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Water

Technology
Sources of water
o Rains, Rivers, Seas, glaciers, Springs,
Lakes etc.

o Rain water is the purest form of water.

o Water has different physical, chemical and


biological impurities which can cause
problems in both domestic and industrial
areas
Impurities in water

o Physical
- Inorganic such as clay, sand
- Organic such as oil globules, vegetable/animal matter
- Colloidal such as Fe(OH)3, Complex proteins, amines

o Chemical
- Anions such as Cl-, SO42- , CO32- ,HCO3-, NO3- of Ca & Mg
- Cations such as Ca2+ , Mg2+ , Na+, K+, Fe3+ , Al3+
- Dissolved gases such as O2, N2, CO2, H2S, NH3

o Biological
- Microorganisms such as algae, fungi, bacteria
(Pathogenic causing Malaria, diohhrrea, typhoid etc.)
Hardness of water
o Hardness of water is due to dissolved salts of mainly calcium and
magnesium as well as iron and other heavy metals.
o Hardness is two types:
a) Temporary :
- Due to dissolved bicarbonates of calcium and magnesium and
carbonates of iron and other heavy metals.
- Can be easily removed by boiling where CO2 gas gets expelled
removing the hardness.

b) Permanent:
- Due to dissolved chlorides and sulphates of calcium and magnesium.
- Can be removed through zeolite, Lime-soda, ion-exchange processes.
Hardness of water
o Water hardness can be identified when soap does not form lather.

o Problems of using hard water:

a) Domestic:
- wastage of fuel & time
- improper cleaning (wastage of soap)
- health related issues ( Urinary infections, kidney stones)

b) Industrial:
- Boiler troubles (scale, sludge, caustic embrittlement,
priming and foaming)
- wastage of fuel
- process related problems
- problems in textile, sugar, paper, laundry, pharma industries
Measurement of hardness
o Hardness of water is measured in parts per millions (ppm.)
as calcium carbonate equivalents.

o Reasons for expressing hardness in CaCO3 equivalents:


- its molecular weight is 100 ; equivalent weight is 50
- it is the most common impurity in water

o Units of hardness:
- parts per million in CaCO3 equivalents (1 mg/L is 1ppm.).
- if 146 mg/L of MgSO4 is present in water, the hardness of
water is 146 ppm. as MgSO4.

o When expressed in CaCO3 equivalents, the formula for conversion


is:
mass of hardness causing substance
Mol. Wt of hardness causing substance X 100 (mol. wt of CaCO3)
Expressing water hardness
1. Ppm. measurement :
1 part of CaCO3 equiv. in106 parts of water (1 mg/L).

2. Clark’s degree:
1 part of CaCO3 equiv. in 70,000 parts of water.

3. French degree:
1 part of CaCO3 equiv. in 105 parts of water.

* Conversion:
1ppm = 1 mg/L = 0.1Fr = 0.07oCl = 0.02 meg/L
Examples of hardness calculations
A sample hard water contains,
8.1 mg/L Ca(HCO3)2 ; 7.5 mg/L Mg(HCO3)2; 13.6 mg/L CaSO4;
12.0 mg/L MgSO4 and 2.0 mg/L MgCl2.

To calculate the hardness and express in CaCO3 equivalents:

Constituent Multiplication CaCO3 equivalents


factor
Ca(HCO3)2= 8.1 mg/L 100/162 8.1 x 100/162 = 5.0 mg/L
Mg(HCO3)2 = 7.5 mg/L 100/146 7.5 x 100/146 = 5.14 mg/L
CaSO4= 13.6 mg/L 100/136 13.6 x 100/136 = 5.0 mg/L
MgSO4= 12.0 mg/L 100/120 12.0 x 100/120 =10.0 mg/L

MgCl2 = 2.0 mg/L 100/95 2.0 x 100/95 = 2.11 mg/L


Disadvantages of hard water
1. Scale and Sludge formation:
a) Sludges:
o Soft, loose, slimy precipitates are sludges
~~~~ o Can be easily scrapped off with a wire brush
~~~~~~~~
~~~~~ ~ o Forms in comparatively colder portions of the
~~ ~ ~~~~~
~ ~
~~~~~~~~~~ boiler such as bends etc.
~~ ~~
~~~~
~~~~
~~~~ ~~~~
~~~~~~
~~ ~~
~~~~~~~~~ o Formed because of MgCO3, MgCl2, CaCl2, MgSO4
~~~~~~~ Mg(OH)2, (more soluble in hot water)
~~~~
Heat
b) Scales:
o Dissolved salts deposit because of continuous
x x xx xx evaporation of water concentration of salts
x x increases
x x
x x o These are hard and stick strongly to the walls
x x
x x o Difficult to be removed even with a hammer and
xx
x xx xx x chisel.
o Formed because of CaCO3, CaSO4, CaSiO3, MgSiO3
Heat
Disadvantages of hard water
2. Priming and Foaming:
a) Foaming:
o Foaming is the production of persistent foam or bubbles in boilers
which do not break easily.
o This is because of presence of oils which reduce the surface tension
of water.
o Can be avoided by adding anti-foaming agents like caster oil or
removing oil from the boiler feed water by adding sodium aluminate.

b) Priming:
o Along with steam, some particles of water are carried (wet steam)
which is called priming.
o This is because of large amounts of dissolved salts, high steam
velocities, sudden boiling, improper boiler design, sudden increase in
steam production rate.
o Priming can be avoided by maintaining low water level in boilers,
avoiding rapid steam generation, efficient softening, installing
mechanical steam purifiers.
Disadvantages of hard water
3. Caustic embrittlement:

o Caused by using highly alkaline water in boiler


o When water is softened by lime-soda process, free Na2CO3 is present in
softened water.
o In high pressure boilers, this Na2CO3 decomposes to NaOH and CO2

Na2CO3 + H2O 2 NaOH + CO2

o This NaOH makes the water caustic.


o This NaOH flows through minute cracks present in the boiler by capillary
action.
o As water is boiling it evaporates and the conc. of NaOH increases.
o This caustic soda attacks the boiler and forms sodium ferroate.
o This makes the boiler parts brittle (embrittlement).
Concentration cell formed during caustic
embrittlement
Caustic attack on boiler parts can be represented as:

+ _
Iron at Conc. NaOH Dil. NaOH Iron at
rivettes, soln. soln. Plane
bends, surfaces
Joints etc.
o The iron in contact with dil. NaOH becomes cathode and the iron in
contact with conc.NaOH becomes anode.
o The anodic part slowly dissolves and corrodes.
o Caustic embrittlement can be avoided by adding:

a) sodium phosphate (Softening agent)


b) tannin or lignin (Blocks hair line cracks)

c) sodium sulphate (Blocks hair line cracks)


Boiler corrosion
o Decay of boiler material by chemical or electrochemical attack by
surrounding environment.
o Reasons for boiler corrosion are:
a) Dissolved oxygen
b) Dissolved carbon dioxide
c) Acids from dissolved salts
a) Dissolved oxygen (DO):
2 Fe + H2O + O2 2 Fe(OH)2

2 Fe(OH)2 + O2 2 Fe2O3.2H2O
Rust or corrosion
o DO can be removed by adding calculated qty. of sodium sulphite or
hydrazine or sodium sulphide:
2 Na2SO3 + O2 2 Na2SO4
N2H4 + O2 N2 + 2H2O
Na2S + 2O2 Na2SO4

o DO can be removed by mechanical aeration also.


Boiler corrosion
b) Dissolved CO2:
o Dissolved CO2 forms carbonic acid which corrodes the boiler
slowly.
CO2 + H2O H2CO3

o CO2 is removed by adding calculated quantity of ammonia:


2 NH4OH + CO2 (NH4)2CO3 + H2O

o It is also removed by mechanical aeration along with oxygen.

c) Acids from dissolved salts:


o Dissolved magnesium salts hydrolyse to form acids:
MgCl2 + 2 H2O Mg(OH)2 + 2 HCl
o This acid reacts with boiler and corrodes:
Fe + 2 HCl FeCl2 + H2
FeCl2 + 2 H2O Fe(OH)2 + 2 HCl

o Small quantity of magnesium salts will large amount of boiler corrosion


Internal treatment methods for boiler
feed water
o Method is also called as Sequestration.
o Ions are complexed to give more soluble salts.
o Internal treatment is carried out to:
a) precipitate scale forming impurities into sludges which can be
removed by blow-down (Partial removal of hard water from
the bottom of the boiler)
b) convert scale forming impurities into compounds with higher
solubility so that they remain in solution.
o The methods are:
a) Colloidal conditioning
b) Phosphate conditioning
c) Carbonate conditioning
d) Calgon conditioning
e) Treatment with sodium aluminate (NaAlO2)
Internal treatment
a) Colloidal conditioning:
o In low pressure boilers, scales are avoided by adding tannin, lignin, agar-
agar.
o These form a layer on the scale forming materials and loose precipitates
are formed which can be easily removed by blow down.

b) Phosphate conditioning:
o In high pressure boilers, scales are avoided by adding sodium phosphate.

o This converts the scale forming impurities to soft sludge of calcium and
magnesium phosphate which can be removed by blow down.

3 CaCl2 + 2 Na3PO4 Ca3(PO4)2 + 6 NaCl

o The phosphates used are:


i) NaH2PO4 (acidic) – for highly alkaline water
ii) Na2HPO4 (weakly alkaline) – for medium acidic/alkaline water
iii) Na3PO4 (alkaline) – for highly acidic water
Internal treatment
c) Carbonate conditioning:
o In low pressure boilers, Na2CO3 is added to the water to convert CaSO4 into
CaCO3 so that CaSO4 scale formation is avoided.

CaSO4 + Na2CO3 CaCO3 + Na2SO4

o CaCO3 forms sludge and is removed by blow down.

d) Calgon conditioning:
o Sodium hexa meta phosphate (NaPO3)6 is Calgon.
o When added to water, it prevents formation of scales and sludges by
forming a soluble complex with CaSO4.

Na[Na4(PO3)6] 2 Na+ + [Na4P6O18 ]2-

2 CaSO4 + [Na4P6O18 ]2- Soluble


[Ca complex ionSO
2P6O18 ] + 2 Na
2-
2 4
Internal treatment
e) Treatment with sodium aluminate(NaAlO2):
o NaAlO2 hydrolyses with water to precipitate Al(OH)3 :

NaAlO2 + 2 H2O NaOH + Al(OH)3

NaOH formed reacts with magnesium salts to Gelatinous


yield Mg(OH)
ppt.
2

MgCl2 + 2 NaOH Mg(OH)2 + 2 NaCl

o The Mg and Al hydroxides trap suspended impurities including oil drops


and silica in the sludge.
o This sludge is removed easily by blow down operation.

f) Electrical conditioning (using sealed electric bulbs), Radioactive


conditioning (using radioactive salt tablets) and complexometric
method (form stable and soluble complexes)
are other internal treatment methods.
Water Softening methods
1. Lime soda
a) Batch process
b) continuous process
- Cold lime-soda
- Hot lime-soda
2. Zeolite (permutit process)

3. Ion-exchange

4. Mixed bed ion-exchange


Reactions of lime and soda
a. Reaction of permanent calcium:
Ca2+ + Na2CO3 CaCO3 + 2Na+

b. Reactions of permanent magnesium:


Mg2+ + Ca(OH)2 Ca2+ + Mg(OH)2

Ca2+ + Na2CO3 CaCO3 + 2Na+

c. Reaction of HCO3- (ex-Na2CO3):


2 HCO3- + Ca(OH)2 CaCO3 + H2O + CO32-

d. Reaction of Ca(HCO3)2 :

Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H2O

e. Reaction of Mg(HCO3)2 :

Mg(HCO3)2 + Ca(OH)2 2 MgCO3 + 2 H2O + Mg(OH)2


Reactions of lime and soda
f. Reaction of CO2:
CO2 + Ca(OH)2 CaCO3 + H2O

g. Reaction of H+:

2 H+ + Ca(OH)2 Ca2+ + 2 H2O

Ca2+ + Na2CO3 CaCO3 + 2 Na+

h. Reactions of coagulants:
i) Reaction of FeSO4:

Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+

Fe(OH)2 + H2O + O2 2 Fe(OH)3

Ca2+ + Na2CO3 CaCO3 + 2 Na


ii) Reactions of Aluminium sulphate (Al2(SO4)3 :

2 Al3+ + 3 Ca(OH)2 2 Al(OH)3 + 3 Ca2+

3 Ca2+ + 3 Na2CO3 3 CaCO3 + 6 Na+

iii) Reactions of sodium aluminate (NaAlO2):

NaAlO2 + H2O Al(OH)3 + NaOH

A. Lime [Ca(OH)2]requirement :
74 {Temp. Ca 2+
+ 2 temp. Mg2+ + Perm(Mg2+ + Al3+ + Fe2+ )
100 {
+ CO2 + H+ + HCO3- - NaAlO2

{2CO3] requirement :
B. Soda[Na
{
100

106 Perm. (Ca2+ + Mg2+ Fe2+ + Al3+ ) + H+ - HCO3-


o Hot lime-soda
process consists of
three parts:

a) Reaction tank to mix


all ingredients

b) Conical sedimentation
vessel where the
sludge settles down

c) Sand filter where


sludge is completely
removed
Advantages of hot lime-soda process

o The precipitation reaction is almost complete


o Reaction takes place faster
o Sludge settles down rapidly; No coagulant is needed
o Dissolved gases (which may cause corrosion) are removed
o Viscosity of soft water is lower, hence filtered easily
o Residual hardness is low compared to cold lime-soda
process
Advantages of Lime – soda process:
1. Economical
2. Process improves the corrosion resistance of water
3. Mineral content of water is reduced
4. pH of water raises thus reducing content of pathogenic
bacteria
5. No skilled labour is required

Disadvantages of Lime – soda process:


1. Huge amount of sludge is formed and its disposal is
difficult
2. Due to residual hardness, water is not suitable for high
pressure boilers
Permutit or Zeolite Process
o Zeolite is hydrated sodium aluminium silicate having a general
formula, Na2OAl2O3.xSiO2.yH2O.

o It exchanges Na+ ions for Ca2+ and Mg2+ ions.

o Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith.

o Other gluconites, green sand (iron potassium phyllosilicate with


characteristic green colour, a mineral containing Glauconite)etc. are
used for water softening.

o Artificial zeolite used for water softening is Permutit.

o These are porous, glassy particles having higher softening capacity


compared to green sand.

o They are prepared by heating china clay (hydrated aluminium


silicate), feldspar (KAlSi3O8-NaAlSi3O8 – CaAl2Si2O8) are a group of
rock-forming tectosilicate minerals which make up as much as 60%
of the earth’s crust) and soda ash (Na2CO3)
Zeolite process
o Method of softening:

Na2Ze + Ca(HCO3)2 2 NaHCO3 + CaZe

Na2Ze + Mg(HCO3)2 2 NaHCO3 + MgZe

Na2Ze + CaSO4 2 Na2SO4 + CaZe

Na2Ze + CaCl2 2 NaCl + CaZe

o Regeneration of Zeolite:

CaZe (or) MgZe + 2 NaCl Na2Ze + CaCl2 or MgCl2

Brine solution
Zeolite Process
o Advantages:
o Residual hardness of water is about 10 ppm only
o Equipment is small and easy to handle
o Time required for softening of water is small
o No sludge formation and the process is clean
o Zeolite can be regenerated easily using brine solution
o Any type of hardness can be removed without any modifications
to the process

o Disadvantages:
o Coloured water or water containing suspended impurities
cannot be used without filtration
o Water containing acidic pH cannot be used for softening since
acid will destroy zeolite.
Ion-Exchange Process
o Ion-exchange resins are cross linked long chain polymers with
microporous structure
o Functional groups present are responsible for ion-exchange
properties
o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for
cations &
o Basic functional groups (-NH2, =NH etc.) exchange OH- for
anions.
A. Cation-exchange Resins(RH+):
- Styrene divinyl benzene copolymers
- When sulphonated, capable of exchange H+
Ion-Exchange Process
B. Anion-exchange resins (R’OH):
- Styrene divinyl benzene copolymers or amine formaldehyde
copolymers with
NH2, QN+, QP+, QS+, groups.
- On alkali treatment, capable of exchange of OH-
Ion-Exchange Process
The Process of Ion-exchange is:

2 RH+ + Ca2+ /Mg2+ R2Ca2+ /R2Mg2+ + 2 H+ (Cation exchange)

R’OH- + Cl- R’+ Cl- + OH- (anion exchange)

2 R’OH- + SO42- R’2 SO42- + 2 OH- (anion


exchange)

2 R’OH- + CO32- R’2 CO32- + 2 OH- (anion


exchange)

Finally,
H+ + OH- H2O

Regeneration of exhausted resins:


Saturated resins are regenerated:
R2Ca2+ /R2Mg2+ + 2H+ 2 RH+ + Ca2+ /Mg2+ (cation) (Stong
acid)
Ion-exchange process

Note: Hard water should be first passed through the cation exchanger and then
Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed
Mixed bed ion-exchanger
o Contains intimate mixture of cation and anion exchangers
o Water is in contact for a no. of times with the two exchangers alternatively
Raw water Anion exchanger
inlet (low density)

NaOH

Mixed
Mixed ionizer Exhausted
ionizer
bed mixed
bed ionizer bed
H2SO4
Cation exchanger
(higher density)

Backwash
water Comp.
air
Washings to
Deminaralised sink
water
Advantages & Disadvantages of
ion-exchange process
o Advantages:

- Can be used for highly acid and highly alkaline water


- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour
Treatment of water for municipal supply
o Drinking or potable water should be safe to drink
and should satisfy the following requirements:

a) Sparklingly clean and odourless


b) Pleasant in taste
c) Perfectly cool
d) Turbidity should not exceed 10 ppm.
e) Free from objectionable minerals like Pb, As, Cr and Mn
f) Free from dissolved gases like H2S
g) Alkalinity should not be too high (pH should be around 8.0)
h) Should be reasonably soft
i) TDS should be less than 500 ppm
j) Free from pathogenic microorganisms
Purification of water for domestic supply
The following are the steps of purification:
A. Removal of suspended impurities:
a) Screening: Floating matter is filter through large screens having large no.
of holes.
b) Sedimentation: To remove suspended particles, water is allowed to
stand in big tanks where suspended matter settles down in the
bottom.
Supernatant water is pumped off.
If water contains colloidial and fine clay particles, a coagulant is added
during sedimentation and the process is called “Sedimentation with
coagulation” .
Coagulant such as alum or ferrous sulphate will form insoluble gelatinous
ppts. and settle them down in the bottom.

Alum (K2SO4.Al2(SO4)3.24H2O, Sodium Aluminate (NaAlO2) and Ferrous


sulphate (FeSO4.7H2O) are normally used coagulants.
Purification of water for domestic supply
e) Filtration: Filtration is a process of removing colloidal matter, most of the
microorganisms etc.

Filtration is carried out using Sand Filter bed containing coarse and
fine sand layers through which water is passed.

The irregular pores in the sand filter hold the sedimented materials
etc., allowing water without these impurities to pass through.

f) Removal of microorganisms: The process of destroying pathogenic


microorganisms etc., from water is called “Disinfection”.
Disinfection can be carried out by:
1. By boiling: Boiling for 15 minutes to kill all microorganisms. This cannot prevent
growth of microrganisms again.
2. By adding bleaching powder:1 kg. of bleaching powder is added per 1000L of
water and allowed to stand for several hours.

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl (Hyporhlorous acid)

Microorganisms + HOCl microorganisms are killed


Drawbacks:
Bleaching powder introduced calcium to water increasing the hardness.
Bleaching powder deteriorates on storage for a long time
Excess beaching powder will gives bad taste and smell to the water.

3. By Chlorination: Chlorine (gas or concentrated liquid) produces


hypochlorous acid which destroys the microorganisms

Cl2 + H2O HOCl + HCl

HOCl H+ + OCl- (Hypochlorite ion)

This HOCl inactivates the enzymes of microorganisms.


By Liquid chlorine: Liquid chlorine is found to be most effective and most
widely used disinfectant throughout the world.

A Chlorinator is used for adding adequate quantity of chlorine so that the


residual chlorine is 0.1 to 0.2 ppm. in treated water.
While chlorination,
time of contact (depends on no. of microorganisms)
temperature of water (higher temperature will kill microrganisms faster)
pH of water (lower pH of water, say 5-6.5, needs lower contact time)
Diagram of chlorinator

Raw water Concentrated


inlet chlorine solution

Baffle plates

High tower

Sterilized water outlet


Chlorination of water
Advantages of chlorine:
o Effective and economical
o Needs very little storage space
o Chlorine is stable and does not deteriorate
o Can be used at low and high temperatures
o Does not introduce any salt impurities to water

Disadvantages of chlorine:
o Excess of chlorine produces characteristic smell and taste
o It also causes irritation to mucus membrane
o Residual chlorine should not exceed 0.1-0.2 ppm.
o It is most effective below pH 6.5 and not very effective at higher
pH.
Break-point chlorination
Oxidn. Of Formation of Destruction Free residual
reducing chloro-organic of chloro- chlorine
compounds
compounds and organic
by chlorine
chloramines compounds
and
chloramines d
Residual chlorine

a
Applied dosage of chlorine
Advantages of break point chlorination
1. Oxidises the organic compounds, ammonia and other reducing
compounds completely
2. Removes colour from water
3. Destroys 100% of the microorganisms
4. Removes bad smell and taste of water
Dechlorination:
Excess chlorine beyond the break-point produces bad taste and smell.
Excess chlorine can be removed by:
a) Passing the excess chlorinated water through a bed of carbon
b) Adding activated carbon and allowing a short reaction time
c) Adding small quantities of sulphur dioxide or sodium sulphite or
sodium thiosulphate:
SO2 + Cl2 + 2H2O H2SO4 + 2 HCl
Na2SO3 + Cl2 + 2H2O Na2SO4 + 2 HCl
Na2S2O3 + Cl2 + H2O Na2SO4 + 2 HCl + S
Disinfection of water
4. By using chloramine (ClNH2):
o When chlorine are added in the ratio of 2:1, chloramine is formed.

Cl2 + NH2 ClNH2 + HCl

o Chloramine is more reactive than chlorine alone and is a better bactericidal agent
than chlorine.

ClNH2 + H2O HOCl + NH3

o Chloramine does not produce any bad smell and also adds good taste to water.

5. Disinfection by Ozone:
o Ozone gas is a very good disinfecting agent.
o Zone is unstable and breaks down to give nascent oxygen.

O3 O2 + [O]

o This nascent oxygen is a powerful disinfecting agent and kills all the microorganisms.
o The disadvantage is that the method is very expensive.
o Advantage is that it removes colour, smell and taste without giving any residue.
Diagram of Ozone sterilizer

Raw water
inlet Ozone inlet

Disinfected
water outlet

Contact tank
Flow diagram of municipal water treatment
Raw Alum
water

Sand filter
Mixing
tank
Fine sand

Coarse sand
gravel

Liquid To
chlorine Supply
Desalination of brackish water
o Water containing dissolved salts with a peculiar salty (brackish)
taste is brackish water
o The process of removing common salt from water is desalination
The methods of desalination are:
1. Electrodialysis
2. Reverse osmosis
1. Electrodialysis:
o Electrodialysis consists of a large container with two membrane
separators, one permeable to positive ions and the other permeable
to negative ions.
o In the outer compartments anode and cathode are arranged to pass
DC Voltage.
o When DC voltage/current is passed through the cell, Na+ will move
towards cathode and Cl- will move towards anode through the
membrane.
o Hence, the concentration of salt decreases in the middle
compartment and increases in the side compartments.
o Water from the middle compartment is collected and this water is
desalinated water.
Electrodialysis diagram

For efficient separation, ion-selective membranes are used which


selectively allow cations or anions to pass through them.
Electrodialysis cell

o Electrodialysis cell consists


of Large number of pairs of
rigid Plastic membranes.

o Saline water at a pressure


of 5-6 kg/cm2 is passed
through the membrane
pairs.

o DC current is applied
perpendicular to the
direction of water flow.

Advantages are:

1. Unit is compact and


installation is economical

2. Best suited if electricity is


available.
Reverse osmosis
oWhen two solutions of unequal
concentrations are separated by a
Semipermeable membrane,
solvent will flow from lower
conc. to higher conc.

oThis phenomenon can be reversed


(solvent flow reversed) by
applying hydrostatic pressure on
the concentrated side

oIn reverse osmosis, pressure of


15-40 kg/cm2 is applied to sea
water.

oThe water gets forced through the


semipermeable membrane leaving
behind the dissolved solids.
Advantages of Reverse
Osmosis
o Advantage is in removing ionic, non-ionic, colloidal and high
molecular wt. organic matter.

o It removes colloidal silica (which is not removed during


demineralisation)

o Cost is only the replacement cost of membranes (life is 2 years)

o Membrane replacement is fast and hence uninterrupted water


supply can be ensured

o Because of the above reasons this process is being adopted for


converting sea water into potable water and for high pressure
boilers.
Estimation of water hardness
1. EDTA method
2. Alkali titration method

1. EDTA method:
o Ethylene diamine tetraacetic acid disodium salt (EDTA disodium salt) is
used as a strong complexing agent with Ca2+ and Mg2+ in hard water.

o The structure of EDTA disodium salt is:

NaOOCH2C CH2COOH
N CH2 CH2 N
HOOCH2C CH2COONa

o Initially, Ca2+ and Mg2+ are treated with Eriochrome black T (EBT) indicator
using ammonia buffer (to maintain pH between 9-10) to get an unstable
complex of Ca2+ and Mg2+ formed with EBT.

pH 9-10
Ca2+/Mg2+ + EBT Ca2+/Mg2+ EBT
(unstable complex – wine red)
EDTA method of water hardness estimation
o After titration with EDTA, EBT gets replaced with EDTA since EDTA forms a
stronger complex with the metal ions.
o This is indicated by the formation of a steel blue coloured complex.
Ca2+ /Mg2+ EBT + EDTA pH 9-10 Ca2+ /Mg2+ EDTA + EBT
(Stable complex - Steel blue)
Procedure:
o First EDTA Solution is standardized using standard hard water (1 mg/ml of
CaCO3 equivalents is prepared as standard hard water).
o For this, first known aliquot of Standard hard water is taken and 10-15 mL of
ammonia buffer is added to bring the pH between 9-10.
o Then a few drops of EBT solution is added to form the unstable complex
giving wine red colour.
o This solution is titrated with the EDTA solution till the solution turns to steel
blue indicating the formation of stable EDTA-Metal ion complex.
o This volume of EDTA is noted as V1.
o The above procedure is repeated with sample hard water of unknown
hardness.
o Volume of EDTA is noted as V2.
EDTA method of water hardness estimation
o Then sample hard water of 250 mL is taken and evaporated to a volume of
50mL when the temporary hard salts settle down.
o The solution is filtered and washed thoroughly and made up again to 250mL.
o From this solution, 50 mL is pipetted out and titrated in similar manner as
done with standard hard water.
o Volume of EDTA is noted as V3.
Calculations:
a) Total hardness:

V1mL of EDTA is consumed by 50 mL of std. hard water


V1mL of EDTA = 50 mg of CaCO3
1 mL of EDTA = 50/V1 mg of CaCO3

EDTA consumed by sample hard water = V2 mL


So, V2 mL of EDTA = 50/V1 x V2 mg of CaCO3
Hence, 50 mL of sample hard water contains 50/V1 x V2 mg of CaCO3
Therefore, 1000mL of sample hard water = 50/V1 x V2 x 1000 mg/L
i.e. Total hardness of sample hard water = V2/V1 x 1000 mg of CaCO3 (ppm.)
EDTA method of water hardness estimation
Permanent hardness:

50 mL of sample hard water after removing temporary hardness consumed


V3 mL of EDTA.

1 mL of EDTA = 50/V1 mg of CaCO3

Therefore, V3 mL of EDTA = 50/V1 x V3 mg of CaCO3

50 mL of sample hardwater after boiling contained 50/V1 x V3 mg of CaCO3

50 V3
x X 1000mg/L
Therefore, 1000 mL of sample hard water contains V1 50
V3
X 1000 mg/L of CaCO3 (ppm.)
Permanent hardness = V1
EDTA method of water hardness estimation

Temporary hardness:

Temporary hardness = Total hardness – permanent hardness

{ V2
V1
X 1000
{
{
V3
V1
X 1000
{

= 1000 X { V2 {
{
V2 { ppm.
V1 V1
[[
[[
[[[[

[[
[[
[[[[

{
V2 – V3 { ppm.
= 1000 X
V1

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