Water Water is colorless, odorless, tasteless liquid…

Water is polar. ...

Water has high surface tension
Water is an excellent solvent. ...
Water has high heat capacity. ...
Water has high heat of vaporization. ...
Water has cohesive and adhesive properties. ...
Water is less dense as a solid than as a liquid.
Water has low electrical conductivity
Sources of water
Rain
Rivers and lakes (Surface water)
Wells and springs (Underground water)
Sea water

Imputities
Metal salts, Bicarbonates, Carbonates, Sulphates,
Chlorides, Fluorides, Sulphides, suspended solid
Physical impurities of Water

➢ Color: Dissolved metal complexes, Biological species

➢ Turbidity: insoluble fine suspensions of salts, soil, microorganisms
➢ Taste: Presence of dissolved salts
➢ Odour: living or dead organisms

Chemical impurities of Water

Inorganic and organic impurities from industries, agriculture, drugs, insecticides
➢ Acidity: Dissolved gases like CO2 etc
➢ Alkalinity: Presence of minerals
➢ Dissolved Gases: CO2, SO2, Nitrogen oxides

Biological impurities of Water

Micro organisms like Algae, Fungai, bacteria
Water bodies
Hardness of water
Hard and soft water : Lather forming ability
Lather formation

Cause of Hardness

Effect of Hardness

Effect of Hardness
 Commercial classification of water on the basis of degree of hardness

Types of Hardness: The hardness of water is two types;

1. Temporary hardness. 2. Permanent hardness.
Caused by Caused by dissolved
❖ Bicarbonates of Ca, Mg and heavy metals ❖ Chlorides, sulphates, nitrates of Ca, Mg and heavy
❖ Carbonates of Iron metals
Removed by boiling ➢ Does not remove by boiling
➢ Only chemical treatment can remove this hardness.

Total Hardness = Temporary hardness + Permanent hardness

Expression of hardness:
Hardness of water is expressed in terms of calcium carbonate equivalents.
1. The Molecular Weight of CaCO3 is 100, which is easy for calculation.
2. CaCO3 is an insoluble salt, and
3. All the dissolved salts of calcium are precipitated as CaCO3
➢ The weights of different salts causing hardness are converted to weights equivalent to that of CaCO3

120 parts by weight of MgSO4 would react with the same amount of soap as 100 parts by weight of CaCO3.
Hence, weight in terms of CaCO3 = weight of MgSO4 in water multiplied by 100/120.
The method of calculating hardness will be clear from the following formula.

weight of the hardness causing salt x 100

Hardness of salt in terms of CaCO3 =
Molecular weight of hardness causing salt

Mass of the hardness causing salt x Chemical equivalent of CaCO3

=
Chemical equivalent of hardness causing salt
Chemical equivalent of CaCO3 = 50
➢ If a sample of water contains two or more than two salts,
Hardness causing Mol. Weight Multiplication Equi.
their quantities are converted in equivalent to CaCO3 salt factor Weight
➢ Then the sum will give the total hardness. Ca(HCO3)2 162 100/162 81

Mg(HCO3)2 146 100/146 73

CaSO4 136 100/136 68

Units of hardness:
There are five units in which the hardness of water is expressed.
1. Parts per million (ppm).
2. Milligrams per litre (mg/L).
3. Degree Clark (0Cl).
4. Degree French (0F).
5. M.eq per litre (meq/L).
1. Parts per million (ppm): the parts of calcium carbonate equivalent hardness per 106 parts of water.
i.e. 1ppm = 1 part of CaCO3 eq hardness in 106 parts of water.
2. Milligrams per liter (mg/L): the number of milligrams of calcium carbonate equivalent hardness present per liter of water.
Thus, 1 mg/L = 1 mg of CaCO3 eq hardness per 1 L of water
But 1 L water = 1 kg = 1000g = 106 mg
1 mg/L = 1 mg of CaCO3 eq per 106 mg of water = 1 part of CaCO3 eq per 106 parts of water = 1 ppm
3. Degree Clark (0Cl): the number of grains of CaCO3 equivalent hardness per gallon of water.
It is the parts CaCO3 equivalent hardness per 70,000 parts of water.
1 0Cl = 1 grain of CaCO3 eq hardness per gallon of water
10Cl = 1 part of CaCO3 eq hardness per 70,000 parts of water
4. Degree French (0F): the parts of calcium carbonate equivalent hardness per 105 parts of water.
i.e. 1 0F: = 1 part of CaCO3 eq hardness in 105 parts of water.
4. M.eq per litre (meq./L).: number of milliequivalents of hardness present per liter
i.e. 1 meq./L : = 1 meq of CaCO3 eq hardness per liter of water= 50mg of CaCO3 eq per liter = 50ppm

1ppm = 1 mg/L = 0.1 0F = 0.07 0Cl = 0.02 meq/L

Disadvantages of hard water:
1. In domestic use:
(a) Washing and Bathing:
(a) Causes wastage of soap
(b) It produces sticky and scummy precipitates of calcium and magnesium
(c) Presence of iron salts may cause stains on cloth.
(c) Cooking and Drinking
a) Presence of dissolved hardness causing salts, the boiling point of water is elevated causing more fuel.
b) Certain foods do not cook soft in hard water.
c) Also, tea or coffee, prepared in hard water has an unpleasant taste and muddy- looking extract.
d) Hard water causes bad effect on our digestive system.
e) Moreover, the possibility of forming calcium oxalate crystals in urinary tracks is increased.

2. In Industrial use:
(a) Textile industry:
(a) Hard water causes much of the soap to go as waste.
(b) Metal stain precipitated by soaps adhere to the fabrics causing stainingOLOGY
(b) Sugar industry:
a) Water containing sulphates, nitrates, alkali carbonates, etc.,
b) If used in sugar refining, it causes difficulties in the crystallization of sugar.
c) Moreover, the sugar so-produced may be deliquescent.
(c) Pharmaceutical industry:
a) Hard water, if used for preparing pharmaceutical product like drugs, injections and ointments etc. may produce certain
undesirable products in them.
 3. In Boilers during steam generation:
If the hard water is fed directly to the boilers, there arise many troubles such as:
(i) Boiler corrosion (iii) priming and foaming
(ii) Scale and sludge formation (iv) caustic embrittlement.
i). Boiler corrosion:
Boiler corrosion is “the decay of boiler material by a chemical or electro-chemical attack by its environment”.
Main reasons for boiler corrosion are:
(i) Dissolved oxygen:
❖ Water usually contains about 8 ppm of dissolved oxygen at room temperature.
❖ At high temperature this D.O. can attack boiler material.

Removal of dissolved oxygen:

by adding calculated quantity of sodium sulphite, hydrazine or sodium sulphide

(ii) Dissolved carbon dioxide:

❖ Carbon dioxide is released by Ca(HCO3)2 inside the boiler, dissolves in
water to form acidic environment
Removal of dissolved CO2: by adding calculated quantity of ammonium hydroxide.

(iii) Acids from dissolved salts:

❖ Acids are liberated inside boilers by the decomposition of Metal chlorides and
sulfides etc
ii). Scale and Sludge formation:
➢ In boilers, water evaporates continuously and the concentration of the dissolved salts increase progressively.
➢ When their concentration reach saturation point, salts gets precipitated
➢ The precipitates sticks on the inner walls of the boiler leads to the formation of Scales and sludge

a). Sludge
❖ The soft, loose and slimy precipitate formed within the boiler.
❖ Sludge is formed by substances which have greater solubilities in hot water than cold water.
E.g. MgCO3, MgCl2, CaCl2, MgSO4, etc.
❖ It is formed at colder portions of the boiler.
❖ Sludge can easily be scrapped off with a wire brush.

Disadvantages of sludge formation:

(a) Sludges are poor conductors of heat, so they tend to waste a portion of heat generated.
(b) Excessive sludge formation disturbs the working of the boiler as it settles in the regions of poor water circulation
(c) Sludge can get entrapped in scale if formed together and deposits as scale.
WATER TECHNOLOGY
Prevention of sludge formation:
(a) By using well softened water which is free from MgCO3, MgCl2, CaCl2, MgSO4 salts.
(b) By frequent “blow-down” operation, i.e. drawing off a portion of the concentrated water.
b). Scale:
❖ The hard precipitate formed within the boiler.
❖ These will stick very firmly to the inner surfaces of the boiler.
Formation of scales may be due to:
(a) Decomposition of calcium bicarbonate:
Due to high temperature and pressure present in the boilers, the calcium bicarbonate salt
decomposes in to insoluble CaCO3 scale.
Ca(HCO3)2 CaCO3 + H2O + CO2
(scale)
(b) Deposition of calcium sulphate:
The solubility of calcium sulphate in water decreases with rise of temperature.
solubility of CaSO4 is 3,200 ppm at 150C
55 ppm at 2300C
27 ppm at 3200C.
Consequently, CaSO4 gets precipitated as hard scale on the heated portions of the boiler.

(c) Hydrolysis of magnesium salts:

Dissolved magnesium salts undergo hydrolysis to form Mg(OH)2 precipitate, which forms a soft type of scale.
MgCl2 + 2H2O Mg(OH)2 + 2HCl

(d) Presence of silica:

SiO2, even present in small quantities, deposits as calcium silicate (CaSiO3) and magnesium silicate (MgSiO3).
These deposits stick very firmly on the inner side of the boiler surface and are very difficult to remove.
Disadvantages of scales:
a) Wastage of fuel: Scales have a low thermal conductivity, so the rate of heat transfer gradually decreased.
In order to provide a steady supply of heat, over-heating should be done
The wastage of fuel depends upon the thickness of scale.

b) Lowering of boiler safety

c) Danger of explosion

Removal of scales:
(i) With the help of scraper or wire brush, if they are loosely adhering.
(ii) By giving thermal shocks if they are brittle.
(ii) Calcium carbonate scales can be dissolved by using 5-10% HCl.
(iv) Calcium sulphate scales can be dissolved by adding EDTA, with which they form soluble complexes.
(v) By frequent blow-down operation, if the scales are loosely adhering.
 iii) Priming and foaming:
Priming (process of ‘wet steam’ formation): Foaming:
➢ When a boiler is producing steam rapidly, some particles of ➢ Foaming is “the production of persistent foam or bubbles
the liquid water are carried along with the steam. in boilers, which do not break easily”.
Priming is caused by: ➢ Foaming is due to the presence of substances like oils,
(i) The presence of large amount of dissolved solids. which greatly reduce the surface tension of water.
(ii) High steam velocities. Foaming can be avoided by:
(iii) Sudden boiling. (i) Adding anti- foaming chemicals like castor oil.
(iv) Improper boiler design. (ii) Removing oil from boiler water by adding compounds
(v) Sudden increase in steam-production rate. like sodium aluminate.
Priming can be avoided by:
(i) Fitting mechanical steam purifiers.
(ii) Avoiding rapid change in steam rate.
(iii) Maintaining low water levels in boilers.
(iv) Efficient softening and filtration of boiler- feed water.

Dis-advantages of priming and foaming:

(i) Dissolved salts in boiler water are carried by the wet steam to turbine blades, where they get deposited as water evaporates.
This deposit reduces their efficiency.
(ii) Dissolved salts may enter the parts of other machinery, where steam is being used, thereby decreasing the life of the machinery.
(iii) Actual height of the water levels cannot be judged properly, thereby making the maintenance of boiler pressure becomes
difficult
 Estimation of hardness by EDTA method:

➢ EDTA is Ethylene diamine tetra acetic acid Ca2+

➢ Hexadentate ligand and usually occurs a disodium salt.
➢ EDTA forms a colorless stable complex with Ca2+ and Mg2+ ions
in water at pH 10.

➢ Ammonia buffer is used to maintain the pH (NH4Cl + NH4OH).

End point
➢ EBT (Eriochrome Black-T) is used as an indicator.
Ca2+
➢ Initially EBT forms an unstable complex with Ca2+ and Mg2+ ions, (Ca-
EBT or Mg-EBT complex) giving wine red color to the solution.
1. Determination of Total hardness
(i) Pipette out 20 ml of well water ion solution into a conical flask.
(ii) Add 5 ml of buffer solution and few drops of Eriochrome Black-T.
(iii) Titrate with EDTA solution taken in the burette, till the wine red color changes to blue
Let the burette reading of EDTA be V ml.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑥 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴
Molarity of the sample (M1) = 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒

Total hardness = 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 water sample x 100 x 1000 𝑝𝑝m (as CaCO3 eq)
Multiply M1 with 105 to covert hardness into parts per million (ppm).
2. Determination of Permanent hardness
➢ Take 100 ml of sample hard water in 250 ml beaker.
➢ Boil it to remove temporary hardness to about half of this volume and cool to room temperature.

➢ Filter through filter paper to remove insoluble CaCO3 and MgCO3. Make up the volume to the original 100 ml by adding
distilled water.
➢ Now pipette out 20 ml of this solution into a clean conical flask and repeat the process for determining molarity
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐸𝐷𝑇𝐴 𝑥 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴
Molarity of the sample (M2) = Multiply M2 with 105 to covert hardness into
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒
parts per million (ppm).

Determination of Temporary hardness

Temporary hardness = Total hardness – Permanent hardness
Softening methods:The process of removing hardness producing salts from water
➢ Water used for industrial purpose should be sufficiently pure (Free from hardness producing salts).
In industry, main methods employed for softening of water are two types.
1. Internal treatment
2. External treatment:
1. Internal treatment : the process of softening water inside the boiler

➢ Adding appropriate reagents for complexing the hardness causing salt to soluble compounds
➢ Precipitating the scale forming impurities in the form of sludge which can be removed by blow down operation.
➢ Converting the scale forming salts into other compounds which stay in ‘dissolved form’ and do not cause any trouble
to the boilers.

The important internal conditioning methods are;

(a) Colloidal conditioning (b) Phosphate conditioning
(c) Carbonate conditioning (d) Calgon conditioning:
(e) Treatment with sodium aluminate (NaAlO2):
(a) Colloidal conditioning

➢ The scale formation in low pressure boilers can be prevented by the addition of kerosene, tannin, agar-agar etc.
➢ The compound will be get coated over the scale forming precipitates.
➢ These forms loose, non-sticky deposits (sludge) that can be removed by blow down.

(b) Phosphate conditioning:

➢ The permanent hardness causing salts in high pressure boilers will be removed by reacting with Sodium phosphate.
3 CaCl2 + 2 Na3PO4 ------→Ca3(PO4)2 + 6 NaCl
➢ The complex formed is soft, non-adherent and easily removable.
➢ The three phosphates employed in this process are
Na3PO4 – tri-sodium phosphate (alkaline),
Na2HPO4 – disodium hydrogen phosphate (weakly alkaline) and
NaH2PO4 – sodium di-hydrogen phosphate (acidic).
(c) Carbonate conditioning:

By the addition of Sodium carbonate to boiler water, the hard and strong adherent scales formed due to CaSO4 are avoided
The CaSO4 is converted to CaCO3, which is loose sludge and it can be removed by blow down.
CaSO4 + Na2CO3 ------→CaCO3↓ + Na2SO4

(d) Calgon (Sodium hexameta phosphate Na2[Na4(PO3)6 or (NaPO3)6) conditioning:

➢ This involes the treatment of boiler water with calgon.
➢ Calgon forms soluble complex compounds with CaSO4.
Na2[Na4(PO3)6 ] -------→2Na+ + [Na4P6O18]2-
2 CaSO4 + [Na4P6O18]2- --------→[Ca2P6O18]2- + 2Na2SO4

(e) Treatment with sodium aluminate (NaAlO2):

➢ Sodium aluminate is hydrolyzed in boiler to give NaOH.

NaAlO2 + H2O-----→ Al(OH)3 + NaOH

➢ The formed NaOH immediately react with Magnesium salts and precipitates Mg(OH)2
MgCl2 + 2 NaOH ------→Mg(OH)2↓ + NaCl

➢ Mg(OH)2 and Al(OH)3 forms a flocculent precipitate with colloidal particles and silica
Caustic embrittlement: a type of boiler corrosion
➢ Caustic embrittlement is caused by using highly alkaline water in the boiler”.
➢ During softening of water by lime-soda process, free Na2CO3 is usually present in small proportion in the softened water.
➢ In high pressure boilers, Na2CO3 decomposes to give NaOH and CO2, makes the boiler water ‘caustic or alkaline’.
Na2CO3 + H2O 2NaOH + CO2

➢ Water containing NaOH flows into the minute hair-cracks present in the inner side of boiler, by capillary action.
➢ At the cracks, water evaporates and the dissolved caustic soda (NaOH) concentration increases progressively.
➢ This caustic soda attacks the surrounding area, thereby corroding the iron of boiler as sodium ferrate.

Caustic embrittlement can be explained by considering the following concentration cell

Prevention of caustic embrittlement:

(i) By using sodium phosphate or sodium sulphate as softening reagent, instead of sodium carbonate.
(ii) By adding tannin or lignin to boiler water, which blocks the hair-cracks, thereby preventing infiltration of caustic soda
solution in cracks.
Caustic embrittlement can be prevented, if Na2SO4 is added to boiler water so that the ratio:
Na2SO4
Na2CO3 = 1:1, 2:1 or 3:1