S.CHAND’S - KopyKitab · 2.12 Problems on water – treatment by L-S process 2.13 Ion-exchange process of water softening 2.14 Zeolite process 2.15 Ion-exchange, Demineralization

S.CHAND’SAPPLIED CHEMISTRY

VOL.1[According to the Syllabus of 1st Semester University of Mumbai]

Dr. S.S. DARA M.Sc., Ph.D.

Former Registrar and DirectorBoard of College & University Development

Nagpur University, Nagpur - 440 010(Formerly Director Priyadarshini College of

Engineering and Architecture, Nagpur - 440 016)[Formerly, Professor & Head, Department of Applied Chemistry

Visvesvaraya Regional College of Engineering, Nagpur - 440 011]

Dr. S.D. SHETE M.Sc., Ph.D.

Professor & Head, Department of Engineering Science, Ramrao Adik Institute ofTechnology, Nerul, Navi Mumbai, Visiting faculty-University of

Central Lancashire, UK Visiting faculty-Padmashree Dr. D.Y. Patil University,Nerul, Navi Mumbai

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PREFACE

It gives us immense pleasure to present this text book on Applied Chemistry-I as per therevised syllabus of Mumbai University which is common to all branches of Engineering. Thisbook is prepared strictly as the revised syllabus prescribed by the Mumbai University.

We have revised this book keeping in mind the academic backgrounds and therequirements of the students of First Year Engineering and Technology. Each chapter beginswith learning objectives and provides clear and succinct knowledge on every topic to thestudents. Since it has been observed that students face difficulty in completing the paper duringexamination because of time constraint, we have tried to reduce the content but we have notcompromised the original concepts and retained the same. Minute details are dealt withprecision in each chapter and different types of numericals are explained in complete details.Solutions to university questions are provided at the end of each topic. We hope that ourendeavour will enable the students to have complete understanding of each and every concept.This book is specifically design to meet the textual requirement of students.

We have also tried to introduce certain modern concepts and recent developments toenrich the knowledge of students. Simple language is used for the benefits of the students.

Dr. S. D. SHETE


ACKNOWLEDGEMENT

I sincerely acknowledge the encouragement; moral support and useful suggestion of all thefollowings.

RAES; Director Mr. U. S. Shende; RAIT - Principal Dr. S. R. Devne; Prof. & Head of Biotech. &Bioinformatics Dr. D. Y. Patil University; Dr. D. A. Bhiwgade; Dr. Mohan Bhagwat; Principal ParshawnanthEng.; College Prof. S. D. Shah; Principal Dr. Ukarande (Tasgawnkar College Karjat). Prof. Dr. S. M. Gawkar(VJTI); Prof. Dr. Dongare (Chemistry Department Mumbai University); Dr. J. J. Kadam; Prof. M. R.Jadhav; Prof. (Mrs.) Preeti Zade; from (BVCOE); Dr. (Mrs.) P. A. Mane; Prof. (Mrs.) Anuradha Pawarfrom MGMCET; Dr. (Mrs.) Prajakta Deshmukh from Saraswati College of Engg.; Prof. (Mrs.) V. S.Khadilkar (VES); Dr. Mrs. Sandhya Mathur (Indira Gandhi College of Engg.) Dr. (Mrs.) S. S. Abhayankar;Prof. (Mrs.) Dolly Babar from LTCE.; Prof. (Mrs.) Anjali Kirkire (TSEC); Prof. G. Bhanu Murthy (TEC)Nerul; Prof. J. S. Pujari (S.S.J.C.E. Dombivali); Prof. M. J. Rajputy. T.I.E.T. Karjat; Dr. (Mrs.) Vina Naik( KJS.C.E.); Dr. (Mrs.) Jayshree Parikh (D.J. Sanghavi College of Engg); Dr. V. M. Balsaraf D.M.C.E.Airoli; Dr. S. N. Singh & Dr. (Mrs.) Kaur from Shah & Anchar Chembur; Prof. Harshal H. Keer FR. AgnelCollege of Engg.; Bandra; Prof. Joshi from Finolex Ratnagiri; Prof. A. A. Khan (M.H.S.S. College); Prof.I. S. Deshmukh (Vidyavardini Vasai Road); Dr. Shanta Sharma SIES, Nerul; Prof. N. R. Dasre; Dr. (Mrs.)Arp1ta Palchaudhari; Prof. (Mrs.) P. P. Patil from RAIT; Nerul, and all other colleagues and friends.

We would like to thank to Shri Navin Joshi Vice President publishing, Shri Bhagirath KaushikGeneral Manager (S & M), Shri. D. R. Parab, Asst. Regional Manager, Mr. Shankar Ghatwal, Asst. SalesManager Mumbai for their whole hearted co-operation in all aspects of the publication and promotionof this book.

AUTHORS


NEW REVISED SYLLABUS OF MUMBAI UNIVERSITY W.E.F.ACADEMIC YEAR 2007-08

APPLIED CHEMISTRY - I

1. Polymers: (Hrs. 10) Introduction, classification, hydrocarbon molecules, thermoplastic, Thermosetting Polymers. Basic concepts molecular weight, molecular shape, polymer crystallinity. crystallization,

Melting and Glass transtition phenomena. Viscoelasticity, deformation fracture, defects inpolymers. Polymerization, addition, polymerization, Copolymerization and condensationpolymerization. Polymer additives plastics, elastomers vulcanization.

Advanced polymer material, conducting polymers, electrical properties of polymersliquid crystal properties. Molecular electronics and polymers and supramolecularchemistry.

Frabrication of polymers(i) Compression moulding

(ii) Injection moulding(iii) Transfer moulding(iv) Extrusion moulding

Synthesis properties and Uses of PE, PMMA formaldehyde resin, polymer composite materials.

2 Water : (Hrs. 08) Hardness of water, effect of hard water in the manufacture sector, types of hardness,

determination of hardness by EDTA method and Problems. Softening of water by

(i) Lime soda method with equations in general. Hot cold lime soda method and problems(ii) Zeolite process and problems

(iii) Ion exchange method(iv) Reverse osmoses, ultrafiltration and its industrial applications.

Methods to determine extent of water pollution(i) BOD

(ii) COD. Methods to control water pollution. Industriallisation—materials cycle and pollution. Recycling issues.

3 Lubricants: (Hrs. 05) Definition, classification, characteristic properties, problems on acid. Value and Saponifica-

tion value. Theories of lubrications. Additives for lubricants, selection of lubricant.

4 Energy: (Hrs. 05) Classification, solar energy hydropower, wind power, Biomass energy using bio technology,

Hydrogen as a fuel.


Solar energy, production of electricity using solar energy, rechargeable alkaline storagebatteries, Nickel Hydrogen batteries. Rechargeable Lithium ion batteries.

5 Phase rule and Alloys (Hrs. 06) Gibbs phase rule, One component system water.

Two component system Iron-Carcon equilibrium diagram with microstructures. Limitations and Application of phase rule. Plain carbon steel, limitations. Introductions to Alloy steels, special steels. Principles of shape memory effect and its applications.

6 Nano—Materials: (Hrs. 06) Introduction to nano—materials. Graphite, fullerence, carbon nanatubes, nanowires, nanocones, Haeckelites. Their electronic

and mechanical properties. Production methods for CNTS. Applications of nano meterials in:

(i) Medicine(ii) Catalysis

(iii) Environmental technologies(iv) Electronics and Ralated fields(v) Mechanics.

List of Experiments:1. To determine total temporary and permanent hardness of water sample.2. Removal of hardnessusing ion exchange column.3. To determine saponification value of a lubricating oil.4. To determine acid value of a lubricating oil.5. To determine COD of a effluent sample.6. To determine CO2 content from air by Orsat’s apparatus.7. To determine flash point and fire point of a lubricating oil.8. To determine conductance of polymer.9. To determine melting point and/or glass transition temperature of a polymer.10. To prepare nano—oxide using combustion method.


CONTENTS1. POLYMERS 1—36

1.1 Introduction Polymers1.2 Classification of polymers1.3 Types of polymerization1.4 Degree of polymerization1.5 Molecular weight of polymers1.6 Molecular shape1.7 Crystallinity of polymers1.8 Melting and Glass Trasition Phenomena1.9 Viscoelasticity

1.10 Plastic Deformation1.11 Resins and plastics1.12 Classification of plastics1.13 Compounding of plastics1.14 Fabrication of plastics

1.14.1 Compression Moulding1.14.2 Injection Moulding1.14.3 Transfer Moulding1.14.4 Extrusiol”Moulding

1.15 Important Thermoplastics1.16 Important Thermosetting resins1.17 Elastomers, Natural Rubber1.18 Compounding of rubber, Vulcanization1.19 Properties and uses of rubber1.20 Synthetic Rubbers1.21 Fibre Reinforced plastics

(Polymer composite Materials.1.22 Advanced polymer Material

1.22.1 Electrical properties of polymers1.23 Liquid – crystal polymers (LCP)1.24 Supramolecular Chemistry1.25 University questions.

2. WATER 37—952.1 Introduction2.2 Sources of Water2.3 Effect of water on Rocks and Minerals2.4 Types of Impurities present in water

2.4.1 Effect of hard water2.5 Dissolved Mineral matter2.6 Hardness of water

(ix)


2.7 Soft and Hard water2.8 Units of Hardness2.9 Estimation of Hardness by EDTA method

2.10 Methods of Boiler water Treatment2.11 Lime – Soda process2.12 Problems on water – treatment by L-S process2.13 Ion-exchange process of water softening2.14 Zeolite process2.15 Ion-exchange, Demineralization process2.16 Reverse Osmosis, Ultrafiltration2.17 BOD and COD2.18 Sewage and Industrial waste water treatment2.19 Trickling Filters2.20 Activated sludge process2.21 Numericals based on EDTA process2.22 Numericals based on L – S process2.23 Numericals based on zeolite process2.24 University Questions

3. LUBRICANTS 96—1223.1 Historical3.2 Introduction3.3 Lubrication3.4 Mechanism of Lubrication3.5 Classification of Lubricants

3.5.1 Solid Lubricants3.5.2 Semi – solid Lubricants3.5.3 Blended oils

3.6 Properties of Lubricants and Tests3.7 Selection of Lubricants for different purposes3.8 Numericals based on saponification value3.9 Numericals based on Acid value

3.10 University questions.

4. ENERGY 123—1484.1 Source of Energy

4.1.1 Fossil Fuels4.1.2 Nuclear Fission and Nuclear Fussion4.1.3 Solar Energy4.1.4 Production of Electricity using solar Energy4.1.5 Solar Trough Collectors4.1.6 Solar Energy for Driving Vehicles4.1.7 Hydropower and wind power

4.2 Biomass Energy4.3 Geothermal Energy and Tidal power4.4. Hydrogen as a fuel4.5 Batteries – Introduction

(x)


4.6 Theoretical principles4.7 Primary cells4.8 Secondary Batteries4.9 Rechargeable Alkaline storage batteries

4.10 Nickel hydrogen batteries4.11 Rechargeable Lithium ion Batteries4.12 Fuel cell4.13 University questions

5. PHASE RULE AND ALLOYS 149—1685.1 Introduction5.2 Gibb’s Phase Rule5.3 Application of phase Rule to One-Component System

5.3.1 The water system5.4 Two – component systems

5.4.1 Reduced phase Rule5.4.2 Silver – lead system5.4.3 Iron – carbon system

5.5 Uses of Phase Rule5.6 Limitations of Phase Rule5.7 Alloys – Introduction5.8 Purposes of Making alloys5.9 Steel – plain Carbon steels

5.10 Composition and Properties of Plain Carbon Steels.5.11 Effect of Alloying elements5.12 Special Steels5.13 Tool Steel5.14 Shape Memory Effect5.15 University Questions.

6. NANO MATERIALS 169—1776.1 Introduction6.2 Two principle factors cause the properties of nanomaterials to differ significantly from

other material.6.3 Graphite6.4 Fullerences6.5 Carbon Nanotubes6.6 Nanowires6.7 Nanocones6.8 Haeckelites6.9 Applications of Nanomaterials

6.9.1 Applications in catalyst6.9.2 Medicine

6.9.3 Applications in Electronics6.9.4 Applications in Environmental Technologies6.9.5 Mechanics6.10 University Questions

(xi)


POLYMERS

Introduction

“In view of the macro-molecular versatility, plastics can be tailor-made for specificuses by selecting the monomer, by combining several materials and by theintroduction of suitable substituents.’’

1·1. PolymenrsThe word “polymer” is derived from two Greek words, Poly (= many) and meros (= parts or

units). A polymer is a large molecule which is formed by repeated linking of small molecules celled“monomers”. For example, the polymer polyethylene is formed by repeated linkages of simple ethylenemolecules which are the monomers :

n n.CH CH CH CH2 2ethylene

2 2polyethylene

b g

The number of repeating units in the chain so formed is called the degree of polymerization.Polymers with a high degree of poly-merisation are called “high polymers” and those with low degreeof polymerisation are called “oligopolymers”. High polymers have very high molecular weights

4 610 to10 and hence are called “macromolecules.”A macromolecule may consist of monomers of identical or different chemical structure and

accordingly they are called homo-polymers and co-polymers (or mixed polymers) respectively.···—A—A—A—A—…homopolymers···—A—B—A—A—B—…copolymers

The monomeric units may combine with each other into a macro-molecule to form polymers oflinear, branched or cross-linked (three dimensional) structures. (Fig. 1.1).

Copolymers may also be linear, branched or cross-linked. In copolymer molecules, the monomersmay be arranged in the chain at random or regularly. Copolymers of the former group are called“statistical” or ‘‘irregular”, whereas those of the latter group are called ‘‘regular”.

Linear copolymers in which the units of each type form fairly long continuous sequences(blocks) are called “block copolymers”.

—A—A—A—A—...—...—B—B—B—...

1

1


2 S. CHAND’S APPLIED CHEMISTRY – VOL. 1

A

A

A

A

A

A

A A A

A

A A A

A

AA

A

A

A

A

A

A

A

A

A

A

A

A

A

A

A

A

A

A

B

B B

B

B B

A

B

A

B B

A

A

A

AA

Cross-linkedA

Block Copolymer

Graft Copolymer

A

A A

A

A

A

Linear

Branched

Fig. 1.1. Linear, branched and cross-linked Polymers. Block-copolymer and Graft copolymer.

Branched copolymers with one kind of monomers, in their main chain and another kind ofmonomers in their side chains are called ‘‘graft copolymers’’.

If the atoms of the same species are present in the main chain, they are called “homochainpolymers”. If the chain is made up of different atoms then they are called “heterochain polymers.”

...—C—C—C—C—...... homochain polymers...—C—C—O—C—C—O—C—C—O...... heterochain polymers

The orientation of monomeric units in a macromolecule can take an orderly or disorderly fashionwith respect to the chain. If the monomers have entered the chain in a, random fashion, it is called an“atactic” polymer. If all the side groups lie on the same side of the chain (cis-arrangement), it is calledan “isotactic” polymer. If the arrangement of side groups is in alternating fashion (trans-arrangement),it is called a “syndiotactic” polymer. Polypropylene chain arrangement is an example of atacticpolymer, natural rubber is isotactic and guttapercha is syndiotactic.

1.2. Classification of Polymers. The capacity of an element to form polymeric compoundsdepends on its position in the periodic table. The elements of I group and other univalent elementsare entirely incapable of forming polymers, because, to form a chain, an element must have at least


3POLYMERS

two valencies. All other elements are capable of forming homochain,3 or heterochain polymericcompounds, the stability of which depends on the interatomic bond strength.

The bond energies between some like atoms and unlike atoms are given in Table 1.

Table 1. Bond energy between like atoms and unlike atoms

Like atoms (Homochain Unlike atoms (Heterochainpolymers) polymers)

Bond Bond energy Bond Bond energyK cal/mole K cal/mole

C—C 80.0 B—O 119.3S—S 63.0 B—N 104.3P—P 53.0 Si—O 89.3Se—Se 50.0 B—C 89.0Te—Te 49.0 P—O 81.7Si—Si 45.0 C—O 79.0Sb—Sb 42.0 C—N 66.0Ge—Ge 39.2 As—O 64.5As—As 39.0 Al—C 61.6N—N 37.0 C—S 61.5O—O 34.0 Si—S 60.9

C—Si 57.6

It is clear from Table-1 that in case of homochain polymers, C–C bond is the strongest whereasN—N and O—O bonds are the weakest. Thus, the most stable homochain polymers can be producedby carbon whereas O and N cannot form homochain polymers. All the other elements can formhomochain polymers.

Bond energies between the atoms in heterochain compounds are higher than those of manyhomochain compounds. Strongest bonds are formed between B—O, B—N and Si—O. Polymerscomprising of these bonds are very strong and have high melting points.

(1) Organic polymers (Hydrocarbon Molecules)These include-compounds containing, apart from carbon atoms, hydrogen, oxygen, nitrogen,

sulfur and halogen atoms, even if the oxygen, nitrogen, or sulfur is in the back-bone (or main) chain.Organic polymers also include polymeric substances containing other elements in their moleculesprovided the atoms of these elements are not in the main chain and are not connected directly tocarbon atoms.

Examples :—Polyethylene CH CH2 2

Polyvinyl alcohol CH CH2 |

OH

PVC —2CH CH Cl

OH |

Epoxy polymers O R O CH CH CH2 2


4 S. CHAND’S APPLIED CHEMISTRY – VOL. 1

Polyurethane 2 2x y- C - N H - C H - N H - C - O - C H - O - … || || O O

Polysulfides R S R Sz z( ) ' ( )starch, cellulose, etc.

(2) Elemento-organic or hetero-organic polymersThese include :(a) Compounds whose chains are composed of carbon atoms and hetero-atoms (excepting N, S

and O).(b) Compounds with organic chains if they contain side groups with C atoms connected

directly to the chain.(c) Compounds whose main chains consist of carbon atoms and whose side groups contain

hetero-atoms (excepting N. S, O and halogen atoms) connected directly to the C atoms in the chain.

Examples. :—Polysiloxanes ...—|

|— —

|— —...

|

R

Si

R

O

R

Si O

R

Polytitoxanes ...—|

|— —

|

|— —...

R

Ti

R

O

R

Ti

R

O

(3) Inorganic PolymersThese are polymers containing no carbon atoms. The chains of these polymers are composed of

different atoms joined by chemical bonds, while weaker inter-molecular forces act between thechains.

Examples :—

Mg

Si

H

H H H

B B B

H

H H

H H

Si Si

O O OMg

Magnesium Oxide

INORGANIC POLYMERS

Hydrogen BoridesPolysitanes

Mg

H


5POLYMERS

P

O O

O O

OSi SiO

NH

HB

BH

BH

HN NH

O

O

OH OHPolyphosphoric Acids

OH

O O

O OP P

Borazoic Silicon Dioxide

Fig. 1.2. Inorganic polymers.

(4) Tacticity :-

Polymers are classified on the basis of Tacticity (Configuration) Tacticity means arrangement ofside groups on the main chain.

(i) Isotactic - Side groups are all on the same side of the main chain.

(ii) Syndiotactic :- Side groups are in alternating fashion on the main chain.

(iii) Atactic :- Arrangement of side groups are at random around the main chain.

1.3. Types of Polymerization : Three types of polymerization are generally distinguished:(1) Addition or chain polymerization : In addition polymerization, the polymer is formed from

the monomer, without the loss of any material, and the product is an exact multiple of the originalmonomeric molecule.

Application of energy in the form of heat, light, pressure, ionizing radiation or the presence of acatalyst, is usually necessary for initiating the chain polymerization.

In general, addition ploymerization proceeds by the initial formation of some reactive species,such as free radicals or ions and by the addition of the reactive species to another molecule, with the

R R R

R R

R

R R R R

R


Applied Chemistry Vol. -I

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S.CHAND’S - KopyKitab · 2.12 Problems on water – treatment by L-S process 2.13 Ion-exchange process of water softening 2.14 Zeolite process 2.15 Ion-exchange, Demineralization