Engineering Chemistry

Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.

Sources of Water

Oceans and seas contain 96.5% water, and snow and groundwater hold 1.74%
and 1.7%, respectively.

Impurities in Water
Biological impurities: Microorganisms

Suspended impurities: Organic matter

Colloidal impurities: Metal hydroxides, oil globules

Dissolved impurities: Dissolved gases and salts

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
Hardness of water:
Presence of Ca+2 and Mg+2 ions in water prevents the
formation of lather with soap.

To know “How hard water prevents the

formation of lather with soap?”

First we have to know how soap work?

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
 How soap works?
Soaps are sodium or potassium fatty acids (Palmitic acid Stearic acid Oleic acid) salts.
Each soap molecule has a long hydrocarbon chain, sometimes called its 'tail', with a
carboxylate 'head'. In water, the sodium or potassium ions float free, leaving a
negatively-charged head.

Na Salt of Stearic acid

Its hydrophilic (water-loving) carboxylate group (-CO2) interacts with water molecules via
ion-dipole interactions and hydrogen bonding. The hydrophobic (water-fearing) part of a
soap molecule, its long, nonpolar hydrocarbon chain, does not interact with water
molecules. The hydrocarbon chains are attracted to each other by dispersion forces and
cluster together, forming structures called micelles.
In hard water the Ca+2 and Mg+2 ions replaces the Na+ ion from
fatty acid salt (in the soap) and make water insoluble fatty acid
salt, thus prevent the formation of foam.

From soap From hard water

Water soluble Water insoluble

Types of Hardness

Temporary hardness: due to presence of bicarbonates and carbonate of

calcium and magnesium; can be Removed by boiling.

Permanent hardness: due to presence of chlorides and sulphates of calcium

and Magnesium; cannot be removed by boiling; removed by softening agents.

Engineering Chemistry
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Degree of hardness:
Expressed in terms of CaCO3 equivalent (in mg/l)

In ppm or mg/l

Degree Clarke ( 0 Cl) = It’s number of equivalent of CaCO3 present in 70,000 parts of
water

Degree Feench (0Fr) = It’s number of equivalent of CaCO3 present in 105 parts of water

1 ppm = 1 mg/l = 0.10Fr = 0.070Cl

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
What is the temporary , permanent and total hardness
of a 1L of water sample containing 12.2 mg of
Ca(HCO3)2 and 5.6 mg of MgSO4 ?
 What is the temporary , permanent and total hardness
of a 1L of water sample containing 12.2 mg of
Ca(HCO3)2 and 5.6 mg of MgSO4 ?

Temporary hardness:

= 7.53 mg/L
Permanent hardness:

= 4.67 mg/L
Total hardness = Temporary hardness+ Permanent hardness
= 7.53 + 4.67
= 12.2 mg/l
A sample water on analysis was found to
contain

Ca(HCO3)2 = 16.2 mg/L,

CaSO4 = 6.8 mg/L,
MgSO4 = 3.6 mg/L,

than calculate temporary and permanent

harness in 0Cl
Determination of Hardness of Water

Soap Solution Method

Hard water does not produce lather until all the ions causing hardness have
precipitated.

Complexometric Ttration Method:

EDTA reacts with calcium and magnesium ions which cause hardness and
forms complex compounds.

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
 Complexometric Ttration Method using EDTA:

1.When indicator is added to hard water it combines with free metal ions present in
water.
HIn-2 + M+2 → MIn- + H+ {M = Mg or Ca}
(Wine red)
When EDTA solution is added to the titration flask it combines with the free metal ions
giving metal EDTA complex, which is stable and colorless.

H2Y2- + M+2 → MY-2 + 2H+

When all the free metal ions are exhausted, next drop of EDTA removes the metal ion
engaged with indicator and the original blue color is restored.
H2Y2- + Min- → MY-2 + HIn-2 + H+
 Hardness calculation using EDTA

-------(1)

Normality of sample is calculated by titrating it against EDTA.

By applying normality equation:
Nsample × V sample = NEDTA × VEDTA

………………….(2)

Substitute Eq. (2) in Eq. (1)

 Hardness calculation using EDTA

If molarity of EDTA solution is given

100 ml of water sample required 13.5 ml of 0.02 M EDTA. What is
the total hardness?
100 ml of water sample required 13.5 ml of 0.02 M EDTA. What is
the total hardness?
Alkalinity of water

Its ability of water to neutralize acid.

Types of Alkalinity

 carbon dioxide

 carbon dioxide and bicarbonate

 bicarbonate and carbonate

 hydroxyl groups

Alkalinity is estimated by titration of water with a standard acid

solution using phenolphthalein and methyl orange as
indicators.
 General Considerations
• Its capacity to neutralize acids or its buffering capacity.

• 3 major classes of materials

A. Bicarbonates, HCO3- - pH 4.0 ≤ pH 8.3

B. Carbonates, CO3- - >pH 8.3 < pH 9.6

C. Hydroxide, OH- - > pH 9.6

 Method of Analysis
 Phenolphthalein Alkalinity
• Phenolphthalein indicator
• pH 8.3 endpoint of titration
• Indicates neutralization of hydoxide ions and half of the Carbonates

 Total Alkalinity
• Methyl Orange indicator
• pH 4.5 endpoint of titration
• Indicates neutralization of hydoxide ions, carbonate and bicarbonate
**It’s practically impossible for the
OH- and HCO3- to exist together
as they will react within to give
CO3-2
 Alkalinity calculation by titrating water sample against acid

-------(1)

Normality of sample is calculated by titrating it against Acid

By applying normality equation:
Nsample × V sample = NAcid × VAcid

………………….(2)

Substitute Eq. (2) in Eq. (1)

Alkalinity Relationships
100 ml water sample required 25 ml of 0.05N acid for phenolphthalein end

point and another 10 ml for methyl orange end point. Determine alkalinity.

P = 25 ml M = 35 ml
 Types of Hardness
* Calcium and Magnesium Hardness
* Total Hardness – Calcium Hardness = Magnesium Hardness

* Carbonate and Noncarbonate Hardness

•When alkalinity < Total Hardness,
then CO3 Hardness = T. Alkalinity

•When alkalinity ≥ Total hardness,

Then CO3 Hardness = Total Hardness

* CO3 hardness removed by boiling or lime (Temporary Hardness)

* Noncarbonate Hardness (permanent) = T. Hardness – CO3 Hardness

* Pseudo-Hardness
* Associated with Na+ which causes soap consumption but not
considered part of hardness.
 Boiler feed water and its treatment

Sludge Formation

In boilers, water continuously evaporates to form steam. This increases the

concentration of dissolved salts and the ionic product of the salt exceeds
the solubility

Fig.a Scale and sludge formation in boiler

product, thus precipitates are for the formed. If the precipitate is soft, loose
and slimy it is known as sludge.' If the precipitate is hard and adhering to
the inner walls of the boiler it is called as scale (fig. a)
Scale and Sludge
 Disadvantages of Scale Formation

1. Wastage of fuel 2. Decreases in Efficiency

3. Lowering of boiler safety 4. Danger of Explosion

Disadvantages of Sludge Formation

1. Chocking of pipes
2. Low supply of heat
3. Wastage of fuel
Na2CO3 is used for softening of water in soda process, the excess
Na2CO3 hydrolyzed to NaOH.

2Fe +2NaOH +O2 2NaFeO2 + H2

 Dissolved O2
4Fe + 2H2O + O2 4Fe(OH)2 +O2 2[Fe2O3. 2H2O]
Rust
Prevention by Hydrazine.
N2H4 + O2 N2 + 2H2O

Dissolved CO2

Carbonic acid has corrosive effect on the boiler material like any other acid.
Hydrolysis of magnesium chloride gives mineral acid, that can do
corrosion.
Techniques for Water Softening

External Treatment for Softening Water

Lime soda process

Engineering Chemistry
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Removal of Carbonate Hardness

***

Removal of Noncarbonate Hardness

Lime is used to remove temporary hardness + Mg-

permanent hardness, Soda Ash is used mainly to remove
permanent hardness.
 Lime-Soda Softening method

Batch Softening ( Lime and soda Continuous Softening ( Lime and soda
Both are mixed together with hard water are added to hard water into different
tank. After completing of reaction, the compartment.)
sludge is filtered off)

Advantage: It not only reduce hardness but also reduce the TDS, alkalinity.

Disadvantage: It cannot remove the water hardness completely.

Before solving numerical problems –take a look
Calculate the lime and soda required for softening 50,000 l of water containing
the following salts: Ca(HCO3)2 = 8.1 mg/l, Mg(HCO3)2 = 7.5 mg/l and CaSO4 = 13.6

mg/l, MgSO4 = 12 mg/l, MgCl2 = 2 mg/l

Ca(HCO3)2 = 8.1 mg/l = 8.1 × 100/ 162 = 5 mg/ l CaCO3.

Mg(HCO3)2 = 7.5 mg/l = 7.5 × 100/146 = 5.13 mg/l of CaCO3
Similarly CaSO4= 10 mg/l, MgSO4 = 10 mg/l, MgCl2 = 2.1 mg/l of CaCO3
equivalent.

So lime required = 74 (MW of Lime)/ 100 (MW of CaCO3)[5+2×5.13 +10 + 2.1] = 20.25
mg/l.
So soda required = 106(MW of soda)/ 100 [ 10 +10 +2.1] = 23.43 mg/l

Now calculate it for 50,000 L.

Reverse Osmosis Process

Water flows from

High conc. of water
To low conc. of water
It results in conc. of all solutes
In one compartment and all pure
Water in another compartment
 Type of membranes based processes
(RO based)
• Microfiltration: Microfiltration employs the
larger pore size of membrane and can remove
sand, clay, algae, bacteria and other
microorganism, inorganic compounds and small
organic molecules
• Nonofiltration: Nanofiltration employs smaller
pore size and provide complete protection
against viruses, organic and inorganic matter and
also reduces hardness and alkalinity of water
 Electrodialysis
• Electrodialysis combines membrane technology with
application of electric current to separate contaminants
based on charge and size exclusion filtering process
 Ion exchange process
Harmful cations and anions are removed by harmless ions from ion exchange resin.
Resins are high molecular weight cross linked polymer having acidic (-SO 3H-
COOH) or basic (substituted amino group) functional group attached with the
polymer chain.

Cationic Exchangers:
- Strongly acidic – functional groups derived from strong
acids e.g., R-SO3H (sulfonic).
Weakly acidic – functional groups derived from weak
acids, e.g., R-COOH (carboxylic).

Anionic Exchangers:
 Strongly basic – functional groups derived from quaternary ammonia
compounds, R-N-OH.
Weakly basic - functional groups derived from primary and secondary
amines, R-NH3OH or R-R’-NH2OH
Water is first passed through the cation exchange resin where Ca+2, Mg+2 is
exchanged with H+ from the resin, then the water is passed through the anion
exchange resin where Cl-, SO4-2 is exchanged with OH-

Water containing CaCl2 M-RCOOH+ Water containing 2HCl

M-RCOOH+ + CaCl2 (M-RCOO)2Ca + 2HCl

M-RN+(CH3)3OH- + 2HCl (M-RN+(CH3)3Cl- + 2H2O

Water free of CaCl2 M-RN+(CH3)3OH-

Cation exchange Resin can be regenerated by passing dil H2SO4 and HCL

through it and anion exchange resin can be regenerated by passing NH 4OH

and NaOH through it.
 Zeolite (Permutit) process
Na2OAl2O3, xSiO2, yH2O

The Na+ ion from zeolite

can be exchanged with
the hardness causing
cation from hard water.
NaCl
Zeolite is naturally occuring hydrated aluminosilicate (Na2OAl2O3,XSiO2,

yH2O) It is a process where hard water containing ions such as Ca+2, Mg+2 is
filtered through either a natural sand called Zeolite or man made beads. In
either case the Ca++ ions and other hard water metallic ions are caught as
they bond to the zeolite or beads. As this happens, Na+ ions are realeased
from the zeolite and flush on into the water supply. (CaX/MgX is attached
with zeolite bed)

Then after the zeolite becomes saturated with hard water ions, it is
"renewed" by flushing it with a rich solution of NaCl where the excess Na+
ions go in and replace the hard water ions, flush them down the drain during
the recharging;cycles when the water softener is disconnected from the
regular water supply. Recharging usually takes place at night when water is
not needed.
 Zeolite (Permutit) process

Zeolites are naturally occurring hydrated aluminosilicate minerals.

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
Internal Treatment for Softening Water: (Carried out inside boiler)

Complexation

Calgon (Sodium Hexametaphosphate) Treatment

Carbonate Treatment

Engineering Chemistry
Copyright  2011 Wiley India Pvt. Ltd. All rights reserved.
 Chlorination
Water chlorination is the process of adding the element chlorine to water as a method of
water purification to make it fit for human consumption as drinking water. Water that
has been treated with chlorine is effective in preventing the spread of waterborne
disease.
chlorine is a highly efficient disinfectant, and is added to public water supplies to kill
disease-causing pathogens, such as bacteria, viruses and protozoans

The chlorination process involves adding chlorine to water, but the chlorinating product does not
necessarily have to be pure chlorine. Chlorination can also be carried out using chlorine-containing
substances. Depending on the pH conditions required and the available storage options, different
chlorine-containing substances can be used. The three most common types of chlorine used in
water treatment are: chlorine gas, sodium hypochlorite, and calcium hypochlorite.

Adding bleaching powder-

CaOCl2 + H2O Ca(OH)2 + Cl2
Cl2 + H2O HOCl + H+ + Cl-
HOCl = HCl + O This O is also disinfectant.
The passage of chlorine gas through water allowing sufficient time for uniform distribution
Till as light excess of 0.1 -0.2 ppm of free chlorine is obtained after complete disinfection is
known as breakpoint chlorination.
This breakpoint chlorination of water corresponds to the point when all the ammonia present
in water is converted to nitrogen trichloride or free nitrogen.

Cl2 + H2O HOCl + H+ + Cl- Chloramines

HOCl + NH3 H2O + NH2 Cl

HOCl + NH2 Cl H2O + NH Cl2

HOCl + NH Cl2 H2O + NCl3

The chloramines act as bactericidal agents.

OCl- = Cl- + O This O is also disinfectant.

By - Dr. Ashish Kumar

HOCl, which is electrically neutral and hypochlorite ions (OCl -, electrically
negative) will form free chlorine when bound together. This results in
disinfection. Both substances have very distinctive behavior. HOCl acid is
more reactive and is a stronger disinfectant than hypochlorite. HOCl acid is
split into hydrochloric acid (HCl) and oxygen (O). The oxygen atom is a
powerful disinfectant.

The disinfecting properties is determined by the pH of water. HOCl is more

effective in acidic pH between 5.5 to 7 whereas OCl - is more effective in
basic pH around 8 . Both are equally effective around 7.5 pH.

By - Dr. Ashish Kumar

 UV light radiation
• Damage the genetic
structure of bacteria,
viruses and other
pathogens.
• Advantages: no chemicals
are used
• water taste more natural
• Disadvantages: high
maintenance of the UV-
lamp
 Ozonation
• Oxidized most pathogenic microorganisms
• Advantages: safer than chlorination
fewer disinfection by-product
• Disadvantage: high cost
 Specification of drinking water
S.No. Parameter ISI (BIS) standards mg/L WHO standards mg/L

1 Color, odor and taste Colorless, odorless and tasteless Colorless, odorless and
tasteless
2 pH 6.9 6.9
3 Total dissolved solids - 1500ppm
4 Dissolved oxygen 3.0 -
5 Chloride 600 250
6 Sulphate 1000 400
7 Nitrate - 45
8 Cyanide 0.01 0.2
9 Fluoride 3.0 1.5
10 Chromium 0.05 0.05
11 Lead 0.1 0.05
12 Arsenic 0.2 0.05
13 Mercury 0.001 0.006
*Bureau of Indian Standards.