Water Technology

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 includes.
(i) Dissolved gases
The water contains mainly carbon dioxide and oxygen as dissolved gases. Some Water may also contain
ammonia and hydrogen sulfide as dissolved gases.
(ii) Dissolved mineral solids
The water contains carbonates of carbonates, bicarbonates, chlorides and sulphates of calcium,
magnesium, iron, sodium and potassium as dissolved solids.
(iii) Suspended impurities
The water contains two types of suspended impurities they are
a) Inorganic type of suspended impurities and b) Organic type of suspended impurities
a) Inorganic type of suspended impurities includes clay, silica, oxides of manganese, iron, etc.
b) Organic type of suspended impurities includes wood pieces, leaf, fishes, etc.
(iv) Microscopic matter: Many pathogenic bacteria and microorganisms are present in water. They are the
main causes for the water borne diseases.
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 bicarbonates of
calcium and magnesium. This hardness can be removed by boiling, where bicarbonates are converted into
insoluble carbonates or hydroxides. Therefore, it can be removed in the form of precipitation.

Ca(HCO3)2  CaCO3 + H2O + CO2

Mg(HCO3)2  Mg(OH)2 + 2CO2

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 therefore it is called permanent
hardness.
The sum of temporary and permanent hardness is referred to as total hardness of water.

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 Unit of hardness: The hardness is expressed in terms of parts per million (ppm) or mg/liter of CaCO3
equivalents. The reason for expressing in terms of calcium carbonate is, it is most insoluble and molecular mass is
100 and therefore calculation become easy.

Estimation of total hardness of water

Hardness of water is determined more accurately by EDTA method.
Principle: The total hardness, temporary and permanent, in water is determined by titrating the water sample against
standard ethylenediaminetetraaceticacid (EDTA) solution in ammonia-ammonium chloride buffer having pH =10
using eriochrome black-T as an indicator. The calcium and magnesium present in hard water forms stable
complex EDTA and less stable complex with eriochrome black-T.

M2+ + EBT  M2+-EBT complex

Blue Wine red

M2+-EBT + EDTA  M2+-EDTA + EBT

Wine red Blue

Procedure

Pipette out known volume (say 25 ml) of hard water into a cleaned conical flask . To which add 10 ml of
ammonia-ammonium chloride buffer and a pinch of EBT indicator. Then the coulur of the solution turns to wine
red. Titrate the solution against standard EDTA solution until the colour changes from wine red to clear blue.

(ii) Calculation
Volume of water sample taken = 25 ml
Concentration of EDTA = X Mol
Volume of EDTA consumed = V ml

Molarity hard water = XxV

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Hardness in terms of CaCO3 in water sample = X x V x 100 g/liter
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= X x Vx 100 x 1000 mg/liter or ppm
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Alkalinity
Alkalinity of the water sample is a measure of its capacity to neutralize acids. Substances that cause
alkalinity are of three types.
(i) OH, (ii) CO32 and (iii) HCO3

Alkalinity of water is mainly classified as (i) Hydroxide alkalinity (ii) Carbonate alkalinity and (iii)
bicarbonate alkalinity. Alkalinity is expressed in terms of ppm of CaCO3 equivalents.

Estimation of alkalinity of water

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Principle: when water sample is titrated against standard acid, the following reactions are taking place.

(i) OH + H+  H2O

(ii) CO32 + H+  H CO3
(iii) H CO3 + H+ H2O + CO2
The titration of water sample with a standard acid up to phenolphthalein end point indicates completion of
reactions (i) & (ii) only. The amount of acid consumed corresponds to hydroxides plus one half of the carbonates
present. Titration of water sample with a standard acid up to methyl orange end point indicates completion of all
the three reactions above. Hence the amount of total acid consumed correspond to the total alkalinity and the
amount of acid used after the phenolphthalein end point corresponds to one half of the carbonate plus all the
bicarbonates.
Procedure:

(i) The alkalinity of water is determined by titrating a known volume of the water sample (say 25 ml) with a
standard acid using phenolphthalein indicator (2 to 3 drops). The end point is detected by the disappearance of
pink color. The volume of acid consumed is noted. The titrated water sample is again titrated against the same
standard acid by using methyl orange indicator (2 to 3 drops). The end point is detected by the appearance of red
color. Again note down the volume of acid consumed.

Calculation

Volume of water sample taken = 25 ml

Concentration of the standard sulfuric acid solution =XN
Volume of acid consumed for phenolphthalein end point = V1 ml
Volume the of acid consumed for methyl orange end point = V2 ml

Concentration of phenolphthalein alkalinity = V1x X

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Phenolphthalein alkalinity in terms of CaCO3 equivalents = V1x X x 50 g/liter
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= V1x X x 50 x 1000 mg/liter or ppm
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Similarly, Methyl orange alkalinity in terms of CaCO3 equivalents = (V1 + V2) x X x 50 x 1000 mg/liter or ppm
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DISSOLVED OXYGEN CONTENT
Dissolved oxygen in water content is determined by Winkler’s method.
Principle: The principle is based on that oxygen dissolved in water oxidizes iodine to iodide in the
presence of oxygen carriers like Manganese hydroxide (Mn (OH)2). The liberated iodine is titrated
against the standard sodium thiosulphate soloution in presence of starch inidicator.

Mn2+ + 2OH-  Mn(OH)2

Mn(OH)2 + ½ O2  MnO(OH)2
MnO(OH)2 + H2SO4  MnSO4 + 2H2O + [O]
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 2KI + H2SO4 + [O]  K2SO4 + H2O + I2
2Na2S2O3 + I2  Na2S4O6 + 2 NaI

Procedure: Known volume of water sample (say 250 ml) is taken in bottle.To which 2 ml of MnSO4 solution
and 3 ml of alkaline potassium iodine solution are added. The bottle is stoppered and shaken well for
10–15 minutes, and allowed to stand for 2 minutes for the precipitate to settle. Then 1 ml of conc. H2SO4
is added, stoppared and shaken well. 100 ml of the solution is pipetted out from the bottle into a conical
flask and titrated against standard Na2S2O3 solution using starch as indicator till the discharge of violet
color.

Calculation:
Volume of water sample taken = 100 ml
Normality of Na2S2O3 solution =XN
Volume of Na2S2O3 solution consumed = Vml
Normality of dissolved oxygen = XxV
100
Weight of dissolved oxygen per liter of water =XxVx8g
100
= X x V x 8 x 1000 mg/liter (ppm)
100
BIOLOGICAL OXYGEN DEMAND
BOD is defined as the amount of dissolved oxygen consumed by the microorganisms to oxidize the
biologically oxidisable 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 waste water sample is refluxed with a known volume K2Cr2O7 (excess) solution in
acidic medium with Ag2SO4 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 using
ferroin indicator. The amount of K2Cr2O7 solution consumed corresponds to COD of the wastewater sample.
Procedure: Pipette out 25ml of the water sample into a clean conical flask. To this add 1gm of HgSO4, 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

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 reddish redish brown. Perform a blank titration taking the same amount of distilled water in place of the
wastewater and 25 ml of K2Cr2O7. 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 waster water = X x (B-A)
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COD of the sample in oxygen equivalents = X x (B-A) x 8 gm.dm-3
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= X x (B-A) x 8 x 1000 mg dm-3

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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 COD of the sample.
Solution:
(M x V)effluent = (M x V)K2Cr2O7
M effluent = 0.001 x 9.8
30
= 0.00032
1 Mole of K2Cr2O7 is equivalent to 48xg of oxygen
COD = 0.00032 x 48 = 0.01568 g of oxygen
COD = 0.01568 x 10000 = 15.68 mg per Lit or ppm

(2) 50 ml of sample for COD analysis was reacted with 15 ml of 0.25 N K2Cr2O7 solution and after the reaction,
the unreacted K2Cr2O7 required 20 ml of 0.1 N FAS for reaction. Under the same condition, 15 ml of
K2Cr2O7 solution mixed with 25 ml of distilled water required 35 ml of 0.1 N FAS. What is the COD of
the sample?
Solution:

COD = (b-a) x NFAS x 8 x 1000

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COD = 240 mg/L
Sewage treatment
Sewage broadly classified into domestic and industrial effluents. Domestic sewage essentially contains
organic waste, pathogenic bacteria, plant material, detergents, etc. Whereas, industrial waste generally

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 contains oils, vegetable and animal matter , complex chemicals like acids, alkali, detergents, phenols,
toxic metals, pesticides and etc.

Generally sewage treatment is carried out in three stages.

(i) Primary treatment or mechanical treatment

(ii) Secondary treatment or Biological treatment
(iii) Tertiary treatment

Primary treatment: Primary treatment involves the removal of settable solids like wood, plastic, paper
floating, rags, etc, using screens, filters, grit chambers.
The non-settable solids are removed by coagulation by treatment with coagulating agents like alum
(K2SO4.12H2O), Ferous sulphate. These coagulates are removed either by sedimentation or by filtration.
The sedimented solids are sent to digester where organic matter is decomposed in the absence of air.
Additionally, in this treatment, oil and greases are removed in skimming tanks.

Secondary treatment: Activated sludge process

The sewage water is mixed with proper quantity of activated sludge containing aerobic microorganism
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

(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.

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Potable water: water, which is fit for domestic purpose is called potable water. It has the following
characteristics
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.

Desalination: It is defined as removal of salts from saline water. The following techniques are commonly
employed remove salts from saline water.
(a) Flash evapaoration
(b) Electrodialysis
(c) Reverse osmosis
(d) Ion exchange method

(a) Flash evapoporation:

Principle: this technique involves boiling of saline water in huge evaporators. The vapours collected are
condensed to give pure water.
Procedure: This method consists in evaporating sea water at 75-80 °C under reduced pressure and then
condensing the vapour under condition of minimum heat loss. The concentrated brine (rich in
dissolved salts) is discharged to waste.

Here, each unit is maintained slightly lower temperature and pressure than the previous one so that heat
produced in one unit is becomes the source of heat in the next. In each evaporator unit, the water vapour
condenses. The condensed water from each unit is collected.

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Softening of water by Ion Exchange Method:
In this method, softening of water is done by exchanging the ions causing hardness of water with desired ions
from an ion exchange resin. Ion exchange resins are high molecular weight, cross linked polymers with a
porous structure. The functional groups which are attached to the chains are responsible for ion exchange
properties. The resins containing acidic groups which are capable exchanging H+ (Na+ ) ions for cations ( Ca2+ or
Mg2+ ) present in water are known as cation exchange resins. The resins containing basic groups which are
capable exchanging OH- for anions present in water are known as anion exchange resins.

Process:In this process, cation and anion exchange resins are packed in separate columns. Hard water is first
passed through cation exchange resins where cations like Ca2+, Mg2+ are removed from hard water by
exchanging with H+ ions are as follows.
Ca2+ + 2R- -H+ → R2 2- -Ca2+ +2H+
Mg2+ + 2R- -H+ → R2 2- - Mg2+ +2H+
Hard water is then passed through anion exchange resins where ions like SO42, Cl are exchanged with OH- ions
are follows;
R+ +OH- + Cl- → R+ - Cl- + OH-
These H+ and OH- ions released combine to form water molecule. Thus water coming out of two resins is ions
free and called as ion exchange d or deionized or demineralized water.
Regeneration:
When the resins exhausted and lose their capacity to exchange ions, they are regenerated. The process of
regeneration is the reversal or the reaction taking place for ion exchange. The cation exchange resin is
regenerated by passing a solution of dilute HCl and H2SO4.
R2 2- -Ca2+ +2H+ → Ca2+ + 2R- -H+
Similarly, anion exchange resin is washed with ammonium or sodium hydroxide solutions.
R+ - Cl- + OH- → R+ -OH- + Cl-
The column is finally washed with deionized with water and the washings are discarded..
Advantages:
1. The ion exchange apparatus, once set up, is easy to operate and control.
2. Both acidic and alkaline water can be softened.
3. Residual hardness is very low and thus water is suitable for high pressure boilers.

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Disadvantages:
1. Equipment and process is costly.
2. Turbid water needs to be filtered first before softening.
Reverse osmosis:
Principle: This technique is based on the principle of osmosis. When a semipermeable membrane separates two
solutions of different concentrations, the solvent moves from lower concentration to that of higher concentration
and this phenomena is called osmosis. If pressure is applied on higher concentration side, the solvent moves in
reverse direction, i.e. from high concentration to low concentration through a semipermeable membrane. The
membrane selected in such a way that it allows only water to pass through it but not ions. Therefor, water of
good quality with less salt concentration and other solution with high salt concentration is obtained.
Process: The process is carried out in a reverse osmosis cell. In this cell, sea water to be desalined is separated
from the fresh water through a semi permeable membrane. The semipermeable membrane consists of nylon or
cellulose acetate thin films. A high pressure of 15-40 Kg/cm2 is applied to the saline water. As a result of
reverse osmosis, fresh water moves down and can be collected from the outlet at the bottom of the cell.

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Electrodialysis
Principle: This method is based on the principle that charged ions move towards opposite charged electrodes
through ion selective membranes when potential difference is applied across salt water solution.

Procedure: The process is carried out in electrodialysis cell. It consists of two electrodes and ion selective
membranes, which are permeable to either cation or anion. The anode is placed neat the anion selective
membrane while the cathode is placed near the cation selective membrane. Saline water is under pressure is
passed from the top of the cell and it passes between the membrane pairs. When emf is applied across the two
electrodes the cations present in salt water move towards the cathode through cation selective membrane and
and anion move towards the anode through anion selective membrane. As a result, pure water and water with
salt is collected separately.

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