The course outcome…

The course CHE124: Chemistry for engineers will…

• Enable you to understand the evolution, basic constituents,

underlying principles and terminologies of Engineering
Chemistry.

• Let you explore the domain in which you as engineers can

build future ready solutions using chemistry.
• And above all make you an engineer expert in engineering
chemistry!!!

© LPU :: CHE124 prep. By Dr.Ashish Kumar

Get Set Go!!!
Gear up
Fasten your seat belts

Explore your chemistry

abilities

Build futuristic solutions…

© LPU :: CHE124 prep. By Dr.Ashish Kumar
Course details
• L:T:P – 3 : 0 : 0 [Three lectures/week]
• Text Book
Course Assessment Model
Marks break up*
 Attendance 5
 CA (Two best out of three tasks) 20
 MTE (MCQ) 25
 ETE 50

 Total 100

 Two Exercises – Two tests before MTE, third test after MTE
 MTE: MCQ to be done on OMR sheets
Unit 1 Water and its Treatment
Some facts about water
Sources of Water
Oceans and seas contain 96.5% water,
and snow and groundwater hold 1.74%
and 1.7%, respectively.
Types of Water
 Soft Water

 Hard Water
Hard Water
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sod. Stearate From hard water Cal. Stearate

2C17H35COONa + MgSO4 (C17H35COO)2Mg + Na2SO4

Hard Water Formation
Types of Hardness
 Temporary hardness of water

 Permanent hardness of water

 Temporary hardness of water
(carbonate or alkaline hardness)

 due to presence of bicarbonates of Ca & Mg

Ca(HCO3)2 Mg(HCO3)2
 removal of temporary hardness

Boiling

Ca(HCO3)2 CaCO3 + H2O + CO2

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

Clark’s method
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O

Mg(HCO3)2 + Ca(OH)2 CaCO3 + MgCO3 + 2H2O

Permanent hardness of water

 due to presence of sulphates & chlorides Ca & Mg

MgSO4 MgCl2 CaSO4 CaCl2

 removal of Permanent hardness

Use of Softening agents

Ion exchange method

Zeolite/Permutit method etc.

CaSO4 + Na2CO3 CaCO3 + Na2SO4

MgCl2 + Na2CO3 MgCO3 + 2NaCl

Harmful effects of hard water
Degree hardness of water

Srength of substance Chemical equivalent

producing hardness (mg/l) x of CaCO3
Equivalent of CaCO3 =
Chemical equivalent of hardness producing substance

 Units of hardness
Parts Per million (ppm)

Milligrams per liter (mg/l)

? Calculate the temporary hardness in terms of calcium

carbonate equivalents in a water sample containing calcium

bicarbonate (12.2 mg). Given that at. Wt. of Ca=40 amu, O=16
amu, C=12 amu, H=1 amu.
? Calculate the temporary hardness, permanent magnesium

hardness, total permanent hardness & total hardness in terms

of calcium carbonate equivalents in a water sample containing
calcium bicarbonate (12.2 mg), magnesium bicarbonate (8.2 mg),
magnesium sulphate (5.6 mg), magnesium chloride (6.2 mg),
calcium sulphate (10.3 mg) & sodium sulphate (7.5 mg). Given
that at. Wt. of Mg=24 amu, S=32 amu, Cl=35.5 amu, Ca=40
amu, O=16 amu, C=12 amu, H=1 amu.
Lecture 3Determination of
hardness of EDTA method
Complexometric Titration

HOOC H2C CH2 COOH

N CH2 CH2 N
HOOC H2C CH2 COOH

EDTA: Ethylenediamine tetraacetic acid

 Used for determining the conc. of hardness causing agents

Form complexes with metal ions viz. Ca2+, Mg2+

How to determine hardness of water
What we need ?
?
EDTA solution
Hard water (Temporary/Permanent)
Erichrome black-T (Indicator-blue, org. dye)

Procedure

Take known quantity of hard water

Add few drops of EBT indicator
EDTA added
 M2+ EBT complex EDTA
wine red colourless

Titration

M2+ EDTA complex Free EBT

colourless blue

 Use of ammonia-ammonium chloride buffer

 A 100 ml sample of water require 13.5 ml of 0.02 M
EDTA for titration using EBT as indicator. Another 100 ml of
water from the same source was boiled and precipitate
removed by filtration, the filtrate requires 6 ml of 0.02 M
EDTA for titration. Calculate the total hardness, permanent
hardness & carbonate hardness of water sample.
Alkalinity of water
Alkalinity: ability of water to neutralize acids

Alkalinity of water is due to presence of carbonates, bicarbonates &

hydroxides of sodium, potassium, magnesium & calcium, alone or in
combination.

* However hydroxide and

bicarbonate doesn’t exist together.

Types
CO2 alkalinity: 4.2-4.5 pH
CO2 & bicarbonate alkalinity: 4.2-4.5 & 8.2-8.4 pH
Bicarbonate & carbonate alkalinity: 8.2-8.4 & 9.6 pH
Hydroxyl alkalinity: above 9.6 pH
Significance:
 Lowers the acidity of water
 Its amount determines its suitability for irrigation processes or waste
water treatment

Estimation of Alkalinity:
 titration against standard acid solution, in presence of suitable
indicators.
 volume of acid used up to the phenolphthalein end point marks
neutralization of HCO3- ions, P-alkalinity.
 volume of acid used up to methyl orange end point indicates OH-
ions neutralization, M-alkalinity.

OH- H H2O

CO3- H HCO3-

HCO3- H H2CO3
Procedure

 Water sample x ml
 Add 2-3 drops of phenolphthalein indicator (pink colour)
 Titrate it against standard acid solution till colour get disappear
 Volume of titre (V1) is noted
 Add 2-3 drops of Methyl orange indicator to solution
 Titrate it against standard acid solution till the pink colour develops
 The titre value is noted (V2)

Phenolphthalein
Methyl Orange
Formula to calculate

P-Alkalinity in terms of CaCO3 equivalents= V1 * x * 50 * 106

105

M-Alkalinity in terms of CaCO3 equivalents= (V1+V2) * x * 50 * 106

105

* x is conc.or strength
 A 100 ml water sample required 25 ml of 0.05N Sulphuric acid for
phenolphthalein end point and another 10 ml for methyl orange end point.
Determine the nature and amount of alkalinity present in the water.
Significance of Alkalinity
Alkalinity is important for fish and aquatic life because it protects or buffers
against rapid pH changes.

Large amount of alkalinity imparts bitter taste in water.

The resultant precipitate can corrode pipes and other accessories of water
distribution systems.

Alkalinity as carbonate and bicarbonate of saline water is very important in

tertiary recovery processes for recovering petroleum.

The alkalinity value is necessary in the calculation of carbonate scaling tendencies

of saline waters.

The alkalinity acts as a pH buffer in coagulation and lime-soda softening of water.

In wastewater treatment, alkalinity is an important parameter in determining the

amenability of wastes to the treatment process and control of processes such as
anaerobic digestion.
 Boiler
Feed Water
Water Absorb heat Expand as steam (carry heat)

Eg : power generation, space heating, sterilization, drying

Impurities: hardness, dissolved gases, some dissolve salts

metal etc,.

Requirements depends upon: quantity of feed water, design

of boiler, other operating parameters.
Low pressure fire-
tube boiler

Sectioned fire-tube
boiler from a DRB Class
50 locomotive.
Characteristics of boiler feed water:

Impurities should not be exceeding tolerance limit

Feed water should be pretreated if it is not meeting the standards/ requirements

Dissolved oxygen below 0.02 mg/L

Total hardness below 0.5 ppm

Fe below 0.03 mg/L, Cu below 0.01 mg/L & Silica 5 mg/L

P-alkalinity below 0.5 ppm & M-alkalinity below 1 ppm.

Boiler Trouble/ Problem

 Precipitation of impurities as scale (Ca(HCO-3) 2, CaSO4, Mg(HCO-3) 2 , MgCl2) or

sludge (MgCl2 , Mg CO3 , MgSO4, CaCl2)

Scales: Ca(HCO-3)2 CaCO3 + CO2 + H2O

Mg(HCO-3) 2 Mg(OH)2 + 2 CO2
Effects of Scales

Danger of explosion
Lowering the boiler efficiency
Waste of fuel
Expenses

Effects of Sludges:

 Colder part may get plugged

Wastage of fuel
Effect on efficiency
Expenses
Priming & Foaming
Wet steam/ carryover

Priming: large drops of water into outlet steam.

occur due to: impurities in BFW

improper constructed boiler

avoided by: lowering impurities, proper construction, maintain proper level of

water and slow discharge of steam

 Foaming: persistent bubble on boiler water surface

Occur due to: alkalis, oils, fats, organic matter & suspended solids

Avoided by: antifoaming agents, removal of oils & greases, removal of clay &
suspended particles, removal of silica with ferrous sulphate etc.
Caustic Embrittlement
 Boiler material become brittle due to exposure to caustic solution

H2O + Na2CO3 CO2 + NaOH

Alkaline water steeps inside the cracks, NaOH react to BFW surface and cause
embrittlement

2Fe + 2NaOH + O2 NaFeO2 + H2

 May cause explosion

Prevention
 Using Sod. Phosphate
 Adding lignin & tanning
 Addition of Sod. Sulphate to avoid cracks
Maintaing pH between 8 & 9
Boiler Corrosion

Decay process due to dissolve gases

2Fe + H2O + O2 2Fe(OH)2

4Fe(OH)2 + O2 2[Fe2O3.2H2O]
Softening Methods:
External Treatment:

Lime soda process

Ion exchange process
Zeolite process

Internal Treatment:

Treatment via chemicals (colloidal, calgon, carbonate &

phosphate condition)
Lime: to remove temporary hardness

Removal of Carbonate Hardness

CaCO3 is precipitated out of the water (sludge) and it’s filtered off.
Removal of Noncarbonate Hardness

Lime is used to remove temporary hardness + Mg-permanent

hardness, Soda Ash is used mainly to remove permanent hardness.
Soda ash: to remove Ca permanent hardness
Na2CO3 + CaCl2 CaCO3 + 2NaCl

Na2CO3 + CaSO4 CaCO3 + Na2SO4

 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.

Ion exchange process
Also known as demineralization of
water
Ion exchange resins are high
molecular weight cross-linked, porous
polymers
 Ion exchange property is due to acidic
(R-SO3H, R-COOH) or basic (R-N-OH, R-
NH3OH or R-R’-NH2OH) functional
groups.

Acidic gr. exchange

H+ or Na+
Basic gr. Exchange
OH-
Regeneration
Advantage:
 easy to operate and control
 works well for variety of hardness of water
 takes less space, better quality and more economical

Disadvantage:
 corrosion may occur when cation exchange takes place with
H exchanger
 Na exchanger when used TDS, alkalinity & silica are not
reduced
 Ion exchange material should not be allowed to get
contaminated
Internal Treatment for Softening Water: (Carried out inside boiler)

 Complexation

 Calgon (Sodium Hexametaphosphate) Treatment

 Carbonate Treatment
Q. 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

Total hardness due to dissolved salts

x mg/l of compound= x. 100/Molar mass

Lime requirement = [ temp. hardness of Ca + 2. temp hardness of Mg + Permanent

hardness of Mg]. Molar mass of Ca(OH)2/Molar mass of CaCO3

Soda requirement = [ Permanent hardness]. Molar mass of Na2CO3/Molar mass of CaCO3

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
Electro Dialysis (ED) is a membrane process, during
which ions are transported through semi permeable membrane, under the influence
of an electric potential. The membranes are cation (+) or anion (-) selective, which
basically means that either positive ions or negative ions will flow through.
Water Disinfection Process

Properties:
Should kill microorganism
Inexpensive
Non toxic to human
Should provide protection against any contamination

Bleaching Powder:

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl

HOCl HCl + [O]

Chlorination
• Most common
• Employed directly
• Advantages: low cost & effective
stable, small space required
work at range of temperature
doesn’t introduce any impurity

• Disadvantages: chlorine residue could

be harmful to environment
bad taste and odour
imparts irritation in mucus membrane
not effective at higher pH
Chloramine (ClNH2)
2NH3 + Cl2  2ClNH2 + H2
ClNH2 + H2O  HOCl + NH3
HOCl  HCl + [O]