Unit-2 Water Chemistry

Hardness: Water which does not produce lather with soap solution readily, but forms a
white scum (mass) is called hard water. The soap consuming capacity of water is called hard
water.
Hard water consumes a lot of soap: This is due to the presence of salts of metal ions like Ca2+,
Mg2+, Al3+, Fe3+, Mn2+ dissolved in water. Such metal salts react with soap (sodium or potassium
salt of higher fatty acid like oleic acid, palmitic acid, stearic acid) to form insoluble white scum.

Chemical reaction: CaCl2 + 2C17H35COONa (C17H35COO)2Ca + 2NaCl

MgSO4 + 2C17H35COONa (C17H35COO)2Mg + Na2SO4

Difference between hard water and soft water:

S.No Hard Water Soft water
1 Water which does not produce lather with Water which easily lathers with soap
soap solution readily but forms a white scum solution is called soft water
is called hard water
2 The presence of calcium and magnesium The absence of calcium and magnesium
salts in water forms hard water salts in water leads to soft water
3 Hard water causes wastage of soap due to Soft water lathers easily and does not
depressed cleansing and detergent action result in wastage of soap.
Presence of calcium and magnesium salts It also does not result in wastage of fuel
results in elevated boiling point of water; and time during cooking due to absence
thus more fuel and time are required for of calcium and magnesium salts.
cooking

Classification of hard water:

Hardness is of two types:
1. Temporary hardness: This type of hardness is caused by the presence of dissolved
bicarbonates of calcium and magnesium and other heavy metals and the carbonate of
iron.
Thus the salts responsible for temporary hardness are Ca(HCO3)2 and Mg(HCO3)2. It is
also known as carbonate hardness or alkaline hardness. Alkaline hardness is due to
presence of bicarbonate, carbonate and hydroxides of the hardness producing metal ions.
Temporary hardness can be removed by boiling of water when bicarbonates are
decomposed yielding insoluble carbonates or hydroxides which are deposited as a crust at
the bottom of the vessel.

Ca(HCO3)2 CaCO3 + CO2 + H2O

Mg(HCO3)2 Mg(OH)2 + 2CO2

2. Permanent hardness: It is due to the presence of dissolved chlorides and sulphates of

calcium and magnesium, iron and other heavy metals. Hence the salts responsible for
permanent hardness of water are CaCl2, MgCl2, CaSO4, MgSO4, FeSO4, Al2(SO4)3 etc.
Permanent hardness cannot be removed by boiling. It is also known as non-carbonate or
non-alkaline hardness. It can be removed by following processes:

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 1

 Unit-2 Water Chemistry

(i) Lime-soda process:

(ii) Zeolite process:
(iii) Ion-exchange process
(iv) Reverse Osmosis

3. Total hardness: Temporary hardness + Permanent hardness

Advantages and disadvantages of hard water:

S.No Advantages of hard water Disadvantages of hard water
1 Hard water tastes better. The dissolved Hard water produces scum with soap.
calcium in water is beneficial for stronger Washing and detergent efficiency of soap
bones and teeth in children. decreases and the economy decreases.
Cooking with Hard water results in more fuel
consumption and more time consumption
due to elevated boiling point of hard water.

Degree of hardness
Hardness of water is expressed in equivalents amounts of CaCO3 because it forms the insoluble
precipitate which can be removed easily in water treatment and also because its molecular mass
is 100 (which makes calculations easier).

Equivalent of CaCO3 (mg/L) or (ppm) =

(Strength of hardness producing substance mg/L)x (Molecular weight of CaCO3/2)

Molecular weight of substance/2

Units of Hardness:
i. Part per million (ppm) It is defines as the number of parts by weight of calcium
carbonate (CaCO3) present per million (106) parts by weight of water.
1 ppm= 1 part of CaCO3 equivalents hardness in (106) parts of water
ii. Milligrams per litre (mg/L). It is defines as the number of milligrams of CaCO3 present
in one litre of water.
1 ppm= 1mg/L
iii. Degree Clarke (oCl). It is defines as the parts of CaCO3equivalen hardness per 70,000
parts of water.
o
Cl = 1 part of CaCO3 per 70000 parts of water
iv. Degree French (oFr). It is defines as the parts of CaCO3 equivalent hardness per 105
parts of water.
o
Fr = 1 part of CaCO3 per 105 parts of water

Relationship between various units of hardness:

1ppm = 0.1°Fr = 0.07°Cl = 1mg/L

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 2

 Unit-2 Water Chemistry

Water Softening
Processes involved in removal of temporary and permanent hardness is called as “softening of
water”. It is very essential process since hard water is unsuitable for domestic and industrial use.
Use of hard water for generating steam in boilers so as to generate electricity results in problems
like sludge formation, priming, foaming, boiler corrosion and caustic embrittlement.
Boiler Hard water can be removed by two ways:
1. External Treatment: Treatment of hard water is done before its entry into the boiler.
This involves lime-soda, zeolite and ion exchange process. All are preventive methods.
2. Internal treatment: Treatment of raw water is done inside the boiler by two processes.
a. Appropriate chemicals are added to the boiler water to precipitate the scale forming
impurities in the form of sludges which can be later removed.
b. Cations causing hardness are converted into compounds which will stay in dissolved
form in water and thus do not cause any harm.
The processes involved are Colloidal conditioning, carbonate conditioning, phosphate
conditioning and calgon conditioning.
Difference b/w Internal and Colloidal conditioning

S.No Internal Treatment External Treatment

1. These are corrective methods These are preventive methods
2. It is carried out inside the boiler It is carried out outside the boiler, before
the entry of water into the boiler.
3. Includes Colloidal conditioning, Includes lime-soda, zeolite and ion
carbonate conditioning, exchange process
phosphate conditioning and
calgon conditioning

Lime soda process:

 The basic principle of this process is to chemically convert all the soluble hardness
causing salts of calcium and magnesium into insoluble precipitates which can then be
removed by settling and filtration.
 Lime [Ca(OH)2] and soda ash (Na2CO3) is added to facilitate precipitation. The
precipitates thus formed are CaCO3, Mg(OH)2, Fe(OH)3, and Al(OH)3. These are then
filtered off.
 But the precipitates formed at room temperature are not coarse and hence do not settle
down and thereby cause difficulty in filtration.
 To facilitate precipitation, addition of lime is done at high temperature. This is
followed by addition of Coagulants like Alum [K2SO4.Al2 (SO4)3.24H2O], Aluminum
sulphate [Al2(SO4)3] or Sodium aluminate [NaAlO2]. By this process coarse
precipitate are formed which can then be filtered off.
 Thus there are two methods of Lime soda: Cold Lime process and Hot Lime process.
Both operate under the same principle but their difference is as follows:

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 3

 Unit-2 Water Chemistry

 Following are the reactions that takes place in this process when the following
substituent is present in hard water:

Constituent Reactions Lime/Soda

required
Ca(HCO3)2 Ca(OH)2 + Ca(HCO3)2 → 2CaCO3 ↓ + 2H2O 1Lime

Mg(HCO3)2 2Ca(OH)2 + Mg(HCO3)2 → Mg(OH)2 + 2CaCO3 ↓ + 2Lime

2H2O

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

Ca2+ +Na2CO3 → CaCO3 +2Na+ S

MgCl2 MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2

CaCl2 +Na2CO3 → CaCO3 +2NaCl

MgSO4 MgSO4+ Ca(OH)2 + → Mg(OH)2 ↓ + CaSO4 1lime+1Soda

CaSO4 + Na2CO3→ CaCO3 + Na2SO4

Ca2+ CaSO4 + Na2CO3→ CaCO3 + Na2SO4 1Soda

CaSO4
CaCl2 CaCl2 + Na2CO3→ CaCO3 + NaCl 1Soda
HCO3- NaHCO3 + Ca(OH)2 CaCO3 ↓ + H2O +Na2CO3 L-S
[NaHCO3]

Advantage of L-S Process:

i. It is very economical
ii. Treated water is alkaline and has less corrosion tendencies
iii. It removes not only hardness causing salts but also minerals.
iv. Iron and magnesium are also removed from water to some extent

Disadvantage of L-S Process:

i. The process results in sludge formation
ii. The process cannot be used for high pressure boilers

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 4

 Unit-2 Water Chemistry

Calculation for Lime/ Soda Requirement:

Lime requirement = [Hardness in ppm] x Volume of water (L)

Soda requirement = [Hardness in ppm] x Volume of water (L)

MW of lime= 74, MW of soda= 106

NUMERICALS on L-S Process:

Q1. Calculate the amount of lime required for softening of 5000L of hard water
containing 72ppm of MgSO4.
Ans: 72 ppm of MgSO4 = 72x100/120 = 60ppm of CaCO3 equivalent.
Lime requirement = 74/100x60x5000 mg = 222g.

Q2. Calculate the amount of lime required for softening 50,000L of hard water
containing Mg(HCO3)2 = 144ppm, Ca(HCO3)2 = 25ppm, MgCl2 = 95 ppm, CaCl2
= 111ppm, Fe2O3 = 25 ppm, Na2SO4 = 15 ppm
Ans:
Constituent Reactions Lime/Soda
required
Ca(HCO3)2 Ca(OH)2 + Ca(HCO3)2 → 2CaCO3 ↓ + 2H2O 1Lime

Mg(HCO3)2 2Ca(OH)2 + Mg(HCO3)2 → Mg(OH)2 + 2CaCO3 ↓ + 2H2O 2Lime

CaCl2 CaCl2 + Na2CO3→ CaCO3 + NaCl 1Soda

MgCl2 MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2 1Lime

Fe2O3 and Na2SO4 do not cause hardness and hence do not require L or S

Hardness causing Amount (ppm) Multiplication CaCO3

salt factor equivalent
Mg(HCO3)2 144 100/146 144x100/146 =
98.6ppm
Ca(HCO3)2 25 100/162 25x100/162 =
15.4 ppm
MgCl2 95 100/95 95x100/95 = 100
ppm

Lime requirement = 74/100 (2x98.6 +15.4 +100) mg/L x50, 0000L = 1156200mg =
11.57kg

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 5

 Unit-2 Water Chemistry

Q3. A water sample on analysis gave the following results:

Ca2+ = 30mg/L; Mg2+ = 18mg/L, K+ = 19.5mg/L, HCO3- = 122mg/L, Cl- = 35.5
mg/L, SO42- = 48 mg/L
Calculate the total hardness and alkalinity present in water sample.
Also, calculate the lime soda required for softening 1L sample of the hard water.

Ans: Total hardness = [Ca2+ +Mg2+ + HCO3-] = 30x100/40 +18x100/24 + 122x100/122 =

250 ppm
Alkalinity = [HCO3 -] = 122x100/122 = 100ppm

Lime required = 74/100[Mg2+ + HCO3- in CaCO3 equiv.] mg/L x V (L) =

74/100[18x100/24 + 122x100/122] x 1 L= 129.5mg

Soda required = 106/100[[Ca2+ +Mg2+ - HCO3- in CaCO3 equiv.] mg/L x V (L)

= 106/100[30x100/40 +18x100/24 - 122x100/122] x 1L = 53mg

Q4. Calculate the amount of lime and soda needed for softening a water sample containing
36ppm Mg2+, 20ppm Ca2+ and 183ppm HCO3-

Ans:
Lime required = 74/100[Mg2+ + HCO3- in CaCO3 equiv.] mg/L =
74/100[36x100/24 + 183x100/122] mg/L = 222ppm

Soda required = 106/100[[Ca2+ +Mg2+ - HCO3- in CaCO3 equiv.] mg/L =

106/100[36x100/40 +20x100/24 - 183x100/122] mg/L= 53ppm

Q5. A water sample contains the following impurities:

Ca2+ = 20ppm, Mg2+ = 18ppm, HCO3- = 183ppm, SO42- = 24ppm
Calculate the lime and soda required for softening

Ans:
Lime required = 74/100[Mg2+ + HCO3- in CaCO3 equiv.] mg/L =
74/100[18x100/24 + 183x100/122] mg/L = 166.5ppm

Soda required = 106/100[[Ca2+ +Mg2+ - HCO3- in CaCO3 equiv.] mg/L =

106/100[20x100/40 +18x100/24 - 183x100/122] = - 26.5ppm
Soda is hence not required

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 6

 Unit-2 Water Chemistry

Zeolite or permutite process:

 Zeolites are naturally occurring hydrated sodium alumino silicate minerals
capable of exchanging reversibly its sodium ions for the ions present and
responsible of formation of hard water.
 Permutite-is the trade name given to sodium zeolites.
 Chemical formula of zeolite is Na2O Al2O3 ySiO2 x H2O. y=2-10, x= 2-6
When y = 2, we get Na2OAI2Si2O8.xH2O.
 For simplicity, we can write zeolites as Na2Z Where Z = OAl2Si2O8.xH2O
 Zeolites are of two types: Natural zeolites and synthetic zeolites.

Process involved:
In this method, hard water is passed through a bed of permutite contained in a
cylindrical vessel. The water percolates at a specified rate through the bed. The loose
sodium ions of the zeolite are exchanged for Ca2- and Mg2+ ions of hard water. Thus
calcium and magnesium salts get removed in the form of the insoluble zeolites and soft
water is collected.

This process removes both temporary and permanent hardness. After long use, the zeolite
bed gets exhausted. It can be regenerated by using chemicals, such as brine solution,
NaCI or sodium nitrate or sodium sulphate. However, NaCl is preferred on account of its

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 7

 Unit-2 Water Chemistry

cheapness, easy availability and low molecular weight. The products ‘calcium chloride
and magnesium chloride are highly soluble in water and can be easily washed out. The
softening and regeneration process can be represented as follows:

Merits of Zeolite Process

1. The equipment used is compact. So time saving process.
2. No impurities are precipitated. So no sludge formation occurs.
3. Requires less time for softening
4. Requires less skill for maintenance.
Demerits
a. Treated water contains more number of Na ions
b. This method leaves acidic ions (HCO3 - and CO3-- ions) in soft water which if
enters a boiler, generates CO2 which leads to corrosion.
c. Turbid water can’t be made soft by this process because it leads to clogging of
the holes of zeolite bed.

Numericals on Zeolite process

Q1. The hardness of 1000L of a sample of water was removed by passing it through a
zeolite softener. The zeolite softener required 30L of NaCl containing 1.5g/L of NaCl for
regeneration. Find the hardness of water sample.

Ans:
Quantity of NaCl in 30L of NaCl solution = 1.5g/L x 30L = 45g
CaCO3 equivalent of NaCl = 45x [(100/2)/(58.5/1)] = 45x50/58.5 = 38.46gm equiv.
1000L of water sample is contains 38.46gm equiv of CaCO3 equiv.
1L of water sample contains 38.46x1000mg/1000L = 38.46 ppm
Hardness of water sample = 38.46ppm
Q2. An exhausted zeolite softener was regenerated by passing 150L of NaCl solution having
strength of 1.5g/L of NaCl. Find the total volume of water that can be softened by this
zeolite softener, if the hardness of water is 600 ppm.
Ans:
Quantity of NaCl in 150L of NaCl solution = 1.5g/L x 150L = 225g

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 8

 Unit-2 Water Chemistry

CaCO3 equivalent of NaCl = 225x [(100/2)/(58.5/1)] = 2255x50/58.5 = 192.308g equiv.

Hardness of water = 600ppm
i.e 600mg of CaCO3 equiv is present in 1L of water
192.308x1000 mg of CaCO3 is present in 192308/600 = 320.5 L

Q3. A zeolite softener was 90% exhausted by removing the hardness completely when
10,000L of hard water sample was passed through it. The exhausted zeolite bed required
200L of 3% NaCl solution for its complete regeneration. Calculate the hardness of water
solution.
Ans:
Quantity of NaCl in 200L of 3% NaCl solution = 3/100x1000x200L = 6000g
CaCO3 equivalent of NaCl = 6000x [(100/2)/(58.5/1)] = 6000x50/58.5 = 5128g equiv.
90% of 10000 L of water = 5128g equiv = 5128x1000mg equiv
1L of water = [5128x1000]/[90/100x10000] = 569.8 mg/L = 569.8 ppm
Hardness = 569.8 ppm

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 9

 Unit-2 Water Chemistry

Ion –exchange method

Ion exchange is a process by which ions held on a porous, essentially insoluble solid
(resin) are exchanged for ions in solution that is brought in contact with it.
Ion exchange resins are insoluble, cross linked, high molecular weight organic polymers
having a porous structure. The functional groups attached to the chains are responsible
for the ion exchange properties.
Process:
The hard water is passed through a cation exchange column. All cations like Ca2+, Mg2+
etc are removed by the resin and equivalent amount of H+ ions are released from the
column to the water.

2RCOO-H+ + Ca2+ (RCOO-)2 Ca2+ + 2H+

After passing through the cation exchange column, the hard water is passed through
anion exchange column, when all the anions like SO42-, Cl- etc present in hard water are
removed and taken up by the resin. An equivalent amount of OH- is released from this
column to the water.
[R-N+(CH3)]OH- + Cl- [R-N+(CH3)]Cl- + OH-
The H+ and OH- ions released from the cation exchange resin and the anion exchange
resin respectively combine to give water molecule.
H+ + OH- H2O
Such water produced is free from any ions; hence is known as demineralised water. Since
it is free from any ions, acidity or alkalinity, it is pure like distilled water.

Demineralization of water by ion exchange process

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 10

 Unit-2 Water Chemistry

Regeneration

During process, both cation and anion exchange the resins get exhausted i.e capacity to
exchange H+ and OH- ions is lost.
The cationic resins can be generated by passing solution of dil. HCI or H2SO4 through
first the 1st column.
The regeneration reactions are:

Washing the column with deionized water releases the Ca 2+, Mg 2+ ions or Cl-, SO42-
ions into the sink.
Similarly the anion exchange resins can be regenerated by passing solution of dil. NaOH
through the second column and regeneration is represented as:

The column is washed with deionized water and ions like Na+, Cl-, SO42- are released
into the sink.

Advantages and disadvantages of ion exchange process are:

Advantages Disadvantages
The ion exchange process can be used to Very costly process as equipment and
soften highly acidic or alkaline waters chemicals are costly
The process produces water of very low Presence of turbidity reduces the
hardness (<2ppm). Very good for use in efficiency of the process
high pressure boilers

For water to be used for domestic purpose, water softening by ion exchange process will
include only cation exchange resin. This is because, only cations responsible for hardness
like Ca2+, Mg 2+ etc need to be removed. Regeneration is carried out by using inexpensive
brine or NaCl solution.

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 11

 Unit-2 Water Chemistry

Reverse Osmosis (RO):

Reverse Osmosis is a process where water is demineralized using a semi permeable

membrane at high pressure. Reverse osmosis is osmosis in reverse.
A semi permeable membrane is a selective membrane which does not permit the passage
of dissolved solute particles.
Osmosis is the phenomenon by which water or any solvent starts to flow from a region of
low concentration to high concentration when the two solutions are separated by a semi
permeable membrane. The flow continues till the concentration is equal on both sides of
the membrane. This is most commonly observed in plants. If you don't water your plants
they wilt. A plant cell is a semi permeable (water flows through the membrane but salts
don't) membrane with the living stuff on the inside in a salt solution. Water is drawn into
the cell from the outside because pure water will move across a semi permeable
membrane to dilute the higher concentration of salt on the inside. This is how water is
drawn in from the ground when you water your plants. If you salt your plants (over
fertilize or spill some salt on the grass), the plant will wilt because the salt concentration
on the outside of the cell is higher than the inside and water then moves across the
membrane from the inside to the outside.
To reverse this process, you must overcome the osmotic pressure equilibrium across the
membrane because the flow is naturally from dilute to concentrate. We want more pure
water so we must increase the salt content in the cell (concentrate side of the membrane).
To do this we increase the pressure on the salty side of the membrane and force the water
across. The amount of pressure is determined by the salt concentration. As we force water
out, the salt concentration increases requiring even greater pressure to get more pure
water.

Diagrammatic representation of Reverse Osmosis

Advantage:
1. It is simple and reliable process of water softening.
2. It is not expensive.
3. It is energy efficient
4. It operates at low temperature.
5. The life of semi permeable membrane is 2 years and can be replaced within
minutes.

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 12

 Unit-2 Water Chemistry

What is calgon conditioning of a boiler feed water?

Ans: It is addition of calgon i.e.: sodium hexa metaphosphate in boiler water to
prevent the formation of scale and sludge. Calgon removes scale forming Ca2+, Mg2+.

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 13

 Unit-2 Water Chemistry

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 14

 Unit-2 Water Chemistry

Q. A sample of water has the following impurities in mg/liter. Find the temporary and permanent
hardness in ppm.

Ca (HCO3)2 = 10.0 pm Mg (HCO3)2 = 8 ppm

CaSO4 = 12.00 ppm.

Q. What are zeolites? Why is water softened by zeolite process unfit for use in Boilers?

Q. Give specifications of boiler feed water.

Ans The specifications of boiler feed water are as follows
i. Water for boilers: Boiler feed water should be free from soluble salts of Mg2+ and Ca2+
It should not contain any organic matter.
ii. Boiler feed water should be free from suspended impurities.
iii. Boiler feed water should not be acidic or alkaline.

Compiled by Dr ARUNIMA NAYAK & Dr BRIJ BHUSHAN Page 15