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ORGANIC CHEMISTRY
A Modern Approach
Volume-I
ABOUT THE AUTHOR
Nimai Tewari is a retired associate Professor, Department of Chemistry,

Katwa College (affiliated to The University of Burdwan), West Bengal.
A PhD in Organic Chemistry from Calcutta University, he has taught
the subject for a period of more than three decades. He has published
various research papers in national and international journals.
Apart from Organic Chemistry—A Modern Approach, Dr Tewari has
authored three more books on Organic Chemistry for undergraduate
and postgraduate students. His research interest includes Organic
Synthesis and Heterocyclic Chemistry.
ORGANIC CHEMISTRY
A Modern Approach
Volume-I
Nimai Tewari
Associate Professor (Retired)
Department of Chemistry
Katwa College
(affiliated to The University of Burdwan)
West Bengal
McGraw Hill Education (India) Private Limited

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Organic Chemistry—A Modern Approach (Volume-I)
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Dedicated to
my daughter Aindrila
and
my son-in-law Ritam Mukherjee
whose forbearance, constant
encouragement and inspiration
made this work possible
CONTENTS
Preface xv
1. Structure, Bonding and Properties of Organic Molecules 1.1–1.313

1.1 Hybridization, Bond Lengths, Bond Strengths or Bond Dissociation
Enthalpies, Bond Angles and VSEPR Theory 1.2
1.1.1 Hybridization 1.2
1.1.2 Bond Length 1.9
1.1.3 Bond Dissociation Enthalpy or Bond Dissociation Energy 1.9
1.1.4 Bond Angle 1.10
1.1.5 VESPR Theory and Molecular Geometry 1.11
Solved Problems 1.13
Study Problems 1.21
1.2 Electronegativity and Bond Polarity 1.22
Study Problems 1.42
1.3 Molecular Formula as a Clue to Structure: Double Bond Equivalent (DBE) or
Index of Hydrogen Deficiency (IHD) 1.44
Study Problems 1.46
1.4 Acids and Bases 1.46
1.4.1 Brönsted-Lowry Theory of Acids and Bases 1.46
1.4.2 Lewis Acid-Base Theory 1.52
Study Problems 1.57
1.5 Inductive and Electrometric Effects 1.60
1.5.1 Inductive Effect 1.60
1.5.2 Field Effect 1.67
1.5.3 Electromeric Effect 1.67
Study Problems 1.73
viii Contents
1.6 Resonance and Resonance Effect or Mesomeric Effect 1.75

1.6.1 Resonance Energy 1.77
1.6.2 Rules for Writing Meaningful Resonance Structures 1.78
1.6.3 Relative Contribution of Resonance Structures towards Resonance
Hybrid 1.78
1.6.4 Resonance or Mesomeric Effect 1.80
1.6.5 Isovalent and Heterovalent Resonance 1.81
1.6.6 Effect of Resonance on the Properties of Molecules 1.81
Study Problems 1.112
1.7 Hyperconjugation 1.117
1.7.1 Sacrificial and Isovalent Hyperconjugation 1.119
1.7.2 Effect of Hyperconjugation on the Physical and Chemical Properties of
Molecules and on the Stabilities of Intermediates 1.119
1.8 Steric Effect 1.125
1.8.1 Properties of Molecules Influenced by Steric Effect 1.126
1.8.2 Proton Sponges 1.132
1.8.3 Face Strain or F-Strain 1.133
1.8.4 Steric Acceleration and Steric Retardation 1.134
1.8.5 Bredt’s Rule 1.135
1.9 Intermolecular Forces 1.147
1.9.1 Dipole–Dipole Interactions 1.147
1.9.2 van der Waals Forces 1.149
1.9.3 Effect of Intermolecular Forces on Different Properties of
Compounds 1.150
1.10 Reactive Intermediates 1.170
1.10.1 Nonclassical Carbocation 1.177
1.10.2 Carbonium Ion and Carbenium Ion or Carbocation 1.178
1.11 Tautomerism 1.218
1.11.1 Mechanism of Keto-enol Tautomerism 1.221
1.11.2 Difference between Resonance and Tautomerism 1.222
1.11.3 Position of the Tautomeric Equilibrium 1.223
1.11.4 Ring-chain Tautomerism 1.228
1.11.5 Valence Tautomerism 1.228
Contents ix
1.12 Aromaticity 1.240

1.12.1 Criteria for Aromaticity 1.240
1.12.2 Antiaromatic Compounds 1.242
1.12.3 Nonaromatic Compounds 1.242
1.12.4 Classification of Compounds as Aromatic, Antiaromatic and Nonaromatic
by Comparing their Stabilities with that of the Corresponding Open Chain
Compounds 1.243
1.12.5 Modern Definition of Aromaticity 1.243
1.12.6 Molecular Orbital Energy Diagram of Some Ions and Molecules 1.244
1.12.7 Use of Inscribed Polygon Method to Determine the Relative Energies
of p Molecular Orbitals for Cyclic Planar and Completely Conjugated
Compounds and to Classify Them as Aromatic and Antiaromatic 1.245
1.12.8 Classification of Some Molecules and Ions as Aromatic, Antiaromatic and
Nonaromatic 1.247
1.12.9 Homoaromatic Compounds 1.251
1.12.10 Some Chemical and Physical Consequences of Aromaticity 1.251
1.13 Thermodynamics, Energy Diagrams and Kinetics of Organic Reactions 1.276
1.13.1 Thermodynamics 1.276
1.13.2 Energy Diagram 1.278
1.13.3 Kinetics 1.281
1.13.4 Catalysis 1.283
1.13.5 Hammond Postulate 1.284
1.13.6 Kinetic Control versus Thermodynamic Control of a Chemical Reaction 1.286
1.14 Methods of Determining Mechanisms of Reactions 1.298
1.14.1 Kinetic Isotope Effects 1.305
2. Principles of Stereochemistry 2.1–2.230

Introduction 2.2
2.1 Projection Formulas of Stereoisomers 2.3
2.1.1 Flying-Wedge Projection Formula 2.3
2.1.2 Fischer Projection Formula 2.4
2.1.3 Sawhorse Projection Formula 2.10
2.1.4 Newman Projection Formula 2.11
2.1.5 Interconversion of Projection Formulas 2.12
Study Problems 2.25
2.2 Symmetry Elements 2.29
2.2.1 Simple Axis of Symmetry or Rotational Axis of Symmetry (Cn) 2.29
2.2.2 Plane of Symmetry (s) 2.33
x Contents
2.2.3 Centre of Symmetry (i) 2.36

2.2.4 Alternating Axis of Symmetry (Sn) 2.37
2.2.5 Symmetric, Asymmetric and Dissymmetric Molecules 2.38
Study Problems 2.56
2.3 Isomerism: Constitutional Isomers and Stereoisomers 2.58
2.3.1 Constitutional Isomers 2.58
2.3.2 Stereoisomers 2.59
2.3.3 Enantiomers and Diastereoisomers 2.59
Study Problems 2.79
2.4 Molecular Chirality 2.84
2.4.1 Chiral and Achiral Molecules 2.84
2.4.2 Source of Chirality 2.85
2.4.3 Stereocentre or Stereogenic Centre 2.88
2.4.4 Meso Compounds 2.89
2.5 Configuration and Configurational Nomenclature 2.108
2.5.1 D, L-System of Configurational Designation 2.109
2.5.2 Specification of Configuration: The R, S-System 2.111
2.5.3 Erythro and Threo Nomenclature of Compounds with Two Adjacent Chiral
Centres 2.124
2.5.4 The E-Z System of Designating Alkene Diastereoisomers 2.125
2.5.5 R, S and E, Z Assignment in the Same Molecule (Geometric
Enantiomerism) 2.127
2.5.6 Syn-anti Nomenclature for Aldols 2.128
2.5.7 Number of Stereoisomers for Compounds with Chiral Centres 2.129
2.5.8 Chirotopic and Achirotopic Atom in a Molecule 2.131
2.5.9 Prostereoisomerism and Topicity 2.133
2.6 Optical Activity of Chiral Compounds 2.182
2.6.1 Plane-polarized Light 2.182
2.6.2 Optical Activity 2.182
2.6.3 Polarimeter 2.183
2.6.4 Specific Rotation 2.184
2.6.5 The Necessary and Sufficient Condition (the ultimate criterion) for Optical
Activity 2.186
2.6.6 Racemic Modification 2.187
2.6.7 Enantiomeric Excess (EE) or Optical Purity (EE) 2.187
2.6.8 Racemization 2.188
2.6.9 Resolution of Racemic Modification 2.192
Contents xi
2.7 Conformation of Acyclic Organic Molecules 2.211

2.7.1 Conformations of Ethane (CH3—CH3) 2.213
2.7.2 Conformations of Propane (CH3CH2CH3) 2.214
2.7.3 Conformations of Butane (CH3CH2CH2CH3) 2.215
2.7.4 Conformations of Chloroethane (CH3CH2Cl) 2.218
2.7.5 Conformations of 1,2-dichloroethane (ClCH2CH2Cl) 2.218
2.7.6 Conformations of Some Typical Acyclic Molecules 2.219
2.7.7 Invertomerism 2.220
3. Nucleophilic Substitution Reactions at Saturated Carbon Atom 3.1–3.180

Introduction 3.2
3.1 The SN2 reaction 3.3
3.1.1 Example of SN2 Reaction 3.3
3.1.2 Kinetics of SN2 Reaction 3.3
3.1.3 Mechanism of SN2 Reaction 3.3
3.1.4 Stereochemistry of SN2 Reaction 3.5
3.1.5 Evidence in Favour of SN2 Mechanism 3.6
3.1.6 Factors Influencing SN2 Reaction Rate or SN2 Reactivity 3.7
Study Problems 3.74
3.2 The SN1 Reaction 3.86
3.2.1 Example of SN1 Reaction 3.86
3.2.2 Kinetics of SN1 Reaction 3.86
3.2.3 Mechanism of SN1 Reaction 3.86
3.2.4 Stereochemistry of SN1 Reaction 3.87
3.2.5 Evidence in Favour of SN1 Mechanism 3.90
3.2.6 Factors Influencing SN1 Reaction Rate or SN1 Reactivity 3.91
3.2.7 Carbocation Rearrangements in SN1 Reactions 3.105
3.2.8 Comparison of the SN2 and SN1 Reactions 3.108
3.2.9 Summary of Reactivity of Alkyl Halide in Necleophilic Substitution
Reactions 3.108
3.2.10 Factors Favouring SN1 and SN2 Reactions 3.108
3.2.11 SNi and SNi¢ Mechanisms 3.109
3.2.12 SN1¢ Mechanism 3.112
3.2.13 Isotope Effects and Salt Effects (Methods used to Distinguish between SN1
and SN2 Type Reactions) 3.113
3.3 Neighbouring Group Participation (NGP) 3.146
3.3.1 Definition 3.146
3.3.2 Mechanism of NGP 3.146
3.3.3 Example of NGP 3.146
3.3.4 Anchimeric Assistance 3.147
xii Contents
3.3.5 Evidence for Participation by a Neighbouring Group 3.148

3.3.6 Various Cases of Neighbouring Group Participation 3.148
4. Elimination Reactions 4.1–4.128

Introduction 4.2
4.1 The E2 Reaction 4.4
4.1.1 Example of E2 Reaction 4.4
4.1.2 Kinetics of E2 Reaction 4.4
4.1.3 Mechanism of E2 Reaction 4.4
4.1.4 Stereochemistry of E2 Reaction 4.5
4.1.5 Evidence in Favour of the E2 Mechanism 4.32
4.1.6 Factors Influencing E2 Reaction Rate or E2 Reactivity 4.33
4.1.7 Factors that Govern the Proportions of E2 and SN2 Reactions 4.34
4.1.8 Regioselectivity in b-elimination Reactions (Orientation of p Bond in the
Product Alkene) 4.37
4.1.9 Hofmann Exhaustive Methylation or Hofmann Degradation 4.43
4.1.10 Fragmentations 4.45
4.1.11 Summary of the E2 Reaction 4.47
Study Problems 4.74
4.2 The E1 Reaction 4.86
4.2.1 Example of E1 Reaction 4.86
4.2.2 Kinetics of E1 Reaction 4.87
4.2.3 Mechanism of E1 Reaction 4.87
4.2.4 Stereochemistry of E1 Reaction 4.88
4.2.5 Evidence in Favour of the E1 Mechanism 4.90
4.2.6 Factors Influencing E1 Reaction Rate or E1 Reactivity 4.90
4.2.7 Regioselectivity of E1 Reactions 4.90
4.2.8 Rearrangement of the Carbocation Intermediate Involved in an E1
Reaction 4.93
4.2.9 Acid-Catalyzed Dehydration of Alcohols 4.95
4.2.10 Dehydration using POCl3 and Pyridine 4.99
4.2.11 Factors Influencing the Extent of E1 and E2 Reactions 4.100
4.2.12 Factors that Govern the Proportions of E1 and SN1 Reactions 4.101
4.3 The E1CB Reaction 4.118
4.3.1 Example of E1cB Reaction 4.118
4.3.2 Kinetics of E1cB Reaction 4.118
4.3.3 Mechanism of E1cB Reaction 4.118
4.3.4 The Nature of the Substrate 4.119
Contents xiii
4.3.5 To Distinguish between E1cB and E2 Mechanisms 4.119

4.4 a- or 1,1-Elimination 4.126
4.4.1 Example of a- or 1,1-Elimination Reaction 4.126
4.4.2 Kinetics of a- or 1,1-Elimination Reaction 4.126
4.4.3 Mechanism of a- or 1,1-Elimination Reaction 4.126
4.4.4 Structure of the Substrate Involved in a-Elimination 4.127
Index I.1–I.6
PREFACE
In the course of teaching Organic Chemistry to undergraduate students, I have been

constantly feeling the need of a concise volume that deals with their important topics on
the subject matter. Students have often expressed their difficulty caused by the absence of
such a compact book. My present effort is to meet this long-felt need and the book has been
designed primarily for the students who have taken a basic course in Organic Chemistry
at the undergraduate level.
The book covers some important topics on Organic Chemistry in four chapters. It starts
with a chapter on Structure, Bonding and Properties of Organic Molecules, highlighting
concepts like hybridization, electronegativity and bond polarity, acids and bases, inductive
effect, resonance, steric effect, intermolecular forces, etc.
Stereochemistry is an essential part of the organic chemistry courses. Chapter 2 deals with
the Principles of Stereochemistry. Chapter 3 covers Nucleophilic Substitution Reactions
at Saturated Carbon Atom and Chapter 4 covers the Elimination Reactions.
By following a modern methodology of learning, the book presents a large number of
reactions with discussions supported with mechanistic explanations and diagrams,
wherever needed. Organic chemistry is best learned by solving problems. Each article of
every chapter concludes with a number of Solved as well as Study Problems to provide an
opportunity to the students for self-evaluation.
I believe that this book will be of great utility for the students who have taken a basic
course of Organic Chemistry in B.Sc. (Chemistry) Hons., besides being equally effective
for advance students of Chemistry because of the in-depth discussion in a reader-
friendly language. The book will also be useful for the students preparing for competitive
examinations like NET, SLET, etc.
Acknowledgements
I offer my sincere gratitude to Mr. Kaushik Bellani, MD, McGraw Hill Education (India)
Pvt. Ltd. and Mrs. Vibha Mahajan, Director, Science & Engineering Portfolio for successful
xvi Preface
publication of this book. I also wish to thank Mr. Sumen Sen, Mr. Amit Chatterjee and
Mr. P L Pandita for taking keen interest in publishing this book. I am grateful to all of
them.
I also owe a debt of gratitude to my colleagues for constructive suggestions and to my
students who encouraged me constantly. I appreciate the interest and enthusiasm shown
by my wife Mrs. Dali Tewari and my daughter Andrila Tewari (Mukherjee) during the
long period of preparation of the manuscript.
Valuable suggestions from the readers for the improvement of the book will be most
welcome.
Nimai Tewari
1
CHAPTER
STRUCTURE, BONDING
AND PROPERTIES OF
ORGANIC MOLECULES
Chapter Outline
1.1 Hybridization, Bond Lengths, Bond 1.6.5 Isovalent and Heterovalent
Strengths or Bond Dissociation Resonance
Enthalpies, Bond Angles and VSEPR 1.6.6 Effect of Resonance on the
Theory Properties of Molecules
1.1.1 Hybridization 1.7 Hyperconjugation
1.1.2 Bond Length 1.7.1 Sacrificial and Isovalent
1.1.3 Bond Dissociation Enthalpy or Hyperconjugation
Bond Dissociation Energy 1.7.2 Effect of Hyperconjugation on the
1.1.4 Bond Angle Physical and Chemical Properties
1.1.5 VESPR Theory and Molecular of Molecules and on the Stabilities
Geometry of Intermediates
1.2 Electronegativity and Bond Polarity 1.8 Steric Effect
1.3 Molecular Formula as a clue to 1.8.1 Properties of Molecules Influenced
structure: Double Bond Equivalent by Steric Effect
(DBE) or Index of Hydrogen 1.8.2 Proton Sponges
Deficiency (IHD) 1.8.3 Face Strain or F-Strain
1.4 Acids and Bases 1.8.4 Steric Acceleration and Steric
1.4.1 Brönsted-Lowry Theory of Acids Retardation
and Bases 1.8.5 Bredt’s Rule
1.4.2 Lewis Acid-Base Theory 1.9 Intermolecular Forces
1.5 Inductive and Electrometric Effects 1.9.1 Dipole–Dipole Interactions
1.5.1 Inductive Effect 1.9.2 van der Waals Forces
1.5.2 Field Effect 1.9.3 Effect of Intermolecular Forces on
1.5.3 Electromeric Effect Different Properties of Compounds
1.6 Resonance and Resonance Effect or 1.10 Reactive Intermediates
Mesomeric Effect 1.10.1 Nonclassical Carbocation
1.6.1 Resonance Energy 1.10.2 Carbonium Ion and Carbenium Ion
1.6.2 Rules for Writing Meaningful or Carbocation
Resonance Structures 1.11 Tautomerism
1.6.3 Relative Contribution of Resonance 1.11.1 Mechanism of Keto-enol
Structures towards Resonance Tautomerism
Hybrid 1.11.2 Difference between Resonance and
1.6.4 Resonance or Mesomeric Effect Tautomerism
1.2 Organic Chemistry—A Modern Approach
1.11.3 Position of the Tautomeric Compounds and to Classify Them

Equilibrium as Aromatic and Antiaromatic
1.11.4 Ring-chain Tautomerism 1.12.8 Classification of Some Molecules
1.11.5 Valence Tautomerism and Ions as Aromatic, Antiaromatic
1.12 Aromaticity and Nonaromatic
1.12.1 Criteria for Aromaticity 1.12.9 Homoaromatic Compounds
1.12.2 Antiaromatic Compounds 1.12.10 Some Chemical and Physical
1.12.3 Nonaromatic Compounds Consequences of Aromaticity
1.12.4 Classification of Compounds 1.13 Thermodynamics, Energy Diagrams
as Aromatic, Antiaromatic and and Kinetics of Organic Reactions
Nonaromatic by Comparing 1.13.1 Thermodynamics
their Stabilities with that of 1.13.2 Energy Diagram
the Corresponding Open Chain 1.13.3 Kinetics
Compounds 1.13.4 Catalysis
1.12.5 Modern Definition of Aromaticity 1.13.5 Hammond Postulate
1.12.6 Molecular Orbital Energy Diagram 1.13.6 Kinetic Control versus
of Some Ions and Molecules Thermodynamic Control of a
1.12.7 Use of Inscribed Polygon Method to Chemical Reaction
Determine the Relative Energies 1.14 Methods of Determining Mechanisms
of p Molecular Orbitals for Cyclic of Reactions
Planar and Completely Conjugated 1.14.1 Kinetic Isotope Effects
1.1 HYBRIDIZATION, BOND LENGTHS, BOND STRENGTHS OR BOND

DISSOCIATION ENTHALPIES, BOND ANGLES AND VSEPR THEORY
1.1.1 Hybridization
The process of intermixing of atomic orbitals of the same atom having slightly different
energies so as to redistribute their energies and give new orbitals of equal energies and
identical shapes and sizes is called hybridization.
The number of hybrid orbitals is equal to the number of pure atomic orbitals reshuffled.
The hybrid orbitals are more effective in forming stable bonds as compared to the pure
atomic orbitals and this is because they can undergo more effective overlapping. The
relative overlap of orbitals decreases in the following order: sp > sp2 > sp3 >> p. The hybrid
orbitals are oriented in space in some preferred directions to have a stable arrangement in
which there is minimum repulsion among themselves. Therefore, the type of hybridization
governs the geometrical shapes of the molecules.
Hybrid orbitals Hybridization Geometry Bond angle
2 s + p = sp Linear 180°
3 s + p + p = sp2 Trigonal planar 120°
4 s + p + p + p = sp3 Tetrahedral 109.5°
Structure, Bonding and Proper es of Organic Molecules 1.3
In fact, the number of groups surrounding a particular atom determines its geometry. A
group is either an atom or a lone pair of electrons. Any atom surrounding by two, three
and four groups are linear, trigonal planar and tetrahedral, respectively, and they have
bond angles of 180°, 120° and 109.5°, respectively.
The hybridization of a C, O or N atom can be determined by the number of p bonds it
forms. If it forms no p bond, one p bond and two p bonds, it is sp3, sp2 and sp hybridized,
respectively. All single bonds are s bonds. A double bond consists of one s bond and one p
bond. A triple bond consists of one s bond and two p bonds.
“Hybrid orbital number” method can be used to determine the hybridized state of an atom
within a molecule.
Hybrid orbital number = (number of s bonds) + (number of unshared pair of electrons)
If the hybrid orbital number is 2, the atom is sp hybridized, if it is 3, the atom is sp2
hybridized and if it is 4, the atom is sp3 hybridized.
The electronic configuration of carbon atom in its ground state is 1s2 2s2 2px1 2py1 2pz°,
i.e., one odd electron is present in each of 2px and 2py orbitals of carbon atom. The number
of odd electrons present in the valence shell of an atom generally gives the measure of
covalency of that atom. So, the valency of carbon should be two. However, the valency of
carbon in almost all organic compounds is 4, except a few extremely unstable compounds,
where its valency is 2, like methylene (:CH2), dichloromethylene (:CCl2), etc.
During chemical reaction, the two electrons present in 2s orbital become unpaired by
absorbing energy and one of them is promoted to 2pz orbital. This is the excited state of
carbon atom and the electronic configuration of carbon atom in this state is 1s2 2s1 2px1
2py1 2pz1. Thus, in the excited state, four odd electrons are present in the outermost shell of
carbon atom. The presence of these four unpaired electrons accounts for the tetravalency
of carbon.
sp3-Hybridization: When one s and three p orbitals of the valence shell of a carbon atom
merge together to form four new equivalent orbitals having the same energy and shape,
it results in tetrahedral or sp3 –hybridization. The resulting orbitals are called sp3 hybrid
orbitals
The four sp3 hybrid orbitals each containing one electron are directed towards the four
corners of a regular tetrahedron, making an angle of 109°28′ with one another and the
atom lies at the centre of the tetrahedron. The hybrid orbitals are oriented in such a fashion
in space that there occurs minimum repulsion between them. The formation of sp3 hybrid
orbitals by the combination of s, px, py and pz atomic orbitals may be shown as follows:
Formation of methane (CH4) molecule: During the formation of methane molecule,

one 2s orbital and three 2p orbitals of excited carbon atom undergo hybridization to form
four equivalent sp3 hybrid orbitals. The hybrid orbitals are directed towards the four
corners of a regular tetrahedron. Each hybrid orbitals containing an unpaired electron
overlaps with the 1s orbital of a hydrogen atom resulting in the formation of four C—H s
bonds. Thus, methane molecule possesses a highly stable tetrahedral geometry with each
H—C—H bond angle equal to 109°28′.
It is to be noted that if the four atoms linked covalently to the carbon atom are not the
same, the geometry of the molecule would still be tetrahedral but it may not be regular
in shape, e.g., methyl bromide (CH3Br), bromoform (CHBr3), etc. In these cases, the bond
angles differ slightly from the normal value of 109°28′.
sp2-Hybridization: When one s orbital and two p orbitals of the valence shell of a carbon
atom merge together and redistribute their energies to form three equivalent new
orbitals of equal energy and identical shape, the type of hybridization occurs is called
sp2-hybridization. The new orbitals formed as a result of this hybridization are called sp2
hybrid orbitals.
All three hybrid orbitals each containing one electron lie in one plane and make an angle
of 120° with each other, i.e., they are directed towards the three corners of an equilateral
triangle with the carbon atom in the centre of the triangle. The unhybridized 2pz orbital
(containing one electron) remains perpendicular to the plane of the triangle with its two
lobes above and below that plane. Therefore, a molecule in which the central atom is
sp2-hybridized possesses triangular planar shape and the hybridization is called planar
trigonal hybridization. The formation of sp2 hybrid orbitals by combination of s, px and py
atomic orbitals is shown below.
Formation of ethylene (C2H4) molecule: During the formation of ethylene molecule,

each of the two carbon atoms undergoes sp2-hybridization, leaving the 2pz orbitals
unhybridized. The three sp2 hybrid orbitals of each carbon atom are planar and oriented
at an angle of 120° to each other. The unhybridized 2pz orbitals are perpendicular to
the plane of sp2 hybrid orbitals. One sp2 orbital of one carbon overlaps axially with one
sp2 orbital of the other carbon to form a C—C s bond. The remaining two sp2 orbitals of
each carbon overlap with the half-filled 1s orbitals of two hydrogen atoms resulting in the
formation of a total of three C—H s bonds. The unhybridized 2pz orbitals of one carbon
overlap with that of the other carbon in a sideways fashion to from a p bond between the
two carbon atoms. The p bond consists of two equal electron clouds distributed above and
below the plane of carbon and hydrogen atoms. Since all the six atoms in the molecule
lie in one plane, ethylene is a planar molecule. Each C—C—H or H—C—H bond angle is
nearly equal to 120°.
sp-Hybridization: When one s and one p orbital of the valence shell of a carbon atom merge
together and redistribute their energies to form two equivalent hybrid orbitals of equal
energy and identical shape, it results in sp-hybridization or diagonal hybridization.
Formation of acetylene (C2H2) molecule: In acetylene molecule, the two carbon atoms
are sp-hybridized. There are two unhybridized orbitals (2py and 2pz) on each C atom. Two
sp hybrid orbitals are linear and directed at an angle of 180°. The unhybridized p orbitals
are perpendicular to the sp hybrid orbitals and also perpendicular to each other. One sp
hybrid orbital of one carbon overlaps axially with the similar orbital of the other carbon
to form a C—C s bond. The remaining hybrid orbital of each C atom overlaps with half-
filled 1s orbital of H atom to form a total of two C—H s bond. Thus, acetylene molecule
is linear. The unhybridized py orbitals of two carbons and the unhybridized pz orbitals of
two carbons overlap sideways separately to form two different p bonds. Electron clouds
of one p bond lie above and below the internuclear axis representing the s bond while the
electron clouds of the other p bond lie in front and backside of the internuclear axis. These
two sets of p electron cloud merge into one another to form a cylindrical cloud of electrons
around the internuclear axis surrounding the C—C s bond. Each C—C—H bond angle is
equal to 180°.
p
2px p 2px
2py 2py
s s s p
s s s
H sp C sp sp C sp H H C C H
1s 1s
180°
H C ∫∫ C H
Linear acetylene molecule
1.1.2 Bond Length

Bond length is defined as the equilibrium distance between the centres of the nuclei of
two bonded atoms in a covalent molecule. Bond length depends on the factors such as
(i) size of atoms, (ii) multiplicity of bonds, (iii) s-character of the orbitals and (iv) resonance,
hyperconjugation, etc. Bond length increases with increase in the size of atoms but it
decreases with increase in bond multiplicity. Thus, a triple bond is shorter than a double
bond which in turn is shorter than a single bond. An s orbital is closer to the nucleus
than a p orbital. So, electrons in the s orbital is more tightly held by the nucleus than
the electrons in the p orbital. For this reason, with increase in s-character of the hybrid
orbital, the attractive force on the electron(s) increases and so, the size of the hybrid orbital
decreases. As a consequence, the length of the bond obtained by overlapping of the hybrid
orbitals with the s orbitals of hydrogen, for example, decreases. The s-character of sp3, sp2
and sp hybrid orbitals are 25 percent, 33.33 percent and 50 percent respectively. Thus, the
lengths of the C—H bonds involving C atoms with different hybridization follow the order:
Csp3 —H (1.093 Å) > Csp2 —H (1.078 Å) > Csp — H (1.057 Å).
1.1.3 Bond Dissociation Enthalpy or Bond Dissociation Energy

The bond dissociation enthalpy or bond dissociation energy which is a measure of bond
strength may be defined as the amount of energy required to break one mole of a particular
type of bond between two atoms in the gaseous state so as to produce neutral gaseous
atoms or free radicals. Bond dissociation energies are usually abbreviated by the symbol
DH° and are usually expressed in kJ mol–1 or kcal mol–1. The greater the bond dissociation
energy, stronger the bond. The factors affecting bond dissociation energy are: (i) size of
the bonded atom, (ii) multiplicity of bonds, (iii) s-character of the hybrid orbital involved
in bond formation, etc.
Larger the size of the bonded atoms, greater the bond length and lesser is the bond
dissociation energy. The bond dissociation energy increases with increase in bond
multiplicity. A C ∫∫ C bond is stronger than a C == C bond which in turn is stronger than
a C – C bond. The bond dissociation energy also increases with increase in the s-character
of the hybrid orbital and this is because with increase in s-character of the hybrid orbital,
the electron density in the region of overlap increases.
Bond type Bond dissociation energy
kJ mol–1 (kcal mol–1)
C(sp3) — C(sp3) 346.3 (82.76)
C(sp3) — C(sp2) 357.6 (85.48)
C(sp3) — C(sp) 382.5 (91.42)
C(sp2) — C(sp2) 383.2 (91.58)
C(sp2) — C(sp) 403.7 (96.48)
C(sp) — C(sp) 433.5 (103.6)
Bond Dissociation Energies (kcal mol–1) of Some Chemical Bonds

Bond DH° Bond DH° Bond DH°
H—H 104 F—F 38 Ph—H 110
D—D 106 Cl—Cl 58 CH2==CH CH2—H 88
C—C 83.1 Br—Br 46 Ph CH2—H 85
N—N 38.4 I—I 36 CH3—F 107
O—O 33.2 CH3—H 104 CH3—Cl 84
N—F 136 C2H5—H 98 CH—Br 70
H — Cl 103 (CH3)2 CH—H 95 CH3—I 56
H — Br 88 CH2==CH—H 108 CH2==CH—Cl 82
H—I 71
Another measure of bond strength is Bond Energy. This is actually the average bond
dissociation energy, denoted by E. For example, cleavage of a C—H bond in methane
requires different bond dissociation energies in successive steps as indicated below and
energy of the C—H bond is determined by an average.
CH Æ .CH + H. DH ∞ = 104 Kcal mol –1
4 3 1
.CH Æ CH2 + H. DH 2∞ = 106 Kcal mol -1
3
CH2 Æ .CH + H. DH ∞ = 106 Kcal mol -1

3
.CH Æ .C . + H. DH ∞ = 81 Kcal mol -1
4
CH4 Æ .C. + 4H. Total: 397 Kcal mol -1
Therefore, EC—H = 397/4 = 99.25 kcal mol–1.

However, bond dissociation energy (DH°) is more convenient than bond energy (E) for our
purpose.
1.1.4 Bond Angle

The bond angle is the angle between two bonds around the central atom in a molecule.
For example, H—C—H bond angle in methane (CH4) is 109.5° and H—O—H bond angle
in water is 104.5°. Bond angle is affected by the factors such as (i) type of hybridization,
(ii) number of lone pair of electrons on the central atom, (iii) electronegativity of the
central atom and (iv) electronegativily of the atom bonded to the central atom. The greater
the amount of s-character of the orbital used by carbon to form the bond, the larger the
bond angle. For example, sp-hybridized carbons have bond angles of 180°, sp2-hybridized
carbons have bond angles of 120° and sp3-hydridized carbon have bond angles of 109.5°.
1.1.5 VESPR Theory and Molecular Geometry

We can predict the arrangement of atom in molecules and ions on the basis of a relatively
simple idea called the valence shell electron pair repulsion (VSEPR) theory.
We can apply this theory on the basis of the following considerations:
1. In a molecule or ion, the central atom is covalently bonded to two or more atoms or
groups.
2. Covalent bonds contain shared pair of electrons which are often called bond pairs
or bonding pairs. The unshared electrons of the central atom are called nonbonding
pairs or unshared pairs or lone pairs.
3. Since electron pairs repel each other, the electron pairs of the valence shell tend to
stay as far apart as possible to avoid electronic repulsion.
4. If the central atom is surrounded by bond pairs as well as lone pairs of electrons,
the repulsions among themselves are different. As a result, the molecule possesses
an irregular or distorted geometry. The repulsive interactions of various electron
pairs decrease in the order: lone pair–lone pair (lp – lp)> lone pair–bond pair (lp –
bp) > bond pair–bond pair (bp – bp).
5. The geometry of a molecule is to be settled by considering all of the electron pairs,
bonding and nonbonding. However, the shape of the molecule is to be described
by referring to the positions of the atoms and not by the position of the electron
pairs.
Let us consider the following examples.
Methane (CH4) molecule: In CH4 molecule, the total number of electrons surrounding
the central carbon atom = 4 valence electrons of C atom + 4 electrons of four singly-bonded
H atom = 8 electron or 4 electrons pairs = 4 s bond pairs. The four bond pairs experience
minimum repulsion if they are tetrahedrally oriented, i.e., if all the H—C—H bond angles
are of 109.5°. Hence, the shape of CH4 molecule is tetrahedral.
H
109.5°
C
H
H
H
Tetrahedral
methane molecule
Ammonia (NH3) molecule: In NH3 molecule, the total number of electrons in the
valence shell of the central N atom = 5 valence electrons of N atom + 3 electrons of three
singly-bonded H atom = 8 electron or 4 electron pairs = 3 s bond pairs + 1 lone pair. All
four electron pairs experience minimum repulsion if they occupy the four corners of a
tetrahedron. As lone pair–bond pair repulsion is greater than the bond pair–bond pair
repulsion, the H—N—H bond angle is slightly deviated from the normal tetrahedral angle
(109.5°) and is reduced to 107°, i.e., the tetrahedron is somewhat distorted. Excluding the
lone pair, the shape of the molecule is trigonal pyramidal.
Water (H2O) molecule: In water molecule, the total number of electrons surrounding the
central O atom = 6 valence electron of oxygen atom + 2 electrons of two singly-bonded H
atoms = 8 electrons or 4 electron pairs = 2 s bond pairs + 2 lone pairs.
In order to minimise the extent of mutual repulsion, these four electron pairs are oriented
towards the four corners of a tetrahedron. However, the tetrahedron is somewhat distorted
due to the strong repulsive forces exerted by the lone pairs on each bond pair of electrons.
In fact, the H—O—H bond angle is reduced to 104.5° from the normal tetrahedral angle of
109.5°. Excluding the lone pairs, the shape of the molecule is angular or V-shaped.
H O or O
104.5° H 104.5° H
H
Angular or V-shaped
water molecule
Boron tifluoride (BF3) molecule: In boron trifluoride molecule, the total number of
electrons in the valence shell of the central boron atom = 3 valence electrons of B atom
+ 3 electrons of three singly-bonded F atom = 6 electrons or 3 electrons pairs = 3 s bond
pairs. The three bond pairs experience minimum propulsion if they remain at 120° angle
with respect to each other. Therefore, the geometrical shape of BF3 molecule is trigonal
planar.
F
120° 120°
B
F 120° F
Trigonal planar
boron trifluoride molecule
Acetylene (HCCH) molecule: The number of electrons surrounding each carbon atom
of acetylene molecule = 4 valence electron of carbon + 3 electrons of one triply-bonded C
atom + 1 electron of one singly-bonded H atom = 8 electrons = 4 electron pairs = 2 s bond
pairs + 2p bond pairs. In order to minimise the repulsive forces between the bond pairs, the
shape of acetylene molecule is linear. The effect of electrons involved in the formation of a
p bond is not generally considered in determining the geometrical shape of a molecule.
180° 180°
H——C∫∫C——H
Linear acetylene molecule
1. Give the state of hybridization of the central atom of each of the following
species and predict their shapes.
! @ @
(a) H2O (b) BF3 (c) C H 3 (d) C H 3 (e) :N H 2

(f) H 2S: (g) NH 3 (h) BF4* (i) H3O≈ (j) HCN
≈
(k) CCl4 (l) CO2 (m) BeH2 (n) NH 4
Solution
(a) (b) (c)
F H +
B F C H
F H
sp2; trigonal planar sp2; trigonal planar
(d) (e) (f)

–
–
C N H S H
H
H H
H H sp3; bent or angular
sp3; bent or angular
sp3; trigonal pyramidal
(g) (h) (i)

F
+
H N –
O H
B
H H F H H
sp3; trigonal pyramidal F F sp3; trigonal pyramidal
sp3; tetrahedral
(j) (k) (l)

H—C∫∫N Cl O==C==O
sp; linear
sp; linear
C
Cl
Cl Cl
sp3; tetrahedral
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HERCULES’ CLUB
Aralia spinosa
Page 162
The meaning of the generic name is unknown. The specific name,

spinosa, is the Latin word meaning prickly, and alludes to the stems.
Southward from Pennsylvania this curious, ungainly tree is found
growing wild, and as it is hardy in the North it is frequently cultivated
in gardens. It is seen at its best in the rich soil of the Big Smoky
Mountains of Tennessee. There it grows to be thirty or thirty-five feet
high, with wide-spreading branches and a true arborescent habit.
Chapter XIII
THE APPLE TREE, PEAR TREE, MOUNTAIN ASH,
CHERRY TREE, AND THE SHAD BUSH
MOUNTAIN ASH
Pyrus americana
Page 170
Chapter XIII
THE APPLE TREE, PEAR TREE, MOUNTAIN ASH, CHERRY
TREE, AND THE SHAD BUSH.
Family Rosaceæ
T HE rose family is a very large order of trees, shrubs, and herbs

belonging to temperate climates. There are numerous genera,
including valuable fruit and ornamental trees which have been
cultivated since the earliest times. Many of the species are so
familiar that they scarcely need description in summer, but in winter
the character of their buds and stems is less easily recognized, and
unless the trees are well grown it is sometimes difficult to identify
them.
A flat-topped tree, 20 to 40 feet high. The bark of
Common Apple the tree scales off in small, thin, brittle plates. The
Tree Pyrus buds and the stems are small and somewhat
malus woolly. The leaf-scars are alternate and
inconspicuous, with three bundle-scars.
The low, flat-topped, broad-headed shape of the apple tree is so
characteristic that it may be easily recognized in winter, even when
there is no surrounding orchard to identify it. So strong in one’s mind
is the association of blossoms with these trees, that even a bare old
apple tree against a winter sky suggests the spring,—an apple tree
always seems to be haunted by the ghosts of its pink blossoms. The
literary history of this tree goes back to the mythologies of the
Greeks, the Scandinavians, and the Druids, and it also figures
prominently in early Christian as well as pagan legends. It has been
cultivated for its fruit since prehistoric times, and there are hundreds
of varieties of it in cultivation.
The wood is fine-grained, hard, and a rich reddish brown color. It is
used for small purposes in turnery. The fruit, however, is the most
valuable product of the tree, and cider has been made from it for
hundreds of years. Its native country is uncertain, but it is probably
indigenous to the Northwestern Himalayas and the forests along the
Black Sea. It was introduced into Britain by the Romans, and it is
widely naturalized in the United States.
The generic name, Pyrus, is the ancient classical name for the
pear tree, and probably was originally taken from the Celtic word
peren, from which the English word was derived. The specific name,
malus, is the ancient classical name for the apple tree.
A pyramidal tree, 30 to 70 feet high. The bark is
Common Pear smooth, and the branches incline to be thorny,
Tree Pyrus especially when the tree has escaped cultivation.
communis Smooth stems and small pointed buds. Alternate
inconspicuous leaf-scars, with three bundle-scars.
As distinctive in shape as the apple tree, but in striking contrast to
it, the erect pyramidal head of the pear tree is easily recognized in
winter, and its small, pointed buds and smooth stems offer other
points of difference. Like the apple tree, the pear tree has been in
cultivation for hundreds of years and there are innumerable varieties.
It seems incongruous that so small a tree should live to a great age,
but Bosc alludes to pear trees more than four hundred years old, and
Knight tells of several which date back to the fifteenth century.
The wood is heavy and compact, and is used in Europe by wood
engravers and turners. A drink called perry is made from pears in
much the same way that cider is made from apples. It was
considered an antidote to mushroom poisoning by the Romans, and
in England it is still taken, “after a surfeit of that vegetable,”
according to Loudon. The pear tree is a native of nearly all the
elevated regions of Europe and Western Asia. Like the apple tree it
was introduced into Britain by the Romans, and it is widely
naturalized in the United States.
A slender tree, or tall shrub, 20 to 30 feet high. Slender spreading
branches with smooth bark. The twigs are downy, becoming smooth
and brownish red in color. Large alternate leaf-
Mountain Ash, scars. The buds are pointed, reddish in color, and
or Rowan Tree gummy to the touch. The inner scales of the buds
Pyrus are coated with down. It has bright scarlet berry-
americana
like fruit, which remains on the tree through the
winter.
A YOUNG BLACK CHERRY TREE
Prunus serotina
Page 171
The mountain ash is seldom associated in our minds with apple

and pear trees, but it belongs to the same genus nevertheless, and
has absolutely nothing in common with the ash tree, as one might
suppose. The American mountain ash is frequently planted as an
ornamental tree, although the European species is more often
cultivated than ours. The buds of the European mountain ash are
blunter and more downy than those of the American, the bark is
lighter in color, and the berries are larger, but apart from these
differences the trees can scarcely be told apart in winter.
Pyrus sambucifolia, the elder-leafed mountain ash, is another
native species which grows wild in the mountains of Northern New
England and is found as far north as Greenland and westward. The
range of Pyrus americana is more limited, but it is found from
Newfoundland to North Carolina and westward.
A tree or shrub, varying from 15 to 100 feet high.
Wild Black The bark is smooth on young trees, with
Cherry Prunus conspicuous horizontal lenticels; on old trees it
serotina cracks and breaks off in small, thin, brittle scales.
The branches are slender, rigid, reddish brown in
color, and bitter to the taste. The buds are pointed, a light chestnut
brown in color, with closely overlapping scales. Alternate leaf-scars.
The black cherry may be identified in winter by its bark and by the
disagreeable bitter taste of its stems,—no other tree has a strong,
peculiar, pungent taste like this. The bark of the young trees is really
beautiful, it is so smooth and has such a rich reddish brown color; in
some characteristics it resembles that of the black birch, but the
larger, coarser lenticels distinguish it from that tree.
The black cherry is a valuable timber tree. The wood is light,
strong, and hard, and takes a fair polish. It is used in cabinet making
and for the interior finish of houses. The bark of the branches and
roots is much used in medicine, and the ripe fruit is used to flavor
alcoholic liquors.
The meaning of the generic name, Prunus, is unknown, but it is
thought to be of Asiatic origin. The specific name, serotina (late
flowering), refers to the blossoms of this tree, which appear in June,
later than those of other cherries. It is found from Nova Scotia to
Florida, and reaches its greatest size in the Western forests.
Prunus virginiana, the choke cherry, and Prunus pennsylvanica,
the wild red, bird, or pin cherry, are two small trees found more or
less frequently in the woods throughout the Atlantic States. They are
both distinguished from the black cherry by their red instead of black
fruit.
The common sweet cherry (Prunus avium), the common peach
tree (Prunus persica), and the common garden plum (Prunus
domestica) all belong to this genus and are widely cultivated in the
United States. They are small trees with many varieties and are
planted for their fruit.
The cherry was brought from Asia to Italy, and from there it was
rapidly carried to all parts of Europe. The peach came originally from
China, and was brought to Great Britain by the Romans, who got it
from Persia during the reign of the Emperor Claudius. It was carried
to North America by the first settlers at the beginning of the
seventeenth century. The difficulty of raising peaches successfully in
the Northern States is not so much due to the cold weather as to the
swelling of the buds on warm winter days and in the early spring,
which are afterwards destroyed if the thermometer goes below zero.
An interesting experiment of whitewashing peach trees, to prevent
the buds from absorbing heat on sunny days, was tried by Mr.
Whitten of the Missouri Experiment Station, and it was found that
whitened buds remained dormant until April, while unprotected buds
swelled perceptibly in February and March. Eighty per cent of
whitened buds passed the winter safely, where only twenty per cent
of unwhitened buds escaped injury by premature swelling.
A small tree, 40 to 50 feet high, with smooth brown bark. Slender
twigs. The buds are brown and covered with slightly downy, silky
scales, and the leaf-scars are alternate.
Shad Bush;
Service Berry;
The shad bush is strongly associated with the
June Berry rich upland woods of New England, and in the
Amelanchier early spring its white flowers are among the first to
canadensis appear among the budding trees and shrubs, when
the streams are full and the shad begin to rise. In
winter there are no marked characteristics by which it may be
known, apart from its general resemblance to other genera in the
family, and its delicate twigs, small pointed buds with overlapping
scales, and inconspicuous leaf-scars.
The wood is close-grained, heavy, and exceedingly hard, and is
used for the handles of tools and other small implements.
The generic name, Amelanchier, is the Savoy name for the
medlar. The shad bush is found from Newfoundland to Northern
Florida and westward.
Chapter XIV
THE WILLOWS AND POPLARS
WHITE WILLOWS
Salix alba
Page 178
Chapter XIV
THE WILLOWS AND POPLARS
Family Salicaceæ
A MONG the willows there are so many hybrids and varieties that
their classification is difficult even in summer when an analysis
of the flowers is possible. Most of the species in the Eastern States
are shrubs, and I have chosen the only large tree, the white willow,
as a representative species for study in winter. The genus Populus
also belongs to this family, of which four species grow commonly in
New England.
A large tree, 50 to 80 feet high, with thick, rough
White Willow bark and lithe branches. The twigs are smooth and
Salix alba often yellow in color, and the small alternate leaf-
scars have three bundle-scars. The buds are
pointed, covered with a single scale and placed close against the
stems. The lateral buds are numerous and are usually larger than
the terminal buds.
The white willow is really a native of Europe, but for generations in
New England it has associated itself with country landscapes, and
there is scarcely a marshy meadow or a stream through a pasture
with a water course unmarked by a row of these trees. It seems
wonderful that the buds of willows should survive our cold Northern
winters as they do, for they are covered with a single scale of
delicate texture, and the little undeveloped leaves seem perilously
near the cold. The soft woolly catkins of some species,—“the pussy
willows,”—which come before the leaves, carry their own protection
from cold weather, and even in January, when a few warm days
bring them out prematurely, they look comfortable; but the little
leaves with their single coverings never come out before the right
time, and they never appear to have suffered.
The wood is weak and soft, and little use is made of it. The value
of the twigs in basket making has been recognized since early
Roman times, Cato having ranked the salictum, or willow field, next
in value to the vineyard and the garden.
The generic name comes from the Celtic words sal, near, lis,
water, in allusion to its aquatic nature. It grows on all kinds of soil,
and is widely naturalized in the United States.
The weeping willow (Salix babylonica) is planted in gardens and
may be distinguished by its very slender, long drooping branches,
which in every limb suggest the sentiment of a hundred years ago. In
allusion to its place among other trees in landscape composition,
Mrs. Van Rensselaer says in “Art Out of Doors”:—
“As soon as we see a weeping willow it almost shouts out its
contrast to the simpler shapes of the trees which determine the
general character of all our landscapes or garden pictures. Yet we
see it everywhere, in every kind of situation.
“In all my wanderings I never once have seen it rightly placed; I
never once have seen it where it did not hurt the effect of its
surroundings, or, at least, if it stood apart from other trees, where
some tree of another species would not have looked far better.”
The black willow (Salix nigra) is the only one among our native
willows which grows to a good size, but even this is seldom more
than thirty feet high.
A medium sized tree, 30 to 60 feet high, with a
Aspen; smooth, greenish gray bark and tapering trunk.
American Aspen The twigs are slender. The buds are long, sharp-
Populus pointed, with smooth, glossy scales covered with a
tremuloides
gummy substance. Alternate leaf-scars.
The aspen is more conspicuous in summer, when the constant
motion of its trembling leaves attracts our attention, than it is in
winter, although in some trees the smooth, olive-green bark of the
trunk is very attractive, particularly in contrast with the snow. There
have been endless allusions in literature to the European aspen,
which resembles our species. In a simile showing the activity of
Penelope’s maidens, Homer says:—
“Some ply the loom; their busy fingers move

Like poplar leaves when zephyr fans the grove.”
Again Spenser uses the same simile:—
“His hand did quake

And tremble like a leaf of aspen green.”
And Sir Walter Scott uses it in the same way to picture quick
changes of facial expression:—
“With every change his features played,

As aspens show the light and shade.”
Gerard, in a way scarcely flattering to the sex, compares the

leaves to women’s tongues, “which seldom cease wagging;” but Sir
Walter Scott restores the balance in the lines:—
“O woman! in our hours of ease

Uncertain, coy, and hard to please,
And variable as the shade
By the light quivering aspen made,
When pain and anguish wring the brow,
A ministering angel thou.”
ASPENS
Populus tremuloides
Page 180
The wood is close-grained, soft, and not strong, but it is made into
pulp and used in the manufacture of paper. The bark is brittle, with a
taste like quinine, but the inner bark is sweet, and in the spring it is
used as food by the Indians.
The generic name, Populus, is supposed to have come from the
Latin arbor populi (the tree of the people), because rows of this tree
were always planted in public places about Rome. The specific
name, tremuloides, refers to the leaves which tremble continually on
account of their long, flattened, pliable leafstalks. The aspen grows
wild throughout the Northern United States and in the mountains of
Lower California and Mexico.
A large tree, 60 to 80 feet high, with smooth
Large-toothed greenish gray bark. The buds are conical with
Aspen Populus somewhat downy scales and spread at right
grandidentata angles from the stem. Slender twigs and alternate
leaf-scars.
This tree is quite distinct from the American aspen, although it is
often confounded with it. It is found much less frequently than the
American aspen.
The wood is close-grained, soft, and light, and is used for making
wood pulp and wooden ware. In old times when it was the fashion for
women to wear high-heeled shoes this wood was used in making
heels, as it was light and best adapted to the purpose.
The specific name, grandidentata (large toothed), refers to the
serrations of the leaf, which are much coarser than those of the
American aspen.
A tall tree, 40 to 70 feet high. The bark ts smooth
Balm of Gilead; and greenish gray, often roughly ridged at the base
Balsam Poplar of the trunk. Large buds with overlapping scales
Populus covered with a sticky, yellow, glutinous substance.
balsamifera Conspicuous alternate leaf-scars.
In the early spring, when the sun has melted the gummy resin
which covers the buds of the balm of Gilead, one can tell the tree
blind-folded by its sweet, pungent perfume, and even in winter the
buds have this same strong, medicinal, aromatic odor which serves
as a means of recognizing the tree.
Pallas says that when grouse and other birds of that family feed on
the buds of the balm of Gilead during the winter, their flesh becomes
imbued with the balsam flavor, which he seems to think adds to the
relish of the meat as food.
This tree grows very fast on almost any kind of soil, and its roots
extend to a great distance. Emerson found a balm of Gilead the
roots of which had passed under a house forty feet wide and thrown
up suckers on the other side.
The wood, like that of other poplars, is soft and light and is used in
making paper pulp, pails, and boxes.
The specific name refers to the balsam on the buds. The balm of
Gilead is found in the Western and Eastern States.
A large tree, 80 to 100 feet high. The bark is
Cottonwood; dark gray and more broken in fissures than that of
Necklace or other poplars. The buds are glossy and resinous,
Carolina Poplar but have less balsam than those of the other
Populus
species. Alternate leaf-scars. Conspicuous five-
deltoides
angled pith in the small stems.
The cottonwood is larger than the other poplars, and in the
Mississippi Valley it sometimes grows to be one hundred and fifty
feet high. The climate of London must be particularly congenial to
this tree, for Emerson alludes to trees there which grew thirty and
forty feet in only seven years. In England it is called the black Italian
poplar. The name necklace poplar comes from the resemblance of
the fruit of the catkins to the beads of a necklace.
The wood is light and soft, and is used for pulp, for making
packing cases, and for fuel.

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Organic Chemistry A Modern Approach

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Nimai Tewari is a retired associate Professor, Department of Chemistry,

McGraw Hill Education (India) Private Limited

Organic Chemistry—A Modern Approach (Volume-I)

Copyright © 2017, by McGraw Hill Education (India) Private Limited.

This edition can be exported from India only by the publishers,

Visit us at: www.mheducation.co.in

1. Structure, Bonding and Properties of Organic Molecules 1.1–1.313

1.6 Resonance and Resonance Effect or Mesomeric Effect 1.75

1.12 Aromaticity 1.240

2. Principles of Stereochemistry 2.1–2.230

2.2.3 Centre of Symmetry (i) 2.36

2.7 Conformation of Acyclic Organic Molecules 2.211

3. Nucleophilic Substitution Reactions at Saturated Carbon Atom 3.1–3.180

3.3.5 Evidence for Participation by a Neighbouring Group 3.148

4. Elimination Reactions 4.1–4.128

4.3.5 To Distinguish between E1cB and E2 Mechanisms 4.119

In the course of teaching Organic Chemistry to undergraduate students, I have been

1.11.3 Position of the Tautomeric Compounds and to Classify Them

1.1 HYBRIDIZATION, BOND LENGTHS, BOND STRENGTHS OR BOND

Hybrid orbitals Hybridization Geometry Bond angle

Formation of methane (CH4) molecule: During the formation of methane molecule,

Formation of ethylene (C2H4) molecule: During the formation of ethylene molecule,

1.1.2 Bond Length

1.1.3 Bond Dissociation Enthalpy or Bond Dissociation Energy

Bond Dissociation Energies (kcal mol–1) of Some Chemical Bonds

CH2 Æ .CH + H. DH ∞ = 106 Kcal mol -1

CH4 Æ .C. + 4H. Total: 397 Kcal mol -1

Therefore, EC—H = 397/4 = 99.25 kcal mol–1.

1.1.4 Bond Angle

1.1.5 VESPR Theory and Molecular Geometry

(a) H2O (b) BF3 (c) C H 3 (d) C H 3 (e) :N H 2

(d) (e) (f)

(g) (h) (i)

(j) (k) (l)

The meaning of the generic name is unknown. The specific name,

TREE, AND THE SHAD BUSH.

T HE rose family is a very large order of trees, shrubs, and herbs

The mountain ash is seldom associated in our minds with apple

“Some ply the loom; their busy fingers move

Again Spenser uses the same simile:—

“His hand did quake

“With every change his features played,

Gerard, in a way scarcely flattering to the sex, compares the

“O woman! in our hours of ease

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