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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
(m) (n)
H—Be—H H
sp; linear
+
N
H
H H
sp3; tetrahedral
2. Draw the structure of a hydrocarbon which contains:

(a) Three sp3-hybridized carbon atoms;
(b) One sp3 and two sp2-hybridized carbon atoms;
(c) One sp and two sp2-hybridized carbon atoms;
(d) Two sp3 and two sp-hybridized carbon atoms.
Solution
(a) (b) (c)
(d)
3. Which orbitals are used to form each bond in methylamine, CH 3 NH 2?

Solution
Each C—H bond is formed by the overlap of an sp3 orbital of carbon with the s orbital of
hydrogen ( Csp3 —H1s). The C—N bond is formed by the overlap of an sp3 orbital of carbon
with sp3 orbital of nitrogen ( Csp3 — N sp3 ) and each N—H bond is formed by the overlap of
an sp3 orbital of nitrogen with the s orbital of hydrogen ( N sp3 —H1s).
: O:
||
4. Answer the following question for the acetaldehyde (CH 3 — C — H)
molecule:
(a) Determine the hybridization of oxygen and the two carbon atoms.
(b) Which orbitals are involved in forming the carbon–oxygen double
bond?
(c) Mention the type of orbital in which the lone pairs reside.
Solution
(a)
(b) The s bond is formed by the end-on overlap of an sp2 orbital of carbon with an sp2
orbital of oxygen and the p bond is formed by the side-by-side overlap of the 2p
orbital of carbon with the 2p orbital of oxygen.
(c) The two sp2 hybrid orbitals are occupied by the two lone pairs of oxygen.
5. Mention the state of hybridization of the starred (*) carbon atoms in each
of the following compounds:
* *
(a) (b) CH 3 C N (c) HC ∫∫ C — CHO
* * –
(d) CH2 == C == CH2 (e) (f)
*
Solution
(a) Three groups around the starred carbon: sp2-hybridized; (b) two groups around the
starred carbon: sp-hybridized; (c) three groups around the starred carbon: sp2-hybridized;
(d) two groups around the starred carbon: sp-hybridized; (e) three groups around the
starred carbon: sp2-hybridized; (f) four groups around the starred carbon; sp3-hybridized.
6. How many s and p bonds are present in each of the following molecules?
(a) CH3—C ∫∫ C—CH == CH—CH3
(b) –CH2CH3
(c) CH3 CH == C == CH CH2 CH3
Solution
(a) s bond = 13; p bond = 3;
(b) s bond = 18; p bond = 3;
(c) s bond 15; p bond 2
7. Designate the state of hybridization of all the atoms of the following
molecule:
Solution The hybridized atoms within the molecule is designated as a, b and c according
to their hybridization status: a = sp3; b = sp2 and c = sp.
8. Draw the orbital picture for each of the following molecules: (a) ethylene
(b) acetylene (c) ketene (CH2 == C == O) (d) acraldehyde (e) acrylonitrile
(f) but-1, 2, 3-triene.
Solution
(a) Ethylene:
(b) Acetylene:
(c) Ketene:
(d) Acraldehyde:
(e) Acrylonitrile:
(f) But-1, 2, 3-triene:
9. Which atoms in each of the following molecules always remain in the

same plane and why?
(a) CH3CH==CH CH3 (b) C6H5C ≡≡ CCH3
(c) CH3CH==C==C==CH2 (d) CH2==CH—C ≡≡ CH
2
Solution The two sp -hybridized carbon atoms and the atom directly attached to them
always remain in the same plane. This is applicable also when the two sp2-hybridzed carbon
atoms are linked through an even number of sp-hybridized carbon atoms. Therefore, in
(a), all atoms excluding the six methyl hydrogens remain in the same plane. In (b), all
atoms excluding the three methyl hydrogens remain in the same plane. In (c), all atoms
excluding the three methyl hydrogens remain in the same plane and in (d), all atoms
remain in the same plane. This is also because the two sp-hybridized carbon atoms and
the atoms directly attached to them remain in the same line.
10. Explain why a p bond is weaker than a s bond.
Solution A p bond is weaker than a s bond because the end-on overlap that forms s bonds
is better than the side-to-side overlap that forms p bonds. This is also because the electron
density in a p bond is farther from the two nuclei as compared to that in a s bond.
11. In CH3CH3, the C—H bond is shorter and stronger than the C—C bond –
explain.
Solution The s orbital of hydrogen is closer to the nucleus than the sp3 orbital of carbon
having less s character. So, the carbon and hydrogen nuclei are closer together in sp3-s
overlap than the carbon nuclei in sp3-sp3 overlap. Because of this, the C—H bond in
ethane (CH3—CH3) is shorter and stronger than the C—C bond. Again, as the percentage
of s character of the overlapping orbitals increases, the electron density in the region
of overlap increases and as a result, the strength of the bond increases. Since there is
greater electron density in the region of sp3-s overlap than in the region of sp3-sp3 overlap,
therefore, the C—H bond is stronger than the C—C bond.
12. Arrange the indicated bonds in each of the following compounds in order
of increasing bond strength and increasing bond length:
bond 1
HC∫∫ C—CH==CH—CH2—CH3
(a) ≠ ≠ ≠ (b) H3C NH—CH2CH3
bond 1 bond 2 bond 3
N CH2—C∫∫ N
bond 2 ≠
bond 3
Solution Greater the bond multiplicity, shorter the bond and greater the bond strength.
Therefore, in compound (a), bond length increases in the order: bond 1 < bond 2 < bond
3 and bond strength increase in the order: bond 3 < bond 2 < bond 1. In compound (b),
the bond length increases in the order: bond 3 < bond 2 < bond 1 and the bond strength
increases in the order: bond 1 < bond 2 < bond 3.
13. Which of the indicated bonds in each pair of compounds is shorter and
why?
(a)
(b)
O
==
(c) CH3—C—H and H—CH2OH

≠ ≠
Solution As the s-character of the overlapping orbitals increases, the nuclei involved in
bond formation becomes closer and the bond becomes shorter. Therefore, (a) the Csp—H
bond in the second compound is shorter than C 2 —H bond in the first compound;
sp
(b) the N sp2 —H bond in the second compound is shorter than the N sp3 —H bond in
the first compound, and (c) the Csp2 —H bond in the first compound is shorter than the
C 3 —H bond in the second compound.
sp
14. Determine the state of hybridization of the indicated atom in each of the
following species:
(a) (b) (c)
– –
–
CH2 NH2
== ≠ ≠
O O2N O2N
(d) (e) (f)
–
O O O O
Ø
== ==
==
==
C6H5—C
Ø– H—C—NH2
O
≠
Solution In any system of the type X = Y – Z:, Z is sp2-hybridized and the unshared
electron pair on it occupies a p orbital to delocalize the electron pair and make the system
conjugated. Therefore, the indicated atoms in (a), (b), (c), (d) and (f) are sp2-hybridized.
However, due to violation of Bredt’s rule (introduction of a double bond is not possible at
the bridgehead position in bridged bicyclic compounds with small rings) delocalization of
the unshared electron pair is not possible in the compound (e) and therefore, the indicated
carbon atom is sp3-hybridized.
15. “Bromination of methane is less exothermic than that of chlorination” —

explain with DH° calculation.
[Bond dissociation energies for C—H = 104 kcal/mol; Br—Br = 46 kcal/mol; H—Br = 87.5
kcal/mol; Cl—Cl = 58 kcal/mol; H—Cl = 103 kcal/mol; C—Cl = 83.5 kcal/mol and C—Br =
70 kcal/mol]
hn
Solution CH 4 + Br – Br ææÆ CH 3 - Br + HBr
DH° (bromination) = [(–70) + (–87.5)] – [(–104) + (–46)]
= (–157.5) – (–150) = –7.5 kcal/mol
hn
CH 4 + Cl – Cl ææÆ CH 3 - Cl + HCl
DH° (chlorination) = [(–83.5) + (103)] – [(–104) + (–58)]

= (–186.5) – (–162) = – 24.5 kcal/mol
Thus, bromination of methane is less exothermic than chlorination of methane.
16. The H—X bond in hydrogen halides becomes longer and weaker as the
atomic mass of the halogen increases—explain.
Solution A p orbital of halogen overlaps with the s orbital of hydrogen to form the
hydrogen–halogen (H—X) bond in hydrogen halides. For bond formation, fluorine uses
the p orbital that belongs to the second shell of electrons while chlorine uses the p orbital
that belongs to the third shell of electrons. Since the average distance from the nucleus is
greater for an electron in the third shell than for an electron in the second shell, therefore,
the average electron density is less in a 3p orbital than in a 2p orbital. Consequently, the
electron density in the region where the s and p orbitals overlap decreases as the size of
the halogen increases. Thus, the hydrogen–halogen bond becomes longer and weaker as
the atomic mass of the halogen increases.
1. A carbon-carbon bond formed by sp2–sp2 overlap is stronger than the one formed
by sp3–sp3 overlap. Explain.
2. Which atom in the ammonium ion (NH≈4 ) has the least electron density and why?
3. What is the state of hybridization of each of the C, O and N atom in the following
compound?
H3 C C∫∫ C—CH—CH2—O—CH3
C
==
O NH2
4. Predict the geometry around each of the indicated atoms:

O
||
(a) B
≠
H3 (b) H 3N Æ B
≠
H3 (c) CH3 —C—OCH3
≠
! !
(d) H 3 O
!
≠
(e) C (CH 3 )3 (f) N H 4
≠ ≠
(g) H C N (h) (CH 3 )2 N H (i) Et 2 N

@
≠ ≠ ≠
@
(j) CH 3 C H 2CH 3 (k) CH 2 = CH– C H 2
≠ ≠
5. Predict the mentioned bond angles:

(a) C—O—C bond angle in CH3COCH3 (b) F—B—F bond angle in BF4@
(c) C—C—N bond angle in C2H5CN (d) H—N—H bond angle in NH ≈4
!
(e) C—O—H bond angle in CH3CH2OH (f) C—N—C bond angle in (CH 3 )2 N H 2
6. Which of the indicated bonds is shorter and why?
(a) (b) CH 3 CH = CH – C ∫ C - CH 3
≠ ≠
NH2
(c) Cl (d) ≠ (e) CH 3 CH = CH – CH = CH - CH 3
9
≠ ≠ OH ≠ ≠
≠
O
||¨
(f) CH 3 — O — CH 2 — C — CH 3 (g) N—CH2CH2N==CHCH2CH3
≠
≠ ≠
7. Give the state of hybridization of the indicated atoms:

≈ ≈
(a) (CH 3 )2 N H 2 (b) (CH 3 )2 O H (c) B F4@
≠ ≠ ≠
@
(d) CH 3 N O2 (e) H3 N Æ BF3 (f) CH2 == CH — CH2
≠ ≠ ≠
(g) CH3CH == CH — NH2 (h) CH2 == C == CH2

≠ ≠
1.2 ELECTRONEGATIVITY AND BOND POLARITY

Electronegativity is the tendency of an atom to pull the bonding electrons towards itself.
It increases across a row of the periodic table (excluding the noble gases) and it decreases
down a column of the periodic table. The electronegativity values of some common elements
are given in the following table.
A bond with the electrons shared equally between the two atoms, i.e., a bond in which
each electron spends as much time in the vicinity of one atom as in the other, is called
a nonpolar covalent bond. For example, the H—H covalent bond, the Br—Br covalent
bond and the C—C covalent bond in ethane etc. are nonpolar covalent bonds. When two
atoms of different electronegativities form a covalent bond, the electrons are not shared
equally between them. The atom with greater electronegativity draws the electron pair
closer to it. As a result of this unequal distribution of the bonding electrons, the bond
acquires a slight positive charge (indicated by the symbol d+) on the end that has the
less electronegative atom and a slight negative charge (indicated by the symbol d–) on
the other end that has the more electronegative atom, i.e., a polarity developes within a
bond. Such a bond is called a polar covalent bond. An example of a polar covalent bond is
the one in hydrogen fluoride (H—F). The fluorine atom, with its greater electronegativity,
pulls the bonding electrons towards itself. As a consequence, the hydrogen atom becomes
somewhat electron deficient and acquires a partial positive charge (d+) while the fluorine
atom becomes somewhat electron rich and acquires a partial negative charge (d–). So,
the hydrogen fluoride molecule is a dipole (Hd+— Fd–). The direction of bond polarity is
indicated by an arrow, the head of which indicates the negative end of the bond. A short
perpendicular line is drawn near the tail of the arrow to indicate the positive end of the
bond.
The extent of polarity in a covalent bond is expressed quantitatively by the physical

property known as ‘dipole moment’ m, which is, in fact, the product of the magnitude of
charge e on any polar end and the distance d between the centres of positive and negative
charges, i.e., m = e × d.
Dipole moment is expressed in Debye unit (D). The charge e and the distance d are of the
order 10–10 esu and 10–8 cm, respectively. Therefore, m is of the order of 10–10 × 10–8 = 10–18
esu.cm (in C.G.S. system). This value of dipole moment is equal to one Debye unit, i.e.,
1D = 10–18 esu. cm. The SI unit of dipole moment is coulomb-meter (C.m.) and 1 C.m. =
2.9962 × 1029 D.
The value of m for a nonpolar molecule is zero. For example, m = 0D for the molecules like
H2, N2, O2, etc. For polar molecules, m has a definite value, e.g., for HF molecule m = 1.91
D. Polarities of molecules increase with increase in the value of m.
Dipole moment is a vector quantity. The dipole moment of a molecule is the result of the
vector sum of the individual bond moments present in the molecule. When a molecule
is formed by two atoms of different electronegativities (i.e., by two different atoms), the
molecule must possess a dipole moment because there is no question to cancellation of the
moment of this only polar bond. However, when a molecule contains two or more polar
bonds, i.e., when a molecule contains more than two atoms, the molecule may or may not
possess dipole moment and in that case the polarity of the molecule depends on the shape
of the molecule. A symmetrical polyatomic molecule possesses no dipole moment because
the individual dipole moments of the bonds cancel each other. It is to be noted that the
symmetry in calculating dipole moment is not the molecular symmetry. H2O molecule, for
example, has a symmetrical structure because it has two planes of symmetry (su planes).
But, it possesses dipole moment (1.85 D) because of its angular structure .
The value of dipole moment of a molecule is equal to the product of the charge e and the
distance, d, between the positive and negative charge centres, i.e., m = e × d, it can be well
understood by the following examples:
(i) Although an H—F (0.92 Å) molecule is smaller than an H—Cl (1.27 Å molecule, it
has a dipole moment larger than HCl (1.75 D compared to 1.03 D). Since fluorine
(electronegativity: 4.0) is more electronegative than chlorine (electronegativity:
3.0), therefore, the magnitude of e in H—F is much higher than that in H—Cl and
for this reason although d in HF is smaller than in HCl (because of smaller size of
F compared to Cl), the product e × d, i.e., m, is larger.
(ii) Chloromethane (CH3Cl) has a larger dipole moment (1.87 D) than fluoromethane
CH3F (1.81 D), even though fluorine is more electronegative than chlorine. Due to
higher electronegativity of fluorine than chlorine, the separation of charge in the
C—X bond, i.e., the magnitude of e in CH3F, is somewhat higher than that in CH3Cl.
However, the C—F bond is shorter than the C—Cl bond (1.42 Å compared to 1.77
Å) and because of this, the value of the product, i.e., m, is larger for chloromethane
than for fluoromethane.
That the polarity of a molecule depends upon the shape of the molecule can
be well understood by the following example. NH3 possesses considerable dipole
moment and although the N—F bonds are more polar than N—H bonds, NF3 (0.26 D) has
a much smaller dipole moment than NH3 (1.46 D). Both NH3 and NF3 with sp3 hybridized
N atom are pyramidal in shape. The unshared electron pair on nitrogen occupying an sp3
orbital contributes a large dipole moment (because an unshared pair has no other atom
attached to it to partially neutralize its negative charge) in the direction opposite to the
triangular base of the pyramid. In NH3, the net moment resulting from three N—H bond
moments adds to the moment contributed by the unshared pair because they act in the
same direction and for this reason, it has considerable dipole moment. In NF3, on the
other hand, the vectorial sum of these N—F bond moments acts in the direction opposite
to that of the moment caused by the unshared pair. Since these moments are of about the
same size, therefore, NF3 has a much smaller dipole moment than NH3.
Resonance often plays an important role in determining the polarities of

molecules. For example:
(i) The dipole moment of ethylchloride, CH3 CH2Cl (2.05 D), is larger than that of vinyl
chloride, CH2 == CH—Cl (1.44 D). Chlorine is more electronegative than carbon
and so, it attracts the C—Cl bonding electrons more towards itself. As a result,
polarity develops in the C—Cl bond in ethyl chloride and the compound shows
considerable dipole moments. In vinyl chloride, on the other hand, the unshared
electron pair on chlorine becomes involved in resonance interaction with the
p-orbital of the double bond. This resonance interaction, therefore, tends to oppose
the usual displacement of electrons towards chlorine. Also, the sp2 hybridized
carbon being more electronegative than the sp3 hybridized carbon is less willing
to release electrons to chlorine. So, although there is still a net displacement of
electrons towards chlorine, it is less than in ethyl chloride. Hence, ethyl chloride is
more polar than vinyl chloride, i.e., the dipole moment of ethyl chloride is greater
than that of vinyl chloride.
(ii) The dipole moment of chlorobenzene is larger than that of fluorobenzene. In

chlorobenzene, the Cl atom withdraws electrons from the ring by its –I effect
and donates electrons to the ring by its +R effect. Because of large size and high
electronegativtiy of chlorine as compared to that of carbon, the resonance electron
donation is much weaker than inductive electron withdrawal. So, the moment
caused by the –I effect is much stronger than the moment caused by the +R effect
and because of this, chlorobenzene possesses a net dipole moment which is relatively
high. In fluorobenzene, on the other hand, the +R effect fluorine even being more
electronegative than chlorine is much more important because of effective p orbital
overlap between the orbitals of carbon and fluorine which are of comparable size.
So, the moment due to inductive electron withdrawal is predominantly balanced
by the moment due to resonance electron donation and the result is that the dipole
moment of fluorobenzene is relatively low.
Aromaticity often plays a role in determining the polarity of a molecule. For

example:
(i) Azulene (a bicyclic hydrocarbon) has a much higher dipole moment. Azulene
contains 10 p-electrons. Redistribution of these electrons between the two rings
generates an aromatic system which consists of an aromatic cycloheptatrienyl
cation and an aromatic cyclopentadienyl anion. Since this aromatic dipolar form is
quite stable and more contributing, azulene has a much higher dipole moment.
(ii) Pyrrole and furan are polar molecules, but the dipole moment of furan is smaller
than and opposite in direction from that of pyrrole. In pyrrole, the unshared
electron pair on nitrogen is highly delocalized with the p-electrons of the ring
for maintaining aromaticily, i.e., to form a delocalized cyclic system of (4n + 2)p
electrons, where n = 1. Since the moment caused by the electron delocalization is
much greater than that caused by the –I effect of nitrogen atom, pyrrole has a net
dipole momemt of 1.81 D and the dipole points towards the ring. In furan, on the
other hand, the unshared electron pair on oxygen is not well delocalized into the
ring due to greater electronegativity of oxygen. Hence, the moment due to electron
delocalization is small and in fact, it is somewhat smaller than that caused by the
–I effect of oxygen. For this reason, the net dipole moment of furan is relatively
small (0.70 D) and the dipole points towards oxygen.
Formation of charge-transfer complex is often responsible for exhibiting dipole

moment by some molecules. 1,3,5-Trinitrobenzene, for example, shows significant
dipole moment in benzene but does not display dipole moment in carbon tetrachloride.
1,3,5-Trinitrobenzene being symmetrical possesses no net dipole moment, i.e., it is a
nonpolar molecule. When it dissolves in benzene, a charge-transfer bonding involving
some kind of donor–acceptor interaction (benzene is the electron donor and the electron
deficient 1,3,5-trinitrobenzene is the electron acceptor) is formed. Due to charge separation
in the resulting complex, the compound shows significant dipole moment in benzene. Since
carbon tetrachloride cannot act as a donor molecule, the compound does not display dipole
moment in carbon tetrachloride.
Conformation plays an important role in determining the polarities of some

molecules. For example:
(i) 1,2-Dichloroethane has a very little dipole moments, where as 1,2-ethanediol
has considersable dipole moment. 1,2-Dichloroethane exists in anti and gauche
staggered form. Since the two C—Cl dipoles in the anti form are antiparallel, its
dipole moment is assumed to be zero. However, the value of dipole moment of the
gauche form is approximately 3.2 D (calculated with reference to C2H5Cl). Because
of dipolar and steric repulsion, the gauche form is less stable than the anti form
by 1.2 kcal/mol and in the vapour phase the compound exists in 88% anti and 12%
gauche form. Because of such distribution of the conformers, the overall dipole
moment of 1,2-dichloroethane is relatively low (1.2 D).
In the gauche conformer of 1,2-ethanediol (ethylene glycol), the two —OH groups
become involved in the formation of intramolecular hydrogen bond. However, in the
anti conformer, no intramolecular hydrogen bond is formed because the two —OH
groups are oppositely placed. The steric and polar repulsion of the hydroxyl groups
in the gauche form is more than outweighed by the energy gained by the formation
of hydrogen bond (5 kcal/mol). Because of this, the compound, particularly in the
gas phase, exists almost exclusively in the gauche form having a finite dipole
moment. For such conformational distribution, 1,2-ethanediol is found to possess
considerable dipole moment.
(ii) The optically inactive (meso) form of 1,2-dichloro-1,2-di-p-tolylethane has a dipole

moment lower than that of the active (d or l) form. The meso form of the compound
exists in the following three conformations:
In the conformer I, bulky tolyl groups are anti to each other and also the two
Cl atoms are anti to each other. So there is no steric interaction caused by the
tolyl groups and repulsive interaction caused by the C—Cl dipoles. Therefore, this
conformer is relatively more stable and it has practically no dipole moment. The
conformers II and III are polar because the two Cl atoms are gauche to each other.
However, these are very unstable because the bulky p-tolyl groups which are
gauch to each other are involved in steric interaction and there occurs repulsive
interaction between the two C—Cl dipoles. Therefore, the most favoured conformer
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Title: Alakuloinen meri

Runoja
Author: Anna Kaari
Release date: January 1, 2024 [eBook #72579]
Language: Finnish
Original publication: Helsinki: WSOY, 1928
Credits: Tuula Temonen
*** START OF THE PROJECT GUTENBERG EBOOK

ALAKULOINEN MERI ***
ALAKULOINEN MERI
Runoja
Kirj.
Anna Kaari [Kaarina Höglund]
Porvoossa, Werner Söderström Osakeyhtiö, 1928.

SISÄLLYS:
KEVÄTYÖ
Kevätyö
Alakuloinen meri
Kaipaus
Meri yöllä
Onnellinen aamu
POLKU
Polku
Laulu sinulle
Maja
Kirje
Jää hyvästi, hyvää yötä
Alakuloinen päivä
Varjolaulu
Murhe
MUSTA TAUTI
Wen-Kiyn'in valitus
Kuin kuolinpaarien lakanat
Musta tauti
Pimeä meri
Ystäville
Kuollut sydän
Sa liian myöhään tulit takaisin
SYVYYDESTÄ
Laiva
Kaupunki
Ilta
Syyssade
Kauhu
Kuutamo kaupungissa
Syvyydestä
AAMU
Lumisade
Akvarelli
Uusi kevät
Aamu
Keväthurmio
Uudestisyntyminen
Pieni laulu
Onnellinen rakkaus
Yö niityllä
VALKEA HÄMÄRÄ
Äiti
Rannalla
Ota mun kädestäni kiinni
Sisarelle
Ametisti
Valkea hämärä
KEVÄTYÖ
KEVÄTYÖ
Meren yllä on pimeät, raskaat varjot: pilvien varjot.

Ranta on paennut viileään, siniseen sumuun.
Laiva on nostanut purjeet yöhön
ja liukuu etenemättä —
Jostakin läikkyy äkkiä valoa veteen,

outoa, kirkasta valoa.
Meri liikkuu aalloitta yössä.
Meri on ihana maailma ääriä vailla.
Valo on sammunut.
Purjeet ovat sulaneet pilvien varjoon.
Varjo on hajonnut pimeään mereen.
Kaikki on yhtä.
Yössä on ainoa kuuluva ääni:

— Salaisiin kiviin särkyvä vesi.
ALAKULOINEN MERI
Oot harmaa, aalloin väsynein sa tumman pilven alla hiljaa

vaellat!
Mun, ihmisen, on hyvä levätä sun rannallas, kun viilee tuuli

unhoituksen levon lupaa.
Oot harmaa, kaiken elämän, sen murheen, epätoivon

pyyhkii aaltos pois.
Ja rannoiltas ja minut, ihmisen, kun hiljaa vaellat sa

tumman pilven alla aalloin väsynein.
KAIPAUS
On kaipaus vienyt linnun rannalta ulapan tuuleen viileään.

Ovat tomuinen maa ja ranta kaukana häipyneet meren
hämärään.
On linnun sydäntä syönyt ikävä

ulapan lintujen vapauteen,
missä punaiset karit nousevat merestä
satoine lokkien pesineen.
On kaipaus vienyt linnun rannalta ulapan aamuun

valkeaan, missä auringon noustessa merestä kirkkaana
unohtaa tomuisen, kuuman maan —
MERI YÖLLÄ
Meri yöllä on kuultavan kirkas, sen vesi on valkoinen, ja

lokkien kaartuvat siivet ei varjosta pintaa sen.
On tiirojen kirkkaus jäänyt

myös rannoille kuolemaan.
Vain kaukaista kohinaa kuuluu:
meri puhelee unissaan,
ja huo'aten joskus syvään se mainingin kohottaa, mi

aaveena edeten liukuu veden pintaa valkeaa.
Nyt ylitse yöllisen meren, veden vaiheilla valkean käy

kutsuva kuiskaus hiljaa meren lempeän jumalan.
ONNELLINEN AAMU
Miten onnelliseen aamuun meren saarella herätä voi! Kuin

vihreään kylpyyn kutsuin meren aallot rannalla soi.
Ja lokkien helminauhaan
on tiirat yhtyneet.
Ne ensimmäisinä meressä
on aamulla kylpeneet.
Meren onnelliseen aamuun kun vielä herätä vois! Meren

vedessä viheriässä surut sairaat huuhtoa pois.
POLKU
POLKU
Sinä kuljet monia, leveitä teitä.

Joka tie vie jonkun ystävän luo.
Eräs kovin kapea, hämärä polku
sinut minun luokseni joskus tuo.
Eräs niityn ruohoon hukkuva polku,

jota tiellä kulkijat eivät nää,
joka sinulta myöskin helposti unhoon
kovin pitkiksi ajoiksi usein jää.
Sinä kuljet monia, leveitä teitä.

Minä turhaan polulla odotan.
Minä pelkään, rakkahin, huomaamatta
polun kokonaan umpeen ruohottuvan.
LAULU SINULLE
Sua päivät iltaan aattelen, kun hiljaa askaroin. Viel' läpi illan
hämärän sun silmäs nähdä voin.
Sa vaikka kuljet kaukana,

olet aina vierelläin.
Kuin tuvan lämmin hämärä
sa kierrät sydäntäin.
Sa olet öinen hiljaisuus,

mi tupaa vartioi,
Sun kuiskaukses unihin
kuin huilun ääni soi.
Sua yöt ja päivät aattelen, sa olet elämäin. Sa vaikka kuljet

kaukana, olet aina vierelläin.
MAJA
Ma sydämestäni nyt majan teen

ja vien sen erämaahan kaukaiseen.
Sen kynnyspuulla istun odottain.

Tuo kaipuu kerran sinut majahain.
Ja takkatulta sulle iltaisin

ma vaalin onnellisin unelmin.
Sa tulet kerran, silmiis suutelen

ma silloin unet syväin metsien
ja vuorten etäisinä siintäväin

ja havun tuoksun, kukkain himmeäin.
Ma oman ikäväni suutelen

ja rakkauden suuren, avoimen
ja yksinkertaisen kuin erämaa,

mi etees rannatonna aukeaa.
KIRJE
Niin pitkän kirjeen kirjoitin

kuin oli ikäväin,
ja ajatuksin kuumeisin
ma odottamaan jäin.
Sa vihdoin muistat kirjoittaa:

Saan kirjeen ohuen.
Sen sanat mua viluttaa
kuin päivä tuulinen
tai linnun huuto suolta päin tai ruutu ikkunan, min jäisen
lasin ääreen jäin ma kädet helmahan.
JÄÄ HYVÄSTI, HYVÄÄ YÖTÄ
Jää hyvästi, hyvää yötä,

ma nukun sulta pois
ja väliltämme kaikki
kuin unhoitettu ois.
Jää hyvästi, hyvää yötä.

On monen käynyt niin.
Tie huipuilta vie aina
alas kuilun syvyyksiin.
Jää hyvästi, hyvää yötä.

Sua vielä suutelen —
Ja nukun pois, mut koskaan
ma aamuun herää en.
ALAKULOINEN PÄIVÄ
On järvi kellanharmaa, ja mustat pilvet kulkemaan jo ovat

väsyneet. Ne riippuu järven yllä kuin kummalliset varjot vaan
tai siivet väsyneet.
Ma askelteni ääntä
kuin joka hetki vavahdan
ja käännyn katsomaan.
Vain jalkojeni alla
ma taitoin kaislan ruskean.
Jään sitä katsomaan —
Niin alakuloisena ma rantaa pitkin kävelen ja jotain ikävöin

— Kuin mustat pilvet raskas on yksinäisyys päivien. — Pois
täältä ikävöin.
VARJOLAULU
Jäät valon lämpöön niinkuin lintu jää, kun varjossa jo viileyttä

on, ja enää varjon pimentoon ei nää sun silmäs, huikaisemat
auringon.
Vain kuumaan valoon yli maisemain

ne tuijottavat kauas, ohi mun.
Oon varjossa ma pieni kasvi vain,
ja silmäis valosta ma huikaistun.
Jäät kauas valoon, minä varjoon jään, ja lehdet sulkee

minut pimentoon. Ma kylmään heinään painan raskaan pään,
sa lennät niinkuin lintu aurinkoon.

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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)

2. Draw the structure of a hydrocarbon which contains:

(a) (b) (c)

3. Which orbitals are used to form each bond in methylamine, CH 3 NH 2?

(f) But-1, 2, 3-triene:

9. Which atoms in each of the following molecules always remain in the

(c) CH3—C—H and H—CH2OH

15. “Bromination of methane is less exothermic than that of chlorination” —

DH° (chlorination) = [(–83.5) + (103)] – [(–104) + (–58)]

4. Predict the geometry around each of the indicated atoms:

(g) H C N (h) (CH 3 )2 N H (i) Et 2 N

5. Predict the mentioned bond angles:

6. Which of the indicated bonds is shorter and why?

7. Give the state of hybridization of the indicated atoms:

(g) CH3CH == CH — NH2 (h) CH2 == C == CH2

1.2 ELECTRONEGATIVITY AND BOND POLARITY

The extent of polarity in a covalent bond is expressed quantitatively by the physical

But, it possesses dipole moment (1.85 D) because of its angular structure .

Resonance often plays an important role in determining the polarities of

(ii) The dipole moment of chlorobenzene is larger than that of ﬂuorobenzene. In