Module 1-Hardness in Water

Content
1. Hardness in water, Types of hardness , Units of Hardness
2. Degree of hardness by EDTA method, Numerical problems.
3. Boiler troubles -Boiler Corrosion, Priming and Foaming, Scales and
Sludges, Caustic Embrittlement
4. Langlier Index
5. Softening of Water - Ion Exchange Process

1. Hardness of water
Water which does not produce lather with soap is termed as hard water. The hardness is
usually expressed in terms of Ca & Mg salts like bicarbonate, carbonate, sulphate,
chloride etc.

Formation of Hard water:

Hard water is formed due to the presence of minerals like Ca and Mg. they are not removed
or separated by sedimentation or filtration. When hard water reacts with soap (sodium salt
of stearic acid or palmitic acid) it gives curdy precipitate.

2C17H35COONa + CaCl2 → Ca (C17H35COO) 2↓ + NaCl

2 C17H35COONa + MgSO4 → (C17H35COO)2Mg↓ + Na2SO4
In above reaction hard water reacts with sodium salt of stearic acid to form calcium
stearate or magnesium stearate which are insoluble and separate out without producing
lather.

2. Types of hardness
a) Temporary hardness:

Temporary hardness of water is caused by Ca and Mg bicarbonate. This can be removed

by simply boiling water. Due to boiling bicarbonate is converted into carbonate
(insoluble precipitate)

Ca (HCO3)2 →CaCO3↓ + H2O +CO2↑

Mg (HCO3)2 → Mg(OH)2↓ + 2CO2↑
Temporary hardness can also be removed by adding hydrated lime to precipitate
insoluble carbonate.

Ca (HCO3)2 + Ca(OH)2 → 2CaCO3↓ + 2H2O

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

b) Permanent hardness:
Permanent hardness is caused by the presence of soluble salt of Ca and Mg other than
bicarbonate such as chloride and sulphate. Permanent hardness cannot be removed by
boiling of water or hydrated lime. It can be eliminated by water softening techniques
like Lime-soda process, Zeolite process, Ion-exchange process etc.

3. Degree of hardness
The unit in which hardness is usually expressed, known as degree of hardness. Degree of
hardness is expressed in terms of calcium carbonate (CaCO3) equivalent because CaCO3 have
molecular weight of 100 and it is easily precipitated. Degree of hardness may be expressed as
in terms of CaCO3 equivalents
  Unit of hardness:
i) Parts per million (ppm): it is the number of equivalent parts CaCO3 present per million
(106) parts of water by weight.
ii) Milligram per litre (mg/lit): it is the number of milligram of CaCO3 present in one litre of
water.
iii) Degree Clarke (oCl): it is the number of equivalent parts of CaCO3 present per 70,000
parts of water.
iv) Degree French (oFr): it is the number of equivalent parts of CaCO3 present per 105 parts
of water.

Correlation between ppm, mg/lit, oCl and oFr:

1ppm= 1mg/lit=0.07 oCl= 0.1 o Fr

 DETERMINATION OF HARDNESS BY
COMPLEXOMETRIC METHOD / EDTA METHOD

EDTA is a well known complexing agent which is widely used in analytical work, on account of its powerful
complexing action.

Principle: The determination of hardness is carried out by titrating the water sample with
Sodium salt of Ethylene Diamine Tetra Acetic Acid (EDTA) using Eriochrome Black-T as an
indicator and keeping the pH of the water at 9.0 - 10.0. The end point is the change in colour
from wine - red to blue, when the EDTA solution complexes the calcium and magnesium salt
completely.

(Ca2+ or Mg2+) + EBT → [Ca – EBT] (or) [Mg – EBT]

Hardness-salts indicator unstable complex (wine red)
[Ca – EBT] (or) [Mg – EBT] + EDTA → [Ca – EDTA] (or) [Mg – EDTA] + EBT

Unstable complex (wine red) stable complex (colourless) blue

Chemicals Required:
i. Preparation of standard hard water (0.01M): Dissolve 1g of pure, dry CaCO3 in minimum quantity of
dil.HCl and then evaporate the solution to dryness on a water bath. Dissolve the residue in distilled water to
make 1 Litre solution. Each ml of this solution thus contains 1mg of CaCO3 equalent hardness.

ii. Preparation of EDTA solution: Dissolve 4 g of pure EDTA crystals + 0.lg MgCl2 in 1 Litre of distilled
water.

iii. Preparation of Indicator (EBT): Dissolve 0.5 g of Eriochrome Black−T in 100mL alcohol.

iv. Preparation of Buffer solution: Add 67.5g of NH4Cl to 570 ml of Conc. Ammonia solution and then
dilute with distilled water to 1 Litre.

 Boiler Problems :
The setup used to produce steam in industries is known as ‘Boiler’. Water is fed to the boiler
and heated to produce steam. The water fed into the boiler is known as “Boiler feed water”.

Requirements for boiler water

Requirements for boiler water If not, it will cause

Free from hardness causing salts Sludge and scale

Free from oil and greases Foaming
Free from dissolved salts, suspended Caustic embrittlement
impurities
Free from dissolved gases, suspended Boiler corrosion
salts

Sludge, scale, priming and foaming, caustic embrittlement, boiler corrosion are
collectively known as boiler troubles.

A. Caustic Embrittlement: (Inter crystalline cracking of boiler metal)

It is the intercrystalline cracking of boilers due to accumulation of caustic substances. This is

caused by the use of highly alkaline water in high pressure boilers.

Residual Na2CO3 present in water undergoes hydrolysis to produce NaOH. This makes water
caustic. The NaOH containing water flows into the minute hair-cracks.
 Na2CO3 + H2O - 2 NaOH + CO2
This NaOH flows into the hairline cracks of boiler metal and converts the insoluble Fe into
soluble Sodium Ferroate. Thus it makes the cracks bigger in bents, joints and crevices.

Fe + 2 NaOH - Na2FeO2 + H2 ↑
(Insoluble) (Soluble)

Prevention of caustic embrittlement:

1. As softening agent, we can use sodium phosphate instead of sodium carbonate.
2. The hair line cracks can be sealed by waxy materials like Tannin and Lignin.

B. Sludges and scales:

If the water contains hardness causing salts like MgSO4, MgCl2 ,CaSO4 , Ca(HCO3)2 on
evaporation, the salts are precipitated to produce scale and sludge.

Differences between sludge and scale:

N Sludge Scale
o
Loose, slim
1 , non-adherent Hard, thick , strong adherent
precipitate precipitate
Due to salts
2 like MgSO4 , MgCl2 Due to salts like CaSO4 , Ca(HCO3)2

Due to 3poor conductance, they Due to poor conductance, they decrease

decrease the boiler efficiency to a the boiler efficiency to maximum
lesser extent and cause choking in extent, causing reduced fuel economy ,
the pipelines. improper boiling, boiler explosion etc.

It can be
4 prevented by periodic
replacement of concentrated hard
water by fresh water. This process
is known as the “blow down”
method.
It can be prevented by special methods
like
i) external treatment of ion exchange
,
ii)Internal carbonate, phosphate,
Calgon conditioning
iii) Mechanical hard scrubbing
methods.

5
C. Priming and Foaming:

Due to rapid boiling, the steam may carry some water droplets along with it. This is called wet
steam .The process of wet steam production is called Priming. It can reduce the heat of the
steam and cause corrosion in the pipelines.

Priming is due to:

a) Improper design of boiler
b) High water level
c) High velocity of steam
d) Uneven boiling

Priming can be controlled by

i) Proper boiler design
ii) Maintaining proper water level
(iii)Proper boiling

If oils and greases are present, they produce stable bubbles on the water surface. This Will
increase the wet steam production. This is known as “Foaming”.

Foaming is prevented by adding

i) Anti foaming agents (e.g.) synthetic poly amides, castor oil
ii) Coagulants (e.g.) Aluminium hydroxide

Foaming and priming are collectively known as ‘Carry over”.

D. Boiler Corrosion

It is the disintegration of boiler body material due to chemical or electrochemical reaction

with the environment.
It may be due to three major reasons:
i) Dissolved Oxygen
ii) Dissolved CO2
iii) Dissolved salts like MgCl2

Corrosion Due to dissolved oxygen:

Dissolved oxygen in the presence of water, causes corrosion.

4Fe + 6 H2O + 3O2 4 Fe (OH)3

(Rust)
Removal of dissolved oxygen:
a) Chemical methods -
i) Adding Sodium Sulphite:
2 Na2SO3 + O2 - 2 Na2SO4
This method results in other precipitates which can have some side effects. So this method is
less preferred.

ii) Adding Hydrazine:

N2H4 + O2 N2 + 2 H2O
This method results in inert gas and pure water, and has no side effects. So it is preferred.

b) Mechanical deaeration method:

This is based on the principle that at high temperature , low pressure and high exposed area,
the solubility of gases in water is decreased. So, the gases can be expelled easily.
Here, the water is fed into the mechanical deaerator which is provided with vacuum pump,
heaters and perforated plates.
The out coming water will be free from dissolved gases.

Corrosion due to CO2

Salts like Calcium bicarbonate on heating produce CO2.CO2 dissolves in water to form
carbonic acid which corrodes the boiler metal.

Ca(HCO3)2 ----CaCO3 + H2O + CO2

H2O + CO2 ------- H2CO3
Prevention from CO2

a) Chemical method: By adding calculated amount of ammonium hydroxide

2NH4OH + CO2 --- (NH4)2CO3 + H2O

b) Mechanical deaeration method (similar to oxygen method)

Corrosion due to Dissolved salts like MgCl2

 Dissolved salts like MgCl2 cause acid formation.
MgCl2 + 2 H2O --- Mg(OH)2 + 2 HCl (Corrosive acid)

Prevention
This will be prevented by alkali neutralisation.
HCl + NaOH − NaCl + H2O(Prevention)

 Langlier Index
LSI is a measure of a solution’s ability to dissolve or deposit calcium carbonate, and is
used as an indicator of the corrosivity of water. It is used for finding the ability of water
for corrosion or scaling in heat exchanger where water is used as heat transfer media in
either side of heat exchanger. The scaling in pipe or heat exchanger tubes can cause
insulation for heat transfer or metal loss in case of corrosion tendency of water. LSI is an
equilibrium model derived from the theoretical concepts of saturation and helps in
indicating the degree of saturation of water with respect to calcium carbonate.

The LSI is expressed as the difference between the actual system pH and the saturation
pH:

LSI = pH (measured) − pHs

● For LSI > 0, water is super saturated and tends to precipitate a scale layer of CaCO3.
● For LSI = 0, water is saturated (in equilibrium) with CaCO3. A scale layer ofCaCO3 is neither
precipitated nor dissolved.
● For LSI < 0, water is under saturated and tends to dissolve solid CaCO3.

The magnitude and sign of the LSI value show water’s tendency to form or dissolve scale,
and thus to encourage corrosion. Although information obtained from the LI is not
quantitative, it can be useful in estimating water treatment requirements for heat
exchanges in the process industry, low pressure boilers, cooling towers and its network,
and water treatment plants, as well as a general indicator of the corrosivity of water.

 Softening of water:
Ion exchange method ( Demineralisation)
Working:

1. Here all the cations and anions are completely removed. It uses two column of cation
exchange column and anion exchange column filled with resins.

2. Resins are long chain, insoluble, cross linked, organic polymers. There are 2 types.
i) Cation exchange resins – RH+(e.g) Sulphonated coals , RSO3H
ii) Anion exchange resins. R’OH-(e.g) Urea formaldehyde, Amines R-NH2
3. The water is fed into cylinder –I where all the cations are replaced by RH2 Resins.
2RH+ + Ca2+-R2 Ca2+ + 2 H+
4. The cation free water is fed to cylinder II, where all the anions are replaced. 2R’OH- +
SO42-- R2’ SO42- + 2 OH

5. So, the resultant water is free from all types of ions.

Diagram:

Regeneration:

On prolonged use, as all the resins are exhausted, there will be no H+ or OH –ions to exchange
the unwanted ions. So, they have to be regenerated.
Cation resins are regenerated by HCl and anion resins by NaOH.

R2 Ca2+ + 2 H+-2RH+ + Ca2+

R2’ SO 2- + 2 OH-- 2R’OH- + SO 2-

44

Advantages of Ion exchange method:

i) Can be used for high pressure boilers also.

ii) It can treat highly acidic or alkaline water.
iii) We can get pure water as hardness as low of 2 ppm.

Drawbacks of Ion exchange method:

i) Expensive
ii) Fe, Mn cannot be removed as they form complexes with resins iii) cannot be used for turbid
water as they clog the resins.