Asim Kumar Das - Fundamentals of Inorganic Chemistry - Volume 2

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Fundamental Concepts of
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Revised Second Edition
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Second eBook Edition: 2019
Fundamental Concepts of
Inorganic
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Printed at Goyal Offset Printers, GT Karnal Road, Industrial Area, Delhi, India
Patna
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Dr. A.V. Saha, DSc
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Head of the Department of Chemistry
Ramakrishna Mission Residential College
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P.O. Narendrapur 743508, 24-Parganas (8)
West Bengal, India
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Foreword
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Present-day inorganic chemistry is no more a collection of unrelated facts. The scenario has undergone
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a drastic change over the last fifteen to twenty years with the applicati.on of kinetic, thermodynamic and
. structural studies to inorganic substances and with newer techniques providing newer information.
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Often the information gathered, has made theoreticians develop/modify valency theories and'principles.
In this situation every teacher and student realise the importance of a textbook that will" help them
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develop the concepts and understanding ofthe subJect. There are attempts by a few authors at achieving
this goal but those seldom cover the whole curricula followed by most of the Indian Universities and
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Institutes. In many of these books the authors virtually neglect ,the evolutionary developments of the
subject, creating undesirable lacunae in the readers' understanding. Here is an honest and sincere attempt
at bridging these gaps and presenting a comprehensive textbook on concepts and understanding to the
readers. The treatment of every topic is elaborate and is marked by remarkable clarity and the author
has not compromised herewith the volume of his work. The book Fundamental Concepts ofInorganic
Chemistry covers the inorganic chemistry curricula at the BSc (honours) arid MSc preliminaries.
A large number of exercises and problems essential.for modem teaching, have been incorporated
meticulously at the end of each chapter to bridge the gaps, if any, in the understanding of the subject.
Hope this earnest effort of Dr. Das, a teacher of distinction, will receive well-deserved acclaim from
the students and teachers of this subject.
A.V. Saha
To
My Teachers and Well-Wishers
Who Paved the Way
to Reach Here
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~~~
One who has shraddha acquires knowledge
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Preface to the Second Edition
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I do endeavour. He gives the strength and patience.
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My beloved readers are requested first to accept my unconditional apology for this long time taken to
shape the second edition of the book. Though the second edition incorporates some aspects of
coordination chemistry, the readers desire the complete Coordination Chemistry which is expected to
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appear in the next volumes and the process is in progress.

I feel delighted to record the warm· response which the first edition of the book has received from
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the students and teachers throughout the country. I have tried my best to incorporate all the suggestions
received from the readers. The present edition has been thoroughly revised and substantially enlarged
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and, in fact, no single page has been left untouched. However, I have taken all the measures to retain
the features for which the first edition has been so popular.
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In this second edition of the book, scope of the book has been broadened by adding new topics and
revisions of the earlier sections. The new topics are atomic units; NMR active nuclei and principles of
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NMR spectroscopy;' nucleosynthesis of elements after big bang; nuclear waste management; Bose-
Einstein condensate (BEC): fifth state of matter; bonding properties of d- and.forbitals: comparison;
application of Woodward-Hoffmann orbital symmetry rules; structure and properties of fluoroalkyl
radicals and ions; structure and properties of zeolites and clay materials; aluminosilicates and surface
acids; heteropoly and isopoly acid anions; hypervalency; molecular orbital diagrams of polyatomic
molecules in terms of group orbitals (Le. TASOs); 3c-4e versus 3c-2e bonding systems; geometry of
the ~olecules in terms of Walsh diagrams; isolobal fragments; reaction-mechanism of the main group
elements; different aspects ofmaterial science; PSPET- Wade's rule, Jemmi's rule; chemistry ofboranes
and carboranes; metal clusters and carbonyl clusters; Zintle ions; symmetry elements and point groups;
fullerenes; intercalation compounds ofgraphite; band theory ofsolids - band splitting and band bending;
electrical and magnetic properties of solids; piezoelectric solids; organic metals and organic semi-
conductors; superconductivity; supramolecular chemistry; aqueous chemistry of amino acids; surface
viii Fundamental Concepts of Inorganic Chemistry
In this second edition of the book, scope of the book has been broadened by adding new topics and
revisions of the earlier sections. The new topics are atomic units; NMR active nuclei and principles of
NMR spectroscopy; nucleosynthesis of elements after big bang; nuclear waste management; Bose-
Einstein condensate (BEe): fifth state of matter; bonding properties of d- andforbitals: comparison;
application of Woodward-Hoffmann orbital symmetry rules; structure and prop~rties of fluoroalkyl
radicals and ions; structure and properties of zeolites and clay materials; aluminosilicates and surface
acids; heteropoly and isopoly acid anions; hypervalency; molecular orbital diagrams of polyatomic
r,lolecules in terms of group orbitals (i.e.·TASOs); 3c-4e versus 3c-2ebonding systems; geometry of
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the molecules in terms of Walsh diagrams; isolobal fragments; reaction-mechanism ofthe'main group
elements; different aspects ofmaterial science; PSPET- Wade's rule, Jemmi's rule; chemistry ofboranes
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and carboranes; metal clusters and carbonyl clusters; Zintle ions; symmetry elements and point groups;
fullerenes; in~rcalation compounds ofgraphitt;; band theory ofsolidS - band splitting and band bending;
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electrical and magnetic properties of solids; piezoelectric solids; organic metals and organic semi-
conductors; superconductivity; supramolecular chemistry; aqueous chemistry of amino acids; surface
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acids and solid acids; agostic interaction; ionic equilibria and related numerical problems; inorganic
photochemistry; lithium battery; fuel cells; solar cells; EMF diagrams - Frost diagram, Pourbaix diagram;
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Tafel equation; stability field of water; chemistry of explosives; electroanalytical techniques-
polarography, coulometry, ampereometry, LSV, CV, polarography; chemical clock reactions and oscilla-
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ting chemical reactions.
In preparing the revised manuscript, I have freely consulted the books and reviews of different
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authors and I have borrowed their ideas whenever it has been required. I am extremely grateful and
indebted to these authors. In fact, I have picked up the flowers from these gardens to prepare the
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garland to worship the goddess of learning.

The golden period of my s.tudent life at Ramakrishna Mission Residential College, Narendrapur,
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gives the foundation of my career. There I got a gifted teacher, Prof. AV Saha whose teaching in the
subject is still remaining vibrant in my memory and his teaching is reflected at many places of this
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book.
The author is thankful to Prof. KL Sebastian, IPC, IISc, Bangalore; Prof. S Basu, Burdwan University;
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Prof. ON Mukherjee, Sir Rashbehari Qhose, Professor of Chemistry; Dr A Sen, Ramakrishna Mission
. Centenary College, Rahara, 24 Parganas; Dr MN Bishnu, City College, Kolkata; Prof. RN Mukherjee,
lIT, Kanpur; Dr SP Banerjee, Retired Professor, Vivekananda Mahavidyalaya, Burdwan; Dr S Roy
Chowdhury, Dinabandhu Andrews College, Garia, Kolkata; Prof. K Dey, Kalyani University; Prof. A
Sarkar, Kalyani University; Dr. G Mukherjee, Kalna ,College, Burdwan; Dr N Koley, Retired Professor,
Raghunathpur College, Purulia; Prof. B Pathak, Retired Professor, Presidency College, Kolkata; Dr B
Saha, Burdwan University; Dr H Karak, St Paul's College, Kolkata, for their encouragement and suggestion.
I am thankful to all my colleagues for extending their moral support. J am specially thankful to my
colleague Dr M Seikh for discussion on many topics and procuring some reference materials.
I am extremely grateful to Mr SK Jain, Managing Director, CBS Publishers and Distributors,
New Delhi for his continued support. I am also thankful to Mr YN Arjuna, Senior Director (Publishing,
Editorial and Publicity) and the staff involved in DTP for taking the troubles in processing the revised
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Preface to the First Edition
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- "No great work can be achieved by humbug. It is through love, a passion for truth; and
tremendous energy, that all undertakings are accomplished. "
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- "I hold every man a traitor who, having been educated at their expense pay not the least
heed to them. "
m Swami Vivekananda
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As a student and also as a teacher, the author has experienced that for a systematic and comprehensive
coverage ofthe present subject, one is forced to consult various books on different disciplines to collect
the reading materials. Consequently, the students are specially constrained. Keeping this idea in mind,
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it has been attempted here to present a complete textbook on the subject. In a logical sequence, the
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book deals extensively with different aspects such as atomic structure (both classical and wave
mechanical) and atomic spectra, fundamentals of quantum mechanics and wave mechanics, nuclear
chemistry and radiation chemistry, different theories of valence forces and chemical forces including
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band and Bloch theory of solids, solid-state chemistry, acids and bases, nonaqueous. solvents and redox
potentials. It also covers the different aspects of materials science which is emerging with a great
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promise. Thus the present book covers the curricula followed by most of the Indian Universities and
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Institutes at the BSc and MSc levels. It also aims to help the students preparing for competitive
examinations like NET, GATE, SLET, etc. Adequate stress on the basic theories and concepts has
been given everywhere to rationalise the pre.sentation. The ideas have been very often illustrated through
solution of related numerical problems. Each chapter is ended with various types of questions and
problems to afford an opportunity to th~ students for self-evaluation.
In writing a book of this nature, one accumulates indebtedness to the previous authors of different
books. The books which have been c0!1sulted are listed separately and gratefully acknowledged.
The author expresses his deep sense of gratitude to Dr AV Saha, a gifted teacher, from whom the
author had started to learn and understand the subject in his student life in Ramakrishna Mission
Residential College, Narendrapur, for writing the foreword. The author's association for a fairly long
period with the said Institute was highly fruitful. in shaping the present ideas and the author must
express his indebtedness to his teachers and the authorities of the Institute. The author. is grateful to his
wife, Dr M Das for various types of help, assistance and cooperation.
x Fundamental Concepts of Inorganic Chemistry
The author is specially grat~ful to Mr SK Jain, Managing Director ofCBS Publishers and Distributors,
New Delhi for his earnest interest in publishing the book. Thanks are also due to his colleagues and
students.
In conclusion, the author's attempt will be amply rewarded, ifit is found helpful to the students and
teachers. In spite ofall precautions, some errors might have crept in. Constructive criticism and valuable
suggestions from the readers will be most welcome.
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Asim K. Das
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Contents
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Foreword m v
Preface to the Second Edition vii
Preface to the First Edition ix
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VOLUME 2
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9. Introduction to Chemical Bonding and Theories of Covalence:

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Valence Bond Theory (VBT) and Molecular Orbital Theory

(MOT) 542-752
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9.1 Historical Background 542

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Development of the Concept of Valency; Lewis-Langmuir Concept; The Octet Rule;

Sugden's View of Singlet Linkage (2c-Ie) in Favour of Octet Rule; Sidgwick's Rule of
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Maximum Covalency; Hypervalence and Hypercarbon Compounds; The Main Types of

Chemical Forces; Isosteric or Isoelectronic Species
9.2 The Theories of Covalent Bond : Born-Oppenheimer Approximation 550
9.3 The Valence Bond Theory (VBT) 551
The Valence Bond Theory for Hydrogen Molecule; The Major Conclusions Drawn from
VBT; The Major Drawbacks in VBT
9.4 Molecular Orbital Theory (MOT) 557
The LCAO-MO Treatment of Diatomic Hydrogen Molecule Ion (H;); The LCAD-MO
Treatment of the Diatomic Hydrogen Molecule: A Two Electron-Two Centre (2e-2c)
System; Comparison of VB and LCAD-MD Treatments on H2; The Important Aspects
of LCAD-MOT; Proof of Three Basic Conditions (EOS) in LCAD-MO Method
9.5 Symmetry and Overlap in Forming Molecular Orbitals in LCAO method 570
xii Fundamental Concepts of Inorganic Chemistry
9.6 Sigma (0)-, Pi (x)- and Delta (~)-Molecular Orbitals, Phi (+) and Mu (1) Bonds 574
9.7 VBT versus LCAO-MOT 575
9.8 The United Atom Method in Molecular Orbital Theory 576
9.9 Simple Molecular Orbital Model for Homonuclear Diatomic Molecules 578
Simple Molecular Orbitals and Diagrams; Molecular Orbital Picture of Some
Representative Homonuclear Diatomic Molecular Species; Limitations of the Simple
Molecular Orbital Model; Simple Molecular Orbital Diagram for the Homonuclear
Diatomic Molecules Involving (n-l)d Orbitals 1
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9.10 Modified Molecular Orbital Energy Diagram for the Homonuclear Diatomic
Molecules (Specially for N 2 and Lighter Molecules) 589
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Symmetry Interaction (Noncrossing Rule) among the Molecular Orbitals Obtained in the
Simple Model; Molecular Orbital Energy Diagram by Considering the Participation of
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Hybrid (s-p interaction) Atomic Orbitals in Generating the Molecular Orbitals; Success
of the Modified MO Energy Diagram : Reactivity of Some Molecular Species
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9.11 Molecular Orbital Picture in Heteronuclear Diatomic Molecules: UV
Photoelectron Spectroscopy and Photosensitivity in the Light of MOT 601
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Molecules (Le. XH) Containing a H-atom; Molecules (XY) in which both the Atoms
(X, Y) Contain s- and p-Valence Orbitals; Ultraviolet Photoelectron Spectroscopy
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(UV-PES): Identification of the Nature of Molecular Orbital Energy Level; Colours and
Photosensitivity of the Compounds in Terms of MOT
9.12 Molecular Orbital Treatment of Triatomic Molecules 620
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Basic Concepts of Group Orbitals; Delocalised and Localised Molecular Orbitals;

Molecular Orbital Treatment for H) and H; Molecular Species; Molecular Orbital
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Treatment for Linear HydridesXH2 Having Valence Electrons Four; Molecular Orbital
Treatment for Bent Hydrides XH2 Having Valence Electrons More Than Four;
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Illustration of Walsh Diagram for XH2 Species; Molecular Orbital Energy Diagram of
Some Representative Triatomic Hydrides in Terms of Hybridisation of the Central Atom;
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Triatomic Nonhydrides (XY2)-Linear Species Having 16 Valence Electrons; Molecular

Orbital Energy Diagram for Some Representative Linear Molecules like CO2 and BeX2
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- Use of Hybridised Orbitals by the Central Atom; Molecular Orbital Picture of the
Bent Molecule XY2 (X and Y Second Period Elements); Molecular Orbital Energy
Diagram for the Trigonal Planar Molecular Species -XY); Molecular Orbital Energy
Diagram of Some Representative Polyatomic Species; Characteristics of Three Centre
Bonding
9.13 Hybridisation of Atomic Orbitals 669
Linear Combination of Atomic Orbitals in Hybridisation; Stereochemistry of the Hybrid
Orbitals; Bonding Potentiality of the Hybrid Orbitals; Energetics of Hybridisation;
Participation of d-Orbitals in Hybridisation in Nonmetals; Equivalence and
Nonequivalence of the Hybrid Orbitals; Bent's Rule of Hybridisation
9.14 Summary of the Concept of Hybridisation 699
9.15 Conjugated Molecules and Delocalisation Energy 699
9.16 Resonance and Delocalisation 70S
Contents xiii
Concept of Resonance in VBT; Resonance Energy; Conditions for Effective Canonical

Forms; Concepts ofFonnal Charge and Lewis-Langmuir Charge in Resonating Structures:
Fonnal Charge and Oxidation Number; Resonance in the Light of Molecular Orbital
Theory; Application of the Concept of Resonance in Some Inorganic Compounds
9.17 Limitations of the' Concept of Resonance;and Hybridisation 716
9.18 Multiple Bonds 717
Bond Length and Bond Multiplicity; Prc-P rc Bonding
9.19 Delta and Quadruple Bond 720
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9.20 Odd Electron Covalent Bonds in Odd Electron Molecules 723
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9.21 Electron Deficient Covalent Bonds and Electron Deficient Covalent Compounds 725
9.22 Molecular Orbital Theory in Explaining Higher Oxidation States of Nonmetals 734
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9.23 Molecular Orbital Theory in Explaining the Bonding in Inert Gas Compounds:
3c-4e Bonding Model 735
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9.24 Isolobal Fragments m 739
Exercise-IX 742
Appendix 9A: FMO Approach to Woodward-Hoffmann Orbital Symmetry Rule
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for Intramolecular Cyclisation and Concerted Intermolecular Cycloaddition
Reactions 748
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10. Covalent Compounds: Characteristics, Structure and

Reactivity 753-976
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10.1 B~nd Energy 753

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Bond Energy in the Diatomic Molecules; Thennodynamics ofBond Energy in the Diatomic
Molecules; Average Bond Energy in Polyatomic Molecules; Thermochemistry in
Computing Bond Energies; Bond Energies of Different Bonds; Intrinsic Bond Energy;
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Different Factors Governing the Bond Energy

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10.2 Covalent Bond Lengths and Covalent Radii 764

Single Bond and Covalent Radii; Multiple Borid and Covalent Radii; Different Factors
Governing the Bond Lengths
10.3 The Inert Pair Effect 770
Meaning and Illustration of the Inert Pair Effect; Interpretation of Inert Pair Effect in
Tenns of Bond Weakening Phenomena for the Heavier Congeners
10.4 Covalent-Ionic Resonance: Partial Ionic Character in Covalent Bonds 774
10.5 Dipole Moment and Molecular Polarity 777
Different Contributing Factors to the Molecular Polarity; Prediction of Geometry of the
Molecules from Dipole Mo~ent and Calculation of Dipole Moment; Dipolar Repulsive
Interaction; Contribution of Hybrid Lone Pair Moments to the Molecular Polarity; Induced
Dipole Moments; Application of the Concept of Dipole Moments
10.6 Covalency in Ionic Bonds: Deformation or Polarisation of Ions: Fajans' Rules 791,
Polarisation and Covalency; Factors Governing the Degree of Polarisation; Fajan's Rules
xiv Fundamental Concepts of Inorganic Chemistry
in Predicting the Melting and Boiling Points and Solubility of Some Compounds;
Application of the Concept of Polarisation
10.7 Effects of x-Bonding (with Special Reference to the Involvement of d-Orbitals) on
the Structural Properties and Reactivity 802
Comparison ofCa~bon and Silicon Compounds; Comparison ofNitrogen and Phosphorus
Compounds; Comparison of Oxygen and Sulfur Compounds; Pi-Boding in Boron
Compounds; Effect of Pre ~ dre Bonding on the Properties of Different Oxyacids and
Periodic Variation of Properties ofOxyacids;Pre-dre Bonding Leading to Aromaticity in
Inorganic Ring Compounds; Changes in Structure due to Electronegative Substituents;
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Synergistic Effect due to the 1t-Bonding and Stabilisation of Low Oxidation States of
Metals in Complexes; 1t-Bonding in Soft-Soft Interactions; 1t-Bonding and trans-Influence,
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trans-Effect in Kinetics; 1t-Bonding and cis-Effect in Kinetics; 1t-Bonding and Isomerism
in Coordination Compounds
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10.8 Structure of Covalent Molecules: Molecular Topologies 824
Helferich's Rule; Concept of Hybridisation and Bent's Rule; Sidgwick-Powell Theory
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and Valence Shell Electron Pair Repulsion (VSEPR) Theory; Shape of the Molecules
Having Stereochemically Active Lone Pairs Predicted from VSEPR Theory; Concept of
Stereochemically Active and Inactive Lone Pairs; Structure of XeF6 and Related Species;
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Limitations of VSEPR theory
Molecul~s
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10.9 Stereochemically Nonrigid Covalent Molecules: Fluxional 848
Atomic Inversion in Amines, Phosphines and Arsines; Berry Pseudorotation and Turnstile
Rotation; Twisting Mechanism; Fluxional Molecule : Fluxionality and Time Scale of
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Observation; 19F-NMR Spectra and Fluxionality of PCI2F] .and CIF]; Examples of

Fluxional Molecules
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10.10 Nucleophilic Substitution Reactions (e.g. Solvolysis) in Some Covalent Molecules of

Nonmetals 861
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Thermodynamic and Kinetic Aspects of Chemical Reactions; Reaction Pathways of

Nucleophilic Substitution Reaction; Energetics of A and D Processes; Some Representative
Nucleophilic Substitution Reactions in Covalent Compounds ofp-Block Elements; Some
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Representative Redox Reactions through Nucleophilic Substitution Reactions

10.11 Structure of Covalent and Molecular Crystalline Solids 884
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Diamond Cubic (dc) Structure; Graphite Structure; Properties of Graphite; Lamellar or

Intercalation Compounds ofGraphite; Reactivity of Graphite; Band Structure of Graphite;
Comparison Between Graphite and Inorganic Graphite (Le. Boron Nitride); Molecular
Crystals; Buckministerfullerene; Carbon Clusters and Allotropic Forms of Carbon
10.12 Structure and Bonding in Higher Boranes and Carboranes 896
Classification and Different Series of Boranes; Nomenclature of Boranes; Structure and
Molecular Framework of Hydrides of Boron; Skeletal Electron Pair Counting and Wade's
Rules : Polyhedral Skeletal Electron Pair Theory (PSEPT); Calculation of the Number
of Electron Deficient Bonds; stxy Numbers and Topology of Boron Hydrides; Molecular
Orbital Picture of Higher Boranes; Carboranes and their Structural Features; Calculation
of Skeletal Electron Pairs (S) in Carboranes; Jemmis' Unifying Electron Counting Rule
for Condensed Polyhedral Boranes
10.13 Synthesis and Reactivity of Boranes and Carboranes 917
Synthesis of Boranes; Reactivity of Boranes; Synthesis and Reactivity of Carboranes
Contents xv
10.14 Molecular Symmetry and Point Groups 931

Introduction; Symmetry Elements and Symmetry Operations; n-Fold Rotation Axis (i.e.
n-Fold Proper Axis of Rotation) (Cn ) and Rotation About a Symmetry Axis; Plane of
Symmetry (i.e. Mirror Plane) arid Reflection at the Plane of Symmetry; Inversion Centre
(Le. Centre of Symmetry) and Reflection Through the Inversion Centre; n-Fold Rotation-
Reflection Axis and Rotation-Reflection (in either order); Identity Element (E or I); Point
Groups and Identification of Point Groups; Special Point Groups with Multiple High-
order Axes (more than one Cn' n > 2); Steps to Select a Point Group (excluding the
special point groups with multiple high' order axes); Symmetry Elements and Optical
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Activity; Symmetry Elements and Dipole Moment; Symmetry Number and Point Groups
Exercise-X 962
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Appendix lOA: Fluoroalkyl Radicals and Carbocations and Fluorocarbenes 972
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11. Structure, Bonding and Properties of Ionic Solids and
Solid-State Chemistry 977-1109
11.1 Characteristic Properties of Ionic Compounds
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11.2 Different Types of Ions and Electronic Configurations of the Ions Involved in
Ionic Bonding 980
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11.3 Electron Density (ED) Maps and Ionic Radii 982
Ionic Radii from X-Ray Electron Density·, Maps; Ionic Radii from Other Methods;
lc
Shannon's Crystal Radii; Comparison among Shannon's Crystal radii, Goldschmidt's Radii
and Pauling's Radii
ea
11.4 Factors Affecting the Ionic Radii 989

11.5 Energetics of Ionic Bond Formation: Born-Haber Cycle 994
th
Born-Haber Cycle in Ionic Bond Fonnation; Drawbacks in the Concept of Born-Haber

Cycle; Factors Favouring the Formation of Ionic Bonds
e/
11.6 Applications of Born-Haber Cycle 997

t.m
11.7 Theoretical Aspects of Crystal Forces: Lattice Energy of Ionic Crystals 1003
Born-Lande Equation of Lattice Energy; Verification of the Born-Lande Equation;
Modification of the Born-Lande Equation; Kapustinskii Equation; Factors Affecting the
Lattice Energy; Hardness of Ionic Compounds
11.8 Radius Ratio Rule and Preferred Structures of Ionic Compounds 1014
Limiting Radius Ratios for Some Common Geometries; Application of the Radius Ratio
Rule; Limitations of the Radius Ratio Rule
11.9 Some Basic Crystal Geometries (i.e. Unit Cells) Involved in the Structure of
Crystalline Solids 1024
Simple Cubic (se) Unit Cell; Body Centred Cubic (bee) Unit Cell; Face Centred Cubic
(fcc) Unit Cell; Diamond Cubic (de) Unit Cell; Graphite Layer Lattice; Close Packing
Models of Spheres; The Body Centred (bee) Lattice in Terms ofClose Packing of Spheres;
Characteristic Features of hep, fcc and bee Structure
xvi Fundamental Concepts of Inorganic Chemistry
11.10 Structures of Ionic Crystals 1035

Structures of Ionic Crystal$ of AB "'ype; Structures of Ionic Crystals of AB 2 Type;
Structures of Ionic Crystals of AB) Type; Structure of Ionic Crystals of A2B) Type:
Corundum (6:4 Coordination Crystals); Structure of Io'nic Crystals Consisting of
Polyatomic Ions; Comparison of the Basic Ionic Crystals
11.11 Structures of Mixed Metal Oxides 1042
The Spinel and Inverse Spinel Structure; The Ilmenite Structure (FeTiO); The Perovskite
ry
Structure (CaTiO); Mixed Oxide"s - Coloured Minerals and Gem Quality Crystals
11.12 Crystal Structure in Relation to Superconductivity and/Ferroelectric Property 1047
ra
YBa 2Cu)07_x; BaTiO)
11.13 Deviations from Simple Ionic Structures 1049
ib
Layer Lattices (Le. Two Dimensional Lattices); Chain Lattices (Le. One Dimensional
Lattices)
yl
11.14 Structures of Silicates and Isopoly and Heteropoly Acids: Representative Examples
of Complex Ionic Crystal 10SI
m
Ch,emistry of Silicates and Cement; Isopoly and Heteropoly Acids
11.15 Crystal Defects in Ionic Solids 1063
he
Stoichiometric (Le. Intrinsic) Defects; Nonstoichiometric (or Berthollide) (Le. Extrinsic)
D~fects
lc
11.16 Magnetic Materials : Magnetic Properties 1076

Terminology in Describing the Magnetic Properties and Different Units; Classification of
ea
Magnetic Substances; Cooperative Magnetism - Aniferromagnetism, Canted Magnetism;

Ferrimagnetism and Ferromagnetism; Magnetic Properties of Metals; Temperature
th
Dependence of Magnetic Susceptibility of Different Types of Magnetic Materials

11.17 Properties of Ferroelectric Materials and Piezoelectric Materials 1088
e/
Ferroelectric Materials; Piezoelectricity and Piezoelectric Materials

11.18 Carbides 1091
t.m
11.19 Glasses and Glass Transition 1092

11.20 Structure of Liquids: General Aspects: Hole Theory of Liquids 1094
Solved Numerical Problems 1095
Exercise-XI 1102
Appendices A·1-A·12
Appendix I: Units and Conversion Factors A-I
Appendix II: Some Physical and Chemical Constants A-4
Appendix III: Wavelength and Colours A-5
Appendix IV: Names, Symbols, Atomic Numbers and Atomic Weights of the Elements A-6
Appendix V: Some Useful Mathematical Relationships A-8
Appendix VI: Books Co.nsulted A-II
Index 1·1-1·20
Contents xvii
VOLUME 1
1. Classical and Vector Models of Atoms 1-110

1.1 Cathode Rays and Electron 1
Electric Discharge through Gases and Production ofCathode Rays; Properties ofCathode
Rays; Detennination of Charge to Mass Ratio (elm) ofan Electron by Thomson's Method;
Detennination of Charge of an Electron by Millikan's Oil-Drop Method
ry
1.2 Anode Rays 8
ra
Production of Anode Rays; Properties of Anode Rays; Analysis of Positive Rays by
Thomson's Parabola Method; Aston's Mass Spectrograph; Dempster's Mass Spectrometer;
Bainbridge Mass Spectrometer
ib
1.3 The Neutron as a Fundamental Particle 16
yl
'The Discovery of Neutron; Properties of Neutron
1.4 Some Important Properties of the three Fundamental Particles
m 18
1.5 The Hydrogen Spectrum 18
Balmer Fonnula; Rydberg Fonnula; Ritz Combination Principle
he
1.6 Thomson's Plum-Pudding Model of Atom 20
1.7 Scattering of a-Particles and Rutherford's Nuclear Model of Atom, 21
lc
Rutherford's Nuclear Model of Atom; Rutherford's Theory of a-Particle Scattering;

Nuclear Dimension from the a-Particle Scattering Experiment
ea
1.8 Bohr's .Atomic Model for the Hydrogen-like Systems 25

th
Bohr's Atomic Model; Numerical Values ofRadius and Energy in Bohr's Atom; Correction
for the Finite Mass of the Nucleus; Bohr's Theory and the Spectral Lines in Hydrogen-
e/
like Systems; Ionisation and Resonance Potential for Hydrogen and Hydrogen-like Systems
in the Light of Bohr's Theory; Bohr's Theory and Correspondence Principle; Moseley's
t.m
Law in the Light of Bohr's Theory; Franck-Hertz Experiments (Nobel Prize in Physics,
1925) in the Light of Bohr's Atomic Model; Merits of the Bohr's Atomic Model;
Drawbacks in the Bohr's Model
1.9 Fine Structure of Spectra and Sommerfeld's Atomic Model 45
Sommerfeld's Atomic Model; Penet;ating Power of the Orbits and Quantum Defect in
Polyelectronic Systems in the Light of Sonlmerfeld's Theory; A'chievements of the
Sommerfeld's Theory; Drawbacks in the Sommerfeld's Model
1.10 Vector Model of the Atom 52
Concept of Spatial Quantisation; Concept of the Spinning Electron; Quantum Numbers
in the Vector Model; Four Quantum Number System and Pauli Exclusion Principle;
Coupling Schemes and Atomic States in the Vector Model; L-S and] -] Coupling
Schemes; Spatial Quantisation of the Resultant Vectors (Le. L, S, J) in Atoms or Ions;
Detennination of Microstates and Russel-Saunders Terms; A Simple Working Procedure
xviii Fundamental Concepts of Inorganic Chemistry
to Determine the Term Symbols; Hund's Rules to Determine the Ground State Term;
Derivation of the Ground State Terms in the Light of Hund's Rules; Spectral Selection
Rules in the Vector Mod~l; Intensity Rules for Spectral Transitions in the Vector Model;
Fine or Multiplet Structure of the Spectral Lines in the Light of Vector Model; Nuclear
Spin and Hyperfine Structure ofthe Spectral Lines; Orbital and Spin Magnetic Moments
ofan Electron; Stem-Gerlach Experiment-An Evidence in Favour of Space Quantisation
and Spin Quantum Number; Explanation ofthe Magneto-Optic Phenomenon-the Zeeman
Effect; Electronic Structure of the Atoms; Merits of the Vector Model
ry
1.11 Electronic Configuration Scheme for Many Electron Systems 86
Rules for Placing the Electrons in Different Energy Levels
ra
ib
Exercise-I 105
yl
2. Origin of the Quantum Theory m 111-132
2.1 Introduction 111
2.2 Nature of Black-Body Radiations 111
he
2.3 Different Laws and Theories of Black-Body Radiations 113
The Stefan-Boltzmann Law; Wien's Law; Rayleigh-Jeans Law; Planck's Quantu~ Theory
lc
2.4 The Photoelectric Effect 118

Characteristics of Photoelectric Effect; Einstein's Theory of Photoelectric Effect; Work
ea
Function and Ionisation Potential

2.5 Compton Effect . 121
th
Theoretical Background of Compton Effect; Compton Shifts at Different Cases;

Characteristic Features of Compton Effect
e/
2.6 Pair Formation 126

t.m
Exercise-II 130
3. Fundamentals of Wave· Mechanics 133-184

3.2 Wav'e Particle Duality and de- Broglie's Matter Wave 133
de Broglie Wavelength for Matter Waves; The de Broglie Wavelength for the Macroscopic
and Microscopic Bodies; Difference between de Broglie Matter Wave and Electromagnetic
Wave; The de Broglie Electron Wave; Relativistic Correction in the de Broglie Electron
Wave; Verification of the de Broglie Electron Wave by Davisson and Germer's
Experiment; Bohr's Quantum Restriction from the de Broglie Concept
3.3 The Heisenberg's Uncertainty Principle and its Implications 140
Uncertainty Principle; Illustration of the Uncertainty Principle in the Determination of
the Position ofa Particle by a Microscope: Compton Effect ,!nd the Uncertainty Principle;
Contents xix
Applicability of the Uncertainty Principle to Large and Small Particles; Some Important
Applications of the Uncertainty Principle
3.4 Schr6dinger's Wave Equation 145
Representation ofSchrodinger's Wave Equation; Physical Significance ofSchrodinger's
Equation and Hamiltonian Operator; Eigen Values and Eigen Functions; Physical
Significance of the Wave Function ('II); Normalised and Orthogonal Wave Functions
3.5 Some Applications of the Sch-r6dinger's Wave Equation 150
ry
Free Particle; Particle in a One-Dimensional Box; Particle in a Three Dimensional Box;
Importance of the Model - Particle in a Box; Some Applications of the Model- Particle
in a Box; Quantum Mechanical Tunnelling Effect
ra
3.6 Approximate Methods of Solving the Schr6dinger's Wave Equation 165
Variation Method; The Linear Combination Method
ib
yl
Exercise-III ~ 177
Appendix 3A: Application of Variation Method in Hydrogen Atom 180
m
4. Wave Mechanical Model of Atom 185-235
he
4.1 Wave Mechanical Model for the Hydrogen-like Atoms or Ions 185
Wave Functions for the Hydrogen-like Systems; Wave Mechanical Genesis of the
Quantum Numbers; Important Features of a Dirac Atom Developed from the
lc
Relativistic Wave Mechanics; The Radial Wave Function and Radial Probability
Distribution of Electron Cloud in Hydrogenic Systems; The Physical and Chemical
ea
Significance of the Nodal Points; Angular Wave Functions and Orbital Shapes;
Electron Cloud Density Representation of the Orbitals in Hydrogen-like Systems;
th
Symmetry ofthe Orbitals; Concept of Atomic Orbitals in Wave Mechanics in Relation

to the Orbits in Classical Mechanics; Energy of the Electron in Hydrogen-like Systems;
e/
The Four Quantum Numbers; Pauli Exclusion Principle in the Light of Wave
Mechanics
t.m
4.2 Wave Mechanical Model for Polyelectronic Systems 219

Self-Consistent Field (SCF) Method; Concept of Slater Orbitals; Concept of Shielding
and Quantum Defect; Slater's Rules in Calculating the Shielding Constant (S) and Effective
Nuclear Charge (Z*) .
4.3 Bonding Properties of d- and I-Orbitals 225
Solved Problems 226
Exercise-IV 234
5. Atomic Nucleus and its Structure 236-308

5.1 The Atomic Nucleus 236
Composition of the Nucleus; Size of the Nucleus; Mirror Nuclei and Nuclear Radius;
Nuclear Density; Shape of the Nucleus; Total Angular Momentum of the Nucleus :
xx Fundamental Concepts of Inorganic Chemistry
Magnetic Properties ofthe Nucleus and Nuclear Magnetic" Resonance (NMR) Frequency
and NMR Spectra of Some Representative Examples; Classification of the Nuclides;
Nuclear Spin Isomerism in Diatomic Molecules: Ortho- and Para-Hydrogen: Intensity
of the Rotational Lines in the Band Spectra of Diatomic Molecules
5.2 The Isotopes 253
Discovery and Characterisation of Nonradioactive Isotopes; Isotopic Shift in Optical
Spectra; Characteristic Features of the Isotopes; Isotopic Composition of the Elements;
Uses of Isotopes; Separation of Isotopes
ry
~.3 Nuclear Stability 268
Even-Odd Nature of the Nucleons (Harkins' Rule); The Neutron to Proton Ratio and
ra
Stability of the Nuclides; The Neutron to Proton Ratio and Different Modes of Decay;
Packing Fraction and Nuclear Stability; Mass Defect and Nuclear Binding Energy (NBE)
ib
5.4 The Nuclear Forces 278
Nature ofthe Nuclear Forces; Exchange Force as the Nuclear Force; The Nuclear Potential
yl
and Nuclear Potential Barrier
5.5 Nuclear Models 282
m
Fermi Gas Model; The Liquid Drop Model; Nuclear Shell Model; The Optical Model
5.6 The Fundamental Particles 296
he
Exercise-V 305
lc
6. Radioactivity and Radiation Chemistry 309-382

ea
6.1 Discovery of Natural Radioactivity 309

th
6.2 Types of Radioactive Emanations 310

6.3 Properties of Alpha, Beta and Gamma Ra-diations 311
e/
Alpha (a)-rays; Beta (~)-Rays; Gamma (y) Rays; Comparison among the Different Types
of Radioactive Emanations
t.m
6.4 Detection and Measurement of Radioactivity 315

6.5 Units of Radioactivity 320
6.6 Different Modes of Radioactive Decay 322
6.7 The Fluorescence and Auger Effect 323
6.8 Disintegration Chain and Soddy-Fajan Group Displacement Law 324
6.9 The Decay Kinetics and Parent-Daughter Growth Relationships 325
Case I : The Daughter Nucleus is Stable; Case II : When the Daughter Element is
Radioactive .
6.10 Radioactive Equilibrium 332
6.11 Energetics of the Disintegration Processes 336
6.12 Some Important Aspects of Alpha Decay 338
Contents xxi
6.13 Some Important Aspects of Beta Decay 340

6.14 Some Important Aspects of Gamma Emission 341
6.15 The Disintegration Series 342
6.16 Artificial or Induced Radioactivity 345
Discovery of Artificial Radioactivity; Production of Artificial Radioactivity
6.17 Applications of Radioactive Isotopes 347
Application of Radioisotopes in the Field of Chemistry; Application of Radioactivity in
ry
Biological Fields; Application ofRadioactivity in Agriculture; Application ofRadioactivity
in the Medical Field; Application ofRadioactivity in Industry; Application ofRadioactivity
ra
in Age Detennination
6.18 Some Important Aspects of Radiation Chemistry 363
ib
Radiation Chemistry; Characteristics of Interaction of Medium Energy Charged Particles
with Matter; Interactions ofNeutrons with Matter; Interaction of Gamma-Radiation with
yl
Matter; Radiation Dosimetry; Radiolysis of Water
m
Exercise-VI 379
he
7. Nuclear Reactions 383-447
lc
7.1 Artificial Transmutations and Nuclear Reactions 383

7.2 Bethe's Notation of Nuclear Reactions 384
ea
7.3 Nuclea"r Reactions Versus Chemical Reactions 385

7.4 Classification of Nuclear Reactions 386
th
7.5 Conservation Laws in Nuclear Reactions 390

Conservation of Energy; Conservation of Linear Momentum; Conservation of Angular
e/
Momentum; Conservation of Neutrons and Protons

t.m
7.6 Threshold Energy of a Projectile for a Nuclear Reaction 392

7.7 Nuclear .Reaction Cross-Section 392
7.8 Mechanisms of Nuclear Reactions 393
The Compound Nucleus Theory; Oppenheimer-Phillip~ Mechanism in Stripping Reactions;
Direct Nuclear Reaction Mechanism
7.9 Charged Particle Accelerators 397
The Linear Accelerator; The Cyclotron
7.10 Filling in the Gaps in the Periodic Table: The Man-Made Elements 401
7.11 Transuranic and Translawrencium Elements: The Man-Made Elements 402
7.1l Nuclear Fission 406
Historical Background; Characteristic Features ofNuclear Fission; Bohr-Wheeler Theory
ofNuclear Fission: Liquid Drop Model; Charge Distribution in Fission Products: Principle
of Equal Charge Displacement
xxii Fundamental Concepts of Inorganic Chemistry
7.13 Fission Chain Reaction: A Source of Atomic Energy 415

Factors Controlling a Fission Chain Reaction; The Fertile and Fissile Nuclides as the
Nuclear Fuels; Atom Bomb; Fermi's Four Factor Formula and Nuclear Reactor or Atomic
Pile for the Controlled Nuclear Fission; Breeder Reactor; A Natural Fission Reactor:
Okla Phenomenon; Nuclear Reactors in India; Re.covery of Uranium and Plutonium from
Spent' Fuel
7.14 Nuclear Fusion:· Thermonuclear Reaction 424
Characteristic Features of Nuclear Fusion; Hydrogen and Cobalt Bomb; Stellar Energy;
ry
Controlled Fusion Reactions: An Innocent and a Never-Ending Source of Energy; Cold
Fusion
ra
7.15 The Origin and Evolution of Elements: Nucleosynthesis of Elements 429
Nl:lcleosynthesis of Elements from the Primordial Element Hydrogen in Stars; Cosmic
ib
-Abundance of Elements
yl
Exercise-V-)) m 444
8. Periodic Table and Periodic Trends of Different

Properties of Elements 448-541
he
8.1 Historical Background of the Development of Periodic Classification 448
lc
-Law of Triads; Pattenkofer's Rule of Integral Multiple; Chancourtois Law of Telluric

Screw; Newlands' Law of Octaves; Mendeleev's and Lothar Meyer's Periodic Laws
ea
8.2 Mendeleev's Periodic Law and Periodic Table 451

Characteristics of Mendeleev's Short Periodic Table
th
8.3 Characteristics and Usefulness of the Mendeleev's Periodic Table 455

Systematic Classification of the Elements; Correction of Atomic Weights; Prediction of
e/
the Missing Elements

t.m
8.4 Defects in the Mendeleev's Periodic Table . 456

8.5 Long Form of the Modern Periodic iable 458
Important Segments of the Long Form of the Modem Periodic Table; Advantages of the
Long Fonn of Periodic Table; Defects of the Long Form Periodic Table
8.6 Extended Periodic Table: Superheavy Elements: Postactinides and Superactinides 462
8.7 Classification of the Elements Based on the Electronic Configuration and
Chemical Affinities 464
Classification Based on the Position ofthe Differentiating Electron; Bohr's Classification
Based on Electronic Configuration; Goldschmidt's Geochemical Classification ofElements
Based on Chemical Affinity
8.8 Characteristics and Position of the Border Line Elements 467
Position of the Zn-Family; Positions of Lu, 1n and Lr; Position of the Lighter Actinide~;
4fSeries (Lanthanides) vs. 5fSeries (Actinides)
Contents xxIII
8.9 Lanthanide and Actinide Contractions (i.e. I-Contractions) 469

Nature ofthe}Contraction; Explanation offContraction; Effects ofLanthanide Contraction
. 8.10 Periodic Trends of Z* and Size of the Atoms and Ions 473
Two Important Factors (n and 2*) to Determine the Size of Atoms and Ions; Periodic
Trends of 2* (Effective Nuclear Charge); Variation of Size along the Periods; Variation
of Size in a Group
8.11 Variation of Atomic Volumes .in the Periodic Table 478
ry
Atomic Volume: Definition and Limitation- of the Parameter; Nature of Variation Trend t
ofthe Atomic Volume with the Atomic Number; Explanation ofthe Atomic Volume Curve
ra
8.12 Variation of Ionization Energies in the Periodic Table (cf. Sec. 9.11 for Ionisation
Energies of Molecules and Photoelectron Spectroscopy) 480
ib
Periodic Variation of the Ionisation Energies; Factors Governing the Ionisation Energies
and Explanations of the Periodic Trends; The Cases which Flout the General Periodic
yl
Trend; Ionisation Energy of Some Typical Molecular Species
8.13 Electron Affinity and its Variation Trend in the Periodic Table 486
m
Concept, of Electron Affinity; Factors Governing the Electron Affinities; Variation of
Electron Affinity in the Periodic Table
he
8.14 Concept of Electronegativity 491
Pauling's Electronegativity; Mulliken's Orbital Electronegativity; Jaffe-Hinze
lc
Electronegativities (Mulliken-Jaffe electronegativity); Allred-Rochow's Electronegativity:

Sanderson's Electronegativity; Calculation of Charge Separation from Electronegativity:
ea
Concept of Electronegativity Equalization; Electronegativity Not an Inherent Property of

the Elements; Examples Illustrating the Variation of Electronegativity Depending upon the
th
Structural Characteristics; Group Electronegativity; Concepts ofAbsolute Electronegativity;

Optical Electronegativity and Spectroscopic Electronegativity
e/
8.15 Periodic Trends of Electronegativity 507

t.m
8.16 Applications of the Electronegativity Concept in Different Fields of Chemistry 507

8.17 Periodic Trends of Cohesive Energy (i.e. Melting and Boiling Points) 511
8.18 The Diagonal Relationship 511
Causes of the Diagonal Relationship; Comparison of the Physical Constants of the Three
Diagonal Pairs; Similarities in the Pair, Li and Mg; Similarities in the Pair, Be and AI;
Similarities in the Pair, Band Si
8.19 Basic Difference in Group Trends Between the Representative and Transition
Elements 517
8.20 Secondary Periodicity : Anomalies among the Post-transition Elements and
Postlanthanides 517
Secondary Periodicity and Consequences of Secondary Periodicities; Explanation of the
Anomalies in Properties of the 4-th and 6-th Period Posttransition Elements; Relativistic
Effects on Chemical Properties of the Fifth and Sixth Row Elements
xxiv Fundamental Concepts of Inorganic Chemistry
8.21 Position of Hydrogen in the Periodic Table 524

8.22 Peculiarities of the First and Second Row Elements 525
Anomalou~ Properties of Fluorine : Superhalogen or Subhalogen? Anomalous Properties
of Lithium
8.23 Comparison of Transition (i.e. d-Block) and Inner Transition (i.e. I-Block) Metals 528
8.24 Variation of Oxidation States of s- and p-Block Elements 530
ry
Exercise-VIII 535
Appendices A-1-A-12
ra
Appendix I: Units and Conversion Factors A-I
ib
Appendix III: Wavelength and Colours A-5
yl
m
Appendix VI: Books Consulted A-II
he
Index 1-1-1-20
lc
VOLUME 3
ea
12. Bonding in Metals and Metal Clusters: Electrical

Conductivities of Solids: Semiconductors and
th
Superconductors 1110-1249
e/
12.1 General Properties of Metals 1110

12.2 Crystal Structure of the Metals and the Effects of Lattice Structure on
t.m
their Properties 1111

12.3 The Free Electron Theory of Metallic Bonding 1114
Drude-Lorentz Classical Free Electron Theory: Electron Sea Model; Sommerfeld's Quantum
Mechanical Free Electron Theory and Fermi Dirac Distribution Function; Quantitative
Aspects of Some Properties of Metals; Electrical Conduc~ivity and Hall-Effect
12.4 The Bloch Theory (i.e. Zone Theory) of Metallic Bonding 1131
Basic Concepts of Bloch Theory; Brillouin Zone, Forbidden Zone and Conductivity
12.5 Molecular Orbital Theory or Band Theory of Metallic Bonding 1136
Formation ofEnergy Bands and Brillouin Zones; Band Structure ofNontransition Metals;
Band Structure of Transition Metals; Valence and Conduction Bands; Explanation of
Electrical Conductivities of Solids in the Light of Band Theory; Optical Properties of
Solids in' the Light of Band Theory; Magnetic Properties Including the Temperature
Independent Paramagnetis (TIP) (Le. Pauli Paramagnetism) of the Metals in Terms of
l,;ontents xxv
Band Theory; Ferromagnetism in Transition and Inner-transition Metals; Band Structure

of Some Inorganic Solids and their Properties
12.6 Valence Bond Approach of Metallic Bonding , 1154
Valence Bond Approach for the SholtPeriod Metals; Valence Bond Approach for the Long
Period Metals; Merits ofthe Valence Bond Approach; Demerits ofthe Valence Bond Theory
12.7 Solid Solutions: Alloys: Intermetallic Compounds 1156
Interstitial Alloys; Substitutional Alloys, Intermetallic Compounds and Hume-Rothery Rule
12.8 Metal-Metal Bonds in Metal Clusters 1161
ry
Binuclear Compounds; Trinuclear Compounds; Octahedral Clusters; Chevrel Phase;
Octahedral Metal Cluster; Carbonyl Clusters; Metal-only Clusters (Zintle Cluster Ions);
ra
Metal-Metal Bonds in Stacked Polymeric Structure; Conditions for Metal-Metal Bonding
12.9 Semiconductors and their Properties in the Light of Band Theory 1181
ib
Characteristic Features of Intrinsic Semiconductor; Characteristic Features of Extrinsic
or Doped Semiconductors; Temperature Dependence of Semiconductor Conductivity;
yl
Optical Properties of Solids; Uses of Semiconductors : Direct and Indirect Gap
Semiconductors; Some Useful Semiconductor Materials and their Properties;
m
Characteristics of p-n Junctions; Characteristic Features of p-n-p and n-p-n Junction
Transistors; Some Applications of Semiconductor Devices
he
12.10 Semiconductivity and Metallic Conductivity of Metal Oxides:
Hopping Mechanism of Conductivity 1209
lc
12.11 Electrical Conductivity in One Dimensional Solids : Peierls Distortion 1214

Electrical Conductivity in KCP [Ptossium tetracyanoplatinate(II)] and Peierls Distortion;
Electrical Conductivity in Polythiazyl (SN)x (Le. ~ [SN] - a one dimensional metal);
ea
Electrical Conductivity in trans-Polyacetylene (C2H 2 )x or (CH)x -an Organic Semiconductor

12.12 Conducting Organic Substances: Organic Metals, Organic Semiconductors,
th
Molec-~Iar Inorganic Superconductors 1218

IntrodUction; Some Representative Examples ofOrganic Salts dConducting Substances:
e/
Organic Superconductors
12.13 Superconductivity 1222
t.m
Concept ofSuperconductivity; Characteristic Features ofSuperconducting Materials; BCS

Theory of Superconductivity; Superconducting Materials; Structural Features of Some
Copper-containing Superconducting Ceramic Materials (Warm Superconductors);
Application of Superconductivity
12.14 Electrical Conductivity of Solid Electrolytes 1232
Exercise-XII 1241
13. Hydrogen Bonding and Other Weaker Chemical Forces

Including Supramolecular Systems 1250-1342
13.1 Hydrogen Bonding 1250
Types of Hydrogen Bonding Depending on the Nature of Electron Clouds on Donor (D);
Types of Hydrogen Bf?nding Depending on the Position of Donor (D); Participation of
xxvi Fundamental Concepts of Inorganic Chemistry
C-HBonds in H-Bonding; Symmetrical and Unsymmetrical Hydrogen Bonding; Hydrogen

Bond Energy and Bond Length; Effects of Intermolecular H-Bonding; Effects of
Intramolecular H-Bonding; Detection of H-Bonding; Theories of Hydrogen Bonding;
Agostic Interaction· vs. Hydrogen Bonding Interaction; Comparison among H-bridge Bond,
H-Bond and Agostic Interaction
13.2 Hydrates and Clathrates or Cage Compounds 1279
Hydrates; Clathrates or Cage Compounds; Configurational Entropy and Thermodynamic
Aspects of Clathrate Compounds
ry
13.3 The Nature of Intermolecular Forces: van der Waals Forces: Lennard-Jones
Potential: The 6-12 Potential 1285
The Attractive Intermolecular Forces; Total Intermolecular Attractive Forces (van der
ra
Waal~ Forces); The Repulsive Intermolecular Forces; Lennard-Jones Potential
13.4 Interaction Between Ionic and Covalent Compounds 1295
ib
Ion-Dipole Interaction; Ion-Induced Dipole Interaction; Metal-Ligand (neutral) Interaction
in Terms of Ion-Dipole Interaction and Polarisation ofthe Metal Ions and Ligands; Hard-
yl
Hard Interaction (Electrostatic Interaction) and Soft-Soft Interaction (Mutual Polarisation)
13.5 Noncovalent Interactions in Supramolecular Systems and Molecular Recognition 1298
m
Interactions in Supramolecules; The Lock and Key Principle in Supramolecular Assemblies;
Representative Examples of Supramolecular System; Double Helical Structure of DNA;
he
Macrocyclic Systems (Synthetic Molecular Receptors for Cations); Molecular Recognition
of Specific Metal Ions by Macrocyclic Systems; Crown Ethers as Receptors; Spherical
Recognition of Metal ions; Molecular Recognition of NHt and RNH; (Primary Alkyl
lc
Ammonium Cation) by [18]-Crown-6; Selective Perching or Nesting of NHt or RNH;

on Crown-6; Cryptands; Synthetic Molecular Receptors for Different Types of Substrates
ea
- Cations, Anions, Neutral Moiecules; Application of Macrocyclic Crown. Ethers and

Cryptands; Polyazamacrocycles and Polyazacryptands as Anion Receptors (Synthetic
th
Receptors); Molecular Recognition by Macrocyclic Systems; Calixarenes as Receptors;

Cyclodextrins (CDs) as Natural Receptors; Cyclophanes-as Synthetic Receptors for Apolar
Guests; H-Bond Directed Molecular Assembly; Metal Coordinated Self-assembly; Molecular
e/
Switch; Catenanes and Rotaxanes; Inverse Crown Ethers : Novel Anion Receptors
13.6 Energetics of Dissolution 1324
t.m
Thermodynamic Aspects and Conditions ofDissolution; Born Equation and Ion Solvation;
Energetics of Solubilities of Ionic Salts in Polar Solvents; Solubilities of Ionic Salts in
Nonpolar Solvents; Solubilities of Nonpolar Solutes in Nonpolar Solvents; Solubilities
of Nonpolar Solutes in Polar Solvents
, - ~ -
13.7 Energetics of Phase Transitions - Melting,' Boning, Sublimation 1332
Phase Transition in Covalent Compounds; Ionic Compounds; Ionic-Covalent Compounds
(Le. Fajans Type Compounds); Ease of Phase Transition Depending on the Nature of
Involved Chemical Forces
Exercise-XIII 1336
14. Acids and Bases and Ionic Equilibria in Aqueous Solutions 1343-1554
14.1 Definitions of Acids and Bases 1343
Contents xxvii
14.2 Arrhenius Theory of Acids and Bases 1343

14.3 Brtinsted-Lowry Concept: The Proton Donor-Acceptor Concept:
Protonic Concept: The Conjugate Acid-Base Theory 1344
Basic Concepts of Brl>nsted-Lowry Theory; Relative Strength of Acids and Bases:
Differentiating and Levelling Solvents in the Light of Brl>nsted-Lowry Concept; Merits
ofthe Brl>nsted-Lowry Concept; Limitations ofthe Brl>nsted-Lowry Concept; Cosolvating
Agents and Acid-Base Strength; Application of Brl>nsted-Lowry Concept in Calculating
pH ofAqueous Solutions: A Generalised Approach to Calculate the pH Values ofDifferent
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Types ofAqueous Solutions; Acid-Base Behaviour ofAm"ino Acids in Aqueous Solution:
Is~electric Point; The Chemistry of Proton in Water: Proton Transport Process
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14.4 Mechanism of Buffer Action: Buffer Capacity 1370
14.5 Selection of Acid-Base Indicators in Acid-Base Titrations 1372
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14.6 Hammett Acidity Function: Superacids 1382
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Concept of Hammett Acidity Function (If); Concept of Superacids and Examples of
Superacids; Application of Superacids m
14.7 The Lewis Concept: The Electron Pair Donor-Acceptor System 1386
Basic Concepts and Characteristic Features ofthe Lewis Theory; Different Types ofLewis
he
Acids; Classification ofthe Lewis Bases; Lewis Acid-Base Reactions and Redox Reactions;
Some Typical Examples of Lewis Acids and Bases, Lewis Acid-Base Adducts; Covalent
and Ionic Contributions in the Stabilities of the Adducts : Drago-Wayland Equation;
lc
Demerits of Lewis Acid-Base Theory; Solvent Properties in the Light of Lewis Acid-
Base Concept; Change of Bond Length in Lewis Acid-Base Interaction
ea
14.8 Strength of Brtinsted (i.e. Protonic) Acids and the Gover~ing Factors Involved and
the Properties of Brtinsted Acids and Bases 1414
th
Strength of Different Protonic Acids and Conjugate Acids of Some Bases; Born-Haber
Cycle and Thermodynamic Parameters to Determine the Acid Strength: Acid Strength of
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Hydracids and Carboxylic Acids: Gas Phase Acidity; Factors Governing the Strength of
Oxyacids; Hydrolysis and Aqua Acid Strength of Metal Ions in the Light of Brl>nsted-
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Lowry Concept; Basicity ofthe Anions; Periodic Variation ofAcidic and Basic Character;
Nucleophilicity and Basicity; Acld and Base Catalysis
14.9 Some Important Factors Governing the Acid-Base Strength (both Br6nsted and
Lewis Acid-Base Systems) . 1437
Inductive Effect : Entropic Effect, d-Orbital Participation; State of Hybridisation of the
Central Atom; Steric Factors: F-Strain and B-Strain; Solvation Effects (cf. H-bonding);
Resonance and 1t-Bonding arid the Possibility of d-Orbital Participation in the Reacting
Species; Effect of Resonance Stabilisation in the Product; Effect of H-Bonding on Acid
Strength
14.10 Lux-Flood Concept 1466
14.11 Solvent System Definition 1468
14.12 Usanovich Concept 1472
14.13 A Generalised Concept of Acids and Bas~s 1472
xxviii Fundamental Concepts of Inorganic Chemistry
14.14 Concept of Ultimate Acids and Bases 1472

14.15 Hard and Soft Acids and Bases (HSAB) 1473
Basic Concept and Principle of Hard and Soft Acids and Bases (HSAB) Theory; Basis
of Classification of the Acids and Bases as Hard or Soft; Characteristics of Hard and
Soft Species; Symbiosis in Hardening or Softening a Centre; Acid-Base Strength versus
HSAB Principle; Application of HSAB Principle; Theoretical Background of HSAB
Principle
14.16 Surface Acids and Solid ~cids : Heterogenous Acid-Base Reactions 1492
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14.17 Aqueous Solutions 01 Salts: Hydrolysis of Salts: Solubility Product of Sparingly
Soluble Salts 1494
Hydrolysis of Salts; Solubility Product and Activity Product of Sparingly Soluble Salts;
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Application of the Principle of Solubility Product I
--.
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Exercise-XIV 1541
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15. Nonaqueous Solvents m 1555-1576
15.2 Classification of Solvents 1555
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15.3 Characteristics of Ionising Solvents 1556
1.5.4 Liquid Ammonia as a Solvent 1558
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15.5 Liquid Hydrogen Fluoride as a Solvent 1564

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15.6 Liquid Hydrogen Cyanide as a Solvent 1565

15.7 Acetic Acid (CHJC02H) as a Solvent 1566
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15.8 Sulfuric Acid as a Solvent 1567

15.9 Fluorosulfonic Acid (HSOJF) as a Solvent and Superacids 1568
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15.10 Liquid Sulfur Dioxide as a Solvent 1569

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15.11 Bromine Trifluoride as a Solvent 1570

15.12 Oxyhalides as Solvents 1571
15.13. Molten Salts (i.e. Ionic Liquids) as Solvents 1572
Exercise-XV 1575
16. Redox Systems and Electrode Potential: Application of

Electrode Potentials: Electroanalytical Techniques 1577-1783
16.1 Some Preliminary Aspects of Redox Reactions 1577
Ion Electron Method of Balancing Redox Reactions; Oxidation Number and Rules for
·Calculating Oxidation Number; Oxidative Addition and Reductive Elimination Reaction;
Equivalent y.Jeights ofOxidants and Reductants; Complementary "and Noncomplementary
Redox Reactions; Redox and Acid-Base Reactions; Disproportionation and
Comproportionation Reactions
Conter ,ts xxix
16.2 Electrode Potentials: Standard Potentials 1596

Electrical Double Layer and Genesis of Electrode Potential; Determination of Electrode
Potential; Standard Electrode Potential : Nernst Equation: Stoichiometric Standard
Potential and Formal Potential : Concept of pE; Sign Conventions of the Electrode
Potentials; Standard Electrode Potentials of Metals and Electrochemical Series; Standard
Reduction Potentials; Reversible Chemical Cells: Cells with and without Transference;
Galvanic vs. Electrolytic Cell: Ohmic Potential and Observed Cell emf
16.3 Formal (Conditional) Potentials (cf. Conditional Stability Constant vs.
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Thermodynamic Stability Constant) 1607
16.4 Effects of Different Factors on Electrode Potential: Application of Such Effects in
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Analytical Chemistry 1610
Effects of pH on Electrode Potentials due to the Participation of Jr or O~ in Electrode
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Process (cf. Pourbaix diagrams); Effects of pH on Electrode Potentials due to the
Formation of Sparingly Soluble Hydroxo-species (cf. Pourbaix diagrams); Effects of
Precipitation (other than hydroxides) on Electrode Potentials;· Effects of Complexation
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on Electrode Potentials; Chemistry of Aqua Regia and Dissolution of Noble Metals:
Enhancement ofOxidisability of Metals through Complexation; Attack ofNoble Metals
m
by HF and by a Mixture of HF and HN03 : Enhancement of Oxidisability of Metals
through Complexation; Dissolution of Antimony by a Mixture ofNitric Acid and Tartaric
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Acid : Enhancement of Oxidisability of Metals through Complexation
16.5 Periodic Trends of Electrode PQtential 1640
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Variation of Standard Oxidation Potential of the Metals; Variation of Oxidising Power

of the Oxyanions in a Group
ea
16.6 Function of Zimmermann-Reinhardt Solution (in Titrating Fe(II) by KMn04

in the Presence of Chloride) 1643
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16.7 Instability of Some Species in Aqueous Solution 1644

16.8 EMF Diagrams 1647
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Latimer Diagram; Frost Diagrams (Ebsworth Diagram); Pourbaix Diagram or Potential-

pH (E-pH) Diagram
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16.9 Equilibrium Constant from the Standard Electrode Potentials 1661

16.10 Disproportio.nation and Com proportionation Reactions 1663
16.11 Potential Profile in a Redox Titration 1672
16.12 Selection of a Redox Indicator 1677
16.13 Potentiometric Titrations 1680
16.14 Practical Applications: Electrochemical Cells and Batteries - Primary Cells,
Secondary Cells, Fuel Cells: Corrosion 1686
Basic Requirements of an Electrochemical Cell to Act as a Power Source; Representative
Examples ofPrimary and Secondary Cells; Some Representative Fuel Cells; Electrochemistry
of Corrosion; Electrolytic Cell vs. Galvanic Cell : Electrolysis of Solutions and
Electrodeposition; Decomposition Voltage of Electrolysis and Electrolytic Separations of
Metals; Some Other Practical Applications of the Knowledge of Electrode Potential
xxx Fundamental Concepts of Inorganic Chemistry
16.15 Kinetic Factors in Electrode Process and Electron Transfer Reactions 1704
Importance of Kinetic Factors; Importance of Overpotential (in Electrode Process and
Cell Potential): Tafel Equation; Redox Reactions Through Electron Transfer; Redox
Reactions Through Atom Transfer
16.16 Photochemical Reactions: Photoredox Reaction and Photochemical Splitting of Water 1708
Some Representative Photochemical Reactions Illustrating the Characteristic Features;
Photochemical Splitting of Water and Photochemistry of Ru(bpyX+; Ti02, an Important
Photocatalyst; Direct Photochemical Reduction ofDintrogen; Charge Transfer Band and
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Redox Stability
16.17 Ellingham Diagram: Reduction of Metal Oxides: Carbon - A Potential
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Reducing Agent 1719
16.18 Hydrometallurgy 1722
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16.19 Electrode Potentials in Nonaqueous Systems 1723
16.20 Examples of Some Common Catalysed Redox Reactions 1724
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16.21 Redox Activity in Relation to Explosive Action
m 1726
16.22 Chemistry of Some Important Electroanalytical Techniques 1727
Polarographic Method of Analysis; Cyclic Voltammetry (CV); Amperometric Titration;
he
Coulometric Analysis
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Exercise-XVI 1763
Numerical Problems 1770
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Appendix 16A: Chemistry of Explosives 1773

Appendix 16B: Chemical Clock Reactions: Oscillating Reactions 1777
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Appendices A-1-A-12
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Appendix I: Units and Conversion Factors A..:J

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Appendix III: Wavelength and Colours A-S

Appendix VI: Books Consulted A-II
Index 1-1-1-18
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VOLUME 2m
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9. Introduction to Chemical Bonding and Theories of

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Covalence: Valence Bond Theory (VBT) and

Molecular Orbital Theory (MOT)
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10. Covalent Compounds: Characteristics, Structure

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and Reactivity
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11. Structure, Bonding and Properties of Ionic Solids

and Solid State Chemistry
Appendices
Appendix I:Units and Conversion Factors
Appendix II:
Some Physical and Chemical Constants
Appendix III:
Wavelength and Colours
Appendix IV:
Names, Symbols, Atomic Numbers and Atomic Weights
of the Elements
Appendix V: Some Useful Mathematical Relationships
Appendix VI: Books Consulted
9
Introduction to Chemical Bonding and
Theories of Covalence: Valence Bond
Theory (VBT) and Molecular
ry
Orbital Theory (MOT)
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9.1 HISTORICAL BACKGROUND
9.1.1 Development of the Concept of Valency
m
At the early dawn of nineteenth century, several distinguished chemists like Berzelius, Leibig, Dumas,
he
Laurent, Gerhardt, Frankland and many others attempted to account for the driving forces responsible
for chemical bonding. It was established that the combining power of the atoms is different for different
elements and for a particular element it is fixed. This is why the combining capacity was referred to as
lc
atomicity by a·erhardt and the term was replaced by quatrivalency by Hoffman (1865). This was
shortened into valency or valence by Wichelhaus in 1868 and it is popularised by this name. After a
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long period of time, in the later part of the nineteenth century, a more or less qualitative idea of the
mechanism of combination of the atoms got crystallised from the contributions of a number of thinkers
th
like Kekule, van't Hoff, Ie Bel, Werner and others.

To explain the structure of the saturated hydrocarbons,. van't Hoff and Ie Bel (1874) independently
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proposed the quadrivalency of carbon and these are projected to the corners of a regular tetrahedron.
This idea of tetrahedral quadrivalent carbon yielded an outstanding achievement in explaining the
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structure, optical activity and isomeric configurations of different organic compounds. Another important
prediction on the nature of bonding in unsaturated organic compounds made by Kekule (1857) somewhat
earlier could also be interpreted by the tetrahedral carbon. Thus the Kekule's theory to explain the
structure and properties of benzene got a sound support from van't Hoff and Ie Bel. In this connection,
the theory of partial valency proposed by Thiele (1899) to explain the behaviour of the organic
compounds having conjugated double bonds made a significant contribution.
On the other hand, to explain the structure of the coordination compounds, Werner ( 1891 ) proposed
the idea of primary or principal valency and secondary or residual or auxiliary valency. This also
made an outstanding contribution in understanding the bonding mechanism in coordination compounds.
All these ideas were developed by the chemists based on the factual observations of the
compounds. But the development of the atomic structure by Rutherford and Bohr provides an
542
Introduction to Chemical Bonding and Theories of Covalence 543
understanding of the inner mechanism of the bondiQg. Actually, the knowledge of electronic configu-
ration of the atoms gave a reasonable interpretation of the bonding mechanism. This is often referred ~o
as electronic theory of bonding. The foundation-stone of the electronic theory of valency was laid
independently almost at the same time by Kossel (1916) in Germany and Lewis (1916) in the USA.
Kossel pointed out that the elements (e.g. halogens) just preceding the inert gases are strongly
electronegative while the elements (e.g. alkali metals) which are immediately following the in~rt gases
are highly electropositive. The electronegative atoms tend to attain the nearest inert gas configuration
by accepting the requisite number of electrons in the valence shell, and the electropositive atoms lose
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their outermost electrons to attain the nearest inert gas configuration. Thus they tend to attain the
stability by acquiring the inert gas configurations. In this way, through the electron transfer process, the
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electronegative atoms form the anions while the electropositive atoms generate the cations. These
oppositely charged ions are bound through Coulombic forces. Thus the Kossel's idea gives the mechanism
ib
of ionic bonding. The number of electrons involved in the transfer process to attain the inert gas
configuration g~ves the valency ofthe element. Thus, the Kossel's idea gives an interpretation of Abegg's
yl
theory ofcontravalency (or simply, the rule of eight), an empirical relationship between the valericy of
an element and its periodic group number. m
The Kossel's theory consi~ered the chemical forces as the electrostatic attractive forces which
were also proposed by Berzelius in his dualistic theory much earlier. But the nature of this force can
he
hardly be rationalised for the nonpolar molecules, specially for the homonuclear diatomic molecules
like H2, e12, N2, etc. The existence of cations and anions of the same element appears unthinkable.
Thus,the Kossel's ide~ is only applicable for the ionic compounds.
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To explain the chemical force involved in forming the homopolar molecules, Lewis in the same
year i 1916) proposed a new idea. According to him, to attain the stable nearest inert gas electronic
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configuration, the complete transfer of electrons is not necessarily required. This can be attained by
sharing the ele~tron pairs by the combining atoms.
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9.. 1.2 Lewis-Langmuir Concept

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When the atoms or other species combine throllgh the sharing of an electron pair (2c - 2e, i.e. two
centre-two electron bond) to attain the inert gas configuration (ns 2 or ns 2 np6), the corresponding
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linkage (very often represented by a bar - ) is called covalent bond. The electrons in the pair residing
in a particular orbital must be of opposite spin. This concept is known as the Lewis-Langmuir concept.
The sharing electron pair (a common property between the combining atoms) may be constituted by
each of the two combining species or by only one of the two species. In the second case, the species
which provides t~e electron pair is called donor (Le. Lewis base) and the one which accepts the pair is
called acceptor (Le. Lewis acid). Classically, this type of bond is called coordinate covalent bond. The
linkage is very often represented by an arrow (~) pointing towards the acceptor species. For example,
in the case ofammonia-boron trifluoride adduct formation, the lone pair residing on nitrogen ofammonia
is donated to boron in boron trifluoride' as H3N: ~ BF3 • This idea of coordinate covalent bond is
extensively utilised in explaining the Lewis acid-base interaction (see Sec. 14.7) and complex compound
formation. However, in the present status of knowledge, it is established that there is no basic
difference between an ordinary covalent bond (where each of the species provides one electron)
and a coordinate covalent bond. This indistinguishability is justified from the experimental facts. For
544 Fundamental Concepts of Inorganic Chemistry
example, in the classical concept, NH; should have three ordinary covalent bonds and one coordinate
covalent bond, but experimentally all the four bonds are found identical to hold the four identical
hydrogens.
The number of covalent linkage between the combining species may be single or double on triple
depending upon the situation to reach the inert gas configuration.
9.1.3 The Octet Rule

In most of the cases, through the covalent linkage formation, each of the combining species attains the
ry
octet, Le. ns 2 np6, configuration. If the species already bears the octet configuration, it will not display
any tendency to form any covalent linkage. In the case of hydrogen, the inert gas configuration of
ra
helium, i.e. ns 2, is attained. This is very often referred to as the rule of duplet. There are a lot of
examples in which the rule of octet and duplet have been satisfied. Some representative examples are
ib
H2 (H-H),N2 (:N=N:),02 (Q=Q), CO2 (Q =C= Q), H20 (H-Q-H), :NH3 ,CCI4 ,etc.
Deviation from the Octet Rule : A number of cases are known where the combining species or
yl
atoms have less than eight (Le. incomplete octet) or, more than eight (Le. expansion ofoctet) electrons
in the covalently bonded molecules.
m
Incomplete Octet: In the molecules such as BeCI2, BCl3 and NO (: N = 0), the central atoms, Le.
Be, B, and N, bear four, six and seven electrons respectively. Here it is nOfeworthy that other atoms
he
except the central ones in the above compounds maintain the octet rule. As a matter of fact, a large
number of compounds formed by Be (quartet), M (sextet) where M = B, AI, Ga are known to have
lc
incomplete octets. These compounds are very often referred to as electron deficient comRou'nds (see
Sec. 9.21) characterised by a profound tendency to receive back a lone pair (for Gr 13 or IlIA elements,
ea
e.g. B, AI, Ga, etc.) or two lone pairs (for Gr 2 or IIA elements, e.g. Be) to attain the octet. This is why,
the electron deficient compounds act as Lewis acids.
Expansion of Octet : In the compounds like, PCls, CIF3, SF6 , SiF62-, etc. the central elements, Le.
th
P, CI, Sand Si, are bearing ten, twelve, and twelve electrons respectively to display the expansion of
octet. Similarly, in OsFs' there are sixteen electrons around Os. Here, also except the central atoms, all
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other atoms satisfy the octet rule.

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9.1.4 Sugden'S View of Singlet Linkage Bond (2c-1 e) in Favour of 9ctet Rule
To explain the expansion of octet which apparently contradicts the rule of octet, Sugden proposed that
to maintain the octet rule, some of the bonds may arise by sharing a single electron (Le. 2c-1 e, two
centre-one electron bond) instead of 2c-2e bonds. This single electron bond (Le. 2c-1 e) is very often
referred to as singlet linkage or half-bond. This singlet linkage is represented by a half arrow (~)
pointing towards the acceptor. Thus, it is believed that in PCls, there are two singlet linkages in addition
to the three ordinary covalent (2c-2e) bonds leading to the octet (Le. 2 x 1 + 3 x 2 = 8) at P. Similarly,
in SF6, there are four singlet linkages along with the two ordinary covalent bonds to give the octet (Le.
4 x 1 +. 2 x 2 = 8) around S.
This concept of singlet linkage is not supported from the experimental facts. In pels or Sf"6 , all the
bonds are found equivalent. Definitely, 2c-Ie bonds are weaker than the 2c-2e bonds, but no such
indication is supported by the fact. This is why, the Sugden's concept of singlet linkage to defend the
octet theory is of no practical importance.
9.1.5 Sidgwick's Rule of Maximum Covalency

According to Sidgwick, it is proposed that the number of maximum electrons which can be
accommodated around an atom in the valence shell depends on the periodic position of the concerned
element. The empirical rule states as : the element, i.e. hydrogen, in 1st period can have maximum 2
electrons (i.e. 1 bond), for each of the elements in the 2nd period (i.e. Li to F) the maximum number of
electrons to be accommodated is given by 8 (i.e. 4 bonds), similarly for the elements in the 3rd and 4th
periods the maximum capacity to accommodate the electrons is 12 (Le. 6 bonds), while for the elements
in higher periods it is limited by 16 (i.e. 8 b:onds). Thus, the maximum capacity to accommodate the
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electrons around an atom in its valence shell in a compound is mainly dependent on the number
of orbitals available for bonding. This is why, the rule of octet is limited only for the elements in the
second period, and it is nothing but a special case of Sidgwick's more generalised rule. Here it is
ra
worth mentioning that because of steric factors and other factors, all the available orbitals for a
particular atom may not always participate in bonding to attain the maximum possible covalency.
ib
Tetravalence and trivalence of oxygen - typic.al examples
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Basic beryllium nitrate [Be 4 0(N03 )6] and basic beryllium carboxylates [Be 4 0(RCOO)6] where
R == H, CH3 , C2H s etc. are the typical examples where the central O-site shows 4 coordination
number and 4 covalence (in terms of2c-2e bonds).
m
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o o
)~ ''\.
- \ N40
,~
or
''\.
- \ C-R
,~
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o o
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Fig. 9.1.5.1. Structure of basic beryllium nitrate or basic berrylium carboxylate.

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In the said compounds, there is a regular tetrahedral arrangement offour Be-centres. The six bidentate
ligands (i.e. NO; or RCO:;) span along the six edges of the tetrahedron; and the basic oxygen
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present at the centre ofthe tetrahedron coordinates the four Be-centres. In this structure, each Be-
centre is tetrahedrally surrounded by four oxygens.
• In the crystal of ice; each O-site is also tetrahedrally surrounded by four hydrogen sites. Two
of these bonds are considered to be H-bonds. In H 30+ (hydronium species), oxygen shows
trivalence (three 2c-2e bonds).
• Hypervalent and subvalent compounds: In hypervalent compounds, the number ofelectrons
around an atom (generally the central atom) exceeds an octet as in SF6 , PCIs etc. In subvalent
compounds, the number of valence electrons around an atom is less than an octet as in PH2 ,
CH2, NO, N0 2, etc. The concept of hypervalence is discussed in detail below.
9.1.6 Hypervalence and Hypercarbon Compounds (cf. Sees. 9.12.12 and 9.13.5)
It has been mentioned (Sec. 9.1.5) that in the formation of covalent compounds by the p-block elements,
the octet rule is limited for the Period 2 elements but expansion ofoctet for the Period 3 and subsequent
elements is very much common. The common examples are: PCls' SiF62- , SF6 , AIF;- , XeF2 , XeF4 , etc.
Such compounds for which Lewis structure (may be an important. resonating structure) needs more
than an octet ofelectrons at least for one atom (generally the central atom) are described as hypervalent
compounds. Thus expansion of octet for the p-block elements leads to hypervalence. The ex-istence of
hypervalence is controlled by the following factors .
• Availability and participation of the postvalence nd-orbitals (cf. Sec. 9.13.5) along with the
ns and np-orbitals in bonding; for participation of nd-orbitals in bonding, the atom should link
with the highly electronegative substituents.
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• Size of the atom showing hypervalence should be sufficiently large to accommodate more than
4 pairs of electrons (bonding + non-bonding).
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The Period 2 elements do not possess the 2d orbitals and they fail to show hypervalence. The
hypervalent molecules (where the central atom shows the hypervalence) are generally represented by
ib
. N-X-L notation where N denotes the number of electrons present at the valence shell of the central
atom (denoted by the symbol X) in the compound and L denotes the coordination number (C.N.) of the
yl
central atom in the compound. Thus in terms of the notation, XeF2 is represented by 1O-Xe-2; similarly,
SF6 i~ represented by 12-S-6.
m
(A) Bonding mechanism to show the hypervalence (cf. Secs. 9.12.12, 9.13.5) : In terms of
VBT, participation of the postvalence nd-orbitals in bonding leading to the hybridisations
he
like sp 3d, sp 3cJ2, sp 3d3 is essential for showing the hypervalence. For participation ofd-orbitals
in such bonding, the atom should combine with the highly electronegative substituents. This
lc
causes the contraction of d-orbitals to facilitate the participation of d-orbitals in bonding

(cf. Sec. 9.13.5). Here it should be pointed out that participation of these postvalence nd-
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orbitals in bonding for the p-block elements is now called in question. By using the concept
of multicentre bond like 3c-4e bond, the four atomic orbitals are sufficient to show the
higher valence like 5, 6 (see Sec. 9.13.5). Thus participation ofnd-orbitals is not an essential
th
condition for the hypervalence. In fact, theoretically existence of the hyperval~nt species
like NF6-, CFZ- (in which there is no question of nd-orbitals) have been predicted and they
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might be isolated in future. Expansion of octet (Le. hypervalence) has been explained by
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using the concept of the multicentre bond in Sec. 9.13.5.

Here it is important to mention that for showing the hypervalence, the linking with the
electronegative substituents is also supported in the 3c-4e bonding process. Here the non-
bonding molecular orbital (NBMO) which bears the electron pair is basically enriched with
the character of the atomic orbitals (AOs) of the substituents (i.e. outer atoms). Thus, the
NBMO pushes the excess electron density to the outer atoms. Thus electron pushing towards
the outer atoms is favoured if the outer atoms are highly electronegative.
In the light of 3c-4e bonding process, hypervalence is redefined as the 3c-4e bonding that
leads'to an expansion of octet. Sometimes, the 3c-2e bonding model can lead to ~lectron
deficient hypervalent compounds where no expansion of octet occurs (Sec. 9.13.5).
(B) Hypercarbon compounds: There are many examples in which carbon attains the coordination
number (C.N.) more than four. Such hypercoordinated carbon compounds are simply
described as hypercarbon compounds. However, they should not be considered as hypervalent
compounds of carbon as the hypervalence is generally defined in terms of 3c-4e bonds
leading to an expansion of octet. The hypercarbon compounds are generally found in carbido
complexes (Fig. 9.1.6.1) where carbon is bounq to only metal atoms. The alkyl or aryl bridged
bonds (M-C).l-M) also lead to hypercarbon centres. The common example is AI2(CHl )6
(Sec. 9.21) where the bridging carbon shows 5 coordination number. The methyl bridging
bonding is explained by considering the 3c-2e bond (cf. Fig. 9.21.6). The 6 coordination
number (C.N.) of carbon in ILi(CHl )]4 has been explained by considering the 4c-2e bond
constituting each Li3C centre (Fig. 9.21.7). In carboranes (Sec. 10.12), organometallics and
cluster compounds (Ch. 12), such hypercoordinated carbon centres are well documented. It
is also argued that in generating the carbocations in superacids, the five coordinated carbon
ry
centres are the intermediates.
In H; (cf. Fig. 9.12.2.2) and other related species (e.g. H-bridge bonds in B2H6) (Sec. 9.21),
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the 3c-2e bond can lead to hypercoordination at the central H-atom.
The valence of carbon is restricted to four by the availability of four valence orbitals. In
ib
hypercarbon compounds, the carbon centre is linked to more than fOUf atoms. In such cases,
the electron deficient multicentre bonds (e.g. 3e-2e bond) are prevailing. The case of
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hypercoordination number through the formation of electron deficient multicentre bonds is
not restricted to carbon only. It happens for other elements also. The common examples are:
m
H;, H-bridge bond as in IJ;H6, azoborane NB 11 H 12 where N is attached to 6 neighbouring.
atoms, aurophilic cation [N(AuPPh3 )5 ]2+ where 'N is attached to 5 Au-centres.
he
Note: In terms of the rigid definition of hypervalence, the compounds like C(AuL);,
C(AuL)~+, CH~+, CH;, N(AuL);+ etc. cannot be considered as the hypervalent compounds,
lc
but these are very often described as hypervalent electron deficient compounds. The bonding
is explained in terms of 3c-2e bond model (cf. Sec. 9.13.5).
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However, according to some authors, it is not absolutely necessary to retain the original idea
ofhypervalence causing an expansion of octet. The expansion of octet is generally explained
by considering the 3c-4e bonding scheme for the main group elements without involving the
th
d-orbitals. In the compounds like CH;, CH~+, N(AuPR3 );+ (Sec. 8.20.3) etc., the bonding
has been explained by considering the 3c-2e bonds by using the p-orbitals. In such cases,
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expansion of octet does not occur. This is why, such compounds are described as electron
deficient hypervalent compounds (cf. Sec. 9.13.5).
t.m
Examples 0/ hypercarbon: Carboranes - in C2Bl0H12 carbon shows the 6 coordination

number; cubic coordination of carbon in theantifluorite structure of Be 2 C, 5 coordinated
carbon in iron carbonyl carbide [Fe5(CO)15C]; 6 coordinated carbon in [Fe 6(CO)16C]2-,
hedgehog cation (an aurophilic cation) [C(AuPPh 3)6]2+ (cf. Sec. 8.20.3); 8 coordinated carbon
in [CoS(CO)lSC]2-etc. Metallic carbides (e.g. Fe 3C) also show hypercoordinated C-centres.
Structure of some representative hypercarbon compounds are shown in Fig. 9.1.6.1.
(C) Bonding mechanism in hypercoordinated carbon compounds (cf. Sec. 9.13.5): In organic
chemistry, carbon always shows tetravalence by using the spn hybrid orbitals and pure
p-orbitals (if remaining, Le. n < 3). Such orbitals make a very good overlap. In the carbido
complexes when the carbon orbitals interact with the metal orbitals, then no such good overlap
occurs. This is why, carbon shows the tendency to increase the coordination number (C.N.)
through the/ormation o/multicentre electron deficient bonds (e.g. 3c-2e bond). For this
purpose, the 4 valence orbitals of carbon are sufficient (cf. Sec. 9.13.5C, 9.21, 9.23).
2+
ry
2-
ra
ib
yl M~~~M
m
·,· /'~
tM,- ---:/_?::,--- ,-M

1
he
,1/
, I /
',1//
lc
/1'
/1'
ea
/ 1 ,
M~IC/M
M
th
(iii) (iv)
Fig. 9.1.6.1. Structural representation of some carbido complexes (in which carbon bil)ds to only
e/
metal centres) illustrating hypercarbon compounds. (i) [Fes(CO)sCj. (ii) [Au6(PPh3 )6Cj2+ (an aurophilic
cation). (iii) [Fe6 (CO)16Cj2-. (iv) metal carbide core of [COaC(CO)1S]2- where the CO groups are not
t.m
shown.
9.1.7. The Main Types of Chemical Forces

The chemicalforces (called valence forces) are responsible to hold the atoms and molecules together
through the chemical bonds. This combination is called bonding. There are different types of chemical
forces to hold the species together..
Except the ionic and covalent forces, other chemical forces leading to combining ofdifferent species
are called weak chemicalforces. These are important in aggregation of species. These weak chemical
forces are discussed in Chapter 13.
9.1.8 Isosteric or Isoelectronic Species
Originally, it was defined as : isoelectronic species contain the same number 01electrons and the same
number olatoms. Such examples are CH4 , NH; and BHi (5 atoms and 10 electrons) which are also
Table 9.1.7.1. Different types of chemical forces

Type of force Example Equilibrium *Dissociation
distance (pm) energy (kJ mol-I)
(i) Ion-ion interaction (Le. ionic bond) Na+·····F- 230 670

(ii) Covalent bond (exchange interaction) H-H 74 458
H
+ /
.(iii) Ion-dipole interaction Na ----~ 240 84
H
ry
(iv) Hydrogen bond (dipole-dipole interaction)
H , O----H, 280 20
"0 / ' H
ra
/
H
"
ib
(v) Hydrophobic interaction CH - -- -H C / - 300 -4.0
/ 2 2"
yl
(vi) Van-der Waals (dispersion force) Ne····Ne - 330 -0.3
* Dissociation energy denotes the energy required to dissociate the combined species into the units, e.g. H-H ~
H + H; Na+----OH 2 ~ Na+ + OH 2, Ne····Ne ~ Ne + Ne.
m
he
isostructural (tetrahedral). Now the definition is broadened as : species having the same number of
valency electrons are called isoelectronic species. Such examples are: (i) CH4 and SiH4 ; (ii) CO2,
lc
+N02 and CS2; (iii) 03 and S02; (iv) BF3, NO;, and COJ-; (v) NX3, PX3 (X= halogen) and C/O;; (vi)
BN and c(jl+.
ea
The isoelectronic species are isostructural. Examples: (i) XY2 (with valence 16 electrons, linear
structure) : CO2, CS2, +N02, HCN etc.
th
Note: (i) With more than 16 valence electrons the species are angular (e.g. N0 2, NOi., etc.);
(ii) XY3 (24 valence electrons, trigonal planar): BF3, NO;, CO;- etc.;
e/
(iii) XY3 (26 valence electrons, pyramidal) : NX3, PX3, C/O;, etc.
t.m
The isoelectronic groups are :

.. .. ..
(i) -CH3, - NH 2 , - QH, -~.: (7 valence electrons)
(it) )CH 2• )NH' )9. (6 valence electrons)

(iii) " "
/CH, / N: (5 valence electrons)
The following series of compounds illustrate the replacement among the isoelectronic groups.
H 3C-C(= O)CH3 (acetate), HII-C(=O)NH2 (urea), HO-C(=O)OH (carbonic acid),
F-C(=O)F (carbonyl fluoride).
Note: Isostoichiometric species are having the same molecular formula with different electronic
configurations, e.g. H;, H 2' H;; and O2 , 0;
0;, 0;- etc.
9.2 THE THEORIES OF COVALENT BOND: BORN-OPPENHEIMeR

APPROXIMATION
The quantitative aspects of a covalent bond can be revealed in terms of wave mechanics. A covalent
bond can be expressed by a suitable wave function describing the electrons under the influence of all
the involved nuclei. Thus, we are to consider the Schrodinger equation for the wave function expressing
the covalent linkage in the molecule and then it would be solved to obtain the eigen values and eigen
functions.
The Schrodinger equation for the wave function of a covalent linkage containing N nuclei and n
ry
electrons is given by :
H\V = E\V ... (9.2.1)
ra
-.
where the Hamiltonian operator, H is given by :
ib
... (9.2.2)
yl
The terms M; and me denote the masses of the i-th nucleus and an electron respectively. The terms
m
Vne , Vee and Vnn represent the nucleus-electron, electron-electron and nucleus-nucleus interactions
respectively. Thus, the wave function \V depends on the coordinates of both the electrons and nuclei.
he
The implicit Hamiltonian operator in Eqn. 9.2.2 involves both the nuclear and electronic motions.
They can be separated by considering the Born-Oppenheimer approximation. According to this
lc
approximation, it is considered that the electrons being much lighter than the. nuclei move faster than
the nuclei. Compared to the electronic movement in a particular time interval, the nuclei can be considered
ea
to remain almost stationary with the constant internuclear distances. Thus, the translational energy of
the whole system can be considered separately as the sum of translational energies of the electrons and
nuclei. Thus, the total wave function (\V) of the system can be regarded as the product of the electronic
th
wave function (\Ve) which depends on both the coordinates of electrons and nuclei and nuclear wave
function (\Vn) which depends only on the coordinates of nuclei. Thus \V = \Ve x \Vn. Similarly, the
e/
Hamiltonian operator can be split as follows:

t.m
H= He+H n
N h2
where, Hn= - L -2- V 2 I
... (9.2.3)
;=181t M;
Nh2 2
and, V
H e = L-2- j +Vne + Vee +Vnn ... (9.2.4)
81t
j=1 me
where V stands for the potential energy for the electrostatic interactions. Thus, the electron wave function
(\Ve) which is important to our present problem is given by,
... (9.2.5)
The eigen values of the electronic wave function can be obtained by solving the above Schrodinger
wave equation, i.e. Eqn 9.2.5. In the case of polyatomic systems, Eqn. 9.2.5 cannot be solved exactly
without any approximation. l~o have the approximate solution, the two methods, Le. valency bond
method (VBn and molecular orbital method (MOn, are well documented. The approaches ofthe two
methods are totally different. But, both the methods after a series ofrefinement produce more or less
the same results.
9.3 THE VALENCE BOND THEORY (VBT)

To explai-n the covalent linkage formation, valence bond theory (VBT) is well known. In VBT, the
ry
interactions among the various valence shell electrons are considered when the combining species
approach close together from infinity. The equilibrium distance is attained when the potential energy
ra
drops to a minimum value. The VBT was proposed by Heitler and London (1927) and it was extended
by Pauling and Slater.
ib
9.3.1 The Valence Bond Theory for Hydrogen Molecule
yl
Heitler and L"ondon proposed the theoretical framework ofthis method by utilising the wave mechanical
concept of atom just one year after the fonnulation ofSchrOdinger's famous wave equation. Let the two
m
separate hydrogen nuclei be represented by A and B and their corresponding electrons be labelled by 1
and 2. Let us consider the process offonnation ofa hydrogen molecule starting from these two isolated
he
hydrogen atoms. The wave functions of the two separate hydrogen atoms in the ground state are given
by,
1 .
lc
\VA (1) = \V B(2) =- exp (- r), (in atomic units) • ... (9.3.1.1)
1t
ea
where r is the distance of the electron from the corresponding nucleus in Bohr unit.
The energies of the isolated species are given by, EA = EB = EH and the corresponding Hamiltonian
th
operators are :
2
e/
h 2
---2
V1 + v:1 ... (9.3.1.2)
81tm
t.m
that, ... (9.3.1.3)
2
Here, VI = -~, (in CGS); v.2 = (in CaS);
rAJ
2 2
__e_ x _1_, (in SI); e 1
- - - x - (in SI),
41tE o rAl 41tE O rB2 '
Here, rAl denotes the distance between the electron 1 and its nucleus A. Similarly, r B2 denotes the
nucleus-electron distance in the iSQlated B atom.
• In atomic units, the distance is expressed in bohr and energy in hartree. These are defined as : 1 bohr = ao = 52.9 pm,
1 hartree = e2/a o = 27.1 eV.
The simplest wave function of the two electron system is given by :

\V' ~ \V A (1)\V B (2) ... (9.3.1.4)
where the respective electron is fully associated with its own nucleus. The Hamiltonian operator of the
system is given by :
... (9.3.1.5)
-, e
2 e
2 e
2 e
2
where, H =- - - - + - + ---;, (in CGS)
ry
r A2 r BI rl2 R
1/47tEo factor is to be incorporated in SI system. Here, 'A2 denotes the distance between ~he electron
ra
2 and the nucleus A, and r BI bears the similar meaning;"12 and R represent the distances between the
electrons and between the nuclei respectively. The energy of the wave function (\II') is given by,
ib
E' = f\jl 'H\jI,d't, which leads to :
E' = E A + E B + Q ... (9.3.1.6)
where Q=
yl
f\jl A (l)\jI B (2) fl' \jI A (l)\jI 8(2) d't
. 2 2
m
- f\jl A(l) -=-\jI A(l) d't - - f\jl 8(2) ~\jI8(2) d't
~I ~2
he
2 2
e e
+ f\VA(I)\VB(2)-\VA(I)\VB(2)dt+- ... (9.3.1.7)
lc
r l2 R
Here, in Eqn. 9.3.1.7, the first term denotes the Coulombic interaction energy between the electron
ea
1 around the nucleus A and the nucleus B via the Coulombic potential; the second term denotes the
similar interaction energy between the electron 2 around the nucleus B and the nucleus A; the third term
th
represents the Coulombic interaction energy between the electrons and the fourth term shows the energy
ofCoulombic interaction between the nuclei. As all the terms in Qcan be expressed in terms ofCoulombic
e/
interaction, Q is referred to as Coulomb integral. The binding energy of the hydrogen molecule is
'given by,
t.m
E:binding= E'-(EA +EB )=E'-2EH =Q ... (9.3.1.8)

where, EA = EB = E H
The solution of the wave function leads to Ebinding = 24 kJ moI- 1 at R o (equilibrium internuclear
distance) = 90 pm compared to the experimental value 458 kJ mol- I at R o = 74.1 pm. Thus the calculated
binding energy can only account for 5% of the experimental one. This poor agreement can be modified
as follows. This binding energy is simply called Coulombic energy (J).
In the real molecule, it is reasonable to consider that at the molec'ular distance, the electron 1 is not
necessarily confined with the nucleus A, and the same thing is true for the electron 2. As a matter of
fact, after the bond formation, the electron 1 has got a. certain probability to be associated with the
nucleus B. Similarly, the electron 2 also spends a certain fraction of its time in the vicinity of the
nucleus A. Considering this electron exchange phenomenon we get the two states, H A(1)HB(2), (I) ;
and, HA(2) H B( 1), (II). This idea of electron exchange phenomenon was introduced by Heitler and
London. The corresponding wave functions are described as Beitler-London wave functions.
The wave functions \VI and \Vn for the states I and II are given by :
\V I = \V A(I) \VB(2) ... (9.3.1.9)

and, \VII =\VA(2)'VB(I) ... (9.3.1.10)
Thus, the true wave function must be a combination of the two, Le.
\V s = c1\V I + c2\V II = c1\V A(I) \V B(2) + c2\V A(2) \VB(I) ... (9.3.1.11)
and, \V a = c3 \V I - c4 \V II = c3\V A(I) \V B(2) - c4 \V A(2) \V B(I) ... (9.3.1.12)
ry
The" H2 molecule is a symmetrical one and gets an equal contribution from \VI and \VII' Le. c 1 = c2
and c3 = c4 • To evaluate c 1 and c3' the conditions/or normalisation of the respective wave functions
ra
are utilised as follows. .
ib
c: f'l'; d't = I; or, c: f('I'[ + '1'11)2 d't = I;
2
+ c)2 + 2Ct2rJ \V I\V II d t =I
yl
or, c)
Now, f'l'[ 'l'lI d 't can be treated as follows:

m
f'l' J'I' II d't = f'l' A(1)'1' B(2) 'I' B(1)'1' A(2) d't]d't 2
he
(in which the general volume element dt is replaced by dt) and dt 2 for the electron I and 2 respectively).
f'l' J'I' IId't = f'l' A(1)'1' B(l)d't l f'l' A(2)'1' B(2)d't 2 =S AB x S AB =S~B
lc
or,
The two integrals, i.e. f'l' A(1)'1' B(I)d't] and f'l' A(2)'1' B(2)d't 2, are equal as they only differ in
ea
labelling the electrons. The integrals denoted by SAB are called overlap integrals.
th
2 2 1
Therefore, 2cI (I + S AB) = I, or, c. = ~ 2 ... (9.3.1.13)
e/
2(1 + SAB)
1
Similarly it can be shown that, c3 =~ ... (9.3.1.14)
t.m
2
2(1- SAB)
Thus, the two possible wave functions are :
... (9.3.1.15)
... (9.3. 1.16)
Here, \VS is symmetric as it remains unchanged by the exchange of the electrons while \Va is
antisymmetric as it changes its sign by the exchange of the electrons. The results are shown in Fig.
9.3.1.1. The symmetric combination leads to stabilisation while the antisymmetric one destabilises
the system.
554 Fundamental Concepts of Inorg,anic Chemistry
+Ve
\ 'V' = 'II A(1) 'IIs(2)
,~ Coulomb Energy
o ,,
" ,,~'IIcov =C1['IIA(1) 'Vs(2) + 'VA(2) 'IIs(1)]
ry
,," ,,"#1'
1 ,,,,
\
,. " ""
" Exchange Energy
ra
J: -Ve "-
w
,, .I~('IIH2 = (1 - A)'V cov + 'Ilion
N
,, .I
ib
I
Covalent -Ionic Resonance energy
, ......-.1_ _
(after considering Z*)
"
---+
yl
Internuclear Distance
m
Fig. 9.3.1.1. Valence bond treatment of H2 molecule.
he
The energy of the system can be evaluated'as usual,
Es = I\jI" H\jIsd't, and Ea = I\jIaH\jI ad't

lc
where,
ea
It leads to
th
Q+A
E.f =2EH + 2 ... ·(9.3.1.17)
1 + SAB
e/
Q-A
Ea =2EH +
t.m
and, 2 ... (9.3.1.18)

I-S AB
where, Q is referred to as the Coulomb integral, and A is referred to as the exchange integral
(A = J\jI A(l) \jI 8(2) i/' \jI A(2) \jI 8 (l)d't). The exchange integral appears due to the exchange of the
electrons between the nuclei. This phenomenon provides a larger space for the electrons to move around
both the nuclei. Thus according to the principle of the model, particle in a box, the energy of the system
gets lowered down. This modified wave function leads to the binding energy,
Q+A
Ebinding = E.'t - 2EH = 2 ... (9.3. 1.19)
1 +SAB
The calculated value of the binding energy is found to be 303 kJ mol-I at Ro = 86.9 pm. The
observed corresponding values are: 458 kJ mol-I and 74.1 pm. Thus, the calculated value can account
for -- 66.6% of the observed binding energy. In the calculated value, Coulombic energy (.I) contributes
about 10% only while the exchange energy (K) contributes about 90%.
The wave function 'lis represents the covalent interaction and this is why, it is very often referred to
as 'V COy' Le.
I'V s = 'V COy =ct ['V A(1) 'V B(2) + 'V A(2) 'V B(1)] I ... (9.3.1.20)
A further modification of the result is obtained by considering the effective nuclear charge z*
instead of Z. This was introduced by Wang. The consideration of T is reasonable. In the isolated
ry
atoms, there is no possibility of electron shielding but'in the molecule, the two electrons are now
prevailing and consequently, the electron screening phenomenon will result. It leads to the binding
energy 365 kJ mol- 1 at Ro = 74.3 pm. Thus the agreement is enhanced to -- 80%.
ra
Another modification leading to the possibility of the existence of both the electrons to a particular
nucleus improves the result further. This probability will introduce the consideration of, H~ H"B or
ib
. H~ H;. Due to the electron-electron repulsion, the electrons will try to avoid each other, but still there
yl
is a small but finite probability for the electrons to coexist. Thus the wave function, 'Ilion describing the
ionic state is given by : m
\Vion = Cs \V A (1) \V A (2) + c6 \V B(I) \V 8(2) ... (9.3.1.21)
Thus, the resultant wave function of the actual hydrogen molecule is given by :
he
I'V Hz = (1 - "') 'V COy + "''Vio" I ... (9.3.1.22)
lc
where A « 1) denotes the mixing coefficient measuring the extent of mixing of the ionic wave function
with the covalent wave function. This phenomenon introduces the idea of covalent-ionic resonance.
ea
The solution of Eqn. 9.3.1.22 yields, Ebinding = 388 kJ mol-I, at Ro = 74.9 pm (i.e. the agreement with
the observation is 85%). Eqn. 9.3.1.22 indicates that the actual hydrogen molecule is some sort of
th
hybrid of the following canonical forms which differ in the pattern of the distribution of the electrons.
covalent ~ H: H; ionic ~ Jr:I1, -H: Jr
e/
No single one of the above canonical forms can explain the behaviour of the ~ctual molecule but the
hybrid can.
t.m
Table 9.3.1.1. Energy values and equilibrium distance for the ground state of H2 °molecule in
vaJence bond approach
. Type ofwave function and modification Energy Internuclear
(kJ mOll) distance (pm)
Uncorrected 24 90.0
Heitler-London (incorporation of exchange energy) 303 86.9
Consideration of shielding and covalent-ionic resonance 388 74.9
Experimental value 458 74.1
Incorporation ofspin wave and Pauli's exclusion principle: Sor far, we have only discussed the
orbital wave function of the electrons. To get the total wave function ('Vtotal)' both the orbital wave
function ('Vorbital) and spin wave function ('Vspin) must be considered. Thus,
'V totaI = 'Vorbital x 'Vspin •.. (9.3.1.23)
Now let us consider the spin wave function of the electrons. It is known that only tWp types of spins
exist. Let, a. and P be the corresponding spin wave functions. If both the electrons (1 .~nd 2) in H2 are
having the same spin, Le. a. or p, then the corresponding combined spin wave functions are given by :
'Vspin(l) = 0.(1) 0.(2) (9.3.1.24)
'V spin(Il) = P( 1) P(2) (9.3.1.25)

If the spins are different, then it leads to spin wave functions a( 1)P(2) and a.(2)P( 1) which are
equally probable. Their linear combination yields:
ry
1
"'spin (III) = J2 [0.(1) 13(2) + 0.(2) 13(1)] ... (9.3.1:26)
ra
1
and, "'spin (IV) = J2 [0.(1) 13(2) - 0.(2) 13(1) ... (9.3.1.27)
ib
where 1/ J2 gives the normalising constant
yl
Here, \V spin(l), \V spin(Il) and \11spin(IIl) are symmetric while \V spin(IV) is antisymmetric.
m
Now to combine the orbital wave function (\Vorbital) and spin wave function ('Vspin)' we must consider
the Pauli's exclusion principle (see Sec. 4.1.12). It can be stated as: the total wave function in any
system (atomic or molecular) must be antisymmetric with respect to the exchange of the electrons.
he
This is why, the antisymmetric spin wave function can only combine with the symmetric orbital wave
function and vice versa. Therefore only the following four combinations are feasible.
lc
~[0.(1) 13(2) - 0.(2) 13(1)] ... (9.3.1.28)

ea
Ground state {"'" x
\V a X [P(l) P(2)] ... (9.3.1.29)

th
Excited state \V a X [0.(1) 0.(2)] ... (9.3.1.30)'

e/
'" a X J21 [0.(1) 13(2) + 0.(2) 13(1)] ... (9.3.1.3 1)

t.m
It has been pointed out that the antisymmetric orbital wave function 'Va leads to only repulsive
energy of the excited state. Hence Eqns. 9.3.1.29 to 9.3.1.3 1 represent the excited states.
Thus the excited state has three spin wave functions leading t~ the triplet state. The symmetric
orbital wave function \V S leads to the ground state whose total function is represented by Eqn. 9.3.1.28
in which there is only one spin wave function leading to the singlet state. Thus, in the ground state the
two electrons are paired up with their opposite spins. Thus, in VBT, the spin pairing phenomenon
automatically arises to make the total wave/unction antisymmetric. This is why, this method is very
_often referred to as the method of electron pairs. Thus, this also supports the quantum mechanical
extension of Lewis theory of the electron pair bond.
9.3.2 The Major Conclusions Drawn from VBT

(i) The covalent bond (2c-2e) is formed due to the pairing oftwo unpaired electrons with the opposite
spins. The number of unpaired electrons gives the maximum possible number of covalent linkage.
If the combining species do not have any unpaired electron, then before to participate in the bond
formation the paired electrons must be unpaired. The paired electron pair can itselfparticipate in
bond formation as in coordinate covalent bond.
(ii) The exchange energy contributes significantly in stabilising a covalent bond. This quantum
mechanical phenomenon can be rationalised from the principle of the model, particle in a box.
(iii) The covalent-ionic resonance is also important even in the homonuclear diatomic molecules.
This factor becomes more important in the case of heteronuclear diatomic molecules where the
electronegativity of the combining species differs significantly.
ry
(iv) The antisymmetric orbital wavefunction being combined with the symmetric spin wavefunctions
leads to the excited states characterised by the triplet state. The symmetric orbital wave function
ra
combines with the antisymmetric spin wave function and produces the ground state characterised
by the singlet state. Here, the electron pairing automatically arises as a demand of Pauli 's exclusion
ib
principle.
Thus, the total wave function describing the ground state is given by,
yl
'Vtotal = 'Vorbital (symmetric)
m x 'V(spin) (antisymmetric)
9.3.3 The Major Drawbacks in VaT

(i) In VBT, it is assumed that each of the combining species will provide an unpaired electron with
he
opposite spin to form a covalent linkage. But in the case of a coordinate covalent bond, both
the electrons are provided by one species. This aspect remains apparently inexplicable.
lc
(ii) In 02' all the 2c-2e bonds along with the lone pairs, support it to be a diamagnetic one. But, in
fact, O2 is a paramagnetic molecule. This aspect also remains inexplicable.
ea
(iii) In VBT, N 2 is supposed to contain a triple bond (Le. N == N) as in the case of acetylene (HC ==
CH). In spite of this close similarity, their activities differ drastically. Nitrogen is very much
th
inert whiie acetylene is fairly active. This difference gets no explanation.

(iv) It cannot explain the odd electron bond in the molecules (e.g. He; , H;). As a matter of fact,
e/
bonding in odd electron molecules cannot be explained by VBT which mainly considers the
pairing of electrons in 2c-2e bonds. To deal with the odd electron molecule in the light of VBT,
t.m
some special types of bonds are invoked (see Sec. 9.20).
9.4 MOLECULAR ORBITAL THEORY (MOT)

The molecular orbital theory was p.foposed and developed mainly by Mulliken, Lennard-Jones and
Hilckel. In this approach, we are to start from the skeleton of the molecule with its nuclei in fixed
positions, then we are to develop the molecular orbitals (MOs) into which the electrons are to be fed as
in the atomic orbitals (AOs) in the atoms. In placing the electrons, it follows the aufbau principle,
Hund's rule arid Pauli's exclusion principle. T~e MOs are polycentric as they involve more than one
nucleus while the AOs are monocentric as t~ey involve only one nucleus. There are two well known
methods of developing the molecular orbitals .(MOs). These are: (i) Linear Combination ofAtomic
Orbitals (LCAO) method, and (ii) United Atom method. The LCAO has got a good deal of similarities
with the VB method. The LCAD method will be discussed here in different cases.
9.4.1 The LCAO-MO Treatment of Diatomic Hydrogen

Molecule Ion (H;)
A. One Electron-Two Centre (1e -2c) System
The entitled system contains two protons (i.e. two nuclei) and
one electron, and it is the simplest molecule. In the ground ARB
state,' the atoms will utilise the lowest atomic orbitals (Le. 1s) Fig. 9.4.1.1. Schematic represen-
to form the MOs. For convenience, the two nuclei are tation of hydrogen molecule ion
represented by A and B (see Fig. 9.4.1.1). When the electron (H; ) skeleton.
ry
spends most of its time to the nucleus A or B alone, its behaviour is controlled by the atomic orbital
wave function \11A or \11 B alone in the ground state. Thus, in the molecule, the molecular orbitals can be
ra
regarded as a linear combination of the individual atomic orbital wave functions \11A or \11 B as follows:
\11 MO = c 1\11 A + c2\11B (9.4.1.1)
ib
•••
The combination between A and B will be effective if the following three conditions are satisfied.
yl
(i) Energy: The combining wave functions should have comparable energy.
(ii) Overlap: The AOs representing the electron cloud must undergo overlapping considerably to
m
produce a significant extent of net overlap.
(iii) Symmetry: The lobes of combining AOs must have the same symmetry with respect to the
he
bond axis. It indicates that the lobes of AOs of the same symmetry can only overlap.
These three conditions are very often abbreviated as EOS conditions where, E stands for the energy
condition, 0 stands for the overlap condition and S stands for the symmetry condition.
lc
The corresponding SchrOdinger wave equation is given by :

ea
H\I1 MO = E\I1 MO ... (9.4.1.2)

2
-. h 2 2 2 2
th
where, H=--2- V -e IrA -e IrB +e IR ... (9.4.1.3)

81t m
e/
(to express in SI units, _1_ is to be incorporated).

41tE o
t.m
To evaluate the energy, we are to consider the following expression:
I\JI MO H \JI MO dt
E= ... (9.4.1.4)
J\V~o dl:
I(C1\JIA +C2\J1B)H(C1'lJ A + c2\J1B) dt
I(C1\JIA +C2\J1B)2 dt
2 2
(C 1 a. A + C2 a. B + 2c1C2 PAB )
2 2 ... (9.4.1.5)
C1 + C2 + 2c1 C2 S AB
where, a A == I\JI A H \JI A d't, a B == J\JIB H \JIB d't, 13 AB == I\JI A H \JIB d't and, S AB == I\JI A \JIB d't; and
J\JI~ dt == J\JI~ d't = I, (from the consideration of normalised AOs).
The integrals a.A and a. B are referred to as Coulomb integrals.

These are very close to the energies of the electrons in the isolated
respective atoms, i.e. a.A ~ EA and a. B ~ EB • Thus in the present
system, the Coulomb integral actually gives the measure of energy
released when an electron separated from the nucleus by an infinity
\VA 'VB
occupies the Is orbital ofa hydrogen atom. Thus a. is negative and
from the definition, the ionisation potential is given by - a.. The Fig. 9.4.1.2. Overlap of two
atomic orbitals to produce' the
integral PAB is referred to as resonance integral which gives the
overlap integral (SAB)'
ry
measure of exchange energy ofan electron. It is a negative quantity
indicating stabilisation through the exchange phenomenon. The integral SAB is called overlap integral
representing the extent of overlap between the atomic orbitals (AOs) as shown in Fig. 9.4.1.2.
ra
To evaluate c 1 and c2' we are to follow the variation principle to find out the condition to minimise
the energy. Thus, aElac 1 = 0 and aElc2 = O. From Eqn. 9.4.1.5 we get:
ib
2 2 2 2
E(c1 + C2 + 2c Ic2SAB) = c1 a. A + c2 a. B + 2c]c 2 PAB ... (9.4.1.6)
yl
Thus, the differentiation of Eqn. 9.4.1.6 with respect to c 1 gives,
m
2 2 aE
E(2c 1 + 2c2SAB) + (C1 + C2 + 2c1c 2S AB) - = 2c1u A + 2c 2PAB
aCI
he
aE "2c1a. A + 2c2 PAB - 2E (C1 + c2 S~B)

lc
or,
Ocl = cf + c; + 2ctcZS AB
ea
By putting the condition, aElac 1 = 0, we get:
C1a. A +c2PAB -E(c1 +C2SAB )=0 ... (9.4.1.7)

th
Similarly from the condition, aElac2 = 0 we get:

e/
c1P AB + c2U B - E(C1S AB + c2 )= 0 ... (9.4.1.8)

t.m
Eqns. 9.4.1.7 and 9.4.1.8 lead to the following pair.
c1(a. A - E) + c2 (J3 AB - ES AB) = 0 ... (9.4.1.9)
and, C1(P AB --ES AB )+c2 (U B -£)=0 ... (9.4.1.10)
The above pair of secular equations gives,
I;~B-_EESAB ~:B_-:SABII:: 1=0

The energy value can be obtained from the following secular determinant,
Thus we get:
2
(a A - E) ( a B - E) = (P AB - ES AB ) ... (9.4.1.11)
For the hydrogen molecule ion, a A = a B = a (say), and thus Eqn. 9.4.1.11 becomes,
2 2
(a - E) = (P AB - ES AB ) ; or, a - E = ± (P AB - ES AB )
Thus, the two values are :
E = a + PAB = a + PAB - asAB
... (9.4.1.12)
ry
+ 1+ SAB 1+ SAB
E =a- PAB =a _ PAB - asAB
ra
and, ... (9.4.1.13)
- 1- SAB 1- SAB
By using the energy values in the secular Eqns. 9.4.1.9 and 9.4.1.10, we get, c 1 = ±c 2• Therefore we
ib
have the eigen functions and eigen values as follows.
yl
a+P AB
'"MO( +) = C+ (", A + '" B)' E + =1 S ... (9.4.1.14)
+ AB
m
and, \V MO(-)
- C (
- - \V A
-
\V B'
) E - a-
- - 1_ S
PAB ... (9.4.1.15)
he
AB
It is evident that the \V MO (+) stabilises the system while the \V MO (_) destabilises the system through
the repulsive energy. Generally, the wave function which leads to destabilisation is called an antibonding
lc
molecular orbital (ABMO), represented by \V ~o. The wave function which imparts stabilisation is
called a bonding molecular orbital (SMO). These are simply represented as follows:
ea
... (9.4.1.16)
th
e/
and, ... (9.4.1.17)
. .
t.m
(Using the convention, \V MO = \V MO(+)' c+ = c, \V MO(-) = \V MO' C_ = C , E+ = E and E_ = E )
C and c· can be evaluated by imposing the condition of normalisation as follows:
J\V Mod'! = I; or, J(\V

2
c2 A + \V B) 2 d'! =. I;
c (1+1+2S AB )=I; or, c=1/~2(I+SAB)

2
or,
Similarly, c· = 1/~2 (1- SAB)

1
c+ =----;:====- ... (9.4.1.17a)
- J2(I±SAB)
1f the overlap integral is negligibly small, then ~e get c =c· = Jz' and
1
\IIMO =12 (\II A + \II B ), E = a. + PAB ... (9.4.1.18)
I ~O ="*
\II (\II A - \IIB)' E· =a. - P I AB ... (9.4.1.19)
This result is shown in Fig. 9.4.1.3.

Here it is worth mentioning that \V MO and \V MO are mutually orthogonal, i.e.
ry
1 1
J\II MO \II ~d't = JJ2 (\II A + \IIB) J2 (\II A - \IIB) d't
ra
J"2 (\II A - \IIB)d't ="21 J\II Ad't -"21 J'¥Bd't
1 2 2 2 2"
ib
1/2 - 1/2, (\V A and 'VB are individually normalised).
The solution for H; produces bond energy = 1.77 eV = 170.8 kJ mol- 1 and bond length 132 pm,
yl
while the observed corresponding values are: 2.79 eV, i.e. 269 kJ mol- 1 and 106 pm. Thus the calculated
bond energy only accounts for about 60% ofthe observed one. Thus the agreement is not good. However
m
it can be improved by a number of modifications.
'VMO
Effect of SAB on the energies of MOs; Existence of
he
He l : Here it must be remembered that the overlap integral
(SAB) can never be zero in forming a real covalent linkage.
l+ve //T'\
lc
Here, it has been neglected (in a mathematical sense)

compared to the other terms. Thus, in the cases where c:
iliA
\
~lO A
\--,-----[--:+-1-'V-
I
8-
ea
W \... I
strong covalent bonds are formed, SAB cannot be \ I
neglected. -Va I
'VMO
th
In actual calcu.lation without neglecting SAB' it is found

Fig. 9.4.1.3. Energies of bonding and
that the destabilization induced by the antibonding molecular anti-bonding molecular orbitals.
orbital (\V ~o) is greater than the stabilization procured by
e/
the corresponding bonding molecular orbital ('liMO). If it were not so, we would get He 2 along with the
t.m
isolated He atoms, because in He 2 the stabilization could get balanced by an equal amount ofdestabilisation
giving rise to no net stabilisatioll or destabilisation with respect to the starting He-atoms. 'Thus it (i.~.
He 2) would have an equal probability of its existence as for the isolated atoms, i.e. 2He. But He 2 does
not at all exist in the ground state. It is due to the fact that in He'], destabilisation by the two electrons
in the 'V ~o is greater than the stabilisation yielded by the two electrons in the 'l'Moe Here it may be
pointed out that entropically the system of 2He is also favoured over the He 2 system.
Graphical representation ofthe MOs : Fig. 9.4.1.4a, b, d show the wave functions of the individual
atomic orbitals and the molecular orbitals of H;.
The antisymmetric combination in \V MO shows its
zero value in the midway between the nuclei. The symmetric combination in \V MO shows a high value
in the range between the nuclei.
In Fig. 9.4.1.4c, e and Fig. 9.4.1.5, the electron probability distribution functions for the AOs and
MOs are represented for H;. It is revealed that the bonding molecular orbital (HMO) leads to an
accumulation of electron density between the nuclei to minimise the nucleus-nucleus repulsion.
On the other hand, the antibonding molecular orbital (ABMO) removes the electron density
'P S (1S)
\jJ A(1 s)
ry
ra
ib
(b) (c)
yl
m
he
A B
lc
(e)
ea
Fig. 9.4.1.4. Qualitative representation: (a) \II A(IS) and \II S(ls) of the isolated (Le. noninteracting H-atoms
HA and Hs; (b) \liMO (Le. bonding molecular orbital) of H;; (c) probability of finding electron density
th
in \liMO of H;; (d) \II~ (Le. antibonding MO) of H;; (e) probability of finding electron density in 'V~o.
e/
,
t.m
1\ (2)
Note: Compared to (4), the higher electron 2 (1 )/\ I \.---'P~
density for (3) between the nuclei is 'PA ./ \
\
'-----tI
expected from the expression of 'liMO' For
'liMO' electron density between the nuclei is I
/ \
,,
I
increased while for \v ~o, electron density
\
I
I
between the nuclei is decreased. /
/
~
~
\v~o = \v~ + 2'11 A \II S + \v~; ~
'V~o = \II~ ~ 2'11 A'VS + 'V~

A B
Fig. 9.4.1.5. Qualitative representation of electron density distribution (relative) curves for and H;
isolated H-atoms HA and Hs. (1) and; (2) for each atomic orbital separately; (3) for the bonding molecular
orbital of H;; (4) sum of probabilities of finding the electron in the isolated H-atoms; (5) for the
antibonding molecular orbital of H;.
from the region between the nuclei giving rise to a repulsive interaction between the nuclei. Thus
the MOs give the pattern of charge distribution as,
'VMO : + - - +, 'V ~o : - + + -
Bonding MO arising from the positive overlap of 'VA and 'VB brings a higher electron density between
the nuclei than the sum of electron density ofthe two isolated H-atoms. This is why, in Fig. 9.4.1.5, the
curve (3) runs above the curve (4).
Evaluation ~f a, PAS and SAS for H;
ry
H in SI unit is given by :
ra
- h2 2 ( 1 lIe
) 2
H =- 81t 2m V - r + r - R 41tl,o
A n
...(9.4.1.20)
ib
(cf Eqn. 9.4.13)
h
yl
It can be represented in terms of atomic units (where m = I, e2 == i, -21t = I , 41tEo == I; cf Solved
problem 4 in Chapter 4) as follows:
m
H=- !2 V2 - (~
r
+ ~ - -!.)
r R
(9 4 1 21)
... · · ·
he
A B
(i) The term a (= energy of the electron in' the isolated H-atom) is given by :
lc
a = a A == ('II1.f(A) H'111.f(A»)' (assuming the electron in Is orbital in ground state)

ea
~2 r: - r: + ~ '111.f(A»)
th
('II1.f(A) - -
~2 r: 'IIt.«A») +('III.«A) 1- r: I'111.f(A) ) +('II ...(A) 1+ ~I '111.f(A») .

e/
('II1.f(A) - -
t.m
(Note: Hamiltonian ofan isolated H-atom is: HO =- ..!- V 2 - ~ (i~ a.u.). Thus the Ist integral
2 rA
leads to : ('II ...(A) IHol 'V ...(A») = ('V1.f(A) IEHI 'V1s(A») = EH')
The first term of the above equation denotes the energy of Is orbital of an isolated H-atom. It
is denoted by EH. The second integral considers the electrostatic attraction between the 1s
electron of A and the nucleus B and it is known as Coulomb integral denoted by J. It represents
the electrostatic attraction and is a negative quantity. The third integral is independent of the
nuclear coordinates and consequently it is independent of R. It simply equals to I/R where R is
*I
the internuclear distance (fixed). Thus we have:
I a = EH + J + .. (9.4.1.22)
(ii) The term PAB called resonance integral is given by :
PAB = ('VIs(A) H'Vb(B») = ('Vb(A) - ~2 r~ - r~ + ~ 'Vb(B»)

-
('Vb(A) - ~2 ~ 'Vb(B) ) +(\l1J.v(A) 1- r~ 1'Vb(B) ) +('Vts(A) 1+ ~I 'Vb(B»)

-
+~ I
ry
or, IP AB =EHSAB + K ... (9.4.1.23)
ra
(Note: The first integral represents :
IH" I'Vb(B») ::: (\JIb(A) IEHI\JIb(B») ::: EH ('VtS(A)'Vb(B») ::: EHSAB)
ib
(\JIb(A)
yl
Here, K gives the exchange integral which considers some sort of exchange of electron
between the nuclei A and B. Physically, it depends on the overlap of the orbitals. It is a negative
m
. quantity. It is favoured maximum when the overlapping orbitals are of the same energy.
Now, E+ and E_ may be expressed as follows:
he
E -- E -- a. + PAB -_ EH+ ~ + J + K ... (9.4.1.24)
lc
+ 1+ SAB R 1+ SAB
(in atomic units)
• a. - PAB 1 J - K ... (9.4.1.25)
ea
and E =E_ = =EH +-+---

1- SAB R 1- SAB
th
The above expressions are given in a.u. For the values of R = 2.5 a.u., I/R = 0.4, J= - 0.39,
K= - 0.287, SAB = 0.458 :
e/
E+ = - 0.564 and E_ = - 0.290 in a.u. (Le. hartree)

t.m
These are calculated by taking E H = - 0.5 hartree.

Note: Here, it should be mentioned that the integrals 1, K and SAB can be expressed in terms of
R. In atomic units, the wave function of Is for H-atom is expressed as follows:
1
\jib = .In. exp (- r) ... (9.4.1.26)
The integrals are expressed as :

1
J ::: - R {I - (l + R) exp (- 2R)} ; K ::: - (l + R) exp (- R);
SAB ::: (1 + R + ~2 ) exp (- R)
(R expressed in atomic units)

9.4.2 The LCAO-MO Treatment of the Diatomic Hydrogen Molecule: A Two Electron-Two
. Centre (2e-2c) System
The Hamiltonian operator for the title system consisting of two nuclei and two electrons (see Fig.
9.4.2.1) is given by :
if =_ _ h_
2
2 2
(V I2 + V22 ) + ~R + ~ _ ~ _ ~ _
2 2 2
-=- _-=-
2 2
... (9.4.2.1)
81t m 'i2 rAI 'BI 'A2 r B2
(in SI unit, 1/47tEo factor is to be incorporated properly in the expression)
ry
ra
ib
yl
m
Fig. 9.4.2.1. Schematic representation of the hydrogen molecule (H2 ) skeleton.
he
It is a two electron system. Hence the total orbital wave function is the product of the wave function
for each electron. For the electron I, it will occupy a molecular orbital given by Eqn. 9.4.2.2, in the net
lc
Coulombic field provided by the two nuclei and the electron 2.

= c I'VA (I) + c2'VB(I)
ea
'VI ... (9.4.2.2)

Similarly, the electron 2 will occupy the molecular orbital given by Eqn. 9.4.2.3.
th
'V2(2) + C2'VB (2)

= c I 'VA ... (9.4.2.3)
Thus, 'VI and 'V2 are the linear combination of the two atomic hydrogen orbitals (i.e. Is). Thus the net
e/
molecular orbital 'V MO is given by :

t.m
'V MO = 'V I x 'V 2 = [c I \VA (I) + C2\VB ( I )] [c I \V A (2) + c2\V B (2)] ·.. (9.4.2.4)
By using the condition to nonnalise the'll MO' we get, J'II~d't = 1.
It produces the normalising constant 1/[2(1 + SAB)] (under the condition, c I = c2) for the bonding
molecular orbital. Therefore, we get the wave function of the bonding molecular orbital as follows,
1 '
'V MO = ['V A(I) 'V A (2) + 'V B (1) 'V B (2) + 'V A(I) 'V B (2) + 'V A,(2) \V A(1')] ... (9.4.2.5)
2(1 + SAB) ! I
The first two terms, Le. 'VA (1) 'VA (2) and 'VB (I) 'VB (2) represent the ionic forms, Le. H~ H; and
H~ H B respectively. The other two terms represe,nt the contribution of the covalent canonical forms
originated from the electron exchange phenomenon. Thus compared to VBT, MOT gives an excessive
weightage to the contribution coming from the ionic canonical forms. In MOT, the ionic and covalent
forms get equal weightage. This unexpectedly high weightage to the ionic form results due to the fact
that in obtaining the molecular orbital the mutual repulsion of the electrons was not taken into account.
As a matter of fact, the simple LCAO-MOT always introduces an excessive ionicity in the
molecules.
The energy of the system can be evaluated by using the variation principle from the following
Schrodinger wave equation.
~ J'l'MO H'l'MO dt
E'V MO = H'V MO; or, E = 2J'V Mo dt
H;
ry
The present mathematical task is more complicated compared to the system because of the
additional terms in the Hamiltonian operator. The solution after consideration of shielding yields the
binding energy (Ebinding = E min 2EH ) ~ 337 kJ mol- l at Ro ~ 73 pm compared to the observed value
ra
'"'J
458.3 kJ mol- t at Ro = 74 pm. Thus the calculated value accounts for 73% of the observed one. Further
modifications can improve the result.
ib
Compared to the H;, the bond energy in H2 is greater. It is reasonable becaus~ the more electron
clouds between the nuclei (Le. + - - +) in the bonding molecular orbital of H2 gives a better stabilisation
yl
compared to the distribution, + - + in the bonding molecular orbital of
m H;.
9.4.3 Comparison of VB and LCAO-MO Treatment on H2
The fundamental approaches in the two treatments are different. In the VBT, we start from the individual
he
atoms to interact with each other as they proceed together. The progress of the process is comparable
with that of ,a chemical reaction. The orbital wave functions of the isolated atoms are 'VA (I) and \liB (2)
lc
where A and B are the nuclei with the electron I and 2 respectively. When they approach within the
bonding distance, the electrons being indistinguishable may exchange the nuclei with an equal probability.
ea
Thus the following two wave functions become equally probable.

'V/ = 'VA(I) 'VB(2), and 'VII = 'VA(2) 'VB(I)
th
Thus the resultant VB covalent wave function is given by :

e/
\II VB (cov) = ct['VA(I) 'VB(2) + \IIA(2) \IIB(I)]

Then after incorporating the contribution of the ionic canonical forms, we get the modified VB
t.m
wave function as follows.

\IIVB = (I - A) cl['VA(I) \IIB(2) + 'VA(2) \IIB(I)] + A[(\IIA(I) \IIA(2) + \IIB(I) \IIB(2)]
On the other hand, the MOT starts with the nuclei at fixed positions in the molecule. The wave
function of the electron 1 in the field of the two nuclei and the electron 2 is given by,
'VI = calVA (I) + Cb'VB (I)

Similarly for the electron 2, we have:
\112 = Ca'VA (2) + Cb'VB (2)
Thus the MO wave function is given by :
'V,
'V MO = 'V t x 'V2 = c2 ['VA( 1) \II A(2) + 1) \V B(2) + \V A( 1) \V B(2) + 'VA(2) 'VB( 1)]
(the present case being symmetrical, ,ca = cb = C say)
In \V MO' the coefficients ofthe four terms are identical. It indicates that each term contributes equally.
In \V MO' the first two terms arise due to the ionic canonical forms of the molecule while the -third and
fourth terms arise from the covalent structures. In \V VB' both the covalent and ionic parts are also existing
as in \V MO' but they do not contribute equally while in \V MO both the ionic and covalent forms are
expected to contribute equally. This is the basic difference between the theories. As a matter of
fact, the simple LCAO-MOT overestimates the contribution coming from the ionic forms. But,
through a series of refinements, both the methods lead to almost the same result.
9.4.4 The Important Aspects of LCAO-MOT
ry
The basic principles are very similar to those of the self consistent field method (SCF method) (see
ra
Sec. 4.2.1). The important features of the treatment are mentioned here.
(i) The molecular orbitals (MOs) are developed from the skeleton of the molecule containing the
ib
nuclei at the fixed positions through the LCAO method. Thus, the MOs are polycentric (involving
more than one nucleus) while the AOs are monocentric (involving only one nucleus).
yl
(ii) The numb~r of molecular orbitals are the number of starting atomic orbitals.
(iii) For an effective combination of the atomic orbitals they must satisfy the EOS conditions (see
m
Sec. 9.4.1) according to which the energy ofthe orbitals should be comparable; they must overlap
and the overlapping lobes must have the same symmetry.
he
(iv) Depending upon the overlap integral (SAB)' the MOs are classified as bonding MO (SAB > 0),
antibonding MO (SAB < 0) and nonbonding MO (SAB = 0).
lc
(v) The energy of each molecular orbital can be calculated by solving the appropriate Schrl>dinger
wave equation.
ea
(vi) All the MOs are normalised, i.e. I"'~odt = I; or, I(", ~O)2 dt = I
I'" ",~dt = 0,
th
The corresponding bonding and antibondingMOs are mutuallyorthogonal, i.e. MO x
(vii) After construction of the MOs, the electrons are placed in the MOs by following the aufbau
e/
principle, Hund's rule of spin multiplicity and Pauli's exclusion principle.

(viii) The molecular orbitals are also defined by the four quantum numbers as in the case of AOs.
t.m
Generally the n and I are retained from the starting AOs, and they bear the same significance.
The magnetic quantum number of the MOs are represented by A. In a_diatomic molecule, the
a-bonding axis, Le. the axis containing the nuclei, is taken as the reference direction. The
corresponding quantised angular momentum is expressed in h/27t units with respect to the reference
axis. It can have values, A. = -I, - (/- 1), ... ,0, ... , (/- 1), I.
For A = 0, the orbitals are symmetrical around the reference axis and the orbitals are called
a-orbitals. For A = ± 1, the orbitals are referred to as 'It-orbitals, and for A = ± 2, the corresponding
orbitals are termed as O-orbitals. The fourth quantum number is the spin quantum number having
the same significance as in the atoms.
(ix) The different MOs have different symmetry elements. Based on these symmetry elements they
can be classified as gerade (g) and ungerade (u), 0'- and 'It-orbitals, bonding and antibonding
orbitals (see Sec. 9.6).
(x) The bonding molecular orbitals concentrate the electron cloud between the nuclei to stabilise the
system while the antibonding orbitals remove the electron cloud from the space betweeJ! the
nuclei to destabilise the system. ....
·(xi) It can explain the odd electron bond (e.g. H;).
(xii) Approximately, the stabilisation created by a bonding molecular orbital (BMO) is balanced by the
destabilisation induced by the corresponding antibonding molecular orbital (AMBO). This is
why, in simple diatomic molecules, the bond order is roughly calculated as follows,
number of electrons in BMOs - number of electrons in ABMOs
bond order =- - - - - - - - - - - - - - - - - - - - - -
2
ry
(xiii) In the case of homonuclear diatomic molecules, both the atomic orbitals contribute equally in
forming the MO, but in the heteronuclear diatomic molecules they contribute unequally. Thus,
ra
\II MO = N(\II A + A'\II B); for homonuclear diatomic molecules A' = 1 while for the heteronuclear
diatomic systems A' 1. *
ib
9.4.5 Proof of Three Basic Conditions (EOS) in LCAO-MO Method
yl
In Sec. 9.4.1, it has been already mentioned that in an effective LCAO, the three basic requirements are
m
(i) energy ofthe overlapping orbitals should be comparable, (ii) overlap should be as much as possible,
(iii) the lobes ofthe orbitals having the same symmetry relative to the molecular axis will only combine.
he
These three conditions are simply described as EOS conditions (E stands for energy, 0 stands for
overlap and S stands for symmetry).
To justify the above conditions, we can select the following trial wave function.
lc
\liMO = c) \II A + c2\11 B •.• (9.4.5.1)

ea
Combination of two atomic orbitals \II A and \liB will produce two molecular orbitals. The coefficients
and energies of the MOs will be given by the following equations.
th
c (u - E) + C (A - ES ) =
) A 2 PAB. AB _
O} (cf. Eqns. 9.4.1.9,10)
c) (P AB -ES AB )+c2 (u B -E)-O
e/
(u A -E)(u B -E)=(P AB -ESAB )2, (cf. Eqn. 9.4.1.11)

t.m
The integrals, u A' u B' PAB and SAB have been already discussed in Sec. 9.4.1. The integrals u A and
u B denote the energies of the electrons in the isolated atoms; PAB is called the resonance integral given
by f\!l A if \!I B d't; SAB is called the overlap integral given by f\!l A \!I B d't.
A. Proof of the condition of energy (E)
• Let us consider u B » u A (e.g. in the case ofheteronuclear diatomic molecules). Consequently,
the size of \II A will be much smaller than that of \liB as the energy of an orbital depends on its size.
It leads to very small values of SAB and PAB . Consequently, the R.H.S. of the above equation
(Eqn. 9.4.1.11) will be very small. To make the L.H.S. of the same equation small, either (u A -
E) or (u B - E) will be small. Ifwe assume (uA - E) to be small, then the approximate solution of
Eqn. 9.4.1.11 can be obtained by putting E = U A in the terms (u B - E) and (PAS - EA.')AB). This
leads to :
or, ... (9.4.5.2)
2
~aA - 13 AB , when SAB is very small
u B -u A
Similarly, for the condition E ~ UB' we have:
ry
... (9.4.5.3)
ra
2
~ aB + 13 AB , when SAB is very small
u B -u A
ib
E+ and E_ denote the energies of the bonding MO and antibonding MO respectively. Since, u B
» u A' Et ~ u A and E_ ~ u B' Le. no effective combination.
yl
• Now let us consider the magnitudes of mixing coefficients. We have (cf. Eqns. 9.4.1.9, 10) :
m
c) (PAR - E+S AB ) .
- = - ( _ E) ,(for the 'V+ orbital)
c2 uA +
he
c (P AB -E_SAB ) .
and - 2 =- E ) ' (for the 'V- orbital)
(u B -
lc
c) _
Under the conditions when E+ ~ u A' c)fc2 is very large for 'V+ orbital and when E_ ~ us' c 2fc) is
ea
also very large for 'V_orbital. It indicates that mixing between \VA and \11 B is very small. This
proves- the condition (i).
• Under the condition, u A ~ u B (Le. homonuclear diatomic system), and 5.- ~ ± 1,
th
the mixing is
c
very high. For, u A = u B = U, we can write; 2
e/
\VA ±\VB
= ~2(l tSAR)'
t.m
\jI± (cf. Eqn. 9.4.1.14, IS)
E = U + PAB -uS AB and E = U _

~
AB
-uSAB
+ ] + SAB' - ~ - S AB
(cf. Eqns. 9.4.1.12, 13)
E+ ~ U + P AB and E_ ~ U - P AB when SAB« 1 (cf. Eqns. 9.4.1.18,19)
• Thus for, u A = Us and SAB« 1, the splitting of the MO's occur roughly by 2p. In such cases, the
molecular orbital wave functions are independent of p.
For, u B » u A ' due to the MO formation, the energy of u A is lowered approximately by
p~H/(aH -u A) neglecting SAB and the upper level is pushed up by the same amount. This is
shown in Fig. 9.4.5.1. For, u A ~ us' the AOs are shifted by ± p, while for u A "# UB' the shift is
approximately proportional to p2 (Le. second order interaction).
lJI MO
/
I "'--r-'
~i
\
\
\ ~ p2 {__ ~~,
'lIMO
~s
~
e> ~A
, 1 '
I \ \}J 1
1
I
I B
Q)
c
w A '---1---"
I
\
\
1
\
B
B
I
I
I
I
I
I
I
I
I I
, 1'
\ f3 "
I
I
, ~. ------.,L -},., /32
I
ry
\ 1
\ ____ 1
A
'------J
\fJMO '1 J MO
ra
(a) (b)
Fig. 9.4.5.1. LCAO for 'V A and \V s· (a) a A = as, (b) as » a A·
ib
B. Proof of the condition of overlap
yl
'lJ B y
If the atomic orbitals do not overlap,
then both ~ AB and SAB will have zero
m
values. This leads to E+ == u A and
A'_ = u B' i.e. no effective combination
he
betw een 'VA and 'VB. For poor x
overlapping, ~AB and SAB are small and
lc
then the mixing between \VA and \VB is

small (as argued in the proof of
ea
condition (i).
c. Proof of the condition of Fig. 9.4.5.2. Overlapping between s (Le. \VA) and Py (Le. \Vs)
th
symmetry orbitals when the molecular axis is x-axis. The marked area
denoted by 1 and 2 are equal but of opposite sign (Le. their
The integral SAB becomes zero, if the . d S 0) .
e/
. d' ff sum IS zero an AB = .

\VA an d \VB are h aVlng I erent
symmetries about the molecular axis. For example, if 1s orbital (say \VA) overlaps with the 2py orbital
t.m
(say, \VB perpendicular to the molecular axis), then SAB becomes zero (Fig. 9.4.5.2). In such cases, no
effective mixing between \VA and \VB occurs.
9.5 SYMMETRY AND OVERLAP IN FORMING MOLECU.LAR

ORBITALS IN LCAO METHOD
The overlap integral S AB = f\jI A\jI BdT. is extremely important in characterising the different types of
molecular orbitals, Le. bonding MO, antibonding MO and nonbonding MO. It actually gives the measure
of electron density between the nuclei. This electron density is measured with respect to the isolated
atoms. The conditions are: SAB > 0, bonding MO; SAB == 0, nonbonding MO; SAB < 0, antibonding MO.
The magnitude of SAB gives the measure of bond strength of the covalent bond formed between A
and B. With the increase of positive value of SAB' the bond strength increases. The value of SAB largely
depends on the symmetry properties of the orbitals.
Combinations of different atomic orbitals leading to the formation of different molecular orbitals
are shown in Fig. 9.5.1. It is evident that overlapping of the lobes with the same sign produces a bond-
ing interaction while overlapping of the lobes with opposite sign produces an antibonding interaction.
Atomic Orbitals Molecular Orbitals
-e- -e-
s s
(+)
)
E® )
E9 crg~ Nodal plane
-e- -e- (-)

)
E® )
@i8
ry
s s
(j~(S)
m m (-)
~
ra
Px Px
)
c::Effi )
agley Nodal plane
ib
(+)
00 00 )
oo:B )
0:>!E(V
yl
P P
x x Og(PJ
0Q)
I
(+)
e<9
00 ~
)
m )
Px s o(SP ll )
he
lc
ea
Fig. 9.5.1. (a) Formation of sigma-type molecular orbitals from atomic orbitals through LCAO.
Note : Px + Px leads to a-type antibonding interaction while Px - Px leads to a-type bonding
interaction. Here it may be pointed out that many authors suggest the following conventions.
th
Px + Px => a-BMO; Px - Px => a*-ASMO;

They use the following pictorial representations.
e/
EXB + ~ => a-SMO; EXB + ~ => a*-ABMO

t.m
Px Px Px Px
Here in drawing the same Px orbital, different conventions are followed. hi one case, the lobe of Px
orbital in the +x direction is given the + sign while in the other case, the lobe in the -x direction is given
the + sign. Th.e practice is not justified.
Symmetry Elements in the MOs
(i) Cylindrical symmetr.v (Coo) : If the orbital is rotated around the bonding axis, Le. molecular axis,
and it remains unchanged with respect to the sign at any angle of rotation, then the orbital is
called cylindrically symmetrical. The corresponding symmetry element is denoted by Coo' The
molecular orbitals having Coo are referred to as sigma (cr) molecular orbitals. These are
associated with the magnetic quantum number, A == O.
(ii) Centre ofsymmetry or centre ofinversion (Ci ) : The centre of symmetry indicates that for every
point there is an equivalent point (in all respects including the sign) in the just opposite direction
at an equal distance measured from the centre of symmetry. Such orbitals having Ci are called
gerade represented by g. The orbitals lacking in C; are termed ungerade and represented
by u. Here it must be mentioned that only in the case ofhomonuclear diatomic molecules providing
identical AOs to form MOs, the question ofe;, i.e. the classification ofMOs by g and u, arises.
)
c:!::>
-e-----+-
r Nodal Plane
~
Py Py
ry
ra
Py Py
ib
8~
+
(-)
~ ---- ..e
.....~ --- {Nodal Plane
yl
---~)
- + - m ~~ .
7t(pd)
Nodal
I~Plane
he
-----.)
<tJ I <;) L/ ~
--e--t-~---
e :e~
lc
1t(pd)
C2:W~
ea
~ ~e ~Nodal
--e---- ..---- Plane
~~
---+)
e c:::> ~
th
e/
C2:W C2:W~(+))
t.m
~~ d xy dxy
1t*
g(d xy)
Fig. 9.5.1. (b) Formation of pi-type molecular orbitals from the atomic orbitals through LCAO. Note:
Py + Pf leads to x-type bonding interaction while Py - Py leads to x-type antibonding interaction.
(iii) Nodal planes: The nodal plane indicates the plane along which there is no electron cloud. If
there is a nodal plane perpendicular to the internuclear axis and lying between the nuclei, the
corresponding orbital is antibonding in nature. If a nodal plane lies in the internuclear axis, the
corresponding orbital is pi (7t) in nature. The a-orbital does not contain the nodal plane containing
the internuclear axis. The &'orbital possesses two such nodal planes containing the internuclear
axis.
AOs vs. MOs in terms ojnodal plane: It is important to note that in terms ojnodal plane sand
a orbitals are equivalent (Le. no nodal plane containing the nucleus or the internuclear axis);
similarly p and 7t orbitals are equivalent; and d and B orbitals are equivalent.
Introduction to Chemical Bonding and Theories of Coval3nce 573
8 s ffi
Py
)
QB
C0 ffi ~
)
Px
ry
- +
0)
~
""
) :
ra
" " .... s + d - + -
.... xy
-x
ib
Fig. 9.5.1. (c) Schematic representation of Fig. 9.5.1. (d) Schematic representation of non-
delta-type interaction between the d atomic bonding type interaction between the atomic
orbitals. orbitals.
yl
+MOs
• 0-, 7t,
m
Band
a bond arises by the overlap of 'J lobe + J lobe', 1t bond arises by the overlap of '2 lobes +
he
2 lobes', 8 bond arises by the overlap of '4 lobes + 4 lobes'. Similarly, <j> bond arises by the
overlap of '6 lobes + 6 lobes'. The s orbital can only show a-type interaction; p-orbital can show
both a- and 1t-type interaction, d-orbital can show a, 1t and 8-type interaction,.forbital can show
lc
a, 1t, 8 and <j>-type interactions.

ea
• (+) and (-) combinations of the AOs

(i) For the spherically symmetrical s-orbitals, the (+) combination gives the sigma bonding
th
molecular orbital (a-BMO) while the (-) combination gives the sigma antibonding molecular
orbital (a-ABMO), Le.
•
e/
a g(2s) = 2s(A) + 2s(B); a U (2s) = 2s(A) - 2s(B)

For the orbitals like p, d, etc. which are not spherically symmetrical, in the a-type interaction,
t.m
the (+) combination gives the a-ABMO while the (-) combination gives the a-BMO; for the
1t-type interaction, the reverse is true.
cr g {2px) = 2Px (A) - 2P x (B); cr:(2px) = 2P x (A) + 2Px (B)
1t u (2py ) = 2pY (A) + 2p y (B); 1t:(2Py ) = 2p y (A) - 2p y (B)
1t u {2pz) = 2p=(A) + 2p={B); 1t:(2Pz) = 2p={A) - 2p={B)

These are illustrated in Fig. 9.5.1.
(ii) According to some authors, the (+) combinations are always considered to give the BMOs. For
this purpose, the combining Px orbitals (taking x-axis as the bonding axis) are drawn in different
ways, i. e. with respect to the nucleus, the left lobe of one orbital is made positive while for the
other combining orbital, the left lobe is drawn negative. However, this practice is not correct.
The signs ofall the lobes ofthe combining orbitals should be shown in the same way.
9.6 SIGMA (0)-, PI (x)- AND DELTA (B)-MOLECULAR ORBITALS,

PHI (<<1» AND MU (Il) BONDS
Sigma (0)- and pi (7t)-MOs in Terms of Symmetry Elements
These can be characterised (see Table 9.6.1) in terms of symmetry elements discussed above.
Table 9.6.1. Characteristics of Mas in terms of symmetry elements..

Nodal plane
c;·
ry
Molecular Perpendicular to the internuclear Containing the
orbitals axis bellveen the nuclei internuclear axis
(MO)
ra
a
. Present Present (Le. g) Absent Absent
ib
a Present Absent (Le. u) Present Absent
7t
. Absent Absent (Le. u) Absent Present
yl
7t Absent Present (i.e. g) Present Present
** Applicable only for homonuclear molecules.
m
tl
Table 9.6.1 indicates that the antibonding pi-molecular orbitals (n are gerade (g) while the
)
he
antibonding sigma-molecular orbitals (0*) are ungerade (u). On the other hand, bonding sigma-
molecular orbitals are of g symmetry while the bonding pi-molecular orbi~als are of u symmetry.
Now we can summarise (see Table 9.6.2) the major points at which the (J- and 7t-molecular orbitals
lc
differ.
ea
Table 9.6.2. Differences between sigma- and pi-bonds and their Mas.
Property a-Bonds n-Bonds
th
(i) Mode of overlap End to end overlap (i.e. one Side to side overlap (Le. two lobes-two lobes)
lobe-one lobe)
e/
(i i) Bond strength Stronger due to better overlapping Weaker due to poorer overlapping.
(iii) Rotation along the No rotation is possible around the bond axis
t.m
Due to cylindrical symmetry around

bond axis the bond axis, the atoms can be freely
rotated around the bond axis.
(iv) Delocalisation a-bonding electrons cannot participate n-electrons being mobile can participate in
in delocalisation. delocalisation in a suitable condition (e.g.
conjugated dienes and polyenes)
(v) Direction a-bond determ ines the direction of the It has no primary effect in determining the
bond. bond direction, but it can shorten the bond
length.
(vi) Symmetry Both the a and cr· contain Coo; a con- Both the 1£ and n· contain the nodal plane
elements tains C;; while a· lacks in C;; no nodal containing the internuclear axis; n· possesses
plane containing the internuclear axis C; while n lacks in it; no Coo axis for both n
exists for both a and cr· and n*
(vii) Magnetic quantum A = 0 A= ±1
number (A) ofth ,-
MOs N f
All the points mentioned above are illustrated in Fig. 9.5.1.
Delta Molecular Orbitals

Two d orbitals lying in parallel planes can overlap each other with all four lobes to produce a delta
bonding. The produced molecu1ar orbital possesses two nodal planes containing the bond axis and the
nodal planes are mutually perpendicular. Such an overlapping interaction is shown in Fig. 9.5.1 c. The
B-MOs can arise from the suitable d ± d and!±fcombinations. The magnetic quantum number (A.) of
the B-molecular orbital is ± 2. On rotating (by 360°) the B-MOs about the internuclear axis, the sign of
the lobes changes four times, while the 7t-MOs experience the change twice, and the a-MOs remain
ry
unchanged. The delta bonding will be further discussed in Sec. 9.19.
Besides the d-d andf-fcombination, B-type interaction can occur in d ± p; - MO in.teraction. In
ra
metal-alkyne and metal-dioxygen (as in dioxygen adduct ofVaska's complex) complexes, one 7t~ of
the O2 or alkyne makes a 7t-type interaction with the metal d-orbital while the other orthogonal 7t*-MO
ib
makes a B-type interaction with the metal d-orbital.
Phi <+) Bonds
yl
The overlap, 6 lobes + 6 lobes produces the ~-bonds.
m The overlap between two suitable .forbitals can
produce the cf> bonds.
Mu (J.1) Bonds
he
The a-bonds are characterised by the presence of Cex:> symmetry elements (i.e. cylindrical symmetrical)
but the a-bonds developed by the donation of elongated x-electron cloud lacks in Cex:>' Such bonds are
lc
formed in different alkene complexes (e.g. Zeise's salt, Sec. 14.7.5 viii) and this type of a-bonds is
sometimes described as Jl (mu)-bonds.
ea
9.7 VBT VERSUS LCAO-MOT

th
Similarities
e/
(i) Both the theories explain the covalent bond.

(ii) Both the theories demand that to form a covalent linkage, the corresponding orbitals must overlap.
t.m
(iii) For stabilisation ofthe covalent linkage, both the theories demand the concentration of electronic
charge between the nuclei.
(iv) Both the theories consider the quantum mechanical exchange phenomenon ofthe electrons among
the nuclei and the covalent-ionic resonance interaction to explain the stabilisation.
(v) Both the theories predict the directional properties of the covalent linkage.
(vi) Both the trial 'VVB and 'liMO can be utilised in the same way to evaluate the eigen functions and
eigen values.
Differences
(i) In VBT, the individual atoms are gradually brought together from infinity to interact through the
overlapping of the atomic orbitals. On the·other hand, in LCAO-MOT, the MOs are developed
through the LCAO from the skeleton of the molecule containing the nuclei at fixed positions.
Then the electrons are placed in the polycentric MOs by using the aufbau principle, Hund's
rule and Pauli's exclusion principle as in the case of atoms.
(ii) In LCAO-MOT, the combining atoms lose their individual identities, while in VBT, the combining
atoms retain their individual identities to a large extent.
(iii) In LCAO-MOT, the odd electron bonds are explainable while these cannot find any explanation
in VBT.
(iv) In VBT, 02 is considered to be diamagnetic, but it is not supported by the experimental fact. The
LCAO-MOT can explain the paramagnetic behaviour of 02.
(v) VBT appears easier tp explain the polyatomic molecules in terms of the localised covalent bonds
between the nuclei in terms of hybridisation leading to the stick- and- ball models ofthe molecules.
ry
On the other hand, in MOT, the molecular orbitals are delocalised and consequently, to correlate
with the stick- and- ball model in terms of MOT, it appears difficult. However, the concept of
delocalised molecular orbitals is very important in some cases to explain the molecular properties.
ra
MOT has been found more promising to explain the molecular properties, at least qualitatively,
in the case of simple diatomic molecules. But the VBT in terms of Linnett's double quartet
ib
theory (it will not be discussed here) produces more or less the identical results as expected from
the simple MOT.
yl
9.8 THE UNITED ATOM METHOD IN MOLECULAR ORBITAL THEORY
m
In the LCAO-MO treatment, we start with the AOs while in the united atom method, we start from a
he
hypothetical atom formed by the coalescence of the two nuclei A and B. This hypothetical united atom
can be considered as a single atom in which the orbitals can be assigned to accommodate the electrons.
The separation is carried out from zero to infinity at which the two isolated atoms exist. Thus in passing
lc
.from zero separation to infinity separation, the system will pass over through the diatomic molecule at
some intermediate internuclear distance. Thus the journey starts from the hypothetical united atom (r
ea
= 0) to the isolated atoms (r == (0) through the diatomic molecule (r == internuclear distance between the
nuclei in the molecule). In this process, the atomic orbitals of the united atom will be converted into the
th
molecular orbitals and finally (at r == (0) into the atomic orbitals of the isolated atoms. Consequently,
the energies of the atomic orbitals of the united atom will pass through the energies of the molecular
e/
orbitals to the energies of the atomic orbitals of the isolated atoms. This gradual change of energies
of the orbitals of the united atom to those of the isolated atoms through the molecular orbitals of the
t.m
diatomic molecule is represented by the correlation diagram developed by Mulliken. In this correlation
diagram, the energies of the different atomic orbitals of the united atom and the isolated atoms are
shown at two extremes at r == 0 and r == 00 respectively.
Before to draw the correlation diagram, we are to consider the conversion suffered by the united
atom orbitals in making the journey, r == 0 to r == 00 (Le. isolated atoms). The state of transformation at
different stages of the journey is shown in Fig. 9.8.1 (assuming the z-direction for movement) for some
orbitals of the first three principal quantum numbers.
From the nature of transformation suffered by the united atom orbitals in the above mentioned
process, they can be :Iassified in two groups.
(i) There are S6me united atom orbitals which retain the same principal quantum number
(n) and azimuthal quantum number (I) on separation. These are (assuming z-axi~ as the
bond axis) : Is, 2s, 2px' 2py, 3px' 3py' 3dxy and 3dx2 _ 2. The 3d; of united atom gets converted
into two 3s orbitals of the isolated atoms. Here, th~ principal quantum number remains the
same, but the azimuthal quantum number changes. The energy of these orbitals increases
Introduction to Chemical Bonding and Theories of Covalence sn
Slightly Normal
United Atom Separated Bond Distance
1s
@) +
1'. \
\_~
2s
ry
ffi 88 8 G)
ra
ib
~ ~~
yl
m
ffiffi
he
nip 1 1
3dxz.yz -12('4Jx,y) 12 ('4Jx,y)
lc
Fig. 9.8.1. Generation of some representative molecular orbitals in the light of united atom method.
(Adopted from K.L. Kapoor, "A Text Book of Physical Chemistry", Vol. 4, Macmillan India Ltd. Reproduced
ea
with permission).
with the increase ofr. It is reasonable as the separation leads to bifurcate the nuclear charge of
th
the atom while the principal quantum number of the orbitals remains unchanged with the
increase of the separation. It is well established that with the increase of Z in the nucleus, the
e/
energy of a particular orbital decreases.

(ii) There are some united atom orbitals in which the principal quantum number decreases by
t.m
unity along with a change ofazimuthal quantum number, t1l = ± 1 with the increase ofseparation
(r). These are: 2pz' 3s, 3pz' 3dxz and 3dyz when the z-axis denotes the course of separation. The
changes from r = 0 to r = 00 are as follows:
2pz ~ Is, Is; 3s ~ 2pz' 2pz; 3pz ~ 2s, 2s; 3dxz ~ 2px' 2px; 3dyz ~ 2py, 2py.
In these cases, the energy of the united atom orbitals decreases as the separation increases
because of the decrease of the principal quantum number.
The correlation diagram for a diatomic homonuclear molecule is shown in" Fig. 9.8.2. The
exact order of energy depends on the extent of separation, i.e. r. There are some cross-over
regions, but in crossing the orbitals there is a rule referred to as noncrossing rule according to
which two orbitals having the same symmetry can never cross each other. In preparing the
correlation diagram, this noncrossing rule is to be satisfied everywhere. Here it is worth
mentioning that the energy changes in passing from r = 0 to r = 00 may not always occur
smoothly. This is why the changes are not always shown by the straight lines.
578 Fundamental Concepts of Inorganic Chemjstry
1t u
3p
au
"
-~ 2p
;",
35 0'9
">---25
2p Og ~~
e;
ry
Q)
25 c:
W
ra
ib
yl
m
United Atom Molecule Isolated atoms
he
---. x-axis
Fig. 9.8.2. Correlation diagram for a homonuclear diatomic molecule (united atom method).
lc
9.9 SIMPLE MOLECULAR ORBITAL MODEL FOR HOMONUCLEAR

ea
DIATOMIC MOLECULES
th
9.9.1 Simple Molecular Orbitals and Diagrams

We have already discussed the MO-theory for H;
and H 2 in detail. Here we shall pay attention in a
e/
general way for the elements from hydrogen tOl)eon a~d shall consider the formation ofMOs from the
AOs, i.e. Is, 2s and 2p. By considering the x-axis to be the molecular axis, according to the EOS
t.m
conditions (see Sec. 9.4.1), we get the following appropriate combinations (cf. Fig. 9.9.1.1).
•
0' g(b) = N1['Vb(A) + 'Vb(B)]' O'u(b) = N 2 ['Vb(A) - 'Vb(B)]
•
(J g(2s) = N 3 [\II2s(A) + \112s(B)]' (Ju(2s) = N 4 [\II2s(A) - 'V2s(B)]
CJ g(2P.) = N s[\jI2P.(A) - \jI2P.(B»)' CJ:(2P.) = N 6 [\jI2P.(A) + \jI2py (B)]
1t u {2py ) =N, [\jI2p y

(A) + \jI2py (B»)' 1t:(2Py ) = N 8 [\jI2py
(A) - \jI2py (B)]
1t u(2P:) =N 9 [\jI2p,(A) + \jI2p,(B»)' 1t:(2Pz) = N IO [\jI2Pz(A) - \jI2Pz(B)]
where N's stand for the normalising constants. The shapes of the MOs are shown in Fig. 9.9.1.1.
Here, to denote the two separate ato~, A""anq B are used but they are of the same kind in the problem
of a homonuclear diatomic molecule. .
Nodal plans
'OiOO~(25)
G)G):;;:
25 (A) 25 (B) o °g(25)
ry
ra
ib
yl
Node
m
he
Node
lc
ea
th
e/
t.m
Fig. 9.9.1.1. Formation of MOs through the LCAO. The AOs are provided by the atoms A and B.
The molecular orbital diagram for the homonuclear diatomic molecules is shown in Fig. 9.9.1.2.
Here, no interaction between the MOs of the same symmetry, and no hybridisation among the
AO~ participating in the formation of the MOs are considered. In the MOs, the electrons are placed.
in order of increasing energy (Le. aujbau principle). Hund's rule ofspin multiplicity and Pauli's exclusion
principle are also applicable in placing the electrons in the MOs as in the case of atoms.
The extent of splitting between the corresponding bonding and antibonding MOs depends on the
extent ofefficiency ofoverlapping (Le. the magnitude ofoverlap integral SAB). In the sigma interaction,
the better overlapping produces more splitting compared to that in the pi-interaction. Thus, if
x-axis is considered to be the bond axis, then the' sigma interaction between the 2px orbitals produces
•
more splitting between CIg( 2px) and CI u (2px) compared to that between the 7t -MOs. In this case, 2py ± 2py
and 2p= ± 2p= interactions produce two sets of 7t-MOs perpendicular to the sigma skeleton. The two sets
of 7t-MOs developed from 2py and 2p= are energetically degenerate but they are mutually perpendicular.
We have already considered that approximately, the stabilisation induced by a bonding MO gets
balanced by the destabilisation introduced by the corresponding antibonding MO. Thus to measure the
net stabilisation in the molecule formed, we are to consider the net effect earned by the electrons
residing in the bonding and antibonding MOs. By considering the covalent linkage as a pair of
electron (Le. 2c - 2e bond), we can calculate the bond order parameter as follows :
No. of the electrons in the bonding MOs - No. of electrons in the antibonding MOs
ry
bon d order = - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
2
ra
Here it is worth remembering that to stabilise the system,
the electrons in the bonding MOs are not to be necessarily
ib
paired up. The Hund's rule of spin multiplicity along with
the Pauli's exclusion principle and autbau principle will
yl
decide whether the electrons will be paired up or not.
It is evident that after He 2, the inner electrons coming
m
from n = I (Le. K-shell) are contributing nothing to stabilise
the system. In representing the electronic configuration, very
he
often the symbol of the inner shell is used to represent the
electrons originated from that inner shell. Thus in Li2, for
lc
the MOs, 0g(ls) and 0:(1.\')' the symbol KKis used. Similarly
for n = },.J.he symbol fL is used. Thus, for Na 2 , the
((f~(1S)
° "-
•
ea
configuration is : KKLL g(3.\'). The electronic configurations

1s ~:_, ",'"
",,,,....,,,'~--1 s
for the molecules H2 to Ne 2 are given in Table 9.9.1.1.
g
--- \. CT (1s)
th
The highest occupied molecular orbital (HOMO) and

--+ x-axis
the lowest unoccupied molecular orbital (LUMO) are jointly
e/
referred to as frontier molecular orbitals (FMOs) of the Fig. 9.9.1.2. Simple molecular orbital
molecule. In F 2, 7t: is HOMO and a:
is its LUMO. The
diagram (for the homonuclear diatomic
molecules).
t.m
singly occupied molecular orbital is called SOMO (e.g.

7t: orbitals of 02). Depending on the condition, the SOMOs of O2 can act as both the HOMOs and
LUMOs. Thus HOMOs and LUMOs of 02 are half-filled.
Note: According to many authors, the MOs are named as follows :
•• •• •
ag(b) as 109; aU(b) as 20 u ; O"g(2.\') as 3a g ; 0U(2s) as 40 u ' 0g(2px) as 5a g ; 7t u (2py ,z) as 17t u ; 1t K (2py.:)
•• •
as 21t g ; 0u(2px) as 60 u •
The energy order (according to MO diagram given in Fig. 9.9.1.2) is :
109 < 20: < 30"g < 40: < 5a g < 17t u < 27t: < 6a:
• For the ~econd period elements, some authors start naming of the orbitals from 0g(2s) as lag;
0U(2s) as 20 u and so on. This convention is also reasonable in the. case where the inner MOs arising
from the K-shell do not contribute in the bond order determination.
Table 9.9.1.1. The electronic configurations of some homonuclear diatomic molecular species and some
characteristic points according to the simple molecular orbital model (see Fig. 9.9.1.2)
Molecular Electronic configuration Bond order Bond dissociation Bond length Magnetic
species energy (kJ mol- J) (pm) properties
•
O'g(h) 0.5 (0') 255.5 . 105 Paramagnetic
2
O'g(b) 1.0 (0) 458.0 74 Diamagnetic
2 ·1
He; 0' g(b} O'I/(I.t) 0.5 (0) 251.4 108 Paramagnetic
ry
2 ·2
0' g(b} O'I/(b} 0.0
2
ra
[He 2 ] 0'g(2.t} 1.0 (0') 108 266 Diamagnetic
2 ·2
[He 2 ] 0'g(2.t} 0'I/(2.t} 0.0
ib
2
[Be2 lO'g(2P.'C} 1.0 (0') 290 160 (a)Paramagnetic
. 2 2
yl
[Be2 0' g(2P'C} 1tu(2py .2pz}
l 1.0 (0), 1.0 (1t) . 600 125 (a)Diamagnetic
2 4
[Be 2 ] 0' g(2P%} 1tu (2py. 2pz} 1.0 (0'), 2.0 (1t) 941.7 110 Diamagnetic
2 3
m
[Be 2 10' g(2P%} 1tu(2py. 2p,} 1.0 (0), 1.5 (1t) 842 112 Paramagnetic
he
·2
[ N 2 1t g (2py. 2pz}
l 1.0 (0), 1.0 (1t) 493 120 Paramagnetic
••
[ N 2 l 1tg (2py. 2pz } 1. 0 (0), 1·.5 (1t) 625 112 Paramagnetic
lc
·4
[ N 2 1t g (2p". 2pz}
l 1.0 (0) 155 ± 30 142 Diamagnetic
ea
·4 ·2
Ne 2 [ N 2 1t g (2py. 2pz} °U(2px}
l 0.0
Note: x-axis is taken as the bond axis
th
(a) Experimental result contradicts the theoretical prediction from simple molecular orbital diagram
9.9.2 Molecular Orbital Picture of Some Representative Homonuclear Diatomic Molecular

e/
Species
t.m
Now let us consider the predictions from the simple molecular orbital picture in connection with the
homonuclear diatomic molecules.
(i) H]. and He]. : The bond order in H 2 is one due to cr~(lS). The electron pair bond is comparable
with the idea of the valence bond theory. But to explain the H;
in valence bond theory, it is
required to invoke a special type of bond (Le. one electron bond in which electron pairing does
not occur). The stabilisation in the system arises due to the resonating structure, H· J-r ~ J-r ·H
Similarly, to explain the stability of He; and HeH, another typical bond, Le. three electron
bond, is to be considered in VBT. Again the stabilisation can be explained from the following
resonating structures.
He :·He+~+He· : He; He :·H~+He·:~
However, in VBT, no sound support in favour ofthese typical bonds is available, but in MOT, no
special consideration is required to explain the species. They automatically arise. From Table
9.9.1.1, it is interesting to note that the bond order in both H; and He; is 0.5 and their bond
lengths are 105 pm and 108 pm respectively. Their bond energies are also very much comparable
as expected from the molecular orbital picture.
In He 2, the bond order is zero. Because of this fact, it is nonexistent. Here it is worth mentioning
that actually the antibonding orbital, Le. O':~IS)' destabilises more than what the bonding orbital,
Le. 0'~(1s)' stabilises. The actual energy expressions (see Eqns. 9.4.1.16-17) are given by :
E=u+P
... (9.9.2.1)
1 +SAB
E. = u - P
ry
... (9.9.2.2)
l-SAB
If it were really, stabilisation by BMO = destabilisation by ABMO, then there would be a finite
ra
probability for the existence of He 2 because under this condition, no net destabilisation in He 2
occurs compared to the system of isolated atoms (Le. He + He). But, in fact, the destabilisation
ib
is more than the stabilisation. This is why, He 2 is nonexistent. However, for practical purposes
(SAB« 1), we can approximately consider E = u + P and g = a. - p.
yl
(Note : In the process, He2 ~ 2He, Mf ~ 0, M = + ve, the entropy factor favours the
decomposition of He z molecule into the He-atoms.)
m
In this connection, it is worth mentioning that He 2 does not exist in the ground state but if it is
*
excited sufficiently to promote at least one electron from O'u(ls) to the next higher MO, Le. 0'g(2s)'
he
then the bond order becomes unity and He; exists.
• . 2 *1 I
He2 (excited): O'g(ls) O'u(ls) O'g(2s); bond order = 1
lc
(ii) Liz: KK 0'~(2.\")' It shows the bond order unity. It really exists as a diatomic species in the gas
phase.
ea
Note: In the above electronic configuration, K stands for the 1st shell K (n = 1). The inner shell
electrons do not contribute anything in the net bonding. This is why, very often the inner shell
th
electrons are denoted by the shells like K (n = 1), L (n = 2), etc. In this convention, the electronic
configuration of Na 2 is given by :
e/
2
KKLL cr g(3$)
(iii) Be z : KK 0'~{2.f) cr:~2.~). Here the bond order is zero, and it really exists as a monoatomic species
t.m
in the gas phase.

2 *2 2 2 *2 2 2
(iv) 8 z and Cz : For B2 , KK crg(2.~) cr u{2.\') O'g{2px) and for C2 , KK O'g(2s) O'u(2s) O'g(2px) 1t u(2p y .2pz>'
The magnetic behaviour predicted from these electronic configurations is not satisfied by the
experimental facts. It indicates the requirement of modification ofthe simple modeL
(v) N 2 : KK 0"~(2.') 0":~2.') 0"~(2P.) 7t~(2PY. 2pz)' It shows the existence of two pi-bonds along with a
sigma bond as in acetylene. Hence, from the knowledge of acetylenic linkage, a high re~ctivity
in N2 is expected. But unfortunately, it is very much inert. Besides this, from the ionisation
potential of N 2 (i.e. N 2 ~ N; + e), it is established that the highest level filled (Le. HOMO) is a
a-orbital in character while it is predicted as a 7t-orbital from this model. Thus, the simple model
can explain the observations in N z qualitatively, butforfiner analysis ofthe data, it requires a
modification which will be discussed later.
• Ionisation energies of atomic nitrogen vs. molecular nitrogen: In spite ofthe above mentioned
drawback, the simple model can explain some important observations. Here it is interesting to
note that the first ionisation energy of the atomic nitrogen is less than that of the molecular
nitrogen Le. IE(N2) = 1503 kJ mol-I> IE(N) = 1402 kJ mol- 1 (cf. oxygen where the reverse is
true, for 0: 1314 kJ mol-I; for O2 : 1164 kJ mol- 1).
N ~ N+ + e, 1402 kJ mol-I; N 2 ~ N; + e, 15Jl3-k.J mol--I
In the case ofN 2, the. electron is to be knocked out from the HOMO, a bonding MO (7t u) which is
stabler than the corresponding AO of nitrogen. This is why, N 2 requires higher energy for its
ionization.
In this connection, the ionisation of NO (which contains one electron excess compared to N2 )
ry
leading to NO+ (i.e. nitrosyl cation, an isosteric species with N 2) is worth considering.
NO ~ NO+ + e, 894 kJ mo]-I
ra
Its ionisation energy is much less than those of oxygen atom (IE = 1314 kJ mol-I) and
.
nitrogen atom (IE = 1402 kJ mo.-I). In .NO, the odd electron to be removed resides in the
ib
HOMO, an antibonding MO (i.e. 7t g ) which is destabilised more compared to the corresponding
AOs of both nitrogen and oxygen. Because of this low ionisation energy, NO+ is easily stabilised
yl
in many compounds such as NO+ H80i ' NO+ BF4- , etc.
(vi) ° 2 ·2 2 4 ·2
2 : KK a g (2.\') au(2.\") a g (2Px) 1t u (2p y ,2pz) 1t g (2py,2pz)··
It produces one sigma (a)-bond along with
m
a pi (7t)-bond. The two unpaired electrons in Ttg are responsible for its paramagnetic
behaviour. The unpaired electrons result from the Hund's rule ofspin multiplicity. These electrons
he
! are. unpaired but they contribute to maintain the bond order. Thus to yield the bond order, the
:. electrons are not to be necessarily paired up (cf. VBT). Thus the MOT does not give any special
lc
weightage to the paired electrons in determining the bond order. It simply reckons the number
ofbonding versus antibonding electrons irrespective oftheir pairing or unpairing. <-
ea
VBT could not produce any unpaired electron in O2 to explain its paramagnetic properties. It
was explained by MOT (Mulliken, 1928) from the electronic configuration designed above. The
•
two unpaired electrons in the HOMO 7t g (2p) (i.e. SOMOs) produce the triplet state (28 + 1 == 3),
th
designated by symbol 3~;, Le. 3°2 . From the molecul~r orbital picture, two excited singlet
(I
states L; and I l1g ) were predicted. In fact, three years after Mulliken's classic explanation,
e/
Child and Mecke established spectroscopically the I~; state, 155 kJ mol-I above the ground
t.m
state. In 1934, Herzberg reported the existence of It!g state, 92 kJ mol-I above the ground state.
It has got a relatively long half-life period. The properties of both the ground triplet and excited
singlet states are given in Table 9.9.2.1. In this connection, it is worth mentioning that the
Table 9.9,.2.1. Characteristic properties of the triplet and singlet oxygen molecules
Molecular state Spin multiplicity Configuration of Bond length Energy
(2S + 1) electrons in 7t~ (pm) (kJ mol-)
(i) I r; e0 2) 1,(S=O) (1)(±) 122.7 155

(t 1/2 ~ 12 s) (singlet)
(ii) I~g (1°2 ) 1 (S = 0) (1±)() 121.6 92
(t 1/2 ~
2700 s) (singlet)
gas phase
(iii) 3 r; (3 02 ) (ground 3 (S = 1) (1)(1) 120.7 0
state, stable) (triplet)
triplet state is kinetically inert in most 0/ the chemical reactions, but the singlet oxygen is very
much reactive to burn away all the organic matter. This is why, the singlet oxygen is very
much toxic. If the oxygen were in the singlet states (as expected from VBT), the biological
kingdom would not survive. .
Now, let us consider the results obtained by adding or removing the electrons to or from the
oxygen molecule.
+e +e 2 +2e
02 --~) 0; ) 02 - --~) 20 2-
(superoxide) (peroxide) (oxide);
ry
02 -e ) 0; (dioxygenyl cation)
•
-
'I
(5
600
ra
The first two added electrons to O2 go to the 7t g
..,E
and as a result, the bond order decreases. After ~ 400
w
ib
adding four electrons to 02' the bonq order becomes c
zero and 0;-
does not exist. Actually, due to the CD
0;-, 1
yl
zero bond order in it produces two oxide ions.
•
On the other hand, on removing electrons from 7t g ,
200
the number of antibonding electrons decreases and

m
consequently, in 0;,
the bond order increases
Ol....--..-.I----a..-----......-----------'
compared to "that in 02. These predictions are
he
1 2 3
supported by the experimental facts as shown in ---+ Bond order
Table 9.9.2.2. The bond dissociation energies Fig. 9.9.2.1. Variation of bond dissociation
lc
(BDE) ofdifferent isostoichiometric species of 02 energy of different isostoichiometric species

are found approximately proportional to the of O2 with the bond order. (For oi-,
BDE
ea
calculated bond order (Fig. 9.9.2.1). has been taken as 200 kJ mol-1).
th
T.able 9.9.2.2. Characteristic features of 0-0 bond in various species

Species 0-0 0-0 0-0
e/
Bond order Bond length Bond dissociation

(magnetism) (pm) energy (kJ mol-I) a
t.m
0;- in H 20 2 1, (diamagnetic) 148 138.6
0;- in Ba02 1, (diamagnetic) 149 200
0;- in F20 2 2, (diamagnetic) 122
0; in K02 1.5 (paramagnetic, Ie) 128 350
°2 2 (paramagnetic, 2e) 120 493
0; (short-lived) 2.5 (paramagnetic, Ie) 112 625
Note: 0;, ° 0;
2, and 0;-
are called isostoichiometric species having the same formula
but different valence electrons.
(a) Bond dissociation involves one product as the neutral atom always
Le. 01- ~0+02-;02~0+O-;02 ~o+o;o; --+0+ +0 \
• ~Special properties ofF20 2 :From Table 9.9.2.2, with the exception of F20 2, all are in conformity
with the expectation. To explain the shorter 0-0 bond length in F 20 2, the following ,resonating
structures are proposed in the light of VBT, Le.
F-o-o-F ~ ~ 0= O+-F ~ F-+O = 0 r.
i.e.
noon·
F-O-O- . -E
.~ f.. .. . ~
.. ' .
ry
The contribution of the ionic canonical forms suggests a partial double bond character in
0-0, and an elongated o-F bond (157 pm) compared to the single o-F bond (141 pm).
However, to explain the observation in 02F2 in the light of MOT, an interaction between an
ra
orbital (probably, sp3) containing an unpaired electron offluorine and one of the singly occupied
7t~ orbitals in 02 is considered. This interaction, Le. 7t~~2P) of 02 + (sp3)1 of F, produces a
ib
3-centred 2-electron (3c-2e) bonding MO along with a vacant 3-centred antibonding MO (cf.
Fig. 9.9.2.2). The electrons occupy the bonding MO which is predominantly enriched with the
yl
character of F-orbital. Thus, the electron originally present in the antibonding orbital of oxygen
moves to the 3c-2e bonding molecular orbital (SMO). In the same way, another 3c-2e bond in
m
the other O-O-F segment is produced. These two 3c-2e BMOs are mutually perpendicular
because the 7t~ SOMOs are mutually perpendicular. Thus in F20 2, there are two 3c-2e 0-
he
o-F bonds in approximately perpendicular directions. The bonding. electrons (Le. 3c-2e) are
mainly concentrated in the o-F segment because of the higher electronegativity of F. In fact, the
lc
3-centred BMO is predominantly enriched with the character of the F-orbital. However, the
bond order in o-F bond is definitely less than unity (Le. 2c-2e bond). A bond order almost two
ea
is maintained in the 0-0 linkage because the 3c-2e bonding involves the antibonding electrons
and antibonding MOs of 02.
-r
th
3c-ABMO ~:;- _ _
" ~ \
e/
I ' ~ \
~~
I
I
I "
u,
1 \
1 i
\
\
\
t.m
I 1 1t* (0 2 ) \ \
g
I I \ \
I I \ \
I I \ \
1 (
(AO of F )", 1
" \\
\ /
/
~ (AO1of F)
' I \ /
~3c-2eBMO~
Fig. 9.9.2.2. Qualitative representation of the formation of 30-2e O-O-F bonds in perpendicular
directions in terms of MOT.
• F 20 2 vs. H 20 2 :The difference in electronegativity between F and H can explain the difference
in bond parameters of F 20 2 and H 20 2. The electronegativity sequence is: F > 0 > H. In F 20 2,
because ofthe very high electronegativity of F, very little amount of additional electron density
is pushed into the 7t~ of 02 through the 3c-2e F-O-O bond formation t9 weaken the 0-0
bond. On the other hand, in H 20 2, because of the higher electronegativity of oxygen than that of
hydrogen, the electron cloud is attracted into the 7t~ of 02 to weaken the 0-0 borf!. It leads
to almost double bond order in 0-0 linkage (as in free 02) of F 20 2 while it becomes 'of unity
bond order in H 20 2•
• Ionisation energies of atomic oxygen vs. molecular oxygen: Lastly, it is interesting to compare
°
the ionisation energies of atomic oxygen and molecular oxygen, Le. ~ 0+ + e, 13 14 kJ mol-I;
02 ~ 0; + e, 1164 kJ mol-I. The first ionisation potential of atomic oxygen is greater than
that of ~,he triplet molecular oxygen. It is due to the fact that in the molecular ox;,gen, the
electron to be knocked out resides in the HOMO (Le. SOMO), an antibonding MO (7t g ) which
ry
is destabilised compared to the outermost AO of the free oxygen atom. It may be noted that the
reverse situation arises for Nand N 2 .
ra
• Colour of 02 : In gaseous state it is colourless but it is blue coloured in solid and liquid state (see
Q. 135 for explanation in terms of MOT).
ib
(Vll F2 : KK a R(2s)
.. ) 2 ·2 2 4 ·4
a u (2.\") a g(2px) 1t u (2py , 2pz) 1t g (2py, 2pz)·
Th e bon d or d er .IS unity
. w h·IC h·IS a Iso
expected from VBT. Here, it is worth noting that all the halogens exist as X 2 (X == F, Cl, Br, I).
yl
The trend of variation of colour of the halogens (i.e. X 2 ) can be nicely explained from the
molecular orbital picture. The visible light being absorbed actually excites the electron from the
•
m •
HOMO 7t g (np) to the next higher level a u(np) i.e. LUMO. The energy gap between these levels
(i.e. HOMO and LUMO) determines the colour of X 2 • The observations are:
he
F 2 (pale yellow) : ~ a:(2P); Cl2 (yellow) : 1t:(3P) ~ a:(3P);
7t:(2P)
Br2 (reddish brown) : 1t:(4P) ~ a:(4P); /2 (violet): 1t:(5P) ~ a:(5P)·

lc
The excitation energy lies in the sequence, F 2 > Cl2 > Br2 > 12• Gaseous F2 actually absorbs the
ea
highest energy light, i.e. violet light, and therefore, it appears pale yellow; whi Ie gaseous 12
absorbs the lower energy light, Le. yellow-green light, and it appears violet. The energy gap
between 1t:(np) (HOMO) and a:(np) (LUMO) decreases with the increase ofthe principal quantum
th
number n. With the increase of n, the larger p-orbitals get more diffused and as a result, the
effectiveness in overlapping to form the MOs decreases. This gradual decrease in the efficiency
e/
of overlap reduces the difference of energy between the bonding and antibonding MOs. It is
known that a better overlap produces a higher splitting between the MOs. Thus the better overlap
t.m
condition stabilises the bonding MOs more and destabilises the antibonding MOs more. This
explains the sequence of energy difference between 1t~ and a:
along the given series.
For F 2, the absorption occurs virtually in the UV region, for Cl2 the absorption band spans both
UV and visible region, for Br2 and /2 the band spans in the visible range.
The present transition, HOMO (7t.) to LUMO (a·) is forbidden (Fig. 9.9.2.3) because of two
different spin states of the ground state (1t~4 a:
i.e. singlet) and excited state (7t~
1
a:
Le. triplet
state) and this is why, the intensity of colour, in general, is less. However, with the decrease of
energy gap, the probability of transition also increases because of the better spin-orbit coupling
to mix the spin states and this is why from F 2 to /2' the intensity of colour increases. In fact, when
the energy gap between the excited state and ground state is small, the spin-orbit coupling can
mix the singlet ground state with the triplet excited state. Consequently, the excited state bears
the character of singlet state to some extent. This partially relaxes the spin forbidden transition.
This relaxation is most efficientfor /2 where the energy gap is minimum. This is why, intensity
of colour of iodine is so high.
Introduction to 'Chemical Bonding and Theories of Covalence 587
(l~ (LUMO) ----{;--
w
~
~
. hv
(forbidden) (allowed)
1l 1 lt g(HOMO) n 1l 1l 1
(Triplet) (Singlet) (Singlet)
ry
Fig. 9.9.2.3. Spin allowed and spin forbidden transition between HOMO (7t~) and LUMO (cr~) of
halogen.
ra
2 ·2 2 4 ·4 ·2
(vii) Ne 2 :KKcr K(2 ...·) cr u (2.\·) cr K(2px) 1t u (2py ,2P:) 1t K (2py .2pz) cr u (2px)" Here the bond order is zero. This is
ib
why, it is monoatomic (cf. the case of He 2 vs. 2He). Because of the same~ fact, all other inert
yl
gases are monoatomic. Removal of one electron from the highest antibonding MO produces the
bond order 1/2 and the positively charged species should exist. We have already mentioned the
m
existence of He;. Similarly, Xe; ion is advocated to exist in strongly acidic solvents which may
provide a high solvation energy. Similarly, to stabilise Xe; in the solid state, the lattice energy
he
should be high.
9.9.3 Limitations of the Simple Molecular Orbital Model

lc
The simple model discussed above can explain a lot of facts but still, it is not satisfactory specially for
ea
the lighter elements, e.g. B2 , C2 , and N 2 ,. Some serIous drawbacks are mentioned below.
(i) Magnetic properties of 8 2 and C2 : The model predicts B2 to be diamagnetic and C2 to be
paramagnetic with respect to two unpaired electrons. But experimentally, B2 is found to be
th
paramagnetic while C2 is found dialnagnetic.

(ii) Properties of N 2 : The bonding pattern, in N 2 is comparable with that of an acetylenic linkage.
e/
Hence it should be reactive like the acetylenic compounds. But, in fact, N2 is very much inert.
t.m
Besides this, experimentally, it has been established that in N2, the highest occupied orbital (Le.
HOMO) is sigma (0') in character not pi (7t) in character.
The above discrepancies arise because the order of energy of the MOs for the lighter species like
B2 , C2 etc. is different from that of the relatively heavier species like 02' F2 • Fig.,9.9.3.1 describes the
variation of energy order of the MOs for Li 2 to Ne 2 •
In terms of the Fig. 9.9.3.1, the ele~tronic configurations (ignoring lcr~ Icr:2 ) of the species Li 2 to
Ne 2 are in conformity with the experimental observation. These are given below.
Li2 : 2cr~; Be 2 : 2O'~ 20':2 (i.e. Bond order = 0); B 2 : 2cr~ 2O':2I7t~ (i.e. paramagnetic)
C 2 : 20"~ 2a:217t~ (i.e. diamagnetic); N 2 : 20"~ 20":217t~30"~ (Le. HOMO is a 0" - BMO)
2 ·2 2 4 ·2· .
02 : 2cr g 2O' u 30 g 17t u 27t g (I.e. paramagnetic)
2 .? ? 4·4 2·2 2 4 ·4. ·2 .
F2 : 20'g 2O' u- 30'; IJt u 27t g ; Ne 2 : 20' g 2O' u 30' g I7t" 27t g 3O' u ; (I.e. Bond order = 0)
30~(2p)
3a~(2p)
11t~(2p) 11t~(2P)
~ ~
0>
~
en
~
Q)
c 3cr g(2p) ...... Q)
c
-- -- -_ . _----
W W
11t u(2p)
_
.... ......~-....
11t u(2p) ======= . . ------ .... ..... _ - - - -
ry
30 g(2p)
2cr~(2s)
2o~(2s)
ra
2ag(2s) 20 g(2S)
ib
(a) Applicable for Li 2 to N2 (b) Applicable for 02 to Ne2
Fig. 9.9.3.1. Variation of energy order of the MOs for the species Li2 to Ne2 of the 2nd period elements.
yl
Note: For Li2 to' N2 , the energy order is : 17t U(2P) < 3crg(2P) while for 02 to F2 the energy order is :
17t U(2P) > 3cr9(2P)· m
The experimental findings are :
he
Li2 Be2 B2 C2 N2 °2 F2 Ne 2
Bond order: 1 0 1 2 3 2 1 0
lc
Bond length (pm) : 267 159 124 110 121 142

Bond energy (kJ mol-I): 110 272 602 941 493 138
ea
Ma-gnesium : D P D D P D
D = diamagnetic, P = paramagnetic
th
9.9.4 Simple Molecular Orbital Diagram for the Homonuclear Diatomic Molecules Involving
(n-1)d Orbitals
e/
For the d-block elements, in many cases, gaseous diatomic molecules have been characterised. The
t.m
bonding in such species of the 1st transition series (Le. 3d series) is complicated in terms of MO
diagram as the 3d orbitals being contracted can give only poor overlap with the 3d orbitals of th~
adjacent centres. However, for the early members of the series (e.g. Ti, Vetc.), the radial extension of
the 3d-orbitals is relatively larger compared to that of the late members of the series. It happens so due
to gradual contraction of d-orbitals along the period with the increase of effective nuclear charge. Thus
overlap between the 3d orbitals is relatively favoured for the early members ofthe series.
For the heavier congeners (Le. members of the 4d and 5d series), because ofthe relativistic expansion
of the d-orbitals (cf. Sec. 8.20.3), the overlap becomes better to produce the MOs. It is illustrated for
the 4d and 5d-series. If z-axis is taken as the bond axis, the d-orbitals can combine as follows:
d=2 ±d=2 (cr-MOs);dx= ±dx= (1t-MOs);
dy= ± d y= (1t - MOs); d xy ± d xy (8 - MOs);
d x 2 -y 2 ± d x 2 -y 2 (8 - MOs);
The stability sequence runs as : crg > 1t u > 8g •
In addition to the (n-l )d, the ns

orbital also participates in the MO
formation. The energy difference
between the ns and (n-l)d orbitals
depends on many factors. This is why,
the relative positions of the MOs
obtained from the (n-l)d orbitals and
ns orbitals cannot be always predicted.
Fig. 9.9.4.1 gives the simple MO
ry
diagram for the homonuclear diatomic
molecular species of the 4d and 5d
ra
series.
In the light of the MO-diagram
ib
given in Fig. 9.9.4.1, the electronic
configuration of M0 2 species of
yl
4d-series can be given as follows:
Electronic configuration of 42 Mo is m
[Kr] 4cP 5s 1; the 12 valence electrons
(2 x 6) are distributed in the MOs in
he
the following way:
2 4 4 2
(J K(J) 1t u (J) 8.l:(J) (J K(.\')
Fig. 9.9.4.1. MO diagram of M2 molecule of the 2nd (Le. 40)
lc
The 12 electrons are in the bonding and 3rd (Le. 50) transition series where the valence orbitals
MOs to give 6 bonds (20 + 21t + 28). are ns and (n - 1)d. Here z-axis is taken as the molecular
ea
It is diamagnetic. axis.
th
9.10 MODIFIED MOLECULAR ORBITAL ENERGY DIAGRAM FOR THE

HOMONUCLEAR DIATOMIC MOLECULES
e/
(Specially for N2 and lighter molecules)

t.m
In the previous section, the limitations of the simple molecular orbital energy diagram (Fig. 9.9.1.2) in
explaining the properties of N2 and lighter molecules have been discussed. Actual variation trend of
energy of the MOs is shown in Fig. 9.9.3.1 It suggests some modifications required. This modification
can be attained in two possible ways:
(i) incorporation of symmetry interaction (i.e. noncrossing rule) among the molecular orbitals
obtained in the simple treatment; ,
(ii) participation ofhybrid orbitals (mixing ofs- and p-orbitals) instead ofpure atomic orbitals to
generate the MO energy diagram.
Both the approaches lead to the same conclusion. This aspect will be discussed and illustrated.
9.10.1 Symmetry Interaction (Noncrossing Rule) among the Molecular Orbitals obtained in
the Simple Model
According to the noncrossing rule ofquantum mechanics, the two orbitals ofthe same symmetry mutually
repel. Consequently, the lower energy level gets lowered down more while the higher one is raised
~ 3a~(2Px) (=: (1)_2)

"
..3(J~(2Px) " " "
J" "
~ l1t g(2P y,z )
----------_. 7' 30 g(2PK) (= <1>_1)
(1 *
1 (I
1t g(2p
Y·Z
)
-------.,.:=::::_-_.
"
;'
r l1t U (2Py,z)
"
1'ru(2py. Z)
,.,,""""
--(
ry
)CT g (2px)
~ 2o~(2S)
' ..... ..........
ra
..........
..........
.......... '
~ 20g(2s)
.......... t 2(J~(2S) (== e1>+2)
ib
..........
" "
" -, 42CT g(2s)(= .<()+1)
--'-
yl
~o~(1S)
----------- m <j'*
(Ju(1s)
IO'g(1S)
----------- la g(1s)
----. x-axis
he
Fig. 9.10.1.1. Symmetry interaction in the simple molecular orbital diagram (for homonuclear diatomic
molecules). (Note : To correlate with <1> ± 1 and <1>± 2' Sec. 9.10.2 may be consulted.)
lc
more. By considering this interaction in the pairs, 0'K(2s) and 0'K(2p,); 0':(2,) and 0':(2P,) developed in
the simple model, we get the result shown in Fig. 9.10.1.1. In this interaction, cr f.{(2p ) is raised above
ea
7t u(2p,. 2P:) which remains unchanged in the symmetry interaction. In f~ct, both 0' g('2S) and 0':(2s) are
lowered down compared to their original positions whilst cr 1{(2Px) and cr u (2px) get raised higher.
th
The said symmetry interaction leading to the modification shown in Fig. 9.10.1.1 is quite important
for N z and lighter molecules, but this
e/
modification is not of much importance for the Li

ITIolecules like F 2 and 02· In fact, the simple - -1000 2p
t.m
MO energy diagram is quite appropriate for \ H N~ o

r'1 and 02' This behaviour can be rationalised ~ F
from the relative positions of the MO energy ~ -2000 Ne
~
levels in different molecules (cf. Fig. 9.9.3.1). ~

For the highly electronegative elements like F ~ -3000
or 0, the 2s atomic orbitals lie far below the (ij
~
2p atomic orbitals (cf. Fig. 9.10.1.2, Table -E
-4000
9.10. 1.1). Such low energy 2s-orbitals are a..
contracted and primarily confined to the
region oftheir respective nuclei and such low
o 5 10
energy atomic orbitals do not overlap Atomic number
extensively. Consequently, the MO crg(2s) i~ not Fig. 9.1 0.1.2(a). Variation of energy of valence orbitals
strongly bonding and similarly the MO cr u (2s) of the 2nd period elements.
Table 9.10.1.1. The energy difference (eV) between the ns and np

orbitals for the 2nd and 3rd period elements
2nd period: Li Be B C N 0 F Ne LU
~
(E 2l' -- £2,\') ( 1.8) (2.8) (4.5) (5.3) (6.0) ( 15.0) (20.5) (26.7)
3~d period: Na Mg AI Si P S CI Ar
(E Jp -- £3.) (2.0) (2.6) (4.5) (5.2) (5.5) (9.8) ( 11.5) ( 13.5) 1 f~E =E np - Ens
is not strongly antibonding. In other words, these contracted 2s
ry
--+ At. No. (along the period)
orbitals remain basically as nonbonding orbitals in the LCAO
process. In fact, these MOs generated from the low energy 2s Fig. 9.10.1.2(b). Qualitive
ra
orbitals are lying far below from the MOs g~nerated from the 2p representation of the variation of
~E along a period for the
atolnic orbitals. In such cases (i.e. highly electronegative
representative elements.
ib
elelnents), the repulsion (origin ofthe noncrossing rule) between
Note : The almost monotonic
the 0' g(2.\') and 0' g(2Px) levels which tend to occupy the same region
increasing trend of ~E is simply
yl
v.f spac.e is al~eady minimised. A similar situation arises for the represented by a straight line.
pair O'u(2.\·) , O'u(2px )· On other hand, for the lighter elements of
low ele~tronegativity, the 2s-orbitals are not so contracted and consequently they are not confined with
m
their respective nuclei. This is why, they can overlap extensively to generate the corresponding MOs
which are strongly bonding or antibonding depending on the condition. In such cases, the orbitals
he
0' K(2.\') and (J K(2Px) which tend to occupy the same region ofspace come closer and experience repulsion.
Thus, for the lighter elements of low electronegativity (where the energy difference between the 2s
lc
and 2p atomic orbitals is relatively small), the symmetry interaction stated in Fig. 9.10.1.1 is quite
significant. In fact, this modified diagram can explain the magnetic properties and other properties of
ea
the lighter molecules (e.g. B2, C2, N2 etc.) (cf. Table 9.10.1.2).
Table 9.10.1.2. The electronic configuration of the homonuclear diatomic molecules
th
according to the modified molecular orbital model (see Fig. 9.10.1.1 and 9.10.1.3)
obtained after symmetry interaction in the simple molecular orbital picture
e/
Molecule Electronic configuration Bond order Magnetic property

2
H2 D
t.m
°g(ls)
*2
He 2 [H 2 lo u(1.f) 0
2
Li2 [He 2 0 g(2s) l D
*2
Be 2 l
[Li 2 0 u(2s) 0
2
B2 [Be2 1t u(2p y • 2pz)
l P
4
C2 [Be2 l 1t u(2py. 2pz) 2 D
l°
2
N2 [C2 g( 2 P.r ) 3 D
*2
°2 l
[ N 2 1t g (2py. 2pz) 2 P
*4
F2 [ N 2 l 1t g (2p". 2pz) D
*2
Ne 2 l
[F2 O'u(2P.r) 0
D = diamagnetic, P = paramagnetic.
Thus it may be concluded that for 02 and F2 the simple model (Fig. 9.9.1.2) is appropriate,
while the modified MO energy diagram (Fig. 9.10.1.1) is appropriate for N 2 and lighter molecules
(e.g. 8 2, e2). The modified energy diagram obtained by introducing the symmetry interaction can be
shown as in Fig. 9.10.1.3.
ry
ra
ib
yl 2a~ (2s) (= <1>+2)
m 2s
~
~
he
Q)
c
W
lc
ea
---
_ _ -__
c ~ 1<1~(1S)
th
1s---ec::,- -- -;~1s
.
~~- C-- __
e/
1<1 (lS)
g
t.m
(Atomic orbitals) (MOs) (Atomic orbitals)

(A) (B)
Fig. 9.10.1.3. Molecular orbital diagram for the homonuclear diatomic molecules by considering the
symmetry interactions (cf. Fig. 9.10.1.1).
Note: Actually, cI>±1 = C10 g (2S) ± C 20 g (2px) and <1>±2 = CIO~(2S) ± C20~\2~x)
Thus 2o g(2S) is actually C1>+1 which is a combination of the following orbitals:
<1>+1 = CA\V2S(A) + CB\V2S(~) + mA\V2Px(A) + mS \V2Px(S)
where ds and mls are the mixing coefficients (with appropriate signs). Thus all the MOs <1>±1 and cI>±2
can be expressed. These aspects are discussed in the next section. This is why, it is better to use
the following to carry the sense :
30~(2Px) = cI>_2 as 30~(2S.2Px); 30 g (2Px) = <1>_1 as 30 g (2S.2Px)
20~(2S) = cI>+2 as 20~(2S.2PlI'); 20 g (2S) = -+-I as 20 g (2S,2Px)
Symmetry interaction among the MOs for the lig,hter and heavier members of the 2nd period
This interaction is important for the molecules like B 2, C 2, N 2 produced by the relatively low
electronegative atoms while the interaction is of no significance for the molecules like 02' F2 produced
by the high electronegative atoms. The reason behind this has been explained in this section.
9.10.2 Molecular Orbital Energy Diagram by Considering the Participation of Hybrid

(s-p interaction) Atomic Orbitals in Generating the Molecular Orbitals
ry
Let us try to understand the results of symmetry interaction (cf. Fig. 9.10.2.1) in terms of mixing
cr K(2.,) and cr g(2pz); and cr:(2") and cr:(2Pz) as follows.
ra
±\= ctcrg (2,,) ± c2 cr g (2pz); ±2 = C\cr:(2.,) ± c2cr:(2Pz)' (cf. Fig. 9.10.2.1)
and <1>+2 = c 1 > c2 ; and for <1>_i and <1>_2' c 2 > c1•
ib
For <1>+1
The wave function <1>+1 can be expressed as follows:
yl
<1>+1 = tC1[N{'¥2s(A) + 0/2s(B)}] + c2[N{'¥2Px(A) - '¥2Px(B)}]
= c; {\V2s(A) + A\V2Px(A)} + ci {\V2s(B) - A\V2Px(B)}
m
= c; {\V '\Px(l)(A) + \V .\Px(I)(B)} ' (Le. in phase, combination)
he
where, c;
=c1N,c; =c2NandA,=c;lci <lasc1 >c2 for <1>+1' Thus it is evident thatJor the hybrid
orbitals sPx(I)(A) and sPx (I)(B) the contributionfrom the respective 2s orbital is more. Similarly, the
wave function can be expressed as : .
lc
<1>_1
<1>_1 = c1[N{ 0/2.\,(A) + 0/2s(B)}] - c2[N{ \V 2Px(A) - \V 2Px(B)}]

ea
c; {A\V2'\'(A) - \V2Px(A)}] + c; {A\V2'\'(B) + \V2Px(B)}

c;{\VsPx(2)(A) + \V.fPx(2)(B)}' (Le. in phase combination)
th
where c; = c2N, c; = c1N and A, = c; I c; c

< 1 as 2 is greater than c1 for <1>_1' Consequently, the hybrid
e/
orbitals \V'\Px(2) (A) and \V'\Px(2) (B) are more enriched with the respective 2px orbital character.
(Note: Thus the two sp-hybrid orbitals, i.e. sPx(l) and sPx(2) of a particular atom, are not
t.m
equivalent. The hybrid orbital. sPx( 1) is enriched more with the 2s-character while the other hybrid
orbital sPx(2) is enriched with the more 2px character. Thus these sp-hybrid orbitals are different from
the equivalent sp-hybrid orbitals discussed in Sec. 9.13).
The wave function <1>+2 is given by :
~2 = c1[N{\V2s(A) - \V2s(B)}] + c2[N{'¥2Px(A) + '¥2Px(B)}]
c; {\V2.f(A) + A\V2Px(A)} - c; {\V2s(B) - A\V2Px(B)}
c; {\VsPx(l)(A) - 'V.fPx(l)(B)}' (Le. out ofphase combination)

<1>_2 = c1[N{'¥2s(A) - 'V2s(B)}] - c2[N{'¥2Px(A) + '¥2Px(B)}]
c; {A\V2s(A) - \V2Px(A)} - c; {A\V2s(B) + 'V2Px(B)}

c; {\V.\Px(2)(A) - \VsPx(2)(B)}' (Le. out ofphase combination)
A B A B A B A B C1I
U)
~
~
+ +
c
+ r"I + --+ ~
"
0.
• • Y\- ~ d+h ~
t 3
CD
~ ~
°g(25) °g(2px) Gg(2s) + 0g(2p)() (<1>+1) .....
~
" .m (")
0
~
0
CD
~
.....
CJ)
e/
0
~
th ----+ II +. - • + I I ----+ I + If - ~ + I
:;-
0
ca
Q)
~
ea
°g(25) -- °g(2s) - °g(2px)
°g(2px) c:r
(")
=r
lc CD
3
Cir
.....
~
he
+ I - + I I - + I -----+ 11-.+1 -6+11 --+
.. . m c:{)tp
(J~(2P .--)
0~25) 0~(25) + a~(2Px) (<1>+2)
yl
ib
ra
-----+ --+
ry (}{)
(<1>_2)
0~(25) 0~(2s) - a~(2p)()
Fig. 9.10.2.1. Symmetry interaction between 0g(25) and 0g(2PIl) and between 0~(2S) and 0:(2Px)O
2s
A<1
ry
ra
Fig. 9.10.2.28. Mixing of 25 and 2px orbitals (x-axis taken as the bond axis).
ib
The conclusions are: (a) <1>+1 is more stable than sPx( 1) while <1>+2 is less stable than sPx( 1); similarly,
yl
CI>_I is more stable than sPx(2) while <1>_2 is less stable than sPx(2); (b) <1>+1 (or <1>+2) concentrates more
electron density between the nuclei compared to that of its main constituent 0g(2s) [or 0:(2S)]' It makes
•
m
CI> +1 and CI> +2 more stable compared to 0 g(2s) and 0u(2s) respectively; (c) similarly <1>_1 and <1>_2 are less
•
stable compared to 0 g(2p,:> and 0u(2p,,) respectively. All these aspects are shown in Figs. 9.10.1.1,
he
9.10.2.1 and 9.10.2.2.
It is evident that the MO energy diagram shown in Fig. 9.10.2.2c is identical with the one obtained
lc
from symmetry interaction (cf. Fig. 9.10.1.1 and Fig. 9.10.1.3).

Possibility ofparticipation ofhybrid orbitals in MO formation: The possibility of hybridisation to
ea
produce the orbitals sPx ( 1) and sPx(2) can be analysed by considering the energy difference between
2s and 2px orbitals. The energy difference between the 2s and 2p-orbitals reaches from ca. 200 kJ mol-
th
1 to ca. 2500 kJ mol-I in moving from lithium to fluorine. From Fig. 9.10.1.2, it is evident that for the
heavier atoms (like 0, F), the energy difference between the 2s and 2p-orbital is quite large and
e/
consequently the mixing between these orbitals to produce the hybrid orbitals is not much important.
On the other hand, for the lighter elements, the energy difference is quite small (cf. Fig. 9.10.1.2)
t.m
and the mixing between the 2s and 2p orbitals is quite significant. This is why, it is reasonable to -
consider the fact that for the lighter elements, the hybrid orbitals (rather than the pure atomic orbitals)
participate in generating the MOs. However, here it is worth mentioning that there is no experimental
evidence to deny the fact that in the case of highly electronegative elements like fluorine or oxygen the
hybrid orbital does not participate in forming the MOs. If the hybridisation is insignificant, then the
MO energy diagram shown in Fig. 9.10.2.2c will automatically be converted into the simple MO
energy diagram shown in Fig. 9.9.1.2. Thus the MO energy diagram given in 9.10.2.2c is of much
general character. The electronic configurations of some representative homonuclear diatomic
molecules are given in Table 9.10.2.1 in terms of the modified energy diagram.
Note: The concept of hybridisation before molecular orbital fomlation simplifies the treatment as
shown in Fig. 9.1 0.2.2c. But this VBT concept is not essential. LeAO of four orbitals, Le. 2s and 2px
(x-direction being the bond axis) orbitals of A and B can produce 4 MOs, Le.
\II MO = cl \112s(A) + c2 \112Px(A) + c3\II 2s(B) + c4 \112Px (B)
A B A . B
°g(2s)
~ ~_(}_+r=D
0- -~-v--v V
ry
(c])_1) sPx(2)(A) sPx(2)(B)
°9(2s)
~~ ~ r1J~_r=D-(}-
ra
00 •• +~~-~-VV V
ib
(f~(2s) °u(2px) (J~2S) + a ~2p.) (<1'+2) $px(1 )(A) sPx(1 )(B)
yl
m
he
MOs and symmetry interaction
lc
Fig. 9.10.2.2b. Formati9n of molecular orbitals through the symmetry interaction among the
O"g(2S)' O"U(2S)' O"g(2Px) and O"U(2px) molecular orbitals and via the mixing s-p hybrid orbitals~ Note: Both
ea
the approaches lead to the same result.

th
<1>-2
I
I~*
\ a u(SPx)
e/
,~\
'/ * , \
~ 1t g (2p) ,\
t.m
2py. z /1J "" 2py z

2P- -
= : 4 "- - ~
--/1 \'--'
j---- -
- - 2P
-,.-.::::==
\\ "" ' - - - ,,<, ' }\
I~
ttI'''
I
1
\ " SPx(2) "'"" <1>_1 ,.) ttl' sPx(2) "

\\ '
\'
'~ -- -
\,
\ I
,'
"
/ \
, \
1t u(2p)
r
,
-}
: \
\
'\ ......--JI:.-.. 1 \ 0' ~(SPx)

1 L--...". ..". , <1> 2 ......... .---1 \
I"~ + ,---, \
2s -----f,"" sPx(1) \\ II sP x(1) ", ~ 2s
\ I
\ I
, I
\~(lg(SP)t)
<1>+1
Fig. 9.10.2.2c. MO diagram for the homonuclear diatomic molecules through the combination of sp-
hybrid orbitals.
Introduction to Chemical Bonding and The~ries of Covalence 597
MOT for the lighter vs. heavier members of 2nd period

&
Conclusion: Both the symmetry interaction and hybridisation ofAOs before combination are
only meaningfulfor the low electronegative elements where 2s and 2p orbitals do not differ largely
in energy.
Designation o/the MOs: Different authors designate the MOs in different ways (cf. Fig. 9.10.2.2d).
Presently, the MOs are named as follows:
• •
o g(ls) as 109; 0U(1s) = 20u ; 0 g(2s) == <1>+1 =30'g;
ry
• •
aU(2.~) == <1>+2 = 40'u; 1t u(2py.z) = I1t u ;
ra
ib
The energy order is :
109
• •
< 20'u < 30' g < 4a u < I7t u < 50'g < 27t g < 60 u
••
yl
(cf. Figs. 9.10.1.1, 9.10.1.3, 9.1 0.2.2c and 9.1 O.2.2d). m Representation (different conventions)
CJu(SPx )
3CJ~(sPJf) 3a~ 6a~
he
I (et>-2)
I
I
I
lc
I
I
I
, 17tg~z) 17t g 2n;
ea
/
I /
I /
I /
I / ag(spx)
(2p + 2p) I / 3ag 5ag
th
3ag(SPM) ~
.1/ /" ,. e»
~ ,. ,." (<J>_1)
!
--- --- W
e/
11tt(y,z) 11tu 11tu

t.m
\',
\ ,
\
\
" ..... , a ~(SPx)
(2s + 2s)
\
\
2a~(sPJf) 2a~ 4a~
\ (<D+ 2 )
\
\
\
\ ag(splf)
2a~spx) 2ag 3ag
(<D+ 1)
, , 1a~1S) 1a~ 2a~

, ,.'
,"
(1s + 1s) < , ,
..... ..... .....
..... ,
1ag(18) 1ag 1ag
AOs MOs
Fig. 9.10.2.2d. Different conventions to designate the MOs of the homonuclear diatomic molecules.
. .
Note: For the 2nd period elements, some authors start naming of the orbitals from cr g(2s), i.e.,
.
0' g(2.t} = 10'g' < O'u(2s) = 20' u' and so on. Here the MOs generated from the valence shells are considered
and the MOs produced from the inner shell are ignored and in fact these orbitals do not contribute in
bonding for the molecules of the 2nd period elements.
Electronic configurations ofthe homonuclear diatomic molecules ofthe 2nd period elements in
terms ofthe modified MO energy diagram: These are given in Table 9.10.2.1. These can explain the
magnetic properties of B2 and C 2 and nature of HOMO of N2•
ry
Table 9.10.2.1. Electronic configuration of the homonuclear diatomic molecules in
terms of the generalised MO energy diagram (cf. Fig. 9.10.1.1, 9.10.1.3, 9.1 0.2.2c
ra
and 9.1 0.2.2d)
Molecule Electronic configuration Bond order Magnetic property
ib
H2 }02 D
g
2 ·2
yl
He 2 }og 20 u 0
2
Li2 [He 2 l30 g D
·2
m
Be 2 [Li2 l40., 0
he
2
B2 [Be2 l17t., P
4
C2 [Be2 l17t., 2 D
lc
2
N2 [C2 l So g 3 D
ea
·2
°2 [N 2 l21t g 2 P
·4
F2 [N 2 l21t g D
th
·2
Ne2 [F2 l60., 0
e/
D = diamagnetic, P = paramagnetic. These electronic configurations can explain the

magnetic properties of the diatomic molecules.
t.m
9.10.3 Success of the Modified MO Energy Diagram: Reactivity of Some Molecular Species
• Magnetic properties: The modified MO energy diagram can explain the paramagnetic behaviour
of B z and diamagnetic behaviour of Cz.
• Inertness of N 1 (dinitrogen) : The inertness of N 1 can also be explained by considering the
modified MO energy diwam. The HOMO is SO'g and LUMO is 21t~ (antibonding). Thus it is very
difficult to remove an electron (Le. oxidation) from the O'-bonding MO; similarly acceptance of an
electron (Le. reduction) into the antibonding LUMO is also energetically unfavourable.
Dinitrogen (N1) cannot act as a good ligand because the HOMO being a a-SMa cannot be used
for O'-donation towards the metal centre. There may be only weak 7t-acceptance in the LUMO (7t.) from
the metal centre. On the other hand, the isoelectronic species CO, NO+ etc. can act as good x-acid
ligands because of their suitable HOMOs (for O'-donation) and LUMOs (for 7t-acceptance). These
aspects will be discussed later. Here it may be mentioned that the unmodifi.ed simple MO energy
diagram (Fig. 9.9.1.2) makes the HOMO ofn-bonding character. /fit were so, it would be more reactive,
and its ionisation energy would be much less.
• Reaction between N z and 0z (cf. Appendix: Woodward-Hoffman,n Symmetry Rule) : Let us
try to explain the origin of high activation energy in the reaction between N z and Oz. The direct
reaction between N2 and 02 occurs only at very high temperature (-- 30000 C).
N2 + 02~ 2NO
This inertness can be explained by considering the MO diagram of N2 and 02. Here the orbital
symmetry rule for a single step concerted reaction of electron flow is to be considered. Oxygen is
ry
more electronegative than nitrogen and consequently, the electron flow from N2 to 02 should occur.
But HOMO (5cr~) of N2 is not suitable to make a positive overlap with the LUMO i.e. SOMO (27[~2)
ra
of 02. Moreover, electron flow from the a-bonding MO of N 2 is not energetically also favourable.
Here, it may be mentioned that the HOMO i.e. SOMO (27[:2) of 02 can make a positive overlap with
ib
the LUMO (27[:)
of N 2 , but this electron transfer pathway is not energetically favoured because of
yl
higher electronegativity of oxygen. Moreover, the electron remova.1 from the ABMO of 0z will
strengthen the 0-0 bond to disfavour the reaction. However, placement of electrons in the ABMO
m
of N 2 will weaken the N-N bond. The possible HOMO-LUMO interactions in the N2 + 02 reaction are
shown in Fig. 9.10.3.1.
he
N=N
---+
tJ--- I
I
N
I
~2NO, r:;; \)
(a) +
ICJ
lc
0=0 °=-=-=---= 0
• • N N LUMO of N2
(1t g)
ea
HOMOofN2 ~m'~~~ (c) Ie

th
2 - I +
~e
(Og )
O--CJo "(1t*)
0--0 HOMO of 02
e/
(b) LUMO of 02
(ltg) I\. + _ 9
\V -
t.m
Fig. 9.10.3.1. Possibility of the reaction between N2 and 02 by considering their FMOs in terms of orbital
symmetry rule. (a) Concerted process involving a square like intermediate; (b) HOMO (N2 ) ~ LUMO
(02) but no overlap; (c) HOMO (02) ~ LUMO (N2); positive overlap but disfavoured electron flow and
strengthening of 0-0 bond. (Note: HOMOs and LUMOs of 02 are actually SOMOs (i.e. singly occupied
7t~ molecular orbitals).
• Orbital symmetry rule for a single step concerted reaction Hz + /z ---+ 2H/.
Previously, the reaction was supposed to occur through a single step concerted mechanism
(biomolecular reaction) involving a square species as the transition state. In the square species, electron
deficient multicentre bonding was argued. But the concerted mechanism is not correct in terms of the
orbital symmetry rule. These are discussed here:
(i) Iodine is more electronegative than hydrogen. Thus in the concerted process, electron flow
from HOMO (crg ) of H2 should occur to-the LUMO (0-:) of 12• But it causes a zero overlap
between the gerade HOMO and ungerade LUMO (Fig. 9.10.3.2).
(a) H H
I+ I
I I
(suggested concerted mechanism)
(b)
HOMO (ag )of H2
ry
LUMO (J~) of 12
ra
a~(p)
(zero overlap)
ib
(c) *
(Ju(s)
LUMO (a~) of H2
yl
m
he
(Positive overlap but dlsfavoured
lc
electron flow and strengthening of I-I bond)

Fig. 9.10.3.2. Application of orbital symmetry rule in terms of FMOs for the proposed bimolecular
ea
reaction, H2 + 12 ~ 2HI (cf. Appendix: Woodward-Hoffmann Symmetry Rule).
(ii) Positive overlap between the HOMO (7t~) of 12 and LUMO (cr:) of H2 can cause electron
th
flow from 12 to H 2 to produce the square intermediate. But it is not acceptable because of two
reasons: firstly, electron flow from the more electronegative species is not energetically
e/
favoured; secondly, electron flow from the antibonding MO of12 will strengthen the I-I bond
though it can weaken the H-H bond byplacing electron cloud in the antibonding MO ofH 2; to
t.m
allow the process to pass through the concerted process the 1-1 and H-Hbonds should weaken
simultaneously and H-I bond should strengthen; this cannot happen for the electron movement
from HOMO (12 ) ~ LUMO (H2 ).
Thus the single step concerted mechanism outlined in Fig. 9.10.3.2 is not acceptable. It is believed
that it is a multistep reaction (high activation energy) in which 12 first dissociates to produce I-radicals
(atoms) which subsequently react. with H 2 to give the product.
12 ~ 2/; I + H 2 ~ HI + H; H + 12 ~ HI + H; H + I ~ HI
• Wittig reaction: R2 C = 0 + H 2 C = PR; ~ R2 C = CH2 + OPR;
The orbital overlap interaction leading to a cyclic transition state has been d~scribed in Fig. 10.7.2.2
(cf. Appendix: Application of Woodward-Hoffmann- Symmetry Rule for the reactions:
CO + X 2 ~ COX2 , 02S + X 2 ~ SO~2; dimerisation of ethylene; Diels-Alder reaction:
R2S + X 2 ~ R2SX2 )·
9.11 MOLECULAR ORBITAL PICTURE IN HETERONUCLEAR

DIATOMIC MOLECULES : UV PHOTOELECTRON SPECTROSCOPY
AND PHOTOSENSITIVITY IN' THE LIGHT OF MOT
If the combining atoms differ in electronegativity, the bonding electron cloud gets nonuniformly distri-
buted between the nuclei. This nonuniform distribution generates a partial ionic character in the molecule.
Because of the difference in electronegativity between the atoms, the corresponding AOs available
from the combining atoms for LCAO are not of the same energy. With the increase of difference of
ry
electronegativity, the energy difference between the combining AOs increases. Then the bonding MO
will predominantly contain the character of the lower energy AO while the antibonding MO will be
ra
close to the higher energy AO. It indicates that the character of the bonding MO will be comparable
with that of the more electronegative atom while the antibonding MO will be enriched in the property
of the less electronegatiye'atom. Thus, in the combination of \VA and \VB where B is more electronegative
ib
than A, we get the MOs as :
if \VM~(bOnding) = a\VA + b\VB; then \VMO(antibonding) = b\VA - a\V B where, a and b are the mixing
yl
coefficients, and b > a. m
Thus, the less electronegative A contributes more to the antibonding MO while the more
electronegative B contributes more to the bonding MO. If A and B were ofthe same electronegativity
then it would be b = a, i.e. the extent of mixing will be identical as in the case of homonuclear diatomic
he
molecules.
Now let us consider the extent of ionic character introduced in a covalent linkage in terms of
lc
MOT. When the electronegativity difference is zero as in the homonuclear species, the bonding and
antibonding MOs are equidistant from the starting AOs. But with the increase of electronegativity
ea
difference between the combining atoms, the bonding MO goes to lie with the starting AO of the more
electronegative element and the antibonding MO goes to coincide with the AO ofthe less electronegative
th
element. In such cases, the bonding electron pair majorly lies with the AO of the more electronegative
atom. It leads to decrease the exchange energy which arises due to the travelling ofthe electron pair
e/
around the both nuclei. In other words, it can be said that the electron from the less electronegative
element is getting shifted to the AO of the more electronegative element.
t.m
The effect of electronegativity difference on the covalent interaction measured by exchange energy
(~c) is illustrated in Fig. 9.11.1.
r---\
A I \
----It \
\ \
\ \
\ \
A B \ \
t . \
\-~-
- - -+)---
\ tlEc
B
(a)A-B (b)As+S&- (C)A+g-
Fig. 9.11.1. Effect of electronegativity difference on the nature of bond. (a) Covalent bond as in a
homonuclear diatomic molecule having the exchange energy (~EJ maximum; (b) reduced exchange
energy with a significant contribution from the ionic form; (c) the bond is almost ionic.
For the homonuclear diatomic molecules, the exchange energy is maximum as the energies of the
combining AOs are matching properly (cf. Fig. 9.11.1 a). With the increase ofelectronegativity difference
(cf. Fig. 9.II.lb, c), the exchange energy decreases and at the limiting case (cf. Fig. 9.ll.lc), the
exchange energy becomes almost zero and it becomes an ionic bond. Here, it should be mentioned that
with the gradual increase o( electronegativity difference, the covalent interaction decreases, but the
degree of ionic interaction increases. This ionic interaction is quite important. In fact, both the ionic
and covalent interaction are important to determine the overall bond strength. It has been found
that when the electronegativity difference between the combining atoms is of intermediate range
ry
(cf. Fig. 9.11.1 b), a strong bond is formed.
The heteronuclear diatomic molecules can be classified in two groups.
ra
(i) One atom is H and another one contains both the s and p orbitals. Examples: LiH, HF, Hel, etc.
(ii) Both the atoms contain sand p orbitals. Examples: BN, CN, CO, NO, etc.
ib
Before to draw the molecular orbital picture for the above mentioned molecules, it must be
remembered that the relative energy order of the MOs depends not only on the difference of
yl
electronegativity of the combining atoms but also on the relative positions of the AOs on each atom.
Thus, the relative energy order of the MOs varies from molecule to molecule even in a particular class
m
of compounds. Here we shall consider the cases in a general way. Generally, the mixing ofns and np (n
= 2, 3) AOs on the isolated atoms is considered before the formation of MOs. This mixing becomes
he
insignificant for the highly electronegative elements where the 2s and 2p orbitals differ significantly
in energy. The bond axis in the discussion has been considered to be the x-axis.
lc
9.11.1. Molecules (I.e. XH) Containing a H-atom

ea
(a) Lithium hydride (LIH)

Ifx-axis is taken as the molecular axis, then Is orbital of hydrogen can combine with 2s and 2px orbitals
th
of lithium to produce three a-MOs.

Le. a 1,2,3 = c)'111s(H) + c2'112s(Li) + C3'112Px(Li)
e/
The lowest one (Le. a 1) is strongly bonding and it contains the highest amount of Is-orbital character
t.m
of hydrogen. The BMO is designated as as. The next one (Le. ( 2) is weakly antibonding and it possesses
a much greater weightage of2s orbital of lithium. This antibonding orbital is also described as a:. The
highest orbital (a 3) is enriched with the 2px orbital character of lithium. This strongly antibonding
orbital is described as 0:..
a 1 (Le. as) is more st~ble than Is orbital of hydrogen; a 2 (i.e. a:) is less stable than 2s and 2p orbital
of lithium and a 3 (Le. a Px) is also less stable than the 2p-orbital of lithium.
.. The other two p-orbitals (Le. 2py and 2P:) of lithium remain as non-bonding 7t-MOs. These two
orbitals are perpendicular to the molecular axis. The MO energy diagram of LiH is shown in Fig.
9.11.1.1. It should be mentioned that Is orbital of lithium remains as a non-bonding one. The two
valence electrons are placed at the lowest MO (i.e. ( 1).
(b) HX (X =el, F)
The low energy ns orbital of halogen remains. as a nonbonding one. Then for a-type interaction, Is
orbital of hydrogen can combine with the npx orbital of halogen. The combination, 'IIb(H) ± 'V npx(X)
,,~(cr3)
/, \
/ , (0'* ) \
// , S \
/ ''''I \ \
/ /,. '" / (0'2) \ \
/~" / \ \
{ ====4---,1-;'---=
-----4~~ , / \ \
2p \\
\ " 1ty Z \ \
\ I I • \ \
V I \ \
(-5.4 eV) ~( \\
ry
2s ~ \ \\
\ \ \ \
\ \ \ \
\\
ra
\ \
\ \ \\
\
,, \
\
\\
\\
ib
\ \\
\ \ \\
\ \ \\
\ \ ~
yl
\ \ \
\\\\ \
\
,\~
m \
~---1s
\~ (-13.6 eV)
, as
he
AO's of AOof
lc
Li H
Fig. 9.11.1.1. Molecular orbital diagram of LiH (energy value not in scale).
ea
will give one bonding and one antibonding orbital. The npy and np= orbitals (perpendicular to the
th
molecular axis) of the halogen remain as nonbonding 7t-MOs. The a-bonding MO is enriched with the
character of 2px orbital of X (which is more electronegative than hydrogen) while the antibonding MO
e/
is enriched with the character of Is orbital of hydrogen. The MO-energy diagram is shown in Fig.
9. II. 1.2. The 8 valence electrons are distributed as : '
t.m
2 2 4 ~
X(ns) cr (1t npy.Z ) , n = 2 (lor X = F), =3 (for X =CI)
Here it should be mentioned that the assumption of keeping the ns orbital of halogen as a
nonbonding one is not fully correct. In the case of fluorine, the 2s and 2p orbitals differ significantly
to prevent the mixing of2s and 2p orbitals. But in the case of HCI, the experimental evidences indicate
that chlorine uses an orbital having both 3s and 3p character. Definitely, this mixing is not much
significant. Ifwe consider that Is orbital of hydrogen combines with the ns and npx orbital of halogen,
then we may have three a-MOs (delocalised) as follows:
°1,2,3 = c1\Vb(H) + c 2 \V n.\"(X) + c3 \V npx(X)

(assuming x-axis as the molecular axis)
The magnitude of the mixing coefficients, c 1, c 2 and c3 depends mainly on the energy difference
among the combining orbitals. In the case of HF, the energies of the respective orbitals are :
,, 0*
\
\
I
\
I
I \
1s I \
( \
\
I
\
\
\
\
\
\
\
\
ry
\
\
\ 2p
~;::::iII::::;::::----, '---
ra
// (-18.6 eV)
/
ib
(Nonbonding)
yl
0nb
m (2s) (-40.2 eV)
cr
AO of AO's of
he
MO's of
H HF F
Fig. 9.11.1.2. MO diagram of HF (as a representative member of HX) (energy value not in scale).
lc
Is(H)= -110 x 103 cm- J (-- -13.6 eV), 2s(F) =- 374 x 103 cm- J (-- - 40.2 eV),
ea
2p(F) = -151 x 103 cm- J (-- -18.6 eV)

th
Thus O"J (of lowest

energy) is basically 2s I' ,
~ °1 and 02: Predominantly F-orbital
e/
.
orbital of fluorine and it is 1S (I
more or less nonbonding. (-13.6 eV)\\

,,
,' 1 t
, 0 3: Predominantly H-orbital
t.m
Similarly, 0"3 (of highest nb: Exclusively F-orbital

energy) is basically 1s
orbital of hydrogen; and 0"2
"
"
""
" "
is enriched with the 2p- "'\ ""
, '1t "
character of fluorine. The " nb(2py.z)" 2p
other two p-orbitals (Le. 2py
\,tt tt .... -)J
~' ft ( ~ (-18.6 eV)
and 2P:, perpendicular to the \ 0'2 \1,
molecular axis) form a

degenerate set of 7t-mole-
1 ,
,
, t
tt
,
I I
II
I\J 2s
(-40.2 eV)
cular orbitals (non-bonding). °1

AD of MO's of AD's of
The MO diagram is H HF F
qualitatively drawn in Fig. Fig. 9.11.1.3. MO-diagram of HF (as a repreventative member of
9.11.1.3. HX). (Energy value not in scale).
9.11.2 Molecules (XV) in which both the Atoms (X, V) Contain 5- and p-Valence Orbitals
B. LiF
Here, the very low energy 2s orbital of fluorine remains basically as a nonbonding one. It remains
mainly confined with the fluorine nucleus. If x-axis is taken as the molecular axis, then the 2s orbital
of lithium can combine with the 2px orbital of fluorine to generate a pair of a-MOs (a, a*) (Fig. 9.11.2.1).
Because of much higher electronegativity of fluorine, the electron pair in the a-bonding MO spends
almost all of its time in the vicinity of F -atom. In other words, the Li 2s-electron is transferred to the
2p-orbital of F. Thus, this polarisation makes liF almost purely ionic.
ry
b. BN, NO, CO, etc.
ra
In such cases, both X and Y will provide s- and p-valence orbitals for combination. In Xl: Y (e.g. 0, F)
is believed to be more electronegative than X. Thus for l: participation of hybrid orbitals in forming
ib
the MOs is not of much importance because, for l: the ns and np orbitals differ significantly in energy
(cf. Fig. 9.10.1.2). If we consider the simple MO treatlnent (without any symmetry interaction or
yl
mixing of s-p orbitals), we can have the MO energy diagram as shown in Fig. 9.11.2.2a illustrated for
NO. The shapes of MOs are shown in Fig. 9.11.2.2b. By considering the symmetry interaction among m
the MOs (cf. Figs. 9.10.1.1 and 9.10.1.3), the MO energy diagram may be constructed as shown in Fig.
9.11.2.2c.
he
(Note: In the case of heteronuclear molecular species, the notation of g and u is not applicable).
Here it should be mentioned "that compared to the homonuclear diatomic molecules, in the
heteronuclear diatomic molecules due to the electronegativity difference, the overlapping interaction
lc
is less efficient to generate the MOs (cf. Fig. 9.11.2.2b).

ea
Symmetry interaction between the cr2s and cr2p MOs

(Fig. 9.11.2.2a) may lead to the energy order: x
th
< cr2Px• This MO diagram is also an

1t(2Py, z)
approximate MO-diagram for CO.

e/
2p
cr cr;': Predominantly
~
,," 2s-orbital of Li
t.m
"" \
\
,,/ " 1 t nb : Exclusively
2s
---4/
(-5.4 ev)\, -
/,,/ \
"
\
cr b: Predominantly
2p-orbitals of F
2p-orbital of F
i
, ,,
\
\
\
,, \
\
".
\
\ \
\ ,
1t nb(2p)
\ y,z
"
\ 2p
"" 1~ 4b -----~~ ,,~

............ ~
cr~,.L}b--......... (-18.6 eV)
2s
cr nb ~- - - - - -" ----4{;;=
(-40.2 eV) AOs
(0)
AO's (L1) MO's (LIF) AO's(F)
Fig.9.11.2.1. MO diagram for LiF (energy value not in Fig. 9.11.2.2a. Simple molecular orbital
scale). diagram of NO as a representative member
of XV, where V is more electronegative.
Fig. 9.11.2.2a leads to the follo\.ving sequence of energy levels:

10' = a(ls) < 20'* = a~lS) < 30' =!a(2s.) < 40'* = a~2s.)
< 50' = a(2px ) < 17t = 7t(2p • .) < 27t * = 7t~2P .) < 60'* = a~2 Px )
y.~ ).~
The simple MO energy diagram given in Fig. 9.11.2.2a for a heteronuclear diatomic molecule is
comparable to the simple MO energy diagram given in Fig. 9.9.1.2 for a homonuclear diatomic molecule.
The diagram of Fig. 9.//.2.2a is more appropriate for the molecules XY where both X and Y are of
high electronegativity and energy difference between the ns and np orbitals of both X and Y is
signijicant(v high to disfavour their mixing.
ry
Fig. 9.11.2.2c gives the following sequence:
ra
10' < 20'* < 30' < 40'* < In < 50' < 2n* < 60'* (cf. positions of 50' and In are interchanged)
Here it may be noted the MO energy diagram given in Fig. 9.11.2.2c is similar to the Fig. 9.10.1.3
ib
given for a homonuclear diatomic molecule.
It is very diffic~1t to predict the exact sequence followed by the molecules under consideration. For
yl
the species where both X and Yare less electronegative (e.g. CN-, BN-, etc.), the Fig. 9.11.2.2c is
more appropriate. However, it may be mentioned that the MO energy diagram given in Fig. 9.11.2.2c
m
he
0(0
lc
2s{X) 2s(Y)
ea
th
e/
t.m
@ p/ \~~
x
8 Node
I
v
1t
(2py)
2py(X) 2py{Y) Y 1t
(2py)
Fig. 9.11.2.2b. Shapes of MO's of the heteronuclear diatomic molecule XV where V is more electronegative
than X.
/
//~\
I \\
2* *
1t = 1ttY,z)
/ )--~\
// ~~ / \ \\
/ ~ I \, \
//~., I \ , \
~~ I \ '\
2p {-----< I \ '\
~,'
,~ ~ 1
\\ ' \\ Sa = O'(2px) or O(&Plf)
~~~ / \\
ry
\\\, 1 "
,\'\ ,\",
, \ \, 1
), "
\
k \~
ra
\ \
v" \ ' ~ 2p
\/ " "
\ 1\
\I\~-~
"
".,.. ~ I,
".,(
, ., /1
/
ib
J \ /' ~ ~ j/ .' -- 1n =1t(y,z)
1\ '( --, \ /
/, ,\
/ \ / ,
,I \, I I
yl
/"I'~
I,~ \
1
/ \ \ I')'"
I,
.A-*
"'to
* *
= 0(2s) or o(sp.)
I'"' , , 1 ,\
1
1 / "."
~,
m "I
, A ,
" ,,' , , I'
25 "", , I' ,
he
' \ 'i ' \
"" I
" ,
\
\
\
,
',\ I ',\'
,\ I , "
lc
" I ,~\
" /. ~
" \ " ,,"" 25
ea
, \ I " ""
", ,,""
,,'
3a =0(2s) or O'(spJ()
th
AD's of X MD's of XY AD's of Y

Fig. 9.11.2.2c. MO energy diagram of the heteronuclear diatomic molecule XV (V is more electronegative)
e/
after considering the interaction of 2s and 2px orbitals (x-axis is the molecular axis). The MO's generated
from the 1s-orbitals of X and V are not shown here (cf. Fig. 9.10.1.3).
t.m
is of much general character. On the other hand, the Fig. 9.11.2.2a is more appropriate for the
highly electronegative elements X and Y where the ns and np orbitals for each atom differ
significantly in energy. Electronic configuration of some heteronuclear diatomic molecular species is
given in Table 9.11.2.1 in terms of Fig. 9.11.2.2c.
• Properties ofNO in terms ofits MO diagram: Now let us consider the MO treatment to explain
the properties ofthe representative molecule NO. For the sake of simplicity, let us consider the simple
MO diagram shown in Fig. 9.11.2.2a. The bond order is 2.5 (= 1cr + 1.57t). The unpaired electron is
present in the antibonding 7t-or6ital which is delocalised over the whole molecule, though the orbitals
possess more weightage ofp-orbital of nitrogen.
The HOMO (i.e.. SOMO) is 7t* whose energy is higher than that of AOs of nitrogen and oxygen
(Fig. 9.11.2.2a). This is why, ionisation energy of NO is less than that of both nitrogen and oxygen.
The first IP values (in kJ mol-I) of NO, Nand 0 are: 894, 1402 and 1314 respectively. The bond order
in NO+ is 3. This is why, N-O bond length in NO+ is shorter than that in NO.
Table 9.11.2.1. The electronic configuration of some representative heteronuclear diatomic molecular species
(ct. Fig. 9.11.2.2c)
Total number A10lecular Electronic configuration Bond Bond dissociation Bond

(~r electrons species order energy (kJ mOll) length (pm)
2 ·2 2 4·2
12 BN 10 20 30 40 17t(y. z) 2.0 385.0 128
2 ·2 2 ·2 4 )
13 10 20 30 40 ht(y, z)50 2.5 775 120
80 }
CN 785 117
CO+ 112
ry
14 3.0 1070 113
CO }
NO+ 2 ·2 2
10' 20 30' 40'
·2 4
ht(y, z)50'
2
106
ra
CN- 114
(a)N 941 110
2
ib
2 ·2 2 ·2 4 2·)
15 NO 10' 20 30 40 ht(y, z) 50' Z1t 2.5 678 113
yl
(a) N2 is a homonuclear diatomic rr.olecule and it may be treated as usual (cf. Fig. 9.10.1.3) discussed earlier.
As the unpaired electron is not localised either on Nor 0, NO is reluctant to undergo dimerisation.
m
It may be mentioned that the MO treatment of N0 2 indicates that the unpaired electron in N0 2 is
housed in a a-type nonbonding MO which is mainly localised on N. This is why, N0 2 undergoes
he
dimerisation. The bond length 113 pm in NO ~s shorter than that in N0 2 (120 pm, bond order == 1.5).
These aspects have been compared and discussed in Sec. 9.12.9.
lc
In terms of the MO picture of NO, its reluctance to dimerise has been explained. However, in liquid
or solid state, it dimerises weakly. The dimer (NO)2 is planar and cyclic (C2v ) with N-N (218 pm) and
ea
0-0 (262 pm) bonds. This cis-structure is more stable than the trans-structure. The dimeric structure
through the N-O bond is also ruled out.
th
218pm !
e/
N--N 1\.'-----·0 N-----O N--N

I \113 pm
I I I \ /
t.m
0- - - - - - - - - - -0 0- - - - --N o N o
262 pm
~ C2v symmetry ~ ~C2h symmetry) (trans) I
Favoured" structure Less favour~d Structure
The C 2v structure of N 20 2 can be explained by considering the overlapping interaction' between the
half-filled HOMOs (i.e. SOMOs) oftwo NO molecules (Fig. 9.11.2.2d). These SOMas (singly occupied
molecular orbitals) are the 1t*-Mas.
The very feeble overlap interaction explains the very weak 0·····0 bond in the dimer. However,
this 0 .... ·0 interaction contributes to some extent in the stability of this dimer. In the trans-isomer, the
overlap between the O-centres is not possible. The dimerisatibn through the formation of N-O hond is
not also favoured because the overlap between the larger lobe of N-end and the contracted lobe of 0-
end is not good.
The cis-structure of N 20 2 is very much comparable to that of cis-butadiene.
cs:~czs:o
I better
I overlap
Vo~
~
G)°VJ
(Half filled Weaker (Half filled
HOMO) overlap HOMO)
ry
Fig. 9.11.2.2d. Orbital interactions (rr*-rr*) between the NO molecules leading to dimerisation.
(rr* + 7t* leads to antibonding interaction).
ra
..N-N..
ib
+ 2e /§l2- ••
II \ g: ) N20~- i.e /N===!':' I
yl
:0:
m :2: (Hyponitrite ion)
The 47t-MOs of cis-(NO)2 can be constructed in the same way as for butadiene (cf. Fig. 9.15.2).
l'he 41t-electrons are placed in the lowest two 7t-MOs. The resultant effect is : no net 7t-bonding in the
he
N-N segment but a net 7t-bonding in the N-O segment. If we add two additional electrons in
N 20 2 , we get N 2 0i- which is hyponitrite. These two electrons are placed in the LUMO of N 20 2 • It
lc
leads to net 7t-bonding in the N-N segment, no 7t-bonding in the N-O segment (cf. Fig. 9.15.2).
• Molecular orbital picture of co and its properties: Now let us compare the chemistry of the
ea
isoelectronic species N 2 and co. N 2 is quite

inert and it cannot act as a potential ligand. a* /(LUMO)
", '"I~'X"
th
In fact, very few complexes are known to 2p I",,~\

contain dinitrogen as a ligand. On the other ~•... ====( / anb (HOMO)
~,)V,' 2
(-10.7 eV), ~----r-~
e/
hand, CO is quite reactive and it can act as p

a potential 11'racid ligand. It can stabilise the
'l
(s \ I \
I ,'V PJ2/
n: ~ ••••~
"". ". ';J_"" , ",,""""'-;--:(-16 eV)
I~ ~~I
t.m
lower valent oxidation states of metals ~// 'V(SP)1\ 1\V(sP)2 /

through complexation. All these can be --.r \ " I
(-19.5 eV) \
\
/
I
\
, ,
I
explained by considering their respective
MO energy diagram.
\
\ r aJ,'
I "
In CO, because of the electronegativity ~ ,"\

difference between carbon and oxygen, a nb~ •••• ~\
" "
some special features are introduced. For 'V(sP)1 "\ 2s
carbon, the energy difference between the --4-
a* (-32.4 eV)
2s and 2p atomic orbitals is much less than 1s ,,~
that between the 2s and 2p atomic orbitals

-4l--....- - - ( "
, "
1s ,
" a ).-.... u
of oxygen. In developing the MO energy Pure Hybridised '--4r-".... Hybridised Pure
diagram (Fig. 9.11.2.3a) of CO, let us
(C) AOs (CO) MOs (0) AOs
consider the participation of s-p hybrid
orbitals in generating the MOs. Definitely, Fig. 9.11.2.3a. The molecular orbita.1 diagram for CO.
the s-p mixing in oxygen is less efficient. In fact, the oxygen hybrid orbital (sP)l is basically the pure
2s orbital of oxygen.
In general, for each atom, the mixed orbital (sP)l is enriched with the character ofrespective 2s atomic
orbital while the other mi~ed orbital (sP)2 is enriched with the character of the respective 2p-orbital
(along the molecular axis). Thus, (sP)l lies close. to the respective 2s orbital while (sP)2 lies close to the
respective 2p-orbitaI. In the present case, (sP)l of the more electronegative centre (Le. oxygen) remains
as a nonbonding one, and the (sP)2 orbital of the less electronegative centre (Le~ carbon) remains also
as a nonbonding one. It happens so when the combining atoms differ significantly in energy.
ry
The other two p-orbitals (perpendicular to the molecular axis) on each centre participate to generate
2 bonding 7t-MOs and 2 antibonding 7t-MOs. The MO diagram for CO may be simply represented as in
ra
Fig. 9.II.2.2c. But by considering ,the energy difference between the 2s and 2p orbitals of C and 2s and
2p orbitals of 0, the more appropriate MO energy diagram of co is shown in Fig. 9.II.2.3a and the
ib
corresponding MOs are shown in Fig. 9.11.2.3b.
°
The energy difference between the 2s and 2p orbitals of is relatively large compared to the
yl
difference between the 2s and 2p orbitals of C. Thus both the 2s and 2p orbitals of C can participate in
°
MO formation but the 2s orbital of remains preferably as a nonbonding one. The 2s(C), 2px(C) and
m
2px(0) orbitals can participate in fDrming three a-MOs; 2py, z(q and 2py, z(O) orbitals can
participate in forming four x-MOs. These are shown in Fig. 9.11.2.3c. Both the diagrams of Figs.
he
9.1I.2.3a and c lead to the same conclusion.
It leads to the bond order 3 for CO (bond energy == 1070 kJ mol-I). In fact, the bond distance (--
113 pm) is much shorter than the single and double bond distances (C-O, 151 pm; C=O, 122 p;n) and
lc
it is very close to the triple bond (C==O, 110 pm). To explain this triple bond in CO, in terms ofVBT,
a coordinate covalent linkage as : C ~ q: has been considered. But, if it were true, it would have a
ea
t 0 I I
th
Enriched with the character

+ of 2p orbital of 0
e/
------·C=o-----n
~
t.m
I
I I
bI !1 ?10 .
HOMO (NBMO)
I I Enriched with the character
o f 25 orbital of 0
-\11(5;); +"-. 8---6 + ijils;~-
~(LOne "pairs)~ It
Enriched with the character I a b I ~
of 2p orbital of C ~I n I NBMO
I I
LUMO~
~ + I
I
~
1_
, n*
------. C·--------O-----
{J I
-. I I'U F>
I I
I I
Fig. 9.11.2.3b. The characters and shapes of the MOs of CO with reference to the Fig. 9.11.2.3a.
Introduction to Chemical Bonding and Theories of Covalence, 611
0·
,
, 1t.
\
,
\
, I • ,
Note : This diagram is also
I'll (LUMO) ',,, approximately applicable for
" ,, \\ other heteronuclear diatomic
·2p
,1 \, )'
(-10.7 eV) \ "" 0nb

'\ '\
',\
molecules like NO
~ \) 1~ '" ~
Q) 2s ),.;" (HOMO) , ~
w
c:
1~ c.;"\ ", ~
ry
(-19.5 eV)',
,, \
\
""
~,
(-16 eV)
\ ~~,
,
1 \
1~1tb ~~ "
~.
ra
AC's of C '\
" l' -- ,
, I
\ 1~(J ,
ib
1~nb - - - - - 1~
yl
(-32.4 eV)
MO's of CO AO's of 0
m
Fig. 9.11.2.3c. Approximate MO energy diagram of CO (energy values not in scale).
Note : a 1,2,3 = ci \V 2s(c) + c2 \112px (c) + c3\112px (0)
he
and a l ,2,3 = denotes a, a nb and a·; x-axis taken as the molecular axis.
lc
high dipole moment which is in contradiction to the experimental fact (-- 0.1 D). This is why, the
following cannonical forms are proposed.
ea
:C = Q(I) ~ :c ~ Q+ (II) ~ : C+ - Q:- (Ill)

Here, the dipole moments of (I) and (Ill) are supposed to oppose the dipole moment of (II), and as
th
a result, the dipole moment is significantly reduced (see Sec. 10.5.3 (iv) ). But it is difficult to realise
the relative contributions of (I), (II) and (III). On the other hand, in the MO theory, it is easy to explain
e/
the high bond order in CO and other properties of co.

• Properties of co and N 2 and other isosteric species as ligands : Now we shall pay a special
t.m
attention to the molecule CO. It can act as a potential pi-acid ligand, specially to stabilise the low
oxidation states of different transition metal complexes. Interestingly, though N 2 is isosteric with CO,
N 2 has got almost no tendency to act as a ligand. We have already discussed CO in the light of the
general molecular orbital diagram (see Fig. 9.11.2.2c). But, here the electronegativity difference
between the combining atoms is sufficiently large to keep \V (.\"P}I of 0 and \V (!;ph of C as the nonbonding
orbitals. The more appropriate molecular orbital diagram of CO is given in Fig. 9.11.2.3a.
The nonbonding orbitals carry the lone pairs. The lone pairs reside in the nonbonding \V(SP}I of 0
and \V(.\"ph of C. The nonbonding \V (.\1'}1 of 0 is enriched in the 2s character (see Fig. 9.11.2.3b) of
oxygen while t~e nonbonding \V(sph of C is enriched in the character of 2p AO of carbon (see Fig.
9.11.2.3b). The nonbonding \V (SP}2 of C is the 110MO and 7t* is the LUMO. CO to act as a 7t-acid
ligand, the HOMO electron pair is to be used in a-donation and LUMO is to be used in receiving the
metal electron through 7t-boniding. Thus when CO acts as a ligand, it first donates the lone pair
residing in \V(.\"ph on carbon and then takes back the electron cloud in H* which is again enriched
612 ·Fundamental Concepts of Inorganic Chemistry
in the properties of 2p orbital of carbon. The lone pair in the nonbonding \V (sp). on oxygen cann~t be
preferably donated as it is tightly bound to the more electronegative oxygen centre through an orbital
which is almost 2s in character. If CO is argued to bind through the a-end by donating the lone pair on
O-end then x-acceptance in the 7t. (Le. LUMO) is disfavoured. Because, the 7t. is mainly concentrated
on the C-end. Thus ligation through the O-end of CO is disfavoured compared to ligation through
the C-end because of both unfavourable ligand to metal a-donation and metal to ligand x-back
bonding (called retro-bonding).
If the picture is compared to that of dinitrogen, it is seen that it has got no nonbonding pair to be
ry
donated to the metal ion. In N 2, the HOMO is a a-BMO i.e. the electron pair to be donated is concentrated
between the nuclei. It is difficult to use this HOMO pair for a-donation. The metal ~ ligand
ra
re-bonding involves the partication of 7t. MO (which is the LUMO) of N 2 and this 7t.-MO is equally
concentrated on both ends. Thus the overlapping in the said 7t-back bonding does not experience any
difficulty but this x-back bonding is not so efficient compared to the case of CO. Because, in CO,
ib
presence of the more electronegative atom oxygen favours the electron flow from metal to ligand. No
such driving force works for N 2 as a ligand. However, it has been proved that the marginal stability
yl
of the metal-dinitrogen linkage arises mainly due to the very weak metal-.+ ligand x-back bonding.
Thus the difference between co and N 2 as ligands arises because of the difference in their MO picture.
m
In N 2, there is no difference of electronegativity between the combining atoms. This is why, N2 cannot
produce a molecular orbital diagram which is present in CO.
he
Thus among the isosteric species, e.g. ClV, CO, NO+, N 2 , except N 2 , all other species can act as
potent pi-acid ligands. Except N z in all other cases, there is a HOMO (which is nonbonding or
lc
weakly bonding) enriched sufficiently in 2p character of the less electronegative element. The
electron pair residing in that orbital is donated (Le. a-basicity) easily and then the electrons from the
ea
metal centre are accepted back (Le. x-acidity) in the vacant 7t. MO (which is LUMO) enriched in the
2p character of the less electronegative atom. Presence of the more electronegative heteroatom acts to
th
favour the electron flow from the metal to ligand. Both the a-basicity and x-acidity act synergistically.
(c) SF VB. CO, N2

e/
These are isoelectronic species. Ifwe construct the MO diagram for BF as in CO (cf. Fig. 9.11.2.3),
t.m
the bond order in BF molecule becomes 3 (1 cr + 27t). But experimentally, the bond energy of BF has
been found very low, 548 kJ mol-I (cf. bond energy of CO = 1070 kJ mol-I). Thus, in BF molecule,
it is reasonable to consider the existence. of a single bond only. In fuct, the molecule BF strikingly
differs from its isoelectronic species CO and N 2 • This can be explained by considering the relative
energy difference among the combining orbitals. In N 2 (which is a homonuclear diatomic species), the
question· of energy match does not arise. In BF, the electronegativity difference is maximum among
these species. The energy values (in eV) of the orbitals are as follows:
COB F
2s: -19.5eV -32.4eV -14eV -40.2eV
2p : - 10.7 eV - 16.0 eV - 8.3 eV - 18.6 eV
Thus in BF, the good match (in terms of energy condition) only prevails between 2s(B) and 2p(F)
orbitals. Thus the MO diagram (Fig. 9.11.2.3c) for CO is automatically converted into the diagram
Introduction to Chemical Bonding and Theories of Covalence 61 a
I a* \ ,,
I
I
,
I
I
I
\
,
2p I
~---- 1t
n
b../ " ,,
~
.
(-8.3 eV) '"
/
, U ", '"
~ 25 // CJnb
' ,,'\ 2p
~ U ~
w (-14 eV) \ It U ----~~
ry
\ 1tb '
\ // (-18.6 eV)
\ I
\
ra
I
\ /
\
, /
flUb I
ib
25
ft - - - - - ---+4U~
yl
CJnb (-40.2 eV)
AOs of B MOs of BF AOs of F

Fig. 9.11.2.4. MO energy diagram for SF (cf. Fig. 9.11.2.3c)
m 0),2,3 =C)\V(2S)(S) + C2'V(2Px)(S) + C3\V(2Px )(F)
°
where 1,2,3 denotes 0b' 0nb and 0* respectively.
he
Note: For CO (Fig. 9.11.2.3a, c), the p-orbitals of C and 0 differ by about 5 eV in energy and they
can participate in forming the 7t-MOs. On the other hand, for SF (Fig. 9.11.2.4), the 2p orbitals of S
lc
and F differ by about 10 eV in energy and consequently they fail to participate in forming the 7t-MOs.
In fact, they remain as nonbonding x-orbitals {7t ntJ.
ea
In terms of the diagram (Fig. 9.11.2.4), the electronic configuration of BF is :

(cr nb)2 (cr b)2 (7t nb )4 (cr nb)2 (Le. bond order = 1)
th
(cf. for CO: (cr nh )2 (cr h )2 (1t h )4 (cr nh )2 and bond order = 3, in terms of Fig. 9.11.2.3a, c)
e/
This is why, BF does not survive and undergoes disproportionation as follows:

t.m
3BF(g) ~ 2B(s) + BF3(g)

(d) C2 , BN, BeD and LiF
All these are isoelectronic species, but their thermodynamic properties differ widely (in gaseous phase):
C2 BN BeO LiF
Bond length (pm) : 124 128 133 156
Bond energy (kJ mol-I) : 602 385 444 568
This change can be understood by constructing their MO diagrams. In moving from C2 to LiF, there
is decreasing trend of energy match of the combining AOs.
(e) CIF, ICI

The MO energy diagram of such interhalogen compounds can be roughly drawn as in 9.11.2.3a and c
for co. The.~-orbital of the more electronegative centre may be roughly kept as a nonbonding one
because of the energy reason. But the p-orbitals of both halogens can participate in MO formation
because their energy difference is not too large (cf. 1st I.P. values: 18.6 eV, 12.95 eV, 10.44 eV for F,
CI, I respectively). Their 14 valence electrons are distributed as follows:
cr~bcr;1t:cr~h7t*4 (cf. Figs. 9.11.2.3c and 9.II.2.3a)

The bond order is I. Here it may be noted that if the general MO energy diagram (as given in Fig.
9. I 1.2.2c) involving all the valence orbitals to participate in MO formation is considered, then the bond
order is also I. In fact, if the energy difference among the valence orbitals is not too large, the general
ry
diagram of Fig. 9.11.2.2c is applicable.
9.11.3 Ultraviolet Photoelectron Spectroscopy (UV·PES) : Identification of the Nature of
ra
Molecular Orbital Energy Level
ib
It may be noted that ordinary electronic spectroscopic technique does not lead to ionisation of the
species. It simply leads to excitation of an electron from one energy level to another. The important
yl
transitions are:
cr ~ cr*, nb (nonbonding) ~ cr*, 1t ~ 1t*, nb ~ 1t*
m
When a molecule (say M) interacts with the photons of high energy UV-radiation, the photon
absorption may lead to the ejection of electrons from the molecule, Le.
he
M+hv~Ar+e
The energy of the photon will be utilised to provide the ionisation energy (I) of the bound electron
lc
and rest ofthe energy will impart the kinetic energy (EK )
~c:
to the ejected electron. A small part of the energy (Ev~ib) UJ~
_ g0 e
ea
will be utilised in exciting the vibrational level of the ~~

~Q)
ionised species (Le. Ar). Thus the energy balance is: Q) .s
c: 0
th
Q).J::.
o a.
hv = 1+ EK + Evib ' or, EK = hv - Evib - I +:
Q)
Q)
.J::.
c: -
~o
e/
In this technique, the monochromatic UV radiation

of21.2 eV [He(I) emission, 2p ~ Is] is generally used.
t.m
For much higher energy, radiation of 40.8 eV [He(II)

line obtained from He+] mdY be used. The ejected
electrons are detected according to their kinetic energies
(EK ) and the peaks in a PES correspond to the E K hv
values of the photoelectrons ejected from different
energy levels (cf. Fig. 9.11.3.1)
E Vib (which is quantised) is much less than the
ionisation energy (I) and thus E K value (~ hv - I) fJ
corresponds to the ionisation energy from a particular Fig. 9.11.3.1. Principle of photoelectron
level. In a molecule, there are several energy levels and spectroscopy. /1 and /2 denote the ionisation
energies from the respective energy levels.
ionisation may occur from different levels and these
hv denotes the energy of the photon. The
different levels require different ionisation energies' (Le. spectrometer records the electron counts
representing different peaks in PES). with different kinetic energy.
The ionised molecule (say Ar) uses some of the energy ofthe incident photon to excite the vibrational
level and the required energy is quantised (EYib = nhv~ib' n = 0, 1, 2,... which gives the change in
vibrational quantum number). It leads to the reduction of E K (= hv - nhv yib- I). This is why, for a
particular I-value, the photoelectron appears with different kinetic energies separated by the quantised
energy (= nhv yib ) required for vibrational excitation.
In actual experiment, intensity (measured by electron count of some certain EK value) versus hv -
EK (= I + nhv vib) is plotted. The lowest energy end ofa band corresponds to the ion~ation energy (Le.
n = 0 leading to EVib = 0).
ry
It indicates that each band corresponds to a particular energy level from which the photoelectron is
ejected and the band at its lowest end gives the ionisation energy for that particular energy level.
ra
The highest energy end of the band indicates the ionisation followed by the dissociation of the
ionised molecule. Thus, the width of a band depends on nhv vib. The highest energy end of the band
ib
indicates the limiting value of vvib leading to dissociation of the excited ionised molecule.
The vibrational frequency (v vib ) is given by :
yl
v 'b
V1
=_1
m27t
if
V;
where f = force constant which increases with the increase of bond strength (Le. bond order), I.l =
reduced mass. In terms of wave number, it is given by :
he
VVib =_1_ {7
V;
lc
27tc
The yibrational frequency of a diatomic species depends on its bond order. Comparison of the
ea
vibrational frequency of the ionised species (M+) and unionised species (M) can tell us the nature
of the molecular orbital from which the electron is lost. If a nonbonding electron is lost, the bond
th
order ih Nr does not change and consequently vvib does not change remarkably compared to that of the
unionised species. If a bonding electron is lost during ionisation, the bond order decreases and as a
e/
result v vib decreases; if an antibonding electron is lost, the bond order increases to increase the v vib' It is
illustrated for NO (stretching frequency = 1890 cnl 1, bond order = 2.5).
t.m
• NO+ (produced for the loss of a 7t-bondi~ electron from_the bonding 7t~li MO of NO, cf. Fig.
9.11.2.2a) : It reduces the bond order and v vib decreases. v vib = 1200 cm < 1890 cm- 1, 1= 18
eVe
• NO+ (produced for the loss of an antibonding_electron from the HOMO 7t;p MO of NO cf. FIg.
9.11.2.2a) : It increases the bond order and Vvib increases. VVib = 2260 cm -1 > 1890 cm -1, 1=
9.3 eVe
Let us now illustrate the UVPES for determination of energy levels in some molecules.
8 2 : The lowest energy end of the UVPES (Fig. 9.11.3.2) band is 15.5 eV (with the separation of
2260 cm- 1) and it gives the ionisation energy (I crb ~ (0). The vibrational separation in the UVPES
band gradually decreases as the band moves towards the dissociation limit 18 eVe Here it is important
to mention that for atomic bydrogen, the ionisation energy is 13.6 eV which is less than that of molecular
hydrogen. In the bonding MO, the electrons are stabilised more compared to those in the atomic hydrogen.
The stabilisation is (15.5 - 13.6) eV = 1.9 eVe The vibrationalfrequency 2260 cm- 1 for H; is less than
616 Fundamental Concepts of Inorganic· Chemistry
} Vibrational
energy levels
~
'ecn
11 5eV
c
(1)
Ionization
energy 0'* 10 eV
i
ry
(H) // 13.6 eV
·15 , , 15.5 eV
17 15
ra
-·crb~"""""'" 18 16
(ab)
(h\.I - EK ) eV ~
18 eV
ib
(b)
(a)
yl
Fig. 9.11.3.2. (a) Energy level diagram of H2 and its UV-photoelectron spectrum. (b) The fine structure
of UV-photoelectron spectrum of H2 due to excitation among the vibrational energy levels in the cation
H2·
m
the vibrational stretching frequency 4200 cm- 1 of H 2 • It also supports that the bond in H; is weaker
he
than that in H 2 • Ordinary electronic spectroscopy gives the measure of cr ~ 0* transition.
N 2 : UVPES (Fig. 9.11.3.3) of N 2 shows three ionisation energies: 15.6 eV, 16.7 eV and 18.8 eV
lc
(cf. 1== 14.5 eV for atomic nitrogen). The lowest ionisation energy (15.6 eV) corresponds to thel-IOMO
Sag level (cf. Figs. 9.9.3.1 and 9.10.2.2c, d), the second value (16.7 eV) corresponds to the'rem?val of
ea
an electron from the 7t-bonding MO (l7t u)' and the third value (18.8 eV) corresponds to the 40 u level.
These level assignments are also in good conformity with the vibrational separation.
th
2 +--- Vibrational
e/
energy levels
11
t.m
~
~
Q)
:;: c
W
<
I 2150 em- 1
m
~ f =15.6 eV (5cr ) ) tI Sag (HOMO)
(I) I.
<
1 ••
I'
+.
It
tI
II
MO levels of
N2 (cf. Fig. 9.10.2.2d)
Fig. 9.11.3.3. UV photoelectron spectrum of N2 in terms of its MO diagram (cf. Fig. 9.10.2.2c, d).
[
(
Vibrational
energy leve Is 1
tI 1= 14 eV (an)
I~ . °nb 14.0
(HOMO)
ry
~
e>
Q)
ra
c
W >
16.0 Q)
t. t. ~
w
ib
1tb
II II I
>
1 E.
yl
m 18.0 1
tI
he
crb
IJ 20.0
MO levels of CO 1690 cm- 1
lc
(cf. Fig. 9.11.2.3a,c)

Fig. 9.11.3.4. UV-photoelectron spectrum of CO.
ea
co: UVPES of CO is shown in Fig. 9.11.3.4. The ionisation energies 14 eV, 19.5 eV and 19.7 eV
th
correspond to the energies of O'nb (HOMO), 7th and O'h respectively.

Characteristic features ofUV-PES of some common diatomic molecules are given in Table 9.11.3.3.1.
e/
Here it should be mentioned that by using the X-ray photon, similarly X-ray photoelectron spectroscopy
(XPS) can be carried out. XPS reflects the effects of nuclear charge and overall electron shells while
t.m
UV-PES mainly provides the information of the valence levels.
9.11.4 Colours and Photosensitivity of Compounds in Terms of MOT

By considering th~. energy difference (~ between the HOMO and LUMO of a particular compound,
its colour can be predicted (hv = 11E, v is the frequency of light absorbed in transition of an electron
from the HOMO to LUMO). This energy difference depends on many factors such as electronegativity
difference, efficiency in overlapping to produce the FMOs (i.e. HOMO and LUMO). The electron
transition from HOMO to LUMO in heteronuclear species causes charge separation and the observed
electronic spectrum is described as a charge transfer band.
• If the energy difference (~E) between the HOMO and LUMO is very large, then electron
transit~on occurs in the ultraviolet (UV) region and the substance looks colourless or white.
• If the energy difference between HOMO and LUMO is small, the band shifts towards the visible
part (approximately 360-750 nm) of the electromagnetic spectrum. If the bandjust tails into
Table 9.11.3.1. UV-PES [using He(I) emission] of some common molecules
I (ev) Vibrational Assignment ofthe Lowest I value

separation (cm~ 1) energy level from corresponds to
which the photo- HOMO
electron is lost
lV'}
(V~vib = 2345 cm-) 15.6 2150 50g (bonding) (cf. Fig. 9.10.1.1,
16.7 1810 17t u (strongly bonding)
] 9.10.2.2d and
ry
18.8 2390 40: (weaklyantibonding) 9.9.3.1)
°2 .
ra
(Vvlb = 1555 em-) 12.1 1780 21t..: (antibonding)
17.0 1010 17t u (strongly bonding)
] (ef. Fig. 9.9.1.2 and
ib
19.3 1110 40g (strongly bonding) 9.9.3.1)
C'O
(v~ib = 2157 em-) 14.0 2160 0nb (nonbonding)
]
yl
16.5 1610 7t b (bonding) (cf. Fig. 9.11.2.3a, e)
19.7 1690 0b (bonding)
m
NO
(vvib = 1890 em-I) 9.3 2260
.
2lt 2p (strongly antibonding) ]
he
16.4 1550 17t2p (bonding) (ef. Fig. 9.11.2.2a)
18.0 1200 502p (strongly bonding)
Hel
lc
(vvib = 2886 em-I) 12.75 2660 nonbonding

HBr
ea
(vvib = 2560 em-I) 11.70 2420 nonbonding (ef. Fig. 9.11.1.2-3)

HI
th
(vvib = 2230 em-I) 10.2 2100 nonbonding

e/
the visible range from the UV-range, it looks yellow. If the band enters more into the visible
t.m
range, the substance looks red. If the band spreads the whole visible range, the substance
looks black.
When the electronegativity difference decreases, the energy gap between HOMO and LUMO
decreases (cf. Figs. 9.11.1, 9.11.4.1) in the compounds (MX) and colour changes gradually from
white to yellow to red to black.
White/colourless ~ Yellow ~ Red ~ Black
~ : ) decreases.
(i) AgF (white), AgCI (white), AgBr (pale yellow), AgI (deep yellow).
(ii) HgF2 (white), HgCl2 (white), HsBr 2 (pale yellow), HgI2 (red).
(iii) PbF2 (white), PbCl2 (white), PbBr2 (white), PbI2 (yellow).
(iv) ZnO (white), ZnS (dirty white).
(v) CdO (white brown), CdS (yellow).
(vi) HgO (red), HgS (black).

(vii) AsBr3 (colourless), SbBr3 (colourless), BiBr3 (yellow-orange).
)
Electronegativity difference decreases and energy difference between HOMO and LUMO
decreases.
• Generally, the salts of alkali metals and alkaline earth metals are colourless as these are ionic
compounds where the energy gap between the HOMO and LUMO is very high (Le.' electron
transition occurs in the UV-region). Sometimes, the observed colour is the colour of the anion
itself (e.g. Na 2PtCl6 - bright yellow due to the anion PtCI;-).
ry
• In the homonuclear diatomic molecules (e.g. X 2 halogens), overlap efficiency of the combining
atomic orbitals decreases gradually for the heavier ~ongeners. Consequently, energy gap
ra
between the HOMO and LUMO decreases and the absorption band shifts towards the visible
range. This aspect has been already illustrated for halogen (cf. Sec. 9.9.2 and Fig. 9.9.2.2).
ib
F2 (colourless/pale yellow), Cl2 (green yellow), Br2 (red-brown), /2 (violet).
The similar trend is also noticed for the Gr. 16 elements.
yl
Oxygen (colourless gas), sulphur (yellow solid), selenium (red), tellurium (black).
m
Photosensitivity: The homonuclear molecular species (X2) which show the strong absorption bands
in the visible range undergo photochemical dissociation easily when the electron transition from HOMO
he
to LUMO reduces the bond order.
X 2 ~2X
lc
The radicals (X) can initiate the chain reaction.

For the heteronuclear substances
ea
(MK), strong absorption in the visible

range causes reduction at the metal @-oo ,LUMO
th
Ii
centre where the LUMO is mainly / \
enriched with the character of metal (6> ec::!),
,, ,, s p
orbital. Thus LUMO is basically a
,, Q-0)(8
e/
metal orbital (cf. Fig. 9.11.4.1) and it ~

~ ,, ,,
\
, LUMO
,, \
t.m
acts as the acceptor of electron. The

,,
Q)
c:
strong absorption in the visible range W
,, ,, M-...J
, "6> e<::!)\\
\
indicates that the LUMO is a low lying
,, ,, \ \
orbital. This low lying LUMO can
accept electron from the external , ,, .\
\
\
\
\ X
r----
sources also. This is why, the salts ~~, x- \ '
(e.g. halides, oxides and sulfides) ,~/'
, 1b /(HOMO)
"EX=> "
\ 1b 'HOMO
which are highly coloured or black
are more prone to reduction than the Q+0X) Q+0X)
colourless or white salts. s P s P
AgBr (pale yellow) is more (a) (b)
photosensitivethanAgCl(white). This Fig. 9.11.4.1. (a) FMOs in the ionic compound MX where the
photosensitivity of AgBr is utilised electronegativity difference is very large; (b) FMOs in MX
in photographic processes. where the electronegativity difference is relatively small.
9.12 MOLECULAR ORBITAL TREATMENT OF TRIATOMIC MOLECULES

9.12.1 Basic Concepts of Group Orbitals, Delocalised and Localised Molecular Orbitals
In dealing with the triatomic molecules, it will be convenient to consider the formation of group orbitals
(\V gr) (or symmetry-adapted iJrbitals) by using the atomic orbitals of the terminal atoms. These group
orbitals are the linear combination of the atomic orbitals of the terminal atoms. These group orbitals are
described as ligand group orbitals (LGOs) or ~ymmetry-adaptedlinear combinations (SALes) or
terminal atom symmetry orbitals (TASOs), Le. 'VTASO. Then these group orbitals (Le. TASOs) will
ry
combine with th~ suitable atomic orbitals (or hybrid orbitals) of the central atom ('VeA) to generate the
Mas ('V+) Le.
c
ra
\V+ = C1'VCA + c 2 'VTASO and 'V- = 3\VCA - c4\VTASO
For e~ample, in the case of hydride~ XH2 (e.g. BeH2 ), the Is orbitals (which are themselves
ib
symmetrical) of the terminal H-atoms will combine to produce the following two H-group orbitals:
{
~H(+) = 'Vh(H A ) + 'V1s(H B )' (symmetrical) }
yl
a-type TASOs . (Fig. 9.12.1.1)
~H(-) = 'V1s(H A ) - 'V1s(H )' (nonsymmetrlca/)
B
m
These H-group orbitals are of a-type. For forming the a-Mas, the symmetrical H-group orbital,
'H(+) can combine with the symmetrical s-orbital of the central atom to produce two- a-Mas (one
he
bonding, one antibonding). On the other hand, the nonsymmetrical H-group orbital ~H(-) can combine
with a nonsymmetrical p-orbital of the central atom to generate two a-Mas. This concept will be
lc
utilised in dealing with the hydrides H 3 , BeH2 , H 20.

Now let us illustrate the formation of group orbitals by using the p-orbitals (which are themselves
ea
nonsymmetrical) of the terminal atoms. In XY2 (e.g. CO 2 , BeCI2 , etc.), if two p-orbitals (say 2px) of the
terminal atoms YA and YB undergo a-type combination, then the following two Y-group orbitals will
be produced.
th
= \V2p (Y
<Pr(x+) ) + \V2p (Y ), (a-type nODs-ymmetriCal)} . -
a-type TASOs (FIg. 9.12.1.1)
e/
% A x B
{ <Pr(x-) = \V2px(Y ) - \V2px(Y ), (a - type symmetrical)
A B
t.m
The symmetrical group orbital ~Y(x-) can combine with the symmetrical s-orbital of the central atom
to generate two a-MOs.
If the 2py-orbitals of the terminal atoms undergo 1t-type combination, then the following two group
orbitals will be produced. "
{
~,(y+) = 'V2p (Y ) + 'V2p (Y )' (n - type nonsymmetriCal)}
x-type TASOs Y. A Y B • (Fig. 9.12.1.1)
,. <Pr(y-) = 'V2Py (YA ) - 'V2P (Y
y B
)' (n - type symmetrical)
The nonsymmetrical group orbitals epy(y+) can combine with a suitable nonsymmetrical p-orbital to
generate the 1t-MOs. On the other hand, the symmetrical group orbital ~y(y-) cannot combine with the
nonsymmetrical p-orbitals of the central atom. -
Formation of different group orbitals (Le. TASOs) is illustrated in Fig. 9.12.1.1. In forming the
group orbitals, the mixing coefficients have nat been shown. In fact, when the terminal atoms are
symmetrically placed with respect to the central atom, the mixing coefficients become identical.
4>H(-)' (Nonsymmetrical)
~
1s 1s ~ <f>H(+)' (Symmetrical)
TASOs (I.e., Group Orbitals) (a-type)
ry
(8)
ra
cPv(x+)'
(Nonsymmetrical)
ib
yl 4>y(x-),
m (Symmetrical)
Central atom
he
TASOs (a-type)
(b)
lc
ea
<f>v(y+)' (Symmetrical)
th
e/
<f>y(y+), (Nonsymmetrical)
t.m
Central atom TASOs (1t-type)

(c)
Fig. 9.12.1.1. Generation of group orbitals (Le. TASOs) in a triatc;nic linear molecule.
Sometimes, for the sake of simplicity, the central atom of a polyatomic molecule may be considered
to use the hybrid orbitals to generate 2c-Iocalised a-MOs. Similarly localised ll-MOs can also be
generated. However, the in phase and out ofphase combinations of the localised MOs can give back
the delocalised MOs.
Use ofhybridised orbitals by the central atom very often simplifies the molecular orbital treatment.
However, the concept of hybridisQtion (idea of VBT) is not essentially required in MOT. In the next
sections, we shall deal with some specific polyatomic molecules.
9.12.2 Molecular Orbital Treatment for H3 and H; Molecular Species and Hn Species (l"General)
In H3 , the terminal H-atoms may be denoted as HA and HB ; and the central atom may be denoted as Hc .,
Let us first consider that H 3 is linear (Le. HA-Hc-HB is linear). This assumption will be justified later
on. The terminal H-atoms may combine using their Is-orbitals to produce H-group orbitals (i.e. TASOs).
{
~H(+) = 'Vls (H ) + 'VIs (H )' (symmetrical) }
TASOs A B • (cf. Fig. 9.12.1.la)
~H(-) = 'VIs (H A ) -'Vts(HB),(nonsymmetncal)
These two H-group orbitals will combine with the Is orbital of the central H-atom (Hc ). The
ry
symmetrical H-group orbital will combine with the symmetrical Is-orbital ofthe central atom to produce
the following delocalised (3-centred) a-MOs (one bonding, one antibonding).
ra
Cf g = Cf b = 'Vt = cI\IIls(Hc ) + c2~H(+) = CI\IIl.\' (He) + C2 ["VIs(H A
) + \111s(H B )]
ib
• •
Cf g = Cf ab = 'V2 = C3 'Vl.\'(H c ) - C4~H(+) = C3'Vb(H c ) - C4 ['Vb(H A ) - \l!ls(H B )]
yl
The central H-atom cannot provide any suitable nonsymmetrical atomic orbital to combine with the
nonsymmetrical H-group orbital. This is why, the nonsymmetrical "-group orbital remains as a
m
nonbonding one and it introduces an antibonding interaction between the terminal H-atoms. Thus
we have:
he
Cfu = Cfnb = \II 3 i. e. ~H (-) = \II Is (H A) - \II b (B) ,
(weakly antibonding interaction between the terminal atoms)

lc
It is evident that a b and Cf:b are 3c-MOs but anb is a 2c-MO.

The molecular orbitals are shown in F~. 9.12.2.1.
ea
HA He HB
~ A.
th
e/
0-0
t.m
1s 1s 1s
(a) (b) (c)
Fig. 9.12.2.1. Molecular orbitals in the homonuclear linear triatomic molecule H3 . (a) Involved orbitals
(Le. TASOs and atomic orbital of the central atom He> and their combinations. (b) MOs of H3t (c) Wave
patterns of the MOs of H3 in terms of the model particle in a box.
Note : If a vertical nodal plane runs through a nucleus, then the orbital of that atom does not
participate in the MO formation as in Gnb in the present case.
I
I
a*g
,\
I
I
I \
,,
I \
I
I \\ (Nonsymmetrical)
I
(
I
I
--- (au)
anb
------~
\,
\ +H(-)
----------.." ',HA
1s \ \"..----',.,,,»---
1S
\ 1s
\
," +H(+)
ry
\
\
,, ,, , (Symmetrical)
\
ra
ADs of2H
,,,
\ " (TASOs) of 2H
\
\
\
,
ib
ab
(MOs)
yl
Fig. "9.12.2.2. Molecular orbital energy diagram of the linear triatomic molecule H3 . m
Note: Without considering the concept ofH-group orbital, the simple LCAO of the three Is orbitals
of H A , H B and He can also generate the three a-MOs. These are:
he
a h = \111 : \lib (H A) + \IIb(Hc ) + \lib (Ha )
lc
a nh = \113 : \II b (H A) ± \II b( He) - ~ Is (Ha)

or • Fig. 9.12.2.3 and (cf. Fig. 9.12.3.1)
ea
a ah =\112 : \II Lv (H A) - \Ills (He) + \Ills (Ha)

•
CJah = \112 ::- \II b (H A) + 'V Lv ( He) - \II Lv (Ha)
th
O+O+Q dd,a,-p,ane
e/
=> CJb = '1'1

t.m
O+O-G) · ·:0 =>

+ I
°nb =~3 }
Weakly
0-0-0 80
.antibonding
=> . 'l'nb = '1'3
0-0+0 ·~0!O!G a~b = '1'2
-O+O-G) ~O!Q!G a~b = '1'2
HA He He MOs
Fig. 9.12.2.3. Schematic representation of MOs. in H3 .
"
For the sake of simplicity, the mixing coefficients are not shown.
Apparently, the expression for crnb in two concepts~are different, but they lead to the same results.
The bonding interaction between H A and He is counterbalanced by the antibonding interaction between
the H B and He.
The three electrons in H] are distributed as cr~ cr~h (i.e. total bond order = 1). In fact, 'l'J (leading
to G nb ) containing an unpaired electron is weakly antibonding. This antibonding effect between the
terminal atoms destabilises the system compared to H; (cr~) where there is no electron in the cr~b. In
fact, in spite of two electrons in the lowest SMO, the species H] is not stable and 'it is transient. It is
ry
evident from the following fact.
H] ~H2 +H,tUf=-34kJmol- 1
ra
2H] ~ 3H2 , ~H =- ve (i.e. exothermic)
In the product (i.e. 3H2), the total bond order is 3 while in the reactant (i.e. 2HJ ) the total bond
ib
order is 2. It makes the process exothermic.
Existence of this transient species H] has been postulated to explain the exchange reaction with
yl
deuterium (D).
D+H2 ~[DHH]~DH +H
m
It is evident that \II] (bearing an unpaired electron) is of antibonding character between the terminal
atoms (HA and HB ). If the molecule tends to bend, the terminal atoms come closer and consequently,
he
this bending is opposed by the antibonding electron. This is why, H 3 is linear. The molecular species,
H; having no antibonding electron does not experience any such opposition in bending the geometry.
lc
In fact, H; gives the geometry ofan equilateral triangle (cf. Fig. 9.21.4). It can be shown that for this
triangular molecule, the energy of the lowest MO (bonding) is lower than that of the crb of the linear
ea
geometry. It must be mentioned that in the triangular species, because of the absence of cylindrical
symmetry the notation of cr-a*-(Jnb is not strictly applicable.
H;
th
The absence of any antibonding electron makes the species more stable than H J •
H; ~ H+ + H 2 , Ml = + 441 kJ mol-
1
e/
H; ~ 2H + H+ , Ml = + 857 kJ mol- 1
It is important to note that in H; (i.e. cr; cr~h) both the bonding and nonbonding MOs are filled in
t.m
(i.e. 3c - 4e bonding mcdel) and the species is linear. The antibonding effect of cr~b destabilises the
species when it tends to bend.
Stability order: H; > H] > Hi, (cf. antibonding effect of crnb ).
It indicates that the number of valence electrons plays an important role to determine molecular
shape and stability. This concept will be illustrated for XH2 (linear and bent shape, cf. Walsh diagram),
XY2 (linear and bent) species in the next section.
3c--4e bonding gives a linear segment - why?

3c-2e bonding gives a bent segment - why?
Bond order: The isostoichiometric species H], H; and Hi are having the electronic configurations
0 an d cr h2 cr nh
cr h2 cr 1nh' cr b2 cr nb • Iy. Th·
2 respective · h·lometnc
e ISOstOIC . specIes
· are h · th
aVlng &lornu
e same ' . I a b ut
different valence electrons.
. .. Total bond order

• Bond order per InteratomIC lInk = - - - - - - - - - -
Number of interatomic links
I
Each interatomic link connects a pair of nuclei. Total bond order = "2 (No. of bonding electrons-
No. of antibonding electrons).
In the linear H 3 molecule, there are two interatomic links with a total bond order is 1( = %). Thus
ry
the bond order per link is 0.5. In the same way, the bond order per link in H; and Hi is also 0.5.
In the hypothetical linear H IO molecule, the total bond order is 5 with 9 interatomic links. It leads to
ra
bond order 5/9 per H-H link.
ib
9.12.3. Molecular Orbital Treatment for Linear Hydrides XH 2 (e.g. BeH 2, BH;, etc.) Having
Valence Electrons Four
yl
The central atom X may be considered as a second period element and it can provide 2s and three 2p-
orbitals for MO formation. If z-axis is considered as the molecular axis for the molecule, HA-X-HB
m
(terminal H-atoms are denoted as HA and HB ), then the central atom (X) can provide 2p= and 2s orbitals
for a-MO formation. For this purpose, the terminal H-atoms provide their Is orbitals. Thus LCAO of
he
these four orbitals 'V2,v(X)' 'V2Pz(X)' 'Vb(H A ) and 'Vb(H B ) will produce four a-MOs. To visualise the
generation of these four a-MOs, let us consider the H-group orbitals (i.e. TASOs) from th~ terminal
H-atoms. The Is orbitals of HA and HB can give the following H-group orbitals.
lc
cPH(+) = 'V b(H ) + 'V h(H )' (symmetrical)

ea
TASOs A' B
{ cPH(-) = 'Vl.\'(H ) - \VIs(H )' (nonsymmetrical)
A B
th
(cf. Fig. 9.12.1.1 a)

The symmetrical H-group orbital will combine with the symmetrical 2s orbital ofthe central atom
e/
to generate two a-MOs (I bonding and I antibonding). Similarly, the nonsymmetric H-group orbital
will combine with the nonsymmetric 2p= orbital of the central atom to produce two a-MOs (I bonding
t.m
and I antibonding). Formation of these four cr-MOs is shown below.

'VI = cr,\, =lcr g = c1'V2s(X) +c2 cPH(+)
c1\II2s(X) + c2 {\II Is(H A) + \IIIs(H B) }
C3'V2s(X) - C4 cPH(+)
= C3\112s(X) - C4 {\IIIs(H A) + \II 1.<(H B)}

• \11
'1'3
= 00*
Pz
= 100· = CS 'V2pz(X) + c6 H (-)
u +
CS\ll2P:(X) + C6 {\IIIs(H A ) - \IIIS(H B )}
'V4 = a Pz = la u = C7 'V2pz(X) - CS'V H(-)
= C7 \112P:(X) - Cs {\II1.«H A) - \II1s(H B)}

ry
ra
(0; )
Node Node
ib
yl
(1s) (2pz) (1s) m
~4: -0+00+0 )
he
(1 s) (2pz) (1 s)
lc
(TASOs & AOs) (MOs)

Fig. 9.12.3.1. Formation of a-MOs in the linear molecule XH2 (i.e. HA-X-H B) by considering the
ea
participation of H-group orbitals.

Note: Without considering the participation of the H-group orbitals, the said MOs may be constructed
th
as follows by following the principle of LCAO (mixing coefficients not shown).

'V1{a s ): 'V)s(H A ) + 'V2S(X) + W)S(Hs );
e/
'V2(a:): 'V.S(H A ) - \V2S(X) + 'V.s(Hs ) or - 'V.S(H A ) + 'V2S(X) - W.S(Hs );
\V3«J~z): \IltS(H A ) + \Il2Pz(X)

t.m
- 'VtS(H s );
\V4{O'Pz): W)S(HA ) - W2pz(X) - 'VlS(Hs ) or - WIS(HA ) + W2pz (X) + 'VIS(Hs );

For the sake of simplicity, here the mixing coefficients are not shown. Both the concepts lead to the
same conclusion.
Generation of these 4a-MOs is shown in Fig. 9.12.3.1. These are delocalised (3-centred) MOs
covering all the three nuclei. The MOs are described by denoting the name of the major contributing
orbital of the central atom. The energy order of these a-MOs is as follows :
10"g (i.e. 0"." \1'\) <10" u (i.e. 0" pz ' \1'4) < 10"~ (i.e. 0":, \1'2) < 10": (i.e. cr~z \1'3) '
Ifz-axis is the molecular axis, then the 2px and 2py orbitals of the central atom wi~llie perpendicular
to the molecular axis. These orbitals of7t-symmetry remain as nonbonding ones because the terminal
iI-atoms cannot provide any orbital of x-symmetry to interact with the Px and Py orbitals of the
central atom. The MO energy diagram of the linear XH2 molecule is shown in Fig. 9.12.3.2.
ry
ra
ib
yl
m
he
lc
ADs of X
(Central element)
ea
Fig. 9.12.3.2. MO energy diagram of the linear molecule XH2 (e.g. BeH2 , Sf{{, etc.). The MOs
(Le. os' a~, opz and a~z) are named after the major contributing atomic orbitals of the central atom.
th
Note : The relative energy values of the AOs are different for differemt molecular species.
e/
Geometry: In the linear XH2 molecule (bond angle 180°), there are two bonding MOs and they can
accommodate maximum 4 valence electrons as in BeH2• In fact, BeH2 is linear. Ifthe species containing
t.m
more than 4 valence electrons (e.g. CH2, BH2, OH2, etc.) are supposed to have the linear geometry, then
these extra electrons are to be placed in the nonbonding and antibonding MOs depending on the condition.
In such cases, the geometry bends to stabilise the species by placing the electrons in the mo~ stable
orbitals. This will be illustrated in the next section.
It may be noted that HgH2 and Be; having 4 va/~nce electrons are also linear.
9.12.4 Molecular Orbital Treatment for Bent Hydrides XH2 (e.g. BH2 , CH2 ,· OH2 , etc.) having
Valence Electrons More Than Four
Let us start from the linear XH2 molecule (H-X-H = 180°). If the linear molecule (lying along the
z-axis) bends in the xz-plane, the 2py orbital (perpendicular to the molecular plane) of the central atom
(X) remains unaffected, but the 2px orbital (which remains as a nonbonding one in the linear molecule)
of the central atom (X) tends to overlap with the Is orbitals of the terminal H-atoms (Fig. 9.12.4.1 a). At
x
+Z~---A:-
HA I Ha
~
+x
ry
ra
A
ib
HA-X-HS (Bent molecule)
= 1800 (Linear molecule) Combination: 'V2s(x) + 'l'H(+) + 'l' 2px(X)
yl
Fig. 9.12.4.18. Interaction of 25 and 2px orbitals of the central atom (X) with the symmetrical H-group
orbital, 'H(+) = 'VIS(HA ) + 'Vls(Hs )' In the linear molecule, 2px orbital of X remains as a nonbonding one
m
but on bending it participates in bonding interaction.
he
lc
ea
)
th
'V2pz(x) + cj)(H)(-) 'l'2pz(x) + cj)(H)(-)

e/
(bonding interaction) (bonding interaction)

(Linear) (Bent molecule)
t.m
Fig. 9.12.4.1b. Interaction of the 2pz orbital of the central atom (X) with the nonsymmetrical H-group
orbital, Le. ~(_) ='VlS(HA ) - 'VlS(Hs )· The interaction becomes poorer on bending the molecule.
the same time, the 2Pz-orbitals of the central atom makes a poorer overlap with the Is orbitals of
the terminal H-atoms (Fig. 9.12.4.1 b) and it enhances the antibonding interaction between the terminal
H-atoms.
In the bent molecule (xz-plane)~ the orbitals available for a-bonding interaction are:
2s(X), 2px(X), 2pz (X), Is(H A ), ls(H B)
These will produce 5 a-MOs. Without the mathematical details, let us try to understand the fonnation
o,fthese MOs in a qualitative way. For this purpose,we may consider the H-group orbitals (Le. TASOs):
+H(+) = 'V1s(H A ) + 'V1s(H B ) and +H(-) = 'V1s(H A ) - 'V1s(H B )·

In terms of symmetry, the symmetrical H-group orbital 'H(+) can combine with the 2px and
2s-orbitals of the central atom (Fig. 9.12.4.1 a). This combination of 'V2s(X)' 'VzPx(X) and +H(+) can
produce three o-MOs (\VI' \V2' \V3) - one bonding, one nonbonding or weakly bonding and one
antibonding. Formation of these three MOs has been illustrated in a similar case (cf. Fig. 9.12.3.1 and
Fig.9.12.9.3a).
The nonsymmetrical H-group orbital <l>H(-) can combine with the nonsymmetric 2p= orbital of the
central atom to produce two a-MOs (Fig. 9.12.4.1 b). Formation of these a-MOs has been illustrated in
a similar case (cf. Fig. 9.12.3.1 and Fig. 9.12.9.3b).
ry
Let us summarise the generation of the 5 a-MOs.
c\\II2.«X) + C2 \112P.(X) + c3cl>H(+) ~ \III (i.e. 0'..), \112 (i.e. 0' p) and \113 (i.e. O'~) (cf. Fig. 9.12.4.1a
ra
and Figs. 9.12.9.1-3). c I ' c2 and c3 are the mixing coefficients with proper sign. Here \V2 is weakly
bonding.
c 4 \112P:(X) + cScl>H(-) ~ \II 4 (i.e. 0' P:) and \115 (i.e. O'~:) (cf. Fig. 9.12.4.1 b). c 4 and Cs are the mixing
ib
coefficients with proper sign.
yl
The Py orbital of X remains as a nonbonding one. The MO energy diagram of the bent molecule XH2
is shown in Fig. 9.12.4.2.
m
Walsh's rules: It has been already mentioned that the linear species like BeH2 , BH; and HgH 2
with 4 valence electrons adopt the electronic configuration O';O'~: (cf. Fig. 9.12.3.2). Now let us consider
he
BH2 having five valence electrons. If it adopts the linear structure, it will have the electronic
configuration: O'~O'~, n~b (cr. Fig. 9.12.3.2). Ifthe molecule bends then thefifth nonbondingelectron
lc
can be placed in cr Px which is weakly bonding (cf. Fig. 9.12.4.2).

Now let us compare the MO energy diagrams (Fig. 9.12.3.2 and 9.12.4.2) for the linear and bent
ea
XH2 molecules. In bending the molecule in xz-plane, the energy of as and a Pz orbitals goes to increase.
It occurs so, as the overlapping interaction of the Is-orbitals of the terminal H-atoms with 2s and
th
2p;-orbitals of the central atom (X) decreases on bending (cf. Fig. 9.12.4.la, b). At the same time, the
energy of Px orbital (which remains as a nonbonding one in the linear molecule) of the central atom
e/
goes to decrease and it becomes a Px in the bent molecule. Thus for BHz to adopt the bent structure,
the lowering of energy of the a Px must be able to compensate the rise of energy of the Os and 0,
t.m
orbitals (cf. Sec. 9.12.5 for explanation) In fact, it has been found that in ground state BH2 is angulai
[0'; O'~:O'~. ' cf. Fig. 9. 12.4.2] but in the excited state, it is linear [0'; O'~: n:u, (cf. Fig. 9. 12.3.2)]. In jact,
it has been noted that the molecules havingfive to eight valence electrons, adopt the angular structure
in the ground state.
- 0 2 2 2
CH2 (H -C~H = 136 ) a.fa Pz a Px
- 0 2 2 2 I
NH2 (H-N-H = 103 ) a.fa Pz a Px 7t nb (cf. Fig. 9.12.4.2)
- 2 2 2 2
OH2 (H-O-H = 1050 ) a.fa P a p" 7t nb
z
UV-photoelectron spectrum (UV-PES) of H 2 0: UVPES indicates the presence of first four

ionisation potentials. Thus UVPES supports the electronic configuration of H20 given above. The four
first ionisation potentials 12.6, 14.5, 16.0 and 27.5 eV correspond to the orbitals 7t nb' cr Px' cr pz and cr.f
/respectively.
x
*
,.,-_O'_P_x----t\ ('1'3)
/1 \
/ 1 *
/ / 1 <Tp, "
/ I.,,~ \('1'5)
/ ~ \ \ z
/ .,,'" 1 \ ,
//.,,'" 1 \ \
2p ~ ." I 1tnb(y) \ \
======f"'" ----/- -- - \ \
\', I \ \
\ , I \ \ y
ry
\\ 'I \ \
.\\ ), \ \
\\ I' op, \
'112 is approximately \\ I) , \\
'J of atz otx 1t~b(y)
ra
\, 1 / ('112) \ H20 :
non-bonding \" I \ t experimentally supported
\V\
, I I '
\ \ by UV-PES
ib
A/( \
25 M\ ' ~
( \ \ \', ''1.\ 4>H(-)
..,
yl
\ \ \ ~.---- ,
\\ \\ \\
\' \
,'" \
,\
,.,##
, 15
" ,~--
m
,, ,,
\ \ \
\ \
\ \
\
, 4>H(+)
", '
he
\\ \
\\ \
\\ \ "
'\ " opz , " (lASOs) (AOs of 2H
lc
\\ ("'4) " of 2H)

\~ "
ea
\ as /'
('1'1 )
(AOsof X
th
(central atom) (MOs of XH2 )
Fig. 9.12.4.2. MO energy diagram for the bent molecule XH2 (e.g. BH2 , CH2 , NH2 , OH2 , etc.). MOs
e/
(i.e. as' a Pz ' a PJI ' a ~z and a ~JI) are named after the major contributing atomic orbitals of the central atom
(X).
t.m
Note : • The relative energy values of the combining AOs are different for different molecular species.
• Because of the lack of cylindrical symmetry (i.e. cao)' strictly a-a* notation is not applicable.
Walsh's rules and molecular geometry of XH2

The XH2 molecular species having 3-4 valence electrons are linear while the XH2 molecular species
having valence electrons 5-8 are bent. The explanation has been already given in terms of MO
energy diagrams (Figs. 9.12.3.2 and 9.12.4.2).
Species : BeH; BeH2 BH; BH2

No. of valence electrons:
Geometry :
3 4
Linear
4
-----------------
5
Angular
Introduction to. Chemical Bonding and Theories of Covalence 631
9.12.5 Illustration of Walsh Diagram for XH 2 Species

VSEPR theory (Sec. 10.8.3) can predict qualitatively the shapes of the molecular species. In terms of
MOT, the electron count also determines the molecular shape. To accommodate the valence electrons,
the energy of the MOs may change. As the energy of the MOs changes, the molecular geometry also
changes simultaneously. All these aspects have been analysed by A.D. Walsh (1953). Here we shall
illustrate the approach by considering the correlation of the MOs of the linear and bentXH2 molecules
(where X is a second period element). In this regard, we can compare the MO energy diagrams of the
linear and bent molecules of the type XH2 (cf. Figs. 9.12.3.2 and 9.12.4.2). Now, let us examine the
ry
change ofMOs in changing the bond angle from 180° to 90°.
Effect on +H(+) T ASO : If the linear XH2 molecule (z-axis is the molecular axis) bends in the xz-
ra
plane, then the change can be expressed as follows:
=as =lag =CI'II2s(X) + C2+H(+); (H -X -H =180 0
and 2px(X) orbital does not participate)
ib
'III, linear
'VI, bent = lal = c3'V2px(X) + c4 'V2s(X) + cS +H (+)' (bond angle between 90° to 180°)
yl
= C6 '112P.(X) + c7 +
H (+); (H -X -H =90 m 0
and 2s(X) orbital does not participate)
(cf. Fig. 9.12.4.1a)
Here, +H(+) denotes the symmetric H-group orbital Le. (TASO).
he
+H ( +) = 'V b( H A) + 'V b( H B )
Thus in changing the bond anglefrom 1800 ·to 90°, the contribution of2s orbital of X decreases
lc
and in fact, it becomes completely off in bonding interaction when the 90° bond angle is attained. At
the same time, contribution of the 2px orbital of the central atom increases in a-bonding interaction
ea
(cf. Fig. 9.12.4.1). The energy of the 2s orbital is less than that of the 2p-orbital, and consequently
the energy of ",increases in bending the molecule. In the bent molecule, it is denoted by la l , while in
th
the linear molecule, it is denoted by la.

Effect on +H(-> T ASO : Now let us consider the interaction between the nonsymmetric H-group
e/
orbital (TASO) and 2pz-orbital of the central atom. It is expressed as :

= cS'V2pz(X) + C9 +H (-) (cf. Fig. 9.12.4.1 b)
t.m
'V2
[+H(-) = 'V1s(H A) - 'Vls(H B)]
In bending the molecule, bonding interaction of the 2pz orbital of the central atom (X) gradually
decreases. Consequently, the H-group orbital, +H(-> produces an antibonding interaction between
the terminal atoms. Thus '1'2 .becomes more stable when the terminal H-atoms are kept more apart.
Definitely, the linear geometry gives the most stable condition for 'V2. In other words, on bending,
energy of'V2 gradually increases. Conventionally, 'V2 (for linear molecule) is denoted by la u while it is
denoted by b2 for the bent molecules.
In linear geometry (along the z-axis), the 2P:x and 2py orbitals remain as nonbonding ones (Fig.
9.12.3.2) but on bending in the xz-plane, energy of the 2P:x orbital (contributing in 'VI MO) decreases
and 2py orbital remains unaffected. Thus the 2py orbital remains as a nonbonding one in both the
linear and angular geometry. In the limiting situation (Le. H-X-H = 90°), the 2s orbital becomes
nonbonding and this nonbonding 2s orbital is denoted as 2a l •
Thus it is evident that in the linear geometry, there are two nonbonding orbitals which are
pure, p-orbitals (i.e. 2px and 2py, cf. Fig. 9.12.3.2) of the central atom. On the other hand, in the
bent geometry (90° bond angle), the nonbonding orbitals are the 2s and 2py orbitals of the central
atom.
Thus in both the geometries, the common nonbonding orbital is one p-orbital (i.e. 2py orbital ofthe
central atom), and consequently its energy remains unchanged in changing the bond angle from 180°
to 90°. The other nonbonding orbital in the bent geometry, Le. 2s orbital (for 90° bond angle) correlates
with the nonbonding pure p-orbital (Le. 2px orbital) of the linear geometry (bond angle 180°). This is
ry
the most noticeable change in effecting the change ofbond anglefrom 180° to 90°. On increasing the
bond angle, energy of this orbital increases sharply until it is converted into one o~.the degenerate p-
ra
orbital at 180°.
The change of energy of the MOs with the change of bond angle (180° to 90°) in XH2 is shown in
ib
Walsh diagram (Fig. 9.12.5.1).
It has been already discussed that the species (e.g. Bell 2' BH;, etc.) havingfour valence electrons
yl
will adopt the linear geometry. On the other hand, the species having valence electrons five to eight
(e.g. BH2,CH2, OH2, etc.) will adopt the angular geometry. Thus the number of valence electrons
m
determines the shapes of the molecules and consequently the energy of the MOs. This aspect will be
illustrated for XY2 species in the next section. It will be seen that the XYz species having valence
he
electrons 16 are linear, but the species having valence electrons 17 to 20 are angular, and the species
with 21 or 22 valence electrons again adopt the linear structure.
Note: Predict the geometries of the species, CH2' CH; , BH2' BH; , BHi. ' NHi. .
lc
9.12.6 Molecular Orbital Energy Diagram of s.ome Representative Triatomic Hydrides In

ea
Terms of Hybrldlsatlon of the Central Atom

The molecules XH2 (both linear and bent) have been already described in general in terms of nonlocalised
th
3-centred MOs. Here, we shall discuss two specific molecules BeH2 (linear) and H20 (angular) in
terms of hybridisation of the central atom. By using the hybridised orbitals of the central atom,
e/
formation oflocalised (I.e. 2-centred) a-MOl will be considered. These localised MOs on combination
can generate the delocalised MOs. Moreover, the VBT concept of hybridisation is not absolutely
t.m
necessary. It just simplifies the treatment.

Note: The MO energy diagram involving the localised 2-centred MOsfaiis to explain the ionisation
energies indicated by UVPES i.e. photoelectron spectrum.
(I) BeH2
It is a linear molecule and the central atom (Be) undergoes sp-hybridisation by using the 2s and
2p=-orbitals (assuming the z-axis as the molecular axis). The two terminal H-atoms (say HA and HB) can
combine with the spz-orbitals of Be as follows to produce the local'ised a-MOs.
CJ Be - HB = 'III,~ = cl'llsPz(I)(B~):r c2'11Is(H B) (bonding)
cr"ae- HII = '" 2, loe = c\ '" SPz (\)( Be) - C2", b( HII ) (antibonding)
CJ Be-H If = '113, loe = C1'V sPz(2) (Be) + C2 'V1s(H A) (bonding)
cr~e- H A ='" 4, loe =C\ '" spz (2)( Be) - C2'" b( H A) (antibonding)
Introduction to Ch~mical Bonding and Theories of Covalence 633
'V2py(x) t----------..;..--~ .... \112p(x) x

(b 1 ) i.e. 2px' 2py +z~---A----
HA
..,
I Hs
+x
(Bent molecule, xz-plane)
ry
HA X Hs
+z ~- - .. --,--~- -
I
I
ra
\112. (linear) (1o u) I
'¥
+x
\111, (linear) (1 Og)
ib
(Linear molecule)
~----------~
9~ 18~
X-
yl
--+ H - H (bond angle)
m (a)
he
lc
ea
.. (Nonbonding) ~
\112, bent.(b2 )
_r--- (Nonbonding)
th
)
e/
'V2s, (28 1)
t.m
r - 2px(x) 2s(x) \
(b) (ct. Fig. 9.12.4.1)
Fig. 9.12.5.1. (a) The Walsh diagram (i.e. qualitative variation of the energies of the MOs with the
change of bond angle) of XH2 • (b) Composition of the MOs at two extreme geometries Le.
H-X-H =90° and 180° (i.e. correlation diagram).
The two sp-hybrid orbitals of Be are denoted as sPz( 1) and sPz(2). These are given by :
1 0
'II"Pz = ..J2 ['II2s(Be) ± '112Pz(Be)]. It leads to :
'VI, loe = c; ['V2s(Be) + 'V2Pz(Be)] + c 2 'VI s (H B )

Similarly 'V2. loe' \113. loe and \II4. loe can be expressed.
These 2-centred localised MOs are confined between the respective nuclei.
The other two p-orbitals (i.e. 2px and 2py) lying perpendicular to the molecular axis remain as
ry
degenerate nonbonding 7t-orbitals. The MO-energy diagram is shown in Fig. 9.12.6.1.
The other linear molecules like BH;, HgH2 , etc. can also be treated in the same way. Now let us
ra
correlate these localised MOs (Fig. 9.12.6.1) with the delocalised MOs given in Fig. 9.12.3.2. The
degenerate localised MOs can combine to generate the delocalised MOs. These are shown below.
ib
0' Be-H A ± 0' Be-H B i.e. \III.loe ± \113.loe produces two delocalised 3 centred a-MOs (bonding) i.e. \III
and \114'
yl
• •
°a Be-H A ± a Be-H B \1121oc ± \II410e produces two delocalised 3 centred a-MOs (antibonding) i.e.
i.e. "
'V2 and \113'
Note: By taking \II SPz -orbitals of Be, as follows:
m
= ~ ['112s(Be) + '112Pz(Be) ] = ~ ['112s(Be) -
he
'IISPz (\) and 'II sPz (2) '112p;(Be) ]
It can be shown that :

lc
\III = 'VI.loe + \113.loc = c 3\112s(Be) + c 4 [\IIIS(H + \IIls(H =c 3\112s(Be) + c 4+H (+) ~ as

A
)
B
)]
ea
\114 = \VI.loe - \113.loc = c 3\112Pz(Be) - c4 [\IIls(H A ) - \IIls(H B )] = c 3\112Pz(Be) - c 4+H (-) = a Pz
\112 = \112.loc + \II'4.loc = Cs\ll2s(Be) - C6 [\IIh'(H A ) + \IIls(HB )] = Cs\ll2.\'(Be) - C6~H(+) = a:

th
•
\113 = \V2.loe - \114.loc =Cs\II 2pz (Be) + C6 [\IIIs(H \IIls(H A
=Cs\ll2Pz(Be) + C6~H(-) = a Pz
) -
B
)]
e/
Here ~H(+)andcl»H(_)denotetheTASOsorH-grouporbitals (cf. Figs. 9.12.1.1, 9.12.3.1 and

9.12.3.2 and Sec. 9.12.3).
t.m
(ii) H2 0
In this angular molecule, the central atom oxygen undergoes sp3 hybridisation. Two of these sp3-hybrid
orbitals [say sp3(1) and sp3(2)] can be utilised to produce the localised a-MOs ~ follows:
•
O'O-H A =C I\Vsp3(lXO) + c2'Vh'(H A );O'O-H A = CI'V sp3(IXO) - c2'VIs(H A )
•
O'O-HB = cI\V sp3(2XO) + c 2'VIs(HB ); O'O-H B = cI'V sp3(2XO) - c 2\11Is(HB )
The other two sp3-hybrid orbitals of the central atom remain as nonbonding ones. The MO energy
diagram of H 20 is shown in Fig. 9.12.6.2.
Here it may be mentioned that the combination a O-H A ± a O-H B can produce two bonding delocalised
• •
(3-centred) a-MOs 'VI and \114. Similarly, crO- HA ± a O- HB produce two antibonding delocalised (3-
centred) cr-MOs \115 and \113' The MO-energy diagram given in Fig. 9.12.6.2 may be compared with the
diagram given in Fig. 9.12.4.2.
. Ha
1s (Ha) sPz (2) (Be)
ry
ra
ib
x
yl
m
y
he
,,
lc
The MO energy diagram based

,, only on the localised 2c-MOs
cannot explain the UVPES
-"
2s ----41~~
ea
th
e/
t.m
AOs of Be Localised MOs

of BeH 2
\
Nonlocalised
MOs of BeH 2
Fig. 9.12.6.1. The energy diagram of localised MOs of BeH2 and relationship between the localised
(Le. 2 centred) and nonlocal,ised (Le. 3 centres) MOs of BeH2 (cf. Fig. 9.12.3.2 for the nonlocalised
3 centred MOs).
Note : Localised MO energy diagram involving 2-centred MOs fails to explain UVPES.
Localised MO. : 'Vl, Ioc' 'V2, Ioc' 'V3, Ioc' 'V4, Ioc
Nonlocallsed MO. : 'Vl' 'V2' 'V3' 'V4 (cf. Fig. 9.12.3.2).
'113
~~'
;Jf~==~'
I ~~.. '115
I ,
-l--------+ Z
I "
I ,
I "
" . . . ,# y
~t~
ry
I /
I
I I (AOs)
I I
I I
ra
2p ~"'''' 2sp3,' 2sp3(nb) ,/
.... ~{ ==F!= f.::FI=
ib
~
C) I
, ' "
\ I
II 2sp3(nb)
(i) I \ aO-H ,
The MO energy diagram
yl
c I AI I
W I \ (J
2 --t--J 0- Ha. I based only on the localised
s \ ~ '114 2c-MOs fails to explain the
',......,--
\
m
1
\ 1/, experimental results of
,1'
,.,
~
, '111 UVPES
Pure Hybridised ' ,
he
...... ....... • ----- ~ T------'
AOs (0) MOs MOs

(Localised) (Non-localised)
lc
Fig. 9.12.6.2. The energy diagram of localised (Le. 2 centred) MOs of H2 0 and generation of nonlocalised
(Le. 3-centred) MOs from ·the localised MOs of H2 0.
ea
Note : MO energy diagram involving the 2-centred localised MOs cannot explain UVPES.
Non/oca/ised MOs : \111' \114' \115 and \113 (cf. Fig. 9.12.4.2)
th
9.12.7 Triatomic Nonhydrldes (XY2)-Linear Species (e.g. Be~, CO2, NO;, N2 0, N3-, OCN-
e/
etc.) having 16 Valence Electrons

In the linear molecule XY2, both X and Yare considered to be second period elements. Thus both X and
t.m
Yatoms can provide their 2s and 2p orbitals for MO formation. Let us consider the z-axis as the molecular
axis (YA-X-YB). Yis more electronegative thanX. The 2s orbitals of Y-atoms are of much low energy
(cf. Fig. 9.10.1.2). For the sake ofsimplicity, the 2s orbitals ofthe terminal atoms (YA and YB ) may
be kept as nonbonding ones. Thus for the a-type interaction, the central atom (X) can provide 2s and
2p= orbitals while the terminal atoms (YA and YB) can provide their 2pz-orbitals. These four orbitals
2s(X), 2pz(X), 2Pz(YA) and 2Pz(YB) can combine to generate 4 (J-MOs (3-centred). To understand the
formation ofthese delocalised (3-centred) a-MOs, let us first consider the Y-group orbitals (i.e. T ASOs)
produced through the combination of 2Pz(YA) and 2Pz(YB).
cj)y(Z-) ='V 2p (Y ) - 'V 2p (~ ) (a-type symmetrical)

a-type TASOs A ZB • (cf. Fig. 9.12.1.1b)
Z
{ cj)y(z+) = 'V2pz(Y ) + 'V2P (Y ) (a-type nonsymmetrlcal)
A z B
Formation"ofa-MOs: The group orbital, ~Y(z-) being symmetrical can combine with the symmetrical
2s orbital of the central atom (X) to generate two (J-MOs (one bonding and one antibonding). These are
shown below:
'VI = (J2s = c l \J!2s(X) + c2~(z-)
cl'V2s(X) + c2 {\J!2Pz(YA) - 'V2Pz(YB )}
\112 = CJ;.t = C3\J!2.f(X) - c 4+r(z-)
C3'V2s(X) ~ C4 {'V2Pz(YA) - 'V2Pz(YB )}
ry
Similarly, the nonsymmetrical group orbital, cl»Y(z+) can combine with the nonsymmetrical 2pz
orbital of X.
ra
•
\J!3 = (J2Pz = c S \J!2Pz(X) + c 6 +r(z+)
ib
cS'V2pz(X) + c6 {'V2Pz(YA) + 'V2Pz(YB )}
yl
\J!4 = CJ 2Pz = c 7 \J!2pz(X) -
m c~+r(=+)
c7'V2pz(X) - Cs {'V2PZ(YA) + 'V 2pz(YB ) }

he
These are shown in Fig. 9.12.7.1.
Formation of'It-MOs : Now let us consider the formation of 7t-MOs. For the formation of 7t-MOs,
the available orbitals are:
lc
2px(X), 2py (X), 2px(YA )' 2px(YB )' 2py (YA ), 2py (YB )
ea
These Px' Py orbitals are perpendicular to the molecular axis. These will combine to produce 67t-
Mas. Let us first consider the Px orbitals of the central atom and terminal atoms (YA and YB). The Px
th
orbitals of the thermal atoms YA and YB will combine (7t-interaction) to produce the following 1t-group
orbitals (Le. TASOs).
e/
+r(x+) = \J!2p (Y ) + \J!2p (Y ); (7t-type, nonsymmetrical)

t.m
'It-type TASOs x A x B • (cf. Fig. 9.12.1.1c)

{ ~(x-) = \J!2px(Y ) - \J!2px(YB ); (7t-type, symmetrIcal)
A
The nonsymmetrical group orbital cl»Y{x+) can combine with the nonsymmetrical 2px orbital of the
central atom (X) to produce one bonding and one antibonding MO.. But the symmetrical group orbital
+Y(X-> remains as a nonbonding one because the central atom cannotprovide any symmetrical orbital
for 'It-bonding. Thus, the 7t-MOs are :
\lis = 7tx '= C9 \J!2px(X) + c10+r(x+)
c9'V2P.(X) + clO {'V2P.(yA) + 'V2P.(yB )}
•
'116 = 1t x = c ll 'V2px(X) - c 12 +r(x+)
clI 'V2P.(X) - cI2 {'V2P.(yA) + 'V2P.(yB )}

7t nb(X) == +r(x--) = \J!2px(YA ) - 'V2px(YB >' (weakly antibonding)
ry
ra
ib
yl
m
he
Node Node
I I
lc
ea
AO of TASOs
central
atom X .
th
x MOs
8- ---~
e/
z Ij1nb(x) = c!lY(x-) i.8.

t.m
y
Fig. 9.12.7.1. Formation of different MOs in the linear molecule XY2 by considering the participation
of group orbitals of terminal (YA and Yal. Generation of 1ty (= 'V7) and 1t;(= 'Ve) can be shown accordingly.
Note : It is evident that for the nonbonding MO, a vertical nodal plane passes through the nucleus
of the central atom and its atomic orbital Le. pxfX) does not participate in the MO formation.
Note: Formation of these three 7t~MOs can also be understood through the following simple LCAO
scheme (Fig. 9.12.7.2).
•
7t x : 'V2PZ(YA) - 'V2px(X) + 'V2px("YB ) Mixing coefficients are not shown
or,
for the sake of simplicity
7tnb(x) : 'V2pz(YA) + 'V2px(X) - 'V.2px(YB )
7t nb(x) : 'V 2pz (YA ) - 'V 2px (X) - 'V 2px(YB )

ry
ra
2Px(YA) 2py(x) 2p~YB) n-MOs
Fig. 9.12.7.2: The delocalised three-centre x-molecular orbitals of the linear YA-X- Y8 molecule.
ib
In the same way, three 7t-MOs can be generated from the 2py orbitals of the central atom and
yl
terminal atoms. These are as follows: m
'V7 = 7ty = c 13 'V2py (X) + c 14 +r(y+)
c13'V2py (X) + cl4 {'V2Py (YA ) + 'V2Py (YB )}

he
'Vs = 7t~ = c1S 'V2py(X) - c 16 +r(y+)
lc
c1S 'V2py (X) - cl6 {'V2Py (YA ) + 'V2Py (YB )}

ea
1t nb (y) == +r(y-) = 'V2py (YA ) - Y2py (YB )
Generation of the different MOs is shown in Figs. 9.12.7.1 and 9.12.7.2.

th
The MO-energy diagram of the linear molecule XY2 is shown in Fig. 9.12.7.3. The MOs (both
bonding and antibonding) are described according to the name ofthe major contributing atomic orbital
e/
of th-e central atom (X). The non-bonding MOs of x-symmetry are basically enriched with the
t.m
character of p-orbitals of the terminal atoms and they introduce an antibonding interaction
between the terminal atoms.
(i) MO picture of CO2 : Now let us consider the electron distribution in CO 2 (with valence electrons
16) in terms of the MO energy diagram given in Fig. 9.12.7.3.
2 222 4 4.
[2S(OA)] [2s(OB)] as a P: [7t x ' 7t y ] [7t nb(x,y)] (cf. FIg. 9.12.7.3)
Thus CO2 houses 8 bonding electrons (4 a-bonding + 4 7t-bonding) and each C-O link is
considered to be double bonded (I cr + 17t bonds): It is evident that up to valence electrons 16,
there is no requirement to utilise the higher energy MOs which are strongly antibonding. In
fact, the triatomic species having valence electrons 1.6 or less than 16 possesses the linear geometry
and their MO-energy diagram is similar to that given in Fig. 9.12.7.3. For example, the transient-
molecules NCO, NCN, CCN and C3 having the valence electrons 15, 14, 13 and 12 respectively
-are linear as expected.
Note: 0- and n-TASOs are

z not of the same energy.
For the sake of simplicity,
y this energy difference is
not shown here.
ry
ra
ib
yl
m CO2 : [2s( 0 A)]2[2s( 0 B)]2
C1: C1~z [1t x,y]4[7tnb(x ,y~4
he
...
lASOs
lc
- - - - -- - 2s
ADs (X) MOs AOs (VA' VB)
ea
Fig. 9.12.7.3. MO energy diagram~ of the linear molecule XY2"

th
(ii) MO picture of BeXz : Now let us try to explain the structure and bonding in BeXz (valence
electron = 16 for X = F, Cl). The distribution of electrons in terms of the MO energy diagram
e/
given in Fig. 9.12.7.3 is :

2 222 4 4·
[2s(X A )] [2s(X B )] a,v a pz [7t x ,7t y ] [7t nb (x,y)] (cf.Flg.9.12.7.3)
t.m
Thus it is expected that as in CO2, in each Be-X linkage there should be a sigma-bond and a
pi-bond (i.e. bond order = 2). But in reality, in BeX2 like BeF2, BeCI2, the 7t-bonding interaction
is very weak. The 7t-bond in c-o linkage is quite efficient as the energy difference between the
2p-orbitals of C and 0 is quite small, but in Be-X linkage, the energy difference between the
2p-orbitals of Be and 2p orbital of F or 3p orbitals of CI is quite large (cf. Fig. 9.10.1.1) to
make 7t-bonding interaction insignificant. Consequently, the group orbitals (i.e. T ASOs)
+X(x ±, y ±>' X = F, CI, etc. remain non bonding.
Thus though the diagram in Fig. 9.12.7.3 is generalised for the linear XY2 molecules, but for
some molecules there may be some specific interactions (as in BeF2 and BeCI2) (see Fig. 9.12.7.4).
In fact, the 7t-bonding orbitals in BeF2 or BeCl2 are majorly concentrated towards the X-nuclei.
Thus though the generalised MO-diagram (Fig. 9.12.7.3) indicates one 1t-bond in each Be-X
linkage, but in practice, it is insignificant.
z ~
Q)
y c
W
'x
ry
(z+), } a-type
ra
ib
yl
m
he
v
lc
TASOs
(2X)
ea
AOs iL 1L --------------- 1L iL
(Be)
MOs Two 3s
AOs (2X)
th
Fig. 9.12.7.4. MO-energy diagram of BeX2 (X = F, GI)

e/
'VI = as = CI 'V2S(88) + c2+X (z-) == CI 'V2SCB8) + c2 {'V p,(XA ) - 'V P,(Xs )}

t.m
'V2 = a: = c; 'V 25(88) - C;+X(Z-l = C; 'V2s(Be) -:-.C; {'V Pz(X A

) - 'VPz(Xs )}
'V4 = a p, = C3'V2Pz(88) - C4+X (Z+) =C3'V2P,(88) - C4 {'VPZ(X A

) + 'Vp,(Xs )}
'V3 = a~z =C;'V2Pz(88) + C~+X(Z+) =C;'V 2Pz (88) + C~ {'V Pz(X + 'V Pz(Xjl)} A)
(cf.· Fig. 9.12.7.1 for these combinations)
BF] vs. CO; XYz vs. BeFz' BeC/z : The bonding pattern in BF is different from its isoelectronic
species eo. The generalised MO diagram is not applicable (cf. Fig. 9.11.2.3c vs. Fig. 9.11.2.4)
for BF. The energy difference keeps the 1t-bonding orbitals as nO}lbonding ones. Because of the
same reason, the generalized MO-energy diagram cannot be utilised for BeC/2 and BeF2•
(iii) MO picture of XYz species having 16 valence electrons :Other species having 16 valence
electrons are N 20, N], es2 , oes, OCN-, NO;, etc. where the Pn-orbitals do not differ in energy
significantly and these can be explained in terms ofthe MO energy diagram given in Fig. 9.12.7.3
and all these species are linear as expected.
(iv) MO picture of the XY2 species having more than 16 valence electrons: If more than 16
valence electrons are to be accommodated in the MO energy diagram of the linear molecule XY2'
then some electrons must be placed in the strongly antibonding orbitals. This is an unfavourable
condition. In such cases, the molecule undergoes bending so that the excess electrons can be
housed in relatively stabler MOs having bonding character. A similar situation arises fo~ XH2
where the species is linear for the valence electrons up to 4, but the species uQdergoes bending if
ry
the number of valence electrons exceeds 4. This aspect has been already discussed in the earlier
sections. The MO-energy diagram for the bent species like N02 (17 valence electrons, bond
ra
angle 135°), N0i. (18 valence electrons, bond angle 115°), 03 (18 valence electrons, bond angle
117°) has been discussed separately in the next section (Sec. 9.12.9).
ib
9.12.8 Molecular Orbital Energy Diagram for some Representative Linear Molecules like
CO2 and BeX2 - Use of Hybridlsed Orbitals by the Central Atom
yl
By using the MO energy diagrams given in Figs. 9.12.7.3 and 9.12.7.4 which consider the 3-centred
m
delocalised MOs, the structure and bonding in the linear molecules like CO2 and BeX2 can be explained.
It has been already pointed out that in BeX2, the pi-bonding is quite inefficient and the appropriate
he
MO-energy diagram for BeX2 is given in Fig. 9.12.7.4. In this section, the MO energy diagrams will be
developed by using the hybrid orbitals of the central atom. The MO picture based on the localised
2c-MOs cannot explain UVPES. .
lc
A. CO2
ea
Now let us illustrate the structure and bonding of CO2 by considering the jp hybridisation ofthe central
atom C. If the molecular axis is the z-axis, then two sPz hybrid orbitals of C can combine with the 2pz
th
orbitals of the terminal oxygen atoms to produce 4 localised 2c-a-MOs as followed :

e/
CJ C - OB ='III.loc = cI'V'fPz(lXC) - c 2 'V2Pz(OB); (bonding)

•
t.m
= '112, loe =CI'V sPz(lXC) + C2'V2Pz(OB); (antibonding)

C1C - OB
(cf. Fig. 9.12.8.1a)
0c-oA = '113, loe =C3 'V sPz(2XC) + C4 'V2PZ(OA); (bonding)
•
CJ C - OA = 'II 4, loe = C3 'V'\'Pz(2XC) - C4 'V2PZ(OA); (antibonding)
The two sp= hybrid orbitals of carbon are denoted as sPz{l) and sPz(2). These are:
\V sPz(l) : \V2s(C) + \V2pz(C); \V sPz(2) : 'V2s(C) - \V2pz(C)
• •
~h:, bonding orbitals CJ c - o and CJ c - o
A B
are degenerate, and similarly the antibonding orbitals
CJ C - OAand CJ C - OB are also degenerate. These are the 2-centred localised MOs (cf. Fig. 9.12.8.la).
The combination, CJ C - OA ± CJ C - OB can. produce. two delocalised (3-centred) a-bonding MOs (Le.
\VI and '114); similarly, the combination, CJ C - OA ± CJ C - OB can generate two delocalised antibonding a-
MOs (Le. '112 and '113)' The delocalised CJ-bonding MOs have been discussed in Sec. 9.12.7 (cf. Figs.
9. 12.7. 1 and 3).
....
O'C_ OA
ry
2spz (1 )(C)
ra
(a)
ib
x
yl
* *
(O'C-OA'O'C-O ~3
S
\ Combination ~~r--I Deloca Ii sed
m
I~~------------<, 3-centred MOs
~----~z I * \ ',-
~x.y) '112
he
" \ ••
" , F=, 'v7tc-oA '7tc-0s
~ ~\
I ~ \ \
y ~ \ \
lc
~~ I \ \
, I \ \
The MO energy diagram based
2p ~~ I \ \ only on the localised ~c-MOs
2p ~\ - - -===( cannot explain the' results of
ea
" \\ \\
\ \ I \ \ UVPES.
\
\
\
,
~
~
I , \
,~
th
\ I , ~
,\ 2spz " ~~
~ ~==(
I
, 7 tnb(x,y)
\
, \' ~
e/
~ I ,
Q)
c: I ,,\ ==F'===- - - - - - - -~ } Six 2p
W I " ",,"/
I ' \ "" I
t.m
I ',\ "" "" /

I \ \ 7t(x) "" "" /
2s~ \ \~"""" ~7tC-OA,7tC-0s
\
,
.- ~
I
\\ . O'c-oA,O'c-Os
", (~~_~~~ET2~~']./'~I "

Deiocaiised
3-centred Mos
'--4r-
nb ~J
==fI:=- - - - - - - - -~ Two 28
AOs
(C)
Localised AOs
MOs (0 ,0 )
(C0 ) A B
2
(b)
Fig. 9.12.8.1. (a) Formation of localised a-MOs. (b) MO-energy diagram for CO2 by considering the
localised 2c-MOs (cf. Fig. 9.12.7.3)
The localised x-bonds can be expressed as follows :
•
7t C - OA =CS'V2P.r(C) - C6'V2P.r(OA)
•
7t C - OB =.C7 'V2 py (C) - CS'V2 py (OB)
ry
It makes 2py orbital of 0A and 2px orbital of 0B nonbonding, Le. :
ra
7t nb = \J!2py (OA) and \J!2P.r(OB)
ib
However, the 7t-bonding interactions can be better explained by considering the formation of
3-centred x-MOs. This aspect is discussed below~
yl
The three Py orbitals (perpendicular to the molecular axis) coming from C and terminal atoms 0A
and 0B can give 3C-7t MOs, 7t y ' 7t nb (y) and 7t~. Combination of \J!2py (C) , \J!2py (OA) and \J!2py (OB) generates
m
the above mentioned three 7t-MOs. This aspect has been already discussed in detail (cf. Fig. 9.12.7.2).
he
Similarly, '-V2P.r(C) , '-V2 P.r(OA) and'V2P.r(OB) can produce another set of 3c-7t-orbitals Le. 7t x ' 7t nb (x) , 7t•.
The MO-energy diagram for CO2, consider~g the use of spz-hybrid orbitals for forming the localised
lc
a-MOs is shown in Fig. 9.12.8.1.

Here, the 2s-orbitals of the terminal oxygen atoms are considered as the nonbonding ones. The
ea
electron distribution indicates that the 4a-bonding electrons and 47t-bonding electrons are responsible
for carbon-oxygen double bond character.
th
B. BeX2 (X =F, el)

e/
It has already been stated that because of energy difference between the p-orbitals of Be and X, the x-
t.m
bonding interaction is insignificant. If, the z-axis is considered as the molecular axis, the two sPz
orbitals of Be can participate in formation of localised a-MOs as follows (cf. Fig. 9.12.8.1) :
•
a Be-XB = c1'V spz(lXBe) - C2 'V2pz (X B ) , a Be-XB = c1'VsPz(lXBe) + c 2'V2pz (XB)
•
a Be-XA = C3'V sPz (2~Be) + C4 'V 2pz(XA)' a Be-XA = C3'V .'ipz(2XBe) - C4 'V 2pz(XA)
Generation of these localised 2-centred MOs have been illustrated in Fig. 9.12.8.1a for CO2• Thus,
without considering the 7t-bonding interaction, the approximate MO-energy diagram of BeX2 can be
shown as in Fig. 9.12.8.2.
>-cG
~-XA' x
'113--......, . aBe-X&,
3c-MOs ~ f - I;:::==:\
1 '112 f J,' \
,J------.z
Combination " "
\
II 1t nb (X,y) \ _
========~\\ - - -=- - , -t - - -= \\ y
ry
2p \ I \
\ '
\ '
\
\
\ I \ The MO-energy diagram based
ra
\~I \ only on the 2c-localised MOs
, 2 \ cannot explaJn the results of
sP z \\
ib
~ " " UVPES.
~
Q)
, \ \ ""-------------~
, \ \
c
W --..1.-----' \\ 1t nb (x,y) \
yl
2s \ ===d: \~~~~a~'~ Six np
(-9.3 eV)
\\
\
=FZ== m /
//
'3'
1 orbitals
(XA, XB )
\ /
\\ /// (-12.95 eV for el.
I " \ / -18.6 eV for F)
he
\114
3c-MOs
1\111
t f:~~~m..b~!t~~\(' ;U~~X~
lc
lUBe-><e.
ea
nb
:::F!=- - - - - - - - ~ Two ns orbitals
th
(XA, XB )
AOs (Be) Localised AOs (XA, XB )

e/
MOs (BeX2 )
Fig. 9.12.8.2. Approximate MO..energy diagram of BeX2 (X = F, C/) involving the localised 2-centred
t.m
MOs.
Note: As in CO2, aBe- X ± aBe- x. produce two 3c-a BMOs(Le. \111 and \114); a~_ X ± a~._ x. produce
A A
two 3c-a* ABMOs (Le. \112 and \113); Then Fig. 9.12.8.2 becomes identical with Fig. 9.12.7.4.
9.12.9 Molecular Orbital Picture of the Bent Molecule XY2 (X and Y Second Period Elements)
It has been already mentioned that for the XY2 type molecule, if the number 0/ valence electron is
more than 16, then it bends so that the strongly antibonding orbitals can be avoided to accommodate
the valence electrons. Such molecular species are: NO z' OJ' C/zO, SOz' NOi, etc. Both X and Y can
provide the 2s and 2p orbitals for the bonding purposes. The terminal Y-atoms (YA and YB ) are more
electronegative than the central atom X. Thus it is reasonable to consider that the energy diffe'rence
between the 2s and 2p-orbitals of Y is significantly large and consequently the 2s orbitals of the
terminal atoms (YA and YB ) remain as nonbonding ones. However, this approximation is not always
justified.
Let us consider that the molecule remains inyz-plane. Then/or a-type interaction, the central atom
can provide 2s, 2py and 2pz orbitals. If the (+) z-axis for each terminal Y-atom is considered to be
directed towards the central atom, then the 2pz-orbitals of YA and YB are also available for a-MO
generation. The· LeAO of these five orbitals Le. 2s(X), 2py(X), 2pz(X), 2pz(YA ) and 2pz(YB)' will
generate 3c 5a-MOs.
Without going into the mathematical detail, we shall try to understand the formation of the 5a-MOs
by using our previous experience (cf: bentXH2 molecule, Sec. 9.12.4). Ifwe start from the linear XY2
molecule (y-axis as the molecular axis), then bending on the yz-plane will introduce the changes illustrated
ry
in Fig. 9.12.9.1.
ra
ib
yl
m
. YB
he
I (a)
I
I
I
X
lc
I
I
I (Bending) +Y + - ~
I I I
---~) VA VB
ea
I
VA X Va
(Linear arrangement)
+
+z
th
e/
t.m
,/(
2py (VA)
(iii) (iv)
"(b)
Fig. 9.12.9.1. (a) The molecule XY2 lies in the yz-plane. Positions of different orbitals on the central
atom X and terminal atoms YA and Ys. (b) Changes of interaction among the atomic orbitals on bending
the linear molecule YA-X-Yso (i) a-type interaction of 2s(X) orbital with the 2pz orbitals of the terminal
atoms; (ii) a-type interaction of 2pj.X) orbitat with 2pz orbitals of YA and Y& (iii) a-type interaction of
2Pr'-X) with .2pz orbitals of YA and Ys; (iv) 2py orbitals on the terminal a~oms remain nonbonding
as these can participate neither in a-type nor n-type interaction with the atomic orbitals of the central
atom.
Bending will allow the 2pz-orbital of the central atom to participate in bonding interaction with the
2p=-orbitals ofthe terminal atoms YA and YB• Here, it is assumed that the z-axis of the terminal atoms are
projected towards the central atom.
To understand the formation of 3c-5cr-MOs, let us first consider the formation of group orbital Le.
TASOs from the 2pz orbitals of YA and YB (Fig. 9.12.9.2). The group orbitals are:
{2pz{YA ) + 2p z {YB )} (Le. +Y(z+) or Y(z+»)
and {2pz{YA ) + 2pz {YB )} (Le·+y(z_) or Y(z-»)
ry
AOs of X
matching
ra
with the
TASOs TASOs
ib
(s + s)} s,P z
i.e. +v(s+)
yl .
(S-S)}
A. .py
m I.e. "y(s-)
he
lc
ea
th
z
e/
x
y (Py-Py)} -
t.m
i.e. +v(y-)
'Y(S±> remain as nonbonding ones due to

energy mismatch. 'Y<m and 'y(x-) remain as
nonbonding ones due to symmetry mismatch. TASOs
(i.e. Group Orbitals
Fig. 9.12.9.2. Formation of group orbitals (i.e. TASOs) by using the ADs of the terminal atoms YA and
YB in the bent molecule XY2 .
The group orbital {2pz(YA ) + 2p z (YB )} Le. +Y(z+) can combine with the 2s and 2pz orbitals of the
central atom to give the three following a-MOs (mixing coefficients not shown).
'VI : 2s(X) + 2p z (X) + {2P z (YA) + 2p z (YB )}; (a-bonding)
'V2 : 2s(X) + 2pz (X) - {2pz(YA) + 2p z (YB)}; (a-antibonding)
'V3 : 2s(X) - 2p z (X) - {2P z (YA) + 2p z (YB)}; (a-nonbonding)
To visualize the above combinations, it is better to consider two sPz hybrid orbitals of the central
atom X. These hybrid orbitals are projected at 180°. Here, it must be mentioned that consideration of
ry
these sp-hybrid orbitals is not essentially required. The same results will be obtained by considering the
LCAO of the involved pure atomic orbitals. Formation of these 3 a-MOs is shown in Fig. 9.12.9.3a.
ra
The group orbital {2Pz(YA) - 2pz(YB)} Le. +Y(z-) can combine with the 2py orbital of the central atom
X to produce the following a-MOs (mixing coefficients not shown).
ib
'V4 :2py(X) + {2PZ(YA) - 2pz(YB)} (a-bonding)
yl
'Vs : 2py(X) - {2P z (YA) - 2p z (YB)} (a-antibonding)
Formation of these two a-MOs is shown in Fig. 9.12.9.3b.
m
(Note: In the bent molecule, the cylindrical symmetry is lost. Thus the notation of a, a·, a nb is not
strictly applicable. For the sake of simplicity, here the a-notation is retained).
he
The 2px orbitals on all the three atoms lie perpendicular to the molecular plane. These will combine
. as in linear Y-X-Y(cf. Fig. 9.12.7.2) to produce a set ofthree 7t-MOs (7t x ' 7t: and 7t nh ). The combinations
lc
are:
7t x : 2px(YA) + 2px(X) + 2px (YB )
ea
7t •x : 2px(YA) - 2p x(X) + 2px (YB)

(cf. Figs. 9.12.7.2 and 9.12.9.4)
7t nh(x) : 2px(YA) + 2px(X) - 2Px(YB) (mixing coefficients not shown)
th
or 1t nh (x): 2p x (YA) - 2px (X) - 2p x (YB)

e/
Formation of these 1t-MOs can also be understood in terms of group orbitals formed by the 2px
orbitals of the terminal atoms YA and YB. This aspect has been discussed in explaining the linear XY2
t.m
species.
These are (mixing coefficients not shown) :
1t x :2px(X)+ {+r(x+)}
1t: :2px(X) - {+r(x+)}
7t nh(x) : +r(x-)
Formation of these 7t-MOs is shown in Fig. 9.12.9.4.

The 2py-orbitals on each of the terminal atoms remain as nonbonding ones.
The MO energy diagram is shown in Figs. 9.12.9.5 to 9.12.5.7.
Fig. 9.12.9.7 describes the MO-energy diagram by considering the sp2 hybridisation of the central
at~m. These three sp2-hybrid orbitals (s + Pz + p y) combine withpz-orbitals ofterminal atoms to produce
5 a-MOs.
IZ IZ IZ
I I I
I I I
I I I
y y
ry
I
I
I
(- '111) (= '112) (= '113)
ra
a-Bonding a-Antibonding o-Nonbonding
(i.e. crb(1» (i.e. 0; ) (i.e. 0nb)
ib
(a)
yl
Z
m
he
lc
ea
(= '114) (= \115)
a-Bonding cr-Antibonding
(crb(2» (cri)
th
(b)
e/
Fig. 9.12.9.3. Formation of 5 sigma MO-s in the yz-plane of the bent molecule XY2' (a) a-type interaction
of the 2s(X), 2p~X) orbitals of X with the group orbital (Le. TASO) cPY(z+) Le. {2pz(YA ) + 2p~ Y~};
t.m
(b) a-type interaction of the 2p~X) orbital of X with the group orbital (Le. TASO), cPy(Z-) Le.
{2Pz(YA) - 2p~ YS>}.
• MO picture of NO z : Now let us consider the electron distribution in the linear molecule NO z
with 17 valence electrons. This is as follows :
2 22 2 2 42 1 •
[2s(OA)] [2s(OB)] ab(l) a b(2) 1t b(x) [Py(OA) Py(OB)] 1t nb (x) a nb (cf. FIg. 9.12.9.6)
Here, there are 4 bonding electrons in two a-MOs and 2 bonding electrons in one 1t-MO; and no
electron is placed in the antibonding electron. These a-bonding electrons lead to 1a-bond and ~ 1t
bond in each N-o linkage (Le. bond in each linkage = 1.5). In NO (cf. Fig. 9.11.2.1), the bond order is
2.5 (Ia + 1.51t) and this is why N-O bond length in NO (= 113 pm) is shorter than that in N02 (120 pm).
Here it is interesting to note that in NO, the odd electron remains in a delocalised 1t*-MO while in
NO z the odd electron resides in a nonbonding (J-MO which is almost localised on the central atom
(N). This is why, N02 can dimeriseeasily but NO is reluctant to dimerise.
ry
)
ra
ib
7t nb(x)
yl
m
he
n-MOs
lc
ea
th
e/
2px (YA ) 2px (X) 2px (Ya) 2px (YA ) -2px (Va)
t.m
(TASO,4>y(x_)
Fig. 9.12.9.4. Formation of 1t-MOs by using the 2px orbitals of X and terminal atoms YA and Ya-
.
Dimerisation of NO and NOl (cf. Sec. 9.20; Fig. 9.11 :2.1 vs. Fig. 9.12.9.6)
• MO picture of some 18 valence electron XYl species: The species like NO-;', OJ' SOl etc.
having 18 valence electrons can also be explained by considering the same diagram. Here, the 18th
electron is placed in CJn/) and it becomes filled. The 7t-BMO (3-centred) bearing an electron pair delocalises
over the whole molecule. But the other electron pair residing in the nonbonding 7t-MO (Le. 7tnb ) is
effectively localised on the tenninal oxygen atoms. This 7t-bonding system is very often referred to as
3c-4e x-bond; and it is applicable for the species following this diagram.
• MO picture of some XYl species having valence electrons more than 18 : Now let us consider
the species NFl and OXl (X= el, F) having valence electrons 19 and 20 respectively. In such cases,
CJ1
,'---""'"'\,'V2
I. \ Z
1'1 , I
~
---/t\-----y
II cr* I
II , ' , 2 " 'V5 I
I I~ ~ , ,
I I' n* "
1~'1 ~ x \"
~'
~ I
I.,"
~ ,," I~
~,.,
I
I"
" ". ~
,
\
\
,
, ,
, , ,
,
\
,
-~2-py--""\~ ., -r " \\',"
ry
----""",'{ I I , , \
2px >(' I "\
-~2-Pz--~\~".. f \~~,
"X ....
ra
\.. I ............ '"
"_.;_CJ_n_b__, 1j13 \~\\
}. \\ .,.,., "
" ,
ib
~ .,.,
" " ~(., x (nb) __ ~~ _ _ _ _ _ __ - - - - - - - ' "
1t
I .".,( , \ Py(nb)', \\ (Px - P x )
yl
~2-s---....t" "',', p -----~---~~-- (p +p)
\
,\ ,\
,\ '' ,, y(nb)
------,---'''\,-
\
,
'\ \
,, ,
m Y Y
(p y - p y )
\
,
\ \
\ \
\ '' \\\
'Y--(~-+-~)
\ '\, ',< ~ , Px Px
.," ,\(~----
he
\ \ \ \
(Pz - Pz)
,
\
\
\
\
\
\
\
., .,.,
, .,
/
)c
",,..----
","", '
\ \ \ \ /
\ \ \ , ,," / / (P z + Pz)
lc
\ \ \ 1tb(x)
...... / /
//'/ ///
\ / /
ea
\
\\ \
\
\\
\
,\ '114 //
/
//
//
/
//
\ \ \ ~ /
\\ CJ /
th
\\ b(2) / /
~ /
, / 'V1
e/
CJb(1)
t.m
(nb)
(s- s) ------------- (s - S) .....
" " .....
., ,,> 2AOs
}2s
(nb) ,
(5 + S) ----------- (S + S) (YA , Ya)
AOs (X) MOs TASOs

Fig. 9.12.9.5. MO energy diagram of the bent molecule XY2.
the 19th and 20th electrons will have to occupy the 1t*-MO (cf. Fig. 9.12.9.6). In the case ofOF2, there
will be 3 pairs of bonding electrons 6 pairs of nonbonding electrons and one anti-bonding pair of
electrons. The net effect leads to 4 bonding electrons pver the three nuclei. It leads to bond order unity
in each D-F linkage. The o-F bond energy (189 kJ mo.-I) is quite small. In VBT, this small bond
energy is explained in terms of repulsion among the nonbonding electrons. In terms of MOT, this bond
weakening phenomenon arises from the antibonding electron in 7t *.
ry
ra
ib
yl
m
he
lc
ea
th
0'b(1)
e/
(nb)
===============
S(YA ), s(YB ) Two 2s
t.m
AO-s MO-s AO-s

(X) (XY2 ) (YA , VB)
Fig. 9.12.9.6. Simplified representation of MO-energy diagram of the bent molecule XY2 like N02
obtained from Fig. 9.12.9.6 without showing the TASOs.
O'b(l)' O'nb' 0'1}

* LCAO of 2s( X), 2pz( X), 2py ( X), 2pz(YA ) and 2pz (YB )
0'b(2)' 0'2
7tb • 7too • 7t*} LeAO of 2pAX). 2pAYA ) and 2px eYe)
• MO picture of the XY2 species having 22 valence electrons: Now let us consider the species
like /3' KrF1 , XeF1 (which will be discussed separately in Sec. 9.12.11) having 22 valence electrons.
If such species are supposed to have the bent structure, the last two electrons will be bound to occupy
the antibonding orbitals (0;) and this is highly unfavourable. This is why, such species do not adopt
0*
, \ ,z
,
I
I
1t(x)
\
\
\
1
I
1
I , \ \ I
,
I' , \
--7T\-
_x
I I \
\
\
\
1- - - - - _.
1
I
Y
II , \
1
======~,
2p (X) ,
---- P x (X)
\II "
\\ ,
I
,
\ \
\ \
\
YA
1
1
1 YB
"
ry
, \)
~\
,\
\\
,
, 1\\
\
\
\\
; ~~ \ \\ The MO-energy diagram based
ra
II sp2 \ \ .... \ ... C1 nb , \' only on the localised 2c-MOs
I (s + Py + Pz) \ \ \ 1tnb(x) '" \\ cannot explain the results of
" ,,\ \ c:-,', \\
ib
UVPES.
--_...I,,' \ \ ' ..........'~~,\~ 1...------------.. .
yl
2p(X) \" (nb) :" ====
\ \ ~I
\ ,py(YA , VB) ~~, 2p(YA )
,
\
\
\
\
m ~~
~
I and
" '. Itb(x) , . / ,/ 2p (Ya)
he
\ I
\ I
\
\
\ I
, I
lc
, I
ea
--- -------- ----

th
L---y--J L---y--J or
ADs - Hybrid MOs
e/
(X) AOs (X) (YA , VB)

Fig. 9.12.9.7. MO-energy diagram of the bent molecule XY2 (e.g. CI2 0, 03' N02-, OF2 etc.) after
t.m
considering the hybridisation of the central atom (X).

Note: For 03' the terminal atoms and the central atom are the same. Consequently, the diagram will be
slightly modified.
the bent structure. If, such species adopt the linear structure (cf. MO energy diagram for linear XY2'
Fig. 9.12.7.3), then 3 pairs of electrons are also to be placed in antibonding orbitals (two'1t· and one cr·),
but probably this effect is not so destabilising compared to the case of bent geometry. In the linear
structure, the 22-valence electrons are distributed as :
4 bonding pairs + 4 nonbonding pairs + 3 antibonding pairs (cf. Fig. 9.12.7.3).
This leads to only 2 bonding electrons over the 3 nuclei, Le. bond order = ~. In XeF2, this is
reflected in bond strength (= 130 kJ mol-I) and bond length (= 200 pm). It may be compared with IF
(having 2c-2e bond) : bond length = 191 pm, bond energy = 278 kJ mol-I. Thus the MO energy
diagram/or 1), XeF1 , KrF1 is similar to that o/COz. The difference is that, 1t-bonding is possible for
CO2, but it is not possiblefor the species with 22 valence electrons, because the p-orbitals (perpendicular
to the molecular axis) to form the 1t-MOs are filled in. In other words, both the 1t-BMOs and 1t-ABMOs
are completely filled in to cancel their effect mutually.
9.12.10 Molecular Orbital Energy Diagram for the Trigonal Planar Molecular Species XY3
(e.g. SF3 , 503 , NO~ , COi-)
Without any mathematical treatment, we shall try to understand the fonnation of a-MOs and then the
7t-MOs. The a-MOs lie in the molecular plane (say xy-plane) while the 7t-MOs will lie above and below
the molecular plane.
ry
The tenninal atoms YA , YB, and Yc are more electronegative than the central atom X. Thus it is quite
reasonable to assume that the 2s orbitals of the tenninal atoms are of low energy· and they remain as
ra
nonbonding ones.
Let us first consider theformation of a-MOs. If the molecule is supposed to lie in the xy-plane, then
ib
the central atom (X) can provide 2s, 2px and 2py orbitals for a-bonding. For the a-bonding interaction,
each terminal atom can provide one p-orbital (say px-orbital, assuming the x-axis of each terminal
yl
atom is directed to the central atom). These six atomic orbitals, 2s(X), 2px(X)' 2py(X), 2px(YA )' 2px(YB )'
2px(Yc ) will combine to generate six 4c-a-MOs (3 bonding MOs + 3 antibonding MOs). The
combinations are :
m
Os -0: pair: Combination of 2s orbital of the central atom (X) and 2px-orbitals of the terminal
he
atoms (YA , YB and Yc) (cf. Fig. 9.12.10.1 a).
..
° °
Py - Py pair: Combination of 2py orbital of the central atom and 2px-orbitals of the tenninal
lc
atoms (cf. Fig. 9.12.10.1 b).

(J P -(J~x pair: Combination of2px orbital of the central atom and 2p orbitals ofthe terminal atoms
x x
ea
(cf.9.12.10.1b).
If the molecule remains in xy-plane and the px-orbitals of the terminal atoms are directed towards
th
the central atom, then the Py-orbitals ofthe terminal atoms remain directed perpendicular to the respective
X-Y bonds in the molecular plane (i.e. xy plane). Definitely, these 2py orbitals of the terminal
Y-atoms remain as nonbonding ones.
e/
Now let us consider the formation of x-molecular orbitals in XY3 • Each of these four atoms is
t.m
associated with a 2p=-orbital (perpendicular to the molecular xy-plane). These four pz-orbitals will
undergo LCAO to generate 41t-MOs (2 nonbonding + 1 bonding + 1 antibonding). The bonding 1t-MO
(of lowest energy) is of the following fonn (mixing coefficients not shown) :
'V 7t h : 'V 2 Pz (X) + 'V 2 Pz (YA ) + \V 2 Pz (YB ) + \V 2 Pz (Yc )
The antibonding 1t-orbital (7t.) can be obtained as follows (mixing coefficients not shown) :
\V 7t. : 'V2pz(X}- 'V2pz(YA } - \V2Pz (YB } - 'V2p z (Yc }
Generation of these bonding and antibonding 1t-MOs is shown in Fig. 9.12.10.1 c. The other two 1t-
MOs are nonbonding (i.e. 1tnb ).
The MO energy diagram (considering the 4-centred delocalised MOs i.e. 4c-MOs) of XY3 is shown
in Fig. 9.12.10.2 which accounts for all 16 atomic orbitals of XY).
For the trigonal planar species like BFJ, NO; , coi-, S03' etc. with 24 valence electrofJs, the electron
distribution pattern can be given as follows:
62222 6 4 •
[2s(YA )2s(YB)2s(Yc )] CJ s CJ px CJ py 1t pz [2p y (YA ) 2Py (YB) 2py (Yc )] [1t nb (pz)] (cf. FIg. 9.12.10.2)
y
y
I
X
/ \
y y
-----~x
(Coordinate axes
for the central atom X)
ry
ra
ib
yl
(a)
m
.
he
yi
--- -----. y
x
lc
ea
th
CJ
px
(b)
e/
Y"
t.m
X- y
y
/
x
7t z
n*z
(c)
Fig. 9.12.10.1. Formation of different MOs in the planar molecule XY~ (a) Formation of as - a: pair;
(b) Formation of a p• - a~. and a py - a~y pairs; for a'·orbitals, the sign of the lobes of the p-orbital of
the central atom is to be reversed; (c) Formation of 7t pz - 7t~z pair.
cr~ (X, y)
I
, \
II cr* \ y
I _-----s::o....-~\ \
I I \ \
I I n*(pz} \ \
x
I I \ \
I '''' , \ \
I ,," , \ \
I ~ , ,
'\'",\
,,", I \
I ' \'
,~"
I"
I ' \ \ ~-----+x
~==3r
= f...... I , \'
ry
.
2p (Y) \
,
..... ".....
I..... ..... nnb(pz} ",
t I ~ ,\\
~I " ~
ra
) " ~
I
~,\ '" '~)===
I " ~
ib
I \\ 2py (YAt Yat Ye ) II~ 2p (YA) 2p (Ya) 2p (Ye )
I , \ III
_ _ _.-.I' \\ I
2s ( X ) ' \ 1,' 1 2p orbitals of YAt Ya and Ye
yl
"\ \\
' \ I
/1,'
I I
\ \ \ I I I
,
\
'\
\,
1tb(pz}
m
,I "
I
I I
I
,\ I I
\ \ I I BF 3: [2s(FAt Fat F c )6 [0'.J2 [O'px. pt
he
,, \, cr p(x, y) I I
I
\ I [1t pz ]2 [2p~FAt FBt Fe )]6 [1tnb(pz~4
\ I
, I
lc
, I
" crs I
ea
====-------
2s Y )
(YA , YB ,
-"""""=-- - - - ---~-
~e ~s (YA ), 2s.za) and 2s (~)

th
~
ADs MDs ADs
(X) (XY3 ) (YA , Y& Yc )
e/
Fig. 9.12.10.2. MO-energy diagram of the planar molecule XY3.

t.m
It is evident that to acconimodate these 24 valence electrons, the highest antibonding orbitals are
not required. Out ofthese 24 valence electrons, there are 4 bonding pairs (i.e. 30' + In) and 8 nonbonding
pairs. It indicates that in each X-Y linkage, the bond order is l~ ( =1(J+~1t). All these MOs are delocalised
(4-centred) over the whole molecule.
Sometimes, the said XY3 planar species can be treated by considering the Sp2 hybridisation
(s + Px + Py' assuming the molecular plane to be xy-plane) of the central atom. These three sp2 hybrid
orbitals can be considered to combine with the 2px-orbitals of the tenninal atoms (assuming the x-axis
of each tenninal atom to be directed towards-the central atom). These will produce 6 localised (J-MOs
(2-centred i.e. 2c-MOs).
2 2 2
sp (1)(X)±px(YA)'sp (2X X )±px(YB )'sp (3XX)±px(Yc )
These combinations will produce three localised a-Mas which are degenerate, and three degenerate
localised cr·-MOs.
aX-YA' a X - YB • a X - Yc (bonding, 2-centred localised MOs, degenerate)

• • •
a x -YA ' a x -YB ' a x -Yc (antibonding, 2-centred localised MOs, degenerate)
Combination among the three localised a-MOs can lead to three delocalised 4c-a-MOs. Similarly,
~combination among the localised 0'. -MOs can also generate three delocalised 4c-0'·-MOs.
The 2py orbital on each terminal atom remains perpendicular to the respective X-Y bond in the
molecular plane (Le. xy plane). Such three 2py orbitals remain as nonbonding_ ones.
The p~-orbitals of the four atoms are perpendicular to the molecular plane and these can combine to
produce 47t-MOs. (1 bonding + 1 antibonding + 2 nonbonding) as discussed earlier. Thus 7t-MOs are
ry
considered delocalised over the whole molecule.
The MO-diagram considering the formation of the localised 2 centred a-MOs (3 bonding + 3 anti-
ra
bonding) by using the sp2-hybrid orbitals of the central atom (X) and Px orbital of the t~rminal atoms is
shown in Fig. 9.12.10.3. Both the diagrams Le. Figs. 9.12.10.2 and 9.12.10.3 lead to the same conclusion.
ib
," a*
yl
I "\
The MO-energy diagram based \
only on the localised 2c-MOs I \ y
I \
cannot explain the results of
UVPES.
I •
I I
m Tt(pz)
\
\
\
\
I , \ \
I' \ \
he
I "
I' \
\ \
\ \
\
====~,,
= ~~
I! \\\\
lc
2p (X) , 2p z (X) ", \\

\ 1\ " '------~x
\ I , , \ \
\
,\ I , \ \
ea
\ \\
I' Ttnb (Pz) \\ \\
, sp2 (X)
\ "
"
~
\
, \\
\\
th
" \ , "
" (s + Px + Py )" ' \\~
,, ,\ '''2p -----~,=======
e/
, \
y (YA' YB' YC) Ii "- - ~------_.----J
----I " " I~' 2p (YA ), 2p (YB ) and 2p (Yc )

t.m
28 (X) \ ' II I
\ ' , I
\ ' , I
\\ ',\,.. ..." I II
\ Ttb(Pz} I
\, I '
\
,, "'
=======-----------
)
2s (YA , VB' Yc
" '- - ~---------'J
~(YA)' 2s (YB ) and 2s (~)

'---v---J '---v---J .......,.
Hybrid MOs (XY3 ) AOs (YA , YB , Yc )
AOs (X) AOs (X)
Fig. 9.12.10.3. MO-energy diagram of'the planar species XY3 like BF3,S03, coj-, NOi,etc. after
consideration of the hybridisation of the AOs of the central atom (X).
MO energy level diagram for planar XHJ

(e.g. BHJ ) : In XH3 , the terminal H-atoms
/
/
,,
provide only Is-orbital while the central atom //
/
,
(X) provides both ns and np orbitals for bonding. ~ // n~b "
Thus the problem is simplified and there is the ~ ~--_. __ .------- \
no 7t-bonding. The 2P:x, 2py and 2s orbitals of X Lfi np"

, "
,
(central atom) and Is orbitals of three terminal \ ," , .
as
......
..... ~
' \
atoms combine to produce 6 a-MOs Le. \, /'------

• ax' cry, cr• •
ry
'\ //," 31s
as' as, x and cry. The a-MOs can be " \ / ,
constructed as done for XY3 (cf. Fig. 9.12.10.1). ,', , \
/
/
'
'
" "===== / ,"
ra
The MO-energy level diagram is shown in Fig. ~ Ox,Oy"
9.12.10.4. ,
,,
ib
------,
9.12.11 Molecular Orbital Energy
X MOs of XH~ AOs of 3H
yl
Diagram of Some Representative AOs·of
Polyatomlc Species
Fig. 9.12.10.4. Molecular orbital energy diagram
B 2H 6 : Each B is sp3 hybridised and each B-
m for the planar XH3 species like BH3 .
centre is linked with two terminal hydrogens (Note: • Compare this Fig. with Fig. 9.12.10.3 for
he
(Ht ) through 2c-2e bonds. There are two planar XY31ike BF3 and Fig. 9.12.11.6 for pyramidal
bridging hydrogens (Hb ). Each bridging XH3 Hke NH3 .)
hydrogen makes a bridging bond (3c-2e). The • The MO diagram of a planar XH3 species (e.g.
lc
delocalised MOs for the bridging bonds and the BH3 ) can be constructed by considering three
TASOs constituted by 1s orbitals of three H-atoms
ea
complete MO-diagram are shown in Sec. 9.21.

(cf. Fig. 9.12.11.7).
The complete MO-diagram shows that the a-
MOs (4 bonding + 4 antibonding) are localised (Le. 2 centred to explain the 4 B-Ht linkages). The
th
three centred MOs (i.e. delocalised) are considered to explain the two B-Hb-B bridging interactions
in terms of 3c-2e bonding. ·Such three centred MOs are: 2 bonding + 2 nonbonding + 2 anti bonding.
e/
Fig. 9.21.3 describes the complete MO energy diagram of B2H6 •

t.m
I; and lei; : They possess 22 valence electrons. It has been already mentioned that their linear
structures can be explained by considering the general MO energy diagram (Fig. 9.12.7.3) of linear XY2
molecule (e.g. CO2). In VBT, to explain their structures, participation of d-orbitals is required. It is
believed that the central atom is sp 3d hybridised and the lone pairs are placed in the three equatorial
places to give the linear structure (see VSEPR). However, formation of I; (and the related species like
lei; with 22 valence electrons) can be explained by considering the 3c-4e bonds without the
involvement of s- and d-orbital. In these species, all the 7t-MOs are filled in (cf. Fig. 9.12.7.3) and
7t-bonding has no effect. Only a-bonding stabilises the species.
In the case of I; ,combination of5px orbitals oftwo terminal I-atoms and the central I-atom (assuming
the x-axis as the molecular axis) generates three 3-centred delocalised a-Mas (cr, a nb and a·). The four
electrons are placed in the lowest two MOs (Le. 0' and a nb ). Thus, it leads to 3c-4e bonding system
(Figs. 9.12.11.1-2). The net bond order is 1/2 in each I-I linkage (i __e... 2 bonding electrons are delocalised
over the three centres). This 1/2 bond order is consistent with the experimental observation (stretching
frequency, v = 215 cm- I for 12 ; v = 113 and 135 cm- 1 for I;). The same thing appears for ICIi. (3c-
4e bond, and bond order = 1/2) and the stretching frequencies are: v = 384 cm- I for ICI; v = 267 cm-
1 and 222 cm- I for leli..
The participation of d-orbital in VBT is objected. But in the MOT, the 3c-4e bonding system
does not require the participation ofany d-orbital. This is an added advantage of MOT compared to
VBT.
XeFz' XeF4 , XeF6 : Without any involvement of d-orbital of Xe, by considering the general
MO-energy diagram of linear molecule XY2' the bonding and structu~e of XeF2 and KrF2 (with 22
ry
valency electrons) can be explained (cf. Sec. 9.12.9 and Fig. 9.12.7.3). This aspect has been already
discussed. By considering the p-orbitals only through the 3c-4e bonding system (as in /; discussed
ra
above), the bonding in x~non compounds has been discussed in Sec. 9.23. Fonnation of the linear
segment F-Xe-F can be explained by considering the formation of TASOs or LCAO of the involved
ib
AOs.
Note: Bending of the 22 valence electron species (XY2) will place the cr~b pair into a cr·-MO (cf.
yl
Sec. 9.12.9. and Fig. 9.1~.9.6). Thus the angular structure of such species is not favoured. m
No requirement of s- and d-orbitals of the central atom
~x 80-08+08
~ la Ie
he
\
I
I
I 0* \
, z
\
lc
I \ [IA - Is - lc]- (ab)

I \
I \
I \ ...
ea
I \
I \
( ---*1~~--- - - - ~)===
5Px (I) \, °nb ,' 5p x (I)
th
(Central I-atom) \\
\
\ ,,
I
I' (Terminal I-atoms)
00-08-00
«(Jnb)
e/
\
\ I
\
, 1b
I
I
00+08+00
t.m
(0'*)
Fig. 9.12.11.1. Simple MO-energy diagram of I; without the involvement of s- and d-orbitals. Formation
of 3-centred MOs is shown at the right hand side.
Note : • Formation of the 3-centred MOs can also be understood through the formation of group
orbitals (Le. TASOs) from the 5px orbitals of the terminal atoms. These are illustrated in Figs. 9.12.1.1 ,
9.12.7.1 and 9.12.7.3. In terms of TASO, G nb is nothing but a group orbital developed by the '-'
combination of the 5px orbitals of the terminal I-atoms. It is evident that though 0b and 0* are the
3-centred MOs, 0nb is basically a 2-centred MO.
• °nb: 'Vnpx(lA) ± \Vnp.(/c ) - 'Vnpx(ls) == \Vnpx(lA) - \VnPx(/c )· Thus CJ is weakly bonding between the terminal
nb
atoms. If the molecule is bent, O~b electron pair will be placed into a o*-MO and it will destabilise the
system (cf. Sec. 9.12.9 and Fig. 9.12.9.6).
• Complete MO picture of I; (22 valence electrons) can be explained in terms of the general MO
energy diagram given in Fig. 9.12.7.3 without the participation of d-orbitals.
cr·
I \
I ,
I \
I ,
I ,
I ,
I ,
I \
z
I , [CI-I-CI]-
e> -5-p~x(-I)----(~ ... ...
>-
"
Q)
c
W
\
\, " '_....;~~L__
'\ No requirement of s- and d-orbitals
of the central atom
iP ", \
ry
, Cfnb ",\
\, ,...-==:r=-
" " 3px (2CI)
ra
\ I
\ I
\ I
ib
\ I
"U "
yl
crb
Fig. 9.12.11.2. Simple MO-energy diagram of leI; without the involvement of s- and d-orbitals.
Note: leI; with 22 valence electrons can be explained in terms of the general MO energy diagram
m
of Fig. 9.12.7.3.
he
CfC. -H '
{ ~_~,ac_~'
B
-H . '
A
cr~. '"'=====
...-.::::
* '*
0p ' CJpy' CJpz
x
*
",
,§~~~\-C-o~bi~ati;n -<..
lc
1 \ ,
I \ '
ea
I \ ''''---- cr*
~==='~
= 1 " I
I \
\
S
2p ( C ) ' , I \
th
, I \
, I \
>- :~' "

e/
e> // (sp3) \ ,.SIi!I~§§

Q) / \ I
c:
W // ~ \ 11s(HA ,HB ,
t.m
- . . .1rt11L_ . . J / Hybrid \ " He' HD)

, AOs (C) \ I
2s(C) \ I ~
\ I AOs
\
\ " (4 H-atoms)
\ I 11
\ I , ,=al'=S::!!:::: a px ' apy' a pz
\\ II "
I'
1: ~;
Combination ' ,
I aC-HA,aC-Ha
aC-Hc,crC-Ho
~
'"
MOs Delocalised. MOs

(CH 4 )
Fig. 9.12.11.3. Simple MO-energy diagram for CH 4 after consideration of sp3-hybridisation of the central
atom. Note : This simple diagram involving the localised 2-centred MOs cannot explain the
UVPES. However, combination of the localised MOs can generate the 5-centred delocalised MOs as
given in Fig. 9.12.11.4b.
CH4 : The central atom carbon is sp3 hybridised. These four sp3 hybrid orbitals can combine with
four Is orbitals of terminal H-atoms to generate 4 localised (Le. 2 centred) a-MOs and 4 localised
a·-MOs.
sp3(IXC) ± Is(HA ), sp3(2)(C) ± Is(HB ), sp3(3XC) ± Is(Hc ); sp3(4XC) ± Is(HD )
The eight valence electrons are placed in the 4 localised 2-centred bonding a-MOs which are
degenerate..The MO-energy diagram is shown in Fig. 9.12.11.3. This simplified MO energy diagram
fails to explain the UV-photoelectron spectrum.
ry
Without considering the hybridisation of the central atom (Le. carbon), formation of the 5-centre~
MOs in CH4 can also be understood. T~e available orbitals are: .
ra
2s, 2px' 2py and 2pz orbitals of C; four Is orbitals of 4 hydrogens (say H A , H B, H c' H D) which are
described as terminal atoms.
ib
The hydrogen atoms can produce/our group orbitals (i.e. TASOs) which combine with the orbitals
of the central atom. Without going into the details of symmetry interaction, formations of the 5-centred
yl
bonding MOs, a,\, and a Px are illustrated in Fig. 9.12.11.4a. Other 5c-MOs can be constructed in the
same way. The 5-centred MOs are: m
0" s and 0":; three 0" p (i .e. 0" P. ' 0" Py and 0" pz ) and three 0": (i .e. 0":. ' O":y and O":z )
a:
he
The 5-centred 0' s and MOs are obtained in the interaction between the symmetric 2s orbital of C
and the symmetric H-group orbital. Other three nonsymmetric H-group orbitals interact with the Px'
•
Py and Pz orbitals to give the six 5-centred MOs (Le. 5c-MOs) designated as a p and a p'
lc
•
The a p MOs are triply degenerate. Similarly a pMOs are also triply degenerate. The MO-energy
ea
diagram is shown in Fig. 9.12.1'1.4b.

The UV-photoelectron spectrum (UVPES) supports the MO diagram shown in Fig. 9.12.11.4b.
The photoelectron spectrum shows two absorption bonds at about 23 eV and 14 eV which correspond
th
to ionisation from O's and a p (which is HOMO) respectively. It may be noted that the oversimplified
MO-diagram given in Fig. 9.12.11.3 fails to explain the photoelectron spectrum.
e/
Note: Formation of the 5-centred MOs in CH4 can be realised by considering the formation of/our
t.m
H-group orbitals.
0" H (s) = \111.f( H A) + \II Is( H B) + \IIls( He) + \111.f(HD) } Symmetric (matching with 2s-orbital of C)
aH(x) = \J!ls(H A ) + \Vb(H B ) - \V1s(H c ) - \Vls(H D )
aH(y) = \J!ls(H
A
) - \J!b(H
B
) + \J!1s(Hc ) - \V1s(H
D
) Non -symmetric (matching with 2p orbitals of C)
a H (z) = \V Is( H A) - \V b( H B) - \V Is( He) + \J! b( H D)
These H-group orbitals combine with the orbitals of C-centre as follows (mixing coefficients not
shown) in terms of appropriate symmetry.
• •
\J!2.\'(C) ± +H(.\,) => as and O's; \J!2px(C) ± +H(x) => a Pll and a Px
• •
\J!2py(C) ± +H(y) => 0' Py and a Py; \V,2Pz(C) ± +H(z) => a Pz and 0' Pz
ry
ra
Os : 2s(C) +1 s(HA ) + 1s(HB ) (Jpx: 2px(C) +1 s(HA ) + 1s(HB )
+ 1s(HC ) + 1s(HD ) - 1s(HC ) - 1s(HD )
ib
Fig. 9.12.11.4~. Formation of 5-centred MOs inCH4 • as and a p are shown. Other Mas can also be
constructed in the similar way because all the p-orbitals are equiv~lent here.
yl
I
I
'* '*
m
'* ,
I 0px' apy' a pz ,
/ \
he
/ \
,
,
r
/
-..
,. " \
lc
" " a; ',', (Nonsymmetric)
::::::ii,;l:l====::::::(( " I ", ,

ea
2p ,, I
I " ',+H(x, y, z)
,.
\ I
I "
y.l',
,1!iE===="
th
,I .1\ : '
( .I , ; I'
I , . I ) " " Four 1s orbitals
e/
" " .1.1 I +H(s) +- of H-atoms

I \ I / " - (Symmetric)
~
t.m
" ,, ' ' Ionisation energy: 14 eV

e>
Q)
c
W I
, I a px ' apy' 0pz
,
,,
~ _ _-oJ'
---ilII1.... I
2s \, I
I
\ I
\ I
" ~ Ionisation energy: 23 eV
\~I
Os
'--v--J "--v-----.J
AOs LGOs
(e)
Fig. 9.12.11.4b. MO energy diagram of CH 4 involving the 5-centred delocalised Mas. Note: Fig.
9.12.11.4b is also applicable for other t~~.rahedral species like, BHi. For B~-, CC/4 etc. similar diagram
may be constructed.
NHJ : Here N is sp3 hybridised and it uses three of its four sp3 hybrid orbitals to combine with the
Is orbitals of three H-atoms (HA, HB and He); and one sp3 hybrid orbital remains as a nonbonding one.
The MO energy diagram in Fig. 9.12.11.5 shows three degenerate localised (2-centred) bonding a-
MOs and three localised a--MOs. The 8 valence electrons are placed in three a-bonding Mas and in
one nonbonding MO which is basically a sp3 hybrid orbital localised on nitrogen. This simple model
fails to explain the UV-photoelectron spectrum which shows three different first ionisation energies
for three different energy levels: 11.0 eV, 16 eV and 23 eVe This can be explained by considering
the formation of multi-centred delocalised MOs as in the case of CH4 . This modified MO energy
ry
diagram is given at 9.12.11.6.
ra
ib
yl
m
he
lc
ea
th
e/
'"--...r--J '"--...r--J
AOs(N) Hybrid
t.m
AOs (N)
Fig. 9.12.11.5". Simple MO energy diagram of NH3 after consideration of sp'3 hybridisation of the central
atom N. Combination of these localised 2-centred MOs can generate the 4-centred MOs that can
explain the UVPES.
H-group orbitals (Le. LGOs) can be generated (cf. Figs. 9.12.11.6a, 7). By considering the Fig.
9.12.11.7, the LGOs are as follows (mixing coefficients not shown) :
at -symmetry {+'(H) : \IIls(HB ) + \IIls(H,4) + \IIls(Hc )
{
~(H) : 'Vls(HB ) ± 'V1s(H... ) - 'Vls(Hc ) == 'Vls(HB ) - 'Vls(H c )
e-symmetry
cI>.J(H} : - 'V1s(HB ) + 'V H1s(H... ) - 'Vls(Hc )
It is evident that in terms of Fig. 9.12.11.7, ~l(H) can combine with the 2s and 2pz orbitals of N; ~2(H)
can combine with the Px orbital of N, and ~3(H) can combine with the 2py orbital of N.
2s(N)
15
ry
ra
ib
yl
"'- ~,--_
m
~J
he
lc
a;z
~
/1 ,
ea
/ / I,. * * '
//",,,,,' ~(JX'
ay ',' Ionisation energy = 11.0 eV
/~'" 1 \,
th
2p /,. I "
:=:iE!'==tl."'-
;;;;i r - - I.,. - /., a n b ' ' , ,'" :-._
... +2(H)' +3(H)
_---.
J, I' sz ,'/ '
,~,)5fI!E=
e/
1\' I /
1\ ' I / / / ') ~ 1S
1\ ~,
I \ 1 t, //,
/ , +
~1(H), ~
t.m
: X(' , //,' LGOs AOs of 3H

I I, '
I I, \ ax' Cfy ,
_ ....~..
s_-e:~ \ "
" " ' Ionisation energy = 16.0 eV
\ \ " ,
" \ ~ Ionisation energy =24.0 eV

\\~'.,
°sz
~ ~
AOs of N MOs of NH 3
Fig. 9.12.11.6. (a) Overlapping interaction in pyramidal NH3 . (b) Approximate MO energy diagram of
pyramidal NH3 molecule.. Note: This diagram is applicable for other pyramidal species like H3 ()+. For
NF3 , similar diagram may be obtained by using its 2p-orbitals.
HA
I \.
I \
@]
I \
I ..-......----.x
Hc./~/J-_~~HB
Projection
ofN ~
@.HAS ]
ry
e-symmetry
ra
Fig. 9.12.11.7. Formation of ligand group orbitals (LGOs) from the 15 orbitals of H-atoms of NH3 .
ib
Combination of the LGOs Le. ~1(H)' ~2(H) and ~3(H) with the orbitals of nitrogen to generate the MOs
yl
has been illustrated i~ Fig. 9.12.11.6a.
The MOs are generated as follows (with the appropriate signs of c's) :
m
c\ \jI2s(N) + c2 \j12pz(N) + C3~(H)' crsz ' cr:: and cr:z Le. 3cr - MOs (for appropriate signs of c 1• c2 and c3)
he
c4 \jI2P.(N) ± C5~(H) : cr x and cr: Le. 2cr - MOs; c6 \jI2py (N) ± C7~(H) : cry and cr: Le. 2cr - MOs
HF2: This hydrogen bonded linear (F-H-F)- symmetrical species can be explained by considering
lc
the 3c-4e bonding system. Very low energy 2s orbitals of fluorine do not participate in bonding. If
ea
x-axis is considered to be the bond axis, then for a-type interaction, the available orbitals are: 2P:x
orbitals of terminal atom (say FA and FB) and Is orbital of the central atom hydrogen. They combine to
produce 3a-MOs (one bonding + one nonbonding + one antibonding). Generation of these a-MOs can
th
be explained by considering the formation of group orbitals (Le. TASOs) from the 2P:x orbitals of the
e/
terminal atoms (FA and F B ).
{
~F(X+) = 'V2p + 'V2p (~ ) (nonsymmetrical and antibonding a-interaction)
t.m
(F ) ,
TASOs x A x B • • • • (cf. Fig. 9.12.1.1)
cl>F(x-) = 'V2Px(F A
) - 'V2Px(F
B
) (symmetrical and bonding a-Interaction)
The symmetrical group orbital ~F(:X-) can combine with the symmetrical Is orbital of the central
atom (H) to generate two a-MOs.
.a b = 'VI = c I'V1s(H A
) + c2~F(x-)
a· = 'V2 = c 3'Vl s (H A ) - c4~F(x-)
The nonsymmetrical group orbital remains as a nonbonding one because it cannot interact with
the symmetrical Is orbital of H.
a nb = 'V3 = ~F(x+) : 'V2Px(FA ) + 'V2Px(FB ) == 'V2Px(FA ) ± 'VIs(H A ) + 'V2Px(FB )
Thus, a"b leads to an antibonding interaction between the terminal atoms because a"b is weakly
antibonding.
The other p-orbitals (Le. 2py and 2pz' perpendicular to the molecular axis) remain as nonbonding
ones. The 2s orbitals of very low energy of the F-atoms also remain as nonbonding. The MO-energy
diagram involving 0b' 0nb and 0* is shown in Fig. 9.12.11.7a. Fig. 9.12.11.7a, b describe the 3c-4e
bonding portion only while Fig. 9.12.11.7c describes the complete diagram.
cr*
t.. .__~)X
ry
ra
1s (H)
ib
yl
m
he
....
AO(H) MOs (HF"2) . TASOs AOs
lc
(FA' Fa) (FA' Fa)

Fig. 9.12.11.7a. MO energy diagram of HFi (after consideration of group orbitals, Le. TASOs).
ea
Note : The nonbonding MO bears an antibonding Interaction between the terminal atoms. The
electron pair in this orbital experiences -minimum antibonding interaction when it adopts the linear
structure. It is the characteristic feature of 30-4e bonding.
th
a*
e/
t.m
i.8. 'V3: '112PX<FA ) ± '111s(H) + 'V2Px(Fs )
Fig'-9.12.11.7b. MO energy diagram of HFi (without considering the TASOs). Not,: The nonbonding
orbit~ls Le. 2s (FA' Fa), 2py, ~FA' Fr) are not shown in Fig. 9.12.11.7a,b for the sake of simplicity.
~-- ... x
y
ry
(-18.6 eV)
ra
ib
Tw02s
yl
15 41' - - - - - - - - ====
(Nonbonding) (-40.2 eV)
~~ ~
AO of H
m
MOs of HF2 AOs of 2F
Fig. 9.12.11.7c. Complete MO diagram of, HF;.

he
The four valence electrons are placed in the lowest a-MOs Le. a b and a nb • It gives 0.5 bond order in
lc
each F-H linkage.

Note: Here it should be mentioned that without the consideration of group orbitals, the simple
ea
LCAO can lead to the MOs as follows (cf. Fig. 9.12.1 1.7b) where the mixing coefficients are not
shown:
th
ah = \VI : \V2Px(FA ) + \Vb(H) - 'V2P x (FB )
a nb = \V3 : \V2Px(FA ) ± \Vls(H) + \V2Px(FB ) == ~F(x+) (weaklyantibonding)

e/
•
a = 'V2 : 'V2Px(FA ) - 'Vb(H) - 'V2Px(FB )
t.m
It is illustrated in Fig. 9.12. I 1.7b.
9.12.12 Characteristics of Three Centre Bonding : 3e-2e Bonding vs. 3He Bonding
We have already mentioned the formation of delocalised 3-centred MOs in both u- ana 1r-bonding. The
characteristics of such a-MOs are given below :
• LCAO of three suitable orbitals produce three 3-centred MOs (one bonding + one nonbonding +
one antibonding). The nonbonding MO is mainly enriched with the character of terminal atoms
(cf. Figs. 9.12.2.1, 9.12.7.3, 9.12.9.4, 9.12.11.1,9.12.11.2,9.12.11.7). In/act, this nonbonding
MO is a TASO (Le. group orbital ofterminal atoms) and thus it is a 2c-MO.
• In 3c-4e bonding (e.g. F-Xe-F, cf. Sec. 9.13.5 and 9.23), the nonbonding MO is occupied by
and thus it is a 2c-MO. 2-electrons while in 3c-2e bonding scheme (e.g. H;, CH;, etc., cf.
Sec. 9.13.5), the nonbonding MO remains vacant. In each model, the bonding MO is occupied
by two electrons. It leads to bond order 0.5 in each linkage in both models.
• In 3c-4e bonding model, the segment (say B-A-B) is linear but in 3c-2e bonding model,
the B-A-B segment i"s bent (cf. H; vs. H;, H 3 in Sec. 9.12.2).
• In 3c-4e bonding model, the nonbonding pair is concentrated on the terminal atoms and it causes
a charge separation. Thus, in 3c-4e bonding, if the terminal atoms are not sufficiently
electronegative, then the nonbonding electron pair cannot be stabilised. This is why, to stabilise
the nonbonding pair, the terminal atoms should be electronegative. On the other bond, 3c-2e
bonding model is favoured by the electropositive terminal atoms.
• Thus the 3c-~e bonding model introduces a partial ionic character which also contributes
ry
to stabilise the bonding. This is favoured by the highly electronegative terminal atoms.
• 3c-2e bonding: H;, CH;, CHi + , C(AuL);, N(AuL);+ where L = PR3 , B - H - B linkage; etc.
ra
with a bent structure.
• 3c-4e bonding: H;, HF; , ICI; , I; , XeF2 etc. All these adopt the linear structure to stabilise
ib
the electron pair in the 3-centred nonbonding MO.
• Hypervalence (cf. Sec. 9.1.6) : Expansion ofthe octet through the involvement of3c-4e bonding
yl
leads t~ hypervalence (in terms of classical definition of hypervalence). However, the 3c-2e
bonding model is required to explain the bonding in electron deficient hypervalent compounds
(cf. Sec. 9.13.5).
m
• Nature ofnonbonding MO in 3c-MOs: It is actually a 2-eentred TASO, and it may introduce
he
a weak bonding or antibonding interaction between the terminal atoms. depending on the nature
ofcombining orbitals. It is illustrated below:
lc
'Vnh : 'Vh(H A ) == 'VI.\'(H A ) - 'V1s(H B) = <flH (-) (in H 3 , H;, H 3 etc.)

± 'V1s(Hc ) - 'Vb(H B )
ea
antibonding interaction between the terminal atoms H A and H B (cf. Figs. 9.12,2.1-3)
'Vnh :'V2Px(FA ) ±\jI1s(H) +'V2Px(FB ) =='V2Px(FA ) ±'V2Px(FB) = <l>F(x+) (in HF;);

th
antibonding interaction between the terminal atoms FA and FB (cf. Fig. 9.12.11.7a)
± 'V2px(/c) = <l>/(x-) (as in 13, Icr;, XeF2 , KrF2 , etc.);

e/
'Vnb : 'V2Px(I A ) - 'V2P (I )

x B == 'V2Px(I A ) - 'V2Px(/B)
bonding interaction between the terminal atoms (cf. Fig. 9.23.2)

t.m
It is important to note that in the formation of the MOs for 3c-4e or 3c-2e bonding, the bonding
and antibonding Mas are 3-centred while nonbonding MO is basically a 2-centred MO.
• 3c-4e bonding gives a linear segment - Why?

• 3c-2e bonding gives a bent segment - Why?
• 3c-4e bonding requires electronegative terminal atoms - Why?
• 3c-2e bonding requires electropositive terminal atoms - Why?
• Geometry ofthe Y-X-Y linkage in 3c-2e and 3e~e bonding: In 3c-2e bonding, the cr-NBMO
remains vacant. If the linkage is bent, the electron pair in the cr-BMO is stabilised more (Sec.
9.12.2, cf. Fig. 9.21.2) and it adopts the angular shape. In 3c-4e bonding, the cr-NBMO is
filled in. The NBMO may introduce either a bonding (e.g. ICli., I:;, XeF2 , etc.) or an antibonding
(e.g. Hi, HF2-; etc.) interaction between the terminal atoms. When the NBMO is itself weakly
antibonding between the terminal atoms, this antibonding effect will be minimum if the terminal
atoms are most widely apart. It gives the linear geometry. In general, on bending, the
O'~b-electron pair is to be placed in a (1*-ABMO (cf. Sec. 9.12.9, Fig. 9.12.9.6) and it will
destabilise the system. This is why, 3c-4e bonding gives the linear linkage.
9.13 HYBRIDISATION OF ATOMIC ORBITAL'S
ry
The idea of mixing or hybridisation was put to consideration in developing the modified MOT. It has
been already mentioned that the concept of hybridisation lies its origin in VBT, and its involvement in
ra
MOT is not of absolute necessity in modifying the theory. Only for the sake of convenience, the idea
was considered in MOT.
ib
• Requirement ofthe concept ofhybridisation : In VBT, the idea of hybridisation was required to
explain the facts: (i) the number of bonds formed, (ii) the equivalence of the bonds in some cases, (iii)
yl
the stereochemistry of the molecules, (iv) the better overlapping of the orbitals.
To clarify the fact, let us take the most classical example, methane (CH4 ). Experimentally the four
m
equivalent C-H bonds are found to project the four comers ofa regular tetrahedron. The central atom,
carbo~ is known to have the electronic configuration in the ground state as : Is 2 2s 2 2p 2. It indicates that
he
there are only two unpaired electrons in the valence shell to form two covalent (electron pair) bonds in
the light ofVBT. To form four bonds, it should have four unpaired electrons which can only be attained
lc
through excitation.
ea
excitation 2 I I I 1. 5
Is 2 2s2 2p 2 (ground state, Jp) ) Is 2s 2px 2py 2p= (excited state, S)
In the excited state, the four unpaired electrons reside in four orbitals which have different spatial
th
orientations. If these pure orbitals of carbon undergo overlapping with the Is orbitals of hydrogens
separately, then three C-H bonds. formed by the three p orbitals of carbon should be mutually
e/
perpendicular. The fourth C-H bond formed by the 2s orbital of carbon should lie nondirectionally
as the s orb.it~1 is spherically symmetrical. This is why, to explain the four equivalent bonds having
t.m
1
bond angles 109.5°, the four orbitals, Le. 2s 2p~ 2p~ 2p~, are to be blended or mixed up to form four
equivalent orbitals having 2s property 25% in each. These orbitals are called sp3 hybrid orbitals and'
these are projected at the four vertices of a regular tetrahedron.
I I I I. hybridisation
2s 2px 2py 2p= (excited state) ) hybridisation 4(2sp3)1 hybrid orbitals
Now let us look into the matter in the light of energetics (cf. Sec. 9.13.4). In the whole process, it
requires excitation energy (-- 406 kJ mol-I) to produce four unpaired electrons (Le. 58 state) from the
ground state (Le. 3P). This excitation energy must be compensated by the release of energy due to
the formation of four C-H bonds by using the hybrid orbitals. We have already mentioned that the
ground state, Le. 3p, can form: CH2 (methylene, singlet carbene) without any excitation energy. In
fact, due to the formation of the additional two C-H bonds with : CH2, the energy released (-- 890 kJ
mol-I) can easily compensate the excitation energy.
• Hybridisation - why? : Lastly, we must mention that the Sp3 hybrid orbital having one
major lobe in a particular direction is much more efficient in overlapping compared to the s
orbital (having no directional property which is essential in producing an effective overlap) and
the p orbitals (having two equal lobes in opposite directions). In fact, the s-p hybrid orbitals, in
general, are more efficient than the pure sand p orbitals in making the directional covalent bonds,
because of the same reason (cf. Fig. 10.1.7.1). This is why, the orbitals even containing unpaired
electrons in the ground state undergo hybridisation to form the stronger bonds. For example, in the
formation of NH3 , the nitrogen atom can provide three unpaired electrons in three pure p orbitals, but
ry
still it undergoes sp3 hybridisation to create a better overlapping in forming the covalent linkages.
However, it should be kept in mind that the process should be energetically favourable.
ra
9.13.1 Linear Combination of Atomic Orbitals in Hybridisation
ib
The orbital wave functions undergo a linear combination to form the hybrid orbitals as in the case of
formation of molecular orbitals. The basic difference is that the hybridisation involves the atomic
yl
orbitals on the same atom to produce a new set of hybrid atomic orbitals while in the case of
molecular <Jrbital formation, it involves atomic orbitals of different atoms.
m
In hybridfsing the orbitals, it must be considered that the involving atomic orbitals should not differ
significantly in the radial parts of their wave functions. In other words, for an effective hybridisation,
he
the combining atomic orbitals should not differ largely in energy. Combination patterns of the
orbital wave functions in forming some common hybrid orbitals are shown in Table 9.13.1.1. It is
evident that the hybridisation leads to a definite stereochemistry.
lc
• Nonequivalent hybrid orbitals : Compared to all other cases mentioned in Table 9.13 .lI, the
mode sp 3d is an exception. In spJd, the five hybrid orbitals are not equivalent. The three hybrid
ea
orbitals arising from s, Px and Py are equivalent lying at an angle 120° in the xy-plane. The- other two
hybrid orbitals made of p~ and d: are projected mutually at 180°, and perpendicular to the xy-plane.
th
The sp 3d3 hybridisation (pentag~nalbipyramid) can also be analysed in the same way giving rise to
two different sets of hybrid orbitals: (s + Px + Py + dxy + d x2 _ ) leading to a pentagon in the xy-
e/
plane; (Pz + d=2) leading to a linear segment perpendicular to the pentagon.

The shapes of some hybrid orbitals are shown in Fig. 9.13.1.1. The directional characteristics of the
t.m
hybrid orbitals are shown in Fig. 9.13.1.2.

• Derivation 0/ the wave functions 0/ the hybrid orbitals (sp, Sp2 and Sp3) : Let us first consider
the wave functions of atomic orbitals (AOs) (cf. Table 4.1.6.2).
'lI2" = R2.\· (r) .Jl /41t; 'lI 2px = R2p (r) .J3/ 41t sin ecos cjl;
'lI2py = R2p (r) .J3/41t sin esin cjl; 'lI2pz = R2p (r) .J3/41t cos e
The radial portions of the orbitals, R(r) are approximately the same for a particular shell (Le. for a
fixed principal quantum number). The angular wave function parts (Le. spherical harmonics Y" m) of
the AOs are important to construct the hybrid orbitals. For the Px' Py and p= orbitals, the maximum value
of the angular wave functions is .J3/47t along the x, y and z axes respectively while for the s-orbital
(spherically symmetrical) it is given by .JI/47t. Taking the magnitude 0/ angular wave/unction/or
the s-orbital as unity, the maximum value of the angular wave function for the p-orbital is 13.
---.) x - 1 - - -............-...----41"-'-. . X
ry
ra
(s) sp-hybridisaiton
ib
----+
yl i.e.
mixing
m
he
I
V
X
lc
x
X
ea
Px
........ .-···fy
, - + -,
.......,.
y ----+ Y} 'IIl=i(lfIs+J2'11p.)
th
........
e/
x
t.m
c:
.9
1ii
CJ)
:.c
~
~
y ----+ Y} _ 1 (
'V2 - ~ 'Vs
_ 1
J2'V P•
J3 )
+J2'¥py
N
~
~ X x
y ----+ Y} 1 ( 1
'V3=~ 'Vs-J2'VPll -"J2'VPy
J3)
(b) sp2-hybridisation
Fig. 9.13.1.1. The shapes of different types of hybrid orbitals (a) sp; (b) sp2; (c) siP; (d) sp'Jd (Contd.).
z
Sp3
--------?I
// I
/ I·
/ I
// I
Sp3 :
.. ) 1
i.e.
mixing I
1
1
---- 3
/ Sp
ry
/
/
/
/ I /
/ _ _ _ _ _ _ _ _ J 1/
ra
ib
(c) sp3-Hybridisation
yl
m
he
lc
ea
(d) sp3d-Hybridisation
th
Fig. 9.13.1.1. The shapes of different types of hybrid orbitals (a) sp; (b) sp2; (c) sp'3; (d) sp'3d (contd.).
e/
(B) Case-I (sp-hybrld orbltBls)

The wave functions of the two hybrid orbitals are given by :
t.m
'V I = al 'V of + hI 'V p; 'V 2 = a2 'V.

f + h2'V p
(i) As the charge density of the s-orbital is equally divided between 'VI and 'V2,'we may write:
2 2 I . 1
al =a2 ='2,I.e.al =a2 = 12
(ii) 'VI is nonnalised. This condition gives:
I'V~d't = at I'V;d't + bt I'V~d't + 2a]b] I'll.,'V pd't = 1

or, a; + b 2
l
= 1, ('V s and 'Vp are independently normalised;
'Vs and 'Vp are orthogonal, Le. third integral is zero).
It leads to: '1 = ~, by using at =.!.

,,2 2
\
\
\
( ) \
sp \
\
(Linear, 180°) \
Sp2
I (Trigonal planar, 120°)
I
I I
I ,
ry
~ - - - - - --'
dsp2
ra
(s + px + Py + dx2 _y2 )
(Square planar, 90°)
ib
Sp3 or d 3s
(s + d xy + dyz + d zx )
yl
m (Tetrahedral, 109·~O)
he
lc
ea
dsp3 or sp3d
th
(s + px + Py + Pz + dz2) (s + Px + Py + Pz + dz2 + dx2 _ y2) (s + Px + Py + Pz + dx2 _ y2)

(Trigonal bipyramidal, d2sp30rsp3d2 dsp30rsp3d
e/
90°, 120°)
(Octahedral, 90°) (Square pyramid, 90°)
t.m
Fig. 9.13.1.2. Directional characteristics of some important hybrid orbitals, the arrows show the directions
of the projected lobes of hybrid orbitals.
(iii) 'V 1 and '112 are orthogonal. The condition leads to :
f'l'I'I'2 d 't = 0 = fCal'l'.r + bl 'I' p)(a2'l's + b2'I' p )d't == a l a2 + bl b2
Thus the wave functions of the hybrid orbitals are given by :

Table 9.13.1.1. Combination of orbital wave functions in some common hybridisation
(i) sp, (say, s + Px) (linear geometry) AO character

1
'VI = .J2 ('V. +'V p) s(50%), Px(50 01O)
'V2 =
1
.J2 ('V. - 'V p) }
AO character
ry
ra
ib
yl
(iii) Sp3 (s + Px + Py + Pz) (tetrahedral geometry) m AO character
+z 1
I
\VI = \V (1, 1, 1) =-2(\V' + \V p + \V pY + \V p
f
x I
)
he
1
"2
\V 2 =\V (1, - 1, - 1) = (\V.f + \V Px - \V PY - \V P, ) s(25%), p(75%)
lc
1
\V 3 = \V (-1, 1, - 1) = "2 (\V s - \V Px + \V P
Y
- \V Pz )
ea
1
\V 4 = \V (-1, - 1, 1) =2" (\V s - \V Px - \V PY + \VP, )
Note: The hybrid orbitals point along the (1,1,1), (1,-1,-1), (-1,1,-1) and (-1,-1,1) directions of the cube
th
where the nucleus resides at the centre of the cube and the x, y and z axes run parallel to the edges of the
cube. Thus \VI lies along the (1,1,1) direction of the cube.
e/
(iv) sp 3d (s + Px + Py' Pz + d ) (trigonal bipyramidal geometry) AO character

i
t.m
x.J 'VI = JJ ('V. +.J2 'V p)

I
I xy-plane 1 1 Jj
I 'V2 = Jj ('V., - .J2 'V p. +.J2 'V p)
1 1 Jj
'V3 = Jj ('V•. - .J2 'V p. - .J2 'II p)
1
\V4 = .J2 (\V P, + \VdZ2 )
1
'Vs = .J2 ('V pz -'Vd) pz(50%), dz 2 (50%)
(contd.)
(v) sp
3
J2 (s +Px +Py +Pz + dz2 +dx2 -l)' (octahedral geometry) AO character
'Vl=
'16
~('V.+.J2'Vd z2
+J3'V p
z
)
J3 J3
'V 2 = J6I ('V. - .J2I 'Vdl +.J2 'Vdx 2 -l + 3 'V p)
1 1 J3 J3
'V3 = J6 ('V., - .J2 'V d .J2 'Vd x
,2 - 2 -l + 3 'V p)
ry
=_1. (\11 1 '" + J3 'V -J3 '" )
*
\II
T4 J6 T.t .J2
__
Tdz2 .J2 dx2 _
i T Px
ra
tIl =_1 (\11
J6 1 '"
.J2
__ _ J3 'V d
.J2 -J3 '" P" )
ib
TS T.t Tdz2 x2 _ T
i
'V6 = ~ ('V. +.J2 'Vd J3 'V p)
yl
,2 -
m
• Angle between the sp hybrid orbitals : Let us consider the Pz orbital to combine with the s-
orbital. By using the angular part of wave functions (cf. Table 4.1.6.2) we get:
he
'1', = ~ (I + Jj cos 9) and '1'2 = ~ (1- Jj cos 9)
2v2n 2v 2n
1
lc
Taking ,J;k as unity (this aspect has been discussed earlier), the 'VI and '112 wave functions are
ea
very often expressed as : .
'1'1 = ~ (I + Jj cos 9) and '1'2 = ~ (1- Jj cos 9)

th
The above wave functions do not contain the angle The angle a gives the measure of the +.
e/
angle of a vector with z-axis. From the expressions, it is obvious that the wave functions lie on
t.m
the z-axis on opposite directions. Hence, the bond angle must be 180°.
Real spherical harmonics i.e. angular wave functions
s: ~;Px: ,/4;
v4n
f3 sin9cos+;
Py : f3 sin9sin+; Pz: '14;

,/4; f3 cos9
• Bonding potentiality ofthe hybrid orbitals : The wave function 'V I is maximum for a = 0, and
\V2 is maximum for a= 180°. The bonding potentiality of an orbital is measured by the maximum
value of the angular wave function. Taking, ~ = I, it is ~ (I + Jj) = 1.93 for '1', and '1'2; 1
v4n v2
. for 'l's and 1.732 (= Jj) for'l'p'
1
Note: Taking ,J4; (= magnitude of the angular wave function of the s-orbital) as th&unity.
(b) C.se // (sp2-hybrld orblta/s)

Considering the Px and Py orbitals, the wave functions ofthe hybrid orbitals may be expressed as follows:
\VI = al\V s + bl\V Px + cl\V Py ; \V2 = a2 \V s + b2\V Px + c2\V Py and \V) = a)\Vs + b) \V Px + C) \V Py
(i) As the charge density of the s-orbital is equally divided among the three hybrid orbitals, we may
write:
ry
2 2 2 1. 1
at =a2 =a3 ='3,t.e.at =a2 =a3 = J3
ra
(ii) If we consider that \V I is pointed along the x-axis, then the Py orbital does not coqtribute in \V I. It
gives c I = 0, Le.
ib
'VI = 0) 'V s + b) 'V Px
Applying the normalisation condition to 'VI' we have:
yl
J\II; d't = 1 = J(at\ll s + q\ll p)2 d't = a~ + q2 l
m
(both 'lis and \Vp are normalised and they are mutually orthogonal)
q =~,( usingal =~)

he
or,
(iii) Applying the orthogonality condition, we have :

lc
J\III\II2 d 't = 0, i.e. ata2 + b1b2 = 0

ea
b = _ a1a2 = __1_
or, 2
b) J6
th
Similarly, J'VI\V)dt=O=ala) · ala)

+~b3; I.e. b3 = - - = - r;
1
bl ,,6
e/
(iv) Normalisation condition applied to 'V2 leads to :

(1- + -1) =-1
t.m
a 22 + b22 + c22 = 1; or, c22 = 1- (a22 + b22 ) = 1-

362
(v) Orthogonality condition for 'V2 and 'V3 leads to :
J'V2'V)dt = 0 = a2a3 + b2b) + c2c) = ,,91 + ,,361 + ,,21 c) = -21 + ,,21 c

~ r:;-; ~ ~ 3
1
Le. c)=--
J2
Thus the three hybrid wave fu:~t\ons are:
Introduction to 'Chemical Bonding and Theories of Covalence 6n
• Angle between the orbitals: By using the angular part of the wave functions (cf. Table 4.1.6.2),
the hybrid wave functions may be expressed as follows :
\jI1 = 21[~ .fi + sin 0 cos,} \jI2 = 21[~ -~ sin 0 cos, + J

J% sin 0 sin'
\jI3 = 21[~ -~ sinO cos, - J% sinO sin.]
ry
The above hybrid wave functions do not contain the Pz orbital. Thus it is reasonable to conclude
that all the three hybrid orbitals lie in the xy-plane and it makes 9 equal to 90° (i.e. sin 9 = I).
ra
1
Taking the factor .J47t as unity, the hybrid wave functions are very often expressed as
ib
follows:
=( JJ + .fi cos.) =( ~- ~ cos, + J% sin.)

yl
\jI1 \jI2
m
and, \jI3 =( JJ-~ cos, - J% sin.)
he
The maximum value of \VI lies along the x-axis. The condition for the direction for which '112
possesses the maximum value is given by :
lc
dW2 =0 = ~ sin' + '/2

II cos.; or, tan' =-.J3 =tan 120 0 0
i.e.' = 120
ea
d~ v2
• Bonding potentiality ofthe hybrid orbitals: Taking the factor ~ as unity, the hybrid orbitals
th
v47t
lead to the following conditions :
e/
WI (max) = .JJ +.fi =1.99 (for' =0, co~ideririg WI will have its maximum 'value along the
t.m
x-axis).
Similarly, it can be shown that 'VI (max) = 'V2 (max) = 'V3 (max) = 1.99.
(c) Case III (sp3 hybrid orblta/s)

Let the wave functions of the hybrid orbitals be denoted as :
\III = a1\II s + ~ 'V Px + cI\II Py + dl \II Pz
\112 = a2 \11.v + b2 \11 Px + c2'V Py + d 2 \V Pz
\113 = a3\11 s + b3\11 Px + C3'V, py + d 3\11 Pz
\114 =a4'V s +b4 \11 px +C4 \11 py +d4 \11pz
(i) The charge density of s-orbital is equally d.istributed among the four hybrid orbitals, Le.
2 2 2 2 1 1
a1 =a2 =a3 =a4 =4';or,a. =a2 =a3 =a4 ='2
(ii) If it is c~nsidered that \VI lies along the x-axis, then there is no contribution of Py and Pz orbitals
in \VI' i.e. c 1 = d 1 = o.
(iii) Normalisation condition applied to \V 1;leads to :
2 2 2 2 2 3 .Jj
J dt =1=a
\Vl 1 +b1 ;or,b1 =l-a =-;orb1 = -
4 2
(iv) Orthogonality conditions ~ead to :
ry
J'I1I'112d 't = 0 = al a2 + qb2 ; J'I1I'113 d 't = 0 = al a3 + qb3 ; J'I1I'114 d 't = 0 = al a4 + qb4
ra
ib
· ·
Itglves. a1a2 1
b:J. =b3 =b4 =-z;;-=- 2.Jj
~ and q = ~) yl
( Here, al a2 =
m
he
(v) Assuming \V2 to lie on the xz-plane, it may be concluded that in \V2' there is no contribution from
the Py orbital, i.e. c2 = o.
lc
(vi) Normalisation of '1'2 leads to :
= ~
ea
J\V2dt =l=ai +bi +di;or,di =1-(ai +bi)=I-(.!.+.!.)=3.i.e.d

4 12 3 '13 2
th
(vii) Orthogonality conditions lead to :

e/
t.m
(viii) Normalisation condition applied to 'V3 leads to :
2 2 2
a3 + b3 + c3 + d 3
2
= 1; or c32 =1- 2 2 2
(a3 + b3 + d 3 ) = 1-
(1- + -1+ -1) =-1.I.e. c 3 = 1r;;
4 12 6 2 ,,2
(ix) Normalisation condition for '114 leads to : c; = 1- (a; + b; + d;) =.!2 and c = - ,,2~
4
Here, the minus root of C4 is taken because fIIJ and f114 are different.
Thus the wave functions may be expressed as follows :
1 J3 11[2
\jI, ="2 \jIs +2" \jI Px; \jI2 ="2 \jI.f - 2J3 \jI Px \jI P z +V3
1 1 1 1
\jI3 ="2 \jIs - 2J3 \jIPx +J2 \jIPy - J6 \jIp z
1 1 1 1
\jI4 ="2 \jIs - 2J3 \jI Px - J2 \jI Py - J6 \jI p z
ry
Note: The above set of equations is mathematically equivalent to the set of equations given in
Table 9.13.1.1 for sp3 hybridisation. These sets differ only in orientation with respect to the
ra
chosen set of coordinate axes which are taken arbitrarily. In fact, depending on the set of
arbitrarily chosen coordinate axes, there will be an infinitely large number ofdifferent sets of
ib
equations, which are mathematically equivalent to express the hybrid wave functions .
• Angles between the hybrid orbitals: Using the angular wave functions (cf. Table 4.1.6.2) and
yl
1
taking r;= as the unity, the above wave functions may be expressed as follows :
",47t
m
\jI, =.!. +~ sin 9cos,; \jI2 =.!. _.!. sin 9cos, +J2 cos9;
he
2 2 2 2
'V =---sln ~ J3·O·~

1 1. 0 cos't'+-sin 1 COS;
sln't'-_o 0
J2 J2
lc
3 22
~ J3·e·~
1 1. 0 cos't'--sin 1 0
ea
'V =---sin sln't'--cos

4 22 12 J2
Here, it has been assumed that the wave function 'VI lies along the x-axis (Le. = 90°, e
th
sin 90° = 1; and eI> = 0°, cosel> = 1) and the wave function 'V2 lies in the xz-plane (Le. eI> = 180°,
cos 180° = -1), we get:
e/
\jI2 =.!. +.!. sin 9 +J2 cos9

t.m
2 2
For the maximum value of'V2' we have the condition: d'V2/dO = 0
Le. d\jl2 =.!. cos9 - J2 sin 9 =0; or, tan 9 =0.354 =tan 19°28'
dO 2
The value of 0 gives the angle between the z-axis and 'V2 axis. Thus the angle between 'VI and 'V2
becomes 90° + 19°28' = 109°28'.
Note: For the equivalent s-p hybrid orbitals, the bond angle (a.) can be calculated by using t.he
relationship: coso. = s P -100 where sand p denote the respective % of the sand p
p
s -100
orbitals respectively (see Table 9.13.6.1).
Bonding potentiality 0/ the hybrid orbitals: The bonding potentiality of an orbital is measured
by its angular strength. For 'VI' it has the maximum value along the x-axis, for 0 = 90°, = 0°,
i.e. \j!l(max) = ~+~= 2 (cf. it is 1 for s orbital, and 1.732 for p-orbital). Similarly for, \j!2(max) =
2 2
I
\j!3(max) = y4(max) = 2. These are measured with reference to the unit 41t = I.
• Relative values ofangular strength and bonding potentialities ofdifferent s-p hybrid orbitals:
The relative values of angular strength are:
Angular strength: sp3 (2.0) > sp2 (1.99) > sp (1.93)
Bonding potentiality should also foll~w the same sequence but the reverse is true. This aspect
ry
has been explained in Sec. 9.13.3.
Bonding potentiality: sp > sp2 > sp3 (cf. Sec. 10.1.7)
ra
9.13.2 Stereochemistry of the Hybrid Orbitals
ib
The stereochemistry attained by the different types of hybridisation is given in Table 9.13.2.1.
It is evident that in the combination of s + p + d, depending on the nature ofthe d-orbitals participated,
the geometry differs significantly. For example, in sp 3d if the d-orbital is d z2 then the combination
yl
m
Table 9.13.2.1. Stereochemistry of the hybrid orbitals
Combining atomic orbitals Common Spatial orientation Angular
he
notation strength·
ns, npx; (bond axis along x axis) sp Linear 1.93
lc
ns, npx' npy; (bonds in xy plane) sp2 Trigonal planar 1.99

nS,nPx,npy,npz sp3 Tetrahedral (Td ) 2.00
ea
(n - 1)dxy' (n - 1)dxz' (n - 1)dyz' ns cPs Tetrahedral (Td) 2.24

(n -l)dx2 - y2, ns, npx' npy dsp 2 Square pla~ar 2.69
th
ns, npx, npy' ndx2 -y 2 sp 2d Square planar

(n - l)di , ns, npx' npy' npz dsp 3 Trigonal bipyramidal
e/
(TBP)
ns, npx' npy' npz, ndi sp 3d Trigonal bipyramidal
t.m
(TBP)
(n - l)dx2 - y2, ns, npx' npy' npz dsp 3 Square pyramidal
ns,nPx,npy,nPZ,ndx2 -y 2 sp 3d Square pyramidal
(n - l)dx2 - y2, (n -l)dz2' ns, npx' npy' npz cPsp3 Octahedral (Oh) 2.92
ns, npx' npy' npz' ndx2 - y2, ndz2 sp3J2 Octahedral (Oh)
(n - l)dx 2 - y2, (n -l)dxy' (n - l)dz2, ns, npx' npy' npz tPsp3 Pentagonal
bipyramidal
(n - l)di , (n -l)dxy' (n -l)dyz' (n -l)dzx, ns, npx' npy' npz cfsp3 Dodecahedral
(n -1)dx2 _ y2' (n -l)dxy ' (n -l)dyz' (n -l)dzx ' ns, npx' npy' npz cfsp3 Square
antiprismatic
(n - 2)1xyz' (n -l)dxy' (n -l)dyz' (n -l)dzx, ns, npx' npy' npz Id3sp3 Cubic
* Assuming unity for ns and 1.73, 2.24 for np and nd respectively.

produces a trigonal bipyramid (Le. s + p x + Py; p = + d _2); but participation of the d x 2 _ y2 orbital in
the combination produces a square pyramid (Le. s + Px + Py + d x2 _ 2; Pz). It is very difficult to
predict whether the trigonal bipyramid geometry or square pyramid ge~metry will be preferred. It is
expected that they are not energetically greatly different. But, most of the ADs type molecules have
been found to adopt the trigonal bipyramid geometry.
In some cases, different combinations lead to the same geometry. For example, the tetrahedral
geometry of MnOi and CrO;- probably constitutes both the combinations sp3 and d 3s. It is believable
as the energies of 3d, 4s and 4p do not differ significantly.
ry
In the combination of d + s + p, if the d-orbital comes from the penultimate (Le. n - 1) shell, the
corresponding combination is very often referred to as inner orbital type while participation of the
ra
d-orbitals from the outermost valency shell (i. e. n-shell) produces an outer orbital type hybridiSaion.
Such possibilities mainly exist for the transition metal complexes. The occurrence of the inner orbital
ib
type combination is energetically more favourable but there are many other factors which may govern
the process. This aspect will be discussed in Sec. 9.13.5.
yl
9.13.3 Bonding Potentiality of the Hybrid Orbitals: Angular Strength and Overlap Integral
m
The hybridisation produces the orbitals which concentrate the electron clouds more in some particular
directions compared to the starting atomic orbitals. This is why, the hybrid orbitals in some particular
he
directions give a better overlapping with the suitable orbitals of other atoms. This is why, the bonding
potentiality of the hybrid orbitals is always greater compared to that of the pure atomic orbitals. For
lc
example, the s-orbitals are spherical having no directional property and the p-orbitals concentrate their
electron clouds in two equal lobes projected in opposite directions but their hybridisation products
ea
mainly concentrate the electron clouds in some specified directions to produce a better overlap integral
in the specified directions.
th
The bonding potentiality is very often

measured by the parameter, angular strength as
proposed by Pauling. It is measured by the'
e/
maximum value of the angular wave function I

I
t.m
(cf. Sec. 9.13.1). It gives a measure of the I I
concentration of the electron cloud of an orbital 1.-1-.1

I I
I I
along the bond axis. Thus the parameter is directly
Fig. 9.13.3.1. Angular strength of the hybrid
proportional to the length ofthe axis ofthe orbital
orbitals.
measured from the nucleus to the periphery. It is
measured with respect to the s-orbitals. .
The spherically symmetrical s-orbitals being nondirectional produce the same overlap integrals in
all directions. The p-orbitals having the directional properties (x, y and z axis) can overlap better than
the s-orbitals in their projected directions. The comparison among the orbitals must be confined for a
particular principal quantum number. If the radius of ns orbital is r, the length of the axis of the np
orbital measured from the nucleus to the periphery is given by 1.73 r (see Fig. 9.13.3.1). Thus, according
to the definition of angular strength measuring the bonding potentiality, if it is unity for the ns orbital
then it is 1.73 for the np orbital. Similarly, in the same scale, it will be 2.24 for the nd orbital.
The scale of angular strength can be understood from the angular wave function of the orbitals
(cf. Table 4.1.6.2, Sec. 9.13.1). For the Px' Py and Pz orbitals, the maximum value of the angular wave
function becomes ~%7t along the x, y and z-axes respectively, while for the spherically symmetrical
s-orbital, it is given by Y.ji;;, in all directions. Taking Y~ as unity, the maximum value of the
angular wave function of the p-orbital is Ji.
This aspect has been discussed in Sec. 9.13.1 to derive the
hybrid wave functions.
The angular strengths ofthe hybrid orbitals are shown in Table 9.13.2.1. It is evident that compared
to the pure orbitals, the hybrid orbitals are more promising for the bonding purpose. Actually,
ry
the angular strength gives the measure of overlap integral to be earned in bond formation.
Thus the bonding efficiency and angUlar strength of the s-p hybrid orbitals should follow the same
ra
order.
ib
Angular strength: sp3(2.0) > sp2 (1.99) > sp (1.93). But, in reality, the bonding efficiency follows
the opposite' trend.
yl
Bonding efficiency: sp > sp2 > sp3.(cf. Fig. 10.1.7.1).
This can be explained by considering the relative size of the major lobes (i.e. bonding lobes) of
m
the s-p hybrid orbitals~ The shapes of the lobes are the same for sp, sp2 and sp3 hybrid orbitals but the
size of the lobes varies in the following order.
he
Minor lobe size: sp3 > sp2 > sp; Major lobe size: sp > sp2 > sp3.
It explains the highest overlap integral for the sp-orbital. The following C-Hbond strength supports
lc
this prediction.
C-H bond energy: C2H 2 > C2H 4 > C2H 6•
ea
The overlap integral also depends on the internuclear separation, e.g. the internuclear separation
between two sp-C centres is less than between two sp3--e centres (cf. Sec. 10.1.7).
th
In/act, overlap integral does not solely depend on the angular strength ofthe s-p hybrid orbitals
(cf. Sec. 10.1.7.1).
e/
9.13.4 Energetics of Hybridlsatlon

t.m
The energy difference between the unhybrid system and hybrid system gives the measure of hybridisation
energy required. As the hybrid orbitals are produced from a linear combination of the atomic orbitals,
the energies ofthe hybrid orbitals are given by the weighted average of the energies of the combining
atomic orbitals. To clarify the fa~ let us- oonsider- the possible combination of sand p-orbitals of
carbon. The energies of the 2s- and 2p-orbitals of carbon are - 1878 and - 1028 kJ mol-I respectively.
.~. · OJ."C : '2s22p 2 exeitation and 2( ~12( ~12 1 1
sp hy brlulSatlon h b °do ° ) SPJ SPJ Py 2Pz
y rt lsatlon
E2(sp) = ~ (E2s + E2px ) = -1453 kJ mol-I

Therefore, the energy required for hybridisation is given by :
Ehy = (2E2(sp) + 2E2p ) - (2E2s + 2E2p) = (- 4962) - (- 5812)
= 850 kJ mol- 1
ee e 2 2 excitation and 2 I 2 I 2 I I
Sp 2 hybrldlsatlon ofC: 2s 2p ... ) 2(sp ) 2(sp ) 2(sp ) 2pz
hybndlsatlon
E2(Sp)2 =} (E2s + 2E2p ) =- 1311.33 kJ mol-I

J
Hence, Ehy =(3E2(sp2) + E2p ) - (2E2s + 2E2p ) =(- 4961.99) - (5812) =850 kJ mol-
e OJa'-C : 2 S 22p 2 excitation and

sp3 hy brledelSat,on ) 2(sp 3)4
hybridisation
ry
E (
2¥)
3 =.!..4 (Eh + 3E2p ) =-1240.5 kJ mol-I"
ra
Hence, Ehy =(4E2(si» - (2Eh + 2E2".) =(- 4962) - (5812) =850 kJ mol-I
ib
Sp3 hybridisation of P : Now let us take the case of phosphorus, where E3s = - 1806 kJ mol-I,
E3p = - 98i kJ mol-I.
yl
3 S23P3 spJ hybridisation
. . ) 3' ( sp3)2 ( sp 3)1 '(sp3)1 ( sp 3)1·I.e. 3(sp3)5
and excitation
1 1
m _I
E( 3) =-(E3s +3E3p )=-[-1806+3(-981)]=-1187.25kJmol
3~ 4 4 ,
he
Hence, Ehy =(5E3(si» - (2~s + 3E3p ) =(- 5936.25) - (- 6555) l'l:l619 kJ mol-
J
In the above calculations, E hy gives the measure of requirement of energy to carry out the
lc
hybridisation. Hence to make the process energeticallyfeasible, the energy released in theformation
of bonds by utilising the hybrid orbitals must be greater than Ehy• It is evident that if the energy
ea
difference between the combining orbitals is very high then Ehy becomes very much large, and the
energy released in the bond formations may not be able to compensate the Ehy.
th
Variation ofstructuralfeatures of the hydrides of Group VA (Le. 15) and Group VIA (Le. 16) :
To clarify the effect of Ehy (Le. cost of hybridisation energy), let us take the hydrides ofthe Group VA
e/
(15) and VIA (16) elements (see Table 9.13.4.1) in which the bond angle gradually decreases to . . ., 90°
with the increase of atomic number. It means that the heavier members prefer pure p-orbitals
t.m
keeping the lone pair in the s-orbital. It occurs so, because the energy released in forming the
bonds cannot compensate the hybridistion cost (i.e. Ehy ) for spJ hybridisation. Actually the larger
size of the heavier members reduces the bond energies and as a result, it becomes difficult to meet the
hybridisation cost.
o The observation can also be qualitatively rationalised in terms ofstericfactorse The lighter members
of the groups being small find the besOt way to minimise repulsion amOl)g the bonding and nonbonding
electron pairs by projecting the orbitals to the vertices of a regular tetrahedron. But, for the heavier
members, because of their larger sizes, the repulsion among the bonding and nonbonding pairs is itself
less pronounced. Hence to avoid the repulsion it does not require essentially to undergo
hybridisation.
In VSEPR theory, it is believed that the bonding pair goes away from the central atom with the
decrease of electronegativity of the central atom and as a result, the repulsion among the bonding and
nonbonding pairs gets automatically reduced for the heavier members (acting as the central atoms
which are relatively less electronegative). In other way, the lone pair (which is more diffusedfor the
less electronegative central atom) on the central atom causes more distortion to contract bond angles.
Table 9.13.4.1. Bond parameters in the hydrides of Group VA(15) and VIA(16).
Molecule Bond angle· Bond energy Atomic tadius Electronegativity of

(kJ mOll) ofthe central atom the central atom
(in pm)
NH) 106°45' 389 74 3.0
ry
PH) 94° 318 110 2.1
AsH) 91 °48' 247 121 2.0
ra
SbH) 91 °18' 255 141 1.9
H 20 104°28' 459 74 3.5
ib
}{2 S 92°15' 363 104 2.5
H2Se 91° 276 117 2.4
yl
H2 Te 89°30' 238 m 137 2.1
* Controlling factors: X-Hbond energy and cost of hybridisation; steric factor; electronegativity of the central
atom (i.e. VSEPR).
he
9.13.5 Participation of d-Orbitals in Hybridisatlon In Nonmetals (cf. Sec. 10.7 for 7t-bondlng):
A Debate
lc
A. Barriers for d-orbita' participation in bonding

ea
We have already mentioned that the participating atomic orbitals in the process of hybridisation should
not differ significantly in their radial distribution functions. In other words, they should not differ
largely in energy since the energy of an orbital is proportional to its mean radial distance. If the orbitals
th
differ largely in energy, the cost of hybridisation energy becomes large.

For the lighter nonmetals, (e.g., Si, P, S, etc.), the nd (i.e. 3d) orbitals differ both in radial size and
e/
energy significantly from the ns- and np-orbitals. For example, in phosphorus, the most probable radial
distances for the 3s-, 3p- and 3d-orbitals are 47 pm, 55 pm and 240 pm respectively. Hence, though the
t.m
hybridisation between 3s- and 3p-orbitals may be possible, the participation of the 3d-orbitals in the
hybridisation with the 3s- and 3p-orbitals is not expected because of their (i.e. 3d-orbital's) much
higher energy. But, if the energy of the 3d-orbitals can be brought down to the comparable range
of the 3s- and 3p-orbitals then their participation in the hybridisation, i.e. 3s + 3p + 3d, may be
permitted. There are number of ways to contract or lower down the energy of the d-orbitals. These are
discussed below.
Besides the large promotion energy (reflected in the cost of hybridisation) required for d-orbital
participation, the highly diffuse character of the d-orbital disfavours its participation in bond
formation. The d-electrons are shielded by the inner electrons and consequently, the d-electrons
experience the less nuclear charge. This leads to their diffuse character which does not allow them
to make a good overlap with the other combining orbitals. Thus the high promotion energy and
diffuse character ofthe d-orbitals are the basic barriersfor the participation ofd-orbitals in bonding
in nonmetals.
The above mentioned barriers can be interpreted as follows. The mean value of radial distance for
nd orbitals of the p-block elements lies far away from the typical covalent bond distanc~t.Thus it
needs the contraction of d-orbitals for covalent bond formation.
In fact, contraction of d-orbital can reduce the required promotion energy and diffuse character and
the radial distance of the orbital matches with the covalent bond distance.
B. Possible ways to allow the contraction of d-orbitals

(i) By increasing the effective nuclear charge
ry
When the atom under consideraJion binds with a highly
electronegative atom such as F or 0 or CI, the bonding pair E
ra
will be shifted to the more electronegative atom giving rise to
o +.charge on the central atom (say, P, Si or S). With the increase
ib
of positive charge on the element, the orbital electrons will be
pulled more towards the nucleus, but the effect is transmitted
yl
more towards the outer electrons. As a result, the energy of
the nd-orbitals falls more sharply compared to that of the
m ----. Positive charge
ns- and np-orbitals with the increase of positive charge on Fig. 9.13.5.1. Qualitative represen-
the central atom under consideration (Fig. 9.13.5.1). ·For tation of the decrease of energy of
example, in spJtP configuration, on accumulation of + 0.6 ns, np and nd orbitals with the
he
charge on S, the most probable radii for 3s-, 3p- and 3d-orbitals increase of .positive charge on the
become 87 pm, 93 pm and 140 pm respectively; but in the atom (cf. Fig. 1.11.1.2).
lc
neutral atom for the spJtP configuration, Le. 3s 13p33cP, the 3d-orbitals possess very high energy (cf.
the corresponding values of neutral S are: 88 pm, 94 pm, and 160 pm).
ea
Ip SF6 , the d-orbital (for sp3cP hybridisation) is heavily contracted so that its radial distribution
maximum lies at 130 pm distance while in free sulfur (3s 23p43J», it occurs for the 3d-orbitals at about
th
300-400 pm away from the nucleus. In free sulfur, the electronic configuration is : 3s 23p43J> Le.
d-orbital is unoccupied. The s- and p-orbitals of sulfur in SF6 are contracted but not to such an extent.
e/
Thus the radius of the maximum probability for the d-orbitallies within the S-F bonding distance.
In other words, in SF6, both the energy and diffuse character of the d-orbital are significantly reduced.
t.m
Because of this fact, to effect the d-orbital participation (e.g. spJd, spJtP, etc,), it generally
requires to bind with the highly electronegative elements (e.g. F, CI, 0). This is why, PHs does not
exist but PCls, PFs exist through the formation of sp3d hybridisation. Similarly, the existence of
SiFi- ~ SF6 and the nonexistence of the hydrogen analogues can be explained by considering the
possibility of occurrence of sp 3cP hybridisation.
Table 9.13.5.1. Effect of charge and extent of population in 3d orbital of

sulfur on <rmax> of 3d orbital of sulfur
Electronic configuration Charge on S <rmax;> (in pm) for 3d of S
sl p cP
3 + 0.6 140
slp 3d2 inSF6 130
s2p 4JJ o 300-400
s2p 3d 1 o 246
slp 3d2 o 160
(ii) By increasing the population in d-orbitals (cf. Table 9.13.5.1)

If the number of electrons occupying the d-orbitals can be increased, then size of the d-orbitals can also
be shrinked. Thi~ fact is well illustrated for the transition elements where it has been found that after
some population density in the (n - 1) d-orbital, its energy becomes lower than that of the ns orbital (cf.
Fig. 1.11.1.2). In the case of S, it has been observed that if only one electron is placed in the d-orbital
(i.e. 3s23p33d) i.e. d)-configuration), the most probable radial distance for the 3d-orbital is 246 pm, but
on placement of two electrons in the d-orbital (Le. 3cP for 3s) 3p33cP configuration), the distance falls to
160 pm from 246 pm (cf. for 3s23p43cfJ, it is about 300~00 pm). In fact, in spltP configuration of
ry
neutral S, the average (Le. the most probable) radial distances for }s-, 3p- and 3d-o~bitals become 88
pm, 94 pm and 160 pm respectively.
ra
S (neutral) : Most probable radial distances for 3d orbital are 300-400 pm (tf>-configuration), 246
pm (d)-configuration) and 160 pm (cP-configuration) (Table 9.13.5.1).
ib
Excitation of electron from 3s and 3p levels to 3d level reduces the shielding experienced by the
3d electron because sand p electrons are more efficient than the d-electrons in shielding mutually. It
yl
reduces the energy and <rmax> of the 3d-orbital.
(iii) By the coupling of spins of the electrons

m
A slight shrinkage in the size of the d-orbitals may be carried out through the coupling of the spins of
he
the electrons occupying different orbitals. This can be explained by considering the origin of non-
Coulombic Pauliforce (arising from the Pauli exclusion principle) which states that the electrons of
lc
the same spin repel mutually. To avoid this spin-spin repulsion, electrons of the same spin will try
keep themselves apart as far as possible. This will lead to an expansion of the orbital (say d-orbital)
ea
in which they are remaining present. When the electrons undergo pairing through spin-spin coupling,
the Pauli force does not operate for such paired electrons with opposite spins. The spin pairing reduces
the number ofelectrons with parallel spins experiencing the Pauli force. This is why, spin-spin coupling
th
leads to a slight shrinkage of the orbital.

e/
c. Objection against the concept of d-orbital participation in hybridisation and an

alternative bonding model without d-orbital participation
t.m
In VBT, the concept of hybridisation like sp 3d, sp 3cP, etc. is- very much useful in explaining the bonding
and geometry of many compounds of main group elements (Le. p-block elements). But, theoretical
calculations supported by experimental verifications indicate that in many cases, the extent of d-orbital
participation is almost negligible. In fact, their contribution in bonding is very. much less significant
than the s- and p-orbitals. Thus the s-p hybridisation like sp, sp2~ sp3 is quite reasonable while the
hybridisations like sp 3d, sp 3cP etc. are called in question.
• Introduction of ionic bonds (Pauling) : Without considering the participation of the d-orbital,
Pauling had attempted to explain the structure of the species like PCls which may exist in the following
resonating structures. '
yl -
"'4Eo--~~. CI-PZCI ...4i------:i~~ 3 more equivalent
61
CI resonating structures
--------------
Here, the central atom P uses its four valence orbitals·{s + p) to produc.e 2c-2e four P-CI bonds to
attain the octet ~onfiguration while the fifth CI is ionically bound. Thus the total species is PCI;CI-.
Each P-CI bond possesses 20% ionic character and 80% covalent character by considering the existence
of 5 equivalent resonating structures. When the electronegativity difference between the combining
atoms is significantly large, the existence of such resonating structure is only meaningful.
The extra bonds formed after the attainment of octet or arganic structure (in hypervalent compounds)
are described as trans-arganic bonds which are weaker than the normal or arganic bonds (e.g. average
P-CI bond energy: 326 kJ mol- 1 in PCI) and 270 kJ mol- 1 in PCI s). However, the said trans-arganic
ry
bonds become stronger with the increase of electronegativity difference (e.g. difference of average P-
CI bond energy for the pair PCIs and PCI) is 56 kJ mol- 1 while this difference reduces to 40 kJ mol- 1
for the pair PF) and PFs).
ra
. According to Pauling concept, in SF6 there are two
ib
trans-arganic S-F bonds and the corresponding
resonating structures are :
yl
• 3c-4e bonding model (i.e. aia;b): Alternatively,
by considering the 3c-4e bonding model (cf. Sec. 9.12.11
m
and 9.23) along with the 2c-2e bonding model, the bonding in the said geometries like trigonal bipyramid,
square pyramid, octahedron, etc. can be explained. It should be mentioned that in 3c-4e bonding model
he
(cf. Figs. 9.12.11.1-2), only one bonding pair is spread over the three nuclei and consequently the
bond order in each linkage is 0.5. Such bonds (with bond order = 1/2) (Le. trans-arganic bonds in the
Pauling concept) are weaker than the normal2c-2e bonds (with bond order = 1). In the 3c-4e bonding
lc
model, the nonbonding pair is mainly localised (cf. Figs. 9.12.11.1-2 and Sec. 9.23) on the terminal
atoms which are more electronegative.
ea
• Correlation between the Pauling concept and 3c-4e bon~ing model: The 3c-4e bonding model
leads to placement of 2e in crnb MO which is mainly localised on the terminal atoms. It leads to an
th
accumulation ofnegative charge on the terminal atoms (Le. separation of charge to develop the ionic
character, cf. Sec. 9.12.12). Thus the 3c-4e bonding model supports the idea of Pauling model which
e/
considers the partial ionic character in such compounds.

• Correlation between VBT concept and 3c-4e bonding model: It is important to note that in
t.m
VBT, for expansion of the octet through the participation of d-orbitals, the central atom is required to
link with the electronegative terminal atoms. On the other hand, in the light of 3c-4e, bonding model
though the participation of d-orbital is not required, it demands that the terminal atoms should be
sufficiently electronegative to stabilise the nonbonding pair (Sec. 9.12.12). Thus both VBT and 3c-4e
MOT suggest that the terminal atoms should be highly electronegative to stabilise the hypervalence
showing an expansion of octet.
Note: • Hypervalence is classically defined as expansion of octet through the formation of
3c-4e bonds. See Sec. 9.1.6 for hypervalence.
• In explaining hypervalences, all the theories, i.e. the Pauling concept, VBT concept and
MOT concept nicely agree with the demand: the terminal atoms must be electronegative.
• In 3c-4e bonding model, the terminal atoms should be electronegative while in the 3c-2e
bonding model (i.e. electron deficient bonding), the terminal atoms should be
electropositive (e.g. H;, CH; etc.). This aspect has been discussed in Sec. 9.12.12. This
3c-2e bonding is required to explain the electron deficient hypervalent compounds. These
are discussed later.
• In both 3c-4e bonding model and 3c-2e bonding model, the bond order in each linkage is
0.5.
• 3c-MOs to explain the geometries : By considering the 3c-2e bonds and 3c-4e bonds, the
molecular geometries like trigonal bipyramid, square pyramid, octahedron, etc. can be explained without
the involvement of d-orbitals. These are illustrated in 'some representative examples.
The linear segment B-A-B (say, along the x-axis) can be explained by the 3c-4e bonding model
ry
(cf. Fig. 9.12.11.1-2 and Sec. 9.23) in which the orbitals, Px(B), Px(A) and Px(B) combine to produce
three a-MOs (Le. a b , a nb , a·) in which the bonding (a b ) and nonbonding (a nb ) MOs are filled in.
ra
(i) PCIS' PFs (i.e. PXs of D3h symmetry)
ib
.tt'
Here the central atom P (3s 2

3p 3) is considered to undergo sp2 hybridisation to bind with the three
yl
equatorial X-atoms (Le. X eq ) through the 2c-2e bonds. The fourth orbital (Le. one p-orbital) filled with
two electrons participates in 3c-4e bonding to bind the two axial X-atoms (Le. Xax ). If the equatorial
m
plane lies in the xy-plane then Px and Py orbitals participate in sp2-hybridisation and the p:; orbital
participates in 3c-4e bonding.
he
P: DO DO
lc
3s 3p sp2-hybrid orbital~ Pz-orbital

ea
Three Sp2 hybrid orbitals: To bind three X eq atoms through 2c-2e bonds as usual.
P:
(Xax) + p; (P) + P: (X ax ): To produce the linear segmentXax-P-Xax through the 3c-4e bonding.
th
It explains the bond angles (Xeq-P-Xeq = 120°, Xax-P-Xeq = 90°, Xax-P-Xax = 180°), bond
lengths (axial P-X bond having bond order 0.5 is weaker than the equatorial P-X bond having bond
e/
order 1.0) and the trigonal bipyramid geometry without the d-orbitals.
t.m
,
Fig. 9.13.5.2. 30-4e bonding in the Iinear•. Xax-P-Xax segment along the z-axis (cf. Figs. 9.12.11.2,
9.12.11.7).
(ii) AB4(lp) like :SF4 (C2v symmetry)
It has got a distorted trigonal bipyramidal structure in which one equatorial position is occupied by
a lone pair (Ip). If the equatorial plane is considered to lie in the xy-plane, then the sp2 hybridisation is
carried out by the s, Px and Py orbitals of sulfur. Two of these sp2-hybrid orbitals bind two equatorial
F-atoms through the normal 2c-2e bonds as usual and one sp 2-hybrid orbital houses a lone pair. The
p;-orbital of S is used to produce the axial segment Fax-S-Fax along the z-axis through the 3c--4e
bonding (expected axial bond angle Fax-S-.Fax = 180°, found 179°).
ry
s: DO Dill]] ~ Dill]] DO
ra
3s 3p sp2-hybrid orbitals filled pz-orbital to
to house the lone pair make the Fax-S-Fax
ib
and to make two segment through the
2c':'2e equatorial bonds 3c-4e bonding
yl
If one does not consider the sp2-hybridisation, then the p~ and P~ orbitals may be considered to
m
participate in 2c-2e bonding to bind two equatorial F-atoms, and the lone pair is housed in the pure
s-orbital (Le. "stereochemically inactive lone pair). This should lead to F'eq-S-F'eq = 90° but the
he
experimentally found bond angle is 103°. It supports the approximate sp2 hybridisation in the equatorial
plane where the lone pair is stereochemically active and the deviation in bond angle (120° ~ 103°) can
be roughly explained by VSEPR. The average bond order in each S-F linkage in SF4 is given by :
lc
-1 (2 x. 1 + 2 X 0.5,_..,) =-3 ( cf. bond order In

. SF =-64 =-32) .
ea
6
4 eq UA. 4
th
(iii) ABs (Ip) like : BrFs (C4v symmetry)

It has got the square pyramidal structure. If the basal plane lies in the xy-plane then the axial
e/
A-Bax bond is considered to be a normal2c-2e by using the p~ orbitals of A and Box. The two equatorial
segments Beq-A-Beq at 90° angle are produced through the 3c-4e bonding by using the fi lied p; and p;
t.m
orbitals of the central atom.
Px Py Pz
Br: DO ~
4s to make the 2c-2e axial bond
In BrFs' the 4s orbital houses the lone pair (Le. stereochemically inactive), the p~ orbital makes
the normal 2c-2e Br-Fax bond. The linear Feq-Br-Feq segments in the equatorial plane are produced as
follows:
2p~(Feq) + 4p;(Br) + 2p~(r:q): r:q-Br-Feq (along the x-axis) through the 3c--4e bonding.
2p~(r:q) + 4p;(Br) + 2p~(r:q): Feq-Br-F'eq (along the y-axis) through the 3c--4e bonding.
(iv) ABJlp)2 'ike :CIF3 (C2v symmetry)

The molecule is T-shaped. The central atom Cl undergoes sp2 hybridi~ation (say in xy plane) and one
sp2-hybrid orbital binds the equatorial F atoms through the normal 2c-2e bond, other two sp2-hybrid
orbitals house the lone pairs in the equatorial plane. The p;
-orbital makes the linear axial segment
Fax-Cl-Fax through the 3c-4e bonding. It gives the T -shape of the molecule.
C/ : DO DO
ry
3s 3p Pz [ to make the linear axial
~ F-C/-F segment through
the 3c-4e bond
ra
If one ignores the sp2-hybridisation then the singly occupied p-orbital makes one 2c-2e bond in the
equatorial plane; one filled p-orbital makes the axial F-Cl-F segment (3c-4e bond); one lone pair is
ib
housed in the 3s orbital and the second lone pair is housed in a p-orbital in the equatorial plane.
yl
(v) Octahedral molecule AB6 'ike SF6 (Oh symmetry)
In SF6 , two sp-hybrid orbitals (say, s + Px) bearing the unpaired electrons make the linear segment
m
F-S-F "along the x-axis through the normal 2c-2e bonds. The other two filled p-orbitals
(i.e. P~ and p;) of S participate to produce two mutually perpendicular segments F-S-F along the y-
he
and z axes respectively through the 3c-4e bonding.
DO
lc
s:
3s 3p
ea
The bonding interactions are:
sp~(S) + p~(F) } Two S-F linkages (2c-2e bond) to produce the linear segment
th
F-S-F along the x-axis

and sp~(S) + p~(F)
e/
1 2 1
py(F) + py(S) + py(F) Linear F-S-F segment along the y-axis (3c-4e bond)
t.m
p~(F) + p;(S) + p~(F) Linear F-S-F segment along the z-axis (3c-4e bond)
Thus the three F-S-F segments lie mutually in perpendicular directions to give the octahedral
geometry. In this model, two S-F linkages are having bond order unity while the other four S-F
linkages are having bond order 0.5. Thus the average bond order in S-F linkage is (4 x 0.5 + 2 x 1.0)/
6 = 4/6 = 0.66. Thus the S-F bond is expected to be longer than normal 2c-2e S-F bond. But, in SF6 ,
the S-F bond is relatively shorter than the estimated single bond length by about 20 pm. It is suggested
that the partial ionic character developed in 3c-4e bonding model stabilises the S-F .bond to some
extent.
(vi) ABI'p) like :XeF6 , :SbCI:-, :SnCI:- etc.

If we consider the formation of three mutually perpendicular B-;-A-B segments (through the 3c-4e
bonding interaction), then it would lead to the perfectly octahedral geometry. In this 3c-4e bonding
interaction, the filled Px' Py and p= orbitals of the central atom participates. This aspect has been discussed
in detail in Sec. 9.23 in connection with the structure of XeF6 • This three centre bonding model keeps
the lone pair in the pure s-orbital of the central atom and thus the lone pair becomes stereochemi-
cally inactive. If the lone pair is not stereochemically active, then it will have If distorted octahedral
geometry. Whether the lone ,pair will be stereochemically active or not depends on many other factors.
However, the 3-centre model cannot predict this. All these aspects' have been discussed in Sec. 10.8.5.
Note: Explain the bonding in the hypervalent elusive molecular species NF6-, CF62- by taking the
help of 3c-4e bonding interactions.
(Viii) Bonding in hyperva/ent electron deficient molecular species
ry
The compounds like CH;, CH~+, C(AuL);, C(AuL)~+, N(AuL);+ (L = PR3 ), etc. are sometimes
described as electron deficient hypervalent compounds. This is explained by considering the 3c-2e
ra
bonds in addition to the nonnal 2c-2e bonds. The 3c-2e bonding model is very much similar to the
3c-4e bonding model. In3c-4e bonding model, the nonbonding MO is filled in by two electrons
ib
while in 2c~3e bonding model the nonbonding MO remains vacant (cf. Sec. 9.12.12). In 3c-4e bonding
scheme, the tenninal atoms should be electronegative while in the 3c-2e bonding model, the terminal
yl
atoms should be electropositive. In both models, the bond order in each linkage is 1/2. It may be
noted that the segment (say B-A-B) is bent for 3c-2e bonding. All these aspects have been discussed
earlier (cf. Sec. 9.12.12). ~
m
Let us illustrate bonding in CH; (which was characterised in superacid matrices) and CH~+.
he
Sp3
lc
C: (4 C-H bonds, 2c-2e bonds)

ea
pz
C: rn Bent HaC-He axial segment, 3c-2e bond

th
three equatorial
10.....-_1
e/
C-H bonds (xy-plane),

2c-2e bonds
t.m
Le. C-Ha , C-Hb

and C-Hc
en; possesses a distorted structure rather than the symmetrical trigonal bipyramidal.structure.
It indicates that three equatorial C-H bonds are produced by thr~e sp2 hybrid orbitals through the
nonnal 2c-2e bonding interaction while the other two axial H-atoms· are linked through the 3c-2e
bonding interaction by using the pure pI orbital of..carbon. This axial HaC-He segment is angular~
c[IIJ
sPz px py
2c-2e bonding 3c-2e bonding interactions, Le. bent Ha-C-Hd
C-He and C-Hf and Hb-f;-Hc segments in xy-plane
along the z-axis
D. Merits and demerits of the 3-centre bonding model without the d-orbital participation in
the compounds of main group elements
It has been discussed that without using the d-orbitals, the molecular geometries like trigonal bipyramid,
square pyramid and octahedron can be explained. It needs the consideration of three centre bonding
model (Le. 3c-2e, 3c-4e). This concept requires the participation of s- and p-orbitals only. In some
cases (e.g. octahedral system, square pyramidal system, etc.), participation of p-orbitals only is
sufficient. Thus the participation of s- and d-orbitals in such cases may be ignored though there is no
objection in s-p mixing. To ignore the contributio~ of sand d-orbitals, it is argued that the s-orbital is
ry
of very low energy (Le. deeply seated) and the d-orbital is of very high energy. Consequently, they
remain as nonbonding ones. However, complete omission ofs- and d-orbitals in these bondings is a
ra
ruthless approximation. .
• Geometry ofthe molecules: The observed bond angles like 90 0 and 1800 in the geometries like
ib
squat:e pyramid and octahedron can be explained by using the p-orbitals only in 3-centre bonding
model. However, this 3-centre MOT cannot explain whether the lone pair will be stereochemically
yl
active or not.
• Bond length parameter : The 3-centre bonding scheme without involving the d-orbitals is a
m
qualitative model. It fails to explain the structural properties in many cases. For example in :SF4
(trigonal bipyramidal geometry having two equatorial and two axial F-atoms, and the lone pair
he
in the equatorial plane), the linear segment F-S-F in the axial direction involves the 3c-4e
bonding (Le. bond order in each S-F linkage along the axial direction = 0.5). On the other hand,
the equatorial S-F bonds are normal 2c-2e bonds (Le. bond order in each linkage = 1). It is
lc
expected that the axial S-F bond should be much longer than the equatorial S-F bond. But in
reality, the bond lengths differ by 10 pm only. Similarly in SF6 , the bond is expected to be longer
ea
than the single S-F 2c-2e bond. But in reality, in SF6 , S-F bond shorter than the S-F bond by
about 20 pm. It is believed that the ionic character in S-F-F (3c-4e) bonds (cf. Sec. 9.12.12)
th
shortens the bond length.

In XeF2 , the Xe-F bond (200 pm) is longer than the calculated single Xe-F 2c-2e bond. It
e/
supports qualitatively the 3c-4e bonding scheme in XeF2•

• Possibility of d7t-P7t bonding (cf. Sec. 10.7) : We have already discussed the possibility and
t.m
objection of participation of d-orbitals in the a-bonding schemes of main group elements. But, in
many cases, participation of d-orbitals in 7t-bonding has been strongly argued (Sec. 10.7).
The d7t-p7t bonding is well documented in Si-X, Si=O, P=O, P = N, .S= Nbonds (cf. Sec. 10.7).
In the tetrahedral species AB4 like SiF4 , 8iO:-, PO~-, the a-bonding framework is constituted
by the sp3-hybrid orbitals of the central atom A, but the empty d-orbitals of A can participate in
pi-bonding with the filled p-orbjtals ofthe terminal atoms B. The filled p-orbitals of B are mutually
perpendicular and these are also perpendicular to the A-B linkage. Among the d-orbitals of A,
the d x2 _ 2 and d.. 2 are more suitable than the other d-orbitals for the said d7t~ P7t bonding
interacti~. This it-interaction using the d x 2 -y2 orbital of A is illustrated in Fig. 9.13.5.3.
Among the oxyanions, the efficiency of 41t-p7t bonding increases as :
CIO; > 80I- > PO~- > 8iO:-
This aspect has been discussed and its effect on the extent of polymerisation has been pointed
out in Sec. 10.7.
Introduction to Chemical -Bondi~g and Theories of Covalence 693
ry
ra
ib
yl
Fig. 9.13.5.3. d1t-p1t interaction in a tetrahedral species AB4 through the overlap of the d 2 2 orbital
m
of A with one p-orbital of B. (The axes of the coordinates pass through- the centres of theYfaces of
the cube).
he
The structural features and Lewis basicity of the species N(CH3)3 (pyramidal), N(SiH3 )3 (planar),
N(GeH3)3 (planar), P(SiH3)3 (planar) can be explained by considering the d 7C-P7C bonding. The
lc
drt-P7C bonding by using the filled 2p-orbital of N and vacant d-orbital of Si and Ge makes
the Si)N and Ge)N arrangements planar. The pi-bondings are:
ea
N(2p) 7t ) Si(3d) and N(2p) _7t---+) Ge(4d) .

th
In fact, ~ecause of this 7t-bonding, the bonds are shorter than the single bonds. In the case of
(CH3)3N , there is no question ofsuch d 7C-P7C bonding as C does not have any d-orbital. In P(SiH3)3'
e/
the P(3p)~ Si(3d) bonding is inefficient because of more diffuse character of

the 3p-orbita/s ofP. It makes, P(SiH)) pyramidal. However, some authors have attempted to
t.m
explain these observation in terms of steric crowding not in terms of dft-Pft bonding. When
steric crowding around the central atom increases, it tends to attain the planar geometry (Le.
bond angle increases from 109° to 120°). Thus compared to N(SiH3 )3' in P(SiH3 ) the steric
repulsion is less important because of the larger size of P. Sin:tilarly, among the C3N, Si 3N and
Ge 3N units, the steric crowding around the N-centre is minimum in C 3N. This aspect has been
discussed in Sec. 10.7(i).
In the cases like, -S-N==S-, F 3S ==N where the S-N bonds are very short, the d 7C-P7C bonding is
probably more important.
9.13.6 Equivalence and Nonequlvalence of the Hybrid Orbitals

The hybrid orbitals in most of the cases are equivalent. These are: sp, sp2, sp3, sp3tfl, etc. But there are
~_cases in which the hybrid orbitals are nonequivalent. This nonequivalence is found in sp 3d and
3 3
sp d hybridisations. '
• sp3d (trigonal bipyramid Le. TBp) : Here, three equivalent hybrid orbitals developed from (s +
Px + p y ) lie in the equatorial plane (Le. xy-plane) at 120°, and other two equivalent hybrie orbitals
developed from (p z + d.,.2) project mutually at 180° in the axial directions. The axial hybrid orbitals
are devoid 0/ any s-character. Thus there are two sets of hybrid orbitals, Le. a set of three equivalent
equatorial hybrid orbitals and a set of two equivalent axial hybrid orbitals. This idea has been
established from the experimental findings in PCls in which the three equatorial chlorines are different
from the two axial chlorines. The equatorial P-CI bond (204 pm) is shorter than the axial P-CI
bond (219 pm). If different atoms of different electronegativity are bound to the central atom, then
ry
Bent's rule (see Sec. 9.13.7) will determine the positions of the different atoms of different
electronegativity in the trigonal bipyramidal geometry.
ra
Note: In a TBP geometry, in terms of VSEPR, each axial electron pair experiences repulsions at
90° from 3-equatorial pairs while each equatorial pair experiences two such repulsions from the axial
ib
pairs. It makes the axial bond relatively larger.
• sp3d (square pyramid) : The combination can be split as : s + Px + Py + d x2 _ 2 and Pz • Thus
yl
the four equivalent hybrid orbitals are lying in the basal plane (Le. xy-plane) while th: fifth one is the
pure p= orbital lying perpendicular to the xy-plane. Here also the Bent's rule is applicable to determine
m
the positions of different atoms of different electronegativity.
For 5-coordination, there are two possible hybridisations leading to trigonal bipyramid (TBP) and
he
square pyramid (SP). Generally, the nonmetals prefer the TBP-structures. Some coordination compounds
are known to have SP-geometry. However, the energy difference between these two configurations for
lc
the compounds like AXs is very small. As a result, in some compounds ofAXs type, there is an
equilibrium leading to TBP ~ SP. In such cases, the structural properties are the weighted average
ea
ofthe two configurations. Some examples ofthis type ofcompounds are CdCl;-, P(C 6 H s)s' Ni( CN)~- ,
etc. As a matter of fact, this low energy difference between TBP and SP gives the key factor in Berry
th
pseudorotation (see Sec. 10.9.2).

• sp3tP hybridisation (pentagonal bipyramid) : This combination can be split into two sets (s + Px
e/
+ Py + dxy + d x2 ~ 2) and (Pz + d z2 ). The first set produces 5 equivalent orbitals in the xy-plane to
t.m
produce the basal Yplane while the'second set produces two equivalent hybrid orbitals (having no
s-character) perpendicular to the basal plane along the axial direction (Le. +z and -z directions).
• Presence 0/ nonequivalent group and lone pairs (cf. Bent's rule) : The above examples show
that these hybrid orbitals are nonequivalentfrom the standpoint oftheir genesis. But the equivalent
hybrid orbitals (e.g. sp3 hybrid orbitals) may become nonequivalent, if the atoms or groups binding
with the central atom differ significantly in electronegativity. Even in some cases when some of the
hybrid orbitals are occupied by the lone pairs, the equivalent hybrid orbitals may lose their equivalent
character in the compounds formed.
To clarify the above points, let us take the following cases. In CH4 and CCl4, all the bond angles are
109°28' as expected from the sp3 hybridisation but in CH3Cl or CHC!.J the bond angles are different. In
CH3Cl, H - C- H angle is 110° which is different from H - C - Cl; similarly in CHCl3 , the
Cl- C- Cl is different from Cl- C- H. These variations can be nicely explained from principle of
Bent's rule based on the electronegativity difference among the combining atoms or groups.
Introduction to .Chemical Bonding and Theories of Covalence 695
The observed bond angles, H - 0 - H (= 104° 28') and H - N- H~(= 106° 48') are different from
the tetrahedral bond angle (= 109° 28') in H 20 and NH3 respectively. This is due to the different effects
(see VSEPR theory) of the lone pairs and bonding pairs occupying the hybrid orbitals. This difference
in bond angles arises due to the nonuniform distribution ofthe character ofdifferent atomic orbitals
in the bonding and nonbonding hybrid orbitals. For example, in the combination of sand p, with the
increase of p-charact~, the bond angle decreases. This is illustrated in Table 9.13.6.1. Hence in H 20,
the decrease of H - 0 - H angle by ~ 5° from the tetrahedral bond angle indicates that the orbitals
holding the hydrogens are containing more p-character (Le. p-character > 75% and s-character < 25%)
ry
and the nonbonding orbitals housing the lone pairs bear p-character less than 75% (Le. s-character >
25%).
ra
Table 9.13.6.1. Bond angles in (s + p) combination.
Hybridisation % character
ib
s p Angle
sp (linear) 50 50 180
yl
1 2
sp2 (trigonal) 33- 66- 120
3
m 3
sp3 (tetrahedral) 25 75 1090 28'
p2 (Le. two pure p-orbitals) o 100 90
he
The higherpercentage ofs-character in the hybrid orbitals housing the lone pair can be explained
by Bent's rule (Sec. 9.13.7).
lc
The percentage ofp- or s-character in two adjacent and equivalent hybrid orbitals can be determined
ea
from the knowledge of the corresponding bond angle (9) as :

cos e:= (p - 100)/p = s/(s -100)
th
where p and s denote the percentage of the corresponding orbital. Thus in water,
cos 104°28' = - 0.25 = (p - 100)/p; or, p = 80%; and, s = 20%.
e/
Thus the percentage of p- and s-character in the two nonbonding orbitals bearing the lone pairs are
obtained as follows:
t.m
I -I
P = 2" (3 - 2 x 0.80) x 100 = 70%, and s = 2" (1 - 2 x 0.20) x 100 = 30%
Now, the angle (cP) between the axes of the nonbonding orbitals housing the lone pairs can be
obtained as follows, .
cos cP = (p -IOO)/p = (70 - 100)/70 = - 0.428 = cos I i5°38'; or, cP = 115° 38'
9.13.7 Bent's Rule of Hybridlsatlon (see Sec. 10.8 for some applications of the rule)
Selection ofdifferent hybrid orbitals (bearing different extents ofdifferent pure atomic orbital characters)
by different atoms or groups differing significantly in electronegativity is .governed by Bent's rule of
isovalent hybridisation. The rule has been formulated as follows:
(i) The more electronegative atom or group will withdraw the bonding pair more from the central
atom to itself. This can be facilitated if the electronegative group or atom shares such a hybrid
orbital in which the central atom has utilised less s-character. This poor s-character indicates that
the central atom has got no strong influence to hold the electron cloud to itself by using this type
of hybrid orbital. Because ,it is known that by using the s-orbitals, the electron cloud can be most
tightly bound. This is why, the electronegative moiety always prefers the hybrid orbital ofthe
central atom in which the s-character is less. Eventually, it leads to more ionicity in the covalent
bond.
(ii) If the electronegativity difference between the bonding moieties (Le. central atom and other
bonding atom or group where the central atom is less electronegative) is significantly large, then
the corresponding bond will possess some ionic character. This will lead to the shifting of
ry
bonding electron pair to the more electronegative terminal atom or group. This electron shifting
is favoured nlore if the central atom utilises a hybrid orbital having less s-character. Thus, with
ra
the increase of difference of electronegativity between the combining species, the covalency
decreases. In such cases, the central atom uses the hybrid orbitals having less s-character towards
ib
the more electronegative bonding moiety, because utilisation of such hybrid orbitals favours
the generation of more ionic character.
yl
Thus the more ionic character (i.e. poorer covalency) in a bond (due to the more electronegative
substituent to the central atom) leads to the utilisation of hybrid orbitals containing more
m
p-character (i.e. less s-character) of the central atom. In other words, the more covalency in a
particular bond encourages the central atom to utilise its hybrid orbitals which contain more
he
s-character.
This poor covalency may result not only due to the electronegativity difference, but it may also origin-
ate due to the poor overlap, as a result ofeither steric hindrance or mismatch of the overlapping orbitals.
lc
Thus, the Bent's rule can be stated as follows:

ea
(a) The central atom projects the hybrid orbitals ofgreater p-character (Le. less s-character)
towards the more electronegative substituent. It leads to more ionicity in the covalent bond.
th
This is 'he classical form ofBent's rule.

(b) The central atom projects the hybrid orbitals ofgreater p-character (Le. less s-character)
e/
towards the more ionic bond and the hybrid orbitals ofgreater s-character towards the
more covalent bond.
t.m
(c) The central atom projects the hybrid orbital of more s-character towards the bond where
covalency is very strong. The strong covalency arises from the factors like small,
electronegativity difference, good overlap and existence ofn-bonding. On the other hand,
the hybrid orbitals enriched with p-character are projected towards the directions where
covalency is weak. This is why, the Bent's rule is restated as follows: s-orbital enriched
hybrid orbital ofthe central atom is concentrated along the strong covalent bonds.
Note: The overlap integral (which determines the covalent bond strength) for the s-p hybrid
orbital is a complicated function of the s- or p-character (cf. Fig. 10.1.7.1). It may be mentioned that
the angular strength (cf. Sec. 9.13.3) is not the sole factor to determine the overlap integral. For
example, sp3 hybrid orbitals having angular strength 2.0 possess smaller overlap integral in the C-C
and C-Hbonds compared to the sp hybrid orbitals of angular strength 1.93 (cf. Fig. 10.1.7.1). It is
due to the fact that the size of the major lobe of the sp-hybrid orbital is higher than that of the sp3
hybrid orbital (Sec. 9.13.3).
Illustration of the Bent's Rule

(i) H]CF: In a perfectly tetrahedral system (i.e. sp3 hybridisation) in each bond, C projects 75%
p-character and 25% s-character. The bond angle is 109°28'. Increase ofs-character and decrease
ofp-character widen the bond angle (cf. 180° for sp, 120° for sp2, 109°28' for sp3). Here, the
C-F bond should have less than 25% s-character of C and consequently the C-H bonds should
have more than 25% s-character of C. Thus, the less p-character (i.e. < 75%) in the C-H bonds
tends to extend the H -C -H angle greater than 109°28'. Besides, the greater s-character in the
C-H bonds tends to shorten the C-H bonds. This enhances the bond pair - bond pair repulsion to
ry
widen the H -C -H bond angle.
(ii) PC/]FZ : The molecule has got a trigonal bipyramid (TBP) structure. The two fluorine atoms
ra
preferably are positioned in the axial directions. The axially orientated hybrid orbitals
(Le. pd; p= + d:: 2 ) having no s-character bind the more electronegative substituent, i.e. F.
ib
The tendency of more electronegative substituents to occupy the axial or apical pd-hybrid orbitals
of low electronegativity in TBP geometries is referred to as apicophilicity. In MePF4, Me 2PF3
yl
the more electronegative F-atoms tend to occupy the axial positions while the Me-groups of low
electronegativity occupy the equatorial positions.
m
CH] radical vs. CF] radical (cr. Sec. 10.8.3)
he
Bent's rule: The CH3 radical is planar and carbon is sp2 hybridised to house the odd unpai.red
electron in a pure p-orbital. On the other hand, CF3 radical is pyramidal i.e. here carbon is sp3
lc
hybridised and the unpaired electron is housed in a sp3-hybrid orbital. This difference can be
" This
explained by considering the Bent's rule. Fluorine is more electronegative than hyqrogen.
ea
is why, fluorine directs carbon to project the s-p-hybrid orbital having more p~character.
Between sp3 (75% p-character) and sp2 (66.6% p-character) hybrid orbitals, fluorine prefers the
sp3 hybrid orbital of carbon having relatively smaller s-character.
th
./,pure-p
, y-Sp3
e/
tJ. . "H 0r Sp3 (C)

t.m
H--O~H Sp2 (C) /c ..

\" F \""F
F
VSEPR theory (cr. Fig. 10.8.3.4) : The C-H bond length is shorter than the C-F bond length
(cf. C-H in CH4 = 109 pm, C-F in CF4 = 136 pm). Because of the higher electronegativity of
fluorine, the bond pair of C-F bond is attracted more towards fluorine. Because of the slightly
higher electronegativity of carbon (with respect to hydrogen), the bond pair of C-H bond is
slightly attracted towards carbon. Thus, the bond pair-bond pair (bp-bp) repulsion in eH] is
much higher than that in CF]. To minimise this bp-bp repulsion in CH3, it adopts the sp2_
hybridisation where bond angle is higher than that in the pyramidal structure having sp3
hybridisation. In fact, in CH3, bp-bp repulsion operates at 120° and the odd electron-bond
pair repulsion which is relatively less operates at 90°. In CF3, bp-bp repulsions are less and it
adopts the sp3 hybridisation and all the repulsions occur at about 109°28'.
(iii) Position of a lone pair: The Bent's rule is very much important in predicting the position of a
lone pair. There is a basic difference (see Fig. 10.8.3.3) between the lone pair and bond pair. The
bond pai~ remains under the control of two bonding nuclei while the lone pair remains under
the influence of the central nucleus alone. Thus the central atom tends to hold the lone pair
cloud tightly and it can be attained if the central atom can utilise the orbital enriched in s-
character in housing the lone pair. This is why, in H 20, the lone pairs are housed in the orbitals
where the s-character is greater than 25 % •
Similarly in elFl (sp 3d, TBP hybridisation), the two lone pairs are housed in the equatorial
ry
hybrid orbitals where the s-character is maximum and the more electronegative F atoms go
preferably to the axial directions where there is no s-character. Of course, the third F atom
ra
having no other option will have to occupy the third equatorial position. The results predicted
from the Bent's rule are in good conformity with those obtained from VSEPR theory.
ib
Bent's Rule vs. VSEPR Theory
VSEPR rule (dealing with the effect of electronegativity of the substituents) and Bent's rule
yl
give the same conclusions in most of the cases.
m .
(iv) Effect ofthe strength ofcovalency and pi-bond on hybridisation : When the bonding atoms are
of comparable electronegativity, the pi-bonding in a particular direction may shorten the bond
he
length in that direction giving rise to a better covalency compared to the direction having only
sigma bond. Thus, the central atom pr_ojects more s-character in the direction where both
the pi- and sigma-bonds are formed to ensure the better covalency. In the phosphate compo1Jnd,
lc
(RO)2P(==O)Br, phosphorous is tetrahedrally hybridised where the least electronegative substituent

ea
is Br. Hence, in terms of the classical form of Bent's rule, it is expected that the P-Br bond
should contain the highest amount ofs-character of P but the P == 0 bond is maximum enriched
in the s-character of P. This is reasonable. The orbitals of Br are larger and more diffuse and
th
consequently the overlapping of the Br-orbitals with those of the relatively smaller P-atom
is inefficient. This weakens the covalent interaction in the P-Br bond. The 7t-bond shortens
e/
the bond length in the P == 0 bond giving a better covalency and as a result, the central atom uses
its maximum s-character in that direction. In fact, the bond energy runs in the sequence :
t.m
P = 0 ) P - 0) P - Br and this is why the P-atom concentrates s-character maximum along the
P = 0 bond.
110 pm
Strongest (maximum ~ 146 pm 105 pm
bond
~II~
0 s-character of P)
~fc C
1 H
(H 1100 1 4 ' \ '-120 pm

/P ~weakest bond
RO Br (minimum a < 109°28' s-character concentrated
1
OR s-character of P) by sp'3-C to form the strong
C-C covalent bond
The relatively smaller sp-C tends to form a stronger covalent bond with the Spl-e, atom. In
fact, the bonding potentiality of the sp-hybrid orbital is maximum (Sec. 9.13.3) among the sp3,
Sp2 and sp hybrid·orbitals (cf. Sec. 9.13.3). It directs the sp3_C atom to project the s-character
enriched hybrid orbital towards the sp-C. This explains the structural features of the above
compound.
Here, it may be noted that in terms of simple electronegativity effect, the more electronegative
sp-C should direct the sp3_C to project the hybrid orbital having less s-character. But the covalent
bond strength factor opposes this demand. Other applications of the Bent's rule will be
discussed in the next chapter (see Sec. 10.8).
Note: The classical form of Bent's rule cannot explain the experimental findings of the above
ry
two examples.
ra
9.14 SUMMARY OF THE CONCEPT OF HYBRIDISATION
ib
(i) The atomic orbitals of comparable energy'on the same atom can hybridise. If the starting atomic
orbitals differ significantly in energy, the cost of hybridisation energy (Ehy) will be high to make
yl
the process insignificant.
(ii) The hybridisation occurs through the LCAO of the combining orbital wave functions. The
~umber of hybrid orbitals is given by the number of participating atomic orbitals.
m
(iii) Promotion of the electrons is an essential step to carry out the hybridisation but the promoted
he
electrons do not necessarily participate in the hybridisation. It occurs in the case of multiple
bonding. Generally, the sigma bonding electrons and lone pairs (i.e. nonbonding pairs)
occupy the hybrid orbitals while the electrons occupying the unhybrid c,rbitals participate.
lc
in pi-bonding.
For the nonmetals, the d-orbitals can only participate when the central nonmetallic atom
ea
combines with the highly electronegative moieties.

The hybrid orbitals are having much greater bonding potentiality compared to ·the starting pure
th
atomic orbitals, as the hybrid orbitals concentrate their electron clouds mainly in some particular
directions of covalent bond formation.
e/
The hybrid orbitals may be equivalent or not.

The hybridisation defines a geometry of the molecule. It depends on the angular distribution
t.m
function of the combining atomic orbitals.

Bent's rule: The central atom projects more p-character to the more electronegative substituent,
and to the bond having more ionic character (Le. poorer covalent character); on the other hand,
the central atom projects more s-character to the lone pairs, less electronegative substituents,
predominant and strong covalent bonds and multiple bonds.
9.15 CONJUGATED MOLECULES AND DELOCALISATION ENERGY

In the conjllgated polyenes, the carbons are sp2 hybridised to provide the sigma skeleton ofthe molecule.
If the skeleton lies on the xy-plane, then each carbon possesses a Pz orbital perpendicular to the c-e
chain. These Pz orbitals may undergo a pi-type interaction through LCAO to form molecular orbitals.
Here we shall pay attention only to the 7t-MOs. The procedure is known as Hackel molecular orbital
method to honour the scientist who contributed as a pioneer in this discipline. The calculation of
energy is done by the variation r.nethod through the establishment of n (when n number ofPz orbitals are
involved in LCAO) number of simultaneous linear equations. The molecular orbital wave function is
expressed as:
n n
\jIpj-MO = LCj\jl2pz(i);and LC; =1
;=1 ;=1
In the present system, the overlap integrals (Sij) are assumed to be zero in the HUckel's approximate
method.
= f'V2 Pz (.) 'V2 Pz(.)J dt = 0
S..IJ
ry
I
It appears that the AOs are orthogonal. Similarly, S.. = f'V2 P (.) 'V2 P (') dt =1,
II I I
since the AOs are
z z
ra
normalised.
Thus the energy ofthe 1t- MOs is always expressed in terms of Coulomb integral (a) and resonance
integral (~) as defined below:
ib
a. = f\jl2pz(i) Ii \jI2pz(i) dot; 13 = J\jI2pz(j) Ii \jI2pz{j) d't
yl
Here, i-th and j-th carbon atoms are directly bonded..The significance of a and Phas been already
discussed in Sec. 9.4.1. Now let us ill~trate the method in some representative cases.
m
(a) Ethylene Molecule (C2H 4) : Here two adjacent C-atoms provide two parallel p= orbitals for
he
LCAO. It leads to two pi-MOs, one of which is bonding and another one is antibonding.
'Vn-MO = N 1 ['V2pz(C + lV2pz(C E = a +~;

1
)
2
)]'
lc
and \jI:-MO =N2 [\jI2pz(C.) -\jI2Pz(c )],E* =0.-13 2

ea
The two electrons will reside in the bonding 1t-MO. Thus the ground state electronic energy of
the 1t-system is given by, 2 (a + ~). The 1t-electrons are distributed as :
th
1t~1t·0
The energy of the two isolated electrons in two 2pz orbitals is 2a. Thus on LCAO the energy is
e/
decreased (~ is a negative quantity).

The orbital picture of ethylene is given in Fig. 9.15.1.
t.m
----+ "<2:)/
C1- - C2 and ~C 1- C2 ~ -
/ ~" - n-ABMO +
n-BMO (HOMO) (LUMO)
Fig. 9.15.1. The orbital picture of C2 H4 •
(b) Butadiene Molecule (C4H,) : Here, four 2pz orbitals on the adjacent C-atoms undergo LCAO to
form a set of four 1t-MOs. Detailed calculations show:
'Vl(n-MO) = c1'V2pz(C + c2 'V2pz(C + c3'V2pz (C + c4 'V2pz(C
1
)
2
)
3
)
4
)
'V2(n-MO) = c 2 'V2pz(C1) + c1'V2p z (C z ) - c4 'V2pz(C3 ) - c3 'V2pz (C4 )

Introduction ,to Chemical Bonding and Theories of Covalence 701
'V 4(n-MO) = CI 'V 2pz(C.) - C 2'V 2p z (C2 ) + C3 'V 2pz {C) - C4 \V 2pz{C4 )
where, c I = c4 = 0.372; and c2 = c3 = 0.602

The 1t-MOs, Le. 'VI' 'V2' 'V3' 'V4' delocalise over the whole molecule. The energies of the MOs are
given by,
£1 = a + 1.618p; £2 = a + O.618p; £3 = a - O.618p; £4 = a - 1.618p.
ry
The four electrons occupy the lowest two 1t-MOs, Le. 'V~ and 'V;. Thus the energy of the system
is given by,
ra
2£1 + 2£2 = 2 (a + 1.618 P) + 2 (a + 0.618 P) = 4a + 4.472p.
ib
The MOs are shown in Fig. 9.15.2.
c__
yl
m ~
+ __
Tt-BMOs
(stabilised
he
with respect to the
the Pz-orbitals)
lc
LUMO
ea
th
HOMO
e/
1t'*-ABMOs
(destabilised
with respect to the
t.m
0\ I,a I (.;) I /) the pz-orbitals)

~ ,VIV,
, I ,
17
----+ C1 --+- C2 --+- C3 --+- C4 '114
~ 11\1,1\1 ~
(7 'tJ'\:)' X)
Energy order: '111 < '412 < '413 < '114
Fig. 9.15.2. "The pi-molecular orbitals of butadiene.
Note: Resonance is possible in C4 Ha Le. HzC ~ CH \ ....P H z. Free butadiene can exist
in cis- and trans forms.
cis-form :
~
1/ \\ i.e.
pq
1.< "\ trans-for.m:
J
r' i.e. F~I I
For the sake of simplicity, we have considered the linear segment.

Delocalisation energy in butadiene: Due to the formation of the delocalised 7t-MOs throughout
the molecule rather than the localised ones (as in VBT), it lowers the energy of the system
according to the principle of the model (see Sec. 3.5.2), particle in a box. If the 7t-MOs were
localised between the adjacent nuclei, then the butadiene molecule could be considered as the
sum of two isolated ethylene molecules. If this were ~he model for butadiene, it would have
energy 2 (2a + 2~) Gust by doubling the energy of an ethylene molecule) instead of(4a + 4.47~)
as obtained through the formation of the deiocalised 7t-MOs. Thus, it is evident that through the
delocalisation of the MOs throughout the molecule, it stabilises the system by, (4a + 4.47~)
ry
(4a + 4~), Le. O.47~. This excess stabilisation energy is called delocalisation energy. Thus the
delocalisation energy can be defined as the difference in stabilisation energy between the actual
molecule considering the delocalised pi-MOs and the hypothetical one in which tt)e 7t-bonds are
ra
localised between the adjacent C-atoms as in the case of ethylene.
Lowest transition (1t MO ~ 1t ~o) frequency: It involves the transition of an electron from the
ib
highest occupied molecular orbitals (HOMO) to the lowest unoccupied molecular orbital (LUMO).
yl
In ethylene, \VI ~ \V2' I1E = (a -~) - (a +~) = - 2~
In butadiene, \V2 ~ \V3' ~ = (a - O.618~) - (a + O.618~) = -1.236~
m
It indicates that butadiene absorbs light at a lower frequency compared to ethylene. The
7t ~ 7t* transition helps to determine the resonance integral from the experimental data. In general,
he
it is found that with the increase of conjugation in the linear polyenes, the frequency of
transition moves to the lower region, i.e. red or bathochromic shift.
lc
(c) Benzene Molecule: By considering the six 2P:: orbitals on six C-atoms we get six pi-MOs
through LCAO as follows (where 'VCi represents.the wave function of2pz orbital of the i-th C-
ea
atom).
1
= J6 [\jICi + \jIC2 + \jIC3 + \jIC4 + \jIcs + \jIC6]
th
\jI1(ll-MO)
1
e/
\jI2(1l-MO) = 2J3 [2\j1 CI + \jI C2 - \jI C3 - \jIC4 - \jI cs + \jI C6]

t.m
1
\jI3(ll-MO) ="2 [0 X \jICI + \jIC2 + \jIC3 + 0 x \jIC4 - \jIcs - \jIC6]
1
\V4(1t-MO) ="2[Ox\VC) +\VC2 -\VC3 +Ox\VC4 +\Vcs -\VC6]
1
\jIS(ll-MO) = 2J3 [2\j1CI - \jIC2 - \jIC3 + \jIC4 - \jIcs - \jIC6]
1
\jI6(1l-MO) = J6 [\jICI - \jI C2 + \jIC3 - \jI C4 + \jICS - \jI C6]
The energies of the lowest three 1t-MOs are: E) = a + 2~, E2 = E3 = a + ~. Thus, the energies of
the three 7t-MOs, Le. 'VI' 'V2 and 'V3' are lowered compared to the noninteracting AO system
while for the other three 7t-molecular orbitals the energy is increased compared to the starting
system. This is why, the first three are called bonding n-MOs (BMOs) while the other three
form a set of antibonding 1t-MOs (ABMOs). Thus, they are: bonding n-MOs = \fI1' \fI2' \fI3;
antibonding n-MOs = \fI4' \fIs, \116. These are shown in Fig. 9.15.3.
The six n-electrons will go to the lowest three n-MOs. Hence, the energy of the system is given
by: 2£1 + 2£2 + 2£3 = 2(a + 2B) + 2(a + B) + 2(a + B) = 6a + 8B. Thus, the delocalisation
energy is given by:
delocalisation energy = (6a + 8B) - 3 x (energy of an ethylene molecule)
= (6a + 8B) - (6a + 6B) = 2B.
ry
;'
;'
(U-2 P)} i
ra
=========== (u - P)
;'
,;
~
,,"
ib
;'
six Pz{c) ,./""""

'1 1 ,.;'" ""
1'I . -<!."
fl '~~"
yl "<:"'"
"""~~" q~1~ /3)} ~ .
m (a +
"'~~f+r~--- {u + 2P
he
-------------
\JI2
lc
3n-BMOs
ea
Fig. 9.15.3. The Huckel pi-molecular orbitals of benzene.

Note: Huckel molecular orbitals cannot explain the 1t ~ 1t* transitions; see Sec. 12.5.10 of Vol. 7.
th
(d) Phosphazene Molecule (PNX2)3: The phosphonitrilic halides (X = F, Cl, Br) produce a large
number of cyclic compounds. In (PNX2)3, through the participation of three p-orbitals of three
e/
nitrogen atoms and three d-orbitals of three phosphorous atoms in LCAO, the delocalised molecular
t.m
orbitals will be formed as in the case of benzene. As a matter offact, the phosphazene molecule
shows the aromaticity (see Sec. 10.7.6) but the delocalisation energy is less compared to that of
the benzene system. It occurs so, because in the lowest pi-bonding MO, there is a node while
no such node exists in the case of benzene at its lowest 1t-MO. The bonding interaction in
(PNX2 )3 has been discussed in Sec. 10.7.6 in terms of both Craig-Paddock model and Dewar
model.
(e) Borazine Molecule (B~~6): It also possesses a delocalised molecular orbital with an aromatic
property. Here, the p-orbitals of Band N undergo LCAO to from the n-BMOs. Here, all B-N bond
lengths are equal (= 144 pm) and these are shorter than the single B-N covalent bonds (156 pm).
It supports deloc~lisation throughout the ring as in benzene. Here no mismatch of symmetry
leading to a node at the lowest n-MO exists. It may be noted that in (NPX2)3, there is a node in
the lowest n-MO (cf. Sec. 10.7.6). The MOs'are very much comparable with those of benzene.
But, due to the difference in electronegativity between Band N, the bonding MOs are enriched
with the properties of the AOs of more electronegative centre nitrogen. Consequently, it induces
a polarity in the bonds. Ultimately, because of the difference of electronegativity, the electron
H
1+
H,_/N0 /H
B ~B-
It I ~
+N N+
H/ '-.BJY 'H
I
H
ry
ra
ib
yl
m(b)
Fig. 9.15.4. Structural representation of borazine (B3 N3 He), benzene (CeH e), and the saturated product
borazane.
he
clouds get preferably localised on the nitrogen atoms. Because ofthis localisation ofthe electron
clouds, the aromaticity ofborazine is reduced and it is more reactive than benzene.
lc
The polar reagents like HX can add to the double bonds of B)N)H6 to give the saturated products
(Le. borazane). The negative group of HX adds to the B-centre through the nucleophilic attack
ea
while the electrophile Jr attaches to the N-centre.

B)N)H6 + 3HCl ~ B)N)H9CI); cf. C6H6 + HCI ~ no reaction.
th
The saturated products (borazanes) of B)N)H6 are comparable to cyclohexane. The saturated
products lose the planarity of borazine. The borazanes may exist in both chair ,and boat
e/
conformations where the chair form is probably more stable.

t.m
(f) Example of a-delocalisation : Delocalisation ofthe n-electron is well known, but the following
example illustrates the delocalisation of a-electron.
~/R
Si
~/ '" /R
fV"r r"R
R~Si )i/
R
fV" /""-
"'-si "R
R R
The extra electron exists in the delocalised cr·-orbital embracing all the six Si-centres.
In fact, electrons present in multicentred a-MOs experience a-delocalisation.
9.16 RESONANCE AND DELOCALISATION
9.16.1 Concept of Resonance in VaT

In discussing the hydrogen molecule (H2) in VBT, contribution of the ionic form (Le. Jr11) was
required to be considered along with the covalent structure, Le. H-H. The actual wave function describing
the molecule was expressed as, 'V H 2 = (1 =- A)'II cov + A'IIion where A « 1) denotes the mixing coeft1cient
measuring the extent of contribution of the ionic wave function. Thus the true wave function of the
molecule can never be expressed by considering only H-H or Jr J1 alone. This phenomenon is referred
ry
to as covalent-ionic resonance. The wave function dealing with the ionic form becomes important in
the heteronuclear species where the electronegativity difference between the combining species is
ra
sigitificantly high.
Besides the covalent-ionic resonance, more than one covalent·structure for a particular molecular
ib
species can be drawn by considering the electron pair (2c-2e) covalent bond in the light of VBT. In
drawing such structures, the positions ofpi-bonds are shifted while the sigma bonding pairs are loc~lised
yl
between the corresponding nuclei. Each Lewis structure can be expressed by a suitable wave function.
Then the actual behaviour of the species called resonance hybrid can be expressed as a linear
m
combination of the separate wave functions expressing the individual structures called canonical
forms. Thus,
he
'V = c I \III + c2'V2 + c3\113 +....
Thus, no single structure can explain the actual behaviour ofthe molecule, but their linear combination
lc
can do the task. This is why, no simple Lewis structure can picture the resonance hybrid. To clarify the
concept, let us take the case ofcarbonate (COi-) for which the following three canonical forms can be
ea
drawn. The canonical forms are related with the double headed arrows (~), i.e. :
/0- _ ~o _ /0-
th
o=c" ("'I)~O-C" ("'2)~O-C~ ("'3)

0_ 0- 0
e/
Thus, \JI = c1\lll + c2\112 + c3\113. Here, aU the· three structures drawn are equivalent. Hence they
t.m
contribute equally, i.e. c I = c 2 == c3 • It is evident that here the pi-bonding electron cloud is getting shifted
from one position to another. As a result, the pi-bonding pair is getting deiocalised over the whole
2-
molecule. Conventionally, the resonance hybrid is drawn as, O=C:(

'0
Thus the fractional 1/3 pi-bond order in each C-O bond can be nicely explained in the light of
MOT by considering the formation of 4-centred 'It-MOs (cf. Sec. 9.12.10).
9.16.2 Resonance Energy
The energy obtained from the actual wave function which is the linear combination ofthe wave functions
representing the canonical forms is always lower than the energy of the individual canonical forms, i.e.
'II == cI'II1 + c 2'112 + c3'113 +... ; and E < E i , i = 1, 2, 3,... ·
When the canonical forms are not equivalent, they do not contribute equally, Le. E I E2 E3•••'* '*
Thus, it is evident that the linear combination yields a wave function which gives an extra stability
compared to the individual canonical forms. This extra stabilisation compared to the most stable
canonicalform (having the lowest energy which is actually calculated theoretically) gives the measure
of resonance energy (Eres). Thus,
E res = energy of the most stable canonical form ~ energy of the actual molecule = theoretically
calculated energy ~ experimentally determined energy.
It is illustrated for carbon monoxide (CO). The resonating structures of CO are:
ry
•• - + + •• -
:C===O: (lowest energy structure) .....~----i~~ C.. 0: .....~~.,. :C-- g:
ra
Energy ofthe actual species is generally obtained from the heat offormation and energy ofthe most
stable canonical form is obtained from the bond energy data relevant to the structure drawn. For CO,
ib
the heat offormationfrom gaseous atoms is - 1072 kJ mol-I and lowest energy ofthe CO structure (i.e.
highest bond energy for C = 0) is -799 kJ mol-I. Thus: .
yl = 273 kJ mol- 1
1
Era(CO) = (1072 -799) kJ mol-
m
For CO2 it can be calculated as follows:
= 0) ~ 154 kJ mol- 1
he
E res (C02 ) = IHeat of formation of CO2 from the gaseous atomsl- 2E(C
where E (C = 0) denotes the C = 0 bond energy.

lc
The extra stabilisation due to the resonance can be rationalised from the standpoin~ of" quantum
mechanics by using the result of the model, panicle in a box. The linear combination of the wave
ea
functions suggests that the electron cloud can delocalise in a larger dimension embracing more than
two nuclei. Thus the resonance energy is basically exchange energy. The resonance energy of carbon
th
dioxide is 154 kJ mol-I. It means that the actual molecule is more stable than the theoretically calculated
one by 154 kJ mol-I.
e/
Note: Eres for benzene (C6H6 ) can be calculated in the following ways:
Ern (C6H 6 ) = IHeat of formation of C6H 6 from the gaseous atoms/ - {6E(C-H) + 3E(C = C) +
t.m
3E(C-C)} ~ 168 kJ mol-I
o o
(Kekule structures)
From the knowledge of heat ofhydrogenation, Eres can also be calculated. The heat ofhydrogenation
of cyclohexene is -120 kJ mol-I. Assuming, benzene as a cyclohexatriene (cf. Kekule structure) having
three localised double bonds, the calculated heat of hydrogenation is -3 x 120 kJ mol-I. But the
experimental heat ofhydrogenation is -209 kJ mol-I. This difference Le. 151 kJ mol-I gives the resonance
energy of C6H 6 •
It may be noted that for cyclohexane (C6 H I2 ), Eres is zero, Le. :
E res (C6H I2 ) = IHeat of formation ofC6H 12 from the gaseous atoms/-{6E(C-C) + 12E(C-H)} = O.
9.16.3 Conditions for Effective Canonical Forms

(i) Resonance vs. tautomerism : The proposed canonical forms should not differ in the atomic
arrangements. Only the position of the pi-electrons (generally the sigma-electrons do not get
delocalised) is changed from one position to another. Shifting of an atom leads to tautomerism
not resonance and such species are related through the equilibrium sign (~). Some examples
of tautomerism are shown below.
(a) The nitrous acid may have two forms in equilibrium,
(H)O (*;0
ry
O~ ~ H-N(
ra
(nitrite compound) (nitro compound)
~O 0
ib
The'coloured organic nitrites and some iriorganic nitrites such as silver nitrite (pale yellow),
mercurous nitrite (pale yellow) probably exist in nitro forms.
yl
(b) The so called phosphorous acid (H3P03) and hypophosphorous acid (H3POZ) exist in
tautomeric equilibria.
0\
m
-H~/!) Q\ ======>===:' ~"
P =0
he
/\
H OH
HO/ 'O-HI H IO-H
lc
OH OH
Phosphorous acid, Phosphonic acid, Hypophosphorous acid, Phosphlnlc acid,
ea
minor tautomer major tautomer minor tautomer major tautomer

(c) Similarly, tautomerism in sulphurous acid is also reported.
th
Q\ ~"
e/
5=0
/~
HO 0
t.m
Ho/II o-H
o
All the examples of tautomerism cited above involve the shifting of a proton and this type of
tautomerism is referred to as prototropic tautomerism which is very important in organic chemistry
(e.g. keto-enol tautomerism).
(ii) Contribution of the canonical forms: The contribution of a canonical form to the resonance
hybrid is inversely proportional to its energy. This is why, the high energy canonical forms
contribute insignificantly.
(iii) Comparable energy of the canonical forms: The resonating structures should be ofcomparable
energy.
(iv) Equivalent canonical forms: If the resonating structures are equivalent as in the case of
coi-, the resonance stabilisation is very high.
(v) Covalent ionic resonance :The covalent-ionic resonance becomes important in the cases where
the combining atoms differ significantly in electronegativity.
(vi) Number of covalent linkages: The canonical forms should have the maximum number of
covalent linkages. The reduction in the number of covalent linkages in drawing a canonical form
reduces its contribution. In the case of carbon dioxide, Le. 0 = C = 0 (I) ~ 0 = c+ - 0- (II), the
canonical form (II) being deficient of one covalent linkage contributes little.
(vii) Geometry of the canonical forms: The canonical forms should not differ in geometry or bond
angle drastically. In the case of nitrous oxide, the cyclic (3-membered) structure (III) is not at all
promising.
ry
o
-N=N+=O(I,linear)~N==N+-O-(II,linear)~ / \ (III,cyclic)
N===N
ra
(viii) Number of unpaired electrons: The canonical forms should have the same number of unpaired
ib
electrons.
(ix) Charge separation: In the case of charge separation, if the adjacent atoms bear the same charge
yl
then the electrostatic repulsion will destabilise the structure. On the other hand, placement of
~pposite charge on the adjacent atoms stabilises the system through an electrostatic interaction
m
as in the ionic compounds. In the case ofundissociated hydrazoic acid, the structure (II) contributes
less compared to the structures (I) and (III).
he
(I) H - N= tv+" = ~ ~ (II) H-tv+" == tv+"-Nl- ~ (III) H - ~ - ~ == N
(x) Placement of charge : The canonical forms in which the negative charge resides on the
lc
electronegative atoms contribute more. On the other hand, placement of the negative charge on
the electropositive centres destabilises the system.
ea
(xi) Number of covalent linkages : The canonical forms in which a larger number of covalent
linkages exists are more contributing to the resonance hybrid. In BF3 , the P1t - P1t bonding places
th
a positive charge on F which is more electronegative than B, but this disfavour is compensated
due to the formation ofan additional n-bond.
e/
t.m
In fact, due to this type of pi-bonding, B - F bond has got the double bond character to some
extent (see Figs. 9.16.5.1 and 10.7.6).
(xii) Requirement of coplanarity : For the delocalisation of the pi-electron clouds, coplanarity of
the involved skeleton is required. This is why, sp and sp2 hybridisations facilitate the process.
This coplanarity is exclusively essential when the pi-bonds made ofp-orbitals are involved.in the
process. But,for the d-orbitals (very oftenfound in inorganic compounds), this coplanarity is
not to be maintained rigidly (see Sec. 10.7 (vi»). The d-orbitals being diffused can participate in
pi-bonding even in nonplanar systems (e.g. 80;-, C/O;, etc.).
(xiii) Pauling's electronegativity principle and the stable resonating structure: This aspect has been
illustrated in Sec. 9.16.4.
9.16.4 Concepts of Formal Charge and Lewis-Langmuir Charge in Resonating Structures :

Formal Charge and Oxidation Number
• Formal charge without considering the effect of electronegativity difference: Conventionally, in
the formation of an additive coordinate bond, the donor atom is believed to bear a positive charge while
the acceptor one bears a negative charge. Ifthe involving atoms were ofalmost the same electronegativity,
then the above consideration would be reasonably correct. However, in distrib';1ting the charge, no
consideration of electronegativity difference is taken into account. This is why, in calculating the
formal charge (qF) of an atom in a compound, all the constituent atoms are considered to be of
ry
the same electronegativity. To calculate the qF of an atom in a compound, the number of electrons
actually owned by the atom in the compound is compared with the number of electrons possessed by
ra
the isolated atom in the neutral state. Thus qF is given by,
I ~ I
ib
qr = n A - nip - n hp
yl
where, nA= number of electrons in the valence shell of the atom at the isolated .and neutral condition,
nip = number of lone pair electrons which are completely owned by the atom under consideration,
m
nbp = number of bond pair electrons which are equally shared by the two combining atoms.
Some examples of formal charge calculation are given below :
he
1
:S: qF (Scentre) = 6 - 0 - - x 12 = 0
2
I 1
lc
2-.
qr (Stenninal)=6-4-"2 x4 =O
S20 J S
~/II'\g~
•
1
ea
q F (0) = 6 - 4 - - x 4 = 0
2
:0:
qr (0-) = 6 - 6 _.!. x 2 =-1
th
2
e/
t.m
--
t:- qF (B)=3-0--x6=0
- 1
:~B / •• 2
· "r.: q F (F) = 7 - 6 -
1
~X
2
2 =0
1
qF (N) = 5 -0 -- x 8 = + 1
NH4+·• 2
1
qF (H)=1-0--x2=0
2
710 Fundamental Concepts of Inorganic Chemistry .
SF4 : q~S) = 0, q~F) = 0; HIV- OH: q~N) = 0, qF(O) = 0; ope/3 (forO~ +PCI3 ):qIP) = +1,
q~C/) = 0, q~O) =-1; 0 =PC/3 : q~P) = q~O) = q~Cl) = 0; NO; (nitronium, O=~= 0): q~N)
= +1, q~O) = 0; PH3 : q~P) = 0, q~H) = 0; PH;: qlP) = + 1, qlH) = 0; BF(:B == F:) : qlB) = -2,
q~F) = +2.
The formal charge on the constituting atoms depends on the structure of the resonating form.
This aspect is illustrated in the following examples. The formal charges on the respective atoms are
shown;' for 0 (zero) formal charge, nothing is shown.
:0
ry
- +.. .. + ..-
:f; :f; + II
:~=N=9'-"N=N-9
.. '- B- f;: +---+ .. , S= F: N+
.. / . . ../ - .. / ,- .. -
ra
:t :t :9 Q=
(3 EQ.ivalErt (3 EQ.ivalErt
ib
structures, structures,
• 1~~. 2~~
1.9. +- "" .... ~ 1.9. - - "" .... yg
yl
3 3
00 EBtl F) on each 0)
~~-C=N: ~ ~=C=N:~>:S=C-N:2-
m
(a) (b) (c)
he
(most favourable)
2- + 3- . . + + _ + ..
lc
:~=N=g: +-+ :g-N=O: +-+:C=N-Q:-

Isomeric fulminate (a) (b) (c)
ea
and cyanate
(cf. Sec. 9.16.6)
th
(a) (b) (c)

e/
For CND- (i.e. fulminate), (c) form bears the most favourable charge distribution while the other
two forms experience the more unfavourable situations. On the other hand, for OCfY (i.e. cyanate
t.m
ion), both the (a) and (b) forms experience the favourable charge distribution and between these two
forms, (b) contributes better where the negative charge lies on the more electronegative atom. Thus in
terms of the resonating structures, it is evident that OCfY is more stable than CNlr. It is also
experimentally verified (cf. Sec. 16.21 for explosive characters of fulminates).
:0:- :·0: 0: :0:- 0:
12 + 11+ 4-+ II ..-. I M2-
s~-: 8 8 8 -8
-:0:/1' :0:- :0:/ 1'-:0: :0#1':0: :0#1I~:0 :0:#II~:0
.. _.. ..
:0: -··-.:9: .. - ··-.:9: .. - .. :0:·· :0: ..
(a) (b) (4 equivalent (c) (6 equivalent (d) (4 equivalent (e)

structures) structures) structures)
For sol-,
the formal charge on 0 is different in different cannonical forms. This is as follows:
3 - 1 1
(a) q~O) = -1; (b) q~O) = - 4"; (c) Q~O) = -"2; (d) q~O) = - 4"; (e) q~O) = O.
Considering the 6 equivalent structure for the c-form of 50;-, the formal charges on Sand 0 are
o (zero) and _..!- (on each 0, i.e. average value) respectively.
2
What are the formal charges on Al and 0 in Al(OH2 )~+ ? Ans : -3 for Al and + 1 for 0
In the above mentioned discussion, to calculate the formal charge, the effect of electronegativity
difference between the combining atoms has been ignored. It has been assumed that the bonding
electron pair is equally shared between the combining atoms.
ry
Pauling's electroneutrality principle: Now let us consider the Pauling's electroneutrality principle
which states that in the stable resonating structure, the electrons are distributed in such a way that
ra
the atoms can carry the minimum charge tending to zero. In other words, it should lead to charge
separation minimum. Thus, for SO;-, the resonating structure a is the most unfavourable condition
ib
while the structure c is the most favourable case. Through the formation of multiple bonds (Le.
7t-bonds), the charge separation can be minimised to satisfy the demand of electroneutrality
yl
principle.
The important predictions ofPauling's electroneutrality principle are:
m
-. minimum charge separation;
• if charge separation - electropositive centres will bear the partial positive charge and electro-
he
negative centres will bear the partial negative charge;
• 7t-bonding to minimise the charge separation when possible; maximum number of covalent
lc
bonds.
ea
• Lewis-Langmuir charge considering the .effect of electronegativity difference: Considering

the effect of electronegativity difference, Allen (J. Am. Chem. Soc., 111, 9115, 1989) has suggested to
th
calculate the charge (called Lewis-Langmuir charge) on the atoms. Thus the Lewis-Langmuir charge
(qL-L) considers the effect ofelectronegativity difference whUe theformal charge (q F) does not consider
e/
the effect 0/ electronegativity difference. When, there is no electronegativity difference, qL-L becomes
qF. The Lewis-Langmuir charge,' qL-L on A in the ABx molecule is calculated as follows:
t.m
qL-L(A)=nA -nIP -2 L (XA XA+ XB )

. hontk
For, B-A-B molecule, the last term considers the sum of 2 single bonds; for A = B molecule, it also
considers over 2 bonds for the double bond. Obviously for XA = XB' qL-L and qF become identical.
Calculation of qL-L is illustrated in the following examples (for x-values, see Pauling's values, Chapter
8).
.. qL-L(N) = 5 - 2 - 2 x3 (_3_)
3+ 2.1
~ -0.53
/N"
(a) H
H
I H
qL_L(H)=1-0-2xl ( -2.1- J ~+0.18
3+ 2.1
X(H) = 2.1, X(N) = 3.0
..
(b) H-9.1:
qL_L(H)=1-0-2XI{ 2.1 }=1-0.82=+0.18
3.0 + 2.1
qL_L(CI)=7-6-2XI{ 3.0
3.0+2.1
}~-0.18
X(H) = 2.1, X(CI) = 3.0
(c) H-C=C-H QL_L(C)=4-0-2X3( 2.5 )-2Xl( 2.5 )
ry
2.5+ 2.5 2.5 + 2.1
= 4 - 3 -1.08 = - 0.08; taking X(H) = 2.I,X(C) = 2.5
ra
Note: To get the more correct result, electronegativity of sp-C should be used.
+ •• - + ••
ib
(d) N 20 (Le. :N,=='Nc-~: ~ :N,= Nc ~) [x(N) = 3.0; x(O) = 3.5]
(I) (II)
yl
N20 possesses two stable resonating structures as shown above.
~
Structure-/: qL-L (N,) =5 -
m
2 - (2 x 3){3 3} =0
he
QL-L(O) =6 -6-(2x 1){~}=-1.07
3.5+3
lc
qL-L (Ne ) = 5 - 0 - 2 x 3 {_3_} - 2 x I (_3- ) ~ 1.07

ea
3+3 3 +3.5
th
Structure-II: QL-L (N,) = 5 - 4 - (2 x 2) { 3.0 } =-1

3.0+3.0
e/
QL-L(Nc ) = 5 - 0 - 2 x 2 {_3_} - 2 x 2 (_3- ) ~ 1.15

t.m
3+3 3 + 3.5
qL-L(O) = 6 - 4 - (2 x 2) {~}
3.5 +3
= -0.15
Experimentally it has been found that the Structure I and II contribute in the approximate ratio 2 :
1 to represent the real N 20 molecule. This is quite reasonable because in structure I, negative charge
is carried by the most electronegative centre while in structure II, negative charge is placed on the
relatively less electronegative centre N It leads to the average value of qL-L as follows:
qL-L (N,) = 2 x 0 +3(-1 x I) =- 0.33
qL-L (N ) = 2 x (+ 1.07); 1x (+ US) = 1.09

e
qL-L (0) = 2 x (-1.07); (t x -0.15) =_ 0.76

Thus, N 20 should be represented as follows:
-0.33 - 0.76
N:::':N~O (in tenns of qL-L)
+ 1.09
Note: In the above mentioned calculations, electronegativity ofnitrogen has taken as 3.0 irrespective
of its hybridisation state in different cannonical forms 7 But electronegativity of an atom depends on its
state of hybridisation.
ry
Formal charge (q,J, Lewis-Langmuir charge (qL-J and Oxidation number (O.H.)
ra
In calculating qF' polarisation ofa covalent bond due to electronegativity difference is not considered,
Le., the compounds are considered to have the 100% covalent character. In calculating the qL-L'
ib
development of partial ionic character in the covalent bonds due to the electronegativity difference
is considered. In calculating oxidation number, it is assumed that the bonding electron pair is
yl
completely.transferred to the more electronegative atom giving rise to 100% ionic character.
Thus the concepts of formal charge and oxidation number consider the two limiting cases i.e.
m
1000k covalent character and 100% ionic character respectively. In covalent compounds,
practically these are hypothetical suggestions. On the other hand, qL-L considers the real situation of
he
covalent bonds where the electronegativity difference is not too large or too small.
NHJ : ql.N) = 0, QL-L(N) = - 0.53, O.N.(N) = - 3
lc
H 20: qF(O) = 0, qL-L (0) = - 0.5, O.N.(O) = - 2

ea
HC/: qF(CI) = 0, qL-L (CI) = - 0.18, O.N.(CI) =-1

th
9.16.5 Resonance in the Light of Molecular Orbital Theory

The concept of resonance is originated in the valence bond
e/
theory (VBT). In VBT, the concept of localis~d bonBs is well

established. On the other hand, the polycentric molec~lar , , n* ,
,,
t.m
\
\
orbital leads to the delocalisation ofthe electron cloud through \
a wide range. The concept of resonance in VBT leads to the

, \ ~
" \ ~
delocalisation of the electrons. Thus the delocalisation of the
-P-z(-A-)~\"
l... " \ ~
Q)
electron cloud through the polycentric molecular orbital is
"'~11', \
equivalent to resonance in VBT. \ 1tnb "\
For the planar ABJ species, e.g. BFj, CO;- , NO;, etc.
(Sec. 9.12.10) the construction of4-centred pi-MOs can nicely
"\
\
",
,
.. It
Three Pz
1
explain the 1/3 pi-bond order in eachA-B bond. Ifthe molecule "
,, ' ( 3 8 )
lies in the xy-plane, each of the four atoms of AB3 can provide
their p= orbitals for LCAO to generate four centred 7t-MOs
\
',.
1tb
,
out of which there are two nonbonding 7t-MOs along with a Fig. 9.16.5.1. The 4c pi-molecular
bonding and an antibonding 7t-MO (Fig. 9.16.5.1). In these orbitals in the ABa type molecular
species, besides the 18 sigma-electrons (including 6 lone pairs) species (e.g. B~, 00;-, NO:;, etc.).
placed in different sigma-orbitals, there are 6 pi-electrons (provided by three B atoms in AB3) which are
distributed in the pi-MOs. These are discussed in detail fn Sec. 9.12.10(cf. Figs. 9.12.10.2 and 9.12.10.3).
The four pi-electrons placed in the two nonbonding pi-MOs have nothing to do with the bond order.
The two electrons placed in the bondingpi-MO produce the total bond order unity which is distributed
in three A-B bonds. Thus the pi-bond order in each A-B bond is 1/3. The electronic configuration (cf.
Fig. 9.12.10.2) is:
6 12 2 4
( 0' b ) ( 0' nb ) ( 1tb ) ( 1tnb) •
Such delocalised pi-molecular orbitals have been discussed (see Secs. 9.12 and 9:15) in some specific
ry
cases, e.g. NO;, conjugated molecules, etc.
The 7t-bonding in 0 3 and related molecular species have been discussed in Fig. 9.12.9.4. Here three
ra
p-orbitals are available for 7t-bonding and these will produce three 3-centred 7t-MOs (one bonding +
one nonbonding + one antibonfing). Four electrons are distributed in the 7th and 7tnb MOs (i.e. 3c--4e
°
ib
7t-bonding) to pr~duce 1/2 7t-bbnd in each linkage (cf. Fig. 9.16.5.2). In 3,18 valence electrons are
distributed as: (O'nb)10 (O'b)4 (1t b )2 (1t nb )2 (cf. Fig. 9.12.9.6). In S02' the same bonding scheme works.
yl
These aspects have been discussed in detail in Sec~ 9.12.9.
,
II
I
m I
I \
Lxy-p,ane I
\
\
I
he
\
I
.. ~ :.. I
\
\
" " " / I
I \
.."
\
" '" I
lc
I \ 2pz
(
\
1b ---, I
\
(OAt Os)
ea
\ I
\ I
\ I
\ I
\
th
I
\ I
\ I
\ I
\
e/
I
\
, I
1~
t.m
--
Fig. 9.16.5.2. Three centred 1t-MOs in 03.
9.16.6 Application of the Concept of Resonanoe In Some Inorganic Compounds

Carbon monoxide (CO) : In CO, the bond length (113 pm) lies between the bond lengths ofC = 0 (122
°
pm) and C == (110 pm). This intermediate value can be rationalised from the resonating structures
Le. : •• - +
:c= Q (I) ~ :C..- 0: (II)
In the structure (II), the positive charge on the more electronegative oxygen atom destabilises the
structure, but this disfavour is 90mpensated due to the formation ofan additional covalent linkage.
It is interesting to note that in the structure (I), the bond moment operates towards 'oxygen, while in
the structure (II), it works in the opposite direction. Probably, because o/these two opposing moments,
the dipole moment ofthe system is very small. The whole picture including the lone pair moments will
be discussed in Sec. 10.5.3.
Introduction to Chemical Bonding and Theories of CovalencEl 715
• Carbon dioxide (C0 2) : Here the C-O bond length (= 115 pm) again lies between the C = 0(122
pm) and C= 0 (110 pm) bond lengths. This increased bond order arises due to the following contributing
resonating structures, Le.
•• •• -.. + + •• -
2===C. Q (I) ~ :~-e==O: (II) ..-. :O==C-g: (III)
The structure (I) is symmetrical, and the two unsymmetrical structures (II) and (III) contribute
equally. This is why, the molecule overall shows no dipole moment
• Nitrogen dioxide (N0z) : The canonical forms can explain the partial double bond character of
° °
ry
the two equivalent N - (119 pm) bonds which are intermediate between N - 0 (136 pm) and N =
(115 pm). The canonical forms are:
ra
~
~N. H
0, ~N.
ib
o 0
• Nitrate ion (NO;): The observed N - ° bond length (121 pm) can be explained from the
yl
contribution of the canonical structures, Le. m
~O ~ /0- _ #0
O=N, f-) O.-N, ~ O=N~ ~ O-N,
o 0 0 0
he
• Hydrazoic acid ion (HN]) and azide (N]): In the undissociated acid, the bond lengths are as
follows: H - N (107 pm), middle N - N (124 pm), terminal (Le. re~ote from H) N - N (113 pm). Thus,
lc
the N - N bond distances .in HN] are unequal. But in azide all the.N - N bond lengths are equal (115.
pm). The above facts can be explained by considering the resonating structures of both HN) and Ni.
ea
In HN) the corresponding structures are :

•• + - _.. +
U:
th
H-N=N (I) ~ H-'!.-N==N:(l1)

Here, the middle N - N has got both the double and single bond character while the terminal N - N
e/
has got both the double and triple bond character. This is why the N - N distances in HN) are" not equal.
In Ni, the corresponding resonating structures are :
t.m
+ 2-.. + + •• 2-
...
N.
:N=N : ' -.
' . ..
:N-N==N:'-' :N==N-N:
Here, all the N - N bonds are equivalent.
The enhanced stability 0/ the ionic azides compared to that 0/ 'he covalent azides can also be
explained/rom the consideration o/resonance energy. The covalent azides have the structure like that
of the undissociated acid with two nonequivalent resonating structures. On the other hand, in the ionic
azides, the azide ion is having three canonical forms in which two forms are equivalent. Thus the
resonance stabilisation in the ionic azides is greater than that in the covalent azides.
• lsosters (N 2 0, Ni, OCN-, CNO-, SCN-, Ni; cf. Sec. 9.16.4): In this connection, it is worth
mentioning that the isosteric species, e.g. nitrous oxide (N20), azide (Ni), cyanate (OClV), fulminate
(CNo-), thiocyanate (SClV), are also resonance stabilised. The species having identical outer electronic
configurations are called isosters. All are linear. Because of this structural similarity, they can form the
isomorphous alkali salts. The resonating structures of SCN"" can be shown as:
716 Fundamehtal Concepts of Inorganic Chemistry
•• •• - + •• 2-
..
:S-C=N:(I) ~ :S=C=N:(II) ~ ..
:S==C-N: (III)
Here, the structure (III) contributes less, as the opposite charges are placed at the largest distance.
The most favourable structure is (II) where the most electronegative atom bears the negative charge.
• ,CND- (fulminate) vs. OCN- (cyanate) : The resonating structures of these two isomeric and
isosteric species are :
2- + _ + •• _ 3 - •• + +
CNO- =:) :~=N=g:(I) ~ ~==N-g: (II) .....~-~~
.....- -.. :~-N==O: (III)
..
ry
+ •• 2-
OCN- =>:()=.C=N:-(l) .....~......; ..
~-:Q-C==N: (II) ...
~--..... :O==C-!i: (III)
ra
In tenns ofcharge placement, for CNo-, the most favourable structure is II. In other two structures,
charge distribution patterns are relatively unfavourable and these are not stable. For OCN", the structures
ib
I and II place negative charges on the electron~gative centres (Le. N, 0). Obviously, structure II is
more favourable than I, because in II, n'egative cHarge is placed on the most electronegative centre. It
yl
is evident that for CNo-, the resonating structures are less stable compared to those for OelV. This is
why, OCN- is more stable than CND- (cf. Sec. 16.21 for explosive character of fulminates).
m
9.17 LIMITATIONS OF THE CONCEPT OF RESONANCE
he
AND HYBRIDISATION
For shifting of the pi-electrons (specially the p-electrons) through resonance, the condition of
lc
coplanarity is to be maintained. Thus to effect the resonance, the state of hybridisation of a

particular atom in a polyatomic species may vary in different canonical forms. The actual molecule
ea
is the resonance hybrid ofall the canonical fonns. Hence it is difficult to define the state of hybridisation
ofthe constituent atoms in the actual molecule. The above fact can be clarified in the following examples.
th
In constructing the structures, it must be kept in mind that generally the pi-bonds can be fonned by
using the suitable p-orbitals.
e/
• HNJ : The states of hybridisation of the different nitrogen atoms are given below.
t.m
+ - +
H-N=N=N .......-.. H-N-N=='N
(sp2) (sp) (sp2) (Sp3) (sp) (sp)
• ~: The states of hybridisation of the nitrogen atoms are shown below :

+ 2- + + 2-
N=N=N H N-N=='N ~ N=='N-N
(Sp2) (sp) (Sp2) (Sp 3) (sp) (sp) (sp) (sp) (Sp3)
• B(OCHJ)J (trimethoxy boron) : In drawing the canonical fonns, oxygen changes from sp3 to
sp2, so that in tht; structure II, the p-orbital can participate in Pft- Pft back bonding with boron. The
bond angle B-O-C is 113 0 and it indicates that the O-atom remains in a state between spJ and
sp2.
Me~.. Me~_ f-
B - OMe (I) ~ / B = OMe (II)
Meo/ (~p3) MeCY (- spl)
• NzOs: The states of hybridisations of different ,atoms in the possible canonical forms are given
below.
O~Sp2) •• (sp2)/O O~Sp2)"to (sp2)~ O~sp2) 2+ (sP)/O

#N-Q-N~ H /N=O-N" ~ N=O=N,
0" (Sp3) 0 Q (Sp2) 0 ~ (sp) l!.
• HzN - PHz : Here to allow the N(PJ --. P(dJ bonding, N-centre should adopt the sp2-hybridisation
state so that the lone pair can be housed in a pure p-orbital. In fact, N-centre remains in a hybridisation
state between the spz and spJ. The bond angle (H - N- P) and the bond length (N - P) support the
ry
proposition.
Thus it is evident that ifthe concept of resonance is taken into account, then the consideration ofthe
ra
state of hybridisation of a particular centre becomes ill-defined. Hence, the prediction ofgeometry of
the molecule by considering the hybridisation becomes uncertain, because the actual state of
ib
hybridisation depends upon the relative contribution ofthe canonicalforms to the resonance hybrid.
yl
9.18 MULTIPLE BONDS
Generally, the multiple bonds arise due to the pi-bonding in addition to the sigma-bonding. We h~ve
m
already discussed the properties ofthe sigma- and pi-bonds. Before to enter into the mechanistic pathways
in developing the pi-bonding, we should highlight the effect of bond-multiplicity on the properties of
he
the molecule. The pi-bonding strongly influences a number of properties such as: structure, acidity-
basicity, stability and reactivity (e.g. cis- and tran~-effects), stabilisation of unusual oxidation states
lc
(e.g. pi-acid ligands to stabilise the very low oxidation states oftransition metals), tendency to polymerise,
etc. These phenomena will be discussed separately in the next chapter (Sec. 10.7). Here we shall pay
ea
attention only to the effect on bond length.

160
9.18.1 Bond Length and Bond Multiplicity
th
In determining the bond length, the bond multiplicity

.-.. 150
e/
(Le. bond order) is extremely important. With the E

increase of bond order, the bond length decreases (see ~
.r::.
t.m
Table 10.2.3.1). Here it is worth mentioning that besides 1»

the bond order, many other factors (see Sec. 10.2.3) can j 140
"C
govern the bond length. These factors are : nature of c
o
hybridisation, nearest environment in the molecule, CD
electronegativity difference between the combining (,) 130

I
(,)
centres, steric factors, etc. But in spite of the facts, it
can be concluded that the bond length decreases with ""C2 H2
the increases of bond order. For C - C system, an 120 ........- - - - - -.......- - . . . . . - - -
1 2 3
empirical relationship between the bond length (r in pm) C - C Bond order
and the bond order (n) has been developed by Pauling. Fig. 9.18.1.1. The variation of carbon-
The relationship is : carbon bond length with the bond order.
r n =r t -71Iogn,
where rn denotes bond length (in pm) for the bond order n. The variation of bond length with the bond
order in C-C system is shown in Fig. 9.18.1.1.
9.18.2 Px-Px Bonding

(A) VB Description of pi-Bonding In Unsaturated Hydrocarbons
Let us start with the series of hydrocarbons, C2H6, C2H4 and C2H2 for which the conventional structural
representations are :
rr
H - C - C ; - H (C H)o
H
" C/
H
(C2H4); H-C::::='C-'-H (C2H 2)
I I 26' /C= "-
ry
H H H H
In the light ofVBT, in the saturated hydrocarbon C2H6 , each carbon is tetrahedrally (sp 3) hybridised
ra
and the four hybrid orbitals are utilised in forming four covalent bonds. In C2H 4, each carbon is sp2
hybridised to form three sigma bonds in a plane. If the sigma-skeleton lies on the xy-plane, then each
ib
carbon atoJ:1l contains a pure Pz orbital.with an unpaired electron perpendicular to the plane. These two'
p=-orbitals laterally overlap to form api-bond (see Fig. 9.15.1). Similarly, in C2H2, each sp carbon
yl
contains two pure p-orbitals (say, Py and Pz' assuming the. x-axis to be the molecular axis) which are
mutually perpendicular (see Fig. 9.18.2.1). Here the lateral overlap of Py - Py and Pz - Pz produces two
m
7t-bonds leading to the triple bond, C iii C. Here it must be remembered that the x-bonds formed due to
the lateral overlap of the orbitals are weaker than the sigma-bonds where the head-on overlap occurs.
he
This is why, a double bond containing one sigma- and one pi-bond is weaker than the sum of two
isolated sigma or single bonds. It explains the higher reactivity ofthe unsaturated compounds compared
to the saturated ones where no pi-bond exists.
lc
ea
H H
I I H H
H-C-C-H (C 2 Ha): )c = c( (C 2H4 ): H - C!!!! C - H (C 2 H2 )
I I
th
H H
H H
z Pz Pz
e/
H,V(:)--------A
--------V/H y ~-------~ p
v3J;~Vt:J
t.m
------x
H/(jC --------
--------
.-
(jC'H -
~tJC---~k)C-" H
- ------- -
-------
Fig. 9.18.2.1. The pj.bondin~ . interactions in C2 H2 and C2 H4 -
To explain the reactivity ofthe unsaturated hydrocarbons and the origin of multiple bond formation,
an alternative approach of bent bond concept has been introduced by Linnett. In this concept, it is
believed that the carbon atoms in the unsaturated compound, e.g. C2H 4, are also tetrahearally hybridised.
Here, two of the four sp3 hybrid orbitals on each carbon atom are involved to unite two hydrogen atoms
through sigma-bonds as usual to form the CH2 groups. The remaining two hybrid orbitals on each
carbon atom undergo an angular overlap sharing the common edge of the two different tetrahedra
around the adjacent carbon atoms to produce two

bent or banana bonds, above and below the plane H, /1T'\ ~H
ofthe rest ofthe molecule (see Fig. 9.18.2.2). Due
to the bent bonds the molecule remains in strain
H
)40f(
\J/ H
H H
H H
which is measured by the deviation of bond angle
(a) (b)
from the tetrahedral bond angle. Because 0/ this
strain, the molecules are believed to be more H,~/H ~
reactive comparedto the saturated hydrocarbons c· C H-C~C-H
~
ry
where no such strain exists. In the same way, the H/ " ' . / 'H
triple bond, C ==C can be explained through the (c) (d)
ra
bent bond. The bent bonds are very often Fig. 9.18.2.2. The bent or banana bonds in C2 H4
represented as shown in Fig. 9.18.2.2. (a, b, c) and C2 H2 (d).
ib
This bent bond concept originating the strain
in the molecule has been invoked in explaining
yl
the higher reactivity of the tetrameric forms of
the elements like P4' As4, Sb 4' ~tc. The M4 species
m
is tetrahedral (see Fig. 9.18.2.3) having the bond
angle M -M- M = 60° where three M-atoms
he
occupy the corners of a triangular face of the
tetrahedron. Pure p-orbitals can make the
minimum bond angle 90°. Hence, to shrink the
lc
(8) (b)
bond angle more, it requires the participation of
the d-orbitals through the hybridisation with the Fig. 9.18.2.3. The angular orbital overlap
ea
p-orbitals. But such a hybridisation involving the interaction in the tetrameric forms of the elements
like P4' As4 , Sb4 (a), only three atoms occupying
higher energy d-orbitals is not energetically
the corners of a triangular face of the tetrahedron
th
possible when the element remains in zero are shown); and in cyclopropane (b).
oxidation states. Thus no suitable hybrid orbital
e/
can be energetically generated to explain this bond angle. This is why, it is believed that the p-orbitals
on each M undergo an angular overlap instead of overlap along the internuclear axis present in the
t.m
sigma-bonds. This type of angular overlap to form the bent or banana bonds introduces a strain in
each M - M bond. This strain makes the species reactive. Similarly, bent or banana bonds are also
existent in cyclopropane (see Fig. 9.18.2.3).
(8) liD-description of the Unsaturated Hydrocarbon

By considering the concept of localIsed MO (i.e. 2-centred MO), we reach almost the same conclusion
drawn in the VBT. In C2H4 , according to MOT, each sp2 carbon atom forms two sigma-type localised
MOs with two hydrogen atoms (providing Is orbital) along with a sigma-type localised MO between
the carbon atoms by using the sp2 hybrid orbitals. These five sigma-MOs will contain ten electrons.
The corresponding five antibonding sigma-MOs (i.e. a*-MO) will remain vacant. In addition to this,.
the two Pz orbitals (assuming the molecule to remain in the xy-plane) of the two carbon atoms fonn a
bonding 7t-MO and an antibonding 7t-MO, in whi~h the bonding 7t-MO contains tw<? electrons and the
7t*-MO remains unoccupied. The MO-picture ofC-/l4 is shown in Figs. 9.15.1 and 9.18.2.1.
720 Fundamental Goncepts of Inorganic Chemistry
Other types of pi-bonding such as P1C-P1C back bonding as in BF3, d1C-p", bonding, d1C-d1C • bonding,
and d 1C-1t* (pi-acid ligands such as CO, ClY, C2H4, etc.) in complexes are extremely important in
determining the different chemical and physical properties of the covalently bonded molecules. These
aspects will be discussed in the next chapter (see Sec. 10.7) in detail.
9.19 DELTA (SEE SEeS. 9.6 AND 12.8) AND QUADRUPLE BOND
In a delta-bonding, four lobes of each d-orbital overlap (see Fig. 9.S.lc) in contrast to two lobes and
ry
one lobe in pi- and sigma-bonding respectively. The orbitals having at least 4-lobes can participate in
o-bonding. Thus the d- andForbitals can participate in o-bonding interactions like d-d,j-f, etc. Delta
ra
bonding can also occur in d-1t~ (as in alkyne complexes) interaction. Obviously, the s- and p-
orbitals cannot participate in &-bonding. For the d-block elements, the o-bonding is important in
ib
many cases. Among the d-orbitals the following two combinations can lead to a-bondings.
•
dxy ± dxy -+ 0b and a (Mas)
d x 2 -y 2 ±dx 2 -y2
yl
-+ab and a• (MOs)
m
• Delta bonding in crl+, Mo1+ , W24+, Re~+ , etc. : The &-bonds are weaker than the 1t-bonds.
he
For the d-block elements, the tendency to form B-bonds increases for the heavier congeners. Relativistic
expansion of d-orbitals for the heavier congeners favour the d-d overlapping interaction. In the
species, Cr24+, Mo~+ , W24+, Re~+, etc. the a-bonding exists. As the a-bonding is very weak, it exists in
lc
multiple bonds like quadruple (4 bonds) bond or quintuple (S bonds) bonds.

ea
• Bonding and structure of Re2Cli- : To illustrate the concept of delta-bonding, let us take the
example of Re"CI:-. In this species, the two square planar ReCl4 units are joined by the extremely
th
short Re-Re bond of length 224 pm. This bond length is shorter than the average Re-Re distance (,.,.,
275 pm) in rhenium metal. The nonbonding CI~1 distance between the planes of ReCl4 units is"'" 332
e/
pm. To minimise the steric hindrance, the chlorines in the two planes are expected to lie in a staggered
configuration. But experimentally, they are found to adopt an eclipsed configuration. All these
t.m
unusual behaviours can be explained in terms ofquadruple bonding (i.e. a + 1t + a bonding) as proposed
by Cotton.
If the Re-Re bond directs along the z-axis, the structure of each planar ReX4 unit can be explained
by considering the dsp'l (i.e. d :x2-y2 + S + P:x + p y ) hybridisation. The pd (Le. p z + d z 2) hybrid orbitals
pointing to each othe~ can directly overlap to form a sigma-bond. The obliquely directed d:xz and dyz
orbitals on each -Re-atom can undergo sideways overlapping to produce two d 1C - d 1C bonds between the
Re-centres. One pi-bond lies in xz-plane while the other lies in the yz-plane. The remaining dxy orbital
on each Re-atom in two parallel planes can undergo a special type of sideways overlap ofthe four lobes
to produce the delta-bond (see Fig. 9.19.1a). The staggered conformation produces zero overlap
between the dxy orbitals lying in parallelplanes. This overlap can only take place when the chlorines
adopt an eclipsed configuration rather than the staggered one. Thus the quadruple bond between the
Re-centres consists of four bonds.
la-bond + 27t-bonds + lo-bond == quadruple bond
Such quadruple bonding (0 +21t +

0) is very much well known in di-
CI
rhenium and di-molybdenum com-
pounds. The bond energy of a such
quadruple bond lies in the range, 330 CI
kJ mol-I (which is less than even a C
- C single bond, but this comparison
with the small atoms where a better
ry
overlap takes place involving the s-p
hybrid orbitals is not very much
ra
meaningful) to 1500 kJ mol-I (which
is stronger than any other bond).-
ib
Re(III) and Mo(II) are isoelectronic with cf configurations. The examples of di-rhenium(III) and
di-molybdenum(II) complexes having o-bonding are :
yl
Re2 Xi-, Re2 (RC02 )2 X 4' Re2 (RC02 )4 X 2' Mo 2 X:-, Mo 2 (RC02 )4' etc.
m
The quadruple bonding in Re~+, Mo1+ ,etc. can be qualitatively explained by considering the
following interactions and the corresponding orbital energy diagram (Fig. 9.19.1 b) assuming the M-
he
M axis to lie along the z-axis.
pd-hybrid ± pd-hybrid ~ 0b and o· MOs -------0*
lc
dxz ± dxz ~ 1tb and 1t. MOs -------1t*

ea
dyz ± dyz ~ 1t
h and 1t. MOs e>
Q) -------0*
c:
W
± dxy ~ 0b and o· MOs
th
dxy -------Ob
In terms of the MO energy diagram (cf. Fig. 9.19.1b), the
I
e/
_______ b
distribution of electrons in different MOs involved in the 1t
quadruple bonding are given below:

t.m
Bond order Magnetic property 0b
IRe1C/s)2-: a; 7t: 0; 4.0 Diamagnetic Fig. 9.19.1b. Relative positions

IMo 1C/s)4-: a; 7t: 0; 4.0 Diamagnetic of the MOs involved in quad~ple
• bonding and electronic configu-
The energy difference 0b and 0 ~10s is very small and
rations of Re~+ or Mo~+ clusters.
transition ab -+ a* explains the intense red colour in IMo 1C/s)4- ~
and the blue colour in (Re 1C/s)2-. The closely related species like W2CI:-, OS2c1i-, TcCI:-, etc.
can be interpreted in terms of the MO-diagram given in Fig. 9.19.1b.
s a; 7t: o~ (Bond order = 4.0); (wi+, d system)

(W1C/ )4- :
8
ITczC/sIJ- : a; 7t: 0; 0. (Bond order 3.5); (Tc~+, d system)

1
=
9
a; 7t: 0; 0. (Bond order = 3.0); (Os~+, d system)

2 lO
(OszC/s )2- :
722 Fundamental Concepts of Inorganic Chemlstry
Thus, in OS2cli- there is no &-bonding and consequently the chloro-groups are in staggered
condition to minimise the steric repulsion (cf. in Re2CI:-, the chloro groups are in eclipsed condition
where o-bonding exists). From the electronic configuration, it is evident that OS2cli- and W2CI:- are
diamagnetic bu Tc 2CI:- is paramagnetic.
• Calculate the metal-metal bond order in [Mo 2(liP04 )4]2-, [Mo 2(S04)4]3-, [Re 2CI4(PMe 2Ph)4]+'
[Re 2C14(PMe2Ph)4]' [Ru(RC02 )4 (OH 2)2]+·
Hints: The relevant electronic configurations are respectively :
ry
2 4 2 4~1 2 4~2~.1 2 4~2~.2 2 4~2~.2 .1
a b 1t b , a b 1t b u b' a b 1t b u b u ,ab 1t b u b u ,ab1tbubu 1t
Note: • The 0b and o· MOs are closely separated and both of them are having the nonbonding
ra
character to a large extent. Consequently, the addition or removal ofelectrons to or from
ib
0b and 0* MOs does not dramatically affect the metal-metal bond strength.
• In terms of addition reaction, the multiple bonded Re2Cli- cluster behaves like the
yl
unsaturated carbon compounds. Consequently the bond order decreases:
Re2Cli- (a~1t:o~) + Cl2 ~ Re2CI; (a~1t:) + Cl-
m
• Dimeric chromium(II) acetate : The dimeric chromium(ll) acetate (see Fig. 9.19.2a) also
he
involves the quadruple interaction. Here the Cr-Cr distance (-- 236 pm) is shorter than that found in the
metallic crystal of chromium (-- 250). Assuming the high spin character, the electrons are distributed as
d~d~d~d~2. In the octahedral geometry, the electronic configuration is I~ge~. Due to 1.-0"1 Jahn-
lc
Teller distortion in the eg-Ievel, the d: 2 orbital is stabilised and consequently the unpair~d electron is
housed in the d z2 orbital. If the Cr-Cr bond directS along the z~axis, then the d~2 orbital from each
ea
Cr(II) can undergo overlapping to form a sigma-bond. The sigma-bond may also "be formed by using
the pd (Le. p; + d z2 ) hybrid orbital. The dxz' dyz orbitals one each on Cr(II) are suitably oriented to
th
form two pi-bonds. The dxy orbitals form the delta-bond. Thus all the electrons are paired to make the
e/
complex diamagnetic. .
The a~1t:o~ (cf. Fig. 9.19.1 b) electronic c~nfigur~tion explains the diamagnetic property but the
t.m
low bond energy for the Cr-Cr bond (-- 45 kJ mol-I) raises a question regarding the quadruple bond
(i.e. bond order 4). In fact, a typical Cr-Cr single bond accounts for the bond energy in the range 45-50
kJ mol-I. Here it should be pointed out that the quadruple bond is quite strong for the heavier
elements. In fact, the Cr-Cr quadruple bonding is much weaker than Mo-Mo or W-W quadruple bonding.
The 3d-3d orbital overlap is not so good compared to that in 4d-4d'or 5d-5d orbital overlap. In/act,
the relativistic expansion o/the d-orbitalsfor the heavier congeners enlarges their radii sufficiently to
allow a good overlap between the d-orbitals of two atoms. This aspect has been illustrated in Sec.
12.8.1. The metal-metal bondforming tendency is pronounced for the heavier congeners ofthe d-
andI-block elements.
• Dimeric copper(II) acetate (cf. Sec. 12.8.1) : In this connection, the dimeric copper(ll) acetate
is worthy to be mentioned. It has got also a metal-metal bond of length 264 pm. The unpaired electron
in the 3dx2 _ y2 orbitals on each Cu(II) (a d 9 system) undergoes a lateral overlap to form a weak delta-
bond (see Fig. 9.19.2b). The unpaired electron in Cu(II) exists in d 2 2 orbital and it happens so due
x - y .
0·---- ----·0 z \
\
/1" /'i' I \
\
~'a
/1 I Cr I '" \
CH3-C'\(v6~ ;; ~J"yC-CH3 \
\
~Cu~ ----(
1 \ f)j ,
)----
1
/i'0·---- ----0"'" ~IW dX2 _ y2 \\ " dx2_ y2
CH 3-C",'. I" ~r I /' yC-CH

1
3 d x2_y2
I
~I
I
I) I I
"I I
\
\
,,,
"--....~ 49+ ,,
\
\
' 1 / ,,;o \
ry
"",
~CU
I I " ---.1.r--- 6
o-----i----- . Y
"",
cjr \t) x '
l\ ~ P (pairing energy)
b
Singlet (6~) ~ Triplet (8~8·1)
ra
OH 2
(a) (b) (c)
Fig. 9.19.2. The quadruple bonding in dimeric chromium(II)-acetate (a) and delta bonding in dimeric
ib
copper(II)-acetate (b and c).
d:
yl
to the z-out J.T. distortion (cf. t~g e;,
the three electrons in the g level are: 2 i e i)' The unpaired
to·.
2 _
electrons in the d x2 _ i orbitals are distributed in the o-MOs giving rise to 0 Here it must be
m
mentioned that this 6-bonding interaction leading to spin-pairing and 'Cu-Cu' bonding is very much
weak. In fact, even at room temperature, the equilibrium, singlet (O~o·o) ~ triplet (O~O·I) exists.
he
It causes only a partial spin pairing. Here no sigma- and pi-bonds are formed in contrast to the quadruple
bond. Here only a partial pairing of the unpaired spins takes place to reduce the magnetic moment from
lc
the spin only value 1.73 8M to 1.4 8M per copper atom. Thus, in dimeric Cu(lI) acetate, there is
only a weak antiferromagnetic coupling through delta-bonding. As a matter of fact, here Cu-Cu
ea
distance (264 pm) is longer than the corresponding metallic distance (256 pm) in the copper crystal.
Moreover, ifsome electron withdrawing groups (e.g. F) on the acetate moiety are introduced gradually,
th
the magnetic moment increases to 1.73 8M per copper atom due to the gradual weakening of the delta-
bonding interaction. The electron withdrawing groups on the acetate moiety produces more positive
e/
charge on the metal centres to weaken the Cu-Cu interaction through the delta-bonding due to the
electrostatic repulsion (cf. Sec. 12.8.1).
t.m
The reduced magnetic moment in the diineric copper(II) acetate may also arise through the
superexchange mechanism by using the 1t-orbitals ofthe bridging carboxylates (cf. Sec. 12.8).
The characteristics of the metal-metal bonding in different cases have been discussed in detail in
Sec. 12.8.
+
(Note: bond: The bonding interaction, 6 lobes + 6 lobes produces the cI>-bond; obviously among
the s, p, d andforbitals, only some suitableforbitals can produce the cI>-bond).
9.20 ODD ELECTRON COVALENT BONDS IN ODD

ELECTRON MOLECULES
In some cases, a covalent bond is made of by sharing one electron or three electrons. Such bonds
formed by an odd number of electrons are described as odd electron bonds and the molecules having
s'uch bonds are called odd electron molecules. Both the theories, Le. VBT and MOT, can explain such
odd electron bonds.
724 FundaQ1ental Concepts of Inorganic Chemistry
VBT for Odd Electron Bonds

The one electron bond in the hydrogen molecule ion, H; is supposed to have stabilisation through the
two equivalent resonating structures, Le. H - If" ~ +H - H. Similarly, the three electron bond in He;
is stabilised through the resonating structures, Le. +He- :He ~ He : - He+. In fact, in the three electron
bond, only one electron is participating in resonance as in the case of on~ electron bond. Thus, it is
expected that both the one and three electron b~nds are of almost the same strength. But such odd
electron bonds are weaker than the normal electron pair bonds. These speculations are confirmed by
experimentally determined bond parameters as given below.
ry
Molecular species Bond length (pm) Bond energy (kJ mOll)
ra
74 458
ib
105 255.5
108 251
yl
In the valence bond concept, it is revealed that the net stabilisation in the odd electron bond is
m
attained through the resonance. When the two resonating structures become equivalent, the resonance
stabilisation energy becomes significant. But, for this purpose, the involved atoms should be very much
he
comparable both in size and electronegativity. In fact, such bonds occur mainly between the like atoms
or those differing by not much more than 0.5 unit of electronegativity. Such conclusions are supported
lc
by the experimental facts.

The odd electron may be considered to remain as a nonbonding electron. The species (e.g. N02)
ea
bearing the odd electron as the nonbonding electron may undergo dimerisation in which all the bonds
are electron pair bonds. In such cases, the nonbonding odd electron cannot earn any extra
th
stabilisation in the monomeric species but dimerisation produces a new electron pair bond. This
is the driving force behind dimerisation ofsuch odd-electron molecules. This is illustrated for dimerisation
e/
of N02•
t.m
Mf=-12.9 kcal mol-I
The dimerisation of N02 is quite understandable but it is apparently very difficult to understand the
cause behind the reluctance of NO to undergo dimerisation (cf. Fig. 9.11.2.2d) :
2 - NO ~ N20 2, Ml = - 1.6 kcal mol- 1
VBT cannot offer any satisfactory explanation for the above mentioned observation. In MOT, it is
found that the odd electron in NO is not localised on nitrogen, rather it is delocalised over the whole
molecule through a 1t* molecular orbital (cf. Figs. 9.11.2.2a, d). This is why, NO is reluctant to undergo
dimerisation. On the other hand, in N0 2 the odd electron remains in a nlJnbonding a-MO which is
basically localised on the central atom, i.e. N (cf. Fig. 9.12.9.6). This is the merit of MOT.
Note: The 2c-3e bond as in He;, HeH, etc. in VBT is equivalent to 2e in the BMO and Ie in the
ABMO, i.e. bond order = 0.5 in the light of MOT.
Examples of Odd Electron Bonds

(a) One electron bond: H;, Li;, Na;, etc.
(b) Three electron bond: He;, HeH, ° NO, N0 CI0 etc·.
2, 2, 2
02 : The common two electron bond concept cannot explain the paramagnetic properties of the
species. Thus it is proposed that in addition to one 'two electron bond, there are two three electron
bonds in 02. Thus the molecule is represented by, :0 ::: 0:. The structure gives two unpaired electrons.
But it is very difficult to predict in advance whether the structure will be Q= Q
or:O ::: 0: without
ry
the prior knowledge of magnetic properties. 'This is the serious limitation in the concept of VBT.
However, in the same way, the electronic configurations of the different oxygen molecule ions and
ra
some other molecules can be represented as follows,
0; ~O..:::.. 0:]+ ; 0; [:o~ 0:]-; 0;- [: Q_:g]2-; NO [: N "::':"0:];
ib
[ ~o:] [/9.:']
yl
NO] N".......... ; C/O] :C/..........
··~O: ··~O:
m
MOT for the Odd Electron Molecules
he
In LCAO-MOT, no special consideration is needed to explain the bonding process in the odd electron
molecules. The bond order concept can nicely ~plain the fractional bond order. The odd electron
lc
molecules such as H;, He;, NO, etc. have already been discussed (see Table 9.9.1.1). The MOtreatment
for such species has been discussed already in this chapter in detail
ea
9.21 ELECTRON DEFICIENT COVALENT BONDS AND ELECTRON

th
DEFICIENT COVALENT COMPOUNDS

(See Sec. 9.13.5 for Hypervslent Electron Deficient Bonds)
e/
There are some cases in which the number of available valency electrons is not sufficient to display the
t.m
normal electron pair bonds (Le. 2 centre-2 electron, 2c -2e) among all the constituent atoms. This type
of compounds is generally referred to as electron deficient compounds. Here it is worth noting that
in a particular compound, all the bonds are not to be necessarily electron deficient. The simplest electron
deficient covalent bond has already been discussed in connection with H;.
Generally, in electron
deficient compounds, for the central atom, the number of valence orbitals exceeds the number of
.valence electrons available for bonding. Such electron deficient atoms acting as the central atoms
can produce electron deficient covalent compounds where some ofthe bonds are electron deficient.
The occurrence of electron deficient covalent bonds is a common feature in some classes of
compounds ofGr IIIB (13) elements. For example, boron contains only three valence electrons while
there are four valence orbitals and it stands as a typical example of electron deficient atoms. Similarly,
beryllium can also be regarded as an electron deficient atom. Here it must be remembered that all the
compounds of these electron deficient atoms (acting as central atoms) are not to be necessarily electron
deficient compounds. To consider a compound as an electron deficient one, it must contain at least
one electron deficient bond. Thus, (BeC/~';~12(~6' BF3 , etc. are .no~ the electron deficient compounds,
because all the bonds are normal electron pair bonds. In BF3, pi-bonding (2c - 2e), Le. 2pz (F) ~ 2pz
(B), removes the electron deficiency in boron. But (BeH2):x, B2H6 , Ga2H6 , (AIH3):x, etc. involve electron
deficient bonds in their constructions..
Note: Sometimes the compounds where the central atom bears electron less than 8 (i.e. octet
is not attained) are simply described as electron deficient compounds. Such compounds like BeX2,
BX3, A/X3, etc. can act Lewis acids to attain the octet. This
convention does not consider the existence ofelectron deficient
bonds.
ry
• Bonding in B#6: To illustrate the idea, we are to
consider the diborane which has been studied extensively. The
ra
simple monomeric hydride, BH3 can never exist. It leads to
dimeric B2H6 • Ifwe consider its ethane-like structure H 3B-BH3,
ib
it will require 7 x 2 = 14 electrons from the standpoint ofnormal
electron pair bonds. But, for the bonding purposes there are only
yl
12 electrons. Before to highlight the theories Qf electron
deficient bonds, we should consider the bonding parameters in
Fig. 9.21.1. Bonding parameters
m
B2H6 (see Fig. 9.21.1). It indicates that all the B - H bonds are in 8 2 He·
not equivalent. The bridging B-Hb (133 pm) bonds are longer
he
than the terminal B-H, (119 pm) bonds. The terminal B - H, bond lengths are in good conformity with
the sum ofthe single bonded covalent radii of boron (88 pm) and hydrogen (30 pm). Thus the terminal
lc
B - H t bonds are normal electron pair bonds, but the longer bridging B - H b bonds are having
bond order less than unity. The two bridging hydrogens (Hb) lie in a plane perpendicular to the
ea
rest of the molecule and prevent the free rotation along the axis joining the boron atoms. In terms
of VBT, the bond angle parameters indicate that for forming the bridging bonds, boron uses almost
th
pure p-orbitals and thus the s-orbitals are mainly concentrated for making the terminal B - H bonds to
widen the bond angle H, - B- H" In fact H, - B- H, is far away from the ideal tetrahedral bond angle.
e/
Several theories have been put forward to rationalise the bridging structure in B2H6 • Except the idea
of three-centre two electron bond (3c - 2e) in the light ofMOT, all other theories are of only historical
t.m
importance.
• MOT of Three-Centre Two Electron B-Hb-B Bond* and Bonding In B2 H6

In B2H6 , each boron is sp3 hybridised. Among the four sp3 hybrid orbitals, one is remaining vacant.
Each boron utilises two sp3 hybrid orbitals to form two normal electron pair (2c - 2e) terminal B-H,
bonds. Thus, the electron pair in each terminal B-Ht bond is localised between the nuclei in the
bonding molecular orbital (2c-2e) formed through combination of Is-orbital of the terminal hydrogen
and 2sp3 hybrid orbital of the boron.
But, for the bridging bonds, the three orbitals, Le. one sp3 hybrid orbital from each boron and Is
orbital of the bridging hydrogen, undergo LCAO to form three three-centre molecular orbitals (see
Fig. 9.21.2), Le. bonding MO, nonbonding MO and antibonding MO.
• For the pioneering work in the bonding theories in the hydrides of boron. Prof. W.N. Lipscomb was awarded Nobel
prize in 1976.
Introduction to Chemic~1 Bonding and Theories of Covalence 727
The combinations are as follows :
'V b : 'V B} (sp3) + 'V H b (1 s) + 'V B2 (sp3 )

'V nb : 'V B}(sp3) ± YHb(b) ...... 'V B2 (sp3) == 'V B1(sp3) - 'V B2 (sp3)
'Va: 'V ~(sp3) - 'V Hb(b) + 'V B2 (sp3) == - 'V B1(sp3) + 'V Hh(ls) - 'V B2 (.'ip 3)
In terms of mixing coefficients, these are given below:
1 1 1
ry
'l'h =2" 'l' ~ (.,i) + J2 'l' H, (Is) + 2" 'l'8 (si) 2
ra
1 1
'l' nh = J2 'l' ~(si) - J2 'l'8 (sp3) 2
(weakly antibonding in character)
ib
1 1 1 1 1 1
'l1 a =2' 'l' ~(si) - J2 'l' H,(Is) + 2" 'l'8 2(si) == - 2" 'l' ~(sp3) + J2 'l' H,(Is) - 2" 'l' 8 (sp3)
yl
2
The above combinations can be interpreted in terms of group orbitals (i.e. TASOs) where the
m
B-atoms are considered as the terminal atoms and H-atom is considered as the central atom. The two
sp3 orbitals of B-atoms can produce 2 TASOs.
he
'V B} ± 'V B2 :::) ~B(+) = ('V ~ + 'V B2 ) and ~B(-) = ('V ~ - 'V B2 )
, ... I
TASOs
lc
The TASOs can combine with the Is orbital of the central atom to produce 3 MOs (3-centred)
where in terms of symmetry, ~B(+) can interact with the Is-orbital of the hydrogen atom but '8(-)
ea
cannot participate in such interactions. Consequently, the antibonding combination +B(-> remains as
a non bonding one. The combinations are given below:
th
'V b : 'V H b + +B(+); 'Va: 'V Hb - +B(+); 'V nb : +B(-)

e/
The nonbo"nding MO can also be simply interpreted as follows:

'V nb : 'V B, ± 'V Hb - 'V B2 == +B(-) (weakly antibonding)
t.m
Thus it is evident that the nonbonding MO is weakly antibonding and the antibonding interaction
remains between the spJ-hybrid orbitals ofthe B-atoms. However, for the sake of simplicity of'Vnb MO
is considered as the simple sp3-hybrid orbital of the B-atom. Thus it is believed that the 'Vnb MO can
neither stabilise nor destabilise the system. The above three 3-centred MOs explain the bonding in the
segment B-Hb-B. Formation of the MOs and the corresponding MO-diagram are shown in Fig. 9.21.2
that explains the 3c-2e bonding in B-Hb-B (Le. H-bridge bond). In the present 3c-2e bonding system,
there is no requirement to place any electron in the NBMO which is weakly antibonding.
Similarly, another set ofthree MOs can be obtained. In each set ofMOs, there are only two electrons
(one from hydrogen, and one from thesp 3 hybrid orbital of one boron atom. while the other boron atom
uses the vacant sp3 hybrid orbital) and these are placed in the bonding MO. These hydrogen bridge
bonds are very often referred to as open type three-centre two electron (3c-2e) bonds. Thus in B2H6
four terminal B-H, bonds are the normal2c-2e bonds while the two bridge (B-Hb-B) bonds are electron
deficient 3c-2e bonds.
ry
ra
ib
yl
I \
(a) I \
I'W*'
I 8 \
m 'VB(sp3) I
I
I \
\
cPS(-) I \ 'Vnb \
'VB(sp3) ,--t- - \ 1 ( ------ \
he
~ I 'Vnb \ \ \
::::4='/ I \ \ \
"---1 \ \ \
<PS(+) \ \ \ \
~ \ \ \
lc
\ \ 'VH(1s) \
~ \ \ 'VH(1s)
CD
c:
\\ I
r+- \ \
, 1
W \
.
ea
\ I \ I
1
\ I I
1
\
\.....ft-I I
'Vb
,
\ I
th
'""-v--' • 'Vb
'---v----J
TASOs MOs MOs
e/
~) (~
Fig. 9.21.2. Three-centre two electrons (30-2e) bonding and 3c open type molecular orbitals (a) in
t.m
bridging B-Hb-B bonds and their energies (b) In terms of TASO. (c) Without the concept of TASO.
In the 3c-2e bonding model (bond order = 2"1 for each B-Hb , linkage), the terminal atoms (Le.
B-atoms) are expected to be electropositive (cr. Sec. 9.12.12) in character and it also happens so
here.
(Note: See Sec. 9.12.12 to compare the 3c-4e and 3c-2e bonding model. In each case, the bond
order per link is 0.5).
The total MO-diagram for B2H 6 is given in Fig. 9.21.3. For the monomeric planar species BH3 , the
MO energy diagram is given in Fig. 9.12.10.4.
• Bond angles in B1,H6 : To explain the bond angle parameters in B2H6 , it is reasonable to consider
the fact that in forming the B-Hb-B bridge bonds, the B-atoms use the s-p hybrid orbitals in which
the p-character is more than 75% and s-characte.r is less than 25%. Consequently, in the formation
Introduction to Chemical Bondmg and Theories of Covalence 729
~~~3 0* (Terminal)
I \
I \
I
I ~ 0* (Bridge)
I~
I
I
~'
, ,
_~
, \
\
r
=
--~
~
;
===:/~ __ - - - - ' !
I
8 sp (28)
,
~
\'
\,
',\
,\
,\
~
,
'onb (Bridge)
J1===== =====
===== ,,- - - - - - - - ~r
Hij) ".~ ....
-H- \ - - - - - - - - - - -~'
\' 1 6 15 (6H)
\' ~ I I I , , I
ry
\ , /I , • r·J / \ I.,. H I
\' ~ I , .' t I
\ \ 1 ' '0/ '/" 0b (Bridge) I Ht • I
\ I I " I
~'.'
ra
\ I I .' " I • I
I \ \ I I I
-----
\ I
· : 7: .0b (Terminal) I \ \/ I I
_'~r:J/- _!.,'
ib
I - -- - /,--,
'--v---J
AOs (28) MOs AOs (6H) Hb
•
Fig. 9.21.3. Molecular orbital energy diagram of B2 He.
yl
Note : The plane containing the bridging hydrogens is perpendicular to the rest of the molecule.
m
he
of B-Ht bonds, B uses the s-p hybrid orbitals in which s character is greater than 25%
(c/. H, - B- H, =121.5°) 109°28).
lc
• Bonding in higher boranes : This aspect has been discussed in detail in Sec. 10.12. In explaining
ea
the higher boranes, close type three centre two electron bonds (B-B-B) are also invoked to operate.
Here each boron residing at the comers of a regular triangle provides one sp3 hybrid _orbital to form the
close type three-centre MOs (see Fig. 9.21.4). Here it is worth mentioning that H; (an equilateral
th
triangle) also involves the similar 3c-2e bonding (cf. Sec. 9.12.2). In some cases, multicentred bonds
covering different boron atoms are also fonned. By considering the suitable combination of 2c-2e B-
e/
H bonds, 2c-2e B-B bonds, open type 3c~2e B-H-B and B-B-B bonds, close type 3c-2e B-B-B
t.m
bonds, multicentred bonds by boron atoms, the structure of higher boranes can be explained (cf. Sec.
10.12). Some representative structures of such higher boranes are shown in Fig. 9.21.5. '
G
B
B~
'Vb
Fig. 9.21.4. Three centre two electron (30-2e) bond (closed type) in B-B-B of higher boranes.
ry
ra
o=s
ib
• = Hb
o = Ht
yl
m
8 SHg
Fig. 9.21.5. Structures of some common higher boranes.

he
• Electron deficient 3c-2e hydrogen bridge bonds in other system: Such electron deficient 3c-2e
lc
hydrogen bridge bonds are noted in (BeH2)x' (AIH3)x' (GaH3)x. The structure of polymeric (BeH2)x is
shown below:
ea
" /Hb , /Hb , /

/Be" H /Be" H /Be"
th
b b
Tetrahedral arrangement around Be

e/
Similarly, such hydrogen bridge structures are also established in the covalent borohydrides of Be,
Ga and Al as shown below. In fact, the simple alane AIHJ does not exist. It undergoes polymerisation
t.m
through the AI-H.-AI bridging bonds giving rise to 6 coordination number to AI.
Al{Hb)B(H 1
) BefHb)B(HI)
Hb H, Hb H,
3 2
Octahedral arrangement Tetrahedral arrangement
around Al around both Be and B
Here it is worth mentioning that in the ionic borohydrides, no electron deficient bridging bond
exists. It contains BH; moiety which is isoelectronic with CH4 •
• Bonding and structure of (A/(CHJ)Jl:z and IBe(CHJ )2)x : The dimer of trimethyl aluminium,
Le. [AI(CH3)3]2' contains the electron deficient bridging three-centre bonds, AI-eb-AI. The bonding
p~ttem in [AI(CH3)3]2 is identical with that of B2H6 • Here four terminal 2c-2e AI-C" anc!. two bridging
3c-2e Al-eb-AI bonds are present (see Fig. 9.21.6). The value of the bond angle, Al - Cb - Al is 75°.
ry
3c - 2e bonding
ra
(a)
ib
yl
m
he
AI···· ·AI (270 pm) (3c - 2e bonding)
lc
ea
th
e/
t.m
Fig. 9.21.6. (a) Structure of [A~ CH3):J2 and 30-2e bonding in AI-eb-AI bridge. (b) Structure of A/2 Phe
having bridging ll 1-phenyl group perpendicular to AICAIC plane. (c) Polymeric ~tructure of Be(CH3 )2
and 30-2e bridge Be-Cb-Be bond. .
Note : • For bulky R-groups. AIR3 predominantly exists as a monomer due to steric factors. It
-P-M8.
Me
happens so for R = mesityl group =
Me
• In presence of a Lewis base, the electron deficient weak bonds like AI-H-AI, AI-Me-AI are
broken to give the 2c -2e bonds.
A/2 Mee + 2NEt3 ----+ 2Me3 AI ~ NEt3
This small value indicates some sort ofdirect overlaPRing between the metal centres. However, such a
direct overlapping is not an important requirement in the formation ofelectron deficient bridge bonds.
The electron deficient three-centre bridge bonds Le. 3c-2e Be-Cb-Be, are found in the polymeric
form IBe(CH3)2Ix • Here all the methyl groups ar~ bridging groups like the hydrogens as in (BeH2)x'
• Bonding and structure ofAI2Ph 6 : In the dimer A12Ph 6 , the bridging 11 I_Ph group is perpendicular
to the AICAIC plane. Th~ symmetric combination of C and Al orbitals produces a 3c-2e AI~-AI
bridge bon~~ In addition to this, a 7t-HOMO (simply a Pn-orbital) makes an antisymmetric combination
with the AI-orbitals. This allows electron donation from the 7t-HOMO of phenyl ring to the AI-atoms.
ry
In fact, the Ph-group makes a better bridge than the Me-group. In A12Me 4Ph 2, the Ph-groups rather
than the Me-groups act as the bridging groups. The bridging efficiency runs as :
ra
x- > H- > Ph-> R-, (probably small H-atom fits better between the metal centres)
• Bonding and structure of ILi(CHJ»)4 : It is quite interesting to consider the structure of the
ib
tetramer [Li(CH3)]4 where the Li-centres occupy the alternate comers of a cube and the CH3-groups
occupy the residu,al 4 corners of the cube (Fig. 9.21.7). Thus the L;4 cluster constitutes a tetrahedral
yl
framework and the 4 methyl groups are positioned symmetrically above the mid-points ofthe tetrahedral
faces. Each Li-centre is considered to be sp3-hybridised. The 3 Li-centres in a tetrahedralface provide
m
three sp3-hybrid orbitals to interact with one sp3-hybrid orbitals of C to generate four 4-centred MOs
i'n which the bonding MO is onlyfilled in. Thus the 4c-2e bonding constitutes the Li3C unit. The ()nly
he
4 electron pairs (4 electrons from 4 Li atoms and 4 electrons from 4 methyl groups) are involved
to constitute the tetramer.
lc
~
\.:
ea
Li CH
3
ABMO
H3C '\:'"
th
\~.. NBMO
Li
~J /Li
e/
1~ SMO
l'Li
t.m
CH a
(a) (b)
Fig. 9.21.7. (a) and (b) structure of LI4(CH3)4; (c) 40-2e bonding and formation of 4-centred MOs in
a tetrahedral face. Note : Ns4 Me4 adopts the similar structure. In the hexamer (LiR)6' 6 Li-atoms are
placed at the corners of an octahedron and the alkyl groups are placed above the 6 faces of 8 triangular
faces. It also experiences the multicentre electron deficient bonding.
Such electron deficient hypervalent bonding and hyper-coordination number are now well
documented (cf. Sec. 9.16, 9.13.5).
(Note: The extent ofpolymerisation of LiR can be prevented by using the bulky R-groups due
to steric hindrance).
• Structures of h~/ides ofBe, B and Al : In this regard, it is important to highlight the structures of
halides of Be and Al as shown below. To remove the electron deficiency (Le. to attain the octet at the
central atom), Cl atoms are acting as the bridging moieties through the utilisation of the lone pair on
the Cl atoms into the vacant orbital of Be or AI.
CI"
CI-B< Be-CI .
C(
Here no bond is electron deficient and all the bonds are 0/normaI2c-2e character. Similarly, in
BF), BCI), through the pi-bonding, the electron deficiency is removed and the octet configuration is
ry
attained and no bond is electron deficient.
ra
ib
In this connection, it is worth mentioning that Ale/3 prefers the dimeric form rather than the
x-bonded (i.e. internal Lewis acid-base interl:'ct;on) monomeric structure as in BX3 to remove the
yl
electron deficiency i.e. to attain the octet. Because ofthe larger size ofthe involving atomic orbitals,
the sideways 1r-interaction in AIXj gets weakened (see Sec. 10.7). This is why, it prefers the a-bonded
m
structure which is attained in the dimeric form. For BX), however, there are some spectroscopic evidences
in favour of the existence of unstable bridging structure. In a mixture of BF) and BCI), the exchange
he
of halides probably occurs through the following bridging structure.
,
F, "XF,
lc
/C/
BF) + BCI) ~ /B," B, ~ BF2Cl + BCl2F
ci'<,,
ea
F C/
(Transition state)
th
It may be noted that for such exchange reactions, enthalpy change (Mi) is more or less zero and the
reactions are mainly entropy driven. In fact, in such exchange reactions, entropy increases.
e/
• Reduced Lewis acidity 0/ BMe3 and BPh 3 : In the BeMe), to remove the electron deficiency
around the central atom, hyperconjugation occurs.
t.m
HjC,"
,
~H
"B - C_/- H ....
HjC
,,-
B=C
H+ H
/
4 ...
~C
/ "H ~C
/"
H
Because o/this/act, BMej is a weaker Lewis acid than AIMej where no such hyperconjugation
occurs. To execute the said hyperconjugation in AIMe3 , the" 3p (AI) - 2p (C) 7t-bonding should occur,
but this 7t-interaction is not efficient (cf. in BMe 3 , the 2p(B) - 2p (C) 7t-interaction is very much
significant). In BPh 3 , the direct 7t-bonding can remove the electron-deficiency at B and consequently
BPh 3 acts as a poorer Lewis acid. In fact, compared to BMe3 , BPh) is a poorer Lewis acid. It indicates
that the direct 1r-bonding interaction is more efficient than hyperconjugation.
• Relative stability of B~4 : In the compounds, B-74 having a B-B linkage, the 7t-bonding is quite
important and the stability of B-74 depends on the efficiency of 7t-bonding. The stability order
is :
x X
B2Cl4 (B2 F4 (B2 (OR)4 ((B2 (NR2 )4; ~B-B(
X X
Here the x-bonding efficiency of X is determined by its relative orbital size with respect to that
of B and Lewis donor strength of X (specially, the electronegativity effect ofthe donor site).
ry
ra
9.22 MOLECULAR ORBITAL THEORY IN EXPLAINING HIGHER
OXIDATION STATES OF NONMETALS
ib
In vsf, through- the concept of d-orbital participation in hybridisation (Sec. 9.13.5), the existence of
PCls and the nonexistence of PHs, PMe s have been explained. The same argument can be extended to
yl
explain the stability of SF6 , SiF62-, XeF6 and the instability of the corresponding hydrides. In general,
AXn --) AXn _ 2 + X 2 occurs when X is less electronegative. In terms of thermochemistry, the enthalpy of
m
the process is given by,
he
AH = nD~ _ X(AXn ) ~.(n - 2)D~ _ X(AXn _ Z ) - D~ - x
When, nD~ _ X(AXn ) - (n - 2)D~ _ X(AX._ z ) ; D~ _x' AXn is thermodyna~ically stable.I!' stands
lc
for the average bond energy in the molecule under consideration. In all cases, DA - X(AXn _ 2 ) > DA - X(AXn )
(irrespective of electronegativity of X). But the bond energy in AXn gets lowered down more when X is
ea
less electronegative. This fact

can nicely be explained in the , \
I 0 \\ s.
th
light of MOT. I
To illustrate the matter let us I , " \\

I , , \
I , ',\
e/
take the example, SX6 • Here, S I I ~

provides four AOs (i.e. 3s + 3p) p~ I I
I ,
IS 11 ----~~§§§
(:
i i - " I , nb , 6 ADs of
t.m
and 6 X provide six cr - AOs for I ' I , h

I sa ·'', I , I, 6)(
LCAO to generate ten MOs. I
II~ , 3p
I I
I I
II
II
I " I I II
Without considering the hybridi- I " , I I,
II
~,
',) " ' /,'
sation of the AOs of S before
participation in LCAO, we get
1/
I/ ".J
" 3s (I "'.. Po " II'' I
II / )
the simple MO diagram (see Fig. 1/ I I ',Ii I
II " I (ADs of S) " /
,so I
9.22.1). The important aspect
of the diagram is that the two
- -'
11
===~---_.
=~
6 AOs of \~"
11
b 'l
n / I
,. I I
1/
I I
' ..
(MOs for low electronegative X)
non bonding MOs (which are 6 )( \ \ '.... , ,,' I /
almost pure AOs of X) are \\ Po I
\ I
occupied by four electrons. ,---+--,
SC'J
Thus, if X is highly electro-
negative then the accommo- (MOs for highly electronegative X)
dation of the electrons in the Fig. 9.22.1. The molecular orbital diagram of SX6 .
nonbonding MOs is favoured, but if X is less electronegative then this accommodation of the
electrons is disfavoured to destabilise the system. Moreover, the bonding electrons are also stabilised
more when X is more electronegative. Thus SX, is stable when X is only highly electronegative. In
SX6 , the total 12 valence electrons are distributed as: 8 electrons in 4 bonding MOs, and '4 electrons in
two nonbonding MOs. The 4 pairs of a-bonding electrons produce a a-bond order of 2/3 ·in each S-X
linkage. For the low electronegative X atoms, the nonbonding electron pairs are not stabilised and
consequently SX6 becomes less stable.
Note : By considering the 3c-4e bonding model along with the 2c-2e bonding interaction in
ry
some bonds, the octahedral geometry of SX6 can be explained by using only the s- and p-orbitals of
S without the d-orbitals. For the stability of 3c-4e bonding model, it needs the highly electronegative
ra
terminal atoms to stabilise the nonbonding electrons. These aspects have been discussed in detail in
Sec. 9.12.12 and 9.13.5.
ib
Similar conclusions can be drawn to explain the instability of SH4 , PHs, XeH2 , XeH4 , XeH6 in terms
yl
of MOT. In such cases the bonds are so weak that the compounds are unstable with respect to the loss
of H2•
m
9.23 MOLECULAR ORBITAL THEORY IN EXPLAINING THE BONDING
he
IN INERT GAS COMPOUNDS : 3c-4e BONDING MODEL
lc
Bartlett's discovery of Xe + PtF6- in 1962 paved the way to isolate several covalent compounds of
xenon within a very short period. In 1962, it was reported by Bartlett that PtF6 reacts with oxygen at
ea
room temperature to form an orange coloured ionic solid, dioxygenyl hexafluoroplatinate(V), 0; PtF6- •
It was suggested that the high electron affinity of PtF6 can compensate the ionisation potential (12.10
th
eV) of O2• Since the ionisation potentials of Xe and 02 are comparable, it was argued by Bartlett that Xe
should also form the same type ofcompound. This prediction put in experiment produced the expected
e/
compound, Xe + PtF; a crystalline red solid.

A large number of xenon compounds with the only highly electronegative elements like fluorine
t.m
and oxygen have been now prepared. These are : fluorides - XeF2 , XeF4 , XeF6 ; oxyfluorides -
XeOF4 , Xe0 2F2 ; oxides - Xe03 ; perxenic acid - H~e06 (Isolated as salts); complex salts - CsXeF7,
Cs~eF8' etc.
Bonding in the Noble Gas Compounds in Terms of VBT

Xenon and others of its group do not contain any unpaired electron to undergo electron pair bond
formation. Moreover, they cannot act as Lewis acids to receive back electrons from the bases, unless
the d-orbitals are getting involved. Thus, to create the unpaired electrons or to receive back the
electrons, participation of the d-orbitals (5d in the case of xenon) is essentially required. We have
already mentioned (see Sec. 9.13.5) that for the participation of d-orbitals, the highly electronegative
elements like fluorine and oxygen are required. This is why, xenon forms compounds with fluorine and
oxygen. This VBT approach along with concept of hybridisation will be discussed in the next chapter
to explain the geometry of the xenon compounds (cf. VSEPR theory).
Bonding in the Noble Gas Compounds in Terms of MOT: 3e-4e Bonding Model
• XeFz : To illustrate the idea, let us take the case of XeF2• ,The valence shell electronic configurations
of Xe and Fare Xe : Ss2Sp 6, F : 2s 22ps. If the bonds lie in the x-direction, then" 2px orbitals of each
fluorine bearing the unpaired.electron (Le. considering the unpaired electron in the 2px orbital) and the
filled 5px orbital of xenon will participate in forming three-centre sigma-MOs. Similarly, the 2py orbitals
of fluorines along with the Spy orbital of xenon will form three-centre pi-MOs. Thus, by using the Pz
orbitals of the fluorines and xenon we get another set of pi-MOs. The corresponding 7t _ and 7tz-MOs
are degenerate as usual. Here the pi-system is of no interest from the standpoint of~tability of the
ry
molecule, as the bonding, non-bonding and antibonding pi-MOs are completely filled in to yield
the pi-bond order zero. Here, we shall restri~t our attention to the three three-centre si~a-MOs as
ra
shown in Fig. 9.23.1.
Formation of the three 3-centred a-MOs can be understood from the following combinations.
ib
•
\Va : \V2Px(F,f)' + \VSPx(Xe) + \V2Px(FB )
yl
\V nh : \V2Px(F,f) ± \VSPx(Xe) - \V2Px(FB ) == \V2Px(F,f) - \V2Px(F,f» FA - Xe - FB
(Mixing coefficients not shown)
\Vh : \V2Px(F,f) - \VSPx(Xe) + \V2Px(FB ) == - \V2Px(F,f) + \VSPx(Xe) - \V2Px(FB )
~
m
FA Xe Fa
ffi
he
\fI a:
CX9 00 y
FA-Xe-Fa
ffi
lc
\fInb: EX:) 00 x
ea
\fib:
00 ffi EX:) Z
th
(8)
e/
a*
No requirement of s- and
d-orbltals ofthe central atom.
t.m
~
~
Q)
c
W
°b
~ ~ ~
AOs (F) MOs AO (Xe)

. Fig. 9.23.1. The molecular orbital picture of XeF2 0
Introduction to Chemical Bonding and Theories of 'Covalence 737
These combinations are shown in Fig. 9~23.1. However, formation of these MOs can also be
interpreted by considering the formation of group' orbitals (i.e. TASOs) by using the 2px orbitals of the
F-atoms (say FA and Fp ).
cI>F(-)' (Symmetric): \V2Px(FA ) - 'V2p (F ) (bonding interaction)
a - type TASOs " x B " . . •
{ cl>F(+) (Nonsymmetrlc): 'V2Px(FA ) + 'V2Px(FB ) (antlbondlng InteractIon)
(cf. Fig. 9.12.1.1 for understanding the formation ofTASOs)
In terms of symmetry, the symmetric TASO cl>F(-) cannot participate in overlapping interaction with
ry
the nonsymmetric 5px orbital of Xe. This is why, cl>F(-) remains as a non bonding one. This produces a
weak bonding interaction between the terminal atoms. The nonsymmetric TASO cl>F(+) can combine
ra
.
with the nonsymmetric p-orbital of Xe to produce the MOs. The resultant MOs are:
. ,.
ib
'Va : 'VSPx(Xe) + cl>F(+); 'Vb :''VSPx(Xe) - cl>F(+); 'Vnb : cl>F(-) (weakly bonding)
The combination and the corresponding MO-diagram are shown in Fig. 9.23.2a, b. It is evident that
yl
the 'IInb (though introduces a weak bonding interaction between the terminal F-atoms) is a 2c-MO
m Xe F
F
'Va:
00 00 00
he
ffi 00
\}J nb:
[= 'F(-~
lc
\II b:
CB 00 00
ea
(a)
,,
th
No requirement of s- and
d-orbltals of the central atom. I
I
,,
,
e/
I
I
I ',--"*ll--
t.m
I 5px
I
I
(Xe)
'F(+) I
=*l:t::l=~. . . "'~'" "

2Px.......... ,
(2F) .......... -----~,--·--1t1-~--
ct>F{-) , \II
Tnb
~ ,
TASOs '
\
,
n
'Vb
~
MOs
(b)
Fig. 9.23.2. Formation of 3-centred MOs in terms of TASOs and bonding in XeF2 "
738 Fundamental Qoncepts of Inorganic Chemistry
I \
and it is basically the AOs of the terminal atoms. I
0* \
\
This is why, the MO energy diagram is very often
I
I
I
\
,
represented as in Fig. 9.23.3.
I
I \
,
The four electrons (one in each 2px of F, two in I \
I ) 1~
5px of Xe) are now placed in the sigma-MOs. These I
I 5Px(Xe)
I I
occupy the lowest MOs Le. bonding and I I
I I
nonbonding MOs. The electrons in the non-bonding ~- - - -
sigma-MO which is richer in the character of 2px
11
2Px(2F) \\
-----.1.-.-
°nb .
,
I
ry
I
orbital of F do not practically contribute in \
\ I
I
\
stabilizing the system. The two electrons in the \ I
I
ra
\
bonding sigma-MO gives the fractional bond order \ I
I
\
to stabilise the system. The bond order in each Xe-
ib
°b
F linkage is 0.5.
Fig. 9.23.3. Simple MO energy diagram of
The model can explain the strong ultraviolet XeF2 (no requirement of s- and d-orbital of
yl
absorption at 158 nm due to the transition, 20 (non- the central atom).
bonding o-MO) -+ 30* (antibonding o-MO).
m
Crucial role of the ~BMO : The NBMO is mainly concentrated on the terminal atoms. The
he
electron pair in the NBMO is stabilised, if the terminal atoms are highly electronegative. This is
the basic requirement for the stability of 3c-4e bonding system (cf. Sec. 9.12.12).
lc
Role. of the highly electronegative F-atoms : Another interesting feature of the model is that the
distribution ofelectrons in the sigma-MOs concentrates towards the fluorine atoms, as both the bonding
ea
and non.bonding sigma-MOs in which the electrons are placed are richer in the atomic orbitals of
fluorine compared to those ofxenon. It develops the polarity, P- -Xe2a+ - P-. Thus in the formation
th
of the compound, the 5px electrons of Xe are moved towards the 2px orbitals of F. This process is
facilitated maximum when the inert gas under consideration possesses the.lowest ionisation energy and
e/
the other combining atoms show the most electronegative character. This is why, Xe which has the
lowest ionisation energy among the stable members 0/ its group (Rn is radioactive, hence it is not
t.m
possible to study the case systematically) andfluorine which is the most electronegative one are the
most suitable partners to undergo compound/ormation. VBT model also supports this demand (Sec.
9.13.5). It may be noted that KrF2 has been characterised and its bonding is similar to that in XeF2•
Note:. The 3c--4e bonding model introducing some ionic character can stabilise the system
only when the terminal atoms are sufficiently electronegative to stabilise the
nonbonding electrons. On the other hand, for the stability of 3c-2e bonding model, the
terminal atoms should be electropositive. The 3c-4e bonding model is very often required
to explain the hypervalence while the 3c-2e bonding model is required to explain the
bonding in electron deficient hypervalent compounds. All these aspects have been discussed
and illustrated in Sec. 9.12.12 and 9.13.5).
• XeF2 (having 22 valence electrons) has been already explained by considering the general
MO diagram given in Fig. 9.12.7.3. In Sec. 9.12.9, it has been explained in a general way
why it/ails to adopt the bent structure.
• XeF4 and XeF6 : From the standpoint of generation of the sigma-MOs, the XeF2 molecule is
linear. The bonding in XeF4 can be explained also in terms of three-centre molecular orbitals. Here, as
in F--Xe-F, there are two sets of three-centre u-molecular orbitals at the right angle to each other
giving rise to the square planar geometry. In the same way in XeF6 , there are three sets ofthree-centre
u-molecular orbitals at right angles to one another giving rise to a regular octahedral geometry. The
prediction regarding the geometry of XeF2 and XeF4 based on the three-centre sigma-MOs is in
conformity with the experimental observation, but the prediction for XeF6 is not fully supported (see
Sec. 10.8.5).
ry
9.24 ISOLOBAL FRAGMENTS
ra
If we compare the species N(CH3)3 and NH3, then it appears that the fragments ·CH3 (7e fragment with
ib
an unpaired electron) and •H (1 e fragment, the electron remains unpaired) are mutually replaceable. In
the modern language, such structurally analogous fragments are described as isolobal fragments.
yl
In terms of orbital picture, both the said fragments are having the similar frontier orbitals (cf. C-sp 3
and H-I s orbitals are of a-symmetry) with an unpaired electron. In fact, the na~e is originatedfrom the
m
lobe /ike shape ofthe frontier orbitals ofthe molecular fragments.
The 17efragment MnH~- or Mn(CO)s (where the ligand 11 or CO is supposed to act as a 2e donor
he
ligand; the ligands may be considered to donate 5 pairs of electron to five cPsp 3 hybrid orbitals of Mno;
6e are present in t2g of Mno; the 7th electron of Mno resides in the 6th cP sp3 hybrid orbital) is isolobal
lc
with the 7e fragment ·CH3 (where three sp3 hybrid orbitals of C produce three 2c-2e C-H bonds, the
4th valence electron of C remains unpaired in the 4th sp3 hybrid orbital). Thus the isoelectronic species
ea
Mn(CO)s and MnH;- are isolobal with CH3.

00
H H CC
th
'\ / \I
H- Mn <:) • • DC - Mn<:)
/\ U
e/
1\
H H CC
(178) 0 0
t.m
(17e)
Fig. 9.24.1. Isolobal fragments CH3 , MnHg- and Mn(CO)s'
For the isolobalfragments, the frontier orbitals are similar in terms oftheir number, symmetry,
energy (approximately) and shape,· and the number ofelectrons in the frontier orbitals are also the
samefor the isoelectronic isolobalfragments. The isolobal relationship is expressed by the symbol
+0+ ,e.g.
In the above fragment family, each member is associated with a singly occupied localised
orbital.
• For a particular family of isolobaI fragments, as their frontier orbitals (which control the reactivity)
are similar in many respects, their chemistry is also similar. The members of the above series can
undergo dimerisation and they also can combine to give the cross-products.
Dimerisation: C2H 6 Le.(CH3)2,Mn2(CO)lO Le.[Mn(CO)s]2,CI2
Combination: CH3CI, CH4, (CO)sMnCH3, etc.
Reduction: CH3 ~ CHi, Mn(CO)s ~ Mn(CO)~; 8 ~ 8 2- , Fe(CO)4 ~ Fe(CO)~- ·
• The following family also gives the examples of isolobal fragments with two localised singly
occupied orbitals.
ry
ra
• Similarly, examples of3e three orbital isolobalfragments are:
ib
yl
H-C , - . R-Si m
• It is important to note that for the hydrocarbonfragments, the nature of frontier orbitals does not
he
change by the removal or addition ofa proton (Le. If"). The examples are :
(a) CH3 +0+ CHi. (7e fragment)
lc
(b) CH2 +0+ CI1 +0+ CH; (6e fragment)

(c) CH +0+ CH; (5e fragment)
ea
(d) C +0+ CIf" (4e fragment)

th
• The isolobal relationship between the organometallic fragments and hydrocarbon fragments
is :
e/
Organometallic fragments with (18 - n)e +0+ hydrocarbon fragments with (8 - n)e.
t.m
Illustration: Fe(CO)4 or Os(CO)4 with 16e Le. (18.- 2)e is isolobal with the 6e Le. {8 - 2)e
system CH2• It leads to:
C3H6 (cyclopropane), Le. (CH2)3 +o+.(CO)12Fe3
Le. [Fe(CO)4]3 +0+ (CO)4Fe(1l2 - C2H4), a metallocyclopronane
Le. (CO)4Fe(CH2)2 +0+ (CO)4Fe~CH2 -Fe(CO)4
Similarly, OS4 (CO)16 Le. [Os(CO)4]4' OS2(CO)S (C2H 4 ) Le. [Os(CO)4]2(CH2)2,Os(CO)4(C3H6)
Le. Os(CO)4(CH2 )3 are isolobal with the hydrocarbon cyclobutane C4 H s Le.(CH2)4·
Ir4 (CO)12 or C04 (CO)12 == [M(CO)3]4 where M(CO)3' a (18 - 3)e fragment is isolobal with the
(8 - 3)e fragment CH. Thus a complex, C0 3(CO)9(CH) is quite likely and M4(CO) 12 +0+ (CH)4
(tetrahedron) where M = Co or Ir.
• Ni(CO)3 with (18 - 2)e is isolobal with' CH2 having (8 - 2)e. Interestingly, Ni(CO)2 with
(16 - 2)e is also isolobal with CH2 having (8 - 2)e. Here the rule is not maintained.
• Cp stands for CsHs. Here, Cp- with 6e is isolobal with three CO groups occupying different
positions. For example (Cp)Fe(CO)2 +-r+ Fe(CO); ~.... Mn(CO)s +-r+ CH3;(Cp)Fe(CO);
+-r+ Fe(CO)s +-r+ Mn(CO)~ +-r+ CH;."
• For the organometallic fragments, heavier congeners can substitute the lighter members to produce
the isolobally equivalent species, e.g. CH3 +-r+ Mn(CO)s +-r+ Re(CO)s; (Cp)W(CO)2 +-r+
(Cp)Cr(CO)2 +-r+ CH; Pt(PR 3)2 +-r+ Ni(PR 3)2 +-r+ Ni(CO)2 +-r+ CH2·
Different families of isolobal fragments
ry
(a) H, CH3, Br, CH 2, R3, RO, Co(CO)4' MnHg-, Mn(CO)s' Re(CO)s' (Cp)Fe(CO)2,(Cp)Cr(CO)3
ra
etc (with one singly occupied orbital on each species).
CO
C).:¢I
ib
< ) . H 3C <).(CO)4F9<).(CO)5·~.n<). ~r~<)
yl
co co CO
R-O·
.. < )·
\/
(Cp)Cr ~ (Cp)Fe(CO)2
.. \~
CO
m
Fig. 9.24.2. Isolobal fragments with a singly occupied orbital.
he
(b) 0, CH 2, R2Si, S, CH-, CH;, Fe(CO)4' Cr(CO)5' (Cp)Co(CO), (Cp)Mn(CO)2' Ni(CO)3' etc.
lc
(with two singly occupied orbitals on each species).

ea
th
e/
t.m
Fig. 9.24.3. Isolobal fragments with two singly occupied orbitals.
(c) N, P, CH;, CH, RSi, Co(CO)3' Ir(Co)3' Mn(CO)4' (Cp)Ni, (Cp)Fe(CO), (Cp)Cr(CO)2' etc.
(with three singly occupied orbitals on each species).
Fig. 9.24.4. Isolobal fragments with three singly occupied orbitals.

742 Fundamenta.1 Concepts of Inorganic Chemistry
(d) C, CH+, Fe(CO)3' Cr(CO)4' (Cp)Co, (Cp)Mn(CO), etc. (with four singly occupied orbitals on
each species).
(e) H+, BH3, (CO)4 Fe, (CO)sCr (orbital without any electron).
6. H3B O. (CO)4 :'~~ O. (cO)s'¢,i' 0

Fig. 9.24.5. Isolobal fragments with a vacant orbital.
ry
Note: Isolobal relationship can predict the existence of many species in advance, but always it
cannot support the experimental findings. For example:
ra
(CO)sMn-O-Mn(CO)s ~ CH3 -O-CH3 , but (CO)sMn-O-Mn(CO)s is not known.
ib
• BH, CH and M(CO)3 : For BH and CH, B or C may be considered sp or sp3-hybridised, where
one hybrid orbital is utilised to hold the H-atom. Thus the frontier orbitals for BH and CH are the
yl
same but they are not isoelectronic. In M(CO)3 fragment, out of the 9 orbitals (five d + three p +
one s) of M, three are involved to hold three CO groups, three remain nonbonded and the residual
m
three orbitals constitute the frontier orbitals. Thus for BH, CH and M( CO)3' in each case, there
are three frontier orbitals. This isolobality was utilised by Wade, Mingos and others to explain
he
the structure of metal carbonyl clustures and polyhedral boron cages.
7J'9
lc
H " , - - - P-Orbitals o
«9B~ · a · C(9~~.-/
'2
e
ea
o·
{iJ (iJ
sp-Hybridisation
Q)
Cii
' - - - - sp-Hybrd .~
th
orbital
H H
I I
e/
Hybrid~B
orbital V'. \B> • U • ~Cf':+)'
CI \!:f a
t.m
(sp3-Hybridisation of B and C)
Fig. 9.24.6. Examples of isolobal fragments but not isoelectronic.
EXERCISE-IX
A. General Questions
1. Carry out the valence bond treatment on H 2 •
2. Carry out the LCAO-MOT treatment on (i) H; and (ii) H 2•
3. Compare the VB and LCAO-MO treatment on H2 •
4. Discuss the characteristic features of sigma-, pi-and delta-molecular orbitals.
5. Discuss the basic principles of the united atom method in MOT.
. 6.Discuss the conditions which favour the participation of the d-orbitals in bonding in nonmetals.
7.How does the Bent's rule govern the pattern of hybridisation?
8.What are the conditions for an effective resonance?
9.Discuss the resonance phenomenon in the light of MOT.
10. What are the limitations of the concept of hybridisation and resonance?
11. Write down the basic concept of quadruple bond.
12. Explain the conditions for attainment. of higher oxidation states in nonmetals in the light of
MOT.
ry
13. Discuss the bonding theories in the electron deficient compounds with special reference to the
hydrides of boron.
ra
14. Discuss the bonding mechanism in the inert gas compounds.
15. Illustrate the isolobal fragments with examples.
ib
B. Justify the Following Statements
yl
(1) He 2 does not exist but He; and He; (excited) exist.
(2) The bond energies in H; and He; are almost identical.
m
(3) Molecular nitrogen is chemically inert.
(4) The ionisation potentials of NO and N2 are remarkably different.
he
(5) The first ionisation potential of N 2 is greater than that of atomic nitrogen while the reverse is true
for 02 and 0.
lc
(6) There are two types of singlet oxygens which differ remarkably in stability.
(7) The bond length of the peroxo-linkage (0 - 0) in F 20 2 is remarkably shorter compared to that in
ea
other peroxo-compounds, e.g. H 20 2, Ba20 2 •

(8) The colours of the halogens (X2) are : F2 (pale yellow), Cl2 (yellow), Br2 (reddish brown), /2
th
(violet).
(9) The °-° bond length varies in the species as : 0; < 02 < O2 < 0;-.
e/
(10) Boron (B 2 ) is paramagnetic while carbon (C2 ) is diamagnetic.

(11) CO and N 2 are isosteric species but CO can act as a potential ligand while N2 cannot.
t.m
(12) On adding two electrons on NO;, the N - 0 bond length increases by '- 9 pm while on adding
only one electron on NO+, the bond length increases by '- 9 pm.
(13) PH3 exists but PHs does not exist while both PCl3 and PCls exist.
( 14) Hybridisation does not necessarily lead to a set of equivalent orbitals.
(15) The geometry of the penta-coordinate system is not rigid.
(16) All the bond angles in CF4 are identical but these are not identical in CH2F 2•
(17) In PCI3F 2 , the fluorines preferably occupy the axial positions of the trigonal bipyramid.
(18) The lone pairs and multiple bonds preferably occupy the equatorial positions in a trigonal
bipyramid.
(19) 1t-Bonds may influence the distribution pattern of the atomic orbitals in the hybrid orbitals.
(20) The ionic azides are stabler than the covalent ones.
(21) The alkali metal salts of azide, cyanate and thiocyanate are isomorphours.
(22) The average bond energy in AXn _ 2 is greater compared to that in AXn .
(23) XeF4 exists while XeH4 does not exist.

(24) XeF2 is linear and XeF6 is octahedral in the light_ 3c - 4e MOs.
(25) Xe can only form compounds with the highly electronegative elements
(26) The stability of SF6 and instability of SH6 can be explained in the light of MOT without the
involvement of the d-orbitals.
(27) In a mixture of BF] and BCI], the halogens interchange to produce BF2Cl and BCI2F.
(28) The bond length in BF] is shorter than that in BF4-.
(29) BI-I] does not exist but BH4. exists.
ry
(30) (AICI])2 is not electron deficient but (AIMe])2 is electron deficient.
(3 1) In B2H6 , all the hydrogens are not identical.
ra
(32) The quadruple bond in Cr(Il)-acetate makes the compound diamagnetic while the delta bond in
Cu(Il)-acetate makes the compound antiferromagnetic.
ib
(33) The metal-metal distance in Re2Cli- is exceedingly small.
(34) In the linear polyenes, with the increase of conjugation, the electronic transition (7t ~ 7t*) suffers
yl
a bathochromic shift, Le. red shift.
(35) The conjugation introduces an additional stability in the system.
m
(36) The delocalisation energy of (NPCI2 )] and B]N]H6 is less compared to that of C6H 6 •
he
(37) Though both N 2 and C2H2 contain a triple bond, their reactivities are totally different.
(38) AICI] dimerises while BCI] remains as a monomeric one.
(39) Both BeCl2 and BeH2 undergo polymerization.
lc
(40) In BF], the 7t-bond order in terms of delocalised MO is 1/J.

ea
(41) In some cases, oxygen can show covalency more than two.
(42) Hypervalence of nonmetals is generally observed during the combination with highly
electronegative elements.
th
(43) Electron deficient hypervalence can arise when the terminal atoms are electropositive.
(44) Period 2 elements fail to show hypervalence.
e/
(45) 3c-4e bonding model operates for the electronegative terminal atoms while 3c-2e bonding model
t.m
works well for the electropositive terminal atoms.

(46) The bonding in the tetramer [Li(CH])]4 can be explained by considering the 4c-2e bonding
model.
(47) Hypercarbon compounds are basically the examples of hypercoordinated carbon compounds.
(48) Hypercarbon compounds may also be described in terms of electron deficient hypervalence.
(49) In aurophile cations hypervalence is observed.
(50) Isoelectronic species are isostructural.
(51) o-Bonds can be formed by d- andforbitals not by s- and p-orbitals.
(52) J..1-Bond is a special type of a-bond.
(53) For the halogens, the intensity of colour increases for F 2 to 12 ,
(54) Excited He 2-molecule (He;) can survive better than the unexcited He 2 molecule.
(55) d-d overlapping interaction is better for the heavier congeners.
(56) The bond order in M0 2 is 6 and the species is diamagnetic.
(57) For the homonuclear diatomic molecular species of2nd period elements, the symmetry interaction
among the molecular orbitals is important for the Ii~hter members only.
(58) The symmetry interaction among the MOs leads to mixing of s- and p-atorhic orbitals.
(59) The activation energy for the reaction N 2 + O2 ~ 2NO is very high.
(60) For the reaction, H2 + /2 ~ 2H/, the so called concerted mechanism involving square intermediate
is not correct.
(61) Both NO and N0 2 possess an unpaired electron each, but N0 2 undergoes diinerisation while NO
is reluctant in this regard.
ry
(62) BF, CO and N 2 are isoelectronic species, but BF is unstable while CO and N 2 are quite stable.
(63) BF and CO are isoelectronic but in BF there is a single bond while in CO, there is a multiple
ra
bond.
(64) The different thermodynamic properties of the isoelectronic species (in gaseous condition) C2,
ib
BN, B'eO and LiF can be explained by their MO energy diagrams.
(6~) The ultraviolet photoelectron spectroscopy (UV-PES) can be used to identify the nature of
yl
molecular orbital energy level. m
(66) In UV-PES, generally He(l) and J/e(/l) emissions are used.
(67) UV-PES can be used to estimate the ionisation energies of molecular species.
he
(68) The colours and photosensitivity of MX depend on their electronegativity difference and these
can be explained in terms of their FMO.
(69) The observed colour sequence (in MX) : white/colourless ~ yellow ~ red ~ black can be
lc
explained by considering the separation between HOMO and LUMO.

ea
(70) HgF2 is white while Hg/2 is red; AgCI is white while Ag/ is yellow; HgO is red while HgS is
black; oxygen is colourless while selenium is red.
th
(71) In photography, AgBr is used but AgCI cannot be used for the same purpose.
(72) In H 3, XeF2 , HF2-, B---H-B (bridging segment in B2H 6 ) , the nonbonding MOs are basically
e/
TASOs.
(73) H; is bent while Hi is linear in tenns of MOT.
t.m
(74) H3 species cannot be bent but H; can be bent. It can be explained by MOT.
(75) The molecular properties of the isostoichiometric species H;, H3 , Hi can be explained by ,
considering their MO energy diagrams.
(76) BH; is linear while BH2 is bent in the light of MOT.
(77) BeH2 and HgH2 are linear in the light of MOT.
(78) NO; is linear but N02 is bent in terms of MOT.
(79) BeCl2 and CO2 cannot be expla.ined by the same MO diagram (though each species possess same
number of valence electrons).
(80) In BeF2, Be-F bond is a single bond.
(81) The species KrF2 is linear and the bond order ,in each linkage is 0.5.
(82) In XeF2, bond energy is only 130 kJ mol-I while the I-F bond energy is 278 kJ mol-I.
(83) From the UVPES ofCH4 , two peaks (23 eV and 14 eV) are noticed.
(84) The concept ofthree centre MO formation can explain the trigonal bipyramidal, square pyramidal
and octahedral geometries ofthe compounds ofthe main group elements without the involvement
of d-orbitals.
(85) In SF6 , the bond order ip each linkage is 0.66 instead of unity, but the S-F bond is very short.
(86) Formation of the elusive species NF6-, CF62- can be explained by considering the 3c-4e bonding
model.
(87) 3c-2e bonding model is used to explain the bonding in hypervalent electron deficient molecular
species like CH;.
ry
(88) The d7t-P ll bonding efficiency runs in the sequence: <:lOi ) 80J- ) pot ) 8;01-·
ra
(89) The structural features and Lewis basicity of N(SiH3 )3' N(CH3 )3' N(GeH3 )3 and P(SiH3 )3 can
be explained by considering the pos~ibility of d7t-p7t bonding.
ib
(90) Ni(SiH3 )3 is planar while P(SiH3 )3 'is pyramidal. This can be explained in terms of steric crowding.
(91) The origin of Bent's rule lies in the concept of overlap-efficiency to strengthen a covalent bond.
yl
(92) In a compound having both 'P=O' and 'P-Br' bonds, the central atom P concentrates more
s-character in the p-o linkage though '0' is more electronegative than Br.
m
(93) The concepts of formal charge and oxidation number in covalent compounds represent two
limiting conditions while the concept of Lewis-Langmuir charge represents the more realistic
he
condition.
(94) The formal charge of an element in a particular compound depends on its conical forms (if
lc
possible) but the oxidation number of an element is fixed in a particular compound.

(95) Formal charge may be fractional but oxidation number cannot be fractional.
ea
(96) Pauling's electroneutrality principle leads to multiple bonding to minimise the charge separation.
(97) The o-bonding interaction is stronger in Moi+ than in Cr24+.
th
(98) In Re 2Cli-, the 'cr centres are in eclipsed condition while in OS2cli-, the ler centres are in
staggered condition.
e/
(99) Re2Cli- is blue coloured and Mo 2CI:- is red coloured.

(100) In the multiple bond of Re 2Cli-, Cl2 can' add with the reduction of Re-Re bond order.
t.m
4
(101) In Cr2 + species, the low Cr-Cr bond energy raises a question regarding the existence of so
called quadruple bond.
(102) Among the s, p, d and .forbitals, only the .forbitals can produce the cI> bond.
(103) BMe 3 is a weaker Lewis acid than AIMe 3•
(104) BPh3 is a poorer Lewis acid th.an BMe3•
(105) CH3 and Mn(CO)s are isolobals.
(106) The '0-0' bond length in the isostoichiometric species 0;, O2 , 0; and 0;- can be explained in
terms ofMO diagram.
(107) The chemical analogy is predominant when the fragments are both isolobal and isoelectronic. .
(108) The fragments BH and CH are isolobal but not isoelectronic.
(109) P4 is highly reactive.
(110) OC~ (cynate) is more stable than CNeJ,(fulminate).
(Ill) In 3c-MOs, the nature of the NBMO depends on the nature of the combining orbitals. T~e NBMO
may be weakly bonding or antibonding between the terminal atoms.
(112) Overlap integral is not solely determined by the angular strength for the s-p hybrid orbitals.
(113) 13, ICIi. and HF2' are linear in terms of 3c-MOs.
(114) In UVPES of NH3, there are three peaks.
(115) Analysis ofUVPES can predict the nature of Mas.
(116) The shapes of the molecular species AB2 depend on the valence shell electron count in terms of
MO~ .
ry
(117) Bonding potentiality of the s-p hybrid orbitals runs as : sp > sp2 > sp3, though the order of
angular strength suggests the opposite sequence.
ra
(118) ·CH3 and ·CF3 radicals are of different geometry.
(119) In basic beryllium nitrate and basic beryllium carboxylate, oxygen shows four coordination
ib
number.
yl
(120) Pauling's exclusion principle states that the total wave function must be antisymmetric.
(121) In He 2, destabilisation by ABMO is higher than the stabilisation by BMO.
m
(122) The dimer (NO)2 adopts the cis-structure through the N-N linkage.
(123) In UVPES of molecules, the vibrational frequency change can tell us the nature of the MO from
he
which the electron is lost.
(124) Walsh's rule can be explained in terms of MOT.
lc
(125) The bond angle follows the sequence: CH2 > OH2 > NH2. It can be explained by Walsh's rule.
(126) BeH2 is linear but BH2 is angular.
ea
(127) The shape of XY2 species depends on the number of total valence electrons (TVE), e.g. linear for
TVE = 16, angular for TVE = 18, 19, 20, linear for TVE = 22.
th
(128) Position of a lone pair can be predicted from Bent's rule.

(129) In H 3C-C==C-H, the H-C-H bond angle is less than 109°28'. It apparently contradicts
e/
the Bent's rule.

(130) Prototropic tautomerism is possible for fIN0 2, H3P03 and H2S0 3.
t.m
( 131 ) OS2ClS2- , W2.Cls4- , Mo2Cls4- , Re2ClS2- are d·lamagnetlc

· but TC2ClS3- IS
. paramagnetIc.
·
(132) The stability order runs as : B2Cl4 < B2F4 < B2(OR)4 < B2(NR 2)4.
(133) The Lewis acid strength runs' as : AlMe] > BMe 3 > BPh 3.
(134) The bonding nature in the dimer Al2Ph 6 is different from that in A12Me 6 •
(135) Gaseous oxygen is colourless but liquid or solid oxygen is blue coloured.
Blue Colour or Liquid and Solid Oxygen

Triplet (dioxygen 02) can be electronically excited to singlet states but this transition in gaseous
state is forbidden. The said transition occurs in infrared region (7920 cm- 1 and 13195 cm- I for the
transitions to I~g and 11:; respectively). But in the condensedphase, a singletphoton ofthe visible
range can simultaneously excite two colliding oxygen molecules and it gives the blue colour.
202 (]L;) + hv (630 nm) ~ 202(l~g); 202 (3 L;) + hv (474 nm) ~ 202(I L;)
c. Write Notes on :
(i)
Sidgwick's rule of maximum covalency,
(ii)
Octet rule and its limitations,
(iii)
Exchange energy,
(iv)
Covalent-ionic resonance in VBT,
(v)
Born-Oppenheimer approximations,
(vi)
Isosteric species,
Cost of hybridisation energy,
(vii)
ry
(viii)
Resonance and delocalisation,
(ix)
Bonding potentiality of the hybrid orbitals,
ra
(x)
Delocalisation energy in the conjugated polyenes,
(xi)
Resonance energy,
ib
(xii)
Tautomerism,
yl
(xiii)
Formal charge,
(xiv)Bent or banana bonds, m
(xv)Delta bonds,
(xvi)Quadruple bond,
he
(xvii)Odd electron molecules,
(xviii)Electron deficient covalent bonds,
lc
(xix)Hydrogen bridge bond,

(xx)2c-2e, 3c-2e, 3c--4e, 2c-1 e, 2c-3e bonds,
ea
(xxi)Hypervalence,
(xxii)UV-photoelectron spectroscopy,
th
(xxiii)Group orbital (TASO)

(xxiv) Hypervalent electron deficient bonding,
e/
(xxv) Participation of d-orbital in bonding for the main group elements.

(xxvi) Walsh's rules and Walsh's diagram.
t.m
(xxvii) MO energy diagram of BF3, H 20, cof-, B2H 6, NH3, CH4 , N0 2, 03' CO, BeX2, N 2, HF, LiF,
NO, XeF6 , lCli., BeH2 , H 3, lCI.
(xxviii) Possible ways of d-orbital contraction.
APPENDIX 9A
FMO Approach to Woodward-Hoffmann Orbital Symmetry Rule for Intramolecular
Cyclisation and Concerted Intermolecular Cycloaddition Reactions
The said Woodward-Hoffmann ortbital symmetry rule states the principle 0/ conservation 0/ orbital
symmetry i.e. phase symmetry of the participating reactant orbitals is retained or conserved in passing
to the product orbitals. In other words, such reactions leading to sigma bond formation in a one-step
reaction can proceed only when the orbitals 0/ like sign overlap Le. a positive lobe overlaps with a
positive lobe and a negative lobe overlaps with a negative lobe. For this symmetry allowed condition,
the cyclic transition state (7:S.) (characterised by a high negative entropy of activation) possesses a
relatively low energy to favour the process kinetically. The principle has been already illustrated in
some reactions (cf. Figs. 9.10.3.1-2, 10.7.2.2). Here, some other representative examples are given.
(i) Diels-Alder reaction (47t + 27t cycloaddition, number indicates the number of pi-electrons of
the reactants): 1,3-butadiene + ethylene (dienophile) ~ cyclohexene.
In the one-step cycloaddition reaction, the HOMO of one reactant will overlap with the LUMO of
the other reactant, if the symmetry condition is maintained. The HOMO (Le. topmost 7t-SMO,
ry
cf. Figs. 1a and 9.15.2) of butadiene is of higher energy than that of ethylene. This is why, the
HOMO of butadiene (rather than the HOMO of ethylene) and the LUMO (Le. 7t*-MO, cf. Figs.
ra
I, 9.15.1) of ethylene will participate in forming the cyclic T.S. Here it may mentioned that these
HOMO and LUMO energetically matc.h better than the alternative possible combination Le.
ib
HOMO (7t-SMO) of ethylene and LUMO (7t*-MO) of butadiene.
The outer lobes of the HOMO (Le. topmost 7t-SMO) of butadiene and LUMO (Le. 7t*-MO) of
yl
ethylene match in terms of symmetry and overlap to form the cyclic T.S. The process (Fig. 1b)
involves: positioning of the reactants in parallel planes to allow the 7t-bond formations; HOMO
m
to LUMO electron transfer (destroying the 7t-bond in both the reactants); rehybridisation of the
.terminal C-atom (sp 2 to sp3) for a-bond formations; localization of a 7t-bond between the inactive
he
C-atoms of butadiene by the lowest filled 7t-SMO.
Thermal vs. Photochemical process: In a thermally controlled intermolecular cycloaddition
lc
process, ,he HOMO of one reactant (in ground state) overlaps with the LUMO of the other
reactant to produce the cyclic T.S. On the other hand, in a photochemically controlled process,
ea
one reactant is photochemically excited to its first electronic excited state (Le. one electron is
excited from its HOMO to LUMO) to produce a singly occupied MO i.e. SOMO which acts as
th
the HOMO to overlap with the LUMO of the other reactant to produce the cyclic T.S.
We have already seen that the thermal cycloaddUion (Fig. 1b) of butadiene and ethylene is
e/
symmetry allowed. It involves the combination· of the HOMO (a 7t-SMO) of butadiene and the
LUMO (a 7t*-MO) of ethylene. The other possible combination Le. the LUMO (a 7t*-MO) of
t.m
butadiene' and HOMO (a 7t-SMO) of ethylene is -also symmetry allowed but this route is
energetically less favourable than the former one.
Now let us examine the photochemical cycloaddition (Fig. 2) of butadiene and ethylene. If
butadiene is photochemically excited leading to the transfe,r of an electron from HOMO (a
7t-SMO) to its LUMO (a 7t*-MO), it will produce a singly occupied MO i.e. SOMO (a 7t*-MO)
which will act as the HOMO. Combination of this SOMO i.e. HOMO (a 7t*-MO) of butadiene
with the LUMO (a 7t*-MO) of ethylene is symmetry forbidden. The other possible route involving
the photochemical excitation of ethylene Le. combination of SOMO (a 7t*-MO acting as the
HOMO) of ethylene and LUMO (a 7t*-MO) of butadiene, is also symmetry forbidden. Thus the
cycloaddition ofbutadiene and ethylene is thermally allowed but not photochemically (Fig. 2).
(ii) Dimerisation of ethylene (21t + 21t cycloaddition) leading to cyclobutane: For ethylene, HOMO
is the 7t-SMO and LUMO is the 7t*-MO (cf.' Figs. la and 9.15.1). Ifwe consider that the HOMO
of one molecule will overlap with the LUMO of another molecule to form the cyclic T.S., it will
HOMO
n4 (Butadiene)
ry
LUMO
(Ethylene)
ra
ib
LUMO
~HOMO (Butadiene) .
~H yl
m
HOMO
he
Ethylene
(Ethylene)
1,3-Butadlene
lc
(a) 7t-MOs of 1,3-butadiene and ethylene (b) Thermally allowed [7t + 27t} cycloaddition
Fig. 1. 1t-MOs of butadiene and ethylene and Diels-Alder reactjon (thermally allowed). For the Mas,
ea
lobes of same phase indicated by the same shade.

th
Excited HOMO (SOMO)

of butadiene
e/
hv + C 2 H4
_ _0_+
----+
t.m
HOMO of SOMO of excited LUMO of ethylene

butadiene butadiene
Bonding
interaction
LUMO of butadiene
H hv
~
H + C 4 H6
~
V Antibonding interaction
HOMO of SOMO of excited Excited HOMO (SO~O)

ethylene ethylene of ethylene
Bonding
interaction
Fig. 2. Photochemically forbidden Diels-Alder reaction Le. (47t + 27t] cycloaddition.
lead to overlapping between the positive lobe and negative lobe (Fig. 3). Thus the reaction is
symmetry forbidden. Of course, the reaction can occur in two steps by a radical path of higher
activation energy.
Antibonding Bonding
interaction interaction
ry
ra
(a) Thermally forbidden reaction
ib
Excited
HOMOorSOMO
yl
Bonding
interaction
m
HOMO SOMO
(Ground state) (Excited state) Bonding
he
interaction
lc
ea
th
(b) Photochemically allowed reaction
Fig. 3. Dimerisation of ethylene Le. [21t + 21t] cycloaddition.

e/
However, if one molecule is photochemically excited so that one electron is excited from the
t.m
7t-BMO (Le. HOMO in ground state) to its 7t*-MO (Le. LUMO in ground state) then the SOMO
(singly occupied MO) ofthis electronically excited species acts as the HOMO in the cycloaddition
process. This 7t*-HOMO (Le. SOMO in the exci~ed state) can overlap with the LUMO (Le. 7t*-
MO) of another molecule to give the required cyclic T.S. This is why, thermal cycloaddition of
ethylenes to cyclobutane is symmetry forbidden but the process is photochemically allowed
(Fig. 3).
(iii) Symmetry forbidden reactions: 02 S +-X2 ~ 02 SX2; CO + X 2 ~ X 2CO,
Symmetry allowed reaction: R 2S (sulphane) + X 2 ~ R 2SX2; (X= halogen, say Cl)
. The bond angel RSR ~ 900 indicates that the pure p-orbitals of sulfur are used for making the
S-R bonds and the lone pairs of sulfur are housed in pure s- and p-orbitals. The cr*-LUMO of X 2
matches in terms of symmetry with the HOMO (p-orbital) of sulfur (Fig. 4). In S02' the OSO
bond angle ~ 1200 indicates that the lone pair resides in a sp2-hybrid orbital. This HOMO (i.e.
sp2-orbital) does not match in terms. of symmetry with the cr*-LUMO of X 2 (Fig. 4). However,
802 can react with Cl2 through the generation of radicals (Le. multi-step process of relatively
. higher activation energy). For CO, the HOMO «Jnb) is the s-p hybrid orbital of C and this HOMO
(cf. Fig. 9.11.2) does not match with the (J*-LUMO of X 2 in terms of symmetry (Fig. 4).
LUMO (0·)
LUMO (0 *)
CI.
CI. eel
ry
Antibonding / ~Bonding
interaction
~Bonding interaction
ra
C
~o
interaction :.' HOMO
(NBMO)
ib
(HOMO) s-p hybrid
(p-orbital)
yl
(a) Allowed LUMO (0 .) (b) Forbidden
eCI. eCI
m
~, ~Bonding
he
Antibonding interaction
interaction HOMO
/OS'
lc
(Sp2)
o 0
ea
(c) Forbidden
Fig. 4. FMO approach to the one-step reactions: (a) R2 S + C/2 ---. R2SC/2 ; (b) CO + C/2 ---. C/2 CO,
th
(c) 502 + C/2 - - - . C/2502.
(iv) Wittig reaction: The reaction has been illustrated in Fig. 10.7.2.2.
e/
(v) N 2 + O2 ~ 2NO: This reactionjhas been illustrated in Fig. 9.10.3.1.

t.m
(vi) H 2 + X 2 ~ 2HX (X = halogen): The symmetry mis-match in the one-step process for the
reaction H2 + H2 ~ 2HXhas been illustrated in Fig. 9. 10.3.2. This symmetry forbidden reaction
can pass through the multi-step reaction paths (involving the radicals) with a relatively higher
activation energy. The radical path is:
X2 ~2X;X +H2 ~ HX + H;H +X2 ~ HX +X;H +X ~ HX
10
Covalent Compounds: Characteristics,
Structure and Reactivity
ry
ra
10.1 BOND ENERGY
ib
10.1.1 Bond Energy in the Diatomic Molecules
For the diatomic molecules like AB,the concept of bond energy (i.e. bond dissociation energy) is well
yl
established. It is measured by the enthalpy change in the reaction,
m
A - B(g) ~ ~g) + B(g)' MI =D A - B
ground state ground state
he
The bond energy slightly varies with the temperature and most of the data in literature refer to the
standard condition (Le., 298 K). The above thermochemical reaction can be considered to take place in
two steps, Le.
lc
Step I • • Step II
A-B(g) (Endothermic) ) ~g) + B(g) (Exothermic» ~g) + B(g)
ea
ground state (excited spin states as ground state

present in the compound)
th
The Step-I describes bond rupture energy known as intrinsic bond energy. The spin states of A
and B in the compound are different from their respective ground states. Thus the Step-II signifies the
e/
relaxation energy released in passing from the spin valence states to the ground spin state.
The bond energies of the diatomic molecules can generally be det~rmined from the spectroscopic
t.m
data.
10.1.2 Thermodynamics of Bond Energy in the Diatomic Molecules

To have the idea of the bond dissociation energy of the diatomic molecules obtained from the
spectroscopic data, we should know the energetics ofthe molecule. The total energy (E,o,al) ofa diatomic
molecule consists of four different types of energy namely, electronic (Eel)' vibrational (Evib )' rotational
(Erot ) and translational (Etr ). Thus, Etotal = Eel + EVib + Erot + Etr . At absolute zero (T= 0 K), Erot and E,r
would vanish to yield, Etotal = Eel + E vib •
753
Now let us consider the potential energy

curve (Fig. 10.1.2.1) for a particular electronic
state and its minim':lm position represents the
electronic energy. At T = 0 K, in the ground
state, the vibrational energy' (Eel) is ~ hv 0
(where the vibrational quantum number u =

o
0, EVib =(u +~) hv v0 = fundamental fre-
ry
0'
quency of vibration of the molecule). This Cl------.,
ra
vibrational energy .!..2 hv 0
gives the measure l-----., B' S'
~-
of zero-point energy. Thus at T = 0 K, u=o ~IN
ib
,1 A' -----------~
2'
E,olol = Eel + hv o'
l; yl
- - -... Interatomic distance
where Vo = 2~ Fig. 10.1.2.1. Potential energy curve of a diatomic

m molecule. Illustration of bond dissociation energy.
k = force constant, J.1 = reduced mass
he
mt m2
fl=-~=--
mt +m2
lc
(m 1, and m 2 are the atomic masses of the constituent atoms).

Bond dissociation at T = 0 K : Now let us consider the change of vibrational energy levels in a
ea
particular electronic state (Le. Eel = constant). From Fig. 10.1.2.1, it is evident that as the vibrational
quantum number (u) increases in a particular electronic state, the distance between the combining
th
atoms increases. Finally when the molecule reaches the level P - P, it gets dissociated. Thus the energy
required to raise the molecule from u = 0 to the level P - P gives the measure of spectroscopic energy
e/
of dissociation at T = 0 K, and it is denoted by D. The concept of bond energy (Del) measured by the
difference between the minimum of the curve and the level P - P is related with the spectroscopic
t.m
energy of dissociation (D) as :

1
Del = D + 2' hvo'
But, due to the zero-point energy (k hv o) even at T = 0 K, the energy required to dissociate the
molecule is given by D. The zero-point energy is very much significant in the molecules containing
light atoms (for example, in H2 it is -- 26 kJ mol-I, Le. 6.2 kcal mol-I) while it becomes insignificant for
the heavier species. However, the concept of Del is very much important in connection with the bonding
theory (refer VBT. for H2 molecule, Sec. 9.3.1), though the parameter is not experimentally accessible.
Bond dissociation at T> 0 K : At T> 0 K, where Erot and Etr exist and the bond dissociation energy
must accommodate the amount of energy required to provide the translational energies (% RT) to the
Covalent Compounds: Characteristics, Stru~ture and Reactivity 755
separated atoms at T (> 0 K). 'This additional required energy is partly compensated by the E tr and Erot
of the starting molecule. As a matter of fact, the dissociation ,energy at T> 0 K differs slightly from the
value at T= 0 K.
Bond dissociation energy i!nd enthalpy ofdissociation: Lastly, the energy of dissociation can be
compared with the enthalpy of dissociation (AX ~ A + X, M-I). These two parametes differ by the
work, p~v (~2.5 kJ mol-I, Le. 0.6 kcal mol- 1 at room temperature). Thus the enthalpy ofdissociation
can be reasonably taken as the bond dissociation energy.
The different parameters for H 2 are given below.
ry
Del Do D298 &1298
(atT=OK)
ra
kJ mol- 1 458 432 433.2 435.9
kcal mol- 1 109.5 103.2 i03.5 104.2
ib
It is evident that Do, D298 and t:J{298 are reasonably comparable to measure the bond dissociation
yl
energy.
Isotopic effect on bond energy (cr. Sec. 5.2.2) : Now we can consider the effect of isotopes on
m
bond energy. It is known thatfor the heavier isotopes, the bond energy is higher. It is illustrated for
hydrogen (If) and deuterium (D).
he
Bond: H-H D-D O-H O-D
(in H 20) (in D 20)
lc
Bond enthalpy (kJ mort): 435.9 443.3 463.5 471.0

The observation can be reasonably rationalised in terms of zero-point energy (Eo) which is given
ea
by:
th
e/
(k = force constant of the bond; J.l = reduc.ed mass)

t.m
The reduced mass (J.l) for D2 and H2 molecules are given by :
mm mm
Jl(D2 ) = D D ~ 1, Jl(H2 ) = H H ~ 0.5
m D +mD mH +mH
Le. ~(D2)/~(H2) = 2
Thus the reduced mass for D2 molecule is much higher than that of H2 molecule. It makes the
zero-point energy of H 2 molecule higher than that of D 2 molecule i.e. E o(H2) » E o(D 2 ).
From the definition of bond energy (cf. Fig. 10.1.2.1), it is evident that the species having higher
Eo values will have lower bond dissociation energy. In other words, the bond dissociation energy is
higher for the heavier isotopes (assuming the same bond length). It explains the higher bond
dissociation energy for the bonds having deuterium species instead of hydrogen.
Hydrogen bond: Because of the same ground, the hydrogen bonds with deuterium is stronger. It
explains the higher boiling point of D 20 (b.p. lOl.42°C) than that of H 20 (b.p. lOO.OOOC).
10.1.3 Average Bond Energy in Polyatomlc Molecules

For the polyatomic molecules, the concept of bond energy is not so clear-cut in contrast to the case of
diatomic molecules. Even for the simplest possibility, AXn (where only one type of substituent exists)
in the binary system, the following facts come into consideration.
(i) The stepwise removal of X leads to, AXn ~ AXn _ I + X, AXn _ I ~ AXn -2 + ~ ..., AX ~ A + X.
At each step, the chemical environment of A is not identical as the molecular fragments, Le.
AXn _ l , AXn - 2, ••• , are not identical. The state ofhybridisation of A and the bond multiplicity in
the different molecular fragments are not identical.
ry
(ii) The relaxation energy (exothermic) for the transition from the spin valence state to that of the
molecular fragment is different for the different steps.
ra
Because of these facts, the enthalpy change in each step is not identical. To clarify the above points,
let us consider some examples.
ib
CO2 : OCO(g) ~ CO(g) + O(g) ~ C(g) + 20(g)
Here, DOC = = 127 kcal mol-I, and Dco = 256 kcal mol-I
yl
0
In each step, the relaxation of oxygen involves (sp)1 (sp)2 7[1 7[2 (Le. sl.S p4.S) to the ground state,
m
s2p 4, while for the carbon, it leads to (sp)1 (sp)1 7[1 7[1 (Le. slp3) to (sp)1 (sp)2 7[1 (Le. sl.S p2.S) in the first
step, and (sp) I (sp)2 7[ I (Le. s 1.5 p2.S) to s2p 2 in the second step. Besides these, in the first step it involves
he
the breaking of a bond of bond order 2, while the second step involves the rupture of a bond of bond
order -- 2.5. This increased bonding in CO and relatively lower relaxation energy (which is released) of
carbon in the second step explains the higher bond dissociation energy at the second step.
lc
HgC/2 : CIHgCI(g) ~ HgCI(g) + Cl(g) ~ Hg(g) + 2CI(g)

ea
Here, DCIHg - CI = 81 kcal mol-I; and DHg _ CI = 25 kcal mol-I

The low enthalpy change in the second step arises probably due to the larger relaxation energy
th
released in passing of Hg from the valence spin state, (sp)1 (sp) I (Le. slpl) to the ground state '6s 2.
H 20: D HO - H = 118 kcal mol-I, D o _ H = 103 kcal mol-I. The values are more or less comparable.
e/
It appears so due to the relaxation of comparable valence spin states.

CH4 : The stepwise four bond dissociation energies are different. The fJrst (Le. DH C _ H) and
t.m
fourth (Le. DC-H) bond dissociation energies are 103 and 81 kcal mol-I respectively. The ~econd and
third values are suggested to be 112 and 99 kcal mol-I respectively. The CH3 radical is planar with sp2
hybridisation. T,J1e larger second bond dissociation energy compared to the first one suggests the greater
bonding strength of the trigonal sp2 hybrid orbitals than the tetrahedral sp3 hybrid orbitals. The average
of these four quantities (i.e. -- 99 kcal mol-I) is taken as the mean bond energy for the C-H bond in
CH4 ,
pels: It is an interesting example. Theoretically, it is believed that in the trigonal bipyramid (sp3d),
the axial P - Cl bonds are weaker than the equatorial P - Cl bonds. Butfrom the experimental data, it
is not possible to verify directly this theoretical prediction. If one 'P - cr bond (axial or equatorial) is
broken, it will form PCl4 moiety which has got only one possible structure. Thus, both the possibilities
(Le. the rupture of either axial Cl4P - Clax or equatorial Cl4P - Cleq bond) lead to the same molecular
fragrrients. The enthalpy change is a state function. Hence it cannot differ in !he two different
possibilities which lead to the same change.
Covalent Compounds: Characteristics, Structure and Reactivity 757
The above enthalpy change consists of two terms, Le. bond rupture energy termed as intrinsic
bond energy and relaxation energy leading to PCI4 • It is believed that when the axial P-Cfix bond is
ruptured, the relaxation process is less exothermic compared to the case .when the equatorial P-Cleq
bond is ruptured.
Because of the above facts, in the polyatomic systems the concept of average bond energy
rather than the stepwise bond energy is introduced as follows :
AXneg) ~ A(g) + nX(g), IiH; D~ _ x = IiH/n
n(D~_x)
ry
Le., = D x n -I A-X + D x n - 2 A-X + ... + D A - X
Limitations in the concept ofaverage bond energy : Though the concept of average bond energy
ra
is useful, it leads to some complications. The average bond energy calculated from a particular compound
will not exactly fit into the other compounds as it varies from compound to compound. For example, in
ib
CH2F2, the C - H bond energy is different from the mean C - H bond energy obtained from CH4 •
Similarly, the C - Fbond energy differs from the average C - Fbond energy in CF4 • In such compounds
yl
having different types of bonds, to calculate the bond energy of a particular bond (say, C - F bond in
CH2F 2) from the thermochemical data, some approximations are required. In this present problem, to
m
compute Dc _ F" the average Dc _ H from CH4 is taken into consideration. Otherwise, the stretching
frequency from infrared spectrum ofthe compound is to be considered to evaluate the bond energy
he
of a particular bond.
Similarly, from the knowledge of heat of atomisation of N 2H 4 and N 2F 4 along with the values of
D N _ H (from NH3 ) and D N _ F (from NF3 ), the bond energy of N - N in both N 2H 4 and N 2F 4 can be
lc
calculated. The calculated values are 38 (in N2H4 ) and 41 (in N2F4 ) kcal mol-I.
ea
10.1.4 Thermochemistry in Computing Bond Energies

The bond energies are very often computed from the principle of thermochemistry. To illustrate the
th
procedure, let us take the following two examples.

(i) D'o_HinHzO:
e/
Given, 2H(g) ~ H 2(g)' M/ = - 104.18 kcal mol-I; 20(g) ~ 02(g)' M/ = - 118.32 kcal mol-I;
t.m
H 2(g) + 1/202(g) ~ H 20(g)' M/= - 57.8 kcal mol- l

Thus we have:
2H(g) ~ H 2(g)' M/ = - 104.18 kcal mol- l
0(g) ~ 1/202(g)' M/= - 59.16 kcal mol-I
H 2(g) + 1/2 0 2(g) ~ H 20(g)' M{= - 57.8 kcal mol-I
2H(g) + O(g) ~ H 20(g)' M{= - 221.14 kcal mol-I,
In H 20, there are two 0- H bonds. Hence, 2(D' 0 _ H) = 221.14; or, D' 0 _H = 110.56 kcal mol-I.
(ii) D'c_Hin CH4 :
Given, CH4(g) + 202(g) ~ CO2(g) + 2H20(l)' M/ = - 215 kcal mol-I, ... (a)
C(s) + 02(g)' ~ CO2(g)' MI = - 94 kcal mol-I, ... (b)
H 2(g) + 1/20 2(g) ~ H 20(l)' M{= - 68.3 kcal mol-I ... (c)
C(s) ~ C(g)' MI= + 171.7 kcal mol-I, ... (d)

2H(g) ~ H 2(g)' MI = - 104.18 kcal mol-I, ... (e)
Thus we have:
2(c) + (b) - (a) - (d) + 2(e) = C(g) + 4H(g) ~ CH4(g)' MI= - 395.66 kcal mol-I.
1
Thus, D'C-H= 4" (395.66) = 98.91 kcal mort,
(iii) D'N-H in ~H3 :
ry
It can be calculated from the following relationship
Ml (NH3) =
f
~DN
2
+~DH
2
-3D'N H
ra
2 2 -
(MIl stands for heat of formation).
ib
10.1.5 Bond Energies of Different Bonds
Based on the above process, bond energies of different bonds can be evaluated. These are given in
yl
Table 10.1.5.1. m
Table 10.1.5.1. Average bond energies in kcal mol- 1 (to get the values in kJ mol-1 , the
multiplication factor 4.185 is to be incorporated) at 25°C.
he
Bond Bond Bond Bond Bond Bond
energy energy energy
lc
H-H 103.2 C=C 200.0 N-CI 72.0

H-C 98.8 C-N 73.0 N-O 48.0
ea
H-Si 76.4 C=N 147.0 0- 0(H20 2) 33.0

H-N 93.4 C=N 213.0 0=0 118.0
H-P 76.4 C-O 84.0 O-F 44.0
th
H-As 58.7 C=O 191.0 0- CI (CIOH) 52.0

H-O 110.7 CEO 256.0 0-1 48.0
e/
H-S 87.1 C-S' 65.0 O-Si 111.0

H-Se 66.1 C-F 115.0 Si -Si 42.0
t.m
H- Te 58.0 C-CI 79.0 Si-C 76.0

H-F 134.5 C-Br 66.0 Si-F 129.0
H-CI 103.0 C-I 51.0 Si - CI 86.0
H-Br 87.5 Ge-Ge 38.0 Si-S 54.2
H-I 71.5 Ge - CI (GeC/4) 84.0 Si -I 51.0
F-F 37.0 Sn-Sn 34.0 P - P(P4) 51.0
CI-F(CIF) 60.5 S - S (S8) 54.0 P-F 119.0
CI- CI 58.0 S - CI (S2C/2) 60.0 P-CI 79.0
Br - CI (BrCI) 52.0 S - Br (S2Br2) 51.0 P-Br 65.0
Br-Br 46.0 Se - Se. (Se 8) 44.0 P-I 51.0
1- CI (/CI) 50.0 Te- Te 33.0 As-F 115.5
1- Br (IBr) 42.5 N-N 38.4 As-Br 62.0
I-I 36.0 N=N 100.0 As-I 48.0
C-C 83.0 N=N 225.0 Sb-Sb 30.0
C=C 146.0 N-F 64.5 Bi-Bi 25.0
• Diatomic molecules: Here, for H - H, F - F, CI- CI, Br - Br, I - I, H - F, H - CI, H - Br, H -

I, CI- F, etc. the values are obtained from the enthalpies of dissociation ofthe respective diatomic
molecules and these are determined thermochemically or spectroscopically.
• Crystalline substance: For Si - Si, Ge - Ge, the corresponding values are obtained from the
heat ofsublimation of the respective crystals. They adopt diamond like structure in which each
atom is tetrahedrally linked with four other atoms. Hence, removal of each atom requi~es the
dissociation of 4 x ~ or 2 bonds. Thus, the bond dissociation energy is halfofthe sublimation
energy (per g atom).
ry
• Polyatomic molecules: For P - P, As - As, the bond energies are one-sixth of the heat of
formation of P4(g) and AS4(g) from their separated gaseous atoms respectively. The molecules,
P4 and AS 4 exist as regular tetrahedra in which each comer is occupied by one atom covalently
ra
bonded to the other three atoms at the other three comers. Hence, in the process P4(g) ~ 4P(g)' six
bonds are to be broken. Similarly, for S - S, Se - Se, bond dissociation energies are given by one-
ib
eighth of the heat offormation of S8(g) and Ses(g) (which exist as eight membered rings with
eight -bonds) from their gaseous atoms respectively. .
yl
• N-N and 0-0 bonds: For N - N bond, the knowledge of N - H bond energy is utilised in the
°
m
enthalpy offormation of N 2H 4• Similarly, for 0- bond, the value is calculated from the heat
offormation of H 20 2 with the knowledge of °- H bond energy in H20.
he
• Multiple bonds : For the multiple bonds, the values for the single bonds are used in the
thermochemical calculations. For example, for C == C bond, both the knowledge of C - H bond
energy and heat of formation of C2H4 are required.
lc
T~e values recorded in Table 10.1.5.1 are applicable under the following restrictions.
ea
(i) The atoms show their normal valencies, e.g. 4 for C; 3 for N, P and As; 2 for 0; and so on.
The values are not applicable for tetravalent N (e.g. NH;, amine oxide), trivalent oxygen
(e.g. HjO~), pentavalent phosphorous (e.g. PCls).
th
(ii) The tabulated values are strictly applicable for the bonds where there is no separation of
charge. But such a situation cannot arise for the heteronuclear bonds in reality.
e/
10.1.6 Intrinsic Bond Energy

t.m
We have already mentioned that in the dissociation process, the enthalpy term consists of bond rupture
energy and the relaxation energy leading to the ground state of the separated fragments from the
valence spin states existent in the molecule. The bond rupture energy leading to the separated fragments
in the same valency spin states (Le. in the same state existent in the undissociated molecule) is called
the intrinsic bond energy. Thus the enthalpy of dissociation measuring the bond energy is expressed
as follows:
enthalpy of dissociation == intrinsic bond dissociation (endothermic) energy +
relaxation or reorganisation (exothermic) energy.
X
I Intrinsic
-------3..~ A· + 4X·
Relaxation
X-A-X A+4X
I
X
Bond energy (Seoarated atoms Energy
(endothermic) in the excited valence (exothermic)
(ground state)
spin state)
The reverse ofthe relaxation process gives the measure ofcost ofhybridisation energy which has
been already discussed (Sec. 9.13.4).
The concept of intrinsic bond energy is very much important in connection with the intrinsic strength
of a particular bond measuring the degree of overlap between the involved atomic hybrid orbitals. An
interesting observation is revealed by considering the following,data (given in kcal mol-I) in Table
10.1.6.1.
Table 10.1.6.1. Concept of intrinsic bond dissociation energy from the knowledge of average
bond energy and relaxation energy.
ry
Element Bond energy (kcal mol-I) Cost ofhybridisation or promotion
(A) (D'A -x), X= H, CH3 , F, 0 energy ofA to the tetrahedral valency state
ra
H CH3 F 0 (- Er(A» (kcal mol-I)
ib
C 98.8 83 115.0 84 150
Si 76.4 73 129.0 III 115
yl
N 93.4 79 64.5 48 228
P 76.4 63 119.0 88 133
0 110.7 86 44.0 33
m 194
S 87.1 62 68.0 109
he
F 134.5 37.0 44 '120
CI 103.0 60.5 52 62
lc
Variation of bond energy in a group for the representative elements. : It is obvious from Table
10.1.6.1 that the bond energy in each group is higherfor the lighter elements compared to the heavier
ea
elements. It gets more vivid, if we consider the intrinsic bond energy. It is illustrated in Si - Hand C-
H bond energies.
th
In CH4, 4(D' C -H) = 4 (intrinsic bond energy) + relaxation energy of C and 4H.
e/
= 4(Ec - H) + E"C) + 4E"H)

(where E c _H stands for the average intrinsic bond dissociation energy, E r denotes the relaxation energy).
t.m
or, 4 x 98.8 = 4 (Ec _ H) - 150 - 0; Ec _ H = 136.3 kcal mol-I

In SiH4, 4(D'Si _ H) = 4(Esi - H) + E"Si) + 4E"H);
or, 4x76.4= 4(Esi _ H)-115-0;
or, ESi - H = 105.15kcalmol- l .
Thus each C - H bond is stronger by about 31 kcal mol-I than the Si - H bond, exclusive of
relaxation energies. It suggests that as the diffuseness of the hybrid orbitals increases, the overlap
becomes poorer to weaken the bond. This is why, the heavier congeners ofthe representative elements
always form the relatively weaker bonds though the cost of hybridisation is less for the heavier
congeners. The same trend as in the hydrides is maintained for the methylated compounds.
Variation of A-F and A-O bond energy in a group for the representative elements : In this
connection, the reverse order for the fluorides and oxides is interesting to be discussed. For oxides
and fluorides, the heavier congeners produce the stronger bonds probably due to the P7t - d7t
bonding. The nonbonding electron pairs residing on the oxygen or fluorine may participate in the
pi-bonding to strengthen the intrinsic bond energy. Due to such pi-bonding, the promotion or the cost
of hybridisation energies for the heavier congeners are more easily compensated compared to the lighter
congeners where no such pi-bonding occurs. Taking into consideration ofthe relevant relaxation energies,
it is found that the intrinsic bond strength in P - F bond is -- 20 kcal mol- 1 larger compared to that ofthe
N - F bond. It is also reasonable because for the lighter members (where no pi-bonding occurs), the
lone pair-lone pair repulsion further weakens the bond as follows.
ry
ra
~ ~
ib
N F-
/" ---
It is important to note that for the too heavy congeners, the d1t +- P1C (0 or F) bonding becomes
yl
less significant because of (i) the large difference in energy and size between the involved d orbital of
m
the other element and 2p orbital of F or 0, and (ii) the elongated sigma bond length.
Generallyfor the heavier congeners, because ofthe increased diffuseness ofthe overlapping atomic
he
orbitals, the efficiency ofoverlap decreases to weaken the bond. This knowledge has been illustrated
by calculating the intrinsic bond energies which are free from relaxation energies. This idea is very
much impo~ant in explaining the inert pair effect (cf. Sec. 10.3).
lc
10.1.7 Different Factors Governing the Bond Energy

ea
Different factors play important roles in detennining the bond energy. These are discussed below:
(i) State ofhybridisation and relaxation energy: This aspect can be illustrated by considering the
th
C - H bond energies in different compounds. It runs in the sequence,

CzHz > CZH 4 > CH4 (or CZH 6) as shown in Table 10.1.7.1.
e/
Table 10.1.7.1. Effect of hybridisation on bond properties.

t.m
Molecule Hybridisation Dc _ H C - H bond

ofC (kcal mol-I) length (pm)
HC=CH 121 106
H 2C= CH2 106 107
CH4 or C2H 6 99 109-111
CHradical p 81 112
Both the pure s- and p-orbitals provide an inefficient overlap compared to their hybrid orbitals.
The relative effectiveness in overlap runs in the sequence,
sp > sp2 > sp3 » s > p. (cf. effect of the size of the major lobe ofthe
s-p hybrid orbitals; Sec. 9.13.3 for discussion).
The hybrid orbital having a greater s-character shows a shorter bond lengths, Le. a higher bond
energy. According to Maccoll, the variation of overlap integral with the s-charact.er in the hybrid
orbital is shown in Fig. 10.1.7.1. It is evident 1.0 1.0

that for 50% s-character, the overlap
becomes most effective. It is also revealed 0.9 0.9
that the pure s-orbitals form stronger bonds
Sc-c
compared to the pure p-orbitals.
0.8 0.8
Bond length in PCls : In this connection,
the axial P - Cl (219 pm) and equatorial co
~ ~
P - Cl (204 pm) bonds in PCls are important g> 0.7 0.7 C)
(1)
:£ :£
ry
to be discussed. The axial P - Cl bonds are c. c.
held through the pd hybrid orbitals while ~ 0.6 0.6 ~
(1) (1)
> >
ra
the equatorial P - Cl bonds are held through o o
the sp2 hybrid orbitals. The axial bonds 0.5 1
ib
having 0% s-character are longer and
weaker compared to the equatorial bonds 0.4 0.4
33~%
yl
having s-character.
3
'P-Cl bond energy in PCls and PCI] : In o 20 ~50 80 100
m
the comparison between PCls and PCI3, it (% 5 character --))
is found that D' P _ CI(PCls ) < D' p - CI(PC/3 )· (~ % P Character)
he
In PCls and PCI3 , the hybrid orbitals utilised Fig. 10.1.7.1. Relative overlap efficiencies of 5,
by Pare sp 3d (Le. sp2 + pd) and sp3 p and s-p hybrid orbitals.
lc
respectively. The higher relaxation energy

(exothermic) and lower s-character (in average) in PCls reduce the bond energy.
ea
Cl-F bond energy in ClF and ClF] : The compounds CIF and ClF3 are very much interesting.
The bond energies of Cl- F are as follows,
th
D' Cl- F(C1F) = 60 kcal mol-I, D' Cl- F(C1F ) = 42 kcal mol-I.
3
In CIF, one sp hybrid orbital is utilised while in e1F3, sp 3d (one Cl- F bond involves sp2 hybrid
e/
orbital of Cl while the other two involve dp hybrid orbitals of Cl) hybrid orbitals are utilised. The
relaxation energy in ClF] is much greater than that involved in ClF. Besides this, in CIF3,
t.m
the utilised hybrid orbitals are poorer in s-character. Both these factors are responsible for the
lower bond energy in CIF3 •
Bond energy in AXn and AXn _ 2 (cf. Sec. 9.22)
In general it is evident that D'A-x(AX ) < D'A -X(AX _ )' The lower bond energy inAXn compared
n n 2
to that in AXn _ 2 can nicely be explained in terms of sigma bond order in MOT. For example, in
SX6 (cf. Fig. 9.22.1) there are eight bonding electrons and four nonbonding electrons. Hence
the average bond order in SX6 is 4/6 == 2/3, while inSX4 (cf. Sec. 9.13.5C) there are six bonding
electrons to provide the average sigma bond order, 3/4.
(ii) Diffuseness of the orbitals: The heavier congeners in which the atomic hybrid orbitals are
relatively more diffused cannot undergo overlapping effectively. This is why, their bonds are
weakened compared to those of the lighter ones. In this connection, it is worth remembering
that ignoring the case ofsecondary periodicity, the promotion energy leading to the appropriate
hybridisation and spin state is lowerfor the heavier ones (see Table 10.1.6.1), but the intrinsic
bond energy for the heavier ones is so lowered due to the poorer overlap that the overall bond
energy is lowered. In some cases, the too low intrinsic bond energy cannot compensate the
promotion energy to. carry out the required hybridisation. This aspect has been already discussed
in Sec. 9.13.4 and in explaining the inert pair effect (see Sec. 10.3).
(iii) Possibility of lone pair-lone pair repulsion : The repulsion among the nonbonding electrons
housed on the bonding atoms lowers the bond energy. Some examples are shown below.
ry
In this connection, the possibility of expanding the nonbonding electron clou"d in some low
ra
lying vacant orbitals to reduce the repulsion is extremely important. In the halogen molecules
(X2, X= F, Cl, Br, /), except the F 2, the nonbonding electrons may expand in the available vacant
ib
d-otbitals to minimise the repulsion. Because of the same ground, the repulsion in the N - F
bond is greater than that in the N - Cl bond in which the nonbonding electrons on chlorine may
yl
get pushed to some extent into its vacant 3d-orbitals. In the case of fluorine, the electrons are
fully localised in the 2p-orbita!§. In addition to this, a pi-bonding, Le. P7t(N) ~ d 7t(Cl), may also
m
enhance the bond energy. Infact, N-Cl bond is stronger than N-F bond.
(iv) Possibility ofpi-bonding : The possibility ofpi-bonding (e.g.,p7t -P7t'P7t -d7t or d 7t -d7t ) introduces
he
the bond multiplicity to enhance the bond strength. This aspect has been already discussed for
the oxides and fluorides (Sec. 10.1.6). Some other examples are given below:
.. .. ..
lc
> P - Q:, Le., 2P7t(O) ~ 3d7t(P); - Si - Q-, Le. 2P7t (0) ~ 3d7t (8i);
8":, (X = F, C/, Br), Le. nP7t(X) ~ 2P7t(B); :i},t - q-, Le. 2P7t(0) ~ 3d7t(Cl);
ea
>B-
> P-8":, (X= F, C/, Br), Le. np7t(X) ~ 3d7t(P);

th
:~ - ~ -, M = heavy transition metals, Le. nd7t(M) ~ 3d7t(S),

e/
(v) Degree of overlap: The end-on overlap in the sigma bonds is better than the lateral overlap in
t.m
the pi-and delta (B)-bonds. This is why, the sigma bond is the strongest one. The bent bonds as
in cyclopropane, P 4 , etc. (Fig. 9.18.2.3) are also weaker due to the poorer overlap.
In a certain group, the stabilitp 0lllle hytJrideSiijthe heavier congeners gradually decreases.
The valence orbital (s or s-p hybrid or p) becomes gradually larger in size for the heavier congeners
and consequently their overlap with the small Is orbital of hydrogen becomes gradually less
efficient. It reduces the bond energy. It explains the following bond energy sequence.
0- H(H2 0») S - H(H2 S») Se - H(H28») Te - H(H2 Te); H - F) H - Cl) H - Br) H-I
In other words, the bond energy of X - H bond decreases with the increase of X - H bond length.
With the decrease of X - H bond energy, the thermal stability of the hydrides decreases. Thus
the thermal stability order is :
H 20) H 2 S) H 2 Se) H 2 Te; HF) HCI) HBr) HI; NH3 ) PH3 ) AsH3
(vi) EJJectoJcovalent-ionic resonance: This aspect has been discussed in Secs. 10.2.3 and 10.4 (cf.
Fig. 10.4.2).
10.2 COVALENT BOND LENGTHS AND COVALENT RADII
10.2.1 Single Bond and Covalent Radii

Covalent bond lengths give the internuclear distances between the atoms covalently bonded. These can
be measured from the X-ray studies ofthe crystals and for the gases, these are done by electron diffraction
and spectroscopic methods.
The bond length of a particular bond A - B remains more or less constant in a majority of the
compounds having the A ~ B linkage provided the valence spin states of A and B in the compounds do
ry
not differ remarkably. It is evidenced from the experimental observation recorded in Table 10.2.1.1. It
indicates that the bond length A - B is the sum oftwo constant distances. As a matter offact, the A - B
ra
bond length is equal to the arithmatic mean of the bond length ofA - A and B - B. Thus it can be
concluded that the A - B bond length is. the sum of covalent radii ofA and B.
ib
Table 10.2.1.1. Near constancy of the bond lengths in different compounds.
yl
Bond Compound Bond length (pm) Bond Compound Bond length (pm)
O-H OH radical 97 C-C C 2H sOH 155

O-H H 2"O 96
m C-C (CH3)2CHOH 154
o -Ii H 20 2 97 C-C n - C 4H 1O 154
he
O-H CH30H 96 C-S (C 2H s )2 S 181
O-H HC0 2H 96 C-S (CF3)2S 183
lc
c-c Diamond 154 C-S C 2H sSH 181

c-c C 2H 6 154
ea
c-c C3H g 154

th
Thus if the internuclear distance of a particular bond is known, then from the knowledge of covalent
radius of one combining atom, the covalent radius of the other atom can be detennined. In this way, the
e/
single bonded covalent radii of diff~rent elements have been determined (Table 10.2.1.2).
t.m
Table 10.2.1.2. Single bonded covalent radii for different nonmetallic

elements (obtained from heteronuclear covalent compounds).
Element Covalent radii (pm) Element Covalent radii (pm)
H (in H 2) 37.5 Sb 141

II (in HX) 30 0 66
B 88 S 104
C 77 Se 114
Si 117 Te 137
Ge 122 F 64
Sn 140 Cl 99
N 70 Br 114
p 110 I 133
As 121
* This value is applicable to other compounds. X-stands for halogens.
The covalent radii reported for F, 0, and N in Table 10.2.1.2

are remarkably different from the values obtained from F - F (=
,
1"·---'-1
.
2 Van dar Walls radii
1 1
144 pm), HO - OH (= 148 pm) and H 2N - NH2 (= 147 pm) 1 I
respectively. The elongated bond lengths in F - F, 0 - 0 and N -
N bonds arise probably due to the repulsion among the
nonbonding electrons housed on the adjacent atoms.
In this connection, it is worth mentioning that the van der Waals I
I
radii or nonbonded radii are longer than the covalent radii. The I
I I
,+---+,
ry
internuclear distance betwe.en the atoms belonging to different
molecules which are adjacently hold through the van der Waals 2 Covalent radii
forces is the sum of van der Waals radii of the atoms under Fig. 10.2.1.1. van dar Waals
ra
consideration. It is well known that the covalent forces are stronger and covalent radii.
than the van der Waals forces. These weaker van der Waals forces will be discussed in Sec. 13.3.
ib
The van der Waals and covalent radii are represented in a particular compound in Fig. 10.2.1.1.
In this connection it is worth mentioning that the van der Waals radius of an element depends upon
yl
the chemical environment of the atom under consideration. For example, the nonbonded radii for Xe
in solid Xe crystal and in XeF4 are 218 and 170 pm respectively. The shrinkage in bond length in
m
XeF4 is due to the contraction of the size of Xe due to the accumulation of positive charges on Xe (i.e.
Xe o+ - F).
he
Variation of Covalent radii in a group of p-block elements
It is illustrated for Gr. 14 elements.
lc
C Si Ge Sn Pb
+40 +5 +18 +14
ea
rcov (pm) : 77 ) 117 ) I 12 ) 140 ) 154

Elect. config. : [He]2s 22p 2 [Ne]3s 23p 2 [Ar]3d 104s 24p 2 [Kr]4d 105s 25p 2 [Xe]4j45dl06s26p2
th
The relatively low increase at Ge and Pb arises due to low shielding d- and I-electrons
experiencing first i.e. d-contraction and I-contraction respectively.
e/
Table 10.2.2.1. Multiple bonded covalent radii for some

10.2.2 Multiple Bond and Covalent Radii nonmetals.
t.m
The multiple bonded covalent radii are related Bond Covalent radii Bond Covalent radii
to the multiple bond lengths in the same way as (pm) (pm)
in the case of single bonded covalent radii. For
-B=B- 76 -p=p- 100
I
example, rC=N =i(rCEC +rNeN ). B=B 68 p=p 93
The C == C and N == N bond lengths are >C=C< 67 N=N 55
obtained from C 2H 2 and N2 respectively. Some -C=C- 60 -As =As- III
multiple bonded covalent radii are given in > Si = Si < 107 -Sb = Sb- 131
Table 10.2.2.1. -Si =Si- 100 0=0 60
Here it is interesting to note that compared > Ge = Ge < 112 S=S 94
to the single bonded covalent radii, the double
> Sn = Sn.< 130 Se =Se 107
and triple bonded covalent radii are about 86-
91 % and 78-85% respectively of the corres- -N=N- 62 Te =- Te 127
ponding single bonded radii. Thus by using some multiple factors, the multiple bonded covalent radii
are obtained from the single bonded covalent radii. These are shown in Table 10.2.2.2.
Table 10.2.2.2. Multiple factors for calculation of multiple bonded

covalent radii from the single bonded covalent radii. .
Elements Multiple factors to get the multiple
bonded covalent radii from the
respective single bonded covalent radii
Double bond Triple bond
ry
B, C, N, 0, Si, P, S 0.86 0.78
ra
Ge,As, Se, Sn, Sb, Te 0.91 0.85
ib
10.2.3 Different Factors Governing the Bond Lengths
(i) Bond order: The bond distance decreases with the increase of bond order (Table 10.2.3.1).
yl
Table 10.2.3.1. Bond multiplicity and bond length.
Bond . Bond length
m Bond Bond length
(pm) (pm)
he
c-C 154 0=0 121
c=c 134 N-N 145
lc
C=C 120 N=N 125

C-O 142 N=N 110
C=O 122 136
ea
N-O
C=O 110 N=O 115
0-0 148 N=O 105
th
The same trend is also followed in metals. For example, W ~ W < W == W < W = W < W - w.
e/
Here the bond order 4 involves the quadruple interaction.

For carbon, it has been empirically established by Pauling that,
t.m
rn = r I - 71 log n
where rn denotes the bond length (in pm) ofa bond of bond order n. The variation of bond length
with the bond order is shown in Fig. 9.18.1.1.
(ii) 7t-bonding: The possibility of 7t-bonding, Le. P n - P n (e.g., B( 0H)3' BF3, etc.), P n - dn (e.g. P -
0, P -X, etc.), dn - dn (e.g. M - S, M= Cu(Il), Ni(Il), etc.) introduces a considerable amount of
shrinkage in the bond distance due to the increased bond order. This aspect has been discussed in
Sees. 10.1.6, 10.1.7 (iv) and 10.7.
(iii) State ofhybridisation : The state of hybridisation significantly influences the bond length. It has
been already discussed (Sec. 10.1.7 (i» how the percentage of s-character influences the C - H
and C - C bond length and bond energy in the hydrocarbons. It has been found that the efficiency
of overlap measured by the overlap integral increases with the increase of s-character up to 50%,
then again it falls (see Fig. 10.1.7.1). In this connection, the following results are important.
- ~ , - --~ -
=C-H</C-H</G-t-t;=C-C=</C-C= <' -?
/C-C, < /'C - C/ , ;
{~ (tV) (sp'3) {~{~ (tV) .{~ (sp'3) (t#) (sp'3) (sp'3)
=C=c= < 'C=C=

/'
< 'C=
/ ,
C/
(Sfi (sp) (tV> (~ (tV) (t#)
Thus, the Bent's rule (see Sec. 9.13.7) which gives the measure of distribution of s-character in
different hybrid orbitals is important to predict the relativp shrinkage in bond length.
ry
The well discussed PCIs is again noteworthy in this connection. The axial P - Clax (pd hybrid
orbital of P) bond is longer than the equatorial P - C/eq (sp2 hybrid orbital of P) one. The S - F
bond length is longer in SF6 conlpared to that in SF2•
ra
(iv) Nature ofstereochemistry: Some other interesting observations in different inorganic compounds
ib
in this regard are noteworthy. In the covalent crystals, the elements may not always exhibit their
normal covalency. The number of covalency and state of hybridisation depend on the
yl
stereochemistry. A particular element may remain in a linear (sp) arrangement or in a tetrahedral
(sp3 or "d3s) arrangement or in an octahedral (sp 3d2 or d2sp3) arrangement or in a planar (dsp2)
m
arrangement depending upon the nature of the crystal under consideration. The covalent radii of
a particular element in different arrangements are different. The octahedral (sp 3eP or ePsp3) and
planar (dsp2) ~adii are identical while the tetrahedral (sp3 or cPs) radii are shorter than the octahedral
he
radii. The linear covalent radii are still shorter than the tetrahedral radii.
octahedral radii ~ planar radii> tetrahedral radii> linear radii
lc
In the cubic crystal pyrites, each Fe(I!) is oc~ahedrally surrounded by six sulphur atoms while
ea
each sulphur atom is tetrahedrally surrounded by three Fe(I!) and one sulphur atom. Thus from
the crystal, we get the octahedral and tetrahedral radii for iron and sulphur respectively.
th
From PhBr62-, SnCli- we get the octahedral radii of Pb(IV) and Sn(IV) respectively. These
octahedral radii are larger than their respective tetrahedral radii by.", 30/0.
e/
In the crystals of Cu 20, Ag20, each oxyg~n atom is tetrahedrally surrounded by four metal atoms
while each metal is linearly (sp) coordinated by two oxygen atoms. From these crystals,we get
t.m
the tetrahedral radius of oxygen and linear covalent radii of the metals, i.e. Cu(!), Ag(!). From
CH3 - Hg - Cl, we get the linear covalent radius of Hg(IJ) and tetrahedral covalent radius of C.
It has been found that the linear covalent radius of Hg(II) is shorter than its tetrahedral radius by
'" 19 pm.
(v) E.ffect of resonance: Due to the delocalisation of the pi-electron clouds, 'the bond multiplicity
increases to shrink the bond length. In C 6H 6 , e'ach C - C bond has got bond order 1.5 having
bond length 139.3 pm. In graphite (layer structure) each double bond is delocalised (see Fig.
10.11.2.1) over three C - C bonds to introduce the bond order 1.33 of bond length 142 pm.
Similarly, in butadiene (H2C = CH - CH = CH2 ), the resonance introduces -- 15% double bond
character in the central C - c; bond and consequently the bond is shorter than the oridinary C - C
single bond.
Other examples in different inorganic compounds have been cit~d in Secs. 9.16, 10.7(vi).
(vi) Steric effect on bond length: Let us take the following examples in Table 10.2.3.2.
Table 10.2.3.2. Effect of steric hindrance on the bond lengths.

Molecule Bond rc+rx rc~-x
(C - X) (calculated) (pm) (experimental (pm)
C- CI 176 176
C - Br 191 194
C-J 210 215
It is evident that as the size of the surrounding halogen atoms around the small carbon atom
ry
increases, the steric crowding among the halogen atoms increases giving rise to lengthening of
the bond. Thus, in CCl4 the steric crowding among the selected compounds is minimum and the
ra
experimental value nicely agrees with the calculated one. For the heavier halogens, because of
the increased steric crowding, the experimental values become larger than the calculated ones.
ib
(vii) Effect of covalent-ionic resonance due to electronegativity difference (ef. Fig. 10.4.2) : It has
been found, that for the heteronuclear bonds in which the atoms differ significantly in
yl
electronegativity, the calculated values of the bond length are much longer than the experimental
values (Table 10.2.3.3). m
Table 10.2.3.3. Comparison between the predicted and experimental bond lengths
(in pm)
he
Molecule Bond rA + r B rA - B
(C-X) (predicted value) (experimental
lc
HF H-F 108 92
Hel 128
ea
H-CI 136
HBr H-Br 151 142
HI H-J 170 161
th
CIF CI-F 170 163

BrF Br-F 185 176
e/
BrCI Br-CI 213 214

CH4 C-H 114 109
t.m
CF4 C-F 148 136
To explain this shrinkage, it is proposed that due to the electronegativity difference, a partial
ionic character is developed. This covalent-ionic resonance (see VBT of H2 , Sec 9.3.1) gives an
additional bond energy and shortens the bond.
Extra ionic bonding interaction due to charge separation in AO+ - BO- ~ond is responsible for.
the shrinkage in bond length. Approximately, this extra bonding energy is :
8+8-
E=-----
(41tE o ) rA - B
Schomaker-Stevenson equation and its modification : The bond length shortening has been
expressed by a relation proposed by Schomaker and Stevenson,
Ir A - B = rA + rB ~ 9 (XA - XB)' (in pm) I
Here rA' r Band rA _ B are expressed in pm and XA' XB are expressed in Pauling scale. To use the
above relation to calculate rA -B' r F is taken as 72 pm (half of the F - F bond distance), and for rN
or ro the value is taken as 74 pm (half of the H-JV - NH2 or HO - OH bond length). For all other
elements, the covalent radii are available from Table 10.2.1.2.
In the case of H - F, the calculated bond length shrinkage due to electronegativity difference
(~X == 1.8 in Pauling scale) is 9 x 1.8 == 16.2 pm. This leads to r H _ F == 108 - 16.2 == 91.8 pm.
Fortunately, this calculated value nicely agrees with. the experimental value (92 pm).
Very soon it was established that the relation proposed by Schomaker and Stevenson cannot be
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used in a general way, because in some cases it increases the discrepancy. According to Pauling,
the Schomaker-Stevenson coefficient (say, c) 9 pm proposed is not universally applicable.
ra
It varies from system to system. The general expression is given by,
rA _ B == rA + r B - c (XA - XB)' (in pm)
ib
where c varies as follows:
(a) c == 8 pm for the bonds involving an atom or two atoms (e.g. B, C, N, 0, F) of the second
yl
period of the Periodic Table.
(b) c == 6 pm for the bonds involving Si, P or S and a more electronegative atom (not from the
second period of the Periodic Table).
m
(c) c == 4 pm for the bonds involving Ge, As or Se and a more electronegative atom (not from the
he
(d) c == 2 pm, for the bonds involving Sn, Sb or Te and a more electronegative atom (not from the
lc

(e) c == 0 for the bonds involving C and the elements of the 5th, 6th or 7th groups (beyond the
ea

This ionic interaction depends on the net separation ofcharge in a particular bond. Among the
th
fluorocarbons, CH3F, CH2F2 , CHF3 , CF4 , the accumulation of positive charge is maximum in
CF4 and minimum in CH3F. Thus the ionic interaction is maximum in CF4 giving rise to the
e/
shortest C - F bond among the cited compounds.

Porterfield equation : To explain the dependence of bond length on the electronegativity
t.m
difference, Porterfeld has suggested the following relationship: .,
Ir A- B = rA + rB - 7 (XA - XB)2 , (in pm) I

This equation leads to the bond length shrinkage by 22.7 pm [== 7 x (1.8)2] in HF. This prediction
does not agree with the experimental value in ·H - F, but it explains the experimental observation
in many other cases. It is illustrated in the following example:
rSb - C/ == rSb + rC/- 7(XSb - Xc/)2

== 140 + 99 -7 (1.9 - 3.0)2 == 230.5 pm
This calculated value nicely agrees with the experimental value. In/act, compared to Schomaker-
Stevenson equation, Porterfeld equation is 0/ much more generalised character to calculate
the single sigma bond length.
Note : Both Schomaker-Stevenson equation and Porterfeld equation are applicable only for
single a-bond length. For the multiple bonds, L. Peter has developed another equation.
Peter equation (cf. J. Chem. Edu., 63, 123, 1986) : L. Peter has suggested the following
relationship to express r A_ B in terms of electronegativity difference (L\X = XA -- 'XB)·
IrA- B =rA +rB -1O~X-(cA +cB -17~x)logn(jnpm) I
(cf. Pauiing relationship: rn = r 1 -7 log n, rn = bond length of bond order n, r 1 = single bond
length, all values are in pm, Sec. 10.2.3i). It is evident that the Peter equation is the combination
ry
of Pauling equation (expressing the effect of bond order) and Schomaker-Stevenson equation
(expressing the effect ofelectronegativity difference).
In the above equation, cA and cB are the unitless multiple bondparameters ofA and B respectively.
ra
This relationship is quite satisfactory in many cases. For some common elements involved in
covalent bonds, the values of c are given as follows :
ib
Element :.C N 0 F Si P, S. Cl Ge As Se Br
c-value: 35 38 45 43 31 32 29 28 22 35 28 27
yl
10.3 THE INERT PAIR EFFECT
m
10.3.1 Meaning and Illustration of the Inert Pair Effect
he
Among the heavy posttransition elements, there is an inherent tendency to display the lower oxidation
state or lower covalency. If the group valency'is G, then the G-2 covalency is preferred gradually
lc
by the heavier congeners. Ifthe general valence shell electronic configuration is ns 2npx (where, x = 1
2,3,4 for the elements ofGr IlIA (13), Gr IVA (14), Gr VA (15) and Gr VIA (16) respectively), th;
ea
heavier congeners tend to keep the s-electrons inert as a nonbonding pair. This tendency is manifeste\
maximum for the 6th period elements (Le. 17, Pb, Bi) and this is why it is described as inert 6r-pai/
effect.
th
Here it should be remembered that the nonbonding electron pair does not necessarily lie in the
e/
s-orbital in the compounds. In the crystalline solids in which Pb(II), Sb(IIl), Bi(IIl) maintain the six
coordination number, it has been found that the nonbonding pair is housed in a comer lying in the
t.m
equatorial plane ofa distorted pentagonal bypyramid. Thus the lone pair is generally stereochemically
active, but it is inert from the standpoint of displaying two additional covalency through unpairing
the pair. However, this phenomenon is very often referred to as the inert pair effect.
Before to put forward any explanation to interpret the phenomenon, we should discuss some suitable
examples to understand the phenomenon.
(i) Gr IlIA (13) elements: Here, the +1 oxidation state compared to the +3 oxidation state is
gradually more stabilised as we move from top to bottom (Le. B to Tl). As a matter of fact,
Ga(l) and Ga(ll) compared to Ga(IIl) are rarely reported while Tl(l) is abundant. Tl(lll)
being unstable, acts as a good oxidising agent to get reduced to Tl(f).
(ii) Gr IVA (14) elements: The stability of +4 state compared to that of +2 state gradually falls
down from C to Pb. C and Si show only the stable tetravalency. The divalent carbons in
carbene or methylene compounds are transient. Ge(ll) and Sn(ll) act as reducing agents to
attain the +4 oxidation state. But the tetravalent lead compounds, such as PbCI4, Pb02 are
the potential oxidising agents to gen~rate the stable Pb(Il) compounds.
(iii) Gr VA (15) elements: Here also the trivalent states are abundantly available for the heavier
congeners while the higher oxidation state (Le. +5) is more frequent for the lighter members.
For nitrogen, pentavalency is not possible because of the othe'r ground, Le. nonavailability of
the orbital to expand the covalency. Bi(V) compounds are unstable with respect'to reduction
to Bi(lll). Sh( V) is much stabler than Bi( V). .
(iv) Inert pair in Hg : In Hg, the 6s 2 pair is energetically more inert compared to that in Zn or Cd
in the same group. This inert pair (very high ionisation energy) governs the chemistry of Hg
to a large extent. It has been discussed later in this section.
ry
.The so called inert pair effect is pronounced maximum for the 6th period elements Hg,
Tl, Ph and Bi.
ra
10.3.2 Interpretation of Inert Pair Effect in Terms of Bond Weakening Phenomena for the
Heavier Congeners (see Sec. 8.20.3 for relativistic effect and inert pair effect)
ib
To understand the energetics of the process, we are to consider the following process.
yl
MXn(g) ~MXn-2(K) +X2 (K)
Here X 2 is considered to be halogen for the sake ofsimplicity. To avoid the crystal forces, the equilibrium
m
in the gas phase has been taken into consideration.-
he
For the dissociation process, the entropy factor (AS) favours always. Hence to rationalise the
energetics (i.e. Gibbs free energy, Le. ~G = Ml- TM), we are to consider the variation of Ml for the
different members in a certain group. M-i of the process is given by :
lc
Ml= [nD'M-X(MX) - (n - 2) D'M-X(MX 2) - D'x-x]

n n-
ea
The enthalpy change in some representative cases is given in Table 10.3.2.1.

To rationalise the trends of relative disfavour for the said dissociation among the same group members
th
from the enthalpy portion, we are to consider the value of the following factor,
[nD'M_ X(MX ) - (n - 2) D'M_ X(MX _ 2)]

e/
n n
Here we are to recall the fact (see Sec. 10.1.7) : D'M -X(MX ~ 2) > D'M -X (MX ) in all cases. For the
t.m
n n
heavier congeners, D' M- X(MX ) drastically falls (see Table 10.3.2.1). Here it must be" remembered that
this drastic decrease in bond ;nergy for the heavier congeners does not arise due to the higher cost of
Table 10.3.2.1. Bond energies (0' M _ x) and enthalpies of dissociation in gas phase of the process,
MXn ~ MXn _ 2 + X2 , for Gr-IVA elements (Le. n = 4) are given in kJ mol-1 . "
Element X=F X=Cl X=Br

D'M-X D'M-X D'M-X D'M-X D'M-X D'M-X
(MX2) (MX4 ) (MX2 ) (MX4 ) (MX2 ) (MX4 )
Si 565 380 310

Ge 481 452 +694 385 354 +402 326 275 +255
Sn 481 414 +539 386 328 +276 329 273 +241
Pb 394 330 +377 304 240 +108 260 200 +87
hybridisation energy (Le. promotion energy), but due to the lower intrinsic bond energy (cf. Sec.
10.1.6.1). This lower intrinsic bond energy arises due to the ineffective overlap of the diffused .orbitals.
Besides this, repulsion by the inner electrons for the immediate posttransition elements (e.g. Ge) and
post-lanthanide posttransition elements (e.g. Tl and Pb) is also important to weaken the bond. Definitely
the second factor (Le. repulsion by the inner electrons) is more predominant for the immediate
postlanthanide posttransition metals.
Thus, Band C form their stable halides as BX3 and CX4 while Tl and Pb produce their stable halides
as TIXand PbX2. It is due to thefact that the intrinsic bond energy released during theformation oftwo
ry
additional bonds in each case cannot compensate the cost ofhybridisation energy in achieving the sp2
(trigonal) and sp3 (tetrahedra!) valence states for Tl and Pb respectively. It does not mean that for Tl
ra
and Pb, the cost of hybridisation energy is necessarily larger compared to those required for their
respective lighter congeners, i.e. Band C respectively. It is due to thefact that bonds in TIXl , PbX4
are weaker mainly due to the interaction of more diffuse orbitals. Here it may be mentioned that for
ib
showing the G-2 valence state compared to the G valence state, the cost ofhybridisation is relatively
less and this can be compensated by the heavier congeners.
yl
Some Events Related to Inert Pair Effect
m
• Inert pair effect and energy difference between the ns and np orbitals (cf. Sec. 8.24) : Because
of the secondary periodicity (originated from the d- and fcontraction), the energy difference
he
(dE = Enp - Ens) becomes relatively higher for the 4th and 6th period elements. Thus in such
cases, ns-electrons adopt more nonbonding properties and it becomes maximum for the 6th period
lc
elements (Le. Tl, Pb,..Bi, etc.). It leads to inert 6s pair effect maximum (cf. Sec. 8.24).
• Inertness ofHg: Hg (6s 2) is typically inert. It is described as inert liquid (cf. inert gas). Both the
ea
relativistic contraction and lanthanide contraction are jointly responsible for this inertness. This
aspect has been discussed in detail in Sec. 8.20.3.
th
• Relativistic effect and inert pair effect: This aspect has been discussed in Sec. 8.20.3.
• Relative stability of zni+ , cdi+ and Hgi+ :Now we are in a right position to explain the relative
e/
stability order of Zni+, Cd;+ and Hgi+. From the arguments so far we have advocated, it is
expected that on descending in a group, the said M - M bond becomes weaker because of the less
t.m
effective overlapping between the more diffused orbitals. Thus Hg-Hg bond should be the .
weakest one among the series, but in fact, Hg - Hg bond is much stronger than Cd - Cd bond
or Zn - Zn bond. To explain this, we are to consider the 1st and 2nd ionisation energies or
potentials (I.P.) of Zn, Cd and Hg (electronic configuration (n - 1) d l ons 2).
J.P. Zn Cd Hg
(kJ morl)
(J.P·)I 906 876 1007

(I.P .)11 1733 1631 1810
It is evident that the first ionisation energy of Hg is much higher compared to that of Zn or Cd
and the sum of (I.P.)I and (I.P.)n is maximum for Hg. In fact, the 6; pair of Hg becomes really
inert for the bonding purpose. In other words, Hg shares the electrons more effectively in
+ Hg : Hg+ in which the 6s electrons are shared between the mercury centres. Here it is worth
mentioning that the elusive cation Cd;+ has been recently isolated by taking the advantage of a
large anion to stabilise the large cation in a crystal lattice.
By considering the relativistic effects on the heavier congeners, this aspect can also be rationalised
(see Sec. 8.20.3).
• Ionisation energy vs. Inert pair effect: Now let us illustrate the phenomen by taking the example
of Gr. 13 elements. For the Gr. 13 elements, the ground state electronic configuration is : ns 2np 1
(for the outermost shell). It is expected that the sum of2nd and 3rd ionisation energy (IE) will
ry
give the approximate measure ofthe energy required to make the nrpair availablefor bonding.
The said sum runs in the sequence : .
ra
In (AI (TI (Ga
2
It indicates that the ns pair is more, inert for Ga than for TI..Similarly in Gr-14, (IE3 + IE4 ) of
ib
Ge > (IE 3 + 1£4) of Ph. It is apparently confusing. To rationalise the so called inert pair effect,
we are not to consider the sum of ionisation energy (loosely called excitation energy) alone. We
yl
should consider whether the energy required to allow the nr pair to participate in bonding
through hybridisation is compensated by the formation of two additional bonds (Le. MX3 vs.
MXfor Gr. 13, MX4 vs. MX2 for Gr. 14).
m
• Alternation effect (cf. Secondary Periodicity, Ch. 8, Sees. 8.20, 8.24» : For the Gr. 13 and 14
he
elements, the inert pair effect is well established. For the Gr. 15(VA) and 16(VIA) elements, no
such straight forward trend of inert pair effect is noticed. This is illustrated in the following
examples:
lc
Gr 15 elements { IPXsl > IAsXs I ISeF I < I TeF I

1
th
6 6 6
(Stability order) least stable most stable
e/
Thus for the Gr. VA (15) and VIA (16) elements, stability of the group oxidation state follows
an alternation sequence. This alternation in property has been described as·alternation effect
t.m
by some authors. This effect may be compared with the secondary periodicity.
For the Gr. 17 (VIlA) and 18 (VIllA) elements, in general, stability of the higher oxidation state
increases for the heavier congeners (e.g. stability : IF;) BrF;) elF;); for the inert gases only the
heavier congeners can form the compounds with the highly electronegative elements. This trend
notedfor the Gr. 17 and 18 elements opposes the inert pair effect trend observedfor the Gr. 13
and 14 elements. The very high ionisation energies for the lighter congeners ofthe Gr. J 7 and
18 element do not allow them io attain the higher positive oxidation state.
Gr. 13 and 14 elements Gr. 15 and 16 elements Gr. 17 and 18 elements

Increa~ing stability of No straight-forward sequence Increasing stability of higher oxidation state for
higher oxidation state for the stability of higher the heavier congeners (i.e. opposing inert pair
for the Iighter congeners oxidation state (i.e. alternation effect). Exception : Relative instability of HBr04
(i.e. inert pair effect) effect or secondary periodicity compared to that of HC/04 and HI04 Le. stability
- a consequence of mixed order) order: HC/0 4 > HBr0 4 < HI0 4
10.4 COVALENT-IONIC RESONANCE: PARTIAL IONIC

CHARACTER IN COVALENT BONDS
A true covalent bond (Le. 100% covalency) does not exist even in a homonuclear diatomic molecule,
e.g. H2• It has already been shown that in H2 , besides the covalent structure~ the ionic forms in - H AH; ~
H;H~ ~ H A : H B contribute'""-J 2%. The ionic character exists here but no dipole moment or bond
moment exists permanently. It arises so, because the two ionic forms having bond moments in opposite
directions contribute equally to nullify the effect. However, the covalent-ionic resonance exists. This
partial ionic character predominates in the bonds involving the atoms of different electronegativity.
ry
In the case of hydrogen halide (e.g. HF) the following structures are possible:
J-r F (II), 11 P- (III)
ra
H - F (I),
Here, I represents the covalent structure while II and III represent the ionic forms.. The two ionic
ib
forms (Le. II and ill) do not contribute equally. Fluorine is more electronegative than hydrogen, and
this is why; II is the predominant ionic form giving rise to a resultant bond moment directed towards
yl
fluorine. Because of the existence of such ionic forms along with the covalent structures, a partial ionic
character is developed. In the heteronuclear diatomic molecules where one specific ionic form exists
m
predominantly due to the electronegativity difference, from the knowledge of dipole moment* (more
correctly, bond moment), the % ionic ~'haracter in the bond can be calculated. The bond moment (Jl) is
he
expressed as, Jl == 0 (separated charge) x r (distance of charge separation). It is generally expressed in
the unit Debye. 1 Debye == 1 x 10- 18 esu cm. In SI unit,. it is expressed as C m. Debye (denoted by D)
and C m can be related from the following relations.
lc
4.8 x 10- 10 esu == 1.602 x 10- 19 C, 1 cm == 10--2 m. Thus, 1 Debye == 10- 10 x 10-8 esu cm
== 3.3375 10-30 C m
ea
Illustration for H-X : Let us take the case of HCI having Jlobs == 1.03 10- 18 esu cm == 1.03 Debye
x
8
and the distance (Le. bond distance) of charge separation == 1.27 x 10- cm.
th
Thus, 1.03 x 10- 18 esu cm == () x 1.27 10-8 cm; or, () == 0.8 x 10- 10 esu.
If the bonds were 100% ionic, it would lead to J-r cr giving rise to, Jlionic == (4.8 x 10- 10 esu) x (1.27
e/
8
x 10- cm) == 6.1 Debye.
t.m
Hence, the % ionic character is given by: % ionic character == Jlobs x 10

Jlionic
0/0 ionic character in H-Cl = (J.Lobs/J.Lionic) x 100 == (1.03/6.1) x 100 == 17.0
The % ionic character in a particular bond can be calculated from the bond moment. For the diatomic
molecules, the bond moment may be taken as the dipole moment (Jlobs). It depends on the difference of
electronegativity of the combining atoms. Let us consider the different hydrogen halides.
HF Hel. HBr HI
Debye (J.lobs) 1.98 1.03 0.79 0.38

% ionic character 45 17 12 5
* Dipole moment of a molecule (even for a diatomic molecule) is not only governed by the partial ionic character. It is
a vector sum ofmany other factors (cf Sec. 10.5). Thus the whole thing is not so simple as treated here.
Pauling equation and % ionic character: To calculate the % ionic character in a bond (say, A - B)
from the electronegativity difference (XA XB) of the combining atoms, Pauling derived an empirical
#'OW
equation as follows:
% ionic character in A - B = 100 [1- exp {- ~ (XA - XB)2 }] ... (10.4.1)
The above equation leads to the following conclusions.
ry
XA '- XB 0.1 0.5 1.0 1.5 1.7 2.0 2.5 3.0
% ionic character: 0.5 6.0 22.0 43.0 50.0 63.0 79.0 89.0
ra
The results are represented graphically in Fig. 10.4.1. It is revealed that to introduce 50% ionic
ib
character in a particular bond, the electronegativity difference between the combining atoms should be
- 1.70. l'hus the bonds having electronegativity difference more than 1.7 are predominantly ionic (i.e.
yl
ionic character'> 50%), while for the electronegativity difference less than 1.7, the bonds are
predominantly covalent~ A careful analysis of the Pauling's empirical equation yields some limitations
m
ofthe equation. These are given below:
(i) For the higher values of (XA - XB)' the agreement is very poor.
he
(ii) The alkali metal hydrides and the hydrides of Ca, Sr and Ba are predominantly ionic though
the electronegativity difference (i.e. x'A - XB) is less than 1.7.
(iii) For HF, the electronegativity difference, XF - Xli = 1.9 predicts it to have 60% ionic character
lc
but, in fact, it is having only 45% ionic character. Here it is worth mentioning that at the time
#'OW
when Pauling proposed this relationship, the dipole moment and 010 ionic character of HF were
ea
not known.
th
100
e/
t.m
oOJ~ 501--------.-r--.......,
co
-5
o
'2
.Q
cfl.
o HBr
o 1 2 3
Electronegativity difference
Fig. 10.4.1. Dependence of % ionic character in a bond on the electronegativity difference between
the combining species.
Hannay-Smyth equation: To remove the above shortcomings, the Pauling's equation has been
modified by Hannay and Smyth as follows :
0/0 ionic character in A - B = 100 [0.16 (XA -.; XB) + 0.035 (XA -.; XB)2]
= 16 (XA -.; XB) + 3.5 (XA -.; XB)2 •.• (10.4.2)
The modified equation reveals that for (XA -.; XB) = 2.1, the % ionic character becomes 50. By using
the Hannay-Smyth equation, we get the following results for the hydrogen halides.
HF Hel HBr HI
% ionic character (approx.) 43 17 13 7
ry
% covalent character (approx.) 57 83 87 93
ra
The Hannay-Smyth equation is graphically
represented in Fig. 10.4.1.
ib
The bonds involving highly electropositive
• • •
-elements characterised by the low ionisation
.~ 1 ••
. ..". /
" ""
yl
energies (e.g. alkali and alkaline earth metals) and -g>.
.- a.
Covalent
the eleme"nts of high electron affinity are
predominantly ionic compounds.
m .0-
_ro
ss
at:
FQ)
"
~
"
~
~
. •
-' •
Note: When charge separation (q) in a bond ",","'Ionic •
he
(say A - B) is 100%, it enjoys only ionic
contribution, i.e. Madelung interaction. On the 20 40 60 80 100
--+ % of charge separation
other hand, when the charge separation is 0%, it
lc
leads to a perfectly covalent bond i.e. homopolar Fig. 10.4.2. Contribution of covalent and ionic
character towards the total binding enthalpy in
ea
bond. In terms ofcharge separation (q), the covalent

a simple binary AS compound.
bond order may be approximately expressed as
follows:
th
Covalent bond order = K (1 - q2)Yz, K = proportionality constant

1, (when q = 0)
e/
0, :(when' q = 1, i.e. 100% ionic interaction)

t.m
Contribution 0/covalent-ionic resonance to the total binding enthalpy: The contribution of covalent
interaction (i.e. sharing of electrons between the combining atoms) and ionic interaction in a polar
covalent bond to the total binding enthalpy can be schematically represented as in Fig. 10.14.2. Here
it is assumed that at the extreme cases (i.e. q = 0 and 1), the total binding enthalpies are equal. Here it
'is evident that partial ionic character stabilises a covalent bond. A bond having some ionic character is
more stable than a pure covalent bond.
Problem: Calculate the percentage of ionic character in Hel molecule. Given: X(e/) = 3.0, X(H) =
2.1.
Solution: Using the Hannay-Smyth relationship," we have:
0/0 ionic character = 16 (XCI - XH) + 3.5 (XCI - XH)2
16 (3.0 - 2.1) + 3.5 (3.0 - 2.1)2
16 x 0.9 + 3.5 x 0.81 ~ 17.2
Problem : Calculate XLi from the given data of LiF.

Dipole amount = 6.32 D; XF = 4.0, bond length = 0.156 nm
Solution: Jlionic = (1.6 x 10- 19 C) x (0.156 x 10-9 m) = 2.496 x 10-29. C m
30 1
0/·
1'0
•
IonIc c haracter = (Jlohs
- - x 100) = 6.32 D x 3.34 x 10-
-29
m D- x 100 =.
84 33 e
Jlionic 2.496 x 10 C m
Using the Hannay-Smyth relationship, we have:
ry
84.33 = 16 (4.0 - XLi) + 3.5 (4.0 - XLi)2
2
3.5XLi - 24XLi + 35.67 = 0; or XLi = 0.9, 13.5
ra
Le.
X'Li = 13.5 is not acceptable as X cannot be greater than 4.0. It leads to XLi = 0.9.
ib
10.5 DIPOLE MOMENT AND MOLECULAR POLARITY
yl
Dipole moment of a molecule is determined by the vectorial sum of different parameters, Le. intrinsic
m
homopolar dipoles, hybrid lone pair moments and bond pair moments. Thus, from the dipole
moment measurement, to calculate the % ionic character (which is nothing but only one of the
he
different factors to introduce the polarity in a molecule, even for the diatomic molecules) is of no
much significance. Before to discuss the dipole moment, we should get familiarised with the different
lc
contributing parameters to the dipole moment.
10.5.1 Different Factors Governing the Molecular Polarity

ea
(i) Intrinsic homopolar dipole : This will arise in the cases (irrespective of electronegativity
difference) when the combining atoms use the pure atomic orbitals/hybrid atomic orbitals differing
th
in size, Le. radial distribution function. This moment exists even for the cases where the
electronegativity difference (XA - XB) is zero leading to pure covalent bonds. This fact is
e/
illustrated in Fig. 10.5.1.1 where B uses a smaller orbital and A uses a larger orbital. Here the
t.m
electron cloud gets mainly concentrated in the overlapping region shown by the shaded area.
Thus the electron charge cloud gets shifted from the mid point
of the bond to the atom which utilises the smaller orbital. This
introduces a moment acting towards the smaller atom. This
moment (acting towards the smaller atom using the more
compact orbital) created due ·to the difference of size of the
combining orbitals is called intrinsic homopolar dipole.
However, its contribution is not too large.
This intrinsic homopolar dipole in the hydrogen halides (H -
X) always acts towards hydrogen because of its more compact
(Le. smaller) orbital utilised in the bonding, though the moment
Fig. 10.5.1.1. Generation of
due to the difference of electronegativity acts towards the more intrinsic homopolar dipole
electronegative atom X. due to the difference in size
(ii) Hybrid lone pair moments: When the lone pairs are housed of the overlapping orbitals.
778 Fundamental Concepts of Inorganic Chemistry .
in hybrid orbitals, it only operates. The unshared pairs residing in pure s- or p-orbitals do not
contribute anything. The s-orbital is spherically symmetrical. Hence it contributes nothing.
Similarly, the two lobes of a pure p-orbital are projected in the opposite directions to cause no
effect. But when the unshared pair houses in the hybrid orbitals, its consideration becomes
accountable. This is why, it is referred to as hybrid lone pair moment. The hybrid orbitals
concentrate the electron cloud in some particular directions and the electron cloud remains under
the control of a single nucleus (cf. the bond pair is placed between the nuclei). The lone pair
moment acts in the direction in which it is projected. Its value depends on the % s-character in
the s-p hybrid orbitals utilised to house the lone pair. It increases with the increase ofs-character
ry
up to -- 50% then it falls down. Thus the lone pair moment for the different s-p hybrids increases
in the sequence:
ra
sp > sp2 > sp3
ib
The sequence can be explained by considering the relative order of the size of major lobe
which follows the same sequence (cf. Sec. 9.13.3). The hybrid lone pair moments are fairly large
in magnitude. For example, for the hybrid orbitals of carbon it varies from 4.4 D (sp-hyrbid) to
yl
3.7 D (sp3 hybrid). This is why, the hybrid lone pair moments make a significant contribution
to the resultant molecular polarity.
m
(iii) Bond pair moment: The interpretation of the bond pair moment is getting complicated due to
the involvement of a number of factors. These are: (a) the more electronegative atom tends to
he
. direct the moment to its own direction; (b) the intrinsic homopolar dipole tends to orient the
moment to the atom with a more radially compact orbital.
lc
• Generally, contribution due to electronegativity difference is more important than the contribution
from the intrinsic homopolar dipole. Consequently, bond moment is directed towards the more
ea
electronegative atom.
• Generally, the bond pair moments are smaller in magnitude than the lone pair moments
th
unless the combining atoms differ largely in electronegativity.

Some of the bond moments are given in Debye units in the following Table 10.5.1.1.
e/
Table 10.5.1.1. Some bond moments in Debye units (1 D = 3.3375 X 10-30 C m)

t.m
Bond Bond moment Bond Bond moment
~ ~
,H-C 0.39 H-N 1.33
N-O 1.51 H-P 0.36
H-S 0.69 C-N 0.22
C-O 0.75 C-F 1.39
C-Cl 1.47 C-Br 1.42
Si-H 0.99 Si-N 1.55
Sn-Cl 3.00 N-F 0.17
P-Cl 0.80 C=N 0.90
C=O 2.30 p=o 2.70
S=O 3.00 C=N 3.53
N~B 2.55 N~O 4.28
P~B 4.40 O~B 3.60
Covalent Compounds: Characteristics, Structure and. Reactivity 779
HH~
(iv) Group moment: Different groups such as -R
(alkyl group), -NH2 , -N02 , -OH, etc. have also
some definite moments (vectorial summation of
all the prevailing moments within the group
under consideration).
-+----+.---- --- C -....--- H
Let us take the saturated hydrocarbons CH4 ,
C 2H 6 , C 3H g, etc. which are nonpolar. Ifwe look
into the stereochemistry (see Fig. 10.5.1.2) of H
ry
the simplest hydrocarbon CH4 , it is evident that Fig. 10.5.1.2. Calculation of group moment
the group moment of -CH3 exactly counter- of -CHao
ra
balances the bond moment of C - H.
Mathematically,
~CH = 3~c _ H cos (180° - 109° 28') == 3~c _ H cos 70° 32'
ib
3
=3~c-~ x 15-= ~C-H ~ 0.4 D
yl
Similarly it can be shown that, ~CH3 = ~C2Hs = ~C3H7 = ... = 0.4 D
. It suggests that if a hydrogen atom in different saturated hydrocarbons is replaced by -OH or
m
-NH2 or -N02 group to generate the homologous series, the molecular dipole moment will remain
the same in a homologous series for a particular functional group. It is evidenced from Table
he
10.5.1.2.
lc
Table 10.5.1.2. Dipole moments in Debye (D) of some homologous series

Alkyl group Alcohols Amines Chlorides Nitriles
ea
(-Oll) (-NH2 ) (-CI) (-C= N)
C2H s- 1.70 1.30 2.04 3.56

th
n - C3H 7 - 1.67 1.40 2.04 3.56

n - C4H 9- 1.66 1.30 2.04 3.56
e/
Generally the group moments in the aromatic compounds are slightly different from those
t.m
in the aliphatic compounds. The moments for some groups in the aromatic compounds are
given below in Debye unit. To understand the group moment, both inductive effect (I) and
mesomeric or resonance effect (R) are to be considered. For some groups like CH3, only inductive
effect operates. For some groups like N0 2 , NH2 , Cl, OH, etc., both inductive effect and resonance
effect operate. For the groups like N02, both the -I and -R effects operate in the same direction
(i.e. away from the ring). For the groups like Cl, OH, NH2 etc. the -I effect is opposed by the
+R effect. For OH and Cl groups, the -I effect predominates while for NH2 group, the +R effect
predominates (cf. electronegativity order: 0> N; dipole moment: pyrrole vs./uran).
-N02 -CHO -OH -Cl -CH3 -NH2 -H
-3.95 -2.8 -1.7 -1.55 +0.4 +1.53 o
(- sign indicates the moment acting away from the aromatic ring, + sign indicates the direction
towards the ring).
10.5.2 Prediction* of Geometry of the Molecules from Dipole Moment and Calculation of
Dipole Moment: Dipolar Repulsive Interaction
Before to shed any light in the present topic, we must remember that the dipole moment is a very
complicated parameter to be interpreted. But still, consideration of the bond moments in some simple
molecules can tell us the geometry of the molecules. Dipole moments of some molecules are given in
Table 10.5.2.-1.
Table 10.5.2.1. Dipole moments (in Debye unit) of some molecules.
ry
Molecules Dipole moment Molecules Dipole moments
(D) (D)
ra
CH4 , C3Hg, C2H4 , C2H2, 0 HBr 0.78
C2H6 , CBr4 , C6H6 , napthalene
ib
HI 0.38
CH30H 1.65 H2O 1.85
yl
CH3CI 1.86 H2S 1.10
CHC/3 1.15 HCN 2.92
m
CH3Br 1.80 NH3 1.46
C2HsBr 2.03 NF3 0.20
he
CH3NH2 1.25 S02 1.63
CH3C0 2H 1.74 N20 0.17
lc
H2, C/2, Br2, 12, N2, CO2, CC/4 , SnC/4 0 CO 0.12

PH3 0.55
ea
HF 2 PC/3 0.78
Hel 1.03 AsH3 0.16
th
(a) Symmetrical molecules: The symmetrical molecules such as CH4, CC/4 , CO2, CS2, C6H6, etc.
e/
do not have any dipole moment, as the resultant of the bond moments in such cases becomes
zero. "
t.m
~~: ~~;
O=C=O S=C=S
(~= 0) (~= 0) (~= 0)
x
!I
c
x¢ll~x A
H a H
X
(~c-x =~cx ;3~ = 0) (J-l ~ 0)
(b) Angular molecules: S02' H20, H2S being angular in geometry possess the net dipole moment.
If the two bond moments J.11 and fl2 act at an angle a., then the resultant J.1 is given by :
• As a matter of fact, due to the complication in the dipole moment parameter, simple consideration of the bond
moments produces correct conclusions only in the cases where no hybrid lone pair moment operates; otherwise it
may lead to dubious results.
I~ =[~~ + ~~ + 2~1~2 cos (1]1/21 ... (10.5.2.1)

In H 20, the observed dipole moment is 1.85 D. It results from the two bond moments acting at an
angle a.. Taking the value, Jlo _ H = 1.7 D, the angle becomes -- 105° according to Eqn. 10.5.2.1.
This calculated value nicely agrees with the experimental one (H - '8 - H = 104.5°). Let us
consider the case of CH30H by using the following bond moments:
JlO-H =1.7D,Jlc_o =0.7D,JlCH3 =JlC-H =0.4D
ry
~~ H
ra
o 110 0
0.7D 1
ib
C
1
yl
/1\ 0.40
H H H m
Fig. 10.5.2.1. Calculation of dipole moment of CH3 0H from its geometry.
From the geometry (Fig. 10.5.2.1), it leads to Jl = 1.56 D while the observed value is 1.65 D.
°
he
Note: Here the lone pair moment arising from two lone pairs on have been ignored. For more
correct calculation, these are to be included.
lc
(c) Dipole moment of chloromethanes : The observed order is :

CH3Cl (1.87 D) > CH2Cl2 (1.55 D) > CHCl3 (1.02 D) > CCl4 (0 D)
ea
CI CI H CI
th
Jl(C-eI) tl It I It
C C.?' C C
/I~ qlt~ qtl~
H /1' H t JJ(CH 3)
e/
H . H CI CI CI CI CI CI CI
H
CH 3CI CH 2CI 2 CHCI 3 CCI 4
t.m
In CH3CI, the C-Cl bond moment and CH3 group moment jointly work in the same direction to
give the resultant dipole moment. It is mainly due to the C-Cl bond moment because the CH3
group moment is very small (0.4 D). Ignoring the contribution of the CH2-group moment, the
dipole moments of CH2Cl2 is expected to be controlled by two C-Cl bond moments working at
about 109°28.'. Thus, the net dipole moment of CHzClz is expected to be larger than that of
CHlCI but the reverse is true. Again, the net dipole moment ofCHCl3 (i. e. chloroform) is expected
-to be comparable to that ofCH3Cl because the Cel3 group moment is expected to be equal to
that ofC-C1 bond moment. But the reverse is true.
The apparent anomaly can be explained by considering the effect ofinduced dipole moment by
s+ s-
each C-Cl bond. Each C-C/ bond is polarised as : C-Cl. This polarisation will induce a dipole
moment in other C-CI bonds in the opposite directions. In CH3CI, this effect on the C-Hbonds
is ignorable. This is why, it records the highest dipole moment. In CH2C~, the induced dipole
moments reduce the bond moments ofboth C-Clbonds. This is why, the observed dipole moment
of CH2Cl2 is less than that of CH3Cl. In CHCl3 , there are three C-Cl bonds. The effect of induced
dipole moment opposing the C-Cl bond moments is more important than that in CH2Cl2• Infact,
in CHCll' the C-Cl bond moment is considerably reduced. This is why, its net dipole moment
is significantly redu·ced compared to both CH3Cl and CH2 Cl 2 • CCl4 is symmetrical and
consequently its net dipole moment is zero. However, it should be mentioned that because of the
effect of induced dipole moment, the C-Cl bond moment is minimum in CCI4 •
(d) Substituted benzenes: Benzene is itself nonpolar, but on substitution it becomes polar.
ry
©~ @@@
ra
@
ib
Jl(D)== 0 1.70 1.40 3.90 1.50 0.40
In the case of his-substituted compounds, C6Hp the dipole moments can easily be calculated
yl
by using Egn. 10.5.2.1, where a == 60°, 120°, and 180° for the ortho-, meta-, and para-derivatives
respectively. Table 10.~.2.2 shows the comparison between the calculated (Jlcal) and observed
m
(Jlobs) val ues.
he
Table 10.5.2.2. Dipole moments (in Debye) of CS H4 XYcompounds
ortho meta para
lc
X y cal obs cal obs cal obs

CH3 Cl
ea
1.39 1.35 1.79 1.78 1.95 1.90

CH3 N0 2 3.76 3.66 4.16 4.17 4.30 4.40
Cl N0 2 5.26* 4.60 3.68 3.69 2.52 2.70
th
NH2 N0 2 3.64* 4.26 4.74 4.85 5.48* 6.2

Cl CN 4.88 4.75 3.40 3.40 2.40 2.50
e/
Table 10.5.2.2 indicates that the calculated values are in good conformity w!th the observed
t.m
ones. In some cases (marked with·), deviation is noticed. This type of deviation becomes
accountable when the two substituents having very high group moments are placed at the ortho-
positions. This ortho effect probably is originated due to the inductive effect, mesomeric
effect and steric effect (specially important for bulky groups). The steric effect widens the
angle of interaction. In some cases, the induced dipole moments work in opposite directions for
the ortho-groups. The steric .effect and induced dipole effect will reduce the net moment. But
coupling of +R and -R mesomeric effects may enhance the moment as in o-nitroaniline. It
happens so in p-nitroaniline also.
When X == Y (Le. C6H~2)' the calculated dipole moments are as follows, (where Jlx denotes the
group moment of X) :
fl(ortho) == .J3Jlx, a =60°; Jl(rneta) = Jlx' a =120°; Jl(para) = 0, a =180°.
This prediction has been confirmed in nlany cases such as, C6H 4(N0 2)2' C6H 4(CH3 )2' etc. But a
serious deviation has been noticed for para C 6H 4(OH)2 for which the observed value is 1.64 D in
contrast to the zero value calculated based on Eqn. 10.5.2.1. This deviation arises probably
due to the lack of planarity of the -Dn groups, with respect to th·e plane of the ring. Thus the
two -OH links are probably remaining inclined to the plane of the ring.
~ 1 + H]
4: (-1.55 D) , (0.4 D)
t (-3.95 D)
ry
N02
Jl = ~(0.4)2 + (-3.95)2 + 2 x 0.4 x (-3.95)cosI80°
ra
= 1.55 D, = 4.35 D, cos 1800 =-1
ib
\;;@-/
yl ». 0 ~ 830
m H "
\ Jl = 1.64 D
H
Jl = ~(0.4)2 + (-3.95)2 + 2 x (0.4) (-3.95) cos 60° (On group moment acts
he
at an angle 83° with-
=3.76 D, (cos 60° =~) the diagonal of the hexagon)
lc
ea
th
t (-
Cl
1.55 D)
e/
Jl = ~(-1.55)2 + (-1.55)2 + 2(-1.55)2 cos 1800

t.m
= 0, (cos 1800 = -I)
Fig. 10.5.2.2. Dipole moments of some representative disubstituted benzenes. (Group moment acting
towards the ring is denoted by + sign; group moment acting away from the ring is denoted by - sign.
Speciality for the -OH and -NH2 groups

For these two groups, the arrangement of the aloms is not symmetrical with respect to the line 01
attachment ofthe group. Consequently, their group moments do not work along the diagonal of the
ring. But, for other groups like -CH3 , -C == N, the group moment works along the diagonal of the ring.
(O»-H H
(e) Simple cis- and trans-compounds : Dip~le moments for the cis- and trans-compounds are totally
l
different. Generally, the trans-compounds show zero dipole moments while the cis-compounds
show large dipole moments. This prediction has been confirmed in many cases.
CI~ ./}CI CI~ /H CI" /PR 3 R3P" / CI

/C=C" ' /C=C~ ; /Pt" , /Pt" I
H H H )I CI CI PR3 CI PR3
cis-isomer trans-isomer cis-isomer trans-isomer
(Jl = 1.86 D) (~ = 0) (Jl =9.9 D) (Jl = 0)
ry
(less stable)
H H H C0 2H
ra
"C=C/ "C=C/
H02C/ " C0 2H H02C/ " H
ib
(Maleic acid) (Fumaric acid)
trans - (J.1 =0)
yl
cis ~ (J.l ~ 0)
Fig. 10.5.2.3. Dipole moments in some simple cis-trans-isomers.
m
(t) Complication due to mesomeric effect: Sometimes, moments due to inductive effect are opposed
by the moments due to mesomeric effect. This aspect is illustrated in some representative organic
he
compounds (Fig. 10.5.2.4).
H307-CH2~CI H2G:1C~I: ---. H2~C~9.I: 1

lc
[
Jl =1.44 0
ea
Jl = 2.050
(Ethyl chloride) (Vinyl chloride, inductive
Only inductive effect effect opposed by
th
mesomeric effect)
e/
04 Of 0t'~0>
t.m
N Q X=CI(m=1.75D) H2N~N"
X = F (m = 1.63 D) 0-
Jl = 1 ~8 0 =
Jl 0.7 0 . (p-Nltroaniline)
(Pyrro/e) (Furan) Monohalobenzene )l =6.200
Fig. 10.5.2.4. Effect of electron delocalisation on dipole moment.
• In ethyl chloride, dipole moment arises due to inductive effect only but in vinyl chloride, the
moment due to mesomeric effect opposes the moment caused by inductive effect.
• Electron delocalisation effect opposes the inductive moment in both pyrrole and furan but in
pyrrole the electron delocalisation into the ring is more important than that in furan. In furan,
electron delocalisation is relatively disfavoured due to the higher electronegativity of oxygen.
The net dipole moment in pyrrole acts towards the ring while in furan it works towards the 0-
atom. Thus, in furan, inductive effect governs the direction of net moment while in pynole, the
delocalisation effect governs the direction of net moment.
• For the chloro- and fluorobenzene, the moment due to inductive effect is opposed by the moment
due to the mesomeric effect. The F(2p) ~ C(2p) 1t-bonding is more efficient than
CI(3p) ~ C(2p) 1t-bonding because of the better matching of orbital size in 2p-2p interaction
compared to 3p-2p interaction. Thus +R effect is more efficient in fluorobenzene. Consequently,
in spite of better -I effect in fluorobenzene, its resultant dipole moment is less. It explains the
higher dipole moment of chlorobenzene though its - I effect is relatively less.
• The group moments of -NH2 and -N02 are + 1.53 D (acting towards the ring) and - 3.95 D
(acting away from the ring) respectively. These two group moments are in the same direction in
ry
p-isomer. Thus the resultant moment inp-nitroaniline is expected to be (1.53 + 3.95) D Le. 5.48
D acting towards the N02• But the observed value (6.2 D) is much higher. It is due to the better
ra
electron delocalisation through the ~oupling of +R effect of NHz group and -R effect of
NO z group. A similar situation arises for o-nitroaniline (3.64 D vs. 4.26D).
ib
(g) Dipolar rep~lsion and stability of a particular conformation : It is illustrated by taking some
specific examples. Butane-2,3-dione is more stable in its trans-conformation in which the
yl
repulsiye interaction between the negative charges of the polarised O-centres is minimum.
Because of the same ground, the anti-conformation of 1,2-dichloroethane is more stable than
m
the corresponding gauche-form. Similarly, the anti-form of 1,2-ethanediol is expected to be
more stable than its gauche-form. But, in reality, the gauche form of 1,2-ethanediol is more
he
stable because of intramolecular H-bonding interaction. Thus, in the present case, the H-bonding
interaction is more important than the dipolar repulsive interaction.
lc
~CI
ea
&-0
H
III /
~/,\~H3 /
[1
th
Hp' H H
e/
&-0 H
trans-form cis-form Anti-form, more stable Gauche-form, less
(Jl =0; more stable (Jl =3.2 D)
t.m
(Jl"* 0) (Jl = 0)
Butane-2,3-dione 1,2-Dichloroethane,
=1.2 0 (in gas phase)
Jlobs
~\ , Intramolecular
\ H-bonding
H ____
, H
~
H H
OH H
Anti-form Gauche-form, more
1-2-Ehanedlol
Fig. 10.5.2.5. Dipolar repulsion and stability of different conformations.
10.5.3 Contribution of Hybrid Lone Pair Mome~ts to the Molecular Polarity

So far we have discussed, we have ignored the lone pair moments. But, in some cases the serious
discrepancy arises due to such simplification. Here we shall cite some examples to illustrate the
importance of lone pair moments.
Z
(i) Hel: If in the bonding, Cl utilises its pure 3pz I
I
orbital (assuming the z-axis to be the bond axis),
then the three lone pairs reside in 3s, 3P:x and
3py orbitals. The s-orbital being spherically
H
t
--~CI----:"--_·X
'10...
ry
symmetrical contributes nothing to the dipole
: sp3 Hybrid orbital
moment. The P:x and Py orbitals being perpendi- (lone pair)
ra
cular to the bond axis show zero components to
the bond axis. Moreover, the lone pair residing
Fig. 10.5.3.1. Contribution of hybrid lone
ib
in a pure p-orbital (having equivalent lobes in
pair moments in the dipole moment of HCI.
opposite directions) cannot produce any
yl
moment. Thus the three nonbonding pairs have nothing to do with the dipole moment. But, if Cl
utilises the hybrid (s - p) orbitals, the situation becomes totally different. For illustration, let us
m
consider Cl to utilise its sp3 hybrid orbital for the bonding purpose. Th~n the three lone pairs will
be housed in other three sp3 hybrid orbitals. It is evident from Fig. 10.5.3.1 that the nonbonding
he
electron clouds are much more concentrated in the region opposite to the H - Cl bonding direction.
Each lone pair will make an angle of about 71 0 with the - z direction (assuming the bond along
the +z direction). If the hybrid lone pair moment is represented by JlI then the total contribution
lc
by the three lone pairs in the - z direction is given by :

ea
lone pair contributions = 3JlI cos 71 0

Thus it is evident that the bond moment due to the electronegativity difference and the lone
th
pair moments get mutually reinforced. But the intrinsic homopolar dipole moment acts in the
opposite direction, Le. towards hydrogen. Thus the resultant dipole moment is the vectorial sum
e/
of the three vectors :

~ -~
intrinsic homopolar moment (H - Cl), bond moment (H - Cl) to due to the electronegativity
t.m
-+--+
difference and lone pair moments (H - Cl).
The lone pair moment depends upon the degree of mixing of sand p. Probably, due to the
different opposing forc~s, the dipole moment of HCI has been so low (Jlobs = 1.03 D).
Now it is evident that the calculation of % ionic character (which arises due to the
electronegativity difference only) from the observed dipole moment in which the difference of
electronegativity is only one of the many contributing factors is not very much meaningful.
(ii) NH] and NF] : The dipole moments of NH3 and NF3 are 1.5 D and 0.2 D respectively. Knowing
the bond angles (H NH ~ 107 0 , F NF ~ 1020 ), the calculated bond moments for the N - Hand
N - F bonds appear to be -- 1.33 D and -- 0.15 D respectively. Such a small value for the N - F
. ~
bond is unbelievable. If we consider the electronegativity difference leading to N - H
I ~
(X N - "i H = 0.9) and N - F ("iF - "iN = 1.0) bond moments and homopolar dipole moments
~ ~
leading to N - Hand N - F moments, it is impossible to explain the apparent small bond
moment value of the N - F bond.
To interpret the result, we are to consider all the different contributing factors, ,i.e. intrinsic
homopolar dipoles (J.1h)' bond moments due to the electronegativity difference (J.1e) and lone
pair moments (J.1/). Let us analyse the factors.
In NF3 :
~
(a) J.1h (N - F): The fluorine atomic orbitals are more compact (Le. smaller) than those of
ry
nitrogen Le. J.lh operates towards F. However, its contribution is relatively small.
~
ra
(b) J.1e ( N - F ) : Fluorine is more electronegative than nitrogen, 'XF = 4 > 'XN = 3. This moment
reinforces J.lh but opposes the lone pair moment of nitrogen.
ib
(c) J.1/ (+-+:N - F: +--+): The fluorine lone pair moments are projected opposite
(approximately) to the nitrogen lone pair moment. Contribution of the fluorine lone pair
yl
moments depends on its state of hybridization.
I~ NH3 :
~
m
(a) J.1h (N - Ii): The hydrogen atomic orbitals are more compact.
he
+----t-
(b) J.1 e (N - H): The electronegativity of nitrogen is greater than that of hydrogen,
'XN = 3 > 'XH = 2.1.
lc
(c) J.11(+-+ :N - H) : The nitrogen lone pair moment reinforces J.le but opposes J.lh which is
ea
relatively less important.
Q1
1
Thus it is evident that in NH3 , J.1e and J.l1 are
mutually reinforced and these are partially
th
cancelled by Jlh whose magnitude is less N

compared to those Jle and Il,. But in NF3, the
e/
H?1i~ ?It'
nitrogen lone pair moment is opposed by all
otherforces. This is why, NH3 shows a higher
t.m
dipole moment acting towards N while in NF3 H F

due to the significant mutual cancellation of Fig. 10.5.3.2. Contribution of bond moments
the different moments, the dipole moment is and hybrid lone pair moments in the dipole
moments of NH3 and NF3 .
drastically reduced. As a matterfact, it is very
difficult to predict the direction ofthe small
resultant dipole moment in NF3• The whole thing is displayed in Fig. 10.5.3.2.
(iii) H 10 and FlO: The roles of different contributing factors to the observed dipole moment of H 2 0
are the same as in NH3 •
~ .
J.lh (homopolar dipole) acts as 0 - H while J.le (bond moment due to the electronegativity
+---+-
difference) directs as 0- H . The hybrid lone pair moments (Jl,) of the two unshared pairs in the
sp3 hybrid orbitals reinforce J.le (Fig. 10.5.3.3). Thus the resultant dipole moment cannot be
evaluated by the bond moments alone.
The dipole moment o/OFz (J.1 = 0.3 D) is very small compared

to that of H 20 (J.1 = 1.84 D). It is due to the two factors (ignoring
the contribution of Jlh with respect to those of Jl e and Jl,):
(i) 0 - F bond moment (~X = 0.5) is less than that of 0 - H bond
(~X = 1.4) and (ii) the two lone pair moments on oxygen oppose
I )
@t
fO~
the 0 - F bond moments. This is very much comparable to
H H
the case of NF3 vs. NH3 • Fig. 10.5.3.3. Hybrid lone
ry
(iv) CO : It is an interesting example having a very small dipole pair moments (J.1,) and bond
moment 0.1 D directed towards carbon. Now let us analyse all moments (J.1J in H2 0.
ra
the contributing factors.
(a) Lone pair moments (J.1,): There is a lone pair on each of the atom (Le. C and 0). This is well
ib
understood in tenns of MOT (cf, Fig. 9 t 11 :2.3). The lone pair moment on 0 is opposed by
the lone pair moment of C. Thus, Jl, is not of much importance.
yl
~ ~
~ :co: ~ : Le. CO or CO for Jl,

(b) Intrinsic homopolar moment: The oxygen atomic orbitals are more compact than those of
m -r-.--+
carbon. Hence, the intrinsic homopolar moment (Jlh) operates towards oxygen, Le. CO for
he
Jlh'
(c) 0- and x-bond moments due to the.. electronegativity difference (J.1e) : Oxygen is more
electronegative than carbon. Hence the (J- and x-electron clouds are shifted towards oxygen
lc
-~
and consequently Jle is directed towards oxygen, Le. CO for Jle •
ea
(d) Dative bond moment (J.1d) : Due to the dative bond, 2p(O) -+ 2p(C), it leads to th~~arge
separation, c- 0+ due to which the bond moment (Jld) directs towards carbon, Le. CO for
th
Ild'
•• -...--+
:C=Q ~ :c=o:
e/
The resultant observed moment is the vectorial sum ofthe above different contributing factors.
Due to their mutual cancellations, the observed dipole moment is very small.
t.m
(v) Low bond moment in B-N linkage:
The dative N ~ B x bond moment cancels partially the bond moment generated from the
electronegativity difference.
(vi) PtC/2(Et 2S)2: This compound is very much interesting in connection with the lone pair moments.
Apparently it is believed that the cis-isomer will have a net dipole moment while the trans-one
will be nonpolar.
EttS.............
/Cl EttS............. /Cl
Pt - /Pt,
Cl/ .............SEt2 EttS C/
trans-isomer cis-isomer
(Jlobs = 2.4 D) (Jlobs = 9.5 D)
This nonzero dipole moment (fairly large, Et

but less than that of the cis - one) for the
trans-isomer cannot be explained from the K:'\ ··
~> - -/Et
/ ' ,
~
~
f
.. - --,( Et
"\ \ \
geometry by considering the bond
moments only. ..
.c··1 I I
--+--"'~y'
\\ \ ,_~
\
'
II··
..
CI:
..
:CI
,I
--r-'
.. ~
~t--r--
_~
I
..
CI:
..
To understand the result, we are to
consider the lone pair moments along Et '1-'" Et .> r...... Et
with the bond pair moments. The lone Et > Et
pair moments on chlorines are cancelled
ry
Fig. 10.5.3.4. Different hybrid lone pair moments
in the trans-isomer along with the Pt - CI and bond moments in trans-PtCI2( SE~)2.
bond moments. Similarly, the Pt - 8 bond
ra
moments are mutually cancelled. But the lone pair moments o/sulphur are not cancelledjully,
and also the S - Et bond moments are not jully cancelled because oj the stereochemically
ib
rigid configuration shown in Fig. 10.5.3.4. Here it is worth mentioning that if the free rotation
of the £t28 molecule around the Pt - 8 axes were possible, then the net dipole moment would be
yl
zero. But, as the rotation is prevented here, the rigid configuration lacks in centre ojsymmetry.
(vii) 03 molecule: The Lewis structure of 03 molecule is :
+
m +
/o~0 ----- cf/Y"....o_
he
- 0
Each bond is polar to possess some bond moment. The resultaf!t bond moment (arising/rom two
bonds) is cancelled to some extent by the lone pair momentfrom the lone pair residing-on the
lc
central O-atom. Consequently, the dipole moment of the molecule will be very small.
ea
(viii) N 2H 4 : The fairly high dipole moment (1.85 D) for N 2H 4 (N-H = 104 pm, N-N = 147 pm,
H- N- H ~H - N- N ~ 1100 ) indicates its unsymmetrical structure as in the case of H 20 2
(2.0 D) having the open-book configuration where the 0-0 linkage is the spine. In N2H4 ,
th
each N-centre is supposed to be sp3 hybridised and the lone pair on each N-centre is also housed
in the sp3-hybrid orbital. In gaseous phase, N 2H4 exists in the gauche conjormation where the
e/
two halves (Le. NH2-fragments) seem to be rotated by about 95 0 from the eclipsed conformation
along the N-N bond. In this gauche conformation, all the N-H bond moments and lone pair
t.m
moments are not cancelled out fully. This makes the fairly high dipole moment. If it were in
the staggered jorm (trans-jorm) then its dipole moment would be close to zero. These are
illustrated in Fig. 10.5.3.5.
Note:. N 2 F 4 (gas) remains in a mixture of both forms (Le. gauche and staggered). Thus N 2 F 4
records an anamolous dipole moment. P2H4 (gas) mainly exists in the gauche form.
In the eclipsed conformation, the lone pair-lone pair repulsion is maximum.
• Both N 2H 4 and H 20 2 adopt the gauche conjormation that separates the lone pairs as
much as possible to stabilise the structures. The dihedral angle in H 20 2 arises from
the lone pair-lone pair repulsion and this angle depends on the chemical surroundings.
Conclusions : All the above examples discussed above establish the fact that without the
consideration of the hybrid lone pair moments, no conclusion regarding ·the resultant dipole
moment from the geometry of the molecule by considering the bond moments alone can be
drawn. Previously, without considering these facts, some conclusions were drawn from the
H H
,,/ H H
N I
,rJ 'NH
/ ~
\:J
H
\ H
(Gauche (Gauche (Eclipsed) (Staggered)
i.8. skew) skew) (cis) (Trans)
(a)
ry
""
ra
""
""
"
ib
I
I
I
I
yl
(C2 ) (C2v ) (C2h ) ,
(Gauche) (Eclipsed) (Staggered)

(skew)
(b)
m
he
lc
ea
.,J
Spine ~
th
90.0 0
(Crystalline)
e/
(e) (Open-book structure)

Fig. 10.5.3.5. (a) Different possible conformations of N2 H4 molecule, (b) Different possible conformations
t.m
of N2X4 (X = H, F) and P2H4 when viewed through the M-N or P-P axis. (c) Gauche conformation
of H2 0 2 i.e. open book structure with 0-0 as spine. (The lone pairs for (b) and (c) are not
shown).
Note : • The dihedral angle In H2 0 2 largely depends on the chemical environment. In organic
peroxides, .it varies in the range 80-145°. In the adduct, N~C204.H202 the dihedral angle
is about 180°, i.e. tran.planar configuration where the lone pairs interact with the Na+
ions. The hypothetical cis-conformation is also planar.
• Both N2H4 and H20 2 are stablest In the gauche conformation where the lone pair-lone
pair repulsion is of modest type. The rotation barriers are as follows:
through trans-form : 16 kJ mol-1 (for N2H4 ); 4.6 kJ mol-1 (for H20 2)
through cis-form : 49.8 kJ mol-1 (for N2H4 ); 29.5 kJ mol-1 (for H20 2)
It indicates very high lone pair - lone pair repulsion in the cis-form.
observed dipole moments supposed to be developed only from the electronegativity differences.
These are surely dubious.
10.5.4 Induced Dipole Moments

We have discussed only the pennanent factors inherent within the molecules to determine the permanent
dipole moments. But in practice, it is getting more complicated due to the polarisation (Le. separation
of the centroids of opposite charges) of the molecules (which may be itself polar or nonpolar) by the
external electrical field or the electrical field provided by the surrounding ions and dipoles. This
polarisation introduces the induced dipole moment in the molecule. The magnitude of this induced
ry
dipole moment depends on the electrical field intensity (E) and the polarisability (a) of the molecule
under consideration. The polarisability increases with the increase of the size of the molecules. This
ra
aspect will be discussed at a greater length in Chapter 13.
Note : Sometimes, polarisation of a bond due to electronegativity difference can induce dipole
ib
moment in other bonds. In such cases, no external field is required. This aspect has been illustrated in
explaining the dipole moments of chloromethanes (cf. the dipole moments: CH3CI> CH2Cl2 > CHCI3).
yl
10.°5.5 Application of the Concept o~ Dipole Moments
m
The interpretation of the dipole moment becomes straightforward for the systems having no unshared
pair or unpaired nonbonding electron. Over-simplification of the idea produced some conclusions
he
(discussed in previous sections) such as % partial ionic character, bond angles ofthe molecules, geometry
(such as cis-, trans-isomers) of the molecules, etc. even for the molecules having lone pairs. Such
dubious conclusions are now called in question. Some typical applications of the concept of dipole
lc
moment are discussed below.

(i) Determination of bond· moments : In the cases where contributions of the lone pairs and
ea
nonbonding unpaired electrons do not complicate, the bond moments can be calculated from the
geometry by using the measured dipole moment.
th
(ii) Diagnosis ofcis-trans isomers: If the complications from the unshared electrons do not arise,
the trans-isomer_ofa square planar complex shows the zero dipole moment while the corresponding
e/
cis-isomer shows a finite dipole moment. For octahedral complexes, similar conclusions may be
drawn. In general, the cis-isomers are more polar than the trans-ones.
t.m
(iii) Monitoring ofisomeric equilibria: The dipole moments are strongly dependent on the geometry
of the molecules. For example, cis- and trans-isomers of a square planar complex, or square
planar and tetrahedral geometry of a particular complex, differ significantly in their respective
dipole moments. Hence, by measuring the resultant dipole moment of such systems under
equilibrium, the position of the isomeric equilibria, e.g. cis- ~ trans-, square planar ~
tetrahedral, etc. can be determined.
10.6 COVALENCY IN IONIC BONDS : DEFORMATION OR

POLARISATION OF IONS: FAJANS' RULES
10.6.1 Polarisation and Covalency
In our previous discussion, it has been revealed that in heteronuclear bonds (even in homonuclear
bonds, e~g. H 2 ) there is always some ionic character. In this approach, ionic character is developed in
the covalent bonds. There is another approach in which some sort of covalency is introduced in the
ionic bonds. Both the approaches lead to the concept of bonds of intermediate type. The second approach
to explain the intermediate character ofthe bond was developed by K. Fajans -( 1923-1928) based on the
. principle of deformatioin or polarisation of the ions. Though the approach carinot be quantitatively
tackled, it offers a good idea t9 understand the problem of partial covalent character in ionic compounds
qualitatively.
According to this concept, it is proposed that when the cations and anions are at vicinity (Le. within
the bonding distance), the electron cloud of the anion is pulled towards the cation. Thus deformation of
electron clouds of the anion in the presence of the attractive electrical field of the cation is referred to as
polarisation ofthe anion, and the cation is termed as the polarising agent. In a similar way, it can be
ry
argued that the electron cloud of the cation will be deformed by that of the anion, but as the electrons in
the cation are much more tightly bound due to the excess positive charge, the polarisation'ofcation by
ra
the anion is negligibly small. However, when the electrons of the cations are relatively loosely
bound as in the case of pseudo-noble gas type cations, the cation polarisation becomes significant.
ib
In such cases (Le. soft-soft interaction), the mutual polarisation works synergistically. This aspect will
be discussed later (cf Fig. 10.6.2.1).
yl
Due to such polarisation of anion, some
electron clouds are ~eing transported from
the anion towards the cation to produce a
m
overlapping zone (Fig. 10.6.1.1) which I II III
he
remains under the control of the nuclei of Fig. 10.6.1.1. Polarisation of the ions (Fajans' rules).
both cation and anion. I => no polarisation; II and III => polarisation leading to
Thus, the polarisation introduces the covalency (without considering cation polarisation).
lc
covalency in the bond. When there is no

polarisation, no overlapping zone exists and the bond is purely ionic. In this connection, it is worth
ea
remembering that if the degree of polarisation exceeds a certain limit, then a portion of the electron
cloud of the anion is completely robbed (Le. limiting polarisation) by the cation. Such a complete
th
transfer of the electron cloud actually leads to the redox reaction. The degree of polarisation depends
on a number offactors. Exceptthe limiting case, with the increase ofpolarisation, the degree ofcovalency
e/
increases.
10.6.2 Facators Governing the Degree of Polarisation

t.m
.The degree of anion polarisation depends on the following factors:

(i) Charge and size ofthe cation: To measure the electrical field intensity which acts as the polarising
field, a new parameter called ionic potential, ,= (chi~ge)
radIus
has been considered by Cartiledge
(1928). With the increase ofionic potential, the polarising power ofthe cation increases.
It is evident that with the increase of positive charge (more correctly, the effective nuclear charge
experienced by the electrons at the periphery of the cation) on the cation, the polarising power of
the cation increases and it runs in the sequence, Na+ < Mg'l+ < A13+ < srt +. Similarly, with the
decrease of the size of the cation, the polarising power increases. This is why, the sequence of
polarising power runs as, Li+ > Na+ > IC; Be 2+ > Mg'l+ > C~+.
It is better to consider the combined parameter, ionic potential rather than the individual parameters
to measure the polarising power. It generally decreases in a group from top to bottom for the
representative elements. For some simple ions, the cI> values are given in Table 10.6.2.1.
'-, Covalent Compounds: Characteristics, Structure and Reactivity 793
Table 10.6.2.1. Ionic potentials (~) of some common cations (radius is given in A).
Cation r + cPM + Cation r M2 +
I
cPM 2+ Cation r M3 +
M 'M 3+
Li+ 0.59 1.7 Be 2+ 0.31 6.4 8+ 3 0.20 15.0

Na+ 0.97 1.0 Mi-+ 0.65 3.1 At 3 0.50 6.0
JC" 1.33 0.75 Ca2+ 0.99 2.0 Ga 3+ 0.62 4.8
(ii) Electronic configuration 0/ the cation: In measuring the ionic potential, we should consider
the actual positive charge experienced by the electrons at the periphery. THis effective nuclear
ry
charge depends on the screening power of the inner electrons. If the inner electrons are very
much efficient to screen the valence electrons, then the effective nuclear charge experienced by
ra
the outermost electron is less.
When we consider the transition metal ions which contain one or more d-electrons in the (n - 1)
ib
shell, these d-electrons are very much inefficient compared to the s-and p-electrons to screen or
shield the outer electrons. Thus if we consider two ions of the comparable size and the same
yl
charge having electronic configurations, (n - 1)s2(n - 1)p6(n·- l)tJXnso (a representative example
of the transition metal ions) and (n - 1)s2(n - 1)p6nsO(a representative example of the alkali and
m
alkaline earth cations), the former one will be more polarising. This is why, for the same charge
and the same size, a pseudo noble gas type cation with J8 electrons in the outermost shell (e.g.
Cu +, Ag+, Cd2+ etc.) is more polarising than a cation 0/ noble gas type with 8 electrons in the
he
outermost shell (e.g. Na+, IC", Ca 2+, etc.).
In fact, because of the poor shielding power of the d-electrons, for the cations with pseudo-noble
lc
gas [18 electrons] type electronic configuration, the effective nuclear charge (Z, which measures
the polarising power) at the periphery is higher to cause more anion polarisation. For Cu+ (ISe
ea
eation), the Z (calculated by Slater's rule) is 3.7 (for 4s level) while for Na+ (8e cation), it is 2.2
(for 3s level). It makes, Cu+ more polarising than Na+. The Z -values at the valenc,e shell used
th
for covalency of the cations of comparable size with noble gas and pseudo-noble gas type
electronic configuration are given in Table 10.6.2.2.
e/
Table 10.6.2.2. Comparison of Z*values (measuring the polarising power) at the valence
shell used for covalency of the noble gas' and pseudo-noble gas type cations having
t.m
comparable ionic radii.

Cation Type r+ (pm) Z· (at the M~lting point of
ns level) anhydrous chloride (OC)
Na+ 8e 95 2.2 801
Cu+ } 18e 96 3.7 422
JC" 8e 133 2.2 776
Ag+ } 18e 126 3.7 455
C2+} 8e 99 3.2 772
C~+ 18e 97 4.7 568
Note: Illustration to compute Z* :
Na+ : (1 S)2 (2s2p)8(3s)0; S =8 x 0.85 + 2 x 1 =8.8; Z* =11 - 8.8 =2.2
Cu+ : (1 S)2 (2s2p)8(3s3p)8(3d) 10; S =18 x 0.85 + lax 1 =25.3; Z* =29 - 25.3 = 3.7
For the (n - 1)s2(n - 1),P or (n - 1)s2(n - 1)p6(n - 1)cJ1 0 cations, nsnp levels are to be
used in covalence.
• Possibility ofcation polarisation: Now let us consider Polarised anion

the possibility of cation polarisation by the anion. For
the pseudo-noble gas type cations, the loosely bound
d-electrons are easily polarised by the repulsion of
the electronic clQud of the anion. Such cation
polarisation reduces the screening of nuclear charge of
the cation towards the anion and consequently the anion Polarised cation
experiences the nuclear charge of the cation better. In Fig. 10.6.2.1. Mutual polarisation,
ry
fact, the cation polarisation concentrates the electron i.e. both cation and anion
cloud of the cation in the back side of the action. polarisation. Spheres with dotted
This greater exposure of the nuclear charge of the line for before polarisation, spheres
ra
cation (due to the cation polarisation) towards the with solid line after polarisation (cf.
anion favours more anion polarisation. Thus the Fig. 13.4.3.1).
ib
cation polarisation and anion polarisation (Fig. 10.6.2.1) (i.e. ~utual polarisation) act
synergistically to favour the covalency. This synergistic polarisation is the basic interaction in
yl
soft-soft adduct in terms ofHSAB theory. The cation polarisation for the noble gas type cations
with (~ - 1)s2p 6 configuration is insignificant as the s- and p-electrons are tightly bound and not
m
easily polarised (Le. perturbed) by the electrical field of the anion.
By considering the above argument, we can conclude that the polarising power among the transition
he
series varies as follows: 1st series (Le. 3d-series) < 2nd series (Le. 4d-series) < 3rd series (Le.
5d-series), because of the increased number of d- andfelectrons in descending a group. In the
lc
4d-series cations, there are ten d-electrons in excess compared to the corresponding congener
cations in the 3d-series. In coming to the 5d-series, in addition to the ten 3d-ele,ctrons and ten
ea
4d-electrons there are fourteen 4felectrons which are still more ineffective in shielding. Thus
the degree of covalency increases in descending a group in the transition metal ions for a
particular oxidation state. For example, the covalency runs in the order
th
ZnCl2 < CdCl2 < HgCI2•

Interestingly, the ionic radii run in the sequence, Zn2+ (74 pm) < CeP+ (97 pm) < Hg'l+ (110 pm)
e/
which could make the Zn(II) compounds most covalent. As a matter of fact, except the salts like
HgF2, Hg(lV03)2' and Hg(CI04 )2 all other salts of Hg(ll) are predominantly covalent
t.m
The concept of calion polarisation by the hard anions has been used to explain the 'structures of
gaseous dihalides of the alkaline earths (cf. VSEPR, Rule 5).
Noble gas type vs. pseudo-noble gas type cations
• Noble gas type cations are more polarising to cause more anion polarisation.
• Noble gas type cations are more easily polarised by the anions to experience cation polarisation.
• Cation polarisation and anion polarisation work synegistically (Le. soft-soft interaction) to
introduce more covalence.
(iii) Size and charge ofthe anion: The larger anions with more negative charges are more polarisable.
In such cases, the nucleus of the anion does not have any strong influence or control over the
electron cloud and as a result, such electron clouds is readily polarised or deformed by the external
field of the cation. This is why, the polarisability sequence is : 1-> Br- > Cl- > F-.
(iv) Hard and soft character ofthe ions: The 'degree of polarisation in a certain pair can be nicely
rationalised in the light of HSAB (hard and soft acids and bases) theory. The hard cations are
highly polarising while the soft anions are highly polarisable. Thus the ion pair consisting of a
hard cation and a soft anion gives an ideal condition for introducing covalency in an iof'iic bond.
Soft cations (e.g. pseudo-noble gas type cations) and soft anions are very good candidates to,
make ideal covalent compounds through both cation and anion polarisation (i.e. mutual
polarisation) acting synergistically.
10.6.3 FaJan's Rules In Predicting the Melting and Boiling Points and Solubility of Some
Compounds
ry
Before to cite any example in explaining the relative order ofmelting points, boiling points and solubility
of the compounds, we must remember that the energetics of the processes involve contributions from a
number a factors. Generally, the covalent compounds show lower melting and boiling points with an
ra
increased solubility in the nonpolar solvents. But this is not a hard and fast rule. For example, diamond,
SiC are purely covalent, but still they show very high melting points. Similarly, BaS04 is predominantly
ib
ionic, but it is insoluble in H 20. Thus from the knowledge of degree of covalency in a compound, we
cannot come to any confirmed conclusion regarding its melting point, boiling point and solubility.
yl
Here we shall pay attention to the cases which/ollow the general trend (i.e. melting or boiling points
decrease with the increase ojcovalency). These physical properties will be discussed in Sees. 13.5 and
m
13.6 at a greater length to consider all the possible contributing factors involved in the overall energetics.
he
(a) Melting and Boiling Point and Degree of Covalency
Some examples are cited below to reveal the fact that with the increase of covalency (Le. the increase of
lc
polarisation) the melting point drops (see Tables 10.6.3.1 to 10.6.3.5). We should remember that this
oversimplification may be misleading in many cases which will be discussed separately (see Sec. 13.6).
ea
Table 10.6.3.1. Effect of the size of the cations on melting points (m.p.) of different
chloride salts
th
M 2+ Be 2+ Mi+ Ca 2+ S?+ Ba 2+
0.31 0.65 0.99 1.13 1.35

e/
r Ml+ (A)
cP M2+ 6.45 3.07 2.02 1.77 1.48
t.m
m.p. of MC/2 (OC) 405 712 772 872 960

Note: More the 'Mil. value, more tbe covalence, less the melting point.
Table 10.6.3.2. Effect of charge of the cations on melting points (m.p.) of different
halides
cPMn+ Melting points (OC)
Na+ 0.97 1.03 800 755

Mi+ 0.65 3.07 712 700
A13+ 0.50 6.00 180 97.5
Si4 + 0.40 10.00 57*
Ti4 + 0.68 5.88 137*
* Indicates boiling points.
Note: More the.M"+ value, more the covalence, less the melting point.
Table 10.6.3.3. Effect of size (Le. polarisability) of the anions on melting points (m.p.) of different
halide (X) salts (*denotes sublimation temperature)
Compound rx~ (A) m.p. (OC) Corrlpound m.p. (OC)

=.
·ccuo ·0Cc.
NaF 1.36 988 LiF 870 =~
c...~
0-
~
c
OIJ
NaCI 1.81 800 LiCf 613 EE

NaBr 1.95 755 LiBr 547 = ~
,J;J...c
cu ....
C'-l C'-l
Nal 2.16 651 Lil 446 .-
S.
C'-l
~
ry
cu-
SnF4 1.36 705 * CaF2 1392 Q ~
c.~
SnCl4 1.81 -33 CaCf2 772 ..c~ c~
.... -
ra
ZnF1 1.36 872 CaBr]. 730 t ~
o 0
ZnCI]. 1.81 275 Cal2 575 ~•• ..c~
ib
AfF3 1.36 1291 *
~ ....
E- ~
o ~
AIC(~ 1.81 192 z e
yl
Complication from the polymeric structure depending on the nature of anions: Sometimes, .
m
prediction of melting point sequence from the knowledge of anion polarisability sequence is not correct.
Possibility of polymeric structure formation is to be reviewed in such cases. The m.p. sequence is:
he
AIF; (1291°C) > AICl3 (192°C) > AlI3 (189°C) > AlBr3 (98°C); } (* bl. )
* su Imes
SnF4 (705°C) > SnI4 (144.5°C) > SnBr4 (31°C) > SnCl4 (-33°C)
The melting point sequence apparently indicates that AIF3 and SnF4 are predominantly ionic and
lc
their heavier halides are covalent. AICl3 shows the higher melting point than AIBr3 and AII3 but Al13
records a higher melting point than AIBr3- It needs an explanation.
ea
. F F/ F /
1/ I F
FF7rFF~F
th
F
I/ F I/F F
e/
-F-M-F-M-F-
/1 /1
F F F F
t.m
/ /
=
(MF4)X (M Sn, Pb) : 2D-layer structure (Sharing of
4 equatorial apexes of MF6 octahedra)
x X X
""AI/ ""AI/
X /"""/""" X X
(AIX3)2 (X = Br, I) : Dimer
(SnF4)X =
(MCI 3 )x (M AI, Fe): Layer structure.
(Sharing of 3 edges of MCI6 octahedra)
Fig. 10.6.3.1. Solid state structures MX4 and MX 3 . (see Sec. 1.12 of Vol. 4 for details)
In solid state, SnF4 exists as a polymeric solid (2D-layer, sharing of 4 equatorial apexes of 'SnFo'
octahedra) while Sn14, SnBr4 and SnCl4 exist as the molecular solids whose melting points increase
with the increase of molecular mass (cf. weak intermolecular forces like London dispersion forces;
see Chapter 13, Vol. 3). PbF4 adopts the same polymeric structure of SnF4 while PbCI 4 adopts the
molecular lattice (cf. PbB.r4 and PbI 4 are unstable and undergo redox .decomposition). GeF4 (low
m.p.) adopts the molecular lattice.
In solid state, AIF3 also exists as a three dimensional (3D) polymeric compound (ReOJ-type 3D
structure through the sharing of all vertices of 'AIF6 ' octahedra). AICI:. also exists as a polymeric
compound (layer structure) but the degree ofpolymerisation is less compared to that in AIFJ (cf. layer
ry
structure vs. 3D structure). On the other hand, AIBrJ and AlI3 exist as the dimeric molecular solids.
This degree of polymerisation of AIX3 explains the melting point sequence. It may be noted that solid
ra
FeF3 and FeCl3 are structurally related with AIF3 and AICl3 respectively (see Sec. 1.12, Vol. 4 for details).
ib
Table 10.6.3.4. Effect of oxidation states of a metal on melting and boiling points of its compounds
Compound m.p. b.p. Compounds m.p. b.p.
yl
(OC) (OC) (OC) (OC)
246 652 TICI 430 720

SnCl 2
m
Snell -33 114 TICI] 25
PbCl 2 501 950
he
PbCl4 -15
Note: Higher the oxidation state, higher the polarising power, higher the covalence, lower the melting and boiling
lc
points.
ea
Table 10.6.3.5. Effect of ps~udo-noble gas electronic structure of cations

on melting points of their halides
th
Compound rM"+ (A) m.p. (C)
( NaG 0.95 801

e/
*CuCI 0.96 422

( KCI 1.33 776
t.m
*AgCI 1.36 455

[ Cael? 0.99 772
*CdCI 2 0.97 568
*HgCI 2 1.10 276
( RbCI 1.48 715
*AuCl 1.37 170 (decomposes)
* Denotes the cations of pseudo-inert gas configuration (cf. Table 10.6.2.2).
Note: Cations of pseudo-noble gas configuration lead to better anion polarisation
and cation polarisation acting synergistically to introduce a better covalence
and consequently the lower melting point.
(b) Solubility and Degree of Covalency

Here we shall proceed based on the oversimplified principle: with the increase of covalency (i.e. the
increase of polarisation), the solubility of the compounds increases in the nonpolar solvents and
decreases in the polar solvents. However, it must be remembered that the energetics of the process
are not so simple and this oversimplification again may mislead in some cases (see Sec. 13.5).
(i) Let us consider the solubility of silver halides. The polarisability of the halides runs as,
/- > Br- > CI- > F-. Hence the covalency in. the silver halides changes as, Ag/> AgBr > AgCI >
AgF. Hence it is expected that their solubilities in water will run in the sequence, AgF> AgCI >
AgBr> AgI. This prediction is supported from their solubility products (Ksp ) (Table 10.6.3.6).
Table 10.6.3.6. Solubility parameters (in water) of silver halides.
AgX
ry
AgF Soluble
Agel 2 x 10- 10
10- 13
ra
AgBr 5 x
Agl 8 x 10- 17
ib
(ii) KJ is soluble in alcohol while KCI is insoluble. It is due to the fact that in Kl, the covalency is
higher.
yl
(iii) LiCI is soluble in alcohol, pyridine, etc. while the other alkali metal chlorides are insoluble in
organic solvents. It is again due to the enhanced covalency in LiCI because ofthe highest polarising
m
power of Li+ among the alkali metal cations.
(iv) FeCI] is soluble in organic solvents like ether while AICI] is insoluble. Because of the existence
he
of low shielding d-electrons (3tf) in Fe 3+, its polarising power is increased to introduce more
covalency in its salts. It is also supported by its lower sublimation temperature (~ 177°C) compared
lc
to that of AlCl3 having sublimation temperature ~ 347°C. -

(v) The effect oflow shielding d-electrons is well pronounced in the properties oftransition metal
ea
salts. CUX, AgX, AuX (X = CI, Br, l) are almost insoluble in water while the analogous alkali
metal salts are highly soluble in water. Many transition metal chlorides and acetates are soluble
th
to some extent in organic solvents such as CHCI3, CH3COCH3, alcohol, etc. while the corres-
ponding salts of alkaline earth metals (e.g. Cc?+, Mg!+, Bc?+) are insoluble in such organic solvents.
e/
10.6.4 Application of the Concept of Polarisation of the Anions by the Cations

t.m
(i) The degree of covalency in an ionic bond: It predicts that the larger the value of~, the greater
is the polarisation and hence the higher is the covalency in the ionic bond. For anhydrous halides
(especially chlorides), it has been observed that if the value of ~~M n+ (r is expressed in A) is
less than '""V 2.2, the halides are predominantly ionic and they conduct electricity in the fused state.
But if ~~M n+ is more than 2.2, the corresponding halides are nonionic and they cannot conduct
electricity in the fused state.
In this connection, the silicates are important to be discussed. Conventionally, the silicates are
considered as inter-ionic solids, but due to the very high polarising power of 8i4+, a good deal of
covalency has been introduced in the silicates.
(ii) Deformation of ionic solids: Here it is worth mentioning that the introduction of covalency in
the ionic solids changes the physical properties. Covalent bonds are directional while the ionic
attractions are omnidirectional. This is why, the tendency ofbending or deformation ofthe solid
may drastically reduce with the increase of covalent interaction. In fact, the solids with a
considerable extent of covalency are very much resistant to deformation or bending.
(iii) Complexing power: With the increase of cI>, the complexing power of a cation increases. This is
why the complexing power of the alkaline earth metal ions is in the sequence : Be(II) > Mg(II) >
Ca(II).
(iv) Tendency ofsolvation: With the increase of cI>, the ion-dipole interaction in the polar solvents
increases. Thus the solvation energy (exothermic) in dipolar solvents follows the sequence: Li+
> Na+ > K~; Be 2+ > Mi'+ > C~+. Because of this fact, most of the lithium salts (e.g. LiCI· 2H20, .
ry
LiCl04 • 3H20) are hydrated. As a matter offact, to get an anhydrous lithium salt is a difficult
task. But, for the other 'alkali metals, anhydrous salts may easily be obtained. This tendency of
ra
hydration may also be explained from the standpoint of packing efficiency of the ions in the
crystal (see Sec. 11.8.2 (iii».
ib
(v) Nature ofoxides: With the increase of cI>, the covalency in the metal oxygen bond increases and
as a result, in the reaction with water, it cannot release oxide «(j-) ion easily. This is why, with
+,
yl
the increase of the basicity (i.e. base strength) of the oxides decreases. In other words,
metals having higher values of cI> form more acidic oxides. Thus the basicity of the oxides runs
as, Na 20 > Li20 > MgO> BeO, where the cI» values (radius expressed in A) are in the sequence,
m
+ + (1.0)<+ .+ (1.7)<+ 2+ (=3.1)<+ 2+ (=6.4).
~ LI ~ &.
he
From the experimental observations, Cartiledge has proposed that the nature of M;+ On (Le.
oxide) is related with cl>M n+ as follows:
lc
basic oxide, when ~'Mn+ < 2.2; amphoteric oxide, when ~'Mn+ = 2.2 to 3.2; and acidic
ea
oxide, when ~'Mn+ > 3.2. (The' values are expressed using the radius in A units).
th
(vi) Tendency ofhydrolysis and BriJnsted acidity of M(H 10):+ (ef. Sec. 14.8.4) : With the increase
e/
of cI>M n+' the tendency ofhydrolysis increases. With the increase of cI>M n+' the electronegativity
of M n+ increases and its electron withdrawing inductive power increases. Because of the
t.m
increased electron withdrawing power of the metal ion, the hydrogens of the coordinated water
molecule are sufficiently protonic in characters to get released as protons (Le. BrOnsted acidity).
Here the electron withdrawing force towards M1t+ is shown by the arrow. Thus, hydrolysis leads
to the release ofprotons from the coordinated water molecules. This is why, Fe(ll/)-salts undergo
hydrolysis more extensively than Fe(l/)-salts, as cI> 3+ > cI> 2+·
Fe Fe
Because of the same fact, SnC/4 hydrolyses more than SnC/z- Because of the low cI> values of
. Na+ and K\ the salts like NaCI, KCI do not hydrolyse. But Be(ll)- and AI(lll)-salts hydrolyse
readily because of the higher cI> values of Be 2+ and AI3+.
The hydrated salts (e.g. AICIJ·nH20) in which the metal is bearing a very high value can- +
not be dehydrated just by heating. The high tendency of hydrolysis which gets further increased
at a higher temperature leads to M-oH. Further heating leads to dehydration of M(OH)x to M 20 x.
(vii) Thermal stability ofthe carbonates, sulfates, etc. : The ease of thermal decomposition, MC03
--+ MO + CO2 for the bivalent metals can be explained again by considering the ~M2+ values.
The metal ions having higher ~M2+ values facilitate the electron movement towards the metal
centres due to the increased electron withdrawing inductive effect. In other words, M2+ polarises
the carbonate ion to split into d- to form MO with the expulsion of CO2• This proposition is
ry
supported by the fact given in Table 10.6.4.1.
ra
i.e. M ~~ - MO + CO 2, (6S = +ve) (cf. entropy effect)
~
ib
Table 10.6.4.1. Variation ot'thermal decomposition temperature of some metal
carbonates with the +M2+ values (cf. Table 11.8.2.4 for thermodynamic aspects)
yl
,~+
Metal carbonate r M1.+ (A) Thermal decomposition
temperature (OC)
m
BeC03 0.31 6.5 < 100
he
MgC03 0.65 3.1 400
CaC03 0.99 2.0 900
SrC03 1.13 1.77 1290
lc
BaC03 1.35 1.48 1360

CdC03 ..... 1.0 350
ea
PbC03 ..... 1.0 350

th
The sequence of thermal decomposition temperature for the alkaline earth carbonates is in good
conformity with the prediction. Cd2+ and Pb2+ are having sizes comparable with that of Ca 2+,
e/
but due to the presence of low shielding d-electrons (Le. pseudo noble gas structure, 18 electrons
in the outermost shell) Cd2+, and Pb2+ are more polarising. This leads to the enhanced cI» values
t.m
for Cd2+ and Pb 2+ compared to that of Cc?+ to facilitate the thermal decomposition of Cd- and
Ph-carbonates.
By using the same argument based on the cI» values, the relative thermal stabilities ofthe sulphates,
nitrates, hydroxides and phosphates can a/so be predicted.
MS04 ~ MO + S03' M(OH)2 ~ MO + H20; etc., (6S = +ve)
The ease of thermal deccmposition ofthe carbonates, sulphates, etc. can also be nicely explained
by using the crystal packing model (see Sec. 11.8.2 (ii)).
Thermal decomposition of carbonates and sulfates is always entropically favoured because,
one of the decomposition products is a gaseous substance (Le. CO2, SOJ). Thermodynamic
parameters for decomposition of different metal carbonates have been discussed in Sec. 11.8.2.
The enthalpy change in decomposition can be estimated from the acidity parameters of the
oxides involved in terms of Lux-Flood concept. This aspect has been discussed in detail in
Sec. 14.10.
(viii) Diagonal relationship: Consideration of ct» values can explain the diagonal relationship (see
Sec. 8.18).
(ix) Melting and boiling points: It has been already discussed (Sec. 10.6.3)'that Fajans' rules can
explain the order of melting and boiling points in many cases.
(x) Solubility of salts: It has been already discussed (Sec. 10.6.3) to reveal the fact that with the
increase of covalency (Le. the increase of polarisation), the solubility of the salts in the polar
solvents ctecreases. '
Solubility in water: AgF> AgCI > AgBr > AgI; HgF2 > HgCl2 > HgBr2 > HgI2
ry
(xi) Charge transfer band (ef. See. 9.11.4) : Ifthe metal ions are highly polarising "and the anions are
polarisable, then the electron transition occurs from the anion to the metal ion. For such transitions,
ra
if the energy is available in the visible range, -the salts become coloured. PbCl2 is white while
PbI2 is yellow. The. degree of polaris~tion in PbI2 is more due to the more polarisability of 1-
ib
than lhat of CI-. This is why, for the transition of electron from iodide to Pb 2+ (more correctly, it
should be said that the electron transition (Le. LMCT) occurs from a molecular orbital Le. HOMO
yl
in which the character of iodine orbital is predominant to the MO Le. LUMO in which the
character of Pb is predominant), the energy is available in the visible range while for PbCl2 the
m
required energy for the corresponding transition lies in the ultraviolet region. In the same way,
the colours of SnS2 (yellow), Sn02 (white) and SbrSJ (orange coloured), Sb 20 J (white) can be
he
explained by considering the fact that S 2- is more .polarisable than 02-.
Anion polarisation increases from CI - to 1-. In fact, many chlorides are colourless but their
iodides are highly coloured.
lc
Colourless: HgCl2 AgCI PbCl2 SnCl4 GeCl4

ea
Coloured: HgI2 AgI PbI2 SnI4 Ge/4

(Red) (Ye'low) (Golden yellow) (Deep red) (Orange)
Here it may be mentioned that the orbital of iodine energetically matches better than that of
th
chlorine with the heavy metal centres like Pb(II), Sn(IV), Ge(IV), Hg(II), Ag(I).
By considering the above argument, we can explain the observation: ZnO is white while HgO
e/
is coloured. The higher polarising power of Hg(Il) due to the presence of low shielding more d-
t.m
andfelectrons facilitates the electron transition from oxide to Hg(Il) and it occurs in the visible
range while in ZnO, it occurs in the ultraviolet region. Similarly, w~ can explain the following
colour sequence.
ZnS (white) < CdS (yellow) < HgS (red)
Here for the electron transition, S2- ~ M(ll) in the above mentioned sulphides, in ZnS the highest
energy (available in UV region) is absorbed and in HgS the lowest energy is absorbed. These
involve the LMCT (ligand to metal ehange"transfer) bands. The orbitals involved in the charge
transfer process are :
CdS: Cd 2+ (5s) +-- S2- (x); HgS : Hg 2+ (6s}+-- S2- (x); Fe2 0 J (red): Fe 3+ (3d, e;) ~ 0 2- (x)
In the oxyanions (e.g. CrO~-, MnO;, etc.), the oxygen lone pairs are transferred into the vacant
d-orbitals. With the increase of oxidation state, the LMCT can occur at lower energy.
Note: For some simple compounds, the origin of colour has been explained in Chapter 9 (Sec.
9.11.4) in terms of energy separation between the HOMO and LUMO (cf. Fig. 9.11.4.1).
(xii) Instabi/;o' of some salts: If the polarisation reaches its limiting level, then the electron cloud
from the anion will be completely robbed by the cation. This type ofcomplete electron transfer
sets up the redox reaction. For example, the nonexistence of PbJ4 can be explained. Here Pb 4+
polarises 1- to such an extent that two electrons from two 1- ions are completely transferred to
Pb 4+ to produce Pb 2+. This Pb 2+ is not too polarising to initiate any further redox reaction with
1-. This is why, Pb 2+ can exist with 1- to produce PbI2• Thus it occurs so, Pbl4 ~ Pbl2 + 12 ,
Similarly, the nonexistence of Fef3 can be interpreted qualitatively. Here it is worth remar.king
that FeCl3 exists, as here the polarisation is not too high.
ry
10.7 EFFECTS OF 1t-BONDING
ra
(with Special Reference to the Involvement of d-Orbitals)
ON THE STRUCTURAL PROPERTIES AND REACTIVITY
ib
10.7.1 Comparis.on of Carbon and Silicon Compounds
yl
(a) Pi-bonding and possibility of polymerisation : C = C is very common in its chemistry, but the
Si===Si is of rare occurrence. Carbon dioxide is a gaseous monomeric compound while silicon dioxide
m
is a polymeric and singly bonded giant solid compound. In a similar way, the unstable gem-diols are
converted into ketones, while the analogous silicon compounds are converted into silicone, a polymeric
he
compound.
Me 2C(Olf)2 ~ Me 2C = 0 + H 20
lc
Me Me
ea
I 1
Me pi(OH) 2 ----i)ll~ -o-sli-o-Si-O-
-H20 I
Me Me
th
All these dissimilarities between the analogous carbon and silicon compounds can be interpreted in
terms of 7t-bonding. To show the multip~e bond character, the sp2 or sp carbon atoms can undergo
e/
lateral overlapping to form Px - P7t bonding. The 7t~bond exists in C - X where X = C, 0, N. Such tr
t.m
interactions are sufficiently strong, as the overlapping orbitals are comparable in size and they are
not/ar apart in the a-bonding C - X skeleton. In the
systems Si - X, where X = Si, 0, N, the same type 7t-
bonding can be argued to occur. But compared to the
carbon system, here the orbitals on Si and X are kept
sufficiently apart to reduce the efficiency ofsideways
overlap because of the longer Si-X a-bond length.
This fact is illustrated in Fig. 10.7.1.1. In Si-O, the 7t-
bonding gets further weakened due to the mismatch in
size between the 3p-orbital of Si and 2p-orbital of O.
This is why the Si-X segment prefers two single a-bonds
compared to one double bond consisting of one a- and
one 1t-bond. This tendency urges the system, Si-X to Fig. 10.7.1.1. Relative 1t-bonding (Px-p1t )
undergo polymerisation. efficiencies in e-C and S~Si systems.
7t-bonding in silenes (>C = Si<) and disilenes (>Si = Si<) is less efficient than that in alkenes
(>C = C<). In fact, the energy gap between the HOMO ('It) and LUMO ('It.) in silenes is much
smaller than that in alkenes (cf. Sec. 14.7.5 viii).
The tendency of Si-X (X = N, 0) bonds to have the single a-bonded structure can also be explained
by the consideration of 7t-bonding through the participation of d-orbitals of Si. Silicon is having the
vacant 3d-orbitals. Hence the filled p-or!>itals on 0 or N can push their lone pairs into the suitable
vacant d-orbitals of silicon (Le. PfC --+ d7C ). This p", -+ d", bonding can strengthen the formal single
sigma bond.
ry
Here it must be remembered that in the present case the P1C --+ d 7C bonding is not very much strong.
If it were so strong as in Cl- 0, S - 0, it would form the pi-bonded monomeric structure. Thus, in Si-
0, the pi-bonding is accountable compared to the C - 0 system where it is absent but negligible
ra
compared to. that in Cl - 0 or S - 0 system. Thus the weak pi -bonding favours the polymeric
structures having only single sigma -bonds while the strong 'It-bonding (P7C-P7C or P 7C--d7C ) favours the
ib
monomeric 'It-bonded species. This aspect will be again discussed (see Sec. 10.7.2) in connection with
the tendency of different oxyanions to undergo polymerisation. Thus in the following possibilities, the
yl
single a-bonded infinite structure (I) getting an additional stabilisation through the weak
p",(X) -+ d",(Si) bonding is energetically more favourable compared to the alternative possibility (II)
m
where the inefficient P7C-P7C bonding instead of a-bonding weakens the system. Thus in Si -X system, 4
single a-bonds by Si as in (I) are more favourable than 2a- and 27t-bonds (P7C - P7C) as in (II) .
he
__.. I ..---.1 .. .. ..
lc
For X = 0 -X-~i -X-~i-X- ,

··--'1
~.. 1 .. X=Si=X
ea
I II
But if Si is replaced by C, the double bonded monomeric structure (II) gets an enhanced stabilisation
th
due to the more efficientp7C(X}-P7C(C)

interaction. Besides these, in (I),
r--'" '" ' ..
e/
carbon cannot bring any extra stabili-

,:
sation through the Pn (X) --+ dx(C) : '~
! ; 3d (Si)
t.m
bonding as car~n is not having any ! ~ ;

suitable vacant d- or any other orbital e>
Q)
! !
to participate in the process. W
c:: ! !
..!.f , .'.f
.,..
Graphite like structure for !
Cand 51? . ,
'
.. ,,
..
'
,.
,
Carbon can adopt the graphite ,
,
structure but silicon fails to adopt :
~........
'
the graphite like structure. For

carbon, the Pn-P n bonding is effi- np (X) . 3d (Si)
np(X) ••••••• --t----i! ,
It
cient while for silicon, the P 7C - Pn
(a) (b)
bonding is very much insufficient
because of longer Si-Si a-bond. Fig. 10.7.1.2. (a) P7t(X) ~ d7t (S/) bonding (X = F, CI, 0); (b)
MO energy level diagram for the said Px ~ dx bonding.
(b) Halides ofcarbon and silicon: In this connection, the comparison between the halides ofcarbon
and silicon is noteworthy. The non-bonding pairs on halogen can be pushed back into th~ vacant
d-orbitals of silicon. Because of this Pn ~ d n bonding, the observed Si -X(X= F, CI, etc.) bond length
is always shorter than the calculated one (Le. the sum of single bonded covalent radii). The observed Si
- CI bond length (= 201 pm) is shorter by about 15 pm from the calculated one. This shortening arises
due to the Pn ~ dn bonding. The similar thing arises for GeX4 and snX4 •
Bronsted acidity of CHC'3 YS. CHF3
ry
Let us consider the relative stabilities of their conjugate bases: CCI:; and: CF3-. In : CCI:; the lone
pair on C can participate in 7t-bonding with the vacant 3d orbital of chlorine. Obviously, for this
ra
purpose it should have the planar structure (Le. sp2-hybridisation of carbon to house the lone pair
in a pure p-orbital). This C(2Pn) ~ C/(3dn) 7t-bonding will stabilise the conjugate base ccr;. No
ib
such stabilisation is poss.ible for CF3- and it maintains the pyramidal structure (cf. Sec. 9.13.7) as
expected from VSEPR theory (Sec. 10.8.3). Ifwe consider the inductive effect (-I effect) only, the
yl
CHF3 is expected to be more acidic. But because of the much more predominant P1t -+ d1t
m
bonding effect, CHCIJ acts as a stronger BriJnsted acid.
he
lc
(Pyramidal) (Planar)
ea
cf. N(SiH3 )3 [Planar, N(2P7t) ~ Si(3d7t )] vs.

N(CH 3 )3 [Pyramidal, No pi-bonding]
th
(c) (SiHJ)JN, (GeHJ);Y vs. (CHJ)JN (structure and reactivity) : Because of the participation of the
e/
vacant 3d-orbitals of silicon in 7t-bonding, the structure of trisilylamine, (SiH3)3N is totally different
from the analogous carbon compound, trimethylamine, (CH3)3N. In trimethylamine, the nitrogen is sp3
t.m
hybridised to provide the bond angle, H 3C - N- CH3 -- 108° while in trisilylamine, the nitrogen is sp2
hybridised to make the system plat:tar with the bond angle, H 3Si - N- SiH3 ~ 120°. In trisilylamine,
nitrogen is forced to adopt the sp2 hybridisation to house the lone pair in a pure p-orbital which in tum
gets involved in N(2p) ~ Si(3d) 7t-bonding. As a matter of fact, the d-orbitals on three silicon atoms
can participate in the P n ~ dn bonding to delocalise the lone pair over the whole molecule (Fig. 10.7.1.3).
Because of this involvement of the lone pair on nitrogen, it is not readily available for showing
the Lewis basicity. Because of the same ground, (GeHJ)JN is also planar. Here 4d orbital of Ge
participates in the 7t-bonding. On the other hand, in trimethylamine, no such pi-bonding operates, and
the molecule assumes the pyramidal spape as usual. Thus it retains the lone pair for Lewis basicity.
ry
ra
Because of the structural difference, they behave differently towards HCI.
+
ib
(CH3)N + HCI ~ (CH3)3NHCI-, (Lewis acid-base adduct)
(SiH3)3N + 4HCI ~ NH4CI + 3SiH3CI, (bond cleavage)
yl
(d) (SiH3)3N vs. (SiH3)3P (stru·cture and reactivity) : It is important'to mention that the an~logous
m
compound of P, Le. :P(SiH3)3 is pyramidal instead of planar. It. is due to the fact in :P(SiH3)3' the
Pn(P) ~ d 7t (Si) bonding is not efficient. The larger P-Si distance brings about the poorer
he
n-interaction. Moreover,. the lower electronegativity of P cannot produce sufficient positive charge
on Si to contract the 3d-orbitals of Si. In fact, contraction ofd-orbital by the electronegative substituent
is an essential condition for d-orbital participation in bonding (cf. Sec. 9.13.5). In the case of:N(SiH3)3'
lc
both the size factor and electronegativity ofN are suitable for P7t ~ d 7t interaction.
ea
In has been pointed out in Sec. 9.13.5, that there is controversy regarding the participation of
d-orbitals in bonding in main group elements. To explain the planarity of :N(SiH3)3' it has been argued
(Glidewell, 1.975) that it is due to the bulkier -SiH3 groups placed around the smaller element
th
nitrogen. To relax the steric crowding, it adopts the planar structure instead ofthe pyramidal structure.
It leads to bond angle opening from 109°28' to 120°. The steric crowding in P(SiHl)l is relatively less
e/
because of the larger size of P. This is why, P(SiHl)J does not show any tendency to adopt the
t.m
planar structure.
(e) (CHl)zO vs. (SiH3)zO (structure and reactivity) : Similarly, the other analogues of carbon and
silicon, e.g. (CH3)20 and (SiH3)20, also bahave differently in both structure and Lewis basicity. In
disilylether, the bond angle Si - a- Si ('- 144°) is expanded more to induce more p-character on the
lone pair on oxygen to facilitate, O(2p) ~ Si(3d) x-bonding while in dimethylether oxygen is
approximately sp3 hybridised (C - 0 - C ~ 110°) to house the lone pairs in the sp3 hybrid orbitals.
Because ofthe P7t ~ d7t bonding, the availability ofthe lone pair on oxygen in disilylether is significantly
reduced to show the reduced Lewis basicity.
In fact, oxygen being highly electronegative is itselfunwilling to donate its electron cloud. In addition
to this, because of the electron withdrawal through the P7t(0) ~ d7t(Si) bonding in disilyl ether, the
oxygen site becomes more electron deficient. Consequent(v the Lewis basicity ofdisilyl ether is drastically
reduced compared to the case ofdimethyl ether where no P1( --+d1(bonding is possible. This is evidenced
in the following reactions :
. (CH3)2 0 + BX3 ~ (CH3)20: ~ BX3 (adduct)

(SiH3)20+ BX3 ~(no adduct)
~ Approximately
pure p-orbital
ry
ra
Oxygen centre
(Lone pairs on 0 are
ib
in pure p-orbitals) ""'- .• / (slrhy~ridised oxygen)
yl
(CsHs)Si -~- Si(C sH S)3
1800 m
Fig. 10.7.1.4. Structure of (CH3)20. (SiH3)20 and (Ph3S/)20.
he
(f) (R ~;)'J.0 vs. (RJC}'J.O (structure and reactivity) : Here, it is important to note that in general, in
R3Si - 0 - SiR3, the Si - 0 - Si bond angle" is larger (ca. 140-180°) than that in the analogous
compound R3C - 0 - SCiR 3. The bond angle opening in (R3Si)20 favours the O(2p) ~ Si(3d)
lc
7t-bonding. The bulkier alkyl or aryl groups (R) favour the Si - 0- Si bond angle opening more.
ea
The limiting bond angle (180°) is attained in (C6 H s )3 Si - 0 - Si(C6 H s )3 (Fig. 10.7.1.4).
(g) HJCNCS vs. HJSiNCS (structure and reactivity) : Because of the same driving force, i.e.
th
P7( --+ d7( bonding, the isothiocyanates of carbon and silicon are structurally different. In
CH3 -N= C= S, the bond angle, CH3 - N- C
e/
o-c=s
is 142° while in SiH3 - N = C = S, the He
3~.
corresponding bond angle is -- 180° to make
t.m
the molecule linear. In the silicon compound,

nitrogen is sp hybridised to house the lone pair
in a pure p-orbital to carry out the
N(2p) ~ Si(3d) 7t-bonding interaction (Fig. Fig. 10.7.1.5. Structural features of H3 CNCSand
10.7.1.5). Consequently, HJSiNCS is a H3 SiNCS.
relatively weaker Lewis base.
(h) HJCNCO vs. HJSiNCO and HJGeNCO (structure>' : The similar situation arises for H 3CNCO
and H3SiNCO and the 7t-bonding makes H3SiNCO a weaker Lewis base and the bond angle sequence
H 3Si - N- C ) 113C - N- C. In H3GeNCO, because of poor matching in size and energy between the
4d orbital of Ge and 2p of N, the 7t-bonding, N(2p) ~ Ge(4d) is very much inefficient. Consequently,
Ge - N - C segment is not linear and it is angular.
Note: The decreased Lewis basicity due to such 7t-bonding in the free bases (e.g. N(SiH3)3' O(SiR3)2'
~JSi(NCO), H3Si(NCS), etc.) can be explained in terms of B-strain (Sec. 14.9iii).
(i) R 3SiOH vs. R3 COH (structure and reactivity) : K3Si - OH is a stronger Bronsted acid than
R3C-OH because of the '0 ~ Si' x-bonding which can stabilise better the conju~ate ~ase
R3SiCT. In the undissociated acid, the x-bonding develops a positive charge on oxygen (i.e. R3Si.t:::= OH)
which also favours the deprotonation process compared to the case of R3C - OH where no such
x-bonding is possible. This x-bonding explains the bond angle sequence, Si - 0 - H ) C - 0 - H.
The structural features and acid-base strength ofthe carbon and silicon analogues h~ve been discussed
in Sec. 14.9.
ry
10.7.2 Comparison of Nitrogen and Phosphorus Compounds
(a) Elemental state of nitrogen and phosphorous: At room temperature, nitrogen exists as N 2
ra
while white phosphorus remains as P4 which is thermodynamically unstable (cf. the bent bond concept,
Fig. 9.18.2.3) compared to the polymeric black phosphorus. Because ofthe longer a-bond in P - P, the
ib
sideways overlap to form 3P7t - 3P7t bonds becomes hindered as in the case ofsilicon. This is why, it is
very much reluctant to form such x-bonds, and it attains the P 4 structure in which four P-atoms at the
yl
vertices of a regular tetrahedron participate in the bent type single P-P a-bond formation (see Sec.
9.18.2). The strain in the structure can explain the reactivity of white phosphorus P4 • At the elevated
m
temperature above 8~OoC, phosphorus exists as P2 which is less stable than N 2 because of the same
ground, i.e. inefficieJt x-interactions.
he
(b) HCN vs. HCP and CsHsN vs. CsHsP: The efficient x-bonding in HC == N can explain its much
higher stability compared to its analogue HC == P (in which the x-bonding is very much weak due to the
lc
mismatch in size and longer C - P a-bond distance). In the same way, the higher stability of.pyridine
(CsHsN) compared to that of its analogue CsHsP can be explained.
ea
(c) Oxides ofnitrogen and phosphorus: The oxides of nitrogen are monomeric (e.g. N20 3, N20 S)
while those of phosphorus are dimeric containing the P4 unit (e.g. P40 6' P40 I0 ).
th
This structural difference is probably originated from the occurrence of back donation of the
nonbonding electrons from oxygen to the vacant d-orbital of phosphorus. This type of additional
e/
stabilisation does not arise in the oxides of nitrogen. In the oxides of phosphorus, phosphorus atoms are
positioned at the four vertices of a regular tetrahedron and six oxygen
t.m
atoms are placed at the mid-way of six edges of the tetrahedron (Fig.
10.7.2.1) to give P406. The lone pair on each phosphorus atom can be
coordinated to the oxygen atoms to produce P4010. Each of these four
P--+O bonds projected away from the tetrahedron in P 40. 0 has got a
double bond character (bond length, 139 pm) due to the O(p) ~ P(d)
7t-bonding.. The twelve P-o bonds along the edges of the tetrahedron
are relatively longer (163 pm). It is interesting to note that the ratio (1.16)
of these two P-o bond lengths is approximately the same as found for
c-o to C =0 or C-C to C =C. The stereochemical positions of the
six O-atoms along the edges of the tetrahedron do not permit any
efficient P7t -+ d", bonding.
(d) RJP vs. RJN: The existence of P7t ~ d 7t bonding can largely
influence the properties of tertiary phosphines (R 3P) compared to those
808 Fund~mental ~oncepts of Inorganic Chemistry
of the tertiary amines (R 3N). The tertiary phosphines are readily oxidised to the phosphine oxide,
R3 P [0]) R3 PO while the tertiary amines are not so sensitive to experience this oxi'dation. It
occurs so due to the enhanced stability of R3PO because of the 0(2p) ~ P(3d) x-bonding. R3NO lacks
in such stabilisation.
(e) Tautomerism in lower phosphorus acid and phosphonic acid : As a matter of fact, the extra
stabilisation obtained from the P - 0 bond through the 0(2p)~P(3d) 1t-bonding always urges the
suitable systems to attain the structure having the P - 0 linkage through tautomerism, ifpossible. This
is why, the lower phosphorus acids preferably tautomerise into the four coordinate systems having the
ry
P - 0 linkage.
H2O \ (HO)2 (H)P = 0
ra
PCl3 ) P(OH)3 ~
0
ib
Hydrolysis 0P~ H
I
yl
P (-3HX) - /r~(dll-Pllbonding)
/1"
X X X Ho/I~H m HO OH 0
OH
P(OH)3 Stable
he
Unstable
Because ofthe same ground, hydrolysis of RPX2 produces phosphonic acid 0 = P(H)R(OH) instead
of RP(OH)2.
lc
(t) lsomerisation ofR(OR)] to diesters ofphosphonic acid (Arbusov reaction) : The same driving
ea
force Le. O(2p)~P(3d) 1t-bonding in the P-O linkage, leads to isomerisation of P(OR)3 to
o = P(R)( OR)2 in presence of a catalytic amount of RX (Arbusov reaction; cf. A.E. Arbusov, J. Russ.
Phys. Chem. Soc., 42, 395, 1910). The said Arbusov reaction follows the following reaction pathway:
th
PCI) + 3ROH -3HCI ~ P(OR)3

e/
"'--"'R'I
[R~O_"
RO" (Oxidative
t.m
,,~ addition)
RO-P~ _ _.... P_ R]+X-
Ro/,,=--9 (Reductive
elimination) RqJ
~
l-RX
-RX RO"
RO- P-R'
(Reductive
elimination) ~
o
Phosphonlc acid ester
The Arbusov reaction actually experiences an oxidative addition of R ' - X followed by reductive
elimination of R - X. The oxidative addition leads to a trigonal bipyramid through the participation of
d-orbital and reductive elimination arises due to the favoured d n - P n bonding in tile P-O linkage.
(g) Racemisation 01 PRIR2~ : A related example is illustrated below:
Li
\:\
R1. - P - R3 + n-BuLi ~ n-Bu- P -
I
R3
R2 , ' . 1
R1 \ R2
Optical activity of phosphine derivative changes.
(h) Dipole moment 01 RlNO and RlPO : The dipole moment of R3NO (5.0 D) is. greater than that
ry
of R3PO (4.37 D). It can be explained from the structural standpoint.
+ _ + _. (1t)
R3N~O;R3P~O~R3P ~ 0
ra
(0) (0) (0)
ib
In R3NO, the charge separation arises due to the single a-bond while in R3PO, the charge ~eparation
produced in the a-interaction can be compensated partially through the O(2p) ~ P(3d) 7t-bonding.
yl
This is why, R3PO shows the less dipole moment. Because of the very high. polarity of R3NO, it readily
forms the hydrates like R l NO·H20. m
(i) Double bond character in P-O linkage and electronegativity olthe substituents : The double
bond character in the P - 0 linkage is evidenced by the higher bond energy (500-600 kJ mol-I) compared
he
to the bond energy (200-300 kJ mol-I) of N - 0 bond. Here it is worth mentioning that participation of
the 3d-orbitals is more facilitated for the more electronegative substituent (see Sec. 9.13.5) on
phosphorus. This is why, for the different halides up to bromide, in FjPO, the double bond character
°linkage is maximum.
lc
in the P'-
The ir-stretching frequencies (v po in cm- I) for the P = 0 bond shows a linear relationship with the
ea
sum of the electronegativities (~X) of the substituents on phosphorus. With the increase of ~X,
participation ofphosphorus d-orbital in 7t-bonding becomes energetically more favoured (cf. Sec. 9.1.3.5).
th
The observed relationship is :

1
e/
I v p-o = 930:+ 301:X, (in cm- >1

Here X is expressed in the Pauling electronegativity scale. This observation strongly supports the
t.m
participation 01 phosphorus d-orbital in back bonding (cf. Sec. 9.13.5). But some workers have
suggested an alternative possibility which will be discussed in the next paragraph.
Note (d or a* in 7t-bonding in P-O linkage) : Here it is important to mention the high ir-stretching
frequency indicates the existence of7t-bond in the P - 0 linkage. In fact, no single bond can account for
such high P - 0 bond energy (ca. 600 kJ mol-I). Thus there is no doubt oln-bonding interaction in
°
the P - linkage. But there is a controversy regarding the nature of phosphorus orbital involved in the
said 7t-bonding. It has been already pointed out (Sec. 9.13.5) that there is an objection against the
d-orbital participation in bonding. This is why, some authors have suggested that the P - R 0* MOs
rather than the d-orbitals participate in 7t-bonding (cf. Fig. 10.7.8.1). Some authors believe that the
d-o* hybrid orbitals participate rather than the pure d-orbital in such 7t-bonding. If this occurs, the
question exists for the relative contribution of the d and a· orbitals in' 7t-bonding. For the sake 01
simplicity, we shall explain the observation in terms 01 the classical idea 01 df(-p"" bonding
interaction.
0) Phosphonium ylids vs. ammonium ylids : In this connection, the relative stabilities of
phosphonium ylids and ammonium ylids are worth mentioning. In the ammonium ylids (R 3N + - -CH2 ),
no extra stabilisation through the back bonding is attained: but in the phosphonium ylids, the additional
stabilisation is secured through the C(2p) ~ P(3d) 7t-bonding.
(J •• 7t
R3P+ ----. -CH2 ~ R3P !;CH2
(J
This is why, the phosphonium ylids are more stable. Because ofthe absence of'It-bonding in the
ry
amm~niumylids, these are more reactive. The ammonium ylids are quite basic due to an accumulation
of negative charge on 'e but the phosphonium ylids are not sufficiently basic to abstract the protons
ra
from water.
The phosphonium ylids are very much important in organic synthesis to replace> C = 0 by > CH2
ib
(known as Wittig reaction, 1979 Nobel Prize,jointly with H.C. Brown for hydroboration). The ylid is
prepared in situ.
yl
+ DuLi + - ••
R3P - CH3 ) C4H 10 + [R3P -:- CH2 ~ R3P = CH2 ]
R'2 C = 0 + H2C = PR 3 R3PO + R'2C = CH2
~
m )
R;C,~ ~ R;C\;"..O
he
H 2C=PR3 I~I
H 2C-PR3
lc
(Cyclic transition state)

Here we can recall the tendency of phosphorus to form the P - 0 linkage that experiences stabilisation
ea
through the O(2p) -+ P(3d) 7t-bonding. It passes through the four membered ring intermediate or
transition state where the P - 0 bond starts to form. The cyclic transition state is attained through the
th
synergic donor/acceptor interaction :

7tco ~ 7t~=c and 1tp=c ~ 1t~=o
e/
0 0 f)
t.m
(1t*c=o)
(1tc=o)
c---o
1_\ ---0 Enriched
Enriched
with O-orbital CJ (0 with C-orbital
Fig. 10.7.2.2..Orbital overlap interaction in Wittig reaction.
(k) Sulfonium ylids vs. phosphonium ylid : Sulfonium ylids (R~ = CH2) are also stabilised t~rough
the C (2p) ~ S (3d) pi-bonding as in the case of phosphonium ylids. Sulphonium ylids react with the
ketones to produce epoxides through a three membered ring intermediate or transition state.
Me2S=CH 2 + ~C=O -
'"' G~
Me2S+)CH2-C~ ---. Me 2S
/\
+ H2C-C~
~. "L/ (Epoxide)
The above reaction can be compared with the Wittig reaction which produces the 'P - a
linkage in
the products. This difference between the said reactions can be explained in terms of7t-bonding. In
fact, the P - 0 linkage is more favoured than the 8 - 0 linkage. It is due to the ,fact, that the 2p
orbitals of oxygen matches better with the 3d-orbital of P (in PRJ)' It makes the RJPO adduct
ry
more stable than the RzSO adduct. This is why, in the case of sulfonium ylid, formation of RzSO
adduct is avoided.
ra
(I) N-H vs. P-H, !V-O vs. P-O, N-F vs. P-F bonds: Generally for the heavier congeners, the bond
energy decreases but, for the bonding with F and 0, the reverse order arises. Thus D' N _ H > D; p _ II but
ib
D' N _ F < D' P _ F" It occurs so due to the fact : in N - N, P - Hand N - F bonds, no 1t-bonding occurs but
in P - F bond, the 7t-bonding, F(2px) ~ P(3d1t ) occurs as in the case of p-o linka~e.
10.7.3 Comparison of Oxygen and Sulfur Compounds
yl
m
(a) Elemental states of sulfur and oxygen: The elemental states of oxygen and sulfur are totally
different. Oxygen exists as O2 while sulfur exists as a stable eight membered ring 8 8 (Fig. 10.7.3.1). In
he
O 2, the 2Pn - 2p x bond is very much efficient because of very good overlapping. In fact, it is about 80
kJ mol-I more stable than the single 0- 0 bond. On the other hand, for the heavier elements like sulfur,
lc
because of the increased a-bond length, the sideways overlap between the p-orbitals Le. 3Pn(S}-3P1t(S)
becomes insignificant. This is why, sulfur and other heavier
ea
members prefer two single a-bonds instead of a a-bond ~ ..

s: '),~ S~/'80
~·S/
and a 7t-bond. To attain the single bonded structure, sulfur .·s;
·S·
th
fonns an eight membered puckered ring in a crown shape

(Fig. 10.7.3.1) having bond length ~ 205 pm (single bond
""
:S:/~:S:·S·
e/
length) and bond angle 108°. The bond angle indicates

#"OW
3
the participation of sp hybrid orbitals of sulfur in the ring. (
t.m
Fig. 10.7.3.1. Structure of Ss'

10.7.4 Pi-Boding in Boron Compounds
(a) Bond length and Lewis acidity ofboron halides: The halidestofboron, Le. BX3, show a consider-
able amount of X(P) -. B(P) 1t-bonding. The electron deficient boron uses three sp2 hybrid orbitals to
fonn three sigma bonds and the vacant unhybrid p-orbital of boron is projected perpendicular to the
plane. The nonbonding pairs residing in the pure p-orbitals of_X can be donated into the vacant.
p-orbital of boron. This X(P) -. B(P) 1t-bonding introduces the double bond character (Fig; 10.7.4.1) in
the B - X bonds and the electron deficiency on boron is neutralised to some extent. This bond multiplicity
had been explained by MOT by considering the formation of 4 centred MOs (see Fig. 9.16.5.1). The
observed B - F and B - Cl bond lengths are 130 pm and 176 pm respectively while the calculated single
bond lengths are 152 pm and 187 pm respectively. The n-bonding in BFJ involving 2p(F) -+ 2p(B) is
most significant while for the other halides, the x-bonds developed from 2Pn +- 3Pn (in B - Cl), 2P1C +-
4Pn (in B - Br), 2Pn +- 5Pn (in B -I) interactions become gradually weakened due to the mismatch in
size and energy of the overlapping orbitals, and the longer B - X sigma bonds.
The observed Lewis acid

strength sequence, BFJ < BCIJ <
BBrJ goes against the prediction
based on the electronegativity
difference or electron withdraw- X /X X
/ iI'/ /
ing inductive effects and the X:B, ...... X-B ..... X-B
steric effects of the halogen. It is X 'X ~X
believed that the better 1t-bonding
ry
reduces the electron deficiency
better _on boron. Thus the better
tr-back bonding makes the
ra
Fig. 10.7.4.1. Pn ~ Pn bonding in BX3 .
boron haNde less strong as a
Lewis acid.
ib
Here it is worth mentioning that in the adduct L:~BXJ' the boron is spJ hybridised and there is no
vacant orbital on B to carry out the 1t-bonding but it is possible in BXJ • Thus the B - X bond length in
yl
L:-+BXJ is 19nger than that observed in BXJ • It explains the longer B-F bond length in tetrahedral
BF4- (Le. -: [: ~ BFJ ) compared to that in planar BFJ •
m
(b) Bond lengths in polyborates : In the polyborates, both the planar BOJ (sp2 hybridised B) and
tetrahedral B04 (sp3 hybridised B) units are present. The cross linking of borons occurs through the
he
BO4 units. The B - 0 bond length in BO4 unit is 142-155 pm while in BOJ unit, it is 128-145 pm. The
shorter bond length in the BOJ units arises due to the 2P1t(O) ~ 2P1t(B) bonding. Thus in the polyborates
lc
there are two typ~s of B - 0 bond lengths.

Note: Here it is worth mentioning that the higher members ofthe boron groups (i.e. AI, Ga, In,
ea
etc.) do not show any pronounced tendency to form 1r-bonds because ofthe longer A-A a-bond length
(A = AI, Ga, In). They very often form the dimeric compounds in which only the single a-bonds exist.
th
(c) Structure ofaminoboranes : The B-N bond length is in the sequence :

B - N bond length: B(NR2 )J > HB(NR2 )2 > H 2 B - NR 2
e/
With the increase ofsteric crowding, planarity of the system is gradually distroyed. Moreover,
the pi-bonding shrinks the B-N bond length to cause more steric crowding around B. Consequently,
t.m
N(2p7t) ~ B(2Pn) 1t-bonding gradually decreases with the-inrease of steric crowding. It explains the
bond length sequence.
10.7.5 Effect of P1t ~ d1t Bonding on the Properties of Different Oxyacids and Periodic
Variation of Properties of Oxyacids
(a) P1t-P1t vs. P1t - d1t bonding: Before to discuss anything regarding the tendency of polymerisation, we
should remember that the P1t - d1t bonding is much more significant than the P1t - P1t bonding from the
standpoint of overlap integral (see Figs. 10.7.11 vs. 10.7.1.2 and 10.7.8.1). In P1t - P1t bonding, the
overlapping lobes are parallel and as a result, there o~curs a pure sideways overlap. On the other
hand, in P1t - d1t bonding, the lobes of the overlapping d-orbitals are at an angle « 1800 to the
lobes of the p-orbital. Thus in the P1t - d1t interaction, the overlap is better.
(b) Tendency of polymerisation of oxyani(jns XO:- (X = Si, P, S, Cl) of the 2nd period
elements: Now let us consider the O(2p) -4' X(3d) 1t-bonding (where, X= Si, P, S, CI, cf. Figs. 10.7.5.1
'Covalent Compounds: Characteristics, Struct~re and Reactivity 813
and 9.13.5.2). In the tetrahedral structure of XO;-,

the d x 1 -y 1 and d z1 orbitals of X can participate
in the said P7E -+ d1t bonding interaction. On moving
from left to right along a period, the effective nuclear
charge generally increases and consequently' the
energy of the 3d-orbitals decreases from Si ~ P ~
S ~ C/. The overlap becomes better when the
overlapping orbitals have comparable energies. Thus
ry
the 7t-bonding efficiency increases from Si ~ P ~
S ~ C/. Now let us consider the oxyanions in the Fig. 10.7.5.1. dn-Pn interaction in a tetrahedral
ra
order of increasing tendency of polymerisation, species xo:- through the overlap of the
d 2 2 orbital of X with one p-orbital of O.
rrhe
ib
SiO:- > PO;- > SO:- > C/O; . Yaxes of the coordinates pass through
the centres of the faces of the cube).
Here, besides the different periodic positions of
yl
Si, P, Sand Cl, it is worth mentioning that the positive oxidation state of the central element increases
as, Si(+4), P(+5), S(+6), C/(+7). With the increase of positive oxidation state, the energy of the
m
3d-orbitals gradually decreases and it favours the x-bonding interaction. Thus the 2P7t(0) ~ 3d7t(X)
bonding in X - 0 increases from Si to Cl. This is why, the systems where the trbonding is not effective,
he
the stabilisati~n is attained through the single bonded structure, Le. through the polymerisation.
Thus the concept of P7t ~ d 7t bonding can explain the observed sequence of tendency towards
lc
polymerisation.
ea
Table 10.7.5.1. Effect of d7t - P7t bonding on bond lengths of some representative
oxyanion
Oxyanion X-o X-O Bond length Efficiency of
th
(XO;-) (in pm) (in pm) shrinkage 2P7t(0) ---. 3d~(X)

(observed) (calculated (in pm) bonding
e/
single bond)
~
8;0:- 163 176 13 c::
t.m
0
:::
P03- 154 171 17 co
c::
4
.~
80 2- 4
149 169 20 ...
~
0
CIO; 146 168 22 .5
Importance of P71 --+ d71 bonding: C/O;) 80;- ) PO:-) 8;0:-.

VO:- vs. CrO;-
In aqueous solution, vanadate can undergo polymerisation to produce a series of polyvanadates
while chromate only dimerises to Cr20i-. The 3d orbital contracts along the period Le. 3d orbital
is contracted more for chromium. Moreover, the higher .positive charge on Cr(VI) (cf> system)
contracts the 3d orbital more. These two factors give the better 7t-bonding in Cr-O linkage compared
to that in v-o linkage. This is why, chromate shows no strong tendency to undergo polymerisation.
Stability and polymerisation sequence: SiO:- > PO:- > SO;- > CIO;
• This stability sequence can be explained by considering the energy difference between the
valence ns and np orbitals (cf. Sec. 8.24). The energy difference, I1E = Enp - Ens increases bTadually
from Si (ca. 5 eV) to C/ (ca. 11.5 eV). Consequently, participation of nil electron in bringing
about the highest possible valence or oxidation state becomes gradually difficultfrom Si to CI
cf. Sec. 8.24).
• The P7t(O) ~ d 7t(X) (X= Si, P, S, Cl) interaction increases gradually from Si to C/ and it explains
the highest tendency of polymerisation for SiO:- and this tendency of polymerisation declines
ry
from SiO:- to C/O;. It indicates that the polymerisation utilising the maximum number of
possible a-bonds stabilises the system more.
ra
(c) Stability of oxyacids of halogens: Now, let us consider the oxyacids of the elements in a
ib
particular group. In the case of halogens, the P7t - d 7t bonding is very much important from the standpoint
of stability of the oxyacids. There is no stable oxyacid offluorine (which is devoid of any suitable d-
yl
orbital) because in this case, there is no possibility ofP7t - d7t bonding which is important to stabilise the
system.. For, the heavier halogens, the oxyacids (except HBr04 ) are well documented because they can
m
earn stabilisation through the P7t( 0) ~ d 7t(X) bonding. Though for X = I, this 7t-bonding is not efficient,
it can earn stabilisation through the extra a-bond formation as in H sI06 • For X= F, 7t-bonding is not
he
possible and also extra a-bond formation is not favoured due to both steric factor and energy factor.
The instability of HBr04 is due to the secondary periodic,ity.
lc
Another interesting observation is that the heavier members in a group form the oxyacids which are
structurally different from those ofthe lighter congeners. These are seen from the following examples:
ea
Oxyacids of Group VIA (16) elements: H2S04 , H2Se04 , H6 Te06

Oxyacids of Group VIlA (17) elements: HC/04 , HBr04 , HsI06 •
th
The lighter congeners where O(2p) ~ X(3d, 4d) 7t-bonding is significant form strong 7t-bonds to
give XOI- /1 - but, for the heavier ones where O(2p) ~ X(5d) 7t-bonding interaction is very much
e/
insignificant due to the incompatible orbital sizes, the single sigma bonds are preferred. This is why,
t.m
in H 6 Te06 and H sI06 the numbers of a-bonds are larger compared to those present in the oxyacids of
their lighter congeners. Here, the steric factor is also worth considering. The sizes of Te, I are sufficiently
large and they can easily accommodate six O-atoms around themselves. The lighter members will
experience a steric hindrance in accommodating the six O-atoms.
sulfate> selenate < te/urate
Stability sequence {
perch/orate> perbromate < periodate
This can be explained by considering the secondary periodicity (a consequence of scandide
contraction and lanthanide contraction, (cf. Sees. 8.20 and 8.24) and alternation effect (cf. ~ec.
10.3.2). In fact, selenate and perbromate are the powerful oxidising agents.
Oxidising power ofthe oxyanions ofp-block elements: The yariation of oxidising power ofdifferent
oxyanions can also be nicely rationalised in terms of P7t - d 7t bonding to stabilise the X - 0 bond (see
Secs. 16.5.2, 16.15.3).
10.7.6 P7[ - d7[ Bonding Leading to Aromatlcity in Inorganic Ring Compounds

(a) Structural features of cyclic (NPCI2)3 : We have already mentioned (Sec. 9.15(d» the possibility
of existence of delocalised 7t - MOs in the trimeric phosphazenes, (NPCI2 )3' In this trimeric compound,
all the N - P bonds are equal (156-160 pm) and these are considerably shorter than the single N - P
covalent bond (177 pm). It supports the delocalisation as in the case of benzene.
(b) Craig-Paddock model of7t-bonding in (NPCI2)3 (cf. Rev. Chern. Soc., 18,68, 1964) : In the
planar six membered ring, each nitrogen is sp2 hybridised while each phosphorus is approximately sp3
hybridised. The four sp3-hybrid orbitals of P-atom contain 4-unpaired electrons and thefifth unpaired
ry
electron is housed in a d-orbital. These sp3-hybrid orbitals participate in forming 4 a-bonds. The two
sp2-hybrid orbitals of N-atom carry two unpaired electrons while the lone pair is housed in the third
ra
sp2-hybrid orbital. The two sp2-hybrid orbitals bearing the unpaired electrons participate in forming
two N - P a-bonds with the adjacent P-atoms. The fifth unpaired electron ofN-atom resides in a pure
ib
p-orbital which participates in rrbonding with the suitable d-orbitals (bearing an unpaired electron)
of P-atom (cf. Fig. 10.7.6.1). The pure p-orbitals (say, p= orbital, cons!dering the sigma skeleton to lie
yl
on the xy-plane) on the nitrogens with an unpaired electron can undergo N(2P1.) - P(3dX 1.) 7t-bonding
interactions. This 7t-bonding interaction occurs in a plane perpendicular to that of the ring. However,
m
the delocalised tr- MO involving three 3dX 1. orbitals of the P atoms and three 2P1. orbitals on the N
atoms produces a node (cf. benzene where no node exists) because of the mismatch of sign of the
he
wavefunctions at one point (Fig. 10.7.6.1). This node reduces the delocalisation energy.
The above N(2p=) - P(3dx=) 7t-type interaction producing a node to destabilise the stability was
lc
proposed by Craig and Paddock. In this Craig-Paddock model, other possible 7t-interactions are:
ea
N(2sp2) - P(3dxy and / or 3d 2 2)

x - y
When the sp2-hybrid o;bital participates in rrbonding, it produces tr-bonding in the plane ofthe
th
r:ing.
(c) Dewar model of tr-bonding in (NPClz)3 (cf. J. Chern. Soc., 2423, 1960) : Besides the Craig-
e/
Paddock model, Dewar and coworkers have suggested an alternative 7t-type interaction. The dx: and dy=
orbitals of each P-atom can interact with the p=-prbitals of the adjacent N-atoms. In other words, each
t.m
N-atom can provide its singly occupied p=-orbital for forming 3-centred 7t-MOs by using the dx=and dy:
orbitals of the adjacent P-centres (Fig. 10.7.6.1). The combination is :
dy=(lj) + p=(N) + d x=(P2 ) (~f. Fig. 10.7.6.1)

Either P( I) or P(2) will provide one d-electron and N will give one p=-electron. These two electrons
will occupy the lowest 3c-x-BMO.This 3c-2e x-bonding interaction produces .lx-bond order (average)
2
on each N- P linkage. This delocalisation is confined on each P-N-P segment and the nodes arise
at each P-centre because the involved two d-orbitals ofP-atom are in two orthogonal planes. It gives
three sets of 3c-7t-MOs around the three N-centres. Thus, in each set, the 7t-orbitals (3-centred) appear
as 'islands' segmented at each P-centre.
Here it is worth mentioning that both the Craig-Paddock and Dewar model explain the less
stabilisation in (NPX2 )3 due to the existence of nodes.
CI CI CI CI H, /H H, /H
,/ '\./
P-N CI P=N CI C-C C=C
~ ~/ +--+ / '/ ~ ~ / '\.
H-C C-H ...-...... H-C C-H
N, /p,C N P'\.
'P=N I
/,
\_1 CI
'\.
C=C
/ ~
C-C
~
/'\. H/ 'H H/ 'H

CI CI CI CI
A A A (b) Structure of benzene
CI- P - CI = 108°, N - P - N = P - N - P = 118°,
P- ~~ = =
= 158 pm (ct. Single P - N 177 pm). P - CI 199 pm.
(a) Structural parameters
N:lIlII1IJ [I]: p:CIIIIJJI] DIIIIJ
sp2 p sp3 3d
(c) Hybridisation states of Nand P
ry
ra
ib
yl
(d) Craig-Paddock model for the lowest n-BMO formation Mis-match in
symmetry; node
m
he
lc
H H
ea
th
C(1) C(2) C(3) C(4) C(5) C(o) C(1)

H H (e) Formation of the lowest n-BMO in benzene
e/
t.m
There 3-centred islands"

II
(f) Dewar model of rr-bonding in (NPCI-j3
Fig. 10.7.6.1. (a) Structural features of cyclic planar (NPC/2)3; (b) Structural features of planar Cs·He
(benzeme); (c) Hybridisation states of Nand Pin (NPC/2)3; (d) Craig-Paddock model: 2pz(N) - 3dxz(P)
n-interaction in (NPC/2)3' ring split for the sake of simplicity to show the mismatch in sign!) of . Iobes
on P(6) and N(1); (e) n-interaction in CeHe by using the pure 2pz orbitals of the sp2 G-atoms; (f) Dewar
model: Formation of 3-centred MOs around each N of (NPC/2 )3' e.g. dyZ(P1 ) + Pz(N) + dxz(P2 ).
[Note: (NPCI2 )3 can be thermally polymerised and these polymers find application in many fields
including medical field.
Cl
A I
(NPCI2 )3 .. -[-1=== N - t (n may be as high as 1500)
Cl
In the polymer, Cl-group can be substituted (nucleophilic substitution) by different groups including
the drugs. In fact, in this way, different drugs can be bound in the polyphosphazene skeleton and
ry
these drugs are slowly released through hydrolysis to maintain a therapeutic steady state.]
(d) Pi-bonding in (NPF2)J : It may be noted that in (NPF2)3 the P-N bond is slightly shorter than
ra
that in (NPCI2)3. It can be explained by considering the better 7t-bonding between Nand P by using the
d-orbital on P. Fluorine is more electronegative than chlorine. Consequently, in (NPF2)J' the d-orbital
of P-centre is more contracted to favour the x-bonding interaction with the N-orbital.
ib
(e) Structure and 1J-bonding of (NPClz)4 : The more flexible tetrameric phosphazene, (NPCI2)4
yl
prefers the non-planar conformer instead of the planar one existent in the trimer. Here it is worth
noting that this loss ofplanarity does not prevent the delocalisation (cf carbon systems where the
planarity is an essential condition as proposed in Huckel's rule). Moreover, in P7t - d7t delocalisation,
m
the Huckel's (4n + 2) rule is not to be obeyed. It appears so, because the Huckel's rule was proposed
in the carbon systems where the P7t - P7t bonding leads to delocalisation. The Hilckel's rule is relaxed
he
in the P1t - d1( system where the more diffuse andflexible d-orbitals can participate in delocalisation
in a nonplanar sy.vtem.
lc
Here it is worth recalling that non-planar CPa is not aromatic but non-planar (NPCI;" is
aromatic. (NPCI2 )4 can exist in two possible conformations (Fig. 10.7.6.2) chair (T-form) and tub
ea
(K-form) forms. The T-form is more stable. In the tetramer, the stabilisation earned by delocalisation
can be explained by both Craig-Paddock model and Dewer model. Dewer model gives four sets of
th
3-centred 7t-MOs (P-N-P) in (NPCI2 )4. Similarly, it gives five sets of 3-centred 7t-MOs in (NPCI2 )s.
Here it is worth mentioning that though (NPClz)4 is nonplanar, but (NPFz)4 is planar because of its
e/
better N(2p) ~ P(3d) 7t-bonding. In 'NPF2', the 3d-orbitals of phosphorous are contracted more to
favour the process.
t.m
CI
),CI /CI
N N=P"CI
CI~P=N N
CI/ ,,;
P
/"
CI cr
Tub conformation Chair conformation
(K-form) (T-form)
(a) (b) (c)
Fig. 10.7.6.2. (a) Nonplanar structure of tetrameric chlorophosphazene i.e. (NPCI 2)4; chair form (T-form)
is the most stable form while K-form is the metastable form; all the P-N bond lengths are equal and
shorter than the single P-N bond, Le. delocalisation of 1t-electron cloud (81t-electrons); (b) Molecular
structure of S4N4; (c) Molecular structure of S3N3 with 61t electrons. --
(f) Cyclic structures o1S~4 and S3NJ: In the cyclic S4N4' all S -N(=163 pm) bonds are equivalent
and it indicates th~ delocalisation of the 7t-electron cloud throughout the molecule as in (NPX2)4' S4N 4
forms an 8-membered ring of cradle shape (Fig. 10.7.6.2) having S-N bond length ~ 163 pm which is
shorter than the calculated ~ingle bond length (178 pm). The N(2P7t) - S(3d7t ) bonding prevails. The
r
approximately equal S-N bond length indicates the delocalisation oln-electron over t~e whole ring.
The 12 7t-electrons participate in the delocalisation. The four N-atoms are coplanar. Thel distance (258
pm) between the nonbonding S-atoms is less than the van der Waals distance (360 pm), but this distance
is larger than the normal S-S covalent bond length (206 pm). It indicates some sort of interaction
ry
existing between the nonbonding S-atoms in S4N4' The planar six membered ring S3N; (obtained
from the reduction of S4N4 by metallic potassium) is an int.eresting example. Here 10 7t-electrons (4n +
2, n = 2) constitute the aromaticity having the electron distribution (7t BMO )6 (7t:BMO )4. The presence
ra
of four electrons in ABMOs weakens the S-N bond. For C6H6 , there are 6 7t-electrons and these are
placed in BMOs. .
ib
The aromaticity in B3N 3H6 through the P 7t - P7t delocalisation has already been discussed (Sec. 9.15,
cf., Fig. 9.15.4).
10.7.7 Changes in Structure due to Electronegative Substituents

yl
m
(a) S~4H4 vs. S~4F4: We have already mentioned (Secs. 9.13.5, 9.15d) that in bonding, effective
participation ofthe 3d,..orbitals of Si, P and S can only be attained when the positive charge accumulation
he
on the atoms is increased by the electronegative substituents. Thus, very often, substitution by the
electronegative groups may carry out significant changes in the structure. For example, tetrasulphur
lc
tetraimide (S4N4H4) bears the puckered ring (crownlorm) structure as in S8 and both are isoelectronic.
S4N4F4 (tetrathiazyl tetrafluoride) shows an alternate double bonded structure in which substitution
ea
occurs on S. But in S4N4H4' substitution occurs on N not on S. These are shown in Fig. 10.7.7.1.
r
th
S-N-f F-S=N-S-F
I+-~ I I
e/
N-H
I I N N
I I
t.m
S--N-S
I
H
F-S-N=S-F
Fig. 10.7.7.1. Structures of S4N4H4 Le. S4(NH)4 and S4N4F4 Le. (SF)4N4'
In S4N4H4' the hydrogens never go to sulphurs while in S4N4F4' fluorines get preferably
attached with the sulphur atoms. The highly electronegative fluorines on being placed on the sulphur
atoms can appreciably contract the 3d-orbitals of S to facilitate N(2P 7t ) - S(3dn ) bonding. This P7t - d 7t
bonding which brings an additional st~bilisation directs the position of the fluorines. But, if in
S4N4H4' hydrogens go to the sulphurs, no effective 7t-bonding occurs through the 3d-orbitals of S. This
is why, it prefers the single sigma bonded structure which is attained by placing the hydrogens on the
nitrogens through the single a-bonds. Moreover, the N - H bond is stronger than the S - H bond.
(b) (NPF<2)3 vs. (NPF2)2(NPPh z) (structures and bonding) : We have already considered the
symmetric phosphazene, (NPX2 )3 as a planar aromatic compound. But if the substituents on the
phosphorous atoms differ significantly in electronegativlty, the planarity ofthe molecule may be destroyed
with a reduced delocalisation. Let us consider (NPF2 )3 and 1, 1 diphenylphosphonitrilic fluoride
trimer. The phenyl group substituted phosphorus atom'lies above the plane containing the rest of the
molecule. It can be explained as : the fluorine substituted phosphorus atoms have contracted the 3d-
orbitals which can participate in N(2P1t) - P(3d1t ) e.g. N(2 p~) ~ P(3d~=) bonding. But the more
electropositive phenyl group cannot lower the energy ofthe 3d-orbitals ofthe substituted phosphorus
and as a result, no effective 1r-bonding through this diffuse d-orbital occurs with the adjacent nitrogens.
This weakens the 1t-bonding system and it allows the ring to defonn at this point. This is why (Ph)2P<
ry
remains out of the plane.
f\
ra
Out of plane
to hinder the
ib
N-P 1t-bonding
141.5 pm
yl
m
Fig. 10.7.7.2. Structures of NSF3 and (NPF2)2(NPPh2).
he
(c) Structure and bonding in NSF] : In this regard, thiazyl trifluoride, NSF) is very much interesting.
This S - N bond length is 141.5 pm, probably the shortest one between Sand N. The bond angle
lc
F - S- F is -- 94°. The three highly electronegative fluorine substituents contract the 3d-orbitals of
sulfur sufficiently to effect the strong 1t-bonding with the filled p-orbitals of the nitrogen. The bond
ea
angle F - S- F indicates the involvement of almost pure p-orbitals of S in binding the fluorine atoms.
It can be supported by the Bent's rule. The very strong bonding (due to multiple bond formation)
th
between Nand S demands the participation of s-character enriched orbitals of sulphur. On the other
hand, the electronegative fluorine atoms intend to bind through the p-orbitals of sulphur. Both these
e/
factors work jointly to direct the involvement of almost pure s-orbital of S in fonning the a-bond
between Sand N, and almost pure p-orbitals of S in 'fonning the S - Fa-bonds..
t.m
(d) (NPF,)4 vs. (NPClz)4: Th tetramer (NPF2)4 is planar while (NPCI2)4 can adopt both nonplanar
chair and tub conformations. In 'NPF 2', the 3d-orbital of phosphorus is more contracted than that in
'NPCI2'. It allows the better 1t-bonding interaction i.e. N(2P1t) ~ P(3d1t ) in (NPF2 )4. This leads to planarity
in the structure of (NPF2 )4 and prevents the system from attaining the puckered ring structure. In
(NPCI2)4' the said 1t-bonding is relatively weaker and consequently the ring is more flexible and it can
adopt the chair and tub conformations (cf. Fig. 10.7.6.2).
(e) Nature of p-o linkage in O}JX] : In the··same way, the highest stretching frequency of the
P - 0 linkage occurs in OPF) compared to all other halogen containing analogous compounds.
v p _ o (em-I) = 930 + 30~x., ~x. = sum of the electronegativities of the substituents on phosphorus.
10.7.8 Synergistic Effect due to the pi-Bonding and Stabilisation of Low Oxidation States
of Metals in Complexes
(a) Pi-acid ligands: The ligands (L) which are having suitable vacant orbitals to receive back the
nonbonding electron clouds present (generally in d-orbitals) from the metals are referred to as 1t-acid
ligands. Thus the 1t-acid ligands not only show the sigma basicity (e.g. a-donation of the lone pairs) but
also display the 1t-acidity (Le. 1t-acceptanceofthe lone pairs from the metals). The vacant orbitals for
1t-acceptance may be the d-orbitals as in PR3, AsR3, SbR3 , etc., or 1t* - MO as in CO, C2H4 , NO+,
CN-, etc. or, a*-MO in some cases like H 2, RJP, alkanes, etc. Thus the three following possibilities of
x-back bonding (called also retrobonding) (Fig. 10.7.8.1) are existent.
(a) M(d,J -+ L(d,J, when the vacant d-orbital of the ligand lies in the plane of the filled d-orbital of
the metal (M).
(b) M(d,J -+ L(x*), when the vacant 1t* MO of the ligand lies in the plane of the filled d-orbital of
ry
the metal (M).
(c) M(d,J -+ L(a*), when the vacant a*-orbital of the ligand lies perpendicular to the a-bond axis.
ra
ib
yl
m
d(M) ~ d(P) d(M) ~ n*(CO) d(M) ~ n*(C 2 H4 )
he
(a) (b) (c)
lc
ea
th
d(M) -+ a*(H 2 ) d(M) -+ a* (P-X) d(M) ~ pel)

(d) (e) (f)
e/
Fig. 10.7.8.1. Different types of pi-bonding involving metal d-orbital and ligand orbitals. (a)-(e) : metal
acts as a 7t-donor and ligand acts as a 7t-acceptor. (f) : ligand acts as a 7t-donor.
t.m
Note: • Ligands like R3 P, R3As, R2 S, r etc. use their vacant d-orbitals for 7t-acceptance. However,
for R3 P or X3 P, it has been argued that the vacant a* MO of P-X or P-R bond is used for 7t-acceptance:
Ligands like CO, CrY, Ncr, RNC, py, bpy, N2 , NO~ olefines, CaHa, Cp-, etc. use n*-MO for
7t-acceptance. Halides (X-) , O~, Ro-, c1-, RS-, etc. use filled p-orbitals for 7t-donation. However,
r can use its vacant d-orbital for 7t-acceptance.
• For the shapes of the MOs in the interaction, d ± p, d ± 7t*, d ± 0*, Fig. 9.5.1 (b) may be considered..
In the bonding process of the 1t-acid ligand, generally both the a-donation and x-aceptance are
interdependent. When the extent ofa-donation increases, the ligand (L) becomes ~ore electron deficient
and consequently it becomes more willing to receive back the electrons from the metal. Thus, with the
increase of a-donation, the extent ofpi -acceptance increases. On the other hand, the increased a-
bonding enhances the electron density on the metal centre and it encourages the metal centre to return
the electron cloud to the ligand through 7t-bonding. Similarly, the 1t-acceptance can also reinforce the
a-donation process. This interdependent process is described by this synergistic action.
Now if we pay attention to the metals (which are at low oxidation states, e.g. 0, + 1, + 2, etc.), it is
evident that if the bound ligands are only a-donors (e.g. NH3, NR 3, etc.) in nature, then there will be an
accumulation of negative charge on the metals which is not surely encouraged by the metals. This is
why, the low oxidation states of the metals do not prefer the purely (J basic ligands. If the bound
ligands are n-acid ligands, then they do not allow the accumulation of negative charge on the metal,
because the accumulated charge by the a-donation is taken back by the 7t-acid ligand through the
7t-acceptance. Thus the principle of electroneutrality is maintained through the synergistic action.
This electroneutrality is very much important for the low oxidation states of the metals. This is why, to
ry
stabilise the low oxidation states of the metals, the n-acid ligands like CO, CN -, NO +, etc. are
important. Some examples of such compounds are given below.
ra
Ni(CO)4' V(CO)6' Fe(H 20)s(NO)2+ , etc.
(b) NFJ vs. PFj as ligands: NF3 cannot act as a ligand while PF3 can act as good 1r-acid ligand.
ib
This can also be explained through the" 7t-bonding properties of PF3 as a ligand. The following examples
can j ustify the fact.
yl
Ni(CO)4 + 4PFj ~ Ni(PFj)4 + 4CO; Ni(CO)4 + NFj ~ no reaction
m
Both CO and PF3 are good 7t-acid ligands. The vacant 3d orbital of P is sufficiently contracted due
to the presence of three F-substituents which are highly electronegative. This contracted d-orbital can
he
receive back the electron through 7t-bonding. Because of the absence of any vacant orbital in NF3, it
cannot act as a 7t-acid ligand. Moreover, because of the presence electronegative substituents, NF3
becomes electron deficient and it acts as a poor a-donor ligand. This property makes PF3 also electron
lc
deficient but it favours PF3 to act as a better 7t-~cc~ptor ligand.

ea
10.7.9 1t-Bonding in Soft-Soft Interactions

The importance of7t-back bonding has been invoked by Chatt to explain the stability ofsoft-soft adduct.
th
The class (b) metal ions (Le. soft Lewis acids) generally bear the loosely bound d-electrons which can
be easily back donated. On the other hand, the ~oft Lewis bases such as, R2S, R3P, R3As, CO, CN-, etc.
e/
are basically 7t-acid ligands having suitable vacant d-orbitals or 7t* - MO (for, CO, CN-, etc.) to receive
back the electron clouds from the class (b) metal' ions. Thus, if an interaction between the class (b)
t.m
metals and hard bases having donor atoms like N, 0, F is considered, no such stabilisation is attained,
rather a repulsive interaction between the filled p-orbitals of the ligands and filled metal d-orbitals will
be set up. Thus the 7t-bonding theory can explain the better soft-soft interaction. The cation-anion
mutual polarisation working synergistically produces a strong covalent interaction in the soft-soft
adduct (cf. Fig. 10.6.2.1).
10.7.10 7t-Bonding and trans-Influence, trans-Effect in Kinetics

(a) Trans-effect (a kinetic phenomenon) : It is very often found that the 7t-acid ligands act as good
trans-directing ligands in the substitution reactio"ns of the square planar systems of Pt(JI)
complexes. According to the idea developed by Chatt and Orgel, it is believed that the process passes
through the trigonal bipyramid intermediate (Le. associative process). The 7t-acid ligand (L) withdraws
the d-electron cloud and the electron density at the trans~position is decreased. This facilitates the
nucleophilic attack by Y(say) at the trans-position of L. Thus activation energy is lowered (Fig. 10.7.10.1).
ry
ra
(a)
ib
yl
m
he
(b)
lc
Fig. 10.7.10.1. L = trans-directing ligand; X = leaving group; Y = incoming nucleophile; L, X and Y

are in the equatorial plane of the trigonal intermediate (TBP)
ea
L-Pt(A)(B)-X ~ TBP~L-Pt(A)(B)-Y
th
A and B non-leaving groups (not shown) occupying the axial positions of TBP.
(a) Approach of the incoming nucleophile leading to the TBP intermediate in the associative path;
e/
reduced electron density in the direction of the approaching nucleophile due to Pt(/I) --+ L 1t-back
bonding; (b) 1t-bonding interaction in the TBP intermediate by the equatorial ligands:
t.m
L with dxy!.Pt); X and Y with d~ _ ;(Pt).
The trigonal bipyramid intermediate is also stabilised by the 7t-bonding properties of L when placed at
an equatorial position. Thus the trans-directing series, amines < phosphines < oletins runs in th~ sequence
of the efficiency of pi-bonding properties of the ligands.
(b) Trans-influence: Trans-influence (a thermodynamic phenomenon which is also described as
static trans-effect) leading to weakening a bond at the trans-position can also be explained by
7t-bonding theory. Two trans-7t-ligands competing for the same metal d-orbital will mutually labilise.
The better tracceptor ligands will dominate and weaken the trans-bond. In Fig, 10.7.10.2, the
competing ligands are Land X.
(c) Pi-bonding and relative stability oflinkage isomers ofsquare planar complexes: In fact, if the
two trans-bonded ligands compete for 7t-bonding, then depending on the situation, the better 7t-bonding
ligand may direct the other competing ligand to change its mode of bonding. It happens so when
the weaker 1!-bonding ligand is an'

ambidentate ligand like 'SCN' whose S-
bonding site is a 1!-bonding site while the
N-bonding site is a non-1!-bonding site.
In Pt(SCN)2(NH3)2' 'SCN binds with its
Y
L
S-end and enjoys the 7t-bonding while in x
Pt(NCS)2(PR3 )2 it binds with its N-site
to favour the 7t-bonding by the better
ry
7t-bonding ligand PR 3 • To determine the Fig. 10.7.10.2. Two trans-bonded ligands (L and X)
relative stabilities of linkage isomers, competing for the back bonding with the same filled
besides the competing 7t-bonding effect, Pt-d orbital.
ra
many other factors like symbiotic principle, steric factors are imp~rtant. These aspects have been
discussed in Sec. 14.15.4 in detail. .
ib
. Thus it is a common practice that the good 7t-acid ligands very often weaken or labilize the groups
in the trans-directions.
10.7.11 . 1t-Bonding and ci.Effect i., Kinetics

yl
m
In ligand substitution reactions ofthe octahedral coordination compounds, the cis-effect in a dissociative
process can be explained in terms of 7t-bonding.
he
The nonleaving 7t-bonding ligand L (e.g. -OH, -NH2 , etc.) at the cis-position can stabilise the
square pyramid intermediate in the dissociative process (D-process) through 7t-bonding. In fact, the
lc
~P+Y'
p
ea
.-:./
Q;f -x
l'
th
A-r-, ---+ A- M -
(D-process)
L ---+ cis-product
(Retention of configuration)
e/
t.m
(cis-isomer) (a) Square pyramid
, i 'i d2sp3 (c:_~AV;X~~t~ns-product)

~ d ~M~
,!
L--M--X
(o-process%f.!
UD
L--M (/somerisation)
• ....-=::. .-
~i~:::~ ;~;;;;'Y(CiS-product)
'. ::;::=::
bipyramid
(Trans-isomer) Square pyramid
Fig. 10.7.11.1. Effect of a 1t-donor ligand (e.g. OH-, Cr) on the nucleophilic substitution (D-process)
at the cis- and trans-position in an octahedral complex e.g. M(A)4LX where L x-donor nonleavlng =
group; X = leaving group; A = nonleaving groups; two other trans-axial ligand (A) are not shown. (a)
L at the cis-position (with respect to X) stabilises the 5-coordinate square pyramid; (b) L at the trans-
position (with respect to X) leads to isomerisation of the 5-coordinate square pyramid intermediate to
a trigonal bipyramidal geometry where L ~ M 1t-bonding can occur to stabilise the intermediate.
vacant orbital created through the departure of the leaving group is utilised by the 7t-donor ligand
residing at the cis-position. This 7t-bond forming tendency will facilitate the expulsion of the leaving
~group at the rate determining step. Thus the nonleaving 1f-donor ligands can labi/ise at the cis-position.
This kinetic phenomenon is called cis-effect. It leads to retention of stereochemical configuration.
If this 7t-donor nonleaving group (L) resides at the trans-position, to stabilise the ·5-coordinate
intermediate, the square pyramid intermediate changes into the trigonal bipyramidal geometry where L
occupies an equatorial position. From this trigonal bipyramidal intermediate both cis- and trans-products
will be produced in the 2: 1 ratio. It leads to·isomerisation.
ry
The above arguments can nicely explain the following experimental findings (L = 7t-donor ligand).
L
/L /L
ra
. C
CIS- 0
lII '<4/
'4"". (-
+y
X)
.
CIS-CO
III
A4" ' trans-Co
III
A4 "".
+Y
(_ X) ) cis- and trans-products.
ib
X y X
The cis-compound reacts faster because the 5-coordinate intermediate needs no rearrangement
yl
for stabilisation. For the trans-compound it needs a rearrangement (Fig. 10.7.11.1).
m
10.7.121t-Bonding and Isomerism in Coordination Compounds
The mode of bonding in linkage isomers for the ambidentate ligands (e.g. SCN -, SeCN - etc.) is
he
highly dependent on the possibility of 7t-bonding (see symbiosis, Sec. 14.15.4). Similarly, the cis-trans
isomerism and tetrahedral-square planar isomerism are also strongly influenced by the possibility of 7t-
lc
bonding.
For an octahedral complex, the t2g orbitals (Le. dxy' dyz and d=x orbitals) of the metal can participate
ea
in 7t-bonding, while in a tetrahedral complex the eg orbitals (Le. dxl _ y2 and dz2 orbit~ls) are in a
suitable position for 7t-bonding. In a trigonal bipyramidal geometry, the ligands residing at the equa-
th
torial position can participate in 7t-bonding with the central element through the dxy and dxl- ;. orbitals.
All these aspects will be discussed separately to explain the isomerism in coordination compounds.
e/
10.8 STRUCTURE OF COVALENT MOLECULES :

t.m
MOLECULAR TOPOLOGIES
10.8.1 Helferich's Rule
Before the developoment of bonding theories (specially, concept ofhybridisation and VSEPR theories),
Helferich proposed some empirical rules to predict the molecular shapes of different species.
From the possible representation of Lewis dot structure of a particular molecule (in which the less
electronegative element is generally treated as the central element), valency shell electrons are to be
placed in such a geometry that the electron-electron repulsion in the valence shell of the central
element is minimised. The effects of the 7t-electrons are ignored in determining the geometry, as the
7t-electrons follow the a-bonds as required. Based on this basic concept, Helferich proposed the following
rules. .
(i) AX2 species: If there is no lone pair on A, it will be linear (Le. X AX = 180°) but the existence
of lone pairs on A makes the molecule angular, Le. V-shaped.
Examples:
(a) Linear molecules: 0 = C = 0, N == N+ - 0-, N- = N+ = N-, Cl- Be - Cl
(b) Angular (i.e. V-shaped molecules): /~"" ~N""/Sn""

H H Cl Cl 0 0-
(ii) AX) species: Absence of any lone pair on A makes the species planar while the existence of a
lone pair on A makes the species trigonal pyramidal.
.
F
/ /0
° ~ C"",
ry
Examples: Trigonal planar: F - B"" ' etc.
F O~
.. ..
ra
Trigonal pyramidal: /N"" )0""
H ~ H R /f"
R R H I H
etc.
ib
H
(iii) AX4 species: If A has no lone pair, it is tetrahedral otherwise it will have the planar or other
yl
geometrical structure.
Examples:
(a) Tetrahedral: CH 4, NH;, BF4-, BH;', BeF4 -, etc.
m 2
F
"" ../F
he
(b) Planar: / !:"" ' etc.
)
lc
F F
A large number of species do not follow this rule. For example, Ni(CO)4' NiCI;- are tetrahedral
ea
while JVi«( ,'V)~- is planar.

The Helferich's rules are not ofmuch importance compared to the other guiding rules to determine
th
the structure of the molecules, but the basis of the rule can now be interpreted in the light of
VSEPR theory.
e/
10.8.2 Concept of Hybridisation and Bent's Rule

The concept of hybridisation in determining the structure of covalent molecules is extremely helpful
t.m
and this aspect has been discussed in Sec. 9.13. By introducing the prediction of Bent's rules (see Sec.
9.13.7) in the concept of hybridisation, the structure of the molecules of the nontransition elements can
nicely be explained.
10.8.3 Sidgwick-Powell Theory and Valence Shell Electron~Pair Repulsion (VSEPR) Theory
The foundation-stone of the theory was laid by Sidgwick and Powell in 1940 and further developed and
popularised by R.l. Gillespie and R.S. Nyholm in 1957. The basic principle of this theory has got a
similarity with that of Helferich's rules. In this theory, it is believed that the valence shell electrons
are oriented in such a way that there is a minimum electron-electron repulsion. The basic geometrical
skeleton is determined by the a-bonding and nonbonding (i.e. lone pairs) electrons. The x-bonding
electrons have got no marked effect in predicting the basic geometry of a molecule. It can only
slightly change the bond angle parameters. In this theory, it is assumed that the inner electrons have
nothing to do with the electron-electron repulsion in the valence shell. The theory yields mainly qualitative
results. It works well for the nontransition elements and symmetrical transition metals, Le. dO,.d 5 (weak
field) and d 10 systems having no crystal field stabilisation energy (CFSE).
The main electron-electron repulsiveforce operating among the valence shell electron pair domains
has been regarded as the Pauli force - electrons bearing the same spin cannot occupy the same space.
However, besides the Pauli forces, the simple Coulombic repulsive forces also work in the electron-
electron repulsive process (cf. Question No. 191). The theory can be formulated as follows.
Rule 1 (No nonbonding electron on the central atom)
ry
If there is no lone pair (Ip) su·rrounding the central atom, then the number of a-bonding electron
pairs will determine the geometry of the molecule and the geometry will be regular shaped. It will
be linear, trigonal planar, tetrahedral, trigonal bipyramidal and octahedral for 2, 3, 4, 5 and 6
ra
a-bonding electron pairs respectively. These correspond to sp, sp2, sp3, sp 3d and cfsp3 (or, sp3cf)
hybridisation of the central element respectively. For 7 a-bonding electron pairs, it may have three
ib
possible geometries, Le. pentagonal bipyramid, capped octahedron and capped trigonal prism. The
existence of pi -bonding electrons doesn't change the basic geometry of the molecules. Table 10.8.3.1
yl
gives the result of the Rule 1.
Actually the geometries given in Table 10.8.3.1 predict the orientation ofthe electron pairs (excluding
m
the 7t-electrons) around the central atom. If all the electron pairs are treated as the a-bonding pairs, then
only the regular geometries are attained. But, if some of the pairs remain as nonbonding pairs then the
he
distorted structures will result which will be discussed in the next rules.
Examples: Some of the examples having only different numbers of bonding pairs are given in Fig.
lc
10.8.3.1.
Application ofBent's rulefor different substituents : The complication arises when the substituents
ea
are different in electronegativity. For examples, CCI4, CF4 are tetrahedral but CHzFz, CHzClz, CH3CI,
CHCI3, etc. are not perfectly tetrahedral. The % s-character utilised in a particular bond depends on the
th
electronegativity of the substituent. With the variation of s-character in the bonding orbitals (Le.
e/
F X X
/~\
I~ , ~oo"" I
t.m
R CI I "1
/ / I .... B\... , X .: .p 120 0
R-B o=c F~--'~~F ',I

" R "CI ' I
" I
'I" I
F X X
(BF-4) (PX s, X =CI, F)
F F F 0
/~~'~\-:tF
Fi-/· ~~
tI", o~/-//~~'
1 :0
,~.~ X,,,'
!,'X S ~
F "90°
\ A I
70°'
F,
, 1\
0"
Xe 'i,
F~-:'lTI'
',\'1
F F~\\._
.~F/ O~-'tl':ffo
',\/1
" F F
"0
(SFa) (AF 7 ) (A=I, Ret) (Xe~ -) (0_= PF 3)
Fig. 10.8.3.1. Structures of some covalent compounds in which no lone pair on the central atom exists.
Table 10.8.3.1. Idealised orientation of the electron pairs leading to the minimum repulsion around the central
atom.
No. of a-bonding Geometrical position Bond angle Shape Examples

pairs (considering of the a-bonding pairs XAX
no non-bonding pair)
(i) 2 linear (sp); • NO;, N20, CO2, Cd12,

:-A-: HgCl z' Ag(CN);, etc.
ry
(ii) 3 trigonal planar (sp2); BX3 (X =F, CI, Br, R),
/.
° = CCI2 , S03' NO;, 'Co;- ,
ra
:-~. CH;, etc.
~"I
ib
(iii) 4 tetrahedron (sp 3); CH4 , NH;, BF4 , AsH;, PH;,
.( .snX4 ' SO;-, 0= PF3 , CIO;,
yl
A PCI;, Xe04 , S20;-, PO~-,
.(.1.\'
SiO:-, BHi, S02C/2 etc.
m --~,\\\\\\\\\\
(iv) 5 trigonal bipyramid (sp 3d) 90 (XaxAX eq )
he
·f/·. 120° (X eq AXeq )
:-f.. . .:
lc
(v) 6 octahedron (sp3d2 ) SeF6 , TeF6 , SF6 , PX~, SiF62-,

ea
:,·f/·. S2Fio, XeO:-, etc.

A
"/.1.'.,
th
(vi) 7* pentagonal bipyramid 90° (X ax ~Xeq)

(sp 3d 3 ) 72° (X eq AXeq )
e/
",1/"
A-:
"/.1.'.,
t.m
capped octahedron
capped trigonal prism
* ZrFi- (both pentagonal bipyramidal and capped trigonal prismatic geometries), NbF/- (capped octahedron),
nonequivalent bonding orbitals), the'bond angle changes. These facts can be explained by using the
Bent's rule (see Sec. 10.8.2 and Sec. 9.13.7) -which has been already discussed. The VSEPR rule on
the electronegativity difference (Le. Rule 3, which will be discussed later) can also explain the structural
changes from the regular geometries.
• In the case of PC/s (where the axial bonds are longer), no problem regarding the distribution of
the five identical substituents arises, but in PC/JFZ the position of the different substituents cannot be
predicted from VSEPR theory very clearly (see the VSEPR rule on electronegativity difference). Bent's
rule predicts that in a trigonal bipyramidal (FBf) geometry, more electronegative atoms will prefer
the axial positions (Fig. 10.8.3.2).
• In 0 = Cel2 and 0 = PF3 due to the 7t-bonding leading to bond F CI

multiplicity in a particular bond, according to Bent's rule, more
s-character is utilised by the central atom to the direction ofthe multiple
bond. This is why, CICCI '< 120° in COCl2 and FPF < 109° 28' in
o = PF3 • This structural change due to the 7t-bond can also be
"",111
CI<.. PI\J:
""', :
rationalized by another rule of VSEPR which will be discussed later. " I
' ... I
F CI
Rule 2 (Effect of nonbonding electrons on the central atom)
Fig. 10.8.3.2. Structure of
ry
When the central atom bears both the bond pairs (bp) and lone pairs PCI 3F2 •
(lp), the structures are deviated from the regular geometries pre-
ra
dicted from the Rule 1. The repulsive power of the lone pairs is much
greater than that of the bond pairs. The order of repulsion varies as:
ib
lone pair-lone pair (lp /lp) » lone pair-bond pair (lp / bp) »
bond pair-bond pair (bp/bp).
(lone pair)
yl
To justify the sequence, we are to compare the nature of spatial
orientation of lone pairs and bond pairs. The bond pair is getting
m
concentrated between the nuclei while the lone pair remains under the
A<:=>X
control ofonly one nucleus (i. e. the nucleus ofthe central atom). This (bond pair)
he
is why, the bond pairs are tightly held between the nuclei while the lone Fig. 10.8.3.3. Distribution
pairs are relatively loosely bound in space. Consequently, the lone pairs of lone pair and bond pair
require more space compared to the bond pairs (Fig. 10.8.3.3). electron clouds with
lc
respect to the nuclei.

With the increase of angle of repulsion, the effect of repulsion
decreases as: 90° > 120° > 180°. As a matter offact, the repulsions at 900 are the most important
ea
factors to be considered and such repulsions provide the key guidelines in predicting the geometries.
Examples:
th
Planar vs. Pyramidal structure of NH3 : If :NH3 adopts the planar structure keeping the lone pair
in a pure p-orbital, then bp-bp repulsions at 120° are less severe compared to the bp-bp repulsions at
e/
about 109.5° of the pyramidal geometry but the planar structure introduces 3 lp-bp repulsions at 90°.
These lp-bp repulsions at 90° will destabilise planar system more compared to the pyramidal system
t.m
where all the repulsions occur at about 109.5°.

Effect of bond length : Shorter bond length makes the bp-bp repulsion more severe to widen the
bond angle. If A-X> A-Ythen X -A-X < Y-A-Y (cf. NH3 vs. NF3 , H2 0 vs. F2 0, CH3 vs. CF3 ).
Steric crowding and bond angle: More steric crowdin.g widens the bond angle more (cf. PBr3 vs.
PCI3 )·
(A) Cases where the number of Ip +-bp = 4, (i.e. sp3 hybridisation, tetrahedral distribution)
Each of the species of NH3,PXJ, CIO:;, SnCI:;, HJO+, CH:;, SOC/2 etc. is containing a lone pair
along with three bond pairs. Because of the higher lplbp repulsions compared to those of the bp/bp
interactions, the angle between the bond pairs will be contracted. Hence, inter-bond angles must be less
than 109.5°. If the number of lone pairs is raised to two as in H20 (Le. 2 lp, and 2 bp), the more severe
Ip/lp repulsion will contract the bond angle more compared to the species having only one lone pair.
This prediction is supported from the comparison of bond angles in CH4 , NH3 , H2 0.
Molecules: CH4 NH3 H 2O

1
No. of lp : 0 1 2
No. of(lp + bp) : 4 4 4
Bond angle: -- 109.5° 107.5° 104.5°
Deviation from the regular
tetrahedron bond angle : 0 2 5
(i) -eHJ vs. -CFJ : The CH3 radical is planar and CF3 radical is pyramidal. The C-F (~ 136 pm)
ry
bond is much longer than the C-H (~ 109 pm) bond and the electronegativity sequence is
X(F»> X(C) > X(H)· This indicates that bp-bp repulsion (cf. electronegativity rule ofVSEPR,
ra
Rule 3) in CHJ is much higher than that in CFJ. In fact, in CH3, the repulsions are: bp-bp »
odd electron-bp, while in CF3 , the odd electron-bp pure p-orbital
ib
H·"'0
repulsion is slightly larger than the bp-bp repulsion.
Thus to minimise the bp-bp repulsion in CH3, the bond
" V- rr--sfi3
angle opens up to 120° (Le. sp2 hybridisation of C)
keeping the odd electron (in a pure p-orbital)-bp
m
repulsion at -- 90°. In CF3, C is approximately sp3
yl
hybridised and all these repulsions occur at 109.5°. In
H/O-H
srJ2
V:,/!\ ~s~
\..) _ .
he
fact, in CF3, the bond angle is slightly decreased due Fig. 10.8.3.4. Shapes of CH3 and CF3
radicals (cf. Fig. 9.13.7.1).
to the odd electron-bp repulsion.
lc
The result can also be explained by Bent's rule. This aspect has been discussed in Sec. 9.13.7..
(ii) +CHJ (planar) -CHJ (planar) -:CHJ (pyramidal)
ea
-(3 bp Le. 6e) (3 bp + 1e Le. 7e) (3 bp + lip, Le. 8e)

+CH3 is planar and -CH3 is pyramidal. These are expected from VSEPR. The planar structure of
th
-CH3 radical can also be interpreted in terms of VSEPR and Bent's rule.
(iii) :N(CHJ)J (pyramidal) vs. :N(SiHJ)J (planar), :C(CN)i (planar) vs.: C(R)i (pyramidal)
e/
VSEPR theory for (3bp + lip) predicts the pyramidal struct~re but :N(SiH3 )3 and :C(CN)]
adoptthe planar structure. This is a/ailare 0/ VSEPR theory. The 1t-bondings N(2p) ~ Si(3d)
t.m
and C(2p) ~ C~(1t·) determine their planar structure. To allow the said 1t-bonding,
sp2-hybridisation of the central atom is encouraged so that the lone pair can be suitably placed in
a pure p-orbital.
(B) Cases where the number of Ip + bp = 5 [i.e. sp 3d hybridisation, trigonal bipyramidal

(TBP) distribution]
(i) 3 bp + 2 Ip : Each of the molecules like CIFJ, BrF3, etc. contains two lone pairs on the central
atonl along with three bond pairs. Now we are to determine the positions to be occupied by the
lone pairs in a TBP in which all the five positions are not equivalent. The set of three equatorial
positions which are equivalent is different from the two axial positions which are equivalent.
Now, three possible is~meric structures of CIF3 (Fig. 10.8.3.5) are to be considered. Here the
repulsions at the angle i'200 which are less important are ignored. We get the following repulsions
at 900 which are important to determine the degree of repulsive forces.
~Oli
F F
~/I~J:
E)CI: <...... CI\JI
G) I Structure I : Ipllp = 0; Iplbp = 4, bplbp = 2
. 1\0
.... I
.::! "1'" :
F F
Structure II : Ipllp ='; Iplbp =3, bplbp = 2
SJructure III : Ipllp =0; Iplbp =6, bplbp =0
F
(i) (if) (III)
ry
Fig. 10.8.3.5. Three possible structures of CIF3 .
In moving from the Structure I to Structure II, one Ip/bp repulsion is converted into a Ip/lp
ra
repulsion which is more severe,
Le. 1 lplbp (Structur,e I) -+ 1 lpllp (Sructure II).
ib
Similarly, in moving from the Structure-I to Structure III, two bp/bp repulsions are converted
into two lp/bp repulsions which are mo~e destabilising,
Le. 2 bplbp (Structure I) -+ 2 lplbp (Sructure III).
yl
m
Thus it is evident that the Structure I leading to the T-shaped molecule is the most stable one. It
may. be noted that the Bent's rule also predicts the same structure. This predictioin has been
he
supported by the experimental fact.
Bond length and bond angles : The finer analysis of the Structure I suggests that the axial
CI-Fax bonds are acted upon by two lone pairs and one bond pair at 90° (other interactions at the
lc
higher angles are ignored). On the other hand, the equatorial CI- F eq bond is acted upon by two
bond pairs at 90°. The lp-bp repulsion is more severe than the bp-bp repulsion. Hence it is
ea
expected that CI- Fax:::'CI- Feq and Fax elF

eq < 90° (cf. experimental data, CI- Fax = 170 pm,
Cl - F eq == 160 pm, Fax CIFeq = 87.5°). The relatively longer bond length in the axial directions
th
can also be explained by considering the nonequivalent hybridisation (Le. sp2 + pel) and Bent's
rule.
e/
Similarly, BrF] also assumes the T-shaped· structure. In XeF3+ (T-shaped), the bond angle
Fax - ~-.Feq is810. •
t.m
(ii) 3 lp + 2 bp : Let us consider the species I:; or lei;' in which three lone pairs and two bond pairs
are to be distributed in the TBP geometry. In the three possible structures of ICI;' (see Fig.
10.8.3.6), the electron pair repulsions at 90° (ignoring the repulsions at 120°) are as follows:
~:'I O·f1~1 CI CI
,," K7"
C1
• I
,," : "
/111
0 "
<''':", I
I
Q ,\:
"
I : ~ I I
~601
I
,~ .... .
1\.:0
CI
r"'",~
V~CI
......• "I
(i) (ii) (iii)
Fig. 10.8.3.6. Three possible structures of ICI 2.
Structure I: Ip/lp = 0, Ip/bp = 6, bp/bp = 0

Structure II: Ip/lp = 2, Ip/bp = 4, bp/bp = 0
Structure III : Ip/lp = 2, Ip/bp = 3, bp/bp = 1 /,fl( ::G;(
Thus in moving from Structure I ~ Structure
II, two Ip/bp repulsions are converted into two
~s\ 1 F~::" s\ l
more unfavourable Ip/lp repulsions; and in
moving from Structure I ~ Structure III, one
l'\:F 'f'\:F
F F
Ip/bp repulsion transforms into one
ry
OJ (il)
bp/bp repulsion which is energetically more
favour-able, but it is accompanied with the Fig. 10.8.3.7a. Two possible structures of SF4 .
ra
much more unfavourable transformations, Le.
F F F
2lp/bp ~ 2Ip/lp. This is why, the Structure J
. ~I'O C· ~~F O=~::::F
ib
is the most stable one which is linear. Because
of the same ground, /; is also linear.
C I 'F
F
I 'F
F
. I F
F
yl
(iii) I lp + 4 bp : In each of the species like :SF4 ,
:TeCI4, : ClOF3 etc. one lone pair and four bond
-
OCIF = 1090
-
FSF =103 0
-FSF =110
0
-
m
pairs are to be distributed in a TBP geometry.
Out of the two possible structures (see Fig.
FSF (SF4) = 179 0 -
(Bond angles at the equatorial plane)
FSF (OSF4) = 178.5°
he
(Bond angles at the axial direction)
10.8.3.7a) of a such species (say, SF4), again
consideration of the electron pair repulsions Fig. 10.8.3.7b. Bond angle parameters in OCIF3 ,
lc
only at 90° (ignoring the repulsions at the SF4 and OSF4 ·

angle> 90°) suggests the Structure I to be more stable. The repulsions are as follows:
ea
Structure I : Ip/lp == 0, Ip/bp = 2, bp/bp = 4; Structure II : Ip/lp = 0, Ip/bp = 3, bp/bp = 3.

Here in moving from Structure I ~ Structure II, one bp/bp repulsion is transformed into a ,Ip/bp
th
repulsion which is energetically more unfavourable.
Position of lone pairs and bond lengths in a TBP geometry: In general, it can be concluded
e/
from the VSEPR rule that in a TBP, the lone pairs preferably occupy the eq'!atorial position.
The lp (equatorial)-bp (axial) repulsion makes the axial bond longer and XaxAXeq bond angle
t.m
less than 900 (cf. CIFJ , XeFJ+ etc.). The same conclusion can also be drawn from the Bent's
rule which has already been discussed (see Sees. 10.8.2 and 9.13.7).
Note: Now let us illustrate the application of Bent's rule to improve the prediction over VSEPR.
In SF4 and OSF4 , the axial F SF bond angles are not far away from the idealised bond angle
180°. The slight decrease is quite expected due to the repulsion at 90° by the lone pair or the
double bond (afat bond) on the axial direction. But the large deviation ofthe bond angle in the
equatorial plane can hardly be explained by VSEPR. When the lone pair or fat bond contracts
the axial bond angle by 1-1.5° through the repulsion at 90°, this repulsion at 120° can never cause
the so large deviation (e.g. 120° - 109° == 11 ° in OCIF3 , 17° in SF4 , 100 in OSF4 ). Consideration
of Bent's rule can improve the result.
In the equatorial plane, three sp2-hybrid orbitals are available. The lone pair (which is under the
control of a single nucleus) predominantly occupies the s-orbital and consequently the p-character
is enriched in the other two equatorial bonds to contract the bond angle. The higher contraction
in SF4 compared to that in OCIF3 can be explained by considering the electronegativity effect
(cf. Rule 3 of VSEPR). The higher electronegativity difference (-- 1.5) between Sand F, takes
away the bond pair electrons more toward~Ft~Jduce the bond pair-bond pair repulsion (cf.
electronegativity difference between CI and O"is '- 0.5 and between CI and F it is -- 1.0). Thus
compared to OCIF3, in SF'4,the bond pair-bond pair repulsion at the equatorial plane is
less severe and the bond angle is less opened up.
In OSF4 , the bonding electrons in 0 = S bond are concentrated °more towards 0 and consequently
the effect ofthis double bond is less than that ofthe lone pair (which is mainly concentrated on
ry
the central S-atom) to contract the equatorial F SF bond angle. This makes the equatorial bond
angle larger in OSF4 compared to that in SF4 • There is another possibility for OSF4 : the x-bond
ra
may not lie in the equatorial plane. This aspect will be discussed later (cf. Fig. 10.8.3.13). See
Fig. 10.8.3.13 to consider the related molecule H 2C = SF4 and the effect ofthe trbond plane.
ib
(C) Cases where the number of Ip + bp = 6 (i.e. sp3d 2 hybridisation, octahedral distribution)
yl
(i) 2 Ip + 4 bp : Let us take the cases like XeF4 , lCI;, BrF4-, etc. where for each species, two lone
pairs are to be placed along with the four bond pairs in six equivalent positions of an octahedron.
Ifwe consider the two possibilities (Fig.
m
F
10.8.3.8) for the species say, XeF4, it is
F~,-_::-Yi-- FI~--_~
he
evident that the Structure I (trans- F ----,
1 I I •• I
directions of the lone pairs) is more 1 I I I
lc
stable. The comparison of electron pair I I I '

1
repulsions at 90 in the Structures I and
' "ON Vi
, Xe I I X -- 1
ea
~ ~ I I
Ld
II is given below: , I \ I I e ,
I I \ I I • 1
Structure I: Ip/lp = 0, Ip/bp = 8,
bp/bp = 4 ,- - V - - - -i '- - I FI 1_ - - :. ~
th
F •• F
Structure II : Ip/lp = 1, Ip/bp = 6, F
r) r~
e/
bp/bp = 5.
Thus in moving from Structure I ~ Fig. 10.8.3.8. Two possible structures of XeF4 .
t.m
Structure II, one Ip/bp repulsion is

converted into a bp/bp repulsion which is favourable, but it also leads to a more unfavourable
conversion, 1 Ip/bp ~ 1 Ip/lp. This is why the Structure I leading to a planar geometry is more
stable.
12C/6 (dimer of lC/ 3 ) possesses two
bridging CI-atoms and there are two square
planar IC/4 units bridged by the bridging CI- :I,f)-;~I
,~ I
atoms. Thus around each I-centre, there are , 1 I
4 bond pairs and 2 lone pairs; and the lone
pairs are in the trans-direction as in XeF4 •
:/I..",:CI
CI--tJ-
The I2C/6 molecule is planar (Fig. 10.8.3.9).
Because of the same ground, lCI; adopts (1 2 Cl s ) (ICI 4 )
the square planar geometry (4 bp + 2 Ip). Fig. 10.8.3.9. Structures of '2 C/s and ICI;,.
(ii) lip + 5bp: Let us consider the species like

TeFs-' BrFs ' IFs ' XeOF4 , XeFs+ etc. in which for each
species, one lone pair is to be accommodated along with F~,--
-"::'n---~IF
I \ I I
'"
the five bond pairs in the octahedral geometry in which the I \ I I
I \ I I
six positions are equivalent. Hence, any position taken by
the lone pair will lead to the square pyramid geometry. The Br ,':
k\
~---\...-I>J.
I \ I I
repulsion (at 90°) by the lone pair on the four adjacent bond I \ I I
pairs will enforce the four adjac~nt fluorine atoms to
F' --; IF
ry
, \ I /
move downward somewhat. Consequently, the central
atom will remain out of plane and the bond angle will be
"
, \
\ . .,
I .,"
'F
~q - A- Fax < 90°, where A stands for the central atom. The
ra
Fig. 10.8.3.10. Structure of BrFs.
structure of BrFs is shown in Fig. 10.8.3.10 as a
representative one in this group.
ib
Bond length in the basal plane of trigonal bipyramidal (TBP) and
yl
square pyramidal (SP) geometry having a lone pair
• TBP: When Ip + bp == 5, it can adopt the TBP geometry by placing the lone pair(s) in the equatorial
m
positions. It happens so for the molecules like AB4(lp), AB3(lp)2' AB2(lp)3. In ABs' there is no loner
pair. In such cases, the bond length in the basal i.e. equatorial plane is shorter than that in the axial
he
direction i.e. A-Bax > A-Beq • This can be explained in terms of (sp2 + pd) hybridisation scheme. The
--+-'ft'IIloAbr-cater s-character in the equatorial bonds makes the bond shorter. In terms o/VSEPR, in TBP,
lc
each axial pair experiences repulsion from the three equatorial pairs at 90° while each equatorial
pair experiences two such repulsions from the axial pairs (ignoring the repulsion at angle higher
ea
than 90°). This is why, in TBP, the axial bond is longer than the equatorial bond. Ifth~re is any
lone pair in the equatorial plane, the lp (equatorial)-bp (axial) repulsion will make BaxABeq _less
th
than 90° (cf. e1F3 , XeF3+ etc.).

• SP : In the case of ABs(lp) as in BrFs' the square pyramidal geometry is attained in terms of
e/
VSEPR. The lone pair (which occupies the lar~er space compared to the bonding pair) will repel the
four basal A-B bonds strongly to make B - A - B less than 90°, It will elongate the basal A-B
bonds. In fact, in BrFs' all the F - iir - F angles are less th.an 90° and the basal Br-F bond is
t.m
longer than the axial Br-F bond.
(D) Cases where the number of Ip + bp =7 or 9

XeFs- (5 bp + 2 lp) is pentagonal planar with the lone pairs in axial directions (Fig. 10.8.3.11) in
which Ip-Ip repulsion is minimum.
XeF4 + [N(CH 3 )4]F ~ [N(CH 3 )4]+ XeFs-
XeF6 (whose structure will be discussed separately in detail later) can
combine with 2r- ions to produce XeFs2- (8 bp + lip) which is a square
antiprism. Simple VSEPR model cannot explain this regular structure
which cannot accommodate the lone pair. This lone pair is
stereochemically inactive. The aspect regarding the stereochemically . Fig. 10.8.3.11. Structure
active and inactive lone pairs will be discussed later on in detail. of XeF s'
(E) Relative effects of nonbonding odd electron and lone pair

In the series, NO; (nitronium ion), eN02 (nitrogen dioxide), :NO~ (nitrite), there is a progressive
-increase in the number of nonbonding electron by one along with a reduction of N - 0 bond order from
NO; ~ N02 ---» NO;. The bond angle 0 -- N- 0 varies in the series as : 1800 (NO;), 135° (N02 ),
1ISo (NO;). l'his observation can be explained from the VSEPR theory by considering the most stable
resonating structures.
o ~ N+ = 0 (NO;): Linear as no nonbonding electron exists on the central atom (cf. Rule I).
I-:~ (N0 2) : Angular because one nonbonding elect~on (i.e. odd electron) repels the bond
ry
0'1 1350 0 pairs and the order of repulsion is : odd electron Ibp > bplbp.
..
ra
;,N\ (NO;): It is angular. The lone pair is more repelling than the odd electron, Le.
//----:.~\ lplbp > odd electron Ibp > bplbp.
ib
0'111500
Rule 3 (Effect of electronegativity difference between the combining atoms; cf. effect of-
yl
polarisation)
The XAX bond angl~
decreases with the increase of electronegativity of X. This can be justified
m
as: with the increase of electronegativit)' of X, the bond pairs will be concentrated towards X and as a
result, the bp/bp repulsion decreases' and consequently, the bond angle decreases (Fig. 10.8.3.12). In
he
this regard, effects of 1/;~bonding, bond length and steric effect are to be considered simultaneously.
Steric crowding widens the bond angle. Here, it is worth noting that the consideration ofBent's rule in
lc
connection with the different electronegativities ofthe substituents leads to the same conc/~sH)n.
A A A
ea
~
Bond length and VSEPR: Shorter
bond length makes the bp-bp repulsion
more severe to widen the bond angle
th
B y
B (e.g. A-H < A-F and HAH > FAF ct.
B
(a) B (b) B (c) 8 NH3 vs. NF3J H2 0 V5. OF2J CH3 vs. CF3
e/
(Bond pairs almost (Bond pairs attrc..cted (Bond pairs attracted etc.
I
on the midways) towards A) towards B) .......- - - - - - - - - - - -

t.m
Fig. 10.8.3.12. Effect of electronegativity (X) difference of the combining atoms on bond angle.
(a) XA ~ Xs; (b) XA > Xs; (c) XA < Xs; bond angle sequence y > a > p.
Examples : Ba~ed on this rule, let us try to explain the bond angle sequence in the following series:
(a) Pl3(---I02°»PBr3(---101.5°»PCI3(---1000» (Eftect ofP1t-dn bonding,
PF) (--- 98°) > PH3 (--- 94°) steric crowding and bond
(b) Asl3 (--- 101°) > AsBr3 (--- 100°) > AsC/3 (--- 98°). length are to be considered
(c) NH3 (--- 107°) > NF3 (--- 102°). also).
(d) OH2 (--- 104.5°) > OF2 (--- 104°).
(e) NH3 (--- 107°) > PH3 (--- 94°) > AsH3 (--- 92°) -- SbH3 (--- 92°); J Cost of hybrid isation and
(f) H 20 (- 104.5°) > H 2S (~ 92°) > H2Se (- 91°) > H 2 Te (- 89.5°). hybridisation state are
also to be considered
(g) O=CX2 (X=CI,Br,H): H-C-H (116.5°» CI-C-CI (112°» F-C-F (i08°)
For the examples (a) - (f), the bond pairs and lone pairs are assumed to be placed in the tetrahedral
arrangement. Because of the existence of the lp/bp and/or lp/lp repulsion(s), the bond angl'e is always
decreased from 109°28'. In (a) and (b), the electronegativity of the halogens runs as, F> CI> Br > I.
Thus the bond pairs are removed from the central atom in the above sequence to decrease the .bp/bp
repulsion. For the halides, steric crowding will widen the bond angle in the sequence, I> Br> CI> F.
In (c) and (d), the bond len~h A-F > A-H makes the bp-E.p repulsion more in the compounds of
hydrogen and it makes the H AH angle larger than the FAF angle. Moreover, fluorine is'more
electron~gativethan hydrogen and as a result, in the fluorine containing compoun<ils the bond angle
ry
is always decreased compared to the corresponding hydrogenous compounds because of the decreased
bp/bp repulsion in the fluorine compounds. Possibility of Pn - dn bonding to widen the bond angle is
to be considered also for the pair PHJ and PFJ•
ra
• Nonapplicability of VSEPR for the hydrides of Gr. VA(15) and VIA(16) : In the hydrides of
ib
Gr VA( 15) and VIA( 16), Le. (e) and (f) series, it can be attempted to explain the bond angle sequence
in terms of electronegativity ofthe central elements. With the increase ofelectronegativity ofthe central
element, the bonding pairs are more concentrated towards the central atom to expand the bond angle.
yl
Here it is worth mentioning that the VSEPR theory is a ~ualitative one. Hence, the small difference in
bond angles in the successive members of a series can only be qualitatively rationalized from the
m
VSEPR theory. But such a large deviation, e.g. 109.5° --+ 90°, cannot be justified from the VSEPR
,heory which can take care of deviation by a few degrees only at best. It is better to tackle the
he
problem in terms of cost ofhybridisation (see Sec. 9.13.4) which' has been already discussed.
lc
Bent's Rule vs. VSEPR Rule of Electronegativity (Rule 3) and Polarisation

For AXn , acc.ording to Bent's rule, with the increase of electronegativity of X, s-p hybrid orbitals Of
ea
more p-character of the central atom (A) will be concentrated along the A-X bonds. This will ler
to shrink the X -A - X bond angle. VSEPR rules of electronegativity and polarisation j
th
predict the bond angle shrinkage with the increase of electronegativity of X Thus, both B
rule and VSEPR theory predict the same result.
e/
Rule 4 (Effect of multiple bonds i.e. 7t-bonds) d It

.bon s.
t.m
The multiple bonds containing the 1r-bonds along with the a-bond are/atter than the sinlre d to the
is reasonable as the 7t-electron clouds are less tightly bound between the nuclei ~'d to a single
a-bonding pairs. Thus, the bonding pairs in a multiple bond occupy more space comto the single
a-bond system. This is why, the multiple bonds create more repulsions comp,'
a-bonds. The magnitude of the repulsion follows the sequence : -bond.
I
ma
multiple bond/multiple bond> multiple bond/sigma-bond> sigma _bontP
(A) Cases where pi-bonding introduces bond multiplicity _ 0)

d PH (HPH ,...,94
(i) When the central atom acts as a 1t-acceptor : Let us take the compo· s ..3 ,. e Rule 3)
- egatlvlty ,l. • ,
and PFj(FPF - 98°) for illustration. According to the rule of elecf n I t egative than
the reverse order ofthe bond angles is expected, because fluorine i~nore: eCpFfon nd PH can
.- 0 .-
hydrogen (cf. NF3 and NH3, F NF = 102 < H - N - H = 107 ). T~
° trend In
.-..
3a 3.
t possible In
be explained by considering the 1t-bonding, i.e. Pll(F) ~ dll(P), in F 3 and thIS IS no
PH3 as hydrogen has got neither nonbonding F ~ P - F ~ F - P ~ F ~ F - P - F

pair nor any vacant orbital. This type of I I It
7t-bonding is also not possible in NF3 and NH3 F F F
because nitrogen is not having any vacant orbital to participate in the pi-bonding. Thus we can
consider the above resonating structures in PF3•
It is evident that each P - F bond gets some 7t-bond character in addition to the a-bond, and the
bond order is greater than unity to introduce the bond multiplicity. Because of this bond
multiplicity, the bond pair/bond pair repulsion is increased to widen the bond angle. In NF3,
NH3 and P~3' only the a-bond/a-bond repulsion exists.
ry
Note: eThe observed bond angle runs as : PF3 (-- 98°) < PC/3 (-- 100.3°) < PBr3 (-- 101°) < PI3
(-- 102°). The Pn~dn bonding is most efficient in PF3 while it is least efficient in PI3 in terms of
ra
orbital size and energy matching. It suggests that bond angle widening effect due to
Pn - dn bonding decrease gradually from PF3 to PI3 • But the effects of electronegativity and
ib
steric factor oppose the sequence. The steric crowding widens the bond angle in the sequence,
PI3 > PBr3 > PC/3 > PF3• From the experimental findings, it is evident that the effect pn-dn
yl
bonding to widen the bond angle is offset by the effect of the electronegativity difference
between P and X and size of the halogens.
m
e The bond angle comparison between PH3 and PF3 in terms of d n ~ Pn bonding only is not
well justified. In terms of cost of hybridisation, in PH3, phosphorous cannot adopt the sp3
he
hybridisation but in PF3 , the required hybridisation is energetically more feasible.
(ii) When the central atom acts as a x-donor: In terms of electronegativity, the bond angles in the
lc
series, OF2 , OCl2 and OH2 should run in the sequence, F - 0 - F < CI- 0- CI < H - 0- H,
but experimentally it is found as: F - 0 - F (= 103°) < H - 0 - H (104.5°) < CI- 0 - CI (111°).
ea
The observed sequence can be explained in terms of 7t-bondig, Le. 2Pn(O) ~ 3dn(Cl), which
only occurs in OCl2 among the above compounds.
th
/~""- ~ ,y0""- ~ /0'c/

e/
CI ·CI C/ CI C/
bjxistence of a such 1t-bonding widens the Cl - 0 - Cl bond angle due to the enhanced
t.m
therepulsion. Here it is worth noting that due to the engagement of the oxygen lone pair in
bonanding, the lpllp repulsion also decreases. It indirectly helps the opening up 0/ the
bond ~{e. For fluorine and hydrogen, no such bond angle widening factor exists. Hence, the
electro 'e order for these two compounds (i.e. H 2 0, F 2 0) will be governed by the
nt ..
r-- ~
..lVlty rule and bond length effect
In this 'd angle widening : Central atom - x-acceptor vs. x-donor
connection..
pair of the i.
. IS Important to cone Iu d e t h at I·f t he 7t- b ond·Ing (.In resonance ) Invo
· Iyes th e 1one
increase of~e~lra 'm as in OCI2 , the bond angle gets opened up due to the two reasons, Le.
repuISion(s): ~ rep<;ion for the enhanced bond multiplicity; and decrease oflp/lp and/or lp/bp
n
the cent~al t 1 e cen'fJI atom. On the other hand, if the 7t-bonding involves the vacant orbital of
a om as in .
repulsion for h J1f3, then the bond angle gets widened only due to the increased bp/bp
~_ _---::__1_e~en:.::h..::a:.:n~c~6b ond multiplicity.
(B) Prediction of the position of a multiple bond in a TBP geometry and the effect of a
multiple bond on bond angles: Plane of the x-bond
We have already noticed that to minimise the repulsion in a TBP geometry, the lone pairs are preferably'.
placed in the equatorialpositions. In terms ofrepulsive power measured by the volume ofspace occupied
by the bonding--electron cloud, the multiple bonds (Le. a + 7t) are comparable with the lone pairs. This
is why, the multiple bonds are positioned preferably in the equatorial plane. In the equatorial plane,
the s-orbital of the central atom is concentrated and the equatorial bonds are relatively shorter. This
reduced bond length favours the better 7t-interaction (sidewise overlap) in the equatorial plane. This
ry
factor operates for the preferential occupancy of the 7t-bonding or multiple bonding ligands at the
equatorial plane. Let us take the case of 0 = SF4 in comparison with :SF4• In SF4, the lone pair is
ra
positioned in the equatorial plane and because of the above mentioned ground, the double bond
(Le. 0 = S) is also placed in the equatorial plane (Fig. 10.8.3.13).
ib
F F PI~ne
t
containing C-S a-bond, F
yl
I ~ 2 C-H and 2 S-Fax bonds.
~ ; /;:
o,/·i~/r1 /--~ ;-;"7:
m
;/1 IH ;/f'1
tS\l l\F! {~/-~~~~~i\!
he
1'.', ' 0:,'
lc
F 1 F 'F
ea
A 0 ,1700
FaxSFax = 179 178.5°
A 970
FeqSFeq = 103
0
110°
th
Fig. 10.8.3.13. Structures of SF4 (sulphur tetrafluoride), OSF4 (thionyl tetrafluoride) and H2 C=SF4
(methylene tetrafluoride (cf. J.E. Huheey, Inorg. Chern., 20,4033, 1981; K.O. Christe and H. Oberhammer,
e/
Inorg. Chern., 20, 296, 1981).

• Fax SFax =180 (ideal TBP), FeqSFeq=120 (ideal TBP).
o o
t.m
H
• In CH2 = SF4 , the sigma skeleton ~C-S lies in a plane perpendicular to 'the basal or equatorial
H
plane of TBP. Thus the 7t-bond lies in the equatorial plane.
Qualitatively, the effect ofa lone pair is comparable to that ofa double bond (cf. Table 10.8.3.2).
Now let us critically analyse the relative effects ofa lone pair and a double bond (10' + 17t) lying in an
equatorial position of a trigonal bipyramid geometry. The examples under consideration are:
:SF4 (sulfur tetrafluoride), O=SF4 (thionyl tetrafluoride) and H2 C = SF4 (methylene su/fur-
tetrafluoride) in each case, one double bond or a lone pair lies in an equatorial position (cf. Fig.
10.8.3.13). '
The lone pair (Ip) is always cylindrically symmetrical in the equatorial position and its effect on
the bond angles is quite straight forward. On the other hand, for a double bond, its effect on the
bond angles depend on the plane in which the 7t-bond exists. In a double bond, the (J and 7t-bond
exist in two mutually perpendicular planes. If the ~bond exists in the equatorial plane, then it
affects the equatorial bond angles more.
It is evident (cf. Fig., 10.8.3.13) that for :SF4 and H2C=SF4, the repu'lsive effect of the double
bond on the equatorial F-atoms is larger compared to the effect of a lone pair. It is due to the fact
that the H-atoms lie in a vertical plane containing the axial F-atoms and the x-bond involving the
p-orbital of carbon atom is concentrated in the equatorial plane. T~e repulsion by this 7t-eleGtron
cloud on the equalorial S-Fbonds causes the severe contraction in F'eqSFeq bond angle. In O=SF4, the
bond angle (F - S - F, equatorial plane) contraction is not so severe. It may be due to two reasons:
ry
'0' being more electronegative concentrates the electron cloud ofthe double bond away from the central
atom; the 7t-bond may not lie in the equatorial plane.
ra
Note: To explain the variation of bond angles in the equatorial planes in the molecules like OCIF3,
SF4 and OSF4 , the knowledge of Bent's rule is quite helpful (cf. Fig. 10.8.3.7b). This aspect has
ib
already been discussed.
yl
(e) More examples to Illustrate the effect of1t-bondlng on bond angles
• Effect of 7t-bonding and multiple bonding in widening the bond angle runs as :
m
multiple bond/multiple bond> multiple bond/single bond> single a-bond/single a-bond.
• If the central atom acts as a x-donor in back bonding then the bond angle opens up more compared
he
to the case where the central atom acts as a x-acceptor.
• In a trigonal bipyramidal geometry, if the 7t-bond lies in the equatorial plane then its bond angle
lc
wiqening effect on the equatorial plane is more compared to the other possibility involving the 7t-
bond in a plane perpendicular to the equatorial plane (cf. H2C = SF4 ).
ea
All these have been already illustrated.

It has already been argued that qualitatively both the double bond and lone pair occupy more or less
th
equal space which is larger than the space occupied by a single a-bond. This is why, the effect of a
double bonded oxygen or sulfur atom is qualitatively equivalent to that of a lone pair (cf. Table 10.8.3.2)
e/
in terms of steric repulsion. However, for a double bond, the repulsive effect depends on the plane in
which the trbonding electron cloud is concentrated.
t.m
Table 10.8.3.2. Comparison of the effect of double bond and lone pair on bond angle
Species X-A-X Species X-A-X

Q=PF3 102.5° (98°) 0=SF2 92.5° (98°)
0= PCl3 103.5° (100°) 0= SBr2 96°
0= PBr3 108° (101°) 0=CF2 108°
S=PF3 100° 0= CCl2 112°
S= PBr3 106° 0=SF4 11 0° (X eq AXeq) (1 03°)
178.5° (XaxAxax ) (179°)
The values within the parentheses correspond the bond angles ofthe nonoxygenated molecules,
e.g. :PF3 , :PCI3, :SF2 and :SF4 • Thus these bond angles represent the effect of the lone pairs.
• 0 = PXJ : For a particular series of compounds (0 = PX3) having different halides, the bond
angles can be interpreted by considering two facts :
effect ofelectronegativity and efficiency of d7t-P7t bonding in the 'P = 0' linkage.
The effect of the strength of such 7t-bonding interaction (cf. Sec. 10.7) is quite important to explain
the bond angle sequence. With the increase of electronegativity of X, the d 1t-p1t bonding
O(2P1t) ~ P(3d1t ) interaction increases because of the contraction of d-orbital of phosphorus atom. The
P = 0 bond length sequence runs as :
0= PBr3 ) 0 = PCI3 ) 0 = PFj
ry
Thus the P = 0 bond is thefattest one in 0 = PFJ and this causes the maximum repulsion between
the 0 = P and P - F bonds. Thus the shortest and. consequently the fattest P = 0 bond causes the
ra
repulsion maximum to contract the F - P - F bond angle and widen the 0 - P- F bond angle. Here
it should be mentioned that in terms of electronegativity rule (Le. Rule 3) also, the bond pair-bond pair
ib
repulsion among the P-X bonds is minimum for the .,P-F bonds among the P-F, P-Cl, P-Br and P-I
bonds. Thus in terms of both O(2p,J --. P(3d7t ) x-bonding effect and electronegativity rule, the
yl
F - P- F angle is expected to be minimum among the halo-compounds. Steric effects of halogen
also support the same bond angle sequence.
m
Thus the bond angle in OPX3 runs as: Br-P-Br >Cl-P-Cl> F-P-F.
• S = PXJ and 0 = SXz : Because of the same grounds (Le. effect of the efficience of
he
d1t ~ Pn (0, S) bonding, electronegativity effect and steric factor), the bond angles run as :
- - ~ ~
lc
SPXJ : Br-P-Br > F-P-F;OSX2 : Br-S-Br > F-S-F

• 0 = CXz : For OCX2, molecules, consideration'of electronegativity rule (Le. Rule 3) can explain
ea
the sequence where the bond length ~ffect (small~t C-H bond~plays also an important role:
F - C - F < CI- C - CI < H - C - H.
th
• 0 = CF2 vs. F2C = CF2 : In the compounds 0 = CF2 and F2C = CF2 where the 'c = C (in C2F4 )
bond is longer than the 0 = C (in OCF2) bond (cf. covalent ~
e/
radii of C and 0, Table 10.2.1.2) Le. C = 0 bohd is flltter F ~ {

than C = C bond. It explains the bond angle sequence : ~260 ~:p~~sTo~) - bp (0)
t.m
C-~~~\
0
. 108
F-C-F:C2 F4 (l14°»OCF2 (108°) ~~
• 0 = CF2 : The 0 = CF2 molecule is expected to have
a symmetrical trigonal planar structure as both the 'F and
F 7
135 pm
120 pm
'0" atoms are of comparable size and electronegativity. But Fig.' 10.8.3.14. Structure of COF2 •
in reality, the molecule is highly distorted (Fig. 10.8.3.14). Combined effect of a-7t electron cloud
It is due to the effect of the C = 0 double bond (10' + In) on bond angle in COF2 •
which requires more space than a single bond. The shorter (120 pm) and fatter C = 0 bond than the C-
Fbond (135 pm) widens the OCF bond angle and con~racts the FCF bond angle.
• 0 = CXz : The X - C- X bond angle sequence in 0 = CX2 where X = H, Cl, Br has been
explained by the electronegativity rule and the effect of bond length.
• C = 0 bond vs. C = C bond: t is important to compare the bond angles in 0 = CF2 and C2F4 (Le.
F 2C = CF2 )·
It has been already explained. It is due to the fact that the C = C bond is larger than the C,,~ 0 bond
(cf. covalent radii of C and 0) Le. C = 0 bond is fatter than the C = C bond. The repulsion caused by
C = 0 bond is more severe to cause F - C- F bond angle contraction more. Similar observations are
noted for the related compounds.
H -C - H (C2H 4 ) ~ 120 0
) H- C- H (0 =CH2 ) ~ 116.5 0
;
Cl-C - Cl (C2CI4 ) ~ 114.50 ) Cl-C -Cl (0 =CCI2 ) ~ 1120

• F 2C= CF2 vs. H 2C= CH2 : The F - C- F bond angle in C2F 4 (114°) is less than the H - C- H
ry
bond angle in C2H4 (120°). It can be explained by considering the Bent's rule according to which more
p-orbitals ofcarbon are concentrated along the C-F bonds (compared to the C-Hbonds) and consequently
ra
more s-character of the C~atoms is concentrated in the C = C bond ofC2F4 (compared to C2!j4). It
leads to two developments. Firstly, the more p-character along the C-F bonds will reduce F - C - F
ib
bond angle to widen the F - C- C angle.
Secondly, because of the more s-character in the C = C bond in C2 F4• Thus it is shorter i.e.
yl
fatter than that in C2H 4• Thus the C = C bond in C2F4 is fatter than that in C2H 4 and it causes the
C - C- F angle to widen and the F - C- F angle to contract more compared to the case of C2H 4 •
m
• C2H 4 : It is important to mention that in C2H4 , the H - C- H angle is slightly shorter than ~he
he
ideal bond angle 120°. It is due to the effect of the enhanced repulsion between the C = C and C-H
bonds. It is also partly due to more p-Character in the C-H bonds to provide more s-character towards
the double bond (cf. Bent's rule).
lc
• 1t-bonding electrons and shapes ofthe molecules: The 7t-bonding electrons have nothing to do
with the shapes (Le. basic geometries) of the molecules. This is illustrated with some examples.
ea
(i) HCN, i.e. H-C ===N molecule: There are 4 bond pairs (20' + 27t) around the central atom C.
The 7t-bond pairs do not contribute to determine the shape of the molecule. Thus, the 2 a-bond
th
pairs make the species linear. This prediction is verified.

e/
(ii) CZH 4• i.e. H)C= C(HH :There are 3 cr-bp + Irc-bp around each C. Ignoring the effect of the
H
t.m
7t-bond pair, the presence of3 a-bond pairs should make each CH2 unit triangular planar. In fact,
the molecule is planar. .
(iii) C1NO i.e. / N~ : There are I lp + 2 bp (cr) + I bp (rc) around the central atom N. The
C/ 0
presence of 2 a-bp and 1 Ip makes the species V-shaped.
(iv) COClz i.e. o=c(CI : There are 3 cr-bp + 1 rc-bp around the central atom C. Ignoring the
Cl
effect of 7t-bp, the molecule should be planar and in fact it is a planar molecule.
(v) COS (carbonyl sulfide) i.e. 0 =C =S : There are 2a-bp + 27t bp around the central atom C.
The 7t-bp electrons are not involved to determine the shape of the species. Presence of 2a-bp
electrons makes the species linear.
Thus it is evident that the 7t-bonding electrons do not contribute to determine the basic geometry
of the molecular species. However, they may contribute to effect the bond angle parameters as
the double bond (a fat bond) can cause more repulsion than a single a-bond. This aspect has been
illustrated in many examples.
Rule 5 (Effect of completely and incompletely filled valence shell)

Any repulsive force (Le. lp/lp or lp/bp repulsion) to contract the bond angle is more significant for
the incompletely filled valence shell compared to the completely filled valence shelL
In the case offilled valence shell ofthe central atom, the electron pairs cover all the space around
the atom. Hence, anyforce intending to contract the bond angle is resisted by the other electron pairs.
ry
Thus for C, N, 0 and F, Le. the members of second row, they can accommodate maximum four electron
pairs tetrahedrally directed. For such systems, the lone pairs can at best alter the bond angle by a few
ra
degrees only from 109.5° as in the case of :NH3 (107°) and :OH2 (104.5°). On the other hand, the
members (e.g. P, S, etc.) of the third row can accommodate mor~ than four pairs due to the availability
ib
~f the 3d-orbitals. If.such members are tetrahedrally surrounded with four electron pairs, then the
repulsion by the lone pairs can more drastically contract the bond angle from 109.5° as in the cases of
yl
PH3 (94°), H 2S (92°), etc. (cf. NH3 , H 20). However it is worth mentioning that the effect of
electronegativity difference is also to be accounted for.
m
But such a large deviation in the case of the hydrides of the 3rd period elements can be better
rationalised in terms of cost of hybridisation as discussed in Sec. 9.13.4.
he
In this regard, it is quite interesting to consider the bond angles for the gaseous alkaline earth
dihalides MX2• For Be and Mg, the bond angle is close to 180° but, for the heavier congeners it approaches
lc
towards 100°. For BeX2 and MgX2, the valence shell is filled, but, for the heavier congeners, the presence
of d-orbitals can allow them to accommodate more than 8 electrons in the valence shell. This is why,
ea
the lone pair - bond pair repulsion is expected to be more severe to contract the bond angle for the
heavier MX2 species. However, for the overall picture, the otherfactors like electronegativit>: difference,
polarisation ofcentral atom, cost ofhybridisation, etc. are to be also considered.
th
• Concept ofpolarisation of central atom and bond angles in gaseous alkaline earth dihalides :
e/
It has been attempted to explain the variation of structural parameters for alkaline earth halides in terms
ofpolarisation of the central cation (M2+).
t.m
Polarisation ofthe central cation (M21 by the anion (X) : It will make the MX2 molecule bent and
this polarisation will be facilitated if the central element projects the orbitals enriched in p-character
towards the halides. Introduction ofmore p-character by the central atom in M-X bonding will make
the molecule more angular [cf. sp (Le. 50% p-character) orbitals produce 180°, sp2 orbitals (Le. 33.3%
p-character) produce 120°, pure p-orbitals produce the 90° bond angle]. This polarisation will be most
favoured for the largest cation (i.e. Ba 2+) and smallest anion (i.e. r). It explains the bond angle
shrinkage from BeX2 to BaX2 (for a particular X) and MI2 to MF2 (for a particular M 2+). In terms steric
factors and electrostatic repulsion by the halides, the bond angle widening is also expected to increase
from r to r. This prediction is in good conformity with the experimental observation.
For PO-: BeF2 (180°») MgF2 (-160°») CaF2 (-140°») SrF2 (108°») BaF2 (-100°)
For cr: BeCI2• MgC12' CaCl2 (180°») SrCI2• (-120°») BaCI2• (_100°)
For Br- and r : All are linear except for BaX2•
Structural parameter of alkaline earth halides M~ : Bond length effect,

VSEPR rules 3 and 5; Bent's Rule
Really it is a vexing problem to rationalise. However, it has been attempted to understand the
problem in terms of the following factors:
electrostatic and steric repulsion by the halides; Bent's rule controlling the distribution ofs- and
p-orbitals of the central atom; polarisation of the central atom; bond length effect; VSEPR
rules 3, 5, etc.
Concept ofpolarisation ofthe central element and bond angle variation in other compounds: In
ry
the same way, by considering the concept ofpolarisation ofthe central element, the bond angle sequence
in each of the pairs like NH3 ) PH3 (P is more polarisable than N), H 2 0) H 2 S (S is more polarisable
ra
than 0), PI3 ) PF3 (F is more polarising than T) can be explained. However, in such cases, we should
consider the effects of bond length, electronegativity difference (VSEPR rule 3), steric factors, cost
ib
of hybridization, Bent's rule etc. for a complete analysis.
yl
Molecular geometry and MOT: Walsh Rule
Walsh Rule can also predict the geometries in terms of MOT. These aspects have been discussed in
m
Chapter 13.
10.8.4 Shape of the Molecules having Stereochemlcally Active Lone Pairs Predicted from
he
VSEPR Theory
Some representative examples are given in Table 10.8.4.1
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Table 10.8.4.1. Shape· of some molecules haVing stereochemically active lone pairs according to VSEPR
ea
theory*
Number Geometry for the Types of Configuration Examples
ofIp + bp distribution ofelec- electron (shape)
th
tron pair domains pairs

3 Triangular (sp2) 2 bp + lip V-shaped
e/
t.m
4 Tetrahedral (sp3) 3 bp + I lp Trigonal pyramidal NH3, NR 3, H30+, PX3, Xe03' NF3,
~
. XO; (X = CI, Br, I), SO;-, CH;
"11
'/1111
~
2 bp + 21p H 20, F 20, C/20, SC/2, XO; (X =
CI, Br, I)
(Contd.)
Number Geometry for the Types of Configuration Examples

of/p + bp distribution of electron (shape)
electron pairs pairs
1 bp + 3 Ip Linear HX, OX- (X = CI, Br, I)
~
.. .
ry
5 Trigonal bipyramidal 4 bp + lip Distorted TeBr 4 , SF4, TeC/4 , Xe0 2F 2
(sp 3d) tetrahedral
ra
ib
yl
3 bp + 21p T-shaped
m
he
2 bp + 3 Ip Linear
lc
ea
6 Octahedral (sp 3cJ2) 5 bp + lip Square pyramidal

th
e/
t.m
4 bp + 21p Square planar
7. Pentagonal bipyramid 6 bp + 1 Ip Distorted octahedron XeF6, XeOFs-

(sp 3tP)
5 bp + 21p Pentagonal planar
* The geometries for the molecules having no lone pair are given in Table 10.8.3.1.
10.8.5 Concept of Stereochemically Active and Inactive Lone Pairs: Structure of XeF6 (xenon
hexafluoride) and Related Species .
• Difference between the stereochemically active and inactive lone pairs : Let us first discuss the
properties of stereochemically active and inactive lone pairs before to T;onsider the structures of
XeF6 , XeF82- and related species. The lone pairs which do not participate in determining the structure
of the species are referred to as stereochemically inactive lone pairs. In such cases (e.g.
: SbBr:- , : TeCli-, : TeBrl-, etc.) the number of bond pairs determine the shape or geometry of the
species. It is believed that in such cases, the stereochemically inactive lone pair exists in an unhybridised
ry
s-orbital inside the shell and-- the lone pair cannot come to the surface of the molecule. On the other
hand, the lone pairs which reside in some hybridised orbitals and actively participate in determining the
ra
molecular shapes as expected from VSEPR theory are called stereochemically active lone pairs.
• Nature of the lone pair in :SbBr:-, : TeCli- and
ib
: TeBr;-: Gillespie has explained that when the steric crowding
is sufficiently high as in the cases of SbBr:-, TeCli- , TeBr62 - ,
yl
the lone pair will be forced to remain in an unhybridised s-orbital
inside the valence shell. Such lone pairs contribute nothing to XeF:
m
increase the steric crowding but shield the valency electrons
from the attractive force towards the nucleus. In such cases, it
he
is quite reasonable to predict that though such lone pairs are not
important to deteffiline-the-shape ofthe molecu1e, the bond lengths
will be elongated because of the shielding effect of the Fig. 10.8.5.1. Structural features of
lc
tetrameric XeFe Le. (XeFe)4 in solid

stereochemically inactive lone pairs residing inside the valence
state. Four square pyramidal XeFs+
ea
shell. This bond length elongation will eventually reduce the

units are bridged by four F- ions
steric crowding around the central element. This prediction has (Xe - F in square pyramidal unit =
been supported in many cases. In TeBr62-, the observed bond 184 pm, Xe-Fin bridge = 230-260
th
length (= 275 pm) is larger than the calculated bond length pm). 0 for Xe, • for bridging F.
(= 250 pm, sum ofthe covalent radii). Her~, it may be mentioned
e/
that the concept of 3c-4e bond model (cf. Sec. 9.13.5 and 9.23) involving only the p-orbitals of the
central atom (cf. Sec. 9.13.5c) also predicts the bond order less than unity.
t.m
• Nature of the lone pair in :XeF6 : In the case of fluorides (smaller in size than cr, Br-), the
steric hindrance is relatively less. In fact, in :XeF6 which is isoelectronic with : TeBr62- , : TeBr62- ,
: SbCli-, etc. the steric crowding is not sufficiently high to confine the lone pair exclusively inside
the valence shell ~s a stereochemically inactive one. The lone pair may exist to some extent to the
molec,:!lar surface. T~us the lone pair in :XeF6 is in the border line in terms ofthe properties ofthe
stereochemically active and inactive lone pairs. This is why, the problem for :XeF6 is more complicated.
• Prediction ofthe structure of:XeF6 in terms of VSEPR : Now let us consider the case of:XeF6
with 6 bb + lip. In terms of simple VSEPR theory (considering the lone pair to be stereochemically
active) :XeF6 should have the pentagonal bipyramid geometry placing the lone pair in one position of
the pentagonal bipyramid geometry through sp 3eP hybridisation (cf. IF7 , ReF7 , etc.). If the lone pair
is considered to be stereochemically inactive, then XeF6 should have the perfect octahedral structure.
In reality, the problem is complicated and the structure depends on the sample phase under
consideration. -
Characteristic features of the lone pair on :XeF6

• Generally, a lone pair occupies more space compared to a bond pair, but in :XeF6 , the lone
occupies less space compared to the bonding pairs.
• It is neither perfectly stereochemically active nor inactive. In other words, it is of border line
character.
• Because of the special properties of the lone pair of XeF6 , the distortion is less than expected
from the VSEPR theory.
ry
• Structure- of XeF6 in solid state : Let us first consider the structural features of XeF6 in solid
state. In solid state, no discrete XeF6 molecule exists and the solid consists of square pyramidal XeFs+
ra
cations extensively bridged by free fluoride ions. In such square pyramid moiety, xenon sits at the basal
plane. However, the bridging fluorides ,maintain a good deal of covalency. Through F-bridging,
hexameric, tetrameric and trimeric rings of XeFs+ F- are produced. : XeFs+ is expected to be of square
ib
pyramid shape (cf.: TeFs-': BrFs ': IFs ': XeOF4 , etc.) as expectedfrom VSEPR (Le. the lone pair is
stereochemically active).
yl
• Structure of XeF6 in vapour phase: In the vapour phase, it exists as a monomer, XeF6 which
appears to have a slightly distorted octahedral structure but the distortion is less than expected from
m
VSEPR theory. Another important characte~istic feature is its fluxional character. If :XeF6 is considered
to possess a stereochemically active lone pair, then it has got three possibilities (Fig. 10.8.5.2), Le. (i)
he
capped trigonal prism (I), (ii) pentagonal bipyramid (II) having th~ lone pair projected along one
corner ofthe equatorial or basal plane (in terms of octahedron, the lone pair is plojected through the
lc
mid:point of an edge); and (iii) capped octahedron (III) (the lone pair is projected through the centre
ofa trigonalface ofan octahedron, Le. the lone pair lies along the C3 axis). Thus in no way, it can have
ea
a regular geometry. Here we can recall the prediction of the simple molecular orbital theory involying
3c - 4e bonding for the F-Xe-F segments lying mutually at right angles. This suggests it to have a
th
regular octahedral geometry (Sec. 9.23). Thus the problem is not settled theoretically.
F
e/
F "
" /"')I ..... , .......... .....
t.m
F~ F I ..... ,
~
.... "F~ __ - --- F
I
I
"~-'"..
J! II .F,,~F
~I ........
, '" Xe /'
,,",," '\ •• ,,~.
I Xe •• 1
l~X\ F~t'~V::,/
F,~~-- I
'~ /
// F F~---1~1
"~
..... II
"'1
. ."
..... ,
.......... I,,"I "
"
..... , 11 '
F
F F
I (Capped trigonal prism) II (Pentagonal bipyramid) III (Capped octahedron)
Fig. 10.8.5.2. Three possible structures of XeFe.
Experimentally, the molecule is found to be dynamic to fluctuate with time. An intramolecular

rearrangement leads to the interchange of the fluorine positions. Thus it shows thefluxional behaviour
(see Sec. 10.9), Le. stereochemical nonrigidity. <It is proposed that the capped octahedron (III) (C3v
symmetry) suffers the configurational interchange with the pentagonal bipyramid (II) (C2v symmetry).
The energy difference between the two

forms (Le. III and II) is not very high.
The conformation III (C3v) is
marginally stabler than the
conformation II (C 2v ). Hence, such an
LfI~
~F~~F~F~r~F~~
4Bs 4~F-
interconversion is highly possible. F F F
Capped Pentagonal Capped
In fact, the lone pair continuously octahedron bipyramid octahedron
interchanges (Le. fluxionality) its
Fig. 10.8.5.3. Fluxional behaviour of XeFs. The lone pair
ry
position among the different possible
interchanges its position between the centr~s of different
positions, Le. centres of the triangular triangular faces and the centres of the edges.
faces and centres of the edges of a
ra
regular octahedron. Thus the time average structure represents the real situation. The interchange
of position,ofthe lone pair is shown in Fig. 10.8.5.3.
ib
Thus for the monomeric :XeF6 species we are left with the following conclusions:
(i) distorted octahedral structure by considering the 6 bp + 1 Ip (stereochemically active
yl
lone pair),
(ii) regular octahedral geomefry by considering 6 bp + 1 Ip (stereochemically inactive lone
m
pair),
(iii) regular octahedral geometry in ter~s of 3c-4e MO formation.
he
• XeF6 vs. TeX:- , SbBrt- : Thus the problem of :XeF6 is much more complicated compared to the
isoelectronic species like: TeXi- (X = CI, Br),: SbBr:- which adopt the octahedral structure keeping
lc
the lone pair (stereochemic~lly inactive) in an unhybridised spherical s-orbital inside the valence shell.
In :XeF6 , probably because of less steric crowding, the lone pair has got some border line character
ea
and it complicates the theoretical prediction.

• :XeF6 vs. :XeFs2-: In this connection, the solution to the problem of XeFg2- (8 bp + lip) is
th
much m~re straightforward. Here, the steric crowding is sufficiently high (compared to :XeF6 ) to
convert the lone pair into a stereochemically inactive one. In fact, it adopts the square antiprism
e/
where the lone pair contributes nothing to determine the molecular shape.
t.m
XeF6 + 2CsF ~ Cs 2 [XeFgl
Structures of fluoro compounds of xenon

..
:XeF :XeFs+ :Xe~- :XeF6 :XeFS2-
4
(4 bp + 2 Ip) (5 bp + lip) 2
(5 bp + Ip) (6 bp + lip) (8 bp + lip)
(Planar) (Square (Pentagonal (Distorted octahedron, (Square
pyramid) planar) fluxionality) antiprism)
Increasing steric crowding around Xe (qualitative sense)
Stereochemically Lone pair of border line Stereochemically

active lone pairs character, and the lone inactive lone pair
pair occupies less space
compared to a bonding pair
• :XeF6 vs. :XeFs+ : In :XeFs+, the steric crowding is relative less compared to :XeF6 and it allows
the lone pair of :XeFS+ to be stereochemically active.& It adopts the square pyramidal structure (5 bp +
1 Ip) as expected from VSEPR. Thus compared to the steric crowding in XeFs+ and XeFl-, the steric
crowding in XeF6 is of an intermediate character (Le. neither too high nor too low) and this situation
imparts the border line character ofthe lone pair ofXeF6•
10.8.6 Limitations of VSEPR theory

The success of the theory has been illustrated in earlier sections. Here we shall 'point out the major
limitations :
ry
(i) Stereochemical activity and inactivity ofthe lone pair~' : The concept ofsteric crowding attempts
to justify whether a lone pair will be stereoc1)emically active or inactive. But, it is very much
ra
difficult to predict in advance which lone pair is stereochemically active and which one is
stereochemically inactive.
ib
For the heavier main group elements e.g. In l , Til, Sn ll , Pb ll , Sblll , Bi lll , Te IV , etc., the lone
pair is stereochemically inactive and it is remaining confined in an inner s-orbital.. A
yl
stereochemically inactive lone pair contributes nothing to determine the shape of a molecule.
This is why, the species like TeXi- (X = CI, Br), SbC/~- (each bearing a stereochemically
m
inactive lone pair) are octah~dral. On the other hand, the isoelectronic species XeF6 (6 bp + lip)
possesses a lone pair having some border line properties because of less steric crowding around
he
Xe (cf. Sec. 10.8.5). Consequently its structure cannot be predicted in a straight-forward manner
from VSEPR theory.
lc
It is quite interesting t,o note that the structure of XeFs- (5 bp + 21p) (having the pentagonal
planar structure) can be explained by VSEPR. Here the lone pairs are considered to be
ea
stereochemically active and they reside in the .trans-axial directions to minimise the repulsion.
But, astonishingly the theory fails to explain the structure of XeFg2- (8 bp + lip) which adopts
the regular square antiprism structure having no provision to accommodate the lone pair. It is
th
believed, that because of an enhanced steric crowding in XeFg2- the stereochemically inactive
lone pair resides in an inner s-orbitaI. Similarly, the lone pair in SnC/l is stereochemically
e/
active but the lone pair in SnCI;- is stereochemically inactive. .

(ii) Pi-bonding andfate ofthe lone pair: The pyramidal structure of :N(CH3)3 or :P(SiH3)3 is quite
t.m
expected from VESPR theory, but the planar structure of :N(SiH3 )3 cannot be explained by the
theory. In fact, strong 7t-bonding interaction can remove the effect of lone pair. Because of
N(P) ~ Si(d) 1t-bonding, :N(SiH3 )3 is planar. Similarly, : C(CN)~ is planar because of strong 1t-
bonding, C(p) ~ CN- (1t.) but :CR~ (R = non-1t-bonding group) is pyramidal as expected from
VSEPR. In fact, the said species changes from pyramidal to planar when 1t-bonding is favoured.
(iii) Large deviation: A large deviation from the ideal bond angles (e.g. NH3 vs. PH3, H20 vs. H2S~
alkaline earth dihalides, etc.), cannot be explained by VSEPR which can accommodate the
structural change by a few degrees only. In such cases, it is required to consider the other concepts
like cost ofhybridisation, polarisation ofthe central atom etc.
(iv) Effect of CFSE : VSEPR theory does not work for the transition metal complexes having CFSE
(crystal field stabilisation energy).
(v) Effect ofionic character: The compounds having ionic character predominantly do not follow
the VSEPR rules. Thus Li20 (with 2 lone pairs on 0) is linear.
(vi) Minimisation of lone pair-lone pair repulsion in different conformations: The structures of
N 2H 4 (with one lone pair on each N) and H 20 2 (with two lone pairs on each 0 atom) are quite
interesting. The lone pairs are kept separated as far as possible in gauche conformations (cf.
Fig. 10.5.3.5).
N2H4 adopts the gauche conformation. However, the lone pair - lone pair repulsion could be
minimised if it would have the staggered or anti-conformation. This is a limitation of VSEPR.
P2H4 in gaseous phase adopts the gauche conformation, but in solid phase, it adopts the staggered
conformation. N2F 4 exists in both forms.
ry
(vii) Nonquantitative treatment: VSEPR cannot yield any quantitative result.
(viii) Effect of delocalised 1t-electron cloud: The systems having the delocalised x-electron cloud
ra
cannot be tackled well in the light of VSEPR theory.
(ix) Alternative bonding model: The alternative bonding model through the formation of multicentre
ib
MOs (without d-orbital participation) can explain the geometries of several molecules (cf. Sec.
9.13.5). This model does not consider the repulsion of electron cloud. For example, the 3c-4e
yl
bonding model predicts the perfect octahedral structure of XeF6 •
m
10.9 STEREOCHEMICALLV NONRIGID COVALENT MOLECULES :
he
FLUXIONAL MOLECULES
There are some cases in which the configuration of the molecules changes without any rupture of
lc
covalent linkage. Some such cases will be discussed here.

ea
10.9.1 Atomic Inversion in Amlnes, Phosphlnes and Arsines

Walden inversion is well known in the chiral centre of sp3 carbon in the SN2 process. A similar inversion
th
(like an umbrella turning inside out and vice-versa) in NH3 without any breaking of N - H bond is
possible.
e/
t.m
Inversion energy barrier: Now let us consider the magnitude of inversion energy. For NH3, it is
23.4 kJ mol-I and the inversion process is very fast (ca. 10 11 S-I, 20°C). For XMe 3 , the inversion
'-J
energies (in kJ mol-I) are: 34 (X= N), 133 (X= P), 122 (X= As) and 112 (X= Sb). The optical isomers
for XR'R"R'" are stable under ordinary conditions, if the inversion energy is at least ca. 100 kJ mol-I.
Thus the asymmetric tertiary phosphines and arsines can be resolved.
Ammonia clock: The inversion process of NH3 occurs at a fixed rate at a particular temperature.
The frequency ofoscillation of its inversion is ,taken -as the basis for the UiiU oftime. It gives the
ammonia clock.
The inversion process in amines and phosphines passes through the planar geometry in which the
central element remains in the sp2 state. Thus the bond angle changes as :
sp3 (N), (- 109°) ~ sp2 (N), (- 120°) ~ sp3 (N), (- .109°)
The magnitude of inversion barrier depends on the energy required in the transition, sp3 ~ sp2. If
the bulky groups are present, then the process requires a higher energy. Generally, in phosphines and
its derivatives the bond angle lies to - 90°. Hence, for these compounds, in reaching the transition state,
the bond angle distortion is much higher than that involved in the analogous nitrogenous compounds.
This is why, the phosphine derivatives always show more activation energies and provide more
ry
optical stability. Besides these, the nature (especially, electronegativity and bulkiness) ofthe substitution
also significantly influences the magnitude of the energy barrier.
ra
NMR time scale and racemisation rate: Now if we start with the trisubstituated amines (e.g.
NRJR//R!//) and phosphines (e.g. PR/R!/R///) which are optically active, then the inversion as in NH3 will
racemize the active molecules. If the energy barrier is high and it cannot be met by the thermal energy
ib
(= kBn available at ordinary temperature then the separation of the optical isomers (i.e. enantiomers)
is possible. In such cases, the progress of racemization can be followed by a conventional technique.
yl
But for the systems having a very low energy barrier, the separation of the enantiomers is not possible.
In such cases, the progress of racemization may be followed by a rapid spectrophotometric technique
m
like nuclear magnetic resonance (NMR) spectroscopy. If the energy barrier lies within the range of25-
100 kJ mol-I, then the rate of rearrangement lies in the range 102-10 5 S-I in the temperature range + 150
he
to -150°C. Thus by selecting a suitable temperature, the chemical environment ofthe individual structures
can be followed by NMR spectroscopy whose time scale is generally in the range of 10-2 to 10-5 s. Very
lc
often, at higher temperature, the rate of interconversion is rapid enough and the NMR technique cannot
detect the individual configurations. It gives the signal for the averaged environment. This is why, -
ea
to follow the rearrangement process, the NMR studies should be carried out in a wide raJl8e of
temperature.
th
10.9.2 Berry Pseudorotation and Turnstile Rotation

(a) Berry pseudorotatlon
e/
To highlight the "idea, let us take the pentavalent phosphorus compounds (TBP, sp 3d hybridisation)
t.m
which are generally stereochemically nonrigid. In PFs' there are two types of fluorine, Le. two axial
fluorines and three equatorial fluorines, but they interconvert so rapidly that all the fluorine atoms
appear indistinguishable by means of 19F NMR. The enthalpy ofactivation (Mf~ ofthis intramolecular
isomerisation (Le. axial fluorine ~ equatorial fluorine) is of the order of20 kJ mol-I. If the entropy of
the activation (M ~ is supposed to be negligibly small (a reasonable approximation), then the first
order rate constant of the process at - 100°C becomes of the order of - 106 S-I. Thus, it takes place
faster than the NMR time scale (generally, 10-2 to 10-5 s) and consequently all the fluorines appear
identical in the NMR study.
In PC12F3 (trigonal bipyramid), in the equatorial plane there are two Cl-atoms and one F-atom;
other two F-atoms are in the axial positions. The axial and equatorial F-atoms rapidly interchange
mutually. At temperature ~ - 22°C, the interchange process is so fast that NMR cannot distinguish
them (Le. one single doublet peak), but they can be distinguished at temperature < - 143°C by NMR.
To explain this low energy requiring rearrangement, R.S. Berry has proposed a mechanism !mown
as Berry pseudorotation. In this mechanism, it is believed that the trigonal bipyramid (sp 3d, Le. s + px
+ py + p: + d;Z) passes through the square pyramid (sp 3d, i.e. s + px + py + p: + dx2 _;) to another
trigonal bipyramid of different configuration. In this pseudorotation process, the two aXial groups are
interchanging with the two equatorial groups while the third equatorial group (referred to as pivot
group) remains as an equatorial group in both the configurations. Thus the transition state is a square
pyramid. The process is illustrated in Fig. 10.9.2.1. In this process, the axial angle (LA 1PA 2) of 180°
closes to 150° and at the same time, the equatorial bond angle (LE2PE3 ) opens up to 150° from 120°.
This situation produces the square pyramid geometry. Then the angle LE2PE3 opens up to 180°
(which leads to E2 and E 3 at the axial positions) and the angle LA 1PA 2 shrinks to 120°. Thus it is noted
that in the change of configuration of PFs' the starting and final products are identical and.
ry
indistinguishable. Hence in the process, ~Go = o.
ra
//~E2 I:~~ //11f 1
ib
E"::"'-P
~I
I
E P,\:
(/
E1~
/ P
1"':
I
yl
1 , ---+ 1 ---+ "\... I
............ : E3 .........
I '~
',I E3
m A .,/ A2
A2 ~ 2 E3
he
TBP (D 3h ) (Configuration II) (Square pyramid) (C4v ) TBP (D 3h ) (Configuration I)
Fig. 10.9.2.1. Berry pseudorotation pathway in a trigonal bipyramid. The bond angles at the intermediate
square pyramid are: LA 1PA2 = LE2 PE 3 = 150°; LE 1PA 1 = LE 1PE2 =LE 1PE 3 = LE1P~ = 105°; LA 1PE2
lc
= LE 3 PA2 = LE2P~ = LE 2PA 1 = 87°.

ea
Now let us consider the compounds MePF4 and HPF4 Here Me and H are less electronegative than
9
F. Hence in the stable TBP configurations, these less electronegative groups will occupy the equatorial
th
positions (Bent's rule). These groups, Le. Me or H, can act as the pivot group in the Berry pseudorotation
process. This is why, the barrier is low. But in R zPF3 (R = H, Me), one R remains as a pivot group
e/
but another R changes from an equatorial position to an axial position which is not energetically
favourable. This is why, such compounds face a higher energy barrier. For such stereochemically rigid
t.m
molecules, the observable exchange among the remaining F-atoms can be noticed.
Thus we can conclude that RPF4 experiences a low energy barrier compared to R2PF3 in
pseudorotation when R strongly favours an equatorial position
to act as a pivot group. It is possible when R is of low A1 A
electronegativity (according to Bent's rule, less electronegetive I/E 2 1 , ,/E2
groups favour the equatorial positions) or of good 7t-bonding E1 P -'

'
E3 I
---.
E-P-E
1 3 I
(R ~ vacant d-orbital of P) properties. The energy barrier
increases as, A2 ~
R PF > R PF > RPF Fig. 10.9.2.2. Turnstile rotation.
3 2 2 3 4·
Different 5-coordinate silicon compounds also show the Berry pseudorotation. It has been found in
connection with the racemization of the optically active silane derivatives (see Sec. 10.10.3.i, and vi).
Turnstile rotation : A second process called turnstile rotation can also lead to the pseudorotation
as discussed in Berry's pseudorotation. In this process, a pair ofsubstituents rotates in a turnstile nlanner
with respect to the remaining three groups. This is shown in Fig. 10.9.2.2. The NMR studies of ABs
molecules cannot discriminate the two possibilities, Le. Berry pseudorotatio"n and turnstile rotation, but
theoretically Berry mechanism is energetically more favoured.
10.9.3 Twisting Mechanism

Racemization of some tris-chelate complexes may be attained through a twisting mechanism without
any bond breaking. For example, the tris(ethylenediamine)cobalt(III) ion may racemise through trigonal
twist (or Bailar twist) and/or rhombic twist (or Ray-Dutt twist) as shown in Fig. 10.9.3.1.
ry
(Trigonal prism D3h
symmetry for M(AAh
ra
ib
yl
m
he
4
lc
(cis(fac~A) (Cis(fac)-A)
ea
(Trigonal prism C2v

th
symmetry for M(AA)3>

e/
t.m
6
I
I
I 60 0
4 6
(L\) (C 2v symmetry) (trans(merj - A)
Fig. 10.9.3.1. Twist mechanism of racemisation of M(A - 8)3 type chelate. (a) Baller twist (Le. trigonal
twist as the transition state is of D3h symmetry for M(AA)3 type chelate) through successive rotation
by 60° about a C3 axis and (b) Ray-Dutt twist (Le. rhombic twist, as the transition state is of C2V
symmetry for M(AA)3 type chelate) through successive rotation by 60° around the imaginary C3 axis
in octahedral tris-chelates leading to racemisation.
Let us illustrate the twist mechanism for M(A - B)3 type chelate. Ifwe consider the M(A - 8)3 type
chelate, the cis-isomer (Le. lac-isomer) possesses a real C3 axis passing through the two opposite
trigonal octahedral faces at which three A's and three B's are present. The cis-complex also possesses
three imaginary C3 axes passing through the other sets of trigonal faces. Thus, the cis-M(A - B)3
complex possesses one real C3 axis and three imaginary C3 axes. Bailer twist involves two successive
60° rotations in the same direction around the real C3 axis while Ray-Outt twist involves two successive
60° rotations in the same direction around an imaginary C3 axis. Thus Bailer twist on cis (~)-M(AB)3
gives cis (A)-M(AB)3 while Ray-Outt twist on cis (~)-M(AB)3 gives trans (A)-M(AB)3 (Le. both
ry
cistrans isomerisation and racemisation).
Ray-Outt twist (I.e. rhombic twist) vs. Baller twist (i.e. trigonal twist)
ra
Ray-Dutt twist: Rotation ofa trigonal face around an imaginary C3-axis generating a C2v transition
ib
state. For M(AB)3 type chelates, both chirality inversion and cis-trans isomerisation occur.
Bailer twist : Rotation of a trigonal face around a real C3 axis generating a trigonal prismatic
yl
transition state of D 3h symmetry. For M(AB)3 type chelates, only inversion of chirality occurs but
no cis-trans isomerisation occurs. m
Bailer twist and Ray-Outt twist can be alternatively represented as in Fig. 10.9.3.2.
he
lc
•
ea
(~) Octahedron (Trigonal prism) (A) Octahedron

th
(= trigonal antiprism) (5trigon~antiprism)
Baller twist: Rotation of upper triangle of chelate atoms by 60° converts octahedron (Le. trigonal
e/
antiprism) into a trigonal prism.

t.m
c > c >
(~) (octahedron) (A) octahedron

Ray-Dutt twist: Keeping one chelate ring fixed, out of the other two rings, one ring moves up
and the other simultaneously moves down through 45° to form the symmetrical intermediate.
Fig. 10.9.3.2. Schematic representation of Bailer twist and Ray-Dutt twist for M(A - A)3.
10.9.4 Fluxional Molecule : Fluxlonallty and Time Scale of Observation

Due to the existence of zero-point energy, even at 0 K the atoms in the moh~cules are vibrating about
their mean positions. Such vibrations are limited to 10-20 pm. Thus in true sense, no molecule is
absolutely rigid. But there are some molecules which suffer conformational rearrangements in
which at least some atoms actually interchange their positions. If the barrier of such stereochemical
changes is not high, then they can change their configurations by using the thermal energies available
at ordinary temperature. Such stereochemically nonrigid molecules are calledjluxional molecules.
The study of the stereochemical nonrigidity is generally carried out by NMR spectroscopy.
• Fluxionality and chemical equivalence ofthe configurations: Here it must be mentioned that
for the stereochemically nonrigid fluxional molecules, the configurations must be chemically equivalent.
For example, the complex NiX2(PR 3)2 may remain in a dynamic equilibrium, tetrahedral ~ square
ry
planar (an example of polytopal rearrangement) in solution. The position of the equilibrium varies
with the temperature. Thus th"e spectral and magnetic properties ofthe solution depend on the temperature.
Infact, these isomeric species are not chemically equivalent (cf. paramagnetic tetrahedral complex is
ra
green, while the diamagnetic square planar complex is brown).
ib
NiX2(P~)2 (planar) ~ NiX2(P~)2 (tetrahedral)
(8 = 0) (8 = 1)
This is illustrated for NiBr2(PEtPh 2 )
rI
:
yl
m
he
an
_/N"
Br PEtPh2
lc
PEtPh2
ea
(Tetrahedral. Green, (Square Planar. Red,

Paramagnetic) Diamagnetic)
th
At 40°C, tetrahedral (ca. 70%); kinterconversion = 1.6 x lOs s-I at 25°C.

Thus though NiXz(PR 3)z is stereochemically nonrigid, but it is not an example ofjluxional
e/
molecule. Examples of other polytopal rearrangements have been discussed below. .

Appearance of Fe(CO)s in terms ofir, Raman and 13C-NMR spectra: Experimental technique is
t.m
of much importance to identify the configurations of stereochemically nonrigid molecules. For example,
Fe(CO)s (penticarbonyliron) when analysed by infrared (ir) and Raman spectra, it indicates the presence
of two types ofcarbonyl groups, Le. axial (with Fe-e longer bonds) and equatorial (with Fe-e shorter
bond length) CO groups. But, llC-NMR studies cannot distinguish the axial and equatorial CO groups,
Le. ai/five CO groups are identicaL
Each experimental technique observes a molecule on a time-scale which is the characteristic feature
of the technique used. The infrared and Raman spectra techniques are much faster techniques
where the incident photon interacts instantaneously with the molecule to record the snapshot of
the structural features of the molecule. On the other hand, the NMR technique is a much slower
process and it actually records the time average structure of the molecule like Fe(CO)s. In fact,
mutual interconversion between the axial and equatorial CO groups in Fe(CO)s occurs much faster
thal1 the time scale ofNMR technique. This is why, the 13C-NMR technique cannot distinguish between
the axial and equatorial CO groups in Fe(CO)s.
Conformations of Molecules and Time Scale of Observation

By using the uncertainty principle, the time required to observe a molecule can be related with the
frequency of the exciting electromagnetic radiation. The energy and life-time of a particular state of a
molecule is related as follo~s :
!1E x ~t = h/21t
where ~ = spread of energy of the state; ~t = life-time of the state. In terms of the frequency spread
(~v) of the interacting electromagnetic radiation, the above relation is given by :
~(hv) ~t = h~v x ~t = h/21t
ry
1 1
Le. ~t~v=-·or ~t= ----
21tx~v 21tc~v
ra
21t"
It indicates that if the life-time of an ,excited state decreases, then its energy becomes less defined
ib
and the peak is broadened by ~v. On the other hand, if the life-time (~t) of the excited state increases,
the peak becomes sharp. Ifa particular state ofa molecule survives for 1 ps (= 10- 12 s), then the exciting
yl
radiation may cover the range of 160 GHz (1 GHz = 109 Hz) (Le. peak broadening occurs by 160 GHz).
Fig. 10.9.4.1 illustrates the peak broadening phenomenon depending upon the lifetime of the excited
m
state.
Note: For the sake of simplicity, ~v can be taken as '- v. It leads to : ~t ex:..!- Le. time scale is
he
v
inversely proportional to the frequency of the exciting radiation.
lc
:1 :1
ea
it
:c~
COO) ..o~
.c~
th
..o~
oe» ~~ COO)
ee» .c~
oe»c:
a.e»c:
~
a.ai ~
a.e»
e/
0 0 0
-+V -+V -+V
t.m
(a) (b) (c)

Fig. 10.9.4.1. Band width (Le. peak broadening) depending on the life time (L\~ of an excited state
(application of uncertainty principle). (a) very high (almost infinite) life time, (b) intermediate life time,
(c) very short life time.
Let us consider a particular molecule that can exist in two different configurations which respond to
'the frequencies VI and v2 for a certain spectroscopic technique. If ~t is the time required for mutual
conversion between the conformations, then each peak will br~aden by ~v (~
1 ). Now the two
x 21t . ~t
conformations will be indistinguishable if, VI and v2 lie within the range !lv. This condition for
indistinguishability is given by : .
The two conformations become distinguishable for the following condition :
1 1
flt > - - =- - - - -
21tfl V 21t (v I -- V2 ) 21tc (v I -- V2 )
The above conditions are illustrated in the Fig. 10.9.4.2. Ifin a molecule, the vibrational frequencies
of two mutually exchangeable groups differ by 50 cm- I , then the life times for the confonnations ml!st
be less than 0.1 ps= 10- 13 S (:::::~= 10 I _I _I) to make them indistinguishable
ry
27tcflv 21t x 3 x 10 cm s x 50 cm
spectroscopically.
ra
~t~_._l_= _
27t~V 27t(V1 - V2)
ib
yl
m
he
Fig. 1O~9.4.2. Shapes and positions of the peaks of two comformations depending on the life time of
the conformations.
lc
If the time requiredfor mutual interconvers;vn between two conformations ofa molecule is ~ery
ea
small, then for their spectroscopic identification, we must seek the interacting electromagnetic
radiation of very high_frequency. Table 10.9.4.1 gives the time scale of different spectroscopic
th
techniques depending upon the frequency· of the used electromagnetic radiation. If for a molecule, the
resonating frequencies (VI and v 2) of two different sites differ by 100 Hz in an NMR study, then the
e/
sites can be identified separately provided the life time of the states is larger than ca. 1.5 ms
( ~ 21t 1100 s). If the two sites show the difference of vibrational frequency by 10
t.m
12
Hz (= 300 cm- 1 in
x
terms of wave number), then the sites can be identified by vibrational spectroscopy if their life time is
larger than ca. 0.15 ps (::::: I 12

21t x 10
s). This is why, the vibrational spectroscopy can record (through
snapshot) the structural characteristics of an instantaneous conformation of a fluxional molecule.
On the other hand, NMR can identify the sites,"iftheir mutual conversion rate is much slower.
Thus the diffraction studies can take the very rapid snapshots of the instantaneous states of the
molecules. In fact, these interactions are much faster than the molecular motions. For the spectroscopic
methods like, ultraviolet, visible and infrared, the time scale is also much faster than the molecular
vibrations leading to interconversions. On the other hand, the techniques like NMR, etc. are much
slower and these can be utilisedforfollowing the molecular vibrations leading to the conformational
changes. In fact, the NMR technique has been widely used to flow the behaviour of the fluxional
molecules.
Table 10.9.4.1. Approximate time scale ( "" 2~V) of some common

spectroscopic techniques used in characterisation of structures.
Spectroscopic technique Time scale (s) (approximate)
Electron diffraction 10-20

Neutron diffraction 10- 18
X-ray diffraction 10- 18
Ultraviolet spectroscopy 10- 1S
ry
Visible spectroscopy 10- 14
Infrared spectroscopy 10- 13
ra
Electron spin resonance 10-4 to 10-8
Nuclear magnetic resonance· 10-2 to 10-5
ib
~ossbauer(Fe) 10-7
Chemical separation of isomers > 10 2
yl
• It may vary in the range 10- 1 to 10-9 s depending on the system.
m
10.9.5 19F-NMR Spectra and Fluxlonallty of PC/2 F3 and CIF3
he
• PC/2 F l : Now let us consider the behaviour of the molecule PCl2F3 (trigonal bipyramid, according
to Bent's rule, out of 3F-atoms, two occupy the axial posi~ions and one occupy the equatorial position).
Thus there are two types of F-atoms (Le. axial and equatorial). Tbe axial F-atom should resonate at
lc
downfield while the equatorial F-atom should resonate at higher field in 19F-NMR technique. It
may be noted that both 19F and 31p nuclei are associated with 1= 1/2. In fact, the signal due to 19F is
ea
split by 31p into a doublet (2 nl+ 1 = 2, n = 1).

At higher temperature ~ -22°C), 19F-NMR cannot distinguish the two types of F-atoms in PCl2F3
th
and it shows only one signal (Le. only one type of F-atoms) which is split into a doublet by 31p Le. the
P-F coupling (2nI + 1 = 2, n = I). However, at very low temperature « -143°C), it can show the
e/
existence of two types of fluorine atoms. The two axial F-atoms generate a downfield doublet 'of
doublets and and the single equatorial F~aiom
t.m
generates a uPfield doublet of triplets (Fig. A single doublet

~ (-22°C)
10.9.5.1). In fact, each component of doublet (by
P-F coupling) for axial F-atoms is further split into
a doublet by the equatorial F-atom. Similarly, each ~U~
component ofthe doublet (by P-F coupling) for the ~ A doublet of doublets
equatorial F-atom is split into triplets by two axial (-143°C) A doublet
F-atoms (2nI + I = 3, n = 2). Thus for PCI2F3 , the ~ 'Y of triplets
intercon-version rate between the axial and
equatorial F-atoms is slower than the NMR
observation time scale at temperature < -143°C. (Axial Fs) (Equatorial F)
The interconversion between the axial and ---+H
equatorial F-atoms occurs through the Berry's Fig. 10.9.5.1. 19FNMR spectra (not in scale)
pseudo-rotation. of PC/2 F3 at different temperatures.
• elF] : Now we s·hall consider the A doublet

1.raXialFS A triplet for the
19F-NMR spectrum of CIF) (T-shaped
1quatOrial F
molecule, 2 axial F-atoms and 1 equatorial
F-atom). At -60oC, it shows two signals: a
downfield doublet for two axial F-atoms
and an upjield triplet for the equatorial H--+
F-atom. At this temperature, the inter-
Fig. 10.9.5.2. 19F NMR spectrum of CIF3 at -sooC.
conversion rate between the axial and
ry
equatorial F-atoms is slower than the NMR observation time scale. Thus, the NMR study records the
static molecule at this temperature and at this condition the molecule is not fluxional. In the T-shaped
molecule, the equivalent axial F-atoms are split by one equatorial F-centre; and the equatorial F-centre
ra
is split by two equivalent axial F-centres.The behaviour of CIF) is shown in Fig. 10.9.5.2. It should be
mentioned that here Cl nucleus does not split the 19F-NMR signal.
ib
10.9.6 Examples of Fluxional Molecules
yl
(i) PFs and other different jive-coordinate molecules 0/ P : We have already discussed the
stereochemically nonrigid character of PFs in connection with the Berry pseudorotation. Different
m
5-coordinate symmetrical complexes of P are also fluxional. The behaviour of PCl2F 3 has been
already discussed in Sec. 10.9.5.
he
(ii) XeF,: ,We have alr-eady discussed the stereochemical nonrigidity ofthis molecule (see Sec. 10.8.5).
(iii) Different 8-coordinate complexes: Generally, octahedral complexes are stereochemically rigid
lc
but the polytopal rearrangements are' favoured for the complexes having coordination number
more than six. For example, in the 8-coordinate system, different structures such as square
ea
antiprism, dodecahedron and cube differ slightly in energy as in TBP and square pyramid in the
5-coordinate system. As a matter of fact, a symmetrical dodecahedron can be converted into
th
either a cubic or a square antiprismatic intermediate at the cost of a little amount of energy and
then from the intermediate, a new dode~ahedron can be attained. Thus we may have :
e/
dodecahedron ~ cube or square antiprism ~ dodecahedron

t.m
Polytopal isomerism and"fluxlonallty

Polytopal isomers actually describe different coordination polyhedra. The examples are : square
planar (D4h ) ~ tetrahedral (Td ); tetrahedral (Td ) ~ distorted tetrahedral (D2d) ~ square planar
(D4h ); trigonal bipyramid (D3h) ~ square pyramid (C4v ). Here it must be tnentioned that the
polytopal isomers which are not chemically equivalent are not the examples of fluxional
molecules because for the fluxional molecules, the conformations must be chemically identical.
Thus, tetrahedral ~ square planar, trigonal bipyramid ~ square pyramid are not the examples of
fluxionality.
(iv) Organometallic compounds:

(a) Let us consider the trihapto (11 3)-allyl complex (see Fig. 10.9.6.1) as a representative one.
With respect to M and the middle hydrogen (Hm ), the four terminal hydrogens are of two
types, Le. syn- or cis~hydrogens (He) and anti- or trans-hydrogens (H,). Ifthe molecule were
Hm
ry
I
H~ /C'& /Hc~
ra
c C
I 1\
ib
Ht M Ht
yl
Fig. 10.9.6.1. Fluxional behaviour in trihapto (tJ3 or tf3)-allyl organometallic complex.
m
stereochemically rigid, we would get two different PMR (proton magnetic resonance) signals
for He and HI along with a signal for Hm' In fact, at low temperatures due to the stereochemical
he
rigidity, we get three PMR signals, but on warming the two different signals for He and HI
converge to make He and HI indistinguishable. On warming, the activation energy of the
barrier is attained to show the stereochemically nonrigid character.
lc
(b) The fluxional behaviour of (rf-csHS)2(T/I-CsHs)2Ti is quite interesting. In this molecule,

there are two types of cyclopentadienyl rings: 11 1-CsHs and "s-CsHs. For the monohapto
ea
rings (1] I -CsHs)' in terms of the point of attachment of the ring with Ti, there are three types
0/ hydrogens in 11 1-CsHs rings. Both the 11 1-CsHs rings are equivalent and similarly both
th
the 11s-CsHs rings are also equivalent. In the "s-CsHs rings, all the protons are equivalent.
Thus in the static molecule there are/our types of protons: 11 1-CsH s rings give three types
e/
and "s-rings give only one type.

t.m
Fig. 10.9.6.2 indicates the structure and IH-NMR spectra (at different temperatures) of
("s-CSHS)2(111-CsHs)2Ti. At relatively higher temperature, IH and 13C NMR spectra indicate
only one type of protons (Le. all the 20 protons appear indistinguishable) and one type of
C-atoms. It indicates the stereochoemical nonrigidity (i.e. fluxional property) of the molecule and
it leads to : (i) rapid interconversion between the 1]1- and "s-CsHs rings, (ii) rapid internal rotation
in a 11 1-CsH s ring to allow the point of attachment to move over all the 5 C-atoms of the ring
(ring whizzer system). At this high temperature (ca. 62°C), this structural change is much faster
than the NMR time scale. However, at relatively lower temperature (ca. -30°C), 1H- NMR spectrum
shows two signals for two types of protons (10 in each type), one due to "s-CsHs rings and the
other for the 11 1-CsHs rings. It indicates that at this temperature, the internal rotation of 11 1-CsHs
ring is yet much faster than the 1H-NMR time scale and consequently all the protons of 11 1-CsH s
remain indistinguishable. However, at this temperature the mutual interconversion rate between
the 11 1- and "s-CsHs rings is slower than the NMR time scale and consequently they can be
ry
ra
(b)
ib
yl
(-27° C)
-----.. H
(a)
m
Fig. 10.9.6.2. (a) PMR spectra (not in scale) of ("s-CS HS)2('l'-Cs Hs)2 Ti at different temperatures. The
he
two signals observed for "s-Cp and 'l'-Cp at low temperature (e.g. -27°C) broaden and collapse into
single peak at higher temperature (e.g. 62°C). (b) Change of mode of bond;ng of Cp-rings in
lc
(rf-CS/!~)2( 'l'-CSHS)2 Ti.

ea
distinguished. If the temperature is lowered down to about -82°C, then the three different types
of protons in 171-CsHs rings can be distinguished in the proton NMR spectrum.
th
(v) Bi- and polynuclear metal carbonyls: Very often in bi- and poly-nuclear carbonlys, due to the
stereochemical non-rigidity, CO ligands are found to scramble over two or more metal atoms.
e/
The process can be followed by NMR spectroscopy.

The cyclopentadienyl protons of the cis- and trans-isomers of(rf-esH5)2 Fe 2(CO)4 resonate at
t.m
different positions in IH-NMR spectroscopy. The activation energy for the cis ~ trans
isomerisation of the complex is 50 kJ mol-I. Thus this isomerisation rate at -70°C is about
8 x 10-2 S-1 at room temperature. The IH-NMR spectroscopy can diITerentiate the protons of cis-
and trans-isomers at low temperature (,..,.; -70°C) while at relatively higher temperature only one
signal is noticed (Le. all the protons become indistinguishable). These are illustrated in Fig.
10.9.6.3.
In binuclear compounds having bridging CO, the process of scrambling of the bridging and
terminal carbonyls occurs through the opening and closing of the bridging pairs of CO group
(Figs. 10.9.6.4 and 10.9.6.~). This allows the cis-trans isomerisation.
A similar process occurs in the following example, Mo 2(CO)6(Tl s-CP)2 (Fig. 10.9.6.5).
A large number of such fluxional bi- and poly-nuclear carbonyls have been reported.
Stereochemical nonrigidity is also observed in different five coordinate organometallic (TBP)
complexes. This occurs through the Berry pseudorotation mechanism.
(a)
~/~~
ry
ra
Fe Fe
/ "'c/ "'"
ib
OC II CO
o
yl
(cis) (b) (trans)
Fig. 10.9.6.3. (a) PMR spectra (not in scale) of ("s-Cp)2Fe2(CO)4 at different temperatures. At low
m
temperature (-700c), two signals for two different types of Cp-rings present in cis- and trans-conformations.
(b) Equilibrium mixture of cis- and trans-forms of (rf-Cp)2Fe2(CO)4.
he
o 0
.~ ·CO ·CO ·CO ~ ·CO
lc
/ "
(CP)I~ /le(CP)~(CP)le--le(CP)~(CP)F,-
I I I / ' "I
/Fe(CP)
ea
CO ·C CO co CO ~C/
II II
th
o 0 0 0
II II
/C~ /C~
e/
oc'- /CP CP, /CP

Fe Fe ~ Fe Fe
t.m
cp/ " ' c / 'co C{ "'c/ 'co

II II
o 0
(trans) (cis)
Fig. 10.9.6.4. Schematic representation of the process of scrambling of the bridging and terminal CO
groups in a representative binuclear complex Fe2(CO)4( Cp)2 (where Cp = 11 s - CsHs).
·C,
(Cp)Mo
OC"f
O
Mo(Cp) ~(Cp)Mo
~.~\,V
o DC
Mo(Cp) ~
CO
c,
(Cp)Mo
O~/O
Mo(Cp)
/'- I / \.............. C~ /"'- I
OC CO ··CO DC CO II DC *·CO CO
o
Fig. 10.9.6.5. Fluxionality in Mo2( C0)6( Cp)2 where Cp = 11s-CsHs.
Covalent Compounds: Characteristics. Structure and Reactivity 861
10.10 NUCLEOPHILIC SUBSTITUTION REACTIONS (e.g. ~OLVOLYSIS)

IN SOME COVALENT MOLECULES OF NONMETALS
10.10.1 Thermodynamic and Kinetic Aspects of Chemical Reactions

For a reaction to occur, the Gibbs free energy (~G) must be negative. It is related with the enthalpy
(Ml) ·and entropy (~ change as follows :
~G = Ml- TIiS
Thus the reactions are thermodynamically favoured for Ml < 0 and liS> O.The knowledge of ~G
ry
can tell us 'how far' a reaction can go on but it cannot tell us 'how fast' the reaction will go on. If a
reaction is not thermodynamically allowed, then it cannot occur, but a thermodynamically allowed
ra
reaction cannot go on if the kinetic barrier is very high and it depends on the magnitude of activation
energy (Ea). The activation energy is expressed by the Arrhenius equation as follows :
ib
Ea
k = A exp ~- EjRTJ or Ink = constant - R.T
yl
The pre-exponential factor (A) has the same unit of rate constant (k). In transition state theory,
m
Eyring equation expresses rate constant in terms of free energy of activation energy (~G ~).
~G~ = ~H* - T liS * where Ml~ = Eo + RT(~n - 1) ~ Eo
he
k=( ¥) exp (1iS~ I R] exp [-Ml~ I RT] (assuming transmission coefficient to be uftity)
lc
(Lln = change in the number of molecules in attaining the transition state, Le. Lln = 0 for a unimolecular
ea
process, Lln = - 1 for a bimolecular process), kB = Boltzmann constant, R = ideal gas constant,
h = Planck constant, T = temperature in Kelvin scale, Ml* = enthalpy of activation (expressed in kJ
mol-I), 1iS~ = entropy of activation.
th
Tunneling effect: Clasically, the activated complex passes over the potential energy barrier. The
e/
quantum mechanical tunneling effect can allow the reactions, specially involving the light particles
(e.g. H, electron), to pass through the potential energy barrier (cf. Sec. 3.5.6). If this path
t.m
contributes, then very high kinetic isotope effect is noted and the lineari~ of Arrhenius plot (log k
vs. 1/1) or Eyring plot (log k vs. 1/1) is not maintained.
Let us consider the following hydrolysis reactions to illustrate the importance of kinetic barrier.
CCl4 (I) + 6H20 ~ CO2 (aq) + 4H30+ (aq) + 4Cl- (aq), ~Go =- 380 kJ mol-I
SiCl4 + 6H2 0 ~ 8i02 (aq) + 4H30+ (aq) + 4Cl- (aq), ~Go =- 290 kJ mol-I
Thus both CCl4 and SiCl4 are thermodynamically unstable with respect to hydrolysis and the
hydrolysis of CCl4 is thermodynamically more favoured. But due to the very high activation energy,
CC(, survives from hydrolysis. On the other hand, SiCl4 hydrolyses very rapidly because of much
lower activation energy. All these mechanistic aspects will be discussed later. Under the drastic conditions
(by superheated steam), CCl4 hydrolyses as follows :
CCl4 + H20 ---+ COCl2 + 2HCl
Similarly, CF4 is highly reluctant to experience hydrolyses due to the high kinetic barriers.
862 Fundamental_ Concepts of Inorganic Chemistry
Entropy driven reactions

There are many reactions where enthalpy change (Mf) is more or less zero but the positive M
value favours the reactions.
Exchange reaction: BCI3(g) + BF3(g) ~ BCI2F(g) + BF2CI(g), M > 0
Racemisation reaction: 2t1[Co(en)3]3+ ~ t1[Co(en)3]3+ + A[Co(en)3]3+, M> 0
10.10.2 Reaction Pathways of Nucleophilic Substitution Reaction
ry
Before to discuss any specific example, we should know the major mechanistic pathways leading to the
substitution reactions, AX + Y ~ AY + X. The important possibilities are:
ra
(i) Dissociative process (i.e. D process or SN1 process, more correctly limiting SN1 process)
ib
slow fast) A_Y
Y +A-X----------+) Y + A+X;A+ Y
rate determining step (rds)
yl
Here the rate determining step (rds) involves the rupture of A - Xbond followed by the rapid combination
m
of Y to A. Thus the D-process represents a two-step reaction. According to Ingold's notation for
organic reactions, such a mechanism is referred to as SN1 (Le. unimolecular nucleophilic substitution).
he
According to Langford (1965), such a process is called D process, as the rate determining step involves
the bond dissociation.
lc
(ii) Associative process (i.e. A process or S~, more correctly limiting S~ process)
ea
Slow .&:ast
Y + A- X ) Y - A-X· Y - A - X Ii ) Y- A+Y
rate determining step (rds) ,
th
Here the rate determining step leading to the intermediate of higher coordination number is attained
through the formation of A-Ybond without the rupture of A-X bond. Thus, the A-process represents a
e/
two-step reaction. According to Ingold's notation, it is called S~ (Le. bimolecular nucleophilic

substitution), an~ according to Langford's notation it is referred to as A process.
t.m
(iii) Interchange or concerted process (i.e. I process)

D and A are the limiting cases, but there are many cases in which at the rate determining step, both the
bond (A - Y) formation and bond (A - X) breaking go on simultaneously to produce the activated
complex or transition state. Such a concerted process has been described by Langford as an interchange
process (i.e. I process). In the I-process, the reactants are smoothly converted into the products through
the activated complex. Thus the I-process represents a single step reaction. Depending on the
predominance of D and A character in the transition state, they can be referred to as Id and Ia processes
respectively. Generally the process is represented as,
Y+A- X slow ) [ Y .... A .... X]# fast) Y- A+Y

rate determining step (rds) (Transition state) .
The limiting situations for Id and 1a processes are actually D and A processes respectively.
Activated Complex or Transition State and Intermediate

Pure dissociative (D) or associative (A) processes are actually two step reactions (Le. rate determining
step followed by a fast reac~ion). The first step (Le. rds) produces an intermediate (cf. Fig. 10.10.3.1)
which is ultimately transformed into the product. In an interchange process (I), the leaving group
and entering group exchange in a single step through the formation of an activated complex (cf.
Fig. 10.10.3.1) which can not be described as an intermediate. Thus, A and D processes pass
through the formation of an intermediate while the I process passes through the formation of
an activated complex. However, in our next discussions, we shall not use strict convention in
ry
describing the activated complex or transition state or reaction intermediate.
ra
Nucleophilic substitutic,n at spl-e centre: For the sp3-e centres, the I-process is very much relevant.
The purely associative path (Le. A path) is not possible for the lack of a vacant orbital on C-centre to
ib
accommodate the incoming nucleophile. Similarly, the purely dissociative path (Le. D path) generating
a carbonium ion is also a remote possibility. The fa path (Le. bond formation by the incoming nucleophile
yl
is more important than the· bond rupture by the leaving group) found as in the case of solvolysis of
CH3-e1 is commonly described as S Nl process. Similarly, the f d path (Le. bond rupture by the leaving
m
group is more important than the bond formation by the incoming nucleophile; it leads to the development
of carbocationic character) found as in the case of solvolysis of R 3C-e1 is commonly described as
he
SNt process.
In the I process at the sp3-e centre, the accommodation of 5 groups can be explained by 3c-4e
bonding model. In the transition state, the C-centre adopts the sp2-hybridisation and the available pure
lc
p-orbital is shared by the both leaving and incoming group to generate three 3c-MOs.
ea
TOP transition state

th
LiJ:tear segment
(3c-4e bonding)
e/
Incoming .
nucleophile LeaVIng group
I-process at Sp3_C centre
t.m
10.10.3 Energetics of A and D Processes

To attain the transition state (TS) in the D process, a bond rupture is required. This is an energy requiring
process. This bond dissociation energy gives the measure of activation energy. On the other hand, in
the A process, a new bond is formed to produce the transition state of higher coordination number. A
new bond formation releases energy. Gener.ally in attaining the higher coordination number, the
hybridisation state of the central element is to be changed, and it requires the cost of hybridisation
energy. In a system of higher coordination number, the bonds are also weaker compared to those of the
starting reactant having a lower coordination number. In spite ofthese facts, formation ofa new bond
in the A process can compensate these disfavours at least to some extent. This is why, in general, the
activation energy of the A process is lower cOqlpared to that of the D process (provided the steric
hindrance in the transition state is not very high) for the covalent compounds ofnonmetals. The energetics
of the two processes are shown in Fig. 10. rO.3.1. In the predominantly covalent compounds,
energetically the A process is preferred. Hence the possibility to increase the coordination number
at the centre by a nucleophilic attack through the availability of some suitable vacant orbital is an
extremely important criterionfor the substitution reaction in such predomin"antly covalent compounds.
1 [ ]~
[ ]~ [X···A···Y]~
~
~
ry
Q)
c
W
Q)
Q)
u.
ra
ib
Associative Process (A)
yl
Reaction Coordinate ---+'
Fig. 10.10.3.1. Energetics of associative (A), dissociative (0) and interchange (I) reaction pathways
in substitution reactions. [ ]~ denotes the activated complexes for each step of A- and D-processes.
m
Note : A. or D process represents a two-step reaction while 1 process represents a single step
reaction passing through the activated complex or transition state of high· energy.
he
Activation parameters in hydrolytic cleavage: In the hydrolytic cleavage through the A-path,
formation of a highly organised intermediate of higher coordination number makes generally M;# less
lc
positive (Le. entropic disfavour and the process is disfavoured kinetically). But formation of a new
bond with the incoming nucleophile in attaining the transition state makes Mr less positive (Le. enthalpic
ea
favour and the process is favoured kinetically). Very often, in the A-process, the enthalpy factor
predominates to favour the rate process. In a dissociative pathway, there is an entropic favour but
th
the bond rupture to produce. an intermediate of lower coordination -number explains the higher enthalpy
of activation (Ml ;#). Very often, this entbalpic disfavour controls the overall rate process in the
e/
hydrolysis ofcovalent compounds ofmain group elements. Here it should be mentioned that sometimes,
solvation and desolvation of reactants may play an important role in determining the activation
t.m
parameters.
10.10.4 Some Representative Nucleophilic Substitution Reactions In Covalent Compounds

of p-Block Elements
(1) Hydrolysis of CCl4 and SiCl4 : It is well known that SiCl4 hydrolyses readily while CCl4 is inert.
H 20 · I H20 OH-
CCl4 ) no reactlQn; SiC 4 ) S;(OH)4' SiCl4 ) S;(OH)4
-He/ _·c/-
Here Olr or H 20 acts as.the nucleophilic agent. CI is more electronegative than Cor Si. Hence,
the bond polarity exists as C~+ "- C/&- or Si~+ - CI&-. Hence the nucleophilic attack will occur at
C or Si in the SN2 or A process. But C has got no suitable vacant orbital to accommodate the
incoming nucleophile. On the other hand, Si can easily accommodate the nucleophile through
the involvement of its vacant 3d-orbital to fonn a trigonal bipyramid (sp 3 d hybridisation) as
shown in Fig. J 0.10.4.1.
CI
I
II
I
Si
fi"
I'
I '
I "
-CI-
--+
c'k:-l~c,
'" ' ~~ ,, ~
CI
(TS)
ry
Fig. 10.1.0.4.1. Nucleophilic substitution pathway in SiC/4 •
Valence state ofSiC/4 : 3d
=
3 (sp3)
ra
[]JJIT]JJIJ
ib
Transition state (trigonal bipyramid, 3 (sp3d) 3d
accommodation of a lone pair (U)
lJIJJITJITi[]J[
=
yl
from the incoming nucleophile) :
The stepwise hydrolysis ultimately leads to Si( OH)4. As a matter 01fact, SiC/4 is so prone to
m
hydrolysis that it is to be protectedfrom atmospheric moisture.
For CCI4 , SN2 process (Le. A process) is not possible because of the nonavailability of any vacant
he
orbital on C to accommodate the incoming nucleophile. Hence, it can only hydrolyse through the
D (Le. SN1) or f process. The D process goes on as follows:
lc
Cl C - Cl (rds») CI C+ + cr; CI3C+ + OH- fast) Cl C - OH

3 3 3
!he bond rupture (C - Cl) is highly energy requi~ing. Hence, CC/4 can only hydrolyse under
ea
drastic conditions.
Note: We have discussed the difficulty in pure A and D paths for the hydrolysis of sp3_C
th
compounds-like CCI4 • Now let us consider the difficulty in I-path. In I-path, approach of the
nuc~eophile with its lone pair is disfavoured because ofthe repulsion arising from the nonbonding
e/
electrons on Cl-atoms. It may be noted that.for CH3CI or R3CCI, no such repulsion arises. Thus
in CC~4' the chlorine atoms disfavour the approach of the nucleophile both sterically and
t.m
electrostatically.
:CI
N ~ r:..
u: :9 /C-~/: .
:~! (I-process)
(2) Hydrolysis ofCH]CI and chloroform (CHC/l ) : CH3CI can hydrolyse by fa or SN2 path. CHCl3
is more easily hydrolysed than CH2Cli(dichloromethane) or CCl4 by the strong bases like OH-.
The mechanism of base catalysed hydrolysis of CHCl3 is different from that of CH2Cl2 or CCI4 •
D-path
H - CCl3 + OH- ~ -CCI3 + H 2 0; CCI) ---~) CCl2 + CI-
(rds)
(Acid) (Conjugate (Ca) (Carbene)
base CD)
H 20
CC/2 ) HCOOH or CO
Here, it may be noted that the acidity of CHCIJ arises due to the electron withdrawing inductive
effect of chlorines and stabilisation of the conjugate base CCI:; through the C(2Pn) ~ CI(3dn)
7t-bonding called d-orbital resonance involving the vacant 3d-orbital of Cl. In fact, CHFJ is
less acidic than CHCIJ because the corresponding conjugate base CF3- does not earn any
such stabilisation through 1t-bonding. Fluorine lacks in d-orbitals.
In the hydrolysis of CHCI3, the conjugate base (CD, C~13) is produced in a preequilibrium
step and then the CB experiences the 'C-ef bond rupture (Le. D-path) at the rate determining
step. Thus the carbene CCl2 produced rapidly hydrolyses to HC02H or CO. The above mechanism
ry
is called D-CB or SN1CB. This D-CB mechanism is not possible for CCl4 which cannot act as
an acid (as there is no proton) and also for CH2Cl2 and CH3Cl which are not sufficiently acidic to
act as the proton donors to generate the CB.
ra
(3) Racemisation ofSi-compounds through A-process: Here it is interesting to note that if we start
ib
with an optically active compound, RtR2R3Si*CI in which silicon is asymmetrically substituted,
then the SN2 process will lead to the Walden inversion as shown in Fig. 10.10.4.2. Regarding
Walden inversion through trigonal bipyramid, it must be mentioned that the inversion isfacilitated
yl
when "the nucleophile (i.e. entering group) and the leaving group are highly electronegative to
occupy the axial positions (see Bent's rule) in the transition state. Under such circumstances,
m
both the entering and leaving groups are suitably oriented in the axial directions to displace the
leaving group. The prediction is complicated when the nucleophile is not sufficiently
he
electronegative to occupy the axial position in the transition state and the leaving group is a poor
leaving group.
lc
ea
~OH
th
e/
t.m
(TS)
Fig. 10.10.4.2. Walden inversion in R, R2 R3 SiCI during nucleophilic substitution.
Factors controlling the associative (A) path in Si, P, Sn, S compounds
The nucleophilic attack in such cases leads to intermediates like TBP (sp 3Ci), 0h (sp 3eP) where
coordination number is increased compared to the starting reactant. The ease of such intermediate
formation depends on the following factors :
• Ease ofd-orbital participation: It is specially favoured when the central atom is attached with
the electron withdrawing groups; this aspect has been discussed in detail in Sec. 9.13.5.
• Steric crowding for the bulky groups will disfavour the increase of coordination number
through the nucleophilic attack in the A-process.
• Higher Lewis acidity will favour the nucleophilic attack.
• In the TBP intermediate (whose bonding positions are not equivalent), the leaving group and
.entering nucleophile should be electronially suitable to occupy the axial positions of the
TBP intermediate.
Similarly, the reduction of R 1R2R3Si*Cl with LiAlH4 produces R t R2R3Si*H along with an inversion.
The racemisation mechanism in silane derivatives is discussed at a greater length in S~~.1 0.1 0.4
(vi) in terms of Berry pseudorotation of the intermediate trigonal bi.pyramid.
(4) Hydrolysis of SnC/4 , SnC/2 and SnMe4 : SnCl4 can hydrolyse very easily through the A-process.
Interestingly, SnMe4 is highly reluctant towards hydrolysis. In the A-path, the first step involves
the nucleophilic attack by the water molecule on Sn. Thefavour to accommodate this nucleophilic
attack by H 20 depends on the Lewis acidity ofthe Sn-centre. Because of the electron pushing
effect of the Me-groups, SnMe 4 is a very weak Lewis acid. On the other hand, SnCl4 is a very
ry
strong Lewis acid because of the electron withdrawing effect of the Cl-groups. Thus, formation
of the 5-coordinate intermediate (TBP, through the accommodation of the nucleophile) is an
ra
easier process for SnCl4 while it is a difficult process for SnMe 4 •
For the formation of 5-coordinate TBP intermediate or T.S. in the associative process, the d-
ib
orbital is to participate in the required sp 3d hybridisation. This d-orbital participation (cf. Sec.
9.13.5) in hybridisation is favoured when the central atom is bonded with the electronegative or
yl
electron withdrawing groups like F, Cl but the process is disfavoured for the electron pushing
groups like CH3• This is why for SnC/4, formation of the TBP by the nucleophilic attack is
m
energetically favoured but it is disfavoured for SnMe4•
It may be noted that SnCl4 can easily form SnC1J- but SnMe 4 fails to form SllMe~-. SnC/4 is
he
more prone to hydrolysis than SnC/2• It is due to higher Lewis acidity of SnCI4 • Here it should
be mentioned that SnCl2 requires the d-orbital participation to act as a Lewis acid. Obviously,
lc
d-orbital participation is more favoured for SnCl4 than for SnCI2 • In the same way, the Si-CHJ
bond (in silicones) is resistant to hydrolysis.
ea
Note : • For SiX4, effect of 7t-back bonding is less important than the effect of electron
withdrawing inductive effect to determine the Lewis acidity. The Lewis acidity runs as :
th
SiF4 > SiCl4 > SiBr4 > Sif4

e/
The ease offormation ofTBP intermediate follows the same sequence based on the consideration
of d-orbital participation and steric factor. The ease ofhydrolysis also follows the same sequence
t.m
because of the same reasons.

• When the d-orbital is required to participate in forming the intermediate in the A-process, the
factors (cf. 9.13.5) governing the participation of d-orbitals must be considered. In the above
mentioned compounds, the ease of d-orbital participation follows the same sequence of the ease
of hydrolysis, Le.
SiF4 >SiCI4 > SiBr4 > Sif4
(5) Hydrolysis of carbonyl compounds: We have already noticed that when carbon is in a tetrahedral
(sp3) state, it cannot accommodate the nucleophilic attack in the SN2 or A pro~ess through the
increase of its coordination number because of the nonavailability of any suitable vacant orbital.
But when the carbon is planar (sp2) as in unsaturated carbonyl group, it can readily expand the
coordination number from 3 to 4 (Le. sp2 ~ sp3) in attaining the transition state. The hydrolysis
occurs as follows:
R
/"
n·
",,0
H
9. l .
~
+f~
"
R - - C --0----. R --C
gO
//
+ HCI
C/ ~, "OH
(6) Hydrolysis of trivalent and pentavalent phosphorus compounds : • PCl3 hydrolyses as
follows:
H20 tautomerisation
PCl3 ) P(OH)3 ) (OX H )P(OH)2' i.e. H3P03;
ry
H 20 H 20
PCls -2HC/) POCl3 -3HC/) OP( OH)3
ra
The bond polarity, ¥'+- Cr- directs the nucleophilic attack (by H 20, 0/1 or OIr) on phosphorus.
Through the involvement of the vacant 3d-orbitals, the central element phosphorus can easily
ib
accommodate the nucleophilic attack to increase the coordination number in the associative
process.
~ yl
m
:PC/J ~ ~ P(OH)CI]
-HCI
he
The intermediate uses the sp3d hybridisation. The lone pair remains in the equatorial plane
lc
(see Bent's rule) in the transition state. The stepwise hydrolysis ultimately leads to P(0H)3
which undergoes tautomerisation to form HP(0)(0H)2' Le. H3P03.
ea
• In the case of pels' after accommodating the nucleophile, it produces the octahedral (sp 3eP)
intermediate from which 0 = PCl3 is obtained.
th
CI
CI, I ·· Cl",CI CI
V
e/
1
" P - CI HO
2•• ~ ~ PCI.,(OH) H 20 ~ PCI (OH)
C// I C// I"OH -HC/ -HC/ +J . 2
t.m
CI CI 1 C/~ =0
o = PCl3 (tetrahedral, sp3) can further hydrolyse stepwise through the trigonal bipyramid as an
intermediate to form H3P04 •
(7) Alkaline hydrolysis ofphosphorus: It leads to disproportionation of phosphorus.
P4 + 30H- + 3H20 ~ PH3 + 3H2P0i.
H 3P02 is hypophosphorus acid. The hydrolytic cleavage can be explained as follows:
H2()~OH2 H
I I
.H
--3 /p~
H</~ {"OH H</

p
"OH HOH1"''0
:OH2
Covalent Compounds: Characteristics, StructlJre and Reactivity 869
(8) Hydrolysis ofP~Jo: Tetra phosphorus decasulfide is structurally similar to P4010. In the tetrahedral
structure of P4' there is a P-S-P bridge along each edge and each P~centre makes a P = S bond.
P4 l}o + 16H2 0 ~ 4H)P04 + 10H2 Y (Y = S, 0)
P4 l}o + 8ROH ~ 4(RO)2 P (= YXYH) + 2H 2Y (Y = S, 0)
Hydrolytic cleavage of P4S10 in presence of alcohol (ROil) or phenol (ArOIl) gives dialkyl or
diaryl dithiophosphoric acids which are industrially very much important. Nucleophilic
attack by ROH on P-centres of P4S 10 is shown in the following structure.
ry
II
RQH RQH
ra
"-..rpK
:Y \' s
R~I i H~ ~I;JH
ib
riP ~1~: yl
m
ftfl~
he
ROH S ROH
Dialkyl dithiophosphoric acid is used as a starting material for the synthesis of organophosphorus
lc
in~ecticides like parathion, malathion, metathion, etc.
(RO)2 P(S)SH + ~12 ~ (RO)2 P(S)CI + HCI + S

ea
~ ~
O~N02 CI-
th
(ROhfl--c.;! + - • (RO)2P-O~N02
II
e/
S (p-nitrophenoxide) S
(Parathion, R = Et)
t.m
RO~~N02 -cr. (ROhfl-O~N02

S R ,s R
(3-methyl-4-nitro (Metathion, R = Me)
phenoxide)
.~ NEt) (Base)
(MeO)2 P -SH + CHC02Et (Hydroquinone,· (MeOhP-S-CHC02Et
I
S
(IICHC0 Et to prevent
polymerisation)
II
S
I
CH2C02 Et
2
(Diethylmaleate) (Malathion)
Industrial importance of P~10 is indicated by its world production, 250,000 tonne~ per
year.
870 Fundamental Concept~ of Inorganic Chemistry
Ease of hydrolysis: Si-X bond ys. P-X bond

Bond polarity is of an important consideration to determine the ease of nucleophilic attack by a
nucleophile like solvent in solvolysis reaction. Now let us consider the relative sensitivity ofthe
P-C/ and Si-CI bonds towards the hydrolytic cleavage. Here, both the P- and Si-centres can
accommodate the nucleophilic attack by H20 as both the centres can provide the vacant d-orbitals.
Si-Cl bond is more polar than P-Cl bonds in terms of electronegativity difference and this is
why, Si-Cl bond is more prone hydrolytic cleavage.
ry
(9) Walden inversion in phosphorus compounds: In the case of optical activity, again the Walden
inversion may arise. For example, the solvolysis (Le. nucleophilic displacement by the solvent)
ra
of chlorodialkyl phosphine oxide leads to inversion.
ib
~ fI ~o
Nu- +R - P - c / - - . Nu-R-C/ • Nu-P-R
yl
} / / '" -Cl- '" 2
R2 R} m R2 R}
Here we must remember the favouring conditions for inversion through the trigonal bipyramid.
The conditions have already been discussed in connection with R 1R2R3Si*CI.
he
(10) Hydrolysis of alkyl phosphates (both C and P as the centres of nucleophilick attack) (Ref.
C.A. Bunton, Acc. Chern. Res. 3, 257, 1970) : The hydrolysis of trirnethyl phosphaJe is quite
lc
interesting. In the base catalysed hydrolysis, 180F as a nucleophile, the following reaction occurs.
(MeO)3 PO + *OH- (MeO)2 PO *0- + MeOH
ea
·OH-
~
th
A-process • II - MeOH
Le. MeO-P-OMe
/
..
./"
HO-P..-OMe • (MeO)2 PO'--Q-
e/
MeO 1Me OJ OMe

Here, Olr as a nucleophile attacks on P in the associative pathway. But, interestingly, in the
t.m
aquation or acid catalysed'hydrolysis, 180H2 as a nucleophile attacks on C (in D or I path) not

on P and consequently the hydrolytic products are different {n comparison with the base
catalysed hydrolytic products. OF, a better nucleophile, favours the A-path while H20, a poorer
nucleophile, favours the D or I-path (see the next reaction for explanation).
• Nucleophilic •
(MeO)3 P = 0 + H 20 -----~) (MeO)2 P (= O)OH + Me OH
attack one
(D or J process)
Note: For the alkyl phosphates, the centres of nucleophilic attack by OF and H20 are different.
The same thing arises for different halides. r attacks on P (favouring d-orbitaIparticipation) in
A-path while the heavier halides (disfavouring A-path due to stericfactors) attack on C in D- or
I path to produce methyl halides.
(11) Hydrolysis ofarylphosphates (only P as the centre ofnucleophilic attack) (Ref. P. W.C. Barnard
et aI., J. Chern. Soc., 2670, 1961) : It is worth mentioning that in the case of aryl phosphates, the
nucleophilic attack by both Olr and H20 always occurs on the P-centre in the A-process. In
such cases, the C-centre is not susceptible to the nucleophilic atta~k by On- or H 20. The
hydrolysis of triphenyl phosphate occurs as follows:
·OH- or H 20. •
(PhO)3 P = 0 ) (PhO)2 PO 0- + PhOH
(A-path)
. In terms of activation parameter for such hydrolytic cleavage (in A path), the entropy ofactivation
(AS'~ is highly negative and the enthalpy ofactivation (Mr) is small. In fact, the associative
(A) path leads to the formation ofa highly organised trigonal bipyramid and explains the highly
ry
negative M* value. The bond formation by the nucleophile explains the low value of tJII. In
the D or I process, Ml~ is relatively high and AS'~ is more positive.
ra
• Difference in the reactivity ofalkyl and aryl phosphates towards the nucleophile : The above
discussion-shows that for alkyl phosphates, there are two centres (Le. C and P) for the nucleophilic
ib
attack while for the aryl phosphates, there is only one centre (Le. P-centre) for the nucleophilic
attack. When the nucleophilic attack occurs on P, the process passes through the A-pathway;
yl
and when the nucleophilic attack occurs on C, the process passes through the D-pathway (or
I-pathway). The position where the nucleophile will attack depends on several factors like:
m
(i) the mechanistic pathway (Le. D or A or I); (ii) matching of hard-soft character;
(iii) steric factor, etc.; (iv) availability of vacant orbital(s); for the vacant d-orbital, its energy
he
Now let us try to understand whether A or D process will occur for the hydrolysis of phosphate
esters. Olr is a much better nucleophile than H 20. In the A-process, the nucleophilicity ofthe
lc
attacking agent is of an important consideration while in the D- or I-process, the

nucleophilicity ofthe attacking agent is ofno important consideration. In the base catalysed
ea
hydrolysis of (MeO)3P=0, the powerful nucleophile Olr favours the A-process (Le. attack on
P-centre) while H 20 being a weaker nucleophile attacks the C-centre in D- or 1 path. PhO is a
better electron withdrawing group than MeO-group. Thus in (PhO)3P=O, the Lewis acidity
th
of the P-centre is very high compared to that of (MeO)3P=0. Here it may be mentioned that
the higher electron withdrawing PhO-groups favour the nucleophilic attack on P through
e/
the A-process byfavouring the d-orbital participation. Consequently, even for water (a weaker
t.m
nucleophile), the nucleophilic attack at the P-centre through the A-process is favoured. In other
words, for (PhO)3P = 0, both Olr and H 2 0 will make the nucleophilic attack on P-centre.
(12) Hydrolysis of cyclic phosphates (cf. F.W. Westheimer, Acc. Chem. Res., 1, 70, 1968) : Let us
now consider the hydrolysis of cyclic phosphate ester (Fig. 10.10.4.3). The hydrolysis of cyclic
phosphate ester leads to the release ofROH and also ring opening. Ring opening occurs when
in the trigonal bipyramid intermediate (Le. A-pathway), the p-o bond in the ring is cleaved. It is
important to note that this cyclic ester hydrolyses muchfaster than the acyclic analog. It is pro-
bably due to the strain in the cyclic compound. It~s interesting to note that phostonate (replacement
of 0 1 by CH2 in the cyclic phosphate ester) exclusively gives the ring opening product. It is due
to the fact that the pseudorotation is not possible when 0 1 is replaced by a CH2 group (cj. in
TBP, axial positions are preferably occupied by the electronegative atoms like 0; Bent's rule).
(13) Hydrolysis ofNFJ , NC/J and PC/J : We have already discussed the hydrolysis of PCl3 through
the formation of a trigonal bipyramid intermediate leading to H 3P03 and HCI, Le.
PCl3 + 3H20 ~ H3P03 + 3HCI. (1)?7 (2)00

...·I·····q(1)
Halides of the heavier members of the' (3)O::~. p/ i
P-0(2) (Attack on the
same group, i.e. AsCI3, SbCI3, BiCI3, also /~ face opposite ··T·~OR
to ring oxygen) (5)OH 2 (4)
follow the same mechanistic path leading RO(4) 0(3)
to M(OH)3 and HCI (M = As, Sb, Bi). (R) +~

For Sb and Bi, M(OH)3 undergoes (2)~
tiP'+ I
dehydration to produce SbO+ and BiO+ ..! f....·Q(1)
+ .::::::
O.::-P~ 1
/ :
cations respectively.
(3) ···T····.OR
ry
NCIJ hydrolyses but the products are (5)OH 2 (4)
different, i.e.
ra
NCl3 + 3H20 ~ NH3 + 3HOCI. llpseudo rotation (Ring opening)l-H+
It vividly indicates that the mechanistic
ib
pathjollowed by NCIJ is totally different (1)0 &5) OH
(1)0/"../'(2)
compared to that jollowed by PCIJ , 1..···QH
i 2
yl
(3) .:::::: /
I
i!i~d
(4)
AsCIJ , etc. P
~?):!.
/~'OR
NFJ is very much inert to hydrolysis. It HO
occurs only in drastic conditions when
m (2)
(5)
0(3)
-H+ (5)
sparked w·ith water vapours, i.e.
he
2NF3 + 3H20 ~ 6HF + N20 3. (1)0~
I (2)/ (4)
Now let us look into the reaction pathway ~\.-O + ROH
lc
/~
followed by :NCIJ • Here nitrogen is HO 0(3)
(5)
tetrahedrally (sp 3) hybridised and it
ea
(R)
cannot expand its coordination number
by accommodating the nucleophile, Fig. 10.10.4'.3. Scheme for hydrolysis of cyclic
th
because it has got no suitable vacant phosphate ester (cf. Bond cleavage along the
orbital. The electronegativities of N and axial direction).
e/
CI are very much comparable. Hence, no strong polarisation normally exists. Though the
nitrogen centre cannot accommodate the nucleophilic attack by H20, the chlorine centre can do
t.m
the task because ofthe availability ofits vacant 3d-orbitals. Hence, ifthe N-CI bond polarises as
No--CI a+ due to the electromeric efject (Le. the direction of the polarisation is not ordinarily
significant, but to carry out some specific reactions, the bond polarises in some specified directions;
such an electromeric effect takes place only when the combining atoms in a particular bond are
almost of the same electronegativity to prevent any strong and permanent polarisation in the
absence of the reaction) to facilitate the nucleophilic attack on chlorine, then the hydrolysis
goes on through the A process.
C/jV - C/~ 2 ..
~ _ +/H] ----.. C/jVH + HOC/
[C/jV-C/-O,
A-process ~H
H 20 H 20
(H)CIN -CI _ NOCI) CI-NH2 _ NOCI ) NH)
In PCI], in spite of the availability of d-orbital on Cl, the nucleophilic attack on Cl cannot occur
because the strong and permanent polarisation (f,-+,P-C?-) opposes the nucleophilic attack on Cl.
On the other hand, in NC/l availability of vacant orbital on CI directs the temporary
polarisation ~C/~N>-) through electromeric effect for the nucleophilic attack on CI.
Thus compared to PC/l , in NC/l the centre of receiving the nucleophilic attack is different.
This is why, the hydrolytic products of NCI] and PCI] are of different types. NCI] leads to Cl-o
bond while PCI] leads to P - ° bond.
The reaction of NCI] in liquid HCI or concentrated HClleads to the release of C12•
ry
NCI] + 4HCl ~ NH4Cl + 3Cl2
It supports the chloronium character of
CI which receives the nucleophilic attack by cr in
ra
NCI].
(14) Ba$e hydrolysis ofNCll , NHC/z and NHzCI : Now-let us consider the base hydrolysis of NH2Cl
ib
or NHCl2 or NCI] which releases both cr and ocr
along with N 2 • It supports that the nucleophilic
attack by Olr occurs on chloronium chlorine, but the nitrogen centre also receives a nucleophilic
yl
attack at some later stage.
+4011 ~ N
2NHCl2
m2 + ocr + 3Cr + 3H20
2NCI] + 6011 ~ N 2 + 30Cr + 3Cr + 3H20
he
The possible steps of nucleophilic attack for base hydrolysis of NHCl2 are outlined below.
\II
lc
H" r ()H "f ~

.0 NH(C/) nCI-N-N-CI
ea
N-CI ~ CI-NH ~
Cl/ - ocr HCI ." ~ ~
~ -2HCI
2 -
(A-process) (I-process) H
th
N2
e/
Thus at the first step, 011 attacks on the electrophile chloronium centre in an associative path
(A-path), while at the second step, :NHCl2'attacks as a nucleophile on the electrophilic N-centre
t.m
of NHCl2 in an interchange pathway (I-pathway) to produce the N-N linkage.

Thus the nucleophilic attack on 'CI' goes through an A-pathway while the nucleophilic attack on
'N' occurs through an I or a D pathway. The centre where the nucleophilic attack will occur
depends on many factors. These aspects have been discussed in relation to hydrolysis oftrialkyl
phosphate which can provide two centres for nucleophilic attack (Le. C-centre which favours the
D or I process, and P-centre which favouJ:s·.the A-process).
(15) Hydrolysis of H-zN-NO z : The possible mechanistic pathways of nucleophilic substitution at
NH2-Xhave been outlined in Sec. 10.10.5. We have already discussed the hydrolysis of NH2-CI
and now we shall compare the hydrolysis of NHz-NO" (nitramide). If H20 (nucleophile) attacks
on 'NH2' group (I-process), it will lead to NH20H and N02; and if H 20 attacks on X (i.~. N0 2 )
in I-process, it will produce NH] + HNO].
NH2 -X +H2 0 NH2 0H+X-(i.e.N02),(I-path)

(attack on N)
+ H 20
NH 2 - X NH3 + J{O- X (i.e. HN03 ), (I-path)
(attack on X)
(X== N0 2 )
But, in reality, NH2-N02 on hydrolysis produces N 2 0 + 011, Le. :

+ H 20
NH 2 -N02 ) N=N=O+OH-
It indicates, that NH2-N02 experiences a different mechanism of hydrolysis. This is outlined
ry
below. Here the 'NH2 ' proton is quite acidic because of the high electron withdrawing effect of
the -N02 group and resonance stabilisation of the corresponding conjugate base (CD). The
ra
conjugate base experiences the expulsion of the leaving group (Olf) in a D-path. Thus the
mechanism is D-CB i.e. SN1 - CB.
ib
-
yl
/0 ;0
]
-BH+ ••
HjJ-N02 + :B (base)::;===: H!V.-N~, m o
1,3-shift
•
(Tautomerism) [
N-N
~OH
CB -OH-!
he
D-path (rds)
N=N=O
lc
The reaction is general-base catalysed. This mechanism of hydrolysis is comparable to that of

ea
hydrolysis of CHC/l •
(16) Hydrolysis ofNFl: Now let us examine the case of NF3 • The N - F bond is strongly polarised as
th
o+N - &-F, but.nitrogen cannot accommodate the nucleophilic attack. In addition to this, fluorine
also cannot accommodate the nucleophilic attack, because it is not having any vacant suitable
e/
orbital. Hence only under drastic conditions, the dissociative process (D) or SN1 process can
operate. The D process goes on as follows:
t.m
2H20
Similarly, F2N-OH -2HF )N(OH)3 -HP )HO-N=O,2HO-N=O~N203
Note: For NF3 , hydrolysis through the I-path involving the nucleophilic attack on nitrogen is
disfavoured as the nitrogen centre is sterically shielded by the F-atoms. Moreover, the
nonbonding electrons on the F-atoms will repel the approach of the nucleophile. The situation
can be compared with that of CCI4 .
(17) Hydrolysis of SF4, SF6 , SeF6 , TeF6 :
H 20 H 20
: SF4 -HF) SOF2 ~HF) H 2 S03 ; SF6 + H 2 0 ~ no reaction
:SF4 is trigonal bipyramidal (sp 3d hybridisation) having the lone pair in the equatorial plane.
The S - F bond is polarised as ~+'- F-. Sulphur can accommodate the nucleophilic attack by
expanding the coordination number through sp 3eP hyb.ridisation (i.e. octahedral geometry).
~I~,o:
~f"'F ~
ry
F
(Sp3d, TBP)
ra
The hydrolysis further proceeds to the final product. But, as the extent of stepwise hydrolysis
goes on, the gradual removal of highly electronegative substituent F reduces the electron deficiency
ib
on sulphur. This reduces the propensity of nucleophilic attack on sulphur. Besides this, in
attaining the required transition state, it needs the participation of d-orbital and this is favoured
yl
when the accumulation of positive charge on S-atom is high. Consequently, nucleophilic attack
at the siJbsequent steps is relatively disfavoured.
m
By following the same SN2 mechanism, SeCI4, TeCI4, etc. can undergo hydrolysis.
SeX4 + 4H20 - 4 [Se(OH)4] + 4HBr;Se(OH)4
he
) H 2 Se03
-H20
In SF6 , sulphur is octahedrally hybridised (sp 3eP). Hence, it is still having some vacant 3d-
lc
orbitals to accommodate the nucleophilic attack through the sp 3d3 (pentagonal bipyramid)
hybidisation. But the size of sulphur is too s~all to tolerate the seven coordination number.
ea
Thus because of steric crowding, the small sulphur cannot pass through A or SN2 process, Hence,
it can only hydrolyse through the dissociative (i.e. SN1) process which requires the rupture of
th
strong S - F bond at the rate determining step. The interchange process (I) is also energetically
costly here due to steric crowding around sulphur. This is why SF6 is so inert to hydrolysis.
e/
Though SF6 is extremely inert to hydroy~e, SeF6 is slightly more reactive and TeF6 undergoes
hydrolysis readily.
t.m
TeF6 + 6H2 0-46HF +-H6 Te06

The size sequence of S, Se and Te :-uns as Te > Se > S. Thus the larger size of Te does not impart
any significant steric hindrance in attaining the higher coordination number (Le. 7) which is
required in the energetically favourable SN2 or associative r~action pathway. Because of the
same ground SeF6 is more reactive than SF6 ,
(18) Hydrolysis ofXeF2 XeF4 and XeF6 : In the same line of argument, the hydrolysis of XeF2 , XeF4
and XeF6 can also be explained in terms of A or SN2 path,
1
XeF2 + H 2 0 -4 Xe + 2HF + -02
2
Actually, Xe(OH)2 is produced and it undergoes redox decomposition into Xe and O2 ,
Similarly, 3XeF4 + 6H2 0 ~ 2Xe + Xe03 + 12HF + ~02; XeF6 + 3H20 ~ Xe03 + 61lF.
2 .
(19) Hydrolysis of silane, SiH4 compared to that of CH4 ; and racemisation of optically active
silane derivatives: Silanes are readily hydrolysed and the process is catalysed by a tracetttmount
of alkali while the analogous hydrocarbons are extremely inert to hydrolysis.
SiH 4 + H 2 0
trace of of
trace
) Si02 , nH2 0 + 4H 2 ; Si2 H 6 + H 2 0 -------.) 2Si02 ·nH2 0 + 6H2 ;
alkali alkali
CH4 + H 20 --+ no reaction
C-Hvs.Si-H
ry
X : C == 2.5; Si == 1.8, H == 2.1
0- 0+ 0+ 0-
ra
Bond polarity: C - H Si- H
Bond energy: Si-H (393), C-H (435), Si-O (452), C-O (353) (kJ mol-I)
ib
The Si-H bond is very weak compared to the C-H and Si-O bond. Thus thermodynamically
hydrolysis of Si-Hbond is very much favourable and it is kineticallyfavoured due to the possibility
yl
of nucleophilic attack on Si-centre by using the vacant d-orbital of Si. Furthermore, protolysis of
the Si-H bond gives an additional benefit to the reaction pathway (cf. Push-Pull mechanism).
m
The polarity directions of C- Hand Si - H bonds are: co- -
Jf+, Si o+- II'- according to the
he
electronegativity difference. Thus in silane, the hydrogen has got the hydridic character to
some extent.
lc
The bond polarisation in silane allows the nucleophilic attack (Le. electron pushing effect) on
silicon which can also use the vacant d-orbitals to accommodate the nucleophile, Le.
ea
SiH4 + 20H- ~ SiH4 (OH);-

Formation of such anoinic complex enhances the hydride character of the silicon bound H.
th
This hydridic hydrogen then reacts (called protolysis Le. pulling effect) with the protonic hydrogen
of water to release H2• This combination of hydridic hydrogen and protonic hydrogen makes
e/
the Si-bound hydrogen a better leaving group. Otherwise, the Si-bound hydrogen is a poor
leaving group.
t.m
2-
H
~/
Push - Pull mechanism: H3(HO)~o+
Pull
In the same way, H 3 Si(OH)i- undergoes hydrolysis through protolysis to rele~se hydrogen.
The hydroxo complex of silicon on dehydration forms Si02 • n1120.

Covalent Compounds: Characteristics, Structure and Reactivity an
Push-Pull mechanism
Hydrolysis of some organometallic compounds also occurs through the nucleophilic attack (Le.
push) on M of M-C bond and protolysis (Le. pull) of the leaving group as outlined apove. This
protolysis makes the metal-bound alkyl groups better leaving groups, otherwise the alkyl groups
are very poor leaving groups. This aspect will be discussed later.
(20) Base catalysed racemisation ofoptically active silanes : Base catalysed racemisation ofoptically
active silane compounds occurs through the nucleophilic attack by 0/7 on silicon to produce the
ry
trigonal bipyramid intermediate. The process is outlined below.
* + OH- Berry; - OH-
Rt /SR3R4 Si ' RtR2 R3R4 Si(OH)- \ '[Rt /SR3R4 Si(OH)]- ;::,======~, Rt RtRt RtSi*
ra
(+) (Td) TBP (I) pseudo- TBP (II) +0/7 (-) (Td)
rotation
ib
No such mechanism is possible for an analogous carbon compound.
(21) Kinetic stability of GeH4 and SnH4 (compared to SiH4 ) with respect to hydrolysis reaction: In
yl
this connection, the stability of germane (Le. GeH4 ) and stannane (SnH4 ) towards hydrolysis is
worth mentioning. Probably, the electronegativities of Ge, Sn are closer to that of hydrogen and
m
as a result, the polarisation UO+ - II- which is required for the hydrolytic process is absent.
(22) Hydrolytic cleavage of organometallic compounds: The organometallic compounds like A12R6 ,
he
GaR3 , etc are predominantly covalent compounds in which the organic moiety is attached to an
electropositive metal. The bond polarisation leads to carbanion character. This carbanion
character very often allows them to act as Bronsted bases to extract proton even from very weak
lc
Bronsted acids like water and alcohols. During solvolysis, the solvent initially makes a nucleophilic
attack (i.e. push effect) on the metal centre which provides the low lying vacant orbitals to
ea
accommodate the nucleophilic attack in the A-process. In this intermediate complex of higher
coordination number, proton transfer (called protolysis) occurs through a cyclic transition state.
th
This protolysis makes the alkyl group a better leaving group (i.e. pull effect).
(C 2 H s )3 Ga + 3H2 0 ~ Ga(OH)3 + 3C2 H 6
e/
AI2 (CH3)6 + 6H2 0 ~ 2AI(OH)3 + 6CH4

t.m
A12(CH3 )6 is a Lewis acid because the electron deficient 3c-2e AI-~H3-AI bond is relatively
weak (cf. Sec. 14.7.2ii) and it can accommodate the nucleophilic attack by the solvent.
In the case of alcoholysis (solvolysis Le. alcohol solvent), the corresponding products are Ga(OR)3
and AI(OR)3.The intermediate (or transition state) of higher coordination number is of following
nature where push-pull effect operates.
~ /R'
~. (A-path) R2Ga-O)
R3Ga + R' OH ---~
Ik~-~1
Pull
(R' = H for hydrolysis, R' = alkyl group for alcoholysis).
It is suggested that protolysis may occur before the nucleophilic attack by the solvent R'OB.
In fact, this protolysis (when the metal bound R-group possesses the sufficient carbanion character)
favours the proper positioning of the nucleophile and the production of a better nucleophile
(Le. R' 0- is a better nucleophile than R'OH). Thus the overall process ofsolvolysis is energetically
favoured. Here it is worth mentioning that during the hydrolysis of silanes (discussed earlier) the
protolysis is also involved.
(23) Kinetic stability ofSi-C bond i.e. Si-R bond compared to Si-Cl and M-R (M= Ga) bonds with
respect to hydrolysis: That the protolysis step is an important step in the hydrolysis of the said
organometallic compounds is supported from the reluctance of 'Si - CH3' bond to undergo
hydrolysis. In fact, the Si-CH3 bond i~ very much resistant to hydrolysis. The electronegativity
ry
difference between Si and C is very much small and consequently polarisation of the Si-C bond
is quite insignificant. Thus in Si-CH] moiety, practically there is no carbanion character on
ra
the alkyl group. It prevents the protolysis steps which is required for the hydrolytic cleavage. In
addition to this, because of the steric hindrance, the nucleophilic attack by OH2 on silicon (in
ib
silicones) is also disfavoured (in the associativ~ pathway). The electron deficiency on Si-centre
in Si-CH3"bond is not sufficiently high to attract the nucleophile in an A -process. Thus it gives an
yl
unfavourable situation for the push-pull mechanism. This is why, the silicones are so much
resistant to hydrolysis and the silicones (e.g. (CH3)(OSi(CH3)20]4nSi(CH3)3] are used as
m
water proofing agents.
Now, we can justify the different hydrolytic products in the following reactions:
he
ISM -:-Cl +3H20~M(OH)3 + HCI + 2RH
(M:; AI, Ga)
lc
R3Si - Cl + H 20 ~ R3Si - OH + HCI

For the Al- and Ga- compounds, both the M-R and M-Cl bonds can experience the hydrolytic
ea
cleavage, but in the Si-compound only the Si-Cl bond can experience the hydrolysis through
protolysis as the Si o+-Clb- bond is sufficiently polar to allow the nucleophile attack on Si-centre
th
(A-process). The Si-C bond is not sufficiently polar to initiate the process.
(24) Hydrolysis of boron compounds: For the boron halides, the ease of hydrolysis runs as :
e/
B/3 > BBr3 > BCl3 > BF3·

It is evident that this sequence is the sequence oftheir Lewis acid strength (cf. Sec. 9.21, 14.7.2ii).
t.m
The trihalide (BX3) which can provide a vacant orbial more readily on boron to accommodate the
nucleophilic attack by water hydrolyses more readily. In the strongest Lewis acid, the
X(P1t) ~ B(P1t) bonding is the weakest one and consequently, the vacant orbital is most easily
available for the nucleophile. The general push-pull mechanistic route of hydrolysis for BX3 (X
== Cl, Br or f) is outlined below.
/xC·
X-B~HlJ. ~ ----.. BX2(OH) + HX
"x(Planar)
(sp2-B) (Tetrahedral)
(sp3-B)
Complete hydrolysis of BX3 leads to :

BX3 +3H20~B(OH)3 +3HX
For BX3 (X= CI, Br, /), the B-Xbond is susceptible to protolysis even by very weak Bronsted
acids like water, alcohol and even amines. Thus, the B-X bond can favour both protolysis
(i.e. pull effect) and nucleophilic attack (i.e. push effect) at the required transition state (cf.
solvolysis ofsilanes and organometallic compounds for which the protolysis step is quite important)
through the rupture ofP7t - P7t bonding.
ry
BFJ is highly resistant to hydrolysis. The efficient P7t(F) ~ p7t(B) bonding cannot release easily
the vacant p-orbital to accommodate the nucleophilic attack. Besides this, in BF3, the hard B(III)
centre (cf. symbiotic effect) prefers F compared to H 20. This is why BFJ tends to retain
ra
r. In fact, the hydrates like BF3.H20 (m.p. = 10.2°C), BF3.2H20 (~.p. = 6.4°C) are quite
stable. On melting of these solids, the hydrolysis occurs as follows :
ib
BFj.2H 2 0 ~ H 30+ + BFj(OH)-
yl
In excess water, BF3 partially hydrolyses to give fluoroboric acid and boric acid.
4BF3 + 6H 2 0 ~ B(OH)3 + 3BF4- + 3H30+
m
It is evident that protolysis of B-F bond is avoided and the hard B(III) centre retains the
hard centre r. This is why, in aqueous NaF solution, BF3 does not hydrolyse and it simply
he
forms BF4-. But in aqueous NaCI solution, BCl3 hydrolyses as usual through the protolysis of
B-CI bond.
lc
Now let us consider the hydrolysis of pyridine (py) adduct of BCI3 •

py.BC13 + 3H20~ py + 3HCI + B(OH)3
ea
It is quite evident that in this case, the associative path for nucleophilic attack on boron is not
possible, as the· boron centre cannot provide a vacant orbital to accommodate the nucleophile.
th
The vacant orbital on boron is engaged in forming the adduct with pyridine (py). Here the reaction
goes on through the dissociative (0) path and it requires the B-CI bond rupture at the rate
e/
determining step.
t.m
D-path + H 20 +
py.BC13 ) pyBCl2 ) py.BCI2 (OH) + H
-c/- (fast)
That the rate determining step needs the B-CI bond cleavage is evidenced from the following
reactivity order.
CHJ
Me~.BCI3 > @.BCI3 > @.BCI3
The stability of the adducts also follow the sequence, Le. the most stable adduct is the most
reactive ·one. Com"monly, it is expected that the least stable adduct is the most reactive one,
but the experimental findings do not agree with this expectation. However, the observed
reactivity order can be explained by considering the D-mechanism of hydrolysis. In the
D-mechanism, the intermediate tends to be stabilised through resonance with the aromatic ring.
For 2-methylpyridine, the steric hindrance prevents the resonance because ofthe lack ofplanarity.
-,+
(Y
-
~ - 11\"
O/Cl
U C/
I
~
<J ,,_
-
-B"
/C/
C/
~ +
0
-
C/
=B(C/ ~
Thus in the case of2-methylpyridine, the transition state is the least stable one and consequently,
the activation energy is very high. It explains the lowest reactivity of the adduct of
2-methylpyridine.
(25) Solvolysis of BR) : Solvolysis of alkyl boranes (BR 3 ) is potentially catalysed by the carboxylic
ry
acids. It may be mentioned that the mineral acids are not so efficient catalysts in this regard. The
nucleophilic attack on boron by carboxyl oxygen and transfer of alkyl group through protolysis
ra
occurs through the push-pull mechanism as outlined below. Inorganic acids can carry out the
protolysis of the leaving group but they cannot provide the required nucleophile. On the otller
ib
hand, R'C0 2H can satisfy both the requirements.
f
yl
R" ,,(R....
-B ~H
~ + Pull t ()J
m
Q,,1+o~ /
~C
he
I
R'
~
lc
R RO,CR"' + RH
~_H_20_ _ r---ll·
ea
R2B(OH) + R'C02H •
In the same way hydroperoxide (-OOH) can catalyse the process.
th
R
R",-I/~
e/
+HO
B 0 --2~)R2B(OH)+ROH+-OH
U "'-H
t.m
Similar mechanism (Le. nucleophilic attack and the protolysis of alkyl group) has been argued in
the hydrolysis of AIR) and GaR).
/
10.10.5. Some Representative Redox Reactions through Nucleophilic Substitution

Reactions
(i) Dehydration of HN02 : The steps are given below:
+
HN0 2
+
+ H H 20, "
"N=O
Here, HN02 makes a nucleophilic attack on the nitrosyl nitrogen of H 2 NO; in an interchange
(I) process. The overall reaction is :
2HN02 ~ N 20 3 + H 20
In N20 3, the nitrogen centres are not equivalent and this is why the dehydration process has been
considered as a redox reaction.
(ii) Raschig synthesis of hydrazine : The process involves the oxidation of NH3 by ocr. Initially,
NH2C/ is produced through the nucleophilic attack (A-process) by NH3 on the chloronium centre
ry
of ocr.
~ A-path
~
ra
H/I: C/-'-cr Hji-C/+ OH-
The next important step is the nucleophilic attack by NH3 on NH2C/ through an interchange (1)
ib
pathway~ .
~ ~ (I-path)
yl
+ +NH
H/I: :NH2-'-C/ ~H/I -NH2 3 ~Hji-NH2
(- C/-) -NH+
4
m
In strongly alkaline media, the conjugate base (CB) of NH2C/ experiences the nucleophilic attack.
he
NH 2 C/ + OH- :::;;;:=:=:== NHC/- (CB) + Hp. HJN~ilH f2i'- N2 H4 + cr
(iii) Synthesis of hydroxyl amine: It involves the reduction of nitrous acid by sulfite under the mild
lc
acidic condition. The steps are :

ea
th
e/
f
t.m
N+ N ....
~t----
I
HO/ "SOJ-
S03H
I
HO/ "SOji
S03H
Thus, (HO)N(S03H)2 may fqrm a zwitterion. The zwitterionic species experiences a hydrolytic
cleavage through the nucleophilic attack on S as follows :
H 20
--~~. H~04 + NH2 0H
In the presence of excess bisulfite, l1H20H is itself oxidised to NH). This is the limitation ofthe
process. The possible steps are:
Note: Some authors suggest the N-O linkage rather than N-S linkage in the intermediates. Thus
they consider the intermediate hydroxylamide-N, N-disulphate as (HO)N(OS02)2.
ry
Nucleophilic displacement in NH2-X : This type of reaction is very much important and finds
applicati9n in hydrazine and hydroxyl amine synthesis. The possible pathways are:
ra
~·0 +
(a) , Nu: + NH2 - X ------. Nu-NH2 +
ib
X- (I-process)
~~ +
+ X NH] ------. Nu- X +
yl
(b) Nu: NH; (I-process)
~ + +
+
Nu: X-NH] ------. [Nu-X-NH1 ]
m ------. Nu-X+ NH1-
(cf. Hydrolysis of NH2Cl) (A-process)
he
(c) NH 2 X +: B (base) ~ NHX-(CB) + BH+
lc
Nu : ~ NH -r;t ------. Nu - NH + X - (I-CD-process)

(CB)
ea
(d) Sometimes, the conjugate base (CD) may participate in D-process (Le. D-CB or SN1-CB)
as in th case of hydrolysis of H1V-N02 (nitramide).
th
All these possible pathways have been illustrated by taking suitable examples. From the
identification ofproducts, the mechanistic pathway can be established. This aspect has
e/
been illustrated by considering the hydrolysis of nitramide (NH2 - N0 2), NCI), NH2CI,
NHCl2 etc.
t.m
(iv) Oxidative addition: A common example of this type of reaction is :
PCI) + Cl2 ---+ PCls

In this bimolecular addition reaction, the lone pair (Le. HOMO) on 'P' is donated to the vacant
0* MO (Le. LUMO) of C12. Donation of electron into the o*-MO (Le. LUMO) of Cl2 weakens
the Cl-Cl bond. Eventually rupture of Cl-Cl bond leads to two cis-P-Cl bonds through the
involvement of d-orbital of P. This occurs through the formation of a three membered cyclic
transition state.
,,~
/~ + C/- C/ ------.
(v) Nitrosation of amines (both primary and secondary) : RIIH + HN02 --. RIIN=O + H 20.
At low concentration of HN02, the rate law is :
rate = k [am~ne] [HN02] [F]
The possible steps are:
HN02 + H+ ===>n~ HO+
2 "N=O
R)J~N=O I-process .,
ry
+ -H+
RI'H-NO (fast)" RI'-N=O
/ (rds)
H~
ra
ib
Here, amine makes a nucleophilic attack ori the nitrosyl nitrogen of H 2NO;.
At higher concentration of HN02, the rate law changes as follows:
yl
rate = k [amine] [HN02]2
HN02 undergoes dehydration to produce N20 3 and the steps have been already discussed in this
m
Section. Then N 20 3 actively participates in the reaction. The possible steps are given below:
he
2HN02 ~ N20 3 + H 20
.~~N-N~"
~ 11
lc
I-process .+ -H+
R¥Ho
., R2(H)N-N~ -(-.c.as-t-)~..
~ RI'-NO
r ~~,
(rds), -NO; ~
' ••
o o
Ii
ea
With the aliphatic primary amines (i.e. R-NH1), the initial product Le. RNH-NO, is not stable.
th
It produces hydroxyimide through 1,3-tautomerisation and then decomposes to N2 and ROH.

On the other hand, for the aromatic compound (i.e. ArNHz), the diazo-salt is produced.
e/
RNH-NO < (1,3-shijt) , R-N=N-OH +W) R-N;

(Tautomerisation) -H20
t.m
(Hydroxyimide)
R - N; (R = alkyl group) is not resonance stabilised and experiences the following reaction.
~.
RL!v+ H 20) R-OH + N + H+
2 (I-process) 2
(1,3-shift) H+
ArNH-NO >na Ar-N=N-OH - - - - - 1.~Ar-N+
.
(TautQmerism) -H20 2
Ar - N; is resonance stabilised.
r~+-0 N=N ~ + 0=+-

_ N=.N ~
(vi) Disproportionation 0/ peroxide:

2R02H ~ 2ROH + 02
The general rate law is :
rate = k [R02 H] [R0i.]
The possible reaction path is :
*
/~-O
*/H Hp (slow)
---o-H-------:~~
*
ROH + HO
*~"""OR
t
ry
R ()-O
" R
ra
• /0""" " 1.3-shift ~ 0*0 (Le. dioxygen) + ROH
Ho'
ib
OR (and decomposition)
or 00 (Le. dioxygen O2 ) + R··OH
At the rate determining step, the peroxide oxygen (a better nucleophile) makes a nucleophilic
yl
attack on a peroxide oxygen of the second molecule.
(vii) Arbuso'v reaction and racemisation 0/ optically active phosphines : These catalysed reactions
m
occur through the oxidative addition followed by reductive elimination. These are discussed in
Sec. 10.7.2.
he
10.11 STRUCTURE OF COVALENT AND MOLECULAR

lc
CRYSTALLINE SOLIDS
ea
Before to discuss the covalent and molecular crystals, it is worth mentioning that the classification of
the crystals in terms of bonding is of no much importance. There are many crystals in which both the
covalent and ionic interactions are prominent. For example, in Cdl2 which forms a chain lattice, both
th
the ionic and covalent interactions are existent along the chains. Thus the classification such as ionic
crystals, covalent crystal, etc. is convenient from the standpoint of qualitative approximation only.
e/
In some solids, the different constituent atoms are bonded throughout the lattice by the covalent
t.m
bonds. These are called covalent crystals or atomic crystals. These are of two types on the basis of
structure:
(i) diamond structure in which the atoms are bound by the a-linkages only throughout the
lattice (examples: diamond, silicon carbide (SiC), aluminium nitride (AIN) etc.);
(ii) graphite structure in which the atoms are bound through both 0'- and 1t;-linkages in different
separate layers which are held through the weak van der Waals forces (examples: graphite,
boron nitride (BN), black phosphorus, etc.).
In the molecular crystals, the different covalent molecules which may be polar or nonpolar are held
in lattice through the weak intermolecular forces. Examples are : ice, sugar, iodine, etc. -
10.11.1 Diamond Cubic (dc) Structure*

In the diamond crystals, the unit cell is constructed by the perfectly tetrahedral units. In each unit, the
* It leads to actually fcc space lattice. In fact, diamond exists in both cubic and hexagonal forms involving the tetrahedral
units. But the dc structure is well known.
four corners are occupied by four C-atoms (Le. one C-atom at each comer) bonded through the single
a-linkages with the C-atom lying at the centre of the tetrahedron. Here, the a-bonded strucltJre runs
throughout the crystals in three dimensions.
Because of the three dimensional network (see Fig. 11.9.4.1) in which all the.sp 3 carbon atoms are
tetrahedrally bonded in a continuous way, the diamond crystal acts as a giant molecule.
The three dimensional network structure of the giant molecule introduces the following properties.
(i) Density: The more compact structure (C-e bond length, 154 pm) compared to the graphite
structure throughout the lattice explains the higher density of diamond (sp. gravity = 3.54)
ry
compared to that of graphite (sp. gravity = 2.26).
In the covalent crystals, the bonds are directed as in the covalent bonding. Thus the bonding
forces are directional while in the ionic crystals the electrostaticforces are omnidirectional.
ra
The directional nature of bonding in the covalent crystals makes the crystals more open
compared to the ionic crystals. The nearest coordination number in the dc crystal is four.
ib
Here the packing efficiency is only 34%.
(ii) Nonconductor of electricity (cf. Question No. 164, Ch. 12) : All the electrons are localised
yl
in the a-bonds, and no mobile electron (Le. x-electrons) exists there. This is why, the diamond
crystal is a nonconductor of electricity. This property can be explained in terms of its band
structure (cf. Sec. 12.5.2).
m
(iii) Extremely hard: Due to the rigid three dimensional network structure, it is very hard. In
he
general, the covalent crystals are characterised by hardness. Because ofthe directional bonding
forces in the covalent crystals, the hardness is often a directional property. For example,
lc
kyonite (aluminium silicate) may be scratched along the prism axis, but it is difficult to scratch
in the direction perpendicular to the axis.
ea
(iv) High melting and boiling points: In melting or boiling, a large number of C-C bonds in the
giant molecule are to be broken down. This is why, it shows very high melting and boiling
points. .
th
Examples of diamond structure: Several other Gr IV (14) elements such as silicon,

e/
germanium and grey tin have the crystalline structure ofdiamond. Different binary compounds
formed by a Or III (13) element and a Or V (15) element or by a Gr II (12) element and by a
t.m
Gr VI (16) element or by a Gr I (11) element and a Or VII (17) element show the diamond
structure. Some of them are important as compound semiconductors (Sec. 12.9.5).
Gr III - Gr V (13-15) compounds: AlP, AlAs, GaP, GaSh, InP, lnAs, etc.
GrifI - Gr VI (12-16) compounds: ZnO, ZnS, CdS, CdSe, etc.
Gr I - Gr VII (11-17) compounds: Cuel, AgI, etc.
SiC has a diamond like structure in which both the C- and Si-atoms are tetrahedrally surrounded.
In the diamond, 50% of C-atoms are replaced by the Si-atoms to generate SiC. Silica and
silicates also possess the diamond structure in which the Si-atoms are tetrahedrally surrounded
by the O-atoms. The zinc blende (i.e. sphalerite) structure can also be regarded as the distorted
diamond structure in which half of the lattice sites are occupied by the Zn-atoms while the
other halfby the sulphur atoms. By considering the tetrahedra, the zinc blende lattice forms a
cubic close packing (ccp), i.e. face centered cube (fcc). It is also possible to place the tetrahedra
in a hexagonal close packing (hcp) model leading to the Wurtzite structure. Examples of
Wurtzite structure are MgTe, CdS, AIN, BeO, etc.
10.11.2 Graphite Structure: Properties of Graphite: Lamellar or Intercalation Compounds

, of Graphite: Reactivity of Graphite
Graphite consists of different parallel layers of C-atoms. In each layer,' the C-atoms are sp2 hybridised
and arranged in a regular hexagonal skeleton. The C-e distance is 142 pm which lies between the
single C-C (154 pm) and double C = C (133 pm) bond lengths. It is slightly longer than the carbon-
carbon distance (139 pm) in the benzene ring. The partial double bond character in graphite structure
can be explained from the resonating structures as shown below:
"/ - "
ry
..-fc-c, ~
"..-fc-~
/=
ra
~ .,c- ~ c-
~ ./
ib
The three sp2 hybrid orbitals of each carbon form three sigma-bonds while the unhybrid p-orbital
(let it be Pz' considering the layer to remain in the xy-plane) with an unpaired electron remains
yl
perpendicular to the layer on each C-atom. The p=-orbitals overlap together sidewise to form a delocalised
pi -system extending above and below each layer (Fig. 10.11.2.1). The adjacent layers are separated
m
at a distance of340 pm which is too long to carry out any covalent interaction between the adjacent
layers. In fact, this distance is more than the sum of two covalent radii of C Le. 2 x 154 pm = 308 pm <
he
340 pm. Thus the layers are weakly held through the van der Waals forces.
lc
1st Layer
:,.E
ea
Ven der walls I 1 I

Forces --+1 I Ie..
I 1
1 I~
('t)
-- :i-
th
2nd Layer~~~~
1 E
10.
e/
~~rtP~
'0
3rd Layer
--i.
t.m
1+---+1
142 pm
(a)
A A
/ \ / \ B B
=c c=c c-
\ / \ #
C=C C-C
/ \ # \
=C C-C C- C
, ,
\ t \ # A
C-C'\. C-C'\.
a-graphite Ji-graphite
(b) (c) (d)
Fig. 10.11.2.1. (a) and (b) denote the layers structure of graphite. Stacking of layers in a-graphite (c)
and ~-graphite (d). (b) denotes the localised C = C and e-C bonds.
In terms of stacking of flat two-dimensional sheets of C-atoms, graphite is found to adopt two
structures: a-graphite (hexagonal) and p-graphite (rhombohedral). The stacking arrangements are as
follows:
a-graphite: ABABAB }
. (cf. Fig. 10.1 1.2.1 )
p-graphlte: ABCABCABC .
In a-graphite, every third layer is the mirror image of the 1st layer Le. hexagonal C6-rings of each
1st and 3rd layer are eclipsed. In this arrangement, a vertical line joining a C-atom of one layer with the
corresponding C-atom of the 3rd layer will pass through the centre of a hexagonal C6 -ring of the middle
ry
layer (cf. Fig. 10.11.3.1). Thus the middle layer remains stacked staggered with respect to the
adjacent upper and lower levels. In the ~-form, every 4th layer is the mirror image of the 1st layer Le.
ra
the 4th and I st layer are eclipsed. It may be mentioned that C-C bond length (142 pm) and interlayer
spacing (340 pm) are the same in both forms. These two forms are almost equally stable and they are
ib
interconvertible.
grinding n.' A heating
a -----.-,) ...,; ..., ->-1-O-25-0-C~) a
yl
Allotropes of Crystalline Carbon
m
The important allotropes of carbon are : diamond, graphite and fullerene. The two other less
important allotropes are chaoite and carbon(VI) obtained when graphite is strongly heated. These
he
are more inert than graphite. They are probably constituted by the -C ==C-C ==C- linkages.
That the hexagonal units in each layer are mutually linked in the graphite structure is supported by
lc
the fact that graphite on being completely oxidised produces a benzene derivative viz. mellitic acid,
C6(C0 2H)2' Le. benzene hexacarboxylic acid.
ea
Complete
th
Graphite -----i~~
Oxidation
e/
co/!
t.m
The layer structure of graphite is in conformity with the following properties of graphite.
(i) Electrical conductivity (cf. Question No. 164, Ch. 12) : Because of the existence of the
mobile 7t-electron cloud in the plane of the layer, it can conduct electricity. It is important to
mention that the electrical conductivity of graphite is anisotropic. The electrical conductivity
in the direction parallel to the planes is about 3 x 104 S cm- 1 (at 25°C) which decreases with
the increase of temperature (Le. characteristic feature of a conductor). On the other hand,
the conductivity in the direction perpendicular to the planes is very low and this conductivity
increases with the increase of temperature (i.e. characteristicfeature ofa semiconductor).
This anisotropic conductivity is consistent with the formation of half-jilled 7t-band extending
over the planes or sheets. Actually, the 7t-band splits (cf. Sees. 12.5.2, 12.11.3 for the driving
force behind such band splitting) into two bands. The lower band constituted by the 7t-MOs
acts as the valence band (VB) while the upper band constituted by the 7t·-MOs acts as the
conduction band (CB). The' x-VB (Le. HOMO) is fullfilled and the x*-CB (Le. LUMO)
remains empty. Theforbiddenenergy gap (Le. energy difference between the VB and CB) is
almost zero. It just allows the overlapping of the VB and CB with DOS (density of states) as
zero at the contact point of VB and CB and it explains the electrical conductivity and graphite
is considered to show the semimetallic conductivity (cf. Sec. 12.4.2). It is important to mention
that in BN (Le. boron nitride called inorganic graphite), there is a finite energy gap (Fig.
10.11.2.2) and it acts as an insulator.
n*-band
ry
1t*-band
Conduction Band
ra
(E g = 0, DOS =0)---+ ~NN"NN~"NNNN"N""NNNNN~
~,,""""""""""""""""""'''''''''''''''''''''''''',,~
~ "''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''''',,~
:::::::. Valence Band -::::::: 1t-band
ib
..,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,'"
1t-band
(Graphite) (Layered 8N)
yl
(Semimetal conductor) (Insulator)
Fig. 10.11.2.2. Positions of valence band (VB) and conduction band (CB) in graphite and layered boron
nitride (Le. inorganic graphite).
m
he
(ii) Soft, flaky and slippery behaviour: As the adjacent layers are held through the weak van der
Waals forces only, they can easily slide or glide on each other by the external pressure. This
lc
is why, it is soft, flaky and slippery. Because of these properties, it is very often ~sed as a
lubricating agent.
ea
(iii) Less dense than diamond: Because of the existence of the well separated layers in graphite
structure, it is relatively open compared to the diamond structure. This is why, it is less dense
than diamond (sp. gravity of diamond = 3.54; sp. gravity of graphite = 2.26).
th
(iv) Reactivity ofgraphite and graphite compounds: It is more reactive than diamond because
e/
of the loosely bonded pi-electron cloud and open structure. Some foreign molecules or ions
can penetrate into the space between the adjacent layers to form lamellar compounds or
t.m
intercalation compounds. The foreign guest species is called the intercalate. Sometimes, the
hybridisation changes to sp3 and the compounds get the puckered structure without any
electrical conductivity.
The chemical reactivity of graphite can be explained by considering the position of HOMO
and LUMO. In fact, the energy separation between HOMO and LUMO in graphite is
marginally small (cf. Fig. 10.11.2.2 and 3. This is why, graphite can act both as an electron
donor and electron acceptor to the species which can intercalate between the sheets. For
example, K-metal can reduce graphite and the extra electron is accommodated in the LUMO
which is a 7t. band (Le. n-conduction band) of graphite. It introduces the metallic conduction
(Fig. 10.11.2.4). IC ion penetrates and resides betWeen the layers (Fig. 10.11.2.3). Because
of such accommodation of IC ions, graphite swells along a particular axis. Formation of such
intercalation compound (known also as lamellar compound) through the oxidation ofgraphite
is also known (during oxidation of graphite, electron is lost from the n-valence band). In
fact, accommodation of guest species between the layers of C-atoms of graphite enforces the
Covalent Gompounds: Characteristics, Structure and Reactivity 889
Carbon layer Layer of guest species

A _ AOOOO A _ A A _ A _
B
A
_
_
AOaOO
AOaoO
AOaOo
B _
A 0'0
B
°° A
B
a °°°
_
"AOOOO
B _
B _ AOaOO BOOOO A A _ A _
A _ AOaOO A _ AOOOO B _ B _
B _ AOOOO AOOOO B BOOOO A _
AOOOO B _ A A _ AOOOO
Graphite
(a-form) Stage-1 AOaOO AOOOO B _ B _
A _
(e.g. MCa)
~0
ry
Stage-2 Stage-3 0 0 0 B _
(e.g. (e.g.
M(C 12 )2 M(C 12 )3 Stage-4 A_--:-_
ra
A 000·0
sMC24 == MC 36 (e.g.
M(C 12 )4 Stage-5
=MC4a
ib
(e.g.
M(C 12 )S
=MCso
yl
Fig. 10.11.2.3. Different stages of graphite intercalation compound (a cross sectional view). Note: Two
m
G-Iayers sandwiching the guest layec..are in an eclipsed arrangement (Le. AA or BS) while the adjacent
layers are in a staggered arrangement (Le.....ABABAB....) in a-graphite.
he
C-Iayers to move further apart. Thus the produced intercalation or lamellar compounds of
graphite (called graphite compounds) are of two types:
lc
• Type-I: Graphite layers are buckeled and x-electron system is lost. Saturation of valence of
C-atoms is attained through the spJ hybridisation. Because of the loss of x-electron systems,
ea
such compounds become nonconducting and colourless.

Examples: (a) Graphitejluoride i.e. (CF)n is obtained by reacting graphite with fluorine at
th
~ 600°C. Here the C-C distance is 154 pm and the distance between the layers is increased to
820 pm. It contains C-F bonds. Though the representation (CF)n indicates monofluoride,
e/
actually the material is nonstoichiometric and it is represented as Cji'. The fluoride content
depends on the reaction condition. (b) Graphite oxide is obtained by treating graphite with
t.m
the oxidising agents like KMn04 , fuming HN03 etc. There may be incorporation of OH or IC
= a group. Its composition may vary· depending on the reaction conditions. The distance
between the layers may be 600-1100 pm.
• Type-II: Accommodation of the guest species does n<?t destroy the planarity of the C-Iayers
but they are separated further. They are coloured and conductors.
Examples: Oxidation and reduction of graphite can produce such components like C; AsF6-
(oxidation of graphite by 0; AsF6-), C~ K+ (reduction of graphite by K). Different stages of
such compounds are discussed below.
When K-vapour reacts with graphite at about 300°C, the following reaction occurs.
Graphite + K ~ C60 K ~ C4s K ~ C24 K ~ CsK (i.e. Ci K+)

(black) (deep~blue) (steel blue) (bronze coloured)
When alkali metal-graphite compound is heated under reduced pressure, the metal is gradually
removed to give a series of intercalation compound CgM and (C 12 )"M (n = 2,3,4,5). On

prolonged evaporation, all alkali metals are lost and finally graphite is regenerated.
In CgK or CgM (M = K, Rb, Cs), there are alternate layers of metal and carbon atoms. The
metal atoms are placed above and below the centres ofC, rings ofthe two C-layers. Here it
is worth mentioning that in pure graphite (a-form), the stacking of layers follows the pattern
... ABABAB.... but the metal ions are placed between either the AA layers or BB layers.
Thus the two adjacent layers accommodating the guest metal ions in their interlayer spacing
remain in eclipsed forms Le. the accommodating layers are the mirror images to each other.
ry
To accommodate the guest metal ions in the interlayer spacing, the distance between the
intercalating layers is increased compared to that in pure graphite. The increase of interplanar
ra
gap depends on the size of the guest metal ions. This is illustrated below.
Graphite CgK CgRb CgCs
ib
lnterplanar spacing: 340 pm 540 pm 561 pm 595 pm
With the increase of the size of the metal ion, the interplanar distance increases. Though the
yl
interplanar distance increases in such intercalation compounds, the C-C distance in each
layer remains almost identical to that in graphite.
m
The metals are trapped between the C-layers. The number of C-Iayers between the intercalating
he
layers trapping the metals describes the stage of the compounds. Accordingly, there are 5
'stages for such compounds. In the compounds Cz4M, C3,M, C4sM and C,oM, there are 2,
3, 4 and 5 layers of C-atoms respectively between the intercalating layers accommodating
lc
the W ions. The CgM, C24M, C36M, C4g M and C60M represent the stage-I, 2, 3, 4 and 5
respectively. The stage x compound (x = 1, 2, 3, 4, 5) indicates that after the every x-th
ea
layer of C-atoms, there is a layer of guest species (cf. Fig. 10.11.2.3).

When graphite is heated in a mixture of HN0 3 and H 2S04 , graphite is oxidised through the
th
removal of electron from the filled 7t-valence band and HSO;' intercalates between the sheets.
It produces the composition C;4HSO;'.2H2S04.
e/
Band structure ofgraphite and its intecalates and their electrical conductivities: The band
structure (Fig. 12.5.1.5, 10.11.2.2) of graphite indicates zero band gap between the filled VB
t.m
(Le. 7t-band) and vacant CB (Le. 7t*-band) but at the contact point of their boundaries, DOS
(density of states) is zero. It gives the semimetallic property of graphite. If electrons are
added to the band structure of graphite, the extra electrons will occupy the CB which will be
partly filled. It will introduce the metallic conductivity. If, electrons are withdrawn from
graphite, then the valence band becomes partially vacant and then this band can show the
metallic conductivity.
This is why, the intercalates like CgK Le. Ci K+ (Le. reduction of graphite accumulates
electrons in the vacant CB), CgBr Le. C; Br- (Le. oxidation of graphite removes electron
from the filled VB) show the metallic conductivity while graphite itselfshows the semimetallic
conductivity. The band structure of the intercalates explains their colour.
Examples of other substances having the graphite-like structure: Boron nitride possesses
a graphite-like structure. Mica, black' phosphorus, arsenic, antimony, etc. form the graphite-
like layer structure. CrCl3 , molybdenum disulphide also form such two dimensional layer
Partly filled
/ CB (1t* band)
ry
Partly filled
Filled VB ~ VB (1t-band)
(1t-band)
ra
DOS...... DOS...... DOS ......
ib
(a) Graphite (b) CaK or CaRb (c) CeBr or CaAsFs or C8HS04
Fig. 10.11.2.4. Schematic representation of band structures of semimetallic graphite (a) and its intercalates
yl
(b, c) having metallic conduction. (DOS = density of states).
m
lattices. The corresponding one dimensional lattices are called chain lattices. Examples are:
CrCI2 , CuCI2 , AlCl3 etc.
he
The forces acting between the adjacent layers or chains are generally weak van der Waals
forces but in some cases, the ionic forces may operate.
Difference in the structures adopted by the elements of C-group i.e. Gr. 14 : Silicon and
lc
germanium, Le. the heavier congeners ofcarbon, adopt the diamond structure and they cannot
ea
adopt the graphite like structure. It is due to the nonexistence of P1t-P1t bond in Si and Ge.
In C-system, the efficient P1t-P1t bonding allows it to adopt the graphite structure.
th
10.11.3 Comparison Between Graphite and Inorganic Graphite (i.e. Boron Nitride)
Boron nitride (BN) adopts the graphite like structure. It is worth comparing the properties of graphite
e/
and boron nitride called inorganic graphite.

t.m
B-N bond is similar to C-C bond in many respects. These are :

• BN group is isoel~ctronic (with 8 valence electrons) with C2 ;
• x-bonding by using the 2p-orbitals is possible in both cases;
• The electronegativity and covalent radius of C are approximately intermediate between those
of Band N; B-N bond is polar but C-C bond is nonpolar.
The common form of boron nitride adopts a graphite like structure where the layers constituted by
the hexagonal rings of (BN)3 are stacked. In the planar hexagon, Band N are alternately positioned and
both of them are sp 2-hybridised. The stacking patterns of the layers are different for boron nitride
and graphite (Fig. 10.11.3.1). In boron nitride, the layers are stacked in a way so that N-atom of one
layer resides directly between the B-atoms ofthe adjacent layers Le. N-atom of one layer is sandwiched
directly by the B-atoms of lower layer and upper layer. On the other hand, in graphite, the hexagonal
(C6 ) rings in alternate layers are placed directly on top of one another.
In boron nitride, the B-N bond length (145 pm) is shorter than the sum of covalent radii of Band N
(88 + 70 = 158 pm). This shrinkage in bond length supports the 7t-bonding in B-N Ifnkage. The distance
"
::
-."
:
'
~ :
:
"
.., . .,,
'
ry
ra
(a) a-Graphite, (- - 'ABA- --)
ib
• denotes C,
C: denotes the centre
yl
of hexagonal ring
m
he
lc
ea
th
(b) a-Graphite (d) Boron nitride

e/
Fig. 10.11.3.1. Structural features of a-graphite (a, b) and boron nitride (c, d). Stacking of parallel layers
constituted by hexagonal rings (a and c); projection of one layer over the other layer residing just below
t.m
(b and d).
between the successive layers of boron nitride is 335 pm while in graphite, it is 340 pm. Like graphite,
boron nitride can also act as a lubricant. It supports the van der Waals interaction between the adjacent
layers. Because of these similarities between graphite and boron nitride, it is reasonably described as
inorganic graphite. However, the remarkable difference between these is :
graphite is lusturous and a conductor ofelectricity while inorganic graphite is colourless ,and an
insulator.
This difference in property can be explained by considering the band theory ofsolids (cf. Chapter
12). The energy gap between the filled 7t-bonding molecular orbitals (Le. HOMOs) constituting the
rt-valence band and the empty antibonding 7t-molecular orbitals (i.e. LUMOs) constituting the
x-conduction band is significantly larger in inorganic graphite than that in graphite. In fact, graphite is
a semimetal where the valence band and conduction band just overlap. This explains the colour and
conducting property ofgraphite and colourless and nonconducting property of inorganic graphite.
In graphite, Eg is almost ,n*-ABMO ,

zero while in inorganic grap- I
" (LUMO) ~,
I ,
hite it is significantly high. This
difference can be explained by n*-ABMO -----.,,
,,
"I ,
,,
,,
considering the energy diffe-
," LUMO \ , ,, ,,
rence of the p-orbitals leading ,, I ,
,, ,, ,,
to the 1t-MOs (Fig. 10.11.3.2). , ,, ,, ,,
,, \
,,
,,
,,
,,
Graphite: C(2P7t)-C(2P7t); 4' \
.. : '. 1
ry
Inorganic graphite: B(2P7t) - C(2pz} ", : 'C(2Pz ) ~ ,
;~---1*~- I
N(2P7t) : In the case ofgraphite, \
\ , I
~ " N(2pz}
the 2p orbitals of carbon are , , , I
,, ,
, I
ra
I
involved. Consequently, it '. 1b ' '''''''''----'Il1b....--'

1t-BMO 1t-SMO
gives a good overlap and the
ib
(HOMO) (HOMO)
bonding and antibonding Mas (a) (b)
are equidistant from the starting
yl
atomic orbitals. In inorganic Fig. 10.11.3.2. Formation of x-MOs in graphite (a) and boron
graphite, the energy of 2p n~tride (b). The x-BMOs generate. the vale~ce band while the
·t
or b 1 a I 0
f · t
nl rogen IS ·
m
x -ABMOs generate the conduction band In the cluster.
significantly lower than that of boron. Thus, the bonding 1t-MO is enriched with the character of 2p
he
orbital of nitrogen while the antibonding 1t.-MO is enriched with the character of 2p orbital of boron.
Thus for inorganic graphite, the conduction band is predominantly constituted by the 2p-orbitals of
boron while the valence band is predominantly constituted by the 2p orbitals of nitrogen. This is why,
lc
theforbidden energy gap (E,J is significantly high in boron nitride.

ea
10.11.4 Molecular Crystals

For the polar molecules (e.g. H 20 in ice), the dipole-dipole force operates while for the nonpolar
th
solids (e.g. 12, solid CO2, sugar, solid benzene, naphthalene, etc.) the weaker dispersionforce mainly
operates. In general, in the molecular crystals, the intennolecular forces responsible to hold the lattice
e/
together are the weaker forces. Consequently, the molecules remain apart as in the liquid or gas phase.
The effect of such weak bonding in the molecular crystals is reflected in the physical properties of
t.m
the crystals. They are generally soft and deformable. The Blelting points are less compared to those
of ionic and covalent crystals. They cannot conduct electricity.
10.11.5 Buckminister Fullerene (Molecule of the Year, 1991, Science Journal) : Carbon
Clusters and Allotropic Forms of Carbon
Several C-cage clusters are now known up to 25 C atoms, both even and odd number of C-atoms are
observed in C-clusters. Above C40 (number may lie in the range 40-600), only even number of C-atoms
are found. These C-clusters may be considered as allotrop·es of carbon. In the series, C60 was first
characterised in 1985. The structures of these hollow closed cage cluster molecules, C n (n = 40~00,
only even numbers) are constructed by fusing the appropriate number- of pentagons and hexagons.
These polyhedral molecules apparently look like geodesic domes used in architecture. The family of
C-clusters containing the hexagonal and pentagonal faces are commonly calledfullerenes. C60 (nick
name, bucky balf) is called buckminister fullerene after the name of the architect, R. Buckminister-
fuller, the inventor of the art geodesic dome used in the building design. It looks like a soccer ball
(Fig. 10.11.5.1) consisting of 12 penta-

gonal faces and 20 hexagonal faces. Now
all the members ofthis family ofC-clusters
are commonly described as fullerenes or
buckminister-fullerenes.
Synthesis: C 60 was first prepared by
laser vaporisation (at about 10,000°C) of
graphite followed by the removal of the
vaporised C-atoms by a blast of high
ry
pressure of helium gas, and then the (a) (b)
vaporised C-atoms were subjected to rapid Fig. 10.11.5.1. (a) A soccer ball, (b) Structure of Gao.
ra
cooling in a vacuum chamber. This exciting
discovery earned the Nobel Prize of 1996 to Richard Smalley (Rice University, Texas) and Harry
ib
Kroto (University of Sussex, UK). In general, the fullerenes are prepared by vaporising carbon (at
about 3500 0 C) by an arc discharge between graphite electrodes under a helium atmosphere of low
yl
pressure (ca. 100 torr). Thus the shoot (calledfullerene shoot) obtained is found to contain mainly the
C-clusters C 60 and C70 . C 60 is more abundant and more stable. The shoot dissolves in organic solvents
m
like benzene or tolune and the solution looks red coloured. From the solution, C 60 and C 70 can be
separated chromatographically on alumina by using hexane solvent (yield, C60 : C 70 = 5 : 1).
he
Solution of C 60 fraction in benzene shows magenta colour while the fraction of C 70 gives an orange
coloured solution.
Structural features: C 60 molecules possess the soccer ball like shape while C 70 molecules look
lc
like rugby balls. Other fullerenes may have the structures like tubes, tubes capped with hemisphere,
etc. ~The !3C-NMR spectrum of C 60 shows a single peak indicating the uniform environment for all C-
ea
sites. However, in terms of bond length, there are two types of carbon-carbon bonds: 150 pm and 140
pm. These bond lengths are different from the isolated C-C (154 pm) and C = C (133 pm') bond
th
lengths.
The cage-like structures (Le. closedpolyhedra) ofthe fullerenes are produced by fusing the pentagonal
e/
and hexagonal faces. To close the spheroid structure, there must be exactly 12 pentagonal faces and
(% -10 ) for C
t.m
the number of hexagonal faces is given by n - Thus for C60 and C 70 clusters; there are 20
and 25 hexagonal faces respectively.
In fullerenes, each C-centre is sp2 hybridised and forms 3cr-bonds with the adjacent C-atoms. Thus,
each C-centre bears an unhybridised p-orbital with an unpaired electron. These p-orbitals may participate
in a delocalised 1t-molecular orbital system. It may introduce some aromatic character in the fullerenes.
The existence oftwo different C-C bond lengths (140 pm and ISO pm) indicates that the aromaticily
is not very much significant in fullerenes. In other words, it may be
said that the double bonds are more or less localised in the fullerenes.
The fullerenes are more reactive than the ideal aromatic systems.
By considering the concept oflocalised double bond, the distribution'
pattern of the single and double bonds in C6o -fullerene can be explained
by considering the structural unit given in Rig. 10.11.5.2.
In the structural unit, it is evident that each C-atom is positioned at Fig. 10.11.5.2. Structural
the juncture of two hexagonal rings and one pentagonal ring. C (A) unit of G60 fullerene.
and C (B) are such two representative C-atoms (Fig. 10.11.5.2). The double bonds are localised in
the hexagonal rings. The edge (e.g. A-B edge in Fig. 10.11.5.2) shared by the adjacent two hexagonal
rings localises the double bond and this edge gives the shorter C-C bond length (140 pm). This distance
also gives the shortest distance between the nearest pentagons. The edges shared by the adjacent
pentagonal and hexagonal rings correspond to the longer C-C bond lengths (150 pm). A-F, A-G, B-D,
B-E (in Fig. 10.11.5.2) represent such longer C-C bonds. Thus C60 possesses ,the structure ofa truncated
icosahedron. In fact, the football like spherical structure (Le. '
truncated icosahedron) is the most symmetrical one among the
all possible structures in three dimensional space.
ry
The high reactivity of C60 arises due to the nonplanarity 0/
the double bonds because the nonplanarity introduces some strain
ra
in the molecule. The high reactivity arises also from the
nonaromatic character of the fullerenes.
ib
Crystal. structure 0/ /ullerenes : The un'it cell of solid
C6o-fullerene is fcc (face created cube) Le. ccp (cubic close
yl
packing) (Fig. 10.11.5.3). At the lattice points, the C 60 molecules
can rotate freely by using the thermal energy.
m
This cubic close packing (ccp) crystal produces large Fig. 10.11.5.3. Representation of
interstitial sites and vacant cages which may mechanically trap a unit cell of face-centred cubic
he
solvent molecules and other impurity molecules during (fcc) lattice of Ceo.
crystallisation. However, pure material may be obtained by low
pressure sublimation. The high melting points 0//ullerenes are due to their close packing structure.
lc
Because of the same ground, they dissolve in organic solvents very slowly.
Properties o/solid C,o/ullerene : C60 ball shows the outer and inner diameter 1018 pm and 348
ea
pm. Thus C60 shows the mean diameter of683 pm. In thefcc lattice ofC60 , the tetrahedral and octahedral
site radii are 112 pm and 207 pm respectively. The 1st and 2nd ionisation energies are 7.6 eV and 11.5
th
eV respectively. The electron affinity ofC6o is 2.65 eVe The band gap (Le. energy difference between
HOMO and LUMO) is 1.7 eVe It indicates that C60 is nonconducting. The mass density ofC6o is 1.72
e/
g cm-3• .
Reactivity 0//ullerenes : Formation of endohedral complexes through the encapsulation of metal
t.m
ions in the cage of en-clusters is a common characteristic feature. If graphite is treated with an aqueous
solution of lanthanum chloride and it is used for gas phase synthesis of fullerene, then encapsulation of
the metals occur in the fullerene cluster. The examples of such endohedral complexel are :
La @ C 60 ' La @ C 70 ' Y2 @ C S2
Here, @ indicates encapsulation. From the esr studies, La @ C60 appears as La3+ @ C~o.
Reduction of C60 can produce the polyhydro/ullerenes ranging from C60HIS to C60HJ6 • Oxidation
of the C-Hbonds can produce/ullerols, C60 (OH)n (n = 24-26). Halogenation ofC6o can give different
halogenated products like CJ60' C6oF4S' C60 Cln (n = 24-26), C60 Br24 , etc.
Solid C60 on being treated with alkali metal va~ur undergoes reduction and different phases like
M3C 60 , M4 C 60 or M6C60 are produced. The alkali~etal ions (W) eccupy the octahedral and/or
tetrahedral sites of close packing structure of C,o' In this process, C60 undergoes reduction and it
exists as anions. The/ulleride anions are C;o (n = 1-6). The M3C60 phase is superconducting with
different Tc values for different alkali metal ions (Tc = 19 K for K 3C 60 ; Tc = 29 K for Rb 3C 6o ; Tc = 33 K
for CsRb 2C6o ). Thus, Tc increases with the increase of the size of alkali metal ions.
It has been already mentioned that in fullerenes, the 'It-electron system is more or less localised and
this is why the fullerenes can form adducts by using the localised double bonds. C60 can form an adduct
with Os04 in benzene containing 4-t-butylpyridine. It indicates the existence of localised double bonds.
CMej
(;;;«0""
o
II / ©f
0
(C60 uses two adjacent
- ~o/ 1r"~ ~-atoms for bonding).
ry
CMe j
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C60 and C70 can form T)2- adducts by using the 1t-electrons of the localised C = C bonds. Thus, the
fullerenes act just like the alkenes.
ib
C60 + fr(CO) Cl(PP~)2 ~ (,,2 - 60)fr(CO)CI(PPh3 )2
(Vaska's compound
yl
C60 + (,,2 - C2H 4 )Pt(PPh3 )2 ~
m (,,2 - 60)Pt(PPh3 )2 + C2H 4
10.12 STRUCTURE AND BONDING IN HIGHER BORANES AND

he
CARBORANES
The structure and bonding of B2H6 have been already discussed in Sec. 9.21 in terms of the electron
lc
deficient 3c-2e (B-H-B) hydrogen bridge bonds.. Here we shall mainly discuss the higher boranes
having the cage-like structures. Alfred Stock, a Gemlan chemist prepared several members of boron
ea
hydrides having different formulas.

Hydrogen poor group represented by B"Hn + 4 (e.g. Bs H9 , BgH 12 , etc.) and hydrogen rich group
th
represented by B"Hn + 6 (e.g. B4H 10' B~Hll etc).

Recently, other series represented by BnH;- (e.g. B 6 Hi-, B10H12o-, B12 H 1;-, etc.) and BnIr;,+7 (e.g.
e/
BsH l-2 ) have been reported.

Most of the boranes are highly reactive towards O2• Among the neutral boranes, only B 1oH14 can be
t.m
handled in air.
10.12.1. Classification and Different Series of Boranes

The boron hydrides are classified in different series:
(a) Closo-serics: These are isoelectronic with B"Hn + 2 or BnH;-. They normally exist as BnH;-.
Examples: BsH;- to B12H122- (Le. n = 5 to 12). .
The closo-borane anions (Greek closo means cage) have closed polyhedral clusters of n-boron
atoms (i.e. n-vertices).
Characteristics :
• Deltahedral structure (deltahedron means a regular polyhedron with triangular faces);
• Cage like structure;
• No BHB (3c-2e) bond;'
• No BH2 group;
• Isoelectronic with the neutral borane B,/in + 2 which is less stable than B,/in2-.
• (n + 1) skeletal electron pairs (SEPs) for B-framework (cf. Wade's rule).
(b) Nido-series: The~e are isoelectronic with B,/in + 4.
Example: B2H6 , B5H9 , BsH8-, B6H 1o , B8H 12 , B 10H 14 , B 10H I3 -. The structure of these boranes
looks like nest-like (Latin word nido means nest).
Characteristics :
• Nest-like deltahedral structure with a missing vertex;
• Isoelectronic with B,/in + 4;
ry
• (n + 2) skeletal electron pairs (SEPs) for B-framework.
(c) Arachno-series: These are .isoelectronic with B,/in + 6.
ra
Examples: B4H 10 ; BsH11 ; B6H 12 ; B8H 14 ; BgH15' etc.
Arachno (Greek word meaning web-like or spider's web) series possess the web-like structure.
ib
Characteristics :
yl
• Web-like deltahedral structure with two missing vertices.
• (n + 3) skeletal electron pairs for boron framework.
m
(d) Hypho-series: These are isoelectronic with B,/in + 8.
Examples: BsHi;, BsH I21-, no neutral borane in this group.
he
Hyphe (Greek word meaning net-like)
Note: Boranes BpHp+q Le. (BH)pHq can be formulated as (BH)n(BH 3)x where n = 0, 1,2,
..., I{) and x = 1,2,3, ..., e.g. B2H 6 == (BH3)2; B3H 7 == (BH)(BH3)2; B5H 9 == (BH)3(BH3)2;
lc
116 H 12 == (BH)3(BH3)3' etc. In fact, for nido-series, x = 2 (and q = 4) and for arachno-series, .
x = 3 (and q = 6).
ea
In general, the thermal stability order is :

cwso-)nido-)~achno-)~ho-
th
Conjuncto-boranes (B"Hm) : These are formed by joining the subunits of two or more of the
different series. The examples of conjuncto-boranes (Latin conjuncto means join together) are:
e/
B8H 18 , B 1oH16' B 15 H23 , B 16H20 , etc.

t.m
The different series are related as follows

-BH 2+ -BH 2+
BnH;- ) BpH p + 4 ) BmHm+ 6
+4H+ +2H+
(closo -) (p=:=n-I) (m = n - 2)
(nido -) (arachno -)
-2BH2+
+6H+
f
-BH 2+, +4H+ -BH 2+,+2H+
B6 H 62- ) BsH 9 ) B4 H 10
(closo-) (nido-) (arachno-)
-BH+, +4H+ -BH 2+, +2H+
B7 Hi- · ) B6 H10 ) Bs H l1
CLOSO-series (BnH~- )
ry
(8H)SH 4 == 8 SHg (BH)4 HS == B4 H 10
=
8 1 - 82 8 1 - 83 =
8 1 - 8 2 185 pm;
ra
= 8 1 - 8 4 =8 1 - 8 s 81 - 83 =172 pm.
= 169 pm,
8 2 - 8 3 , etc. =180 pm.
ib
yl
m
he
(8H)sH S == 8 5 H 11
= =
8 1 - 8 2 8 1 - 8 5 187 pm
= =
8 1 - 8 3 8 1 - 8 4 172 pm.
lc
=
8 2 - B3 8 4 - 8 5 = 176 pm.
(8H)sH 4 == 8 sH 10 .=
8 3 - 8 4 177 pm.
ea
8 1 - 8 2 =170 pm, 8 1 - 8 4 ~'
=
=180 pm, 8 2 - 8 3 179 pm,
8 3 - 8 4 = 174 pm,
th
8 4 - 8 5 =160 pm.,
e/
t.m
(8H)10 H4 == 8 10H 14
=
8 1 - 8 3 171 pm, 8 2 - 8 s
= 8 4 - 8g = 172 pm, 8 1 ~ 8 2 .4.7,8
=B2 - 8 5,7 = 8 6 - 8 5•7
2- 2- = 8 4 - 8 8,10 = Bg - 8 8,10
(8H)g == 8gHg =177 pm.
Fig. 10.12.1.1. Framework of some representative boron hydrides (0 for B • for H)
10.12.2 Nomenclature of Boranes

(a) Neutral boron hydrides are named as boranes. The Greek prefix (e.g. di, tri. tetra,penta, hexa,
hepta, octa, ennea, deca, etc.) indicates the number of B-atoms. For neutral species, an Arabic
number in the parentheses gives the number of H-atoms.
Examples: B 1H 6 : diborane (6) [commonly called diborane as there is no alternative possibility];
B sH 9 : pentaborane (9); B 6H IO : hexaborane (10); B'//14 : octaborane (14); B ull14 : decaborane
(14); Bc/lls : enneaborane (15); B I4H 20 : tetradecaborane (20) etc.
(b) The anionic species are named as hydroborates and the Greek prefix indicates separate~y the
ry
number of hydrogens and borons. The charge of the anions is given within the parenthesis.
Example: B sH8: octahydropentaborate (1-); BloH;;: decahydrodecaborate (2-); BI1H;;:
ra
dodecahydrododecaborate (2-).
Note: Sometimes, the structural typ_~ is also specified.
ib
Examples: BsH8 : octahydro-nido-pentaborate (1-); BI1H~- : dodecahydro-closo-dodecaborate
(2-); ~OH14: nido-decaborane, etc.
yl
10.12.3 Structure and Molecular Framework of Hydrides of Boron
m
With the exception of B2H6 and B3 H;, boranes' cage structures are formed based on polyhedra or
polyhedral fragments having equilateral triangular faces with the BH groups at the vertices. Such
he
polyhedra are commonly called deltahedra. The triangular faces of the polyhedra look like the upper-
case Greek delta (~). This is why, such polyhedra are called deltahedra. The deltahedra from n = 4 to
lc
n = 12 (where n gives the number of vertices) are: tetrahedron (n = 4), trigonal bipyramid (n = 5),
octahedron (n = 6), pentagonal bipyramid (n = 7), dodecahedron (n = 8), tricapped trigonal prism (n
ea
= 9), bicapped square antiprism (n = 10), octadecahedron (n = 11), and icosahedron (n = 12). In this
list of polyhedra, the example of cube is excluded.
th
The deltahedral geometry is common for different cluster structures like boranes, carboranes,
Zintl ions etc.
e/
For a deltahedron with n-vertices for the Mn cluster, there are n + 1 bonding MOs. Always the
clusters may not adopt the geometries of closed deltahedra. If no vertex is missing, then it gives the
t.m
closo-geometry, if one vertex is missing, it gives the nido-geometry, if two vertices are missing, it
gives the arachno-geometry. This is illustrated for boranes and carboranes.
If all the vertices of a deltahedron are occupied as in closo-series (BnH;-, n = 6 to 12), the structure
becomes closo type. The dicarboranes Bn _ 2C2Hn (n = 5 to 12) also belong to this group.
Nido-series : If one BH unit from a closo-structure is removed but the electron pair is retained by
the residual structure, then the resultant structure becomes nido-type which looks cup-like or nest-
like. Thus, in a nido-structure, one vertex remains missing compared to the parent closo-structure. On
reduction of a closo-molecule, a nido-molecule may be obtained.
closo - B9 C2 H)) + 2e ~ nido - B9 C2 H)2)-
Some common examples of nido-boranes are: B2H6 (a triangle lacking in one B-atom), BsH9 (an
octahedron lacking in one B-atom), B6H 10 (a pentagonal bipyramid lacking in one B-atom).
Arachno-series: If two vertex B-atoms (= 2BH2+ units) are removed from a closo-structure, then it
leads to a arachno (web-Iike)-structure. Thus, an arachno structure is more open than the corresponding
Trigonal
Tetrahedron (4) bipyramid (5) Octahedron (6) Pentagonal
(Td ) (D 3h > (Oh) bipyramid (7)
ry
(D Sd )
ra
ib
yl
Capped Dodecahedron (8) Tricapped trigonal
octahedron (7) prism (9) (C3v )
(D 2h )
m
he
lc
ea
Bicapped square Octadecahedron (11)

antiprism (10) Icosahedron (12)
th
(D4d ) (/ >
h
Fig. 10.12.3.1. Structures of deltahedra (Le. regular polyhedra with triangular faces) for boron hydrides
e/
and' carboranes. B or G-atoms are placed at the vertices.

Note : The lines joining the vertices do not represent the bonds.
t.m
nido-structure which is again rnore open than the parent closo structure. In the arachno structure, the
resemblance to the parent closo-structure is less apparent. The gradual transition from closo- to arachno-
structure is illustrated in the following example:
-BH 2+, +4H+ -BH 2+, +2H+

B6 HJ- ) BsH 9 ) B4 H 10
(octahedral) (square pyramid (butterfly like structure
== octahedral minus == octahedron minus
one vertex) two cis-vertices)
It is important to note that each of the above three species possesses 7 framework or skeletal
electron 6airs. In fact, the number of skeletal pairs (8) available for framework bonding determines
the nature of structure (cf. Wade's rule, to be discussed later on).
A similar situation is illustrated below:
2 -BH2+ +4H+ -BH2+, +2H+

closo - B7 H 7 - , ) nido - B6 H 10 ) ~rachno - BsH ll
There is a good correlation for the structures of closo-, nido- and arachno boranes. It is illustrated
in Fig. 10.12.3.2 and 3 (cf. R.W. Rudolph et al., Inorg. Chern., 11, 1974, 1972; R.W. Rudolph, Ace.
Chern. Res., 9, 446, 1976).
ry
ra
ib
yl
m
he
lc
ea
Nido-B aH10
th
e/
t.m
Fig. 10.12.3.2. Generation of arachno-BsH11 (a) and arachno-B4 H10 (b) from their precursor closer
structures through the successive removal of BI-P+ groups. (0 for B, • for H).
Nid~Bn-1Ht1
ry
ra
ib
yl
m
he
lc
ea
th
e/
t.m
Fig. 10.12.3.3. Generation of nido- and arachno-boranes from their precursors through the successive
removal of BH 2+ groups. (0 for B, • for H).
Regular polyhedron Removal of Removal of

Closo-structure - - - - - - + ) Nido-sttucture - - - - - 4 ) Arachno-structure
(n-vertices) one BH2+ (n - 1 vertices) of one BH2+ (n - 2 vertices)
group group
e.g. Octahedron (Oh) ----~) Square pyramid ------..) Butterfly
(n = 6) (n = 5) (n = 4)
(Oh - 2 cis
vertices)
ry
Note:. The regular polyhedra with triangular faces are also described as deltahedra.
• In attaining the nido-structure from its precursor closo-structure, the most highly connected
vertex of the closo-framework is to be removed. This is illustrated in Figs. 10.12.3.2 and 3.
ra
Table 10.12.3.1. Characteristics of some common closo-, nido- and arachno-boranes
ib
(cf. PSEPT I.e. Wade's rule)
Type Skeleton electron Geometry
yl
pair (SEP)
n+l n = 5 (Trigonal pipyramid, TBP)
m
= 6 (Octahedron, 0h)
= 7 (Pentagonal bipyramid, PBP)
he
= 12 (Icosahedron)
n+2 n = 4 (Tetrahedron, Td == TBP - one axial vertex)

lc
= 5 (Square pyramid == 0h - one axial vertex)
= 6 (Pentagonal pyramid == PBP-one axial vertex)

ea
Arachno- n+3 n = 3 (Triangular == TBP - both axial vertices)

(Bn H n + 6 ) = 4 (Butterfly == 0h - 2 cis-vertices)
th
= 5 (PBP - 2 vertices)
H:
Structure of boranes in terms ofstructure of B12 2 : The structure of symmetrical borohydride
e/
ion, B12H122- is very much important in understanding the structure of higher boranes. It gives a regular
t.m
icosahedron (called B I2-icosahedron) with 20-equilateral triangular faces (cf. Fig. 10.12.3.4). All the
H-atoms are present in B-H terminal 2c-2e bonds. Both B-B (2c-2e) and B-B-B (3c-2e) bonds are.
involved in developing the structure. Starting from the Bl 2-icosahedron unit, B 1c1l14 can be obtained by
removing the B1 and B6 atoms from the B l2H l2-framework and the extra/our H-atoms are involved to
produce the B-H-B bridges (3c-2e bonds).
B6H 10 (pentagonal pyramid) possesses the skeleton equivalent to the apical fragment of the.
icosahedron skeleton of BI2HI22-' Similarly, structures of many other boranes can be derived from the
skeleton of BI2H122-'
10.12.4 Skeletal Electron Pair Counting and Wade's Rules: Polyhedral Skeletal Electron
Pair Theory (PSEPT) (cf. Sees. 10.12.7, 12.8.5-6)
The structure ofboranes can be predicted from their formula. Wade's rule can calculate the number of
electrons for framework ofthe deltahedron. These framework electrons are called skeletal electrons. It
is assumed that the building block of the deltahedron are the B-H units (2c-2e bond). Each B-atom
Removal of.
8 1 and 8 s
ry
(BH)f2" ==B 12 H f2"
(Icosahedron)
ra
ib
yl
Removal of
8 7 to 8 12 m
he
(BH)sH 4 == BsH 10
Fig. 10.12.3.4. Development of the skeleton of 8 10 H14 and 8 s H10 from the icosahedron skeleton of
lc
8 12 H:2-·
ea
uses one sp-hybrid orbital and one valency electron for the B-H linkage. If a B-centre forms more than
one B-H terminal bonds then except the one other bonding pairs will be considered for skeletal bonding.
th
It indicat~s that each B-atom can provide 3 orbitals (1 sp + 2 pure p-orbitals) and 2 electrons for
framework bonding. The sp orbital of B available for skeletal bonding is called radial orbital pointing
e/
towards the interior of the fragment. The remaining two p-orbitals of B available for skeletal bonding
are called tangential orbitals which are perpendicular to the radial orbital. For a closo-borane B"Hn + 2
t.m
Le. (BH)"H2' the number of skeletal electrons is 2n + 2 (= n + 1 pairs) where each BH unit provides 2
electrons and 2H-atoms provide 2 electrons. Similarly, a nido-borane B"Hn +4 Le. (BH)"H4 can provide
2n + 4 electrons (i.e. n + 2 pairs) for framework bonding. In fact, depending on the number ofskelE!tal-
electron pairs (SEP simply denoted by S), the different series can be classified.
B"Hn + 2 (closo-series) : n + 1 skeletal pairs; B"Hn + 4 (nido-series) : n + 2 skeletal pairs; B"Hn + 6
(arachno-series) : n + 3 skeletal pairs; B"Hn + 8 (hypho-series) : n + 4 skeletal pairs.
For (BH)llq +clC+ (see Sec. 10.12.6, 9), S = p + 1 (closo-series), = p ~ 2 (nido-series), = p + 3
(arachno-series), = p + 4 (hypho-series). However, it may be convenient to c~i1culate the value of S by
considering the neutral boron hydride.
For calculation of S and identification of carboboranes, it has been discussed in Sec. 10.12.9.
Wade's Rule, PSPT : Carbonyl Clusters and Zintle Cluster Ions
These aspects have been discussed in Sees. 12.8.5 and 12.8.6.
10.12.5 Calculation of the Number of Electron Deficient Bonds

By calculating the total number of available valence electrons and valence orbitals, the number of
electron deficient bonds (Le. 3c-2e bonds) can be calculated. This aspect is illustrated in the following
examples.
Table 10.12.5.1. Calculation of the number of electron deficient bonds in boron hydrides
Species No. ofvalence No. ofvalence Deficiency ofelectrons No. of3c-2e
orbitals electrons to fill in the bonding MOs bonds
ry
2 x 4 + 6 x 1 = 14 2 x 3 + 6 x 1 = 12 14-12=2 2
4 x 4 + lOx 1 = 26 4 x 3 + lOx 1 = 22 26 - 22 = 4 4
ra
5 x 4 + 9 x 1 = 29 5 x 3 + 9 x 1 = 24 29 - 24 = 5 5
ib
These electron deficient 3c-2e bonds may be of different types (cf. Fig. 10.12.5.1).
Involved orbitals MD-dlagram
yl
H Representation
H
m r'\
8 ,8
H
he
or
H or M
A 8 B
B B
lc
ea
(a) 3c - 2e 8 - H - 8 bridge bonds

th
,
,~
,
8 ,' ,,
8
~ " ~ ~
e/
p " , or
B B B B
",,~,"
,
, " B
t.m
~--
" " s-p hybrids
\---*-,'
(b) 3c - 2e open B - B - B bridge bond
,,J
8 "
---~-----
SP3_~Ybrid~ ""'-f-
(c) 3c - 2e closed B - B - B bond
Fig. 10.12.5.1. Representation of 3~2e bonds involved in the structure of boranes (cf. Sec. 9.21 fo~
details).
906 Fundamental Concepts \I. Inorganic Chemistry
~
H
• 3e:-2e hydrogen bridge bo~d :

or
B B
or n
B B
B
• 3o-2e open boron bridge bond :
~
~ ~
or
B
~B
~S
ry
• 3o-2e close boron bridge bond :
ra
• 2o-2e boron-boron bond : B-B
ib
• 2o-2e terminal boron-hydrogen bond: B-H or BH
Fig. 10.12.5.2. Five bonding constituents and their topological representations used in the structures
yl
of boranes.
Note : 5 gives the no. of 3o-2e BHB bonds; t gives the sum of 3o-2e BBB bonds (both open and
m
close);·y gives the no. of 2o-2e B-S-bonds; x gives the no. of additional 2o-2e B-H bonds, Le. no.
of BH2 groups (if no BH3 group).
he
H
H H I H
lc
H,f\/H H,rSI)/H
B B
B B
H/"-../'H H/( )'H
ea
H H'--f~
(B 2H6) H
th
styx =2002 (84 Hg)

styx = 4012
e/
H
I
t.m
H(S~H.
H-s,",",,--I:-s- H
H,A/H
ByB) l JJJ
H ( Iti\ H I iyS,
B 1\ B
H/I HH I'H
H-Bfl.B~B-H
H H
(Canonical structures of 8 sH11 )
~~~
I
=
(styx 3203) H
A representative canonical
structure of 8 10H14
(styx = 4620)
Fig. 10.12.5.3. Representation of bonding in some representative boranes in terms of Lipscomb's
semitopological (styx) scheme.
The B-H-B bonds are numbered as sand B-B-B (both open and close type) bonds are numbered
as t. By using the 5 bonding units (cf. Fig. 10.12.5.2) Le. 2c-2e B-H terminal bond, 3c-2e B-H-B
hydrogen bridge bond, 2c-2e B-B bond, 3c-2e open boron bridge bond, and 3CL-2e close boron bond,
Lipscomb developed the semitopological descriptions of the structure and bonding of the boranes
(Fig. 10.12.5.3). .
10.12.6 stxy Numbers and Topology of Boron ~ydrldes
In all boron hydrides and carboranes, each B-centre is at least bonded with one H-atom through a 2c-
ry
2e a-bond and it gives a terminal B-H bond. In addition to this, there may be B-H-B (3c-2e) bonds
(numbered by s), 3c-2e B-B-B (both open and close types) bonds (numbered by t), 2c-2e B-B bonds
(numbered by y) and additional 2c-2e B-H (numbered by x). Thus, x denotes the number· of BH2 group
ra
(ifno BH3 group). By calculating the values of s, t, y and x, Lipscom and coworkers developed a system
to describe the topology of the boron hydrides. The values of s, t, y and x can be calculated by using the
ib
equations of balance.
yl
Case-I: Neutral borane SpHp + II' I.e. (SH)pHq
(a) Hydrogen balance equat/on: I q =s + x I
m
The q H-atoms are distributed in B-H:B (s) and additional B-Hterminal bonds (x).
he
(b) Three centre orb/tal balance equation: Ip=s +t I
In (BH)/lq' the number of electron deficient bonds is p (cf. Table 10.12.5.1), Le. per B-atom, one
lc
3c-2e bond is produced. Thus the sum of the number of B-B-B bonds (both types t) and B-H-B
bonds (s) equals to the number of B-atoms.
ea
OO~~~~~~~~:I-p-+-~-q-=-s-+-t-+-y-+-x-o-r-p-=-t-+-y-+-_--o-r-y-=---~-~---X~)I
th
Each B-centre provides three electrons and each H-atom provides one electron. Thus the total number
of bonding electrons = 3p + (p + q) x 1, Le. (2p + q/2) electron pairs. The total number of bonds = (p +
e/
x) + + t + y = number of bonding pairs Le. 2p + 1 = p + s + t + y + x; or, p + 1 = s + t + y + x.

S
t.m
2 2
Here, (p + x) gives the total number of terminal 2c-2e B-H bonds.
Using the hydrogen balance equation, q = s + x, and three centre orbital balance equation,
p = s + t, we can write:
p =t + y +1; or s + t =t + Y +
2
(x s);
+
2
or, y =.!. (s - x)
2
By using the equations of balance, the topology . o f the neutral boron hydride (BH)/lq Le. B/lp + q
can be expressed by styx numbers. In solving the equations, thefo//owing conditions or restrictions
must be satisfied: .
I-i-~-s-~-q-an-d-S-'t-,-y-a-n-d-x-~-o I
Clarification ofthe restrictions: The number (s) of BHB bridges lies in the range of q to q/2. The
additional q Hs atoms are distributed in s number of BHB bonds and x number of additional BH
terminal bonds, Le. q = s + x, and consequently s ~ q.
We have: p = 1 + Y + q/2; or (s + I) = 1 + Y + q/2; or s = y + q/2; Le. s ~ q/2.

It is evident that there are four variables (s, I, y and x) but only three independent equations are
available. By using the above restrictions the allowed solution is to be taken into consideration.
Examples:
B1,H6 , i.e. (BH)1,H4 : It leads to p = 2 and q = 4. The involved equations are:
q = 4 = s + x; p = 2 = s + I; P + q/2 = (s + x) + I + Y
or 2 + 2 = 4 + 1 +Y
1+ Y = o.
ry
Le.
The solutions are:
ra
s y x q
ib
2 o o 2 4 } Acceptable, s, t, y, x ~ 0, q/2 ~ s ~ q
3 -1 1 1 4
} Not acceptable as t < 0
yl
4 -2 2 o 4
m
The acceptable styx number is 2002. It indicates that there are two 3c-2e B-H-B bridges (s), no
3c-2e B-B-B bond (I), no 2c-2e B-B bond (y) and two addilional 2c-2e B-H terminal bonds (x). Thus
he
the structure:
H H H
" /
"B/ (styx = 2002)
lc
/8, / '
H IY H
ea
B sH 9 : Now let us consider the case of BSHg Le. (BH) sH4 (nido-species). It leads to p = 5, q = 4'and
the required balance equations are:
q = 4 = s + x; p = 5 = s + I; P + q/2 = (s + x) + 1 + Y
th
Le. 5 + 2 = 4 + 1 + y, or t + y = 3
e/
The solutions are:

s y x q
t.m
2 3 o 2 4 ] All are acceptable. Thus an unequivocal structure is not predicted. This

3 2 1 1 4 is the limitation. However, the structure with the highest symmetry is
4 1 2 o 4, always pre/erred. The 4120 structure explains the properties ofthis borane.
H
.~~/H
Structure of B 58 9 (4120) is: HC>-~H
~~
H
All the possible structures of BSHg are shown in Fig. 10.12.6.1 a.
Some topological representations in terms of styx number of neutral boron hydrides are given in
Figs. 10.12.5.3 and 10.12.6.1.
H, /H
B-H-B)
H( >-B~ H
B B 1
H/ '-!!.-/ 'H
H
styx =3211
(a) Semitopological representation of BSH g ; The most

=
ry
preferred structure is given by styx 4120
ra
H
I
H HrB,H H
ib
H>'tIJ<H
HBH
I
yl
H
styx = 4012 styx = 3103
(b) Semitopological representation of B 4 H10
m
(Most preferred structure is:
styx = 4012)
he
H
I
tl
H H
lc
y!",\ H H
H-B~B-H HH(\~t~)HH H-B~~~B)H

ea
H'B~B
th
B---H-B B R_B
/ '-----/ "H HI \H I I
e/
H H H H
styx = 3311 styx = 4220 styx = 2402
t.m
(d) Structures for 8 6 H10 ; most stable for styx =4220

H H H H
\/ I I
H(B H
H-BA B/
H\r
B
~/H
B H
H~(BJ:HB}~
(~I B/ \ \
H' / ,H H H( 7 "' H-B- --< >-- -B-H
/B yB - H- B.J...B.J...B- H \ \ I B I~ )
H B)H ~~~ H~B!L-l-B~H
/\ I I I
HH H H H
styx =4212 styx =4212 styx = 4620
(e) Two canonical forms of B eH12 (f) 8 10H 14
. Fig. 10.12.6.1. Semitopological representation of some boranes in terms of styx number.

B 4H 10 : This is (BH)4H6 (Le. a member of arachno-series). The required balance euations 'te given
below: .
p = 4; q = 6; s + t = p = 4; and s +. x = q = 6
It leads to :
s + t + y + x = p + "2 7 ·I.e. y + x = "2

q = 4+3= q =3
The solutions are:

s y x q
ry
3
4
1
o
o
1
3
2
6
6
} All are acceptable (~:!> s :!> q)
ra
The structures for styx = 3103 and 4012 are shown in Fig. 10.12.6.1 b.
ib
BsH11 i.e. (BH)sH, : It is a member of arachno-series.
q
= 5; q = 6; s + x = q = 6; s + t = p = 5; y + x = "2 = 3
yl
p
..
Restrlctlons : "2
q ~
· 3 ~ s ~ 6·
s ~ q I.e.
m
s y x q
he
3 203 6 ]
4 1 1 2 6 All are acceptable solutions (Structures are shown in Fig. 10.12.6.1 c)
lc
50216
t=
ea
B 6H 10 i.e. (BH)6H 4 : p = 6; q = 4; s + t = p = 6; s + x = q = 4; Y + x = 2.
t
th
Condition: .5 s .5 q, i.e. 2 .5 s .5 4
e/
s y x q
2 4 o 2
t.m
3 3 1 1 : ] All are acceptable solutions (Structures are shown in Fig. 10.12.6.1 d)

4 2 2 o
Case-II: Charged species [(BfflpHq+ JOt-
Here the relevant equations are:
s + x = q + c; s + t = p + c; y = "21 (s - x - 3c); and p = t + y + c + ql2
The relation, p = t + y + C + q/2 can be attained as follows :

In [(BH)pHq+c]c+, theframework electron counting is obtained in the following way.
1 1
1 electron pair from each BHunit; 2" electron pair from each of the extra H-atoms, Le. (q + c); - 2"
electron pair from each + charge, Le.
No of skeletal pairs(S) = p+k(q + c) -k c = p +f =s +t + y+ x =q +c+ t+ Y

S = s + t + Y + x (cf. definition for S, Secs. 10.12.4, 10.12.6).
or, Ip =t + Y + c + f I and Iy =k(s - x - 3d I

Total electron count (TEe) = S + no. of electron pairs involved in forming the (BH) units =
(S + p) pairs. r
ry
Thus the total number of bonds = p + S + t + Y + x.
Note: The series is determined by the value of S.
ra
s = p +f = P + I (closo-series), p + 2 (nido-series), p + 3 (arachno-series), p + 4 (hypho-series).
ib
B2Hi: For B 2H 7-, i.e. (BH)2HS-: p = 2, q + C = 5, C = -1, i.e. q = 6. Restrictions: t, x, y ~ 0;
f = 3, i.e.
yl
2c + ql2 $ s $ q + c, i.e. 1 $ s $ 5. It leads to: s
m = 1, t = 0, Y = 0, x = 4, arachno type.
The relevant structure is:

H"", /H l-
he
H - B-H - B - H (i.e. styx = 1004)
H / "'" .H
lc
B#18-: For B3H g-, i.e. (BH)3H5~: p = 3, q + c =5, c =-1, i.e. q = 6, f =3, i.e. arachno type. The
ea
allowed solutions are: styx = 1104 and 2013. Thus, the structures are:
l-
th
H""'I/H
e/
H"", A /H
t.m
H/BY"H
H
(styx: 1104)
Note: Resonating structure: The topological structure of pentaborane (9), i.e. BsHg has been shown
in Fig. 10.12.6.1 a. From the structural studies, all the 4 basal B-atoms are equivalent with respect to
the apical B-atom. In fact, all the Bapical - Bbasal distances are equal (= 169 pm), and all the 4 edge
lengths in the basal plane are equal (= 180 pm). To interpret these observations, 4 equivalent canonical
structures of the skeleton for 4120 topology (cf. Fig. 10.12.6.1a) of BsHg are proposed.
B B ByB B"" /B
~B
>-B( • B ~---..
.. i B
B
"B
/ ~
B
B B
B
/'"B B
A B
Because of this delocalisation, its stability is enhanced. The above resonating structures are drawn
by involving the localised 3c-2e boron-boron-boron bonds and 2c-2e boron-boron bonds. However,
the observation can be also explained by considering the formation of seven 5-centred delocalised
MOs in which the lowest three MOs are occupied by three electron pairs. In constructing the B s-
framework, the basal 4 B-atoms provide 4 AOs and the apical B-atom provide 3 orbitals (one sp + two
p). Other resonating structures for B sH9 (styx = 4120) having the open BBB bond instead of the ~losed
BBB bond are also possible.
H H
ry
((D~ (BWB)
ra
H /a'".. )H --. H ~~ H
~ "-.Y
ib
H H
Here the above resonating structures are drawn by involving 3c-2e open BBB bond and 2c-2e B-B
yl
bonds.
In B sH 11 , out of26 electrons, there are 2 pairs for the formation of3c-2e BBB bonds. These 2 pair
m
electrons may be involved in two ways: two closed 3c-2e BBB bonds or (one closed + one open)
3c-2e bonds. The possible resonating structures are shown in Fig. 10.12.5.3 for the 'styx' no. 3203.
he
It may be pointed out that for B1(1I14' there are 24 canonical forms.
Limitations ofstyx number method: The styx number method is convenient to represent the structure
lc
and bonding ofboranes. However, there are some limitations:

(i) It does not always yield a unique set of styx number. Consequently, different structures are
ea
predicated. The most preferred structure is then selected by considering other criteria.
(ii) Even for a particular styx number, different structures can be drawn by varying the number of
th
3c-2e open and closed BBB bonds keeping their sum (t) constant.
For example, B sH 11 (styx = 3202) can be drawn in two ways: 1 open BBB bond + 1 closed BBB
e/
bond or 2 closed BBB bonds. These two canonical forms are shown in Fig. 10.12.5.3.
Structure of B sH 9 (styx = 4120) can -be -drawn in two ways: 1 open or closed BBB bond. The
t.m
structure containing the closed BBB bond is shown in Fig. 10.12.5.3. The possible resonating
structures for this form have been discussed already. .
10.12.7 Molecular Orbital Picture of Higher Boranes (cf. Sec. 10.12.4)

A terminal B-H 2c-2e bond is constituted by using one electron and one orbital of the B-atom. It
leaves three orbitals and two electron per B-atom for skeletal bonding. To produce the segment
BH, the boron centre uses one of its sp-hybrid orbital and another sp hybrid is kept for skeletal bonding
pointing towards the interior of the fragment. This is called radial orbital. The remaining two
p-orbitals (for skeletal bonding) are called tangential orbitals which are perpendicular to the
radial orbital. Thus each boron can provide 3 orbitals (1 radial orbital + 2 tangential orbitals) and 2
electrons for skeletal bonding.
In closo- B6Hi-, there are 18 Mas for skeleton. There are 7 skeletal pairs (cf. Sec. 10.12.4) and
these are housed in the lowest 7 Mas (one a lg + three t lu + three t2g ). There is a large energy gap
between the HOMO (Le. t2g set) and LUMO (Le. t2u set).
Thus in B6 Hi-, the 7 MOs (mainly bonding in character) are remaining filled in and it is stable.
Thus the MO picture supports the Wade's rule. In the hypothetical species, B6H~-, the 15th electron
will go to the t2u MO which is antibonding in character and it explains its instability. In the neutral
species, B6H6 the 6 skeletal pairs will not be sufficient to fill in the 7 bonding MOs. Thus the neutral J
species, B,H, is expected to be less stable than B,H:-.

10.12.8 Carboranes and their Structural Features
Carboranes clusters contain both Band C atoms in the framework. Carbon possesses one more electron
ry
than boron, so Bn- is isoelectronic and isolobal with CH unit. These two isolobal fragments possess
the uppermost orbitals (Le. frontier orbitals) with the same symmetry. It is represented as follows:
ra
H H
p~~ID ~ID~
ib
orb~B~ • ~ c~ JH)~bitals
o
yl
0/7.~
sp/~
orbital
m ~ sp-orbital
he
Thus in boron hydrides, the BF fragments can be replaced by ~he CH units. Thus when two BF
units in BnH;- are replaced by two CH units, the electroneutral species C2Bn_2Hn is produc~d.
lc
-BH- BH-
B H 2- CB H- - )C B H
n n + CH) n- 1 n + CH 2 n- 2 n
ea
Thus, the carborane B4C2H6 is an analog of B6Hi- (cf. Fig. 10.12.8.1). BIOC2HI2 is related with
th
B12H122- ·
The carboranes also obey the electronic rules as in boranes and they can also exist as in closo-,
cn
e/
nido- and arachno series. In calculating the number of skeletal electrons (cf. Sec. 10.12.9), each
group contributes three electrons for framework bonding. The different forms may be related in a
t.m
redox couple, e.g.

closo - C2B9H 11 + 2e ~ nido - C2B9H121-
+2e. +2e
Le. c/oso - ) nldo - ) arachno-
c/oso-compounds can be converted into nido-compounds by the action of a Lewis base (acting as 2e
donor).
c/oso-C2B4H 6 +NR3 ~nido-C2B4H6(NR3)
./
Similarly, nido-compounds can be converted into the hypho-compounds by the addition of Lewis
bases on the electron deficient bonds.
nido:..BsH9 + 2PMe3 ~ hypho-BsH 9(PMe 3)2
This hypho-compound is the first well characterised boron hydride in hypho-series.
ry
ra
ib
yl
m
he
lc
ea
th
e/
t.m
1.2-B10C2H12 1.7-B10C2H12 1, 12-B10C2H12

(Ortho-carborane) (Meta-carborane) (Para-carborane)
Fig. 10.12.8.1. Some representative structures of neutral closo-carboranes and their respective closo-
B"H~- (0 for B, • for C, • for 1-1).
c
10.12.9 Calculation of Skeletal Electron Pairs (S) In Carboranes [(CH).(BH)pHq+cl +
Out of the four valence electrons of C, one is involved in .making the CH bond, and the three are
remaining for skeletal bonding. The framework electron counting is done as follows :
3 1
2" electron pair from each CH unit + 1 electron pair from each BH unit +"2 electron pair from
1
each extra H + - 2" electron pair for each + charge.
Thus the total number of skeletal pairs (S) in [(CH)a(BH)pHq+,:f+ is given by :

3 1 1 1· 1
8=-a+ p+-(q+c)--c=(a+ p)+-(a+q)=n+-(a+q)
2 2 2 2 2
The number of vertices of the polyhedron is given by n (= a + p), and the extra hydrogens are
distributed in 3c-2e B-H-B bridge bonds and in additional B-H (2c-2e) terminal bonds.
The series are characterised as follows:
8 = n + 1 (closo-series), = n + 2 (nido-series), = n + 3 (arachno-series), where n = a + p.
ry
Illustration: C"BsH1'" Le. (CH)2(BH) sH2 gives the values: a = 2, P = 8, q = 2, C = 0, n = a + p = 10,
I 1
S = n + 2" (a + q) = 10 + 2" (2 + 2) = 10 + 2 = n + 2. Th,us it is having the nido-structure. In C1,BIl"
ra
1
Le. (CH)2(BH)4' a = 2, p = 4, q = c = 0, 8 = 6 + 2" x2 = 6 + I, Le. it is a closo 'compound. Similarly,
ib
~"B3H7' is 1,2-dicarba-nido-pentaborane(7) and the heteroborane PB 11 H 11, can be named as
phospha-closo-dodecaborane( 12) where the position of P is not required to be specified as all the
yl
icosahedral vertices are equivalent. m
Examples 0/ carboranes :
(i) Closo-series: C2B3Hs' C2B4H 6 , C2B sH7, C2BIc#I2 etc. These may be represented by (CH)2(BH)p
he
which is isostructural and isoelectronic with (BH)~-+2 e.g. C2B4H6 is isostructural and
isoelectronic with B6 H;-. .
lc
(ii) Nido-series: C2113H7 Le. (CH)2(BH)3H2 (isoelectronic with B sH9), CB sH9 Le. (CH)(BH) sH3
(isoelectronic with B6H 10 ), C 2B sH I2 Le. (CH)2(BH) sH 2 (isoelectronic with B Ic#I4)' CB9Hi;
ea
(isoelectronic with BI c#I4).

It is illustrated for B 1c#14.
th
- BH- + - BH- 2+
B
C~[:2H+ CN
e/
IO l4
nido-B H + CN ) ) C2 S[:2H+
t.m
nido-C~Hu nido-C2 BsHI 2

(iii) Arachno-series: 1,3-C2B7H I3 Le. (CH)2(BH)7H4 (only this example is known.)
3 1
SEPs = 2 x - + 7 + (13 - 9) x - = 3 + 7 + 2 =9 + 3.
2 2
C2B7H 13 is isoelectronic and isostructural with Bgll1S •
arachno-B9 H ls - 2BH- ) c Ii H 2+ - 2H+ ) C B7 H I3

2
+ 2CH 2 7 IS
For [(CH)a(BH)pHq+c]c+, the number of available v~lence atomic orbitals for constructing the
skeletal MOs is 3 (a + p) + (q + e) and at most'! {3n + (q + e)} where n = a + p bonding MOs can be
2
produced.
Structures of some common carboranes are given in Fig. 10.12.8.1. In naming the carboranes, the
position of C-atoms is to -be mentioned, e.g. B4C2H6 is 1:6-dicarba-closo-hexal1orane (6).
Note : The generalformula of a neutral borane or hydroborate (i.e. anionic borane) or carborane
can also be expressed as follows :
[(CH)a(BH)pHq]C-
The number of electron pairs for framework bonding is given by :
3a 1 1
S=-+ p+-(q+c) =(a+p)+-(a+q+c)
ry
2 2 2
=n +.!. (a + q + c), n = no. of vertices
2
ra
Total AO's available fQr skeletal bonding = 3n + q.
1
Maximum no. of bonding skeletal MOts (possible) = "2 (3n + q).
ib
Conditions for different series :
yl
closo- : a + q + C = 2
nido- : a + q + C = 4
m
arachno- : a + q + C = 6.
he
10.12.10 Jemmls' Unifying Electron Counting Rule for Condensed Polyhedral Boranes
(Ref. E.D. Jammls et al., J. Am. Chem. Soc., 123, 4413, 2001; Chem. Rev., 102, 93,
lc
2002; Acc. Chem. Res., 36, 816, 2003)

Wade's skeletal electron pair counting rule (Sec. 12.8.5) is applicable only for monopolyhedral
ea
boranes. It states:
S = n + 1 + p, S = no. of skeletal electron pair; n = no. of vertices; p = no. of vertices missing Le.
th
p = 0 (closo-series), = 1 (nido-series), = 2 (arachno-series) for monopolyhedral boranes.

Jemmis' mno rule is applicable for both monopolyhedral (Le. m = 1) and condensed polyhedral or
e/
macropolyhedral (Le. m = 2, 3, ...) boranes. According to this mno rule:

t.m
S=m+n+o+p
m = number of polyhedra condensed; n = no. ofvertices; 0 = no. ofsingle vertex shared in developing
the macropolyhedral system; p = no. of vertices missing from the ideal polyhedra.
From Jemmis' rule, Wade's rule is obtained as a special case for the condition:
m = 1, 0 = 0 and p = 0 (cltJso), = 1 (nido), = 2 (arachno)
Jemmis' rule is applicable for polyhedral boranes, carboranes, metalloboranes and metallocenes. It
is illustrated in some representative examples:
• closo-BsHi- (hexagonal bipyramidal): m = 1, n = 8, 0 ~ 0, p = 0; Le. S = 9.
• closo-B1 4 H;i (condensation of 8sH;- through one edge sharing) : m = 2, n = 14, 0 = O,p = 0;
Le. S = 16.
• nido-B7 H~- (hexagonal pyramidal) : m = 1, n = 7, 0 = 0, p = 1 Le. S = 9.
• bis-nido-B12 Hfi (condensation of hexagonal pyramidal nido-B7 Hi- through one edge sharing):
m=2,n= 12,o=0,p=2Le.S= 16.
• arachno-B6 H;- (hexagonal planar) : m = 1, n = 6, 0 = 0, p = 2 Le. S = 9.
• bis-arachno-Bl0H~0- -(condensation of hexagonal arachno-B6 H2- through one edge sharing) :
m = 2, n = 10, 0 = 0, p = 4 Le. S = 16.
Note: In the above examples, it has been illustrated for the hypothetical hexagonal boranes, Le.
-BH 2+ -BH 2+
ry
closo-BsHi- ) nido-B7 H ll ) arachno-B6 H l2
+4H+ -2H+
(Le. B7H7 + 4) (Le. B6H6 + 6)
ra
Missing of Missing of
(Hexagonal one axial verttx
) (Hexagonal one axial vertex ) (Hexagonal
ib
bipyramidal) pyramidal) planar)
• (Cp)2Fe (ferrocene): m = 2, n = 11,0 = l,p = 2.
yl
Here condensation of two pentagonal bipyramids through the sharing of one axial position is
considered (Le 0 = 1). It leads to : m = 2, n = 11, 0 = 1, p = 2 Le. S = 16.
m
• Condensation of pentagonal pyramidal nido-B6Ht- through edge sharing gives the products
he
(Fig. 10.12.10.1) bis-nido-B1oH:-, tris-nido-BI4H~o.
nido-B6 Ht bisnido-B10Hr tris-nido-B14 Hfo

lc
S=m+n+o+p: 1 +6+0+ 1 =8 2+10+0+2=14 3 + 14 + 0 + 3 = 20

ea
Condensation.
th
of 2-unlts
e/
nido-BsHt bis-nido-B 10 Ht fa
tris-nido-B 14 H
________ ___ _ _ _ _ _J+
I condensation of
t.m
3 units
Fig. 10.12.10.1. Condensation of 86H:- units through the sharing of one edge.
• Condensation of two icosahedral closo-BI 2Hf2- (m = 1, n = 12, 0 = 0, p = 0) units through
sharing of one edge gives clos.o-B2oHI6 (m = 2, n = 20, 0 = 0, p = 0 Le. S = 22).
.10.13 SYNTHESIS AND REACTIVITY OF BORANES AND CARBORANES

10.13.1. Synthesis of Boranes
(a) BII6 is obtained by the reduction of boron halides.
8BFj + 6NaH ~ 6NaBF4 + B2 H 6 ; 4BCl3 + 3LiAIH4 ~ 3LiCI + 3AICl3 + 2B2 H 6
Note: BeCl2 on reduction by LiAIH4 produces Be(AIH4 )2.
918 FundamentaJ Concepts of Inorganic Chemistry
(b) Stock prepared boron hydrides by the acidic hydrolysis of magnesium boride. Many ~oranes are
hydrolysed in aqueous m.edia. This is why, Stock could isolate Blilo onl1 as it reacts with
water very slowly. B4H 10 on pyrolysis produces B2H6 and higher boranes.
2MgB2 + 12HCI + 4Mg --. B4 H 10 + 6MgCl2 + H 2

B4 H\0 ~ B2 H6 and higher boranes.
(c) Pyrolysis of B2H6 in a certain temperature range can produce different higher boranes which can
ry
be separated by fractional distillation under vacuum.
The boranes (Bjlp + q) can be formulated as (BH)n (BH3)x where n = 0, 1, 2, ...., 10; x = I, 2, 3
e.g. B2H6 == (BH3)2; B3H7 == (BH)(BH3)2; BsH9 == (BH)3(BH3)2; B 1cfi14 == (BH)s(BH3)2; B 1cfi16 ==
ra
(BH)7(BH3)3; in fact, x = 2 for nido-series, and x = 3 for arachno-series. During pyrolysis,
there is a gain or loss of BH3 units; and gain or loss of H2 (Le. BH3 --. BH + H2) and it can explain
ib
the route of conversion among the boranes. It is illustrated in the following examples:
yl
B3H9 --. B3 H 7 + H 2 ; 2B3H9 m --. 3B2H 6 ; B2H 6 + B3H 7 --. BsHll + H 2;
B3 H9 + B4 H 10 B2H 6 + BsH11 + H 2, etc.
--.
(d) The bridging H-atom in lower boranes is sufficiently acidic to be abstracted as a proton.
he
Thus the corresponding conjugate base anion bears the B-B bond which can act as the site
of insertion of the .electrophilic reagent like BH3• In fact, It" abstraction followed by the
insertion of a BH3 group can lead to polyhedral expansion. This allows the synthesis of higher
lc
boranes. It is illustrated in the following cases.

ea
B4 H 10 + KH ~ K[ B4 H9 l + H 2 ;
I H+
th
K[B4 H9 l + '2 B2H6 ~ K[BsH I2 l ) BsH l1 + H 2

1 .
e/
BsH9 + KH -+ K[BsHsl + H2; K[BsHsl + '2 B2H6 -+ K[B6H l1 l

H+
t.m
K[B6 H l1 l ) H 2 + B6 H 10
(e) The stable closo - B1oHto- and B12H122- are obtained as follows:
150°C 2
B10 H 14 + 2R3 N ---~) B10H1o- + H 2 + 2R3NH+
150°C 2
6B2 H6 + 2R3 N ----.) B12 H 12- + I1H2 +- 2R3 NH+
10.13.2. Reactivity of Boranes

(a) Combustion in air: The boron hydrides can bum explosively and their heat of combustion is
about 1.5 times higher than those of comparable hydrocarbons. This opens the possibility ofuse
of boranes as a rocket fueL However, the combustion product B 20 3 (solid) can block the
engine. -
(b) Thermal stability : In general, thermal sta~i1ity depends on the nature of boron hydri~s. The
thermal stability order is: closo- > nido- > arachno- > hypho-. In general, the higher boranes in
a particular series are less stable.
(c) Hydrolysis: All boron hydrides (except B 1oH14 which is solid and stable to air and water) are
unstable with respect to hydrolysis and the products are B( 011)3 and H 2 • However, the species
H:
like BIOH12o- and B12 2- are kinetically stable with respect to hydrolysis. In general, the closo-
boranes are less reactive than the nido- and arachno-boranes.
A
ry
B4 H 10 + 12H20 ~ 4B(OH)3 + IlH 2
(d) Reaction with the Lewis base (L) : Because ofthe electron deficient character, the boranes are
ra
expected to react with the Lewis bases. Depending on the nature of base, three important types
of reactions may occur. These are cleavage (both symmetric and unsymmetric), addition and
ib
bridging proton abstraction (Le. bridging hydrogens are acidic).
(i) Cleavage reactions are illustrated as follows :
~ /H" /H
B B + 2L ~
yl
2 LBH3 , (Symmetric cleavage)
H/ "H/ "H
m
~
he
V
H/~H/B"H
H
" /H
lc
B2H 6 + 2£ ~ 2LBH3 (symmetric cleavage)

ea
B2H6 + 2CO ~ 2H3 BCO; B2H6 + 2NR3 ~ 2H3 BNR3

B2H 6 + 2L ~ [L2BH2]+ [BHi], (unsymmetric cleavage for L = NH3)
th
The unsymmetric cleavage is mainly done by the small and hard Lewis bases (e.g. NH3)
e/
while the soft Lewis bases (with the bulky substituents) promote the symmetrical cleavage.
- /:t 0 ~
t.m
_ I"\. /H :L
Jr 1 rr "H
/K- L
(Symbiosis)
Unsymmetric cleavage
:LL Symmetric cleavage
The above mechanistic steps indicate that for the bulky Lewis base, attack on the same
B-centre at the second step is sterically disfavoured and it prefers the symmetric cleavage.
Small and hard Lewis bases like 011, NH3 lead to the unsymmetric cleavage where attack
on the same B-centre at the second step is favoured due to symbiotic and steric reasons.
Symmetric and unsymmetric cleavage of B4 H 10 are illustrated below.
B4 H 10 + 2L ~ [H 2 BL2 ]+ [B3 H g ]-, (L = NH3 , OH-, etc.) (unsymmetric cleavage)

B4 H 10 + 2L ~ LB3 H 7 + LBH3 , (L = Me3 N, ~O, Me3 P, etc.) (symmetric cleavage)
ry
ra
ib
yl
The Lewis bases like NH), PMe 3, CO cleave the boranes as follows:
m
B4H IO + 2NH3 ~ [H 2B(NH3 )2l+ [B)HSl-
he
BsH I1 + 2NH3 ~ [H 2B(NH3 )2]+ [B4H 9 ]-
B6 H I2 + 2NH3 .-+ [H 2B(NH3 )2]+ [BsHlo ]-

lc
BsHIl + 2CO ~ H 3 BCO + B4H 8 (CO)

ea
B6 H I2 + PMe3 H 3 BPMe3 + BsH 9

~
(ii) Proton abstraction from the B-H-B bridging bonds is illustrated in the following examples.
th
BIO H I4 + OH- ~ Blo H I3 + H 20, (pKa = 2.7)

e/
B loH I4 possesses four bridging H-atoms which are acidic. KH can abstract the bridging protons
from B6H lo •.
t.m
B6 H IO + KH ~ K[ B6 H 9 l + H 2
In general the deprotonation process can ~e illustrated in the following way:
Here, a 3c-2e B-H-B bond is converted into a 2c-2e B-B bond. Thus, the electron count
and boron cluster remain unchanged. In fact; the deprotonation does not lead to any major
structural change. However, the electron rich B-B site in the deprotonated species can
react with the electrophiles to insert them into the bridging position. Insertion of a BH3
group to this B-B bond can lead to polyhedral expansion. This method can be utilised to
generate the higher boranes. This aspect has been discussed earlier.
The relative acidities of the bridging hydrogens are measured by considering the following
type of competitive reaction. 1
B10 H 14 + B4H; ~ B4H 10 + B10H o

The above reaction indicates that B1oH14 is more acidic than B4H 10 .
The bridging protons in nido- and arachno-boranes are quite acidic and the acid strength
sequence is given below:
Nido-series: BSHg (B6H 10 (B10 H 14 (B16 H 20
ry
Arachno-series: B4H)O (BsH 11 (B6H 12
Generally the higher boranes are more acidic than the lower boranes and the arachno-
ra
boranes are more acidic than the nido-boranes of comparable size.
The acid strength sequence can be qualitatively explained by considering the relative stabilities
ib
of their corresponding conjugate bases. The delocalisation of charge on the conjugate
base stabilises the species and greater the delocalisation, greater the acid strength (cf.
yl
methanol versus phenol).
(iii) Base addition may occur in the BHB bridging portions which are electron deficient. In fact,
m
the Lewis bases do not always lead to cleave the boranes. In some cases, the Lewis bases as
nucleophiles can attack the electron deficient BHB portion. In fact, formation of B2Hi
s
(from B2H6 ) or BsH (from BsH7 ) through the nucleophilic attack by Jr is well known.
he
Other examples are:
Nido - BSHg + 2PMe3 ~
Hypho - BsH9 (PMe3 )2
lc
B10 H 14 + 2L ~ H 2 + B10 H 12 (L)2' L = PR3 or CH3CN

ea
The compound, B 1oH12(L)2 is isoelectronic and isostructural with BIOH124- (which can be
obtained by the 2e-reduction of B 1oHI4). The chemistry of B 1oH12(L)2 is quite interesting.
th
~OH12L2 + 2R3 N ~ 2R3 NH+ + 2L + closo - B10 H)20- (very stable)

BIOHI2~ + HC == CH ~ BIOC2H12 (ortho-carborane) + H 2 + 2L; L = Et2S
e/
Different types of reactions are illustrated in Scheme 10.13.2.1 and Fig. 10.13.2.1 taking
B 1#14 as a representative example.
t.m
+2L,-H 2
(L = PR 3, RCN)
(BH),oH4 == B10H 14 (B10H12L2)
Fig. 10.13.2.1. Structure of B10H12~ (L = R3 N, R3 P, RCN, Et2 S) (0 for B, • for 1-1).

Note : The ligands (Le. L) bind with the borons at the open faces.
2Et3N·BH 3
~~~~~~~~~~~~~~~[Et3NH]2 [B 12 H12],(Condensationand closu~ ~action
(-3H 2) leading to closo-B 12H?2")
ry
ra
ib
H H
I I
yl
?IB~B0\
H-B-t~B>-tYI )BH
m
\
H~B~~
\ 8
NaH,
(Base = OH-,
he
etc.)
/ \
H "H
lc
ea
(Reduction by Na) ,
th
e/
RX/AICI 3
t.m
2-RB 10H13 + 2, -4 -R2B10H12 + .

(Electrophilic substitution) (Substitution in the 1, 2, 3, 4 positions)
Scheme 10.13.2.1. Some representative reactions of B10 H14 Le. decaborane(14).
Note : • 8 10 H14 is highly stable and available in crystalline condition. It can be easily handled and
consequently its chemistry has been well studied.
• The distribution of electron density on the B-centre is not uniform. Electrophilic substitution
(e.g. Friedel-Crafts alkylation) occurs at the 1, 2, 3 and 4 position (preferential sequence 2,
4 > 1, 3) while nucleophilic substitution (e.g. attack by LiCH3 ) occurs on 6 and 9 position.
(d) Electrophilic substitutions: Electrophilic substitutions in boranes are well known. The
position of attack depends on the electron density at different sites. B)oH120- bears two types
of B-atoms - apical and equatorial (i.e. basal) but in icosahedral B12H122-' all positions are
equivalent (cf. Fig. 10.12.3.3). Molecular orbital calculation indicates that the electron density
on B-centre runs as follows :
apical- B)oH)20- > equatorial- B 10 H)20- ~ B 12 H)2;
It explains the reactivity order: BIOHI2o- ~ BI2HI22-.

The electrophilic attack occurs more favourably on the apical B-side than on the equatorial or
basal B-site in B1oHto because of the higher electron density on apical boron. This
electrophilic substitution at the apical position leads to the kinetically controlled product.
At higher temperature, it may isomerise to a thermodynamically controlled product.
Friedel Crafts alkylation (Le. electrophilic substitution) on BSHg occurs at the apical B-site at
lower temperature and it occurs at the equatorial position at higher temperature.
ry
ra
ib
yl
m Nido-BSH g .
Fig. 10.13.2.2. Electrophilic substitution on BSHg Le. pentaborane(9).

he
The I-alkyl derivative is the kinetically controlled product and it is obtained at lower
temperature. But at higher temperature, the alkyl group migrates to the 2-position to give the
lc
thermodynamically controlled product.

Electrophilic substitution by halogens (in the presence of Friedel-Crafts catalyst, the reactivity
ea
order: Cl2 > Br2 > /2) is illustrated in the following examples:
BSHg + /2 ~ BsHs/ + H/
th
Here I-/BsHs (apical isomer) is the kinetically controlled product which can isomerise to
e/
2-/BsH s (equatorial isomer). The kinetic favour arises jrom the higher electron density at
the apical B-site.
t.m
B10 H I4 + /2 ~ BIOHI2/2 + H 2
BIOHI2/2 (2,4- or-I, 3-disubstituted product)
For B t oH14' MO calculation shows that the B-atoms at the positions 2 and 4 bear excessive
negative charge and B-atoms at 1 and 3 positions are almost neutral, while all other B-
atoms bear the positive charge. This is why, the 1,2,3,4 positions can be electrophically
substituted although the positions 2 and 4 are slightly preferred.
In fact, alkylation (Friedel-Crafts reaction) on B 10H I4 produces predominantly 2-RB 1oHI3.
BIO H 14 RX) 2 - RBIO H 13 (major product) + 1- RBIO H 13 (minor product)

Aiel)
(e) Hydroboration : Hydroboration reaction considers the addition of diborane to the alkene$
and alkynes in the solvents like either, tetrahydrofuran, etc. in N 2 atmosphere. The reaction
involves the anti-Markownikoffaddition ofthe fragments Hand BH2 groups and the product
is cis (s)'n). These hydroboration reactions are highly important in organic synthesis and
these were mainly developed by Prof. H.e. Brown and for this contribution, he was awarded
the Nobel Prize in 1979. Though Prof. Brown is now well known as an organic chemist, but
initially he was trained as an inorganic chemist. The hydroboration reaction is shown below:
I I
" /
/C=C"
BH3 -EI2 0
~ -T-f-
BH2 H
ry
ra
ib
yl
The trialkylboron (R 3B) is the final product when the starting alkene is sterically unhindered,
m
but for the sterically hindered alkenes, the reaction may stop at the R2BH or RBH2 stage.
B/l6
(Me)HC=CH(Me) ----i~~ (MeCH2-CHMe)3 B
he
Me" /Me
lc
/C=C,
Me H
ea
Me" /Me
/C=C,
Me Me
th
The alkyl or aryl boranes are converted into varieties of organic compounds in situ. Some
e/
illustrative examples are given below:

H+ NaOH,H 20 2
R3 B . ) 3RH; R3 B ~
3R - OH (alcohol)
t.m
protonolysis .
[0] NH2SOjH Br2
B(CH2 R)3 ---~ 3RC02 H; BR3 ) 3R - NH 2 , BR3 ) 3RBr
H 2Cr 04
(Norbornene)
(exo-2-norborneol) .
NH2
(exo-product)
In the above cases, the cis-hydroboration leads to the stereoselective reactions.
1. BJl6
R-CH=CH2 ~ R-CH-CH3 + R-CH2 -CH20H
2. H 20 2, OH I
OR
(R = bulky alkyl group) (Markownikoff (Anti-Markowni-
product, minor) koUproduct, major)
i~J
ry
6~H
ra
2.H20 2,OH-
( I-methylcyclo- (trans-2-methylcyclohexanol)
ib
, hexene) (Stereoselective product)
~
3H
yl
OH
H
2.H;02,OH-
m
(l-methylcyclo- (trans-2-methylcyclopentanol)
he
pentene) (Stereoselective product)
Mechanism of hydroI,oration involves the addition ofelectron deficient BH) (which actually
remains as BH)- solve"ilt adduct) to the double bond. BH) takes up the 7t-electron cloud to
lc
produce some sort of carbo-cationic character. Then the electron deficient C-centre attaches
ea
to a hydrogen atom of BB) to produce a cyclic transition state. Then within the cyclic transition
state, hydride transfer to the electron deficient C-centre produces the product. It may be
noted that in the case ofMarkownikoffelectrophi/ic addition ofHX to a double bond, hydrogen
th
adds as F. The cis-hydroboration leads to stereoselectivity.
'2 '2 12
e/
1/ . S+ 1/ S+ &-11
/c ~c"
+ BH] ----. /\:----,9, ----. -1---\-~-
, , . "'-.
t.m
',,' ;~:0+
6-BH3 0- H--BH 2
(I) (II)
In attaining the cyclic transition state (II), the carbocationic centre may arise either at C-I or
C-2 centre. The centre which is more substituted is the better candidate to develop the
carbocationic character. It explains the ..a .nti-Markowniko/f and cis addition of BBl.
S+ 0-
H C-CH==-==CH2
3 I
I
~II
I I
n-' -BH
I~
&--
I
S+ 2
(f) Substitution of BH fr~gment by isolobal organometallic fragments leading to metallo-

boranes : BSHg can react with Fe(CO)s to produce a metalloborane B4HsFe(CO») through
the substitution of the apical 'BH vertex by Fe(CO)3 fragment. In fact, the BH and Fe(CO)3
moieties are isolobals. BH group provides one skeletal electron pair (SEP). Fe(CO)3 fragment
1
also provides 1 SEP = 2" (8 + 3 x 2 - 12)]
-BH
nido - BSHg + Fe(CO)s _ 2eO ) Bg H gFe(CO)3 (square pyramid)
ry
ra
ib
yl
m
10.13.3 Synthesis and Reactivity of Carboranes
he
Carboranes are obtained by replacing the BI1 groups by the isoelectronic and isostructural fragment
CH. Replacement of two BI1 units by two CHunits gives the neutral closo-carboranes. For example,
lc
addition of C2H2 to B 1oH14 in presence of Lewis base Et2S produces closo-l,2-BlOC2H12 (1,2-dicarba-
closo-dodecaborane). The Lewis base (L) adds first to the electron deficient BHB bridging portions to
ea
produce the adduct B 1oH12(L)2 with the release of a molecule of H2-gas. The compound B 1oH12(L)2 is
isoelectronic and isostructural with BIOH124-.
th
B10 H 14 + 2Et2S ~ BIOH12(Et2S)2 + H 2

(Lewis base addition)
e/
BIOH12(Et2S)2 + C2H 2 ~ 1,2 -C2BIOH12 + 2Et'J.S + H 2

t.m
In general, the most common preparative route involves the reaction of boranes with acetylene.
500-6000 C
BSHg +C2H 2 ------+) 1,5-C2 B3 H s +1,6-C2 B4H 6 +2,4-C2 BsH7 ,(closo-products)
(-H 2 )
-- 200°C
BSHg + C2H 2 ) 2,3 - C2B4H g , (nido-product)
At low temperature (-- 200°C) nido-products predominate while at higher temperature (-- 500-6000 C),
the closo-products predominate. It indicates the higher stability of the closo-products.
Et2S
B10 H 14 +C2 H 2 ) 1,2-C2BIOH12
(-H 2 ) .
(Note: The chemistry of B1oH14 which is fairly stable has been studied rather extensively. By
adding a 'C-C' handle on the open face ofthe decarborane 'basket' (nido-structure), the closo-dicarborane
(Le. C2B 1oH12) 'is obtained and it earned the attention of chemists. In fact, this carborane is highly stable
and its property has been extensively studied. Thus closo-C2B1oH12 and the precursor (from the standpoint
of synthesis) nido-B 1oH14 are well characterised and well studied).
Depending upon the relative positions of the two C-'centres in the icosahedral framework, three
isomers of BIOC2Hl2 are possible. The 1,2-isomer (called ortho-isom~r) obtained in the above process
can be thermally converted into the 1,7-isomer (called meta-isomer) and 1,12-isomer (called para-
isomer). The isomers are shown in Fig. 10.13.3.1.
ry
ra
400- 500°C
•
ib
yl
12
(1,2-Carborane (1, 7-Carborane
Le. ortho-carborane) Le. meta-carborane)
m
he
The isomerisation leads to the most stable para-carborane.

lc
400-S00o C -700°C
ortho-carborane ) meta-carborane - - - - - + ) para-carborane
ea
(Le. I,2-carborane) (Le. 1,7-carborane) (I, 12-carborane)

(isomerisation of C2B u#12)
th
For the isomerisation, ortho ~ meta, the DSD (diamond-square-diamond) mechanism is very
often argued. In the DSD mechanism, the icosahedron structures of 0- and m-isomer remain in a dynamic
e/
equilibrium via a cubo-octahedron. The icosahedrons are produced by reclosing the square faces of
the cubo-octahedron. The cubo-octahedron is produced from the icosahedron through the opening of ~
t.m
pair of adjacent triangular faces into a square face. This is illustrated below:
It may be noted that the DSD mechanism cannot explain the meta ~ para isomerisation.
(Note: The C-centres in carboranes are the most electronegative centres (cf. 'Xp = 2, 2.1 and 2.5 for
B, Hand C respectively) and in the most stable isomer, there is a maximum separation between the
electronegative C-centres. This is why, 1,12-carborane is the most stable isomer).
• closo-hydroborate anions vs. closo-carboranes : Carbon being more electronegative than boron
polarises the B-e bond as ~+B-c&-. Compared to ~OHI2o-, the neutral carborane BIOC2Hl2 is much less
pron~ to the electrophilic attack. If, at all, an electrophilic attack occurs, it will occur on the B-centres
as far as possible away from the C-centres. It is understandable from the nafure of B-C bond
polarisation. On the other hand, it is more sensitive than ~oHto- towards the nucleophilic atf4£k and
it will occur on the B-centres as close as possible to the electronegative C-centres.
The electron withdrawing inductive effect of carbon is reflected in' the acidity of carboxylic
acids of carboranes.
1,2 - HC(B10H10)C -C02 H(pKa = 2.S0)}
1,7 - HC(B10H10)C -C02 H(pKa = 3.0)
ct. C6 HsC02 H(pKa =4.2)
The carborane-carboxylic acid is stronger than benzoic acid. It indicates the better electron
ry
withdrawing inductive effect of the carborane cage (Le. B10CZ cage) compared to that of the phenyl
group. The higher acid strength of the 1,2-isomer compared to that of the 1,7-isomer is due to the
ra
better cooperative electron withdrawing inductive effect exerted by the two ortho-electronegative C-
centres compared to that in the meta-isomer.
ib
Reactivity of carborane BIOCzHIZ : The H-atoms attached with the relatively ~ore electronegative
C-atoms in C2B 1oH12 are slightly acidic. The acid strength of the CH-group runs in the three isomers
yl
as: ortho > meta> para (cf. effect of the cooperative inductive effects of two C-atoms). Such acidic
hydrogens may be replaced by Li+ when treated with n-butyl lithium.
m
B4H 6C2 + 2LiC4Hg ~ B4H 4C2 Li2 + 2C4H 10 ; Bl0HIOC2H2 + 2LiC4Hg'~ BIOHI0C2Li2 + 2C4H 10
The dilithiocarborane is a quite reactive nucleophile and Li may be substituted by many electrophilic
he
reagents. These are shown below:
lc
Li-C--C-Li H-C--C-H
\0/ \0/
ea
B10H10 B10H10
1 cO 2 + H20.
(Ortho-isomer)
th
B10H10C2(C02H)2 -RH1 +RMgX

e/
N Le. H-C--CMgX B10H10C212

UN H02C - C - - C - C02H
~ \0/ \0/ i.e.
I-\O/C-I)
t.m
B 10H 10
B10H10
( B10H 10
/F\COb
Fe(CO)5
• Ph2P PPh 2
c-c
I I
\0/
B 10H10
1,2-BIOH10C2H2 is quite stable but the B-atoms (i.e. 3 and 6 positions) adjacent to the C-atoms
are the centres olattack by nucleophilic reagents. It happens so because of the electron withdrawing
effect ofthe adjacent C-atoms which are the more electronegative centres. This is why, 1,2-B1oHI0C2H2
2- 2-
ry
ra
(a)
C2 BgH f1" (dicarbollide anion)
ib
yl
m
he
lc
ea
th
(b)
e/
[(TIS - 7,'8-C2B~H11)Fe]- [('1 5 - 7, 8-C2BgH11)2Re(CO)Jl-

(c) (d)
t.m
Fig. 10.13.3.2. Structure of dicarbollide anion and dicarbollide complexes. (a) Available orbitals projected
towards the missing B-atom in the open face of dicarbollide anion; (b) Pot-like structure of dicarbollide
anion; (c) Sandwich complex of Fe(lI) with the carbollide anion; (d) Re-complex with dicarbollide anion.
(0 for BH• • for CH)
experiences nucleophilic attack by the strong bases like 0](, with the removal of a BH2+ unit. It gives
a nido-carborane anion. Thus one of the B-atoms (either from 3 or 6 position) is lost as B(OR)3 (when
treated with OK).
c/oso -1,2 - C2BIOH12 + NaDEt + 2Et - OH ~ nido -7,8 - C2B9H l-2 + B(OEt)3 + H 2 + Na+
NaH can abstract one more proton from 1,2 - C2B9H l-2 to produce another nido-carborane dianion
(cf. Fig. 10.13.3.2).
C2B9H l-2 + NaH ~ Na+ + H 2 +nido-7,8-C2B9H121- (dicarbollide anion)

This nido - C2B9H121- is a quite strong base and itmay readily recombine with the F ion to give
back the species like C 2 B9 H 12 , C 2 B9 H I3 (a neutral nido-carborane).
2- H+ - H+" Heat
C2B9H II ) C2B9H I2 ) C2B9H I3 ) 2,3 -C2B9H lI + H 2
closo-I,7-C 2B loH I2 (Le. meta-isomer) can also behave in the same way to produce
nido - 9,11- C2B9HI21-. In this isomer, the B-centres adjacent to C-centres are to receive the
nucleophilic attack.
ry
The nido - C2B9H121- (obtained from ortho- and meta-carborane) is quite interesting. This II-vertex
dianion provides a pentagonal C2B3 open face. It gives the pot-like structure (Fig. 10.13.3.2) and this
is why, it has the trivial name dicarbollide (Spanish olla meaning pot). In the open face, all the 5-atoms
ra
may be considered to be sp3-hybridised. Each atom can provide one sp3-hybrid orbital to generate five
ib
5-centred MOs in which 6-electrons are accommodated as in Cp- i.e. CsH; (cyclopentadienyl anion).
It is important ~o note that C2B9H121- can act as a 6e-donor (cf. BH2+unit has two valence electrons).
yl
Thus, these two anions can provide 12 electrons which are required by Fe 2+ to attain the next inert gas
configuration of Kr (3d 6 --+ 3d 10 4s 2 4p6).
N
m
2C2BgH121- + FeC/2 2) [Fe("s -C2BgH ll )2]2- + 2CI-
he
(cf.2CsH; + FeC/2 --+ Fe("s -CSH S )2 + 2C/-)
In fact, the nido - C2B9H121- ion is isolobal with the ligand cyclopentadienyl (CsH;) which acts
lc
as a six-electron donor. Thus, the above Fe(II) complex is very much ~omparable with ("s - CsHs)2Fe
(known.asferrocene). Both the complexes experience reversible oxidation in air.
ea
[Fe II (Cp)2] ~ [Fe Ill (Cp)2]+ + e

th
[Fell(C2~Hl1)2]2- ~ [FeIII(C2B9Hll)2]- + e
Co(III) being isoelectronic (3rt) with Fe(II) also forms a similar metal complex [CollI (C 2B9H 11 )2]-.
e/
Symmetrical sandwich type complexes are formed by C2B9H121- with the metal centres like Cr(III),
t.m
Fe(III), Fe(II), Co(III), Ni(III), Ni(IV), etc.
In fact, nido - C2BgH121- binds in the same way in the mixed ligand complex like,
s s
Na[(" - CsHs )Fe (11 - C2B9H lI )]
The following dicarbollide complex has been prepared as follows :
C2B9H121- + Re(CO)s Br --+ ("s - C2B9H II )Re(CO)3 + Br- + 2CO
Carborane-siloxane polymer : Because of high thermal and oxidative stability of carboranes,
meta-BIOC2HI2 moiety has been incorporated into the backbone ofcarborane-siloxane polymer. Ortho-
derivative is not used to avoid cyclisation. The monomer R -e. . . C -R (R = -SiMe2---O--SiMe2Cl)
produced undergoes polymerization through hydrolytic condensation.
. ~ . (i) CI-SiMe 2 -O-SiMe 2 -Cl . ~. . ~
LIC~CLI .. [-SIMe2-C~C-SIMe2-0-SIMe2-]
(ii) Hydrolysis n
10.14 MOLECULAR SYMMETRY AND POINT GROUPS

10.14.1 Introduction
Molecular shape can be described in terms of its symmetry. A highly symmetrical molecule can have a
large number of equivalent orientations (Le. look-alike orientation) which are indistinguishable from
the original one but not necessarily identical with the original one. In terms of symmetry elements, the
molecules can be classified into different groups.
10.14.2 Symmetry Elements and Symmetry Operations
ry
There are 5 different symmetry elements and the symmetry operations on °a molecule can produce
indistinguishable orientations. In the symmetry operation, the energy and the centre ofgravity ofthe
ra
molecule remain unchanged. The five basic symmetry elements and their corresponding symmetry
operations are given below.
ib
(Note: In a symmetry operation, the configuration or orientation attained is indistinguishable from
the original one but it may not be necessarily identical with the original one.)
yl
(i) n-Fold Rotation Axis (i.e. Proper Axis of Rotation) denoted by Cn (C originates from
'Cyclisch') : rotation about the axis by 3600 /n Le. 21t/n.
m
(ii) Plane ofSymmetry (i.e. Mirror Plane) denoted by cr : reflection at the plane.
(iii) Inversion Centre (Le. Centre ofSymmetry or Point ofSymmetry) denoted by i or C; : reflection
he
0
of all atoms through the point.

(iv) n-Fold Rotation-Reflection (i.e. Improper Axis ofRotation) denoted by Sn : rotation {ollowed
lc
by reflection (in either order) Le. rotation about the axis by 3600 /n followed by reflection
through a plane perpendicular to the axis of rotation.
ea
(v) Identify denoted by E or I: no change in the molecule.

Note: • Lone pair orbitals are not considered to examine the symmetry operations.
th
• In a symmetry operation, the configuration or orientation developed is always

indistinguishable from the original one but not necessarily identical with the original
one. In identity symmetry operation (E), the configuration attained is identical with
e/
the original one.

t.m
10.14.3 n-Fold Rotation Axis (i.e. n-Fold Proper Axis of Rotation) (en> and Rotation About a
Symmetry Axis .
If the molecule is rotated by 3600 /n about the axis, it will produce the equivalent (i.e. look-alike)
orientation of the molecule in space. For Cn' successive n-rotations (each time by 3600 /n) give n-
equivalent orientations for the molecule. After the end ofn-times operations, it will generate the original
orientation of the molecule.
• The successive operations are denoted by Cn (Le. rotation by 21t), C; (Le. rotation by 2 x 21t), C~
n n
. rotatIon
( I.e. 3 x-21t
· by - m (.
) , ..., Cn •
I.e. rotatIon m-
by - x 27t)
- ,..., enn (.I.e. rotatIon
• n x-
by - 27t = 27t ) .
n n n
Thus, n-successive rotations (Le. C;) give the symmetry operation, Le. C;
= E.
• n = 1, 2, 3, 4, 5, 6 etc. indicates rotation by 360°, 180°, 120°, 90°, 72°, 60° etc. respectively
around the axis in a symmetry operation and the corresponding symmetry elements are C 1' C2'
C3' C4' C s and C6 respectively.
• Cnx means rotatIon

• by -
x x-
21t aroun d t he axIS.
. Th e symmetry operatIon
· C42 means rotatIon
•
by 2( 241t) or 221t · Thus wencan write:

2
C4 =C2
Thus for C6 axis, the symmetry operations can be expressed as follows:
12 3 4 2 5 6
C6 ,C6 (=C 3 ),C6 (=C 2 ),C6 (=C3 ),C6 , C6 (=E)
Illustration
ry
(a) C 2-axis in H 20 lee HOH (V-shaped molecule) : Here, the C2-axis passes through the O-atom to
bisect the H - 0 - H bond angle.
ra
C2 c~ = E
01 I
ib
I
I
yl
m
(a) (c)
he
(b) 21t
0
Fig. 10.14.3.1. C2 axis in H2 0. C2 operation Le. rotation by 2 = 180 around the C2 axis produces
ci -operation
lc
(b) from (a) which are equivalent in configuration. Another C2-operation on (b) Le. on (a)
produces (c) which is identical with- (a)
ea
(b) CJ and C2 axes in trigonal planar species AXJ (e.g. BFJ , BC/J , CO;-, NO;, SOJ etc.) : There
is a C 3 axis passing through the central atom A and perpendicular to the "l0lecular plane. There
th
are 3C2 axes (each passing through one A - X bond and bisecting the X - A - X angle produced
by the remaining two X-atoms) in the molecular plane. These are shown in Fig. 10.14.3.2 to
e/
10.14.3.4.
c~
t.m
c~ (= E)
Fig. 10.14.3.2. C3 axis perpendicular to the molecular plane ofAX3 (a triangular planar species). (a).
(b) al'!d (c) are equivaqlent orientations generated through the C3 and C32 symmetry operations. C33
symmetry operation gives back the original orientation.
(Note : In the trigonal planar species AX3' there are both C3 and C2 axes. In such cases, the
highest fold axis (Le. C3 for the planar AX) species) is called the principal rotation axis and it is
generally taken as the x-axis of the cartesian coordinate system).
(c) CJ axis in the trigonal pyramidal X2 x3

C2-axis / C2 /
molecular ~]Jecies like NHJ : In NH3, the •••·••••·••• X 1-V- A " ----...X 1- - A "
three H-atoms are placed at the comers of x3 x2
an equilateral triangle lying in the plane of (a) (b)
the paper and the N-atom is above the centre Fig. 10.14.3.3. One C2 axis (at the molecular plane)
of the triangle. There is a C3-axis passing in AXa (a trigonal planar species). There are two
through the N-atom and centre of the other such C2 axes.
triangle.
ry
(Note: Both BX3 and NH3 are having the
same type of molecular formula, but their
ra
symmetry elements are different).
(d) CJ and Cz axes in tetrahedral species
ib
AX4 , CH 4 , NH;, PH;, SiF4 etc.: There
are 4C3 axes (each passing through one
yl
A-X bond and centre of the hypothetical
equilateral triangle produced by placing the
other 3X-atoms at the vertices).
m
Fig. 10.14.3.4. Position of 1C3 and 3C2 axes in the
he
planar AX3 species.
lc
ea
th
e/
(a) (b) (c) (d)
1_--_-_-c_~--=-~---=-J __I
t.m
C~(= E)
Fig. 10.14.3.5. C3 axis and its symmetry operations in NH3 (a trigonal pyramidal molecule).
The tetrahedral species AX4 may be constituted by placing A at the centre of a cube and 4X-
atoms at the alternate corners of the cube. There are 3C2 axes (each passing through the centres
of opposite faces of the cube). The C3 and C2 axes for AX4 (tetrahedral species) are shown in
Fig. 10.4.3.6.
(e) Cz axis in cis- and trans-NzFz (dinitrogenfluoride) : If the molecule is drawn in the plane'ofthe
paper, for the cis-configuration, the C2 axis lies at the plane o.fthe paper (Le. molecular plane)
and it is perpendicular to the N-N segment and passing through the mid-point of N-N segment.
For the trans-configuration, the C2-axis is perpendicular to the plane ofthe paper (Le. molecular
plane) and bisecting the N-N segment. These are illustrated in Figs. 10.14.3.7 and 10.14.3.8.
.C2
I
C3
.I
I
,I
xt'Kt---r--
r--.L;1i-----
,II
I
I
I
I
J
,I
IX
I
I
I
I I I I I
X C2 I I. I I
I "--i-"~'-- t~----7":--~-:
II I I
L___ ---T--7I
A ,IX I
/11" 1,1 I
~-----
I ,I
ry
V ,I
X I X
I
X I X
I
(a) (b)
ra
Fig. 10.14.3.6. C3 and C2" axes in tetrahedral AX4 species. (a) One C3 axis shown there are total 4C3
axes - eaC?h passing through one A-X bond. (b) two C2 axes shown; there are total 3C2 axes. each
ib
passing through the centres of opposite faces of the cube.
yl
(f) CJ and C2 axes in trigonal bipyramidal species (e.g. PFs' Fe(CO)s' etc.) : There is a C3 axis
passing through the Xax-A-Xax Iffiear segment and there 3C2 (i.e. 3C;) axes (each passing though
m
one A-Xeq ) and these are perpendicular to the C3-axis. These are shown in Fig. 10.14.3.9.
he
lc
~ ~
C2 /F 1 C /F 2 C
ea
N =t=N --4 N =t=N --4

F/ F/
2~ 1~
th
(a) (b) (c)

Fig. 10.14.3.7. In trans-N2 F2 • C2 axis (denoted by.) perpendicular to the N= N bond and perpendicular
e/
to the plane of the paper (Le. molecular plane). The orientations (a) and (c) are identical.
fC 3
t.m
I
! IIC'
X ' 2
C2 C2 C2
I ax
/Xeq
"
F2 F1 b C2, +-----X - - A"

b F1
" •P /2F F2 F1
I"
/ C2 C2
~N+=N/
"
I
N=t=N -+ N=t=N -+ eq Xeq
I I I "
I I I X ax C'
I
! I ""
• I
I
I I
2
c~ !
Fig. 10.4.3.8. In cis-N2 F2 • C2 axis (perpendicular to the Fig. 10.14.3.9. 1C3 and 3C2(C2 l.
N = N bond) in the plane of the paper (Le. molecular plane). C3 ) axes in trigonal bipyramidal
species AXs' Note : C2 axes
perpendicular to the principal axi3
are denoted by C2 axes.
(g) Cn-axes/or the octahedral species (e.g. SF6, SiF62-, FeF6, Fe(CN)~-/4-, W(CO)6' etc.) : There
are 3C4 axes (each passing through the X -A -X linear segment); 4C3 axes (each passing through
the centres of the opposite octahedral trigonal faces); 6C2 axes (i.e. 6C~) (each passing through
the centres ofopposit~ octahedral edges). These are shown in Fig. 10.14.3.10.
•I c4' C2' 52
I
I
X
ry
I
I ."..".X
X X,A"""" X C;+--
ra
ib
X C3
yl
AXs
Fig. 10.14.3.10. Different Cn axes (Le. C4 , C3 and C2 ) in the octahedral species AXe·
m
(h) C4 and C2 axes in square planar AX4 species (e.g. XeF4, PtCI;-, etc.) : There is a C4 axis
perpendicular to the plane of the molecule and it passes through A. There are 4C2 (i.e. 4C~) axes
he
in the plane of the molecule. These are shown in Fig. 10.14.3.11.
(i) C6 and C2 axes in benzene: There is a C6 axis perpendicular to the plane of the molecule and it
lc
passes through the centre of the molecule. There are 6C2 (i.e. 6C~) axes in the plane of the
molecule.
ea
G) CS and C2 axes in cyclopentadienyl anion (Cs"S): There is a Cs axis perpendicular to the

molecular plane and passing through the centre. There are 5C2 axes in the plane of the molecule.
th
• C2
e/
'" I ~~JfC2
", II ~'
'r~--------r-/-------- r ,~
t.m
II II II
---~-/-------·~~·_-------i---·C2
I I I
I, II II
/
/
.
,~' X---------~---------x.
II
C2
.',,
~
C2
Fig. 10.14.3.11. C4 and C2 axes in square planar Fig. 10.14.3.12. 6C2 axes (at the molecular plane)
AX4 species. 4C2 axes shown in the molecular of C6 H6 . C6 axis (perpendicular to the molecular
plane and 1C4 axis (not shown) perpendicular to plane) passes through the centre of the molecule
the molecular plane and passing through A. (C6 not shown).
Note: Seventh C2 axis lies along the C6 ; C3 and
56 are also colinear with the C6 axis.
(k) Cn-axes in linear molecules: In all linear moleculeS:, the molecular axis is regarded as Coo. The
molecule can be rotated around this axis at any angle to produce an indistinguishable 'orientation
of the molecule. The symmetry operation can generate an infinite number of indistinguishable
orientation of the molecule and this axis of rotation (Le. molecular axis) is denoted by Coo.
°
For the centrosymmetric linear molecules (e.g. H-H, C/-C/, H-C ==C-H, = C =0, etc.)
there are also infinite number of C1 axes perpendicular to Coo. For the, non-centrosymmetric
'linear molecules (e.g. H-C/, C==O, etc.) there is no C2 axis.
c2
ry
·_··c/ r C/--(j~ ....•; .. oH-;~C-H.g .. S~.; .. _.H-X··Vo.S ",+
ra
Fig. 10.14.3.13. Cao axis in some linear molecules.
ib
(I) Cn axes in C1H 4, CH1Cl1 and allene: These are illustrated in Fig. 10.14.3.14.
yl
m H CI
,/
---- c----.. C2
he
H/ " CI
= C bond. 2nd
lc
One C 2 along the C The single C 2 axis bisects the

,... 6
C 2 .1 C = C bond and .1 molecular CICCI and HCH bond angles.
(in CH 2CI 2)
ea
plane at the mid point of the C = C

bond, 3rd C 2 .1 C = C bond and (b)
bisecting the C = C bond at the
th
molecular plane.
(in C2 H4 )
e/
(a)
t.m
C 2 axis along the C=C=C bond.

(in allene)
(c)
Fig. 10.14.3.14. 3C2 -(in C2 H4 ), 1C2 (in CH2 C/2 ), and 1C2 (in Allene) along the C = C = C bond (two
other C2 axes passing through the middle C are perpendicular to the molecular axis; they are also
mutually perpendicular).
10.14.4 Plane of Symmetry (I.e. Mirror Plane) and Reflection at the Plane of Symmetry
The plane of symmetry passes through a molecule and the plane separates the molecule into two halves
which are the mirror images to each other. This symmetry element is generally denoted by cr. The
symmetry operation is the reflection at the plane. The alphabet Y (upper case) po~esses a symmetry
plane passing through the leg and bisecting the angle between the hands.
• If the symmetry plane contains the principal rotation axis, the plane is described as a vertical
mirror plane (denoted by a v ). The horizontal mirror plane (denoted byah) is perpend(a.dar to
the principal rotation axis. The vertical planes which bisect the angles. between the C~ -axes are
called dihedral mirror planes (denoted by ad) (cf. Fig. 10.14.4.4).
• x-times a-operation can be denoted by cr;
and cJl (= E) leads to the original configuration/
orientation. Thus cr= E (x = even), cr
= a (x = odd).
Illustration of symmetry planes

f2,
,,
I
ry
(a) Symmetry planes in H 20 Le. H - 0 - H (V-
I
, I
I
shaped) molecule: It has been already stated
~·9 6
H/l""'-H
ra
Oy ~~,
that the molecule possesses a C2 axis as the H~~ I
principal axis of rotation. There two a v (Le. ,, ,I
,
ib
containing the C2 axis): one (denoted byav ') ,I
in the plane of the molecule and the other
Fig. 10.14.4.1. Mirror planes (Oy and Oy')
yl
(denoted by a v ) perpendicular to the
molecular plane and bisecting the containing the principal axis of rotation C2 •
H - 0 - H angle. These are shown in Fig.
m
10.14.4.1.
he
(b) Symmetry planes in the trigonal planar AX3 species
(e.g. BF3 , BC/3 , CO;-, NO;, S03' etc.): There is a C 3
axis as the principal axis of rotation perpendicular to the
lc
molecular plane. There are three a v (Le. containing the C3

axis) and one a h (Le. perpendicular to C3). Each a v contains
ea
one C22 axis (Le. one A - X segment and bisecting the

X - A - X bond angle constituted by the- other two
th
X-atoms). The molecular plane is the O"h. These are shown

in Fig. 10.14.4.2.
e/
(c) SymmetryplanesinNH3 (atrigonalpyramidalmolecule): Fig. 10.14.4.2. Mirror planes (Oy

There is a C3 axis as the principal rotation axis. It possesses and 0h) in the trigonal planar AX3
t.m
3CJv (containing the C3 axis), each of which contains a N- species.

H segment and bisects the hypothetical line joining the
other two H-atoms.
(d) Symmetry planes in tetrahedral species AX4 (e.g. NH;, PH;,
CH4 , SiF4 , SO;-, etc.): There are six planes of symmetry. These
are shown in Fig. 10.14.4.3. If the X-atoms are numbered as 1, 2, 3
and 4. The 6 symmetry planes contain the atoms as follows:
AX1X 2 , AX1X 3 , AX1X 4 , AX2 X 3 , AX2 X 4 , AX3X 4
Note: In AX3 Y (e.g. CHlCI), there are 3 symmetry planes as in
NH3 • The segment A - Yalways lies in these planes. InAX2 Y2 (e.g. Fig. 10.14.4.3. Six vertical
CH2C/2), there are two mutually perpendicular symmetry planes. mirror planes (containing
One such plane contains the AX2 fragment while the other contains the C3 axis) in the
the AY2 fragment. In A(XYZp) e.g. C(HCIBrF), there is no plane tetrahedral species (AX4 ).
of symmetry. Thus the number of symmetry planes in the tetrahedral species depe{nds on the kind
of substitution.
(e) Symmetry planes in borazine (B JN JH 6) and benzene: In borazine, there are 3crv (each passing
through opposite corners of the hexagon) and there is a crh which is the molecular plane.
In benzene, there are 6crv (containing the C6 axis) and they contain the C2 (Le. C~) axes (passing
through the opposite comers of the hexagon and passing through the mid-points of the opposite
edges). These vertical planes are actually dihedral planes (cr d) bisecting the angles between the
C~-axes.
ry
ra
ib
yl
m
he
(a) (b)
Fig. 10.14.4.4. (a) 3a v (only one shown) and 1ah (Le. molecular plane) in borazine (B3 N3 He); (b) Sad
lc
(containing the Ca axis, not shown) and 1ah (Le. molecular plane) in benzene.
(f) Symmetry planes in trigonal bipyramidal molecules AXs (e.g. PFS) : There are 3crv (containing
ea
the C3 axis, Le. Xax - A - Xax linear segment). Each contains one A - X eq segment Le. C2 axis.
There is a O"h which is the basal plane.
th
(g) Symmetry planes in square planar species AX4 (e.g. XeF4 , PtCI;-, AuCI;, etc.) : There are 4crv
(containing the C4 axis) and lcrh (which is the molecular plane). Each O'v plane contains a C2
axis.
e/
(h) Symmetry planes in octahedral species AX6 (e.g. SF6 , SiF62-, FeFi-, etc.) : There are three
basal planes as symmetry planes. Each plane contains the planar fragment AX4' e.g. AXIX~:0'4
t.m
taking X s and X6 as the axial points and similarly AX~~SX6' AX1X:0'sX6 are two other symmetry
planes. These are basically crh perpendicular to the C4 axis. There are 6crv (containing the C4
axis). Each O'v passes through A containing two opposite vertices. One such plane contains AXsX6.
(i) Symmetry planes in linear molecules : X . '
s
There is a Coo and there are infinite number
of 0v containing the Coo. If the molecule
(e.g. X - X, H - C == C - H, etc.) is
symmetric (Le. characterised by the
presence of C2 perpendicular to Coo) then
there is a 0h perpendicular to Coo and
bisecting the molecule. Xa X6
For the nonsymmetric linear molecules Fig. 10.14.4.5. Symmetry planes in octahedral
(e.g. CO, HCl, etc.) there is no 0h. species AX6 •
0) Symmetry planes in allene : In H2C = C = CH2, there are two vertical mirror planes. These are
dihedral planes (ad) and they lie between the C2~axes).
C2 C
tI ,1 2
,
I ,
I ,
.. : ______ H
r
,~ ~
cr
,
,,': I
:,'
1,'
D. ..-- ~ A
,'1 I, , "
H~--~---------~-~------~'
~.,
ry
: I
-----~---- ... C===C===C .. -----:----. s c

: I / ,. I ~: I 4' 2
H- - - - - - p -
:
I
,,' : ,,':
... - - - - - - - - , - - - - -)
,,' o B
ra
I ' , I I ,
~~----~-r':-----~--------- "
.'" .: H
ib
Fig. 10.14.4.6. Symmetry planes in allenes. (J (containing C = C = C, and A, B and bisecting the DeD
angle); obviously for A = B = D = H (as in allene) there are two such CJ. In allene. CJ v is actually CJ rt
10.14.5. Inversion Centre (i.e. Centre of Symmetry) and Reflection Through the Inversion
yl
Centre
m
The symmetry operation is the reflection of all the atoms through the inversion centre. In other words,
he
all the straight lines joining the symmetrically equivalent atoms are bisected at the inversion centre,
• If the inversion centre is considered as the origin of the Cartesian coor~inate system, then for
lc
each point (x,y, z) there must be an equivalent point at (-x, -y, -z). If the operation is denoted by
i, we can write :
ea
i - - -
(x, y, z) ~ (-x, - y, - z) or (x, y, z)
• Inversion centre i must lie within the molecule but at the inversion centre, an atom may remain
th
present or may not remain present.

• In the molecule like N 2 0 4 , C2 H 2 , C2 H 4 , C6 H 6 C12 , there is no atom at the centre of symmetry
!
e/
while in the species BeF2 , CO2 , etc. there is.·an atom at the centre of symmetry.
t.m
q,~ ~,o
'N-----N'
iI ~o
® F-B~F o=c=o
• In the geometrical figures like straight line, circle, ellipse, square, hexagon, rectangle, octahedron, .
etc. there is a centre of symmetry in each case but it does not exist for the geometries like
triangle, tetrahedron, pentagon, etc.
• n-times symmetry operation Le. in = E (n = even), in = i (n = odd).
• i is absent in the following species like NH3 , BX3, H20, AX4 (tetrahedral), CsH etc. s'
Illustration
(a) Linear molecules: The symmetrical linear molecules (e.g. X 2, CO2, BeF2, C2H 2, etc.) having
<x>C~ axes perpendicular to the Coo axis (Le. molecular axis) are possessing the centre ofsymmetry.
In such cases, the centre ofsymmetry lies on the molecular axis at the point bisecting the molecules
(Le. containing the C~ -axes).
(b) Square planar geometries: In the species like XeF4 , PtCl;-, AuC1i, etc. there is a centre of
symmetry. In trans-AX2 Y2 there is a centre of symmetry but in the corresponding cis-isomer, it is
absent.
ry
ra
Fig. 10.14.5.1. Centre of inversion in the square planar AX4 and trans-AX2 Y2 species. No centre of
inversion in cis-AX2 Y2 •
ib
(c) Octahedral species: In AX6 and trans-AX4 Y2 (but not cis-AX4 Y2), there is a centre of symmetry.
yl
Xs X6 Y X
X
4
" I/X I
inversion (;) X2 ,I/X3 X"I/X X"I/y
A A
X/I" X
~
m A
3 2 Xl
/A"
I X4 /I"x /I"r
X6 Xs Y X
he
(frans- with i) (Cis-No i)
. Fig. 10.14.5.2. Centre of inversion in octahedral species AXe' trans-AX4 Y2 (cf. cis-AX4 Y2 does nqt have
lc
I).
10.14.6 n-Fold Rotation-Reflection Axis and Rotation-Reflection (in either order)

ea
The symmetry operation is the combination of two successive operations Le. rotation by 21t/n Le. 360°/
n about the axis followed by reflection at a plane perpendicular to the axis. It can also be done in the
th
order - reflection at O"h followed by rotation by 360o/n about the axis. This combined operation is called
the improper rotation and the symmetry element is described as the n-/old improper axis of rotation
e/
denoted by 8 n (8 comes from the word spiegelung). The characteristic features ofthis symmetry operation
are given below :
t.m
.~=~X~ill~X~ .
• In this combined symmetry operation, the individual components of the operation may be or
may not be themselves symmetry operations independently by their own right.
In BF3, 8 3 (= C3 x O"h) is a symmetry element and at the same time C3 and O"h are also the
symmetry elements by their own right. In CH4, 8 4 (= C4 x O"h) is a symmetry element but the
components C4 and O"h are not independently the symmetry elements.
• 8 1 = C10'h = EO"h = 0". C 1 means rotation by 360°/1, Le. C 1 = E.
• 8 2 means inversion, Le. 8 2 = i. It can be rationalised as follows:
8 2 =C2 XO"h =i
[x, y, z] C2 ) [x, y, z] Oh) [x, y, z]

I t
Le.
Note: Here C2 lies along the z-direction,

. C2 (z) --
I.e [x, y, z] ) [x, y, z]
and 0h lies in the xy-plane Le. C2 1.. C1h •
- - - C1h(XY) - - -
ry
Le. [x,y,z]------~)[x,y,z]
ra
ib
Le. 8 2 [x, y, z] = i [i, y, z] =[x, y, z]
yl
• The symmetry element 8n generates the following set of operations :
2 3
Sn,Sn,Sn'········
m
If the Sn axis is considered to lie in the direction of z-axis, the reflection is carried out at the
xy-plane.
he
• S" (n = even) generates the following se~. ofsymmetry operations.
2 22 2 3 33 3
Sn (= CnC1 h ), Sn (= CnC1 h = Cn ), Sn(= CnC1 n = CnC1 h ), .....,
lc
S: (= C: C1~ = E because C: = E and 0': = E when n is even).

ea
Let us illustrate for 8 6 :
S6(=C60'h)'S~ (=c~O'~ =C~ =C3)'S~ (=C~O'~ =C20'h =i)

th
S:(=C:C1: =C: =C;),S: (=c~O'~ =C:C1 h ),S: (=E).

e/
b 2 x 27t 21t. C C3 b 3 x 27t 27t. C C4

y - 6 - or 3 I.e. y - 6 - or 2 I.e.
2 • •
C6 means rotatIon 3; 6 means rotatIon 2; 6
t.m
. 4 X 27t 2 x 27t . 2
rotatIon by - - or - - I.e. C3 •
6 3
In the above set of symmetry operations (generated by 8 6), the sub-set C 3 (Le. S;), (Le. S:) C;
and E (= C;)can be generated by the symmetry element C3 • Thus, existence ofS, indicates the
existence of CJ by its own right
In general, for S" (n = even, !!.. =
odd or even), there must be the symmetry element C"n by its
2 n .
own right; and for n = even but "2 = odd, i exists by its own right, S:/2 (= C':a~ = C':a,,)
operation is equivalent to i; for S" (n and "2n = even), G" and i do not exist by their own right.
• For S" (n = odd), we get the following set of symmetry operations.
Sn'S;'S~, ....,S:-I,S: (=C:C1~ =C:C1 h =EC1 h = C1 h ), ...,S;n
The condition, S; = (Jh indicates that if Sn (n = odd) exists, a h exists by its own right (cf. BF3
having S3' C3 and (Jh).
n C (Jh
Configuration 1 - - - - -
I
- - -....) Configuration 11---.) Configuration III
(i.e. rotation by 2n
1t
) Sn !
If (Jh is itself a symmetry element, the configurations II and III are equivalent, and if Sn is a
ry
symmetry element then the configurations-I and III are equivalent. It indicates that the
configurations-I and II are also equivalent, Le. Cn is itselfa symmetry operation and the symmetry
ra
element Cn exists by its own right.
• In general, for Sn (n = odd), the symmetry elements Cn and ah exist by their own right and Sn
ib
generates 2n symmetry operations.
yl
m
S+4 9 10 S+S 10
he
8 5+3 8 3 9 4
Ss (=C s =Cs),Ss(=Cs (Jh =CS(Jh)'Ss (=C s (Jh
(Jh = E);
(cf. ~ = E for x = even, ~ = (J for x = odd).
lc
The next operation Le. s~ 1 (in general S;n + 1) starts to repeat the sequence:
ea
11 S+S+1 11 1
Ss (= Cs (Jh = CsCJ h = Ss)
S: S:
th
For SS' the 5 symmetry operations (= Cs ), S; (= C;), S; (= C;), (= C:), S10 (= E) can be
generated by Cs itself. The remaining 5 operations can be expressed in terms of Cs and CJh•
e/
Illustration for Sn axis

t.m
(a) S 4 axis in tetrahedral species AX4 (e.g. CH4' BF4- , SiF4 , etc.): The tetrahedral species AX4 can
be described by placing the central atom at the centre of the cube and 4 X-atoms at the alternate
four comers of the cube. It has 3S4 - each passing through the centres of the opposite faces of the
cube (Le. along the three Cartesian axes). The symmetry operation is illustrated in Fig. 10.14.6.1.
Thus the three S4 axes lie along the C2 axes (cf. Fig. 10.14.3.6). Fig. 10.14.6.2 illustrates that si
operation is equivalent to C 2 operation.
(b) S4 axis in allene : The planes containing the fragments H2C = are mutually perpendicular. It
can be described by placing the C = C = C linear segment at the centre of a rectangular box along
the length and for H-atoms at the alternate corners of the cube. Then C = C = C molecular axis is
the S4 axis (which is itself a C 2 axis) (Fig. 10.14.6.3).
(Note: C2 and 8 4 axes lie along the C = C = C molecular axis; there are two more C2 axes (cf.
Fig. 10.14.4.6) perpendicular to the molec'ular axis; there are two a v • Thus these vertical planes
are actually dihedral planes (ad).
x • _
z
4
,
",.:~
I •
....... :
• I
..
I
~&.&~
I 7: •• .)(1_--[7'
. I
: : A I :
I I ~: 0h
I ----i.-~X
I I" 3
I ~ • "
X2- - - - - - - - - -~ ,
(b)
1 Reflection at (fh
ry
(a) y
"':----/------~X3
,'1 ,'1
ra
X2 -...: - ~- - - -.,' :
I~ •
: I
~
A: :
ib
I I I
: I __ ~~----~
I
I , ' , X4 I
,, "
~~--------·X'
yl
(c) 1
Fig. 10.14.6.1.54 operation in tetrahedral species AX4 . (a) and (b) are not equivalent (Le. C4 operation
m
is not a symmetry operation). (a) and1c} are equivalent (Le. 54 = C4 x a h is a symmetry·operation).
There are three 54 axes along the C2 axes lying with the cartesian axes.
he
r
S4,C2
+
{I,
lc
~ 't"" X X2
"i-----/f---------)~4
.~Q x,~~:~f~~~ll-71-~~~~-~~,I~'::,; /~~~l

~-~~~~~~~~~~~?1 , I , I
, I , I
~3·~-t---------- -1
ea
2 :I
m I I I I I C I
I"
t-- -----~~-~
/ I 'I
I
I I
I
I I
4 /1
: !/A~::
.... : I A I I -+ : A : /:
~ l ~(J.~---l.-j (1'I~ :~LJL-~~h

th
I I I •
I I I I
iii : " /------------r,:'

l·~~~=sl,' X4
I
I
I ~ X--------
2 --·,--1
, ,
I
I
k~______________
, ' I ,
~ ~'------!4)--r--- ~4 X3-------~:---~~'
e/
X1
(c)
t.m
c •
:§ tV (S~) 1
~ ~---,----------- X4 X4 "i-.---/f---------~~1
x~'~---~----- --/' l t'~~~-~~~~~-----x(!
a_ea.
, , I , I
8 ,
~2.~-~---------- -~
I , I
:
.~ ~,,' C ,F\-r. . . -.,. ~ I I I
i X~ /t~:
- --'- - - - --- , - - t! ~·l~~~/!---~4ah
I 'I I I I I
4
ig- :: ':/A~::
I
: .
I I I
~
I
2:
I "t - - - - - - - - - - - - , - -
X1
I
I
X-------- ---,--t , 4 I ,
C/) k':-----_:.
I,
------- I,' I ' :
X :
-,,' " I ,
~~-----------_.- '
I ,
~ : X1 2 X3
N (C)· (d) (e)
Fig. 10.14.6.2. 54 (= C4 xaJ and 5: (=C; x(J~ =C2 ) operation in tetrahedral species AX4 • It indicates:
2 2 •. 2 X 27t . 27t
54 =C2 (cf. C4 means rotation by - 4 - I •e·T i.e. C2 operation).
c2 c
ran ,:t 2
•
~~4••••• ~ •••••,-'•••Jt.
..... :;...,'
.....·f~·····7···· 1 ,•••••••••••••/•••• H4
H ," : : , ' /: : :
H f'L
3.
.... •
I
. I
,
: I
~......
I
:
•
t'· -: .... ~ .••,! ••
. II I,'
H1 :
II 1N
H
,
1 I
....
I
I
: I : : : • :
I I, •
I
I a : I I :
--------:---~ c =:= c: = c -:---;-.

~ ~ 1J=C=C\~ ~
I I I.. I I
S4(C2 ) :
I
:/
•
H ••••• L
:
I :I \ "' : :J ,'.:
: :c=c=c: :
~:
~ • • • • • • ~~ I • I
I
~,
~~
,
, 4 I
I ,
"
_•••• J.~ •• _• • • •• '

,
, ..
.. '
. :
: ",'
'(_ ..,/
I• • • ..'• •
,':
~
: ...... H2
~"
.,
I
• ,
H~··"·······,··;
't'. • • • • • • • • • • • • ••
I
..
. ..
H2 H3 ,/ : H3
ry
Fig. 10.14.6.3. 54 axis (colinear with the C = C = C bond) in allene.
ra
(c) Sz in trans-N2F 2, trQn~j-N2F4' trans-H(Cl)C=C(Cl)H. It is illustrated in the Fig. 10.14.6.4. It
may be again pointed out that the 8 2 operation is equivalent to inversion operation.
ib
yl
m
he
lc
ea
(c)
Fig. 10.14.6.4. Illustration of 52-axis and its 5 2-operation in (a) trans-N2 F2 , (b) trans-configuration of
th
N2 F4 , and (c) trans H(C~C=C(C~H.

e/
(a) 52 .1 N=N (at the molecular plane); 0h containing N=N bond and perpendicular to the molecular
plane.
(b) 52 .1 N-N and 0h containing the N-N bond and bisecting the bc~d angles RNF2 and~N~.
t.m
(c) )c=c( as the S2 axis; CIh 1. C=C bond and perpendicular to the molecular plane.
(d) SJ axis in BFJ (trigonal planar) and PFs (trigonal bipyramidal) : Along the C3 axis, the 8 3 axis
lies. In such cases (Le. n = odd), both the Cn and a h are symmetry elements by their own
rights.
Fig. 10.14.6.5. 53-symmetry operation in planar AX3 species (e.g. BF3 ). Here, (a), (b) ~nd (c) are
equivalent as both C3 and 0h exist by their own rights.
(e) S, axis in staggered ethane: This is illustrated in the Fig. 10.14.6.6.
Ss,C 3
H~H
ry
H
ra
H H
H H
ib
(a) (b) (c)
yl
m
he
lc
ea
th
(d)
Fig. 10.14.6.6. Representation of staggered conformations of ethane (a, b and c). 56 axis along the
e/
e-C bond and 56 symmetry operation shown in (d) in terms of numbering of H-atoms.
t.m
Here, the C-e linkage is itself a C3 axis (but not a C6 axis) and S6 lies along this C3 axis.
(f) S4 axis in octahedral species AX, : There are three 8 4 axes lying along the C4 axes passing
through the opposite vertices. These are also C2 axes.
There are also 4 S6lying along the C3 axes passing through the .centres of the opposite triangular
faces.
10.14.7. Identity Element (E or I)

This symmetry operation performed on a molecule produces a co~figuration which is identical with the
original one. Thus it leaves the molecule unchanged. Except this symmetry operation, all other
symmetry operations produce the equivalent (not identical) configuration of the molecule. Repeated
symmetry operations may lead to identity symmetry operation.
nC n operations in succession i.e. rotation by :
21t n 2 3 5
nx-=Cn --=Ee.g.C1 =E1,C2 =E,C3 =E,CS =E,etc.
n
2a operations in succession = a2 = E
Le. a" = E (n = even), a" = a (n = odd)
n Sn operations in succession = S; = E (~= even)
2n Sn operation in succession = S;n = E (n = odd)
10.14.8 Point Groups and Identification of Point Groups
ry
Depending on the existence of symmetry elements, the molecules can be classified into different point
groups. These are discussed below.
ra
Note: Symmetry operations that can be carried out on a particular molecule constitute a mathematical
group which can satisfy the four mathematical conditions. The group constituted by the symmetry
ib
operations is called symmetry group or point group.
4 mathematical conditions to constitute a group (illustration by taking some simple symmetry
yl
operations) :
• There must be an identity operation (E), Le. AE = EA = A, A is another operation.
m
• If A and B are symmetry operations of a particular group, then their product AB is also an
operation of the same group. Operation AB means operation B foHowed by A. If AB = BA, the
he
operations are commutative. Otherwise, AB -:t; BA.
lc
Cn xcr h =a h xCn }
a(xz) x cr(..vz) = cr(yz) x cr(xz) = C2 (z) Commutative condition
ea
C2 (z) x a(yz) = cr(yz) x C2 (z) =a(xz )

• In a group, there must be an inverse operation that will give back the original object. For A
th
operation, the inverse operation A-I leads to : A- 1A ::: AA- 1 == E.

cr(xz) x a(xz) = E; C 2 (z) x C2 (z) = E, Le. the inverse of a cr or ~2 is the operator itself.
e/
C~ x (C;) = E Le. C~ is the inverse of C; .

• The operations in a particular group must obey the associative law of:nultiplication Le. ABC =
t.m
(AB)C = A(BC).
cr(xz) x a(yz) x C 2 (z) = cr(xz) x [a(yz) x C2 (z)] =cr(xz) x a(xz)
a(yz) C2 (z) ( - )
(x,y,z) ) (x,y,z) + x,y,z
I (J xz t
cr(xz) x cr(yz) x C2 (z) =C2 (z) x C2 (z) = E
a(xz) a(yz) (- - )
(x,y,z) ) (x,y,z) ) x,y,z
I C2 (z) f
(a) Coov and Dooh (for linear molecules) : The molecular axis of the linear molecules is the Coo axis.
In symmetrical linear molecules, the existence of i indicates the presence of CXJC2 and one a h
(Molecular plane)
o
ry
F
ra
CI, /H /
C=C N=N
H/ 'CI /
ib
X (C 2h ) F
(C 2 .L molecular
yl
(C1h-C.> plane bisecting
(e.g. S02CI2' =
C C bond; 0h =
POBr2CI, CH 2BrCI)
m molecular plane)
he
Br
, /
H A
/1'
lc
CI/C-C,CI
X X X
H Br
(C 3v)
ea
(CI)
Staggered (A = N, P; X = H, F, CI)
configuration
th
y O--H
I /H " I
A o " I
, I
e/
/1' --~-.: II
X X X OC 2 II .
"'- H
.0'':- II
t.m
(C 3v )
(Open book
structure) H
(H 20 2 ) ~ (C 2) .•
. .'"
~(9)' P
8
i.e. 8~b
b C2
(C 2 ) (C 3)
Fig. 10.14.8.1. Some. representative examples of Cn' Cnh and Cnv point groups.
H ,. /
H X
H
/
C=C ,H X
"A-X
/
(02h) (D 3h )
(e.g. BF3 • CHj ,

CO~-, NOi, etc.)
ry
(e.g. PF s,
Fe(CO)s etc.)
ra
ib
yl
m (e.g. XeF 4' ptCli- I
AuCI4" , etc.)
Tris-chelate
he
Le. M(A-A)3
(°3)
lc
C , S6 H
X y X H .. 3
,1/
/A,
, I ........ H
H, I'H
C
H~H $H
ea
or, or H H
X 1 X
Y
C i H
(D4h ) H H
th
H/"! H H
(D 3d )
e/
(Staggered ethane)
t.m
"
(Cyclopropane)
H
'-......
----- - -....-v-...-----'-'
(Eclipsed ethane)
C3 .1 plane of the ring
(03h)
(D 3h )
Fig. 10.14.8.2. Some representative examples of On' 0nh and 0nd point group.
* B2 Ha : The two B-atoms are joined by two BHB brid~es lying in a plane perpendicular to the plane
of B-H terminal bonds.
(perpendicular to Crx) . Such molecules constitute the D ooh point group. For the unsymmetrical
linear species, absence of i Le. absence of ooC2 and 0'h will constitute the Coov point group where
ooO'v containing the Coo axis exist.
Examples: D«Jh : H 2, N 2 , C/2 , C2H 2, CO2, BeF2 etc.
C«Jv : HCI, CO, etc.
(b) Cn' Cnh and Cnvgroups: In these groups, Cn exists but no C2 perpendicular to Cn exists. Then
the presence ofa O'h generates the Cnh point group; presence of nO'v produces the Cnv point group,
and absence of both O'v and O'h gives the Cn group.
ry
Note: In Cnh there is no O'v; in Cnv there is no O'h. But in D nh both O'h and O'v Le. O'd are present;
in Dnd' only (Jd (no 0'h) is present.
ra
• Ct point group (e.g. CHFCIBr) possesses only E symmetry which is present in all molecules. C1h
ib
point group (e.g. tetrahedral species like CH2BrCI, POCIBr2) is described by Cs having the
symmetry elements C 1 (= E) and 0'. C, point group (e.g. staggered HCIBrC-CHCIBr) possesses
yl
the symmetry elements C1 (== E) and i.
(c) Dn, Dnh and Dnd groups: Dihedral group is generated by the presence of Cn and nC2
m
perpendicular to Cn. Then presence of a O'h produces the Dnh point group while the presence of
nO'd (these vertical planes pass betwt!en the C2 axes) and the absence of O'h produce the D nd
he
point group. Pr~sence ofCn and nC2 pe'rpendicular to Cn but absence of both O'h and O'dgenerates
the Dn group.
lc
Distinction between Dnh and Dndgro.ups : Cn' nC2 .l Cn' O'h =:> Dnh ; C2 x (Jh = O'd Le. ud is also
present in Dnh group. In Dnd' all the symmetry elements of Dnh group except O'h are present.
ea
(d) Sn group : 8n group is characterised by the presence of only 8n axis (n = even) and no other
independent symmetry element is present.
th
• Ifn is odd, then Sn group becomes identical with the Cnh group. It is illustrated by taking C3h
and 8 3 groups as examples.
e/
C3h symmetry group having the C 3' 83 and O'h symmetry elements can generate the following
symm~try operations :
t.m
C3-axis: C3 ,c;,ci (== E); crh-plane:O'h
8 3-axis: S3(= Cx O'h)' s;(= C; x (J~ = C;), S; (= cicr~ = Ex cr

3 h = O'h)'
=ci+ =ExC3 =c3 ),Si (=cicr~ =ci+ cr:+ =C;O'h),S:(==E)
1 2 1
Si(=ci x 0':
Thus from the S3 axis, except 83 and si,

all other operations are indicated in the symmetry
operations arising from C3 and O'h. Thus from C 3h group, the symmetry elements C3' .O'h and 8 3-
axis give the following operations :
2 3 5
C3 ' C3 ,C3 (== E), cr h , S3' S3
83 axis (for the proposed S3 group) gives the following operations:
/ 2 23 4 56
S3' S3 ' == C3 ' S3 ' == 0' h' S3 == C3' S3 ,S3 == E
These are the same for the C 3h group, Le. C3h == SJ.
54
•: R
I
I
i'l
\
\
\
\
>~Ry (.for C)
=
(R Me)
R
ry
Fig. 10.14.8.3. 54 symmetry element (only symmetry element) in 1.3.5.7-tetramethylcyclooctatetraene.
Note: In unsubstituted cyclooctatetraene, besides the 54 element. there are 3C2 axes mutually
ra
perpendicular; one C2 is colinear with 54. There is no 0h but there are 20 ct Thus its point group is
D2d•
ib
• If n is even, then Sn gives a distinct group and the symmetry operations are:
yl
8~,8;, ....,8:-I,S: (=E).
m
Thus 8 2 (= C; group), 84 ,86 groups are possible. However, such point groups are rare. 1, 3, 5, 7-
tetramethylcyclooctatetraene belongs to 8 4 group Le. the molecule possesses only 8 4 axis.
he
10.14.9 Special Point Groups with Multiple--High-order Axes (more than one en' n > 2)
lc
The regular polyhedra tetrahedron, cube, octahedron, dodecahederon, icosahedron are the members in
this group. Here we shall discuss the symmetry elements in tetrahedral (Td ), octahedral (Oh) and
ea
icosahedral (Ih) point groups.
(a) Td point group

th
(i) 3S4 (colinear with the C2 axes) along the three Cartesian axes: Each 8 4 generates the following
e/
operations :
S~,S; (=C;CJ =C; =C2 ),8:,S: (=E)

2
t.m
Thus excluding E, we get 3 x 3 = 9 symmetry operations from 384• These are: 6(84) + 3(C2).
(ii) 4CJ (each passing through one vertex and centre of the opposite face) : Each C3 generates
the following operations:
I 2 3
C3 ' C3 and C3 (= E)
Thus excluding E, 4C3 generate 4 x 2 = 8 symmetry operations.
(iii) 3C2 (colinear with S4) : The symmetry operations arising from these C2 axes have been already
included in the symmetry operations obtained from the S4 axes.
(iv) 6CJd : Each of these planes produce one operation (excluding E). Thus 60 produce 6 symmetry
operations. Thus total symmetry operations are:
19 (from 384) + 8 (from 4C3 ) + 6 (from 6CJd ) + I (i.e. E) = 241

C2
......-+-...... C41 5 41 C2
ry
C'2
ra
ib
C3
Tetrahedron (AX4 ) Octahedron (~)
yl
Fig. 10.14.9.1. Symmetry elements in (a) tetrahedral AX4 and (b) octahedral AXe geometries.
m
By considering the C2-symmetry axes, these 24 symmetry
operations are :
he
lc
(b) 0h point group (cf. Figs. 10.14.3.10,10.14.4.5 and 10.14.9.1)

ea
The symmetry elements are:

(i) 3S4 (colinear with C4 and Cz) passing through the opposite
th
vertices.
(ii) 3Cz and 3C4 (colinear with 84 ).
e/
(iii) 6C; passing through the centres of opposite edges. Fig. 10.14.9.2. Structure
t.m
(iv) 4S, (colinear with C3 ), passing through the centres of opposite of icosahedron (20
triangular faces. equilateral triangular
faces, 12 vertices shown
(v) 4C3 (colinear with SJ. bye; 30 edges).
(vi) i.
(vii) 3crh , each containing 4 vertices in a basal plane.
(viii) 6<Td' each containing two trans-axial positions and bisecting a pair of opposite edges.
It can be shown that these symmetry elements can produce total 48 symmetry operations.
(c) 'h point group

The typical boron hydride Bt2Ht22- ion adopts the icosahedral geometry. The symmetry elements present
in it are:
10.14.10 Steps to Select a Point Group (excluding special point groups with multiple high order
axes)
Step-I: For the linear molecules
Linear molecules (Coo)
I .?
+I •
~Yes
ry
Dooh
ra
Step-I: For the nonlinear molecules without Cn(n > 1)
Nonlinear molecules with no Cn(n > 1)
ib
~ I?
t (J •
yl
!Yes m lNO
c;(=Clh )
he
lc
Subsequent steps: For the molecules with Cn(n> 1)

ea
Nonlinear molecules with C (n> I)

......--------------.
* S2n group: In such cases, Cn
(Cn•Cm •Cnh • Dn• Dnh • Dnd • eve~ order Sn) exists as a simple consequence of
th
S2'! but no other symmetry element

!
'?
C2 ..L Cn • eXIsts.
"'------------_....
e/
-------
I Yes !NO
t.m
Dn , D nh , D nd Cn' Cm" cnh ' S2n

lah? I S2n?
INO l Yes !NO
*S2n" Cn' C nv ' Cnh
_---!-O'-h-?---
!NO l Yes
Cn' C nv Cnh
___ina.
~Yes
Cnv
Note: For the special point groups like tetrahedron (Td), octahedron (Oh)' icosahedron (Ih), there
are multiple noncoincidenrCn axes with n > 2).
H e"" /F C'"
' : 'C--+-c--
i p-B-sr
/
.....
\ .... H cI~CI
F CI
(c;)
ry
(R,S -1,2 - dichloro-
1,2 - difluoroethane)
(Anticonformation)
ra
Fig. 10.14.10.1. Some representative examples having no Cn (n > 1).
ib
Illustrative examples
(a) H"O: There are only lC2, and two vertical planes (O'v and 0':). (Note: No O'h and Sn). Thus it
yl
belongs to C"v point g-roup.
(b) BFCI Br and NOCI : There is no en (n > 1). There is only crh (molecular plane). Thus they
m
belong to Cs point group.
c/"
he
c/
B-F O=N/
Br/
lc
(c) CH"BrCI, POCIBr" : These tetrahedral molecules may be represented by AX2 YZ. There is no Cn
(n > 1) but there is a cr containing A-Y and A-Z bonds. Thus, these belong to Cs point group.
ea
r
th
/A\'X
Z
e/
(d) CH"CI,,: There is no Sn. There is a C2 (no other C2) and two vertical planes (cr v and cr:). Thus it
t.m
belongs to C1v point group.
(8) (b)
Fig.jO.14.10.2. (a) Vertical mirror planes in CH2.CI2. la v contains the CC1a.. segment and bisects the
H-C-H angle; other a v contains the CH2 segment and bisects the CI-C-CI bond angle. (b) 2a v
in CH2 CI2 ; (b) C2-axis in CH2CI2 .
(e) NHJ : There is no Sn axis. There is a C3 axis but there are no C2 axes at all. There is no CJh but
there are three vertical planes (Le. 3CJv). Thus it belongs to CJv point group
(C3' No C2' 3CJv ~ C3v)
(f) BFJ : In this planar trigonal species, there is no even order Sn axis, though it bears a S3 axis
colinear with the C3 axis. There is a C3 axis with 3C2 axes perpendicular to C3 • There is a CJh (Le.
~olecular plane). It may be noted that it contains 3crv but the presence of CJh makes it a D Jh point
group molecule.
ry
(C3 ,3C2 ..LC3 ,CJh ..LC3 =>D3h )
(g) PFs : There is no even-order Sn axis but it possesses a S3 axis colinear with the C3 axis. The
ra
presence of a C 3 axis (along the Xax-P-Xax ) and 3C2 axes perpendicular to C 3 and lCJ h
perpendicular to C3 make it a DJh point group molecule.
ib
(h) Benzene: There is a C6 axis perpendicular to the molecular plane and the C6 axis is not the
consequence ofeven order Sn (Le. S12 does not exist here). It possesses a S, axis .but there are
yl
other symmetry elements independent ofthe S, axis. Thus it does not belong to S6 group. There
are 6C2 perpendicular to C6 and there is a CJh• Thus it belongs to D 6h group
m
(C6,6C2 ..L C6, CJh ..L C6 ~ D6h ).
-..•. H
he
/ ..'
H
H')_l./H H')_l./H H
H~H H~H
lc
C2 ······H H·····. C2 H
ea
Hi H Hi H H H H H
...,..
c6• 8 6 c
8 6, 3• C2 c;" c2 C C2
th
Fig. 10.14.10.3. Symmetry elements in benzene C6 H6 . (a) C6 axis (1. molecular plane); (b) 56' C3 and
e/
C2 colinear with C6 . (c) 3C2 axes (passing through the opposite C-centres) in the molecular plane (otJ.
(d) 3C2 axes (bisecting the opposite edges) in the molecular plane (oh).
t.m
~S' 8 10 ~S
I
............
~ I
@
I
- - - - - -Fe- - - - - - - • C
I 2
- - - - - Cr-
. - - - ... C2
~
I
(a) DSh (b) DSd

r$J I
(c) DSd
Fig. 10.14.10.4. (a) Eclipsed ferrocene (DSh point group). (b) Staggered ferrocene (point group DsJ;
(c) Staggered dibenzenechromium.
Uneer Molecules
o=c=o H-O
(Dooh ) (DOOY)
Angular Molecules
S 0
o~ ~
0
H/ "CI
(C 2y) (C 2v)
ry
Trigonal pyramidal
ra
/CH 3 H
/
X X X
0 0
"A-X )A-V (AXVZ)
ib
"A-X I I
X/ /
V Z HC B H B
(AX2 Y) 3 '0/ '0 '0/ '0
N0"3 '
yl
(e.g. BX 3, (e.g. BFCI Br, I 1
CO~- CHi ,etc.) (e.g. C0 2S 2-) BFCIH, etc.) CH 3 H
B(OMe)3
(H 3B0 3)
(D 3h ) (C 2v)
m
(C s ) (C 3h ) . (C 3h )
he
Trigonal pyramidal
C N P N N S f~ is
lc
Xe
/1" /1" /1" /1" /., /I~ /1" /'
/1" F I H CI CI a R R H "-'R
H H H H H H F F F
°0° H f H CI
CI
0
ea
(C.) (C I ) (C 1)
(C 3v ) (C 3v ) (C 3v ) (C 3v) (C s =- C1h ) (C ) 1
th
Tetrahedral
x y y z P
e/
A
1 ~ (AX 3Y) I
A
1 1
A(XYZP)
A A
X/1" x/1'
XX /1" /1' /1'
t.m
X X X X V XYX Z y X
(e.g. POBr3' SF 3 N.
(e.g. NH4" ' BF4" ' PCI; , (e.g. CH 2 CI 2 , S02CI2' (e.g. POCIBr2' (e.g. POCIBrF, CHFCIBr)
CHCI 3 • etc.)
soi- , SnCI4 , SiF4 , etc.) (C 3v )
SnMe2F2' etc.) _CH 2BrCI, etc.) (C 1)
(Td ) (C 2v ) (C I )
Square planar
X X y X
' A / (AX4 ) )A( (Trans-AX2Y 2) y X
X/ X " X y )A( (Cis-AX 2 2) Y
Y X
(e.g. PtCI:-, Pt(NH 3 >:+ , (e.g. Trans-Pt(NH3)2CI2)'
(e.g. Cis-Pt(NH3>2CI2)
AuCI;, XeF 4 , lei; I etc.)
(C 2v)
(D 4h )
Fig. 10.14.10.5. Point group of some common molecules.....(Contd.)

.....(Contd.) Fig. 10.14.10.5. Point group of some common molecules

Trigonal blpyramldal
x Y X
X,I X 1 Y 1
/A-X (AXs ) )A-X (AX4 Y) )A-X (AX4 Y)
X I X I X 1
X X X
(e.g. PF s, Fe(CO)s. (e.g. PCI 4 F. M(CO)4L etc.) (e.g. PF4C1)
s
Cuel etc.)
(C 3v ) (C 2v )
ry
(D 3h )
y
X I
ra
X T-shaped
'A-X (AX 3Y2)
x/I X 1
y )AG F
~d'-F
ib
X 1
(CIF 3)
(e.g. PCI 3F2 • X
M(CO)3L2' etc.) (e.g. SF4 )
0/1
yl
F
(D 3h ) m (C 2v ) (C 2v)
Square pyramidal Octahedral
X I X
X z,1/
Y X X
,1/
Y Z
he
)A( (AXs) A, A,
X X z/ 1 X z/ 1 X
Y Y
lc
(e.g. BrF s, Ni(CN)g- , etc.)

(C 2v)
(C 4v )
ea
X Octahedral
X I X
)A( (AXs)
th
X I X
X Y X
X· 1 X Y 1 X
,
e/
(e.g. SF6 • SiF~- , PtCI~- , (AXsY) /'A/ (Trans-AX 4 Y2) 'A/ (Cis-AX4Y2)
X I X Y/1' X
Cr(NH3)~+ • FeFt. etc.)
t.m
Y X
(Oh) (D4h ) (C 2v )
X I X·
x, Y I Y
X,
( ' A / A(X - X)3 (X - X stands ( 'A/ A(X - Y)3
X/ I 'X for a bidentate ligand) X/ I 'X
XJ YJ
(e.g. M(en)3' M(ox)3' etc.) (e.g. M(gIY)3
. (03) (C 3)
rX Y
X'l/ Y Cis-A(X - Xh Y2 X
(X'l/ ) Trans-A(X - X)2y 2
X/1' Y X/1' X
,"-X Y
(e.g. Co(en)2C1i) (e.g. Trans-Co(en)2CI2)
(C 2) (D 2h )
(i) Ferrocene (eclipsed) : There is no even order Sn

(CS ,5C2 ..LCs ~DSh)'
-l-CS'O'h
Ferrocene (staggered) : It contains S10 colinear with C s' But in addition to Cs' it possesses
other symmetry elements independent of Sloe Thus it is not belonging to 8 10 group. It actuaily
belongs to D set It may be noted that Dnh group also possesses vertical planes of symmet~y.
(CS ,5C2 1. Cs , 50 d , (No O'h) ~ DSd )
Ruthenocene RU(CP)2 can a;so be treated in this ·way. Here it is important to Inention that
ry
Cr(C6H 6 )z Le. staggered dibenzenechromium is with D6d symmetry.
U) Trans-N2F2 : There is a C~2 axis (no other C 2 axis) and a a h (i.e. molecular plane). It belongs to
ra
C2 group. The C2 axis h~Sr~Ct5 the N-N bond and it is perpendicular to the molecular plane.
(C" 2, Icrh => C"'2h)
ib
(Note: It.contains a ~C;2 axis~ but there are other symmetry elements independent of 8 2, Th.us it
yl
does not belong to &.)2 group).
(k) . ~. quare planar species (e.g. XeF4 , PtCI;-, ete.) : They belong to D 4h group.
m
(C4 , nC2 1. C 4 , O'h ..L C4 ~ D4h )
(Note: There are also ~O'd)'
he
(I) Trans (CoX4 YZ] : It belongs to D4h group.
(m) Cis-IPtXzYz] : (C 2 , 20'v => C2v )'
lc
One 0' is the molecular plane and the other 0' bisects the X - Pt - _X' bond angle and it is
ea
-perpendicular to the molecular plane.

th
e/
(n) Hydrogen peroxide (H:.C"2) : The equilibrium configuration of H 20 2 is gauche (which is

t.m
nonplanar). It has got the open-book structure.

There is only one C2 axis (cf. Fig. 10.14.8.1). There is no plane of symmetry. 1here is no other
symmetr.y element. Thus it belongs to C2 group.
(0) Point group of some common structural geometries (ignoring the H's of CH3 and NH3 as
groups or ligands). These are illustrated in Fig. 10.14.10.5.
(p) Cyclohexane (C6H 12 ) : Chairform (Fig. 10.14.10.6) ofC6H 12 possesses the following symmetry
elements.
(i) 1Cl (principal axis) passing through the centre of the chair conformation and parallel to the
axial bonds.
(ii) 3Cz ..L Cl , each bisecting a pair of opposite edges (Le. C 1-C2 and C4-CS; C2-C3 and Cs-
C6 ; C3-C4 and C6-C)).
(iii) IS6 (colinear with the C 3 axis).
(iv) 30'v (containing the C3 axis). These are O'aplanes.
__ L ad
r---
I
I
I
I
I
I
Fig. 10.14.10.6. Symmetry elements of cyclohexane (chair form).
ry
(v) i (centre of inversion).
ra
IC3 ,3C2 1.. C3 , 30 v => DJd point group for chair form of cyclohexane
ib
Boat conformation (Fig. 10.14.10.7) of C6H 12 possesses the following symmetry elements.
(i) tC2 (principal axis) passing through the centre of the boat and perpendicular to the plane of
yl
C2-C3 and C S-C6 bonds.
(ii) 2uv (containing the C 2 axis) : One cr v bisects the C2-C3 and CS-C6 bonds; other O"v bisects
m
~
the ifC bond angles at C 1 and C4 .
he
IC2 , 2cr v => C 2" point group for the boat form of cyclohexane.
lc
(Jv
r--_I_-_~
ea
I I
I I
I
th
e/
t.m
Fig. 10.14.10.7. Symmetry elements of cyclohexane (boat form).
Twist boat conformation (Fig. 10.14.10.8) of c.yclohexane possesses the following symmetry
elements.
(i) 3C2 axes: IC2 passes through the C 1 and C4 centres; there are two other C2 axes which are
mutually perpendicular and perpendicular to the first one. It has no other symmetry element.
Thus it belongs to D 2-point group.
3
Fig. 10.14.10.8. Symmetry elements of cyclohexane (twist boat form).
Table 10.14.10.1. Symmetry elements of some point groups (~ == ~ .L en)

Point group Symmetry elements Examples ofmolecules
E CFHCIBr, P(O)FCIBr (tetrahedral)
PBrCIF, NHCIBr (pyramidal)
E,a BFCIBr, HOCI, R2NH, NH2F, SOCI2, POCIBr2, CH2BrCi
B", /H
E, i CI-C-C-CI
/ "B
ry
H r
(Anti or staggered conformation)
ra
E, C2 H20 2 (gauche), cis-[Co(en)2C/2]+
E,C3 P(C6 Hs), A(X-Y)3' e.g. [Co(gIY)3l
ib
E, C2 , 20'y H2CO, H20, S02' CH2C/2, S02C/2' cis-N2F2, CO~2
(thiocarbonate), cis:Pt(NH3)2C/2' cis-[Co(NH3)4C/2l+,
yl
trans-Co[(NH3)3C/3l, CIF3 (T-shaped), :SF4, C6HsCI
C3v E, C3, 3av NH3, PF3 , CHC/3, POCI3 , CH3-, cis-[Co(NH3 )3C/3]'
mPCl4 F
C4v E, C4, 40'v IFs,XeOF4
he
C"-. /H
C2h E, C2, ah' S2' i trans-N2F2, /C--C" (trans-form)
lc
H CI
C3h E, C3, a h, S3' i H3B03 (i.e. B(0H)3
ea
D3 E, C3, 3C; 1. C3 C2H6 (gauche), Co(ox)~-, Co(en)~+
H,,~/H
th
.
D2h E, 3C2, 2av' O'h' i N20 4, C2H4, trans-MX2Y2' B2H6 I.e. /B B"
i.e. trans-MA2B~2 H y H
e/
D3h E, C3, 3C2 1. C3, 3av' ah' S3 BF3 , PFs' CH;, C2 H 6 (eclipsed), cyclopropane (C3H 6 ),
B3N 3H6
t.m
D4h E, C4' 4C2 1. C4' 40'", O'h' S4' i C4H s (cyclobutane),XeF4, PtCI4, trans-MX~2' Re2Cli-
DSh E, C S' 5C~, 5uv' ah' Ss Fe(lls - Cp)2 (eclipsed), IF7
D6h E, C6' 6C2 1. C6, 60'", ah' S6' i C6H 6, Cr(1l6 - C6H6)2 (eclipsed)
/C","
D2cJ E, 3C2, S4' 2ud H2C=C= CH2 (allene), B2C14 i.e. CI--B'C?-CI
D3cJ E, C3' 3C~ 1. C3, S6' 3aei' i C2H6 (staggered), cyclohexane (chair form), R3 Wa WR 3
4
D4cJ E, C4, 4C2 1. C4, Ss' 40'd S8' S2 F IO,ZrF8 -
Ca:>v E, Ca:>' ooav CO,Hel,HCN
Da:>h E, Ca:>' ooC;, O'h' ooov' i H 2, N2, CO2, BeF2
TcJ E, 4C3, 3C2, 3S4, 6ad CH4 , 80;-, SiF4, NH;
E, 4C3, 6C2, 3C4, 4S6, 3S4, i, 3ah' 6ad SF6, UF6, PtCI;-, SiF6 -, WF6, Co(NH3)~+
2
°h
10.14.11 Symmetry Elements and Optical Activity

A: chiral molecule (Le. optically active) possesses a non-superirilposable mirror image. Chiral
molecules must be asymmetric (Le. no symmetry element except C 1) or at least dissymmetric (Le. no
other symmetry element except Cn). Thus the dissymmetric molecules can possess the en axis only.
For optical activity (Le. chirality), the conditions ofdissymmetry is sufficient. A molecule possessing
i and/or cr must have two equivalent halves and consequently, it will have a superimposable mirror
image. Such molecules are achiral (Le. optically inactive). The condition of chirality or achirality can
be best understood in terms of Sn (improper axis of rotation). The molecules without any Sn (i.e.
ry
improper axis of rotation) may be considered as dissymmetric molecules and these are optically
active.
ra
Note: • Sn (n == odd) indicates the presence of crhand Cn by their own right. Presence ofcrh introduces
S;
the achiral ity (cf. = a h).
ib
• Sn (n == even, n/2 == odd, e.g. n == 6) indicates the presence of i by its own right. Presence of
..
llntro duces t he ac h·Ira I·Ity (cf. Snn/2 =C n/2 ann/2 =C a =8 = i, n/2 = odd).
n 2 h 2
yl
• For Sn (n == even, and n/2 == even, e.g. n == 4), crh and i do not exist by their own right. But
such molecules possess the superimposable mirror images. This can only be realised by
performing the symmetry operation.
m
• Molecules
he
I Sn axis?
lNO
lc
Achiral
!
Asymmetric, Dissymmetric}
ea
(Optically inactive) (CI ) (Cn , Dn ) Chiral (Optically active)
NoCn
th
Asymmetric (CI )
Presence of SI == cr, 8 2 == i, S3 (which can generate cr from Si), 8 5 (which can generate, a from S~),
e/
8 6 (which can generate i from S~), etc. will make the molecules optically inactive. S4 axis cannot
t.m
generate i and cr, but still, such molecules are superimposable on their respective mirror images. Thus,
we can conclude that, if there is an Sn axis, the molecule will possess a superimposable mirror image
and it will be optically inactive.
We can conclude that the molecules belonging to the following point groups will be chiral and
optically active and these groups lack in the symmetry elements i, (1 and Sn.
C 1 (asymmetric), Cn (dissymmetric), Dn(dissymmetric). All these point groups lack in the symmetry
elements i, a and Sn. These are optically active. Co(ox)i-, Co(en)i+, etc. belong to D3 (Le. both C3 and
C2 elements) group.
10.14.12 Symmetry Elements and Dipole Moment

• Presence of i (centre of inversion) leads to cancellation or. charge effect on two opposite sides of
the molecule, Le. presence of i leads to dipole moment zero.
• Presence of two or more Cn (n > 1) as in Dngroups (Le. Dn, Dntl' Dnh ), Ttl' 0h' Ih etc. will make the
dipole moment zero. It is due to the fact that the resultant dipole moment vector cannot lie
along more than one axis at the same time. .
• Presence of a CJh (.1 tQ C,,) as in Cnh , D nh point groups will make the dipole moment zero. Tbe
dipole moment vector cannot lie simultaneously along the Cn axis and in tbe CJ" plane. Tbe
dipole moment vector acts along tbe Cn-axis and at tbe same time it cannot lie in tbe plane
(a,,) perpendicular to Cn• Tbus tbe presence of CJII indicates dipole moment zero~
• Here it may be mentioned that the presence of one or more vertical planes does not lead to dipole
moment zero. For Cnv group, the dipole moment vector lies in the CJv planes along the Cn axis.
ry
Thus we can conclude that dipole moment can existfor the molecules belonging to thefollowing
point groups :
ra
C I , C3, Cn"Cnv' C«)v (all lacking in i, Sn, CJw multiple Cn symmetry elements).
ib
Note ': In this symmetry condition, we have ignored the effect of lone pair moment. It may
complicate the prediction based on symmetry consid~ration (cf. NF3 vs. NH3).
10.14.13 Symmetry Number and Polnt Groups
yl
m
The term symmetry number is defined by the number of equivalent configurations a molecule can
attain through the simple symmetry operation rotation around the proper axis or axes (Cn ).
he
• Benzene has the following Cn axes: IC6 ,6C2 .1 C6 •
The C6 axis produces 6 symmetry operations [C~, ci, C~, C:, C: and C: (== E)l i.e. 6 equivalent
lc
configurations including the original one. Each C2 axis produces two equivalent configurations denoted
by C~ and C; (== E) symmetry operations.The original configuration due to C; is already included in
ea
the symmetry operations of C6 • Thus, each C2 generates one equivalent configuration for counting the
symmetry number. Thus C6 contributes 6 and 6C2 contribute 6 x 1 to the symmetry number i.e. symmetry
th
number is 12.
• Let us take the planar species AX3 (e.g. BF3). There are 1C3 and 3C2 axes (.1 C3). From the C3-
axis, the equivalent configurations are obtained from the symmetry operations: C~, ci, ci
e/
(== E). From

each C2' we get two equivalent configurations by C~ and C; (= E), but C; == E has been already
t.m
considered in C3 • Thus 1C3 gives 3 to the symmetry number and 3C2 give 3 x 1 = 3 to the symmetry
number. Thus the total symmetry number is 6.
• The symmetry number for different point groups is given belo~ :
Point group Symmetry No.
C l ' Cs' C; and C«)v 1
Cn' Cnh and Cnv (n ;I; (0) n
Dn , end and Dnh 2n
D«)h 2
Td 12
0h 24
~ 48
EXERCISE-X
(A) General Questions

(1) Discuss the different types of bond energy for the diatomic molecules.
(2) Discuss the ofconcept ofaverage bond energy and stepwise bond energy in a polyatomic system.
(3) Discuss the different contributing factors in determining the bond energy and bond length.
(4) Interpret the inert pair effect in terms of bonding properties ofthe orbitals ofthe heavier congeners,
ry
secondary periodicity (Le. alternation effect) and relativistic effect.
(5) Discuss the different contributing factors in determining the molecular polarity.
ra
(6) Discuss the important factors to determine the degree of polarisation in an ion pair.
(7) Discuss the concept of polarisation in explaining the different phenomena in chemistry.
ib
(8) Discuss the role of pi -bonding in controlling the comparative chemistry of : (i) carbon and
silicon, (ii) nitrogen and phosphorus.
yl
(9) Discuss the basic principles of VSEPR theory.
(10) Discuss the different mechanistic pathways of nucleophilic substitution reactions in covalently
m
bonded compounds.
( 11) What are the characteristic features of closo-borane, nido-borane, arachno-borane, and hypho-
he
borane? How do you correlate them in terms of structure?
(12) How do you apply the Wade's rule and .Gemmis' rule to classify the boranes?
lc
(13) Discuss the styx number to determine the topology of boranes.

( ~ 4) What do you mean by carboranes? How can you classify them in terms of skeletal electron pair?
ea
(15) Discuss the general methods of synthesis of boranes.

(16) Discuss the reactions of boranes with the different types of Lewis bases.
th
(17) Discuss the acidic property of boranes.

(18) Discuss the electrophilic substitution reactions of boranes.
e/
(19) Discuss the mechanism of hydroboration reaction and application of the reactions.
(20) Discuss the synthesis, structure and reactivity of C 2B1oH12 and B 1oH14.
t.m
(21) Discuss the chemistry of nido - C2B9Ht21- .
(B) Justify or Contradict the Following Statements

(1) The bond dissociation energy of H 2 used to verify the bonding theory is different from the
I experimentally determined value.
(2) The bond dissociation energy of the diatomic molecules does not vary significantly with
temperature.
(3) The average bond dissociation energy in the polyatomic species is different from the stepwise
bond dissociation energy. .
(4) The relaxation energy plays an important role in determining the bond energy.
(5) In CO2, Doc = 0 < D co while in HgCI2, D CIHg - CI » D Rg - Ct
(6) In PCls (TBP), it is not possible to determine Dp _ cl and D p _ cl experimentally.
eq ax
(7) D'A -X(AXn ) < D'A -X(AXn _ 2)·
(8) The intrinsic bond energy for P - H is less than that of N - H but for P - F and N - F, the reverse
is true.
(9) Very often, the promotion energy leading to valence spin state for the heavier congeners is lower,
but they form generally weaker bonds compared to the lighter members.
(10) The possibility of x-back bonding largely influences the bond energy and bond length.
(II) van der Waals radii are always larger than the covalent radii.
(12) ,Both the van der Waals radius and covalent radius for a particular atom depend on the chemical
environment.
ry
(13) The bond length ofa particular bond depends on the state of hybridisation of the involved atoms.
( 14) The nature of crystal may govern the bond length of a particular bond.
ra
(15) The calculated value of C - Cl bond length (in CCI4) nicely agrees with the experimental one,
but the calculated value of C - I (in Cf4) is shorter than the observed one.
ib
(16) The bond length ofa particular bond depends on the electronegativity difference of the involved
yl
atoms.
(17) The lone pair responsible for the inert pair effect is not stereochemically inert.
m
(18) The inert pair effect gets originated due to the diffuseness of the bonding orbitals of the heavier
congeners in a certain group.
he
(19) Calculation of % ionic character of a bond from the observed dipole moment is dubious in many
cases.
(20) Para-dihydroxy benzene is polar while para-dimethyl benzene is nonpolar.
lc
(21) The observed polarity in HCI is not only due to the electronegativity difference.
ea
(22) The dipole moment of NH3 is larger ~han that of NF3 •

(23) The dipole moment ofH 20 cannot be calculated by using the knowledge ofbond (0 - H) moments
and bond angle only.
th
(24) The dipole moment of CO is exceedingly small.

e/
(25) The transition metal ions are more polarising compared to the alkali and alkaline earth metal ions
of comparable size for a particular oxidation state.
t.m
(26) The solubility of the silver halides in water runs as : AgF> Agel> AgBr > Agl.
(27) Many of the transition metal salts are soluble in organic solvents.
(28) LiCI is soluble in organic solvents while NaCI is insoluble in such solvents.
(29) It is difficult to get anhydrous lithium salts.
(30) SnCl4 hydrolyses more readily than SnCI2•
(31) HeC03 is thermil1ly more unstable compared to MgCO).
(32) PbCl2 is white while PbI2 is coloured.
(33) PbI4 , FeI3 do not exist while PbCI4 , FeCI) exist.
(34) CO2 is gaseous while Si02 is solid.
(35) Compared to Me 3N, (SiH)3N has got almost no basicity.
(36) CH3NCS is angular while SiH3NCS is linear.
(37) The molecular formulas of nitrogen and phosphorus are N2 and P4 respectively~ similarly oxygen
exists as 02 while sulphur exists as Ss.
(38) R3N is more stable than R3P with respect to atmospheric oxidation.
(39) The dipole moment of R3NO is much greater compared to that of"R3PO and R3NO forms the
hydrate more easily.
(40) Phosphonium ylids are more stable than ammonium ylids.
(41) The Lewis acid strength of the boron halides runs as : BF3 < BCl3 < BBr3•
(42) All the B - 0 bond lengths are not identical in polyborates.
(43) The tendency ofpolymerisation of the oxyanions lies in the sequence: SiO:- > PO;- > SO;- >
CIOi·
ry
(44) The molecular formulas of the following oxyacid are: (a) H2S04, H2Se04, H6 Te06 (Or VI Le.
16); (b) HCI04, HBr04, H sI06 (Or VII Le. 17).
ra
(45) HUckel's rule of aromaticity is not strictly followed for P1t - d1t interactions.
(46) The molecular structures of S4N4H4 and S4N4F4 are different.
ib
(47) In NSF3, F - S- F is - 90°.
°
yl
(48) The stretching frequency of P - linkage is maximum in OPF3 compared to all other analogous
halogen compounds. m
(49) NF3 cannot act as a ligand but PF 3 acts as a good .ligand specially for the low oxidation states of
the metals.
he
(50) The x-acid ligands are extremely important in stabilizing the low oxidation states of metals.
(51) The stability in many soft-soft interactions can be explained in terms of1t-bonding.
lc
(52) In the trigonal bipyramid structure, the lone pairs and pi-bonding moieties preferably occupy the
equatorial positions. .
ea
(53) The structural geometries of NO;, N02 and N0i. are different.
(54) The bond angles are:
th
'(i) H-P-H (PH3 ) < F-P-F (PFj), but F-N-F (NFj) < H-N-H (NH3 );
(ii) H ~O-F < H -O-H < CI-O-CI;
e/
(iii) Br-P-Br (OPBr3 ) > CI-P-CI (OPCI3 ) > F -P-F (OPFj);

(iv) 1200 < H -O-N > 109° in BN02
t.m
(v) H-C.....H (Cli4) > H-N-H (NH3 ) > H-O-H (H 2 0)

(vi) H-C-H runs in the sequence, CH; > CH4 > CH;
(55) XeF6 is a fluxional molecule.
(56) In PFs all the fluorine atoms appear indentical in the 19FNMR studies.
(57) The activation energies for Berry pseudorotation of the compounds are: R3PF3 > R2PF3 > RPF4.
(58) Five and eight coordinate systems are very often fluxional in nature.
(59) The ease of hydrolysis is in the sequence: SiCI4 > CCI4; NCl3 > NF3 ; SF4 > SF6 ; TeF6 > SeF6 >
SF6 ; SiH4 > CH4·
(60) The hydrolytic products of NCI3, NF3 and PCl3 are of different types.
(61) Optically active silane derivatives racemise in the presence of a trace amount of alkali, but the
process is not so facilitated for the analogous carbon compounds.
(62) In the presence of moderately concentrated alkali NHCI2, NH2CI and NH~02 behave differently.
(63) Diamond is hard while graphite is soft and slippery.

(64) Hgi+ is a stable species while cdi+ is almost nonexistent.
(65) The degree of covalency in the following compounds runs as : HgX2 > CdX2 > znX2.
(66) ZnS is white, CdS is yellow while HgS is red.
(67) Covalent crystals are more open compared to the ionic crystals.
(68) Both XeF6 and TeCI~- are having the same number of electron pairs in the valence shell but
their structures are different. The lone pair in XeF6 is streochemically active while it is
ry
stereochemically inactive in TeCI~-.
(69) The boiling point of D 20 is higher than that of H 20.
ra
(70) The bond energy of D2 is higher than that of H2•
(71) The dipole moment of N2H4 is fairly high and it can be explained from its gauche conformation.
ib
(72) In the open-book structure of H 20 2, the dihedral angle arises from the lone pair-lone pair repulsion.
(73) For the Gr. 13 and 14 elements, the inert pair effect is well documented while for the Gr. 15 and
yl
16 elements the alternation effect is well noted.
(74) Sometimes, ionisation energy bears a correlation with the inert pair effect.
m
(75) The sum of2nd and 3rd ionisation energies follows the following sequence for the Gr. 13 elements.
In < Al < TI < Ga
he
It apparently contradicts the concept of inert pair effect.
(76) The colour of CdS, HgS, Fe 20 3, CrO;-, MnOi etc. is due to th~ charge transfer band.
lc
(77) The structures of N(SiH3)3 and P(SiH3)3 are different.

(78) The structures of (R3C)20 and (R3Si)20 are different.
ea
(79) R3Si-DH is a stronger acid than R3C-DH.

°
(80) The ir-stretching frequency ofthe P = bond depends on the electronegativity ofthe substituents
th
onP.
(81) The basicity of ammonium ylids is higher than that of phosphonium ylids.
e/
(82) Sulphonium ylids are also quite stable.

(83) Sulphonium and phosphonium ylids react with R2C = 0 in different ways.
t.m
(84) Both Craig-Paddock and Dewar model can explain the delocalisation of x-electron cloud in
(NPCI2)3·
(85) The delocalisation of x-electron cloud in both S4N4 and S3J:1i- is experimentally verified.
(86) (NPCI2 )4 is nonplanar, but it gains delocalisation energy.
(87) In NSF3 , the sulfur-nitrogen bond is very small.
(88) In PtCI3(C2H4 )-, all the Pt-el bonds are not of the same length.
(89) The x-donor ligands can show cis-effect in the ligand substitution process ofoctahedral complexes.
(90) The structure of 12Cl6 can be realised from the structure of lei;.
(91) Simple VSEPR theory cannot explain the structures of XeF;- (pentagonal planar), XeF6 (slightly
distorted octahedron) and XeF82- (square antiprism).
(92) The stereochemical activity of a lone pair depends on the steric crowding.
(93) The p 1C-d7t back bonding in PX3 (X= F, CI, Br, l) can explain the variation of bond angles.
(94) In 0 = SF4 and H 2C = SF4 , there is a double in&the equatorial plane in each case, but their effect
on the bond angles is not the same.
(Hints : Consider the plane of x-bond). ;
(95) In C2H4 , the H-C-H angle cannot have the ideal bond angle 120°.
(96) In C2H4 and C2F4, the H-C-H and F-C-F bond angles are not of the same value.
(97) The bond angles change as follows :
- -
H-C-H (in C2H 4) > H-C-H (in CH20)
ry
(98) The simple VSEPR theory cannot explain the bond angle sequence in gaseous alkaline earth
dihalides (MX'2).
ra
(99) The fluxional·behaviour of XeF6 can be explained by considering the border line character of
the lone pair in terms ofstereochemical activity ofthe lone pair.
ib
(100) -CR3 is p~midal while C(CN)"J is planar.
yl
(101) Diffraction studies cannot follow the fluxionality of a molecule but NMR study can follow this.
(102) PCl2F3 and CIF3 are fluxional in 19F-NMR study.
m
(103) NiX2L2 (planar) ~ NiX2L2 (tetrahedral). This is not an example ofa fluxional molecule.
( I04) The following molecules are fluxional :
he
(11 5 - Cp)2(11 1 - Cp)2Ti, (11 5 - Cp)2 Fe 2(CO)4
(105) CCl4 does not hydrolyse but CHCl3 hydrolyses in' presence of a base.
lc
(106) SnCl4 hydrolyses but SnMe 4 does not hydrolyse.

(107)"CH2CI2 and CHCl3 behav~ differently in hydrolytic reactions.
ea
(108) (MeO)3 P = 0 and (Ph0)3P = 0 behave differently in hydrolyt~c reactions:

th
H2~ •
(MeO)3P = 0 ) (MeO)2P (= O)OH + Me OH
H2()* •
e/
(PhO)3 P = 0 > (PhO)2 PO OH + PhOH

• Hydrolysis of cyclic phosphates leads-to both cyclic and acyclic products.
t.m
(109) NH2-X can hydrolyse in different possible ways depending on the nature of X.
H 20
NH2 -X ) NH2 -OH +X-
HO
NH2 -X 2 ) NH) +HO-X
(110) The following reactions occur as indicated :

(i) SiH4 OH-) H 2 + Si(OH);-
OH- .
(ii) CH4 ) no reactIon
(iii) AI2 (CH3)6 H 20) CH4 + Al(OH)3
HO
(iv) R3Si - CI 2) R3Si - OB + HCI
HO
(v) ~AI- CI 2) AI(OH)3 + HCI + RH
2 H 0
(vi) py"BC/3 ) py + B(OH)3 + HCI
The reactivity order is :
CH 3
Me-@- . BCI) >@. BCI) > @. BCI)
HO
(vii) R3B 2 R2B(OH) + RH (catalysed by R'C02H)
)
"I" I") dehydration
ry
(VI HN02 ) N 20 3
(ix) NH3 + OC/- ~ NH 2 - NH2 (Raschig synthesis of N 2 H 4 )
ra
(x) HN02 + HSO; ~ NH 20H + H 2S04
OH-
ib
(xi) NH 2 - N02 ) N 20
(xii) R2NH + HN02 ~ ~NN = + H 20 °
yl
The rate law depends on the concentration of HN02"
disproportionation
°
(xiii) ROON
m
) ROH + 2"
OH-
PH3 + H 2P0i.
he
(xiv) P4 )
H 20
ROH
(xv) P4 Yio ) (RO)2 P(Y)(YH) + H 2Y, (Y = S, 0)
lc
(xvi) (RO)2P(S)SH as the starting material for the synthesis of organophosphorus insecticides
ea
like parathion, malathion, metathion.

(xvii) P(OR)3 RX) P(OR)2(O)R(Arbusov reaction).
th
(xviii) PR 1JilR3 n-BuLi) Racemised product.

°
e/
(xix) Me 2S= CH2 + =CR2 ~ Me~ + epoxide

(xx) Me 3P=CH2 + 0=CR2 ~ Me 3P=0 + R2C =
CH2 (Wittg reaction)
t.m
(Ill) Graphite shows an anisotropic electrical (Le. inorganic graphite) conductivity.

(112) Electrical conductivities of graphite and boron nitride (Le. inorganic graphite) are different.
(I 13) Lamellar or intercalation compounds obtained from graphite either through oxidation or reduction
are also electrically conducting. These are also coloured.
( 114) All graphitic compounds are not electrically conducting and coloured.
(115) Lamellar compounds obtained by the treatment of alkali metals with graphite may have different
compositions depending on the stage ofthe compounds.
(116) Fullerene is an allotropic fonn of carbon.
(117) In C60-fullerene, all carbon-carbon bonds are not of the same length.
(118) The cage-like structures of fullerenes are produced by fusing the pentagonal and hexagonal
faces.
(119) In the cage-like fullerenes, the aromaticity is not very much pronounced"
968 Fundamental Concepts of Inorganic Ch~mistry
(120) The cage-like fullerenes can form the endohedral complexes by encapsulation of guest species.
(121) The chemical reactivity ofcage-like fullerenes indicates that the C = C bonds are mainly localised.
(122) The boron hydrides can be classified into different series.
(123) In terms of skeleton electron pair (SEP), the boron hydrides can be classified as closo-, nido-,
and arachno-series.
(124) A particular styx number may represent more than one structure.
(125) B6H~- is more stable than the neutral B6H 6.
ry
(126) The bridging hydrogens in boranes are acidic.
• Higher boranes are more acidic.
ra
(127) Boranes can act as Lewis acids.
(128) Boranes can experience both symmetrical-and unsymmetrical cleavage depending on the reaction
ib
conditions.
(129) All the B-centres in Bl0HI20-' BI0C2H12 are not equally sensitive in electrohilic substitution
yl
reactions.
• Compared to Bl0HI20-' BI0C2H12 is less sensitive to electrophilic attack but more sensitive to
nucleophilic attack.
m
(130) The nature ofproduct in Friedel Crafts alkylation of BsH9 depends on the temperature ofreaction.
he
(131) Hydroboration leads to anti-Markownl1Eov addition at the double bond (C = C).
(132) The carborane C2B lC/f12 can produce three isomers of different stability.
lc
(133) The ortho ~ meta-isomerisation for C2B lC/f12 can be explained by DSD (diamond-square-
diamond) mechanism.
ea
(134) In C2B 1oH12' some boron centres are" very much sensitive towards the nucleophilic agents.
• In C2Bl0H12' electrophilic substitution occurs away from the C-centres but nucleophilic
th
substitution occurs close to the C-centres.

• Acidity order: 1,2-HC(B 1oHl0)C-C02H> 1,7-HC(B 1oHl0)C-C02H> C6HsC02H
e/
(135) In C2B 1oH12' there are two acidic protons that may be replaced by Li+.
(136) The nido- C2B9H121- anion is described as dicarbollide (Spanish Olla == pot).
t.m
(137) The chemistry of nido-C2 B9 H:1- is very much comparable to that of CsH;.
(138) B1oHI0C2Li2 (dilithocarborane) is a reactive nu~leophile.
(139) NF) and BF) are of similar formula but they belong to different point groups.
(140) BF4- and PtCl;- are of different point groups.
(141) BF), PFs, PC1)F2 are of the same point group.
(142) PF) and BF) are of different point groups.
(143) S2 and i operations lead to the same result.
(144) Existence of Sn (n = even) indicates the presence of Cn/2 but its own right.
(145) Existence of Sn (n = odd) indicates existence of Cn and a h by their own right.
(146) For Sn (n = even, n/2 = odd) indicates the presence of i.
(147) Optical activity can be determined by considering the existence of Sn axis.
(148) Existence of dipole moment of a molecule depends on the point group to which it belongs.
(149) Symmetry number of a molecule depends on the point group to which it belongs.
(150) Co(ox)~-, cis-Co(ox)2 Cl~-, gauche (Le. skew)-H2 0 2 are all optically active.
(151) AX4 (tetrahedral) is optically inactive.
(152) Ferrocene belongs to different point groups for its staggered and eclipsed conformations.
(153) Ethane belongs to different point groups for its staggered and eclipsed conformations.
(154) Cyclohexane shows different symmetry elements in its different conformations.
(155) SiF4 and SF4 are of different point groups.
ry
(156) Cis- and trans-isomers of PI (NH3)2CI2 are of different point groups.
(157) The pseudo-inert gas cations are more polarising and more polarisable to introduce more covalency
ra
specially in soft-soft interaction.
(158) CF3 and CH3 radicals are of different structure.
ib
(159) The structural features of -CH3, CH; and CHi are different.
(160) Wade's rule can be obtained from Gemm.is' rule.
yl
(161) Hydroboration gives the stereoselective products.
m
(162) ·The sign of group moment in benzene derivatives is determined by both inductive effect and
mesomeric effect (cf. + 1.53 for -NH2, - 3.9 for -N02).
he
(163) The dipole moment sequence is : CH3CI> CH2CI> CHCI3 > CCI4•
(164) For -OH and -NH2 groups, the group moment does not work along the diagonal of the benzene.
ring.
lc
(165) The dipole moments follow the sequence:

CH3CH2Cl > H2C=CH-CI; C6H sCI> C6H sF; pyrrole > furan.
ea
(166) Dipolar repulsion is of an important consideration to determine the structures of butane-2,3-

dione; 1,2-dichloroethane and 1,2-ethanediol; N 2H4 ; H 20 2.
th
(167) CHCl3 is a stronger Bronsted acid than CHF3.

(168) P(0H)3 ~ HP(=O)(OH)2' P(OR)3 ~ R-P(=O)(OR)3·
e/
(169) Stability sequence runs as :

8iO:- > pol- > sol- > CIO; ·
t.m
(170) F-C-F:C2F4 >OCF2 ;0=CX2 :F-C -F <Cl-C -Cl <H -C -H;

C = C(C2F4 ) < C = C(C2H 4 )
, (171) Tertiary phosphines and arsines can be resolved. The magnitue of inversion barrier depends on
the bulkiness of the groups.
(172) At low temperature, 19F-NMR of PCl2F 3 shows a downfield doublet of doublets and a upfield
doublet of triplets.
(173) At low temperature, 19F-NMR of ClF3 shows a downfield doublet and a upfield triplet.
(174) The ir-spectra can distinguish the CO groups of Fe(CO)s but 13C-NMR cannot distinguish them.
(175) The ease of hydrolysis : SiF4 > SiCl4 > SiBr4 ; Si-Cl> P-Cl; SiH4 > GeH4 ; BBr3 > BCl3 > BF3.
(176) NC1) hy;:i7.

o YSIS
)NHt +C12 ;NC13 (b
ase
: : I .) )N2 + ocr +cr
0 YSIS
OH-
NH2 -N02 )N20
(177) Stacking patterns of layers in graphite and inorganic graphite (BN) are different.
(178) Stacking patterns of layers in graphite and graphite intercalation compdunds are different.
(179) Graphite is a condu.ctor while inorganic graphite is an insulator.
(180) 1,12 isomer of C2B 1oHI 2 is the most stable one.
(181) In C2B 1oH12' all the B-centres are not equally sensitive to nucleophilic attack.
(182) The molecules bearing ah cannot have dipole moment.
(183) S2 indicates the presence of i.
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(184) Sn can represent a point group when n is even only. If n is odd, then it becomes Cnh group.
(185) The symmetry element Sn generates n-symmetry operations when n is even but· it generates 2n
ra
symmetry operations when n is odd.
(186) The reactivity of closo-hydroborate anion is different from that of closo-carborane.
ib
(187) In the production ofcarborane-siloxane polymer, m-carborane instead ofo-carborane is preferably
used.
yl
(188) Graphite shows the semimetallic conductivity while its inercalates show the metallic conductivity.
(189) Cis-CoIII(NH3)4CI2 aquates faster than the trans-isomer. For the cis-compound, the retention of
m
configuration occurs while for the trans-compound, isomerisation occurs.
(190) Some ligands like PX 3, H2 can use their vacant a·-MOs to accept electrons from the metal
he
centres.
( 191) NonCoulombic Pauli repulsive force (arising from the Pauli exclusion principle) operating among
lc
the electron pair domains is the basis of VSEPR model.

• Free ions or species having the octet configuration are spherical in shape. It can be explained by
ea
the Pauli principle.

th
Hints: The Pauli principle and electron pair Domains (cf. R.J. Gillespie and
E.A. Robinson, Angew. Chern. Int. Ed. Engl. 35, 495, 1996;
e/
R.J. Gillespie, Coord. Chem. Rev., 252,1315,2008)

According to the Pauli principle, two electrons of the same energy and same spin in a particular
t.m
system will repel mutually and they will remain apart as far as possible in space. This
nonCoulombic Pauli repulsive force does not operate among the electrons of opposite spin. In
the octet configuration of a free ion or species, there are four electrons with upward spin (say a)
and there are four electrons with downward spin (say 13): To minimize the Pauli repulsive
force, fOUf electrons with the same spin will have a tetrahedral arrangement. Thus there
will be two separate tetrahedral arrangementS for the a and 13 spins. There will be an electrostatic
repulsion between the two tetrahedral sets of electrons but no Pauli repulsive force operates
between these two tetrahedral sets. If there is no external force to restrain the free movement
of the two tetrahedral sets of electron, then the free species (e.g. Ne, (jl-, F- etc.) with octet
configuration will show an overall spherical distribution oCtotal electron density. It indicates
that the simple Coulombic electrostatic repulsive force (a ++ a, a ++ p, P ++ P) operating
between the tetrahedral sets of spins is not sufficiently strong to restrict the free rotation of
the two tetrahedral sets of spins.
When the free species (say A) experiences a bond formation with X, the positive core of X can
attract the valence shell electrons ofopposite spin ofthe central atom (A) Le. a~ pair of electrons
lies in the direction of A-X bond. For the molecular species AX4 (Le. 4 A-X bond), the a- and ~
spin tetrahedra will coincide in space giving rise to four a~-electron pairs projected tetrahedrally.
In these four a~-pairs, the a spins experience the Pauli repulsive force mutually and similarly
the ~-spins experience the Pauli force. There is no Pauli force in a a~ pair. Obviously, the
Coulombic electrostatic repulsion (independent of the nature of spin) also works among the
a~ pairs and it is minimum for the tetrahedral orientation of the a~ pairs. The region in which
ry
the a~ pair resides is called electron pair domain and among the electron pair domains, the
Pauli repulsive force (a ~ a and ~ ~ ~) operates.to keep the domains apart as far as possible.
ra
It determines the shape of the molecular species AX4 •
Lastly it may be pointed out that there is a debate regarding the predominance of the Pauli
ib
repulsive force (a. ~ a, ~ ~ ~) or electrostatic repulsive force (a ~ a, a ~ ~, ~ ~ ~, a ~ ~
a ~) in the execution of VSEPR mode.
yl
m x
he
lc
x
ea
(a) (b) (c)
Fig. X. Tetrahedral orientation of a- and p-spins to minimise the Pauli force; tetrahedral orientation
of 4 ap pairs.
th
(C) Write Notes on

e/
(i) Zero-point energy and spectroscopic bond dissociation energy, (ii) Intrinsic bond energy and
t.m
relaxation energy, (iii) Partial ionic character and covalent bond length, (iv) Inert pair effect, (v)
Electronegativity difference and partial ionic characater, (vi) Lone pair moment, (vii) Bond moment
and group moment, (viii) Intrinsic homopolar moment, (ix) Fajans' rule, (x) Synergistic effect in
pi -bonding, (xi) pi -Bonding and trans-effect, (xii) Helferich's rule in molecular topology, (xiii)
Berry pseudorotation, (xiv) Twisting mechanism, (xv) Fluxiona! molecules, (xvi) Walden
inversion, (xvii) Diamond and graphite structure, (xviii) Fullerenes (xix) Stereochemically active
and inactive lone pairs, (xx) Arbusov and Wittig reactions, (xxi) Wade's rule and Jammis rule,
(xxii) Push-Pull mechanism of hydrolysis.
(D) Write Down the Most Stable Conflgur~tlon. of the Following Species
s2of-, Xe04, S2F IO' ReF7, H30+, Xe0 3, XeOt, ocr, F20, SiF62-, XeF2, SbCIs, PClt, BrF3, /),
BF3 , BF4-, A12C16 , XeF4 , XeOF4 , XeFs+, CIOi~ OPC/3 , SF4 , BrF4-, BrFs' H20, GeF2, CI0i., sof- ,
Xe0 2F 2·
Stereochemistry of xenon In some compounds with fluorine and oxyge.,

Xe03 (pyramidal, Td with lip); Xe0 4 (tetrahedral, no lp); XeF1, (linear, TBP with 3 lp); Xe03F1,
(TBP, no lp); XeF3+ and XeOF1, (T-shaped, TBP with 2 Ip); Xe01,F1, (see-saw, C2v' TBP with 1
lp); XeO:- (Oh no lp); XeF4 (square planar, 0h with 2 lp); XeOFs- and XeF, (distorted 0h and
fluxional, PBP or capped 0h with lip); XeOF4 and XeFs+ (square pyramidal, 0h with lip);
XeFs- (pentagonal planar, PBP with 2 lp); XeFs2- (square antiprismatic with one inactive lp); (cf.
a- = F in terms of electron count).
ry
APPENDIX 10A
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FLUOROALKYL RADICALS AND CARBOCATIONS AND FLUOROCARBENES
ib
Refs. Xian-Man Zhang, J. Org. Chern., 63, 3590 (1998);
H. Zipse, Top. Curr. Chern., 263, 163 (2006)
yl
(A) Properties of Fluoromethyl Radicals and Carbocatlons : Effect of a-Fluorine Substituent.
m
• Stability order: CH2F> CHF2 > CH3 > CF3 (cf. C-Hbond energies of the parent hydrocarbon);
he
CHF2+ > CH2 F+ > CF3+ > CH; (cf. x-bonding effect and pyramidalisation effect).
• Inversion energy barrier: CH2F < CHF2 < CF3 (cf. ease of attaining the planar structure).
• CF3 radical is an efficient fire extinguishing agent.
lc
Different factors to stabilise the system

ea
(i) CH3 radical is planar (i.e. sp2_C) while CH2F, CHF2, CF3 radicals are pyramidal (Le. sp3_C) (cf.
Fig. 10.8.3.4); degree of pyramidalisation increases with the increase of the number of
th
electronegative F-substituents: CH2F < CHF2 < CF3 (cf. Bent's rule: an electronegative
substituent prefers the more p-orbital enriched s-p hybrid orbital of carbon). In terms of MO, the
e/
unpaired electron of the radical resides in a SOMO (singly occupied molecular orbital).
(ii) Bond Dissociation Energy (BDE) for the homolytic fission of the C-Hbond increases with the
t.m
increase of s-character of carbon in the bond and it follows the sequence: H-CH'j,F < H-CHF2 <
H-CF3 (cf. effect of electron withdrawing inductive effect and Bent's rule: more the p-character
in the C-F bond, more the s-character in the remaining C-H bonds).
(iii) Radical Stabilisation Energy (RSE) of R· is given by the enthalpy change in the following
reaction:
R-H + ·CH3 ~ R· + CH4 , RSE = Ml
Thus RSE depends on the difference ofBDE of H-CH3 and H-R. The RSE values (in kJ mol-I)
are: CH2F(-12.9), CHF2 (-10.4), CH3 (0), CF3 (+10.3). The negative value ofRSE indicates
that the radical is more stable than the methyl radicaL It is evident that one or two a-Fsubstitution
can stabilize the fluoromethyl radicals (i.e. more stable with respect to the methyl radical) but
three a-F substitution leads to destabilization in CF3 radical (i.e. less stable with respect to the
methyl radical). It may be noted that one a-F shows the highest stabilization and the placement
ofsecond a-F introduces some degree ofdestabilization and this destabilization is further increased
on placing the third a-F. This can be explained by considering the degree of pyramidalisation
which increases with the increase of the number of fluorine substituents. This pyramidalisation
prevents the pi-donor property offluorine. Probably in CF3 radical, due to its strong preference
for the pyramidal structure, the stabilization through the 2c-3e pi-bonding (Le. pi-donor property
of F) is highly disfavoured. Moreover, the strong electron withdrawing inductive effect (Le.
a:-acceptor properlJ!) of the F-substituents and steric effect (repulsion among the nonbonding
electrons of the F-substttuents) destabilize the CF3 radical.
(iv) Lower BDE ofthe C-H bond in the parent alkane indicates the higher stability ofthe radical.
ry
BDE (in kJ mol-I) (C-H bond) varies as:
H-CH2F(425) < H-CHF2 (433) < H-eH3 (440) < H-eF3 (448)
ra
The higher BDE for the H-C bond of CH4 compared to those of CH3F and CH2F 2 cannot be
explained in terms of simple Bent's rule.
ib
(v) F is a a:-acceptor but at the same time it can act as a tr-donor to the vacant orbital (for the
carbocations) or to the singly occupied MO Le. SOMO (for the radicals) of the carboTLCeIttre (cf.
yl
electron push-pull effect or captodative effect). This 1t-bonding stabilizing the system represents
the 2c-3e bond for the radicals and the 2c-2e bond for the carbocations. In a radical, the
n-bonding involving the singly occupied p-orbital of carbon (i.e. SOMO in terms of MOT) and
m
filled nonbonding orbital (i.e. HOMO) of fluorine stabilizes the nonbonding pair and destabilizes
he
the SOMO electron. But, there is a net stabilization, a characteristic property of 2c-3e bond.
Here it may be mentioned that the adjacent pi-acceptor groups (e.g. vinyl, phenyl, carbonyl,
cyano, etc.) can also stabilize the radical through 2c-le 7t-bonding (SOMO-LUMO interaction)
lc
where the SOMO electron is stabilized (cf. stability of the radicals like allyl, benzyl etc.).
ea
I \
I \
I \
LUMO
,--4-\ \
th
I
I \
\
I
I \ I
\ ,
I \ I
e/
I
I \ I I
I \ I I LUMO
I \ I
I I (n"'-MO)
\_+--l~
t.m
I I
~ I
C) I
I I \ I
(i) I
c I \
W
-+-( I
I
I SOMO
(p-orbital)
\
\
\~'
\ I
I
I
+
\ I
\ I
HOMO \ I
(NBMO) \
''----4t--/ ,/
HOMO
/'
" '-" "
Radical stabilisation by SOMO-LUMO
~
Radical stabilisation by SOMO-HOMO

interaction (2c-3e bonding) as in interaction (2c-1e bonding) as in
)6-X
o
. II .
(X = F, Sr, NH 2 ,OH etc.) )c - C == N, )C - C "-
R
Fig. 1. Schematic representation (in terms of MOT) of radical stabilisation by x-donor groups (Le.
SOMO-HOMO interaction) and 1t-acceptor groups (Le. SOMO-LUMO interaction).
The x-donor property ofa-fluorine is favoured for the planar structure (Le. sp2_C) but disfavoured
for the pyramidal structure (Le. sp3_C). Thus this x-bonding is most disfavoured for CF3+ and
CF3• Bent's rule prefers the pyramidal structure in CF3+ and CF3 but the P1t(F)--+P1t(C) prefers
the planar structure. According to VSEPR, CF3+ should adopt the planar structure but Bent's
rule leads to its pyramidalisation.
(vi) Radicals are stabilized by hyperconjugation, o:-donor group, tracceptor group, trdonor group,
and captodative effect (simultaneous presence of the electron donor and electron acceptor
substituents at the radical centre; Ho-eH-eN, a representative captodative radical) but the
ry
radicals are destabilized by the a-acceptor substituents.
ra
C\~A
== N +-+ R-CH=C=N.
ib
R-CH-C
(Resonance)
yl
••• _.+
H2C - - X +--+ H2C - X ; (X =F, Sr, NH2,OH)
(Resonance) (7e) (8e) (Be) (7e)
m
(via 2c-3e 1t-bond formation)
he
lc
ea
(HyperconJugatlon)
th
Fig. 2. Schematic representation of different types of radical stabilizing effects like resonance, hyper-
conjugation, etc.
e/
Illustration (stability order) : Me 3C > Me 2CH> MeCH2 > CH3 (effect of hyperconjugati.on and
t.m
a-donor group); Ph 3C > Ph 2CH> PhCH2 (p-x c.~njugation, effect of x-acceptor moiety);
H2C - X (X = F, Br, OH, NH2) > H2C - H (effect of x-donor property of X).
(vii) Inversion of the radicals occurs through the planar structure. Thus the species which is more
reluctant to adopt the planar structure shows the higher inversion energy. Bent's rule and VSEPR
predict the ease of planar structure as : CH3 > CH2F> CHF2'> CF3 (cf. Fig. 10.8.3.4).
CF3 radical Is an active fire extinguishing species

It can remove the Hand OH radicals which are the active species present in the combustion zone.
It may be noted that Br radical generated from the thermolysis of halons (Le. bromofluorocarbons
used as flame retardants) acts as a fire extinguisher in the same way:
CF3 + H --+ CFjH; CFjH + H --+ CFj + H 2 ; CFjH + OH ~ CF3 + H 2 0
(cf. Br + H --+ BrH; BrH + H ~ Br + H 2 ; BrH + OH ~ Br + H 20)
(B) Properties of Fluoroethyl Radicals: Effect of p-Fluorine Substituents

• Stability order: CH3CH2 > CH2FCH2 > CHF2CH2 > CF3CH2 ; CH3CF2 > CH3CH2 > CHF2CH2 •
Different factors to stabilise the system

(i) B-Fluorine shows only the electron withdrawing inductive effect (i.e. a-acceptor property) and
it destabilizes the radical and carbocation. On the other hand, a-fluorine can stabilize the radical
and carbocation through its pi-donor effect (if the pyramidalisation effect is not very much
strong).
ry
(ii) Lower BDE (bond dissociation energy) of the C-H bond in the parent alkane indicates the
higher stability of tlte radical. BDE (C-H bond) varies as:
ra
CH3CH2-H < CH2FCH2-H < CHF2CH2-H < CF3CH2-H· (cf. Bent's rule)
(C) Anomeric Effect (i.e. Negative Hyperconjugation) by the Fluorine Substituents
ib
In CH2F 2 , theOnonbonding electron pair of one F-atom can be donated into the antiperiplanar a*-MO
yl
(antibonding MO) of the another C-F bond (i.e. n ~ a*). This gives F-CH2F+ (no bond, double bond
resonance where there is a carbon-fluorine double bond) which stabilizes the system. In the same way
m
(i.e. the electron pair of carbanion is pushed into the vacant antiperiplanar a*-MO of the C-F bond
at B-C), B-F can stabilize the carbanion.
he
F
II
~ C, +--+ F C ""H
lc
+F/ I "H 1
H H
ea
\J O"C-F(app)
F\
th
\J
HIIIIIIII"'oC-F
D.-~nb(F)
e/
H'
C(lp)-+0"C-F(8PP)
t.m
F(lp) -+0"C-F(8PP) (Stabilisation of carbanion)

Fig. 3. Schematic illustration of negative hyperconjugation effect (n ~ cr*) in CH2 F2 and carbanion
(with ~-F).
Note: Stability of the adducts, R3N~O, F3N~BX3 (unstable), F3N~O. Electron pushing inductive
effect of R (alkyl group) stabilises the adduct, R3NO. F3NO is resonance stabilised by using the 2p-
electron of oxygen, i.e. O(lp )--+(J~-F(app). It makes the N-O bond sh<?rter and the unusually long
N-Fbond.
F"", +
F"", F
F - N ==0 ....----.. F- N==0 .....--.... F- N==O
F- / /
,: F
(0) Properties of Carbenes and Halocarbenes

(i) Singlet carbene (CH2 ) possesses the planar structure (i.e. ~p2_C) but the bond angle is contracted
to 103 0 due to th~ bond pair-lone pair repulsion (VSEPR). Triplet carbene shows the bond angle
136° indicating sr-C (1 < x < 2).'Ideally, triplet carbene is expected to have the linear structure
(i.e. sp-C) with two pure p-orbitals housing the unpaired electrons.
(ii) Triplet carbene is more stable than singlet carbene because the triplet one enjoys the exchange
energy and it avoids the electrostatic repulsion in housing the two electrons in a single orbital.
(iii) For the halocarbenes, i.e. CX2 andCHX (X = F, CI, Br), the
singlet carbene is more stable than the triplet one because, H,
in the singlet one, the vacant-orbital of carbon may be utilized
in P1lX) ~ P1l C) pi-bonding to stabilize the system. In terms ---.~
:F",G
ry
of the size of the orbitals, efficiency of this pi-bonding ••\.tI
decreases with the increase of the size of the halogen orbital Fig. 4. Schematic representation of
ra
because, for the heavier halogens, it leads to a mismatch in stabilization of singlet CHF carbene
size between the overlapping orbitals. Thus, stability and life through pi-bonding.
time run as: CHF> CHCI > CHBr.
ib
(iv) Electron affinity (EA) order: CH2 ~ CHF < CHC.z < CHBr < CHI; CBr2 > CCl2 > CH2 > CF2• The
EA order indicates that in the case of fluoro derivative, the pi-bonding effect, i.e. Pn(F) ~ Pn( C)
yl
is very much important while for the heavier halocarbenes, the said pi-bonding effect (to neutralize
the electron deficiency caused by the a-acceptor, i.~. electron withdrawing inductive effect of the
m
halogen) is not so important (due to mismatch in size and energy between the involved orbitals).
Thus, this pi-donor property decreases with the increase of size of the halogens and EA incr~ases
he
for the halocarbenes of heavier halogens (though less electronegative). .
(v) The singlet carbene can act as a Lewis base by donating its nonbonding electron pair and al tbc
lc
same time it can act also as a Lewis acid by using its vacant p-orbital. In fact, singlet carbLl1e can
act as a pi-acid ligand and it can introduce a metal-carbon double bond character in the carbene
ea
complexes (ef. Fisher carbene and Schrock carbene complexes; see Vol. 6).
(E) Relative Stability Order of Carbocations and Carbanions in Gas Phase

th
The stability order, 3° > 2° > 1° (for both carbanions and carbocations) can be explained by considering
the concept ofpolarisability or charge capacity parameters (measured by b value, see Sees. 8.14.9,
e/
14.8.2, 14.9.4) of the R-groups (cf. R-group is more polarisable than hydrogen) and hyperconjugation
t.m
effect. The R-groups being more polarisable can accommodate or delocalise both the pusitive and
negative charge through the ion-induced dipole interaction (Fig. 5), and it explains the stability
order, 3° > 2° > 1° for both the carbocations and carbanions. Hyperconjugation effect of the R-groups
(positive hyperconjugation producing H+ for the earbocations and negative hypercol1jugation producing
H- for the carbanions) leading to the delocalisation of charge also supports the stability sequence
3° > 2° > 1° for hath carbocations and carbanions. .
Planar Tetrahedral
/~-
I )
8+ f R/
5-:', y.<.. - . .
::C'·+R
"~ ~~ -_/
)6-
Sp3J . . C"" - "-
<5+\ R \
'-/8-
(a) (b)
Fig. 5. Charge delocalisation in carbocationF and carbanions: (a) through the polarisation of R-groups to
introduce the ion-induced dipole interactions; (b) through hyperconjugation. .
11
Structure, Bonding and Properties of
Ionic Solids and Solid State Chemistry
ry
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11.1 CHARACTERISTIC PROPERTIES OF IONIC COMPOUNDS
ib
(i) Complete Transfer of Electron(s) from One S'pecies to the Other
The electrovalent or ionic bond is formed between the combining species through the complete transfer
yl
of one or more valence electron(s) from one species to the other. By transferring the electron(s), the
species transforms into a cation while the other species by accepting the electron(s) transforms into an
m
anion. The electrostatic Coulombic attraction between the oppositely charged species (Le. cation and
anion) prevails to hold the species. Examples:
he
-e
(a) NaCI: Na (ls 2 2s2 2p 6 3s 1 ; Le. 2, 8, I) ---..) Na+ (ls2 2s 2 2p 6, Le. 2, 8 )
lc
+e
Cl (ls2 2s2 2p 6 3s2 3p 5; Le. 2, 8, 7) - - - - + ) C, (ls 2 2s 2 2p 6 3s 2 3p 6 , Le. 2, 8, 8)
ea
Na+ + C, ~ NaCI (crystal)

~e ~e
(b) MgO: Mg (2, 8, 2) ) Mg2+ (2, 8); 0 (2, 6) ) (jl- (2, 8)
th
Mg2+ + (jl- MgO (crystal)

~e +2e
e/
(c) CaFz : Ca (2, 8, 8, 2) ) cQ2+ (2, 8, 8); 2F (2, 7) ) 2r (~, 8)

2 2
Ca + + 2r ~ Ca + (r)2 (crystal)
t.m
(ii) Nondirectlonal Combining Force

The attractive force between the cationic and anionic species is purely electrostatic in nature and it is
equally probable in all directions. Thus the ionic forces are quite strong and omnidirectional while the
covalent forces are very much directional. The attractive Coulombic force within the ion pair is given
by, F= q+ q-/(41tEr) where-q+ and q- are the charges of the cation and anion respectively and r stands
for the interionic separation. In a solid crystal, Eo stands for the permitivity of vacuum. The attractive
force extends throughout the lattice.
977
" (iii) Physical State

Because of the omnidirectional nature of the ionic forces, the ionic compounds form three dimensional
solid aggregates ofthe cations and anions which are arranged in some well defined geometrical patterns.
Thus the electrovalent compounds form crystalline solids. They never exist as isolated'molecules "in
contrast to the covalent molecules. At ordinary conditions, they remain as solids.
(iv) Electrical Conductivity

In the solid state, the ions remain in the well defined lattice points and they cannot move freely to
ry
conduct electricity. But on fusion, the ions can move freely to carry electricity. In some cases, the
conductivity of the ionic solids may rise due to the crystal defects. When the ionic compounds are
ra
dissolved in water, the ions become more free to move and as a result, the solutions are very good
conductors of electricity.
ib
(v) Hardness and Brittleness
l~he ionic compounds are hard because of the omnidirectional strong electrostatic force extending
yl
throughout the crystal but they are brittle. When an external pressure is exerted on the ionic crystal, it
may set up the anion-anion and cation-cation repulsions. Because of the repulsive forces, the crystals
m
break down. It explains the cleavage properties ofmany minerals.
he
(vi) Melting and Boiling Points
The reason behind the hardness can again explain the high melting and boiling points of the ionic solids.
lc
(vii) Solubility
ea
The ionic compounds are generally soluble in polar solvents having high dielectric constants or
permitivities. It is known that the Coulombic attractive force holding the ions is inversely proportional
th
to the permitivity (E) of the medium, Le. F ex:: lIE. The relative permitivities of the different media are:
air or vacuum (I), H20 (82), CH3CN(33), NH3 (25). Thus with the increase ofpermitivity ofa medium,
the attractive force between the oppositely charged species decreases. This is why, when an ionic
e/
compound is placed in water, the attractive force responsible for holding the ions in the c.rystallattice is
significantly dropped to facilitate the breakage of the crystal lattice. In ger~eral, a solvent with a
t.m
higher permitivity is more promising to dissolve the ionic solids.

The phenomenon can also be interpreted in terms of ion-dipole interaction. The energy required to
break down the ionic lattice is largely compensated through the hydration energies of the cations and
anions. The dipolar solvent molecules can solvate both the types of ions through the proper orientation
of their polar ends.
(viii) Isomorphism (Greek isos means equal and morphe means form)
Many pairs of ionic compounds are known to crystallise simultaneously in the same form and they are
referred to as isomorphous crystals (noted by Mitscherlich, a student of Berzelius). Such isomorphous
compounds can crystallise simultaneously from a solution to form the mixed crystals. They can also
form overgrowth. Some isomorphous pairs are given below :
Cu 2S, Ag2S; KCI04, KMn04; ZnS04 · 7H20, MgS04.7H20; NaN0 3, CaC03; KMn04, BaS04 ; KI04,
CaW04; NiS04·7H20, NiP03F.7H20; K 2S04 · AI2(S04)3 . 24H20, (NH4)2S04.A12(S04)3·24H20
Structure, Bonding and Properties of Ionic Solids and Solid State Ghemistry 979
The basic condition for the isomorphism is the similarity o/the internal structure o/the crystals in
all respects. It does not depend on the chemical propertie~ and even also the total number ofatoms (e.g.
last pair). The isomorphous crystals have similar unit cells with almost the"same dimensions, i.e.,
the same interfacial angle and axial ratio. But the crystals with almost the same crystal dimensions
are not necessarily isomorPhous.
The detailed analysis ofthe isomorphous compounds reveals that for the isomorphism (characterised
by the mixed crystal/ormation and overgrowth) the following conditions must be satisfied.
(a) 'fhe two compounds must have the same type of formula to provide the same number of
ry
lattice points (not necessarily the same number of atoms, the atoms can be replaced by some
suitable radicals to maintain the constancy of the number of lattice points).
(b) The size of the corresponding constituent units must be comparable.
ra
(c) The stereochemical orientation of the corresponding constituent units in the compounds
must be identical.
ib
(d) The polarising power and polarisability of the corresponding constituent units in the
compounds must be comparable. .
yl
(e) The crystals should have the same type of crystal structure (Le. the same type of unit cell)
with the comparable crystal dimensions (Le. interfacial angle and axial ratio).
m
(f) The molar volume of the oompounds should be comparable.
The fulfilment of the above conditions can be illustrated through the following examples.
he
NaNOJ and CaCOJ (calcite): Molar volume of NaNO) = 37.4; Molar volume of CaCO) = 36.9;
r Na+ = 95 pm; r cdl+ = 99 pm. Both coi- and NO; are planar where three oxygen atoms are at the
lc
comers of an equilateral triangle. Both the central atoms (Le. C and N) are sp2 hybridised. The axial
ratios of the unit cells are also 'comparable. Hence NaN03 and CaC03 are isomorphous.
ea
NaNO J and KNOJ : rNa+ = 95 pm < rJC" = 133 pm. Thus, the relative size ratio, r+/r_ is different for
NaN03 with respect to that of KNO). Hence these are not isomorphous.
th
BaS04 and KMn04 : r Bdl+ = 135 pm, r r = 133 pm. Both MnOi and 80;- are tetrahedral and
their sizes are also comparable. The axial ratios of the unit cells are also comparable. Hence, these are
e/
isomorphous.
KN0 3 and KCIOJ : C/O; is pyramidal (sp3 hybridisation of Cl) while NO; is planar ( sp2
t.m
hybridisation of N). Hence, they are not isomorphous.

RaS04 and BaS04 : They are isomorphous and they can be isomorphously coprecipitated. From
the standpoint of ionic radii, Ra2+ (152 pm) and Ba2+ (143 pm) are close and they can produce
isomorphous crystals. Ca2+ (106 pm) is much smaller and CaS04 is not isomorphous with RaS04•
From a solution having a very low concentration of·Ra 2+ (i.e. [Ra 2+] [SOl-] < K sp ), it can be
coprecipitated with BaS04 • By using this carrier or collector technique, Ra2+ can be separated even
when Ra2+ concentration in solution is exceedingly small.
Note : Isomorphous crystals lead to coprecipitatioil which is important in analytical chemistry (cf.
Sec. 14.17.3).
(ix) Variable Electrovalency
Generally the d and/block elements show variable valencies. For the d block elements (Le. transition
metals), the d levels remain incompletely filled for which the successive ionisation potentials do not
increase too rapidly (see Sec. 8.12.2). The energy required to raise the oxidation state from a lower
oxidation state can be compensated through the higher lattice energy (or, solvation energy in solution).
This is why, under the identical conditions, the existence of more than one stable oxidation state becomes
energetically possible. Thus the occurrence of Fe 2+ and Fe3+; Cu+ and Cu 2+; Co 2+ and Co 3+; etc. are
well documented. The heavier congeners (i.e. 4d and 5d series) show a marked tendency towards
the higher oxidation state (see Sec. 8.20.3 for relativistic effects). For example, though +2 and +3
states are known for Co, for Rh and Ir the +3 state (or, higher state) is more well documented; stability
of +4 stable runs as Pt > Pd> Ni; C,J+ is the most stable state for Cr while both Mo and W possess the
stable +6 state. To explain such variable oxidation states both the lattice energy (Le. Madelung energy)
ry
and /igandjield effects are to be considered.
'To consider the effect of ionisation potentials on the variable valencies, let us consider, Cu, Ag and
ra
Au which display the common states ~ 1and +3; but the stability of the +3 state increases in descending
the group ( cf. relativistic effects, Sec. 8.20.3). On the other hand, the stability of +2 state decreases in
ib
descending the group. The ionisation ~nergies (kJ mol-I) of Cu, Ag and Au are given in Table 11.1.1.
Table 11.1.1. Ionisation energies of Cu, Ag and Au
yl
Ionisation energy (kJ mOil)
Element 1st 2nd 3rd 1st + 2nd + 3rd 1st + 2nd
m
Cu 745 1959 3551 6255 2704
he
Ag 731 2074 3361 6166 2805
Au 889 1939 2943 5771 2828
lc
Thus it is evident that to attain the trivalency (+3), the less energy is required for Au compared to Cu
and Ag while for the +2 state,Cu is more favoured compared to Ag and Au. However to explain the
ea
relative stabilities of the states, consideration of the ligand field effect is extremely important. For the
present system, the Jahn- Teller effect is extremely important. The ninth electron (tP -system) in d~2 _I
th
orbital (z-out distortion) is destabilised maximum in Au(II). It favours the oxidation of Au(II) to
Au(III) compared to oxidation of Cu(ll) and Ag(II).
e/
Similar arguments also hold good for the variable valencies in the lanthanides and actinides.
Lastly, the inert pair effect (see Sec. 10.3) in the just posttransition elements also leads to the
t.m
variable valency.
11.2 DIFFERENT TYPES OF IONS AND ELECTRONIC CONFIGURATIONS

OF THE IONS INVOLVED IN IONIC BONDING
(i) Inert Gas Structure
The ions tend to have the inert gas configuration, ns 2np6 (exception: Be 2+, L,O+ and 11 of Is 2 helium gas <
structure; Jr , no outer electron). The configuration is attained by the elements (Le. metals) ofGr I (1),
II (2) and III (13) by the way of complete loss of their valence electrons and by the elements (Le.
nonmetals) of Gr VII (17), VI (16) and V (15) by the way of capturing 1, 2 and 3 electrons respectively.
Some representative examples are shown below.
11----+ He (Is~).+-- LzO+, Be2+
N3-, (jl-, r~ Ne (2s 22p 6) <f--Na+, Mg2+, A13+
Structure, Bonding and Properties of Ionic Solids and Solid State Chemistry 981
81-, C,----+ Ar (3s 23p6) +-- Kt, cQl+, SC3+, Ti4+

Se 2-, Br- ----+ Kr (4s 24p 6) +-- Rb+, S,J+, y3+, Zr4+
Te 2-,I- ----+ Xe (Ss2Sp 6) +-- Cs+, Ba2+, La3+, Ce 4+
Ar ----+ Rn (6s 26p6) +-- Fr+, Ra2+, Ac3+, Th 4+
(ii) The Eighteen Electron Structure (I.e. pseudo noble gas configuration)
The anIons (exception: Au- in CsAu, Au- --+ Ss2Sp6Sd10 ) do not have the 18 electron structure, but it is
frequently observed for the cations of the posttransition elements. The posttransition elements of Or I
ry
(11), II (12), III (13) and IV (14) lose their outermost electrons I (ns l ), 2(ns 2), 3(ns 2np l) and 4(ns 2np2)
respectively to attain the structure, (n - l)s2 (n - l)p6 (n - l)dl0. Some examples are:
ra
Cu+, Zn 2+, Ga3+, Ge4+--+ 3s23p63d10 ;
Ag+, cJ2+, In 3+, Sn4+--+ 4s24p64d10 ;
ib
Au+, Hg2+, TI3+, Pb4+--+ Ss2Sp 6Sd10 •
yl
In this category Cu, Ag and Au show variable valencies of + I, +2, +3 characterised by 18, 17 and 16
outermost electrons respectively. The general stability orders are (see Sec. 11.1 (ix) :
m
Cu 2+> Cu+ » Cu 3+; Ag+ > Ag2+; Au3+> Au+ » Au2+.
he
It shows that the attainment ofjust outermost 18 electron structure cannot assure the stability
necessarily. It is proposed by some authors that the nuclear charges. of these species are not sufficiently
lc
high to bind the outermost 18 electrons firmly. It is highly pronounced (see Table 11.1.1) in the case of
Au which leads to +3 state as the most stable one. But Zn 2+, cJ2+, Hg2+, etc. attain the stability with the
ea
18 electron structure. Thus the explanation is not correct. The relative stability ofsuch variable oxidation
states can be rationalised by the simultaneous consideration ofthe endothermic effect (i.e. ionisation
energy) and the exothermic effects (i.e. lattice or solvation energy and ligandfield stabilisation energy).
th
For the heavier posttransition elements, due to the inert pair effect (see Sec. 10.3), instead of the 18
electron structure, the 18,2 structure, i.e. (n - I )s2(n - I )p6(n - I )dl0ns2, is preferred. Some representative
e/
examples are: Tr-, Pb 2+, Bi3+--+ 2, 8, 18, 32, 18, 2; Sb 3+--+ 2, 8, 18, 18, 2 .
t.m
(iii) The Transition and Inner-transition Metal Ion Structure

The transition metal ions are characterised by (n - I )s2 (n - 1)p6 (n - 1)d1-9. The incompletely filled
d-Ievel shows the variable valency because of the small difference in stabilitY of two or more oxidation
states for a particular metal. For example :
Fe (3£f4s 2) --+ Fe 2+(3£f), Fe 3+(3tP); Co (3d'4s2) --+ C0 2+(3d'), C0 3+(3£f); etc.
For the inner-tran~ition metal ions (i.e. lanthanides and actinides), the incompletely (n - 2}ffilled
level leads to the variable valency. The electronic configuration of the inner-transition metal ions is
given by, (n - 2)dl0 (n - 2)(1-13 (n - 1)s2 (n - 1)p6, (n = 6 for lanthanides, n = 7 for actinides)
(Iv) Polyatomlc Ions

Many covalently bonded Rolyatomic species can act as the constituent ions in some ionic crystals. Such
anions are : CO;-, NO; , BF4-, BeF42-, MnO;, CIO;, CrO;-, 80;-, Fe(CN)~-/4-, etc. and such
cations are: NH;, CU(NH3)~+'Co(NH3)~+' etc.
(v) Ions with Irregular Configurations

There are some polynuclear cluster species which cannot be classified into any particular group.
2+ Ge2+ ' etc.
Examp Ies.· H g2' 2
11.3 ELECTRON DENSITY (ED) MAPS AND IONIC RADII

11.3.1 Ionic RadII from X-Ray Electron Density Map,
The X-ray studies can precisely determine the internuclear distance, but it cannot estimate directly the
ry
size of the individual ions which is governed by the radial distribution probability of the outermost
electrons. But it can record the electron density maps (ED maps) which arise due to the scattering ofthe
ra
X-rays by the electrons. From the ED maps,
it is observed that the electron density ~
ib
.Ci)
gradually falls from the nucleus ofan ion with ~
the increase of the distance along the ~
yl
internuclear axis of the adjacent ions and at a ~
particular distance it falls to a minimum value
m m .. •.
then it rises gradually as the distance towards rF-
the nearest next nucleus decreases (see Fig. Fig. 11.3.1.1. Electron density (ED) maps in NaF
he
11.3.1.1). Now we can assume that at the crystals (variation of electron density around the
point of minimum electron density, one ion nuclei).
lc
stops and the next one starts. Thus we may define an ionic radius of an ion as tbe distance from its
nucleus to the point of minimum electron density along the line joining the centres of the adjacent two
ea
ions (Le. generally cation and anion). Some representative values of ionic radii obtained from X-ray
electron density maps of alkali halides are given in Table 11.3.1.1. Here it is worth mentio~ing that the
ED map very-often passes through a very broad minimum instead ofa sharp minimum and it complicates
th
to parametrize the size of ions.

e/
Table 11.3.1.1. Some representative ionic radii derived from X-ray electron
density maps
t.m
Ion Ionic radius Ion Ionic radius

r+ (pm) r_ (pm)
Na+ 117 Ci 164

~ 149 Br- 180
Rb+ 163 1 205
Cs+ 186
In comparison with the ionic radii obtained from other methods (say, Pauling's method, see Table
11.3.2.1) these values are different.
11.3.2 Ionic Radii from Other Methods

In the crystals, the ions are at an equilibrium distance where the attractive and repulsive forces balance
each other. This equilibrium internuclear distance can be easily obtained from the X-ray studies. The
internuclear separation (R o) is the sum of the radii of the involved ions, Le. Ro = r+ + r_. Thus if the
Stru~ture, Bonding and Properties of Ionic Solids and Solid State Chemistry 983
radius of one ion is known, then by subtraction, the radius of the other ion can be obtained. To solve the
problem, it is assumed that the ionic radius of an ion is its own characteri~tic property and it is
constant and it does not depend on the neighbour with which it exists. This approximation is at least
grossly supported from the exper~mental fact. For example, the difference between the radii of K+ and
Na+ ions derived from the measurements of four different alkali halides is fairly constant.
r JC" - r Na+ = RO(KF) - RO(NaF) = 35 pm; RO(KC/) - RO(NaCl) = 35 pm;
RO(KBr) - RO(NaBr) = 32 pm; RO(K/) - RO(Na/) = 30 pm.
ry
Now to start the process to compute the ionic radii, it is required to have the knowledge ofthe value
ofionic radius ofat least one. Then we can go for the others by using this value. Hence, it is important
ra
to determine the ionic radius of the starting one by an independent method. The validity or accuracy of
the computation process for the other ions depends on the accuracy of the starting value determined
ib
separately. Some methods developed by different workers are discussed below.
(i) Lande's Method: Lande' (1920) started with the crystal of Lil in which the size of the anion is
yl
much larger compared to that of the tiny cation, Li+. Here it is assumed that the large sized anions
touch with one another. Thus half of the internuclear separation between the adjacent anions
m
, gives the value of ionic radius of the anion, i.e. rr =~ Rou -I) =~ (426) pm =213 pm.
he
By using this value for 1- , the ionic radius of K+ is evaluated as,
r + =R + _ -r _ =(353-213)pm= 140 pm.
lc
K O(K -I) 1
By continuing the process, ionic radii for the other ions have been determined.
ea
(ii) Bragg's Method: Bragg in 1927 assumed the radius of (j2- as half of the internuclear distance of
the adjacent oxide ions in silicates. Thus Bragg started with the silicate in the same way as
th
followed by Lande' in the case of LiI. Thus, ro2 - =~ Ro(o-o) in silicate, =~ (270) pm = 135
e/
pm. By using this value, Bragg and West computed the ionic radii for more than 80 ions.
t.m
(iii) Molar Refractivity Method: Goldschmidt's Radii: -By using the Lorentz-Lorenz equation (see
Eq. 11.3.2.1) the molar refraction (R M ) can be determined experimentally.
2
n -I M
RM = - 2 - · - ... (11.3.2.1)
n +2 P
where n is the refractive index of the substance of molecular mass M and density p. R M is an
additive property of the constituent atoms or"ions and bonds. Thus, for the ionic compounds, the
refraction by the constituent individual ions can be determined.
The molar refraction has the dimension ofvolume.(= M/p). Thus if RM(i) is the ionic refraction by
the i-th ion, then the radius (r i ) of the ion can be calculated as follows :
... (11.3.2.2)
where C is the proportionality constant. By using the above relation, for two different ions we
have:
I/3 1/3
RM(i) . 'i ~ RM(i)
[
'i/rj = - -
RM(j) J
or, - - =
. 'i + rj
1/3
RM(i) + RM(j)
1/3 ...(11.3.2.3)
Thus if the ionic refractions of the individual· ions and the corresponding interionic seperations
are known, then by using Eqn. 11.3.2.3, the ionic radii of the constituent ions can be evaluated.
This method was developed by Wasastjema in 1923.
By using the interionic distances in the alkali halides and alkaline earth oxides, the ionic radii for
r- and (jl- are found to be 133 pm and 132 pm respectively. Goldschmidt (1929) utilised these
ry
values to compute the ionic radii for a number of ions. These values are very often referred to as
Goldschmidt's ionic radii.
ra
(iv) Pauling's Method and Pauling's Univalent Radii: Now we can recall the quantum mechanical
analysis of the hydrogen like system for which the radius of the species having the electron in the
ib
outermost principal quantum number n is given by :
rn = n2h2/(41tme 2Z) ' in CGS unit·' nr ="Gon2h2/(1tme 2Z) ' in SI unit·,
Le. rn = Cn 2/Z
yl ... (11.3.2.4)
m
where, C is constant, m = mass of an electron, e = charge of an electron, Ze = nuclear charge.
For a many-electron species, the radial distribution function of the outermost electron determines
he
the size of the ion and such electrons are attracted towards the nucleus. In a polyelectronic
system, because of the screening effect, the outermost electron experiences the nuclear charge
lc
(Z - S)e, where 8 is the screening constant, which can be evaluated by the Slater's rule (see Sec.
4.2.4). Thus the radius of an ion can be expressed as :
ea
2
Cn Cn 2
r: =--=-- ...(11.3.2.5)
Ion Z - 8 Z·
th
For the isoelectronic species, n (the outermost principal quantum number) is identical. In each of
the compounds, Na+r-, ~Cl, Rb+Br- and Cs+/-, the constituent ion pairs are isoelectronic.
e/
For such isoelectronic ion pairs we can write·:

t.m
•
r+ Zanion - S Zanion
• ... (11.3.2.6) .
r_ Zcation - S Zcation
Cn 2 and S are identical for the isoelectronic species, because these depend only on the electronic
configuration..The constant Cn 2 is different for different inert gas configurations. For the ions of
neon gas configuration (e.g. (jl-, F-, Na+, Mg2+, AI3+, etc.), its value is 614 pm. The value ofCn2 .
for the argon gas configuration (e.g. ~, Cl, Ca2+, 8 2- , etc.) is 1036.5 pm. Similarly it can be
calculated for other species also. Eqn. 11.3.2.6 reduces to,
rcation
. Zanion - 8
• • ...(11.3.2.7)
rcation + ranion Zcation + Zanion - 28 Z cation + Zanion
r+ Z•
Le.
The internuclear distance (Ro = rcation + ranion) can be obtained from the X-ray studies and the
shielding constant S can be obtained by using the Slater's rule for the lighter elements, and from
the values of molar refraction for the heavier members. Thus, r+ and r_ can be easily computed.
Let us illustrate the process for Na+F- in which the isosteric species are having the electronic
configuration, Is22s22p 6. The shielding constant S, for this configuration is obtained by the
Slater's rule:
S = 7 x 0.35 + 2 x 0.85 = 4.15
The interionic separation is 231 pm, i.e., rNa + rr- = 231 pm. Now by using Eqn. 11.3.2.7 we
+
ry
get:
rNa + ZF- -4.15 9-4.15 4.85
------ = =- - - - - - -
ra
Z + +Z _ -2x4.15 11+9-8.3'0 11.70
Na F
rNa + =95.7 pm and rF- =135.3
ib
OT,
Note on calculation o/Z*: In calculating S for the isosteric species Na+ and~, some authors
yl
consider all 8 electrons in the valence shell instead of 7 electrons shielding the last valence
shell electron. It leads to :
m
S = 8 x 0.35 + 2 x 0.85 = 4.50, and ~ = 6.5 (for Na+), and ~ = 4.5 (for ~).
Thus the ~ values obtained are very close to those of Pauling's values (cf. 6.48 and 4.48 for
he
Na+ and y- respectively). This is the justification for considering all the 8-valence electrons,
but it definitely does not obey the Slater's rule. However, in thiSc method, the calculated ~Iues:
lc
r+ = 94.5 pm and r_ = 136.5 pm do not differ significantly from the values obtained by using
the Slater's rule strictly.
ea
In the case of ~Cl, the ions are isosteric having the electronic configuration Is22s22p63s23p6.
The shielding constant for these isosteric ions is obtained as follows:
th
S = 7 x 0.35 + 8 x 0.85 + 2 x 1.0 = 2.45 + 6.80 + 2 = 11.25

By using the value, rr + rcr = 314 pm, we get:
e/
rK + Zc/- -11.25 17 -11.25 5.75

t.m
-----=--
r + +r /- Z + +Z -2xll.25 19+17-22.5 13.5
K c K CI-
or, rr = 1"33 pm and rcr = 181 pm.

(v) Pauling's Crystal Radii: Now let us try to apply the method utilised in computing the ionic radii
of 1-1 salt (where ITI = 12"""1 = 1) in the cases where the cationic and anionic charges are not unity.
Let us take the case of CaS which has the NaCI structure. The electronic configurations of Ca2+
and 82- are: Is22s22p63s23p6 (i.e. Ar configuration). Thus, the ions are also isoelectronic with ~
and Ct. Hence we can write:
r /r =(Z -8)/(Z _8)=19-11.25
Ca 2+ K+ K+ Ca 2+ 20 - 11.25
Using the value of r r obtained from KCI, we get, r Ca2+ = 117 pm.
Similarly, by using the relation, rS2Jrr- = (Zr -11.25)/(Zs2- - 11.25), we get, rS2- = i 19 pm.
,These values can also be evaluated by using the constant Cn 2 (see Eqn. 11.3.2.5) which is 1036.5
pm for the argon gas configuration.
Thus we get the calculated internuclear distance, rcdl+ + rs2- = (117 + 219) pm = 336 pm. This
value is much larger than the experimentally observed value 284 pm. Thus the process is erratic
for the polyvalent ions while it is good Jor the uni-univalent s)'stems. In fact, radii calculated
for the polyvalent ions in this way are referred to as their hypothetical univalent radii when the
ions act hypothetically as univalent ions in the Coulombic field.
To clarify the above drawback we are to consider the Born-Lande equation (see Sec. 11.7.1) in
ry
which it is found that the equilibrium internuclear distance (R o) is related as follows.
=( nB47tE o )1/(n -I)
ra
Ro AZ+ Z- i · · · ( 1 1.3.2.8)
ib
It shows that the internuclear equilibrium distance (Ro) is proportional to (1/zt z-)I/(n - 1) for
which the Born exponent (n) is the same for the isosteric species, i.e.
yl
RO oc (1/zt m Z-)I/(n -1) ..• (11.3.2.9)
l'hus if for the uni-univalent salt, the interionic separation is RO(II) and RO(ij) is the separation for
the i - j type lattice (Le. Izt I = i, IZ-I = j), then they are related as :
he
Ro(ll) -
_ (1)
D ];]
1
I( n - 1)
...(11.3.2.10);
lc
_ (1 )1 I(n -I)
ea
RoC'IJ ) - D -ij ... (11.3.2.11)
-I)
th
where,
D =( n::~Eo )I/(n
e/
If, nand B are the same then we can write :

t.m
Row) = (1/ ij)I/(n -I)

... (11.3.2.12)
Roo I)
Thus by using Eqn. 11.3.2.10, for i - j type lattice, we get the univalent ionic radii for the
multivalent ions. These are the hypothetical radii for the multivalent ions, when they retain
the electronic configurations but act in the Coulombic field as the univalent ions. Thus Eqn.
11.3.2.10 leads to the real values only for the 1-1 type lattice structures. However, by using
Eqns. 11.3.2.11-12 we can calculate the real ionic radii for the polyvalent ions by using their
hypothetical univalent radii obtained from Eqn. 11.3.2.10.
For example, the isosteric species r ,
Cr, Ca2+, S2- are having the argon configuration for
which the Born exponent is : n = 9 . The internuclear distance of the hypothetical uni-univalent
CaS is 336 pm, Le. RO(II) = 336 pm. Therefore, RO<.cQl+ ~ S2-) = 336 (1/4)1/(9 - I) = 336 x 0.84 =
282.2 pm. This calculated value is in good agreement with the observed one, 284 pm.
For calculating the ionic radii of the polyvalent ions, we can proceed as follows:
RO( ij) -- RO( 11) x (")-(1/n-l)

lJ ... (11.3.2.13)
From Eqn. 11.3.2.13, taking i == j Le. RO(ij) == 2r; and R O(II) ::; 2r 1, we get:
Ir; = r 1(it 2/(n - 1) I ... (I 1. 3.2. 14)
where r; == crystal field radius for the i-valent ion, and r 1 == univalent radius of the i-valent ion.
ry
Let us apply Eqn. 11.3.2.14 for Ca 2+ and S2- for which n == 9, r 1(ca2+) == univalent radius of Ca 2+
== 117 pm, and r 1(S2-) == 219 pm
ra
Therefore, r 2(Ca2+) == ionic radius of divalent Ca 2+ = 117 x (2)-2/8 == 117 x 0.84 = 98.3 pm; and,
r2(S2-) == 219 x 0.84 = 184 pm.
ib
The best value obtained in this method for the radius of (j2- ion is 140 pm. Using this value,
Pauling estimated the ionic radii for most of the common ions. T'hese are very often referred to as
yl
Pauling's ionic radii. These are given in Table 11.3.2.1 for some representative ions.
Table 11..3.2.1. Pauling's ionic radii (values in pm) for some representative ions (6:6 coordination system,
,+/,_ = 0.7)
m
Ions of main group elements
he
Li+ 60 Be 2+ 31 11 208
Na+ 95 Mg'2+ 65 A13+ 50 Si4+ 41 (j2- 140 r 136
Ca 2+ Ga3+ Ge 4+ S2-
lc
JC" 133 99 62 53 184 Cr- 181

Rb+ 148 Sr2+ 113 In 3+ 81 Sn4+ 71 Tr 144 Se 2- 198 Br- 195
Cs+ 169 Ba 2+ 135 T13+ 95 Pb 4+ 84 Pb 2+ 120 Te 2- 221 J 216
ea
Transition metal ions·

th
Ti 4+ 68 Ti 3+ 76 Mn 2+ 80· Cu+ 96 Zn 2+ 74
Zr4+ 80 Fe 3+ 53 Fe 2+ 75 Ag+ 126 cJl+ 97
e/
Ce 4+ 101 Cr3+ 55 Co 2+ 72 Au+ 137 Hg'2+ 110

Co 3+ 63 Ni 2+ 69
t.m
• value largely depends on spin state, Le. high spin or low spin state.
(vi) Yatsimirskii's Thermochemical Radii: The methods already discussed are not suitable for the
polyvalent ions such as CN-, CO;- , 80;- , BF4-, etc. The problem is further complicated in
these cases because most of the polyvalent ions are nonspherical in shape. But it is very
often required to know thier ionic radii for calculating the lattice energy of the systems involving
such polyvalent ions.
To solve the problem, Yatsimirskii developed a method to calculate the ionic radii for such
species from the lattice energy of the compounds containing the species by using the. standard
equations such as Born-Lande equation (see Eqns. 11.7.1.13-15), Kapustinskii equation'(see
Eqn. 11.7.4.1), etc. From such equations the interionic separation is obtained. Then if the radius
of one of the ions is known, then the radius for the other ion can be obtained. For example, in the
case of KN03, the radius of ~ is known and hence from the knowledge of interionic separation,
the radius of NO; can be estimated. Some representative values are given in Table 11.3.2.2. '
Table 11.3.2.2. Yatsimirskii·s thermochemical, radii adjusted to be compatible

with Shannon·s crystal radii for some representative polyvalent ions."
Ion Thermochemical Ion Thermochemical
radius (pm) radius (pm)
151 011 119
148 C~ 177
218 NO; 165
164 NO; 178
ry
242 CIO; 226
215 CIO; 157
ra
244 BrO; 140
181 10; 108
ib
Except for the perfectly tetrahedral ions (e.g. SO;-, Mn.O;, CrO;-, BeFi-, BF4-, C/O;, etc.) and
octahedral ions (e.g. SiFl-, A/F;-, PFf,-, etc.) which tend to adopt the spherical (at least pseudo-
yl
spherical) symmetry, ~he thermochemical radii are of no use. However, these values can be used
m
approximately in the thermochemical treatments.
11.3.3 Shannon's Crystal Radii

he
Shannon has considered all the factors such as oxidation state, crystal structure, covalent-ionic interaction,
coordination number (C.N.), crystal vacancies and distortions, etc. which influence the ionic radii. He
lc
has defined a set of crystal radii for different coordination numbers based on r0- 2 = 124 pm (C.N. =
4), 126 pm (C.N. 6), = 128 pm (C.N. = 8).
ea
11.3.4 Comparison among Shannon's Crystal radii, Goldschmidt's Radii and Pauling's Radii
The basic principles of these methods have been already discussed. Goldschmidt started with the ionic
th
radius of (jl- as 132 pm while Pauling started with the value 140 pm for (jl-. Except for 11, the
differences in the values are not remarkable (see Table 11.3.4.1).
e/
Table 11.3.4.1. Comparison among different types of ionic radii

t.m
Ion Shannon's Goldschmidt's Pauling's Ion Shannon's Goldschmidt's Pauling's

crystal radii value (pm) value (pm) crystal radii value (pm) value (pm)
(pm)
H- 154 208 Be 2+ 59 34 31
r 119 133 136 Mg2+ 86 78 65
Ci 167 181 181 Cd2+ 126 106 99
Br- 182 196 195 s,2+ 132 127 113
J 206 220 216 Ba2+ 149 143 135
(jl- 126 132 140 A13+ 68 57 50
S2- 170 174 184 Sc 3+ 89 83 81
Li+ 90 68 60 y3+ 104 106 93
Na+ 116 98 95 Si4+ 54 39 41
~ 152 133 133 Ti4+ 75 64 68
Rb+ 166 149 148 Zr4+ 86 87 80
Cs+ 181 165 169 Ce 4+ 101 102 101
The ionic radius for J1 is astonishingly high. This high value appears due to the presence of a
single charge in the nucleus which weakly binds the two outer electrons. Besides this, the electrons
repel strongly each other and screen each other from facing the nuclear charge.
It is interesting to note that in the alkali hydrides, the Pauling's high value for 11 is never attained
(see Table 11.3.4.2) and it gradually increases with the increase of electropositive character of the
alkali metal. In other words, with the increase 0/ covalency (i.e. the increase 0/ polarisation) the
ionic radius/or J1 decreases. The value reported by Goldschmidt is the crystalographic value obtained
for CsH.
ry
Table 11.3.4.2. Apparent radius of H- in C:\lkali metal hydrides.
ra
Compound RO(W-H-) rH-=Ro-rw
!pm) (pm)
ib
LiH 204 126
NaH 244 146
285 152
yl
KH
RbH 302 153
CsH 319 154
m
The nonattainability ofthe high valuefor 11 calculated by Pauling is due to the easy compressibility
he
of the diffuse 11 in which the electrons are loosely bound and a certain degree of covalency (which
cannot be avoided for a such polarisable anion) in the M - H bond. With the increase of covalency,
lc
the radius of an anion decreases. The effect of covalency o.n the radius of 11 is nicely reflected (see
Table 11.3.4.2) in the alkali metal hydrides. In LiH, the covalency is maximum and hence the ionic
ea
radius of 11 is minimum in LiH.

Compared to the traditional ionic radii, the Shannon's crystal radii are better to represent the
th
reality. The Shannon's crystal radii take care of partial covalency present !n the systems and these
ionic radii are generally larger for the cations and smaller for the anions than the traditional ionic radii.
e/
11.4 FACTORS AFFECTING THE IONIC RADII

t.m
(i) Principal quantum number for the outermost electrons: In general, we have the relation (see
Eqn. 11.3.2.4),
2
r ion = Cn 2/(Zion - S) = Cn /Zi: n,
where C is a constant and n is the principal quantum number for the outermost electrons. Thus
with the increase of n, the radius increases. But we should simultaneously consider both the
factors nand 'L. If'L remains more or less constant then the radius increases with the n as in the
alkali metal ions and nonmetals (specially away from the transition metals) ofGr VI (16), VII
(17). But ifboth nand 'L increase simultaneously at a comparable rate as in the heavier transition
metals, then the variation of r ion with the n"is not so marked. These aspects have been discussed
in detail in discussing the periodic trends of radii ofthe ions (see Sec. 8.10).
Li+ (90 pm) < Na+ (116 pm) < ~ (152 pm)'< Rb+ (166 pm) < Cs+ (181 pm) (Shannon's values)
r (119 pm) < C, (167 pm) < Br- (182 pm) < 1 (206 pm) (Shannon's values)
Hydrated ions vs. Bare ions

The smaller bare ions are more hydrated because of their higher electrical field intensity compared
to the larger bare ions. Thus size sequence ofthe hydrated ions very often opposes the size sequence
ofthe bare ions.
Size of hydrated ions: Li+ > Na+ > ~ > Rb+
Size of bare ions: Li+ <: Na+ < ~ < Rb+
(ii) Charge on the ion: With the increase of positive charge (more correctly, the effective nuclear
ry
charge, 2*) on the cation (retaining the same outermost principal quantum number for the outermost
electrons whose radial distribution function governs the size of the ion), the outermost electrons
ra
experience an increased attraction towards the nucleus. Thus with the increase of positive
charge of the cation, there is a shrinkage in the size.
ib
Fe 2+(75 pm) > Fe 3+(53 pm); Pb 2+(120 pm) > Pb 4+ (84 pm);
Mn 2+ (80 pm) > Mn 3+ (66 pm) > Mn 4+ (54 pm).
yl
These are the Pauling radii.
m
• Covalent radii vs.. ionic radii: The covalent or atomic radii are always larger than the cationic
radii. For examples (Pauling's value) :
he
Li (152 pm) > Li+ (60 pm) ; K (231 pm) > ~ (133 pm); Ba (217 pm) > Ba2+ (135 pm).
It occurs so, because in these cations, the outermost principal quantum number decreases by
lc
unity compared to the neutral species. Besides this, the enhanced positive charge on the cationic
species also favours the size shrinkage.
ea
For the anions, an increased negative charge increases the electron-electron repulsion and decreases
the effective nuclear charge experienced by the outermost electrons and as a result, with the
th
increase of charge on an anion, the size increases. This is why, the anionic radii are larger than
their corresponding covalent or atomic radii. For examples (Pauling's value) :
e/
C, (181 pm) > Cl (99 pm); (j2- (140 pm) > 0 (66 pm); 82- (184 pm) > 8 (104 pm).
t.m
Here it is worth mentioning that the increase of anionic charge contracts the interionic
cation-anion separation due to the increased Coulombic interaction. This fact tends to introduce
a shrinkage in the anionic radius with the increase of the anionic charge. This aspect will be
illustrated in the case of isosteric anions (see Table 11.4.2).
• Lanthanides and actinides: By considering the effect of Z and relativistic effect, the lanthanide
and actinide contractions have been explained in Sec. 8.9.
La3+ (117 pm) > Nd3+ (112 pm) > Gd3+ (108 pm) > H0 3+ (104 pm) > Lu3+ (100 pm)
- - - - -....) Increasing trend of 2* along the period from left to right
• Halide vs. halate : In this connection, it is interesting to consider the trend of ionic radii of the
halides in comparison with that of their oxyanions.
1 (206 pm) > Br- (182 pm) > C, (167 pm) (Shannon's data for C.N. = 6, an effect
of the principal quantum number of the outermost electrons)
while, CIO; (157 pm) > BrO; (140 pm) > /0; (108 pm) (thermochemical data).
It is not fully justified to compare the thermochemical radii of the halate ions with the ionic radii
of their corresponding halides, but still, the reverse trendfor the two series is really int~esting.
In the halates, the central atom is in +S oxidation state. For the h~avier congeners of XS't",
presence of low shielding d- and I-electrons leads to more effective nuclear charge
experienced by the electrons at the periphery.
• !sosteric species: Now let us consider the effect of charge on the ionic radii among the isosteric
species having identical extranuclear configurations. Two factors work. (a) For the cationic
isosteric species, the ionic radius decreases rapidly with the increase of positive charge. This is
ry
in conformity with the prediction from the relation, r ion = Cn2/(Zion - S) (for the isosteric species
Cn 2 is constant). (b) In addition to the above factor, the increased cationic charge attracts the
ra
coordinating surrounding anions more closely resulting a shrinkage in the interionic separation
and hence in the ionic radii. Thus the two factors work in the same direction to decrease the ionic
ib
radius.
yl
Table 11.4.1. Ionic radii of some isosteric cations
Ion: Na+ Mg'l+ A13+ Si4+ IC" Ca2+ Sc 3+ T;4+ Au+ Hg'l+ T13+ Pb4+
m
Electronic configuration : +- [He]2s22p6~ +- [Ne]3s23p6~ +- [Xe]4f45dl0~
he
Total no. of extra-nuclear electrons: +--10 ) +--18 ) +--78 )
Units of nuclear positive charge: 11 12 13 14 19 20 21 22 79 80 81 82

lc
Radius (in pm) (Pauling's value) : 95 65 50 41 133 99 81 68 137 110 95 84

ea
Now let us consider the isosteric anionic species (see Table 11.4.2). It is evident that with the
increase of the anionic charge, the anionic radii change but not so markedly in contrast to the
th
isosteric cationic species. The fact can be rationalised by considering the two opposing factors.
(a) The increased electron density increases the electron-electron repulsion and decreases the
e/
.effective nuclear charge to be experienced by the outermost electrons. This aspect increases the
ionic radii. (b) But due to the increased anionic charge, the Coulombic attraction betw~en the
t.m
cation and anion increases. and consequently the interionic separation shortens. It leads to a
shrinkage in the anionic radii. This fact is also concluded from the Born equation (see Sec. 11.7),
Le.
1/<n -I)
Ro = (r+ + rJ; and, Ro oc ( z+~- ) (cf. Eqn.I1.3.2.8); and Ii ='i (i)-2/(n -I), (cf. Eqn. 11.3.2.14)
Table 11.4.2. Ionic radii of some Isosteric anions

Ion: N3- (j2- r p3- S2- C, Se 2- Br-
Electronic configuration : +- [He ]2s22p6~ +- [Ne]3s23p6~ +- [Ar]3d I 04s24p6------+

Total no. of extranuclear electrons: +--10 ) ~18 ) ~36 )
Units of nuclear positive charge: 7 8 9 15 16 17 34 35

Radius (in pm) (Pauling's value) : 170 140 136 212 184 181 198 195
Because ofthe two opposingfactors, the ionic radius does not change so remarkably with the
change ofcharge on the isosteric anions.
(iii) Influence of coordination number, Le. crystal geometry: With the increase of coordination
number, the interionic separation and consequently the ionic radius increases. It is due to the fact
that the more the number of surrounding ions, the less is the share of the attraction to be
experienced by each of the oppositely charged ions. In addition to this, it can be said that with the
increase of coordination number, to avoid the steric hindrance among the coordinating or
surrounding ions they tend to keep themselves away from the central ion. For example, if 8 CI
ions instead of 6 CI ions are to coordinate the central ion, e.g. Na+, then the CI ions in the 8
ry
coordination system cannot approach towards the Na+ ion up to the distance as attained by the
CI ions in the 6 coordination system. Ifwe want to place the 8 CI ions at the same distance as in
ra
the 6 coordination number, then there will be a severe repulsion among the CI ions due to the
steric hindrance. This is why, the interionic separation between the adjacent opposite ions always
ib
increases with the increase of the coordination number.
The fact can be quantitatively supported by the Born equation (see Sec. 11.7) which leads to :
yl
I/(n-l) ( )I/(n-I)
Ro =r + r_ = nB 41tEO = n41tE o (B I A)I/(n-1)
+ ( AZ+Z-e 2 )
m Z+Z-e 2
From the above equation, it is evident that the interionic separation (Ro) depends on B, i.e. the
he
type ofthe crystal. Ifwe consider that an ionic compound AB may be crystallised in both common
salt structure (i.e. NaCI, 6:6) and cesium chloride structure (i.e. CsCI, 8:8), then the interionic
lc
separations (Ro) in AB in ,the two forms are related as follows:
Ro{NaCl} 1Ro(C.vCl) = [(BNaCl~.vCl )/(Bc.vC1ANaCI )]I/(n -I)

ea
where B measures the short range repulsive force. Hence to measure B, we can reasonably
th
consider the only nearest neighbours. Thus we get:

BNacIBCsC/ = 6/8
e/
The ratio of the Madelung constants is given by,

t.m
AcscIANaC/= 1.76267/1.7~.755 ~ 1.0

Thus, RO(NaCr/RO(CsCl) = (BNacIBCsc/)I/(n - I) = (6/8)1/(n - 1).
For, n = 9 (Le. Ar gas configuration), RO(NaCdRO(Cscl) = 0.965.

Thus if a compound exists in both NaCl and CsCl structure, the interionic separation in the
CsCI crystal will be - 30/0 larger than that in the NaCI structure. Similar calculations may be
done for other crystals to illustrate the dependance of ionic radii on the crystal structure. It is
found that the interionic separation in the NaCl structure is ,..., 5% more compared to that in the
zinc blende (ZnS) structure. Thus we can write,
Coordination No : (ZnS, Zn - blende, 4:4), (NaCl, 6:6), (CsCl, 8:8)
Ro(=r++rJ 0.95 1.00 1.037
(relatively)
C.N. : 4 5 6 . 7 8 12
r(Na+) (pm): 112 114 116 125 132 138
Thus it is evident that the absolute difference in the values for different crystals is not significantly
large. But, ifrequired, we can use the multiplication factors to compute the ionic radii from one
crystal system to another. Here it is important to mention that the Pauling's radii were calculated
assuming the 6:6 coordination number as in NaCI and NaF.
(iv) Influence ofthe radius ratio: As the radius ratio (r+/r_) tends to the lower limiting value for a
particular geometry, the anion-anion repulsion increases (see Sec. 11.8) and it will tend to
increase the interionic separation and consequently the ionic radii. For the octahedral geometry
as in the NaCI structure, the limiting radius ratio is -- 0.41 and the structure can be attained in the
ry
range of ratio -- 0.41 to 0.73. However, if the radius ratio tends to the limiting value, 0.41
then the interionic separation increases. It is evident from Table 11.4.3.
ra
Table 11.4.3. Effect of radius ratio on the interionic separation (in pm) in
ib
NaC/type (6 : 6) structure
Compound Ro=r++r_ Ro (experimental)
yl
(calculated from
Pauling's radii)
m
RbBr 0.76 343 343
KBr 0.68 328 329
he
NaBr 0.49 290 298
lc
In computing the Pauling's radii, no such anion-anion repulsion was considered. In fact, no
such repulsion exists in reality when r+/r_ ~ 0.7 as in NaF. Thus for the systems having the radius
ea
ratio -- 0.7, there is no discrepancy between the experimental and calculated value, but as the
ratio tends to the limiting value (e.g. 0.41 in the octahedral system), the repulsion increases to
th
increases the interionic separation leading to an appreciable discrepancy. In explaining the

relatively lower melting points (see Fig. 11.7.5.1) of LiF (r+/r_ = 0.44) and Nal (r+/r_ = 0.44),
e/
the anion-anion repulsion was considered to reduce the cohesive energy. Fig. 11.7.5.1 thus
establishes the fact that in tending towards the lower (r+/r_) limiting radius ratio value, the anion-
t.m
anion repulsion increases.

(v) Effect ofpolarisation (i.e. covalency) : The ionic radius of a particular ion in a compound is
dependent on the degree of polarisation or covalency present in the compound. With the increase
of covalency, the radius of a cation increases while the rodius of an anion decreases. The
effect of covalency on the radius of !1 is well noted in the alkali metal hydrides (see Table
11.3.4.2). If in attaining the covalency, the cation utilises its new principal quantum number as in
the case of alkali and alkaline earth cations, the size of the cation gets remarkably increased. The
alkali and alkaline earth cations use the next outer ns orbital to introduce the covalency.
(vi) Crystalfield effect: In terms of crystal field theory (eFT), a transition metal ion in an octahedral
geometry shows a lower value of its ionic radius in low spin state compared to its value in high
spin state. In fact, various factors /ike spin state, geometry and electronic configuration are
important to determine the crystal radii oftransition metal ions. Discussion on these aspects is
beyond the scope of the present book.
In octahedral systems some representative Shannon's values (in pm) are:
Ions: c,-2+ Mn 2+ Fe 2+ Co 2+ Fe 3+ co3+

r (low spin) : 87 81 75 79 69 68
r (high spin) : 94 97 92 89 78 75
11.5 ENERGETICS OF IONIC BOND FORMATION: BORN-HABER CYCLE

11.5.1 Born-Haber Cycle in Ionic Bond Formation
ry
In predicting the possibility of an ionic bond formation in a particular compound, it is more important
to consider the energetics of the process of formation rather than the concept of attaining the stable
ra
electronic configuration of the constituent ions in the compound under consideration. If the process is
exothermic· (Le. Mi < 0) the compound is stable, but' if the process is endothermic (Le. Mi > 0) the
ib
compound is unstable. The enthalpy change (Le. M-l) of the process can be computed from the Bom-
Habe~ cycle which is based on the basic principle (Hess's law) of thermochemistry. Mi being a state
yl
function does not depend on the path through which the process is carried out but on the initial and final
state.
m
Ml ofthe process leading to an ionic crystal may be obtained experimentally by the direct combination
of the constituent elements. It can also be computed by using the Born-Haber cycle which involves the
he
following steps:
(i) Vaporisation of the involved reactant elements.
lc
(ii) Formation of the required ions from the isolated gaseous atoms.
(iii) Combination of the gaseous ions to produce the solid product.
ea
To illustrate the principle of Born-Haber cycle, let us consider the formation of the simple ionic
compound u+-X- (e.g. NaCl) in computing the standard molar enthalpy of formation (Mit) which is
defined as the change of enthalpy in the formation of one mole of the ionic compound u+-X- from its
th
constituent elements in their most stable physical states at 298 K and 1 atm. pressure.
Formation of u+-X- can be considered to take place in two paths (assuming M and X2 to exist in solid
e/
and gaseous state respectively at ordinary condition) as shown in the Scheme 11.5.1.1.
t.m
/iHsub Ii H'E
1 - - - ' . M(g) - - -.... M(g)
+ I
tJ.HEA • X(g)!
=
MX(s)
- - - - -Scheme- 11.5.1.1. Possible paths leading to the formation of M+ X- crystal.

* More correctly, to predict the stability we should consider ~G (= MI- TM) rather MI alone. But in the formation
of an ionic lattice starting from a solid metallic crystal, AS is not very much significant. Here, at an ordinary
condition consideration of MI predicts almost the correct result.
Path II consists of the following steps :

(i) First step: It involves t~e sublimation of solid M into its vapour. It requires the sublimation
energy, tJlsub .
(ii) Second step : It involves the ionisation of the isolated gaseous atoms of M. It requires the
ionisation energy (Le. first IE), tJl1E.
(iii) Third step: It involves 'the bond dissociation ofthe halogen gas X 2 (say C/2) to fonn gaseous
atoms. As the process requires half mole of X2 to fonn one mole of MX, the requirement of
1
ry
energy is 2" 8Hdi.'tS ·
(iv) Fourth step: It involves the gaining of an electron by the isolated gaseous atom (X) to fonn
ra
X-. It measures the electron affinity, tJlEA •
(v) Final step: It involves the combination of the oppositely charged isolated gaseous ions (in
ib
the gaseous phase, they may exist as ionp~irs, but here we are ignoring this aspect for the
sake of simplicity) to fonn a solid crystal in which the omnidirectional electrostatic force
yl
4
works throughout the crystal. It leads to the release of lattice energy, UMX. Thus, we get the
following relation with appropriate signs ofthe energy terms (according to the convention of
m
thennodynamics).
he
1
8Hf =~H.'tuh +tJl1E +'2 8Hdi:U +~HEA +UMX ...(11.5.1.1)
From the standard convention ofthermodynamics, when the energy is released (Le. exothennic)
lc
it is associated with a negative sign (-ve) while for the energy requiring (Le. endothennic)
ea
process, the energy term is associated with a positive sign (+ve). In fonning the lattice from
the isolated gaseous ions, the energy measured by lattice energy (UMX) is released. Generally
the energy tenn (tJlEA ) measuring the electron affinity is exothennic.
th
In the case of NaC/, by using the calculated value of lattice energy and other energy tenns
e/
experimentally detennined, let us calculate the enthalpy of formation (tJI}98). tJlsub = 108.8
1
kJ mol-I, tJl1E = 493.8 kJ mol-I, "2 (tJldiss) = 121.3 kJ mol-I, tJlEA = -348.5 kJ mol-I, UNaCI
t.m
= -757.3 kJ mol-I. By using these energy values in Eqn. 11.5.1.1 we get, Mlf = - 381.9 kJ
mol-I. This calculated value can be compared with the experimental one, - 411 kJ mol-I. The
calculation from the Born-Haber cycle shows that the fonnation of Na+C/~) is exothennic
and it occurs so in reality.
11.5.2 Drawbacks in the Concept of Born-Haber Cycle

The calculated values of lattice energy or electron affinity from the Born-Haber cycle are found to
deviate significantly in many cases from the values reported from other reliable sources. It is due to the
fact that in constructing the Born-Haber cycle, 100% ionic character is considered, but in reality, in
many cases this approximation does not agree with the actual nature of bonding existing in the
compounds. When the degree of covalency as predicted from the Fajans' rules becomes significant, the
discrepancy between the prediction from the Born-Haber cycle and the finding from other sources
becomes prominant.
11.5.3 Factors Favouring the Formation of Ionic Bonds

From the consideration of the Born-Haber cycle representing the formation of an ionic bond, it is
evident that the sublimation energy· (t:Jlsub) of M(s) and bond dissociation energy (t:Jldiss ) of X 2 are
always positive (Le. endothermic) though these values are relatively smaller compared to the other
terms involved. The ionisation energy of Mg is always positive. The electron affinity process leading to
X(~) for the halogens is exothermic but for the chalcogens leading to X't;) , it is positive (because
during the second electron capture, X~) is forced to accept the second electron in spite of the
severe electron-electron repulsion). However, in all the cases, the summation of sublimation energy
ry
of M(s)' half of the bond dissociation energy of X 2(g)' ionisation energy of M(g) and electron affinity
energy of X(g) is always positive. Thus to make the overall proc·ess exothermic, the lattice energy
ra
(exothermic) should be high. Therefore, in general we can conclude for the formation of ionic MX as :
1
ib
IUMX I>1 (Ml sub +-Mldiss +Ml/E + Ml EA ) I
2
Thus to favour the formation of an ionic compound, the following factors are to be considered.
yl
(i) Low sublimation energy ofthe metal and low bond dissociation energy ofthe nonmetal: The
values ofsublimation energy (t:Jlsub ) and bond dissociation energy (t:Jldiss ) are in general relati~ely
m
smaller compared to the other energy terms involved. The bond dissociation energies for N 2 (941
kJ mol-I) and O2 (507 kJ mol-I) are fairly high, but still compared to the other energy terms these
he
are small. But, for the noble metals, the high sublimation energy may direct the process towards
endothermicity.
lc
(ii) Highly electropositive character of the metal : The ionisation energies of the metal under
consideration should be small. This condition is well satisfied by the alkali and alkaline earth
ea
metals. The ionisation energies increase successively. Hence, a very high positive oxidation
state is not favoured in the formation of an ionic bond. Let uSrtake the case of AICI3•
th
3
AI(s) + - CI2(g) ~ AICI3(s) , 1Vf/(expt)
2 _
= +ve
e/
It requires the successive ionisation energies in the corresponding Born-Haber cycle as follows,
AI(g) ~ A/~) + e, = 577.4 kJ mol-I; AI(~) ~AI't;) +e,tJ./E(2) = 18330.0 kJ mol-I;
t.m
t:Jl/E(l)
AI(2;) ~ Ait;)·+ e, tJ./E(3) = 2703.5 kJ mol-I Le. ~t:Jl/E = 5113.9 kJ mol-I.

Thus, in forming the A/~; ion, the process has become so endothermic that the electron
affinity and lattice energy cannot compensate the endothermicity ofthe process. Hence, Ale/J
is predominantly covalent. However, on hydration (exothermic process) of AICI3 , the process
becomes exothermic giving rise to AI(H20)~+ and 3CI~q. Here it is worth mentioning that the
high positive charge bearing metal ions are highly polarising to introduce a good deal of covalent
character in the compounds.
AlCl3 (significantly covalent) Hydration) Hydrated A13+ and cr ions, (Exothermic process)
(iii) High electron affinity of the nonmetal: The electron affinity (which leads to the release of
energy) of the nonmetal under consideration should be high, so that it can help to direct the
whole process in the exothermic direction. Formation of high negative charge bearing anions
such as N 3-, p3-, etc. is so endothermic that they can never exist in the ionic compounds. In fact,
such anions are highly polarisable to favour covalen~y rather than ionic v~lency.
(iv) High lattice energy: The lattice energy (exothermic process) should be high to favour the process.
The lattice energy whi~h is a Coulombic energy (extending throughout the cluster) depends on
the product ofthe charges ofthe cation and anion involved, interionic separation, and the Madelung
constant A (Le. geometry of the crystal) of the crystal structure. It is related as follows:
U ex (z+)(Z-), U ex I/(r+ + r_), and U ex A
All the above factors should run in favour to direct the overall process in the exothermic direction.
ry
From the standpoint of electron affinity, formation of (jl- is energetically unfavourable, but
many o~ides are ionic because of the high lattice energy, a consequence of higher charge. It
ra
is evident that the small ions such as r, (jl- are the better candidates for forming the ionic
compounds. These inyolved factors will be discussed at a greater length in Sec. 11.7.5.
ib
From tpe above discussion, it is evident that the conditions predicted for the formation of an
ionic compound from the concept of energetics in the light of the involved Born-Haber cycel are
yl
in conformity with the predictIons from the Fajans' rule. These aspects are compared below.
m
Nature 0/ the ions Predictio1Jfrom Fajans' Rule Prediction/rom Born-Haber cycle
(i) High charge on the cation High polarising power High ionisation energies make Mlf positive
he
disfavours ionic bonding to disfavour ionic bonding
(ii) High charge on the anion High polarisability disfavours High endothermicity in creating the highly
lc
ionic bonding charged anions disfavours t:JIf . Besides

this, the large ionic radius lowers the lattice
energy to disfavour ionic bonding
ea
th
11.6 APPLICATIONS OF BORN-HABER CYCLE

(i) Computation of lattice energy : The lattice energy of a particular ionic compound can be
e/
determined by using Eqn. 11.5.1.1 from the knowledge ofthe other energy terms (with appropriate
t.m
signs) involved. Except the electron affinity, other energy terms such as heat offormation (Mf),
ionisation energy (MfIE ), sublimation energy (Mfsub ) can be experimentally determined. MfEA
can be taken from other sources (generally determined by using the Born-Haber cycle for other
compounds containing the species under consideration). Here it is worth remembering that the
method does not work good when the degree of covalency is significant. A comparison between
the Born-Haber value and the calculated value by considering the electrostatic interaction is
shown in Table 11.7.2.1.
Here it is worth mentioning that ~he Born-Haber value is an experimen~1 quantity which takes
care of both electrostatic interaction and crystal field stabilisation energy (CFSE), if any, but the
theoretically calculated value only considers the electrostatic interaction. Hence the agreement is
good only when CFSE is zero.
(ii) Computation of electron affinity : By using the Born-Lande equation (see Sec. 11.7.1), the
lattice energy of a particular ionic compound can be theoretically calculated. By using the
calculated value of lattice energy and other energy terms (with appropriate signs) which can be
experimentally detennined, the electron affinity of the concerned element can be calculated from
Eqn. 11.5.1.1. Here it is worth mentioning that it is very difficult to detennine the elctron affinity
by any other method. But, for the compounds having a good degree of covalency, the
procedure is not applicable.
The application of the process can be illustrated in evaluating the electron affinity of chlorine
from different alkali metal chlorides which are predominantly ionic. These are shown in Table
11.6.1.
ry
Table 11.6.1. Born-Haber data for alkali metal chlorides to evaluate the electron affinity of
chlorine (in kJ mol-1)
ra
Compound -Mlf(MCl) Mlsub(M) Mldiss(C/2 ) "MIIE(M) -VMC1 -MlEA(Cl)
(MCI)
ib
LiCI 405.9 163..2 · 242.7 518.9 841.2 368.2
NaCI 410.1 108.8 242.7 493.8 770.0 364.1
yl
KCI 435.2 83.7 242.7 418.5 703.1 355.7.
RbCI 439.4 79.5 242.7 401.7 678.0 364.0
m
From this table, it is evident that the almost constancy in the calculated values of ~EA(C1) evidences
he
the validity of the procedure. The direct detennination of electron affinity of chlorine from the
electron emission experiments gives the value 360 kJ mol-I which is in good confonnity with the
lc
calculated value.
In this way, the electron affinity of many other species can be calculated.
ea
(iii) Computation of proton affinity : The Born-Haber cycle can· be used to detennine the proton
affinity of a species. The proton affinity of a chemical species X is measured by the enthalpy
th
change (MlpA ) in the process, X(g) + H"fg) ~ HX~). From the definition, proton affinity =
- MlpA (cf. definition of electron affinity). Let us illustrate the process for NH3• The lattice
e/
energy of the ammonium salt (say, NH4Cl) is to be detennined first by using the Born-Haber
cycle. Then the following treatment is to be carried out :
t.m
UNH4CI +
I ~HNH4CI
NH4 CI(S) +-- NH4 (g) + CI(g)
I 6HpA(N~)
NH 3(g) + HCI(g) NH 3(g) + H(g) + Cl(g)
AHdiSS(HCI)
""'----------+
r NH 3(g)
AH'E + AHEA(CI)
+ H(g) + CI(g)
where, UNH4CI = lattice energy of NH4Cl, IVlPA( NH3) = - proton affinity of NHl , MIlE =
ionisation energy of H, MlEA = electron a~finity of CI, ~d;ss(HC1) = bond dissociation energy of
HCI, IVl NH4C1 = heat of the reaction, NH3~) + HCI(g) ~ NH4CI(s).
Thus,
/)Jf NH4C1 = t:Jfd;ss(HCf) + t:JfIE + t:JfEA(Cf) + t:JfPA (NH ) + UNH4CI
3
and from the knowledge of the other energy terms, t:JfpA(NH ) can be computed.
. 3
Now let us consider the proton affinity of HzO to be determined. NH4 Cl04 and H 3 0Cl04 have
been found isomorphous and from the comparison ofX-ray maximum intensity reflection of the
two species, they are found to have almost the same crystal constants (Le. axial ratios, interfacial
angles, etc.). Hence it is assumed that they are having almost the same lattice energy Le.
ry
U NH4CI04 = U H30C104.
From the consideration, of two separate cycles as ~one for NH4 CI, we have:
ra
U NH4CI04 = Mf NH4CI04 - [~diSS(HCI04) + t:Jf IE + tJf EA + MI PA( NH 3)]
and, U H3 0C104 = AHH3 0C/0 4 - [t:Jfdiss(HC/04} + MIlE + Ml EA + t:JfPA(H2 0 )]
ib
Equating the above relations, Le. UNH4C104 = UH3OC104' we get:
yl
t:JfNH4C/04 - t:JfPA( NH3) = Mf H30C104
m - AHPA(H20 )
or, /)Jf PA(H2 0 ) = /)Jf H30C/0 4 - Mf NH4CI04 + M-l PA( NH3)
Thus, by using the value of t:JfPA (NH )' the proton affinity of H 20 can be calculated. The proton
he
3
affinities (in gas phase) of NH3 and H20 are 895 kJ mol- 1 and 760 kJ mol- 1 respectively. These
values indicate the amounts ofenergy to be released in the concerned process ofproton acceptance.
lc
(iv) Prediction of stability of an ionic compound: By considering a suitable cycle, the enthalpy of
formation of an ionic compound in question"can be calculated. To evaluate the lattice energy,
ea
Born-Lande equation (see Sec. 11.7.1) can be used and for this purpose, the ionic radii can be
obtained by Pauling's method (see Sec. 11.3.2). If the process is found to be endothermic, the
th
corresponding ionic compound does not form while for the exothermic process it exists. For
example, by using some approximations, t:Jf1 for NaCl2 has been found to be highly positive.
e/
Hence it cannot exist.

Let us consider the predictive stability of the compound dioxygenyl tetrafluoroborate, 0;BF4-.
t.m
To evaluate the enthalpy of formation, let us consider the following Born-Haber cycle, in which
the elemental fluorine is used as a vigorous oxidising agent to carry out the oxidation of oxygen
molecule to dioxygenyl cation.
~2(9) + BF3(g) + 02(g)~ O;BF.i(s) ....- - - - - - - - - - - .

1~ bond dissociation energy of F2
F(g) + BF3(g) + 02(g)
1 Electron affinity of F
F (g) + BF3(g) + 02(g)
1 Formation of B~g)
- + 0-.
BF4(g) -~g) .
Ionisation of °2 , BF-(4 g) + 0+2(g)
7
1
All! = ionisation energy of 02 + '2 bond dissociation energy of F2 + electron affinity'i.-of F +
enthalpy offonnation of BF4(g) from Fe;) and BF3(g) + lattice energy. = (1164 + ~x 158 - 326 '
- 385 - 500) = + 32 kJ mol-I.
In calculating the lattice energy, the ionic radii of 0; and BF4- are approximately taken as - 177
pm and - 218 pm respectively from thermochemical data (see Table 11.3.2.2). Then from the
approximate knowledge of r +/r_, the lattice energy is calculated from the Born-Lande equation.
It is found to be -500 ± 20 kJ mol-I. The calculated Mlfis slightly positive. We are to mention
ry
that the lattice energy used is an approximate one. Hence, we can conclude that if at all, the
compound exists, it will have a low stability. In fact, the compound has been synthesised and
ra
the prediction, Le. low stability, has been verified experimentally.
A similar calculation helped Bartlett to predict the existence of Xe + PtFi and it was ultimately
ib
realised.
Similarly, it can be shown that the compound dioxygenyl superoxide (Le. 0;°2) cannot exist
yl
because the corresponding Allfis highly positive (- + 600 kJ mol-I).
(v) Prediction of disproportionation of an ionic compound in its lower oxidation state: Metals
m
generally do not form ionic compounds in their lower oxidation states such as : CaCI, MgCI,
AIO, Zn 20, etc. Instead of these, they form CaCI2, MgCI2, AI20 J , ZnO respectively. From the
he
standpoint of ionisation energies (which are endothermic in nature), formation of the compounds
in the lower oxidation states appears to be mo~e favourable compared to the involvement of the
lc
higher oxidation states which require more ionisation energies for their generation. But this
disfavour in the participation of the higher oxidation states can be easily overcome in many cases
ea
through the enchanced lattice energy (which is exothermic) due to the higher charge and lower
interionic separation.
th
For example, let us consider the relative thermodynamic stabilities (measured by Allf ) of CaF
and CaF2 : Allf(CaF) = - 260 kJ mol~l, Allf(CaF } = - 1243 kJ mol-I. These values are computed
e/
from the corresponding Born-Haber cycles (ander some approximations). It is evident that
independently, CaF should exist but with respect to the following disproportionation process
t.m
leading to CaF2 which is much stabler, CaF becomes nonexistent.

2CaF ~ CaF2 + Ca, (disproportionation)
Here, the enthalpy change (Mf) is given by, Ml = MI/(CaF ) - 2M1/(CaF) = - 1243 - 2 (- 260) =
- 723 kJ mol-I. Here all the species are solid. Hence the eTfect of entropy change (l\S) is of no
significance to predict the direction of the above disproportionation process.
In some cases for the lower oxidation states, the lattice energy is too low to make the overall
process exothermic.
(vi) Prediction of the standard electrode potential (i.e. noblity of the metals) of the metals (cf.
Sec. 16.5.1) : Several factors are involved in measuring the electrode potential (E) of the process,
M(s) ~ MZ;rated + nee In fact, to treat the problem, we are to consider the free energy change,
~G (= MI - Tl\S) in the process, but for the sake of simplicity, to measure the potentials for a
comparison we shall pay attention only to All determined by a suitable Born-Haber cycle. Here
it is worth mentioning that the reactant in the process is solid and the product remains in a
hydrated condition yielding an electrorestriction over the solvent molecules in the hydration
sphere. As a result, the contribution of AS is relatively small compared to that of MI in
determining the position of the process. Thus, flG = - nFE = MI- TM ~ MI, F= faraday; Le. E
is controlled mainly by MI. In fact, for EJ, all the thermodynamic parameters are in standard
states Le. fl(jJ = -nFEJ = tUfJ -Tt:SJ.
To compute the MI, we are to consider the following Born-Haber cycle :
I
Electrode n+
M(S) -------.a M (hydrated) + ne(hydrated)
ry
process
Sublimation j Hydration
ra
(~Hsub) (~Hhyd)
Ionisation M n+
ib
M(g)----------.. (g)+ne
(~HIE)
yl
Thus, under the approximation as stated above, E (electrode potential) is determined by the
summa~ion, Mlsub + MIlE + tufhyd- Here both Mlsub and MIlE are endothermic. Hence to favour
m
the process, Mlhyd (which is exothermic) should be high. The metals having high sublimation
and ionisation energies are noble. The heavy transition metals are in this group, and it is nicely
he
reflected for the heavy metals like, Ag, Au, PI, etc. On the other hand, the low values of Mlsub
and MIlE make the alkali and alkaline earth metals more reactive.
.!. FzIF-
lc
Abnormally high electrode potential ofthe couple: The electron affinity of chlorine
2
is higher than that of fluorine, but the electrode potential of .!. CI2 /Cr (Eo = 1.33 V) is much
ea
~ 2
smaller compared to that of .!. F/F- (Eo = 2.87 V). Apparently it is contradictory but it can be
2
th
explained by considering the involved Born-Haber cycle.

1
e/
+e
1 '2 6Hdiss
2X~) • ~(g) - - -.... XiQ)
t.m
~H~Hhyd t Hydration
Electrode process
'-------------. X(hyd)
Though the electron affinity (MlEA ) favours the couple.!. Cl2 fcr more, the exceedingly small
2
bond dissociation energy of F 2 and high hydration energy of Jr can drive the cycle more in
1 _.
favour of the couple 2" F 2 /F ·
(vii) Prediction of solubility of a compound: For an ionic compound, the Born-Haber cycle involving
the hydration energies and lattice energy is very much important in predicting the solubility of
the compound. This aspect will be discussed in Sec. 13.5.
Here we shall cite two interesting compounds, Aiel] (anhydrous) and Hel (anhydrous) which
are covalent in nature, because tuff values corresponding to the hypothetical ionic compounds
become positive. But these compounds in an aqueous solution dissociate into the constituent
ions. Actually the hydration energies of the ions can compensate the disfavour due to the
high ionisation energies inivolved to produce the ions (i.e. Jr, A/3+). It is worth noting that
though anhydrous AIC/3 is covalent, the hydrated salt AICI3, 6H20 is ionic. For such hydrated
salts, in the Born-Haber cycle, hydration energy is to be incorporated in calculating Mit
3 3
Al(s) +"2 CI2(g) ~ AICI3s ' MIf = +ve; Al(s) +"2 CI2(g) +6H20 ~ AICI3·6H2 0(s) , MIf =. - ve
ry
(viii) Halogen exchange reaction : The reaction, "C - Cl + MF ~ ~C - F + MCI is most
/ /
favoured for CsF. Ifwe construct a Bon-Haber cycle for the reaction, then the overall enthalpy
ra
change will be approximately determined by the lattice energy difference of MF and MCI. MF
will have the lowest lattice energy for CsF and the process will be most favoured.
ib
(ix) Participation of higher oxidation states in ionic bonding: Generally to produce a cation of its
higher oxidation states is disfavoured due to the gradual increase in ionisation energies. But in
yl
such cases,'oxygen and fluorine are highly promising to introduce the ionic character· because
of the facts: (a) high electron affinities of oxygen and fluorine favour the exothermicity, (b)
m
low ionic radii of the small anions favour the lattice energy, (c) in the case of fluorine, the
unusually low bond dissociation energy makes the process more exothermic. It will be shown
he
that oxidative halogenation is very much thermodynamically favoured by F2•
(x) Oxidative halogenation and reductive dehalogenation : For the oxidative halogenation reaction,
lc
.!. X 2 + MX ~ MX 2' the enthalpy change will be controlled mainly by the following factors :
2 _
ea
1
... formation of X- in the reaction "2 X 2 + e ~ X ; it will be favoured most for fluorine having
very low bond dissociation energy and high electron affinity (though chlorine possesses
th
1 _
slightly higher electron affinity), iil fact, "2 F2 + e ~ F is a more favourable process than
e/
1 I2 +e~CI - ;
-C
2
t.m
• second ionisation energy of the metal and it is constant for a particular metal.
• lattice energy difference ofMX and MX2 for which the Madelung constants are different; th~
thermodynamic favour from the lattice energy is measured by :
~ _2_ ,(assuming, r(M+) > r(M 2+) « r(X-)

r(X-)
The above approximation is fairly correct because the anions are, in general, much larger
than the cations. Thus, the thermodynamic favour is maximum for flourine.
For different halogens (considering the same entropic effect for all halogens), the process is
favoured most when X = F because of both lattice energy factor and formation of X -. In
fact, fluorides are well known to stabilise the higher oxidation states of metals e.g. Ag(II),
Co(III), Mn(IV), etc. On the other hand, the reverse reaction, i.e. reductive elimination is
most favoured for X= I. This is why, many higher valent iodides are known to be unstable,
e.g. PbI4, FeI3, CuI2, etc.
11.7 THEORETICAL ASPECTS OF CRYSTAL FORCES:

LATIICE ENERGY OF IONIC CRYSTALS
ry
11.7.~ Born-Lande Equation of Lattice Energy
The model assumes that the ionic crystals are constructed by a well defined and regular orientation of
ra
the oppositely charged ions which are considered to be hard spheres. The ions are held together by the
electrostatic forces..Within the crystal in addition to the Coulombic forces, there is a short range
ib
repulsive force. When the two ions approach each other, their electron clouds gradually experience a
repulsive force. Thus the repulsive force originates due to the interpenetration of the electron clouds.
yl
At the equilibrium, the attractive and repulsive forces get mutually balanced.
The short range repulsive potential due to the interpenetration of the electron clouds is given by bl
m
r" as suggested by Born where r is the internuclear separation, n is the Born exponent (a constant), and
b is a constant called repulsive coefficient in a particular lattice.
he
Thus the total potential energy is due to both the Coulombic potential and short range repulsive
potential, very often referred to as Born repulsive potential. For a pair of ions of charges Zle and Z2e,
.the potential energy, E for the ion pair is given by : .
lc
2
Z e
E = ZI (= Coulombic potential) +.!!..-- (= Born repulsive potential) .. ~(11.7.1.1)
ea
2
n
41tEor r
In the actual crystal, we are to take care of all the possible interactions developed from all the ions
th
throughout the crystal. Thus the potential energy U; for an

ion having the charge Z,e in an ionic crystal
is the sum of the potential energy terms originating from the interaction with each of the ions in the
e/
lattice. It is given by :
t.m
_" ZjZje 2 b
U. - L..J +-) ...(11.7.1.2)
I j ~j [ 47tE rij
O r;
where, rij gives the distance from the i-th ion to thej-th ion. Ifwe start with N-ion pairs (i.e. 2N ions) for
the AB type ionic crystal then the total potential energy, i.e. lattice energy, is given by NU;- The factor
2 is required to eliminate the counting of an interaction twice between the ions in pairs.
The distance r ij can be expressed in terms of the nearest interionic distance, R as follows:
rij = aij R ... (11.7.1.3)
where aij appears as a proportionality constant which depends on the crystal geometry.
Therefore, from Eqns. 11.7.1.2 and 11.7.1.3, we get:
ZjZje 2 b
u.=
~ [ 41t&oRaij
)
+--
n ...(11.7.1.4)
, anR
J ~I IJ
If the ionic crystal consists of the cations and anions of ,,

charges Z+e and Z-e respectively, then Eqn. 11.7.1.4 is ,,
s;implified as : ,,
...(11.7.1.5) 1 ,,
\
" Repulsive potential
where, ~
,
... (11.7.1.6) ,
"-
ry
... (11.7.1.7)
ra
A plot of Vi vs. R is shown in Fig. 11.7.1.1.
ib
Here the constant A is called the Madelung constant,
and the corresp0!1ding electrostatic energy is desc.ribed as
Interionic separation --+
yl
Madelung energy after the name of the scientist who
calculated the value of the constant. It is a characteristic Fig. 11.7.1.1. Variation of potential
property of the lattice. energy with the interionic separation
m in ionic crystals.
In the olden literature, Coulombic energy (Ecou1 ) was
expressed as :
he
lc
where Z = highest common factor of z+ and Z- (e.g. for NaCI, CaF2, Na20, MgCI2, A120 3, Z = I; for
ea
MgO, Ti02 , Z = 2 ).
The olden M-adelung constant, M is related with the new one A as follows,
th
Z+Z-A
M = 2 ,(Z= highest common factor of zt and Z- ... (11.7.1.9)
e/
Z
However, presently the olden concept is of no use. For the sake of comparison, the values of both M
t.m
and A are given in Table 11.7.1.1.
Table 11.7.1.1. Madelung constants.

Structure A M Coordination
(Present concept) (O/den concept) number
Sodium chloride (NaC/) 1.74756 1.74756 6:6

Cesium chloride (esc/) 1.76267 1.76267 8:8
Zinc blende (ZnS) 1.63806 1.63806 4:4
Wurtzite (ZnS) 1.64132 1.64132 4:4
Rutile (Ti02 ) 2.408 4.816 6:3
Anatase (Ti0 2 ) 2.400 4.800 6:3
Fluorite (CaF2 ) 2.51939 5.03878 8:4
Corundum (A120 3 ) 4.17186 25.03116 6:4
Structure. Bonding and Properties of Ionic Solids and Solid State Chemistry 1005
Now let us use Eqn. 11.7.1.5 and 11.7.1.6 to find out Ecou1 and Madelung constant for NaC/. In the
NaCI structure each Na+ is surrounded as follows (at equilibrium R = Ro) : 6 Cl at Ro ' 12 Na+ at Ji
J2 Ro,8 Cl at Ro' 6 Na+ at J4 Ro' 24 Ct at
13 Ro' 24 Na+ at J5Ro and so on. 16
A similar situation arises in surrounding each Ct. On comparison with Eqn. II~ 7.1.3 we get
uij =Ji, J2, 13, J4, J5, ... in NaCI.
1 [6(Z+ e) (-Z- e) 12(Z+ e) (Z+ e) 8(Z+ e) (-Z- e) 6(Z+ e) (Z+ e) ]

Ecout = 41tE
O
Ji Ro + J2 Ro + .J3 Ro + J4 Ro + ...
ry
ra
ib
-Z+Z-e
2
~ Zj -I.
LJ-uij' (cf.Eqns.II.7.1.5and 11.7.1.6)
47tE o Ro . .Z-
yl
I ~ }
In the present system, Iztl = IZ-I = I, thus E cou1 becomes : m

Ecou• =- 41tE
e
2
(6 12 8 6 24) Ae
Ro Ji - J2 + 13 - J4 + .J5'" =-
41tE Ro
2
he
o o
where the sum of the infinite series converges towards 1.747558. This is the Madelung constant for
the sodium chloride structure.
lc
Though for the AB type crystals, zt/Z- becomes unity, for the AB2 type crystals it is different. For
Ti0 2, CaF2, etc. it is 2. Thus the infinite series representing the Made/ung constant is constant for
ea
an ionic crystal 0/ a given geometry as it depends only on the geometry.

In evaluating the Born repulsive potential which arises due to the interpenetration of the electron
th
clouds, only the nearest interactions are important because it varies inversely with ~. Thus for
Na+ in NaC/, the immediate 6 surrounding Ct ions are only important. Thus in NaC/, B = 6b.
e/
If we consider the lattice energy for a mole of the crystal lattice (AB type) containing an Avogadro
number (N) ion pairs (Le. N ions of each kind), from Eqn. 11.7.1.5, we get:
t.m
2
U=NU. =_ ANZ+Z-e + BN ... (11.7.1.10)
I 41tE R
O
Rn
At equilibrium, Le. R= Ro' the potential energy is minimum. Hence, (dU) =0

dR R=Ro
Thus,
It leads to :
...(11.7.1.11)
AZ+Z- 2 Un-I
B= J e .&'0
and, ...{11.7.1.12)
4XE on
Thus, by using the value of B, from Eq. 11.7.1.12, we get the lattice energy per mole, Uo at the
equilibrium distance Ro (i.e. 'R = Ro),
...{11.7.1.13)
ry
=- 1.39 x 10 S kJ mol -I pm (z+RoZ- A)(1- ;;I )
ra
It is evident that the r.epulsive energy term contributes (lOOln) % to the total energy and n
ib
varies from ~-12. Hence, it contributes ~ 16 - 8%. Thus a small error in n is of no much significance.
yl
This cohesive energy Uo is the Madelung energy at R = Ro multiplied by the factor (I - lIn).
By using the value of B in terms of Ro in Eqn. 11.7.1.10 'we get:
m
2
U=_tVAZ+Z-e [Ro -!(RoIRt] ...(11.7.1.14)
41tEoRo
he
R n
Now using Eqn. 11.7.1.13 in the above Eqn. 11.7.1.14 we get:
lc
nUo [Ro
U= (n-l) R
_!(Yo I
n"
R)n] ... (11.7.1.15)
ea
Eqns. 11.7.1.13 - 11.7.1.15 are called Born-Lande Equations. The Born-Lande equation for
calculating Uo in the cas system is given by :
th
Uo =- NAZ+Z- e
2
.( I)
e/
1-- ...(11.7.1.16)
Ro n
t.m
By using the numerical constants, the Eqn. 11.7.1.13 reduces to :
Uo = - 1389 ~+Z- A (I-;)X 10-10 kJ mol-I; (Ro in m)
I-I 11 In
or, U 0 = - 1389Z+Z-AxI02 (1 - -l)kJ mo;.&'O •
pm, 1 pm = 10- m)
12
Ro . .n
Magnitude of Born exponent: "In expressing the short range repulsive force due to the
interpenetration of the electron clouds, the Born exponent was introduced. The value of n increases
with the increase of electron density around the ions (Table 11.7.1.2).
C,
If the cation and anion have different configurations, then the average value of n is used. In NaCl,
the ions are Na+ (2s 2 2p 6) and (3s 2 3p 6) having n = 7 and 9 respectively. So the average value of
8 = {7 + 9)/2 should be taken for calculation.
Table 11.7.1.2. Values of the Born exponent (n) for various types of ions.
Ion type (Electronic configuration) n
He (is 2 ) 5
Ne(~ 2p 6) 7
Ar (3s 2 3p 6), Cu+ (3s 2 3p 6 3d10 ) 9
Kr ( 4s2 4p6), Ag+ (4s2 4p 6 4d10) 10
Xe (5s 2 5p 6), Au+ (5s 2 5p 6 5d10 ) 12
ry
The repulsive term exponent n can be determined from the knowledge of compressibility (P) of
the crystal at 0 K. When a material is subjected to a uniform pressure, the shrinkage of volume will be
ra
proportional to the pressure change and volume of the material, and the corresponding proportionality
con~tant is called compressibility. Thus, at,O K it is expressed as :
ib
P= -(IIVo) (av)
yl
...(1 1.7. 1. 17)
ap T
From the thermodynamic equation of state, we have: dU = TdS - PdV;
m
or, (aU)T =T(aS)T -P(aV)r;or,(aUlaV)r =T(aSlaV)r- P
he
or,
( au)
av T
= T (ap) _P,
aT v
(by using the Maxwell relation)
lc
or, P=T(:~)v -(~~l

ea
T=OK,p=_(au) ;or, (ap) =_(ol~)

th
Hence, at ... ( 11.7.1.18)

av T av T av T
e/
Combining Eqns. 11.7.1.17 and 11.7.1.18 we get:

1I VoP =(a 2U I av2 )T ••• ( 11.7.1.19)
t.m
To express the potential energy of an ionic crystal in terms of volume, we are. to consider the
volume to be proportional to the cube ofthe interionic distance. Hence, (Ro'R) = (Vo'V)1/3. By using this
relation, Eqn. 11.7.1.15 reduces to :
U= nUo [(Vo/vi
/3 -.!..(Vo/V)n/3]
...(11.7.1.20)
(n -I) n
On differentiation we get:
au nUo [V~/3 Von 1 ]

3
av = - 3 (n -1) V 4/3 - V(1+,./3)
or,
flu =
av 2
nUo
9 (n - 1)
[4 V~13 _
V'/3
(n + 3)VonIJ]
V(2 + n/3)
Under the approximation, V = Vo' we get from the above equation :
nUo(l- n)
2 ...(11.7.1.21)
9 (n -1)V0
Combining, Eqns. 11.7.1.19 and 11.7.1.21 we get:

2
1 nUo n ANz+z-e (n-lJ
T~1l =---2 =-2 x 4 1) -- (using the value ofUofrom Eqn. 11.7.1.13)
y~ 9~ 9~ ~o~~ n
ry
n = 1 + 9Vo!lo(41tEO)
or, ...(11.7.1.22)
ra
ANZ+Z-e 2 p
By determining the compressibility (P), Vo and Ro' n can be computed. Then by using the value of
ib
n, V o can be determined.
yl
11.7.2 Verification of the Born-Lande Equation
(i) Calculation of lattice energy: To apply the Born-Lande equation, we require the knowledge of
m
the Madelung constant for which the knowledge ofthe crystal structure is required. It also requires
the shortest (Le. equilibrium) interionic distance Ro. Both the Ro and geometry of the crystal
he
structure can be determined accurately from the X-ray studies. The Born exponent can be taken
from the standard table or it can be evaluated as discussed earlier. Let us apply the equation to
lc
evaluate V o for NaC/.

A = 1.74756, N= 6.022 x 1023 ion pairs per mole, zt" = 1 ,Z- = 1, e = 1.60 x 10- 19 C,
ea
1 1
EO = 8.854 x to-I 2 C 2 J- I m- I , Ro = 2.81 x to-lOrn, n = 2" [n + (Ne) + ncr (Ar» = 2" (7 + 9) =8.0
Na
th
It leads to Uo = - 754.8 kJ mol-I.

Lattice energy can also be calculated by using the following relation :
e/
U -- - 1389Z+Z_A x 10-
10
- - kJ mo, I-I R0 In
· m. (1 1J
Ro n
t.m
For NaC/, n = 8, Ro = 281 pm = 2.81 x 10- 10 m, Le.

10
U(NaCl) = _ 1389 x 1 x 1 x 1.74756 x 10- x 2 kJ mo)-I = _ 755.85 kJ mo)-I
2.81 x 10- 10 8
Calculation of lattice energy of Th02 adopting the rutile structure (A = 2.519).
R ='r(Th4+) + r«(jl-) = 108 + 126 = 234 pm = 234 x 10- 12 m.
o
n«(jl- : 2s2 2p 6) = 7; n(Th4+ : 6s 26p67so) = 14 (extrapolated value)

. 1( ,
I.e. nav =-
2 7+14)=10.5
10
U(ThO ) =_ 1389 x (4) x (2) x 2.519 x 10- (1- _1_J = -108.22 x 102 kJ mol- 1
2 234 x 10-12 10.5·
A comparison between the calculated (by Born-Lande Eqn.) and experimentally determine<ijBom-
Haber Cycle) values is given in Table 11.7.2.1.
Table 11.7.2.1. Some experimental (Born-Haber cycle) and calculated (Born-Lande equation)
values of lattice energy (in kJ mol-1). In terms of thermodynamic convention, lattice energy
(U) is associated with a negative sign.
Compound Calculated Experimental Difference Structure
(Experi.- Calcu.)
902 914 +12
ry
NaF NaCI
NaCI 755 770 +15 NaCI
KCI 688 701 +13 NaCI
ra
Kl 623 632 +10 NaCI
CsF 723 744 +21 NaCI
ib
CsCI 623 630 +07 CsCI
CaF2 2595 2591 -04 CaF2
yl
SrC/2 2067 2126 +59 CaF2
AgCI 699 904 +205 NaCI
MgBr 2 2138
m2394 +256 Layer
Mgl2 1984 2314 +330 Layer
he
MnF2 2762 2775 +13 Rutile
MnBr2 2176 2440 +264 Layer
lc
Mnl2 2009 2381 +372 Layer

CdF2 2645 2775 +130 CaF2
ea
Cdl2 1988 2436 +448 Layer

HgF2 2611 2762 +151 CaF2
th
The calculated values deviate significantly from the experimental ones in the cases where
polarisation is sufficient to introduce the covalency. This is why, the deviation is significant
e/
for the systems having small cations with a high positive charge and large polarisable anions.
Thus the deviation is larger for the systems having the cations of pseudo noble gas configurations
t.m
compared to those having the cations of inert gas configurations ( e.g. alkali metals).
The deviation is more marked for the systems having the layer type structure. This type ofdeviation
is reasonable, because in the Born-Lande method, the salt was supposed to be 100% ionic
consisting of hard spheres. In spite of the fact, it was a great success to calculate the lattice
energy theoretically. The process is fairly correct, at least for the systems which are predominantly
ionic.
(ii) Calculation of ionic radii : Calculated ionic radii by Born-Lande equation are also supported
experimentally.
11.7.3 Modification of the Born-Lande Equation

Consideration of lOO°A. ionic character (Le. assumption of the hard sphere ions) is only reasonably
valid in few cases where the degree of polarisation is negligibly small. Besides this, the following
corrections are needed for finer calculations.
(i) Inclusion of van der Waals and London dispersion forces: These weak forces always prevail,
but these become appreciable when the degree of polarisation is significant.
(ii) Inclusion of zero-point (Eo) energy : Even at 0 K, the lattice points vibrate and the crystal
possesses the zero-point energy.
(iii) Modification of Born repulsive potential: In calculating the repulsive potential, more rigorous
expressions can be used. The repulsive energy arises from the overlap of the orbitals and the
orbitals decay exponentially. Consequently, the repulsive energy is a function of exp (-RoIp)
where p is a constant. By considering this fact, the following Born-Mayer equation is obtained
ry
in the same way as in the Born-Lande equation.
2
Uo =- AnZ+Z-e ( p)
1 - - ;(p=34.5pm)
ra
...(11.7.3.1)
47tE O Ro Ro
(iv) Temperature correction: Very often, it is required to calculate the lattice energy at higher
ib
temperature rather than at 0 K at which the Born-Lande equation (see Sec. 11.7.1) is strictly
applicable. Hence, at higher temperatures, the correction factors due to the heat capacity must
yl
be taken -into consideration. The correction term M for the MX crystal is given by:
m
T
M = J[CV(U¥) - Cv(M+) - Cv(r)]dT,

he
o
3
where Cv = '2 R, and R is the ideal gas constant. Here the species M(~) and X~) are believed to
lc
behave as the monoatomic ideal gases.

(v) Incorporation of crystal field stabilisation energy: For the transition metal salts, very often
ea
the contribution of crystal field stabilisation energy (CFSE) enhances the lattice energy.
By considering the above facts, more refined equation has been developed as given below by
th
Born, Mayer and Helmholtz :

e/
AZ+Z-e2 N :.- NC
U=- +NBexp(-Roln)--6 +NEo ...(11.7.3.2)
Ro ~
t.m
47tEo
where, 1st term represents the Coulombic energy, 2nd term represents the repulsive energy
proportional to exp (-Rain), 3rd term represents the van der Waals energy involving a constant
C, 4th term denotes the zero-point energy.
By considering these different contributing terms, the lattice energy of NaCl has been calculated
by using the following energy terms:
Coulombic energy = - 860 kJ mol-I,
Repulsion energy = + 99 kJ mol-I,
van der Waals energy = - 13 kJ mol-I,
Zero-point energy = + 8 kJ mol-I
It leads to Uo = - 766 kJ mol-I while Uo (expt) = - 770.3 kJ mol-I. The calculated value from
Born-Lande equation = - 754.8 kJ mol-I.
11.7.4 Kapustlnskll Equation

For the cases where the crystal structure is not known, we cannot determine the Madelung constant. To
predict the possibility of synthesis of a new ion;ic compound it is required to know the approximate
value of the lattice energy. In such cases, the Born-Lande equation has nothing to do with the
problem. This is a serious limitation with the equation. To overcome this difficulty with the Madelung
constant (A), Kapustinskii pointed out a relation between the Madelung constant and the number (v) of
ions present per unit formula. It was found that the ratio of the Madelung constant and the number
of ions per unit formula (i.e. A/v) is essentially constant, ranging from 0.80 (for Rutile) to 0.88
ry
(for CsC!). Based on this fact that the Madelung constant is interrelated with the empirical formula (i.e.
stoichiometry) of the ionic compound, he proposed the following equation (where Ro in pm),
ra
s
1.2xIO vZ+Z- ( 34.5)
Va =- Ro l-R; kJ mol-I, Ro in pm ...{ll.7.4.1)
ib
yl
where v gives the number of ions per formula representation. For example, v = 2 for NaCI, CsCI~ MgO;
v = 3 for CaF2, Ti02, etc. By using Eqn. 11.7.4.1 for NaCI, the calculated lattice energy becomes -752
kJ mol-I.
m
11.7.5 Factors Affecting the Lattice Energy
he
(i) Charge o/the ions: The Born-Lande equation shows that the lattice energy largely depends on
the product of the ionic charges. For example, for a uni-univalent ionic crystal, it ranges from
lc
600- 800 kJ mol-I (two extreme cases: LiF, Uo = - 1004 kJ mol-I and CsI, Uo = - 569.5 kJ
mol-I) while for the van der Waals crystals (i.e., covalent crystals) where no Coulombic potential
ea
exists, it is about 10 to 20 times less. For the crystals consisting of bivalent ions (e.g. MgO, CaO,
BaO) the cohesive energy should be about four times greater compared to that of the uni-
th
univalent salts. This prediction is approximately true. The cohesive energies for CaO and BaO
are -3523 and -3125 kJ mol-I respectively. This high lattice energy can compensate the
e/
endothermicity produced in generating the higher valent ions (e.g. Ca2+, Bcr+, AI3+, Q2-, etc.) to
make the compounds ionic'.
t.m
(ii) Interionic separation: From the Born-Lande equation, it is evident that, Uo ex: 1/(r+ + r_). Thus
the larger ions reduce the lattice energy. For example, LiF (R o = 201 pm), Uo = - 1004 kJ mol-I .
and CsI (R o = 395 pm), Uo = - 569.5 kJ mol-I.
(iii) Madelung constant vs. interionic separation: The lattice energy is directly proportional to the
Madelung constant which depends on the geometry of the crystal. Sometimes, simultaneous
consideration of the contributions originated from both (r+ + rJ and Madelung constant
becomes important in predicting the nature of the crystal geometry to be adopted by some ionic
compounds. Generally, it happens so at the border line 0/ limiting radius ratio (cf. Sec. 11.8).
It has been observed that a number of salts adopt the NaCI structure though they are supposed to
adopt a CsCI structure from the prediction of the radius ratio rule. This/act can be rationalised
by considering the relative values 0/ Madelung constants (A) and interionic separations (R o)
in the two structures. The Madelung constant for CsCI structure is larger than that of the NaCI
structure. Hence, the Madelung constant would tend to increase the lattice energy for the CsCI
structure, but the increased interionic separation in CsC/ would lower the lattice energy. Thus
the Madelung constant and interionic separation contribute in the opposite directions to cancel
the effects each other. Hence the actual structure to be adopted is governed by the relative
magnitudes of the two opposing contributions. It is mainly important when the radius ratio rule
lies at the border line oftwo different geometries. Thus, with respect to the NaC/ structure, if the
larger interionic separation in the CsC/ structure reduces the lattice energy more compared to the
gain in. lattice energy due to the increased Madelung constant in the CsC/ structure, then the
NaC/ structure is energetically more favoured though the adoption ofthe CsC/ structure is permitted
ry
from the radius ratio rule.
• RbBr (CsCI structure vs. NaCI structure) : For example, in the case of RbBr which is having
ra
the radius ratio in the border line of the NaC/ structure (6:6 coordination) and CsC/ structure (8:8
coordination), in attaining the CsC/ structure, with respect to the NaC/ structure the lattice energy
ib
gets increased by 0.88% due to the increased Madelung constant in the CsC/ structure but then it
gets decreased by 3.7% due to the larger interionic separation in the CsC/ structure. This is why,
yl
RbBr adopts the NaCI structure.
• KCI (CsCI structure vs. NaCI structure) : A similar situation arises for KCI which adopts the
m
rock-salt (6:6) type structure though the radius (r + / r _ > 0.73) supports the CsC/type structure
K CI
(8:8). It can be rationalised from the following analysis:
he
r + = 138 pm (for 6 C.N.), = 151 pm (for 8 C.N.), r _ = 181 pm
K a
Ro (for NaC/ type Le. 6:6) = 138 pm + 181 p~ = 319 pm
lc
Ro (for CsC/type, Le. 8:8) = 151 pm + 181 pm = 332 pm

ea
It leads to :
U NaCl type = ANaCl x Ro(CsC/) = 1.747 x 332 ~ 1.03
th
UCsCltype Acsc/ Ro(NaCl) 1.762 319

Thus for the rock-salt type of structure, the lattice energy is relatively larger (about 3%) and this
e/
is why, KCI adopts the rock-salt type structure.

• SrO and BaO (CsCI structure vs. NaCI structure) : In terms of radius ratio, SrO and BaO
t.m
should adopt the CsC/ type structure (cf. Table 11.8.3.2), but in reality ~hey adopt the HaC/ type
structure. It has been illustrated in Sec. 11.8.3iL
(iv) Effect ofthe radius ratio (i.e. r+'rJ : The limiting radius ratio for a particular crystalline geometry
can be calculated (see Sec. 11.8) by considering the ions as hard spheres. The limiting value of
r +/r_ for a particular geometry indicates that if the ratio decreases from the limiting value,
there will be anion-anion repulsions. Thus for the stability, the limiting value gives the minimum
possible value of the ratio. For example, in the NaC/ structure (octahedral symmetry), r+/r_ can
vary from 0.414 to 0.73 and the minimum possible allowed value is 0.414.
In fact, the ions are not nonpolarisable hard spheres. The quantum mechanical analysis establishes
that the concept of ionic radii develops from the radial distribution probability function of the
outermost electron cloud. Thus we can conclude that,for a particular crystalline geometry, as
the r.lr_ value tends to attain the minimum limiting value, the possibility of anion-anion
repulsion gets increased. In other words, the more the away from the minimum limiting r+/r_
value, the less is the possibility of the anion-anion repulsion. The anion-anion repulsion
destabilises the system to reduce the lattice energy. This is why the ionic crystals which are in
the vicinity of the minimum limiting r+/r_ value possess lower lattice energies and consequently
the lower melting points.
The above fact can explain the lower melting points (see Fig. 11.7.5.1) of LiF(r+/r_ 0.44) and
Nal (r+/r_ = 0.44) (which adopt the NaCI structure) with respect to the expected values obtained
by extrapolation of the smooth curves (see Fig. 11.7.5.1). It is interesting to note that for the
other salts which lie on the smooth curye in the graph (except Li salts), the ratios of r+/r_ are far
ry
away from the limiting value (Le. 0.414).
ra
1200
ib
1000
()
yl
0
900 (1.24)
e
.a
m (0.93)
~ 700 (0.80)
!.
E '-(0.78)
~ 500
he
300
Li Na K Rb Cs
lc
Fig. 11.7.5.1. The melting points of th~ alkali metal halides - an effect of radius ratio ('+1'_) calculated
ea
by Pauling's values.
Now let us consider the lithium salts in which except the LiF in all cases, r+/r_ «0.414. But
th
they crystallise in the NaCI structure. Thus, the anion-anion repulsion destabilises the crystals
to lower the lattice energy and melting points. This fact can also be explained (see Sec. 11.8.3)
e/
by considering the enhanced covalency, a consequence of polarisation.

It should be pointed out that in reality due to the covalence, the r+lr_ value increases compared
t.m
to the values calculated by using the concept of nonpolarisable hard sphere models of the
ions.
(v) Matching of sizes of the cations and anions for efficient crystal packing: Large cations
favour large anions to earn the efficient crystal packing (i.e. to favour the lattice energy). If the
cation is small and the anion is large then during crystal packing, the anion-anion repulsion will
disfavour the process. Similarly, if the cation is large and the anion is small, then the cation-
cation repulsion will disfavour the lattice formation. Thus, the cations and anions ofcomparable
size will give an efficient crystal packing. Though, the statement is a qualitative only, it is very
much important in understanding the tendency of hydration and solubility of different salts (cf.
Secs. 11.8.2, 13.6.2).
11.7.6 Hardness of Ionic compounds

Hardness is generally measured in a relative scale (called Moh's scale) and the corresponding numerical
scale ranges from I (talc) to 10 (diamond). A compound which is mechanically stable in scratching on
the surface of a second one is considered to be harder.
Higher lattice energy protects the compound/rom its de/ormation under compression. Thus the
ionic compounds with small and non-polarisable cations and anions are hard. For a particular element,
the hardness follows the sequence :
fluoride> oxide> sulfide
Note : Hardness 0/ elements - depends on many factors like nature of crystal structure, element-
element bond strength, slip systems in the unit cell, etc. The elements having rigid infinite lattices
ry
with strong element-element bonds are hard, e.g. diamond. The elements having neutral layer structure
where the adjacent layers are bonded by weak van der Waals forces are soft, e.g. graphite. In fact,
ra
other layer structured substances like talc, MoS2 , etc are also soft.
Examples of some inogranic hard materials with hardness (in Moh's scale) are given below.
ib
Diamond and boron nitride (BN) (10), Quartz (7.0), Silicon carbide (SiC) (9.3), Tungsten Carbide
(We) (9.0).
11.8 RADIUS RATIO RULE AND PREFERRED STRUCTURES OF

yl
m
IONIC COMPOUNDS
he
11.8.1 Limiting Radius Ratios for Some Common Geometries
In the perfectly ionic compounds, each ion tends to be surrounded by the largest possible number of
lc
oppositely charged ions. The number of these nearest neighbours gives the coordination number.
Considering the ions as hard spheres, attainment of the highest possible coordination number is deter-
ea
mined by the relative size of the cations and anions. In attaining the maximum possible coordination
number, the cations and anions will remain in contact with each other to favour the Madelung energy.
th
In attaining the geometry, the anion-anion repulsion should be minimised. Thus to gain the maximum
Madelung energy in a certain ionic compound, the preferred geometry must satisfy the following points.
e/
(i) Attainment of maximum possible coordination number around each ion by the oppositely
charged ions.
t.m
(ii) The oppositely charged ions will

remain in contact with each other.
(iii) The anion-anion and cation-cation
repulsion in providing the highest
coordination number must be
minimum. I II III
(More anions (No cation-anion (Limiting situation)
The facts are illustrated in Fig. 11.8.1.1 can coordinate) contact but anion-
by considering the case where the highest anion repulsion)
possible coordination number to be attained Fig. 11.8.1.1. Different possible orientations of
is three. Here, Fig. 11.8.1.1 (III) indicates the cations and anions for coordination number three
limiting situation. around the cation.
Mathematically the limiting condition for a particular structure can be predicted by considering the
limiting radius ratio. For example, in the case of coordination number 3, the limiting radius ratio of the
cation and anion (Le. r+Ir_) is 0.155. It means that if the radius ratio is less than this value then it will
lead to destabilise the system due to anion-anion repulsion without the cation-anion contact as
shown in Fig. 11.8.1.1 (II). Similarly, for each structure such as NaCI (6:6), esCI (8:8), ZnS (4:4),
there is a limiting radius ratio. which is different for different structures. Hence, from the knowledge of
radius ratio, we can predict the structure which can be attained by the compounds.
(a) Limiting radius ratio (r+'rJ in a body centred type cubic
(bcc) lattice, i.e. CsCI structure (8:8) : In a body centred
type cubic lattice, the anions are at the comers of the
ry
cubes and the cation is placed at the centre of each cube.
In the limiting condition (see Fig. 11.8.1.2), the spherical
ra
anions will just mutually touch each other along the edge;
and along the body diagonal the cation will remain just
ib
in contact with the two anions (placed at the comers) on
opposite sides. Thus in the condition we have:
yl
edge length of the cube = 2 r_, Le. a = 2r_ ...(11.8.1.1)
and length of the body diagonal of the cube
m
= 2(r+ + r_) = J3 a ...(11.8.1.2) Fig. 11.8.1.2. Determination of
limiting radius ratio in a body
he
where a = edge length of the cube. centred cubic (bee) type lattice.
Thus from Eqns. 11.8.1.1 and 11.8.1.2, we get:
lc
ea
Hence, by considering the ions as noncompressible hard spheres, to attain the 8 coordination
th
number around the cation as in a body centred type cubic lattice (e.g. CsCI structure), the
radius ratio ofr+lr_ must be at least 0.732. /fit is less
e/
than 0.732, it cannot adopt the structure. Thus the

required condition is given by, r+lr_ ~ 0.732.
t.m
(b) Limiting radius ratio in an octahedral lattice, Le. NaCI

structure (6:6) : The limiting situation in an octahedral
lattice is shown in Fig. 11.8.1.3 where four anions are
placed at the comers of a square and the cation is placed
at the centre. One anion remains below the plane and
another anion remains above the plane alQJ1g with the Fig. 11.8.1.3. Determination of
axis (C4 ) passing perpendicularly to the square plane limiting radius ratio in an
through the centre of the square (these two axial anions octahedral (Oh) lattice \ (two
axial positions are not
are not shown in the figure). At the limiting condition shown).
we get:
edge length of the square = 2r_ , Le. a = 2r_ ...(11.8.1.3)
and, length of the diagonal = 2(r+ + r_) = J2 a ... (11.8.1.4)
where a = edge length of the square.
8
From the above equations, we get :
,,
Thus to attain the octahedral lattice, Le. 6 coordination ,,
number around the cation, it must have, r+lr_~ 0.414. ~.+
(c) Limiting radius ratio in a tetrahedral lattice, Le. znS
~ ,,,
structure (4:4) : By considering the alternate comers
,,
ry
of a cube, a tetrahedron can be constructed (see Fig.
11.8.1.4). Thus to provide the tetrahedral coordination
ra
geometry around the cation, the cation is placed at the
centre of a cube, and four anions are placed at the Fig. 11.8.1.4. Determination of
ib
four alternate corners of the 'cube. At the limiting limiting radius ratio in a tetrahedral
condition, the two anions mutually touch along the lattice (e.g. ZnS structure).
yl
face diagonal while each anion touches the cation along the body diagonal. Thus in the limiting
condition we get :
length of the face diagonal of the cube
m
= 2r_, Le. Jia ...(11.8.1.5)
he
= 2r_
1 1
and, 2" of the length of the body diagonal = r+ + r_; i.e. 2" (Jja) = r+ + r_ ...(11.8.1.6)
lc
where a = edge length of the cube. Thus, from the above equations we get:
ea
r+ + r_ = Jja. r+ + r_ _ Jj . r+ _ .J6 _1_ 0 225

2r_ 2Jia' or, r_ - Ji' or, r_ - 2 -.
th
Thus, for the tetrahedral arrangement of the anions around a cation the condition, r+/r_ 2::
0.225 must be obtained.
e/
(d) Limiting radius ratio for a planar trigonal lattice (i.e.

t.m
coordination number = 3) : For a planar trigonal lattice, to

introduce the three coordination number around a cation, the
anions are placed at the corners of an equilateral triangle and the
cation is placed at the centre of the triangle (see Fig. 11.8.1.5).
Thus in the limiting stable condition, we get: Fig. 11.8.1.5. Deter-
edge length of the triangle = a = 2r_ ...(11.8.1.7) mination of limiting
2 . 2 radius ratio in a planar
and, 3" of the median = r+ + r_; or, 3" AD = r+ + r_; trigonal lattice.
or, "3 · 600 -r++r_,or,

2 AB SID - . (2/3) aJj _ .
T -r++r_,or, a_
Jj -r++r_ ...(11.8.1.8)
From the above equations we get:

r+ + r_ _ a. r+ + r_ _. 2. r+ _ 2 _
- - - ~ ,or,--- ~,or-- ~-1-0.155
2r_ v3a r_ "13 r_ "13
Thus the limiting condition for attaining the coordination number 3 around the cation is
given by, r+/r_ ~ 0.155. If the radius ratio of ,+,,_
falls below the value 0.155; then no
crystal lattice except the linear arrangement of the ions is possible. As a matter of fact,
for such low values, r+/r_ < 0.20 , the cationic charge density is tremendously increased
giving rise to a high polarising power to the cation. Under the circumstances, the compounds
become predominantly covalent.
Limiting radius ratios for other geometries and coordination numbers (C.N.) are given in
Table 11.8.1.1.
ry
Table 11.8.1.1. Limiting radius ratios for some geometries
ra
Geometry C.N. Limiting radius
(around the cation) ratio (r+/r j
ib
Trigonal prism 6 0.528
Capped octahedron 7 0.592
yl
Dodec~hedron 8 0.668
Icosohedron 12 0.902
Cubooctahedron
m 12 1.000
he
These geometries are not important in ionic compounds.
11.8.2 Application of the Radius Ratio Rule

lc
(i) Prediction of the crystal geometry : By considering the limiting radius ratios for different
ea
possible geometries, it is possible to predict the geometrical structure and coordination number
to be adopted in a particular ionic crystal. Ifwe consider the arrangement of X moietes around A,
we are required to consider the radius ratio, rA /rx. This aspect is illustrated in Table 11.8.2.1.
th
Table 11.8.2.1. Radius ratio values for different coordination numbers around A by X
e/
Radius ratio Maximum coordination Geometrical arrangement Examples

t.m
(rA/rxJ number around A by X of X around A
Below 0.155 2 Linear

0.155 to 0.225 3 Trigonal planar
0.225 to 0.414 4 Tetrahedral
0.414 to 0.732 4 Square planar
0.414 to 0.732 6 Octahedral NaCI, Ti02
0.732 to 1.000 8 Body centred cubic type CsCI, CaF2
AB type crystals : The predictions from Table 11.8.2.1 are supported by the experimental
observations (see Table 11.8.2.2) in different AB type crystals. In the AB type crystal, r +/r_ < 1 is
considered (but r_/r+ > 1 is not considered). From the values of r+/r_, the coordiination number
around the cation can be predicted from Table 11.18.2.1. The coordination number around the
anion will be the same as the AB type compounds contain the stoichiometry, cation: anion = 1: 1.
1018 Fundamental Concepts of Inorganic Chemistry-
Thus in the AB type crystals, r./r_ determines the coordination number around th~~cation
while the coordination number around the anion is governed by th.e stoichiometry and the
coordinatio!' number ofthe cation and anion will be the same.
AB2 type crystals: Now let us consider the AB2 type crystals such as SrF2, Ti02, K 20, etc.
• In SrF2, r 2+ / r _ = 113/135 = 0.83; and r _ / r 2+ = 1.19. It indicates that the maximum possible
Sr F FSr .
coordination number (C.N.) of sr2+ is 8, and it is also attainable for F -. But from the
stoichiometry it is evident that the C.N. of sr2+ must be twice that of r-. Thus the feasible
ry
arrangement is : C.N. of sr2+ = 8 and C.N. of r = 4 . It is also experimentally verified.
• Similarly in Sn02 where the ratios are: r 4+ /r 2- =0.51, (Le. maximum possible C.N. = 6);
ra
Sn 0
and ro2 - / r + = 1.96. From the stoichiometry, the possible coordination numbers are: C.N. of
Sn4
Sn 4+ ,= 6 (octahedral); and C.N. of (jl- = 3. Thus it adopts the Ti02 structure.
ib
• In K 20, r
o
2- / r
K
+ =1.05; and rK + / r0 2- =0.95. From the stoichiometry, the feasible coordination
yl
numbers are: C.N. of (jl- = 8, and C.N. of ~ = 4. This predicted antijluorite structure is also
supported by the experimental finding.
m
Thus it can be concluded that for the AB2 type crystals, the coordination number of A is
governed by the radius ratio of rAlrs as predicted from the limiting radius ratio rule, while
he
for determining the coordination number of B, the stoichiometry and the coordination
number of A will come in consideration. Thus the coordination number of B is half of the
lc
coordination number attained by A. This aspect is illustrated in Table 11.8.2.3.

ea
Table 11.8.2.2. Verification of the prediction of crystal geometry from the

limiting radius ratio (by using Pauling's value) rule in ABtype crystals
th
Compound r+/r_ Predicted crystal Actual

(A B) geometry geometry
e/
LiF 0.44 NaCI type NaCI type

NaF 0.71 NaCI type NaCltype
t.m
NaCI 0.53 NaCI type NaCI type

NaJ 0.44 NaCI type NaCI type
KBr 0.68 NaCI type NaCI type
KCI 0.73 NaCI type NaCI type
CaS 0.54 NaCI type NaCI type
CaO 0.71 NaCI type NaCI type
CsBr 0.87 CsCI type CsCI type
CsCI 0.93 CsCI type CsCI type
CsJ 0.78 CsCI type CsCI type
ZnS 0.40 ZnS type ZnS type
ZnSe 0.37 ZnS type ZnS type
Table 11.8.2.3. Verification of the radius ratio (using Pauling's value) rule for AB2 type crystals
Compound r~rB Predicted max. C.N. around Predicted Actual crystal

(AB-)
'}/ possible C.N. B = -1 oifthe crvstal
·.r
flJpe
.;,
around A 2
C.N alA type
SrF2 0.84 8 4 Fluorite Fluorite
BaF2 1.00 8 4 Fluorite Fluorite
Ti0 2 0.48 6 3; Rutile Rutile
ry
Sn02 0.51 6 3 Rutile Rutile
MgF2 0.46 6 3 Rutile Rutile
ra
K 20 1.05 8 4 Antifluorite Antifluorite
ib
Thus in many cases the prediction runs in good conformity with the experimental results. Here it
is worth mentioning that it works well for the predominantly ionic compounds. But it yields
yl
poor results in the compounds in which there is a good deal of covalency, and in the
compounds in which the radius ratio lies in the border range of two possible geometries.
These aspects will be discussed later.
m
(ii) Prediction of thermal stability of some ionic compounds (cf. Sec. 10.6.4) : For the very small
he
values ofr+/r_ «< 0.22), the anions are much larger than the cations. In such cases, the compounds
cannot have a good cation- anion contact which stabilises the systems, rather it leads to the
lc
anion-anion repulsion. This is why, the systems having very low values ofr+/r_ are not stable.
Examples of such salts involve the small cations such as L,-+, Be 2+, A/3+, Mg'-+, etc. ,and the large
polyatomic anions like CO;-, C/O; , NO; , SO~- , 02 ' BF4-, etc. or large monoatomic anions
ea
such as Br-, 1. Such systems are thermally unstable because ofthe inefficient crystal packing
and they decompose to form small anions (e.g. (jl- for CO;-, NO;, O~, SO;-, etc.) which
th
introduce the better packing. Some examples are given here.

Li2C03 ~ Li20 +: CO2;7Na202 ~ Na 20 + %O2;
e/
~ BeO + S03; LiBF4 ~ LiF + BFj

t.m
BeS04
Thus for the smaller values of r+ for a particular large anion, the thermal stability falls with the
decrease of r+. This is why, among the alkali metal salts of a particular such large anion, the
lithium salt is the least thermally stable one. Similarly, for the alkaline earth metals, Be-salt of
this type is the least stable one. For example, the thermal stability runs in tHe sequence:
BeCO) (100°C) < MgCO) (300°C) < CaCO) (840°C) < SrCO) (11 OOOC) < BaeO) (1300 0 C)
Here it is worth mentioning that the same results can also be explained by using the concept of
polarising power ofthe cation (see Sec. 10.6.4).
Thermodynamic aspects of a thermal decomposition procesj' : Thermodynamic stability of an
ionic compound depends on the lattice energy. This fact can be explained in a quantitative way
by considering the thermodynamic aspects of a thermal decomposition process. Let us illustrate
the concept by considering MC03(s) as the r~presentative ionic solid.
M(C03)(s)~MO(s)+C02(g),I1G=Ml-TI1S
To make the process thennodynamically feasilbe, !:1G must be negative. The thermodynamic
decomposition temperature (Td) is defined as : &
. . !:1H
li.G =0 = !:1Hd ,-Td ASd ,l.e.Td = AS d
d
Td denotes the temperature at which the decomposition starts. It is given for some representative
metal carbonates (cf. Tables 10.6.4.1 and 11.8.2.4).
Table 11.8.2.4. Thermodynamic parameters for decomposition of MC03
ry
MC0 3 M-Id(kJ mol-I) Md(J K- 1 mol-I) Td(K)
ra
Mg~03 + 100.6 + 175.0 574.8
CaC03 + 178.3 + 160.5 1111.0
ib
SrC03 + 234.6 + 171.0 1372.0
BaC03 + 269.3 + 172.0 1565.7
yl
It is evident from Table 11.8.2.4 that the decomposition entropy (Md ) (which is positive) due to
m
the formation of gaseous CO 2 is almost the same for different metal carbonates. The
decomposition enthalpy (!:1Hd) may be evaluated in tenns of lattice energy as follows:
he
!:1Hd =A - {U(MO) - U(MC03 )} = A -!:1U
lc
Here A is a constant (independent of M) and it is related to the fonnation of CO2• Thus, the
variation trend of !:1Hd is detennined by IiU for a particular series of compounds. The lattice
ea
energy difference (!:1U) is governed by the following equation.

1
!:1U ex: 2 2 - 2 2 (cf. Born-Lande Eqn.)
th
r(M +) + r(O -) r(M +) + r(C03 -)

Lattice energy of the oxide is higher than that ~f the carbonate as r( COi-) > r( 0 2-). It makes
e/
the decomposition process more exothermic. Thus it is evident that the thermodynamic favour
(Le. ent~alpic favour) for the decomposi~ion process arises from the replacement of larger CO;-
t.m
ion by the smaller (jl- in the lattice. If r(M2+) is large, the difference of the two denominators in
the above equation is not very much significant but it becomes significant for the smaller values-
of r(M2+). This is why, the said decomposition process becomes thermodynamically most
favoured for the minimum value of r(M2+) in a particular series of compounds. The same
conclusion can be drawn from the concept of polarisation theory (i.e. Fajans' rule) and efficient
crystal packing model by the solid spheres of the cations and anions.
Dependence of !:1U on the charge of ~ can be expressed as follows:
!:1U ex: n { 1 _ 1 }
r(M n +) + r(02-) r(M n +) + r(CO;-)
Z+Z- ]
cf U ex: ~' Born-Lande equation
(
This indicates that the thermal decomposition is favoured more for the higher values of n. This is
why the alkaline earth carbonates (M2+) are thermodynamically less stable than the alkali
metal carbonates (M").
In the same way, solubilisation of different ionic solids can be explained by considering the
relative contribution of lattice energy and solvation energy and they depend differently on the
ionic radii (cf. Sec. 13.5.2).
(iii) Prediction of tendency of the metal ions to form hydrated salts : The salts having very low
values of r+/r_, Le. salts involving small cations and large anions, suffer from unfavourable
packing (Le. anion-anion repulsion) as discussed earlier. Such salts like MgC/04 , LiC/04, etc.
ry
tend to form hydrated salts in which the cations get surrounded by the water molecules at least
partially to increase the effective size of the metal ion, e.g. LiC/04 --+ LiC/04, 3H20
ra
. L+ C/O-) H
( I.e. hyd 4· ere, r+
Li
/r
C/04
«r
Li(hyd)+
/r
C/04 •
ib
Thus due to the hydration in such cases, a better packing is attained. As a matter of fact, other
alkali metals which are larger in size do not have any such strong tendency to form hydrated
yl
salts. The fact has been previously explained in terms of polarising power (see Sec. 10.6.4) ofthe
metal ions. m
In the same way, formation of the hydrated salts like FeSiF6 .6H20; Na 4Xe0 6 .8H20;
H2[PW12040].29H20, etc. can also be rationalised.
he
(iv) Prediction of solubility: The salts having very small values ofr+/r_ are more readily soluble in
water because of the anion-anion repulsion which reduces the lattice energy in the solid
compounds. The relative solubility trend of the alkali metal perchlorates, LiC/04 : Nac/04 :
lc
KC/04, RbC/04, CsC/04 = 10 : 1 : 10-3, can be explained from the trends of r+/r_ ~alues and
packing efficiency of the ions in the crystals.
ea
(v) Instability in the systems present in the vicinity of limiting radius ratio: For an octahedral
coordination around a cation, the ratio r+/r_ should be in the range 0.414 to 0.732 in which 0.414
th
is the limiting value. As the value tends towards the limiting value, the possibility of anion-anion
repulsion increases. Thus in the NaC/-type structure, the systems such as LiF (r+/r_ = 0.44), Nal
e/
(r+/r_ = 0.44) having the radius ratios close to 0.414 are relatively unstable. This effect has been
reflected in melting points (lowering) (see Fig. 11.7.5.1), solubility (increased) and other properties.
t.m
This aspect has been already discussed in Sec. 11.7.5 (iv).
11.8.3 Limitations of the Radius Ratio Rule

(a) Approximations in the radius ratio rule
Before to discuss the poor predictions from the radius ratio rule in many cases, we should point out the
approximations based on which the rule was framed out. These approximations cannot be supported
theoretically in a finer analysis. These points are discussed below.
(i) Consideration of ions as noncompressible hard spheres : From the knowledge of quantum
mechanical treatment, it is established that the radial distribution function ofthe outermost electron
cloud determines the size of the ions. Hence such an approximation is not supported.
Moreover, many of the polyvalent ions such as CH3C0i., CN- , N0i. ' N), etc. except the
tetrahedral or octahedral moieties are far removed from the spherical shapes. Thus the ionic
compounds consisting of such species can hardly be treated by the radius ratio rule.
(ii) Concept o~ nonpolarisation of the ions : The electron clouds of the adjacent ions will not be
mutually affected from their idealised spherical shapes by their mutual electrical fields - such
an assumption is only true in 100% ionic compounds. But the practical situation is very often
significantly different from the mentioned idealised situation.
(iii) Overlooking the effect of Madelung constant : The stability of a particular system is also
influenced partially by the Madelung constant (see Sec. 11.7.1). But this fact is not taken into
consideration in formulating the radius ratio rule.
(iv) Overlooking the effect of crystal geometry on the ionic radii: In formulating the radius ratio
ry
rule, the radius of an ion was considered as its inherent property which is not dependent on the
nature of the crystal in which it exists. But it has been shown that ionic radius of a particular ion
ra
differs in different crystal structures. This aspect has been quantitatively supported by the Born
equation (see Secs. 11.4 (iii) & 11.7.1). It has been found that, r 4 : r 6 : r s = 0.95 : 1.00 : 1.03
ib
where rn denotes the radius of a particular ion in a geometry where the coordination number
around the ion is n.
yl
(b) Examples illustrating the deviation from the limiting radius ratio rule
m
(i) Lithium salts (effect of covalence) : From the radius ratios of lithium halides as given in Table
11.8.3.1, the prediction is only supported in LiF. Other halides are expected to have the ZnS
structure but actually they adopt the NaCI structure.
he
Table 11.8.3.1. Radius (Pauling's value) ratios and coordination number in lithium halides (LiX)
lc
Compound Radius ratio Predicted structure and Observed structure and

(LiX) rL;+/rx- coordination number coordination number
ea
LiF 0.44 NaCI (6:6) NaCI (6:6)

LiCI 0.33 ZnS(4:4) NaCI (6:6)
th
LiBr 0.31 ZnS (4:4) NaCI (6:6)

Lil 0.28 ZnS (4:4) NaCI (6:6)
e/
It is believed that the compounds are not 100% ionic as assumed and the covalency increases
t.m
from LiF to LiI according to Fajans' rule. With the increase ofcovalency, size ofthe lithium ion
increases while size ofthe corresponding halide decreases. Due to such covalency, it will exist
as LifJ+~ (where 0 < 1) rather than Li+Ji. Under the circumstances we have:
rL;o+ / rx o- »rL;+ / rx-' because rLio+ > rLi+ and rx o- < rx- ·
Specially, in the case of alkali and alkaline earth cations, to introduce the covalency outer
s-orbitals are to be involved. Due to this opening of the new principal quantum number with,
respect to the completely ionic form, the size of the cation in the covalent compound is greatly
increased.
The increased r+/r_ ratio in the compounds having some covalency leads to the 'accommodation
of higher coordination number. Thus the apparent deviation from the radius ratio rule occurs
due to the overlooking the covalency which very often coexists in the said ionic compounds.
Here it is worth mentioning that in terms of Shannon's crystal radii (which take care of the
effect of polarisation introducing covalency), LiCI does not violate the radius ratio rule and LiBr
and LiI are at the borderline of 6:6 and 4:4 coordination system. The Shannon's crystal radii for
the alkali metal ions (especially for the lighter ones) are considerably larger than thos~ given by
Pauling due to the introduction of covalency (see Sec. 11.3.4)..
(ii) Alkaline earth metal salts (effect of covalency; relative contribution of Madelung constant
and interionic separation) : The compounds having highly polarisable anions such as S2-, Se 2-
adopt the higher coordination nUlnber compared to the prediction. For example, the radius ratios
(r+/r_5 for MgS and MgSe are 0.35 and 0.33 respectively. Hence they should adopt the ZnS (4:4)
structure, but in reality they adopt the NaCI (6:6) structure. The consideration of covalency as
ry
in the case of lithium salts can explain the cause of this apparent devitation. Here it is worth
mentioning that consideration ofShannon 's crystal radii instead ofthe Pauling's radii can improve
the prediction ofthe radius ratio rule as in the case oflithium salts.
ra
Now let us consider (see Table 11.8.3.2) the oxides of the alkaline earth cations. Here the
ib
predictions made for SrO and BaO are not supported by the experimental fact. The compounds
are predominantly ionic but still the predictions do not hold good..For SrO and BaO, the r+/r_
yl
ratios lie in the border line region of NaCI (6:6) and CsCl (8:8) structures. The higher coordination
number (Le. CsCI structure) is favoured due to the increased Madelung constant (A csci = 1.76267,
m
A.NaCI = 1.74756) , but the increased interionic separation [RO(CsCl) : RO(NaCl) = 1.036 : 1] disfavours
the CsCl type structure. Relatively, the enhanced Madelung constant enhances the lattice energy
he
by -- 0.9% in adopting the CsCI type structure instead of the NaCl structure, while the increased
interionic separation in the CsCI type structure reduces the lattice energy by -- 3.7% with respect
to that of the NaCI type structure. This is why, they probably favour the NaCI structure rather
lc
than the CsCI structure predicted from the radius ratio rule.
ea
Table 11.8.3.2. Radius (Pauling's value) ratios and crystal geometry in the oxides
of alkaline earth metals.
Compound r M2+ lro2- Predicted structure Actual structure
th
and C.N. and C.N.

0.22
e/
BeO ZnS (4:4) ZnS (4:4)

MgO 0.44 NaCl (6:6) NaCl (6:6)
t.m
CaO 0.56 NaCI (6:6) NaCI (6:6)

SrO 0.81 CsCl (8:8) NaCl (6:6)
BaO 0.96 . CsCl (8:8) NaCl (6:6)
(i~) RbX (effect of the relative contribution of Madelung constant and interionic separation) :
In tenns of radius ratio rule, RbCI (f"Rb+/rCi = 0.82) should adopt the CsCl structure, but it leads
to the NaCl structure at ordinary condition. The same explanation as mentioned above operates
here also. Here it is interesting to note that RbCI adopts the CsCI structure when crystallised at
high temperature. It indicates that the systems lying at the border line of two geometries (specially
NaCl and Cs·CI geometries) do not differ significantly in their cohesive energies for the two
geometries. A similar situation in RbBr has been explained in Sec. 11.7.5iii.
(iv) Kel (effect of the relative contribution of Madelung constant and interionic separation) :
rI0"/rCi > 0.73 predicts its CSCl type structure but it adopts the NaCI type structure. This aspect
has been explained in Sec. II.7.5iii.
(v) Sulphides of pseudo inert gas cations: The pseudo inert gas cations (e.g. Zn 2+, C"cP+, Hg'l+,
etc.) are highly polarising as well as polarisable and the sulphides (which are highly
polarisable) of such cations are predominantly covalent. In fact for soft-soft combination,
mutual polarisation acting synergistically gives an ideal situation of introducing covalence
in the bond (cf. Fig. 10.6.2.1). From the radius ratios (r+Ir_), Le. ZnS (0.40), CdS (0.52), HgS _
(0.55), it is expected that CdS and HgS should have the six coordination structure (Le. NaCI
type). Ifcovalence is considered, then the r+Ir_ ratio increases further to favour higher coordination
number. But in fact, they adopt the ZnS structure. Here again the relative contributions of the
ry
Madelung constants and interionic seperations are to be considered.
ra
Ro(NaC/)
ANaCI 1AZnS = 1.74756/1.63806 = 1.067, =1.05
.: Ro(znS)
ib
The ~adelung constants for the two forms (Le. wurtzite and sphalerite) of ZnS structure are
almost the same. Here it is el:ident that both the factors (i.e. A and Ro) contribute almost to
yl
the same extent in the opposite directions. Hence, in this case no clear-cut conclusion can be
made from these factors, though it was possible in the case ofNaCI and CsCI structures.
m
For such predominantly covalentcompounds, it is better to consider as covalent crystals rather
than the ionic crystals. In fact, ZnS, CdS and HgS are covalently bonding through the Sp3
he
hybridisation.
(vi) Strongly hydrogen bonded crystals (e.g. NH4X) : All the NH~ (X = CI, Br, l) crystals have
lc
either the CsCI or NaCI structure and it indicates that the polyatomic ion NH; remains in a free
rotation to attain the effectively spherical shape. Its radius is worked out to be ~ 148 pm. In the
ea
case of NH4F, from the radius ratio (r+lr_ ~ 1 ) it is expected to have the CsCI structure, but in
fact it attains the wurtzite (4:4) structure in which each ion is tetrahedrally surrounded by the
th
oppositely charged ions having interionic distance 266 pm instead of284 pm as anticipated from
the CsCI structure. It is· believed that the strong hydrogen bonding in NH4F effectively locks
e/
the NH; ion in the tetrahedral hole to introduce a better hydrogen bonding. For the other
halides, the hydrogen bonding is not so important and this is why, for such salts the radius ratio
t.m
rule works well.
11.9 SOME BASIC CRYSTAL GEOMETRIES (i.e. UNIT CELLS) INVOLVED

IN THE STRUCTURE OF CRYSTALLINE SOLIDS
The concept of unit cell is extremely important in understanding the structure of crystalline solids. The
unit cell is the smallest unit having a~l the characteristic properties of the entire crystal. The entire
crystal can. be built by the repeated translation of its unit cell in three dimensions. Thus the entire
crystal consists of a large number of its unit cells placed adjacently in three dimensions.
Here we shall discuss the characteristic properties of some common unit cells such as : three Bravis
lattices ofthe cubic system, i.e. simple cubic (sc), body centred cubic (bee) and face centred cubic (fcc)
lattices; diamond cubic (de) crystal; close packing geometries, Le. hexagonal close packing ~hcp)_ and
cubic close packing (ccp == fcc) crystals.
11.9.1 Simple Cubie (se) Unit Cell

The simple cubic (sc) unit cell (see Fig. 11.9.1.1) contains eight lattice
points at the eight corners. In the three dimensional continuous a
structure, each comer is shar~d by eight adjacent simple cubic units.
a
Thus each lattice point contributes only 1/8 to each cube. Hence the
total contribution is 1 (= 8 xi) lattice point in each unit cell. At the

centre, it possesses a cubic hole. Thus, per lattice point (because only
ry
one lattice point effectively contributes per unit cell) there is a single Fig. 11.9.1.1. Simple cubic
hole. To calculate the packing efficiency in the sc cubic system, we (se) unit cell (. denotes the
ra
are to find the actual space occupied by the lattice point. Space lattice points).
=.±3 1tr =radius of the lattice point considered to be spherical in
ib
3
occupied by the lattice point (where r
shape). Volume ofthe unit cell = Q3 (where a = egge length ofthe cube). Considering the noncompressible
yl
spherical lattice points to touch each other along the edge we get, 2r = a.
3
(4/3)xr
m
Therefore we get, % space occupied = 3 x 100
a
he
3
47tr x 100 = 52.
3(2r)3
lc
Symmetry elements in the cubic system : The following symmetry elements are present in the
cubic crystal system.
ea
(i) Centre ofsymmetry (C;) : It has got it at the centre.

(ii) Axis ofsymmetry (Cn )· : It has got six two-fold (6C2) axes passing through the mid-points of
th
the two opposite edges and the centre of the cube; three four-fold (3C4 ) axes passing through
the mid points of the opposite faces, and four three-fold (4C3) axes lying with the body
e/
diagonals.
(iii) Plane ofsymmetry (cr) : It has got three mutually perpendicular rectangular and six diagonal
t.m
planes passing diagonally.

Thus it has got total 23 symmetry elements.
11.9.2 Body Centred Cuble (bee) Unit Cell

Here in addition to the eight lattice points at the corners there is a
lattice point at the centre (see Fig. 11.9.2.1). Thus the total contribution
by the lattice points to each unit cell is given by :
n =!8 N C
+ N.
I
=!8
x 8 + 1 =2 (where N c = number of lattice points
.
at the corners; N; = number of lattice points inside the unit cell.)
0
Fig. 11.9.2.1. Body centred
* en means a rotation
. around t h 360- cubic (bee) unit cell (.
· by -
e axiS brings an equlva Ient con fiIguratlon.
• • .
n denotes the lattice points).
Assuming the three lattice points (out of which two reside at the comers) along the body diagonal to
touch one another'we get, 4r = length of the body diagonal ~ 13a (where r = radius of the spherical'
lattice point and a = edge length of the unit cell).
3 3
2( 41 3)1tr x 100 81tr x 100 = 68
Thus, % space actually occupied = 03 3( 41 13)3 r 3
11.9.3 ·Face Centred Cubic (fcc) Unit Cell

Here in addition to the eight lattice points at the eight comers, there are six lattice points at the centres
ry
of the six faces (one lattice point in each face) (see Fig. 11.9.3.1). Hence the effective conLribution of
, 1 1 1 1
the lattice points to each unit cell is given by: n =8" N e + 2" N f =8" x 8 + 2" x 6 =4,
ra
(where NI =number
of lattice points on the faces). The factor 1/2 for Nt comes, because
ib
each lattice point at the centre ofa face is shared by two adjacent unit
cubes. Assuming the three fattice points (out of which two reside at
yl
the corners) along the face diagonal to remain in touch with one
another, we get, 4r = length of the face diagonal = Jia where rand m
a bear the same significance as in the previous cases.
3
4(4/3)7tr x 100
he
Therefore, % space actually occupied = 3
a
3
167tr x 100
lc
= 3(4IJi)3 r 3 = 74 Fig. 11.9.3.1. Body centred

cubic (fcc) unit cell
ea
Octahedral and tetrahedral holes in a fcc lattice: For the fcc (. denotes the lattice
lattice, there are two distinct types ofholes which are shown in Fig.
11.9.3.2. The unit cell can be divided into eight small cubes (see Fig. 11.9.3.2 (i)). The alternate comers
th
of the small cubes are occupied by the lattice points. This arrangement creates a tetrahedral (Td) hole
(see Fig. 11.9.3.2 (iii)) at the centre of each small cube. Thus the whole unit cell creates eight tetrahedral
e/
t.m
~--'7----·
/-L __ • , /f
/', /Tl---,,( ,
~-,- - ~ ~.J - 4 , ,
, ,__ , L.L T' ,
, 'I', I, ",-.,-" CD
L..I.I' I
, /.J __
, '7", :g
1.' -t--.f' , , .&:.
"'-~~"'-L...J....."" 0
-"
------- ----
/"
-
...
(i)
-I-
/
-./
_ l."
~
~
j .A
(ii) (iii) (iv)
Fig. 11.9.3.2. Analysis of a face centred cubic (fcc) unit cell : (i) splitting into eight small cubes, (ii)
representation of an octahedral (Oh) hole at the centre of the unit cell, (iii) representation of the
tetrahedral (TJ holes at the centres of eight small cubes. (iv) representation of the octahedra' (Oh)
holes at the mid-points of the edges of the unit cell (. denotes the lattice points).
Structure, Bonding "and Properties of Ionic Solids and Solid State Chemistry 1027
holes. Since there are effectively four atoms or lattice points per unit cell, there will be two Tdholes per
lattice point. In the fcc unit cell, the centre is not occupied by any lattice point. The six latti~points
placed at the centres of the six faces produce an octahedral (Oh) hole at the centre of the cube (see I
Fig. 11.9.3.2 (ii». Besides this, the centre of each edge acts as an octahedral hole (see Fig. 11.9.3.2
(iv». Thus the centres of the twelve edges provide 12 octahedral holes which contribute effectively
three holes per unit cell, because each edge is shared by the four adjacent cubes. Thus the total number
of effective octahedral holes per unit cell is 4 (three from the centres ofthe 12 edges and one at the
centre ofthe cube). Thus per lattice point (4 per unit cube) there is one octahedral hole.
ry
• Lattice planes and interplanar distancesfor the cubic systems: The lattice planes are defined in
terms of Miller indices (hkl) and the common lattice planes of the 'cubic crystals are shown in Fig.
ra
11.9.3.3. The interplanar distance in the cubic system is given by :
a
ib
dhJcJ =--;:::=====
~h2 +k2 +P'
yl
a = length ofthe cube side, h, k and I are the Miller indices of_the pla~es. The fa~es of a cubic crystal
are defined as follows in terms of h, k, I: (100), (010), (001), (100), (010) and (001). These equivalent
m
planes (in terms of symmetry) may be represented as {IOO}. Such a plane is perpendicular to one axis
and parallel to other two axes. Thus for 100 plane, the Weiss indices are 1 : 00 : 00 while its Miller
he
indices are 1 : 0 : o. Different lattice planes of a cube are shown in Fig. 11.9.3.3. The (200) plane is
parallel to the (100) plane but it cuts at i a where a = edge length of the cube.
lc
ea
th
(a)
E
e/
(100) (110) C
Y
t.m
(b)
(200) (220) BDHF (100),

AEDB (101),
ABC (111),
CDHE (010)
(c)
(200)
(110) (222)
Fig. 11.9.3.3. Lattice planes in terms of Miller indices in cubic lattice. (a) simple cube (sc); (b) face-
. a a
centred cube (fcc), (c) body centred cube (bee) (d100 = a, d200 = al2, d110 = I = ~' etc.,
vI2+12+0 "12
a = length of the side of the cube).
The spaci.ng of different lattice planes of cubic systems are given below (in terms of a = edge of the
cube).
a a
(sc) d lOO : d llo : dIll = a: J2 :fj = 1 : 0.707 : 0.577
a a a
(fee)d200 : d220 : dill = -: ~:~ = 1: 0.707: 1.154
2 2v2 v3
a aJ2 a
(bee) d200 : d llo : d222 = -:-: ~ = 1 : 1.414 : 0.577
ry
2 2 2v3
11.9.4 Diamond Cubic (de) Unit Cell
ra
It is a special type of face centred cubic (fcc) lattice. Here, four additional atoms (or ions) are present
ib
within the face centred cU.be. These four additional lattice points are distributed in a symmetrical fashion
so that each one has got the identical environment. This condition is satisfied by placing the atoms at
yl
the centres of the alternate eight small cubes within the face centred cube (see Fig. 11.9.4.1 (i) and Fig.
11.9.3.2 (i». Thus the four atoms are placed at the four alternate tetrahedral holes out of eight. A
m
plan view of the positions of the lattice points is shown in Fig. 11.9.4.1 (ii) where the numbers indicate
the height of the positions in terms of the edge length (a). In this arrangement, each atom, i.e. lattice
he
point, is tetrahedrally surrounded. The total contributions of the lattice points per dc unit cell is given
by:
=!8 N.(; + ~2 N f " + N. =!8 x 8 + ~2 x 6 + 4 =8
lc
n (where N c' Nfand N" bear the usual significance).

I
ea
...----8---...
th
e/
t.m
(i) (ii) (iii)

Fig. 11.9.4.1. The diamond cubic (de) unit cell. (ii) Plan view of the lattice point position in the unit
cell. The numbers denote the height from the base of the unit cell. The height of the unit cell is a.
(iii) Perspective view of the diamond structure.
It is evident that the four internal lattice points lie along the four body diagonals of the fcc
unit cell. Each one lies at a point quarter-way measured from the comer along the body diagonal.
Considering the two lattice points (one at the comer and other at the nearest position along the body
diagonal) to remain in contact, we get: 2r = ± of the body diagonal = ± (J3a) or, a = ~.
3 3
8 x (4/ 3)1tr x I00 8 x 41tr x 100
Thus, % space actually occupied = 3 = 3 3 = 34
a 3(8/3) r
Many covalent compounds crystallise in dc structure. These have been discussed separately in Sec.
10.11.1. It will be seen that the zinc blende, ZnS crystals are basically dc crystals.
ry
11.9.5 Graphite Layer Lattice
ra
The characteristic properties of this lattice have been discussed in Sec. 10.11.2.
ib
11.9.6 Close Packing Models of Spheres
It has been observed that the crystals of inorganic solids are constructed by the methods which lead to
yl
the most efficient packing (having a minimum repulsive potential) of the lattice points which a~e either
atoms or ions or molecules and these are supposed to be spherical in shape. Now let us discuss the ways
m
of packing in three dimensions by the spheres of equal size. .,
Ifwe start with solid spheres to place in a plane in rows, we have two possibilities (see Fig. 11.9.6.1).
he
The possibility (i) leads to a more close-packed system compared to the second one (ii). In the orientation
(i), each one is surrounded by six nearest spheres in a hexagonal symmetry (C6 ) providing the
lc
coordination number 6. This arrangement leads to '- 60.50/0 packing ofthe space. Hence the unoccupied
space is '- 39.5%. But such an arrangement is stable only for the neutral spheres (e.g. metal, inert
ea
gases). For the ionic crystals (considering the cations and anions ofthe same size) consisting ofoppositely
chargecfions, it will lead to a severe repulsion among the like charges which cannot be compensated by
the attraction among the opposite charges. For such ionic crystals, in which the ions ofopposite charges
th
are ofalmost the same size (Le. r+/r_ = 1), the second arrangement (ii) is more favourable though it
leads to a structure having more void spaces.
e/
Now let us pay attention to the arrangement (i) for'which there is a hole or void space for each set
ofthree touching spheres. If the 'layer (considered to b~ the first layer) consists of n spheres, there will
t.m
be 2n such holes. Now to construct the secolrd -layer by using the spheres of the same size, these are
placed on the holes created in the first layer. But, in this way the spheres in the second layer can only.
cover half of the holes created in the first layer. Thus from the positions of spheres in the first and
second layer, half of the holes created in the first layer act as the basal sites for the positions of
the spheres 'in the second layer. Such holes are called tetrahedral (Td) holes while the other positions
of the remaining holes created in the first layer remain also unoccupied in the second layer. Such
holes are referred to as octahedral (Oh) holes (Fig. 11.9.6.1 (iii, v and vi».
Now in constructing the third layer (see Fig. 11.9.6.1 (iv») by the same type of spheres shown by the
thick circles on the second layer, we are left with two possibilities: first, placement of the centres of
the spheres on the centres of the spheres of the first layer and second, placement of the spheres on the
octahedral holes created in arranging the first and second layer.
• First way (Hexagonal close packing) : The centres ofthe spheres of the third layer can be placed
directly on the centres of the spheres of the first layer. Thus the third layer appears as a mirror
Td hole (T)
(i) (iv)
ry
ra
ib
yl
m
B
he
A A
lc
B C
A B
ea
B A
th
A C
(T for tetrahedral hole)
B B
e/
A A
t.m
(vii)
B
c
A
A
(0 for octahedral hole)
(VI)
B B
(vm) (~)
Fig. 11.9.6.1. Close packing models of spheres. (i) A single layer of close-packed spheres. (ii) Relatively
inefficient packing of spheres in a single layer. (iii) Placing of two layers of spheres in closed-packed
models to generate tetrahedral (T) and octahedral (0) holes. (iv) Three layers of close packed spheres.
(v) & (vi) Illustration of T and 0 holes. (vii) Two types of closed-packed spheres : ABABAB-pattern
(Le. Hexagonal close-packed (hcp) and -ABCABC-pattern Le. cubic close-packed (CCP) pattern. (viii)
hcp-structure. (ix) CCP-structure.
image of the first layer. This type of arrangement is described as

ABA type arrangement where A, B and A denote the arrangement
A
of the spheres in the first, second and third layer respectively. Such
an arrangement may be continued indefinitely leading to the system
.. ABABABA ... (Fig. 11.9.6.2). Such a pattern ofpacking ofthe spheres
in three dimensions is referred to as hexagonal close packing (hcp)
because of the existence of the hexagonal (C6 perpendicular to the B
planes ofthe close-packed spheres) symmetry ,in all the stacked layers.
ry
Now let us consider the relationship between the simple hexagonal
crystal system and hexagonal close packing model. In the ABA
stacked layers, the seven spheres in both the 1st layer (i.e. A) and 3rd
ra
layer (Le. A) occupy the simple hexagonal lattice points while the
three spheres of the second layer (i.e. B) are placed within the unit
ib
cell in such a fashion that the nearest environment of all the three
spheres becomes "identical. These are placed actually at the corners
yl
Fig. 11.9.6.2. Hexagonal
of an equilateral triangle placed in the mid-way of the two parallel close-packed (hcp) structure
hexagonal planes (i.e. 1st and 3rd layer). The position of a such - ABABA- (D3h symmetry).
m
1 2 1 cJ
a,3"a'"2 ---
point is given by ( "3 where c is the height of the unit celJ /- "\
he
/ \
/ \
(Le. distance between the 1st and 3rd layer) and a is the length of the / \
\ ) A
side of the hexagon. Here we can recall the analogous relationship \ /
lc
\ /
between the diamond cube (de) and face centred cube -(fcc). In \
I
I
the de crystal, the four interior atoms are not in the lattice sites of a
ea
fcc. Similarly, here in hcp, the three interior lattice points are
not in the lattice sites of a simple hexagonal crystal system.
th
The coordination number of each sphere (i.e. atom) is 12. A

sphere is hexagonally surrounded by six spheres in a plane, and it
e/
touches three spheres below the plane and other three spheres above
the plane. Thus the total coordination number is 12 (i.e. 3 + 6 + 3)
t.m
(see Fig. 11.9.6.2). \

,
\
Now let us try to calculate the packing efficiency in hep. In the \
\ A
ABA type hcp unit cell, the C6 axis runs through the centres of the I
I
two hexagonal planes (A and A) and the centre (cross -section point
of the three medians) of the equilateral triangle formed by the three - -_/
/
--
spheres in the B layer. By joining the centres of the three atoms in the Fig. 11.9.6.3. Representation
B-Iayer to the centres of the top and bottom hexagonal layers we get of hexagonal close packing
(hcp) model, M, N, R denote
two regular tetrahedra with a common base produced by the triangular
the atoms lying within the hcp
distribution of the three atoms in the B layer (see Fig. 11.9.6.3). unit cell.
From Fig. 11.9.6.3, it is evident that the height of the unit cell is
twice the length of the normal drawn from the apex of a tetrahedron to its base. Thus, e = 2PO. In the
unit cell, the atom at the centre of each of the hexagonal basal planes (A, A) touches'the three atoms in
the mid-layer (Le. B layer). Thus we have,
a = side of the hexagonal basal plane = diameter (i.e. 2r) of the atom = side of the tetrahedron = PM
=MR=NR.
Thus we get, cia = 2POIMR; MX is perpendicular to NR. Hence, MR 2 = XR 2 + MX2
or, MX -= ~MR2 - XR 2 -= ~a2 - a 2 14 -= (.J3 12)a

From the property of the triangle, 6.MNR, we get,
MO = 3. MX = 3. x .J3 ~ = .!!-
ry
3 3 2.J3
From the triangle, MJOM we get,
ra
PO-=JPM2-0M2-=Ja2-a2/3-=~a
.J3
ib
2PO J2a . 2J2a
yl
Thus, cla=--=2 ~ =1.633 l.e.c=~
MR ,,3a ,,3
m
Now let us consider the number of effective lattice points per unit cell, i.e. n -= .!.. N c + .!.. N f + N;.
· 6 2
The factor 1/6 for the lattice points at the corners arises due to the fact that such a point can be shared
he
by six adjacent unit cells. The lattice point at the centre of each hexagonal basal plane is shared by two
1 1
such unit cells. Therefore, n = "6 x 12 + "2 x 2 + 3 = 2 + 1 + 3 = 6.
lc
Volume of the unit cell = area of the hexagonal basal plane x height of the cell.
ea
The regular hexagonal basal plane consists of six equilateral triangles of side a. The area of such a
triangle is .!..a2 sin 60°. Thus we get the area of the hexagonal basal plane = 6 x.!..a x asin 60°
2 2
th
2
-= 3a 2 .J3 -= 3.J3a .
e/
2 2
2
3.J3a 2J2 J2 3
t.m
Therefore, volume of the unit cell = - 2 - x .J3 a = 3 2a
3 3
6 x (4/3)1tr x 100 24 1tr x 100
Therefore, % packing efficiency = ~ 3 =- = 74
3,,2a 3 3J2 (2r)3
• Second way (cubic close packing) : The spheres in the 3rd layer are placed (see Fig. 11.9.6.1
(iv» on the octahedral holes (Le. the void spaces which are created in the first layer remain also uncovered
in the second layer). Thus with respect to the positions of the centres of the spheres in each layer, the
three layers are different. This is why, it is very often referred to as ABC type arrangement of the
spheres, where ABC denote the three different layers. If the stacking of the layers in this fashion is
continued indefinitely, we get the arrangement ... ABCABCABC ... This close packing model is referred
to as the cubic close packing (ccp) because of the development of a cubic symmetry. It does not mean
the destruction of the hexagonal symmetry which remains in all the stacked layers. The cubic symmetry
is identified by the existence of 4 C3 axes passing through the body diagonals of the cube. It can be
ry
c
ra
ib
A
yl
m ~
(a) (b)
he
Fig. 11.9.6.4. Development of a face-centred cubic (fcc) unit cell from the cubic close-packed (ccp)
arrangement. In (b) : 0 (lattice points on the faces of the fcc unit), • (lattice points at the comers
of the fcc unit)
lc
realised as : placing of a face centred cube on one vertex

7~8A
ea
with the body diagonal passing through the vertex vertical, I I

the horizontal close-packed lattice plane of the ccp lie in I 9 I
th
I I I
the ABC ... pattern (see Fig. 11.9.6.4). Development ofa
000
I I I
I I I
fcc unit cell from the ... ABC ... model is shown in Fig. I I I
e/
11.9.6.4. Because of this fact, the cubic close packing

(ccp) is also referred to asfcc packing (D3d symmetry). B
t.m
Here also the coordination number of a sphere is 12

(see Fig. 11.9.6.5). A sphere touches six spheres hexagonally
in its plane and three spheres above the plane and another
three spheres below the plane.
The packing efficiency in ccp or fcc is 74% as in hcp.
C
• Third way (mixed type) :In some cases the succ..e~sive
layers are stacked randomly as ... ABABABCABA ... Le. both Fig. 11.9.6.5. Cubic close-packed
hcp and ccp patterns are mixed up. This type of random (ccp) structure, ---- ABCABC ----- .
arrangement is described as stacking fault.
11.9.7 The Body Centred (bee) Lattice In Terms of Close Packing of Spheres
Lastly, in the light of packing of the spheres, we are to describe the bcc structure. In this model, the
atoms are not closely packed. The structure can be attained as follows (see Fig. 11.9.7.1).
1034 Fundamental- Concepts of Inorganic Chemistry
(i) The spheres are placed side- by side in a layer in a way so

that they are slightly opened up. As a result, no sphere
touches with each other.
(ii) The spheres in the second layer are placed on the holes
created in the first layer; so that each sphere in the second
layer touches four spheres of the first layer. Fig. 11.9.7.1. Development of
(iii) In constructing the third layer, the spheres are placed in body centred cubic (bee) structure
such a way-that the centres lie just above the centres of from the packing of spheres (the
third layer is not shown).
ry
the first layer. It leads to ---- ABA---- type of stacking.
Thus, the-first and third layers are mutually mirror images
ra
as in the hep model.
The important characteristic feature of this arrangement is
ib
that the spheres in a particular layer nev~r touch mutually. Each
sphere touches with the nearest eight spheres : four in the layer
yl
just above and four in the layerjust below. Thus the coordination
number of each sphere is 8 (see Fig. 11.9.7.2). The symmetry
m
of this _arrangement leads to the bee structure having packing Fig. 11.9.7.2. Unit cell of a body
efficiency 68%. centred cubic (bee) lattice.
he
11.9.8 Characteristic Features of hep, fcc and bee Structure
Table 11.9.8.1. Comparison of hep, fcc and bee in terms of packing of spheres in different stacked layers
lc
Characteristics Structure
ea
hcp (D 3h ) ccp (i.e·fcc) (D 3d) bee

- (i) Nature of packing Close-packed Close-packed Slightly open-packed
th
in each layer in each layer in each layer

(ii) Pattern of stacked layers ... ABABABA ... ... ABCABCABC ... ... ABABA ... (but each layer is
open-packed)
e/
(iii) Packing efficiency 74% 74% 68%

(iv) Coordination number 12(=3+6+3) 12 (= 3 + 6 + 3) 8 (= 4 + 0 + 4)··
t.m
(A + B+ A) (A+B+C) (A + B + A)
(v) Malleability and Less malleable More malleable Malleable and ductile
ductility· (for metals) and ductile and ductile
(vi) Examples of metals ~-Cr, Mo, Mg, Cu, Ag, Au, Pt, Na, Rb, Cs, B, a-Cr, a-Fe,
Zn, etc. y-Fe, etc. an different other alkali metals
* Causes will be explained later (see Sec. 12.2.2).
** These are more six next neighbours slightly ( 15 %) away compared to the closest 8 neighbours.
A A
B B
c A
(hcp) (cop) (bee)

Fig. 11.9.8.1. Representation of hep, eep and bee structure.
11.10 STRUCTURE OF IONIC CRYSTALS

Before to discuss the structures of different types of ionic compounds we should highlight the two
important approaches to explain the structures. The structures can be explained either in terms ofthe
three Dravis lattices of the cubic system forming the sublattices or by the close packing models. We
have already mentioned that the close packing models are not important for the ionic compounds because
it introduces a severe repulsion among the like charges. However, the concept is very much useful in
explaining some ionic crystals. The close-packed models formed by the anions are the limiting
cases. Ifthe close-packed lattice expands slightly, it will significantly reduce the anion-anion repulsion.
ry
Under such circumstances, the tetrahedral and octahedral holes may be occupied by the cations. Generally
the hole selection by the cations is governed by the radius ratio (e.g. for the Td holes, r+/r_ = 0.414 to
ra
0.732). But sometimes the other factors such as the possibility of covalent bonding leading to the
preference between sp3 and sp3Jl hybridisation, ligand field stabilisation energy-LFSE (which is
ib
important in determining the spinel CJr inverse spinel structures), etc. are important.
We shall discuss the application ofthe concept ofthe close packing model in explaining the structures
yl
of different types of ionic compounds. From the stoichiometric composition, the ionic crystals can be
classified in different types such as AB, AB2, AB3, etc.
m
11.10.1 Structures of Ionic Crystals of AS Type
he
These are of/our types: NaCI, CsCI, ZnS (zinc blende),
ZnS (wurtzite) structures. In a particular type, the most
lc
commonly naturally occurring mineral represents the type.
1:;·~; :~ ~: 1~1.~: ~ ~ ~
(i) NaCI (i.e. common salt or rock salt) structure (6:6
ea
coordination crystal) : A unit cell ofthe NaCI lattice

is shown in Fig. 11.10.1.1. The structure can be
th
interpreted in terms of cubic close packing (ccp, • =Na+ ..

i.e.fcc) of Cr- ions in which each of the octahedral o = CI ···::::6······
e/
(0Il) holes is occupied by Na+ ions. The occupancy

ofthe octahedral holes by Na+ ions i.s supported from "Fig. 11.10.1.1. NaCI (Le. common salt
t.m
or rock salt) crystal (6:6 coordination)

theradiusratioO.414< r + /r _ ='95/181 =0.524 structure.
< 0.732. In thefcc struc~~e onhe c, ions, there is
one octahedral hole per C, ion. Hence in ~he AB type crystal all the octahedral holes are occupied
by the Na+ ions. In the extendedfcc lattice, the positions (see Fig. 11.9.3.2 (ii) & (iv» of the 0h
holes are the mid-points of the 12 edges and centre of the unit cell. These are the positions of the
Na+ ions. The coordination number of each Na+ ion is 6. Hence the coordination number of each
C, ion is 6, because it is aABtype"crystal. As a matter offact, each ion is octahedrallysurrounded
by the opposite ions. From the X-ray studies, the edge length (i.e. a = 2r + + 2r _) of the unit
cell cube is found to be 563 pm. Thus the interionic distance between tSe adja~ent oppositely
charged ions is 281.5 pm.
The NaCI structure can also be rationalised in terms oftwo face centred cubic lattices constructed
by the chloride ions and sodium ions respectively. The two suchfcc lattices have interpenetrated
"halfway. Thus, the NaCI structure is really afcc lattice olet" ions into which afcc lattice of
Na+ ions has interpenetrated in such a way that it is displacedfrom

the Cr-Iattice by the vector 1/2, 1/2, 1/2.
Many other compounds such as NaF, KCI, KBr, AgCI, AgBr, CaS,
CaO, LiCI, LiF, LiI, etc. adopt the NaCI structure. Compounds like
KOH, KCN, KSH, etc. having nonspherical polyatomic anions also
adopt the NaCI structure in which the nonspherical anions appear
spherical in the crystal through the rapid tumbling of the anions.
(ii) CsCI structurp (8:8 coordination crystal) : The structure of the unit • = cs+ 0 = CI-
ry
cell of CsCI is shown in Fig. 11.10.1.2. Here the radius ratio Fig. 11.10.1.2. CsCI
structure (8:8 coordina-
r + / r _ = 169/181 = 0.933 lies between 0.732 and 1.000. Hence the tion).
ra
cgordi~ation number of Cs+ ion is expected to be 8 in a cubic
arrangement. As it is a AB type crystal, Ct ion will also have 8 coordination number by the
ib
opposite ions in a cubic arrangement. In fact, it adopts the body centred type cubic lattice structure
in which at the centre Cs+ ion exists. Here it should be remembered that it is not an ideal bcc
yl
lattice in which all the lattice points should be identical. Here the lattice points (Le. Ct ions)
taking the positions at the 8 corners of the cube are different from the one (Le. Cs+ ion) present at
m
the centre of the cube. This is why the CsCI structure is referred to as a body centred type lattice
to describe the distribution pattern of the lattice points.
he
From the structure of the unit cell of CsCI, it is evident that in the simple cubic lattice of the Ct
ions, Cs+ ion takes the position of the cubic hole at the centre. Thus the cesium chloride structure
can be interpreted in terms of two interpenetrating simple cubic (sc) sublattices of Cr- ions
lc
and Cs+ ions respectively. Both Cs+ and Ct ions take the positions in the cubic holes formed by
ea
the sublattices of the opposite ions. Thus each ion has a coordination number 8. Thus the CsCI
structure is really a simple cubic lattice ofCs+ ions into which a simple cubic lattice ofCt ions
has interpenetrated in such a way that it is displacedfrom the Cs+ lattice by the vector 1/2, 1/2,
th
1/2.
The alkali halides which adopt the CsCI structure at ordinary conditions are CsCI, CsBr, CsI.
e/
RbCI, RbBr; and RbI adopt the structure under high pressure. Different complex salts consisting
of the ions of high symmetry such as [Be(H20)4]S04' [Ni(H20)6] [SnCI6], K[SbF6], etc. have the
t.m
CsCI structure. The compounds like CsCN, CsSH containing

nonspherical polyatomic anions adopt the esCI structure in which
the nonspheri.cal anions adopt the spherical shape effectively in
the crystal geometry through the rapid tumbling ofthe nonspherical
anions.
(iii) Zincblende or sphalerite (ZnS) crystal (4:4 coordination
number) : Here the S2- anions are distributed in a ccp pattern (Le.
S2- ions take the lattice points of a fcc lattice) and half of the
tetrahedral holes are occupied by the cations, i.e. Zn 2+. Thus, o =S2-(CCp);
in the fcc lattice of S2- ions having one 0h hole per S2- ion and • = Zn 2 +
two Td holes per S2- ion, only half of the 8 alternative Td holes are
Fig. 11.10.1.3. Zinc blende
occupied by Zn 2+ ions keeping the 0h holes and half of the Td or sphalerite (ZnS) crystal
holes vacant (see Fig. 11.10.1.3). Here it is worth mentioning (4:4 coordination) structure.
that znS is predominantly covalent. Hence the hole selection

is better governed by the ease of hybridisation between the
possibilities : spJ and sp Jd 2 • As a matter of fact, in the
compounds having the ZnS structure, the metals are suitable to
adopt the sp3 hybridisation and the metal ions do not have
CFSE. In the zinc blende structure, each ion is tetrahedrally
surrounded.
This zinc blende structure has got a similarity with the diamond
ry
cubic (de) crystal in which in the fcc lattice of C, half of the
alternate tetrahedral holes are occupied by C. o = S2-(hcp):
The compounds like znX, CdX, HgX (where X == S, Se, Te),
• =Zn 2+
ra
Fig. 11.10.1.4. Wurtzite (ZnS)
CUX (where X == C/, Br, /), BeS, etc. possess the zinc blende
crystal (4:4 coordination)
ib
structure. The structure of the mineral, eha/eopyrites CuFeS, structure.
can be rationalised in terms of the zinc blende structure. In the
ZnS structure, on replacing the Zn atoms by the atoms of Cu and Fe in the alternate positions, the
yl
structure of chalcopyrites can be attained. m
Polymorphs
Polymorphs represent the different crystal structures of a particular substance. Thus zinc blende
he
and wurtzite are the polymorphs of ZnS.
(iv) Wurtzite (ZnS) crystal (4:4 coordination number) : The unit cell of the wurtzite crystal is shown
lc
in Fig. 11.10.1.4. The structure is very much cOJ!lparable with the zinc blende structure. Here the
S2- ions are distributed in a hcp lattice (while in zinc blende, S2- ions are in a ccp lattice) and
ea
Zn 2+ ions occupy half of the tetrahedral holes. Here each ion is tetrahedrally surrounded by the
opposite ions. Examples of the compounds having the wurtzite structure are MgTe, CdS, A/N,
th
BeD, etc.
The Madelung constants (1.63806 for zinc. blende and 1.641 for wurtzite) for the two structures
e/
are very much comparable. This is why, the energy difference between the structures is also
small. Because of this fact, some compounds crystallis~_d in any form of the two may be changed
t.m
into the other. For example, for CdS, the transition from cubic to hexagonal form occurs at about
room temperature while for ZnS, the transition from cubic to hexagonal geometry occurs at
I040°C.
(v) Nickel arsenide (NiAs) structure: It is equivalent to NaCI structure in tenns of hexagonal close
packing. Nickel atoms occupy the octahedral holes produced by the hcp array of the arsenic
atoms. Thus, Ni-centres are in octahedral geometry while each arsenic atom resides at the
centre of a trigonal prism constituted by the Ni-atoms. FeS adopts this structure.
Note: Effect ofelectronegativity difference (~X) and average principal quantum number (n)
on the structure of the AB type crystal: The average principal quantum number n (obtained
from the principal quantum numbers of the valence shells of A and B, e.g. n == 3 for MgS where
Mg and S are the 3rd period elements) gives the approximate measure of the size of the anion.
For the larger values of n, coordination number (C.N.) of 4 is favoured. If the electronegativity
difference (~X) value is large, then the ionic interaction is predominant and such compounds
preferably adopt the rock-salt type structure (C.N. == 6).
In general, C.N. = 6 isfavoured for the larger Liz value and smaller n value while the reverse
is true for the C.N. = 4.
11.10.2 Structures of Ionic Crystals of AB2 Type

(i) Fluorite (CaF2) crystal (8:4 coordination crystal) : The unit cell of CaF2 is shown in Fig.
11.10.2.1. The structure can be interpreted in terms of interpenetrating simple cubic (sc) and. face
centred cubic (fcc) lattices of ions.
There are two approaches to attain the CaF2 structure. The Ca 2+ ions are distributed in a ccp
ry
pattern (i.e. Ca 2+ ions are placed at the lattice points ofafcc lattice) and the all tetrahedral holes
(Le. 8 holes) are occupied by the r ions (see Fig. 11.10.2.1 (a)). The stoichiometry is supported
ra
because the fcc sublattice of Ca 2+ ions contributes 4 Ca 2+ ions per unit cell in which the 8 Td
holes possess 8 r ions. Thus each F- ion is tetrahedrally surrounded by four Ca 2+ ions
ib
while each Ca 2+ ion is cubically surrounded by 8 F- ions (see Fig. 11.10.2.1 (a».
The unit cell can be constructed in an another way. The unit cell can be divided into 8 sm~1l
yl
simple cubic sublattices of r ions and at the centres of such four alternate cubes (Le. cubic
holes) out of the eight cubes, four cations (Le. Ca 2+) are placed (see Fig. 11.10.2.1 (b)). Thus in
m
this light, it bears a similarity with zinc blende structure in \\'"hich in thefcc lattice of S2- ions half
of the Td holes are occupied by the cations while in the fluorite structure the anions from a sc
he
sublattice in which half of the cubic holes are occupied by the cations.
lc
ea
th
e/
t.m
I _---\..r'
.~ ~/ 0 =Ca +(fcc) • =F
2
• =F-(sc) 0 = Ca 2 +
(a) (b)
Fig. 11.10.2.1. Fluorite (CaF2) crystal (8:4 coordination) structure.
In the seco~d approach, the fluorite structure has got a good similarity with that of CsCl structure.
In both the structures, the anions are at the lattice points of sc crystals but in CsCl all the cubic
holes are filled in by the cations while in the fluorite structure only the alternate cubic holes (Le.
only half of the cubic holes) are occupied.
Here it is important to mention the antifluorite structure in which the distribution patterns of the
cations and anions are reversed with respect to those of the fl uorite structure. Thus both the
fluorite and antifl' ~orite structures can be interpreted as given in Table 11.10.2.1.
Table 11.10.2.1. Characteristics of fluorite and antifluorite structures.

Fluorite structure (AB 2) Antinuorite (B_~ )
(i) fcc sublattice of cations (A) in which all the (i) fcc sublattice of anions (A) in which all the Td holes
Td holes are occupied by the anions (B) are occupied by the cations (B) _
(ii) In terms of sublattices of the ions, anions (ii) Anions are infcc, and cations are in sc
are in SC, cations are infcc
(iii) C.N. of cation = 8 (cubically), C.N. of anion (iii) C.N. of cation = 4 (tetrahedrally), C.N. of anion = 8
= 4 (tetrahedrally) (cubically)
ry
Examples of fluorite structure: CaF2, SrF2, BaF2, BaC/2,
ra
M0 2 (M== Zr, HI, Ce, Th, Np, Pu), etc.
Examples of antifluorite structure: Li 20, Na 20, etc.
ib
(ii) Rutile (TiO z) structure (6:6 coordination crystal) : The unit
cell of the rutile lattice is given in Fig. 11.10.2.2. Here the
yl
cation is octahedrally surrounded by the six anions while
the each anion (i.e. (jl-) is trigonally surrounded by three
m
cations. Rutile consists of a low symmetry sublattice of
o
=0 2- 0 =Ti4 +
4
(body centred Tetragonal for Ti +)
the anions which does not fit either in the sc lattice or fcc
he
Fig. 11.10.2.2. Rutile (Ti02 )
lattice. On the other hand, the sublattice for the cations is a
crystal (6:3 coordination)
distorted body centred cube, because one of the side of the structura. ~
lc
cube is different from the other sides. The cation sublattice

is actually body centred tetragonal. Thus the unit cell is
ea
tetragonal. Examples of the compounds having the rutile

structure are NiF2, MgF2 , M0 2 (M == Sn, Pb, V, Nb, Mo, Mn,
th
etc.).
As in the case of fluorite structure, in rutile we can have also
e/
the antirutile structure in which the immediate symmetries

of the cations and anions are interchanged with respect to
t.m
those in the rutile structure.

(iii) p-cristobalite (SiO z) structure (4:2 coordination crystal) : It
is closely related with the zinc blende structure. By substituting
the lattice sites of Zn 2+ and S2- ions by S;4+ ions and placing • =Si4+ 0 =0 2-
the (jl- anions between the adjacent /);4+ ions in the zinc blende Fig. 11.10.2.3. p-cristobalite
structure, we get the ~-cristobalite structure (see Fig. (Si02 ) crystal (4:2 coordina-
11.10.2.3) in which each silicon is tetrahedrally surrounded tion) structure.
by four oxygens while each oxygen is linearly surrounded by two silicons.
It can also be interpreted in terms ofa diamond cubic (de) crystal in which all the C-atoms are to
be replaced by the S;-atoms and oxygen atoms are placed between the adjacent Si-atoms. Like
the diamond crystal, it is also a pure covalent crystal. .
(iv) Tridymite (Si0 2) structure (4:2 coordination crystal) : It is related with the wurtzite (ZnS)
structure in the same fashion as the ~-cristobalite is related with the zinc blende structure.
11.10.3 Structures of Ionic Crystals of A83 Type

(i) Cryolite and anticryolite structure: In the cryolite
structure, the anions from afcc sublattice in which
all the octahedral and tetrahedral holes. are filled -
up with Jhe cations. In the fcc sublattice of the ~en
.c::
anions there are two Td holes and one 0h hole ~
o
per anion. In the anticryolite structure, the positions b
of the cations and anions are inter-changed, i.e.

e
~
ry
cations from thefcc sublattice in which the 0h and ~
Td holes are occupied by the anions. Examples of E
c
ra
cryolite structure : Na 3AlF6 , etc. Examples of u_
anticryolite structur~/: [Co(NH3 )6]13' etc.
ib
(ii) Rhenium. trioxide (ReO J ) structure (6~2
2
coordination crystal) : The structure is shown in 0 =0 -
yl
Fig. 11.10.3.1 where the eight Re atoms occupy the Fig. 11.10.3.1. Rhenium trioxide (Re03 )
8-corners of a cube and at the centres of the 12 crystal (6 : 2 coordination) structure.
°
edges there are 12
m
atoms. The eight Re atoms
effectively contribute one Re atom per cube and the 12 0 atoms contribute 12 x ~, i.e. 30
he
atoms
4
per cube. Thus the stoichiometry is satisfied. Here each Re atom is octahedrally surrounded by
the six oxygen atoms. Oxygen atoms are present at the vertices of corner shared octahedra.
lc
Examples: W0 3, AlF3 , FeF3 , etc. The perovskite structure can be derived from the Re03 oxide
structure (see Fig. 11.11.3.2).
ea
11.10.4 Structure of Ionic Crystals of A2 8 3 Type: Corundum (a-AI2 0 3 ) (6:4 Coordination

th
Crystals)
It has a hcp array of the oxide ions in which 2/3rd of the octahedral holes are occupied by the cations.
e/
It is not a layered structure. Examples: Fe 20 3, Cr 20 3 , V20 3 , Rh 20 3 , etc. Al20 3 forms a hard crystal
with a high· melting point. In the Al20 3 structure, it is possible to substitute a part of the Al3+ ions by
t.m
some trivalent cations of comparable size. A partial replacement by C?+ produces ruby used in ruby
LASER (Light Amplification through Stimulated Emission of Radiation). Similarly, the substitution
by Fe 3+ produces blue sapphire used in jewelled bearings and cutting tools.
11.10.5 Structure of Ionic Crystals Consisting of Polyatomic Ions

The basic structural types (i.e. NaCl, CsCl, ZnS, CaF2 , Ti02 , etc.) are adopted by different ionic crystals
consisting of monoatomic ions and the polyatomic ions which are almost spherical (i.e. tetrahedral and
octahedral moieties). But the problem is complicated for the cases having nonspherical polyatomic
ions (e.g. coi-, N03- , NO:;, etc.) and very often such compounds produce the structures which are
slightly distorted with respect to the basic structures to accommodate the polyatomic ions. For example,
CaC03 and NaN0 3 basically adopt the NaCl structure but to accommodate the large nonspherical
anions, the basic structural unit gets distorted. In fact, in NaN0 3 , the unit cell is compressed along the
C 3 axis of NO:;. Thus the effects of the constituent ions are reflected on the crystal structure. In this
connection, it is important to mention that the nonspherical ions such as CN-, 811, etc. which tumble
rapidly in the crystal structure at ordinary temperatures 'attain the sphericity.
11.10.6. Comparison of the Basic Ionic Crystals
Table 11.10.6.1. Comparison of the characteristic features of the common basic ionic crystals.
Crystal Characteristics ofarrangement ofthe ions C.N. Examples
--------
Cation Anion
AB Type:
(1) Common salt (i) Two fcc sublattices of the cations and 6 (Oh) 6 (Oh) KCI, NaF,
or rock salt anions are interpenetrating KBr, CaS, LiX
ry
(NaCI) (ii) In afcc sublattice of the anions, all the (X = F, CI, Br,
0h holes are occupied by the cations I), MO (M =
Mg, Ca, Sr, BaJ
ra
(2) Cesium (i) Two sc sublattices of the cations and 8 (cubically) 8 (cubically) CsX (X = CI,
chloride anions are interpenetrating Br, /) TIX (X =
ib
(CsC!) (ii) Both the cations and anions occupy Br, /), K[SbF6l
the cubic holes formed by the opposite ions
yl
(iii) Body centred type cubic crystal
(3) Zinc blende The anions from afcc sublattice in which Agl, CuX(X=
or sphalerite half of the Td holes are occupied by the CI, Br, /); MX
(ZnS) cations
m (M=Zn, Cd,
HgandX=S,
he
Se, Te, etc.)
(4) Wurt=ite The anions have a hcp sublattice in which MgTe, CdS,
(ZnS) half of the tetrahedral holes are occupied AIN
lc
by the cations
AB 2 Type:
ea
(1) Fluorite (CaF2 ) (i) The cations form afcc sublattice in 8 (cubically) 4 (Td ) BaF2 • SrF2 ,
which all the Td holes are occupied by BaCI2 , CdF2
the anions
th
(ii) The anions form a sc sublattice in

which half of the cubic holes are occupied
e/
by the cations
(2) Antifluorite The positions of the cations and anions
t.m
are reversed with respect to those of the

fluorite structure, Le. the anions in afce
(sublattice) and the cations are in a sc
(sublattice).
(3) Rutile (Ti0 2 ) The cations lie in a body centred tetra- 3 (triangular) MF2 (M = Mg,
gonal symmetry Co, Ni), Sn02,
Mn02
(4) Antirutile The positions of the cations and anions are 3 (triangular) 6 (Oh)
reversed with respect to the rutile structure
(5) p-cristobalite In the diamond cube (de) all the positions 2 (linear)
(Si0 2 ) of C atoms 'are replaced by silicon atoms
and oxygen atoms are placed between the
silicon atoms; or in the zinc blende structure
all the positions of Zn 2+ and S2- ions are
replaced by the silicon atoms and oxygen
atoms are placed between the silicon atoms
(Contd.)
Crystal Characteristics 0/ arrangement 0/ the ions C.N. Examples

Cation Anion .
(6) Tridymite (Si0 2) In the wunzite structure all the positions 4 (Tel) 2 (linear) Si02
of Zn 2+ and S2- ions are replaced by the
silicon atoms and oxygen atoms are
placed between the silicon atoms
ABJ Type:
( 1) Cryolite The anions form a/cc sublattice in which 2/3rd of the Mixed type Na3[AIF6]
ry
(Na 3[AIF6 ]) all the octahedral and tetrahedral holes are cations:
occupied by the cations. (Tel);
ra
1/3rd of the
cations:
(Oh)
ib
(2) Anticryolite The cations form a/cc sublattice in which Mixed type 2/3rd of the [Co(NH3)6]J3
all the 0h and Tel holes are occupied by anions:
yl
the anions (Tel);
1/3 of the
m anions:
(Oh)
he
(3) Re03 The 8 comers of a cube are occupied by 6 (Oh) 2 (linear) W0 3,AIF3,
8 Re atoms while at the mid-points of FeF3
the 12 edges there are 12 oxygen atoms
lc
A 2B J type:
Corundum 02- are in a hcp sublattice and 2/3rd of 6 (Oh) 4 (average) Fe203' Cr203
ea
(a-A 12°3) the Oh-holes are occupied by the cations

th
11.11 STRUCTURES OF MIXED METAL OXIDES

e/
Many mixed metal oxides which are essentially ionic in nature adopt the structures which can be
interpreted in tenns ofthe basic structures already discussed. The different classes are generally named
t.m
after the most important naturally occurring minerals represe.nting the different classes.
11.11.1 The Spinel and Inverse Spinel Structure

It is named after the naturally occurring mineral spinel MgAI20 4• It consists ofa ccp array of oxide ions
in which the divalent metal ions (Le. Mg2+) occupy 1/8th of the Tdholes and the trivalent metal ions (Le.
AI3+) occupy 1/2 of the 0h holes. In a ccp (i.e.fcc) sublattice of the anions, there is one 0" hole and
two Td holes per anion. There are four Qxide ions per molecular formula, and consequently there are
four 0h holes and eight Td holes. Thus it can be generally expressed as AB'1.04 where A occupies 1/8th
of the tetrahedral holes and B-s occupy 1/2 of the octahedral holes. A and B may have different types of
charge combinations such as : AIIB~II04' AIV B~I04 and AVIB~04.
In the inverse spinel structure, it is represented as B(AB)04 where half of B-s occupy 1/8th of the
Td holes; and A and half of the B-s occupy half of the 0h-holes in the ccp array of (jl- ions. Thus, here
A has a strong tendency t~ occupy the 0" holes. This generally takes place in transition metal
oxides. Generally the site selection is governed by the relative change of crystal field stabUisation
energy (CFSE) in occupying the 0" and Tdholes by A. Ifin placing A in the 0h holes instead of the Td
holes, it brings more CFSE, then the inverse spinel structure is favoured, provided in shifting B from
the 0h site to the Td site, the CFSE change is negligible. This condition is generally attained when A is
not a ()5 or dlo system and B bears a cP or d lo configuration (e.g. Fe 3+) because in the weakfield (which
favours the high spin .complexes) provided by the (jl- ions, the cP and d lo systems do not have any
CFSE in both the 0h and Td fields. The condition to attain the inverse spinel structure is :
ry
gain of CFSE in shifting A from a Td hole to an 0" hole> loss of CFSE in
shifting B from an 0" hole to a Td hole.
ra
Besides the CFSE, many other factors may contribute to determine the spinel or inverse spinel
structure, but the prediction from CSFE calculation is in good agreement with the experimental fact. It
ib
is illustrated in some cases. To calculate the CFSE, the pairing energy has been ignored and it has
been assumed IDq(o,,> AS 2Dq(Td)for a particular metal ion and IDq(~II) AS 1.5Dq(~lr The two forms
yl
may be represented as follows : ~
Mil (Td )[M~II (Oh )]04 (spinel);

II
MIll (Td )[M (Oh )M III (Td )]04 (inverse spinel)
m
Thus in changing the spinel structure to an inverse spinel structure, the required changes are :
he
MII(Td ) ~ MIl (Oh); MIII(Oh) ~ MII(Td )
• In Fell(Felll)104 (i.e. Fe J04), for the conversion of the spinel form into the inverse spinel form,
lc
the CFSE changes are :

Fe II [Td ,et
3 3
2 ,CFSE=6Dq
I1[ 4 2
1I)]~Fe 0h,t 2g eg ,CFSE=4Dq II ~8Dq II
]
ea
(Tdt Fe (Oht Fe ) (Tdt Fe )
It leads to gain of CFSE = 2Dq II

(Td·Fe )
th
III 3 2 III 2 3
Fe [Oh,t2geg,CFSE=O]~Fe (Td,e t 2 ,CFSE=O)
e/
i.e. no gain or loss of CFSF in this change.

Thus, in converting the normal spinel structure to the inverse spinel structure for Fe 30 4 , there is a
t.m
net gain of 2Dq II CFSE where 10 Dq II gives the crystal field splitting energy of Fell in the
(Td,Fe ) (Td·Fe )
tetrahedral crystal field of (jl-. This is why, Fe J 0 4 adopts the inverse spinel structure denoted by
FellI ( FellF e11I)04.
• In the case of eoD Fe~04' the inverse spinel form is p~ssessing 4Dq
(Td·Co
II
)
CFSE more
compared to the nonnal spinel form. For changing FellI (Oh' t~ge;) to Felli (Td , e2t~), there is no change
of CFSE. The gain of CFSE for changing the site for CoIl is obtained as follows :
Co II [(Td,e 43
12 ,CFSE=12Dq
II S 2
II ]~Co [(Oh,/ 2g eg ,CFSE=8Dq II ~16Dq II
]
(Td.Co ) . (Oh'co ) (Td, Co )
Le. the gain of CFSE = 4Dq II

(Td,Co )
• The case of Co J 0 4 is quite interesting. In calculating the CFSE, it has been assumed that MIl
remains in high spin state in the octahedral ligand field of (jl-. But, in the case of COllI, it remains in a
higli spin ~ low spin equilibrium (Le. critical lODq co III ) value). Thus for Co 30 4 , the change of
(Oh'
CFSE for the conversion, normal spinel to inverse spinel is obtained as follows. If it is assumed that
CollI remains in a low spin state exclusively, then we can write:
III 6 0 . III 3 3 ]
Co [Oh,1 2g eg ,CFSE=24Dq III ~48Dq III ]~Co [Td,e 12 ,CFSE=6Dq III
(Oh' Co ) (Td.Co ) (Td·Co )
Le. loss ofCFSE = 42Dq III ~ 63Dq II

(Td.Co ) (Td·Co )
(Note: It is assumed that in changing M2+ to M3+ the splitting energy goes to increase by ca. 50%).
ry
For the change CoIl(Td) ~ CoIl( 0h)' there is a gain of CFSE = 4Dq II .
(Td • Co )
ra
Thus in converting the normal structure to the inverse spinel structure for Co 30 4 , there is a net loss
ofCFSE=(63-4)Dq II =59Dq II .
(Td.Co ) (Td·Co )
ib
Here it is important to mention that COllI does not remain exclusively in the low spin state and
consequently the loss of CFSE is not so high as given above. If COllI remains exclusivel·y in the high
yl
4 2
spin state in the octahedral site, then for the change, m COllI (Oh' t1ge;) to CollI (Td , e t ) the loss of
CFSE = 2Dq III ~ 3Dq(T C II)' Thus in such cases, there would be net gain of CFSE =
(Td.Co ) d' 0 .
IDq II for the conversion of normal spinel to inverse spinel.
(Td·Co )
he
Experimentally, Co 30 4 is found to have the normal spinel structure. In reality, CollI does not
remain exclusively in the high spin state, but it remains in a high spin ~ low spin equilibrium,
lc
in which contribution of the low spin form is quite significant.

Generally, the octahedral sites are favoured by the metal ions having high charges and electronic
ea
configurations such as d3 , cf, If, etc. These are: C,J+ (d3 ), Mn 3+ (cf), Co 3+ (If) etc. They generally
remain in high-spin state in the weak ligand field provided by (j2-. But, Co 3+ brings such a high value
of CFSE in its low spin state that it can form (at least partially) the low spin octahedral complexes
th
even in the weak field provided by the (jl- ions. Some representative examples are given in Table
11.11.1.1.
e/
Table 11.11.1.1. Some representative examples of spinel and inverse spinel structure.
t.m
Type Formula Examples

Spinel All Bill 0 A = Mg, Zn, Cd, Mn, Fe
2 4
B=Al, Cr
TiZn 20 4
A = Mo, B=Na
Inverse spinel A = Fe(d'), Co(J7), Ni(c!'); B = Fe(tP)
Ferrites andferrimagnetism : The inverse spinels AFe20 4, Le. FeIlI(AIIFeIlI)04 (where A = Fe, Co,
Ni, etc.) commonly called ferrites show the ferrimagnetism where the Fe(III) centres in tetrahedral
holes undergo antiferromagnetic coupling with the Fe(III) centres in octahedral holes. Thus, the
resultant magnetic moment is detennined by the magnetic behaviour of All. This aspect has been discussed
in Sec. 11.16.3. If All is itself diamagnetic (e.g. A = Mg II ), then the inverse spinel, Le. FeIII(MgIIFeIII) is
diamagnetic below the Neel temperature.
Electrical conductivity ofinverse spinels and normal spinels (cf. Sec. 12.10, Question N(}f'~26) :
The inverse spinels like Fe 30 4 Le. (Fell~teiFell, FellI)oct04 show the hopping semiconductivity and ,
sometimes metallic conductivity while the normal spinels like Mn 30 4 Le. {MnII)tet(Mn~lI)oct04 are
the insulators. The octahedral sites are the edge-shared octahedra. This is why, the octahedral sites
are close to one another. Thus, in Fe 30 4, Fell and FellI centres present in octahedral sites can participate
in electrical conduction through hole migration (hopping mechanism). In the normal spinel structure
of Mn 30 4, Mn II and Mn III centres present in Tdand 0h sites are widely separated. In fact, comers of the
tetrahedral sites share the corners of octahedral sites (cf. Fig. 11.9.3.2). This long Mnll-Mn III distance
ry
does not allow the positive hole migration. This is why, it cannot conduct electricity. Here it may be
noted that the closely spaced octahedral sites carry only Mn III centres which cannot lead to hole migration.
ra
11.11.2 The Ilmenite Structure (FeTi03 )
ib
It is named after the mineral FeTi03 • It adopts the structure of
corundum. Here 1/3rd of the 0h holes are occupied by Fe 2+
yl
ions and other 1/3rd of the 0h holes are occupied by Ti+ 4 ions in
the hcp array of the 0 2- ions. The structure is generally
represented as : AIIB1V 0 3, AIIIBIII03' A 1Bv 0 3•
m
Examples: A II B1V 0 3 (A = Fe, Cd, Mg, Co; B-= Ti), A 1Bv 0 3
he
(A = Li, B = Nb).
• = Ca 2• 0 = 0 2- • =Ti 4 '
11.11.3 The Perovskite Structure (CaTi03) Fig. 11.11.3.1. Perovskite (CaTi03 )

lc
structure.
It is named after the mineral CaTi03• Here (jl- ions along with
ea
the larger cations (Le. Ca2+) from a ccp or fcc array in which the 0h holes formed by (jl- ions are
occupied by the smaller cations (Le. Ti4+) (see Fig. 11.11.3.1). In the unit cell, 8 comers of a cube are
th
occupied by Ca2+ ions, (jl- ions are placed at the centres of the 6 faces of the cube, and Ti4+ is placed
at the centre of the cube. Contribution of ca2+ ions is
e/
I ( =8 x k), contribution of (jl- ions is 3 ( =6 x ~) and

t.m
contribution of Ti 4+ is 1 to the unit cell. It leads to

stoichiometry CaTi03 •
The structure can also be interpreted in terms of Re03
structure (see Fig. 11.10.3.1) in which the positions of
Re atoms are occupied by Ti 4+ ions while Ca 2+ ion
occupies the centre of the cube. Thus Ti 4 + ion is
octahedrally surrounded by (jl- ions while Ca2+ ion is
surrounded by twelve (jl- ions residing at the centre of
the edges of the cube (see Fig. 11.11.3.2). I t is generally
represented as: A IIB IV 0 3, AIIIBIII03' A 1Bv 0 3• Examples:
AIIIBIII03 (A = La; B = AI, Ti, Cr, Mn); A IIB IV 0 3 (A =
Fig. 11.11.3.2. Development of perovskite
Ca, Sr, Ba; B = Ti, Zr, Ge, Sn); A 1B v 0 6 (A = Na, K; B = .- (CaTiO~) structure from rhenium trioxide
Nb, Ta). Re0 3 , (cf. Fig. 11.10.3.1) structure.
Some mixed fluorides (ABF3 ) such as KZnF3 adopt the perovskite structure. In general, it is
represented by A 1B II F 3(A = K; B = Mg, Mn, Fe, Co, Ni, Cu, Zn). Some other salts like, A 1B II Cl3 (A = Cs;
B = Cd, Hg, Ca); AIIB1VS3 (A = Sr; Ba; B = Ti) also adopt the perovskite structure.
11.11.4 Mixed Oxides - Coloured Minerals and Gem Quality Crystals

The minerals like spinel, alumina, beryl and quartz are colourless. The silicate structure of beryl and
qualtz are discussed in Sec. 11.14. In such crystals, replacement of the native metals by the transition
metals through the isomorphous substitution to some extent can produce different types of coloured
ry
crystals (due to d-d transitions). Replacement of Mg 2+ by Co 2+ in spinel (MgAI20 4 ) produces blue
spinel; addition of Cr203 (1 %) in MgAl20 4 gives ruby red spinel. Beryl AI2Be3[Si601S] can produce
ra
different gemstones through the isomorphous substitution and the involved transition metal ions are:
pink morganite (Mn 2+), blue aquamarine (Fe 2+), green emerald (Cy3+), etc. Addition of Cr203 (ca.
ib
1%) in alumina gives ruby red; while blue sapphire contains both iron and titanium. Dispersion of
small Ti0 2 crystals produces scattering in the gems like rubies and sapphires. Amethyst is obtained
yl
through the partial replacement of silicon by iron. '
Here, it is interesting to note that the same transition metal ion doped (through the isomorphous
m
substitution) into different crystal lattices gives different colours. For example:
he
• Cr1+ into corundum (AI20 3) gives ruby red colour.
• Cr1+ into beryl, A12Be3[Si601s] gives the green colour in gemstone emerald.
lc
This can be explained in terms of crystal field splitting. In terms of ionic radius (Shannon crystal
ionic radius), A13 + (r = 67 pm) is smaller than Cy3+ (= 75 pm). If cy3+ is placed in the position of A13+
ea
in Al20 3 crystal, CrIII-O distance becomes shorter than the normal CrIlI-O distance. Thus, Cr(III)
experiences a stronger crystal field splitting in corundum than in Cr203 or Cr(H20)g+ that looks
th
bluish violet. This is why, Cr(III) in corundum gives the unusual ruby red colour. The following
electronic transitions are responsible for the ruby red colour.
e/
4A (F) violet li~ht ) 4~ (F) 4 A (F)_g_re_e_n_li_gh_t~) 4 (F)

t.m
2g absorption 19 '2g absorption T2g Sec. 7 . 14.,

( see 5
absorption 4 (p)
Vol. 5)
4 A (F) T19
2g in ultraviolet region)
Absorption of violet and green light gives the characteristic ruby red colour. The above mentioned
transitions in Cr(H20)t+ occur in lower energy region because of the relatively less crystal field
splitting. On the other hand, when CrIll is placed in beryl through substitution of AI(III), there is an
elongated Cru-O bond determined by the structural parameters of beryl lattice. This is why, Cr(III)
in beryl lattice experiences relatively less crystal field splitting compared to that in ruby. This is
why, emerald gives green colour.
Ti 3+(r = 81
pm) being larger than A13+ (r = 67 pm) experiences the shorter TiIII_O distance in
corundum compared to normal TiIII_O distance as in Ti(H20)g+. This is why, Ti(III) experiences u
higher crystal field splitting when placed in corundum through the substitution of AI3+. It explains the
blue colour (2T2g ~ 2Eg , i.e. t~g ~ e~; see Sec. 7.14.1, Vol. 5) of the gemstone sapphire (cf. Ti(H20)g+
looks violet where crystal field splitting is relatively less).
Structure, Bonding and Properties of IOfilic Solids and Solid State Chemistry 1047
11.12 CRYSTAL STRUCTURE IN REL!'TION TO SUPERCONDUCTIVITY

AND FERROELECTRIC PROPERTY
Here we shall specially discuss the structure· of barium titanate BaTiOJ which is well known as a
ferroelectric material and the ceramic material YBa 2Cu J O,_J. which can show the superconductivity
up to -- 90 K. Both the compounds are very much important from the standpoint ofpractical applications.
Both of them adopt the perovskite structure (see Sec. 11.1 1.3).
Note : Ferroelectric materials and superconductors have been discussed separately in Sec. 11.17
ry
and Sec. 12.13 respectively.
11.12.1 BaTI03
ra
Ferroelectric materials are known to have very large dielectric constants. As in the ferromagnetic
ib
substances, the electric dipoles in a ferroelectric solid are oriented in a particular direction even in the
absence of an external electric field. The ferroelectric property of BaTiO) can be interpreted in terms of
yl
its crystal structure. It adopts the cubic perovskite structure, Le. (jl- ions and the larger cati9ns, BQl+
are in alcc or ccp array and the smaller cations, T"'~+ occupy the octahedral holes formed by the (jl- ions
m
(see Fig. 11.11.3.1). Thus in the unit cell, 8 comers of a cube are occupied by the BQl+ ions, at the
centre of each face there is an (jl- ion, and at the centre of the cube Ti4+ ion is housed. Thus the
he
contributions of the lattice points per unit cell are : Ba2+ ions at the comers = 8 x .!.. = I· 0 2- ions at the
~ 8 '
six faces = 6 x .!.. = 3; Ti 4
+ ion at the centre = I x I = I ..
lc
2
This cubic perovskite structure is retained above the Curie temperature, 120°C. The centres of the
ea
positive and negative charges coincide at the centre of the cube and as a result, there is no
spontaneous dipole moment. But when the crystal is brought to below the Curie temperature, 120°C,
th
then Ti4+ ion mov~s from the centre of the cube to one side along with the simultaneous displacement
of the (jl- ions. Thus the crystal structure changes from cubic to tetragonal on cooling below 1200C.
e/
In this tetragonal structure, the centres ofthe negative andpositive charges do not remain coincident
and the local dipoles are developed throughout the crystaL These dipoles remain aligned in a particular
t.m
direction to produce a large polarisation in the solid.

Here it is important to note that Ti4+ is too small compared to the space provided by the oxygen
octahedron and Ti 4+ is highly polarising. This increases the polarisabilitY. of the crystaL In fact, the
spontaneous polarisation below Curie temperature (Tc> is possible because of these reasons.
Ferroelectric property of BaTi03 and other materials has been discussed in Sec. 11.17.
11.12.2, YB~Cu3o,_x
Development of a superconductor at room temperature is the most challangeable task to the present
scientific community. The highest temperature up to which superconductivity is reported (1986-88) is
90 K in YBa2Cu 30 7 _ x which is informally referred to as 123 compound by considering the molar
proportions of the metals ~ Ba and Cu in the compound. This temperature is about 13°C above the
boiling point of liquid N 2• The above mentioned mixed oxide is prepared by heating (950-9600 C) a
homogeneous powder mixture of Y20 3 , BaCO) and CuO at their appropriate proportions. At this
temperature, BaC03 decomposes and the mixture is annealed at -- 400-500oC in an atmosphere of
oxygen. Depending on the partial pressure of O2, the number of oxygen atom per stoichiometric formula
varies from 6.5 to 7.
The crystal structure of the mixed oxide

is related to the cubic perovskite lattice.
ry
The structural and other characteristic
features of the 123 compound and other
ra
ceramic materials as warm superconductors
have been discussed in detail in Sec. 12.13. o 8a 2+
ib
The structure of the 123 compound can be
considered to have a unit cell where three
yl
perovskite units (ABO J ) are stacked. The () 0
2
- (vacant)
middle unit CuY03 is stacked between two
CuBa03 units.
m
The structure (see Fig. 11.12.2.1) can be
he
interpreted in terms ofthe Re03 structure (see
Fig. 11.10.3.1). Three body centred cubic
lc
(bee) unit cells are stacked one above another.

Each corner of the cubes is occupied by Cu 2+
ea
ions Gust like the Re atoms in Re03), (jl- ions

are placed at the centre of each edge and y3+
Fig. 11.12.2.1. Crystal structure of the super-
th
ion occupies the centre of the middle cube

while Ba2+ ions occupy the centres of the top conductor, YB~Cu307 - x (123 compound).
e/
and bottom cubes. Thus the distribution pattern of the lattice points and their contributions are as
follows: Cu 2+ ions at the corners of the three cubes: 8 x.!- x3 = 3; Ba2+ ions at the centres of the top
t.m
8
and bottom cubes: 1 x 2 = 2; y3+ ion at the centre of the middle cube: 1 x 1 = 1; (jl- ions at the centres
of all the edges of the three cubes: 12 x ~ x 3 =9. Thus, the stoichiometric formula of the perfect
4 11
perovskite structure is YBa 2 Cu J 0 9• It leads to average oxidation state 3 for copper Le. existence of
both Cu(II) ana Cu(IV) in the stoichiometric compound YBa 2Cu 30 9 . But existence of Cu(IV) is quite
unlikely and YBa 2Cu 30 9 is improbable. In fact, the number of oxygen atoms lies between 6.5 and 7.
Thus some of the oxygen sites remain vacant to produce the nonstoichiometric compound in which
the electrical neutrality can be attained in a number of ways (see crystal defects, Sec. 11.15). The
superconductingproperty of the mixed oxide is dependent on the oxygen content, i.e. number of
crystal defects. This oxygen content depends on the partial pressure of oxygen present at the time of
preparation of the compound.
For YBa 2Cu 30 7, the average oxidation state for Cu becomes +2.33. It indicates that this
superconducting material contains both Cu 2+ and Cu J+.
11.13 DEVIATIONS FROM SIMPLE IONIC STRUCTURES

We have already seen (see Table 11.7.2.1) that when the covalency is significant in an ionic compound,
the calculated lattice energy significantly differs from the observed one. Some compounds having
properties between those of representative ionic and covalent compounds may adopt some typical
structures such as: chain structures, sheet structures, etc.
11.13.1 Layer Lattices (i.e. Two Dimensional Lattices)

(i) CdCI2 structure: Here the anions (Le. :Ct) are distributed in a ccp pattern, in which half of the
ry
0h holes are occupied by the cations (Le. CcP+). The structure is related to the NaCI structure in
which all the 0h holes formed by the ccp distribution of the Ct ions are occupied by the cations
ra
(Le. Na+). From the stoichiometry of CdCI2, only half of the 0h holes can be occupied by CcP+
ions. This can be attained theoretically in two ways :
ib
(i) half of the 0h holes in each layer can be o~cupied, or, (ii) all the 0h holes in alternate layers
can be occupied.
yl
In fact, CdCl2 has the sheet structure in which all the 0h holes in alternate sheets are occupied by
m
CcP+ ions giving rise to a sheet of CcP+ ions sandwiched between the adjacent layers of anions.
Thus the anions of one layer adjacent to those of the next layer are held through weak van
he
der Waals forces. This is why, such crystals cleave into parallel sheets easily. Examples: MCl2
(M= Mg, Mn, Fe, Co, Ni), Ni/2, ZnBr2• .-
(ii) CrC/3 structure: The anions are distributed in a ccp pattern as in CdCl2 structure and NaCI
lc
structure but here only 113 rd of the octahedral holes are occupied by the cations as demanded
from the stoichiometry. In the layer structure of CrCI3,. only 2/3rd of the octahedral holes in
ea
alternative layers are filled in by the cations. Here again the anions of two different adjacent
layers are held through weak van der Waals forces.
th
(iii) Cdl2 structure: It (see Fig. 11.13.1.1) has a similarity with that of CdCI2, but here the anions are
distributed in a hcp pattern instead of the ccp pattern
e/
prescnt in CdCI2. Here, half ofthe 0h holes are occupied

by the cations. This is attained by filling in the octahedral
t.m
holes in the alternate layers as in CdCl2 structure.

Examples: MBr2 (M = Fe, Co, Ni, Cd), M12 (M = Mn,
Fe, Co, Zn, Mg, Ca, Pb), M(OH)2 (M = !vfg, Ca, Cd,
Mn, Fe, Co, Ni) .
(iv) Bismuth iodide (BiI3) structure: Here the anions (Le.
1) are distributed in a hcp pattern and 2/3rd of the
octahedral holes in alternate hole sheets are occupied
by the cations (Le. B;3+). It is related to Cd12 structure in
the mode of anion distribution. The difference between
the CrCl3 structure and Bil3 structure is that the anions
in CrCl3 structure are in a ccp pattern while the anions
in Bi13 structure are in a hcp pattern. Examples: FeCI), o =r e = Cd 2
+
TiCI3, VCI3, etc. Fig. 11.13.1.1. Cdl2 structure.

Afo~ vs. FeS2

Many metal disulfides (e.g. MoS'l) adopt the layer structure ofCdl2. It is interesting to note that in
MoS2, Mo(IV) is present while in pyrite FeS2, iron is in +2 oxidation state. Thus FeS2 consists of
Fe(II) and si- not Fe(IV) and S2-. In fact, Fe(IV) being a powerful oxidising agent will oxidise
S2- to elemental sulfur, while Mo(IV) is not a so strong oxidising agent and it can coexist with
S2-. In FeS2 crystal, si- ions occupy the octahedral holes of fcc sublattice produced by Fe(II).
Thus, MoS2 bears the CdJ2 type structure while FeS2 bears the NaCI type (i.e. rock salt) structure.
ry
Note: FeS2 (pyrite known as fool's gold for its golden metallic lusture) should be described as
mono(disuljides) while MoS2 should be described as di(monosuljides). Other examples of
ra
mono(disulfides) group are: FeAsS (arsenopyrite), PtAs 2 (sperrylite); WS2 belongs to the group of
MoS2 •
ib
. (v) Mercuric halide (HgX2) structure: HgF2, HgCI2, HgBr2 and Hgl2 have different structures.
yl
HgF2 being ionic having radius. ratio, r+/r_ = 0.81 adopts the fluorite strilcture. HgC/2 cannot
adopt the fluorite structure (cf. Fig.· 11.10.2.1) because the too small radius ratio
(rHi+ I r
m
cr =0.61) does not allow the cations to get properly fitted in the cubic holes of simple
cubic sublattices of C, ions. On the other hand, it cannot adopt the CdCl2 structure because the
he
cation is probably too big (due to the significant amount of covalence) to get accommodated in
the 0h holes. Thus the explanations based on the radius ratio rules are not very much convincing
lc
because the covalency in HgC/2 is signifICantly high. As a matter of fact, HgCl2 remains as
discrete molecules and the crystal consists of packing of the linear Cl-Hg-Cl molecules.
ea
HgBr2 gives the radius ratio (r

Hg
2+ / r _
Br
=0.56) which is more accommodating compared to
HgCl2 to the CdCl2 type structure. But still the radus ratio is too large. Probably, this is why, it
th
adopts a structure which is intermediate in nature between the molecular lattice structure of
e/
HgCl2 and layer lattice structure ofCdCl2. Here the octahedral arrangement is distorted with the
two trans-Hg-Br distances shorter compared to the other Hg-Br distances. This tetragonal
t.m
compression (Le. axial compression leading to z-in distortion) indicates the reflection of the
linear molecular structure of HgCI2 ,
HgI2 has got a layer type lattice structure. Here the 1 ions are distributed in a ccp pattern in
which half of the Td holes in the alternate hole sheets (i.e. layers) are occupied by Hg'-+ ions.
Each Hg'-+ ion is tetrahedrally surrounded. This is why it is considered to consist of Hgl;-
tetrahedra in which each 1 ion bridges two Hg'-+ ions in two adjacent tetrahedral moieties. .
11.13.2 Chain lattices (I.e. One Dimensional lattices)

In some compounds where covalency is extremely high, the bridging halides produce the one dimensional
chains. Again, here the van der Waals forces operate between the adjacent chains. Some examples of
this group are: BeCI2, CuCl2 and PdCI2. In BeCI2, the bridging chlorines share the adjacent tetrahedra
of BeCl4 subunits. In PdCl2 and CuCI2, because of the inherent tendency of the metal ions to attain the
square planar geometry, here the bridging chlorines share the adjacent square planar moieties.
\
" /CI, /CI" /CI" / . 3

/Be, Be, /Be.............. ~Be . (Be,sp)
CI/ CI'" CI"""'"
, ~CI" ~CI, / C I , / _ . 2
M "-.... ./'" M ........ . / ' M"'-.. . / M ............. (M - Cu, Pd, dsp )
/ CI "CI CI
11.14 STRUCTURES OF SILICATES AND ISOPOLY- AND HETEROPOLY
ry
ACIDS : REPRESENTATIVE EXAMPLES OF COMPLEX .IONIC CRYSTAL
11.4.1 Chemistry of Silicates
ra
In the silicates, oxide ions fonn a close-packed array in which the cations like Si4+, AI3+, Be2+, Mg2+,
Fe 2+, etc. occupy the octahedral (Oh) and tetrahedral (Td ) holes depending the radius ratios (see Table
ib
11.14.1.1). AI~+ can occupy both the holes as required.
yl
Table 11.14.1.1. Selection of holes by the cations by radius (using Goldschmidt's
value; Table 11.3.4.1) ratio rule. .m
Cation (M'+ ) Radius rati" (r 2+ Ir 2-) Type ofthe hole occupied by Ar
M 0
Be 2+
he
'1):25 Tetrahedral
8;4+ 0.29 Tetrahedral
A13+ 0.43 (border line) Tetrahedral and octahedral
lc
Mg2+ 0.59 Octahedral

Fe 2+ 0.68 Octahedral
ea
The tetrahedral moieties Si04 can form different types of structure depending on the number of
th
oxygens in each Si04 unit shared by the adjacent tetrahedra. In mixed silicates, besides the Si04, other
units like M04 (M= Be2+, AI3+), M06 (M= AI3+, Mg2+, Fe 2+) are also present.
e/
Important structuralfeatures ofsilicates are:

• strong Si-D bond having both ionic and covalent interactions (~X = 1.7); each Si-centre is sp3
t.m
hybridised;
• the ionic radii of A13+ and 8i4+ are comparable and 8i4+ may be replaced by A13+ to give
aluminosilicates;
• the tetrahedral 8i04 units are the basic structural units whose 1,2,3 or 4 cornen may be shared
to produce cyclic groups, chains, infinite'layers or infinite three dimensional frameworks,
respectively; Me-group is formally isoelectronic with 0- (Le. unshared O-centre of silicates)
and replacement of 0- centres of silicates by Me-groups gives the structures of silicones (cf.
Question No. 127).
• the edges of tetrahedral Si04 units are never shared.
Different classes of silicates are discussed below. Different types of silicate structure are shown in
Fig. 11.14.1.1.
(i) Orthosilicates (neso-silicates) : They contain discrete Si04 tetrahedra (with Si : 0= 1 : 4) where
no oxygen atom shares with the other tetrahedra (see Fig. 11.14.1a) and oxygens coordinate
various types of cations and get electrical neutrality. Examples: Willemite, Zn 2Si04; Phenacite,
Be 2Si04; Forsterite, Mg2Si04; Olivine; (Mg, Fe)2Si04. In olivine isomorphous substitution
between Fe 2+ and Mg'l+ can occur at any proportion. Sometimes A13+ ions can replace Si4+ ions
from the discrete Si04 moieties but it requires additional positive ions to balance the charge.
(ii) Pyrosilicates (disilicates, soro-silicates) : The adjacent Si04 units are joined by sharing one
°
oxygen atom giving rise to Si20~- ion (Le. Si : = 1 : 3.5) (see Fig. 11.14.lb). Examples :
Thortveitite, Sc 2Si 20 7 ; Hemimorphite, Zn 4(OH)2(Si 20 7 }H20.
(iii) Cyclic silicates (cyc!o-si/icates) : Here two oxygens ofeach SiO4 unit are shared by the adjacent
ry
Si04 units giving rise to closed rings of triangular shape, (Si20 3)~- (see Fig. 11.14.1 c) and
°
hexagonals shape, (Si03 )~2- (see Fig. 11.14.1.ld) each. having the ratio Si : = 1 : 3. Examples:
ra
Wollastonite, Ca 3(Si0 3)3; Benitoite, BaTi(Si03)3; Beryl, Be3AI2(Si601S).ln beryl, the hexagonal
ib
-A- (a)
(Si04 )4- (Orthosilicate)
m
(b) yl
(Si 20 7 )6- (Disilicate)
he
(c)
(Si 30 9 )6-, Triangular
lc
(Cyclic silicate)
ea
(e)
th
~[SiO;-] or (Si03)~n-(Single chain),

(Pyroxene)
e/
t.m
(d)
(Si 60 18 )12- Hexagonal (Cyclic silicate)
(~ . (g)
~[Sip?l] or (Si4 01,)n60- Double chain, (Amphibole) ~Si P to]or (SiPs):n-lnflnite sheet silicate
Fig. 11 ~ 14.1.1. Different types of silicate structure. • Oxygen
rings, (Si03)~2- are superimposed one above the other to produce a channel into which small
gas molecules like He can be easily occluded.
In beryl, partial substitution by transition metals can produce coloured gemstones (cf. Sec.
11.11.3). Presence Cr (1-2%) in beryl produces emerald having deep green colour.
Table 11.14.1.2. Structural features of different types of silicates
Type ofsilicate Number ofO-atoms

shared ofeach SiO4-unit
ry
(i) Orthosilicates Le. neso-silicates o
ra
(ii) Pyrosilicates Le. soro-sllicates 1
(iii) Cyclic silicates Le. cyc/o-silicates 2
ib
(iv) Chain silicates Le. ino-silicates 2 (pyroxenes),
{ 2,3 (amphiboles)
yl
(v) Sheet silicates Le. phy//o-silicates 3
(vi) 3D-silicates Le. tecto-silicates m 4
(iv) Chain silicates (ino-silicates) : These are of two types - single chain (called pyroxenes) and
he
double chain (called amphiboles). In pyroxenes, each tetrahedral S;04 unit shares two oxygens
while in amphiboles some tetrahedra share two oxygens and others share three oxygens. The
general formulae for the single chain pyroxenes (see Fig. 11.14.I.le) and double chain amphiboles
lc
° °
(see Fig. 11.14.1 f) are (Si03)~n- (Si : = 1: 3) and (Si40 11 )~n- (Si : = 4: 11) respectively.
ea
Examples: Pyroxenes - Enstatite, MgSi0 3; Spodumene, LiAI(Si03)2. Amphiboles - Term 0 lite,

Ca#gs(0H)2 (S;40 11)2. The amphiboles always contain OH groups attached to the metal ions.
• The asbestos minerals very often contain amphiboles. The examples are: Na 2Fe s(0H)2[Si 40 1tl2
th
(crocidolite known as blue asbestos), (Mg, Fe)1(0H)2[Si40 11 ]2 (amosite, known as grey brown
e/
asbestos). It may be noted that asbestos is a commercial term. It is used for the materials which
are fire and heat resistant and can be woven. Commercial asbestos mainly consists ofchrysotile
t.m
(called white asbestos) which belongs to sheet silicate group (Le. serpentine structur-e).
Both in pyroxenes and amphiboles, the metal ions hold together the parallel chains through
electrostatic interactions. These forces are weaker than the directional forces forming the chains,
Le. (Si03)~n- and (Si4011)~n- units. This is why, the minerals undergo cleavage in directions
parallel to the chains. The chain polysilicates may be represnted as ~[SiOi-] and ~[Si40116-].
(v) Sheet silicates .(Phyllo-silicates) : Through the sharing of three oxygens of each Si04 unit by
the adjacent tetrahedra, the two dimensional sheet structure (see Fig. II.I4.I.lg) having the general
°
formula (Si 20 S )~n- (Si : = 1 : 2.5) gets developed. The sheets are held together by the metal
ions through the electrostatic forces. This is why, such minerals suffer cleavages in parallel
directions to generate thin sheets. The two dimensional layers are constructed by the combination
of Si04 (Td ), Al04 (Td ), Al06 (Oh) and Mg0 6 (Oh) units. Examples: Talc or Soapstone,
Mg 3(OH)2(Si 20S)2; Kaolin, AI2(OH)4(Si 20 s); Phlogopite (Mg-mica), KMg3(OH)2(Si 3AI0 10 );
Muscovite (mica), KAI2(OH)2(Si 3AI0 10 ); Biotite (mica), K(Mg, Fe)3(0H)2 (Si 3AI0 10 ).
Table 11.14.1.3. Structural features of sheet silicates
2-layer structures
With gibbsite layer With brucite layer
Kaolinite Chrysotile Le. Serpentine (fibrous serpentine)
A12( OH)4(Si 20 S ) Mg 3( OH)4(Si20 S )
3-layer structures
Prophyllite Talc or soapstone
ry
A/2( OH)2(Si40 I0 ) Mg3(OH)2(Si 40 I0 )
Montmorillonite Vermiculite
ra
Muscovite (mica) Phologopite (mica)
Biotite (mica)
ib
• Layered structure of silicates are quite interesting. Al(011)3 and Mg(OH)2 can crystallise in
layer structures maintaining the octahedral coordination Le. Al06 and Mg06 • Thus Al(OH)3 gives
yl
y-gibbsite sheet and Mg(0H)2 gives brucite sheet. If a silicate sheet Le. (Si20s)~n- is placed
m
over the y-gibbsite Le. Al(0H)3 or brucite sheet Le. Mg(0H)2 then some of the OH groups may
be removed in the interaction with the silicate layer. These will give layered (2-layer, 3-layer)
he
structure of silicates. Serpentine and talc are the Mg-analogues (Le. gibbsite layer is replaced by
brucite layer) of kaolinite and prophyllite respectively.
lc
Silicate sheet, Le. (Si20 s)~n- Silicate sheet

ea
y-Gibbsite sheet Le. Al(0H)3 sheet y-Gibbsite sheet.

(a) Kaolinite (2-layered) neutral Silicate sheet
th
Siiicate sheet (b) Pyrophyllite (3-layered) neutral

Brucite sheet Le. Mg(0H)2 sheet Silicate sheet
e/
(c) Serpentine or Chrysotile Brucite sheet

(white asbestos, neutral) (2 layered) Silicate sheet
t.m
(d) Talc or soapstone (3-layered),

neutral
In talc, there is no metal ion to hold one sheet to the next sheet electrostatically. It makes it soft
and slippery. It is used as a dry lubricant•
• Mica : Mica minerals are characterised by the presence of the structural unit (Si 3AI0 1o ).
Replacement of 8i 4+ by A13+ gives more negative charges in each layer. This allows more
electrostaic attraction between the sheets held together by the ~ ions compared to talc. It makes
mica harder than talc and in fact, micas cleave in sheets. The less electrostatic attraction
between the sheets in talc makes it soft and it is used as a solid lubricant. Muscovite (Le. white
mica) is related to prophyllite and biotite (Le. black mica) is related with talc.
• Clay minerals: These are polymerised aluminosilicates of two dimensional nature. In clays,
there are layers of polysicate or polyaluminosilicate anions. The parallel layers of A106 or Mg06
units produced by bridging 0/1 and (jl- ions are positively charged and remain sandwiched to
o
[(Si 40 10 ):n-]
----------
[{Al4 (OH)8}:n+] [{Al 4(OH)4 }:n+]
i.e. y - gibbisite i.e. y - gibbisite
--------------
Kaolinite (2 -layer) [(Si 40 10 ):n-]
. (neutral)
Pyrophyllite (3 - layer)
; {[AI 4 (OH)8][Si 40 10 ]} (neutral)
ry
(a)
~ {[AI 4 (OH)4 ][Si 4 0 IO ]2}
(b)
ra
. .
2n- 4n-
[(Si 4 0 10 ):n-] Isomorphous [(AlSi30Io)~n-]
------------------- ------------------
ib
[{AJ2Mg2(OH)4}~n+] Substitution [{Al2Mg2(OH)4}~n+]
------------------- ----------------- ..
[(Si 40 Io ):n- ] [(AlSi 30 I0 )~n-]
Montmorillonite (3 - layer)
yl Vermiculite (3 -layer)
excess negative charge
m excess negative charge
neutralised by monovalent neutralised by M(H 20);+
he
cations like K(H20)~, Le. M+ where M = C~ Mg
~ {M x (Mgx A1 4 ~ x (OH)4 ][Si 40 10 ]2} ~ {(Ca, Mg)2[AI2Mg2(OH)4][AISi30Io]2}

lc
(x =2 in the present illustration) (d)

(c)
ea
Fig. 11.14.1.2. Layer structure of some representative clays. Note: In talc (3-layered silicate mineral),
if at the brucite layer, Mg2+ is partially substituted by AP+, it gives montmorillonite while partial
th
substitution of Si4+ by AP+ in the silicate layers along with partial substitution of Mg2+ by AP+ in brucite
layer of talc gives vermiculite.
e/
hold electrostatically the negatively charged polysilicate layers. Some examples of clay minerals
t.m
are given in Fig. 11.14.1.2.

The bilayer clays like kaolinite are electrically neutral. These bilayer sandwiches (1 : 1) are
bound to the neighbouring bilayer units by weak H-bonding. In pyrophyllite, the electrically
neutral trilayer sandwich units (2 : 1) are also hold together by H-bonding. This is why, kaolinite
and pyrophyllite can cleave into sheets easily. If in the kaoHnite structure, Al is replaced by
Mg, then serpentine structure, Le. Mg 3(OH)4(Si 20 S) is obtained. Chrysotile (Le. white asbestos)
belongs to this group. The dimension of brucite layer is larger than that of Si20s-sheet. This is
why, the bilayer chrysotite tends to curl. From this curled layers, fibres of white asbestos are
obtained.
Montmorillonite and vermiculite are also the examples of trilayer clays (2 : 1) but here the
negative charges of the outer layers remain partially unneutralised. They can electrostatically
bind the cations like~, Ca2+ etc. Such cations are exchangeable by other cations like Jr. These
metal ions (e.g. ~, Mg'l.+, Ca2+) are used as plant neutrients. When vermiculites are strongly
heated, the dehydrated materials look like little earth worms. It gives the name vermiculites~ /
It may be mentioned that the clay minerals are secondary minerals which are produced through
the weathering of igneous rocks. Kaolinite is produced from feldspars.
H+,C02 ,H20 C
2[KAISi30 s] . ) AI2 (OH)4 Si20 s + 4Si02 + K 2 03
(weathenng) (K I·· ) ao Inlte
• Practical importance ofkaolinite : It is largely used for filling paper and as a refractory material.
It is used in making porcelain, china cups and plates and other ceramic materials. It is mined in
the name kaolin or china clay.
ry
• Practical importance ofmontmorillonites : In the triple-sheet structure, to balance the negative
charge, some hydrated metal ions (which are exchangeable) remain electrostatically bound and
ra
these minerals are described as hydromicas. Finely divided suspended particles ofthese minerals
shows the thixotropic properties. These plate like particles bear negative charges on the surface
ib
and positive charges on the edges and they orient to earn the + .... - attraction and attain/the semi-
solid gel like mass. If the mass is stirred, the + .... - attractions are broken and it becomes watery
yl
with a reduced viscosity. Because of this thixotropic property, these minerals are used as drilling
muds and in water based emulsion paints. These minerals can act also as ion-exchangers.
m
Fuller's earth is Ca-montmorillonite is a good absorbent. It is used to decolourise and deodorise
vegetables and mineral oils.
he
(vi) Three dimensional silicates (tecto-silicates) : By sharing all the four oxygens of each Si04
unit, the three dimensional net work having the general formula (Si02)n (Si : ° = I : 2) gets
developed. It may be represented as :[Si02 ]. The' important crystalline forms of silica (Si02)
lc
are: cristobalite, tridymite and quartz. Here it is important to mention the noncrystalline silica
glass in which the Si04 units are randomly bonded to other tetrahedra. In soda lime glass (Fig.
ea
11.19.2), the added oxides such as Na20 or CaO break up the net work of the silicate tetrahedra
in the noncrystalline silicate (cf. Sec. 11.19). At the regions ,of rupture, the external cations exist
° °
th
for electrostatic interaction. These Na - or Ca - electrostatic interactions are weaker than

the Si - ° interactions. This is why, soda lime glasses are softer. In the same way, the lower
e/
softening temperature of pyrex (Si02 80~, B20 3 14%, Na20 4%) compared to that of fused
silica (~i02 '" 99%) can be explained. The crystalline form, quartz is extremely important in
t.m
opitcal and electronic components. It has got the piezoelectric property. Due to this property,
external pressure distorts the structure to induce an electric polarisation and the reverse thing can
also be induced. Quartz crystals are used in clocks for an accurate frequency. In clocks and
watches, a thin silver plate oscillates at a certain frequency to produce a small oscillating electric
field which generates the electromechanical effect (Le. piezoelectric property). The function of
quartz crystals in clocks and watches has been discussed in detail in Sec. 11.17.2.
In silica, the tetrahedral holes may be occupied by A13+ ions to produce Al04 (Td ) units. In such
cases, additional positive ions are required to balance the charge. Such substitution leads to three
different groups of minerals - feldspars, zeolites and ultramarines.
(A) Feldspars: The feldspars constitute about 2/3 rd of igneous rocks. These are of two types :
• Orthoclase feldspars: Orthoclase, KAlSi 3 0 s Le. K(AI02)(Si02)3; Celsian, BaAl2Si 2 0 s Le.
Ba(AI0'l)2(Si02)i ~ and Ba2+ ion are of proper size to fit into the lattice.
• Plagioclase feldspars: Albite, NaA1Si30 s, i.e. Na(AI02)(Si02)3; Anorthite, CaA12Si20 s,
Le.Ca(AI02)2(Si02)2. Here the

smaller Ca 2+and Na+ ions do not
fit into the lattice site properly and
a distortion in the lattice arises.
(B) Zeolites : These are the examples of
framework (3-dimensional) alumino-
silicates. Its basic structural unit is
(Si, AI)O;- (where Si 4 + and A13+
ry
experience isomorphous substitution).
These basic structural units may
(a) (b)
ra
undergo oligomerisation to produce the Fig. 11.14.1.3. (a) Representation of a sodalite
6-membered [(Si, AI)02]6 and 4- cage where the vertices are occupied either by
ib
membered [(8i, A/)02]4 rings. These Si4+ or A(J+ with a bridging Cf-- along each edge.
(b) The cage like structure of zeolite Linde A where
rings may interlink to give the larger
yl
the square faces of sodalite cages are linked to
polyhedral cluster [(Si, AI)2404s]
give the a-sided channel.
known as sodalite cage (truncated
m
octahedron) having both square and hexagonal faces. The sodalite cage is constructed by
24(Si04, AI04) tetrahedra. These sodalite cages interlink in different ways by using the square
he
and hexagonalfaces to generate the three dimensional structure ofzeolite with open channels
(Fig. 11.14.1.3). The diameter of the open channels depends on the mode of combination of the
(e~g.
lc
sodalite cages. There are about 80 naturally occurring zeolites natrolite commonly Galled
Na-zeolite used as Permutit water softeners) and about 200 synthetic zeolites (e.g. Linde-A,
ea
ZSM-5, etc.). The zeolites can act as molecular sieves to accommodate the mole"cules of
appropriate size in their open channels.
th
Table 11.14.1.4. Characteristic features of some zeolites

Name Formula No. olO-atoms Window or pore opening
e/
in rings into the channel (pm)

t.m
Sodalite Na6A16Si6024.24H20 4, 6 220 (6)

Mordenite NasAlsSi40096.24H20 4, 5, 6, 8, 12 670. x 700 (12), 260 x 570 (8)
Linde A (zeolite A) Na12A112Si1204S.27H20 4,6, 8 410 (8)
ZSM-5 (silicalite) Na3Al3Si930192.l6H20 4,5, 6, 7,8,9, 10 530 x 560 (10)
Faujasite IVassA IssSi 13403S4·240H20 4, 6, 12 740 (12)
Note: Internal cavity diameter may be larger than the window size, e.g~ window or pore opening (410 pm) for an
8-ring window of zeolite A is smaller than the internal cavity (1140 pm). But the window size is the important
factor whether a particular guest molecule will be absorbed in the cavity or not. The windows to the channels fonn
the three dimensional channels.
• Exchangeable cations and molecular sieves in zeolites: To neutralise the negative charge of
the polyaluminosilicate ions, hydrated cations (which are .exchangeable) are trapped into the
channels. By heating, the water ofhyration ofthe trapped/metal ions can be driven off to produce,
the dehydrated zeolite with open channels commonly/known as molecular sieves which can
selectively trap different small molecules of app~opriate size. These channels can produce
clathrate type complex, i.e. guest-host interaction.
• Lewis acidic property ofzeolites : Lewis acidic property of zeolite is another important property.
The dehydrated metal ions can act as Lewis acids. The zeolite on being treated with acid produces
zeolite in Fr-form through the replacement of exchangeable metal ions by Ir. This Jr-form of
zeolite on dehydration produces the coordinatively unsaturated cationic Si-centres that can a.ct as
strong Lewis acids (Scheme 11.14.1.1).
ry
Na+ Na+
"./0"_/0,, /0,,_/
/SI'O/AI,O/ Si, O/AI,
ra
j (Zeolite)
ib
H+ (-Na+)
H H'
yl
I
+0 0 +0
I
"S·/ "A-I/ "/ S·I/" "A- / (H+ -form. 0 f zeo I't)
/ " /
°" / I" Ie
Q
m
Q.
(Dehydration)
1
he
(-H 20)
"s·+ °"s·/ 0 "A-I/

/ I"°/ "°/ '"°/ "
lc
AI/
ea
Scheme 11.4.1.1. Generation of Lewis acid centres in zeolite (charges shown indicate the formal
charges).
th
Practical applications ofzeolites : Zeolite finds several important applications based on the two
properties : presence of molecular sieves and presence of Lewis acid centres. '
e/
• Drying agent : The dehydrated metal ions present in the molecular sieves can adsorb the
water molecules to rehydrate the metal ions. Thus, zeolite can be used as a drying agent
t.m
• Water softening: The metal ions present in the molecular sieves are exchangeable and higher
valent metal ions are more electrostaticaly bound in the channel. Thus the hardness causing
metal ions like Ca2+ can be removed by using the zeolite natrolite Na2[A12SiJ010l2H20 (may
be represented as Na 2Ze). /
Na 2 Ze + Ca 2+ ~ CaZe + 2Na +
The equilibrium may be driven to the left side to regenerate the active form of zeolite by the
treatment with concentrated NaCI solution. Thus Na 2Ze can be used for water softening.
• Separation of hydrocarbons : The channels can only accommodate the molecules of
appropriate size. From a mixture of straight chain and branched chain hydrocarbons, only the
straight chain hydrocarbons are trapped in the channels. Thus, the straight and branched
chain hydrocarbons may be separated.
• Catalytic activity (cf. Sec. 14.16) : Shape selectivity and Lewis acidity are the important
characteristics of an enzyme and these two properties are present in zeolite. In fact, zeolite
finds many applications as a heterogenous catalyst. ZSM-5 (Zeolite Socony-Mobil), a new

synthetic zeolite (pore size: 530 pm x 560 pm, approx) Na3[A13Si93019i 16H20] is used for
selective synthesis ofp-xylene from toluene.
2 @-
0 ZSM-5
CH3 (Rearrangement) ~
@
0 + H3C·
-@-
0 CH 3
(p-xylene)
@- 1:~~5 C-@-OCH
ry
CH3 +CH 30H" • H3 3
(A atlon)
ra
In the molecular sieve ofZSM-5, the rod-shaped p-xylene is accommodated but the o-isorriers
cannot fit into the channel. Thus, fonnation of the unwanted isomers can be avoided.
ib
ZSM-5 can catalyse the following reaction :
@ @-
yl
ZSM-5'
C 2H4 + ~ C 2H s
m
Rho is a synthetic silicate, Nal~112SiJ6096.44H20 and it can catalyse the following reaction:
Heating
he
MeOH + NH3 Rho) MeNH2 + H 2 0
Mobil processfor the production ofsynthetic gasoline: ZSM-5 is used in the production of
lc
gasoline from methanol.

ZSM-5
nCH30H )-(CH2 )n-+nH2 0
ea
The interconnecting channels in ZSM-5 can just fit for condensation and accommodation of
methylene group. It can accommodate the hydrocarbon ofchain length upto CIO. Thus the
th
obtained hydrocarbon can be used as a gasoline of high octane value.

Cu(II)/Cu(I) exchanged zeolites in catalytic converters : These are produced from the
e/
exchange of some Na+ ions. Such exchanged zeolites can be used as catalysts in the catalytic
t.m
converters of automobile engines for the removal of unburnt hydrocarbon and conversion
of NOx to !V2 and 02.
2NO
Cu(II)/Cu(I)
. ) N2 +
Zeohte
°
2; Unbumt hydrocarbon + NOx
Cu(II)/Cu(I) zeolite
) H 20 + N 2
(C) Ultramarines: The aluminosilicates, ultramarines are generally synthetically prepared. These
are coloured. In addition, to balance the charges, some suitable cations and equivalent amounts
of anions (e.g. CI- , si-,
80;-) are present in the structure. The blue ultramarine contains si-
ions which probably participate in charge transfer transitions to give the colour. The mineral
lapislazuli is a naturally occurring ultramarine. Examples: Ultramarine, Na8(AI02)6(Si02)6S2;
Sodalite, Na8(AI02)6(Si02)6CI2; Nosean, Na 8(AI02)6(8i02)6(S04).
In these three examples only the anions (Le. si-,
2C/- and SO;-) are changing.
Lapis-lazuli finds its use in oil-painting for its beautiful colour. Synthetic ultramarine (blue) is
commercially used in washing white clothes (to mask the yellow tint), and as a blue pigment in
ceramics and oil-painting. It is prepared as follows:
ignition
Kaolinite + Sodium carbonate + Sulfur -------~) Ultramarine
(in absence of air)
(D) Silica gel (Amorphous silica) : Sodium silicate on hydrolysis gives the precipitate of gelatinous
silicic acid acid (Si02.!!20) which on dehydration gives the amorphous mass of silica gel.
• Structure 0/ silica gel: The matrix of silica gel particles is constituted by siloxane. bonds (Le.
~Si-o-Si-O-) bearing some uncondensed hydroxyl groups of the polymeric silicic acid.
These uncondensed OH groups (called silanol groups) are on the surface' of the silica matrix
and these provide the polar properties of silica gel. There are three types of silanol groups:
ry
single sil~nol group, double (Le. geminal) silanol group and triple silanol group. Silicon found
in plants and in many biological materials bears the structure of silica gel.
ra
Double silanol groups attached to a Si-centre joined to the silica matrix by two siloxane bonds.
}
ib
Single silanol group attached
U 01H 0H
1
QH
I
to a ~i - centre jo~ned to the silica
matnx by three slloxane bonds
yl
HO-,i-O-r-O-l i-
(
I I" I
m
Double silanol groups ?H } Triple silanol group attached
-Si-O-Si-O-Si--o-Si-OH to a Si -centre joined to the silica
he
1 1 1 1 matrix by single si/oxane bonds
OH
lc
• Properties ot silica gel: The porous s-ilica gel is havIng a large surface area. The silanol groups
make the surface polar. The silanol groups on the silica matrix can adsorb water molecules both
ea
chemically and physically. These adsorbed water molecules are lost on heating. This is why,
silica gel can be used as a dehydrating agent. Silica gel in presence of the indicator CoIl-salt
th
looks pink coloured when it adsorbs water molecules and it becomes blue coloured when it is
heated to dry.
e/
II Water
Silica gel (+ Co - salt) ~ Light pink colour
adsorption
(Dry, blue colour) (wet silica gel)
t.m
t ------..jl
Mild heating
Commonly used Co(II)-salt is (NH4)2CoCI4. Hydrated Co(II)-salt is light pink coloured due to
the octahedral species CO(H20)~+. In dehydrated condition, it becomes deep blue due to the
tetrahedral species Coclf-. Different lODq values give different colours: 10Dq for
Coclf- (blue) < 10Dq for CO(H20)~+ (pink)..·Spectral selection rule is better relaxed in th~
tetrahedral species. This is why, intensity of the colour of the tetrahedral species is more.
Wetting
Coclf- (blue,E ~ 500) + 6H20 &< >z CO(H20)~+ (light pink, E ~ 2) + 4CI-
Drying
The silanol groups can also react with silane reagents like dichlorodimethylsilane, SiCI#e 2 to
produce the bonded phase and the silical gel surface becomes nonpolar. This modified silica
gel can act as a support of chromatographic exchangers.
The large surface area of porous silica gel can also act as a support of many catalysts.
• Uses of silica gel : The properties like porous structure of large surface area, polar surface
bearing hydroxyl groups, water adsorbing capacity, etc. make silica gel quite useful. It is widely
used as a dehydrating agent, as a support of catalysts and chromatographic exchangers, etc.
(E) Kieselguhr: This white powder is another form of Si02. It is used as an abrasive and as an inert
filler.
11.4.2 Cement
ry
The portland cement is a mixture ofcalcium silic.ates and aluminates having the approximate composition
as follows:
ra
(a) dicalcium silicate (Ca 2Si04 Le. 2CaO.Si02) : 26%
(b) tricalcium silicate (Ca 3SiO s Le. 3CaO.Si~2) : 51%
ib
(c) tricalcium aluminat~ (Ca3AI2~6,Le. 3CaO.A120 3) : 11%
(d) tetracalcium aluminoferrite (Ca~12Fe2010 Le. 4CaO, A120 3, Fe 20 3) : 1%
yl
In terms of oxide, it is :
CaO : Si02 : Al20 3 : Fe 20 3 = 70 : 20 : 5 : 3
m
The presence of Fe 20 3 gives the grey colour of cement. White cement is free from Fe 20 3. The
natural limestone found in Portland (UK) possesses the property of the above synthetic cement
he
and this is why it is named as Portland cement.
Setting of cement occurs through the hydrolysis and hydration of the product. The process is
lc
exothermic and this is why, to avoid cracking it needs cooling by· repeated water-spray after a
certain time interval. The process goes on slowly over weeks. .
ea
2Ca2Si04 + 4H20 ~3CaO.2Si02.3H20 + Ca(OH)2

2Ca3SiOs + 6H20 ~ 3CaO.2Si02.3H20 + 3Ca(OH)2
th
These hydrolytic products undergo hydration and they crystallise through interlocking over the
e/
weeks. Formation of these interlocking crystals is the setting of cement. Flash setting (Le.
quick setting) is due to the hydrolysis and hydration oftricalcium aluminate. In/act, high alumina
t.m
content cement sets quickly in a very short time.
11.14.3 Isopoly and Heteropoly Acids

The oxo-anions of Mo(VI) and W(VI) show a pronounced tendency to produce polyoxoanions. V(V),
Nb(V), Ta(V), etc. also show a limited tendency to form such polyoxoanions. The acids of the
corresponding polyoxo-anions are. called poly acids. If there is only one kind of oxometal ion, it is
described as isopoly acids. Sometimes, they may incorporate other oxoanions like 8iO:-, PO;-, etc.
to produce the heteropoly acids.
Examples of isopoly acid anions:
2
M070~4' MOsoii, VjOO~8' H~W60~2' W6 0 19-, W70~4' H2~20:0' etc.
In the poly acids, the basic structural unit is MO(f Oxide ions produce a closed-pack array into
which the octahedral hole is occupied by the metal ion. The vertices and edges of the M06 octahedra
may be shared. In isopoly acids, the edges of M06 octahedra are shared (Fig. 11.14.3.1). In VjOO~8'
• for M and
o forO
(M 100 28 • e.g.,
V10ot)
ry
(8) (b)
ra
ib
yl
m
he
lc
ea
th
(d) M60 19 (one octahedron (e) MS0 26

e/
is obscured) (one octahedron is

obscured)
t.m
Fig. 11.14.3.1. (a) MOe octahedral unit; (b) M10 0 28 structure (e.g. ~oO~i) constituted by 10 fused MOe
octahedra; (c), (d), (e) and (f) structures of isopoly anions and their relations with the structure of M10 0 2S .
10 octahedra are stacked through edge sharing. This is the largest stacked octahedral isopoly acid
anion (cf. Question No. 125)-
In the Keggin structure of 12-heteropoly acid, Le. H8 _ n [XMI2 0 40 ] where M = Mo(VI) or W(VI);
X = P, As, Si, Ti; n =. formal charge on the central xn+ ion; the central tetrahedral XO4 unit is surrounded
by 12 MO6 octahedra. These 12 octahedra are in 4 groups of 3 edge-shared octahedra forming a M 12 0 36
cage tllat encapsulates the tetrahedral X04 unit. These 4 groups of octahedra tetrahedrally surround
about the hetero atom X. Each O-atom ofthe X04 central unit is shared by 3 octahedra (Fig. 11.14.3.2).
In qualitative detection of phosphate, the yellow precipitate (NH4 )3[(P04 )(Mo03)12].6H20, ammonium
12-molybdophosphate belongs to this group.
.In 6-heteropoly acid anion, [XM60 24 ](12 - n)- where M = Mo(VI) or W(VI); X = Te(VI), [(VII), etc.
6 M06 units are arranged to produce a central octahedral hole for X (Fig. 11.14.3..3).
*e
ry
for Mo or W; 0 for 0 (oxygen)
for the heteroatiom (X) like Te, Co, AI etc.
ra
Fig. 11.14.3.2. Keggin structure of 12-hetero- Fig. 11.14.3.3. Structure of 6-heteropoly acid anion
polyacid anion e.g. [P(M030 10 )4]3- Le. (l2-x)- (M=Mo W)
XM 6
° 24 ' ,.
ib
[(P04 ) (M0120 36 )]3-
yl
11.15 CRYSTAL DEFECTS IN IONIC SOLIDS
Formation of defects (Le. disorders) in a crystal is a thermodynamic demand. The Gibbs free energy
m
of a solid is given by : G = H-TS. Development of disorder in a crystal increases the entropy (Le. M>
0) to favour the process, but formation of a defect is an endothermic process (Le. Mf> 0). Thus the
he
concentration of defect depends on the temperature as the
process is controlled by the entropy factor. Because .0/ this
lc
entropic favour, the defect 0/ concentration increases with ~H/

the increase of temperature.
,,','!!ii)
ea
Now let us consider the effect of introducing defects into ~ ,/ Mainly enthalpy
a perfect crystal at a particular temperature. -Introduction of ~ ,/ controlled region
w
th
defects is always disfavoured in terms of enthalpy change (Le. ~ Mainly entropy

Mf == +ve) but it experiences an entropic favour due to the \,T!!iS controlled region
-- .. -. __ ..
e/
positive value of M (Le. increase of entropy). When only a

few defects are created, these can be distributed in many No. of defects ~
t.m
probable ways. Thus, the configurational entropy (cf. Sec. Fig. 11.15.1. Effect of introducing
13.2.3) change (~S = klnp, k = Boltzmann constant, defects into a perfect crystal on
p == number of probable ways of distribution of the defect) free energy change at a partiCUlar
temperature.
becomes large. When the number of defects increases, the
entropy change is less because the crystal is already disordered and addition of extra defects cannot
increase the disorder much. It can also be understood in terms of p (to be discussed later). Besides the
configurational entropy change, the entropy change may also partly occur due to the disturbance/
distortion around the points of defects. However, M (a measure of disorder in the crystal) becomes
more important when the number of defect is relatively less. When the number of defect increases,
MI becomes relatively more important. This is why 6.G (= M - TM) becomes negative due to the
entropicfavour when the number ofdefect is less while 6.G becomes positive due to enthalpic disfavour
when the number of defects is more. Thus, 6.G passes through a minimum when 6.G is plotted against
the number of defects. At this position, a thermodynamic equilibrium is attained. The number of
defects increases with temperature because of the increasing contribution of the TM term.
1064 ~undam'ental Concepts of Inorganic Chemistry
In crystalline compounds there are different types of imperfections such as point imperfections, line
imperfections, surface imperfections and volume imperfections. These defects may be divided into two
groups: point defects of zero dimension (occurring at the single lattice sites) and extended defects
which may be of one, two and three dimensions (e.g. stacking faults). The defects can also be classified
as intrinsic and extrinsic defects. The intrinsic defects (e.g. Schottkey and Frenkel ~efects) occur in the
pure crystals while the extrinsic defects originate from the impurities present in the crystal. The defects
can largely influence the physical properties such as mechanical strength, electrical conductivity, colour
and also chemical reactivity. In the ionic crystals, only the point imperfections are important. Other
ry
types of imperfections are important to the metallic crystals which are of interest to the metallurgists.
The point imperfections are very often referred to as zero dimensional imperfections. Such
ra
imperfections are localised in some point like regions in the crystal. It may arise due to the: (i) vacancies
in the lattice sites, (ii) substitutional impurity, (iii) occurrence of the constituent ions in the interstitial
ib
spaces and (iv) nonstoichiometric proportions of the constituent ions. However, the point defects in the
ionic crystals can be classified in two groups -stoichiometric defects and nonstoichiometric defects.
yl
SuclJ defects can significantly alter the properties of the crystals.
11.15.1 Stoichiometric (i.e. Intrinsic) Defects

m
These defects in a crystal run in such a way that the ratio of the number of constituent positive and
he
negative ions remains the same as indicated by the chemical formula of the ionic crystals. There are two
types of defects, Le. Schottky (or Schottky-Wagner) and Frenkel defects leading to the stoichiometric
defects. At absolute zero, the crystals tend to have the perfectly ordered crystals but as the temperature
lc
increases, the number of defects increases. This is why, the defects are also referred to as the
thermodynamic defects.
ea
Stoichiometric defects
I
th
+ +defects
e/
Schottky defects Frenkel

(Missing of both cations and anions in equivalent "(Displacement of ions, generally cations, to the
t.m
proportions to maintain the electrical neutrality). interstitial positions from the lattice sites).
(a) Schottky defects: In a A+n- type crystal, the missing of a cation and an anion produces a pair of
holes leading to a Schottky defect (see Fig. 11.15.1.1). The cations and anions will remain missing
in such a proportion that the crystal will remain overall electrically neutral. In the NaCI crystal,
1
the missing of a Na+ ion requires the missing of a C, ion while in the CaCl2 crystal, the missing
of one Ca 2+ ion requires the missing of two C, ions. In the case of metallic crystals, no question
of missing of lattice points in pairs or stoichiometric proportions occurs because they consist of
electrically neutral constituents of the same type.
Generally the Schottky defects are important in highly ionic crystals with high coordination
numbers having cations and anions ofcomparable size. Examples of such compounds' are: CsCl(r+/
r_ = 0.93,8:8), KCI(r+/r_ = 0.73,6:6) and KBr(r+/r_ = 0.69, 6:6).
(b) Frenkel defects: When some of the constituent ions occupy the interstitial positions rather than
their lattice sites, it leads to the Frenkel defects (see Fig. 11.15.1.1). Generally the cations having
smaller sizes tend to occupy the interstitial sites.
Structure, Bonding .and Properties of Ionic Solids and Solid State Chemistry 1065
@--0--e--0--@ ~--8--@--0--@
0--~-0--~-0
0 1
0: ---@--
1 : I : :
B( B( ---@--0
Ag'6 + I
: 6 1
:
~--0--@--6--~ ~--v--O---~--@
6 : : : :
ry
~--~--ch--~--0 v--@--0--@--8
ra
Sohottky Defect Frenkel Defect
ib
Fig. 11.15.1.1. Stoichiometric defects - Schottky and Frenkel defects.
yl
Such defects are predominant in the lattices where the ions are having low coordination number
because of the low r+/r_ values. Low coordination numbers are preferred, because it will require
m
a lower amount of energy to break down the fewer attractive interactions. Because of the low r+/
r_ values (Le. small cations and large anions), the polarisation is significant to introduce a good
he
deal of covalency in the compounds. Examples of such compounds are: AgBr (4:4), AgI (4:4),
ZnS (4:4), etc. Here the cited compounds have the ZnS structure.
lc
(A) Energetics of Schottky Defects

ea
To cre(lte a Schottky defect, Le. removal of ions in stoichiometric proportions from the lattice points, it
requires some energy, but the creation of a such defect increases the entropy of the system. In the
perfect crystal, all the lattice points are perfectly ordered to make the entropy of the system minimum,
th
but the defect introduces some sort of disorders in the system. Thus, creation ofa defect is disfavoured
from the standpoint of enthalpy factor but the proc.ess is favoured from the standpoint of entropy
e/
factor.
Let us proceed by considering the removal Qfa lattice point (which generally occurs in the metallic
t.m
crystals consfsting of neutral lattice points). Above the absolute zero temperature, there will be a/ways
some disorders in the crystals. The degree of disorder will measure the entropy change (~ of the
system,
M=klnp ...(11.15.1.1)
where k = Boltzmann constant and p = number of ways in which the defects can be distributed among
the available lattice sites, Le. number of possible configurations. This is why, the entropy is referred to·
as configurational entropy (cf. Sec. 13.2.3).
If there are n vacant sites among the N lattice sites, the number of possible configurations is given
by:
N!
p= ...(11.15.1.2)
(N - n)!n!
Therefore, we get, ~S = k In N'.

(N - n)!n!
Using the following Stirling's approximation which is valid for n» 1,

In n! = n In n - n ...(11. 15-.+~3J
we get:
M = k[N In N - (N - n) In (N - n) - n In n] ... (11.15.1.4)
If E s denotes the energy required to create a vacancy (Le., removal ofa lattice point from its site
to the open surface), then for the n vacancies, the required energy is nEs • Thus the enthalpy change is
given by:
ry
MI= nEs ••• (11.15.1.5)
Hence the change in Gibbs free energy (AG) is given by :
ra
AG = MI- TM= nEs - kT[N In N - (N - n) In (N - n) - n In n]
ib
At equilibrium, [O(~G)] =0= E s - ~T [0 - {-I x In (N - n) + ~Z =:~ x -I}-{I x In n + n x -!;}]
= Es - kT [In (N - n) -In n]
yl ...(11.15.1.6)
m
N-n
It leads to : Es = kT [In (N - n) -In n] = kT I n - - ...(11. 15. 1.7)
he
n
or; n/(N - n) = exp (-Es / kD;
lc
or, I~
n N exp (- E/kn, (N)> n) I ...(11:15.1.8)
ea
In the case of ionic compounds like AB, one Schottky defect involves the removal of one ion pair
of opposite charges leading to two vacancies to maintain the electroneutrality. In such cases, the number
th
of ways in which n pair vacancies can be distributed among the N lattice sites is given by :
e/
N! ]2 ...(11.15.1.9)
p= [ (N-n)!n!
t.m
By using the Stirling's approximation, it leads to :

M = 2k[N In N - (N - n) In (N - n) - n In n] ...(11.15.1.10)
If E Scb denotes the energy required to create a pair of vacancies, Le. one Schottky defect, we
get:
nSch = (N - nSch ) exp (- ESc,/2kD ...(11.15.1.11)
or, nSch ~ N exp (- Esc,/2kn ...(11.15.1.12)
where nSch gives the number of Schottky defects in a AB type ionic crystal.
In a NaCI crystal, the energy (Esch ) required to create a Schottky defect (Le. removal of a pair of
oppositely charged ions) is 2 eVe The number of Na+ and C,
ions in I cc is about-I022 • Thus it appears
that at room temperature, the number of Schottky defects is about 106 per cc ( Le. one Schottky defect
per 10 16 ions).
(8) Energetics of Frenkel Defects

If in a crystal, there are n Frenkel defects in N lattice sites and N i interstitial sites, then the number of
ways in which the n Frenkel defects can be distributed is given by :
N! Ni !
P = (N - n)!n! x (N; _ n)n! ... (11.15.1.13)
Thus, the change in configurational entropy is given by :
=k In p = k In. N' N.'
ry
M · x I •
(N - n)!n! (Ni - n)!n!
By u~ing the Stirling's approximation we get,
ra
M= k [N In N + N j In N j - (N - n) In (N - n) - (N j - n) In (Nj-n) -2n In n] ...(11.15.1.14)
ib
If the energy required to create a Frenkel defect (Le. removal of a lattice point from its proper
position to an interstitial site) is EFre' then for such n defects, the enthalpy change is given by :
yl
Ml= nEFre ••• (11.15.1.15)
Therefore, llG = Ml- TM = nEFre - kT [N In N + N i In N j (N ~ n) In (N - n)

m -
- (Ni - n) In (Ni - n) - 2 n In n] ( 11.15.1.16)

he
At equilibrium, O(AG) = 0 = E r _ kT In (N - n)(N; - n) (11.15.1.17)
an rre n2
lc
(N-n)(N;-n)
E Fre = kTln 2
ea
n
Assuming, N» nand N; » n, we get:
th
E Fre ~ kT In( ~; )
e/
or, In Fre = (NN;)112 exp (- EFre I2kT}J ...(11.15.1.18)

t.m
where n Fre gives the number of Frenkel defects.

(C) Effects of Schottky and Frenkel Defects on the Properties of the Crystals
(i) Change in dielectric constant of the crystals : In the Frenkel defects, the proximity of like
charges (generally cations) leads to a high dielectric constant. This increase ofdielectric constant
reduces the Coulombic attraction which is inversely proportional to the dielectric constant of the
media and as a result, the lattice energy is decreased. Due to this reduction ofCoulombic force,
the energy required in displacing an ion from the lattice site to an interstitial site is reduced.
(ii) Change in lattice energy: Due to the defects (both types), the lattice energy is decreased.
(iii) Change in electrical conductivity: Before to discuss the change of electrical conductivity due to
the formation ofdefects, we shall discuss the general aspects relating to the mechanism ofelectrical
conductivity in ionic solids (see also Chapter 12).
Electrical conductivity can arise either from ionic conduction (Le. migration of ions) or electronic
conduction (as in metals and semiconductors where the conduction band is partly filled). Ionic
conduction (i.e. transport of holes or ions) is explained by hopping model not in terms of band
model. In ionic solids, the electronic conduction is not possible. In such cases, the conductivity
arises due to the ion migration which may occur in three possible ways:
(a) Vacancy migration: If there is any vacancy (Le. crystal defect) at a lattice site, then an ion
of the type which is missing at the lattice site can migrate from a lattice site to the vacant
site.
(b) Interstitial mechanism: Ifan ion (generally cation) can be accommodated in the interstitial
site (which is generally a tetrahedral or octahedral hole), then it can migrate from one
ry
interstitial site to another interstitial site.
(c) Interstitialcy mechanism: This concerted pathway combines both the routes. One ion can
ra
migrate from its lattice site to an interstitial site to create a vacancy which may be occupied
by another ion of the same type.
ib
Due to rigid structure of the ionic lattices, the ions cannot move to carry the electricity. This is
why, generally the perfect ionic crystals show only we.ak electrical conductivity. But due to both
yl
the types of defect, the electrical conductivity is increased because the ionic mechanism is
facilitated. An ion can move from its lattice site to a hole. Thus it creates a new hole in its
m
original position. Thus the hole can migrate across the crystal which is equivalent to the
movement of an ion in the opposite direction. In the Schottky defects, cations and anions are
he
generally comparable in sizes. Hence both the ions can move through the holes in opposite
directions. In alkali metal halides, at a low temperature the cationic contribution is predominant
but with the increase of temperature, the anionic contribution increases to about 10% of the total
lc
conductivity. Frenkel defects may contribute in two

~
ways in electrical conductivity, i.e. movement of the e>
ea
tQ)
holes and movement ofthe cations from one interstitial c:

Q)
position to another interstitial space. co

:g Starting point
th
Quantitative treatment (cf. Sec. 12.10) of ionic Q)

(5
of the jump
.....
",' End point of
conduction. in imperfect ionic crystals: In such cases, 0-
~
~
" the jump
e/
electrical conductivity arises from the mobility of the

defects. Mobility (u) of the ions or vacancies depends 1 /
/
/
Ea ",I
t.m
---+ Path of movement

on the activation energy (Eo) required to jump or hop
(Fig. 11.15.1.2) and it is given by Arrhenius equation. Fig. 11.15.1.2. Schematic represen-
tation of a charge carrier migration
Iu ac exp (-Eo / kT); or u = U o exp (-Eo / kT)1 through jumping or hopping.
where the proportionality constant Uo is called the preexponential factor which depends on
many factors like frequency of lattice vibration (called attempt frequency), the distance to be
moved by the ion, etc. In terms of temperature dependence, Uo is inversely proportional to
temperature (Le. Uo oc liD. Ionic conductivity or electronic conductivity is given by the same
equation.
o = nZeu, n = number of charge carrier per unit volume,
Ze = charge of the carrier, u = mobility of the charge carrier
By considering the value of u, we can express the ionic conductivity (0) of a particular ionic
crystal as follows :
I 0" = (0"0 /T)exp (-Eo / kT) = A exp (-Eo / kT) I

Temperature dependence of the exponential term is more important than the temperature
dependence of the preexponential term (A). This is why, for the sake of simplicity, A may be
considered approximately temperature independent. The above relations lead to :
E E
In(aT) = In a 0 - ---!!-, or In a = In A - -!!.
kT kT
ry
1
The slopes of the plots, In (a1) vs. - and In a vs. are almost the same. It indicates the
T T
validity of the approximation taken in defining A i.e. the term A is approximately independent of
ra
temperature.
In most of the cases, th~ plot gives two straight lines of different slopes (Fig. 11.15.1.3) where
ib
slope for the higher temperature range is relatively higher.
In the low temperature region, the number of intrinsic defects is too small to be considered. In
yl
this region, the weak conductivity arises from the cation mobility through the vacancies caused
by the extrinsic defects. These extrinsic defects (due to impurities) are always existent, even in
a pure sample of NaCI. The number of
m
Ex
extrinsic defects which governs the Slope =--,
he
k
conductivity depends on the amount of
Ex = EF or Es ;
impurity and it is constant for a particular b
.5 EF = Ea + ~ EFre • Es = Ea + ~ Esch
lc
sample. This number ofextrinsic defect does

not change with temperature. Thus in the Ea
ea
low temperature range called extrinsic Slope=--,

k
range (where the intrinsic defects are not
important), conductance arises due to the
1
th
mobility of the extrinsic defects and

consequently, conductance changes with --+1..
e/
T
temperature due to the mobility change Fig. 11.15.1.3. Conductivity change of an ionic
governed by Arrhenius equation Le.
t.m
solid (e.g. LiI, NaC~ with temperature.

u ex: exp (-Ejk1).
At higher temperature, intrinsic defects start to occur and the number of intrinsic defects increases
with temperature exponentially (E sch or E Fre denotes the required energy to create the
corresponding defect) :
nSch EsCh
ex: exp ( - - -Fre
- ) and nEre ex: exp ( - E -)
2kT .. '. 2kT
Thus in the higher temperature range (Le. intrinsic range), conductivity depends on both mobility
of the defects and the number of defects. Both these factors are the exponential functions of
temperature. So, in the intrinsic range, we can write :
a =-a' (E) exp (E)

exp - -
---!L =-a' exp {- ( 2E + E )} ,(for a system wIth
Sch . Schottky defects)
a Sch
T kT 2 kT. T , 2 kT
=~ exp (- Es ), Es =Ea +.!. ESch , Es = resultant activation energy

T kT 2
Similarly, for a system with Frenkel defects,
0" = ~ exp (- EF ), EF = Ea +.!. EFre EF = resultant activation energy

T kT 2'
In the intrinsic range, slope of the plot, In(O"1) vs. ! is governed by EF or Es while in the
extrinsic range, slope of the plot is determined by Ea lrtd EFor Es > Ea'
ry
(iv) Change in density: Generally due to the creation of holes, the density ofa crystal decreases. In
Frenkel defects, the presence of the ions in the interstitial sites may expand the lattice dimension
ra
and sometimes the lattice structure may also be collapsed partially due to the too many holes. In
such cases, the direction of change in density is unpredictable.
ib
(D) Differences between the Schottky and Frenkel Defects
yl
Property Schottky defects m Frenkel defects
(1) Nature of It leads to the missing of cations and It leads to interstitial occupancy by the cations
defect anions in an appropriate proportion to (generally) keeping their lattice sites vacant
maintain the electrical neutrality
he
(2) Nature of the Highly ionic compounds having high It occurs preferably in the compounds having
crystal coordination numbers with the cations small cations and large anions to provide low
and anions of comparable sizes are coordination numbers to the ions. In such ionic
lc
the ideal crystals to bear such defects compounds, the degree of covalency due to
Examples: Nael, KCI, etc. polarisation is relatively large. Examples :
ea
AgBr, Agl, ZnS, etc.

(3) Change in Not significantly changed Due to the accumulation ofthe like charges in
di-electric a small region, dielectric constant is signifi-
th
constant cantly increased

(4) Electrical Due to the movement of the holes Due to the movement .of both the holes and
e/
conductivity the interstitial ions

(5) Density change, Generally the density is significantly Generally the density is not significantly
t.m
reduced affected
(6) Energy It requires a lower amount of energy to The process is more energy requiring
requirement create a defect
11.15.2 Nonstoichlometrlc (or Berthollide) (I.e. Extrinsic) Defects

In such defects, the ratio of the numbers of the cations and anions in a compound is different from that
one.expected from the chemical formula ofthe compound. The electrical neutrality is attained either by
the accommodation of extra electrons or extra positive charges. The different possible ways to create
the nonstoichiometric defects in the A+ ~ type compounds are shown below .
Nonstoichlometrlc Defect In A+8-
Metal excess Metal deficiency Substitution by impurities

A1 + 6 B (A 1 - 6 Bf (A~:n6 X~+ a-)
(~) Metal Excess 0·' Nonmetal Deficiency

It can occur in two ways.
(i) Replacement ofanion by electron: When the lattice site of an anion is occupied by the electron
instead of the anion, it leads to metal excess in the crystal. The, trapped electron maintains the
electrical neutrality. The lattice site In which the electron is trapped is called a F-centre (F stands
for the German word Farbe which means colour). The trapped electron in a F-centre can be
compared with the problem 'particle in a box.' Thus the trapped electron at the F-centre can
absorb light in the visible range for its transition to a higher level and the compound appears
ry
coloured. This type ofF-centre (i.e. single trapped electron) imperfection appears in the crystals
which are prone to Sc~ottky defects. For example, when NaCI is treated with Na-vapour or a
ra
small amount of metallic sodium is doped into a NaCI crystal, this type of defect originates. The
crystal energy ionises the sodium atoms. The produced Na+ ions occupy the correct lattice sites
C,
ib
but the released electrons occupy the lattice sites which are supposed to be occupied by the
ions. Thus the produced nonstoichiometric material (see Fig. 11.15.2.1) can be represented as
yl
Na l + aCI (where a is very small with respect to 1). It looks yellow coloured. Similarly, the
nonstoichiometric K) + aCI can be prepared and it looks blue coloured. F-centre in LiF makes it
m
pink coloured. The nonstoichiometric compounds with F-centres are paramagnetic. The F-centre
in fluoride (CaF2) gives a beautiful blue-purple colour.
he
E>-~0-~@--0--@ ~--0--~--0--@
lc
~ : ~ : : 6 :'A : :
ea
~--~-~--~-0 ~--~-~--fY-0
: A: 6 : : 6 +: 6 :
th
A9
e
E>--\J--E>--~--@ ~--v--@--~--@
e/
6 : : : II 6 : : : :
v-- Q --@--Q--0
t.m
v--6J--(0--6J--0
F-centre imperfection (Na 1 +oCI)
Fig. 11.15.2.1. Metal excess defect.
The colour due to a F-centre (Le. single trapped electron) depends on the nature of the host
crystal but not on the source of the electron. Thus, if NaCI is treated with eithe~ Na- or
K- vapour (electron source), it becomes yellow coloured in both cases. It may be noted that in
alkali halides, besides the F-centre, many other colour generating defects like H-centre, V-centre,
etc. may also occur. These will be discussed later (Fig. 11.15.2.2).
Note : Powdered NaCI on being irradiated by X-rays becomes yellow coloured due to the
generation of F-centres. But this generation of F-centre is not due to the nonstoichiometric
metal excess defect. It probably originates from the ionisation of C, anions within the crystal.
(ii) Accommodation ofexcess metal ions in the interstitial sites: Metal excess can also arise when
an additional cation takes up the interstitial site and the required electrons to balance the ~ltarge
are placed in some interstitial sites around the interstitial cation (see Fig. 11.15.2.1, illustrated as
Ag)+oBr). This type of defects generally occurs in the crystals where the Frenkel defects
predominate. Zn) + (,0 is an example in this group. The trapped electron gives the colour and
electrical conductivity.
Effects of Metal Excess Defects
ry
(i) Electrical conductivity: Both the processes described above, lead to the trapped electrons either
in the lattice sites or in the interstitial sites. These electrons can carry the electricity through
ra
hopping mechanism (cf. Fig. 11.15.1.3, extrinsic range). The defects may be generated by the
irradiated light and then the crystal shows electrical conductivities. This phenomenon is called
ib
photoconductivity and the crystals are called photoconductors. The photoconductors are of
immense importance in different fields.
yl
However, the conductivity introduced by the trapped electrons is far less compared to that of
metals or fused salts or aqueous solutions of ionic salts. This is why, the nonstoichiometric
m
compounds of At + (,B type are called semiconductors. As the conduction is carried out by the
electrons, these are very often referred to as n-type semiconductors.
he
(ii) Colouration: The trapped electrons' in F-centres behave just like the particles in a box and
they may absorb light from the visible range to get excited to the higher levels. This is why, the
lc
nonstoichiometric compounds of this type, Le. A) + (,B, are very often coloured. For example,
Na) + (,CI (yellow), K) + (,CI (blue), Zn) + (,0 (white when cold, yellow when hot). Actually in the
ea
case of Zno, on heating, it loses oxygen ( 0 - - 2e ~ ~02 ) on releasing the electrons which
2
th
are ultimately trapped in the crystal. Thus on heating, it leads to Zn) + (,0. CdO also' behaves
similarly and on heating it loses oxygen to form Cd) + (,0 and the 'colour changes.
e/
Note: Besides the F-centres (Le. single trapped electron), H-centres and V-centres (Fig. 11.5.2.2)
can also act as the colour centres in alkali halide crystals. In NaCllattice, H- and V-centres bear
t.m
Cli. (Le. chlorine molecule ion). Ionisation of C, (by X-ray irradiation) produces neutral CI-
atom which combines with a C, anion to produce Cfi. molecular anion. In H-centre, Cli. ion
occupies one lattice site while in V-centre, Cli. occupies two adJacent sites of C, ions through a
Na CI Na CI Na Na CI Na CI Na CI
CI Na(C! Na CI CI Na CI Na
Na CI Na CI Na Na CI Na CI
CI Na CI Na CI CI Na CI Na CI Na
Na CI Na CI Na Na CI Na CI Na CI
H-centre V-centre
Fig. 11.15.2.2. Representation of H-centre and V-centre in NaCI.
Cl-Cl bond. H and V centres may be also produced when the alkali metal halide is heated in a
vapour of halogen (X2).
The electron transition in the molecular anion Cl:i. present in the H-centre and V-centre gives the
characteristic colour. If a F-centre and a H-centre combine together, then they may cancel
each other giving rise to a region of perfect crystal.
(iii) Paramagnetism: The trapped unpaired elctrons introduce the paramagnetism in the metal'excess
nonstoichiometric compounds.
ry
(B) Metal Deficiency or Nonmetal Excess
This type of nonstoichiometric deficiency can be attained in two ways. It predominates in the compounds
ra
where the cations can exist in two different stable oxidation states.
(i) Missing ofcation: If a cation is missing from a particular lattice site and the electrical neutrality
ib
is maintained by the oxidation of another cation, then it leads to the defect, At _ ()B. It generally
predominates in transition metal compounds. Fe) _00 (known as wustite), Fe) _ oS, Ni) _ ()O are
yl
some representative examples in this group. In the ferrous compounds, missing of one Fe2+ ion is
electrically compensated by the oxidation of two Fe 2+ ions into Fe 3+ ions (see Fig. 11.15.2.3).
m
Thus the nonstoichiometric compounds actually exist as, Fe:~30Fe~; X(X = 0 2- , S2-);
2
Ni)2~ 3aNi~; 0 -. Pure NiO (pale green) is of very poor conductivity but on heating in air, it
he
produces the nonstoichiometric oxide through
the partial oxidation of Ni(II) to Ni(III) and
lc
reduction of atmospheric oxygen to Q2- which

gets incorporated in the crystal. Thus the.
ea
obtained black mass is a good conductor of

electricity. The typical behaviour of the
th
nonstoichiometric monoxides of the 3d-

metals has been discussed in Chapter 12. A
e/
similar defect is known to occur in c'u2S

structure. It may exist as Cu 2 _ as (0 = 0 - 0'.23)
t.m
and the charge is balanced by the proportionate

oxidation of Cu(I) to Cu(II).
(ii) Placement excess anion in the interstitial site:
If an extra anion resides at the interstitial site,
then oxidation of the cations can balance the Fig. 11.1 ~.2.3. Metal deficiency defect.
electrical neutrality. But to fit an ani~n which is generally larger in size in the interstitial site is a
difficult task. Thus, this possibility theoretically exists, but no example is reported.
Note : K2Pt(CN)~O.3.3H20 (X= C, or Br-) is commonly known as KCP(cf. Sec. 12.8.5) and· it
is a typical example of nonstoichiometric defect. The mechanism of electrical conduction in
KCP is quite interesting. .
Effects of Metal Deficiency Defects

(i) Electrical conductivity: The defect in the compound A+n- (say) leads to oxidation of A+ to A 2+
ions which are placed at the- defined lattice sites. Now the electron transfer from A+ to A 2+ leads
to the same A2+, A+ pair but the positions

of A+ and A 2+ are interchanged. Thus the
electron transfer in successive steps in a ; 'e-0-e-0-0 r r
0-~0-$-0
particular direction leads to the movement
of A 2+ in the opposite direction which in
tum leads to an electrical conduction (cf.
Fig. 11.15.2.6). This is equivalent to the
Inovement of the positive hole as in
E>-0-¢-0-$
ry
p-type semiconductors. This is why,
nonstoichiometric compounds of the
0-@-0-@-0
ra
type, Al _{)B are referred to as p-type semi-
conductors.
ib
Each A 2+ centre acts as a source of Fig. 11.15.2.4. Nonstoichiometric defect due to
positive hole (Le. A 2+aA+ + one positive impurity doping.
yl
hole). The electrical conductivity can be
explained by considering the hopping
6--6--e--®--~
mechanism of hole migration (Chapter
m
12). I Y I I I
he
The mechanism of electrical conduction
in the nonstoichiometric monoxides of
~: : : :
3d-metals and KCP has been discussed ~--e--®--e-0
lc
in detail in Chapte~ 12. I I I I I
e--6--0--e-B
ea
The metallic conductivity in inverse

spinel Fe 3 0 4 can be explained by
positive hole migration involving
th
I I I I I
Fe 3+-Fe 2+ centres (Sec. 11.11.1).
(ii) Colouration : Because of the existence
e--0---0--e--~
e/
of higher valent oxidation states of the

cation~ new charge transfer bands at tl}e
t.m
Fig. 11.15.2.5. Doping of Li2 0 in NiO crystal to

lower frequency may appear. SOllletimes, generate NP+ centres.
the new ligand field band of the higher
valent cation introduces a new colour.
Hopping semiconductor
The nonstoichiometric crystal defects leading to p-type or n-type semiconductivity are quite
important. Their semiconductivity is explained in terms ofhopping mechanism but not in terms of
.band theory which is applicablefor intrinsic and extrinsic (both n-type andp-type) semiconductors.
This aspect is discussed in Sec. 12.10.
(C) Nonstolchiometric Defects due to Substitution by Impurities

Sometimes, the cations are missing and the electrical neutrality is maintained by some foreign cations.
To carry out the substitution, the ionic radii of the foreign cations should be comparable with those of
the parent cations, otherwise they will not fit properly in the lattice sites. For example, in the AgCI
crystal, two vacancies of the cations can be compensated by the placement of one cJl+ ion in one
vacant site (see Fig. 11.15.2.4). Here the crystal ionic radii of cJl+ and Ag+ are comparable. In general,
m
in the compound, Am+Bm- the substitution of Am+ by .xn+ leads to ~m_+naX~; B - where n > m. Another
interesting example of doping of Li20 in NiO (here n < m) is discussed here (Fig. 11.15.2.5). The
subtitution of one Ni 2+by one L,-+ requires the oxidation of one Ni 2+to Ni 3+to balance the charge. This
second type of impurity substitution (Le. n < m) introduces the properties ofp-type semiconductors
and a colour change due to the oxidation of A m+.
ry
Now let us explain the electrical conductivity of such systems. It is evident that when Li20 is doped
in NiO, each Li+ introduces a positive hole, i.e.
ra
· AT· x 0 == L·+
L 'X1V'l_ 'x
AT·3+ AT·2+ 0 2-
lV'X lvl1_ 2x
ib
It has been noted that 0.05% Li in NiO increases the conductivity by a factor ca. 104•
Each NP+ centre can serve the purpose of a hole (i.e. NP+ == Ni2+ + one positive hole). When the
yl
positive hole from a Ni 3+ centre moves towards another Ni 2+ centre, it gets oxidised to Ni 3+ and the
parent Ni 3+ centre gets reduced to Ni 2+. Thus the directions of the movement of the Ni 3+ centre and
m
electron are opposite (Fig. 11.15.2.6). Ni 3+is more polarising than Ni 2+. This is why, when the positive
hole hops from one Ni 3+ centre to an adjacent Ni 2+centre, the migrating hole must carry the polarisation.
he
It is· reflected in the activation energy of hopping conduction (cf. Chapter 12).
lc
HINi2+------- Ni2+------- N~i3+-------Ni +(+) 2

ea
~ 1
th
H (+)
INi2+------- Ni2+------- Ni3+------- Ni2+------- Ni2+1
e/
I~ 1
t.m
H
Ni2+------- Ni3+------- Ni2+------- Ni2+------- Ni 2+ I (+)
Fig. 11.15.2.6. Schematic representation of the movement of NP+ centre and electron in the Li2 0 doped
NiO crystal in presence of an electrical field.
Note : Positive hole migration (hopping mechanism) through the Fefl.+ and FEfJ+ centres residing in
octahedral sites of inverse spinel Fe3 0 4 explains the electrical conductivity of Fe3 0 4 (cf. Sec. 11.11.1).
Ionic conduction: Electrical conduction In ionic crystals

Transport of charge carriers e.g. ion, hole, electron through hopping mechanism.
Electronic conduction in metals, semiconductors and insulators

Movement of charge carriers in the conduction band.
11.16 MAGNETIC MATERIALS: MAGNETIC PROPERTIES

11.16.1 Terminology in Describing the Magnetic Properties and Different Units (cf. Sec. 1.10.17)
Magnetic induction (B) : When a body is subjected to a magnetic field of strength H, the total magnetic
flux coming out per unit area of the body gives the measure of B.
B = H + 41tI, (in CGS system)
Magnetic field H indicates H lines of force per unit area; and 41tI denotes the additional field due to
induced magnetisation where I (may be d~n~ted by M also) is described as intensity ofmagnetisation.
ry
Magnetic permeability (P) is defined as :
ra
P = B/H= 1 + 41t (I/H) = 1 + 41tX v (in CGS system)
P gives the ratio of the density of lines of force within a body and that under vacuum. Xv is called
ib
volume magnetic susceptibility of the substance. I~ fact, we can write : I ex: H and I = xji.
Gram susceptibility (X,) is related with Xv as fo"nows :
Xg
yl
=h, (p = density)
p
m
'XM (molar susceptibility) = Xg x M, M = molecular mass of the substance.
he
Units: Weber (Wb) is the unit of magnetic flux.
Wb = kg m2 's--2 A-I, Wb = V s
lc
B (magnetic induction, magnetic flux density) is expressed as Wb m-2 or tesla (T).

ea
T = Wb m-2 = kg S-2 A-I

Unit of H (magnetic field strength) is ampere per meter (A m- I).
th
P (magnetic permeability) is expressed as H m- I (henry per meter); H = Wb A-I.

'XM is expressed in m3 mol-I.
e/
Magnetic moment: Basic unit of magnetic moment is called the Bohr magneton (J.LB) :
~B =~,
t.m
(inCGSunit)
41tme c
= 9.274 x 10-21 esu erg g-I cm -l s 2
= 9.274 x 10-21 erg a-I
~B =~, (in Sf unit)

41tme
=9.274 x 10-24 C J S kg-I
= 9.274 x10-24 J T- I
[1 G (gauss) = 10-4 T (tesla)]
'XM (molar susceptibility) = NAJl~ /(3k BT), (in cas system).
XM = NAJlOJl~ /(3k BT), (in SI unit).
Structure, Bonding and Properties of Ionic Solids and Solid State Chemistry 10n
fl m= magnetic moment of the substance.

flo = permeability of free space (Le. vacuum) = 41t x 10-7 H m- I
= 41t x 10-7 Wb A-I m- I = 41t x 10-7 N c-2 s2 = 41t x 10-7 J c-:2 m- I s2
In terms of flo' we can write: B == flo(H + I) = fl o( 1 + Xv)H = JlH

fl (= P, defined earlier) is called permeability ofthe medium, and the relative permeability (flr) is
defined as :
fl r = Wfl o
ry
It leads to : fl = flo (I + Xv); or Xv = fl r - 1
If an atom possesses more than one unpaired electron, then the resultant magnetic moment (flm) due
ra
to the spins of the unpaired electrons is given by :
ib
fl m = 2flBJS(S + I); S =!: where n gives the number of unpaired electrons
2 .
2
yl
XM = NA~m ; or ~m = 2.63 x 10-20 JXMT erg a-I = 2.83 JXMT B.M.
3kB T m
21
(I 8.M. = I flB = 9.27 x 10- erg a-I)
he
3k BTXM ~
Le. J-l m = 2 = 2.83 VXM T B.M.
NAJ-lB
lc
XM = N A [2J.1B J
~S(s + 1) = 1.68 x 10-3 erg a-2 mo\-IS(S + 1), (at 298 K)
ea
3kB T
= (1.68 x'10-3 cm3 mol-I) S(S + I), (in cas system), (at 298 K)
th
In SI unit, 'V = NAfl fl2

3k T m ' or rm =
0 II
3kBTXM
2 = 797.6 fi:J
'VMT 8.M.
e/
AM A
B NAfloJlB
t.m
(I 8.M. = 1 flB = 9.27 x 10-24 J II)
XM = N AJ.1o J.1~ = N A J.1o [2J.1B~S(S + 1)

3kB T 3kB T
J
= 41t(1.68 x 10-9 J T-2 N C-2 S2 mol-I) S(S + I), (at 298 K)
= 41t(1.68 x 10-9 m 3 mol-I) S(S + I), (at 298 K)
11.16.2. Classification of Magnetic Substances

Depending upon the magnetic properties of the substances, these are classified in different ~oups.
These are discussed below :
(a) Diamagnetic substances: The property, diamagnetism makes a substance to repel the external
magnetic field. The presence of closed shells of electrons is responsible for this property. Such
substances do not have any net magnetic moment. The external field induces a magnetic moment
ry
(a) Diamagnetism (b) Paramagnetism (c) Ferromagnetism
ra
Fig. 11.16.2.1. Different types of magnetic bodies in a magnetic field. (a) Diamagnetism - repelling the
Jines of force; (b) Paramagnetism - attracting the lines for force; (c) Ferromagnetism - attracting strongly
ib
the lines of force.
yl
on a diamagnetic substance and the induced magnetic moment does not interact with the spins of
the paired electrons, but the orbit as a whole precesses about the direction of the applied
m
field (H). Thus the planes of the orbit are slightly altered to produce a net orbital moment
which opposes the applied mafnetic field. Diamagnetism is independent of temperature.
Magnitude of 'Xg is approximately -1 x 1O~ (in CGS unit). ~
he
The magnetic permeability (P or Jl) is less than unity. Thus such substances allow the passage of
fewer number of lines of forces (as compared to that in vacuum).
lc
(b) Paramagnetic substances (see Sec. 1.10.17) : Paramagnetic substances are attracted in a magnetic
field and paramagnetism originates from the spinning and orbital motion 0/ the unpaired
ea
electrons. For paramagnetic substances, the magnetic permeability is greater than unity (Le.
more lines of forces are concentrated within the substance).
th
In the case of free gaseous metal ions, both the orbital and spin angular momenta contribute for
paramagnetism, but when the metal ions remain in the complexes, the orbital contribution gets
e/
very often quenched. In such cases, the spinning motion 0/ the unpaired electrons is primarily
responsible/or paramagnetism (Le. spin only magnetic moment is denoted by Jls). The quenching
t.m
ofthe orbital contribution arises from the interaction ofthe electrons with the environment present
in the complex. This quenching phenomenon is more important for the d-electrons (Le. d-block
elements) than for thefelectrons (Le.fblock elements) because the/-electrons are deeply buried
and they can hardly interact with the environment. The Sf-orbitals ofactinides are more exposed
than the 4f-orbitals of lanthanides and thus quenching of orbital contribution is more probable in
the case of actinides, specially the lighter ones.
If both the spin and angular momenta of afree ilJn contribute, then the magnetic moment is given
by:
llefT = Ils + L = ~4S(S + 1) + L(L + 1) BM
(provided multiplet width is small as compared to kBl)
In such cases, spin-orbit coupling is ignored and the spin and angular momenta o/the electrons
are supposed to contribute independently. This mainly occurs for the free ions of 1st transition
series. But, if the orbital contribution is ignorable (as in the complexes), then effective magnetic
moment is given by :
lletT = Ilsp in-only = ~4S(S + 1) B.M. = ~n(n + 2) B.M.

(n =-number of unpaired electrons)
The magnetic moment of a free atom or ion can be calculated in terms of the resultant spin and
angular momentum quantum numbers L, Sand J.
ry
J.lefT = g)J(J + 1) 8.M. (multiplet width is large as compared to kBn
ra
. . _ 1 + J(J + 1) -+= S(S + 1) - L(L + 1)
g (Lande splitting factor) - 2J(J + 1)
ib
In fact, in such cases, spin-orbit coupling is important and it occurs so in the case oflanthanides
(4fseries).
yl
In a paramagnetic substance, if the paramagnetic centres are widely separated, then no mutual
interaction among the neighbouring centres occurs. Such substances are called magnetically
m
dilute. But in a magnetically concentrated substance, the individual magnetic centres can mutually
interact to develop different properties like ferromagnetism, ferrimagnetism and antiferro-,
he
magnetism. These are described as cooperative magnetism.
11.16.3 Cooperative Magnetism - Aniferromagnetism, Ferrimagnetism, Canted Magnetism

lc
and Ferromagnetism
ea
The orientation of different magnetic centres to produce the different types cooperative magnetism is
(a) Antiferromagnetism: In a paramagnetic substance, when the magnetic moments ofneighbouring
th
centres are oriented into an antiparallel alignment, the substance has got a very low re~ultant
e/
II III , 1/ I\ I-I \ 1/ III

t.m
(8)
11111 1 111111
(b) (c) (d)
Canted antiferromagnetism Canted ferromagnetism

(e) (a-canting angle)
Fig. 11.16.3.1. Alignment of individual magneti9 dipoles in (a) paramagnetic, (b) ferromagnetic,
(c) antiferromagnetic, (d) ferrimagnetic and (e) canted magnetic substances.
magnetic moment. In some cases, the substance may be converted into a diamagnetic one. Such
substances are referred to as antiferromagnetic substances.
The antiferromagnetism is attained through the pairing of spins (Le. Pauli's exclusion principle)
in a common orbital produced through overlapping. This overlapping interaction (Le. covalent
interaction) may occur through direct interaction (e.g. o-bond formation as in dimeric
Cu(II)-acetates; quadruple bond formation as in dimeric Cr(II)-acetate, etc. cf. Secs. 9.19, 12.8)
.or through the intervening ligands (by a special mechanism called superexchange). For all these
spin pairing interactions (it may be pointed out that pairing may not be always complete), the
ry
magnetic centres must have the right alignment and right interatomic separation for such
interaction. But thermal energy tends to randomise the orientation. This is why, above a particular
ra
temperature (called Neel temperature, TN)' the antiferromagnetic interaction is broken down,
and above this temperature the substance behaves like an ordinary paramagnetic substance (where
ib
the paramagnetic centres remain noninteracting).
• Antiferromagnetism in metal oxides and chalconides : Bridging ligating sites (e.g. (jl-) with
yl
the paired electrons can participate in developing the superexchange interaction (180° super-
exchange) It occurs in different metal oxides below the Neel temperature. The examples are:
m
0
MnO(TN =-151 C), FeO, NiO, Cr2 0 3 (TN =3.7°C)
The intervening oxide ions «(jl-) with paired electrons in 0- and 1t-orbitals (which are almost
he
pure p-orbitals) remain between the metal ions in a colinear structure.
_M n+ -O-M n+ -O-M n+ -
lc
ea
x-interaction : (M)d~ + p;(02-) - d~(M), (M)d~z + p;(02-) - d~(M), etc.

th
Overlapping of the d-orbitals containing the unpaired electrons of the metal centres may occur
through the filled oxygen p-orbital (Le. 3c-4e molecular orbitalformation). In terms of 3c-4e
e/
MO formation, the four electrons are placed in one bonding MO and in one nonbonding MO to
bring about the pairing of the electrons. In a simple way, it can be said that one electron from the
t.m
electron pair on oxide ion will move towards the overlapping d-orbital (with an unpaired electron
of opposite spin) of one metal centre and it leads to pairing of the electrons. The other p-electron
of that pair of oxide ion will undergo overlapping in the same way with the other metal centre.
The superexchange mechanism is shown in Fig. 11.16.3.2.
This type of antiferromagnetic interaction discussed in the case of transition metal oxides may
also occur in chalconides (where 81- sites act as the interVening ligating sites).
In the linear segment M-D-M, the efficient a-type interaction occurs to bring about the spin
pairing interaction (Le. 3c-4e a-MOformation). Superexchange interaction can be illustrated in
MnO (TN = 122 K) which remains in a rock salt structure (Fig. 11.16.3.3). The high spin Mn 2+
ion is t~ge;. The unpaired electrons in the eg orbitals of Mn 2+ can participate in a-type
superexchange, (1800 superexchange) interaction, and the unpaired electrons in the t~g orbital
can also participate in x-type superexchange (1800 superexchange) interaction. Above the Neel
temperature (122 K), the thermal agitation destroys the required a/ignment~for superexchange
x
(J
~
c::
ry
~g>
E=a (t2g )dxy Py dxy<t2g )
g5 0
Q)(J M 0 M
ra
~
C (b)
<
ib
t ~t ~ t~ t ~t
+ ~~
M
yl
m
he
(a) e = Oxygen
lc
(c)
Fig. 11.16.3.2. Antiferromagnetic coupling through 1800 superexchange mechanism by using the paired
ea
electrons of the bridging ligand site (e.g. oxygen). (a) Sigma type 30-4e bonding model; (b) 7t-type
30-4e bonding model (M denotes the metal centre with an unpaired electron); (c) spin pairing through
superexchange (7t-type) by using the electron pair on the intervening oxide ion in metal oxide.
th
y
e/
t.m
~-- .... x
Px
z Mn o Mn
(a) .= Mn, 0 =0, (b)

Fig. 11.16.3.3. (a) Antiferromagnetic MnO crystal (below 122 K); (b) Antiferromagnetic interaction
(30-4e a-type bonding) in MnO crystal through superexchange.
interaction and then the interacting magnetic centres remain randomly oriented. Thus above TN'
it behaves /ike an ordinary paramagnetic substance.
• Antiferromagnetism in ferrites : The antiferromagnetic interaction in the inverse spinels
MFe~I104 [M' = Fe (II), Co(II), Ni(II), etc.] called ferrites have been discussed in Sec. 11.11.1
and in the discussion of ferrimagnetism.
• Antiferromagnetism in metal clusters: The several examples of antiferromagnetic interaction

in different metal clusters e.g. Re2 Xi-, Mo 2 X:-, Re3 X 9 , etc. have been discussed in Sec.
12.8.
• Antiferromagnetism in brown ring complex and nitropruside : These are discussed in Sec.
16.1.21 ).
(b) Ferrimagnetism: This property arises when the magnetic moments ofthe individual centres are
aligned to oppose one another (cf. Fig. 11.16.3.1) as in the antiferromagnetic interaction. In the
ferrimagnetic substances, the opposing magnetic moments are of different magnitudes and
ry
consequently there is only a partial cancellation ofthe magnetic moments. Thus a ferrimagnetic
substance always possesses a finite resultant magnetic moment. As in the antiferromagnetic
ra
substances, above the TN' the required opposing alignments ofthe interacting magnetic moments
of the individual centres are lost in the ferrimagnetic substances. Ferrimagnetic interaction very
ib
often arises from the participation of the intervening ligand as in the case of superexchange
interaction for the antiferromagnetic substances. In fact, it is very difficult to distinguish between
yl
the ferrimagnets and antiferromagnets where only partial quenching of spins occur.
The ferrites MIl Fe~I104 (M = Fell, CoIl, Ni Il , Zn II , etc) are the common examples of ferri-
m
magnets. In these inverse spinel ferrites, half of the Fe(III) centres occupying the octahedral
holes can interact antiferromagnetically with the other half of Fe(III) centres occupying the
he
tetrahedral holes. Thus the resultant magnetic moment arises from the unpaired electrons of
M(II).
(c) Ferromagnetism (cf. Sec. 12.5.8) and related phenomena like magnetic domains, hystresis
lc
loop: Ferromagnetism appears when the individual magnetic dipoles align in the same direction
to enhance the paramagnetism. This happens for the metallic iron lattice up to 1041 K (I.e.
ea
768°C). Above this temperature, the thermal energy is sufficiently high to randomise the parallel
alignment. The temperature at which this parallel alignment is destroyed is called the Curie
th
temperature (Tc). Thus above the Tc (which is differentfor different substances), allferromagnetic
substances behave like the ordinary paramagnetic materials.
e/
When the unpaired electrons ofdifferent magnetic centres come within the overlapping distances,
it leads to spin pairing Le. antiferromagnetic interaction. If the unpaired electrons are widely
t.m
separated, then no mutual interaction is possible. In a ferromagnetic substance, the unpaired

electrons are placed at such distances that no overlapping or covalent interaction is possible,
but spin exchange interaction among the parallel spins is possible. This exchange interaction
energy stabilises the parallel alignment of the spins. Thermal energy tends to randomise the
alignment while the exchange energy phenomenon favours the parallel alignment provided they
are at the optimum distances. In fact, the systems having higher stabilisation through exchange
interaction record the higher Tc.
Distribution of ferromagnetic property among the transition metals and inner transition metals
has been explained by considering the sign of exchanK.e integral discussed later (see Sec. 12.5.8).
• The hysteresis loop and the domain structure: Magnetic induction (B) of a ferromagnet does
not vary linearly with the applied magnetic field of strength H. With the increase of field H, the
magnetic induction (B) initially increases slowly and then more rapidly, and ultimately it attains
a saturation value Bs' After the attainment of B~, there is no change in magnetic induction with
the increase of H. Now, if the field is applied in the reverse direction, the B-H curve is not
(Magnetization B)
o
~---- Domain rotation (CD path)
Irreversible domain
wall displacement (AC path)
Reversible domain
ry
wall displacement (OA path)
---------:IIJ---~---l~--------
- - - - . . Applied field (H)
ra
ib
(OAC ~ Domain growth through the displacement
of domain wall i.e., Bloch wall)
yl
m
Fig. 11.16.3.4. Hysteresis loop in the magnetisation curve of ferromagnetic materials.
he
retraced. In fact, with the reversal of the field, the induction decreases slowly and it attains the
residual value (Br ) for H = O. After reaching the Br v~lue, if the field is further increased in the
lc
reverse direction, the induction becomes zero at a certain value offield (He) described as coercive
field, Le. at He the induction is lost. If the process is still continued in the reverse direction, then
ea
the magnetic induction occurs in the opposite direction and it becomes saturated (Bs ). After the
attainment of Bs' if the fielq is restored in the original direction, it gives a hysteresis loop.
To understand. the origin and shape of the B-H curve (Fig. 11.16.3.4), it is important to know the
th
structure of ferromagnetic materials in terms of magnetic domains. The Curie temperature

(Tc = 768°C) of iron is far above the room temperature and consequently the magnetic moments
e/
of the individual magnetic centres are aligned.parallel at room temperature. But in the absence
of any extt!rnal field, a piece of iron is IWt magnetic at room temperature. To explain 'this
t.m
. behaviour, it is suggested by Weiss that

the unmagnetised crystal of iron consists ... 1 ,. .
of several magnetic domains and in each "l 1
-+ ~
domains, the spins are oriented parallel.
I I **' t
Thus, below Tc' each domain is itself
ferromagnetic. In the unmagnetised 1 1 l t "
condition, the magnetic domains are / " tI
randomly oriented and the overall ,... ,,;r
magnetic ·.JrJoment cancels (Fig. (a) (b)

11.16.3.5). The· .magnetic domains are
Fig. 11.16.3.5. Unmagnetised domain structure
separated from one another by domain
(a, b) of a ferromagnetic substance. (a) for a
walls called Bloch walls. In the process single crystal; (b) for a poly-crystal. Net magne-
ofmagnetisation by the external field, the tisation in each case is zero in absence of an
magnetic domains are oriented parallel. external field.
Process of magnetisation : The domain walls are separating the magnetic domains. The
magnetisation process (in the presence of field H) involves the alignment of the domains. This
alignment can be attained in two ways (Fig. 11.16.3.6) : (i) to rotate a particular domain in the
direction ofthe field; (ii) growth ofmorefavourably oriented domains through the movement
of Bloch walls at the expense of less favourably directed domains.
1 H (Applied field)
ry
--+
!!!
ra
!
ib
Unmagnetized (b)
yl
......_----~----~/
'---
Magnetisation by Magnetlsatlon by domain growth
domain rotation (movement of Bloch wall)
(a)
m
Fig. 11.6.3.6. (a) Magnetisation process in the presence of an external field (H) in a ferromagnetic
he
substance; (b) Magnetic saturation attained through magnetisation.
To rotate an entire domain which is unfavourably oriented is more. energy requiring than to move
lc
its domain walls to allow the growth of a bigger domain in the direction of the field. "
ea
When the applied field is weak, the domains which are already remaining oriented parallel to
the field grow in size through the movement of Bloch walls at the expense of relatively less
favourably oriented ones. This step at the early stage is more or less reversible and is represented
th
by OA path (Fig. 11.16.3.4) of the B-H curve. At the relatively higher field, the domain wall
movement becomes stronger and it occurs more sharply (indicated by the AC path in the B-H
e/
curve). This path (AC) is irreversible and the process goes to attain the saturation at the point C
(Fig. 11.16.3.4).
t.m
If still higher fields are applied, then the unfavourably oriented domains start ,to orient in the
direction ofthe field. This path is represented by CD in the B-H curve (Fig: 11.6.3.4). It completes
the magnetisation.
The process occurring at the early stage of the magnetisation process is less energy requiring
than the process occurring at the late stage. This is why, the slope ofthe B-H curve decreases in
the range of saturation of magnetisation.
After the attainment of saturation value (Bs )' if the field is reversed, the material tends to get back
its original structure. But this restoration process needs the displacement of Bloch walls and this
is prevented by the lattice impurities and crystal defects. This is why, more energy is required to
restore the original configuration (i.e. zero magnetisation). It explains the origin of coercive
field (HcJ to bring the material to zero magnetisation. The energy spent to overcome the opposing
forces for the displacement of Bloch walls is not recoverable and this loss of energy is called
hysteresis loss which is measured by the size 0/ hysteresis loop.
• Hard and softferromagnetic materials (Fig. 11.16.3.7) : Depending on the shape and size of
hysteresis loop, the ferromagnets are classified as hard ferromagnets (e.g. high carbon steel,
chrome steel, tungsten steel,AI-Ni-Co (alnico) alloy, etc.) and softferromagnets (e.g. commercial
iron, Fe-Si alloy, etc). For the hard ferromagnets, the hysteresis loop is broad and the residual
magnetic induction (B r) is fairly large when the applied field is reversed to zero. Consequently
the coercive field (Hc ) is very high. Such hard materials are used to generate the permanent
magnets. In such cases, the energy loss (measured by the loop area) is of no much importance,
because no rapid reversal ofthe magnetisation is required in a permanent magnet.
ry
ra
B
ib
yl
m
he
Applied field (H)----+
lc
ea
th
(a) Hard ferromagnet (b) Soft ferromagnet

Fig. 11.16.3.7. Hysteresis loops for (a) hard ferromagnet - large loop area, large coercive field (HJ
e/
and large residual magnetisation (B,), (b) soft ferromagnet - small loop area, small He and Br
t.m
For the soft ferromagnetic materials, the hysteresis loop is narrower and such materials are
characterised by the low values ofBrand H c • These materials are used in the cases wherefrequent
reversal ofthe direction ofmagnetisation occurs. Each time, the hysteresis loop is reversed and
in this process, energy equal to the area ofthe loop is lost as heat. Thus if the loop area is large,
energy loss due to hysteresis is significant, specially when there is a frequent reversal of the
direction of the field. This is why, the soft ferromagnetic materials are used in transformers
which is subjected to a rapid oscillating field.
(d) Canted magnetism (cf. Fig. 11.16.3.1e) : In ferromagnetism and antiferromagnetism, parallel
and antiparallel spin alignment occur respectively. In general, the spins are ofthe same magnitude.
In ferrimagnetism, the antiparallel spins of different sublattices are of different magnitudes. But,
if the spins of sublattices are neither perfectly parallel nor antiparallel but are canted, then a
special case of weak ferromagnetism will occur in both canted antiferromagnetic and canted
ferromagnetic interactions. The canting angle (a) is generally of small magnitude « 1S°). Canted
magnetism is known to occur in different oxide minerals e.g. a-Fe 20 3•
11.16.4 Magnetic Properties of Metals (cf. Sec. 12.5.7-8)

The magnetic moment of an atom decreases in its solid state compareq to its isolated atomic state. In
fact, in solid state, the outermost orbitals bearing the unpaired electrons interact and form e~ergy bands.
The different bands may overlap to allow the redistribution of the electrons. All these aspects have
been discussed in detail in Chapter 12.
The conditions for ferromagnetic interaction in metals have been discussed in Sec. 12.5.8.
The temperature independent paramagnetism (TIP) known as Pauli magnetism is a special
characteristic feature and this aspect hil,s been discussed in Chapter 12.
ry
11.16.5 Temperature Dependence of Magnetic Susceptibility of Different Types of Magnetic
ra
Materials
Diamagnetism is independent of temperature. Temperature independent paramagnetism (TIP) of
ib
metals and of some inorganic complexes are also known.
. For the substances having permanent magnetic centres, thermal agitation tends to randomise the
yl
orientation of the magnetic moments of the individual centres but the cooperative interaction needs
their specified alignments.
m
Molar susceptibility (XM) of a simple paramagnetic substance is given by Curie's law.
XM =CIT,orI/X m =TIC
he
where C is called Curie constant (a characteristic property of the substance) and T gives the absolute
temperature. The above Curie's law indicates that the paramagnetic susceptibility varies inversely with
lc
the absolute temperature of the substance. This paramagnetism due to free spin is called Langevin
paramagnetism to honour the scientist who developed the mathematical expression of Curie constant.
ea
Note : He~e it should be mentioned that Langevin paramagnetism (due to free spin) follows the
Curie law but Van Vleck paramagnetism (due to 2nd order Zeeman effect) and Pauli
th
paramagnetism of metals are temperature independent (Le. TIP). It may be noted that Langevin
paramagnetism is due to 1st order Zeeman effect. Diamagnetism (characterised by negative value
e/
of X) is also temperature independent. Thus, Curie equation should be written as :

t.m
C
XM =A+-
T
where the temperature independent term A takes care of diamagnetism, Van Vleck paramagnetism
and Pauli paramagnetism depending on the condition. By neglecting the term A, the ordinary
expression of Curie law Le. XM = CIT is obtained.
According to Curie law, the plot of I/XM vs. T should be linear passing through the origin, but in
many cases it produces finite intercepts. It is given by Curie-Weiss law.
CIT e
e; or, XM == C -
XM == T - c
e is called Weiss constant required to explain the origin of the intercept in the plot of l/XM vs. T. In
fact, e arises for cooperative magnetism existing in magnetically concentrated substances. For ordinary
paramagnetic substances without any cooperative interaction, e~ O;for antiferromagnetic substances,
e = -ve;for ferromagnetic substances, e = +ve.
c C
Thus we can write: XM = T _ T (for ferromagnetism) and XM = T _ TN (for antiferromagnetism).
c
Curie's law is actually given by :
XM = N AIl~ /(3k BT) = ~, (in CGS system or Gaussian system or emu)
Il m = J3k:: XM = 2.63 x 10-

20 ~XMT erg G- I = 2.83~XMT B.M.
ry
A
ra
3kBTXM 1/2
It leads to : ~m = ~eff = 2 B.M. = 2.83 (x'M T ) B.M.
ib
NAJ.1B
=~=9.274xIO-21
yl
IlB ergG-I )
( 4mm c .
e
m
Thus, Curie constant (C) is given by :~c = NAJ.1~~~ /3k B , (in CGS system)
he
Taking 9 into consideration we can write: J.1 eff = 2.83 [XM(T - 9)]1/2 B.M.
lc
~
ea
>
.t..
~
t
t--------
th
o
Q) T(K)-+
1
e/
'\ Diamagnetic
t.m
Ferromagnetic
~
I
I
I
~
~
~
II ---+ T(K)
I II
II
T (K) -----+ I
~ ~ :
(i) (ii)
Fig. 11.16.5.1. Temperature dependence of magnetic susceptibility (X) of different types of magnetic
substances; (i) magnetic susceptibility - temperature (x. vs. 7) curves; (ii) 1/x. vs. Tcurves, (b) for Curie
equation; (a) and (c) for Curie-Weiss equation.
In SI system we can write :

'XM(T - 8)3kB I
Jl m = Jleff = 2 = 797.6 v'XM(T - 8) B.M.
NAJloJlB
18.M. = ~B =~ = 9.274 X 10-24 J r l

where
41tme
and XM = N AJloJl~ /(3k B T)
ry
Jl o == permeability of free space == 41t x 10-7 H m- 1
Note: See Sec. 1.10.17 for units and dimensions of the different terms mentioned above.
ra
11.17 PROPERTIES OF FERROELECTRIC MATERIALS AND
ib
PIEZOELECTRIC MATERIALS
yl
11.17.1 Ferroelectric Materials
The ferroelectric materials are characterised by very high dielectric constant. Barium titanate (a
m
representative ferroelectric material) possesses a relative dielectric constant in the order of 2000 (cf.
ordinary dielectrics possess the value close to 10). Ferroelectric materials acquire electric dipole moments
he
which are aligned in a parallel fashion below a certain temperature calledferroelectric Curie temperature
(cf. ferromagnetic materials where the magnetic dipole centres remain oriented parallel below Tc )' In
lc
fact, ferromagnetic materials are characterised by high magnetic susceptibility and magnetic permeability
and ferroelectric materials are characterised by high dielectric constant and spontaneous polarisation
ea
(Ps to be discussed later).

Thermal agitation tends to randomise the orientation of the electric dipoles and this is why, the
th
ferroelectric property of a substance exists only below the Curie temperature (cf. Curie temperature for
ferromagnetic substances). When a ferroelectric material is placed in an electrical field, theflux density
e/
within the material is very high. This is why, if a condenser is made ofa goodferroelectric material,
then its charge capacity becomes very high. If the working temperature is far below the Tc ' then
t.m
practically all the electric dipoles remain oriented in the direction of the field. !n fact, the condensers
made of BaTiO] can concentrate the electric energy with a small space (cf.ferromagnetic materials
can concentrate magnetic energy).
The ferroelectric materials of very high dielectric constant are usedfor storing electrical energy
in small sized capacitors.
. Just like the ferromagnetic materials, in a ferroelectric material, the electric dipoles of the adjacent
dipoles are aligned, but there is no nei polarisation in the absence ofan externalfield. The reason can
be understood if we consider that a ferroelectric material is constituted by differentferroelectr;c domains
which are randomly oriented (cf. domain structure of ferromagnetic materials). It may be pointed out
that in each domain, all the electric diRoles remain oriented parallel below the Tc. When an electric
field is applied, theferroelectric domains tend to orient in the direction ofthefield and netpolarisation
occurs. The polarisation (cf. magnetisation in a ferromagnetic material) process involves both the
domain growth and domain rotation and it produces aferroelectric hysteresis loop (cf. B-H curve and
hysteresis loop in ferromagnetic materials).
In the P-E curve (E denotes the electrical field and P denotes the polarisation which is defined as
dipole moment per unit volume) (Fig. 11.17.1.1), the development of a hysteresis loop suggests that the
substance possesses an spontaneous polarisation (Ps) and it is obtained by extrapolating the linear
~urve backwards to the zero field. The residual polarisation (P r) and corec;ve field (Ec) are obtained
from the hysteresis loop (Le. P-E curve). Ps exists if the P-E curve is drawn below Tc and Ps increases
with the increase of Tc (cf. Table 11.17.1.1). Above Tc for a particular substance, P-E curve is a
straight line (Le. no hysteresis loop) (cf. Fig. 11.17.1.1). In fact, Ps decreases with the increase of
temperature and it becomes zero at 2: T.c
ry
Table 11.17.1.1. Properties of some common ferroelectric materials
ra
Crystal Curie temperature Spontaneous polarisation
Tc (in K) Ps (C m-2) .
ib
Rochelle 297 to 255* 0.24 x 10-2
BaTi03 393 0.26
yl
KH2P04 123 4.95 x 10-2
KNb03 712 0.30
m
PbTi03 763 0.50
he
* It shows the ferroelectric property only in the range of-18°C to +24°C.
Three main groups of ferroelectric materials are: tartarate group (e.g. Rochelle salt which is the
lc
sodium potassium salt of tartaric acid); dihydrogen phosphates and arsenates of alkali metals (e.g.
KH2P04 known as KDP); and perovskite group consisting of niobates and titanates (e.g. KNbO))
ea
BaTiO), etc.).
th
Q..
p
B
1 I
e/
c
t.m
Pr·~- . . ""
o - - -...·E
---+ E
-- --
-P
-~ ,
- -Ps
(a)
•
(b)
Fig. "11.17.1.1. (a) Hysteresis loop for a ferroelectric material below To (b) P-E curve for a ferroelectric
material above Tc-
The ferroelectric property of KDP has been discussed in terms of its H-bonded structure (cf.. Fig.
. ~
13.1.6.4). .
Just like the antiferromagnetic materials, in antiferroelectric materials (e.g. PbZr0 3 ), the
neighbouring electric dipoles are antiparallel to e,ach other.
The crystal structure in relation to ferroelectric property of BaTi03 has been discussed in Sec.
11.12.1.
11.17.2 Piezoelectricity al1d Piezoelectric Materials
ry
Piezoelectricity of a crystal refers to electromechanical effects (i.e. electrical response ofa crystal to
a mechanical stress or mechanical response to an electricalfield). Thus, a piezoelectric crystal possesses
ra
the ability to generate an electrical field when the crystal is subjected to an external pressure. Reversely,
when an electric field is applied to such crystals, the dimension of the crystal also changes.
ib
A piezoelectric crystal lacks in centre of symmetry. In the absence of an external field, if the
centres of positive and negative charges are separated by a distance d in the crystal, then with the
yl
application of a compressive stress on the crystal, the separation distance (d) dereases and it develops
a potential difference (V, say). Similarly, the application ofa tensile stress will also generate a potential
m
difference in opposite direction (compared to the effect of compressive stress).
Piezoelectricity cannot occur in crystuls having a centre of symmetry and it is illustrated in Fig.
he
11.17.2.1 by using a two dimensional model of an ionic solid. H;ere, the position of the anion (AlJ.s
the centre of symmetry. If the crystal is compressed,. the dipole moment acting in the direction BA
lc
decreases and at the same time, the dipole moment acting in the opposite direction Le. CA also decreases
by the same amount. Thus, due to the compression, there is no net change in polarisation.
ea
Dipole moment (SA)
r !
th
o e 0BleJ
.r;:' 0
(Pressure)
Compression
o e GaLe 0
e 0 eA 0 e e o eA ~0 e ::>
e/
Dipole moment
o e 0c~ ~ o e 0cre 0
t.m
Dipole moment (CA) 1 1 (Pressure)
Fig. 11.17.2.1. No change of net polarisation under compression of an ionic crystal with a centre of
symmetry.
On the other hand, a structure without the centre of symmetry (cf. Fig. 11.17.2.2) experiences a
polarisation when it is subjected to a mechanical compression.
Here it is important to mention that the noncentric structure is the common feature for both the
ferroelectric andpiezoelectric crystals. Ferroelectric crystals (below Tc) always show the piezoelectric
property. But all the piezoelectric materials may not be necessarily ferroelectric. For example, quartz
(used in clocks and watches) is a piezoelectric crystal but not a ferroelectric crystal.
Applications ofpiezoelectric mate.~ials : Piezoelectric materials are used in many practical purposes
such as sound detectors, microphones, pressure transducers. In fact, when a piezoelectric crystal is
Compression
•
(Compressed lattice)
ry
Fig. 11.17.2.2. Change of net polarisation under compression of an ionic crystal (two dimensional
representation) without a centre of symmetry. (. for cation, 0 for anion).
ra
placed between the electrodes and an alternating field with a fixed resonant frequency is applied, the
ib
oscillation of the crystal will occur at the frequency of the field. The quartz crystals are widely used for
this purpose. In a transducer, the mechanical pulses are converted into electric pulses and vice versa. In
marine resear~h, acoustic pulses are used and these acoustic pulses are generated by the piezoelectric
yl
oscillations from a transducer. ' m
11.18 CARBIDES
he
The carbides are classified into three groups : saline carbides (ionic solids formed by the Or 1 and 2
metals and aluminium) metallic carbides (formed by the d-block elements) and metalloid carbides
lc
(covalent compounds formed mainly by boron and silicon). Here we shall discuss the important features
of metallic carbides which are very useful materials~ For example, WC which is very hard (tungsten
ea
carbide) and it is used for preparing high pressure apparatus and cutting tools, FelC (cementite) is the
major component of steel and cast iron. In fact, the C-content in steel determines the properties 0/
steel to a large extent.
th
The metal carbides formed by the d-block elements are also described as interstitial carbides. This
is named so because in such carbides, the C-atoms occupy the octahedral holes produced in the close
e/
packing models of the metal atoms in their crystal. It is important to mention that the C-atoms
t.m
present in the octahedral holes can participate in bonding interaction with the adjacent metal
centres. Thus, such interstitial carbides can be regarded as compounds in which carbon may show its
hypervalency (more correctly hyper coordination). The hardness and other properties of such carbides
support the existence of strong metal-carbon bonding interaction.
'It has been empirically established (known as Hagg's rule) that a C-atom can'be positioned in the
octahedral hole of a close-packed metallic crystal, if the following condition is satisfied :
rC/rM < 0.59
where rM denotes the metallic radius of the metal and r c denotes the covalent radius of carbon.
Metallic carbides of the MC composition arises when all the octahedral holes of the close packing
models (hcp orfcc) ofthe metal are occupied by the C-atoms. Ifhalfofthe octahedral holes are occupied
.by the C-atoms, then the carbide may be represented by M2C. In this way, composition of the metal
carbides can be determined.
If a C-atom present in an octahedral hole is octahedrall}'_coordinated by the metal atoms, then it
gives the hypercoordination of the C-atom as one C-atom can provide only four valency orbitals (i.e. 4
coordination number). However, such hypercoordipation of carbon is well kinown in different

organometallic ompounds (Sec. 9.1). It is proposed that by using the valence orbitals' of carbon and
metal a delocalised bonding system is obtained.
11.19 GLASSES AND GLASS TRANSITION

Glassy matter is a rigid supercooled state and it differs from the crystalline solid matter. A glassy
substance is in a vitreous state characterised by the absence of long-range order. When a molten
ry
substance is rapidly cooled, glassy state may be obtained. On cooling, a molten liquid may adopt
either the glassy state or crystalline state. During this cooling process, the viscosity increases in different
ra
ways for attaining the glassy state and crystalline state (Fig. 11.19.1 a).
If a molten liquid mass is to crystallise on cooling, its viscosity will increase sharply at the freezing
ib
temperature (Tm). On the other hand, if the liquid mass tends to attain the noncrystalline glassy state,
then with the pro~ess of cooling, the viscosity increases steadily and no sharp change occurs (at the
yl
range of glass formation temperature denoted by Tg , the viscosity change becomes the highest): It
passes through the metastable supercooled state which exists below the Tg • In fact, there is no sharp
m
transition point between the solid glassy state and supercooled liquid state. This is why, the glassy state
of matter cannot have any sharp melting point.
he
Similarly, the pattern of change of specific volume (Le. volume per unit mass) during cooling of a
liquid is different for the glassy and crystalline state of matter. It is shown in Fig. 11.19.1(b).
lc
When a molten mass crystallises on cooling, at Tm the specific volume changes sharply while for a
glass forming material (cf. cooling is done sufficiently rapidly), the liquid state passes through the
ea
metastable supercooled liquid state and below the Tg , the supercooled liquid becomes rigid. This rigid
supercooled glass is thermod>'namically is less stable than the crystallin~ solid material. In fact,
th
A Liquid
e/
"Q)
E
::::s
B g
t.m
~ Glass
'g E F
~ ~I C£,/sta\ B
l
A~:
I I
I
I
I
I
Su
I· J:!er Cooled
Iquld ~. Liquid
I
I
I
I
I
I
I
I
Tg Tm
Temp. Temp.
(a) (b)
Fig. 11.19.1. (a) Change of viscosity during cooling of a liquid. ABCD path for crystallisation; EFCD
path for glass formation; Tm denotes the melting point of the crystal; T denotes the glass transition
9
temperature. (b) Volume change during the cooling of liquid. ABeD path for crystallisation. EFCD for
glass formation.
crystallisation does not occur due to kinetic brriers. Theoretically, a kinetically controlled glassy
matter on waiting (the period may be very high) may experience crystallisation.
Molten silica on rapid cooling gets converted into the vitreous quartz. This vitreous mass (Le.
noncrystalline solid mass) does not have any long-range periodicity evidenced from X-ray diffraction
studies, but throughout the matter each Si-centre is tetrahedrally surrounded by four oxygen atoms. The
absence of long-range periodicity arises from the variation ofSi-O--si bond angles. Generally, for
the glass forming materials, even in the liquid state, strong and directional covalent bonds (e.g. Si-O
bond in silica) remain present. On the other hand, for the crystal forming materials (e.g. metals and
ry
simple ionic compounds), no such directional strong covalent bonds remain present. However, a
very rapid cooling may lead to a glassy state even for the crystalforming materials.
ra
Pure silica can form glass, but its glass transition temperature (Tg ) is very high. Addition of modifier
like Na 20 or CaO can lower the glass transition temperature. This occurs due to the rupture ofcontinuous
ib
-Si-O-Si-O-linkage at some points to produce the -Si-o-u+- ends (Fig. 11.19.2). Soda glass contains
Na 20 and CaO as modifiers. Borosilicate glass can be obtained by adding the modifier, B20 3 •
yl
m
he
lc
ea
th
e/
t.m
(c)
Fig. 11.19.2. Two dimensional representations (cf. Fig. 11.14.1.1) of (a) quartz crystal (crystalline form
of silica), (b) glass (noncrystalline form of silica), (c) modified glass in presence of modifiers like Ca2+,
Ncr.
Borosilicate glass possesses the lower thermal expansion coefficient than that of soda glass. This is
why, borosilicate glass is used for laboratory work and oven-ware.
The oxides (e.g. B 20 3, Ge02, P20S etc.) of many elements close to Si in the periodic table are good
glass forming materials.
The Tg value for different organic polymers (e.g. polyethylene, polyvinylchloride, polystyrene, etc.)
depend on their molecular weights and structural features. Plasticisers (just like the modifiers in
silicate glass) can reduce the Tg values ofsuch organic polymers. For example, by adding a suitable
plasticizer in PVC (polyvinyl chloride, Tg = 8-5°C), its Tg value can be significantly reduced. It allows
ry
the manufacture of PVC sheets, rain coats made of PVC, etc.
ra
11.20 STRUCTURE OF LIQUIDS : GENERAL ASPECTS :
ib
HOLE THEORY 9F LIQUIDS
A solid on melting gives its liquid state. On melting, the molar volume ge nerally increases by 10%. The
yl
4
entropy also increases on melting but this change is much smaller than the entropy of vaporisation.
Different properties of a substance, just below and just above its melting point are similar at
m
least in kind. For example, X-ray diffraction pattern of liquid argon just above its melting point shows
only very few maxima and minima which become broader and diffuse in shape. with. the rise of
he
temperature. The presence of such maxima and minima supports that the molecular arrangement in the
liquid state is not completely random. An idedi amorphous substance will exhibit the continuous
lc
scattering of X-rays without maxima and minima indicating the random molecular arrangement.
X-ray diffraction studies indicate that in the .liquid state, there is only some sort of short-range
ea
order of molecular arrangement (cf. structure of glass which is considered as a super-cooled liquid).
The X-ray diffraction pattern represents a time average position ofthe atoms/molecules experiencing
th
their translational motions.

The degree of order in liquid state gradually decreases with the rise of temperature. In fact, the
e/
degree oforder is maximum in the crystalline solid state and it is minimum in the gaseous state, and
in terms of order, the liquid state is intermediate between these two.
t.m
The decrease of density (Le. increase ofmolar volume) on melting arises due to the creation of more
vacancies in the liquid close-packed structure. This vacancy is minimum in the solid state. Due to the
formation of such vacancies in the liquid state, the coordination number (CN) decreases. In the solid
state, the eN is maximum and consequently the intermolecular attraction is maximum. On warming,
each molecule/atom acquires the kinetic energy kBT(kB = Boltzmann constant). If this acquired thermal
energy is sufficiently high then the species can migrate from its lattice position by forcing the surrounding
lattice sites aside. This possibility is governed by Maxwell-Boltzmann distribution law (Le. number of
vacancies ex: exp (-E/kB 1), where E denotes the acquired energy to create a vacancy). Due to the presence
of such vacancies in the liquid state, the lattice sites can move through the vacancies. As the order in
the liquid state is not completely destroyed, the lattice sites present in the ordered portion of the
liquid crystal cannot acquire the translational energy but the vibrational energy.
In terms of Eyring hole theory of liquids, liquid state possesses the structural features of the two
limiting phases, Le. solids and gases. The presence of vacancies can cause volume expansion in the
liquid state. If VI and Vs are the volumes of a certain amount of a particular substance in the liquid and
solid state respectively, then the excess volume (VI - Vs ) gives the ~easure of vacancies which are
randomly distributed in the liquid state. The mole fraction (V,- Vs)/V, gives the fracti~n existing in
the gas-like structure and the mole fraction VIV, measures the fraction possessing the solid
structure. Thus the physical property of a liquid can be explained by considering the coexistence of
two extreme states, Le. solid state and gas-like state. For example, the heat capacity of argon in liquid
state is given by :
Cv(J K- 1 mol-I) =~ R x (gas-like fraction) + 3R x (solid-like fraction)
ry
2
12.47 (Vi ~~' )+24.95(~)
ra
=
ib
w.here 3R/2 = 12.47 J K- I mol-I, 3R = 24.95 J K- I mol-I.
yl
This prediction has been experimentaHy verified.
Liquid crystals : In this regard, it is relevant to mention the properties of liquid crystal which
m
represents the intermediate phase between the solid and normal liquid. This intennediate phase possesses
both the characters ofsolids and nonnalliquids. The molecules present in the liquid crystal are described
he
as mesogens which can fonn the solid like structure having the long-range order. The mesogenic
structures can flow fast indicating their liquid-like property. Interestingly, during their sliding motion,
their structure is not disturbed (Le. solid-like character). Sometimes, the polymer liquid crystals possess
lc
the structural rigidity. Liquid crystals are often used in display purposes (e.g. in watches, clocks,
ea
calculator, television in place of cathode-ray tubes etc.).

th
SOLVED NUMERICAL PROBLEMS

e/
Problem 1. Calculate the electron affinity of chlorine with the help of the given data: MlI = heat of
fonnation of RbCI = - 441 kJ mol-I, Mlsub = heat of sublimation of Rb = 80 kJ mol-I "Mldiss = bond
t.m
dissociation energy of Cl2 = 243 kJ mol-I, MIlE = first ionisation energy of Rb = 403 kJ mol-I, U =
lattice energy of RbCI = - 680 kJ mol-I. '
Solution: From the Born-Haber cycle offonnation of RbCI, we get:
MI.f(RbCI) = IVlsub(Rb) + IVlIE(Rb) + 112 Midiss(C12 ) + MlEA(CI) + URbCI
(the terms bear the usual significance).
1
Thus, MfEA(CI) = IVlj{RbCI) - tJlsub{Rb) - tJlIE(Rb) - 2" MfdiSS(C/2) - URbCI
1
= - 441 - 80 - 403 - - x 243 + 680 = - 365.5 kJ mol-I.
2 .
Thus electron affinity of chlorine is 365.5 kJ mol-I.
Problem 2 : Calculate the lattice energy of Kel from the given data: interionic separation = 314
pm, born exponent for Ar configuration = 9, Madelung constant (A) = 1.746.
Solution: By using the Born-Lande equation, we get:
U =_ ANZ+ Z- e
2
(1-~) =_ 1.746 x 6.02 x 1'0 mol-I x I x t X (1.61< 10-
23 19
ci x!
o 47tEO(r+ + ~_) n 47t(8.85 x 10-12 C 2 J- 1 m-1) (3.14 x 10- 10 m) 9
= - 686.5 kJ mol-I
Note: See text for calculation of lattice energy for NaCI and ThO z crystals by ,Using Born-Lande
equation.
Problem 3 : MgO adopts the structure in which the anions are in a ccp (Le. fcc) array and the
ry
cations occupy the octahedral holes. Calculate the density of MgO. (Given: r 2+ =0.78 A, r 2- =1.32 A.
Mg 0 .
At. wts. of Mg and 0 are 24.3 and 16 respectively).
ra
Solution: It is evident th~t MgO adopts the rock salt (i.e. NaCl) structure. In the unit cell, all the
lattice sites of~fcc crystal are occupied by (jl- ions, and the octahedral holes (at the centre of the fcc
ib
and at the mid-points of 12 edges) are occupied by Mg2+ ions.
yl
Therefore, total number of (jl- ions per unit cell = 8 x .!. + 6 x .! = 4 and total number of Ml!+ ions
8 2
per unit cell = 12 x ~ + 1 = 4.
m
4
(Each of the lattice points at the comers, at the centres of edges and faces are shared by 8, 4 and 2
he
adjacent unit cells respectively. The lattice point at the centre of the cube is completely owned by the
cube.)
lc
In the NaCI structure, 2(rMi+ + ro2-) = edge length of the unit cell
= 2 (0.78 + 1.32) A = 4.2 x 10-8 em
ea
· mass of the lattice points 4(24.3 + 16)/N

Th us denslty = =- - - -8 -
, volume of the unit cell (4.2 x 10- )3
th
4(24.3 + 16) -3 3 61 -3
----
23 - -24- - - g cm =. g cm
e/
6.02 x 10 x 10- x (4.2)3

=3.61 x 103 kgm-3
t.m
Problem 4 : The density of NaCI is 2.17 g cm-3 • Calculate the interionic distance. Find the glancing
angle for the first order reflection on 200 plane for the X-rays of 0.59 A wavelength. (Given, formula
weight of NaCI is 58.45).
Solution: In the NaCI structure, per unit cell there are 4Na+ ions.and 4C, ions, i.e. 4Na+CI ion
pairs.
Therefore we get :
denSl'ty (p) = masses of the lattice points. 2 17 _ 4 x 58.45.

3 ,or,. - 3 '
volume of the unit cell (a ) N xa
or, a=[ 4x 5~;45 ]1/3 cm = 5.63 x 10-8 cm = 5.63 x to- 10 m

6.02 x lOx 2.17
8
or, 2(r + +r _)=a; or,r + +r _ =a/2=2.815x10- cm
Na CI Na CI
In the ro~k salt structure~ d 200 = interplanar distance between 200 planes = r + + r /- = a/2. Now
Na c
from the Bragg's equation, n'A = 2d sin 8, where, n = order of reflection, d = interplanar distance
between the planes on which the reflection occurs, 8 = glancing angle, we get:
1 x 0.59 x 10-8 = 2(2.815 x 10-8) sin 8; or, sin 8 = 0.104 = sin 6.01° or, 8 ~ 6°.
Problem 5 : Diamond shows the density 3500 kg m-3• Calculate the packing efficiency and covalent
radius of carbon.
Solution : In the diamond cubic (de) unit cell, C atoms are at the lattice points of the fcc unit cell
ry
and within the unit cell at the four alternate tetrahedral holes out of the 8 Td holes, there are four
additional C atoms. Thus the actual number of C atoms per· unit cell = .!. x 8 corner atoms + .!. x 6
8 2
ra
atoms at the faces + 1 x 4 atoms in the Td h?les within the unit cell = 1. + 3 + 4 = 8 .
From the density we get :
ib
. mass of 8 C atoms
denslty = 3
yl
volume of the unit cell (a )
3 3 26
=8xI2xlO- = 8 x I2xI0- =( 96x10- )1/3 =357 10- 10
or 3500 3 23
m •
3 ' or, a m . x m
N xa 6.02 x lOx a 6.02 x 3500
he
The whole unit cell can be divided into 8 small cubes having edge length a/2. C atoms are at the
alternate Td holes, Le. at the centre of these small alternate cubes.
lc
Therefore, 2rc =.!. of the body diagonal of the small cube of. edge length a /2 =Y2( fja/2);
2
ea
or, rc = ~a = 7.7 x 1O-ll m. (a = 3.57 x 10-'10 m)
__ ~) "
3
th
volume of 8 C atoms 3 __ 8 x (4/ 3)1tr " (a

Packing efficiency = 3
volume of the unit cell (a ) a fj
e/
3
8x4 x 7tr (fj)3 = 32x3fj X1t =0.34.
t.m
3 (8r)3 3 x 64 x 8
Thus, % packing efficiency = 34.
Problem 6 : Chromium crystallises in a bee lattice. Calculate the distance between the successive
200 planes and the radius of chromium atom. The density" of chromium is 7.2 x 103 kg m-3• (At. wt. of
Cr.= 52).
Solution : In a bee lattice the number of effective lattice points is 2 ( = 8 x ~ + I) per unit cell.
2 x 52 x 10-:3 3 2 x 52 x 10-3
Thus, p= "3 ; or, 7.2x10 = 3"
aN aN
3 )1/3
or, a= 2X52~XIO- 3 =2.88xlO- IO m
( 6.02xlO x7.2xlO
In a bee crystal, body diagonal = 4r; or, J3a = 4r; or, r = J3a 14;
or, r= J3 x 2.88 x 10- 1014 = 1.25 x 10- 10 m.
Thus, the radius of a chromium atom = 1.25 x 10- 10 m.

In a bec crystal, 2d200 = a; or, d200 = interplanar distance between the successive 200 planes = al2 =
1.44 x 10- 10 m.
Problem 7 : Calculate the packing efficiency in the ideal rock salt, fluorite and zinc blende structures.
Solution: Rock salt structure: Anions are at the lattice points of afce lattice and cations are at the
ry
0h holes.
From the concept of limiting radius ratio for octahedral coordination of the cations we get the
ra
condition, r+lr_ = 0.414 ; or, r+ = 0.414 r_.
In the rock salt structure, there are four cations and four anions per unit cell having edge length =
ib
2(r+ + r_).
Therefore, packing efficiency =
yl
m
he
lc
Fluorite structure: Cations in afce array and anions in the Td holes. There are 8 Td holes in afce
lattice. Thus, no. of cations = 4 and no. of anions = 8.
ea
From the concept of limiting radius ratio for the. tetrahedral sites occupied by the anions, we get:
r_ /r+ = 0.225 ; or, r_ = 0.225 r+.
th
The fcc unit cell can be split into eight small cubes of edge length a/2. The tetrahedral holes lie at
the centre of these small cubes of edge length a12.
e/
Thus, r+ + r_ = ~ of the body diagonal of the small cube of edge length a 12 = ~ J3 ~;

t.m
4 4 4 x 1.225r+
or, a = J3 (r+ + r_) = J3
(r+ + 0.225r+) = J3
3
Hence, a = 22.62r+3 .
4( ~xr;) +8( ~xr!)
Therefore, packing" efficiency = - - - - - - -
a3
16 3 3
-3 7t(r+ + 2r_ )
~ = 16x [1+2(r Ir+)3]= 16x [1+2(0.225)3]::::0.75
22.62r: 3 x 22.62 - 3 x 22.62
Zinc biende structure : The anions are in an array of a fcc lattice and the cations occupy the
alternate Td holes within the unit cell as in a dc crystal. Here, we can have the conditions, r+/r_ = 0.225
and a3 = 22.62r~. "
These can be derived as in the fluorite structure. There are four anions and four cations per unit cell.
Therefore, the packing efficiency is :
4(~7tr3) + 4(~7tr3)
packing efficiency = 3 + 3 - =~ X _7t_ [I + (r / r )3]
22.62r! 3 22.62 +-
161t [I + (0.225il lll: 0.75

3 x 22.62
ry
Problem 8 : Metallic iron changes from bcc to fcc at 910°C. Atomic radii of iron at this temperature
are 0.1258 nm (in bcc) and 0.1292 nm (infce) respectively. Calculate the volume change and density
ra
change during this structural change.
Solution : In bce structure, 4r = .J3a = length of the body diagonal
ib
or,
a=~= 4xO.1258 =0.290nm
.J3
yl
1.732
Effectively, 2 Fe atoms occupy the unit cell of bce, Le.
I I
m
volumeofl Fe atom = _a 3 = -(0.290 x 10-9)3= 12.26 x 10-30 m3= VI (say). (I nm= 10-9 m).
2 2
he
Infce structure, 4r = J2a ~ length of a face diagonal
a = ~ = 4 x 0.1292 = 0.365 nm .
lc
or,
J2 1.414
ea
!
Infcc, 4 Fe-atoms occupy a 3 volume, i.e. value of 1 Fe-atom = '4I a3 = '41 (0.365 x 10-9)3
= 12.199 x 10-30 m 3
th
= V2 (say)
e/
Thus percent of volume decreases in changing from the bcc to fcc is given by :
t.m
VI - V2 ) x 100 = (12.260 -12.199) x 100 = 0.493

( JI} 12.260
A A
The density is given by: Pi =v: and P2 =V (A = atomic weight)
I 2
Thus percent of increase of density is :
P2 -PI)XI00= (A/12.199)-(A/12.260) =0.496

( PI (A/12.260)
Problem 9 : The concentration of Schottky defects in an AB type ionic crystal is I in 10 10 at 300 K.

Calculate the energy required to create a Schottky defect.
Solution: In an AB type ionic crystal, one Schottky defect involves the removal ofa pair ofoppositely
charged ions. The number of Schottky defects is given by :
n = N exp [-E sch 12k BT]

n 1
Le. - = --w = exp (-ESch 12kB T) = exp (-ESch 10.050)
N 10
19
(kBT = 1.38 x 10-23 J K- I x 300 K = 0.025 eV, at 300 K, 1eV = 1.6 x 10- J)
It leads to :
10 ESh
exp (ESch 10.050) = 10 ,or, _c_ = 10 In 10 = 10 x 2.3 log 10 = 23
0.050
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or, ESch = 23 x 0.05 = 1.2 eV for producing one Schottky defect
Problem 10 : The fraction of vacancy sites in a metal is 10- 10 at 500°C. Calculate the fraction of
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vacancy sites at 10000 C and the energy (Esch ) required to create a vacancy.
ib
Solution : In metals, the number of Schottky defects is given by :
n ~ N exp [-EscJkBTJ
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-nsoo = 10-10 = exp [-Esch 1kBT] = exp - [E
SCh
23 ]
N
m 1.38 x 10- x 773
(kB = 1.38 x 10-23 J K- I )
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Le., ESch = 1.38 x 10-23 x 773 x 10 In 10
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1.38 x 10-23 x 773 x 23 J per vacancy

2.45 x 10- 19 J per vacancy
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1.53 eV per vacancy (1 eV = 1.6 x 10- 19 J)

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19
n1000 [
x 2 (say) = - - = exp [-ESch / kBT] = exp -
2.45 x 2310- ]
= exp (-13.94)
e/
N : 1.38x 10- x 1273

t.m
Of, ,In x 2 = - 13.94; Of, 2.3 log x 2 = - 13.94 '.

Of, log x 2 = - 6.06 = log (8.7 x 10-7)
Of, x2 = 8.7 x 10-7
Alternative method:
xI (say) = n500 = exp

N
[-E] Sch
k x 773
B
and, x (say);:: n1000 = exp [

2
-. ESch ]
N k B x 1273
In xI = ESch x k B x1273 = 1273 =1.647

Of,
In x 2 k B x 773 E Sch 773
or, Inx l =I.647Inx2

or, In (10- 1°) = 1.647Inx2; or,-23= 1.6471nx2
or, Inx2 =-13.96; or,2.310gx2 =-13.96 or,x2 =8.51 x 10-7
Problem 11 : The thermodynamic parameters for creation of vacancies in A/-crystal is : Mi = 68
kJ mol-I. Calculate the concentration of vacancies at 0 K and 300 K.
Solution: We have:
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n
N=ex p
[MiSch]
-~
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3
n _
[68 x 10 ] _ 0
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At 0 K: N - exp - 8.314 x 0 -
yl
3
At 300 K · -n = exp [-6 8 x 10 ] = exp (-27.26)
· N 8.314 x 300
m
or, ( n) (n)
-27.26
In - =-27.26; or,log - =--=-11.85
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N N 2.3
or, .!!- = 1.4 x 10- 12

lc
N
Problem 12 : Calculate the lattice energy of KN03 using the Kapustinskii equation.
ea
(Given: r + = 138 pm, r _ == 189 pm)

K NOj
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Solution: Interionic separation (R o ) = (138 + 189) = 327 pm. T~e lattice energy is given by :
5
e/
U = -:- 1.2xI0 yZ+Z- (I. - ' -

34.5)kJ
- I-I (R·
mo, 0 In pm
)
Ro Ro
t.m
5
_ 1.2 X 10 x 2 xl (1_,34.5) kJ mol-I
327· 327
~ - 661 kJ mol-I
Note: In the above equation, y gives the number of ions in the formula unit, for KN03 it is 2).
Problem 13 : Comment on the thermal decomposition temperature (Td ) of BeC03 and CaC03 (see'
Sec. 11.8.2). .
Solution: 'MC03(s) ~ MO(s) + CO2{g)
~Go= MfO- Tp = 0
At the thermodynamic decomposition temperature (T10, ~Go becomes zero, Le. Td = MfO/!::JSO.
,!::JSO is positive and it is reasonably constant for both BeC03 and CaC03• MfO depends mainly on the
difference of lattice energies of MC03 and MO. For BeC03, the lattice energy is relatively less compared
, to that ofCaC03 • The reduced lattice energy of BeC03 arises because of the following two reasons:
• packing of large and soft (i.e. polarisable because of 1t-electron cloud) coi-
with the smaller
2 2
Be + ions in the crystal is inefficient compared to the packing with Ca + ion (which is relatively
larger).
• Be 2+ is more polarising than Ca2+ and consequently covalency in BeC03 is more. It further
reduces the lattice energy of BeC03.
As the lattice energy of BeC03 is less than that of CaC03 the thermal decomposition temperature of
BeC03 is relatively less.
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Note: More correctly :
1
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~U oc - -------
2 2
r(M +) + r(02-) r(M +) + r(CO;-)
Ifr(M2+) is relatively larger, the difference between the two denominators is not very much significant,
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but if r(M2+) is small then it becomes significant. Thus the enthalpic favour of the decomposition
process is more for the smaller cation (cf. Sec. 11.8.2).
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EXERCISE-XI
A. General Questions
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1. Give a brief account of characteristic properties of the ionic compounds.
2. Classify the ions in terms of electronic configurations.
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3. What do you mean by the electron density (ED) maps? How do you get the idea of ionic~radii
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from the ED maps?

4. Give a short account of different methods to determine the ionic radii.
5. Define Pauling's univalent and crystal radii. How are they related? Discuss the theoretical
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background of this method.

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6. Discuss the different factors influencing the ionic radii.

7. Discuss the applications of Born-Haber cycle in computing the lattice energy and proton affinity.
t.m
8. Discuss the factors which favour the formation of an ionic bond.

9. Deduce the Born-Lande equation to estimate the lattice energy. How do you get the Born exponent?
What are the drawbacks of Born-Lande equation?
10. Discuss the different factors governing the lattice energy.
11. Discuss the characteristic features of (i) three Bravis lattices of cubic system, (ii) diamond cubic
(dc) crystal, (iii) hexagonal close packing (hcp) and cubic close packing (ccp) models.'
12. Give a comparative discussion of hcp, ccp and bcc structures.
13. Discuss the different types of crystal structures of AB, AB2 and AB3 •
14. Discuss the structures of mixed oxides.
15. Discuss the perovskite structure in connection with the ferroelectric properties of BaTi03 and
superconductivity of YBa 2Cu 30 7_x •
16. Discuss the characteristic properties of layer, chain and molecular lattices.
17. Give a brief account of the structures of different types of silicates.
Structure, Bonding and Properties ~f Ionic Solids and Solid State Chemistry 1103
18. Discuss the different types of stoichiometric defects in the ionic crystals. Calculate the number
of Schottky defects at a particular temperature in a AB type ionic crystal.
19. What are the major effects ofSchottky and Frenkel defects on the properties ofthe ionic crystals?
What are the differences between these two types of defects?
20. Give a short account of different types of nonstoichiometric defects.
21. What do you mean by the F-centres? How does it influence the colour and electrical conductivity
ofthe ionic crystals? Discuss the semiconductor properties ofthe nonstoichiometric ionic crystals.
22. Write notes on :
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(i) isomorphism, (ii) variable electrovalency, (iii) Shannon's crystal radii, (iv) thermochemical
radii, (v) Madelung constant, (vi) Born-Haber cycle, (vii) radius ratio rule, (viii) Born repulsive
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potential, (ix) close packing models, (x) perovskite structure, (xi) layer lattices, (xii) chain lattices,
(xiii) metal carbides, (xiv) glass and ~rystalline materials, (xv) ferromagnetic and ferroelectric
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materials, (xvi) piezoelectric materials.
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B. Justify or criticise the Following Statements
1. The electrical conductivity of the ionic solids is negligibly small while their solutions are good
conductors of electricity.
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2. NaNO) and CaCO) are isomorphous while NaNO) and KNO) are not.
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3. When BaS04 is precipitated in the presenc&,of KMn04, the pink colour associated with the white
precipitate cannot be discharged by oxalic acid.
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4. The transition metals very often show variable valencies.

5. Among Cu, Ag and Au, the +2 and + 1 oxidation states are well documented for Cu while + 1 and
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+ 3 states are well known for Au; and Ag is best characterised in + 1 state.
6. Pauling's univalent radii are longer compared to the actual values for the polyvalent ions.
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7. Pauling's crystal radii for the polyvalent ions can be estimated from their univalent radii.
8. In most ofthe cases, Yatsimirskii's thermochemical radii for the polyatomic ions are ofno physical
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significance.
9. The Pauling's ionic radius of 11 is extremely high and it never gets attained in the real crystals.
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10. Due to the covalency, the cationic radii increase while the anionic radii decrease.
11. The cationic radii of the alkali and alkaline earth cations are very much sensitive to the degree of
covalency in their compounds.
12. The different isosteric cations drastically differ in their ionic radii while the variation of ionic
radii in different isosteric anions is not so pronounced.
13. The ionic radius of an ion depends on the crystal structure in which it crystallises.
14. For, 4, 6, and 8 coordination numbers, the relative values of ionic radii of a particular ion are
0.95, 1.00 and 1.03 respectively.
15. As the radius ratio (r+/r_) runs towards the minimum limiting value for a particular crystalline
geometry, the interionic separation increases compared to the calculated value.
16. Aiel) and HCI are covalent, but on hydration they behave just like the ionic compounds.
17. CaF undergoes disproportionation as : 2CaF -.. Ca + CaF2•
18. Ag, Au, PI, etc. are noble metals while the alkali metals are active.
19. The estimated lattice energies for different ionic solids 'from the Born-Haber cycle do not always
agree with the values obtained from the Born-Lande equation.
20. The Madelung constant d~pends only on the crystal geometry.
21. From the radius ratio (r+/r_ = 0.76), RbBr can adopt the CsCI structure but in practice it crystallises
in the NaCI structure. A similar situation arises for KCI.
22. The relative magnitudes of the Madelung constant and interionic separation can discriminate the
possibilities of two crystal structures in the systems having the radius ratio in the border line
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region.
23. LtF and NaI possess very low melting points (both of them crystallise in the NaCI structure).
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24. The thermal stabilities of the carbonate, sulfate and nitrate salts of the alkali and alkaline earth
metals are lower compared to those of their respective oxides.
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25 .. The ionic compounds having the very low values of r+/r_ are thermally unstable, senstitive to
hydration and highly soluble in water.
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26. Very often the lithium and alkaline earth salts disobey the radius ratio rule.
27. From the radius ratio (r+/r_) values, CdS (0.52) and HgS (0.55) are expected to adopt the NaCI
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structure but, they actually crystallise in the ZnS structure.
28. From the radius ratio, NH4F is expected to crystallise in the NaCI structure like other NH~(X=
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CI, Br, 1) , but it crystallises in the ZnS structure.
29. Formation of (jl- is energetically unfavourable, but MgO is formed and it is ionic.
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30. In afcc lattice, per lattice point there are one 0h and two Td holes.
31. The diamond cubic (dc) and zinc blende (ZnS) crystals are related in the same way with the fcc
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lattice.
32. The hexagonal crystal is not the hcp crystal and similarly the fcc crystal is not the dc crystal.
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.33 .... ABCABC ... model is described asfcc lattice but it does not indicate the loss of hexagonal
symmetries in it in the layers.
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34. Many compounds can crystallise in both the zinc blende and wurtzite structures and the transition
temperature between these configurations is not very high.
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35. CdCl2 can be cleaved easily.

36. HgF2 gives an ionic crystal of the NaCI type, HgCl2 gives the molecular crystal, !igBr2 gives the
distorted CdCl2 structure while Hg/2 gives a perfect layer lattice structure.
37. The adoption of inverse spinel structure can be explained from the crystal field theory (eFT).
38. The ferroelectric properties of BaTiO) can be explained from the distorted perovskite structure.
39. The superconductor YBa 2Cu)07_x crystallises in a defective perovskite structure.
40. In the beryl crystal, there is a channel into which many small molecules can remain trapped as in
the clathrate compounds.
41. Both the pyroxene and amphibole minerals undergo cleavages.
42. Talc is slippery and flaky. Mica is harder than talc and mica cleaves in sheets.
43. Incorporation of Na 20, CaO (as in soda lime glass) and B20) (as in pyrex glass) in silica lowers
the softening temperature compared to that of the fused silica.
44. Zeolites can act as the ion exchangers and molecular sieves.
45. The colouration in the ultramarines and lapislazuli arises due to some charge transfer bands.
46. The Schottky defects in the metallic crystals and ionic,crystals are different.
47. The Schottky defects are predominant in the highly ionic compounds while the Frenkel defects
predominate in the crystals having a good degree of covalency.
48. With the increase of temperature, stoichiometric defects in the crystals increase.
49. Due to Frenkel defect, the dielectric constant in the ionic crystals increases.
50. Both the Schottky and Frenkel defects introduce the electricity conducting power in the ionic
crystals.
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51. Sometimes, the direction of change of density due to stoichiometric defects cannot be predicted.
52. The metal excess (A 1 + oB) defect in an ionic crystal gives the properties of n-type sem~conductor
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while the metal deficiency (A 1 _ oB) defect gives the properties ofp-type semiconductor.
53. The perfect AB crystal may be colourless but the defective Al + JIJ crystal is very often coloured.
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54. The NaCI crystal being irradiated with the Na or K vapour becomes yellow while the KCI crystal
in the same way looks blue.
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55. ZnO and Sn02 are white when cold but they look yellow when hot. CdO also changes its colour
on heating. .
56. FeO, FeS and NiO very often act as semiconductors.
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57.. By doping CdCl2 in AgCI and Li20 in NiO, they can be converted into semiconductors.
58. To explain the crystal structure of lithium salts in terms of radius ratio, the Shannon's crystal
he
radii are better parameters than .the Pauling's radii.
59. The reaction, CH3-e1 + MF ~ CH3-F + MCI, is most favoured when MF is CsF.
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1
60. MX +2X2~ MX2.
ea
The forward oxidative addition reaction is favoured most when X = F while the backward reductive
elimination reaction is favoured most for X = I.
th
61. The thermodynamic favour for the following thermal decomposition reaction can be estimated
by considering the lattice energy difference between MO and MC03 •
e/
MC03 (s) ~ MO(s) + CO2 (g)

62. Structure of AB type crystal depends on the electronegativity difference and average principal
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quantum number of A and B.

63. Fe 30 4 adopts the inverse spinel structure while Co 3 0 4 adopts the normal spinel structure.
64. Ferrimagnetism is very often found in ferrites.
65. The colouration in gem stones arises generally due to the presence of transition metal ions.
66. Ferroelectric property of RaTi03 develops due to the presence of the highly polarising Ti4+ ion.
67. Mica is harder than talc.
68. The metal ions like K+-, Mg2+, C~2+, etc. present in montmorillonite and vermiculite type clays
are exchangeable and available as plant nutrients.
69. The zeolite structure is produced by sodalite cages.
70. The presence of molecular sieves provides the unique properties like catalytic activity, separation •
of hydrocarbons, etc. of zeolites.
71. Zeolites can act as strong Lewis acids.
72. Zeolites can be used as drying agents, and water softening agents.
73. Zeolites can act as good catalysts in many reactions.

74. (NH4 )3 [(P04 ) Mo 12 0 36 ] adopts the Keggin structure of 12-heteropoly acid.
75. In poly acids, oxide ions are distributed in a ccp pattern.
76. 123 compound is an example of warm superconductor.
77. MoS2 [to be described as di(monosulfide)] adopts CdI2 type structure while FeS2 [to be described
as mono(disulfides)] adopts the NaCI type structure.
78. Generation of crystal defects is a demand of 2nd law of thermodynamics.
79. Electrical conductivity of ionic solids is due to the ionic conduction.
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80. KCP is a typical example of nonstoichiometric defect.
81. Li20 doped NiO crystal is electrically conducting.
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82. Cooperative magnetism arises in magnetically concentrat~d substances.
83. The antiferromagnetic interaction ill MnO, FeO, NiO can be explained by considering the
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superexchange mechanism.
84. In brown ring complex [Fe(H20)s(NO)]2+, iron exists as Fe 3+ and in nitropruside [Fe(CN) sNO]2-
iron exists as Fe 2+.
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85. The exchange interaction energy is the key factor for ferromagnetism.
86. Ferromagnetic property of a substance can be explained by considering its domain structure.
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87. Ferromagnetic property of a substance arises only in presence of an external magnetic field.
88. The B-H curve ofa ferromagnetic substance can be explained by considering the domain structure.
he
89. The hard and soft ferromagnets differ in terms of the shape and area of their hysteresis loop.
90. Hard ferromagnets are used to prepare the permanent magnets while the soft ferromagnets are
lc
used in transformers.
91. Temperature dependence of magnetic susceptibility can differentiate the different types of
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cooperative magnetism.
92. The P-E curve of ferroelectric materials resembles the B-H curve cf ferromagnetic materials.
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93. BaTi03 shows the ferroelectric property.

94. A piezoelectric crystal lacks in centre of symmetry.
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95. Ferroelectric crystals show the piezoelectric property.

96. Quartz crystals are used in clocks and watches.
t.m
97. The C-content in steel determines the property of steel.

98. Glassy matter represents the supercooled liquid.
99. In terms of melting point, the crystalline state and glassy state differ.
100. On prolonged standing, a glassy state may attain the crystalline state.
101. The roles of plasticisers and glass modifiers are similar.
102. The glass transition temperature (Tg ) of pure silica remarkably drops in presence of Na20 and
CaD.
103. A liquid crystal represents the intermediate phase of normal solid and liquid state.
104. Montmorillonite clay shows the thixotropic property.
105. Kaolinite is a 2-layer clay while talc, pyrophyllite, montmorillonite and vermiculite are 3-layered
clays.
106. White a.,bestos is structurally related with kaolinite.
107. Mon ~m~.trj 150nite and vermiculite are structurally related 'with talc.
108. Perovskite structure can be explained in terms of Re03 structure.
109. Cr(III)-doped corrundum gives the ruby red colour, while Cr(III)-doped beryl gives ~he green
colour of emerald.
110. Ti(H20)~+ looks violet while Ti(III) in gemstone sapphire gives blue colour.
Ill. White asbestos tends to curle.
112. Gibbsite and brucite play important roles in developing the sheet silicate structure.
113. Silica gel is polar due to the presence of different types of silanol group.
114. Silica gel can be used as a drying agent. For this purpose Co(II) salt e.g. (NH4 )2 [CoC/4] is used
as an indicator.
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lIS. Chemical treatment on silica gel can make it suitable for its use as a support of chromatographic
exchanger.
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116. The B-H curve of hysteresis loop can be explained by considering the domain rotation and
domain growth through the Bloch wall movement.
ib
117. In spite of higher electron affinity of chlorine, F2 is a better oxidising agent than Cl2 in terms of
£0 value.
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118. AICI) and HCI are covalent compounds but they ionise in aqueous solution.
119. Ionic radii follow the sequence: i > Br- > C, while CIO) > BrO) > /0).
m
120. Inverse spinel Fe 30 4 is a conductor while normal spinel Mn)04 is an insulator.
he
121. Besides the F-centre, there may be other colour centres like H-centre, V-centre in alkali halides.
122. Canted magnetism always leads to a weak ferromagnetism.
123. Crystal defect is always disfavoured in terms ofenthalpy but the extent ofentropic favour depends
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on the concentration of defect.

1
ea
124. For many ionic solids, the log (J vs. T plot gives two straight line portions with different slopes.
125. V(V) gives the largest stacked octahedral isopoly anion VjOO~8 through edge sharing of M06
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octahedral units.
• In isopoly anions, metal ions (Mn+) occupy the octahedral holes produced by the close packed
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array of oxide ions. In other words, the polymerization occurs through the edge sharing 01
octahedral units MO,. It leads to an electrostatic repulsion among the MTtt- centres residing
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in the adjacent octahedral holes. To minimize this repulsion, some distortion occurs during
polymerization through the edge sharing of octahedral M06 units. This distortion occurs so
that the repelling metal ions can move away from each other.
If polymerization continues through the edge sharing of M06 octahedral units, a limiting
situation will arise when the requisite amount of distortion to minimize the electrostatic
repulsion among the Mn+ centres becomes impossible. At this point, polymerization stops.
Obviously, the said repulsion is less lor the smaller metal ions (M"+) and the required
distortion is also less. Thus for the smaller metal ions, the degree of polymerization is more.
It is illustrated below.
Ionic radius (in pm for C.N. 6): V S+ (68) < Mo 6+ (73) < JP6+ (74) < Nb s+ (78).
Edge shared isopoly anions : VjOO~8' Mo7 0!4' MOsoii , W6 0 129- , W7 0!4' Nb6 0 189.
In the large isopoly anions like "l20l~- or H 2"l2 0 So edge sharing givesJhe way to vertex
sharing 01 MO, octahedral units.
126. The Li-spinels LiMn1.04 and LiV1.04 show different types of conductivities.
• Here it is worth mentioning that sometimes the metal centres residing in the octahedral holes
of edge-shared octahedra can experience a d-d overlap to produce ad-band. Ifthe d-band is
partially filled then it can introduce a metallic conductivity. Ifthe octahedral holes are occupied
by the same metal ions of different oxidation states, then positive hole migration (involving
the metal ions in the octahedral holes) through hopping mechanism can lead to electrical
conductivity. These aspects are illustrated in the following two Li-spinels.
LiMn20 4 Le. (LiI)tet(MnIIIMnIV)oct04 and LiV1.04 Le. (Li I)tet(JAIIyIV)oct0 4 : Presence of MIl
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and MY centres in the octahedral holes of edge-shared octahedra should give the hopping
semiconductiv;ty in both cases. But in reality, LiMn20 4 shows the hopping semiconductivity
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as expected but LiV20 4 shows the metallic conductivity. For the early members like vanadium,
the d-orbitals are sufficiently larger to make a good 3d-3d overlap to produce a d-band which
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is partially filled in and it gives the metallic conductivity through electronic conduction. On
the other hand, for the late members like Mn, Fe, Co, Ni, the 3d-orbitals are contracted and
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consequently, a good d-d overlap is not possible. Thus formation of d-band in such cases is
not favoured. This is why, the present example LiMn20 4 experiences only the hopping
m
semiconductivity not the metallic conductivity. The favourable conditions for a good d-d
overlap to produce a d-band will be discussed in Sec. 12.10.
he
Failure of d-band formation for the Mn-centres in spinel Mn J 0 4 Le. (MnII)tet(MnIIIMnIII)oct04
is also evidenced from its nonconductivity..It can neither participate in hopping conductivity
lc
nor in metallic conductivity (through d-band formation).

127. Silicones are structurally correlated with the silicates.
ea
• Replacement of 0- sites in silicates by the formally isoelectronic Me-groups gives the

structures of silicones. It is illustrated here.
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SiO:- (orthosilicate) and SiMe4 (tetramethylsilane)

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3-03Si - 0 - SiO;- (disilicate) and Me3Si - 0 - SiMe3 (hexamethyldisiloxane)

o0- 0-
t.m
Me Me Me
t t l
-Si-O-Si-O-Si-
I I I
-Si-O-Si-O-Si-
and
oI I
0-
I
0-
I
Me
I I
Me Me
(pyroxene) polydimethyl siloxane
(silicone oil)
o 0- 0- Me Me Me
I I I
-Si-O-Si-O-Si-
I I I
and -Si-O-Si-O-Si-
I I I I I I
I
-Si-O-Si-O-Si-
I I I
-Si-O-Si-O-Si-
I I
I
0-
I
0-
I
0-
I I I
Me Me Me
(amphibole) (siloxene)
c. Numerical Problems
1. Calculate the electron affinity of iodine from the following data :
/!Jlf(Nal) = - 289 kJ mol-I, /!Jlsub(Na) = 108.8 kJ mol-I, /!JldisS(h) = 214.2 kJ mol-I, /!JlIE(Nti) =
497.3 kJ mol-I, UNal = - 694.7 kJ mol-I.
(Ans. : /!JlEA(l) = - 307.5 kJ mol-I, Le. the electron affinity of iodine is 307.5 kJ mol-I).
2. Titanium crystallizes in a hcp model. Calculate its density (Given: a = b = 295.3 pm, c = 473
pm.)
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(Ans. : 2.13 x 10 3 kg m-3).
3. Calculate the packing efficiency in antifluorite and corundum structure.
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Ans. (Antifluorite = 75%, Corundum = 77%).
4. In a crystal, anions from a hcp array and the cations take the position ofthe body centred octahedral
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holes. What is its empirical formula? Calculate the packing efficiency.
(Ans. Formula: AX4 • Packing efficiency: 75%).
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5. The density of sodium chloride is 2.165 g cm-3• The interionic separation is 282 pm. Calculate
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the value of Avogadro number.
(Ans. 6.02 x 1023 ).
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6. KCl crystallises in the rock salt structure. Distance between the successive 200 planes is 3.14 A.
Calculate the density of KCl. (Formula weight of KCl = 74.6 ).
(Ans. 1.99 g cm-3).
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This Page is Intentionally Left Blank
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APPENDICES
APPENDIX-I
Units and Conversion Factors
Table 1. Basic physical quantities in 81 units

Physical quantity Symbol for quantity Name of unit Symbol for unit
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Length I metre m
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Mass m kilogram kg
Time t second s.
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Electric current I ampere A
Temperature T kelvin K
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Amount of substance n mole mol
Luminous intensity Iv m candela cd
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A-1
A-2 Fundamental Concepts of Inorganic Chemistry
Table 2. Derived physical quantities in 81 units
Physical quantity Name of Sl unit Symbol and definition Named after

of Sl unit
Force, weight newton (N) N = kg m S-2 = J m- I Isaac Newton (1642-1727)
Work, energy, joule (J) J=Nm James Prescott Joule (1818-1889)
quantity of heat
Power watt (W) W = J S-I James Watt (1737-1819)
Pa = N m-2
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Pressure pascal (Pa) B. Pascal (1623-1662)
Electrical charge coulomb (C) C=As Charles Auguste de Coulomb
(1736-1806)
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Electrical potential volt (V) V = kg m2 S-3 A-I Allesandro Volta (1745-1827)
= J A-I S-I
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=J C-I =W A-I
Electric capacitance farad (F) F = C V-I Michael Faraday (1791-1867)
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Electric resistance ohm (0) O=V A-I Georg Simon Ohm (1787-1854)
Electric conductance siemens (S) S=O-1
m W. von Siemens (1816-1892)
Magnetic flux weber (Wb) Wb=V s W. Weber (1804-1891)
Magnetic flux density tesla (T) T = Wb m-2 Nikola Tesla (1856-1943)
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Inductance henry (H) H=VsA-1 Joseph Henry (1799-1878)
~requency hertz (Hz) , Hz = S-I Heinrich Hertz (1857-1894)
Radioactivity becquerel (Bq) Bq = S-I ~. Henri Becquerel (1852-1908)
lc
Absorbed dose of gray (Oy) Gy = m2 S-2 Louis H. Gray (1905-1965)

radiation = J kg-I
ea
Area (A) square metre m2

Volume (V) cubic metre m3
th
Density (p) kilogram per kg m-3

cubic metre
e/
Velocity (u, v, w, c) metre per second

Acceleration metre per square
second
t.m
*Concentration (c) mole per cubic metre mol m-3

*for concentration (c ) in mol per litre, it is given by mol dm-3
Table 3. 81 prefixes
Fraction Prefix Symbol Multiple Prefix Symbol
10- 1 deci d 10 deka da
10-2 centi c 102 hecto h
10-3 miDi m 103 kilo k
10-6 micro J.1 106 mega M
10-9 nano n 109 giga G
10- 12 pica p 10 12 tera T
10-IS femto f lOIS peta P
Appendices A-3
Table 4. CG5 and 51 units for some common physical quantities
Physical CGS units Sf Units

quantity Name Symbol Name Symbol
Length centimetre cm metre m
Angstrom A
(10-8 cm)
Mass gram g kilogram kg
Time second sec second s
ry
Temperature celsius °C kelvin K
kelvin oK
ra
Energy calorie cal joule J
kilocalorie kcal kilojoule kJ
litre-atmosphere lit-attn
ib
ergs erg
= 103 kg, Ib = 453.59 g, Btu = 1.055 x 10 10 erg = 252 cal
yl
• tonne (t)
Table 5. Conversion of CGS units to SI units

m
Physical quantity Relation between the units
he
Length Angstrom (A)-.~ 10- 10 m = 10- 1 nm = 102 pm
micron (Jl) = 10~ m
Volume lIitre (L) = dm 3
lc
Force dyne = 10-s N

ea
Energy· erg = 10-7 J

cal = 4.185 J
eV = 1.602 x 10- 19 J; eV/molecule = 96.484 kJ mol- J
th
Pressure atm = 1.013 x 106 dyne cm-2 = 101.33 kN m-2

atm = 760 torr
e/
mm Hg or torr = 133.32 N m-2

bar (106 dynes/cm 2) = lOs N m- 2
t.m
Viscosity poise = 10- 1 kg m- I S-I

Magnetic flux density gauses = 10-4 T
• I cm- I (wave number) = 2.86 cal mol-I, reciprocal centimetre is known as Kayser (K)
I kK (kilo Kayser) = 1000 cm- I, 1 eV per molecule = 23.06 kcal mol-I, 1 erg = 2.39 x
10- 11 kcal. 1 eV = (charge of an electron) x 1 V = 1.6 x 10- 19 C x V = 1.6 x 10- 19 J,
1.6 x 10- 19 x 6.02 X 1023
1 eV/molecule = 1000 kJ/mole = 96.488 kJ mol-I.
1 kK molecule-I = 103 cm- I molecule-I
= he x 103 em-I molecule-I (c/. E = hv = ~ )

= 6.62 x 10-34 J s x 2.99 x 10 8 m s-I x lOS m- I molecule-I
= 1.985 x 10-20 J molecule = 11.96 kJ mol-I
Table 6. Atomic Units (see text, Chapter 1, Sec. 1.8.2)
APPENDIX-II
Some Physical and Chemical Constants
Table 1. Values of some physical and chemical constants
Constant CGS and other units SJ units
Acceleration due to gravity (g) 980.665 cm sec-2 9.80665 m S-2
ry
Avogadro's number (NA ) 6.02217 x 1023 molecules mole-I 6.02217 x 1023 mol-I
Bohr magneton (J.lB) 9.274 x 10-21 erg gauss-I 9.274 x 10-24 J T-I
ra
Nuclear Magneton (J.lN) 5.04 x 10-24 erg a-I 5.04 x 10-27 J T-I
5.2918 x 10- 11 m
ib
Bohr radius (ao) 0.52918A
Boltzmann constant (kB or k) 1.3806 x 10- 16 erg (degree K)-I 1.3806 x 10-23 J K-I
yl
Debye 10- 18 esu cm m 3.3356 x 10-30 C m
F;lectronic charge (e) 4.80298 x 10- 10 esu 1.60216 x 10-19C
Electronic rest mass (me) 9.10953 x 10-28 g 9.10953 x 10-31 kg

he
Faraday (F) 96487 coulomb equiy-I 9.6487 x 104 C mol-I
Gas constant (R) 8.3144 x 107 erg (degree K)-I mole-I 8.3144 J K-I mol-I
lc
8.31441 Joules (degree K)-I mole-I 8.3144 N m K-I mol-I

ea
82.053 x 10-3 Iitre-atm (degree K)-I mole-I 8.3144 Pa m3 K-I mol-I

1.987 cal (degree K)-I mole-I
th
Permitivity of vacuum (Eo) 8.854188 x 10- 12 C V-~ m- I

(C V-I m- I = C2 N-I m-2)
e/
Permeability of vacuum (J.lo ) 41t x 10-7 H m- I

t.m
Planck's constant (h) 6.62618 x 10-27 erg s~c 6.62618 x 10-34 J s
Rest mass of proton (mp ) 1.672648 x 10-24 g 1.672648 x 10-27 kg
Rest mass of neutron (m n ) 1.674954 x 10-24 g 1.674954 x 10-27 kg

Atomic mass unit (u) 1.660565 x 10-24 g 1.660565 x 10-27 kg
(I ~ = 10-3 kg mol-I/NA ) (= 931.48 MeV)
Vacuum speed of light (c) 2.99793 x 10 10 cm sec-I 2.99793 x 108 m S-I
Standard atmospheric pressure 76 cm Hg 101.325 kPa

760 mm Hg (or torr) 1.01325 bar
1.1032 x 106 dyne cm-2
Hartree energy (Eh ) 4.3597 x 10- 18 J
Zero of the Celsius scale 273.15 K

Appendices A·5
APPENDIX • III
Wavelength and Colours
Table 1. Spectral Wavelength and Colours
Range of the wavelength Colour of the radiation Complementary

absorbed (nm) absorbed colour observed
400-450 Violet Green-yellow
ry
450-470 Indigo Yellow
470-490 Blue Orange
ra
490-500 Blue-green -Red
500-560 Green Purple
ib
560-575 Green-yellow Violet
yl
575-590 Yellow Indigo
590-640 Orange m Blue
640-730 Red Blue-green
he
lc
ea
th
e/
t.m
APPENDIX-IV
Names, symbols, atomic numbers and atomic weights· of the elements
Element Symbol Atomic Atomic Element Symbol Atomic Atomic

number weight number weight
Actinium Ac 89 227.03 Hafnium HI 72 178.49
Aluminium AI 13 26.98 Helium He 2 4.00
ry
Americium Am 95 (243) Hoimium Ho 67 164.93
Antimony Sb 51 121.75 Hydrogen H 1 1.008
ra
Argon Ar 18 39.95 Indium In 49 114.82
Arsenic As 33 74.92 Iodine I 53 126.90
At n
ib
Astatine 85 (210) Iridium Ir 192.2
Barium Ba 56 137.34 Iron Fe 26 55.85
Barkelium Bk (247) Krypton Kr 36 83.80
yl
97
Beryllium Be 4 9.01 Lanthanum La 57 138.91
Bismuth Bi 83 208.98 Lawrencium· Lr 103 (260)
m
Boron B 5 10.81 Lead Pb 82 207.19
Bromine Br 35 79.91 Lithium Li 3 6.94
he
Cadmium Cd 48 112.40 Lutetium Lu 71 174.97
Calcium Ca 20 40.08 Magnesium Mg 12 24.31
lc
Californium CI 98 (251) Manganese Mn 25 54.94

Carbon C 6 12.01 Mendelevium Md 101 (258)
ea
Cerium Ce 58 140.12 Mercury Hg 80 200.59

Cesium Cs 55 132.91 Molybdenum Mo 42 95.94
Chlorine CI 17 35.45 Neodymium Nd 60 144.24
th
Chromium Cr 24 52.01 Neon Ne 10 20.18

Cobalt Co 27 58.93 Neptunium Np 93 237.05
e/
Copper Cu 29 63.54 Nickel Ni 28 58.71

Curium Cm 96 (247) Niobium Nb 41 92.91
t.m
Dysprosium Dy 66 162.50 Nitrogen N 7 14.01

Einsteinium Es 99 (252) Nobelium No 102 (259)
Erbium Er 68 167.26 Osmium Os 76 190.2
E~ropium Eu 63 151.96 Oxygen 0 8 16.00
Fermium Fm 100 (257) Palladium Pd 46 106.4
Fluorine F 9 19.00 Phosphorus P 15 30.97
Francium Fr 87 (223) Platinum PI 78 195.09
Gadolinium Gd 64 157.25 Plutonium Pu 94 (244)
Gallium Ga 31 69.72 . Polonium Po 84 (209)
Germanium Ge 32 72.59 Potassium K 19 39.10
Gold Au 79 196.97 Praeseodymium Pr 59 140.91
(Contd.)
* Previously it was represented by Lw. Now as per IUPAC recommendation, it is represented by Lr.
Appendices A-7
Element Symbol Atomic Atomic Element Symbol Atomic . Atomic

number weight number weight
Promethium Pm 61 (145) Technetium Tc 43 (99)

Protactinium Pa 91 231.04 Tellurium Te 52 127.60
Radium Ra 88 226.03 Terbium Tb 65 158.92
Radon Rn 86 (222) Thallium TI 81 204.37
Rhenium Re 75 186.2 Thorium Th 90 232.04
Rhodium Rh 45 102.91 Thulium Tm 69 168.93
ry
Rubidium Rb 37 85.47 Tin Sn 50 118.69
Ruthenium Ru 44 101.07 Titanium Ti 22 47.90
ra
Samarium Sm 62 150.35 Tungsten W 74 183.85
Scandium Sc 21 44.96 Uranium U 92 238.03
ib
Selenium Se 34 78.96 Vanadium V 23 50.94
Silicon Si 14 28.09 Xenon Xe 54 131.30
yl
Silver Ag 47 107.87 Ytterbium Yb 70 173.04
Sodium Na 11 22.99 Yttrium Y 39 88.91
m
Strontium Sr 38 87.62 Zinc Zn 30 65.37
Sulfur S 32.06 Zirconium Zr 40 91.22
he
16
Tantalum Ta 73 180.95
lc
• Values are based on the presently accepted physical scale of 12C = 12.00000 as the standard. The ratio of
these atomic weights to those on older chemical scale assuming the value 16.00000 for the atomic weight of
ea
natural oxygen (composition: 160, 99.757%; 1'0, 0.039%; ISO, 0.204%) is 1.000279. The values given within
the parentheses are the mass numbers of the most commonly known isotopes.
The true atomic weight of natural oxygen is given by: 16 x 0.99757 + 17 x 0.00039 + 18 x 0.00204 = 16.00447.
th
. . Physical atomic weight = 16.00447 = 1.000279

It gives. Chemical atomic weight 16.00000
e/
Presently the term atomic weight is replaced by atomic mass or relative atomic mass (RAM). These are
t.m
expressed in terms of amu or u or Da (Dalton). These aspects have been discussed in Sec. 5.2.3.
•.• For the translawrencium elements with Z > 103, the currently used names (cf. Chemistry of the Elements
by N.N. Greenwood and A. Earnshaw and IUPAC, 1997) are : I04R/(rutherfordium), losDb (dubnium), I06Sg
(seaborgium), lo,Bh (bohrium), losHs (hassium), IO~t (meitnerium). However, other names to these elements
have also been suggest~d from time to time. These are: Z = 104 (kurchatovium, Ku; dubnium, Db), Z = 105
(hahnium, Ha, neilsbohrium, Ns, joliotium, JI), Z = 106 (rutherfordium, Rj), Z = 107 (neilsbohrium, Ns), Z = 108
(hahnium, Hn). The IUPAC (1977) recommendation, i.e. a hybrid Latin-Greek numerical method (cf. Sec. 8.6),
is free from such confusions. The elements with Z = 110, Ill, 112, 114, 116, 118 have been characterised.
APPENDIX-V
Some Useful Mathematical Relationship
(A) Differentials
(u and v are the functions of x; a and m are constants).
dx d du d du dv
(i) -=1 (ii) -(ou)=o- (iii) -(u+v)=-+-
dx dx dx dx dx dx
ry
d m m-I d 1 dlnu ldu
(iv) - x =mx
dx
(v) -Inx=-
dx x
(vi) --=--
dx udx
ra
d x x
.!!- (e U
= eU du
d dv du
(vii) -(e )=e (viii) )
(ix) -(uv)=u-+v-
dx dx dx dx dx dx
ib
.!!-(~)= v(:)-u(:)
yl
(x) (xi) .!!- (sin x) = cos x (xii) .!!-
dx
(cos x) = -sin x
dx v v
2 dx
de) du d( ) .
m
(xiii) ~ ( tan x) =sec2 x (xiv) - sinu =cosu- du
(xv) - cosu =-slnu-
dx dx dx dx· dx
he
(B) Integrals
lc
(uand v are the functions of x; a and m are constants; for the indefinite integrals, there should be an
addition of arbitrary constant ofintegration).
ea
(i) Jdx = x (ii) Jaudx = a Judx (iii) J<u + v)dx = Judx + Jvdx
m+1
x
th
(iv) J m
x dx=--,(m*-I)
m+1
(v) Jdxx = In x (vi)
e/
1 ax
dx=-e
(vii) Je ax
o
(viii) Jln ax dx =x In ax - x (ix) JSin x dx =- cos x
t.m
(x) Jcos x dx = sin x (xi) Juvdx =uJvdx - {: Jvdx] dx. (by parts)
GO ,
(xii) JUdv = uv - JVdu (xiii) Jxne-

ca
= :~I' (n positive integer)
o a
(C) Trigonometric relationship

(i) sin (90
0
- 9) = cos 9
(ii) cos (90 0
- 9) = sin 9
(iii) exp (± im9) = cos (m9) ± i sin (m9), (Demovier's theorem)
cos (me) =.!.2 [exp(ime) + exp(-im9)]

sin (me) = ~i [exp(im9) - exp(-ime)]
Appendices A-9
(iv), sin 2 9 + cos 2 9 = 1

(v) sin 29 = 2sin9 cos 9
2 2 2 2
(vi) cos 29 = cos 9 - sin 9 = 2cos 9 -I = 1- 2sin 9
(vii) sin (a ±~) = sinacos~ ± cosasin~
(viii) cos (a ± ~) = cos a cos ~ +sin a sin ~
(ix) sina ± sin~ = 2sin! (a ±~) cos! (a +~)

2 2
ry
1 1
(x) cosa + cos~ = 2cos - «(1 +~) cos - (a -~)
2 2
ra
(xi) cos a - cos~ = - 2sin! (a +~) sin! (a -~)
2 2
ib
(xii) sina sin~ =! cos (a -~) _! cos (a +~)
2 2
yl
(xiii) cosa cos~ =! sin (a -~) +! cos (a +~)
2 2
m
(xiv) sin a cos~ =! sin (a + ~) + ! sin (a - ~)
2 2
he
\0) Some Useful Expansions (r ~ 1)
(I + x)-l = 1 - x + x2 -x3 + .
lc
(I - x)-l = I + x + x2 + x 3 + .
ea
(I - x)-2 = I + 2x + 3x2 + 4x3 + ....
x2 x
3 4
x
th
In (I + x) = x - - + - - - + ....
234
x2 x
e/
3 4
x
In (I - x) = - x - - - - - - ....
234
t.m
x2 x3 x
4
exp (x) or eX = 1 + x + - + - + - + .... , (for all x)
2! 3! 4!
2 3
-x x x
exp(-x)ore =I-x+---+ ....
2! 3!
3 5 7
. x x x
sin x = x - - + - - - + ...., (for all x)
3! 5! 7!
x2 x4 x6
cos X = 1- - +- - - + ...., (for all x)
2! 4! 6!
x
In x! = x In x - x or x! = ~ (Stirling approximation, 1730)
eX
(for x > ca. 10)
(E) Progressions
(i) Arithmatic progression : a, a + d, a + 2d, ....
n-th term (Tn) = a + (n - l)d;
Sum of first n terms (Sn) =!!. (1) + Tn) =!!. {2a + (n -I)d}
2 2
, n(l+n)
Sum of first n-natural numbers = 1 + 2 + 3 + .... + n = 2
ry
(ii) Geometric progression: a, ar, ar2, ••••
ra
a(l- r n )
n-th term (T ) = am - 1. Sum of first n terms (Sn) = when r < 1
(1- r)
ib
n '
n
a(r -I) .. _ a
yl
Sn= (r-I) whenr> l;sumtomfintty (S«»-I_r whenlrl<1
(iii) Useful results :

m
n
he
~:>2 =~ (n + 1)(2n + I)
x=1
For first n natural numbers, I, 2, 3, ...., n
lc
tx =[%(n + I)T 3
ea
x=1
(F) Permutations and combinations

th
np' __ n! . nD __ n! __ n! __ n'. nC __ n! np' ,nC nC nC nC "C 1

r (n-r)!' r n O! 1 ., r -r-!(n---r-)!; r=r. r; r= n-r; n= 0=
e/
=1x 2 x 3 x =1
t.m
n! x (n - 2) x (n - 1) x n; O!
(G) Logarithms
log(mn) =log m + log n; log ( : ) =log m -log n,

log (m n ) = n log m; log 1 = 0; loga a = I; In(x) = 2.3 log x
Natural logarithm (base e); common logarithm (base 10).
(H) Mathematical Constants
7t = 3.14159265 ....., e = 2.71828...., In x = 2.30258 ... logloX
Appendices A-11
APPENDIX-VI
Books Consulted
Akhmetov, N. General and Inorganic Chemistry

Alexeyev, V. Quantitative Analysis
Anantharaman, R. Fundamentals ofQuantum Chemistry
Amikar, H.J. & Rajurkar, N.S. Nuclear Chemistry through Problems
ry
Amikar, H.J. Essentials of Nuclear Chemistry
Banerjea, D. Inorganic Chemistry - Elements and Compounds
ra
Banerjee, D. Inorganic Chemistry (Principles)
Banerjea, D. Fundamental Principles of Inorganic Chemistry
ib
Beiser, Ao Concepts of Modern Physics
Castellan, G.W. Physical Chemistry
yl
Chanda, M. mAtomic Structure and Chemical Bonding
Chandra, A.K. Introductory Quantum Chemistry
Charlot,G Qualitative Inorganic Analysis
he
Cotton, F.A. & Wilkinson, G Advanced Inorganic Chemistry
. Cotton, F.A., Wilkinson, G., Murillo, C.A. Advanced Inorganic Chemistry
lc
and Bochmann, M.
Cotton, F.A. & Wilkinson, G Basic Inorganic Chemistry
ea
Das, Asim K. Bioinorganic Chemistry

Das, Asim K. Inorganic Chemistry: Biological & Environmental
th
Aspects
Das, Asim K. Environmental Chemistry with Green Chemistry
e/
Day, M.C. & Selbin, J. Theoretical Inorganic Chemistry

Day (Jr), R.A. & Underwood, A.Lo Quantitative Analysis
t.m
Dorain, PoB. Symmetry in Inorganic Chemistry

Douglas, B.E. McDaniel, D.H. & Concepts and Models of Inorganic Chemistry
Alexander, J.J.
Dutta, P.K. General & Inorganic Chemistry
I;:meleus, H.J. & Anderson, J.S. Modem Aspects of Inorganic Chemistry
Evans, R.C. An Introduction to Crystal Chemistry
Glasstone, S. Textbook of Physical Chemistry
Glasstone, S. Sourcebook ofAtomic Energy
Greenwood, N.N. & Earnshaw, A. Chemistry of the Elements
Halliday, D., Resnick, R. & Walker, J. Fundamentals of Physics
Huheey, J.E. Inorganic Chemistry - Principles of Structure &
Reactivity
Huheey, J.E., Keiter, E.A., Keiter, R.L. and Inorganic Chemistry - Principles of Structure &
O.K. Mehdi Reactivity
Jolly, W.L. Principles of Inorganic Chemistry
Kaplan, I. Nuclear Physics
Kapoor, K.L. A Textbook of Physical Chemistry (Vol. 1--4)
Kittel, C. Introduction to Solid State Physics
Krisnan, K.G. Atomic & Nuclear Physics
ry
Lairller, K.J. & Meiser, J.H. Physical Chemistry
Lee, J.D. Concise Inorganic Chemistry
ra
Mackay, K.M. & Mackay, R.A. Introduction of Modem Inorganic Chemistry
Mahan, B.H. U~iversity Chemistry
ib
Mingos, D.M.P. Essentials of Inorganic Chemistry
yl
Moeller, T. Inorganic Chemistry, A Modem Introduction
Mukherjee, G.N. mSemi-micro Qualitative Inorganic Analysis
(University of Calcutta)
Orchin, M. & Jaffe H.H. The Importance ofAntibonding Orbitals
he
Potterfied, W. W. Inorganic Chemistry: A Unified Approach
Purcell, K.F. & Kotz, J.C. Inorganic Chemistry
lc
Rajam, J.B. Atomic Physics

Raghavan, V. Materials Science & Engineering
ea
Rakshit, P.C. Physical Chemistry

Rao, C.N.R. (edited) University General Chemistry
th
Shriver, D.F., Atkins, P.W. & Langford, C.H. Inorganic Chemistry

e/
Sarkar, R. General & Inorganic Chemistry (Part I & II)

Sharpe, A.G. Inorganic Chemistry
t.m
Smart, L. & Moore, E. Solid State Chemistry - Introduction

Skoog, D.A., Holler, F.J. & Nieman, T.A. Principles of Instrumental Analysis
Sodhi,GS. Fundamental Concepts of Environmental
Chemistry
Vogel, A.I. Inorganic Analysis - Quantitative and Qualitative
West, A.R. Solid State Chemistry and its Applications
Wulfsberg, G Inorganic Chemistry
Acknowledgement
The above listed references and sources have been freely consulted to borrow their views and
ideas. The present authors are indebted to all these authors to an endless extent. The present
author expresses his heartiest thanks and grateful acknowledgement to all of them.
ry
Index
ra
I
ib
(T) indicates Table
yl
hypothesis 468 Amidine 1462
vs. lanthanides 468, (Sec. 8.8.3) Amino acids 1361ff
a-Emission 273 Actinium series 344 Aminoboranes 812
a-Decay 322, 338.0: (Sec. 6.12)
m
Actinoids 453, 454 Ammine complex formation 1507
a-Particle nuclides 271 Activated complex 863 Ammonia clock 848
he
a-Particle scattering 22, 23 Activation energy 413 Amperometric titration 1749, (Sec.
Activation of alkane 1278 16.22.3)
Abegg's rule ofcontravalency 453,
Activation parameters 864 Amphiboles 1053
543
lc
Active methylene group 1458 Amphiprotic compounds 1345

Absolute electronegativity 496,
Activity product 1496 Amphoteric behaviour 1561
506, 1475, 1476
ea
Aerial oxidation ofFe(II) 1659 Amphoteric behaviour of metal

Absolute hardness 496, 1476
Agostic interaction 1253, 1278, ions 1433
Acceptor number (A.N.) 1413 (Sec. 13.1.10) Amphoteric oxides 1346
th
Acceptor-donor interaction 1392 Alkali metals 452,453, 454 Angular equations 187
Acetic Acid (CH3C02H) as a Alkali storage cell 1688 Angular molecules 780
solvent 1566
e/
Alkalides 1309, 1560

Angular orbital overlap 719
Acetylacetone 1268 Alkaline earth dihalides (MX2) 841
Angular probability function 207
Acid and base catalysis 1437 Alkaline earth metals 454
t.m
Angular strength 679, 680.0: (Sec.

Acid dissociation constants 1415(T) Alkenes 1405
9.13.3)
Acid storage cell 1688 Allotropes of carbon 893
Angular volume 1481
Acid strength 1270, 1414ff Allotropes of crystalline
Angular wave functions 200, 203
Acid strength of aqua metal carbon 887
Alloys 1156 Anion
ions 1430 complexation 1447
Acid-base indicators 1372ff Allred-Rochow's electronegativity
500 polarisation 794
Acid-base strength principle 1482 receptors 1312, 1322
Alpha decay 338
Acidity parameter 800, 1467 solvation 1260
Alternation effect 531, 532,
Acids and Bases 1343.0: (Ch. 14) 773, 1642 water 1260
definitions 1343 Ambidentate Anode rays 8
Actinides 453, 454, 468 ligands 824, 1480, 1487 canal rays 8
contraction 469ff solvent 1413 positive rays 8
1-1
1-2 Fundamental Concepts of Inorgan,ic Chemistry
Anodic protection 1693 Atmophiles 466, 1486 Band'edge 1191

Anomalous behaviour of ice 1266 Atom bomb 417 Band gap 1191
AnomalouspK-value 1426 Atomic inversion 848 Band spectra . 253, 2S4
Anomalous properties of Atomic mass 258 Band splitting 1141, 1142, 1215
lithium 528 Atomic mass unit (amu) 258 Band structure of diamond 1144
Anomalous Zeeman effect 84 Atomic models (Ch. 1 and 4) Band structure of
Anomeric effect 975 Atomic pile 418 ionic comp9unds 1150
Antiaromatic 1460, 1461 Atomic states 57 nontransition metals 1140
Antielectron 296 Atomic units (au) 30 transition metals 1144
Antiferromagnetism 1079 Band theory of
ry
Atomic volume 478
Antifluorite structure 1038 Atomic volume curve 450 metallic bonding 1~ 36ff
Antimatter 297 Atomic weight 258 solids 1140jf
ra
Antineutrino, see antiparticles Aufbau filling ofad-band 1147 Banana bonds 719
Antineutron 297 Aufbau principle 86, 220 Band width 144, 854, 1138
ib
Antinucleus 297 Auger effect 268, 273, 323 Barn 240, 393
Antiparticles 296, 299 Auger emission 366 Basic beryllium
Antiproton 297 carboxyIates 545
yl
Aurophilic cation 522, 547
Antirutile structure 1039 Aurophilic interactions 523 nitrate 545
Antisubstance 297 Auro)Shilicity 522 Basicity 1436
Antisymmetric or odd functions 156
m
Autoionisation of solvents 1468 ofanions 1434
Aphelion 48 Autoprotolysis constant 1349 of carbonyl compounds 1408
he
Applications of radioactive Autoradiography 358 Bathochromic shift 162, 1273
isotopes 347ff Batteries 1686, (Sec. 16.14)
Avalanche break-down 1201
Aprotic solvents 1555 BCS theory of superconductivity
Average life period 329
lc
Aqua acid strength of metal 1227ff

Average oxidation state 1581
ions 1429 Becquerel rays 309, 321
Azeotropic behaviour 1259
ea
. Aquaacids 1429 Bent's rule (Secs. 9.13.7, 10.8;

Azeotropic mixtures 1260
Aqua regia 1629, 1638, (Sec. Appendix lOA)
16.4.5) Azide 1587
Bent bond concept 718, 807
Azimuthal quantum number,
th
Arbusov reaction 808, 884 Bent bonds 694-696,697,763,

see quantum number
Arganic structure 687 819,825,835,972
Azulene 1461
e/
Aromatic stability 1460 Benzoid form 1381

Aromaticity 815, 818 Berry pseudorotation 849.0: (Sec.
Arrhenius equation 861, 1068 I P&B I 10.9.2)
t.m
Arrhenius plot 164 p- decay 336, 337, (Sec. 6.13) Beta (p)-rays 312
Arrhenius theory of acids and p+ (Le. positron) decay 322, (Sec. Beta decay 340, (Sec. 6.13)
bases 1343 6.13) Betaemission 271, (Sec. 6.13)
neutralisation 1343 p-aiu,mina 1232 Bethe cycle 426
Artificial radioactivity 345, 346, p-hydrogen elimination 1278 Bethe-Slater curve 1153
(Sec. 6.16) Back bonding 612 Bethe's notation 384
Artificial transmutation 383.0: (Sec. Back emf 1694, i io I Biacetyl 1269
7.1) Back strain (B-strain) 1444, 1448, Big~bangtheory 429
Asbestos minerals 1053 -1456 Binuclear clusters 1162
Associated laguerre polynomials 188 Bailer twist 851, 852 Black rain 418
Associative process 862 Bainbridge mass spectrometer ' 15 Black-body radiation IlIff, (Secs.
Aston's mass spectrograph 12 Balancing redox reactions 1577jf 2.2,2.3)
Aston's whole number rule 257 Balmer formula 18 Bleaching powder 1584
Asymmetric fission 411, 412 Balmer series 34 Bloch theory 1131
Ate complexes 1389 Band bending 1195, 1196 - Bloch walls 1083
Index 1-3
Bloch wave function 1132 Bonding properties of Briggs-Rauscher (BR) oscillating
Bloomington shuffle 1166 3d and 4forbitals 225,528, reaction 1779, 1783
Blue shift 1273, 1401 (Sec. 4.3) Brillouin zone 1133, 1134, 1136,
Body centred cubic (bee) unit 4fand 5forbitals 225,468, 469, 1138
cell 102~ (Sec. 4.3) Broadening ofpeaks 126, 162
Bohr megneton (B.M.) 77 Boranes 896ff, 917, (Sees. 10.12- Bromine trifluoride as a solvent 1570
Bohr yield curve 407 13) BrOnsted
Bohr-Bury scheme 86 Borazanes 704 acidity 799, 1344ff
Bohr-Wheeler constants 410 Borazine 703, 1584 equations 1437
Bohr-Wheeler theory of nuclear
ry
Border line elements 462, 467ff relationship 1436
fission 409
Border line species (HSAB) ·1474 BrOnsted-Lowry theory 1344jJ,
~ohr 's atomic model 25,. (Sec. 1.8)
Born equation 1326ff (Sec. 14.3)
ra
Bohr's correspondence principle
Born expQnent 986, 1003, .. 007 Brown ring complex 1590
36,156,157,164,174
Bohr's classification ofelements Born repulsion 1295 Brucite sheet 1054
ib
466 Born repulsive potential 1003 Buckminister fullerene 893ff
Bohr's orbit 26, 27 Born-Haber cycle 993ff, 997.ff, Buckshot type capture reactions
yl
Bohr's quantum restriction 139 1325, 1414, 1416, 1640, 395
Bohr's periodic table 458 (Secs. 11.5, 11.6) Bucky ball .893ff
Buffer action 1370, (Sec. 14.4)
Boltzmann distribution function
m
drawbacks 994
1117 proton affinity 997 Buffer capacity 1370, 1371
~ond dissociation energy 755 Born-Lande equation 986, 1003jJ, Buffer solutions 1356ff
he
Bond (Ch. 10) 1006, (Sec. 11.7) Bumingice 1282, 1283
energy 753fJ, 758 Born-Mayer equation (Sec. 11.7.3) Butadiene 162, 701
lengths 764ff
lc
Born-Oppenheimer approximation Butanone 1270

multiplicity 717, 765
550 BZ reaction 1780, 1782
order 568
Borosilicate glass 1093
ea
pair moment 778.ff

characteristics of carbonyl Bose-Eeinstein condensate (BEC) I C
group 1175 237 14C-dating 362
th
3e-2e Bonding 667fJ, 687fJ, 726fJ, Bose-Einstein statistics 237, 252

Cage compounds 1279ff
815, 1452, (Sees. 9.12.12,9.21) Bosons 218, 237, 252, 1227 Calix[4]arene 1313
e/
Jc-4e Bonding 667fJ, 687fJ, 735fJ, Brackett series 34 Calixarenes 1313ff

1274ff, (Sees. 9.12.12,9.23, Bragg's equation 138
13.1.9) Calomel electrode 1596, 1597,
t.m
Bragg's law 1629

3c-4e vs. 3c-2e Bonding 667.ff,
ofdiffraction 138 Canal rays 8
(Sec. 9.12.12)
Bragg's method 983 Canonical forms 707
~c-2e Bonding 732
2c-1 e Bonding 973, (Appendix Bragg's reflection 1132 Canonical structures 911
·10A) Braking radiation 365 Canted magnetism 1079, 1085
2c"-3e Bonding 973, (Appendix BrQ,Ss 1636 Capping principle 1178
lOA) Bravis lattices 1024 Captodative effect 973
Bonding in higher boranes 729fJ, Bray-Liebhafsky (BL) reaction 1779 Captodative radical 974
896fJ, (Sees. 9.21, 10.12) Break-down voltage 1201 Carbanion 1459
Bonding in the noble gas Bredt's rule 1454 Carbenes
compounds 735ff
B.reeder reactor 422, (Sec. 7.13.5) properties 975, (Appendix lOA)
Bonding potentiality 677, 679,
680ff Bremsstrahlung 365 Carbides 1091
Bonding potentiality of the hybrid Bridge cleavage . 1392 Carbido complexes 548
orbitals 681ff Bridging alkyl goups 1392 Carbocations 547, 1385
overlap integral 681ff Bridging bonds 726 Carbon clusters 893
1-4 Fundamental C-oncepts of Inorganic Chemistry
Carbon-nitrogen cycle 426, 427 Charge separation 502 Cohesive forces 1111 ,
Carbon-nitrogen-oxygen (CNO) Charge to mass ratio (elm) of an Coinage metals 452,453, 454
bicycle 427 electron 2 Coincident states 73
Carbonium ion 1385 Charge transfer Cold fusion 429
Carbonyl clusters 1171fJ, (Sec. band 617,801,1717 Collector technique 979
12.8.5) compound 1219, 1393 Colour and hardness 1479
Carbonyl complexes 1171fJ, 1406 Chelate effect 1351 Colour centres 1072
Carbonyl hydrides 1408, 1589 Chelation 1253 Common ion effect 1496ff, 1507
Carl;lorane-siloxane polymer 930 Chemical actinometer 368 Compensation method 1597, 1598
Carboranes 897fJ, 917ff, (Sees.
ry
Chemical clock reactions 1777, Competitive 1t-bonding 1481
10.12-13) (Appendix 16B) Complementary redox reaction 1595
Carotene 162 Chemical dosimeter 368 Components 85
ra
Carrier mobilities 1194 Chemical equilibrium 335 123 Compound (superconductor)
Carrier technique 309, 345 Chemical exchange method 265, 1229
ib
Cascade effect 267 Compound nucleus 284, 393, 410
isotope separation 262 Chemical forces 548, 549 theory 393ff
X-ray generation 38 Chemical shift 248, 249
yl
Compound semiconductor 885,
Catalysed redox reactions 1724, .Chemical vapour deposition 1184,1192, 1193
(Sec. 16.20) (CYD) 1193, 1194 Compounds
Catalytic converters 1059
m
Chemiluminescence 1709 hypercarbon 545
Catenanes 1320 Chevrel phases 1169, 1229 photosensitivity 617
he
Catenation bond 1581 China clay 1056 Compressibility 1007
Cathode rays I Chloromethanes 781, 791 Comproportionation
Cathodic protection 1693, 1702 Chromium(II) acetate monohydrate reaction 1596, 1651, 1663,
lc
Cation polarisation 794 722, 1163 (Sec. 16.10)

Cation receptors 13 12 Chromophore 1273 Compton effect 121, 141, 313, 366,
ea
Cavity model 1550, 1559 Chronoamperometry 1744 (Sec. 2.5)

Cells Circular orbit 47 Compton shift 124ff
with transference 1605 Cis-effect 823 Compton wavelength 124
th
without transference 1605 Cladding 421 Condensation centres 320

Cement 1061 Classical kinetic energy 136, 144 Condition of orthogonality 148
e/
Centre of mass 31 Clathrate ·type complex 1058 Conditional or formal potential 1599,
Centrifugal method 266 Clathrate-hydrate 1283ff 1607, (see formal potential)
t.m
Chadwick 16, 383 Clathrates I 279ff, (Sec. 13.2) Conditional stability constant 1607
Chain lattices 891, 1050 Clay minerals 1054ff Conduction band (CB) 1148
Chain structure 1264 Clock reactions 1777, (Appendix Conductors 1135
Chalcogens 454 168) Cone angle 1405
Chalcophiles 466, 1486 Close packing models 1029jJ 18e-Configuration 1406
Chancourtois law of telluric Cloud chamber 3 19 Configurational entropy 1063, 1065,
screw 449 Cluster anions 1561, 1563 1279, 1280, 1284
Channel compounds 1283 Cluster bonding 1169 Consecutive reaction 331
Characteristic X-rays 37, 273, Cluster bonding electrons 1170 Conservation laws in nuclear
323,366 Cluster valence electron (CYE) reactions 390jJ
Charge capacity 499, 505 count 1171 Conservation ofangular momentum
parameter 1420, 1421, 1438 Cobalt bomb 425, 426 391
coefficient parameter 505, Codeposition of copper and Conservation of energy 390
1419, 1420, 1438. zinc 1636, 1698 Conservation of linear momentum
Charge exchange force 279 Coercive field 1083 390
Charge of an electron 4 Cohesive energy 5 11, 1147 Conservation of momentum 123
Index 1-5
Continuous spectra 112 Craig-Paddock model 703,815,816

18 &D I
Continuous X-ray spectrum 38 Cristobalite (Si0 2) structure 1039
Contraction of d-orbitals 685 Critical deformation 410 8-bonding 720ff, 1162
Controlled fusion reaction 428 Critical magnetic field (He) 1224 d-band formation 1212
Controlled nuclear fission 418 Critical mass 417 d-block elements 465, 528
Coolant 421 Critical potential 40 d-block vs. f-block elements 528ff
Cooper pairs 1227 Critical size 415 d-contraction 469, 475
Cooperative magnetism 1079 Critical temperature 1224 d-orbitial participation 686ff, 867,
aniferromagnetism 1079 Crookes dark space 1 1437.0; 1440, 1451.0; 1473,
ry
canted magnetism 1079 Cross-section (nuclear reaction) (Sees. 9.13.5, 10.7)
ferrimagnetism 1079 392 d-orbital resonance 1422
d-orbitals 204, 225, (Sec. 4.3)
ra
ferromagnetism 1079 Crown
Coordination polymers 1282 ethers 1301, 1308ff, (Sees. d-orbital vs.f-orbital 225ff
Copper(II) acetate monohydrate 13.5.6,13.5.9) DABCO 1439
ib
722, 1162ff form 818 Dalton 259
Coprecipitation 979, 1506 shape 811 Dating by tritium 363
yl
Corands 1301 Crown-anthracene system 1318 Dative bond moment 788
Corona discharge 1208 Cryolite and anticryolite structure
m Davisson and Germer's experiment
Coronands 1301 1040 136
Correspondence principle 36, 156, Cryptands 1301, 1306fj, (Sees. DCD (Dewar, Chatt and
Duncanson) model 1402
he
157,164,174 13.5.6, 13.5.8-9)
Corrosion 1686, 1693 Cryptate alkali metal cations 1180 de Broglie 134ff, (Sec. 3.2)
Corrosion of copper 1702 Cryptates 1307ff electron wave 135, 136
lc
Corrosion of iron 1702 Cryptospherands 1302 matter wave 133, 135

Corrundum 1040 Crystal defects 1063ff, 1209, (Sec. wavelength 134
ea
Cosmic abundance 269 11.15) de Moivre's

of elements 433ff Crystal field effect 226 theorem 200, 202
Cosolvating agents 1350ff Crystal field stabilisation energy Debye (dipole moment) 774
th
Cottrell equation 1729, 1743, 1745 (CFSE) 1634 Debye forces 1287
Coulomb barrier 281 Crystal packing model 800 Debye-Huckellimiting law
e/
Coulomb integral 166, 552, 554, Crystal radii (DHLL) 1498

559,563 Shannon's 988 Decay kinetics 325
t.m
Coulomb potential barrier 281 Crystal structure of the metals 1111 Decomposition potential 1694,
Coulombic energy (J) 552, 555 Cubic close packing 1032 1699,1701,1731
Coulombic interaction energy 552 Cubic perovskite structure 1047 Decomposition voltage 1698
Coulombic potential 411 Curie temperature 1082 Degeneracy of the energy levels 159
Coulombic potential barrier 412 Curie-Weiss law 1086 Degree of covalency 795ff
Coulometric analysis 1751 Curie's law 1986 Delayed neutrons 408
Coupling schemes 57 Cyanuric acid (CA) 1317 Delayed reactions 1711
Covalent bond order 776 Cyclic voltammetry (CV) 1741 Delocalisation 161,705
Covalent crystals 767 Cycloaddition 749 energy 699ff, 702ff
Covalent lattice energy 1291 Cyclodextrins 1283, 1314ff Delocalised MOs 642
and symmetry 1292 Cycloheptatriene 1460 Delta bonding 720ff, 1162, (Sees.
Covalent radii 764 Cyclonite 1727 9.6, 9.19, 12.8)
Covalent-ionic resonance 555, 705 Cyclopentadione 1269 Delta molecular orbitals 575
763, 768, 774ff, (Sec. 10.4) Cyclophanes 1316 Delta-bond 720,1162, (Sees. 9.6,
energy 491, 495 Cyclotriphosphazene 1284 9.19,12.8)
Cow and milk system 268 Cyclotron 399 Deltahedra 900
Cradle shape 818 Cylindrical.cryptand 1308 Dempster's mass spectrometer 14
1-6 Fundamental Concepts of Inorganic Chemistry'
Density of energy states Dioxygenyl tetrafluoroborate 999 E

(DOS) 1117, 1139ff Diphenylamine 1679
Density of states (DOS) 1139, Ebsworth diagram 1649
Dipolar repulsion 780, 785, 1268,
1146 1269 Eclipsed conf~nnation 789
Depolarizers 1698 Dipole moment 777fJ, 780, 960, Edison cell 1688
Designation of the MOs 597 1401, 1556, (Sec. 10.5) Effective mass 1182
Detection ofH-bonding 1273 of R3NO and R3PO 809 Effective nuclear charge 473,474fJ
Detonation velocity 1776 Dirac atom 191 Effects of different factors on
Detonator 425, 1773, (Appendix Dirac model 192 electrode potential 1610ff
16A) Eigen functions 148
ry
Direct and indirect gap semi-
Dewar model 703, 815, 816 conductors 1190 Eigen values 148
Di-molybdenum(II) complexes 721 Direct gap materials 1192 Eighteen electron (18e) structure
ra
Diagonal relationship 511ff Discharge potential 1694 981, 1406
Diamagnetism 1086 Disilenes 1405 Einstein's equation 120
ib
Diamond cubic (de) Dismutation reaction Elastic collision 41
structure 884 see disproportionation reaction Elastic scattering 366, 386
unit cell 1028
yl
Disintegra~ion series 342fJ, (Sec. Electric quadrupole moment 240
Diamond structure 1184, 1248 6.15) Electrical conductivities ofsol ids
Di borane 726 Dispersion force 1288ff 1148fJ, (Sec. 12.5.5)
Dicarbollide
m
Disproportionation reaction 1596, conductors 1149
anion 929, 930 1651, 1663, (Sec. 16.10) insulators 1149
he
Dichoric 1180 Disproportionation of peroxide 884 semiconductors 1151
Dielectric constant 1261, 1327, Dissociation constants of some semimetals 1149
1556 acids 1415 Electrical conductivity 1120
lc
Dielectric saturation 1327 Electrical double layer 1195

Dissolution 1258
Diels-Alder reaction 749 Electrides 1309, 1560, 1561
Dissymetric 960
ea
Differentiating electron 464 Electroanalytical techniques 1727ff

Distortion polarisability 1288
Differentiating solvent 1347fJ,
Dithionate 1586 Electrochemical cells 1686
.(Sec. 14.3.2)
th
Dithionite 1586 Electrochemical polarisation 1698

Diffuse (D) series 74
Dobereiner's law of triads 448 Electrochemical series 1602, 1603
Diffusion cloud chamber 320
Electrodeposition 1693
e/
Diffusion current 1732 Donor numbet: (D.N.) 1413

Donor-acceptor compound 1219 of brass 1698
Diffusion method 262
Dopant 1184 of copper and zinc 1638, 1698
t.m
Dihdrogen adduct 1407

Dihedral angle 790 Doppler effect 73, 430 Electrolysis of solutions 1693
Dihedral mirror planes 937 Dosimeter 367,368 Electrolytic cell 1606, 1607, 1693
Dihydride complex 1407 Double bond character in P-O Electrolytic method 264
Dihydrogen 1592 linkage 809 Electromagnetic method 261
Dimeric chromium(II) acetate 722, Double helical structure of Electromagnetic wave 135
1163 DNA 1265-66, 1301 Electron affinity 486fJ, (Sec. 8.13),
Dimeric copper(II) acetate 722, Downhill migration 1195, 1197 997
1162 Drago-Wayland equation 1411fJ, Electron capture (EC) 337
Dimerisation 724 1491 Electron cloud density 210
of NO and N02 650 Drift velocity 1121 Electron compounds 1158, 1160
Dinitrogen adduct 1396, 1400 Dropping mercury electrode 1728ff Electron deficient bonds 905
Dinitrogen complexes 1396fJ, 1400 Drude-Lorentz classical free electron Electron deficient compounds 544,
Diode 1194,1202 theory 1114 725, 1391
Dioxygen 1592 DSD (diamond-square-diamond) 927 Electron deficient covalent bonds
Dioxygen adduct 1396ff Dulong and Petit's law 455 725jJ, (Sec. 9.21)
Index 1-7
Electron deficient covalent Entropic effect 1437, }633, 1635 Factors governing
compounds 725ff, (Sec. 9.21) Entropic favour 864, 1258, 1285, the acid-base strength 1414ff,
Electron deficient hypervalent 1298, 13~O, 1419, 1438, 1777 (Sec. 14.8)
compounds 691 Entropy of the bond lengths 766.ff
Electron deloca~isation effect 784 decomposition 1020 the degree ofpolarisation 792fJ
Electron density maps 982 Entropy driven 733 the electrode potential 1610ff
Electron emission effect 323 process 1285 the molecular polarity 777ff
F;lectron exchange phenomenon 552 reactions 862 Fajans'rule 705, 791fJ, 997, (S·ec.
Electron orbit 32 Eotv()s-Ramsay-shields 10.6)
Fajans' type compounds 1335
ry
Electron sea model 1114 coefficients 1258
Electron transfer reaction 353 Equilibrium constant 1661 Faraday dark space I
Electron waves 139 Equipartition of energy 1125 Fast breeder reactor 423
ra
Electron-hole pair 1192 Equivalence and nonequivalence of Fast neutrons 17
Electron-phonon interaction 1125 the hybrid orbitals 693fJ Fat man (atom bomb) 418
ib
Electronegativity - 491ff, (Sec. 8.14), Equivalent weights of oxidants and Feldspars 1056
1431 reductants 1595 Fermi 238
equalization 502' Estimation of Fe(lII) 1675 Fermi energy level 1182
yl
Electroneutrality 821 Ethyl acetoacetate 1269 Fermi gas model 271,282
principle 711 Even (+) parity 294
m Fermi level 1117, 1188
Electronic conduction 1076 Even and odd functions 156 Fermi potential 283
Electronic spectra 256 Even and odd series 452 Fermi sphere 1160
Fermi temperature 1120
he
Electronic wave function 550 Exchangeenergy 92,94,555,559,
706 Fermi-Dirac distribution law 1183
Electroplating 1697
Exchange force 279 Fermi-Dirac energy distribution
Electroscope 315
III 7, 1118fJ
lc
Elemental semiconductors 1193 Exchange integral 554, 564, 1152

Fermi-Dirac statistics 237, 252,
Ellingham diagram 1719, (Sec. Exchange interaction 1145, 1152
1117
ea
16.i 7) Excitation energy 409

Fermions 218, 237, 252, 291
Ellipsoidal cavity 1312 Excitation potential 35
Fermi's four factor formula 418
Elliptic orbits 45, 76 Exhaustion region 1189
th
Ferrate ion 1658

EMF ~agrams 1647, (Sec. 16.8) Exoergic process 392
Ferrimagnetism 1044,1079,1082
Emission spectrum 18 Expansion of octet 544
Ferrhes 1044, 1082
e/
Endoergic process 392 Explosive material~ 1702, (Sec. Ferroelectric crystals 1262
Endohedral complexes 1621, Appendix 16A)
Ferroelectric material 1047fJ,
t.m
see fullerenes Extended periodic table 462 1088ff

Energetics ofA and D processes 863 Extrinsic excitations 1192 Ferroin indicator 1678
Energetics of dissolution 1324fJ, Extrinsic or doped semiconductors Ferromagnetic materials 1085
(Sec. 13.6) 1184,1189 Ferromagnetic property I 146
Energetics of fissionability 413ff Eyring equation 861 Ferromagnetism 1079, 1082,1144,
Energetics of hybridisation 682ff Eyring plot 164 I 151ff
Energetics of phase transitions Fertile nuclides 416, 417
I 332fJ, (Sec. 13.7) F Fifth state of matter 237
Energetics ofsolubilities 1328 .fblock elements 465, 528 Fine spectra 44, 48
Energetics of the disintegration .fblock vs. d-block elements 528fJ Fine structure (spectra) 53, 73
processes 336 F-centre 1071 Fine structure constant 49
Energy bands 1136 .fcontraction 469.ff Finite mass of the nucleus 31
Enthalpic disfavour 1301 .forbitals .208, 225, (Sec. 4.3) Fire extinguishing species 974
Enthalpic favour 864, 1450 .forbitals vs. d-orbitals 225fJ Fissile nuclides 416
Entropic disfavour 1303, 1418, Face centred cubic (fcc) unit Fission 277,389,406
1433, 1450, 1633, 1635 cell 1026 Fission chain reaction 415
1-8 Fundamental Concepts of Inorganic Chemistry
Fission yield curve 407 Free particle 150 Goldschmidt's radii 983, 988
Fissionability 412 Frenkel defects l064fJ Goldstein's discharge tube 8
Fluorescence 323, 1318, 1708 Fricke dosimeter 368 Graphite 1144
switch off 1318 Front strain (F-strain) 1444 compounds 889fJ
switch on 13 ~8 Frontier atomic orbitals 506, 1475, layer lattice 1029
Fluorescence emission 323 1476 like structure 803, 890
Fluorescent radiation 366 Frontier molecular orbitals 'structure 886.0: 1248
Fluorite (CaF2 ) crystal 1038 (FMOs) 506, 580, 1475.0: Gray (Gy) 367
~Iuorite structure (AB 2 ) 1039 (Appendix 9A) Green photocatalyst 1214, 1717
Fluoro compounds of xenon
ry
Frost diagrams 1649, (Sec. 16.8.2) Green solvents 1574
see xenon fluorides Fuel cells 1686, 1691 , (Sec. Grotthus mechanism 1266, 1369,
Fluoroacetylacetone 1270 16.14.3) 1557
ra
Fluoroalkyl radicals 972, Fuel gas 1711 Ground state tenns 67-69
(Appendix lOA) Group analysis 1484.0: 1499
Full-filled level 484 .
Fluorocarbenes 972, 975,
ib
Fullerenes 894fJ, (Sec. 10.11.5) Group displacement rule 324, (Sec.
(Appendix lOA) 6.8)
Fuller's earth 1056
Fluorocarbons 1290 Group electronegativity 504, 1421
yl
Fulminates 710, 1727
Fluoroethyl radicals 975, Group moment 779
(Appendix lOA) Fulvene 1461
Fundamental (F) series 51, 74 Group orbitals (LGO) 620
Fluoromethyl radicals 972,
(Appendix lOA)
m
Fundamental particles 16, 18, 296, Groups (periodic table) 452
299, (Sees. 1.4, 5.6) Guanidine 14f2
Fluorosulfonic acid 1568
he
Furan 784 Guest-host
Fluorosulfuric acid 1383, 1384
Fusion 277,424 chemistry 1298
Fluxional behaviour 845.0; 1403,
1591 compounds 1284
lc
Fluxional molecules 248, 848.0; G interaction 1058

852,853, 857, (Sec. 10.9) Gunpowder 1726
Galvanic cell 1606, 1693
ea
Fluxionality 848.0; 856 Gutmann rule 1413

Gamma (gamma) rays 313 Gyromagnetic ratio 78
Football ligand 1307
Gamma emission 341, (Sec. 6.14)
Forbidden energy gap 1134, 1149
th
Gas hydrate clathrate 1283fJ H

Forbidden transitions 71
Gas hydrate structure 1280fJ
Forbidden zone 1134 H-bonded ferroelectrics 1262
Gas hydrates 1282, 1284
e/
Forces 1285 H-bonded structure of ice 1280

long-range 1285 Gas multiplication factor 316
Gas phase acidity 1419.0; 1421 3c-4e H-bonding 1275
short-range 1285
t.m
Gauche confonnation 789 H-bridge bond 1277fJ

Fonnal (conditional) potentials 1607,
Geiger range 318 Hagg's rule 1091
(Sees. 16.3, 16.4)
Geiger threshold 318 Half l,ife (t 1/2 ) period 327, 328
Fonnal charge 709.0; 713, 1578,
Geiger-Muller (G-M) Halfvalue thickness 366
1579, (Sees. 9.16.4, 16.1.2)
counters 3 16, 3 17 Half-filled and full-filled level 91
Fonnal potential 1598, 1607,
1615, (Sees. 16.3, 16.4) Geiger-Nuttall rule 290, 329, 339, Half-filled level 484
Forward biased junction ,1196 340 Half-peak potential 1748
Fractional distillation method 264 Gem qual ity crystals 1046 Half-wave potential 1734fJ
Framework bonding 1168 Gemstones 1046 Half-wavelength 156
Franck-Hertz experiments 40 Geodesic dome 893 Hall-coefficient 113 1
critical potential 40 Giant neutron star 429 Hall-effect 1 130
ionisation potential 40 Gibbsite sheet 1054 Halocarbenes
resonance potential 40 Glass tr~sition 1092 properties 975, (Appendix lOA)
Free electron theory 1115 Glasses 1092 Halogens 454
Free electron theory of metallic Goldschmidt's geochemical Halons 974
bonding 1 114fJ, (Sec. 12.3) classification 466 Hamiltonian operator 147, 166
Index 1-9
Hammett acidity function 1382fJ, Hopping conductivity 1074-75, Hydrogen-like systems 25, 26, 29,
1470 1210jJ, 1212 213
Hannay-Smyth equation 775 Hopping semiconductivity 1045, Hydrogenic systems 192
Hard and soft acids and bases 1074, 1210 Hydrolysis 1429
(HSAB) 1473jJ, (Sec. 14.15) Hopping semiconductors 1074, Hydrolysis constants of aqua metal
Hard-hard interaction 1488, 1489 1209jf ions 1431.0; 1433
Hard-soft interaction 1488, 1636 Hot atoms' 267 Hydrolysis of alkyl phosphates 870
HSAB principle 1473Jf, 1482, (Sec. Hydrolysis of aryl phosphates 870
Hardness (HSAB) 1405.0; 1475
14.15) .Hydrolysis of metal ions 1429
Hardness of ionic compounds 1013
atmophites 1486 Hydrolysis of salts 1349, 1494.0;
ry
Harkins' Rule 269
chalcophiles 1486 (Sec. 14.17)
Harmonic oscilator 255 Hydrometallurgy 1722
Iithophiles 1486
Hartree 30
ra
siderophiles 1486 Hydron 1344
Heat capacity I 125 . Hydronic concept 1344
HUckel molecular orbital
Heaviest nuclide 412 method 699 Hydronium ion 1369
ib
Hedgehog cation ~23, 547 Huckel's rule 817 Hydrophilic interaction 1298
Heisenberg's uncertainty principle Hume-Rothery rule 1157, 1158ff Hydrophobic effect 1299
yl
45,140,161, (Sec. 3.3) Hund's rule 68,69,94, (Sec. Hydrophobic interaction 1290
Heitler-London wave functions 552 1.10.11) Hydroxo acids 1429
Helferich's rule 824 Hydroxyl bond 1254
m
Hybrid lone pair mOrt:lents 777.0;
Hyper carbon 545ff
Helical structure 1318 786.0; (Sec. 10.5.3)
Heme group 1396 Hybridisation 716, 825 Hyperconjugation 736, 1452, 1466
he
Hemerythrin 1592 Hybridisation energy 683, 760 Hyperfine quantum number 241
Hybridisation"of atomic orbitals I-Iyperfine splitting 75
Hemispherands 130 Iff
669jf Hyperfine structure of the spectral
lc
Hemocyanin 1592
lines 74
Hemoglobin 1397, 1592 Hybridisation of nucleons 295
Hyperons 298
Henderson equation 1357 Hybridistion cost 683
ea
Hypervalence 545ff, 1391

Heteronuclear Zintl ions 1178 Hydrated electron 370
Hypervalent electron deficient
Heteropoly acids 1061 Hydrates 1279fJ, (Sec. 13.2)
molecular species 547, 691
th
Hydration energies 1330

Hexafluoroacetylacetone 1270 Hypophosphoric acid 1583
Hydration spheres 1327 Hypophosphorous acid 707, 1425,
Hexagonal close packing 1029
Hydride sponge 1447 1583
e/
High temperature superconductors

1228 Hydroboration 923 Hypsochromic shift 1273
Hydrodynamic electrode 1729 Hysteresis loop 1082, 1083, 1089
Higherboranes 730
t.m
Hydrogen (ortho and para) 251

Highest occupied molecular orbital
(HOMO) 580, 749-52, 973 Hydrogen bomb 425
Hydrogen bond 755, 1250ff, (Ch.
Hole formalism rule 70 Ice (structure) 1254, 1280
13)
Hole theory of liquids 1094 Iceberg 1327
Hydrogen bond energy 1254
Holes I1kovic equation 1733
Hydrogen bonding 1250.0: (Sec.
octahedral 1026, 1030 13.1) Ilmenite structure (FeTiD3) 1045
tetrahedral 1026 Hydrogen bridge 1278, 1408, (Sec. Imaging agent 268
HOMO-LUMO interaction 750.. 13.l.tO) Imidazole 1462, 1463
1386, (Appendices 9A, lOA) Hydrogen electrode 1597 Imidazoline 1462
Homologous series 1289 Hydrogen molecule (VBT and Impact parameter 23
ofalkanes 1293 MOT) (Secs. 9.3, 9.4) Impurity acceptor level 1186
Homonuclear diatomic molecules Hydrogen overvoltage 1699 Impurity donor level 1186
(MOT) 578ff Hydrogen spectrum 18, 20, (Sec. Impurity semiconductor 1184ff
Homopolar bond 776 1.5) Induced dipole moments 791
Homopolyatomic species 1178 Hydrogen valency 453 Induced radioactivity 345
Inductive effect 505, 779, 1418, Iodide clock reaction 1777 Isomeric equilibria 791
1437, 1438.ff Iodometric titrations 1703 Isomeric transition (IT) 250, 268,
Inductive effect of different Ion electron method 1577ff 341, 385
groups 1420 Ion solvation 1326.0: (Sec. 13.6.2) Isomerisation 824
Inelastic collision 41 Ion-exchange process 473 Isomorphism
Inelastic scattering reactions 386 Ionic and covalent compounds 1295 overgrowth 978
Inert gas compounds 735jJ, 972 interaction 1295 Isomorphous
Inert gas elements 466 Ionic compounds (Ch. 11) coprecipitations 1506
Inert pair effect 521, 531, 532, characteristic properties 977 Isomorphous substitution 1046,
761, 763, 770jJ, 980, 1143, 1052, 1057
ry
disproportionation 1000
(Sec. 10.3) thermal stability 1019 Isopoly acids 1061, 1107
Infrared (lR) spectrum 1262 Ionic conduction 1067, 1075 Isopolyanion 1061, 1107
ra
Inorganic benzene 1584 1584 Ionic conductivity 1068 Isosbestic point 1400
Inorganic graphite 888, 893 Ionic crystals of AB type 1035.ff Isosteric anions 991
ib
Insulators 1135 Ionic crystals of AB2 type 1038ff Isosteric cations 991
Intensity ofNMR signal 244 Ionic crystals of AB3 and A2B3 Isosteric or isoelectronic species 548,
Intensity rules 72 type 1040ff 985,991
yl
Intercalated compound 1169, 1690 Ionic equilibria 1343 Isosters 71 5
Intercala~es of graphite 1222 Ionic liquids as solvents 1572jJ, Isostoichiometric species 549, 584
Intercalation compounds 886.0:
m
(Sec. 15.13) Isostructural 549
888,1169,1171,1213,1690 Ionic mobility 1266, 1369 Isotones 249
he
Interchange or concerted process 504, Ionic potential 792 Isotope effect 385
862 Ionic radii ·987, 989jJ, (Sec. 11.4) Isotope labelling 347
Interferring acid radicals 1499 Pauling's 987 Isotopes 11, 33, 249, 253, 256,
lc
Interhalogens 1401 Ionic solution 1325 (Sec. 5.2)

Intermetallic compounds 1156, Ionisation energies 481fJ, (Secs. discovery 33
ea
1157 8.12,9.11) separation 260jJ, (Sec. 5.2.6)

Intermolecular attractive Ionisation potential 35, 40, 120, uses 347jJ, (Sec. 6.17)
. forces 1.293 481ff Isotopic dilution analysis 355
th
Intermolecular forces 1286 Ionising solvents 1557 Isotopic effect 256

Intermolecular H-bonding 1251 Ionophores 1307 Isotopic effect on bond energy 755
e/
Internal conversion 267, 268,322, IR-shift 255 Isotopic shift 253, 257
341 see detection ofH-bonding and
t.m
Internal H-bonding 1370 carbonyls J

Internal nodal points 155 IR-stretching frequency 1263
Jablonski diagram 1711
Interstitial alloys 1156 Irving-Williams stability order 1483
Jaffe-Hinze electronegativities 497
Intersystem crossing (lSC) 1708 Island of stability 289, 405
Isobaric nuclides 249, 408, 414 Jahn-Teller destortion 160, 163,
Intramolecular H-Bonding 785,
980, 1215, 1634
1251,1253,1267,1455 Isobaric relationship 313, 341
Jemmis'mnorule 916,1171
Intranodal maxima 198, 222 Isobars 249
Jemmis' unifying electron counting
Intrinsic bond energy 753, 759 Isoelectric points 1361, 1364,
rule 916
Intrinsic excitation 1192 1366
Joesphson junction 1232
Intrinsic homopolar dipole 777 Isoelectronic groups 549
Junction laser 1205
Intrinsic semiconductor 1182, Isoelectronic hydrides 1441
Junction potential 1605
1189 Isoelectronic species 549
Inverse crown ethers 1322jJ, (Sec. Isoionic point 1366
13.5.19) Isolobal fragments, 739fJ
K
Inverse spinel structure 1042 Isolobal groups 913, 1166 Kaolin 1056
Inversion energy barrier 848 Isomeric distribution 1267 Kaolinite 1054, 1055
Index 1-11
Kaons (see Sec. 5.6) Layer lattices 1049 Lithium titanium disulfide battery
Kapustinskii equation 1011 LCAO method 570jJ 1213
Katapinands 1310 LCAO-MO treatment 558 Lithophiles 466, 1486
Katapinate 1310 Le Chatelier's principle 1497 Little boy (atom bomb) 418
KCP 1180 Lead-acid battery 1688 Localised MOs 647
Keesom forces 1286 Leclanche or dry cell 1687 Lock and key principle 1299
Keggin structure 1062 Legendre polynomial 188 London dispersion forces 1284ff
Kepler's law of area 46 Lennard-Jones potential 1285, London force. 1284, 1288ff
Keto-enol tautomerism 1268jJ, 1295, 1296, (Sec. 13.3.4) Lone pair-lone pair repulsion 761,
1459 Levellingsolvents 1346, 1347fJ, 763
ry
Kieselguhr 1061 (Sec. 14.3.2) Lone pair moments 777jJ, 786jJ,
Kinetic factors 1704 Levitation effect 1223, 1231 (Sec. 10.5.3)
ra
Kinetic isotope effect 165, 256 Lewis acid and base property of the . Long form ofthe periodic .table 458
Koopman's theorem 1476 same substance 1410 Lorenz number 1114
Lothar Meyer's periodic laws 450
ib
Kossel's theory 543 Lewis concept 1386jJ, (Sec. 14.7)
Lewis dot structure 1581 Lotka-Volterra model 1780
L Lewis-Langmuir charge 709fJ, 713, Lowest unoccupied molecular orbital
yl
(Sec. 9.16.4) (LUMO) 580, 750-52, 973
L-S coupling 62 Luminescence 1709
Lewis-Langmuir concept 543
Lactams 1442
Lactones 1442
LFER. 1436
m Lummer-Pringsheim curve
Ligand group orbitals (LGOs) 620 see black body radiation
Lamellar compounds 888 Lux-Flood concept 1466ff
he
Light emitting diode (LED) 1192,
Lande g factor 79, 84, 1079 1204 Lyate 1348, 1468
Lande interval rule 69, 79 Light-emitting solids 1205 Lyman series 34
Lande splitting factor 1079
lc
Line spectra 111, 253 Lyonium 1348, 1468

Lande's method 983
Linear accelerator 397
Landolt reaction 1778 I~&MI
ea
Linear combination method 166

Langevin paramagnetism 1086,
Linear combination ofatomic J.1 (mu)-bond 1402
1151
orbitals (LCAD) 167,557 Macrocyclic crown ethers 1308
Lanthanide contraction 469jJ, 471,
th
Linear energy transfer (LET) 365 Macrocyclic effect 1305

477, 519, (Sec. 8.9)
Linear tree energy relationship (LFER) Macrocyclic systems 1301
Lanthanides 453, 454, 468
e/
1436 Macroscopic and microscopic

vs. actinides 468, (Sec. 8.8.3)
Linear sweep voltammetry (LSV) bodies 134
Lanthanoids 453,454 1743
t.m
Macroscopic particle 134

Lanthanum series 454 Linkage isomers 822, 824, 1480 Madelung
Lapis-Lazuli 1059 Liquid ammonia as a solvent 1558.0; constant 1005
Laplacian operator 145 (Sec. 15.4) energy 1004, 1006
Lariat crown ethers 1303 Liquid crystals 1095 interaction 776
Lannorfrequency 83 Liquid drop model 284, 409 Magic acid 1385, 1568
Larmor precession 55 Liquid hydrate 1280 Magic number 288,435
Laser 1040 Liquid hydrogen fJ~.oride as a solvent Magnetic bottle 429
Latimerdiagram 1647, (Sec. 16.8.1) 1563 Magnetic domains 1083
Latimer equation 1327 Liquid hydrogen cyanide as a Magnetic materials 1076jf, (Sec.
Lattice energy 997, 1003jJ, 1011ff solvent 1564, 1565 11.16)
Lattice planes 1027 Liquid Na-S battery 1234 Magnetic moment 79, 80, 217
Lattice-electron scattering 1121 Liquid sulfur dioxide as a solvent Magnetic properties 1076jJ
Law of equipartition of energy 113 1569 Magnetic quantum number of the
Law oftelluric screw 449 Lithium battery 1689 MOs 567
Law of triads 448 Lithium ion banery 1690 Magnetic susceptibility 80
Magnetisation 1084 Metal-olefin complexes 1402jJ triatomic molecules 620jJ

Magnus' green salt 1180 Metal-only clusters 1178 trigonal planar molecular species
Malathion 869 Metallic conduction 1136 654ff
Malleability and ductility 1111, in the monoxides 1211 Molecular polarity 777
1112 Metallic conductivity 1209 Molecular recognition 1285, 1298,
Man-made elements 401, 402, Metallic lustre 1110, 1114 1312, (Sec. 13.5.11)
(Secs. 7.10, 7.11) anion coordination 1312
Metallic orbitals 1154, 1155
Manxine 1443 anion receptors 1312
Metallophthalocyanins 1220
Markownikoff addition 923 cation receptors 13 12
Metastable isomer 250, 347
Mass action law 1183, 1196 linar anion recognition 13 12
ry
Metathion 869
Mass defect 275, 409 molecular chameleon 1313
Methane hydrates 1283
Mass spectrograph 9, 12, 14 spherical recognition 1312
Methyl orange 1382
ra
Mass spectrometer 15 tetrahedral recognition 13 13
Methyl red 1382
Mass-energyequivalance 133, 385 Molecular ribbon 1317
Methyl viologen 1714
Matter wave 133, 134 Molecular sieves I O~
ib
Mica' 1054
Mattheissen rule 1125 Molecular solution 1325
Micelles 1299, 1301 Molecular superconductors 1221
MaxBom 149
yl
Microscopic particle 134 Molecular switch 1318jf, (Sec.
Maximum suppressor on
polarograms 1741 Microstates 65, 66 13.5.17)
Migration current 1732
Maxwell-Boltzmann distribution
m
Miller indices (hkl) 1027, 1133
Molecular symmetry 931jf, (Sec.
10.14)
law 1183
Measurement of cell EMF 1597 Millikan's oil-drop method 4 symmetry operations 93 Iff
he
Mechanisms of nuclear reactions 393 Mirror nuclei 239, 239, 287 Molecular topologies 824.0: (Sec.
Meissner effect 1223 Mischmetal 454, 530 10.8)
Melamine (M) 1317 Mixed fluorides (ABF3 ) 1046 Monoisotopic elements 257,
lc
Melting and boiling points of Mixed metal oxides 1042.0; (Sec. 259, 269, 270
salts 795jJ 11.11 ) Montmorillonite 1055
ea
Melting and boiling points of Mobil process 1059 Morpholine 1439

alkanes 1289 Mobility of the defects 1068 Moseley's law 37ff
Melting point of dicarboxylic Moderator 366, 420 Mu (J.1) bonds 575
th
acids 1292 Modes of radioactive decay 271, Mulliken-Jaffe electronegativity 497

Mendeleev's periodic law 451jJ 322 Mulliken's electronegativity 495,
e/
Mendeleev's periodic table 455.ff Modifier 1093 1476

Mendeleev's short periodic Moh's scale 1013 Multiisotopic elements 269
t.m
table 451 Molar refractivity method 983 Multiple bonds 717jJ, 765
Mercaptan 1488 Molecular chameleon 1308 Multiplet structure 53, 72
Mercuric halide (HgX2) structure Molecular crystals 893 Multiplet width 79
1050 Multiplication factor 415, 419
Molecular inorganic superconductor
Mesogens 1095 1221 Muons 279
Mesomeric effect 784 Molecular metals 1220 Mutual polarisation 794, 821, 1297,
Meson exchange theory 280 1432, 1488, 1558, (Sees. 10.6, ,
Molecular orbital picture of higher
Meson particles 279 13.4.3)
boranes 912, (Secs. 9.21,
Mesons 279, 298 Myoglobin 1397, 1592
10.12)
Metal basicity 1408 Molecular orbital theory (MOT)
Metal clusters 1161jJ, (Sec. 12.8) 557fJ
N
Metal disulfides 1050 heteronuclear diatomic molecules n-type extrinsic semiconductors
Metal framework 1177, 1178 601fJ 1184
Metal-ammonia solution 1559.ff homonuclear: diatomic molecules n-type superconductors 1231
Metal-metal bonds 1161jJ, 1166, 578Jf Naked cluster ions 1178
1180 polyatomic'species 658jJ Natural fission reactor 423
Index 1-13
Natural gas hydrate 1282, 1283 Nonequivalent hybrid orbitals 670 Nuclear spin 74, 240, 292
Naughty element 525 Nonequivalent hybridisation 830 Nuclear spin isomerism .251
Neel temperature 1080 Non-Faradic current 1729, 1740 Nuclear spin quantum number (l)
Negative hyperconjugation 975, Nonstoichiometric compound 1048 241
1466 (Appendix lOA) Nonstoichiometric defects 1070, Nuclear stability 250,268,273,
Neptunium series 343; 1189 289, (Sec. 5.3)
Nemst e,quation 1598 Nonstoichiometric oxides 1211 Nuclear wave function 550
Neutrino 297 Nordheim rules 294 Nucleus 236jJ, (Sec. 5.1)
Neutron 16, 17 Normal Zeeman effect 82 density 239, 299
fast neutrons 17 Normalisation ,154, 533,.560 shape 240
ry
neutron stars 17 Normalisation condition 676 size 237
slow neutrons 17 Normalised and orthogonal wave stability 250, 268fJ, (Sec. 5.3)
ra
thermal neutrons 17 functions 150ff Nucleons 236
Neutron activation analysis 355 Normalising constants 150, 578 Nucleophilic attack 503
Nuclear binding energy (NBE) 275,
ib
Neutron emission 272 Nucleophilic substitution reactions
Neutron stars 17 409 861
Neutron to proton ratio 271, (Secs. Nuclear binding energy curve 276 Nucleophilicity 1409, 1436
yl
5.3.2-3) Nuclear configuration 292 Nucleophilicity vs. basicity 1436
Newlands' law of octaves 449 Nuclear density 239, 299
m Nucleosynthesis of elements 429,
Nickel arsenide (NiAs) structure Nuclear dimension 24 43 Off
1037 Nuclear ellipticity 241 Nuclides 249ff
Nickel storage cell 1688 Nuclear fission 277, 406jJ, (Secs.
he
Nickel-cadmium cell 1689 7.12, 7.13) o
Niels Bohr 25 Nuclear fQrces 278 Oblate ellipsoidal 241
lc
Nitrating mixture 1567 Nuclear fuels 406,416 Oblate spheroid 240

Nitroalkanes 1287 Nuclear fusion 277,424.0; (Sec. Octahedral and tetrahedral
7.14)
ea
Nitroprusside 1590 holes 1026

Nitrosation of amines 883 Nuclear g-factor 242 Octahedral metal cluster 1167,
Nitrous oxide 1587 Nuclear isomers 250 1169
th
NMR frequency 243 Nuclear magnetic moment 242 Octet rule 544
NMR shift reagents 529 Nuclear magnetic resonance (NMR) Odd (-) parity 294
241
e/
NMR spectra 245, 856 Odd electron bond 568, 724, 725
NO (nitric oxide) as a ligand 1591' Nucle"ar magneton 17, 78, 242 Odd electron molecules 725
Noble gas compounds 736 Nuclear model ofatom 21 (Sec. Odd-even rule for oxidation
t.m
Noble gas hydrates 1288 1.7) states 532

Noble gases 454 Nuclear models 282fJ, (Sec. 5.5) Oddo-Harkins rule 269, 434
Noble gases as Lewis bases 1410 Nuclear orbit 32 Oddo's rule 435
Noble liquid 522 Nuclear potential 281, 283 Ohmic potential 1606, 1693
Noble metals 1641 Nuclear potential barrier 281 Ohm's law 1121, 1122
Nodal points 199 Nuclear potential well 292 Okla mine 423
Nodal surface 206 Nuclear quadrupole moment 295 Okla phenomenon 423
Non-aufbau filling 1147 Nuclear radius 239 One dimensional (I D) molecular
Nonaqueous solvents 1555jJ, (Ch. Nuclear reactions 366, 386ff metal 1215, 1216
15) mechanism 393jJ, (Sec. 7.8) One dimensional lattices 1050
I:Jonaufbau filling ofad-band 1147 Nuclear reaction cross-section 392, One dimensional solids 1214 I
Noncomplementary redox rea~tion (Sec. 7.7) Onium salt 1389

1595 Nuclear reactor 418, 420jJ Open circuit potential (OCP) 1686
Noncoordinating solvents 1574 Nuclear reactor accidents 423 Open-book configuration
Noncrossing rule 577, 589 Nuclear shell model 288 (H20 2 ) 789
Oppenheimer-Phillips mechanism Oxygen balance 1775 Pauli force 217, 219, 970 .
390,396 Oxygen carrier 1396 Pauli magnetism 1086
Optical activity 960 Oxygen overvoltage 1699 Pauli paramagnetism 1086,"', 129,
asymmetric 960 Oxygen scavanger 1324 1151
dissymetric 960 Oxygen valency 453 Pauli repulsive force 970
Optical electronegativity 506 Oxyhalides as solvents 1571 Pauling equation and % ionic
Optical model 295 Ozone 1587 character 775
Optical properties of solids 1151, Pauling relationship (bond
1190
In & P I length) 770
ry
Orbital electron capture 322 Pauling-Allred-Rochow con~ept 499
Orbital electronegativity 495 Jr-n Junctions (Diodes) 1194 Pauling-Pearson paradox 1488,
Orbital energies 88, 93 7t-acid ligands 1388, 1394, 1402 1489
ra
Orbital magnetic moment 75 p-block elements 465 Pauling's crystal radii 985
Orbital multiplicity 68 7t-bonding 802jJ, (Sec. 10.7) Pauling's electronegativity 491,
ib
Orbital or K-electron capture 273 p-contraction 519 1432
Orbital penetration 221 p-n-p and n-p-n junction Pauling's electroneutrality
transistors 1202 principle 711
yl
Orbital shapes 200, 205
Orbital symmetry rule 599 p-n junction 1195 Pauling's empirical rule (acid
Orbitals 185jJ, (Sec. 4.1) p-process 433 strength) 1424
Orbits vs. orbitals 211
m
p-type extrinsic semiconductors Pauling's ionic radii 987
Organic ionic liquids 1574 1187 Pauling's univalent radii 984
he
Organic metals 1220, 1394 p-type semiconductors 1074, pE 1598, 1599
1075 Pearson's equation 1490
Organic semiconductors 1217, 1218
p-type superconductors 123 1 Peierls distortion 1180, 1214, 1221
Organic superconductors 1217,
lc
1219,1221,1229,1394 P. Ray 351,851-52 theorem 1215

Organometallic compounds 857 Packing fraction 273-275 Pendantarm 1303
ea
Organometallic hydrides 1345 Pair fonnation 126, 296, 314, 366 Penetrating power 198, 222, 485
Organophosphorus insecticides 869 Parabolic curves 10 Penetrating power of the orbit 49·
malathion 869 Parallel paths of decay 330 Per cent ionic character 774
th
Ortbital symmetry rule 748 Parallel plate ionisation chamber 315 Perching complexes 1306
Ortho- and para-hydrogen 251 Paraquat 1316 Perdisulfate 1587
e/
Orthogonality 154 Parathion 869 Perihelion position 48

Orthogonality condiiion 676 Parity 292, 342 Periodic table 451fJ
t.m
Oscillating reactions 1777, Parity of nuclides 293 Periods 452

(Appendix 168) Partial ionic character 774 Pennitivity 1556
Overall stability constant 1389 Participation of d-orbitals 684, 867 Perovskite structure (CoTi03 ) 1040,
Overlap integrals 553, 559, 568, 761 Particle accelerators 397fJ, (Sec. 1045, 1047, 1229
Overpotential 1695, 1705 " 7.9) Peter equation 770
Oxidation number 713, 1578, 1593 Particle in a box 144, 160, 161, Pfund series 34
Oxidation states 530, 1579 1116, (Sec. 3.5) pH scale 1353, 1469, 1562
Oxidative addition 882, 1389, Particle in a one dimensional box 151, pH values (calculation) 1353fJ,
1407, 1594 (Sec. 3.5.2) (Sec. 14.3.6)
Oxidative halogenation 1002 Paschen series 34 Phase diagram of Cu-Zn system
Oxidisability of metals 1639, 1640 Paschen-Back effect 85 1159
Oxidising oxyanions 1707 Passivity 1693 Phase transfer catalyst (PTe) 1309
Oxo acids 1429 Pattenkofer's rule of integral Phase transition 1333
Oxyacids 1423 multiple 449 Phenolphthalein 1381
Oxyacids for phosphorous 1426 Pauli exclusion principle 53, 57, Phi (+)bonds 575
Oxyanions 1642, 1708 86,217,219,555 Phonons 1124,1227
Index 1-15
Phosphazenes 815fJ, ·818 Polar diagrams 205 Powerful oxidising agents 1604
Phosphazene bases 1465 Polar graphs. 137-138 Powerful reducing agent 1605
Phosphazene molecule 703 Polarisability 499, 1290, 1291, Primary cells 1686, 1687, (Sec.
Phosphinic acid 707, 1425, 1583 1420 16.14.2)
Phosphonic acid 707, 808, 1425 Polarisation 836, 1698 Primary isotope effect 257
Phosphorescence 1708 Polarisation and covalency 791fJ Primary oxides 1643
Phosphors 1205 Polarisation ofcentral atom 841 Primary process 316
Photocatalyst 1213,1715, (Sec. Polarisation of ions 791ff Primary radiolytic products
16.16.3) Polarographic method of analysis (prp) 365, 370
1728~ (Sec. 16.22.1) Primordial element 430
ry
Photochemical reactions 1708,
(Sec. 16.16) Polaron 1222 Principal (P) series 74
Photochemical redox decomposition Poly acids 1061 Principle of conservation of
ra
1769 Polyacetylene 1217 energy 122
Photochemical reduction of Polyatomic species 658 Principle of electroneutrality 821
Polyazacryptands 1310 Principle of relativity 122
ib
dintrogen 1717
Photochemical splitting of water Polyazamacrocycles 1310 Probability density 189
1711 PoIyborates 812 Prolate ellipsoidal 241
yl
Photochemical yield 364 Polyhedral frameworks of ice 1280 Prolate spheroid 240
Photoconductivity 1072, 1206 Polyhedral skeletal electron pair
m Prompt neutrons 408, 420
Photocopying process 1208 theory (PSEPT) 903jJ, 1171, Prompt reactions 1709, 1711
Photodiode 1206-1207 (Secs. 10.12.4, 10.12.7, Propellants 1773
12.8.5~) Prophyllite 1054
he
Photodissociation 431
Polymeric structure 796 Proportional counter 316
Photoelectric effect 118, 313, 366,
Polymerisation of oxyanions 812 Protolysis 876, 877
1114, (Sec. 2.4)
Polymetallic ring 1324
lc
Photographic processes 619 Proton affinity 486, 998, 1348,

Polymorphs 1037 1419
Photography 1718
Polynuclear metal c8[bonyls 859 Proton emission 273
ea
Photoinduced electron transfer

Polyphosphazene skeleton 817 Proton in water 1369
(PET) 1318
Polyphosphoric acid 1426fJ Proton magnetic resonance
Photonuclear reactions 387
(PMR) 249
th
Polythiazyl (SN)x 1216

Photosensitivity 617, 619
Polythionates 1586 Proton reservoir 1370
Photovoltaic effect 1207
Polytopal isomerism 857 Proton reservoir concept 1371
e/
Pi-acid ligands 819

Polytopal rearr~geme!lt 853 Proton sponge 1370, 1445-1447
Piezoelectric materials 1056, 1088,
Porterfield equation 770 Proton transfer equilibrium 1353
1090ff
t.m
Position of hydrogen 524 Proton transport process 1369

~iezoelectric property 1056
Positive rays 8 Proton-proton cycle 427
Pions 279
Positron emission 272 Protonic concept (acid-base) 1344.ff
Piperazine 1439 Prototropic tautomerism 707jJ,
Post-precipitation 1506
Piperidine 1439 I 268ff, 1427
Postactinides 462ff
Planck's equation 116 . Prout's hypotnesis 257
Postlanthanides 471
Planck's quantum theory 114 Prussian blue 1581
Potassium tetracyanoplatinate (KCP)
Plasma state 426, 428 1180,1214 PSEPT 903jf, 1175, (Secs.
Plastic deformation· 1125 Potential energy curve 754, 1254 10.12.4, 10.12.7, 12.8.5~)
Plasticisers 1094 Potential-pH (E-pH) diagram 1655 Pseudo noble gas configuration 981
Platinum metals 452, 455 Potentiometric titrations. 1680, Pseudo-noble gas type cations
Plum-pudding model ofatom 20 (Sec. 16.13) 794,981
Point defects 1064 Pourbiaxdiagram 1646,1655, (Sec. Puckered ring 818
Point groups 931jf, 946, (Sec. 16.8.3) Pulsars 17
10.14) of iron 1656ff Purple benzene 1310
identification 946 ofmanganese 1660 Push-pull mechanism 876ff
Pyramidalisation 972, (Appendix Radioactive decay 322, (Sec. 6.6) Reductive dehalogenation 1002
lOA) Radioactive decay kinetics 327, Reductive elimination 808, 1003,
ryridine 1463 (Sec. 6.9) 1594
Pyrite 1050 Radioactive emanations 310, 3 14 Reference electrode 1597
Pyrophyllite 1055 Radioactiveequilibrium 332,335, Refractory metals 1181
Pyroxene 1053 (Sec. 6.10) Relative atomic mass (RAM) 258
Pyrrole 784, 1463 Radioactive isotopes (applications) Relative cosmic abundance 433
347ff, (Sec. 6.17) Relativistic contraction 136, ~20
Q Radioactivity 309jf, (Ch. 6) Relativistic correction 4, 48, 213
Radioactivity in age determination Relativistic effects 464, 470, 517,
ry
Quadruple bonding 720jf, 1164,
361 520jf, 980
(Secs. 9.6,9.19, 12.8)
Radioactivity in agriculture 358 Relativistic expansion 225, 226,
Quadruple interaction 766" 1163
ra
Radioactivity in industry 360 517,520
Quadrupole moment 240, 241 Relativistic kinetic energy 136, 144
Radioactivity in the medical
Quantum defect 19, 50,.221
ib
field 359 Relativistic wave mechanics 191
Quantum numbers 54, 188, 213, Relaxation energy 753, 756, 759,
Radiocarbon dating 362
(Secs. 1.10.3, 4.1.2, 4.1.11) 761
Radioimmunoassay (RIA) 360
yl
Quantum restrictions 45 REM (Rontgen equivalent ~anl 167
Radiolysis of water 369ff
Quantum theory 43: 1~ 1, (Ch. 2) Representative elements 466, 476
Radiopharmaceuticals 359
Quantum yield 1771 '
Quark particles 18, 299
m
Radioscintigraphic agents 359 Reproduction factor (K) 415
Radius ratio rule I 014.tJ: (Sec. 11.8) Repulsive intennolecular
Quenching agent 1713,1715 forces 1294
he
Randles-Sevcik equation 1748
Quinonoid form 1381 Resonance 705, 713, 714, 716,
Raoult's law 1259
Quintuple (5 bonds) bonds 720 1451, 1457
Rare earths 453
Quinuclidine 1439, 1444 Resonance and exchange
lc
Raschig synthesis of hydrazine 881

phenomenon 161
I R
Ray-Dutt twist 851, 852
Resonance caputre 393
ea
Rayleigh-Jeans Law 113

r-process 432 Resonance effect (R) 779
RBE (relative biological
Rabi magneton 78, 242 Resonanceenergy 705,706lr
effectiveness) 367
th
Racemisation 809, 849,866, Resonance integral 166, 559, 564,

RDF 192, 196ff, (Sec. 4.1.4)
876, 884· 568
RDF curves 197, 225
Rad (R) 367 Resonance potential (RP) 35,40
e/
RDX (cyclonite) 1727

Radial distribution function Resonating structure 911
(R1)F) 194, 196,225,475, Reaction quotient 1600 Retrobonding 612, 820
t.m
(Sec. 4.1.4) Reactor shield 422 Reverse biased junction 1197

Radial equation '187 Real angular wave functions 205 Rhenium trioxide (Re03)
Radial nodal points 193 R~ceptors (molecular recognition) stru~ture 1040
Radial nodes 197, 211 1298, 1302jf Rhombic twist 851
Radial probability density 193, Recoil energy 267 Ring compounds 815
194 Recoil nuclide 267 Ring whizzer system 858
Radial probability distribution 192 Recovery factor 1533 Ritz combination principle 19, 50
Radial wave function 192, 193 Rectifier 1201, 1204 Rocket fuel 1775
Radiation chemistry 363ff, (Sec. Rectifier equation 1198 Rocking chair model 1690
6.18) Red giant stars 426,430 Rontgen (R) 367
Radiation dosimetry 367ff Red shift 162, 1274 Room-temperature ionic liquid
Radiation emission 323 Redox indicator 1677, (Sec. 16.12) (RTIL) 1573ff
Radiation hazard 428 Redox stability field of water 1655 Rosette 48
Radiative capture 387 Redox stability of water 1645 Rotational energy level 253
Radical stabilisation energy Redox titration 1672, (Sec. 16.11) Rotational lines 253
(RSE) 972, (Appendix lOA) Reduced mass 32, 185, 265 Rotational spectra 254
Index 1-17
Rotaxanes 1320 Secondary periodicity 517jf, 532, Simultaneous deposition of copper
Ruby 1040 773, 1642 and zinc 1636
Ruby red colour 1046 Secular determinant 559 Singlet linkage bond 544
18e Rule 1175 Secular equations 167, 559 Singly occupied molecular
Rule of duplet 544 Secular equilibrium 268, 334, 335 orbital (SOMO) 580, 749,
Rule ofeight 543 Secular or permanent equilibrium 973
Rule of maximum spin multiplicity 333 Size ofthe nucleus 237
94 Segre chart 271 Skeletal electron pairs 900, 914
Rule ofOddo 270, 271, 275 Selection rules 70 Skeletal pairs 900
ry
Russel-Saunders states 67 Self-association 1275 Slater orbitals 221
Russel-Saunders terms 65 Self-consistent field (SCF) 220 Slater's rules 36,37,222,471,474,
Russell-Saunders coupling 58 Semi-empirical mass equation 286 500, 984, (Sec. 4.2.4)
ra
Rutherford (Rd) 21, 321 Semiconductor conductivity 1189, Slip direction 1112
Rutherford's model 23 1209 Slip forces 1112
ib
Rutile (Ti02) structure 1039 Semiconductor materials 1193 Slip plane 1113
Rydberg 30 Semiconductors 1135, 1181jJ, Slip system 1113
yl
(Sec. 12.9) Slow neutrons 17
Rydberg constant (R) 19, 28, 30
Rydberg formula 18 Semimetals 1136 Smith acidity functions 1467, 1537
Soccerball cryptand 1307, 1308
m
Semitopological representation 909
s Separation factor 261 Soda glass 1093
Soda lime glass 1056
Separation of Cu 2+and cJ2+ 150 I
he
s-block elements 464 Sodalitecage 1057
Separation of isotopes 260
s-process 432 Soddy-Fajan group displacement
Separation of lanthanides 473
Sacrifical anodes 1693 324jf, (Sec. 6.8)
lc
Serpentine 1054
Salt effect 1497 So~ide 1309, 1560
Shannon's crystal radii 988
Salting in 1498 Sodium D-Iine 53, 74
Shape ofthe nucleus 240
ea
Salting out 1499 Sodium nitropruside 1590

, Sharp (S) series 74
Salting-out term 1499 Sodium-sulfur battery 1234
Sheet structure 1264
Sanderson's electronegativity 501 Soft-soft adduct 794
th
Sargent's curve 341 Shell closure effects 411

Soft-soft interaction 794, 821,
Scandide contraction 469, 475, Shielding 221
1488, 1626, 1636
e/
477,519 Shielding constant 37, 222, 245, Softness parameter 1477

Schmidt limit 242, 243 248
Solar cell 1207
Shielding effect 35
t.m
Schomaker-Stevenson equation Solid acids 1492.ff

768jf, 770 Shielding power of the orbits 49
Solid electrolyte 1213, 1232.tJ,
Schottky defects. 1064jJ Short range repulsive force 992 (Sec. 12.14)
SchrOdinger angular wave Siderophiles 466, 1486 Solid gas hydrates 1284
functions 202 Sidgwick-Powell theory 825 Solid surface acids 1493
SchrOdinger's wave equation 145, Sidgwick's rule ofmaximum Solubility 797
147, 150, (Secs. 3.4,3.5) covalency 545 Solubility product 1494jf; 1496,
Schwesinger phosphazenes 1464 Siemens 1123 1499
Scrambling ofthe bridging and Silanol groups 1060 Solvation effects 1449.ff
terminal carbonyls 859 Silenes 803, 1405 Solvay process 1265
Screening effect 221 Silica gel 1060, 1494 Solvent cavity 1559
Screening power ofthe orbits 49 Silica surface 1493 Solvent extraction 1272
Sea of instability 289' .Silicates I051jJ, (Sec. 11.14) Solvent system definition 1468jf,
Secondary cells 1686, 1687, (Sec. Silicones 802, 1108, 1051 (Sec.14.tl)
16.14.2) Siloxane bonds 1060 Solvolysis 861
Secondary isotope effect 257 Simple cubic (sc) unit cell 1025 Solvolysis reactions 1562
Sommerfeld's atomic model 45, Stabilisation of unusual oxidation Stopping potential 119
(Sec. 1.9) states 1486 Storage cell 1688
Sommerfeld's free electron Stability constants 1389.0: 1629, Strength of acids and bases 1414jJ,
model 1115, 1120lr 1738 (Sec. 14.8)
Sommerfeld's orbits 47 Stability field of water 1645, 1646, Strength of hydracids 1414ff
Sommerfeld's quantum mechanical 1655, 1660 Strength oforganic carboxylic
free electron theory 1115lr Stability island 289,464 acids 1417ff
SOMa 580, 749, 973 Stability of the isotopes 259 Strength ofoxyacids 1423ff
Space charge region 1195 Stability ratio. 501 Stripping 389
ry
Space quantisation 81, 241 Stacking fault· 1034 Stripping reactions 387ff
Spallation 388, 389 Stacking interaction 1298, 13 16 Structure breaking 1328
Spallation reactions 434 Staggered fonn 789 Structure making 1328
ra
Spatial quantisation 53, 65 Standard electrode potential 1598 Structure of ionic crystals 1035jJ,
Specific heat capacity 1126 Standard hydrogen electrode 1596 (Sec. 11.10)
ib
Specific heat of metals 1127 Standard reduction Rotentials 1603 Structure of liquids 1094
Spectral lines 34 (T) say numbers 907ff
yl
Spectral selection rule 217 Standing sine wave 139, 146 Subatomic particle 134
Spectral series of alkali metals 51 Standing wave 139,146 Subcritical size 415
Spectral transitions 72 Stark effect 45, 85
Spectroscopic electronegativity 507
m
Stationary electrode 1729
Subgroups 452
Subhalogen 525ff, 5~7
Spent fuel 423 Stationary orbit 140 Substitutional alloys 1157
he
Sphalerite 885, 1036 Stationary state 25 Subvalent compounds 545
Spherand 1301, (Sec. 13.5.6) Statistical concept.... 1428 Sugden's view 544
Spherical coordinates 186
lc
Stefan-Boltzmann law 113, 116 Sulfation of battery 1688

Spherical harmonics 200, 201, 204 Stellar energy 426 Sulfuric acid as a solvent 1567
Spherical nodal surface 210 Stellarater 429
ea
Superacids 1382jJ, 1384, 1564,

Spherical recognition .1304, 1305, Stepwise stability constants 1389 1568jJ, (Sees. 14.6, 15.9)
1307 Stereochemical nonrigidity 845 Superactinides 462ff
th
Spherical recognition ofmetal Stere~hemically active and inactive Superatoms 505

ions 1301 lone pairs 689,842,844 Superbases 1446, 1464
Spin 342
e/
Stereochemically active lone Superconducting electrons 1226

Spin angular moment 217 pairs 842 Superconducting gap 1225
Spin exchange force 281 Stereochemically inactive lone
t.m
Superconducting materials 1228

Spin magnetic moment 77 pair 689 Superconductivity 1047, 1222fJ,
Spin multiplicity 58, 68 Stereochemically nonrigid (Sec. 12.13)
Spin quantum number 191 molecules 845,853 Superconductors 1048.0: 1228ff
Spin-orbit coupling 291, ~24 Stereochemistry 767 Supercritical mass 417
Spin-orbit coupling constant 69 Stereoselective reactions 925 Supercritical size 415, 417
Spin-spin coupling 247 Steric factors 1444ff Superexchange mechanism 1080,
Spin-spin coupling constant 247 B-strain 1444 1162
Spinel and inverse spinel F-strain 1444 Superhalogen 525, 526
structure 1042lr Stem-Gerlach experiment 81 Superheavy elements (SHE) 289,
Spinning electron 53 Stirling's approximation 1066 405, 462jJ, 464, 524
Spontaneous fission 413 Stoichiometric (Le. intrinsic) Superlattice 1157
Spurs 365 defects 1064 Supernova explosion 403,433
Squids 1232 Stoichiometric standard Supramolecular interaction 522,
Stabilisation of low oxidation potential 1598 1285, 1298.0: (Sec. 13.5)
states 819 Stoke's law 5 Supramolecular polymer 1317
Index 1-19
Supramolecular systems 1298jJ, Tetracyanoethylene (Icne) 1392 Triads of Dobereiner - 448

(Sec. 13.5) Tetrahedral (Td) hole 1026 Trial wave function 166
Surface acids 1492fJ, (Sec. 14.16) Tetrahedral recognition 1308, 1313 Triatomic molecules (MOT) 620jJ
Symbiosis 1479jJ Tetramethylsilane 249 Tridymite (Si02 ) structure 1039
Symbiotic effect 1475 Tetrasulphur tetraimide 818 Triflic acid 1383, 1385
Symbiotic theory 1282, 1480 Tetrathiazyl tetrafluoride 818 Trigonal twist 851
Symmetric fission 412 Tetrathionate 1586 Triiodide 1587
Symmetric or even functions 156 Thermal conduction 1128 Trinuclear clusters 1166
Symmetrical and unsymmetrical Thermal diffusion method 263 Triplet and singlet oxygen
hydrogen bonding 1253 Thermal stability of the carbonates, molecules 583
ry
Symmetrical molecules 780 sulfates 800 Trisilylamine 1456
Symmetry allowed reaction 751 Thermal stability of the hydrides Trithionate 1586
ra
Symmetry elements 931jJ, (Sec. 763 Tropone 1461
10.14) Thermionic emission 1110, 1114 ITF 1219
Symmetry elements in the cubic Thermistor 1190, 1206 Tungsten bronze 1213
ib
system 1025 Thermochemical radii Tunnelling effect 164, 282, 340,
Symmetry elements in the Yatsimirskii's 988 413,861
yl
. MOs 571 Thermochemistry 757 Tunnelling of Copper pairs 1232
Symmetry forbidden reactions 751 Thermonuclear reactions 389, 424 Turnstile rotation 849, 850
Symmetry interaction 589, 594
Symmetry ~umber 961
m
Thiazyl trifluoride 819, 1584
Thiosulfate 349-50, 1585
Twisting mechanism 851.ff, (Sec.
10.9.3)
Symmetry of the orbitals 207, 211 Thixotropic properties 1056 Ray-Dutt twist 851
he
Symmetry operations 931 Thomson's mass spectrograph 9 Rhombic twist 851
Symmetry-adapted linear Thomson's method 2 Two dimensional lattices 1049
combinations (SALCs) 620 Thomson's parabola method 9 Two fluid model 1225
lc
Symmetry-adapted orbitals 620 Thorium series 343

~nchrocyclotron 400 Three centre bonding 667fJ, (Sec. u
ea
Synergistic action 819ff, (Sec. 9.12.12) Uhlenbeck and Goudsmit 53

10.7.8) Threshold frequency 118, 120 Ultimate acids and bases 1472
Synergistic polarisation 794 TIP 1086,1129,1151
th
Ultramarines 1059
Synthetic natural gas (SNG) 1722 TMTSF 1219 Ultraviolet catastrophe 114
Szi lard-ehalmers' process 266 Tokomak 429 Ultraviolet photoelectron
e/
Tolman cone angle 1405jJ spectroscopy (UV-PES) 614jJ

T Topology of boron hydrid~s 907 Uncertainty principle 140, 141,
t.m
Tafel equation 1647. 1705. 1706 Tracer technique 349 143,144,154,157,163,280,

Talc 1054 Trans-effect 821 854, (Sec. 3.3)
TAsa 620jJ Trans-influence 821 Unified atomic mass unit scale 259
Tautomeric forms I 268fJ, 1459, Transactinides 404, 462 Unit cell 1024
1585 Transient radioactive J United atom method 557, 576
Tautomerism 707jJ, 808, 868, equilibrium 268,333, 334 Units of radioactivity 320
I268b: 1427.1585 Transistors 1202-1204 Unsaturated hydrocarbon 719
TCNQ 1219 Transition elements 452 Uphill migration 1195, 1197
Technetium (Tc) 401 Transition state 863 Uranium series 344
Telnperature Independent Paramagne- Transition state theory 164 Urea crystal 1283
tism (TIP) 1086, 1129, 1151 Translawrencium elements 402, Usanovich concept 1472
Langevin paramagnetism 1151 404, 452, 454, 462, 464 Uses of isotopes 260, 347jJ, (Sec.
Pauli paramagnetism 1151 Transmission coefficient 861 6.17)
Term symbols 66 Transmutations 383ff UV photoelectron
Terminal atom symmetry orbitals Transuranic elements 402, 454 spectroscopy 60 Iff, 615fJ
(TASOs) 620!f Triad elements 452 UVPES 60 Iff, 615ff, 617
v Wade's rule 900, 903jJ, (Sees.

10.12.4, 10.12.7, 12.8.5~)
x
Valence bond approach ofmetallic Walsh diagram 631ff x-process 434
bonding 1154, (Sec. 12.6) Walsh's rules 629ff, 630, 842 X-ray (generation) 37, 273, 323,
Valence bond theory (VBT) 55 Iff Warm superconductors 1229 366
Valence shell electron pair repulsion Water gas reaction 1722 X-ray photoelectron spectroscopy
(VSEPR) theory 825fJ, 970, Water gas shift reaction, (XPS) 617
(Sec. 10.8.3) WGSR 1722 Xenon fluorides 735ff, 844fJ, 972,
Valency 542ff Water of constitution 1261 1410, 1467
secondary or residual or auxiliary Water of crystallisation 1261 Xenon hexafluoride (XeF6 ) 844ff
ry
valency 542 Watson-Crick base pairing 1265 Xerox 1208
Val inomycin 13 10 Wave function 145, 149 y
ra
van der Waals forces 1285fJ, 1293, orbital 185fJ, (Sec. 4.1)
(Sec. 13.3) Wave mechanical model 185ff Yatsimirskii's thermochemical
van der Waals radii 765 radii 987
ib
Wave mechanics 133, (Ch. 3)
Variation method 166, 559, Wave number 27, 1115 Ylids 810
(Appendix 3A)
Wave-particle dualism 133ff, 177
yl
Vaska'scomplex I 397fJ, 1404,
Weiss constant 1086 . z
1407,1591,1592, 1594
Weiss indices 1027 Zeeman effect 45, 53, 82
Vector model of the atom 52, (Sec.
1.10)
m
Weston cadmium cell 1598 Zeise's salt 1394, 1402jJ
White dwarf 431 Zener break-down- 1202
. Pauli exclusion principle 52
he
Wiedemann-Franz law and Lorenz Zener diode 1201, 1204
Verkade base 1464
number 1127 Zeolites 1057ff, 1493
Vermiculite 1055
Wiedemann-Franz's law 1110, Zero-point energy 153, 147, 159,
Vi brational spectra 254
lc
1114 161,163,255,256,265,854
Vibrational wave numbers 256 Wien's equation 117 Zimmermann-Reinhardt (Z-R)
Vinyl chloride 784 Wien'sLaw 113,117
ea
solution 1643, (Sec. 16.6)

Viscosity 1259 Wilson cloud chamber 319 Zinc blende 885, 1036
Vitamin A 162, 163 Wittig reaction 600, 752, 810 Zintle anions 1561, 1563
th
VSEPR theory 683, 694, 825fJ, Woodward-Hoffmann orbital Zintle cluster ions 904, 1178jJ
970, (Sec. 10.8.3) symmetry rule 748fJ, Zintle phase 1161
(Appendix 9A) Zone theory of metallic bonding
e/
w Work function 120 1131ff

Wade-Mingos Lahure rules Wurtzite 1037 ZSM-5 1059
t.m
see Wade's rule Wurtzite structure 885 Zwitterionic forms 1360, 1365
t.m
e/
th
ea
lc
he
m
yl
ib
ra
ry

Asim Kumar Das - Fundamentals of Inorganic Chemistry - Volume 2

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, CBS 'Publishers & Distributors Pvt Ltd

Published by Satish Kumar Jain and produced by Varun Jain for

Ph: +91-484-4059061-65; Fax: +91-484-4059065; E-mail: kochi@cbspd.com

appear in the next volumes and the process is in progress.

garland to worship the goddess of learning.

9. Introduction to Chemical Bonding and Theories of Covalence:

Valence Bond Theory (VBT) and Molecular Orbital Theory

9.1 Historical Background 542

Development of the Concept of Valency; Lewis-Langmuir Concept; The Octet Rule;

Maximum Covalency; Hypervalence and Hypercarbon Compounds; The Main Types of

Basic Concepts of Group Orbitals; Delocalised and Localised Molecular Orbitals;

Triatomic Nonhydrides (XY2)-Linear Species Having 16 Valence Electrons; Molecular

Concept of Resonance in VBT; Resonance Energy; Conditions for Effective Canonical

10. Covalent Compounds: Characteristics, Structure and

10.1 B~nd Energy 753

Different Factors Governing the Bond Energy

10.2 Covalent Bond Lengths and Covalent Radii 764

Observation; 19F-NMR Spectra and Fluxionality of PCI2F] .and CIF]; Examples of

10.10 Nucleophilic Substitution Reactions (e.g. Solvolysis) in Some Covalent Molecules of

Thermodynamic and Kinetic Aspects of Chemical Reactions; Reaction Pathways of

Representative Redox Reactions through Nucleophilic Substitution Reactions

Diamond Cubic (dc) Structure; Graphite Structure; Properties of Graphite; Lamellar or

10.14 Molecular Symmetry and Point Groups 931

11.4 Factors Affecting the Ionic Radii 989

Born-Haber Cycle in Ionic Bond Fonnation; Drawbacks in the Concept of Born-Haber

11.6 Applications of Born-Haber Cycle 997

11.10 Structures of Ionic Crystals 1035

11.16 Magnetic Materials : Magnetic Properties 1076

Magnetic Substances; Cooperative Magnetism - Aniferromagnetism, Canted Magnetism;

Dependence of Magnetic Susceptibility of Different Types of Magnetic Materials

Ferroelectric Materials; Piezoelectricity and Piezoelectric Materials

11.19 Glasses and Glass Transition 1092

1. Classical and Vector Models of Atoms 1-110

Rutherford's Nuclear Model of Atom; Rutherford's Theory of a-Particle Scattering;

1.8 Bohr's .Atomic Model for the Hydrogen-like Systems 25

2.4 The Photoelectric Effect 118

Function and Ionisation Potential

Theoretical Background of Compton Effect; Compton Shifts at Different Cases;

2.6 Pair Formation 126

3. Fundamentals of Wave· Mechanics 133-184

Symmetry ofthe Orbitals; Concept of Atomic Orbitals in Wave Mechanics in Relation

4.2 Wave Mechanical Model for Polyelectronic Systems 219

5. Atomic Nucleus and its Structure 236-308

6. Radioactivity and Radiation Chemistry 309-382

6.1 Discovery of Natural Radioactivity 309

6.2 Types of Radioactive Emanations 310

6.4 Detection and Measurement of Radioactivity 315

6.13 Some Important Aspects of Beta Decay 340

7.1 Artificial Transmutations and Nuclear Reactions 383

7.3 Nuclea"r Reactions Versus Chemical Reactions 385

7.5 Conservation Laws in Nuclear Reactions 390

Momentum; Conservation of Neutrons and Protons

7.6 Threshold Energy of a Projectile for a Nuclear Reaction 392

7.13 Fission Chain Reaction: A Source of Atomic Energy 415

8. Periodic Table and Periodic Trends of Different

-Law of Triads; Pattenkofer's Rule of Integral Multiple; Chancourtois Law of Telluric

8.2 Mendeleev's Periodic Law and Periodic Table 451

8.3 Characteristics and Usefulness of the Mendeleev's Periodic Table 455

the Missing Elements

8.4 Defects in the Mendeleev's Periodic Table . 456

8.9 Lanthanide and Actinide Contractions (i.e. I-Contractions) 469

Electronegativities (Mulliken-Jaffe electronegativity); Allred-Rochow's Electronegativity:

Concept of Electronegativity Equalization; Electronegativity Not an Inherent Property of