Engineering Chemistry

(CHY1701)
Schedule (G1+TG1)
Monday: 12:00 noon
Tuesday : 09:00 am
Thursday : 10:00 am

Dr. Arup Sinha

SJT 710-A3
[email protected]
 Course Assessment Configuration
Assessment Title Max. Weightage Date
Marks %
Quiz I 10 10
Quiz II 10 10
DA I 10 10
CAT I 50 15
CAT II 50 15
FAT 100 40

Last Instructional Day: 22th January, 2020

 Assessment Rubrics
 Quiz 1:
• Ten ‘mcq’ type questions - 1 mark for each question
 Quiz 2:
• Ten ‘mcq’ type questions - 1 mark for each question
 DA 1:
• Six marks for the assignments
• Two marks for the overall class performance
• Two marks for class discipline
 Class discipline :
• Mobile must be switched off or in silent mode and
to be kept inside bag or pocket
• No unnecessary talking or chatting during class
• Biometric will be closed after 10 mins
 Syllabus
 Module – 1: Water Technology
 Module – 2: Water Treatment
 Module – 3: Corrosion
 Module – 4: Corrosion Control
 Module – 5: Electrochemical Energy Systems
 Module – 6: Fuels and Combustion
 Module – 7: Polymers
 Text Book(s)
 Sashi Chawla, A Text book of Engineering Chemistry, Dhanpat
Rai Publishing Co., Pvt. Ltd., Educational and Technical
Publishers, New Delhi, 3rd Edition, 2015
 Jain and Jain, Engineering Chemistry, Dhanpat Rai Publishing
Co., Pvt. Ltd.
 Mukhpadhyay and Datta, Engineering Chemistry, New Age
Interatinal
 O.G. Palanna, McGraw Hill Education (India) Private Limited,
9th Reprint, 2015.
 B. Sivasankar, Engineering Chemistry 1st Edition, Mc Graw
Hill Education (India), 2008
 S. S. Dara, A Text book of Engineering Chemistry, S. Chand &
Co Ltd., New Delhi, 20th Edition, 2013
 Module 1

Water Technology
 Characteristics of hard water - hardness, DO, TDS in
water and their determination
 Numerical problems in hardness determination by
EDTA
 Modern techniques of water analysis for industrial use
 Disadvantages of hard water in industries
 Sources of Water
 Surface water: Flowing water - streams, rivers and
Stillwater-ponds, lakes and reservoirs.
 Rain water: Purest form of natural water
• Often contains dissolved toxic gases like CO2, SO2, NO2 etc.
and other solids. Also its supply is unpredictable
 Sea water: Most impure form of water containing about
3.5% dissolved salts of which about 6% is NaCl. Other salts
present include sulphates, bicarbonates, bromides of sodium,
potassium, magnesium etc.
 Underground water: Ground water refers to any source of
water that lies beneath the soil layer. Ground water can exist
in the soil itself or between rocks and other materials
• Contains less suspended materials
• High in mineral content
We generally depend on ground and surface water after
removing different impurities that are present in them, as
required
Factors that control water characteristics
• Sedimentation
• Runoff
Hardness
• Erosion
• Dissolved oxygen (DO)
• pH
• Temperature
• Decayed organic materials
• Pesticides
• Toxic and hazardous substances
• Oils, grease, and other chemicals
• Detergents
• Litter and rubbish
 Hardness of Water
 Hardness of water is the characteristic of preventing lather
formation of water with soap.
 This is a common quality of water which contains dissolved
compounds of calcium and magnesium and, sometimes,
other divalent and trivalent metallic elements
 Symptoms of Hard Water include: Hardness Scale
• Stiff, dingy laundry
• Mineral deposits on dishes and
glassware 
• High soap usage & need for fabric
softeners 
• Extra work to remove soap curd on
bathtubs & shower stalls 
• High energy costs, possibly due to scale
build-up in pipes and on appliances
• Scale build up in sinks, tubs, faucets, etc
 Hard water and soap solution
Hard water on treatment with soap, which is stearic or palmitic
acid salts of sodium or potassium, causes white precipitate
formation of calcium or magnesium stearate or palmitate

Precipitation of the soap in form of calcium and magnesium

stearate or palmitate prevents lathering at first
 Types of Hardness
 Temporary Hardness:
• Caused due to dissolved bicarbonates of calcium and
magnesium and carbonates of iron and other heavy metals.
• Hence it is also called as carbonate hardness
• Can be easily removed by boiling where CO2 gas gets expelled
removing the hardness.
Heat
Ca(HCO3)2 CaCO3 + H2O + CO2
Heat
Mg(HCO3)2 Mg(OH)2 + CO2

 Permanent Hardness:
• Caused due to dissolved chlorides and sulphates of calcium and
magnesium. Also called as non-carbonate hardness
• Can be removed through zeolite, Lime-soda, ion-exchange
processes
 Measurement of hardness of water:
Calcium carbonate (CaCO3) equivalent
 Hardness as well as non-hardness constituting ions are
generally expressed in terms of equivalent amount of CaCO3
 Reasons being:
• Molecular weight of CaCO3 = 100
• Equivalent weight = 50
• It is the most common insoluble impurity in water
Mass of Hardness
Hardness in terms of Producing Substance X Equivalent Weight of CaCO3
Equivalents of CaCO3 = Equivalent Weight of hardness-producing substance

Mass of Hardness
Producing Substance X 50 Mass of Hardness
=
Equivalent Weight of hardness
= Producing Substance
X f
producing substance
f = multif ication f actor
 Units of water hardness
 Parts per million (ppm):
Parts of CaCO3 equivalent hardness per 106 parts of water
 Milligrams per liter (mg/L):
Milligrams of CaCO3 equivalent hardness present per liter of
water
 Degree Clark (°Cl):
No. of grains (1/7000 lb) of CaCO 3 equivalent hardness per
gallon (10 lb) of Water (or) parts of CaCO 3 equivalent
hardness per 70,000 parts of water.
♦ 1 Clark = (1 grain of hardness)/(1 gallon or 70,000
grains)=1/(7 x 104)
1 grain (64.8 milligrams) of calcium carbonate dissolved in 1
 Degree French (°Fr):
Parts of CaCO3 equivalent hardness per 105 parts of water.
♦ 1 French Degree of hardness = (1 part of hardness)/(10 5
parts of water)

Relationship between units of water hardness

 1 ppm = 1 mg/L = 0.1 °French = 0.07 °Clark

 1 °Clark = 14.3 ppm = 1.43 °French
 °French = 10 ppm = 10 mg/L = 0.7 °Clark
Q1. Calculate the temporary hardness and permanent hardness of a
sample water containing Mg(HCO3)2 = 7.3 mg/L; Ca(HCO3)2 = 16.2
mg/L; MgCl2 = 9.5 mg/L; CaSO4 = 13.6 mg/L
(atomic weight of Mg = 24, Ca = 40, Cl = 35.45 and S = 32)
Solution: Conversion into CaCO3 equivalent
Constituent Molecular Weight CaCO3 equivalent
Mg(HCO3)2 = 7.3 mg/L 146 5 mg/L
Ca(HCO3)2 = 16.2 mg/L  162 10 mg/L
MgCl2 = 9.5 mg/L 95 10 mg/L
136 10 mg/L
CaSO4 = 13.6 mg/L

 Temporary hardness is due to Mg(HCO3)2 and Ca(HCO3)2

= (5 + 10) mg/L = 15 mg/L or 15 ppm
 Permanent hardness, due to MgCl2 and CaSO4
= (10 + 10) mg/L= 20 mg/L or 20 ppm
 Total hardness = Temporary hardness + Permanent hardness
= 35 mg/L or 35 ppm
 Calculate the temporary hardness and total hardness of a sample
water containing Mg(HCO3)2 = 73 mg/L ; Ca(HCO3)2 = 162 mg/L ;
MgCl2 = 95 mg/L; CaSO4 = 136 mg/L (atomic weight of Mg = 24, Ca
= 40, Cl = 35.45 and S = 32)
 A sample hard water contains, 8.1 mg/L Ca(HCO3)2; 7.5 mg/L
Mg(HCO3)2; 13.6 mg/L CaSO4; 12.0 mg/L MgSO4 and 2.0 mg/L
MgCl2. Calculate the hardness and express in CaCO3 equivalents
 How many grams of FeSO4 dissolved per liter gives 210.5 ppm of
hardness? (Atomic weights: Fe = 56, S = 32, O = 16, Ca = 40, C = 12)
 Estimation of water hardness
 O. Hehner’s method:
i. Temporary Hardness: Acid-base titration is performed
before and after boiling the hard water
Boiling
Ca(HCO3)2 CaCO3 + H2O + CO2
Boiling
Mg(HCO3)2 Mg(OH)2 + CO2

ii. Permanent Hardness: Chloride and sulphates of Ca and Mg

are removed as insoluble CaCO3 and MgCO3 by boiling the
hard water with excess Na2CO3. Acid-base titration is
performed before and after removal
Boiling
CaCl2 + Na2CO3 CaCO3 + 2 NaCl

Boiling
MgSO4 + Na2CO3 MgCO3 + 2 Na2SO4
 Soap titration method:
Hardness is estimated by adding a soap solution of known
strength to a sample water solution until a permanent lather
is formed after shaking

2 C17H35COONa + Ca(HCO3)2 (C17H35COO)2Ca + 2 NaHCO3

2 C17H35COONa + MgCl2 (C17H35COO)2Mg + 2 NaCl

2 C17H35COONa + CaSO4 (C17H35COO)2Ca + Na2SO4

 EDTA method
 Water hardness can be readily determined by complexo-
metric titration with the chelating agent EDTA
 EDTA is ethylene diamine tetraacetic acid.
 Corresponding disodium salt is used for the hardness
estimation, as this slat forms very strong and stable complex
with Ca2+ and Mg2+.
 EDTA solution is colorless
 The structure of EDTA disodium salt is:

HOOC CH2 H2C COONa

N CH2 H2C N
NaOOC CH2 H2C COOH
 Principle
 Initially, Ca2+ and Mg2+ or the are treated with Eriochrome
black T (EBT) indicator using ammonia buffer (to maintain pH
between 9-10) to get an unstable Ca2+/Mg2+ complex which
imparts wine-red colour to the solution
NO2 NO2

O O
ONa ONa
S M2+ S
O M = Ca, Mg
O
N N
N Ammonia buffer
N
OH O
OH O M

EBT Ca2+ / Mg2+- EBT complex

Steel blue Wine red

 EBT is blue in a buffered solution at pH 10,

 Turns red when Ca2+ or Mg2+ ions were added
pH 9-10
Ca /Mg
2+ 2+
+ EBT Ca2+/Mg2+ – EBT
(unstable complex – wine red)
 Procedure
 First EDTA Solution is standardized using standard hard
water (1 mg/mL of CaCO3 equivalents is prepared as
standard hard water).
 For this, first known aliquot of Standard hard water is
taken and 10-15 mL of ammonia buffer is added to bring
the pH between 9-10.
 Then a few drops of EBT solution is added to form the
unstable complex giving wine red colour.
 This solution is titrated with the EDTA solution till the
solution turns to steel blue indicating the formation of
stable EDTA-Metal ion complex.
 This volume of EDTA is noted as V1.
 On addition of EDTA, EBT gets replaced by EDTA since EDTA
forms a stronger complex with the metal ions
NO2

O
ONa
S
O
N EDTA
N + EBT
O
O M Steel blue
M = Ca, Mg

Ca2+ / Mg2+- EBT complex

Wine red Ca2+/Mg2+ – EDTA complex (colorless)

 Overall process
EBT
Ca2+ (blue) Ca-EBT EDTA Ca-EDTA
EBT (blue)
Mg2+ Buffer Mg-EBT Mg-EDTA
pH = 9-10
Wine red Colorless