M
K2Cr2O7 solution for oxidation. Calculate the CO0D of the sample.

Solution:
K2Cr2O7 + 4H2SO4——->K2SO4 +Cr2(SO4)3 + 4H2O + 3(O)

So ,1 mole of K2CR2O7 produces 3(O)

= 48 gm Oxygen.

1000 cm3 of 1M K2Cr2O7 = 48 gm of O2

9.8 cm3 of .001M K2Cr2O7 = 48 x .001x 9.8 gm of O2
1000x1
30 cm of an effluent required = 0.4704 mg of O2
3

1000 cm3 COD of the effluent sample = 0.4704 x 1000

30
= 15.69 mg of O2 / dm3

(2) Calculate the COD of an effluent sample, when 25 cm3 of an effluent requires 8.3 cm3 of
0.001M K2Cr2O7 for oxidation.
Solution:
K2Cr2O7 + 4H2SO4——->K2SO4 +Cr2(SO4)3 + 4H2O + 3(O)

So ,1 mole of K2CR2O7 produces 3(O)

= 48 gm Oxygen.

1000 cm3 of 1M K2Cr2O7 = 48 gm of O2

8.3 cm3 of .001M K2Cr2O7 = 48 x .001x 8.3 gm of O2
1000x1
= 0.3983 mg of O2
COD of the effluent sample = 0.3983 x 1000
25
= 15.93 mg of O2 / dm3
(3) Calculate the COD of an effluent sample, when 25 cm 3 of an effluent requires 8.3
cm3 of 0.001N K2Cr2O7 for oxidation.
Solution:
1000 cm3 of 1N K2Cr2O7 = 8 gm of O2
 8.3 cm3 of .001N K2Cr2O7 = 8 x .001x 8.3 gm of O2
1000x1
= 0.0000664 gm of O2
COD of the effluent sample = 0.0000664x 1000
25
= 2.656 mg of O2/ dm3

Sewage treatment:
Sewage treatment carried out in three stages
Primary treatment
Secondary treatment
Tertiary treatment
Primary treatment: Primary treatment involves
 Screening
 Silt and grit removal
 Removal of oil and grease
 Sedimentation
Screening: It is a physical process, which removes large suspended and floating matter in
the sewage. When water is passed through bar screens and mesh screens, floating and
suspended coarse particles are retained by them.
Presedimentation: (Silt and grit removal) Grit i.e. sand, broken glasses etc are removed
by passing sewage through grit chambers, in which the velocity of flow of sewage is
reduced. Being heavier, silt and grit particles settle down at the bottom.
Microstraining: After pre-sedimentation the water is passed through a microstrainer which
is a free floating rotating drum consisting of fine stainless steel mesh. By this process small
aquatic organisms like algae, fungi and diatoms are removed.
Removal of oil and grease: Oil and grease etc are removed in skimming tanks.
Sedimentation: When sewage water is passed into a sedimentation tank where it is allowed
to settle. The non- settle able solids are removed by coagulation by treatment with
coagulating agents like alum, ferric chloride or lime.
Pre-aeration It is the aeration of waste water before primary treatment. It helps to reduce
BOD, assist in the removal of grease and oil in waste water and to freshen up septic water
prior to further treatment. For this, waste water is agitated with air in an aerator so that the
lighter impurities float and are skimmed off.
Prechlorination It is the chlorination of waste water prior to primary treatment.
Prechlorination does not disinfect water but prevents further decay of waste water. It is used
to control odour, prevent decay of organic matter and reduce the biological oxygen demand
of water.
Primary treatment is capable of removing 80–90% of total dissolved solids, 65% of
suspended solids and upto 45% of BOD substances. After this stage a homogenous liquid is
obtained which is capable of being treated biologically.
Secondary treatment:
Activated sludge process
The sewage water is mixed with proper quantity of activated sludge and the mixture is sent
to the aeration tank, in which the mixture is aerated and agitated for several hours. During
this process, organic matters are oxidized. After the process is complete, the effluent is sent
to a sedimentation tank, where sludge is deposited and water free from organic matter is
drawn off. The effluent from secondary treatment has much lower organic load.

Tertiary treatment: the process includes:

Phosphorus removal It is removed by precipitation. The effluent after secondary treatment is
mixed with calcium oxide which reacts with phosphorus compounds in waste water
forming calcium phosphate which is removed and used as a fertilizer.
Nitrogen removal A nitrification – denitrification process is used for the removal of nitrogen
from waste water. In the first step nitrogen is converted into nitrates with the help of
microorganisms and then these nitrates are released into the atmosphere by converting
them into nitrogen using denitrifying bacteria
By adding bleaching powder Bleaching powder (CaOCl2) is a very good disinfectant. About 1
kg of bleaching powder per 100 kiloliters of water is mixed and water is allowed to stand
undisturbed for several hours. The chemical action produces hypochlorous acid which is a
powerful germicide and kills all the germs.
CaOCl2 + H2O → Ca(OH)2 + Cl2
Cl2 + H2O → HCl + HOCl
Germs + HOCl → Germs are killed
Direct chlorination Chlorine (either gaseous or in concentrated solution form) produces
hypochlorous acid, which is a powerful germicide.
By adding chloramines (ClNH2 ): Chloramine is formed by reacting chlorine and ammonia
in the ratio 2:1. It produces hypochlorous acid that kills the germs.
Ozonisation Ozone is produced by passing silent electric discharge through cold and dry
oxygen silent electric discharge
Ozone is highly unstable and breaks down liberating nascent oxygen
Nascent oxygen is a powerful oxidising agent and kills all the bacteria as well as oxidises the
organic matter present in water.
(i) Treatment with lime to remove the phosphates as insoluble calcium phosphate.
(ii) Treatment with S2- ions to remove the heavy metal ions as insoluble sulphides
(iii) Treatment with activated charcoal to adsorb remaining organic compounds
(iv) Treatment with alum to remove the colloidal impurities not removed in the
previous treatments to further reduce the BOD level.
(v) Disinfection of water i.e. elimination of harmful pathogenic bacteria by passing
Chlorine gas or Ozone or UV – light, here B.O.D. level is further reduced.
Potable water: water, which is fit for domestic purpose, is called potable water.
Characteristics of potable water:
1. It should be free from odor
2. It should be free from pathogenic bacteria
3. It should be free from methane and hydrogen sulfide
4. It should be free from lead and arsenic elements.

Purification (or) Desalination: The process of removal of dissolved salts from sea water or
brackish water to the extent, that water becomes usable is described as desalination or
desalting.
Reverse osmosis:
Principle: In reverse osmosis process, the water is separated from dissolved salts by using
membrane, which permits the flow of water through it but not the salts. If such a
membrane is placed between brine and pure water, water has a natural tendency to flow
through the membrane into the brine due to osmotic pressure. This natural process may be
reversed by applying a pressure on the brine side higher than that of osmotic pressure,
when fresh water tends to flow from brine into fresh water.
Process:
A series of tubes made up of porous material is lined on the inside with extremely thin film
of cellulose acetate semi- permeable membrane. These tubes are arranged in parallel array
in fresh water.
Brackish water is pumped continuously at higher pressure (>25atm) through these tubes.
Water flows from brackish water into fresh water. The flow of water is proportional to
applied pressure. Greater the number of tubes, larger is the surface area and, hence, more
production of fresh water.
Thus in reverse osmosis, pure water is separated from its contaminants rather than
removing contaminants from water. This process is also known as super-filtration or hyper
filtration. The semi permeable membranes are usually made up of cellulose acetate,
polymethacrylate or polyamide polymers.
Advantages: This process removes lead, calcium, magnesium, sodium, potassium,
 aluminium, chloride, nitrate, fluoride, sulphate, boron, most microorganisms and organic
chemicals from water.
Disadvantages: It requires large volume of water. It may take as much as 90 liters water to
recover 5 liters of useable water.
Normal osmosis Reverse osmosis

The process of reverse osmosis

Electrodialysis

Electrodialysis (ED) is used to transport salt ions from one solution through ion-
exchange membranes to another solution under the influence of an applied electric
potential difference. This is done in a configuration called an electrodialysis cell. The cell
consists of a feed (dilute) compartment and a concentrate (brine) compartment formed by
an anion exchange membrane and a cation exchange membrane placed between
 two electrodes.

(Anode)
(Cathode)

Principle and working: Consider a cell which is divided into three compartments using
semi permeable membranes. Two electrodes (anode and cathode) are placed in the outer
compartments and saline water is introduced in all the three compartments. When electric
current is passed through saline water, the sodium ions (Na+ ) move towards cathode
(negative pole) and the chloride ions (Cl– ) move towards anode (positive pole) through the
membrane. Hence the concentration of brine decreases in the middle compartment and
increases in the two side compartments. Desalinated (pure water) is obtained from the
middle compartments, while the concentrated brine solution in side compartments is later
replaced by fresh sea water. A = Anion permeable membrane C = Cation permeable
membrane.
For more efficient separation ion selective membranes are employed. An ion selective
membrane has permeability for one kind of ions only. For example, anion selective
membrane allows the passage of anion and the cation selective membrane allows the
passage of cations. An electrodialysis cell consists of alternate cation and anion selective
membranes.
The cathode is placed near the cation selective/permeable membrane and the anode is
placed near the anion selective membrane.
Saline water is passed under a pressure of about 5–6 kg m–2 between membrane pairs and
an electric field is applied perpendicular to the direction of water flow.
Under the influence of the strong electric field the sodium ions (Na +’) start moving towards
cathode through the membrane. As a result, there is depletion of ions in the even
numbered compartments and the concentrations of ions in the odd numbered
compartments increases. The desalinated water, free of ions is collected separately,
whereas concentrated water of the odd numbered compartments is replaced from time to
time by fresh lot of saline water.