third edition inorganic chemistry

Fundamental Concepts of

Inorganic Chemistry

Volume 1Third Edition Volume

1

Fundamental Concepts of Inorganic Chem

istry

4819/XI, Prahlad Street, 24 Ansari Road, Daryaganj, New Delhi 110 002, IndiaE-mail: [email protected], [email protected]; Website: www.cbspd.comNew Delhi | Bengaluru | Chennai | Kochi | Kolkata | Mumbai

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ISBN: 978-93-89565-97-3 Das

ThirdEdition

Volume 2: Bonding Theories (VBT and MOT) of Covalency; Structure and Reactivity of Covalent Compounds; Stereochemical Nonrigidity and Fluxionality; Molecular Symmetry and Point Groups; Hydrogen Bonding and other Weak Chemical Forces; Supramolecular Systems and Molecular Recognitions.

Volume 3B: Nonaqueous Solvents and Ionic Liquids; Redox Potentials, Formal Potentials and Applications; EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating Reactions; Principles of Metallurgy and Refining and Purification of Metals; Different Techniques of Separation—Solvent Extraction, Ion Exchange and Chromatography.

Volume 5: Coordination Chemistry: Inorganic Reaction Mechanisms (Ligand Substitution, Isomerisation, Racemisation, Electron Transfer and Photochemical Reactions), Electronic Spectra of Metal Complexes.

Volume 1: Atomic Structure; Wave Mechanics and Quantum Chemistry; Nuclear Structure; Nuclear Chemistry; Nuclear Reactions and Nuclear Energy; Radiation Chemistry; Nucleosynthesis of Elements; Chemical Periodicity of the Elements.

Volume 7: Application of Metal Complexes in Analytical Chemistry and other Fields; Applications of Spectrophotometric Methods (IR, Raman, NMR, ESR, Mossbauer, UV-VIS, UV-PES); Theory of Errors and Statistical Treatment of Data.

Volume 3A: Solid State Chemistry—Structure and Bonding; Magnetic and Ferroelectric Materials; Bonding in Metals and Metal Clusters; PSPT—Wade's Rule and Jemmi's Rule; Electrical Conductivities of Solids; Semiconductors and Superconductors; Acids and Bases and Ionic Equilibria.

Volume 6: Coordination Chemistry: Magnetochemistry and Magnetic Properties of Metal Complexes; Structure, Bonding and Reactivities of Organometallics including Metal Carbonyls and Nitrosyls; Organometallics as Catalysts.

Volume 4: Coordination Chemistry: Introduction, Structure, Stereochemistry and Isomerism, Nomenclature, Bonding Theories (VBT, CFT, LFT and MOT), Applications of CFT, JT Distortion, Spectrochemical Series, and Stabilities of Metal Complexes.

Asim K Das BSc (1st Class 1st, CU), MSc (Gold Medalist, CU), PhD (CU), DSc (Visva Bharati)is currently Professor, Department of Chemistry, Visva Bharati University, Santiniketan, West Bengal. He has over 30 years of teaching experience at both undergraduate and postgraduate levels. He passed both BSc (Hons in Chemistry) in 1981 and MSc (specialization in Inorganic Chemistry) in 1983, standing First Class First, from the University of Calcutta. He received his PhD degree from the same university under the supervision of Prof D Banerjea, the then Sir Rashbehari Ghose Professor of Chemistry. He received his DSc degree from Visva Bharati in 2002. Dr Das has published more than 80 research papers in the field of thermodynamic and kinetic aspects of metal complexes in reputed national and international journals. He has written the books, Bioinorganic Chemistry; Environmental Chemistry with Green Chemistry; Biophysical, Bioorganic and Bioinorganic Chemistry; An Introduction to Nanomaterials and Nanoscience and An Introduction to Supramolecular Chemistry.


InorganicChemistry

Third Edition

Volume I

Contents at a Glance

1. Classical and Vector Models of Atom

2. Origin of the Quantum Theory

3. Fundamentals of Wave Mechanics

4. Wave Mechanical Model of Atom

5. Atomic Nucleus and its Structure

6. Radioactivity and Radiation Chemistry

7. Nuclear Reaction

8. Periodic Table and Periodic Trends of Different Properties of Elements

Volume 1

9. Introduction to Chemical Bonding and Theories of Covalence—Valence Bond Theory

(VBT) and Molecular Orbital Theory (MOT)

10. Covalent Compounds—Characteristics, Structure and Reactivity

11. Hydrogen Bonding and other Weaker Chemical Forces Including Supramolecular Systems

Volume 2

15. Nonaqueous Solvents

16. Redox Systems and Electrode Potential—Application of Electrode Potential:

Electroanalytical Techniques

17. Metallurgy: Principles, Pyrometallurgy vs Hydrometallurgy—Extraction and Purification of

Metals, Physicochemical Methods of Separation of Metals

Volume 3B

12. Structure, Bonding and Properties of Ionic Solids and Solid State Chemistry

13. Bonding in Metals and Metal Clusters—Electrical Conductivities of Solids:

Semiconductors and Superconductors

14. Acids and Bases and Ionic Equilibria in Aqueous Solutions

Volume 3A

Appendices (common to all three volumes)

Appendix I: Units and Conversion FactorsAppendix II: Some Physical and Chemical ConstantsAppendix III: Wavelength and ColoursAppendix IV: Names, Symbols, Atomic Numbers and Atomic Weights of the ElementsAppendix V: Some Useful Mathematical Relationships


InorganicChemistry

Third Edition

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Volume I

Asim K. DasMSc (Gold Medalist, CU), PhD (CU), DSc (Visva Bharati)

Professor, Department of ChemistryVisva Bharati University, Santiniketan 731235

West Bengal, India

Mahua DasMSc (CU), PhD (Visva Bharati)

Formerly Research AssociateDepartment of Chemistry

Visva Bharati University, Santiniketan 731235

West Bengal, India

Ankita DasMSc (Visva Bharati)

ISBN: 978-93-89565-97-3

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Disclaimer

Science and technology are constantly changingfields. New research and experience broaden thescope of information and knowledge. The authorshave tried their best in giving information availableto them while preparing the material for this book.Although all efforts have been made to ensureoptimum accuracy of the material, yet it is quitepossible some errors might have been leftuncorrected. The publisher, the printer and theauthors will not be held responsible for anyinadvertent errors or inaccuracies.Fundamental Concepts of

InorganicChemistry

Third Edition

Volume I

to

my dear students and readers, the living source of inspiration

and

the memory of my mother

Maharani Das

who struggled silently and tolerated the extreme pains of povertyjust to bring up us and to the memory of my second elder brother,

Late Pramatha Nath Das

who had an ambition,his younger brother to study in the premier institute,

Ramakirishna Mission Residential College, Narendrapur, Kolkata.

Asim K Das

Present-day inorganic chemistry is no more a collection of unrelated facts. The scenario has undergonea drastic change over the last fifteen to twenty years with the application of kinetic, thermodynamicand structural studies to inorganic substances and with newer techniques providing newer information.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 themdevelop the concepts and understanding of the subject. There are attempts by a few authors at achievingthis goal but those seldom cover the whole curricula followed by most of the Indian universities andinstitutes. In many of these books the authors virtually neglect the evolutionary developments of thesubject, creating undesirable lacunae in the readers' understanding. Here is an honest and sincereattempt at bridging these gaps and presenting a comprehensive textbook on concepts and understandingto the readers. The treatment of every topic is elaborate and is marked by remarkable clarity and theauthor has not compromised with the volume of his work. The book Fundamental Concepts ofInorganic Chemistry covers the inorganic chemistry curricula at the BSc (honours) and MSc(preliminaries).

A large number of exercises and problems essential for modern teaching, have been incorporatedmeticulously 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 fromthe students and teachers of this subject.

Dr AV Saha DSc

Head of the Department of ChemistryRamakrishna Mission Residential College

P.O. Narendrapur, 24-Parganas (S)West Bengal, India, Pin: 743508

Foreword

“All power is within you, you can do anything and everything. Believe in that, do not believe that you are weak.”“The secret of religion lies not in theories but in practice. To be good and to do good – that is the whole ofreligion.”“Have faith in yourselves, and stand up on that faith and be strong; that is what we need.”

—Swami Vivekananda

We feel delighted to record the warm response which the first and second editions of the book hasreceived from the students and teachers throughout the country. We have incorporated all the aspectsof choice based credit system (CBCS) syllabus recently introduced in all universities and institutesand the suggestions received from the readers. In this edition, each chapter has been thoroughlyrevised, updated and rewritten to accommodate the recent views. To rewrite the Volumes 1–3, it hasbeen so enlarged that these volumes have been rescheduled as 1, 2, 3A and 3B. In this enlargedversion, scope of the book has been broadened by adding new topics and revisions of the earliersections. In revising the book, we have taken all the measures to retain the basic features for whichthe earlier editions have been so popular.

In preparing the manuscript, we have again freely consulted the original research papers, booksand reviews of the earlier authors and have borrowed their ideas whenever it has been required. Weare grateful and indebted to them. We are grateful to Ms Udita Das, for her assistance in revising thetext.

All the facilities provided by our Institute, Visva Bharati, are thankfully acknowledged. We areextremely grateful to Mr SK Jain, Managing Director, CBS Publishers & Distrubutors, New Delhi,for his hearty support and encouragement. We are also thankful to Mr YN Arjuna, Senior VicePresident (Publishing, Editorial and Publicity), for his kind cooperation and suggestions. We are extremelythankful to the concerned DTP section for taking the troubles in processing the manuscript.

In spite of our best efforts, some mistakes and misconceptions might have again crept in and forthese inconveniences, we beg to be pardoned in advance. Suggestions and constructive criticisms arealways welcome to better the presentation.

Asim K DasMahua DasAnkita Das

Preface to the Third Edition

Jðkoku~ yHkrs Kkue~Jðkoku~ yHkrs Kkue~Jðkoku~ yHkrs Kkue~Jðkoku~ yHkrs Kkue~Jðkoku~ yHkrs Kkue~One who has shraddha acquires knowledge

As a student and also as a teacher, I have experienced that for a systematic and comprehensivecoverage of the present subject, one is forced to consult various books on different disciplines tocollect the reading materials. Consequently, the students are specially constrained. Keeping this ideain mind, it has been attempted here to present a complete textbook on the subject. In a logical sequence,the book deals extensively with different aspects such as atomic structure (both classical and wavemechanical) and atomic spectra, fundamentals of quantum mechanics and wave mechanics, nuclearchemistry and radiation chemistry, different theories of valence forces and chemical forces includingband and Bloch theory of solids, solid state chemistry, acids and bases, nonaqueous solvents andredox potentials. It also covers the different aspects of material science which is emerging with agreat promise. Thus the present book covers the curricula followed by most of the Indian universitiesand institutes at the BSc and MSc levels. It also aims to help the students preparing for competitiveexaminations like NET, GATE, SLET, etc. Adequate stress on the basic theories and concepts hasbeen given everywhere to rationalise the presentation. The ideas have been very often illustratedthrough solution of related numerical problems. Each chapter is ended with various types of questionsand problems to afford an opportunity to the students for self-evaluation.

In writing a book of this nature, one accumulates indebtedness to the previous authors of differentbooks. The books which have been consulted are listed separately and gratefully acknowledged.

I express a deep sense of gratitude to Dr AV Saha, a gifted teacher, from whom I have started tolearn and understand the subject in my student life in Ramakrishna Mission Residential College,Narendrapur, for writing the foreword. I express my deep gratefulness to the teachers and authoritiesof the said institute, for shaping my career. I am grateful to my wife, Dr M Das, for various types ofhelp, assistance and cooperation.

I am especially grateful to Mr SK Jain, Managing Director, CBS Publishers & Distributors,New Delhi, for his earnest interest in publishing the book. Thanks are also due to his colleagues aswell.

In conclusion, my attempt will be amply rewarded, if it is found helpful to the students andteachers. In spite of all precautions, some errors might have crept in. Constructive criticism andvaluable suggestions from the readers are most welcome.

Asim K Das

“No great work can be achieved by humbug. It is through love, a passion for truth; and tremendous energy,that all undertakings are accomplished.” Swami Vivekananda

“I hold every man a traitor who, having been educated at their expense pay not the least heed to them.”Swami Vivekananda

Preface to the First Edition

Foreword by AV Saha viiPreface to the Third Edition ixPreface to the First Edition xi

1. Classical and Vector Models of Atom 1

1.1 Cathode Rays and Electron 1Electric Discharge through Gases and Production of Cathode Ray; Properties of Cathode Rays;Determination of Charge to Mass Ratio (e/m) of an Electron by Thomson’s Method; Determina-tion of Charge of an Electron by Millikan’s Oil-Drop Method; Drawing of Millikan’s Method

1.2 Anode Rays 9Production of Anode Rays; Properties of Anode Rays; Analysis of Positive Rays by Thomson’sParabola Method; Aston’s Mass Spectrograph; Dempster’s Mass Spectrometer; Bainbridge MassSpectrometer

1.3 The Neutron as a Fundamental Particle 17The Discovery of Neutron; Properties of Neutron

1.4 Some Important Properties of the Three Fundamental Particles 19

1.5 The Hydrogen Spectrum 19Balmer Formula; Rydberg Formula; Ritz Combination Principle;

1.6 Thomson’s Plum-Pudding Model of Atom 21

1.7 Scattering of -Particles and Rutherford’s Nuclear Model of Atom 22Rutherford’s Nuclear Model of Atom; Rutherford’s Theory of -Particle Scattering; NuclearDimension from the -Particle Scattering Experiment

1.8 Bohr’s Atomic Model for the Hydrogen-like Systems 25Bohr’s Atomic Model; Numerical Values of Radius and Energy in Bohr’s Atom; Correction for theFinite Mass of the Nucleus; Bohr’s Theory and the Spectral Lines in Hydrogen-like Systems;Ionisation and Resonance Potential for Hydrogen and Hydrogen-like Systems in the Light of Bohr’sTheory; Bohr’s Theory and Correspondence Principle; Moseley’s Law and Characteristic X-ray inthe Light of Bohr’s Theory; Franck-Hertz Experiments (Nobel Prize in Physics, 1925) in the Lightof 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 48Sommerfeld’s Atomic Model; Penetrating Power of the Orbits and Quantum Defect in PolyelectronicSystems in the Light of Sommerfeld’s Theory; Achievements of the Sommerfeld’s Theory; Draw-backs in the Sommerfeld’s Model

1.10 Vector Model of the Atom 55Concept of Spatial Quantisation; Concept of the Spinning Electron and Fine Structure vs. Multi-plet Structure of the Spectral Lines; Quantum Numbers in the Vector Model; Four Quantum Num-ber System and Pauli Exclusion Principle; Coupling Schemes and Atomic States in the VectorModel;

��

–L S Coupling Scheme; –��

J J Coupling Scheme; Spatial Quantisation of the ResultantVectors (i.e. , , )

��

L S J in Atoms or Ions; Determination of Microstates and Russel-Saunders Terms;

Contents

xiv Fundamental Concepts of Inorganic Chemistry

A Simple Working Procedure to Determine the Term Symbols; Hund’s Rules to Determine theGround State Term; Derivation of the Ground State Terms in the Light of Hund’s Rules; SpectralSelection Rules in the Vector Model; 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 andHyperfine Structure of the Spectral Lines; Orbital and Spin Magnetic Moments of an Electron inthe Light of Orbital and Spinning Motion: Magnetic Moment of an Atom; Stern-GerlachExperiment—An Evidence in Favour of Space Quantisation and Spin Quantum Number (OttoStern, Nobel Prize for Physics in 1943); Explanation of the Magneto-Optic Phenomenon - theZeeman Effect; Electronic Structure of the Atoms; Merits of the Vector Model

1.11 Electronic Configuration Scheme for Many Electron Systems 94Rules for Placing the Electrons in Different Energy Levels

1.12 Spherical and Nonspherical Atoms: Unsold’s Theorem 105

Solved Numerical Problems 105

Exercise I 114

2. Origin of the Quantum Theory 120

2.1 Introduction 120

2.2 Nature of Black-Body Radiations 120

2.3 Different Laws and Theories of Black-Body Radiations 121The Stefan-Boltzmann Law; Wien’s Law; Rayleigh-Jeans Law; Planck’s Quantum Theory

2.4 The Photoelectric Effect 126Characteristics of Photoelectric Effect; Einstein’s Theory of Photoelectric Effect; Work Functionand Ionisation Potential

2.5 Compton Effect 130Theoretical Background of Compton Effect; Compton Shifts at Different Cases; CharacteristicFeatures of Compton Effect

2.6 Pair Formation 136


Exercise II 140

3. Fundamentals of Wave Mechanics 143

3.1 Introduction 143

3.2 Wave Particle Duality and De Broglie’s Matter Waves 143de Broglie Wavelength for Matter Waves; The de Broglie Wavelength for the Macroscopic andMicroscopic Bodies; Difference between de Broglie Matter Wave and Electromagnetic Wave; Thede Broglie Electron Wave; Relativistic Correction in the de Broglie Electron Wave; Verification ofthe de Broglie Electron Wave by Davisson and Germer’s Experiment; Bohr’s Quantum Restric-tion from de Broglie Concept; Particle in a Box in the Light of de Broglie Hypothesis

3.3 The Heisenberg’s Uncertainty Principle and its Implications 151Uncertainty Principle; Illustration of Uncertainty Principle from the Thoughtful (Hypothetical)Experiments; Applicability of the Uncertainty Principle to Large and Small Particles; SomeImportant Applications of the Uncertainty Principle

3.4 Schrödinger’s Wave Equations 160Representation of Schrödinger’s Time Independent Wave Equation; Physical Significance ofSchrödinger’s Equation and Hamiltonian Operator; Eigenvalues and Eigenfunctions; PhysicalSignificance of the Wave Function (); Normalised and Orthogonal Wave Functions; BasicPostulates of Quantum Mechanics; Algebra of Operators; Degenerate Wave Functions and theirLinear Combination

Contents xv

3.5 Some Applications of the Schrödinger’s Wave Equation 176Free Particle in One Dimension; Free Particle in Three Dimensions; Particle in a One DimensionalBox; Particle in a Three Dimensional Box; Energy States of a Particle Confined in a Two-dimen-sional Box; Importance of the Model - Particle in a Box; Some Applications of the Model -Particle in a Box; Quantum Mechanical Tunnelling Effect

3.6 Approximate Methods of Solving the Schrödinger’s Wave Equation 207Variation Method; The Linear Combination Method


Exercise III 231

Appendix 3A 234

Appendix 3B 242

4. Wave Mechanical Model of Atom 246

4.1 Wave Mechanical Model for the Hydrogen-like Atoms or Ions 246Wave Functions for the Hydrogen-like Systems; Wave Mechanical Genesis of the QuantumNumbers; Important Features of a Dirac Atom Developed from the Relativistic Wave Mechanics;The Radial Wave Function and Radial Probability Distribution of Electron Cloud in HydrogenicSystems; The Physical and Chemical Significance of the Nodal Points: Does an Electron Exist atthe Nodal Point?; Angular Wave Functions and Orbital Shapes; Electron Cloud Density Represen-tation of the Orbitals in Hydrogen-like Systems; Symmetry of the Orbitals; Concept of AtomicOrbitals in Wave Mechanics in Relation to the Orbits in Classical Mechanics; Energy of theElectron in Hydrogen-like Systems; The Four Quantum Numbers; Pauli Exclusion Principle in theLight of Wave Mechanics: Pauli Force

4.2 Wave Mechanical Model For Polyelectronic Systems 281Self-Consistent Field (SCF) Method; Concept of Slater Orbitals; Concept of Shielding and Quan-tum Defect; Slater’s Rules in Calculating the Shielding Constant (S) and Z*

4.3 Bonding Properties of d- and f-Orbitals 286

4.4 Spherical and Nonspherical Atoms: Unsold’s Theorem 288


Exercise IV 298

5. Atomic Nucleus and its Structure 301

5.1 The Atomic Nucleus 301Composition of the Nucleus; Size of the Nucleus and Concept of Nucleus Radius (R); MirrorNuclei and Nuclear Radius; Nuclear Density; Shape of the Nucleus; Total Angular Momentum ofthe Nucleus: Magnetic Properties of the Nucleus and Nuclear Magnetic Resonance (NMR) Fre-quency; 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 314Discovery and Characterisation of Nonradioactive Isotopes; Isotopic Shift in Optical Spectra;Spectra of Isotopes; Characteristic Features of the Isotopes; Isotopic Composition of theElements; Uses of Isotopes; Separation of Isotopes

5.3 Nuclear Stability 327Even–Odd Nature of the Nucleons (Harkins' Rule); The Neutron to Proton Ratio and Stability ofthe Nuclides; The Neutron to Proton Ratio and Different Modes of Decay; Packing Fraction andNuclear Stability; Mass Defect and Nuclear Binding Energy (NBE)

xvi Fundamental Concepts of Inorganic Chemistry

5.4 The Nuclear Forces 336Nature of the Nuclear Forces; Exchange Force as the Nuclear Force; The Nuclear Potential andNuclear Potential Barrier

5.5 Nuclear Models 340Fermi Gas Model; The Liquid Drop Model; Nuclear Shell Model; The Optical Model

5.6 The Fundamental Particles 355


Exercise V 364

6. Radioactivity and Radiation Chemistry 368

6.1 Discovery of Natural Radioactivity 368

6.2 Types of Radioactive Emanations 369

6.3 Properties of Alpha, Beta and Gamma Radiation 369Alpha ()-rays; Beta ()-Rays; Gamma () Rays; Comparison among the Different RadioactiveEmanations

6.4 Detection and Measurement of Radioactivity 373

6.5 Units of Radioactivity 379

6.6 Different Modes of Radioactive Decay 380

6.7 The Fluorescence Emission and Auger Effect 381

6.8 Disintegration Chain and Soody–Fajan Group Displacement Law 382

6.9 The Decay Kinetics and Parent–Daughter Decay—Growth Relationships 383Case I : The Daughter Nucleus is Stable; Case II : When the Daughter Element is Radioactive

6.10 Radioactive Equilibrium 388

6.11 Energetics of the Disintegration Processes 392

6.12 Some Important Aspects of Alpha Decay 395

6.13 Some Important Aspects of Beta Decay 399

6.14 Some Important Aspects of Gamma Emission 400

6.15 The Disintegration Series 401

6.16 Artificial or Induced Radioactivity 404Discovery of Artificial Radioactivity; Production of Artificial Radioactivity

6.17 Application of Radioactive Isotopes 406Application of Radioisotopes in the Field of Chemistry; Application of Radioactivity in theBiological Fields; Application of Radioactivity in Agriculture; Application of Radioactivity in theMedical Field; Application of Radioactivity in Industry; Application of Radioactivity in AgeDetermination

6.18. Some Important Aspects of Radiation Chemistry 421Radiation Chemistry; Characteristics of Interaction of Medium Energy Charged Particles withMatter; Interactions of Neutrons with Matter; Interaction of Gamma Radiation with Matter;Radiation Dosimetry; Radiolysis of Water


Exercise VI 436

Contents xvii

7. Nuclear Reaction 440

7.1 Artificial Transmutations and Nuclear Reactions 4407.2 Bethe’s Notation of Nuclear Reactions 441

7.3 Nuclear Reactions vs. Chemical Reactions 441

7.4 Classification of Nuclear Reactions 442

7.5 Conservation Laws in Nuclear Reactions 446Conservation of Energy; Conservation of Linear Momentum; Conservation of Angular Momen-tum; Conservation of Neutrons and Protons; Conservation of Nucleon's Statistics

7.6 Threshold Energy of a Projectile for a Nuclear Reaction 448

7.7 Nuclear Reaction Cross-Section 448

7.8 Mechanisms of Nuclear Reactions 449The Compound Nucleus Theory; Oppenheimer–Phillips Mechanism in Stripping Reactions;Direct Nuclear Reaction Mechanism

7.9 Charged Particle Accelerators 453The Linear Accelerator; The Cyclotron

7.10 Filling the Gaps in the Periodic Table: The Man-Made Elements 457

7.11 Transuranic and Translawrencium Elements: The Man-Made Elements 458

7.12 Nuclear Fission 461Historical Background; Characteristic Features of Nuclear Fission; Bohr–Wheeler Theory of NuclearFission: Liquid Drop Model; Charge Distribution in Fission Products: Principle of Equal ChargeDisplacement

7.13 Fission Chain Reaction: A Source of Atomic Energy 471Factors Controlling a Fission Chain Reaction; The Fertile and Fissile Nuclides as the NuclearFuels; Atom Bomb (A-Bomb): Fission Bomb; Fermi's Four Factor Formula and Nuclear Reactoror Atomic Pile for the Controlled Nuclear Fission; Breeder Reactor; A Natural Fission Reactor:Okla Phenomenon; Nuclear Reactors in India; Recovery of Uranium and Plutonium from SpentFuel; Nuclear Waste — Hazard, Management and Safety

7.14 Nuclear Fission—Thermonuclear Reaction 483Characteristic Features of Nuclear Fusion; Hydrogen and Cobalt Bomb; Stellar Energy; Con-trolled Fusion Reactions: An Innocent and a Never-Ending Source of Energy; Cold Fusion

7.15 The Origin and Evolution of Elements: Nucleosynthesis of Elements 491Nucleosynthesis of Elements from the Primordial Element Hydrogen in Stars; Life Cycle of a Starand Fusion Reactions Leading to the Nucleosynthesis of Elements; Cosmic Abundance ofElements


Exercise VII 506

8. Periodic Table and Periodic Trends of Different Properties of Elements 511

8.1 Historical Background of the Development of Periodic Classification 511Law 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

8.2 Mendeleev’s Periodic Law and Periodic Table 513Characteristics of Mendeleev’s Short Periodic Table

8.3 Characteristics and Usefulness of the Mendeleev’s Periodic Table 517Systematic Classification of the Elements; Correction of Atomic Weights; Prediction of theMissing Elements

8.4 Defects in the Mendeleev’s Periodic Table 518

xviii Fundamental Concepts of Inorganic Chemistry

8.5 Long Form of the Modern Periodic Table 520Advantages of the Long Form of Periodic Table; Defects of the Long Form Periodic Table

8.6 Extended Periodic Table: Superheavy Elements—Postactinides andSuperactinides 524

8.7 Classification of the Elements Based on the Electronic Configuration andChemical Affinities 526Classification Based on the Position of the Differentiating Electron; Bohr’s Classification Basedon Electronic Configuration; Goldschmidt's Geochemical Classification of Elements Based onChemical Affinity

8.8 Characteristics and Position of the Border Line Elements 529Position of the Zn Family; Positions of Lu, Th and Lr; Position of the Lighter Actinides (i.e. 90Th,91Pa, 92U, etc.): 4f Series (Lanthanides) vs. 5f Series (Actinides)

8.9 Lanthanide (Lanthanoid) and Actinide (Actinoid) Contractions(i.e. f-Contractions) 531Nature of the f-Contraction; Explanation of f-Contraction: Relativistic Effects and Increasing Trendof Effective Nuclear Charge (Z*); Effects of Lanthanide Contraction

8.10 Periodic Trends of Z* and Size of the Atoms and Ions 536Two Important Factors (n and Z*) to Determine the Size of Atoms and Ions; Periodic Trends of Z*(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 541Atomic Volume: Definition and Limitation of the Parameter; Nature of Variation Trend of theAtomic Volume with the Atomic Number; Explanation of the Atomic Volume Curve

8.12. Variation of Ionization Energies in the Periodic Table 543Periodic Variation of the Ionisation Energies; Factors Governing the Ionisation Energies andExplanations of the Periodic Trends; The Cases which Flout the General Periodic Trend of IonisationEnergies; Ionisation Energy of Some Typical Molecular Species

8.13 Electron Affinity and its Variation Trend in the Periodic Table 554Concept of Electron Affinity; Factors Governing Electron Affinities; Variation of Electron Affin-ity in the Periodic Table

8.14 Concepts of Electronegativity 559Pauling’s Electronegativity (

P); Mulliken’s Orbital Electronegativity (

M); Jaffe–Hinze Electro-

negativities; Allred–Rochow’s Electronegativity; Sanderson’s Electronegativity (S); Calculationof Charge Separation from Electronegativity: Concept of Electronegativity Equalization;Electronegativity: Not an Inherent Property of the Elements; Examples Illustrating the Variationof Electronegativity Depending upon the Structural Characteristics; Group Electronegativity;Concepts of Absolute Electronegativity, Optical Electronegativity and Spectroscopic Electro-negativity

8.15 Periodic Trends of Electronegativity 576

8.16 Applications of the Electronegativity Concept in Different Trends of Chemistry 578

8.17 Periodic Trends of Cohesive Energy (i.e. Melting and Boiling Points) 581

8.18 The Diagonal Relationship 585Causes of the Diagonal Relationship; Comparison of the Physical Constants of the Three DiagonalPairs; Similarities in the Pair, Li and Mg; Similarities in the Pair, Be and Al; Similarities in the Pair,B and Si

8.19 Basic Difference in Group Trends between the Representative andTransition Elements 589

Contents xix

8.20 Secondary Periodicity: Anomalies among the Post-transition Elements andPostlanthanides 590Secondary Periodicity and Consequences of Secondary Periodicities; Explanation of the Anoma-lies in Properties of the 4th and 6th Period Post-transition Elements; Relativistic Effects on ChemicalProperties of the 5th and 6th Row Elements

8.21 Position of Hydrogen in the Periodic Table 599

8.22 Peculiarities of the First and Second Row Elements 600Anomalous Properties of Fluorine : Superhalogen or Subhalogen?; Anomalous Properties of Lithium

8.23 Comparison between The Transition (i.e. d-Block) andInner Transition (i.e. f-Block) Metals 603

8.24 Variation of Oxidation States of s- and p-Block Elements 605

8.25 Comparison: Lighter Transition Metals vs. Heavier TransitionMetals (i.e. 3d Series vs. 4d, and 5d Series); Lanthanides vs. Actinides(4f Series vs. 5f Series) 608Comparison between the Lighter and Heavier Transition Metals (i.e. 3d Series vs. 4d, and5d Series); Comparison between the Lanthanides and Actinides (i.e. 4f-series vs. 5f-series)


Exercise VIII 613

Bibliography B1–B2

Appendices A1–A10

Appendix I: Units and Conversion Factors A1

Appendix II: Some Physical and Chemical Constants A4

Appendix III: Wavelength and Colours A5

Appendix IV: Names, Symbols, Atomic Numbers and AtomicWeights of the Elements A6

Appendix V: Some Useful Mathematical Relationships A8

Index I1–I11

third edition inorganic chemistry

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