Water & it’s Treatment

Types of water
▪ Soft water :
• Water which is free from hardness causing impurities
• Water which produces lather(foam) immediately after mixing with soap solution

▪ Hard water :
▪ Water which contains hardness causing impurities
▪ Water which does not produce lather(foam) immediately after mixing with soap solution

Hardness of water:
• It is the soap consuming tendency of water
• It is caused by certain salts of Ca ,Mg & other hardness producing metals
e.g. Ca(HCO3)2, Mg(HCO3)2 ,CaCl2, MgCl2 etc.
• These salts react with the soap solution to form insoluble precipitate of calcium and magnesium soaps
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Soap solution Hard water Precipitate
Types of Hardness
▪ Temporary Hardness/ Carbonate / alkaline hardness
• It is caused by the of presence of carbonates & bicarbonates of Ca , Mg etc.
• It can be completely removed by just boiling followed by filteration of hard water
Ca(HCO3)2 Δ CaCO 3 ↓ + H2O + CO2 ↑
Hard water ppt

Mg(HCO3)2 Δ Mg(OH)2 ↓ + 2CO2↑

Hard water ppt

▪ Permanent Hardness-/Non-carbonate/ Non-alkaline

• It is caused by dissolved chlorides, sulphates and nitrates of Ca , Mg etc.
• This hardness cannot be removed by just boiling the hard water sample
• Permanent hardness can only be removed by lime-soda, ion exchange or zeolite processes
CaCl2 + Na2CO3 CaCO3 ↓ + 2NaCl

MgCl2 + Ca(OH)2 Mg(OH)2 ↓ + CaCl2

 Temporary Hardness Permanent Hardness

1. It is due to presence of bicarbonates & 1. It is due to presence of chlorides, sulphates,

carbonates of Ca, Mg, and other heavy meals nitrates of Ca, Mg, & other heavy metals

2. It can be easily removed by just boiling of water 2. It can not be removed by just boiling of
water

3. Temporary hardness causing salts are 3. Permanent hardness causing salts are
alkaline in nature, hence the hardness neutral in nature, hence the hardness is
is called alkaline Hardness called Non-alkaline hardness

4. Examples Ca(HCO3)2, Mg(HCO3)2 etc. 4. Examples CaCl2, MgCl2, CaSO4, MgSO4 etc.
CaCO3 Equivalents

• It is very difficult to understand hardness by considering individual hardness producing salt

• It is (hardness) therefore expressed in term of CaCO3 equivalent

Mass of hardness producing substance

CaCO3 equivalent = ---------------------------------------------------------- × Equi. weight of CaCO3
Equi. weight of hardness producing substance

Equi. Weight = Molecular weight

Valency

Units of hardness

1. Mgs/lit
2. PPM – Parts per Million, 1 mg/lit = 1ppm
3. °Cl - Degree Clarke, 1 °Cl = 14.4 ppm
4. °Fr – Degree French, 1°Fr = 10 ppm
1 mg/lit = 1ppm = 0.07 °Cl = 0.1°Fr
 Determination of Hardness by EDTA method
Principle :
Buffer solution
Ca +2 / Mg +2 + EBT Ca +2 / Mg +2 EBT
Hard water in (Eriochrome black- T) Wine red complex
PH 10
Indicator
conical flask

EBT + EDTA EDTA + EBT

Wine red complex From burette Colourless complex Blue

• Total hardness is determined by titrating unknown hard water against EDTA

• Permanent hardness is determined by titrating boiled hard water

• Temporary hardness is determined as

Temporary hardness = Total hardness - Permanent hardness

 Determination of Hardness by EDTA method
Procedure
Step-1. Standardization of EDTA

Step-2. Estimation of total hardness

Step-3. Estimation of Permanent hardness

Step-4. Estimation of Temporary hardness

 Determination of Hardness by EDTA method

Calculations :
1. Standardization of EDTA
50 ml of standard hard water(SHW) = V1 ml EDTA solution
(1 g/Lit CaCO3 equivalent hardness)
But, 50 ml of standard hard water(SHW) = 50 mg CaCO3 eq. hardness

 50 mg of CaCO3 eq. hardness = V1 ml EDTA solution

 V1 ml of EDTA solution = 50 mg of CaCO3 eq. hardness

 1 ml of EDTA solution = 50/V1 mg of CaCO3 eq. hardness

2. Estimation of Total hardness:

50 ml of unknown hard water (UHW) = V2 ml of EDTA solution

But, 1ml EDTA solution ≡ 50/ V1 mg of CaCO3
V2 ml EDTA solution ≡ V2 X 50/V1 mg CaCO3 Hardness
50 ml of UHW = V2 X 50/V1 mg of CaCO3 Hardness
1000 ml of UHW = V2 X 50/V1 X 1000/50 mg of CaCO3 Hardness
1000 ml of UHW = V2/V1 X 1000 mg of CaCO3 Hardness

 Total hardness = [1000 V2/V1] ppm

2. Estimation of Permanent hardness:

50 ml of boiled hard water (BHW) = V3 ml of EDTA solution

But, 1ml EDTA solution ≡ 50/ V1 mg of CaCO3
V3 ml EDTA solution ≡ V3 X 50/V1 mg CaCO3 Hardness
50 ml of BHW = V3 X 50/V1 mg of CaCO3 Hardness
1000 ml of BHW = V3 X 50/V1 X 1000/50 mg of CaCO3 Hardness
1000 ml of BHW = V3 /V1 X 1000 mg of CaCO3 Hardness

 Permanent hardness = [1000 V3 /V1] ppm


Now,

Temporary Hardness = Total Hardness Permanent Hardness

= [1000 V2/V1] [1000 V3 /V1]

= 1000/V1 X [ V2 - V3] ppm
50 ml of standard hard water containing 1 g CaCO3 eq. hardness per liter consumed 20 ml EDTA . 50 ml of water sample
consumed 25 ml EDTA . 50 ml of boiled hard water consumed 18 ml of EDTA. Calculate various types of hardness.
0.5 g of CaCO3 was dissolved in HCl and the solution made up to 500 ml with distilled water. 50 ml of the solution
required 48 ml of EDTA . 50 ml of hard water sample required 15 ml of EDTA and after boiling and filtering required
10 ml of EDTA. Calculate the Temporary hardness of water.
 Disadvantages of hard water for industries

▪ In boilers, it leads to the formation of scales and sludges which reduce efficiency of boilers.
Sometimes it may cause explosion in boiler.

▪ In textile industry, calcium/magnesium soap precipitates adhere (stick) to the fabric material and interfere
with dyeing process which affects the shades.

▪ In paper industry, smooth and proper colour and finish cannot be obtained if hard water is used.

▪ In sugar industry, presence of calcium magnesium salt interfere with the crystalisation of sugar.

▪ In pharmaceutical industries, if hard water is used for preparing medicines it may cause health injury.

▪ In concrete making, If the water containing chlorides, sulphates etc affects setting of cement and hence
reduces final strength of concrete.
 Softening of Water

1. Lime – Soda method

a) Cold lime-soda method
b) Hot lime-soda method

2. Zeolite or Permutit
3. Ion-exchange or De-ionization or De-mineralization
De-Ionization or De-Mineralization method
• It uses ion-exchange resins which remove both hardness causing cations and anions to make water soft
• Ion exchange resins are high molecular weight polymers which are capable of exchanging their cations(H+) with
hardness causing cations(Ca2+,Mg2+,Fe2+,etc.) and anions(OH-) with hardness causing anions(Cl-,SO42-,etc.) to make water soft

▪ There are two types of resins

1. Cation exchange resins
2. Anion exchange resins
Cation exchange resins
• They are polymers having acidic functional groups like -COOH and –SO3H
• The H ions are loosely bonded to the groups and easily exchanged with all cations( like Ca2+,Mg2+,Fe2+,etc.)
present in water
H
• It is represented as - R E.g. AMBERLITE IR 120
H
Anion exchange resins
• They are polymers having basic functional groups like (CH3)3 NOH
• The OH ions are loosely bonded to the group and easily exchanged with all anions( like Cl-,SO42-,etc.) present in water

• It is represented as - OH
R
OH E.g. AMBERLITE IRA 400
De-Ionization or De-Mineralization method
HCl for regeneration NaOH for regeneration
Cation exchange Anion exchange
resin resin De- gasifier
Hard water

De-ionized water (soft water)

Washings Washings
Process
▪ It operates on alternate cycles of softening process and regeneration process
Softening process -:
• Initially, hard water is passed through cation exchange resin column
• When all hardness causing cations (Ca2+,Mg2+,etc.) are exchanged by H+ ions

H Softening
R Ca + 2HCl
CaCl2 + R
H Exhausted resin water containing anions
Hard water Cation exchange resin

Cation exchange
resin
Anion exchange
resin
Hard water

De-ionized water (soft water)

Process
Cation exchange
resin
Anion exchange
resin
Hard water

De-ionized water (soft water)

• Water free from cations is then passed through anion exchange resin column
• When all hardness causing anions (Cl-,SO42-,etc.) are exchanged by OH- ions and water becomes soft
• After softening both the resins are exhausted(saturated) and stop softening
OH Cl
Softening + 2H2O
+ R R
2HCl Cl
OH Soft water
Water containing anion exchange resin Exhausted resin
anions
Regeneration process -:

▪ The exhausted zeolite columns can be regenerated and reused

▪ Exhausted cation exchange resin column is regenerated by passing dil. HCl solution through it

H
+ CaCl2
2 HCl Regeneration R
R Ca + H
Exhausted cation Regenerated cation Washings
exchange resin exchange resin column

HCl for Cation NaOH for

Anion
regeneration exchange regeneration
exchange
resin resin
▪ Exhausted anion exchange resin column is regenerated by passing dil. NaOH solution through it

OH
Cl
Regeneration R + 2NaCl
R + 2 NaOH
OH
Cl
Regenerated anion
Exhausted anion exchange resin column
exchange resin

HCl for Cation NaOH for

Anion
regeneration exchange regeneration
exchange
resin resin
Advantages :-

1. Water of 0 to 2 ppm hardness which is suitable for high pressure boiler can be obtained
2. It removes both hardness causing cations and anions
3. Highly acidic or alkaline water can be softened
4. Softener adjusts itself for water of any hardness

Limitations :-
1. The equipment and resins are very costly
2. Hard water should be free from turbidity
Drinking or Municipal water

Potable water standard (BIS-Bureau of Indian Standards)

PH = 6.5 to 8.5
TDS = 500 ppm (Desirable) and 2000 ppm (Permissible)

Hardness = 300 ppm (desirable) and 600 ppm (Permissible)

Alkalinity = 200 ppm (desirable) and 600 ppm (permissible)

Electro Dialysis –
▪ It is based on the fact that the ions present in salty water migrate towards respective electrodes under the influence of
applied potential
• Electro dialysis unit consists of two electrodes ( cathode & anode) and ion-selective membranes
• Direct electric current is passed through saline water(sea water) e.g. containing NaCl
• Na+ ions start moving towards cathode(-ve electrode) and Cl ions starts moving towards anode(+ve electrode)
through membranes as shown in figure below
• As a result, the concentration of NaCl decreases in the central compartment, while it increases in two side compartments
• Pure water(free from NaCl) is then removed from middle compartment

Sea water Sea water Sea water

Concentrated Sea water Pure water Concentrated Sea water

Advantages

• The equipment is very compact and occupies less place

• Installation, operational and maintaining cost is low
Reverse osmosis or Super Filtration or Hyper Filtration
• In case of osmosis, when two solutions of different concentrations are separated by a semi-permeable membrane
flow of solvent takes place from a region of low concentration to high concentration
• The driving force for osmosis is osmotic pressure
• If however, a hydrostatic pressure in excess of osmotic pressure is applied on the concentrated side, the solvent
flow reverses, i.e. solvent is forced to move from concentrated side to dilute side across the membrane
• This is the principle of reverse osmosis.
• Thus in reverse osmosis method pure solvent (water) is separated from its contaminates, rather than removing
contaminants from the water
• Semi-permeable membranes are polymers like cellulose acetate, poly methyl acrylate and polyamide polymers
• Membrane allows only solvent molecules to pass through it and dissolved solutes, suspended particles etc. are dis-allowed
Pressure
Piston

Semi-permeable membrane

Pure water
 • In actual process a pressure of 15 to 40 Kg/cm2 is applied to the sea water (impure water) to force it’s
pure water(solvent) out through membrane leaving behind dissolved solids (solutes)
• It is used for purification of sea water for drinking and industrial purpose
Advantages
• It removes ionic as well as non-ionic, colloidal and high molecular weight organic matters
• It removes colloidal silica which is not removed by ion exchange method
• Operating and maintenance costs are low
• Life span of membrane is about 2 years and it can be replaced very easily

Ultrafiltration
• It is fundamentally similar to Reverse Osmosis with two major differences as follows
1) Pore sizes of membrane which is comparatively larger than that of reverse osmosis membrane
2) Pressure at which it operates ( which is comparatively low)

• Ultrafiltration removes only high molecular weight substances, colloidal materials and polymeric compounds
and ions such as sodium, calcium, magnesium, chloride and sulphates are not removed

• In ultrafiltration, impure water is forced against a semi-permeable membrane in the presence of hydrostatic pressure

• A pressure of only 3-10 kg/cm2 is sufficient for ultrafiltration

• Water and low molecular weight solutes which pass through membrane are collectively called permeate
and solutes of high molecular weight which are not able to pass through it are collectively called concentrate

Applications
• It is used for removal of bacteria, viruses, colour, odour etc. from drinking water

• It is used as a pre-treatment of industrial waste water before treating such

waste water with reverse osmosis or Electrodialysis

• Paint recovery in the automobile industry

• Protein isolation

• To separate suspended solids from solution

Ultrafiltration cell
 Water pollution –
Any alteration in the physical , chemical and biological properties of water which would constitute a health
hazard or otherwise decreases the utility of water is called as water pollution.

BOD – Biological Oxygen Demand

Def n - It is a measure of amount of oxygen required for the biological oxidation of organic matter in
sewage under aerobic conditions at 200C and for a period of five days.

Significance -
• The higher the BOD of a sample, the higher the amount of decomposable organic matter in the sample and
higher the pollution of the water
• Therefore BOD gives an idea about the extent of pollution at any time in the sewage sample
• Helps in pollution control
 Chemical oxygen demand (COD)-
It is defined as the amount of O2 required for chemical oxidation of chemically degradable organic matter in
hot conditions with the use of oxidant like acidified K2Cr2O7
Process –
• A known volume of the sewage sample(waste water) is refluxed with a known excess of standard K2Cr2O7
and dil H2SO4in presence of little Ag2SO4 catalyst for1 ½ hrs.
• The unreacted K2Cr2O7 is then determined by titrating against standard FAS (FeSO4(NH4)2.SO4.6H2O)
• This is called as back titration reading
• Blank titration reading is then determined by performing same steps as above but without sewage sample
• The amount of K2Cr2O7 reacted with sewage = Blank reading(Total K2Cr2O7) – Back reading (Unreacted K2Cr2O7)

8 X Volume of K2Cr2O7 reacted X Normality X 1000

COD = PPM
Volume of Sewage

8 X (Blank reading – Back reading) X Normality X 1000

COD = PPM
Volume of Sewage
 Significance

• COD is a measure of both biologically oxidisable as well as biologically inert organic matters
• COD values are therefore higher than BOD values
• It takes less time (about 3 hrs) as compared to BOD (takes about 5 days)
• It helps in designing water treatment plant
After treating 104 lit of water by ion exchanger, the cationic resin required 200 lit of 0.1 N HCl and anionic resin
required 200 lit of 0.1 n NaOH. Find the hardness of water.
The exhausted ion exchange resins consumed 250 L of 0.1 N HCl and same of NaOH solution for regeneration.
The resins were used to soften 10^5 L of water . Calculate the total hardness in ppm.
Prob. 1 A 50 ml of sample contains 840 ppm of dissolved oxygen. After 5 days the dissolved oxygen value becomes 230 ppm
after sample has been diluted to 80 ml. Calculate BOD of the sample.

BOD = (DOb - Doa ) X Dilution factor (Where Dob is dissolved O2 before incubation & Doa is dissolved O2 after incubation)
= (DOb - Doa ) X ml of sample after dilution
ml of sample before dilution
= (840 - 230 ) X 80
50
= 976 ppm
 A 25 ml sewage sample was refluxed with 10 ml of 0.25 N K2Cr2O7 solution in presence of dil H2SO4, Ag2SO4 and HgSO4.
The unreacted dichromate required 5.5 ml of 0.1 N Ferrous Ammonium Sulphate (FAS). 10 ml of the same K2Cr2O7 solution
And 25 ml of distilled water, under the same conditions as the sample, required 15 ml of 0.1N FAS. Calculate the COD of the
sewage

8 X Volume of K2Cr2O7 reacted X Normality X 1000

COD =
Volume of Sewage

8 X ( Blank - Back ) X Normality X 1000

COD =
Volume of Sewage
A 5 ml of water sample was refluxed with 30 ml of potassium dichromate solution and after refluxing the excess unreacted
Dichromate required 23 ml of 0.1 N FAS solution. A blank of distilled water on refluxing with 30 ml of dichromate solution
required 36 ml of 0.1 M FAS. Calculate COD of water.
Calculate the COD of an effluent sample if 25 cc of the effluent sample required 8.3 cc of 0.001 M K2Cr2O7 for oxidation
20 ml of SHW containing 1.2 g CaCO3 per lit required 35 ml of EDTA. 50 ml of hard water required 30 ml of the same EDTA
100ml of hard water sample after boiling required 25 ml of the same EDTA. Calculate various hardness.