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INORGANIC CHEMISTRY
 ABOUT THE AUTHORS

Rajni Garg is working as Head, Department of Applied Chemistry, RITM,

Faridabad. She received her doctorate degree in Chemistry from Gurukula Kangri
University, Haridwar, Uttar Pradesh, and postgraduate degree in Chemistry
(Honours) from Panjab University, Chandigarh. She has more than 12 years
of research and teaching experience and has authored several national and
international publications.

Randhir Singh is working as Professor and Head in the Department of

Chemistry, Gurukula Kangri University, Haridwar, Uttar Pradesh. He received
his doctorate degree in Chemistry from University of Roorkee, India (now IIT)
and postgraduate degree in Chemistry from University of Meerut, India. He has
been Postdoctoral Research Associate in the Department of Biochemistry and
Molecular Biology, University of Southern California, Los Angeles, USA, and
visited University of Southern California, Los Angeles, as scientist exchange
programme. He has more than 35 years of research and teaching experience and
has guided many MSc, MPhil. and PhD students in their theses work. He has received many academic
honours from Council of Scientific and Industrial Research, India, for his research contributions and
has several national and international publications.
INORGANIC CHEMISTRY

Rajni Garg
Associate Professor and Head
Department of Applied Sciences
Rattan Institute of Technology and
Management Faridabad, Haryana

Randhir Singh
Professor and Head
Department of Chemistry
Gurukul Kangri Vishwavidyalaya
Haridwar, Uttar Pradesh

McGraw Hill Education (India) Private Limited

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Inorganic Chemistry
Copyright © 2014 by McGraw Hill Education (India) Private Limited.
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 CONTENTS

Preface ix

1. Structure of Atom 1.1–1.27

1.1 Introduction 1.1
1.2 Rutherford Scattering Experiment 1.1
1.3 Planck’s Quantum Theory of Radiation 1.2
1.4 Photoelectric Effect 1.3
1.5 Atomic Spectrum of Hydrogen 1.3
1.6 Bohr’s Model of the Atom 1.4
1.7 Sommerfeld’s Extension of Bohr’s Atomic Model 1.9
1.8 Dual Character of Matter 1.10
1.9 Heisenberg’s Uncertainty Principle 1.11
1.10 Compton Effect 1.12
1.11 Schrodinger Wave Equation 1.12
1.12 Quantum Numbers 1.17
1.13 Probability Distribution Curves 1.18
1.14 Rules for Filling of Orbitals and Electronic Configuration of Elements 1.20
Summary 1.23
Solved Examples 1.23
Exercises 1.27
2. Nuclear Chemistry 2.1–2.23
2.1 Nucleus 2.1
2.2 Composition of the Nucleus 2.1
2.3 Nuclear Forces 2.4
2.4 Nuclear Stability 2.5
2.5 Nuclear Models 2.7
2.6 Nuclear Reactions 2.8
2.7 Radioactivity 2.14
2.8 Radioactive Disintegration 2.15
2.9 Law of Successive Disintegration: Radioactive Equilibrium 2.15
2.10 Soddy-Fajans and Russel Group Displacement Law 2.16
2.11 Artificial Radioactivity 2.17
2.12 Applications of Radioactive Isotopes 2.18
Summary 2.19
Solved Examples 2.20
Exercises 2.23
vi Contents

3. Chemical Bonding 3.1–3.65

3.1 Introduction 3.1
3.2 Ionic Bond or Electrovalent Bond 3.1
3.3 Covalent Bond (Lewis–Langmuir Concept) 3.3
3.4 Dipole Moment 3.7
3.5 Coordinate Covalent Bond or Dative Bond 3.8
3.6 Van der Waals’ Forces or Intermolecular Forces 3.9
3.7 Hydrogen Bond 3.10
3.8 Orbital Overlap Theory 3.13
3.9 Molecular Orbital Theory 3.19
3.10 Metallic Bond 3.36
3.11 Hybridisation 3.39
3.12 Sidgwick – Powell Theory 3.49
3.13 Valence Shell Electron-pair Repulsion Theory (VSEPR theory) 3.49
3.14 Shapes of Some Common Molecules 3.50
3.15 Linnett Double Quartet Theory (LDQ Theory)—
Modification of Lewis Longmuir Octet Theory 3.57
3.16 Resonance 3.60
Summary 3.62
Solved Examples 3.63
Exercises 3.64
4. Molecular Symmetry 4.1–4.72
4.1 Introduction 4.1
4.2 Symmetry Element 4.1
4.3 Multiplication of Symmetry Operations 4.5
4.4 Mathematical Group 4.5
4.5 Matrix Representation of Symmetry Operations 4.10
4.6 Terms Symbols of Diatomic Molecules 4.20
4.7 Applications of Group Theory 4.22
4.8 Structure of Soilds 4.40
Summary 4.67
Solved Examples 4.68
Exercises 4.71
5. Redox Reactions 5.1–5.21
5.1 Introduction 5.1
5.2 Electrochemical Cell 5.2
5.3 Kinetics of Redox Reactions 5.6
5.4 Redox Reactions in Aqueous Systems 5.8
5.5 Diagrammatic Representation of Potential Data 5.12
Summary 5.17
Solved Examples 5.18
Exercises 5.20
 Contents vii

6. Non-aqueous Solvents 6.1–6.39

6.1 Introduction 6.1
6.2 Classification of Solvents 6.2
6.3 Liquid Ammonia 6.3
6.4 Liquid Sulphur Dioxide 6.10
6.5 Anhydrous Hydrogen Fluoride 6.14
6.6 Anhydrous Sulphuric Acid 6.16
6.7 Acetic Acid 6.18
6.8 Liquid Dinitrogen Tetroxide, N2O4 6.20
6.9 Molten Salts and Ionic Liquids 6.21
6.10 Concept of Acid – Base 6.24
6.11 Acid Strength Behaviour in the Periodic Table 6.33
Summary 6.35
Solved Examples 6.36
Exercises 6.38
7. Extraction of Elements 7.1–7.10
7.1 Introduction 7.1
7.2 Occurrence of Elements 7.1
7.3 Metallurgy 7.2
7.4 Purification of Impure Metals or Refining 7.5
7.5 Thermodynamics of the Metallurgy: Ellingham Diagram 7.6
Summary 7.9
Solved Examples 7.9
Exercises 7.10
8. Periodic Table and Periodic Properties 8.1–8.23
8.1 Introduction 8.1
8.2 Mendeleef’s Periodic Table 8.1
8.3 Modern Periodic Law and Periodicity 8.2
8.4 Long form of Periodic Table 8.2
8.5 Periodic Properties 8.6
8.6 Shielding or Screening Effect 8.17
Summary 8.19
Solved Examples 8.20
Exercises 8.22
9. Hydrogen and its Compounds 9.1–9.16
9.1 Introduction 9.1
9.2 Position of Hydrogen in the Periodic Table 9.2
9.3 Occurrence and Production of Hydrogen 9.3
9.4 Physical Properties of Hydrogen 9.3
9.5 Chemical Properties of Hydrogen 9.3
9.6 Uses of Hydrogen 9.4
9.7 Different Forms of Hydrogen 9.5
9.8 Spin Isomers of Hydrogen 9.6
9.9 Isotopes of Hydrogen 9.7
viii Contents

9.10 Compounds of Hydrogen 9.9

9.11 Water H2O 9.12
9.12 Heavy Water (D2O) 9.13
Summary 9.14
Solved Examples 9.15
Exercises 9.15
10. Chemistry of Group 1 Elements 10.1–10.20
10.1 Introduction 10.1
10.2 General Characteristics of Group I Elements 10.1
10.3 Chemical Properties of Alkali Metals 10.3
10.4 Lithium (Li) 10.7
10.5 Sodium (Na) 10.11
10.6 Potassium (K) 10.16
10.7 Rubidium, Caesium and Francium 10.18
Summary 10.19
Solved Examples 10.19
Exercises 10.20
11. Chemistry of Group 2 Elements 11.1–11.20
11.1 Introduction 11.1
11.2 General Characteristics of Group 2 Elements 11.1
11.3 Chemical Properties of Alkaline Earth Metals 11.3
11.4 Beryllium (Be) 11.6
11.5 Magnesium (Mg) 11.10
11.6 Calcium (Ca) 11.12
11.7 Strontium (Sr) 11.14
11.8 Barium (Ba) 11.14
11.9 Radium (Ra) 11.15
11.10 Portland Cement 11.16
Summary 11.18
Solved Examples 11.19
Exercises 11.19
12. Chemistry of Group 13 Elements 12.1–12.31
12.1 Introduction 12.1
12.2 Electronic Structure 12.1
12.3 General Physical Properties 12.1
12.4 Diagonal Relationship between Boron and Silicon 12.3
12.5 Chemical Properties of Group 13 Elements 12.4
12.6 Boron 12.5
12.7 Aluminimum (Al) 12.22
12.8 Gallium (Ga) 12.26
12.9 Indium and Thallium (Th) 12.27
12.10 Comparision of Compounds of Group 13 Elements 12.29
 Contents ix

Summary 12.30
Solved Examples 12.30
Exercises 12.31
13. Chemistry of Group 14 Elements 13.1–13.39
13.1 Introduction 13.1
13.2 General Properties of Group 14 Elements 13.1
13.3 Anomalous Behaviour of Carbon 13.3
13.4 Carbon and Silicon—Comparison of Properties 13.3
13.5 Carbon 13.4
13.6 Silicon (Si) 13.18
13.7 Germanium (Ge) 13.29
13.8 Tin (Sn) 13.31
13.9 Lead (Pb) 13.34
13.10 Comparative Account of Compounds of Group 14 Elements 13.37
Summary 13.38
Solved Examples 13.38
Exercises 13.39
14. Chemistry of Group 15 Elements 14.1–14.42
14.1 Introduction 14.1
14.2 General Properties of Group 15 Elements 14.1
14.3 Chemical Properties of Group 15 Elements 14.3
14.4 Nitrogen (N) 14.5
14.5 Phosphorus (P) 14.23
14.6 Arsenic (As) 14.35
14.7 Antimony (Sb) 14.37
14.8 Bismuth (Bi) 14.39
Summary 14.40
Solved Examples 14.41
Exercises 14.42
15. Chemistry of Group 16 Elements 15.1–15.28
15.1 Introduction 15.1
15.2 General Properties of Group 16 Elements 15.1
15.3 Anomalous Behaviour of Oxygen 15.3
15.4 Oxygen (O2) 15.3
15.5 Sulphur (S2) 15.7
15.6 Selenium (Se) 15.22
15.7 Tellurium (Te) 15.24
15.8 Polonium (Po) 15.26
15.9 Comparative Account of Compounds of Group 16 Elements
Summary 15.27
Solved Examples 15.27
Exercises 15.28
 x Contents

16. Chemistry of Group 17 Elements 16.1–16.46

16.1 Introduction 16.1
16.2 General Characterisation 16.1
16.3 Chemical Properties 16.4
16.4 Fluorine (F) 16.6
16.5 Chlorine (Cl) 16.17
16.6 Bromine (Br) 16.23
16.7 Iodine (I) 16.25
16.8 Astatine (At) 16.31
16.9 Interhalogen Compounds 16.32
16.10 Polyhalides 16.38
16.11 Pseudohalogens and Pseudohalides 16.41
Summary 16.44
Solved Examples 16.44
Exercises 16.45
17. Chemistry of Group 18 Elements 17.1–17.15
17.1 Introduction 17.1
17.2 History and Discovery 17.1
17.3 Occurrence and Isolation of Noble Gases 17.2
17.4 Uses of Noble Gases 17.4
17.5 Physical Properties 17.4
17.6 Chemical Properties 17.5
17.7 Chemistry of Xenon (Xe) 17.6
17.8 Compounds of Krypton (Krf2) 17.12
17.9 Compounds of Radon (Rn) 17.13
Summary 17.13
Solved Examples 17.14
Exercises 17.14
18. Chemistry of d-block Elements 18.1–18.10
18.1 Introduction 18.1
18.2 Classification of d-block Elements 18.2
18.3 General Characteristic of d-block Elements 18.3
Summary 18.8
Solved Examples 18.8
Exercises 18.9
19. Chemistry of Elements of 3d Series 19.1–19.53
19.1 Introduction 19.1
19.2 Scandium (Sc) 19.1
19.3 Titanium (Ti) 19.3
19.4 Vanadium (V2)
19.5 Chromium (Cr) 19.13
19.6 Manganese (Mn) 19.20
19.7 Iron (Fe) 19.26
 Contents xi

19.8 Cobalt (Co) 19.36

19.9 Nickel (Ni) 19.38
19.10 Copper (Cu) 19.42
19.11 Zinc (Zn) 19.46
Summary 19.49
Solved Examples 19.51
Exercises 19.51
20. Chemistry of Elements of 4d Series 20.1–20.21
20.1 Introduction 20.1
20.2 Yttrium (Y) 20.1
20.3 Zirconium (Zr) 20.2
20.4 Niobium (Nb) 20.3
20.5 Molybdenum (Mo) 20.6
20.6 Technetium (Tc) 20.10
20.7 Ruthenium (Ru) 20.11
20.8 Rhodium (Rh) 20.12
20.9 Palladium (Pd) 20.13
20.10 Silver (Ag) 20.15
20.11 Cadmium (Cd) 20.18
Summary 20.19
Solved Examples 20.19
Exercises 20.20
21. Chemistry of 5d Series 21.1–21.19
21.1 Introduction 21.1
21.2 Hafnium (HF) 21.1
21.3 Tantalum (Ta) 21.2
21.4 Tungsten (W) 21.2
21.5 Rhenium (Re) 21.4
21.6 Osmium (Os) 21.5
21.7 Iridium (Ir) 21.6
21.8 Platinum (Pt) 21.8
21.9 Gold (Au) 21.10
21.10 Mercury (Hg) 21.14
Summary 21.17
Solved Examples 21.17
Exercises 21.18
22. Chemistry of Lanthanides and Actinides 22.1–22.26
22.1 Introduction 22.1
22.2 Lanthanides 22.1
22.3 Lanthanum (La) 22.11
22.4 Actinides 22.12
22.5 Thorium (Th) 22.15
22.6 Uranium (U) 22.17
xii Contents

22.7 Plutonium (Pu) 22.22

Summary 22.24
Solved Examples 22.25
Exercises 22.25
23. Coordination Compounds-I Basics Concepts: Nomenclature 23.1–23.18
and Stereochemistry
23.1 Introduction 23.1
23.2 Important Terms 23.2
23.3 Rules for Nomenclature of Coordination Compounds 23.5
23.4 Rules for Formula of the Coordination Compounds 23.6
23.5 Classification of Complexes 23.7
23.6 Isomerism 23.9
Summary 23.15
Solved Examples 23.16
Exercises 23.17
24. Coordination Compounds— II Theories of Bonding 24.1–24.35
24.1 Introduction 24.1
24.2 Techniques for Study of Complexes 24.1
24.3 Theories of Coordination 24.3
24.4 Crystal Field Theory (CFT) 24.9
24.5 The Ligand Field Theory–Molecular Orbital Theory 24.17
Summary 24.32
Solved Examples 24.33
Exercises 24.34
25. Coordination Compounds III: Quantitative Basis of 25.1–25.35
Crystal Field Theory
25.1 Introduction 25.1
25.2 Determination of Octahedral Crystal Field Potential 25.2
25.3 Determination of Tetragonal Crystal Field Potential 25.11
25.4 Determination of Square Planar Crystal-Field Potential 25.15
25.5 Determination of Tetrahedral Crystal-Field Potential 25.16
25.6 Determination of Cubic Crystal-Field Potential 25.20
25.7 Structural and Thermodynamic Effects of Splitting of Orbitals 25.21
25.8 Jahn–Teller Effect (Distortion of Geometry) 25.28
Summary 25.33
Solved Examples 25.33
Exercises 25.34
26. Coordination Complexes IV: Spectroscopic and Magnetic 26.1–26.58
Properties of Coordination Compounds
26.1 Introduction 26.1
26.2 Coupling Schemes 26.2
26.3 Energy Terms and Energy States 26.3
26.4 Electronic Spectra of Transition–Metal Compounds 26.11
 Contents xiii

26.5 Orgel Diagrams 26.16

26.6 Racah Parameters 26.24
26.7 Terms Correlation Diagrams under the Effect of Weak and Strong Field Effects 26.26
26.8 Tanabe-sugano Diagrams (T-S Diagram) 26.29
26.9 Charge-Transfer Transitions 26.34
26.10 Types of Magnetism 26.39
Summary 26.55
Solved Examples 26.56
Exercises 26.57
27. Coordination Compounds -V The Reaction Mechanisms of 27.1–27.30
Transition-Metal Complexes
27.1 Introduction 27.1
27.2 Ligand-substitution Reactions 27.10
27.3 Oxidation–reduction Reactions in Coordination Compounds 27.22
Summary 27.27
Solved Examples 27.28
Exercises 27.29
28. Complexes of p-Acceptor Ligands 28.1–28.12
28.1 Introduction 28.1
28.2 Complexes of Carbonyls 28.1
28.3 Complexes of Nitric Oxide 28.7
28.4 Complexes of Phosphines 28.8
28.5 Complexes of Cyanide and Isocyanide Ligands 28.10
Summary 28.10
Solved Examples 28.11
Exercises 28.11
29. Chemistry of Organometallic Compounds 29.1–29.22
29.1 Introduction 29.1
29.2 Organometallic Compounds of Alkali Metals 29.3
29.3 Organometallic Compounds of Alkaline Earth Metals 29.4
29.4 Organometallics of Group 13 Elements 29.5
29.5 Organometallics of Group 14 Elements 29.6
29.6 Organometallics of Group 15 Elements 29.8
29.7 Organometallic Compounds of Transition Elements 29.9
Summary 29.19
Solved Examples 29.20
Exercises 29.21
30. Metal Clusters 30.1–30.13
30.1 Introduction 30.1
30.2 Polynuclear Compounds of Oxygen and other Chalcogens 30.1
30.3 Clusters of p-block Elements other than Chalcogens 30.2
30.4 Low-valent Metal Clusters 30.3
xiv Contents

30.5 High-Valent Metal Clusters or Halide-type Clusters 30.7

Summary 30.11
Solved Examples 30.12
Exercises 30.12
31. Inorganic Nomenclature 31.1–31.10
31.1 Introduction 31.1
31.2 General Nomenclature and Formulae of Compounds 31.4
Solved Examples 31.9
Exercises 31.9
32. Inorganic Polymers 32.1–32.30
32.1 Introduction 32.1
32.2 Classification of Inorganic Polymers 32.1
32.3 General Characteristics of Inorganic Polymers 32.2
32.4 Important Inorganic Polymers 32.2
Exercises 32.29
33. Bioinorganic Chemistry 33.1–33.14
33.1 Introduction 33.1
33.2 Metalloporphyrins 33.2
33.3 Cytochromes 33.6
33.4 Peroxidases (Molar Mass ~40,000) 33.7
33.5 Catalases 33.7
33.6 Ferredoxins 33.7
33.7 Metallo-enzymes 33.8
33.8 Biological Nitrogen Fixation 33.10
33.9 Na-K pump 33.11
Summary 33.12
Solved Examples 33.12
Exercises 33.13
34. Pollution 34.1–34.24
34.1 Introduction 34.1
34.2 Air Pollution 34.3
34.3 Water Pollution 34.15
34.4 Soil Pollution 34.22
Summary 34.23
Exercises 34.24
35. Analytical Chemistry 35.1–35.34
35.1 Errors 35.1
35.2 Detection and Minimisation of Errors 35.3
35.3 Precision 35.4
35.4 Ways of Expressing Precision 35.4
35.5 Analysis of Data by Using Statistical Techniques 35.6
35.6 Detecting Outliers 35.7
 Contents xv

35.7 Significance Tests 35.8

35.8 Significant Figures 35.8
35.9 Expressing Error or Accuracy of a Measurement 35.10
35.10 Error Propagation in Final Results 35.11
35.11 Volumetric Analysis 35.13
35.12 Preparation of Standard Solution 35.14
35.13 Volumetric Methods 35.14
Summary 35.27
Solved Examples 35.28
Exercises 35.33

Index I.1-I.10
 PREFACE

“Most of the fundamental ideas of science are essentially simple, and may, as a rule, be expressed in a
language comprehensible to everyone.”
Albert Einstein

Inorganic chemistry is a dynamic and fascinating field of chemistry growing at a rapid pace in both
research and theoretical aspects. The lusty impact of this field has introduced the subject as an essential
part in the curricula of all universities. The first edition of Inorganic Chemistry aims to provide the
essentials of the subject in an easy and understandable manner. The book is an outcome of the teaching
and research experience of the authors so that students can learn concept formulation instead of just
rote memorization.

Target Audience
The book is primarily aimed for students at undergraduate (BSc pass and honours) and postgraduate
(MSc pass and honours) levels taking inorganic chemistry as a special subject for a one semester or a
full-year course.

Secondary Readers
This book is designed to provide concise information about various aspects of inorganic chemistry
that can also be used by students from various fields involving inorganic compounds, such as
environmental science, polymer science, industrial chemistry, bioinorganic chemistry and metallurgy.
However, they can skip the irrelevant topics as per their field. This book will also be a source of
reference for the students doing BTech courses or taking inorganic chemistry as an ancillary subject.
It will also be helpful for the challenging requirements of various competitive exams such as CSIR,
SLET and GATE.

About the Book

The content of this book has been framed in an easy-to-understand language that would generate interest
in the subject. All the chapters provide descriptive information and are enriched with illustrations,
comprehensible articles, solved examples, both numerical as well as theoretical, to satisfy the needs
of students. At the end of each chapter, a concise summary has been given for quick revision before
examinations. The chapters have been enriched with exercises comprising theory-based general
questions and objective-type questions to provide an insight about the examination pattern.
The book introduces descriptive and illustrative information about structure of atoms and nuclei,
radioactivity, chemical bonding, molecular symmetry, structure of solids, redox reactions, non-aqueous
solvents, acids and bases, extraction of elements, Periodic Table, chemistry of known elements,
coordination chemistry, organometallics, inorganic polymers, bioinorganic chemistry, environmental
chemistry and analytical chemistry. Although it is very difficult to include such a vast subject in a single
xviii Preface

book, a reasonable attempt has been made to cover a variety of important topics. We hope this book will
prove very helpful in providing the complex concepts of inorganic chemistry in an easy way.

Salient Features
Comprehensive coverage of topics as per the latest syllabi of various universities—covers all
important topics such as Atomic Structure, Periodic Table, Chemical Bonding, Group Theory,
Coordination Chemistry, Organometallic Compounds
Special emphasis given to theoretical aspects of the concepts
Applications/Case Studies provided throughout for better understanding of the subject
In-depth exploration through solved examples and exercises for self-assessment and skill evalua-
tion
Concise presentation of chemistry of elements and their compounds
Special emphasis on coordination chemistry, including various theories and organometallics
Chapter-end pedagogy designed as per the Indian university examinations
Learning Objectives and Summary with each chapter
More than 750 figures and tables for correlation of data
150 illustrative solved examples
Over 950 unsolved exercises in the form of Review Questions and Objective-Type Questions

Online Learning Center

The text is accompanied by an Online Learning Center that can be accessed at https://www.mhhe.com/
sing/ic1 which contains supplementary material.

Acknowledgements
We feel immense pleasure to place on record our sincere thanks to McGraw Hill Education (India),
New Delhi, for presenting our efforts into reality in the form of this book. Special thanks are due to
Ms Smruti Snigdha, Mr Amiya Mahapatra and Ms Renu Upadhyay, Mr Satinder Baveja, Ms Sohini
Mukherjee and Mr Anuj Shriwastava for their sustained interest in this project. We are also grateful
to our students for their much valuable criticism and suggestions during the development of this book.
Our most heartfelt acknowledgment must go to Prof. Rishav Garg for his assistance and encourage-
ment in all ways. Above all, we would like to thank Ayush Garg and Anusha Garg who silently endured
all the unpleasantness and sacrificed most.

Note of Thanks to Reviewers

We are highly indebted to all the expert reviewers for their generous comments and suggestions on the
manuscript.
Ramesh C Kambhoj Kuruskshetra University, Haryana
Sandeep Kaur University of Delhi, New Delhi
Nand Kishor Singh Banaras Hindu University (BHU), Varanasi, Uttar Pradesh
Ashu Chaudhary Kurukshetra University, Haryana
Debasis Das University of Calcutta, Kolkata, West Bengal
A Jeya Rajendran Loyola College, Chennai, Tamil Nadu
B B V Sailaja Andhra University, Hyderabad, Andhra Pradesh
 Preface xix

Feedback Request from Author

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suggestions and criticisms from readers are highly welcome and will be gracefully acknowledged.
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 chapter

Structure of Atom 1
After studying this chapter, the student will be able to

discovery of the nucleus

effect

principle

1.1 INTRODUCTION
Atom was considered as the smallest indivisible particle of matter till the discovery of fundamental particles,
namely the following: 1
—A negatively charged particle having a mass of about the mass of a proton
1836
(9.1091 × 10–31 kg) and charge equal to 1.60206 × 10–19 C (unit negative charge)
—A positively charged particle having a mass equal to 1.6727 × 10–27 kg and charge equal and
opposite to that of electron (unit positive charge)
—A neutral particle having a mass equal to 1.6748 × 10–27 kg.

1.2 RUTHERFORD SCATTERING EXPERIMENT

The location of the fundamental particles was first described by Rutherford’s a-particle scattering experiment,
in which a-particles from a radioactive element were allowed to strike on a very thin gold foil. The direction of
the deflected a-particles was detected with the help of a movable circular screen (Fig. 1.1).
Rutherford’s observations and conclusions are as follows:
1. Most of the a-particles passed through the gold foil without any deflection. It was concluded that most
of the space in the atom was empty.
1.2 Inorganic Chemistry

Radium
– –
a-particles a-particles Undeflected
a-particles
Rebounded
+
a-particles –
a-particles –
Lead
block Slit –
Thin gold foil

Circular ZnS Largely deflected

screen a-particles
Fig. 1.1 Rutherford experiment and simplified representation of three types of deflection

2. Some a-particles were deflected back through large angles. It was concluded that there is a positively
charged part in the centre of the atom, called as .
3. A few a-particles completely rebounded to their original path. It was concluded that nucleus is very
dense and the whole mass of the atom is concentrated in it.
On the basis of these conclusions, Rutherford proposed nuclear model of atom.

1.2.1 Rutherford Model : Nuclear Model or Solar Model or Planetary Model of

the Atom
According to Rutherford’s model, the following postulates hold:
1. An atom consists of a positively charged body located at its centre, called nucleus. The nucleus is
made up of protons and neutrons. Since, the mass of electron is negligible, the mass of the atom is
almost concentrated in the nucleus.
2. Electrons revolve around the nucleus in different orbits to balance the positive charge on the nucleus.
Therefore, atom is electrically neutral.
3. Most of the surrounding space around the nucleus is empty (volume of the atom is very large as
compared to that of nucleus).

1.2.2 Drawbacks
1. According to classical electromagnetic theory, if a charged particle is subjected to acceleration around
an oppositely charged particle, it emits radiations and hence its energy and speed go on decreasing. It
means, electrons revolving around the nucleus should continuously emit radiations and lose energy.
Due to this, the electron would gradually fall into the nucleus following a spiral path and atom should
be unstable. However, it is not unstable.
2. Due to continuous emission of light radiations, the atomic spectrum should be continuous instead of a
line spectrum.
This means that Rutherford’s model of atom failed to explain the stability of atom and line spectrum of
atom.

1.3 PLANCK’S QUANTUM THEORY OF RADIATION

In 1901, Max Planck studied the spectral distribution of energy emitted by a black body and put forward a
theory known as Planck’s Quantum Theory of Radiation.
 Structure of Atom 1.3

The main postulates of this theory are as follows:

1. The emission or absorption of energy by a body does not take place continuously, but discontinuously,
in the form of small packets of energy called (singular quantum).
2. The energy of each quantum is directly proportional to the frequency, n, of radiation, i.e.,
n or = hn
where, h = 6.626 × 10–34 Js (in S.I. units) and is called Planck’s constant.
3. A body can emit or absorb energy in whole number multiples of quantum, i.e. = n
where, = 1, 2, 3 ............. etc.
This is called quantisation of energy.

1.4 PHOTOELECTRIC EFFECT

Sir J. J. Thomson and P. Lenard observed in some of their experiments that when light beam of suitable
frequency is allowed to strike on the surface of a metal, the electrons are ejected (emitted) from the
surface of the metal. This phenomenon is called photoelectric effect, and the ejected electrons are called
photoelectrons.
It was further observed that only these radiations, which have a certain minimum frequency, called
threshold frequency, can eject the electrons. Different metals have different magnitudes of threshold
frequency. The metals with low ionisation energy mainly show photoelectric effect. An increase in the
intensity of the incident light increases the number of electrons emitted per second from the surface;
however, kinetic energy of photoelectrons remains the same. An increase in the magnitude of the frequency
of the incident radiations increases the magnitude of the kinetic energy of photoelectrons.

Explanation of Photoelectric Effect

In 1905, Einstein afforded an explanation of the photoelectric effect with the help of Planck’s quantum theory
of radiation. He suggested that when a photon of light of frequency, , strikes on the surface of a metal, some
of its associated energy (equal to binding energy called threshold Light beam ejected photoelectron
energy or work function h 0) is consumed to separate the electron of energy ho –
from the atom and the remaining energy is imparted to the ejected
1
electron as kinetic energy (= mu2) (Fig. 1.2). That means,
2
1
h =h 0 + mu2 (1.1)
2 ho0
1
or mu2 = h ( – 0) (1.2) Fig. 1.2 Diagrammatic representation
2 of photoelectric effect

where, 0 is the threshold frequency.

Millikan used Eq. (1.2) to calculate the value of h equal to 6.570 × 10–34 Js, an excellent agreement with
the experimental value equal to 6.626 × 10–34 Js.

1.5 ATOMIC SPECTRUM OF HYDROGEN

If a discharge is passed through hydrogen gas kept at low pressure and the emitted light is studied by a
spectrometer, hydrogen spectrum is obtained, consisting of a number of lines in the visible, ultraviolet and
infrared region. The lines observed in the spectrum are grouped as given in Table 1.1.
1.4 Inorganic Chemistry

In 1885, Balmer found that the wave number n Table 1.1 Spectral series for atomic spectrum of hydrogen
of any line in the visible region of the atomic Name of series Spectral region
spectrum of hydrogen is given by
Lyman series Ultraviolet region
Ê 1 1ˆ Balmer series Visible region
n=R Á - 2˜
Ë 2 2 ¯ Paschen series Infrared region
Brackett series Infrared region
where = 3,4,5 ...... and R is the Rydberg
Pfund series Infrared region
constant or Rydberg number with its value
equal to 109,678 cm–1. Humphries series Infrared region

Rydberg’s Formula
In 1889, Rydberg gave a general relationship for the lines in the hydrogen spectrum as
1 È1 1˘
n= = RÍ 2 - 2 ˙ (1.3)
l ÍÎ n1 n2 ˙˚
for Lyman series, 1 = 1; 2 = 2, 3, 4, 5 ................
for Balmer series, 1 = 2; 2 = 3, 4, 5, 6 ................
for Paschen series, 1 = 3; 2 = 4, 5, 6, 7 ................
for Brackett series, 1 = 4; 2 = 5, 6, 7, 8 ................
for Pfund series, 1 = 5; 2 = 6, 7, 8, 9 ................
for Humphries series, 1 = 6; 2 = 7, 8, 9, 10 ................
In order to explain the line spectrum of hydrogen and to remove the drawbacks of Rutherford’s model,
Neil Bohr put forward an atomic model in 1913.

1.6 BOHR’S MODEL OF THE ATOM

The main postulates of Bohr’s model are as follows:
1. In an atom, electrons revolve around the nucleus in fixed concentric circular shells called energy
shells or energy levels, numbered as = 1, 2, 3, ... and designated by K, L, M..., respectively.
2. Energy levels are associated with a definite amount of energy , which increases with the increase of
distance from the nucleus, i.e.. 1 < 2 < 3 < .........
As long as an electron revolves in a particular orbit, it cannot absorb or emit energy. Thus, these orbits
are also called stationary states or ground states.
3. Energy is emitted or absorbed, by an electron, when electron jumps from one energy level to another.
This energy is equal to the difference in the energies associated with these two levels, i.e.
D = 2 – 1 = hn
where n is the frequency of the energy emitted or absorbed.
This means, energy of an electron cannot change continuously but changes abruptly by a fixed amount,
i.e. energy of an electron is quantised.
4. The angular momentum of an electron in a particular orbit is also quantised, i.e. the angular
h
momentum of an electron can have only definite or discrete values as mnr = n where = 1, 2, 3 ...
2p
 Structure of Atom 1.5

1.6.1 Bohr’s Model for Hydrogen Atom and Hydrogen-like Species (One-electron
Species)
Consider a hydrogen-like species with atomic number equal to Z and an electron of charge e, revolving
around the nucleus, in an orbit of radius r. The charge on nucleus must be +Ze. Let m be the mass of electron
and n be its tangential velocity.
The centripetal force acting on the electron tends to attract the electron towards the nucleus and is equal
Ze2
to (in CGS system of units). While, the centrifugal force acting on the electron tends to take it away
r2 mn 2
from its orbit and is equal to .
r
For an electron to remain in its orbit, these two forces must be equal, i.e.
Ze2 2
= mn (1.4)
r2 r
Ze2
or n2 = (1.5)
mr
According to Bohr’s postulates,
h
mnr = n (1.6)
2p
nh
or n= (1.7)
2p mr
Squaring Eq. (1.7),
n2 h 2
n2 = (1.8)
4p 2 m 2 r 2
From equations (1.5) and (1.8), we get

Ze2 n2 h 2
= (1.9)
mr 4p 2 m 2 r 2

n2 h 2
or r= (1.10)
4p 2 Zme2
th
For radius of the orbit,
n2 h 2
r = (1.11)
4p 2 me2 Z
In the CGS system,
h = 6.626 × 10–27 erg s, p = 3.14, m = 9.108 × 10–28 g, e = 4.8 × 10–10 esu

n2 ¥ (6.624 ¥ 10 -27 erg s)2

Thus, r =
4 ¥ (3.14) ¥ (9.108 ¥ 10 -28 g ) ¥ (4.8 ¥ 10 -10 esuu)2 ¥ Z
2

n2 ¥ (6.624 ¥ 10 -27 )2 erg 2 s2

=
4 ¥ (3.14)2 ¥ (9.18 ¥ 10 -28 ) ¥ (4.8 ¥ 10 -10 )2 ¥ g esu2 ¥ Z
1.6 Inorganic Chemistry

=
0.529 ¥ 10 -8 n2
¥
(
g cm 2 s-2 s2) Èerg = g cm 2 s-2
Í
˘
˙
( ) ÍÎesu = g1/ 2 cm 3 / 2 s-1 ˙˚
Z 2
g. g1/ 2 cm 3 / 2 s-1
0.529 ¥ 10 -8 n2 0.529 ¥ n2
= cm = Å
Z Z
2
0.529 ¥ n
Thus, r = Å (1.12)
Z

For a hydrogen atom, Z = 1, the radius of ground state is designated as the Bohr’s radius (a0).
0.529(1)2
r1 = a0 = = 0.529 Å
(1)
Dividing Eq. (1.5) by Eq. (1.7), we get
n2 Ze2 2p mr
= ¥ (1.13)
n mr nh
Ze2 .2
or n= (1.14)
nh
Again putting all the values, we get
Z (4.8 × 10 −10 )2 × 2 × 3.14 cm s−1 0.2183 × 109 Z
n= , n= cm s−1
n × 6.626 × 10 −27 n
0.2183 × 107 Z
or n= m s−1 (1.15)
n
The total energy of the electron revolving is an orbit in equal to the sum of its kinetic energy  mν 2 
1
 2  2 
and the potential energy  − Ze  , i.e.
 r 
 
1 Ze2
= mν 2 − (1.16)
2 r
Ze2
From Eq. (1.5), mn2 = (1.17)
r
From Equation (1.16) and Eq. (1.17), we get

Ze2 Ze2 − Ze2

= − = (1.18)
2r r 2r
From Eq. (1.11) and Eq. (1.18), we get
− Ze2 4π 2 Zme2
= ×
2r n2 h 2
−2π 2 Z 2 me 4
= (1.19)
n2 h 2
 Structure of Atom 1.7

th
Hence, the energy of an electron in the orbit is given by
2 2 4
−2π Z me
= (1.20)
n2 h 2
Again, putting all the values, we get

−2 × (3.14)2 × Z 2 × (9.108 × 10 −24 ) × (4.8 × 10 −10 )4

= errg
n2 × (6.624 × 10 −27 )2

−11 Z2
= −2.18 × 10 erg
n2
Z2
More accurately, = −2.18 × 10 −11 2
erg atom–1
n
Z2
= –(2.18 × 10–11) × (6.022 × 1023) erg mol–1
2
n
Z2
=– 13.12 × 1012 2 erg mol–1
n
Since 1 erg = 107 J
Z2
= – 13.12 × 105 2 J mol–1
n
Z2
or = – 1312 2 kJ mol–1 (1.21)
n
Since 1 erg = 6.2419 × 1011 eV
Z2
= –(2.18 × 10–11) × (6.022 × 1023) × (6.2419 × 1011) eV mol–1
n2
Z2
= 13.6 eV mol–1
n2
If an electron jumps from the 1, level to the 2 level then

(D ) = – = hn (1.22)
2– 1 2 1

-2p 2 Z 2 me 4 2p 2 Z 2 me 4
Since = & En2 = -
1
n12 h 2 n22 h 2

Equation (1.22) reduces to

2p 2 Z 2 me 4 Ê 1 1ˆ
hn =
2 Á 2 - 2˜ (1.23)
h Ë n1 n2 ¯

2p 2 Z 2 me 4 Ê 1 1ˆ
n=
3 Á 2 - 2˜ (1.24)
h Ë n1 n2 ¯
Since n = nc
1.8 Inorganic Chemistry

from Eq. (1.24), we get

2p 2 Z 2 me 4 Ê 1 1ˆ
nc = 2 Á 2 - 2˜ (1.25)
h Ë n1 n2 ¯

1 2p 2 me 4 Ê 1 1ˆ Ê 1ˆ
For H atom, Z = 1 n= = 3 Á 2
- 2˜ ÁË since v = l ˜¯ (1.26)
l h c Ë n1 n2 ¯

1  1 1 
and n= =R 2 − 2  (1.27)
λ n 
 1 n2 
2p 2 me 4
where R is Rydberg’s constant and is equal to .
h3c
The value of R can be calculated as
2 × (3.14)2 × (4.8 × 10 −10 )4 × (9.108 × 10 −28 )
R= = 109,678 cm–1
(6.624 × 10 −27 )3 × (3 × 10 −10 )

1.6.2 Explanation of Spectral Lines of Hydrogen Atom

The emission spectrum of the hydrogen atom consists of a large number of lines. Bohr provided an
explanation based on his postulates. Any given sample of hydrogen contains a very large number of atoms.
When energy is supplied to this sample of the gas, different atoms will absorb different amounts of energy.
The single electron present in different hydrogen atoms shifts to different energy levels depending upon the
amount of energy absorbed by the atoms. The electrons in higher energy levels are unstable and drop back
to the lower energy levels, emitting energy in the form of line spectrum containing various lines of particular
frequency and wavelength. As depicted in Fig. 1.3, the wavelength of these spectrum lines can be calculated
by using Rydberg’s formula. An excellent argument between the experimental and the calculated values
strengthened Bohr’s model of the hydrogen atom.

8
7
6
Humphries series
5
Pfund series
4 Brackett series

3
Paschen
series
Energy level (not to scale)

2
6562.8 Å

4340.5 Å
4861.3 Å

4101.7 Å

Balmer
series
Continuum

Hα Hb Hγ Hδ H3
1
Lyman series

Fig. 1.3 Energy-level diagram for hydrogen spectrum

 Structure of Atom 1.9

1.6.2 Limitations of Bohr’s Model

1. Bohr’s model cannot explain the origin of the spectra given by multi-electron species.
2. Bohr’s model cannot explain the fine spectrum of hydrogen atom.
3. When an excited atom giving a line emission spectrum is put in a magnetic field, its spectral lines get
split up into a number of closely-spaced lines. This phenomenon is called Zeeman effect.
Similar splitting of the spectral lines is observed in the presence of an electric field. This phenomenon
is called Stark effect. Bohr’s model fails to explain these effects.
4. Bohr’s model considers the electron as a material particle of small mass moving around the nucleus.
But according to De broglie, the electron has a dual character.
5. Bohr’s model contradicts with Heisenberg’s uncertainty principle.

1.7 SOMMERFELD’S EXTENSION OF BOHR’S ATOMIC MODEL

Sommerfeld extended Bohr’s model in 1915 to account for the fine structure of the line spectrum of hydrogen
atom by putting forward the idea of elliptical orbits.
According to Sommerfeld’s modification, electrons revolving around the nucleus can set their motion
in elliptical orbits under the influence of the nuclear charge. These elliptical orbits have a major axis and a
minor axis with different lengths. As the size of the orbit increases, these two axes become equal in length
and the orbit becomes circular.
In Bohr’s model, orbits are numbered as = 1, 2, 3, 4 .... where is known as the principal quantum
number. Sommerfeld used two quantum numbers, radial quantum number nr and azimuthal quantum
number, nf.
These quantum numbers are related to the geometry of the ellipse as
nr + nφ Length of the major axis
= =
nφ Length of the minor axis
There can be the following possibilities:
1. If f < , length of the minor axis will be greater than that of the major axis and the orbit remains
elliptical.
2. If f = , length of the major axis will become equal to that of the minor axis and the orbit becomes
circular.
This means, f and have maximum of values, i.e.
if = 3; f = 1, 2, 3; two elliptical orbits and one circular orbit
= 2; f = 1, 2; one elliptical and one circular orbit
= 1; f = 1; one circular orbit (Fig. 1.4)
Applying the principle of quantisation of momentum to the electron revolving in an elliptical orbit,
Sommerfeld deduced the energy of the electron in the hydrogen atom as
-2p 2 me 4
= 2
(nf + nr ) h2
This means, the energy of an electron depends upon the two quantum numbers f and r. Hence, the
electronic transition from one energy level 1 to another energy levels 2 will result into closely spaced lines
in the hydrogen spectrum depending upon the various possible values of f.
However, Sommerfeld’s theory could not predict the correct number of lines observed in a fine structure.
1.10 Inorganic Chemistry

1.8 DUAL CHARACTER OF MATTER

In 1905, Einstein suggested that light has a dual character, i.e. particle as well as wave character. In 1924,
de Broglie postulated that all forms of matter like electrons, protons, atoms, molecules, etc., also have dual
character. He also derived an expression showing the relationship between momentum and wavelength.

1.8.1 Derivation of de Broglie’s Equation

According to Planck’s quantum theory, the energy of a photon is given by
= hn (1.28) nφ = 3
According to Einstein’s mass–energy relationship,
nφ = 2
= mc2 (1.29)
Equating equation (1.28) and (1.29) nφ = 1
hn = mc2 (1.30)
Since n = c/l, Eq. (1.30) becomes
c
h = mc2 (1.31)
Fig. 1.4 Bohr–Sommerfeld orbits
l when n = 3
or l= (1.32)
mc
For an ordinary particle, c can be replaced by n, the velocity of the particle
h h
l= = (1.33)
mν p
where p is the momentum of the particle. Equation (1.33) is known as de Broglie’s equation.

1.8.2 Experimental Verification of de Broglie’s Equation

The wave nature of electrons was verified experimentally by Davison and Germer in 1927 (Fig. 1.5).
They obtained diffraction pattern of electrons similar to that of X-ray diffraction. Since X-rays have wave
character, electrons should also have wave character.

Beam of electrons
Heated tungsten
filament
Photographic plate

Collimator
Nickel
plate

Diffraction pattern
Fig. 1.5 Representation of Davisson and Germer experiment

1.8.3 Quantisation of Angular Momentum

Consider an electron moving round the nucleus in a circular orbit. According to de Broglie, an electron
behaves as a standing or stationary wave. Its motion can be described in two waves as shown in Fig. 1.6.
 Structure of Atom 1.11

For an electron wave to be in phase, the circumference of the Bohr’s orbit (2pr) must be equal to the
whole number multiple of the wavelength (l) of the electron wave, i.e.
2pr = l (1.34)
λ
2 r
or l= (1.35)
n
h
According to de Broglie l = (1.36)
m
From equations (1.35) and (1.36), we get
2 r h Out of phase In phase
= (1.37)
n m Fig. 1.6 (a) Electron wave out of phase
nh (b) Electron wave in phase
or mnr = (1.38)
2
It is quite evident that electrons can move in only those orbits for which the angular momentum is an
h
integral multiple of , otherwise the electron wave will be out of phase and will emit radiations.
2
Thus, de Broglie concept leads to Bohr’s postulate of quantisation of angular momentum.

1.8.4 Significance of de Broglie’s Concept

The de Broglie concept is significant only for microscopic objects such as atomic and sub-atomic particles.
However, in case of macroscopic bodies, this concept loses its significance. For example, the wavelength
associated with the electron of mass, 9.11 × 10–31 kg with a velocity of 105 ms–1 can be determined as
h 6.626 × 10 −34 Js
l= = 0.7 Å
mν 9.11 × 10 −31 kg × 106 ms−1
whereas, the wavelength associated with a ball weighting 2 × 10–3 kg moving with the same velocity as that
of electron will come out to be
h 6.626 × 10 −34 Js
l= = 3.3 × 10–36 m 3.3 × 10–26 Å
mν 2 × 10 −3 kg × 105 ms−1
This wavelength is too small to be measured and hence is insignificant. This proves that the
de Broglie’s concept is insignificant for macroscopic bodies.

1.9 HEISENBERG’S UNCERTAINTY PRINCIPLE

According to this principle, it is impossible to measure simultaneously the exact position and momentum (or
velocity) of a microscopic moving particle.
h
Mathematically, Dx . Dp (1.39)
4
where, Dx and Dp are the uncertainties in position and momentum of the particle respectively.
Since Dp = mD , where D is the uncertainty in velocity and m is the mass of the moving particle.
Equation (1.39) can be rewritten as
h
Dx . mD (1.40)
4
1.12 Inorganic Chemistry

It means that Dx and Dp (or D ) are inversely proportional to each other. Thus, if Dx is very small, i.e. the
position of the particle is determined with more precision, Dp (or D ) would be large, i.e. uncertainty in
determination of the momentum (or velocity) would be more.
Significance of de Broglie Concept
It is well known that all observations are done by the impact of light rediations. When a moving electron
collides with a photon of light, its velocity and path changes due to transfer of energy from the photon to
the electron. But the position or velocity of an object of reasonable size, will not be altered by the impact
of light radiations. Its quite evident that this concept is significant only for microscopic particles.

1.10 COMPTON EFFECT

Arthur Compton suggested that the photon-electron Scattered
interaction can be considered as a collision between two photon
balls—one moving and the other at rest. He found that
if monochromatic X-rays are allowed to fall on solid
matter, an electron is ejected and X-rays associated with θ
smaller energy are scattered from their original path. Electron
Photon
This decrease in energy or increase in wavelength at rest
of the received photon is known as Compton effect.
According to Compton, if l is the wavelength of the
incident X-rays, l is the wavelength of the scattered Scattered
electron
X-rays, m is the mass of the electron and q is the angle
of scattering, then
Fig. 1.7 Illustration of Compton effect
l
Dl = l – l = (1 – cos q)
mc
Here, Dl is called Compton shift (Fig. 1.7). It is evident that Dl is independent of the nature of the
substance and the wavelength of the incident X-rays. It depends only on the magnitude of the angle of
scattering. He suggested the following:
1. If q = 0°, Dl = 0. It means the scattered photon is parallel to the incident radiation, i.e. there is no
wavelength shift.
h 6.626 × 10 −34 Js
2. If q = 90°, Dl = =
mc (9.11 × 10 −31 kg) (3 × 108 ms−1 )
= 0.2424 × 10–11 m = 0.0242 Å
l
Here, is called Compton wavelength.
mc
2h
3. If q = 180°; Dl = = 2 × 0.0242 Å = 0.0484 Å.
mc
It is evident that the wavelength of the scattered photon is always longer than that of the incident
photon.

1.11 SCHRODINGER WAVE EQUATION

Erwin Schrodinger, in 1926, proposed that if an electron behaves as a wave, there must be a wave equation
to describe its wave motion. This wave equation is called Schrodinger wave equation and for an electron
wave propagating in three dimensions in space, it can be written as
 Structure of Atom 1.13

∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2 m
+ + + (E − V ) ψ = 0 (1.41)
∂x 2 ∂y 2 ∂z 2 h2
 ∂2 ∂2 ∂2  8π 2 m
or  2 + 2 + 2 ψ + 2 ( E − V ) ψ = 0 (1.42)
 ∂x ∂y ∂z  h
2
or 2
y + 8π m ( E − V ) ψ = 0 (1.43)
h2
2  ∂2 ∂2 ∂2 
where, = 
 2
+ 2 + 2 
 ∂x ∂y ∂z 
m is the mass of the electron.
is the total energy of the electron.
V is the potential energy of the electron.
2
is known as the Laplacian mathematical operator.
y is a mathematical function of the space coordinates x, y and z and should be written as y (x, y, z). For
the sake of convenience, it is generally written as y only.
∂ 2ψ ∂ 2ψ ∂ 2ψ
, 2 and are the double differentials of y with respect to x, y and z respectively.
2
∂x ∂y ∂z 2

1.11.1 Derivation of Schrodinger Wave Equation

Schrodinger assumed that the electron waves are similar to the stationary waves. For stationary waves of
wavelength l and displacement in x direction, the amplitude y can be written as
2π x
y = A sin (1.44)
λ
Differentiating Eq. (1.44), with respect to x, we get
∂ψ  2π x   2π 
= A cos (1.45)
∂x  λ   λ 
∂ψ 2π A 2π x
or = .cos (1.46)
∂x λ λ
Differentiating Eq. (1.46) again with respect to x, we get
∂ 2ψ 2π A  2π x   2π 
=  − sin (1.47)
∂x 2
λ  λ   λ 

or ∂ 2ψ −4π 2  2π x  (1.48)
= 2 
A sin
∂x 2 λ  λ 
From equations (1.44) and (1.48), we get

∂ 2ψ −4π 2
= 2 ψ (1.49)
∂x 2 λ
1.14 Inorganic Chemistry

This is the equation for unidimensional stationary wave propagating along the x-axis. For wave motion
extended to three dimensions, Eq. (1.49) can be written as
∂ 2ψ ∂ 2ψ ∂ 2ψ −4π 2ψ
+ + = (1.50)
∂x 2 ∂y 2 ∂z 2 λ2
This equation is applicable to all microscopic particles like electrons. The total energy of an electron is
the sum of its kinetic energy  mν 2  and the potential energy, V
1
2 
1
i.e. = mν 2 + V (1.51)
2
or 1 2 = ( – V) (1.52)
m
2
2
1 ( mν )
or = ( – V) (1.53)
2 m
1 h2 from de Broglie equation 
or = ( – V) (1.54)
2 2m  
λ = h 
1 2m  mν 
or = (E −V ) (1.55)  
λ 2 h2 h
 mν = 
From equations (1.50) and (1.55), we get  λ 

∂ 2ψ ∂ 2ψ ∂ 2ψ −8π 2 m
+ + = ( E − V )ψ (1.56)
∂x 2 ∂y 2 ∂z 2 h2

∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2 m
or + + + ( E − V )ψ = 0 (1.57)
∂x 2 ∂y 2 ∂z 2 h2
8π 2 m
or ∇ 2ψ + ( E − V )ψ = 0 (1.58)
h2
1.11.2 Other Forms of Schrodinger Wave Equation
-h 2
Multiplying both sides of Eq. (1.58) by , we get
8p 2 m
-h 2 2
y + (V – ) y = 0 (1.59)
8p 2 m
-h 2 2
or y + Vy = y (1.60)
2
8p m
 −h 2 2 
or  2 ∇ +V y = y (1.61)
 8π m 

or Ĥ y = y (1.62)
 Structure of Atom 1.15

 −h 2 2 
where Ĥ =  ∇ + V  is called Hamiltonian operator and consists of two parts, i.e. the kinetic
 8π m
2

 
energy part  −h ∇ 2  and the potential energy part (V).
2

 8π 2 m 
 
In terms of polar coordinates,
1 ∂ Ê r 2 ∂y (r , q , f ) ˆ 1 ∂ Ê sin q ∂y (r , q , f ) ˆ 1 ∂2y (r , q , f )
Á ˜ + Á ˜ +
r 2 ∂r Ë ∂r ¯ r 2 sin q ∂q Ë ∂q ¯ r 2 sin 2 q ∂f 2

8p 2 m Ê e2 ˆ y (r , q , f ) = 0
+ Á E + ˜
h2 Ë r¯
Schrodinger wave equation has many solutions for y. However, only some significant values which give
certain definite and acceptable values of the total energy are acceptable. The acceptable values of the wave
function are called eigen (acceptable) wave functions and the acceptable values of total energy are called
eigen values.

1.11.3 Conditions for an Eigen Wave Function

1. It should be finite.
2. It should be single valued.
3. It should be continuous

∂ 2ψ ∂ 2ψ ∂ 2ψ
4. , and must be continuous functions.
∂x 2 ∂y 2 ∂z 2
5. The function should be normalised, i.e. Ú y dt = 1. Fig. 1.8 Electron charge cloud

It should be noted that y has no physical significance. However, y2 gives the probability of finding an
electron in a given region round the nucleus. Thus, there are regions of space around the nucleus in which
there is higher probability of finding an electron. This three-dimensional region is called atomic orbital. An
orbital can be represented by means of electron probability distribution in three-dimensional space around
the nucleus, known as electron charge cloud (Fig. 1.8).

1.11.4 Schrodinger Wave Equation for Hydrogen and Hydrogen-like Species

In terms of polar coordinates,

1 ∂ Ê r 2 ∂y (r , q , f ) ˆ 1 ∂ Ê sin q ∂y (r , q , f ) ˆ 1 ∂2y (r , q , f ) (1.63)

Á ˜ + Á ˜¯ +
r 2 ∂r Ë ∂r ¯ r 2 sin q ∂q Ë ∂q r 2 sin 2 q ∂f 2

8p 2 m
+ ( E - V ) y (r , q , f ) = 0
h2
1.16 Inorganic Chemistry

e2
For a hydrogen atom, potential energy of the electron V = (1.64)
r
From equations from (1.63) and (1.64), we get

1 ∂ Ê r 2 ∂y (r , q , f ) ˆ 1 ∂ Ê sin q ∂y (r , q , f ) ˆ 1 ∂2y (r , q , f ) (1.65)

2 ∂r Á ˜ + 2 Á ˜ + 2 2 +
r Ë ∂r ¯ r sin q ∂q Ë ∂q ¯ r sin q ∂f 2

8p 2 m Ê e2 ˆ
Á E + y (r , q , f ) = 0
h2 Ë r ˜¯
The function y can be written in the form
R(r) Q (i) Φ (z)
y (r, q, f) = (1.66)
radial wave function angular wave function

where, R(r) is a function which depends only on r .Q (q ) is a function which depends on q only and F(f) is
a function which depends only on f.
It corresponds to
∂y ∂R ˘
=QF◊
∂r ∂r ˙˙
∂y ∂Q ˙ (1.67)
= R◊F◊
∂q ∂q ˙
˙
∂y ∂F ˙
= R◊Q
∂f ∂f ˙˚
2 2
After substituting equations (1.66) and (1.67) in Eq. (1.65) and multiplying both sides by r sin q , we get
RQF
sin 2 q ∂ Ê 2 ∂R ˆ sin q ∂ Ê ∂Q ˆ 1 ∂2 F 8p 2 m Ê e2 ˆ
◊ Ár ˜ + ◊ Á sin q ˜ + ◊ 2 + 2 Á E + ˜ r 2 sin 2 q = 0 (1.68)
R dr Ë ∂r ¯ Q ∂q Ë ∂q ¯ f ∂f h Ë r¯

This equation can be split into three simpler equations as

2  2 
1. 1 ∂  r 2 ∂R  − β R(r ) + 8π m  E + Ze  R = 0
  2 2  
2
r ∂r  ∂r  r h  r 

 2 Z   n - l - 1  - ρ / 2 l 2l +1
3
Its solution gives R ( r ) =    e ρ Ln + l ( ρ ) (1.69)
 na0   2 n ( n + 1) 
n,l 3

 2Z 
 r ; Ln + l ( ρ ) is the associated Laguere polynomial;
2 l +1
where ρ =  and are the two integral
na
 0
quantum numbers and a0 is Bohr’s radius.

2. 1 ∂ Ê ∂ˆ ml2 (1.70)
sin q - +b =0
sin q ∂q ÁË ∂q ˜¯ sin 2 q
 Structure of Atom 1.17

(2l+1) l - ml ml
Its solution gives F l,ml (q ) = Pl (cos q ) (1.71)
2 l + ml
where, Plml (cos q ) is the associated Legendre polynomial and m is the third quantum number.
∂2 F
3. 2
+ ml2 F = 0 (1.72)
∂f
1
Its solution gives F = e ± i mlf (1.73)
2p

1.12 QUANTUM NUMBERS

Solution of Schrodinger’s wave equation results into three integral quantum numbers, viz. , and m. The
fourth quantum number has been included to discuss the spin angular momentum of the electron. These
numbers are discussed below in detail.

1. Principal Quantum Number (n)

As already discussed, the principal quantum number represents the number of the main energy level or
energy shell (orbit) in which the electron revolves round the nucleus. It gives the following information:
(a) = 1, 2, 3, 4 ............ represents 1st, 2nd, 3rd, 4th shell, etc. designated as K, L, M and N respectively.
(b) It gives the radius of an orbit (distance of electron from the nucleus) by the equation
n2 h 2
r = (CGS units)
4 2 me2 Z
(c) It gives the energy of an electron in an orbit by the equation
-2p 2 Z 2 me 4
= (CGS units)
n2 h 2
(d) It gives the maximum number of electrons that can be accommodated in a given shell as 2 2.

2. Azimuthal Quantum Number or Subsidiary Quantum Number or Orbital Angu-

lar Momentum Quantum Number (l)
It represents the existence of energy subshells in the principal shell and explains the appearance of the group
of closely spaced lines in the hydrogen spectrum.
For a given value of , total number of values is equal to . The possible values of range from 0 to ( – 1).
This means:
For = 1, = 0; only one subshell for 1st shell
= 2, = 0, 1; two subshells for 2nd shell
= 3, = 0, 1, 2; three subshells for 3rd shell, and so on.
The subshells are designated as
= 0, 1, 2, 3, 4.....
, and so on.
It gives the following information:
(a) Total number of subshells in a given shell =
(b) Maximum number of electrons that can be accommodated in a given subshell = 2 (2 + 1). Thus
subshells can have 2, 6, 10, 14 electrons respectively.
1.18 Inorganic Chemistry

h
(c) Orbital angular momentum of an electron = l (l + 1)
2π
3. Magnetic Quantum Number or Orientation Quantum Number (ml or m)
Orbital angular momentum is a vector quantity and can have a number of orientations in space. As a result,
the accompanying magnetic momentum can also have a number of orientations in space represented by
magnetic quantum number, m.
For a given subshell, m can have its value from – to + (through zero) and each represents a particular
orbital, a three-dimensional space in which probability of finding an electron is maximum.
It means,
Z-axis
For = 0, m = 0; only one orbital in -subshell, known as -orbital
= 1, m = –1, 0, +1; three orbitals in p-subshell, known as p-orbitals
= 2, m = –2, –1, 0, +1, +2; five orbitals in d-subshell, known as d orbitals
It gives us the following information:
(a) The maximum number of orbitals in a given subshell = 2 +1
(b) The maximum number of electrons in any orbital = 2
(c) It accounts for the Zeeman effect, i.e. splitting of spectral lines in
presence of strong magnetic field. Orbital angular momentum can
have (2 + 1) components along any chosen direction. For example, l=2
the d-orbital can have five orientations of its orbital angular Fig. 1.9 Orientation of orbital
momentum in the presence of external magnetic field as shown in angular momentum
Fig. 1.9. Thus, a spectral line splits into five lines in the presence of
an external magnetic field corresponding to electronic transition from a higher to a lower orbital of an
atom.

4. Spin Quantum Number (s)

An electron spins about its own axis either in a clockwise direction or anticlockwise direction and behaves
like a small magnet. Thus, the spinning of the electron generates a magnetic moment known as spin angular
h
momentum of the electron given by s(s +1) , where is known as spin quantum number of the
2π
electron corresponding to the two possible spin directions. The spin quantum number can have two values,
1 1
i.e. (corresponding to clockwise direction) and (corresponding to anticlockwise direction).
2 2

1.13 PROBABILITY DISTRIBUTION CURVES

Depending upon the probability of finding the electron in a particular region at a given radial distance and in a
particular direction from the nucleus, two types of probability distributions are discussed below:

1. Radial Probability Distribution Curves of Electrons

The curves obtained by plotting the radial distribution function (4pr2R2) as a function of radial distance,
r give the probability of finding of the electron at different radial distance from the nucleus. The radial
probability distribution curves for a hydrogen atom are shown in Fig. 1.10. As can be seen in these diagrams,
the probability is zero at r = 0, i.e. at the nucleus for every orbital. Each plot shows one or more peak, i.e.
 Structure of Atom 1.19

Fig. 1.10 Radial probability distribution for hydrogen atom

region of maximum probability of electrons. The number of peaks for an orbital is equal to ( – ). The
surface at which the probability of finding an electron comes out to be zero is called node. Any orbital can
have a maximum of ( – – 1) nodes (neglecting the nodes at infinity) (Fig. 1.10)

2. Angular Probability Distribution Curves or Shapes of Orbitals

The angular function depends only on the direction and is independent of the radial distance, r. The angular
probability distribution curves are noted as polar diagrams and symmetry of the angular functions are shown
by the sign (+) and (–) as shown in the Fig. 1.11.

Fig. 1.11 Angular probability distribution curves

It is evident that there is a different shape for every orbital. The s-orbitals can have only one orientation
and hence are spherically symmetrical. The p-orbitals can have three orientations (px, py and pz orbitals
depending upon the direction) and are of dumb-bell shape. The two lobes of a p-orbital are separated by
1.20 Inorganic Chemistry

a nodal plane of zero electron density perpendicular to the corresponding axis. The d-orbitals can have
five orientations, i.e. there are five d-orbitals. The three d-orbitals, namely dxy, dyz and dxz have their lobes
lying in the planes, and the two d-orbitals, namely dx2–y2 and dz2, have their lobes lying along the axis.

RULES FOR FILLING OF ORBITALS AND ELECTRONIC CONFIGURA-

1.14 TION OF ELEMENTS

The atomic orbitals are filled up according to the following rules:

1. Aufbau Rule
According to this rule, the orbitals are filled in increasing order
of energy, i.e. the orbital with the lowest energy is filled up first
followed by the orbital with the higher energy.
Energy of the orbital is determined using the ( + ) rule.
According to this rule, the orbital with lowest ( + ) value has
lowest energy. For two orbitals with same ( + ) values, the orbital
with lower has lower energy. Using these rules, the sequence of
filling of the various orbitals has been represented in Fig. 1.12.

2. Pauli’s Exclusion Principle

This principle was put forth by Wolfgang Pauli in 1925. According Fig. 1.12 Sequence of filling of
various atomic orbitals
to this principle, it is impossible for any two electrons in the same
atom to have all the four quantum numbers same. For example,
for a K shell, two combinations of the quantum numbers can be
=1 =0 m=0 =+½
=1 =0 m=0 =–½
It is evident that three quantum numbers are same but the fourth is different. In other words, two
electrons in the same orbitals have opposite spins. Since, the third electron has to acquire either of these two
combinations, which is not possible, it is excluded from the orbitals. Thus, an orbital can have maximum of
two electrons, with opposite spin.
This principle is used to determine the maximum number of electrons in a subshell and shell.
Table 1.2 Maximum number of electrons for subshells and shells
Principal quan- Azimuthal quantum Magnetic quantum Spin quantum Maximum number of
tum number (n) number (l) number (m) number (s) electrons
1 0 0 +½
2 electrons
1 -subshell 1 -orbital –½
2 0 0 +½ 2 electrons
2 -subshell 2 -orbital –½
–1 +½
1 –½ 8 electrons
2p-subshell 0 +½
–½
+1 +½ 6 electrons
2p-orbital –½
 Structure of Atom 1.21

Principal quan- Azimuthal quantum Magnetic quantum Spin quantum Maximum number of
tum number (n) number (l) number (m) number (s) electrons
3 0 0 +½ 2 electrons
3 -subshell -orbital –½
–1 +½
–½
1 +½ 6 electrons
3p-subshell 0 –½
+½
+1 –½ 18 electrons
3p-orbitals
–2 +½
2 –½
3d-subshell –1 +½
–½
0 +½ 10 electrons
–½
+1 +½
–½
+2 +½
3d-orbitals –½

3. Hund’s Rule of Maximum Multiplicity

Spin multiplicity is represented by 2S + 1, where S is the total spin of electrons. According to Hund’s rule,
in case of degenerate orbitals (orbitals of same energy), orbitals are filled up to have maximum multiplicity.
For example, in case of 2p orbitals with 3-electron arrangement I has maximum spin multiplicity and is
more stable because of the following reasons:

I II III
2S + 1 = 2 × 3 +1 2S + 1 = 2 × 1 +1 2S + 1 = 2 × 1 +1
=4 2 =2 2 =2 2
(a) Symmetry An arrangement with symmetrical distribution of charges is more stable because of
lesser electrostatic repulsion as in case of the arrangement I.
(b) Exchange Energy Two electrons with parallel spins can exchange their positions and lead
to decrease in energy known as exchange energy. It means that arrangement I has least energy
because of more possible exchanges and hence is more stable.
(c) Pairing Energy Due to considerable repulsion between two electrons in the same orbital, some
energy for pairing of two electrons known as pairing energy is required. This means that pairing
increases the energy of the system and destabilises it.
In short, Hund’s rule can be stated as : in the ground state, pairing of degenerate orbitals is not done till
each orbital is singly occupied.
1.22 Inorganic Chemistry

n=6 6p
6s 5d 4f

n=5 5p
5s 4d

n=4 4p
n=4
4s 3d
4s 4p 4d 4f

Energy
n=3
n=3 3p
3s 3p 3d
3s
Energy

n=2

2p n=2 2p
2s
2s

n=1
n=1
1s 1s
For hydrogen atom For multi-electron atoms
Fig. 1.13 Energy-level diagrams
Table 1.3 Electronic configurations of first twelve elements
Name Symbol Electronic configuration Representation
1
Hydrogen 1H 1

2
Helium 2He 1

Lithium 3Li 1 22 1

Beryllium 4Be 1 22 2

Boron 5B 1 2 2 2 2p1

Carbon 6C 1 2 2 2 2p2

Nitrogen 7N 1 2 2 2 2p3

Oxygen 8O 1 2 2 2 2p4

Fluorine 9F 1 2 2 2 2p5

Neon 10Ne 1 2 2 2 2p6

Sodium 11Na 1 2 2 2 2p6 3 1

Magnesium 12 Mg 1 2 2 2 2p6 3 2
 Structure of Atom 1.23

Anomalous configurations of chromium and copper are the result of more stability of exactly half-
filled and completely filled orbitals, reasons being the decrease in energy due to more symmetry and more
exchange energy in half-filled and completely filled orbitals (as discussed earlier).
¼ ¼ ¼ ¼ ¼
¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼
d5 d10
(The more symmetrical distribution and more the chances of exchanges between electrons of parallel spin)
¼ ¼ ¼ ¼
¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼ ¼
d4 d9
(the less symmetrical distribution and less chances of exchanges between electrons of parallel spin.)

The first successful attempt to explain the stability of an atom was made by Rutherford
during his scattering experiment. He proposed that an atom consists of a positively
charged central nucleus surrounded by electrons revolving in their orbits. However,
this model couldn’t justify the stability of an atom and its spectrum. To remove
these drawbacks, Bohr formulated his theory of atomic structure. He postulated that
electrons move in circular orbits with a definite amount of energy associated with the
orbits. These orbits are known as stationary or ground states. An electron can absorb
some fixed amount of energy and move to a higher energy state. When it comes
back to its ground state, it releases energy equal to the difference in energies of the
0.529 n2
two levels. According to Bohr, the radius of the th orbit is equal to r = Å, velocity of an electron,
Z
7 1312 Z 2
v = 0.2183 ¥ 10 Z ms–1 and energy of an electron in the th orbit, is = kJ/mol. However,
n n2
according to de Broglie, every matter has a dual character, i.e. particle as well as wave character and the
wavelength associated with a particle, λ = h . Heisenberg pointed out in his uncertainty principle that it
mν
is impossible to determine both the position and momentum of a microscopic particle simultaneously with
complete accuracy. The uncertainty in measurement is given by
h
Dx.mDn
4
Thus, the probability concept came into light and Schrodinger formulated the wave equation for the
∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2 m
behaviour of a small particle as + + + 2 ( E − V )ψ = 0
∂x 2 ∂y 2 ∂z 2 h
The accepted valued of these wave function y are known as eigen functions and the corresponding energy
values are known as eigen values.

EXAMPLE 1 When light radiation of wavelength 300 mm strikes a metal surface, the ejected
electrons possess the kinetic energy equal to 1.68 × 105 J mol–1. Calculate the work function of
the metal and the threshold wavelength.
1.24 Inorganic Chemistry

Kinetic energy of 1 mol of electrons = 1.68 × 105 Jmol–1

1.68 × 105
Kinetic energy of one electron = = 2.789 × 10 −19 J
6.022 × 1023
Now, hn = hn0 + K.E.
or hn0 = hn – K.E.
hc
hn0 = – K.E.

 6.626 × 10 −34 Js × 3 × 10 −8 ms−1  −19

=
  − 2.789 × 10 J
 300 × 10 −9 m 

= 6.626 × 10–19J – 2.789 × 10–19J = 3.837 × 10–19 J

Work function of electron = 3.837 × 10–19 J
hc
i.e. = 3.837 × 10–19 J
0
6.626 × 10 −34 Js × 3 × 10 −8 ms−1
l0 = = 5.181 × 10–7 m
3.837 × 10 −19 J

EXAMPLE 2 Using Bohr’s theory, calculate the energy of an electron in first shell of H atom
and Li2+ ion.

According to Bohr’s theory, energy of an electron is given by the expression

1312 Z 2
= kJ/mol
n2
For electron in first shell of H-atom; Z = 1 and = 1
1312 (1)2
1 = = – 1312 kJ/mol
(1)2
For 1s electron of Li2+ ion, Z = 3 and = 1
1312 (3)2
= = – 11808 kJ/mol
(1)2

EXAMPLE 3 Calculate the wavelength of the emitted photon, when an electron in the H-atom
returns from n = 2 to n = 1.

1  1 1 
= 109678  2 − 2  cm −1
λ  
 1 2 

1 1 1 
= 109678  2 − 2  cm −1
λ 1 2 
1 3
= 109678 × cm −1
λ 4
 Structure of Atom 1.25

4
l= cm–1 = 12.20 × 10–6 cm
109678 3
= 122 nm

EXAMPLE 4 Calculate the ionisation energy of the Be3+ ion.

For ionisation energy of the Be3+ ion, 1= 1 and 2 =
D = 2– 1

 −1312 Z 2   −1312 Z 2 
= 
  −   kJ/mol
 n22   n12 

 1 1  1 1 
= −1312 Z 2  − = −1312 (4)2  − 2  = 1312 × 16
 n2 n2   ∞ (1) 
 2 1 

= 20 992 kJ/mol.

EXAMPLE 5 Calculate the radii of the first and third orbits of the hydrogen atom.
0.529 2
Radius of an orbit, r = n Å
Z
For hydrogen atom, Z = 1 and for first orbit, = 1
r1 = 0.529 Å

For third orbit, = 3r3 = 0.529(3)2 = 4.761 Å

EXAMPLE 6 Calculate the velocity of an electron in second orbit of hydrogen atom.

Z
Velocity of an electron, n = 0.2183 × 107 ms–1
n
For hydrogen atom, Z = 1 and for second orbit, = 2
0.2183 ¥ 107
n2 = = 1.095 × 106 ms–1
2
EXAMPLE 7 Calculate the wavelength associated with a body of mass 5 mg moving with a
velocity of 2 ms–1.
h
According to de Broglie’s concept, l =
m
h = 6.626 × 10–34 Js, m = 5 mg = 5 × 10–6 kg, n = 2 ms–1

h 6.626 × 10 −34
l= = = 6.625 × 10 −29 m
mν 5 × 10 −6 × 2
1.26 Inorganic Chemistry

EXAMPLE 8 Calculate the uncertainty in the velocity of a body of 0.02 kg mass whose
position is known with an uncertainty of 0.5 × 10–5 m.

According to the uncertainty principle,

h h
Dx × m Dn = or Dx =
4 4π × m∆x
–34 –5
h = 6.626 × 10 Js; m = 0.02 kg and Dx = 0.5 × 10 m

6.626 × 10 −34
D = −5
ms–1 = 5.3 × 10–28 ms–1
4 × 3.14 × 0.02 × 0.5 × 10

EXAMPLE 9 Which of the following orbitals are allowed: 2p, 5p, 6d, 5h

2p n=2 l =1 Allowed
Èl = n - 1 to 0 ˘
5p n=5 l =1 Allowed Í ˙
Í and ˙
6d n=6 l=2 Allowed
ÍÎl π n ˙˚
5h n=5 l=5 Not allowed

EXAMPLE 10 What are the possible values for the quantum numbers for an electron in the
3p orbital?

For the 3p orbital, = 3, = 1, m = –1, 0, +1 and ms = +½ and -½ for each value of m.

EXAMPLE 11 How many subshells and orbitals are possible for the n = 5 energy level?

For = 5, = 0, 1, 2, 3, 4

Thus, there are five corresponding subshells, viz. 5 , 5p, 5 5 and 5 .

2
The total number of orbitals for any shell =
For = 5, the total number of orbitals = (5)2 = 25

EXAMPLE 12 Calculate the wavelength of the first and limiting line of the Lyman series in the
H atom.

For first line of Lyman series, = 1, 2 =2

1  1 1  3 4
= 109678  2 − 2  = 109678 × , λ = = 122 nm
λ  (1) (2)  4 109678 × 3

For limiting line of Lyman series, 1 = 1, 2 =0

1  1 1  1 –6
= 109678  2 − 2 
= 109678 , λ = 109678 cm = 9.117 × 10 cm = 9117.6 nm
λ  (1) (∞) 
 Structure of Atom 1.27

QUESTIONS
Q.1 Discuss Rutherford’s model and its drawbacks.
Q.2 Enumerate the postulates of Bohr’s model. How does Bohr’s model explain the spectrum of
hydrogen?
Q.3 Derive an expression for the radius of an orbit, velocity, and energy of an electron in the hydrogen
atom.
Q.4 Calculate the radii of the second and fifth orbits in hydrogen.
Q.5 Calculate the frequency of light emitted when an electron in an excited state undergoes transition
from the third orbit to the first orbit.
Q.6 Calculate the wavelength of the first and limiting line of the Balmer series.
Q.7 Calculate the ionisation energy of the Li+ ion.
Q.8 Calculate the de Broglie wavelengths of an electron moving at 20% the speed of light.
Q.9 Calculate the uncertainty in the position of an electron if uncertainty in its velocity = 3 × 10–2 ms–1.
Q.10 State Heisenberg’s uncertainty principle and discuss its significance.
Q.11 What are the drawbacks in Bohr’s theory of atomic structure?
Q.12 Write down the Schrodinger wave equation and define each of the terms in it.
Q.13 What is eigen function and what is its significance?
Q.14 Define quantum numbers and explain the significance of each of these numbers.
Q.15 Explain the following:
(a) Photoelectric effect (b) Compton effect
(c) Pauli’s exclusion principle (d) Exchange energy
Q.16 Describe Hund’s rule of maximum multiplicity.
Q.17 Differentiate between an orbit and orbital.
Q.18 Why are half-filled and completely filled orbitals more stable? Justify your answer with the help of
suitable examples.
Q.19 Discuss Schrodinger wave equation for hydrogen atom.
Q.20 Draw probability distribution curves for 2s and 3p orbitals.

MULTIPLE-CHOICE QUESTIONS
1. The electronic level in hydrogen atom that can absorb a photon but not emit is
(a) 1s (b) 2s (c) 2p (d) 3s
2. What will be the uncertainty in the momentum of an e–, if uncertainty in its position is zero
(a) Zero (b) ½ (c) 2 (d) > h/2
3. The ratio of energy of two radiations with wavelengths 1000 Å and of 2000 Å respectively would be
equal to
(a) ¼ (b) ½ (c) 4 (d) 2
4. In the ground sate of chromium atom, the total no. of orbitals populated by the electrons are equal
to
(a) 14 (b) 20 (c) 16 (d) 15
5. In the third Bohr orbit of Li2+ ion, the velocity of the electron is equal to
(a) 6.6 × 108 cm/s (b) 19.8 × 108 cm/s (c) 2.2 × 108 cm/s (d) 4.4 × 108 cm/s
 chapter

Nuclear Chemistry 2
After studying this chapter, the student will be able to

disintegration

2.1 NUCLEUS
We have already discussed the structure of an atom in Chapter 1. The Rutherford scattering experiment
revealed the existence of a positively charged central part of an atom termed nucleus. The experiment proved
that size of the nucleus is incredibly small, of the order of 10–15 m. Further experiments have shown that
the radius of the nucleus is given by r = R0A1/3 where R0 is a constant with a value equal to 1.5 × 10–15 m
and A is the mass number of the element. Nuclear radii are measured in femtometres (1 fm = 10–15 m). For
example, the nucleus of oxygen has a radius of 2.5 fm. Studies have proved that most of the mass of an atom
is concentrated in the nucleus. Hence, the density of the nucleus is very
Nuclear mass
high and is given by the relation, r = g/cm 3
4p 3
¥ (Nuclear radius)
3
Density of the nucleus is found of the order of 2.4 × 1014 g/cm3.

2.2 COMPOSITION OF THE NUCLEUS

Early studies established that the nucleus is composed of protons and neutrons collectively called nucleons
and were considered as fundamental particles. But after the experimental verification of the dual character of
the electron, a British scientist, Dirac presented a quantum mechanical treatment of an electron in the form
2.2 Inorganic Chemistry

of antiparticle theory. He suggested that in the universe, there are some unstable fundamental particles along
with the stable fundamental particles.
He considered that to every particle in the universe, there is a corresponding antiparticle. Thus, there must
exist anti-electrons, antiprotons and antineutrons corresponding to electrons, protons and neutrons respectively.
The first antiparticle was discovered by Carl Anderson in 1932. He bombarded light elements with alpha
particles and was successful to discover a new particle as anti-electron which was later called positron.
10
5B + 42He $ 137N + 10n
13
7N $ 136C + +10 e
anti-electron
(positron)
An electron and positron mutually annihilate each other producing gamma ray photons.
0
+1e + (–1)0e $ hn + hn´
In 1930, Wolfgang Pauli put forth the theory of beta decay and indicated the existence of the neutrino
to explain the loss of mass during the decay of free neutron into a proton and an electron. A neutrino has
zero charge and variable mass, always less than the mass of an electron. The existence of other particles was
demonstrated later in 1952, by Allen and Rodeback. In 1934, Enrico Fermi indicated the existence of the
antineutrino, a particle identical to neutrino but with opposite spin. The existence of the antineutrino was
proved by Reines and Cowan in 1953. A Japanese physicist, Hideki Yukawa in 1934, combined the theory of
relativity and quantum theory and described the nuclear interactions by the exchange of new particles called
mesons, between protons and neutrons. Mesons were actually detected later in certain radiation experiments.
In 1949, Enrico Fermi and C.N. Yang suggested that a nucleon and an antinucleon exist as a composite
particle called pyion. Nowadays, with the existence of the modern high-technology equipments, many more
particles have been discovered. These particles can be divided into two categories, i.e. elementary particles
and composite particles.

2.2.1 Elementary Particles

The elementary particles are the fundamental particles and are not composed of other particles. These are
classified according to spins of these particles into two types:

1. Fermions
These elementary particles have half integer spin (½) and have their own distinct antiparticle. These are
further divided its two types, viz. quarks and leptons.
(a) Quarks Quarks are the fundamental constituents of nucleons and are subjected to strong nuclear
forces. The name was given by Murray Gell–Mann in 1964. These are in six forms and can be
arranged into three families as given in the Table 2.1. Their respective antiparticles are known as
antiquarks which carry the opposite electric charge.
(b) Leptons Leptons are lighter particles and are not subjected to strong forces. They are not found
in the nucleus, but may be produced in the nucleus and are quickly expelled. The leptons also
come in six forms arranged in three families as given in Table 2.1. The neutral leptons are
collectively called neutrinos.
2. Bosons
Bosons are the particles which mediate the fundamental force of nature and carry integer spin. The elemen-
tary bosons are listed in Table 2.2.
 Nuclear Chemistry 2.3

Table 2.1 Fermions (spin = ½)

Family Quarks Leptons

Name Symbol Electrical Rest mass Name Symbol Electrical Rest mass
charge in MeV charge in MeV

I Up u +2/3 ~5 Electron e –1 0.511

Down d –1/3 ~7 Electron- e 0 <0
neutrino

II Strange s –1/3 ~ 150 Muon m –1 105.7

Charged c +2/3 ~ 1500 Muon- m 0 < 0.170
neutrino

III Bottom b –1/3 5000 Tau t –1 1784

Top t +2/3 >41,000 Tauneu- e 0 <15.5
trino

Table 2.2 Bosons

Name Symbol Electrical Rest mass Spin Force mediated

Charge in GeV
Photon g 0 0 1 Electromagnetic
W boson W– –1 80.4 1 Weak nuclear
Z boson Z 0 91.2 1 Weak nuclear
Gluon g 0 0 1 Strong nuclear
Higgs boson H0 0 116 – 130 0 Mass
Graviton G 0 0 2 Gravitational

2.2.2 Composite Particles

These are the particles which are not the fundamental particles and are composed by elementary par-
ticles. These are commonly called hadrons and are held together by strong forces. These are grouped
into two families, viz. baryons and mesons.
1. Baryons
Baryons are composite fermions and are made up of three valance quarks. The common baryons are listed
in the Table 2.3. Each baryon has its corresponding antiparticle.
Table 2.3 Baryons
Symbol Quark composition Charge Rest mass (MeV)
Proton p uud +1 938.27
Neutron n udd 0 939.56
Delta D– ddd –1 1232.00
Lambda Å uds 0 1115.68
Sigma S+ uus +1 1189.37
Omega W– sss –1 1672.00
Xi X° uss 0 1315.00
2.4 Inorganic Chemistry

2. Mesons
Mesons are composite bosons and are made up of a valence quark and an antiquark. Each meson has its
corresponding antimeson. Some common mesons are listed in Table 2.4.
Table 2.4 Mesons

Particle Symbol Antiparticle Quark Rest mass Charge

composition (MeV)
Positive pion p+ p– ud 139.6 +1
Negative pion p– p+ ud 139.6 –1
Kaon K+ K– us 493.7 +1
–
Upsilon Y self bb 9460.4 0

2.3 NUCLEAR FORCES

The earliest attempt to describe the nature of the nuclear force was made by Hideki Yukawa in 1934. He put
forth his meson theory emphasing the interaction between two nucleons through mesons. Further studies
revealed that nuclear force is a strong interaction mediated by gluons
that binds quarks to force the nucleons. These forces are short-range p
form but strong enough to bind two different or even same neutrons as n
shown in Fig. 2.1. r
n
proton + p0 proton p+ + neutron p
neutron + p0 neutron p– + proton
Fig. 2.1 Nuclear forces
Nuclear Binding Energy
It has been seen that except for hydrogen, all other atoms, have the atomic mass less than the sum of the
masses of electrons, neutrons and protons present in it. This difference in mass, termed the mass defect,
assures of the binding energy, the energy responsible for binding of nucleons together in the nucleus. The
mass defect can be converted into energy using Einstein’s relation, E = mc2.
The energy corresponding to one unit of amu can be obtained as
1 amu = (1.66054 × 10–27 kg) × (2.99792458 × 108 m/s)2
= 1.4922 × 10–10 J
Since 1 MeV = 1.602 × 10–13 J
1.4922 × 10 −10
The energy equivalent to 1 amu = MeV = 931.5 MeV
1.602 × 10 −13
Now, consider the case of one helium atom, consisting of 2 protons, 2 neutrons and 2 electrons.
Mass of one helium atom = 4.00260361 amu
Total mass of its constituents = 2(1.00782522) + 2(1.00866544) + 2(0.000548) amu
= 4.0329812 amu
Mass defect = (4.0329812 – 4.00260361) amu = 0.0303176 amu
Thus, the energy equivalent to mass defect for one helium atom = 931.5 × 0.030776 MeV = 28.29 MeV
This means the binding energy of one helium atom is 28.29 MeV.
2p + 2n $ 24He + 28.29 MeV
Thus, binding energy of a nucleus = Mass defect (in amu) × 931.5 MeV
i.e. B.E. = m × 931.5 MeV
Another random document with
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The Project Gutenberg eBook of Jewish fairy stories
 This ebook is for the use of anyone anywhere in the United States and most
other parts of the world at no cost and with almost no restrictions whatsoever.
You may copy it, give it away or re-use it under the terms of the Project
Gutenberg License included with this ebook or online at www.gutenberg.org. If
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country where you are located before using this eBook.

Title: Jewish fairy stories

Translator: Gerald Friedlander

Illustrator: Beatrice Hirschfeld

Release date: February 5, 2024 [eBook #72880]

Language: English

Original publication: New York: Bloch Publishing Company, 1917

Credits: Jeroen Hellingman and the Online Distributed Proofreading Team at

https://www.pgdp.net/ for Project Gutenberg (This file was produced
from images generously made available by The Internet
Archive/American Libraries.)

*** START OF THE PROJECT GUTENBERG EBOOK JEWISH FAIRY STORIES ***
[Contents]

[Contents]

JEWISH FAIRY STORIES

[Contents]

AN EXCELLENT PRIZE BOOK. 2/6

JEWISH FAIRY TALES

AND FABLES
By AUNT NAOMI
Illustrated by E. STRELLETT and J. MARKS

Square Crown 8vo. Handsome Illustrated Cover. Cloth, 2s. 6d.

“Children, both Hebrew and Christian, into whose hands it may fall, will
agree that it ought to have a companion volume.”—Pall Mall Gazette.

“They are not merely of passing interest, but are of the stuff that winds
into the fibre of those who read them.”—Daily News.

“This little book is perhaps mainly intended to give Jewish children a

chance of learning some of the beautiful stories to be found in Jewish
folk-lore and legends; all the same they will be welcome to children of
the Gentiles also.”—Publishers’ Circular.

“Non-Jewish readers will enjoy in the possession of this altogether

charming volume one of the few opportunities which are afforded to
experience, in the medium of the vernacular, the human interest of the
Rabbinical writings.”—Liverpool Post.

“Its attractive ‘get-up’ and the excellence of its contents combine to

render it an ideal gift-book, and we may add that it is not only Jewish
children who will be delighted to possess it.”—Jewish World.

“Though intended primarily for Hebrew children, it should have, as it

deserves, a warm welcome from those who are not of the ancient
faith.”—Cassell’s General Press.

LONDON: ROBERT SCOTT, PATERNOSTER ROW, E.C.

[Contents]
 Jewish Fairy Stories

TRANSLATED BY
GERALD FRIEDLANDER
ILLUSTRATED BY
BEATRICE HIRSCHFELD

BLOCH PUBLISHING COMPANY

NEW YORK

[vi]

[Contents]
 Preface

THE tales in this book have been gathered together from various Jewish writings.
The translation is not literal in any sense of the word. In fact, each story has been
recast and presented in a modern setting. Some of the stories are fairy tales. Jewish
fairy tales reveal an aspect of the Jewish soul in much the same way as the various
national fairy tales embody something of the spirit of the different peoples and
nations.

G. F.

September, 1917. [vii]

[Contents]
 Contents
PAGE

King Solomon and the Worm (from the Babylonian Talmud) 3

Falsehood and Wickedness (from the Yalḳuṭ) 19
The Wicked King and his Bride (from the Ma’aseh Book) 25
The Two Jewels (from the Shebet Jehudah) 43
The Beggar at the Wedding (from the Midrash Tanchuma) 53
The Clever Wife (from the Yalḳuṭ) 69
The Coins of Elijah (from the Yalḳuṭ) 77
The Fox and the Raven (from R. Berachyah’s Fox Fables) 87

[viii]

[Contents]
 List of Illustrations

PAGE

Benaiah setting out on his journey 2

The Queen sprinkling the Water of Life on Chaninah 24
Abraham being carried to his new quarters 68
Elijah bestows his gift 76
“Good-day, dear friend Raven” 86

[1]

[Contents]
 KING SOLOMON AND THE WORM

[2]

BENAIAH SETTING OUT ON HIS JOURNEY.

[3]

King Solomon and the Worm

KING Solomon, the wisest of men, resolved to build a temple dedicated to the glory
of the God of Israel. He remembered the sacred words of Scripture: “And if thou
make me an altar of stone, thou shalt not build it of hewn stones: for if thou lift up
thy tool upon it, thou hast polluted it” (Exod. xx. 25). The tools of iron symbolized
the sword, the instrument of war and death; whilst the altar and temple were the
symbols of peace and life. Solomon desired that not only the altar, but all the stone-
work in the sacred edifice should be made ready for the builders at the quarry
without using any metal implement, so that in the course of building the temple no
instrument of iron should be employed.

How was this wish to be realized? Even Solomon, the wisest of monarchs, did not
know how to set about his task. Again and again he asked himself, How is it possible
to split [4]the immense blocks of stone or to cut down the huge trees if the workmen
are not allowed to use metal implements? In despair the King summoned his great
council of state, consisting of the wisest men in his kingdom. He told them his
difficulty and asked them if they could help him to achieve his purpose. The
counsellors listened to the words of their beloved monarch in profound silence. After
a while one of the most venerable of those present arose and, turning to the King,
spake as follows:—

“Long live the King! Mighty Sovereign! Hast thou not heard that among the countless
creatures of the Most High there is one which can serve thee as thy heart desires? It
can cut stone better than the sharpest tool of iron. I refer to the tiny but wonderful
worm called the Shamir, or diamond insect. Dost thou not know, O wisest of rulers,
how the Almighty created ten marvels in the twilight of the eve of the first Sabbath
in the week of creation? Among these marvels was the worm Shamir. Its size is that
of a grain of barley. It is endowed with miraculous power, for, behold! it can split the
hardest stone by merely touching it. Moreover, iron is broken by its mere presence.”

“Excellent wisdom is this which thou shewest [5]forth, beloved counsellor,” cried
Solomon with joy in his heart. “Now tell me, where is this marvellous little worm to
be found?”

“May thy days be as glorious as the days of David thy father,” replied the wise
servant of the King, “but more than I have already told thee I know not. No mortal
being has ever discovered the home of the Shamir. It is useless to seek the
information thou desirest by consulting the sons of men; has not God bestowed upon
thee, knowledge and understanding more than He has given to any one else? Is it
for nought that thy wisdom exceeds that of all the children of men? Art thou not
ruler of all the spirits and demons? Seek their aid, Sire! and thou wilt find the Shamir.
Invoke the wisest of the spirits who will reveal to thee even the secrets of the
heavens above, of the earth beneath, and of the waters under the earth.”

The good advice of the counsellor appealed with irresistible conviction to Solomon’s
heart, and after thanking his wise minister, dismissed his council in order to carry out
the suggested plan. He looked at the ring on his right hand and read the Holy Name
of God engraved thereon. No sooner had he pronounced the Divine Name than a
demon appeared before him and, making obeisance, cried,— [6]

“What is thy wish, Solomon, King of Israel?”

“I command thee,” said Solomon, “to tell me where is the worm Shamir to be
found?”

In a trembling voice the demon replied,—

“Mighty King of man and spirits! I am thy servant, I will always obey thee if I have
the power so to do. Be not angry with me, for I fear I cannot help thee now. The
secret thou desirest to know has not been revealed to any of the inferior demons. It
is only Ashmodai our King who is in possession of the secret.”

“Tell me,” interrupted King Solomon, “where does Ashmodai, the King of the demons
dwell?”

“May it please your gracious Majesty,” the demon responded, “Ashmodai lives far, far
away from the haunts of men. His palace is built on the top of a very high mountain.
In this same mountain he has had a very deep well dug. Daily he fetches his drinking
water from this well. When he has obtained sufficient water for his immediate needs,
he closes up the mouth of the well with an enormous rock which he seals with his
signet-ring. He then flies up to heaven to receive the orders of those who are his
superiors. His tasks take him to the ends of the earth, even beyond the great sea.
With the going down of the sun in the west, [7]he returns to his own home. He
examines very carefully the seal on the rock at the mouth of the well, in order to find
out if it has been tampered with in his absence. He then proceeds to uncover the
well and he partakes of the water. Having quenched his thirst he covers up again the
mouth of the well and seals it afresh.”

King Solomon sat on his wonderful throne of gold whilst the demon told his tale. Not
a word escaped the memory of the wise King. He then dismissed the demon, who
disappeared in less than a second. Thereupon Solomon summoned to his presence
his brave captain and friend Benaiah, son of Jehoiada. He told him briefly the nature
of the task he was chosen to undertake, saying,—

“Go, trusty servant Benaiah, and capture Ashmodai, the King of the demons, and
bring him before my presence. To assist thee in thy arduous and perilous undertaking
I will give thee this golden chain on the links of which the letters forming the Divine
Name are engraved. I also will entrust to thy care my signet-ring which is also
engraved with the Holy Name of the Most High. Take with thee also this large bundle
of white wool and these skins full of strong wine.”

After giving him minute instructions about [8]the journey and the way to overcome
Ashmodai, he sent Benaiah on his way, wishing him complete success in all his
undertaking.

The brave warrior, confident of success, set out on his dangerous expedition. After
many days of hard riding across the great desert he ultimately reached his
destination. Never had he seen such a desolate spot. In front of him stood the
towering mountain without sign of any human habitation in the vicinity. The
mountain seemed to be the abode of silence and death. Undaunted by the uncanny
scene, Benaiah began the ascent of the rugged mountain with a stout heart. He
feared neither man nor spirit, for he was wearing on his little finger King Solomon’s
signet-ring. When half-way up the mountain he bored a hole in order to discover the
whereabouts of Ashmodai’s well. Great was his delight when he discovered the
position of the well. He drew off the water and stopped up the hole with the wool
which he had brought with him. Quite near to this hole, Benaiah pierced an aperture
which ran into the well. Through this channel he poured all the wine in the skins.
After this labour was completed he concealed himself behind a large crag and waited
impatiently for the arrival of the King of the demons.

Soon after sunset Ashmodai drew nigh. He [9]carefully examined the seal on the rock
over the mouth of the well and found it intact, even as he had left it early in the
morning. After he had rolled away the rock, he descended into the well to quench his
thirst. The strange odour of the fragrant wine overpowered him so that he quickly
returned to the mouth of the well to inhale the fresh mountain air. Realizing that the
well had been tampered with, he again examined the seal, but it did not appear to
have been touched. Meanwhile a burning thirst in his throat forced him to descend
again in order to obtain something to drink. No sooner had he tasted the wine than
he desired to drink more and more. After he had partaken very freely of the strong
wine, he felt quite drowsy. All his senses were overpowered. His head became heavy,
his body staggered and his knees gave way. At last he fell to the ground and slept
soundly.

Benaiah now came forth from his hiding-place and crept very quietly to the sleeping
demon. Without wasting a moment, the good captain threw the golden chain around
Ashmodai’s neck and secured it and sealed it with the golden signet-ring engraved
with the Divine Name. Benaiah sat on the ground close by waiting for the effects of
the strong wine to wear off. After a while Ashmodai awoke and [10]found that he was
no longer free, for he saw the golden chain around his neck and he beheld the Holy
Name on the seal. He uttered such a terrible groan that the mountain shook. In vain
Ashmodai endeavoured to rise up. In his anger sparks of fire flew from his eyes and
foam covered his mouth.

He continued to wriggle and to struggle with the air, but all to no purpose. He could
not arise. He looked at Benaiah and cried in bitter anger,—

“Is it thou who hast bewitched me?”

“Verily,” replied Benaiah, “behold the Name of the Lord of lords is upon thee.”

Ashmodai immediately became quiet and calm. He knew that he was vanquished and
realized that all further resistance would be futile. He told Benaiah that he was quite
ready to obey his orders.

“Come then,” cried Benaiah, “we will go at once to King Solomon, thy master. Arise
and follow me.”

Ashmodai arose and followed Benaiah, who was surprised at the peculiar behaviour
of his captive on their way to the Holy City. Wherever they passed, Ashmodai left
behind him a trace of his might or intelligence. In one village he brushed against a
palm tree. After its foliage had been shaken off by the terrific impact, [11]he uprooted
it with one hand. In another place he knocked his shoulder against a house and
overturned it. In a market-place in a large town they met a happy bridal procession.
When the bride and bridegroom passed, Ashmodai began to weep.

“Why dost thou weep?” Benaiah asked in surprise.

“Alas!” replied Ashmodai, “within three days the bridegroom will be a corpse. Do I
not do well to weep?”
In the next town on their journey they overheard a farmer asking a bootmaker to
make a pair of shoes which were to last him for seven years. Whereupon Ashmodai
burst out laughing.

“Tell me, Ashmodai” cried Benaiah, “why dost thou laugh?”

“Because the poor fellow will not wear his shoes for even seven days; behold within
a week he will die—yet he asks for shoes to last him seven years.”

One day they met a blind man going astray. Ashmodai hastened to set him on the
right path. He showed a similar kindness to a drunkard whom they met at the cross-
roads. On another occasion they saw a magician who was exhibiting his skill in
public. He claimed to be able to read the future and to disclose secrets. Here again
Ashmodai found occasion [12]for mirth and laughter. When Benaiah asked him to
explain his strange conduct, he remarked,—

“Wouldst thou not laugh also at a man who pretends to reveal secrets, whilst at the
same moment he is unaware of the fact that a treasure lies buried at his feet? We
demons judge persons and things according to their true value and not according to
their deceptive appearance in the eyes of man.”

After many strange adventures they finally came to the Holy City. Benaiah conducted
his captive to the royal presence. As soon as Ashmodai beheld King Solomon, fear
seized him and he began to tremble violently in every limb. He held a long staff in his
hand on which he supported himself. After his attack of nervousness had subsided,
Ashmodai threw his staff before the King.

“What art thou doing?” asked Solomon.

“Mighty Sovereign, gracious master,” replied Ashmodai, “dost thou not know that in
spite of all thy splendour and glory thou wilt occupy after thy death no more space in
the earth than is measured by yonder staff, yet thou art not satisfied with ruling the
children of men, but thou must needs hold the spirits and demons in subjection.”

“Be not vexed,” Solomon said in a gentle [13]tone of voice; “thou wilt not find me a
hard master. I merely demand one little service at thy hands. Know then that I wish
to build a great Temple to the glory of the Creator of heaven and earth, and for this
purpose I require the services of the wonderful worm Shamir. Tell me now, where
can I find this tiny creature?”

“O wisest of mortals,” replied Ashmodai, “dost thou not really know that the Shamir
has not been placed in my charge? Why then hast thou brought me here?”
“Where is it?” thundered Solomon; “speak, slave! and speak truly.”

Ashmodai with a trembling voice replied,—

“Mighty master! Since the days of Moses, who employed the Shamir when writing on
the tablets of stone, the worm has been entrusted to the care of the Prince of the
Sea who has given it into the charge of the wood-cock. The latter has sworn to the
Prince of the Sea to carry the Shamir with him at all times. The wood-cock lives in a
big nest built on the top of a very lofty pinnacle in a mountain range. He has
employed the Shamir to split the hard rock so as to plant seed in the clefts. The new
vegetation which grows there is used for food by the wood-cock. Whenever he goes
from his nest he takes the Shamir with him, carrying [14]it beneath his wing, mindful
of his oath to the Prince of the Sea.”

“Enough,” cried Solomon; “thou shalt abide with me till the Temple is built.”

Once again King Solomon summoned his trusty captain Benaiah, telling him to
discover the nest of the wood-cock and to obtain the Shamir and to bring it back to
the Holy City.

“Take with thee,” said the King, “a glass cover, a little wool and a small leaden box.
May thy journey be as successful this time as thy former one.”

Benaiah obeyed with a glad heart all the instructions which King Solomon had given.
He set out on his journey, crossing hill and dale, stream and desert. At last he
discovered the nest of the bird he sought. The wood-cock was away on one of his
expeditions. In the nest were the fledgelings. Benaiah now covered the nest with the
glass cover which he had brought with him for this purpose. He then concealed
himself and awaited events.

When the wood-cock returned he attempted to enter his nest, but found himself
foiled, for the glass was very hard and strong. He saw through the glass his helpless
young; and flapping his wings and screeching loudly tried [15]to break the glass. All
his efforts were in vain. The young birds frightened by the noise also began to
screech.

“What is to be done?” cried the wood-cock in the language of the birds.

Again and again he tried to smash the glass, but without success. As a last resource,
he determined to make use of the precious treasure entrusted to his care. He
produced the Shamir from beneath his wing and put it on the glass which split into
pieces as soon as it was touched by the wonderful worm. At that instant Benaiah
raised a lusty cry and frightened the wood-cock so that he dropped the Shamir. It
had barely fallen upon the ground when it was seized by Benaiah, who carefully
placed it in the wool and secured it by putting it in the small leaden box which he
had brought for this special purpose.

Without lingering a moment, Benaiah set out on his homeward journey, rejoicing
greatly at his complete success. In chagrin the wood-cock killed himself, fearing the
terrible vengeance which the Prince of the Sea would execute when the
disappearance of the Shamir became known. Benaiah reached the Holy City in safety
and delivered to King Solomon the wonderful worm. With its marvellous help the
wise King built the Temple, and thereafter [16]the Shamir has disappeared and no
one knows where it is to be found.

(Babylonian Talmud Giṭṭin, 68 a and b.)

[17]

[Contents]
 FALSEHOOD AND WICKEDNESS

[18]

[19]
 Falsehood and Wickedness

AFTER good old father Noah had completed the building of the ark, the animals were
gathered together near it by the angels appointed over them. They came in pairs,
and Noah stood at the door of the ark to see that each one entered with its mate. As
soon as the waters of the flood rose upon the surface of the earth, the children of
men hid themselves in their homes for safety. All traffic and business ceased, for the
angel of death was abroad. This state of affairs caused Falsehood to realize that
henceforth there was no chance of her plying her trade. Was it not quite evident that
the ever-increasing waters of the flood would soon sweep away the wicked folk
[20]who had rebelled against their Heavenly Creator? Where should Falsehood betake
herself for safety?

Forthwith she hastened to the ark, but its door was shut. What was to be done?

Falsehood knocked at the door with trembling hand. Noah opened the window of the
ark, and put out his head to see who was knocking. It was a strange creature before
his door. Noah had never seen her before, because he was a righteous man who
never told lies.

“What dost thou want?” he cried.

“Let me come in, please,” she replied.

“Gladly,” cried Noah, “would I admit thee if thy mate were with thee, for only pairs
are admitted here.”

In grief and disappointment Falsehood went away. She had not gone a few yards
before she met her old friend Wickedness, who was now out of employment.

“Whence cometh thou, dear friend Falsehood?” asked Wickedness.

“I come,” said Falsehood, “from old father Noah. Just listen. I asked him to let me
come into the ark, but he refused unless I complied with his rules.”

“What does he require?” asked Wickedness.

“The good old man stipulated that I must have a mate, because all the creatures
admitted [21]into the ark are in pairs,” Falsehood replied.

“Now, dear friend, is this the truth?” queried Wickedness with a merry twinkle in his
evil eye.

“Of course it is the truth, on my word of honour,” rejoined Falsehood. “Come now,”
she added, “wilt thou be my mate? Are we not just fit to be joined together, two
honest and poor creatures?”

“If I agree,” said Wickedness, “what wilt thou give me in return?”

Falsehood thought awhile and with a cunning look at her friend she exclaimed,—

“I faithfully promise to give to thee all that I earn in the ark. Have no fear, I shall do
excellent business even there, because I feel very fit and energetic.”
Wickedness agreed to the terms immediately, and there and then a proper
agreement was drawn up, and duly signed and sealed. Without further delay they
both hastened to Noah, who readily admitted the happy pair.

Falsehood soon began to be very busy and earned good money. She often thought of
her agreement with Wickedness with regret, as she realized that she alone did all the
business. She even said to him one day,—

“Look here, how easily can I carry on my trade single-handed?”

He merely reminded her of the agreement, [22]and day by day he wrote down in his
ledger the sum total of the day’s takings.

At the end of the year, for the flood lasted twelve months, they came out of the ark.
Falsehood brought home much treasure, but Wickedness came with her and claimed
the whole of the hard-earned fortune. Thereupon Falsehood said to herself, “I will
ask my mate to give me some of my earnings.”

She approached Wickedness and in a gentle voice said,—

“Dearest friend, please give me a share of what I have so honestly earned, for I
alone did all the work.”

Wickedness looked at her in contempt and with harsh voice cried aloud,—

“Thy share is nought, O cheat! Did we not solemnly agree that I was to take
everything which thou shouldst earn? How could I break our agreement? Would this
not be a very wicked thing to do, now would it not?”

Falsehood held her peace and went away, well knowing that she had been foiled in
her attempt to cheat her friend Wickedness. True indeed is the proverb: “Falsehood
begets much, but Wickedness taketh all that away.”

(Yalḳuṭ, Psalms § 638.) [23]

[Contents]
 THE WICKED KING AND HIS BRIDE

[24]

THE QUEEN SPRINKLING THE WATER OF LIFE ON CHANINAH.

[25]

The Wicked King and his Bride

LONG, long ago there lived in the Holy Land an old peasant and his wife. They had
an only son who was also married. The family all lived happily together in a little
house in a village near Samaria. The son, whose name was Chaninah, was a very
good man, deeply learned in the Holy Scriptures and the ancient lore of Israel.

In course of time the old father, feeling his end drawing near, called his beloved son
to his bedside and said to him,—

“Hearken, my son, to the words which I am [26]about to speak. Your mother and I
will soon die. After our death and burial you will observe the customary period of
mourning and lamentation. On the day following go to the nearest market-place and
buy the first thing offered to you, be the price what it may. I also charge you to
continue the study of the Holy Word of the Bible by day and by night, keep the
Divine Commandments, support the poor and be kind to the dumb creatures.”

After he had spoken these words he blessed his son and closed his eyes in the sleep
of death.

Chaninah went to tell his mother of the death of his father. The sad news was too
much for the poor woman and the shock killed her instantly. The pious son buried his
beloved parents in the village cemetery and returned home to keep the customary
period of mourning and lamentation, which lasted seven days.

Mindful of his father’s dying words, Chaninah went on the following morning to the
nearest market-place. One of the merchants, carrying a beautiful silver casket in his
hands, came to him and said,—

“Will you buy this casket?”

“What is the price?” asked Chaninah.

“I will take eighty pieces of silver for it,” answered the merchant, and he added, “I
will not accept any less.” [27]

Chaninah agreed, and there and then paid the large sum of money demanded,
thinking all the while of his dear father’s last wish. The money which he had spent in
buying the casket was nearly all the fortune he possessed.

Without any further delay he returned home with his purchase, which he was
anxious to show to his wife.

“Look here,” he cried, “I have spent nearly all our money in buying this casket, even
as dear father told me to do just before he died.”

“Open it,” said his wife; “there is sure to be something very valuable inside it.”
He lifted the lid of the casket and was astonished to find that it contained another
silver box. He took this out and opened it, curious to learn what was inside. To their
great surprise a little green frog leapt out.

“Well, I never,” cried Chaninah, “this is an expensive creature.”

“Do not forget,” his wife said, “your father’s command to be kind to the dumb
creatures.”

“Quite right,” says her husband, “we will provide for the frog even as though the little
fellow were one of us.”

The frog grew larger and larger and the silver box was no longer large enough for its
quarters. Chaninah therefore made a nice roomy cupboard for their new friend’s
abode. After a [28]while the wife told her husband that there was no more money left
to buy food. With a very sad heart the good man called the frog to his side and said,
—

“I am awfully sorry to tell you, dear little friend, that we cannot feed you any longer
because we have no food left even for ourselves.”

“Please don’t worry,” cried the frog, “I hope you will believe me when I tell you that I
am indeed more than grateful to you both, for all your kindness and hospitality. Let
me prove my gratitude by giving you this piece of advice. In the box where you
found me, you will see a strip of parchment. If you place it in the fold of your turban
you will be able to understand not only the different languages of mankind but also
the speech of birds, fish and beasts.”

Chaninah did exactly as the frog told him, and calling his wife told her that they
would accompany the frog to his new home wherever it might be. The frog said this
should be in a pond in the wood near by.

They all went to the wood feeling sad that poverty was forcing them to part
company.

As soon as they came to the wood the frog told them to rest themselves. Then at the
bidding of the frog, the birds and beasts in the wood brought to Chaninah and his
wife an immense [29]quantity of valuable gems and an assortment of roots and
herbs. The kind-hearted frog gave these gifts to his good friends, explaining how the
herbs and roots were to be used for healing purposes. Then at last the frog bids his
friends farewell and tells them that he was really a son of Adam and the demon
Lilith, and that he had the power of changing himself into any shape.
Chaninah and his wife gathered up the precious gems, roots and herbs and returned
home. On the way they met a caravan and offered some of the gems for sale. A
good bargain was struck and Chaninah and his wife found themselves with plenty of
money. They left their old home and bought a nice house. Riches did not spoil them,
for their hearts were kind. Moreover Chaninah kept faithfully the charge of his
beloved father. He studied the holy words of Scripture by day and by night and
observed the Divine precepts with a good will. Their home was always open to the
poor. The good fortune of Chaninah spread far and wide. His reputation as a
charitable man reached the ears of the King who invited him to visit his Court.

The King took a great fancy to Chaninah and persuaded him to take up his abode in
the palace. The King was by no means a pious [30]man, in fact he was very wicked
and cruel. He was unmarried, and this fact alone displeased his subjects. His
counsellors urged him to find a good wife, saying to him,—

“Let us, O King, remind you that we require not only a king but also a queen and
little princes; for there will surely come a time when a new king will have to be found
—because kings and queens are mortals and they cannot live for ever.”

They did not tell the King what their real motive was in advising him to marry. They
thought that if the King were to find a true and good wife it might be possible for her
to use her influence and make him a better man.

The King dismissed his counsellors, promising to see them again in a week’s time,
when he would tell them whether he would marry or not. When they came to the
palace at the appointed time the King’s valet met them and told them that His
Majesty would receive them in the palace garden.

They went there and found the King sitting on his throne. As they approached he
rose up and bade them welcome. At that moment a beautiful bird flew over the King
and dropped a long golden hair upon his shoulder. The King took the hair in his hand
and turning to his counsellors said,— [31]

“I will marry only the maiden to whom this golden hair belongs. No other wife shall
be mine. You wish me to marry—well and good—so be it. I now command you to
discover the owner of this golden hair, and mark you, if you do not bring her to me
within a year from to-day I will have you and all your families put to death.”

The counsellors were greatly distressed at the turn of events. They feared that their
lives would be forfeit. How were they to find the lady whose golden hair had brought
misfortune to them and their families? With sad hearts they left the royal presence,
and when they were outside the palace they asked one another, “What is to be
done?”

Chaninah, who was now one of the King’s counsellors, offered to find the lady
destined to be their queen. He hastened home to bid his wife farewell and to prepare
for his journey. He took a bag into which he put six loaves, a small assortment of his
precious herbs and roots and twelve silver coins. Having blessed his wife he set out
on his quest.

He walked during the best part of the day and at sunset, feeling very tired, he sat
down on a large stone beneath a tree. He was just about to doze off when he was
suddenly startled by hearing a raven’s croak. He listened and [32]understood that the
bird had not found any food for three days. He at once opened his bag and gave the
raven a large piece of bread. On the morrow Chaninah met a dog howling miserably.

“Come and tell me,” he said to the dog, “all your troubles. I understand the speech
of beasts and birds.”

The dog said that he was very ill and hungry, for it was just a week since he had
eaten any food. Chaninah gave him one of the healing roots and a loaf of bread. The
dog devoured the bread and ate the root and thanked his good friend.

Next day Chaninah came to a river and found some fishermen trying in vain to pull in
their net, which contained a large fish. The fishermen pulled so hard that they feared
their net would break. Chaninah lent them a willing hand and then they were able to
pull in the net. The fishermen shouted with joy,—

“We have enough now for dinner to-day and to-morrow.”

Chaninah asked them to sell the fish and he would give them twelve pieces of silver
as its price. They agreed and gave him the fish as soon as he had paid them. They
could hardly believe their eyes when they saw Chaninah throwing the fish back into
the river. [33]Bidding them farewell he continued his journey.

At last he came to a large town where, unknown to him, dwelt the maiden whom he
was seeking. She was a princess, the only daughter of the King of that country.

Chaninah came to the courtyard of the palace and stood still awhile gazing around.
The Princess was looking out of the window of her room, and saw Chaninah, whose
strange attire attracted her attention. She sends her chamberlain to bring him to her
presence.
In reply to her inquiry as to the why and wherefore of his visit to her father’s land,
Chaninah tells her the story of his quest. Looking at her he sees that she is the very
lady whom he has to find to be the wife of the King, his master, for her tresses were
golden even like the hue of the hair which the King found upon his shoulder.

“Come, good lady, with me,” he cries, “and save my people, the wise men of Israel
and their families, who are in mortal danger. Come and be Queen in our land and
save the soul of our lord the King.”

The Princess had listened very attentively to all the strange story told by Chaninah,
and in reply she said,—

“Well do I remember drying my hair one day [34]last month in the garden of our
palace, and whilst doing so a strange bird flew over my head three times and then
plucked out one of my hairs. He flew away with the hair and I can now believe that
this is the very bird which brought my hair to the King of your land. I will accede to
your wish and consent to become the Queen of your land if you fulfil two tasks which
I will set you. The first I will mention at once. Here I have two empty flasks. You
must bring them back to me full of water. I do not mean the water of the brook or
well, but the one flask must contain water from Paradise and the other must be filled
with water from Hell. When you have done this task I will tell you all about the
second one.”

With a kind word of farewell the Princess dismissed Chaninah. He left the palace with
a sad heart and prayed to God to help him in his difficulty. Was he not trying to save
the lives of his brethren in the Holy Land?

After a little while he hears the croak of a raven speaking as follows:—

“Dear friend! do you no longer remember me? Did you not give me bread when you
met me? I was so hungry then, for I had not tasted any food for three days. Now
just tell me, How can I be of service? I will gladly do my best to please you.” [35]

Chaninah told the raven all about the task which the Princess had set him to do.

“Here are the flasks,” he said; “one must be filled with water from Paradise and the
other must be filled with water from Hell.”

The raven told him to tie a flask to each wing and at sunset to be at the spot where
they were conversing. The raven flew to the netherworld and singed his wings in
passing through the flames of Hell. At last he reached the black boiling waters in the
centre of Hell and filled one flask. He then flew to the gates of Paradise and found
the spring which flows from its midst and bathed in its cool water to heal his wings.