General
Chemistry

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General
Chemistry
S. Ekambaram
Former Scientist
Authentix Inc.
Texas, USA

Chennai • Delhi • Chandigarh

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Dedicated to My Teachers

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Contents
Preface
Acknowledgements

xv
xvii


1

Chemical Foundations
Theories of atoms, molecules, and ions
First atomic model
Periodic Table of elements
Stoichiometry
Understanding Chemical Foundation
Review Questions

1
2
6
7
10
29
31

2

Quantum Chemistry
Limitations of classical theories and old quantum theories
Need for quantum chemistry
Electromagnetic radiation
Photoelectric effect
de Broglie Equation
Heisenberg’s uncertainty principle or Heisenberg’s
complimentary principle
Absorption and emission spectra
Atomic spectrum of hydrogen

Quantum mechanical approach for the atom
Schrodinger’s time-independent equation
Hermitian operators
Quantum numbers
Valence electrons
The particle in a box
Harmonic oscillator
Rigid rotor
Understanding Quantum Chemistry
Review Questions

32
32
33
33
38
42

Thermodynamics and Thermochemistry
Basic terms
Types of energy

74
75
77

3

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46
48
48
51
53
54
55
60
64
69
70
72
73


viii

CONTENTS

The first law of thermodynamics
The second law of thermodynamics
Other applications of thermodynamics
Maxwell’s equations
Joule–Thomson coefficient, μJT
Third law of thermodynamics
Properties of liquid helium
Understanding Thermodynamics and Thermochemistry
Review Questions

78

88
96
99
109
110
110
111
111

4

Chemical Kinetics
Rates of reaction in general
Order and molecularity
Rate laws or rate equations
Model for chemical kinetics
Activated complex theory
Uni-molecular reaction
Catalysis
Photo-catalysis
Understanding Chemical Kinetics
Review Questions

113
113
114
114
128
131
137

140
144
146
147

5

Photochemistry
Difference between thermal and photochemical reactions
Absorption and emission of energy
First law of photochemistry (or Grotthus and Draper law)
Second law of photochemistry (Einstein’s law of
photochemical equivalence)
Aspects of chain reaction
Understanding Photochemistry
Review Questions

149
149
151
151
152
155
160
161

6

Chemical Equilibrium
Reversible and irreversible reactions

Chemical equilibrium and equilibrium constant
Understanding Chemical Equilibrium
Review Questions

162
162
163
175
177

7

Chemical Bonding
Bonding between different atoms
Bonding between identical atoms

179
180
180

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CONTENTS

Types of chemical bonding
Coordinate bond
Hydrogen bonding
van der Waal’s Forces
Understanding Chemical Bonding

Review Questions
8

9

Ideal Gas Laws and van der Waal’s Gas Equation
of Real Gas
Boyle’s law
Charles law
Gay–Lussac’s law
Avogadro’s law
The ideal gas law
Molar mass of gas
Dalton’s law of partial pressures
Concept of mole fraction of gas in the mixture
Kinetic molecular theory of gases
Root mean square velocity
Graham’s law of rate of diffusion/effusion
Understanding Ideal Gas Laws and van der
Waal’s Gas Equation of Real Gas
Review Questions
Properties of Solutions (Colligative Properties)
Terms required to understand colligative properties
Properties of a solvent
Effect of solute on vapour pressure of solution
Effect of added non-volatile, non-electrolyte
Solute on the boiling point of a solvent
Effect of added non-volatile, non-electrolyte solute on the
freezing point of a solvent
Osmosis

van’t Hoff’s law of osmotic pressure
Experimental measurement of osmotic pressure of a
solution
Abnormal molecular weight
Subnormal (lower) molecular weight for electrolyte solution
van’t Hoff’s Factor, i
Reverse osmosis
Important equations to remember in this chapter

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ix
181
207
207
207
208
208

210
211
213
215
215
217
226
227
229
231
234

236
237
239
241
242
242
243
252
259
264
265
266
268
269
270
271
275


x

CONTENTS

Understanding Properties of Solutions
(Colligative Properties)
Review Questions

272
275


10 Phase Rule
Terms used in phase rule
Derivation of Willard Gibbs phase rule
Application of phase rule
Phase diagram
Understanding Phase Rule
Review Questions

277
277
279
280
283
286
286

11

287
287
288
289
294
317
318
319

Acids and Bases
Classical definition
Arrhenius theory of acids and bases

Lowry–bronsted theory
Lewis theory of acids and bases
Ostwald’s acid–base theory
Understanding Acids and Bases
Review Questions

12 Electrochemistry
Types of conductors
Basic laws of electrochemistry
Kohlrausch’s law of independent migration of ions
Galvanic cell (definition and property)
Relationship between cell potential and free energy
Concentration cell
Irreversible cells (electrolysis)
Batteries
Fuel cells
Balancing the redox reactions
Corrosion
Potentiometic titrations
Hall process of production of aluminium
Understanding Electrochemistry
Review Questions

321
322
322
325
325
332
335

337
339
344
346
362
364
365
365
367

13 Colloidal State
Definition of colloids
Solids in liquids (sols)

369
370
370

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CONTENTS

Liquids in liquids (Emulsions)
Liquids in solids (gels)
Understanding Colloidal State
Review Questions
14 Chemistry of s-Block Elements and Their
Useful Compounds
Occurrence and preparation of alkali elements

Physical properties of alkali elements
Chemical properties of alkali elements
Uses of alkali metals
Sodium hydroxide
Occurrence and preparation of alkaline earth metals
Physical properties of alkaline earth metals
Chemical properties of alkaline earth metals
Cements
Hard water
Understanding Chemistry of s-Block Elements and Their
Useful Compounds
Review Questions

xi
377
378
379
380

381
381
382
383
385
386
389
391
391
392
393

393
396

15 Main Group Chemistry
Boron chemistry
Chemistry of nitrogen
Chemistry of phosphorus
Chemistry of sulphur
Chemistry of oxygen
Chemistry of halogens
Chemistry of interhalogen compounds
Understanding Main Group Chemistry
Review Questions

398
399
404
411
416
420
426
429
431
433

16 Coordination Chemistry
Complex or coordination compunds and their types
Ligands and their types
Types of ligands
Lewis acids and bases in complex compounds

Chelates, chelate effect, and steric effect
Kinetics and thermodynamic stability
Theories for complex compounds
Crystal field theory (CFT)

435
436
437
437
443
446
447
448
454

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xii

CONTENTS

Molecular orbital theory
Isomerism
Nomenclature
Understanding Coordination Chemistry
Review Questions

462
466

472
475
476

17 Chemistry of Lanthanides and Actinides
Chemistry of lanthanides
Chemistry of actinides
Understanding Chemistry of Lanthanides and Actinides
Review Questions

478
478
484
485
486

18 Solid State Chemistry
Synthesis of solid state materials
Structures of some simple and complex materials
Crystallography and general characterizations
Liquid crystal
Theory of liquid crystals (the Swarm Theory)
Glass or vitreous state
Experimental techniques
Exotic properties and exciting applications
Heterogeneous catalysis—three-way catalysts
Recent trends in solid state chemistry
High-temperature superconductors and Meisner effect
Understanding Solid State Chemistry
Review Questions


488
489
493
499
512
513
513
513
516
524
526
531
532
533

19 Chemistry of Hydrocarbons and Their Derivatives
Chemistry of alkanes (hydrocarbons)
Chemistry of alkenes and alkynes
Chemistry of aromatic hydrocarbons
Chemistry of alcohols and phenols
Chemistry of carbonyl compounds
Chemistry of carboxylic acids and esters
Chemistry of amines
Hofmann and Curtius rearrangements
Some important named reactions
Understanding Chemistry of Hydrocarbons and Their
Derivatives
Review Questions


535
535
542
553
557
565
569
573
575
576

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583
587


CONTENTS

xiii

20 Chemistry of Synthetic and Natural Polymers
Definition and examples
Polymer synthesis and its mechanism
Thermoplastic and thermoset plastics
Synthetic polymers and their uses
Elastomers
Fire retardant polymers
Silicones
Natural polymers

Understanding Chemistry of Synthetic and
Natural Polymers
Review Questions

589
590
590
592
592
598
599
601
604

21 Nuclear Chemistry
Definition of basic terms
Radioactive elements and their decay
Nuclear stability
Magic numbers
Types of radioactive decay
Artificial radioactivity
Nuclear fission
Nuclear fusion
Hydrogen bomb
Mass defect—Binding energy of the nucleus
Kinetics of radioactive decay
Radioactive series
Nuclear reactors
Understanding Nuclear Chemistry
Review Questions


608
609
610
610
612
612
613
615
616
616
617
618
619
624
625
627

Index

606
607

629

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Preface
General Chemistry has been written with the aim of removing the ‘burden of
studying chemistry’ from the minds of the students and readers. It is written
in a lucid and easy-to-understand language and is envisaged in such a way
that every reader would find it enjoyable while studying the subject. It deals
with the fundamentals of various topics in chemistry starting from the first
principles and proceeds in order to discuss quantum chemistry, thermodynamics and thermochemistry, chemical kinetics, photochemistry, chemical
equilibrium, chemical bonding, ideal gas laws and van der Waal’s gas equation of real gas, properties of solutions, phase rule, acids and bases, electrochemistry, colloidal state, chemistry of s-block elements and their useful
compounds, main group chemistry, chemistry of coordination compounds,
chemistry of lanthanides and actinides, solid state chemistry, chemistry of
hydrocarbons and their derivatives and chemistry of synthetic and natural
polymers.
A strong understanding of these concepts will enable the students to
progress to the advanced topics in the subject. Therefore, each chapter is
provided with plenty of numerical problems that help the student to imbibe the
theory, logically. There are also unsolved numerical problems given in each
chapter, to enable the student to test his own understanding. Additionally, a
concise conspectus at the end of the chapter provides main ideas in a nut-shell
which facilitates quick recapitulation of the concepts discussed.
S. Ekambaram

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Acknowledgements
I have great pleasure to thank Ms. R. P. Mathivathani, Assistant Acquisitions
Editor, the Production Editor and Reviewers at Pearson Education for their
immediate and fruitful help and valuable comments that helped to enhance
the content of this book.
I recall with gratitude my teachers who guided me, and without whose
teaching this book would not have been possible.
I am obliged to my wife, Kalyani, and my daughter, Nandhini, for their
encouragement and support in writing this book and for showing immense
interest in its progress.
I acknowledge my parents for their dedication to my academic and personal career.
Indeed, I am also thankful to Mr. R. Shanmugam, Ex. M.L.A, for his support and confidence in my career growth. I would also like to thank all my
relatives and friends for their help.
I hope this book could be useful, fruitful and enjoyable for students and
teacher, alike.
S. Ekambaram

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CHAPTER 1

Chemical Foundations

OBJECTIVES
1. To state with the need for Chemical Foundations chapter.
2. To begin with Dalton’s atomic theory.
3. To describe the discovery and production of electron by cathode ray
tube, one of the constituents of atom followed by the salient properties of
electron.
4. To describe the production and detection of anode rays and to outline
some selective properties of anode rays.
5. To arrange known elements, based on their atomic number to get the
Periodic Table.
6. To highlight the meaning of molecules and ions, chemical species that are
involved in the chemical reactions.
7. To define meaning of stoichiometry.
8. To define terms needed to get stoichiometry such as concept of mole and
the use of Avogadro’s number.
9. To describe principle and experiment involved in determining the empirical
formula of an organic compound.
10. To describe stoichiometry of chemical reactions and to highlight the terms
such as molarity, normality and oxidation numbers.
11. To elaborate the stoichiometry of precipitation reactions in aqueous solution.
12. To elaborate the stoichiometry of acid–base reactions in aqueous solution.
13. To elaborate stoichiometry of oxidation–reduction reactions.

NEED FOR THE CHAPTER
There is no life without chemistry. We live in the universe due to several
chemical reactions taking place simultaneously in our body. In the modern
world, for example, the function of batteries is due to electrochemical
reactions, combustion reaction of fossil fuel is able to pull the vehicle to fly
overseas or travel quickly inland. On the other hand, ozone depletion, greenhouse
effect, shortage of non-renewable fossil fuel, to name a few, are issues

that need redressal when we enjoy in the modern world. How do we go about
fixing these issues? Understanding the chemistry of these issues will definitely
direct the scientist, for instance learn and lead technique, to overcome these

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2

GENERAL CHEMISTRY

issues. Here are two valuable examples how chemistry helped in the past and
is helping scientists currently for similar issues.
Dmitri Mendeleev was awarded a medal for predicting properties of
unknown elements using the Periodic Table. An interesting aspect about the
medal was that the medal was made up of aluminium metal, which was a
more precious metal than gold during those days. However, aluminium metal
is widely explored in the form of wire for carrying electricity, aluminium foil
to wrap hot foods, or aluminium utensils to cook food fast. All the benefits
of aluminium metal came to light after the American scientist, Charles
Martin Hall, invented an easy, simple, and most importantly. inexpensive
electrochemical method for the production of aluminium metal from its ore.
Thus, electrochemistry played an important role in achieving it.
Yet another important issue that we face currently is shortage of
non-renewable fossil fuel and green house effect due to combustion of fossil
fuel. The former one can be overcome by considering renewable fuel such
as hydrogen from water by solar splitting and interestingly, combustion
of hydrogen fuel yields only healthy water. Thus, green house gas can be
avoided. Therefore, research on photo-catalytic breakdown of water into
hydrogen fuel is of worldwide interest.

In order to lead the chemistry, we need to learn chemistry and thus, as
a general chemistry, it starts chemical foundations. Therefore, this chapter
includes theories of atoms, molecules and ions, stoichiometry of chemical
reactions, concepts of molarity, molality, mole fraction and normality, and
highlights the types of chemical reactions and solution stoichiometry.

THEORIES OF ATOMS, MOLECULES, AND IONS
Dalton's Atomic Theory
In 1803, Dalton proposed a theory known as Dalton’s atomic theory. The following summary shows some salient features of his theory of atom:
1. All the matter is made up of extremely tiny particles called atoms, which
cannot be broken down further.
2. Atoms that belong to a particular element are identical. Or every element
has its own characteristic atoms.
3. A chemical compound consists of two or more different atoms of elements.
4. Rearrangement of atoms take place during a chemical reaction and thus
atoms do not get altered their identity.
Dalton’s atomic theory did not last even though the theory was beginning of
development of chemistry. It was due to his incorrect assumption on molecular
weight of certain compounds. Later, the existence of several sub-atomic

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CHEMICAL FOUNDATIONS

3

particles such as electrons, protons and neutrons in atoms was experimentally
proved. Therefore, it is important to know development of chemistry that has
been taking place from the beginning of twentieth century for understanding

the nature of the atom. The experiments of interest at that time defined the
development of chemistry. Thus, in the beginning of twentieth century, the
English physicist J.J. Thompson was studying electrical discharge tubes at
low pressure. During his investigation, production of cathode rays was found
when high voltage was applied. Thompson named the cathode rays as electron
rays since their production from cathode or negatively charged metallic
electrode. Detailed description of production or discovery of electron and
properties of electron is given in the following section.

Discovery/Production of Electron in the Cathode Ray Tubes
Figure 1.1 shows schematic representation of cathode ray tubes. Cathode
(negative electrode) on one side and anode (positive electrode) on other side
are separated by a certain distance. Thus, the tube is evacuated by a vacuum
pump to a certain level of pressure only. When a high voltage (of around
10,000 V) is applied across the metallic electrodes, the vacuum tube starts
to glow. Thompson thus gave a name for a stream of negatively charged
particles as electrons. Thus, discovery and production of electrons resulted
from the investigation of effect of high voltage to the partially evacuated
cathode ray tubes.

Figure 1.1 Representation of Cathode Ray Tube or Discharge Tube

Properties of cathode rays or electrons
1. The glow due to the application of high voltage in the cathode ray tube
is essentially a stream of negatively charged particles. The property of
negatively charged particles has been confirmed by an experiment in
which deflection of cathode rays was caused by an applied electric field as

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4

GENERAL CHEMISTRY

Figure 1.2 Deflection of Cathode Rays by the
Application of Electric Field in Their Path
shown in Figure 1.2. The deflection is due to repulsion between cathode
rays and negative charge metal electrode.
2. When different metals are used as electrodes, similar property of production of
stream of cathode rays is observed. It confirms that all metals contain electrons.
3. When a magnetic field is applied as shown in Figure 1.3, cathode rays are
deflected and it further confirms that cathode rays are negatively charged.

Figure 1.3 Deflection of Cathode Rays by the Application of Magnetic Field
4. Phosphor property of some solids is observed when they are put in the
path of cathode rays.
5. Different gases inside the cathode ray rube glow with different colours.
6. Cathode rays have property of reducing characteristics.

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