Volume 3B

Third Edition Volume

Fundamental Concepts of 3B
Volume 3B
Inorganic Chemistry

Fundamental Concepts of
Third Edition
Volume 1: Atomic Structure; Wave Mechanics and Quantum Chemistry; Nuclear Structure;
Nuclear Chemistry; Nuclear Reactions and Nuclear Energy; Radiation Chemistry; Nucleosynthesis
of Elements; Chemical Periodicity of the Elements.
Volume 2: Bonding Theories (VBT and MOT) of Covalency; Structure and Reactivity of Covalent
Fundamental Concepts of

Inorganic
Compounds; Stereochemical Nonrigidity and Fluxionality; Molecular Symmetry and Point Groups;
Hydrogen Bonding and other Weak Chemical Forces; Supramolecular Systems and Molecular
Recognitions.
Volume 3A: Solid State Chemistry—Structure and Bonding; Magnetic and Ferroelectric Materials;
Bonding in Metals and Metal Clusters; PSPT—Wade's Rule and Jemmi's Rule; Electrical
Conductivities of Solids; Semiconductors and Superconductors; Acids and Bases and Ionic

Inorganic Chemistry
Equilibria.
Volume 3B: Nonaqueous Solvents and Ionic Liquids; Redox Potentials, Formal Potentials and
Applications; EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating

Chemistry
Reactions; Principles of Metallurgy and Refining and Purification of Metals; Different Techniques of
Separation—Solvent Extraction, Ion Exchange and Chromatography.
Volume 4: Coordination Chemistry: Introduction, Structure, Stereochemistry and Isomerism,
Nomenclature, Bonding Theories (VBT, CFT, LFT and MOT), Applications of CFT, JT Distortion,
Spectrochemical Series, and Stabilities of Metal Complexes.
Volume 5: Coordination Chemistry: Inorganic Reaction Mechanisms (Ligand Substitution,
Isomerisation, Racemisation, Electron Transfer and Photochemical Reactions), Electronic Spectra
of Metal Complexes.
Volume 6: Coordination Chemistry: Magnetochemistry and Magnetic Properties of Metal
Complexes; Structure, Bonding and Reactivities of Organometallics including Metal Carbonyls )
O(s
and Nitrosyls; Organometallics as Catalysts. 2Cu
(g)®
Volume 7: Application of Metal Complexes in Analytical Chemistry and other Fields; Applications + O2 (g)
(s)
2Cu 2CO
2
of Spectrophotometric Methods (IR, Raman, NMR, ESR, Mossbauer, UV-VIS, UV-PES); Theory of Errors (g)
and Statistical Treatment of Data. O (g)® HO
)®2 2 –
2
( g I2/2I
(g) + g) +
O2
2CO 2H 2(
Asim K Das BSc (1st Class 1st, CU), MSc (Gold Medalist, CU), PhD (CU), DSc (Visva Bharati)
is currently Professor, Department of Chemistry, Visva Bharati University, Santiniketan, West Bengal. He has over C(s) + O2(g)®CO2(g)
30 years of teaching experience at the both undergraduate and postgraduate levels. He passed both the BSc 3– 4–
(Hons In Chemistry) in 1981 and MSc (specialization in Inorganic Chemistry) in 1983, Standing First Class First, [Fe(CN)6] /[Fe(CN)6]
from the University of Calcutta. He received his PhD degree from the same University under the supervision of 2C(
s) +
Prof D Banerjea, the then Sir Rashbehari Ghose Professor of Chemistry. He received his DSc degree from Visva O(
2 g)
Bharati in 2002. Dr Das has published more than 80 research papers in the field of thermodynamic and kinetic ®2
CO
aspects of metal complexes in reputed national and international journals. He has written the books, (g)
Bioinorganic Chemistry; Environmental Chemistry with Green Chemistry; Biophysical, Bioorganic and pH
Bioinorganic Chemistry; An Introduction to Nanomaterials and Nanoscience and An Introduction to
Supramolecular Chemistry.
Third
Edition

ISBN: 978-93-90709-12-0 Das Asim K Das

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 Volume 3B
Fundamental Concepts of

Inorganic
Chemistry
Third Edition
 Contents at a Glance
Volume 1

1. Classical and Vector Models of Atom

2. Origin of the Quantum Theory
3. Fundamentals of Wave Mechanics
4. Wave Mechanical Model of Atom
5. Atomic Nucleus and its Structure
6. Radioactivity and Radiation Chemistry
7. Nuclear Reaction
8. Periodic Table and Periodic Trends of Different Properties of Elements

Volume 2

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

Theory (VBT) and Molecular Orbital Theory (MOT)
10. Covalent Compounds—Characteristics, Structure and Reactivity
11. Hydrogen Bonding and Other Weaker Chemical Forces Including Supramolecular
Systems
Volume 3A

12. Structure, Bonding and Properties of Ionic Solids and Solid State Chemistry
13. Bonding in Metals and Metal Clusters—Electrical Conductivities of Solids:
Semiconductors and Superconductors
14. Acids and Bases and Ionic Equilibria in Aqueous Solutions

Volume 3B

15. Nonaqueous Solvents

16. Redox Systems and Electrode Potential—Application of Electrode Potential:
Electroanalytical Techniques
17. Metallurgy: Principles, Pyrometallurgy vs Hydrometallurgy—Extraction and
Purification of Metals, Physicochemical Methods of Separation of Metals

Appendices (common to all three volumes)

Appendix I: Units and Conversion Factors
Appendix II: Some Physical and Chemical Constants
Appendix III: Wavelength and Colours
Appendix IV: Names, Symbols, Atomic Numbers and Atomic Weights of the Elements
Appendix V: Some Useful Mathematical Relationships
 Volume 3B
Fundamental Concepts of

Inorganic
Chemistry
Third Edition

Asim K Das
MSc (Gold Medalist, CU), PhD (CU), DSc (Visva Bharati)
Professor, Department of Chemistry
Visva Bharati University, Santiniketan 731235
West Bengal, India

Mahua Das
MSc (CU), PhD (Visva Bharati)
Formerly Research Associate
Department of Chemistry
Visva Bharati University, Santiniketan 731235
West Bengal, India

Ankita Das
MSc (Visva Bharati)
DST INSPIRE Research Fellow (IACS, Kolkata)

CBS Publishers & Distributors Pvt Ltd

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 Disclaimer
Science and technology are constantly changing
fields. New research and experience broaden the
scope of information and knowledge. The authors
have tried their best in giving information available
to him while preparing the material for this book.
Although all efforts have been made to ensure
optimum accuracy of the material, yet it is quite
possible some errors might have been left
uncorrected. The publisher, the printer and the
authors will not be held responsible for any
Volume 3B inadvertent errors or inaccuracies.
Fundamental Concepts of

Inorganic
Chemistry
Third Edition

ISBN: 978-93-90709-12-0
Copyright © Authors and Publisher

Third Edition: 2021

First Edition: 2000
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Second Edition: 2010
Reprint: 2012, 2013, 2014, 2016, 2017, 2019
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 to
my dear students and readers, the living source of inspiration
and
the memory of my mother
Late Maharani Das
who struggled silently and tolerated the extreme pains of poverty
just to bring up us and to the memory of my second elder brother,
Late Pramatha Nath Das
who had an ambition,
his younger brother to study in the premier institute,
Ramakirishna Mission Residential College, Narendrapur, Kolkata.

Asim K Das
 Foreword
Present-day inorganic chemistry is no more a collection of unrelated facts. The scenario has undergone
a drastic change over the last fifteen to twenty years with the application of kinetic, thermodynamic
and structural studies to inorganic substances and with newer techniques providing newer information.
Often the information gathered, has made theoreticians develop/modify valency theories and principles.
In this situation every teacher and student realise the importance of a textbook that will help them
develop the concepts and understanding of the subject. There are attempts by a few authors at achieving
this goal but those seldom cover the whole curricula followed by most of the Indian universities and
institutes. In many of these books the authors virtually neglect the evolutionary developments of the
subject, creating undesirable lacunae in the readers' understanding. Here is an honest and sincere
attempt at bridging these gaps and presenting a comprehensive textbook on concepts and understanding
to the readers. The treatment of every topic is elaborate and is marked by remarkable clarity and the
author has not compromised with the volume of his work. The book Fundamental Concepts of
Inorganic Chemistry covers the inorganic chemistry curricula at the BSc (honours) and MSc
(preliminaries).
A large number of exercises and problems essential for modern teaching have been incorporated
meticulously at the end of each chapter to bridge the gaps, if any, in the understanding of the subject.
Hope this earnest effort of Dr Das, a teacher of distinction, will receive well-deserved acclaim from
the students and teachers of this subject.

Dr AV Saha DSc
Head of the Department of Chemistry
Ramakrishna Mission Residential College
P.O. Narendrapur, 24-Parganas (S)
West Bengal, India, Pin: 743508
 Jðkoku~ yHkrs Kkue~
One who has shraddha acquires knowledge

Preface to the Third Edition

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

We feel delighted to record the warm response which the first and second editions of the book has
received from the students and teachers throughout the country. We have incorporated all the aspects
of choice based credit system (CBCS) syllabus recently introduced in all universities and institutes
and the suggestions received from the readers. In this edition, each chapter has been thoroughly
revised, updated and rewritten to accommodate the recent views. In this enlarged version, scope of
the book has been broadened by adding new topics and revisions of the earlier sections. In revising
the book, we have taken all the measures to retain the basic features for which the earlier editions
have been so popular.
In preparing the manuscript, we have again freely consulted the original research papers, books
and reviews of the earlier authors and have borrowed their ideas whenever required. We are grateful
and indebted to them. We are grateful to Ms Udita Das, for her assistance in revising the text.
All the facilities provided by our institute, Visva Bharati, are thankfully acknowledged. We are
extremely grateful to Mr SK Jain, Managing Director, CBS Publishers & Distrubutors, New Delhi,
for his hearty support and encouragement. We are also thankful to Mr YN Arjuna, Senior Vice
President (Publishing, Editorial and Publicity), for his kind cooperation and suggestions. We are extremely
thankful to the concerned DTP section for taking troubles in processing the manuscript.
In spite of our best efforts, some mistakes and misconceptions might have again crept in and for
these inconveniences, we beg to be pardoned in advance. Suggestions and constructive criticisms are
always welcome to better the presentation.

Asim K Das
Mahua Das
Ankita Das
 Preface to the First Edition
“No great work can be achieved by humbug. It is through love, a passion for truth; and tremendous energy,
that all undertakings are accomplished.” Swami Vivekananda
“I hold every man a traitor who, having been educated at their expense pay not the least heed to them.”
Swami Vivekananda

As a student and also as a teacher, I have experienced that for a systematic and comprehensive
coverage of the present subject, one is forced to consult various books on different disciplines to
collect the reading materials. Consequently, the students are specially constrained. Keeping this idea
in mind, it has been attempted here to present a complete textbook on the subject. In a logical sequence,
the book deals extensively with different aspects such as atomic structure (both classical and wave
mechanical) and atomic spectra, fundamentals of quantum mechanics and wave mechanics, nuclear
chemistry and radiation chemistry, different theories of valence forces and chemical forces including
band and Bloch theory of solids, solid state chemistry, acids and bases, nonaqueous solvents and
redox potentials. It also covers the different aspects of material science which is emerging with a
great promise. Thus the present book covers the curricula followed by most of the Indian universities
and institutes at the BSc and MSc levels. It also aims to help the students preparing for competitive
examinations like NET, GATE, SLET, etc. Adequate stress on the basic theories and concepts has
been given everywhere to rationalise the presentation. The ideas have been very often illustrated
through solution of related numerical problems. Each chapter is ended with various types of questions
and problems to afford an opportunity to the students for self-evaluation.
In writing a book of this nature, one accumulates indebtedness to the previous authors of different
books. The books which have been consulted are listed separately and gratefully acknowledged.
I express a deep sense of gratitude to Dr AV Saha, a gifted teacher, from whom I have started to
learn and understand the subject in my student life in Ramakrishna Mission Residential College,
Narendrapur, for writing the foreword. I express my deep gratefulness to the teachers and authorities
of the said institute, for shaping my career. I am grateful to my wife, Dr M Das, for various types of
help, assistance and cooperation.
I am especially grateful to Mr SK Jain, Managing Director, CBS Publishers & Distributors,
New Delhi, for his earnest interest in publishing the book. Thanks are also due to his colleagues as
well.
In conclusion, my attempt will be amply rewarded, if it is found helpful to the students and
teachers. In spite of all precautions, some errors might have crept in. Constructive criticism and
valuable suggestions from the readers are most welcome.

Asim K Das
 Contents
Foreword by AV Saha vii
Preface to the Third Edition ix
Preface to the First Edition xi
15. Nonaqueous Solvents 1
15.1 Introduction 1
15.2 Classification of Solvents 1
15.3 Characteristics of the Ionising Solvents 3
15.4 Liquid Ammonia as a Solvent 5
15.5 Liquid Hydrogen Fluoride as a Solvent 19
15.6 Liquid Hydrogen Cyanide as a Solvent 21
15.7 Acetic Acid (CH3CO2H) as a Solvent 22
15.8 Sulfuric Acid as a Solvent 22
15.9 Fluorosulfonic Acid (HSO3F) as a Solvent and Superacids 25
15.10 Liquid Sulfur Dioxide as a Solvent 25
15.11 Bromine Trifluoride as a Solvent 26
15.12 Oxyhalides as the Solvents 27
15.13 Molten Salts (i.e. Ionic Liquids) as the Solvents 28
Exercise XV 30

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

Electroanalytical Techniques 34
16.1 Some Preliminary Aspects of Redox Reactions 34
Ion Electron Method of Balancing Redox Reactions; Oxidation Number and Rules for Calculating
Oxidation Number; Oxidative Addition and Reductive Elimination Reaction; Equivalent Weights
of Oxidants and Reductants; Complementary and Noncomplementary Redox Reactions; Redox
and Acid-Base Reactions; Disproportionation and Comproportionation Reactions
16.2 Electrode Potentials: Standard Potentials 54
Electrical Double Layer and Genesis of Electrode Potential; Determination of Electrode Potential;
Electrochemical Cells: Galvanic and Electrolytic Cells: Reversible and Irreversible Cells;
Thermodynamics and EMF (Electromotive Force) of Electrochemical Cells and Standard Electrode
Potential; Standard Electrode Potential: Nernst Equation: Stoichiometric Standard Potential and
Formal Potential: Concept of pE; Sign Conventions of the Electrode Potentials; Types of Reversible
Electrode; Membrane Electrode and Ion Selective Electrode; Standard Electrode Potentials of
Metals and Electrochemical Series; Standard Reduction Potentials; Cell Representations and Cell
Reactions and Function of Salt Bridges; Electrochemical Cells — Chemical Cells and Concentration
Cells; Reversible Chemical Cells: Cells with and without Transference: Galvanic vs. Electrolytic
Cell: Ohmic Potential and Observed Cell
xiv Fundamental Concepts of Inorganic Chemistry

16.3 Formal (Conditional) Potentials 79

16.4 Effects of Different Factors on Electrode Potential: Application of such Effects
in Analytical Chemistry 82
Effects of pH on Electrode Potentials due to the Participation of H + or OH – in the Electrode
Process; Effects of pH on Electrode Potentials due to the Formation of Sparingly Soluble Hydroxo-
species; Effects of Precipitation (other than Hydroxides) on Electrode Potentials; Effects of
Complexation on Electrode Potentials; Chemistry of Aqua Regia and Dissolution of Noble Metals:
Enhancement of Oxidisability of Metals through Complexation; Attack of Noble Metals by HF
and by a Mixture of HF and HNO3: Enhancement of Oxidisability of Metals through Complexation;
Dissolution of Antimony by a Mixture of Nitric Acid and Tartaric Acid: Enhancement of
Oxidisability of Metals through Complexation
16.5 Periodic Trends of Electrode Potential 110
Variation of Standard Oxidation Potential of the Metals; Variation of Oxidising Power of the
Oxyanions in a Group
16.6 Function of Zimmermann-Reinhardt (Z-R) Solution (in Titrating Fe(II) by
KMnO4 in the Presence of Chloride) 114
16.7 Instability of Some Species in Aqueous Solution 115
16.8 EMF Diagrams 119
Latimer Diagram; Frost Diagrams (Ebsworth Diagram); Pourbaix Diagram or Potential-pH
(E-pH) Diagram
16.9 Equilibrium Constant from the Standard Electrode Potentials 133
16.10 Disproportionation and Comproportionation Reactions 135
16.11 Potential Profile in a Redox Titration 149
16.12 Selection of a Redox Indicator 159
16.13 Potentiometric Titrations 164
16.14 Practical Applications: Electrochemical Cells and Batteries — Primary Cells,
Secondary Cells, Fuel Cells: Corrosion 170
Basic Requirements of an Electrochemical Cell to Act as a Power Source; Representative Examples
of Primary and Secondary Cells; Some Representative Fuel Cells; Electrochemistry of Corrosion;
Electrolytic Cell vs. Galvanic Cell: Electrolysis of Solutions and Electrodeposition; Decomposition
Voltage of Electrolysis and Electrolytic Separation of Metals; Some Other Practical Applications
of the Knowledge of Electrode Potential
16.15 Kinetic Factors in Electrode Process and Electron Transfer Reactions 190
Importance of Kinetic Factors; Importance of Overpotential (in Electrode Process and Cell
Potential): Tafel Equation; Redox Reactions through Electron Transfer; Redox Reactions through
Atom Transfer
16.16 Photochemical Reactions: Photoredox Reaction and Photochemical Splitting
of Water 194
Some Representative Photochemical Reactions Illustrating the Characteristic Features;
Photochemical Splitting of Water (i.e. Artificial Photosynthesis) and Photochemistry of [Ru(bpy)3]2+;
TiO2, an Important Photocatalyst: Oxidation of Organic Matter and Photoelectrolysis of Water;
Direct Photochemical Reduction of Dinitrogen; Charge Transfer Band and Redox Stability
16.17 Ellingham Diagram: Reduction of Metal Oxides: Carbon –
A Potential Reducing Agent 210
16.18 Hydrometallurgy 217
 Contents xv

16.19 Electrode Potentials in Nonaqueous Systems 217

16.20 Examples of Some Common Catalysed Redox Reactions 219
16.21 Redox Activity in Relation to Explosive Action 221
16.22 Chemistry of Some Important Electroanalytical Techniques 222
Polarographic Method of Analysis; Cyclic Voltammetry (CV); Amperometric Titration; Coulometric
Analysis
Solved Numerical Problems 255
Exercise XVI 274
Numerical Problems 283
Appendix 16A 287
Chemistry of Explosives
Appendix 16B 291
Chemical Clock Reactions: Oscillating Reactions

17. Metallurgy: Principles, Pyrometallurgy vs. Hydrometallurty—Extraction and

Purification of Metals, Physio-Chemical Methods of Separation of Metals 297

17.1 Classification of Metals and their Occurrence in Nature 297

Chief Modes of Occurrence of Metals and Classification of Metals based on their Standard Electrode
Potentials; Goldschmidt’s Geochemical Classification of Elements based on Chemical Affinity
17.2 The Major Sources of Metals — Earth’s Crust and Sea Water: Minerals,
Ores and Gangue 300
Earth’s Crust — Minerals and Ores; Sea-Water and Sea-Bed as the Sources of Metals; Classification
of Ores Depending on the Nature of Chemical Composition of the Principal Constituents; Gangue
17.3 Metallurgy and its Main Steps 303
17.4 Concentration of Ore 303
17.5 Conversion of Concentrated Ore and Metallic Oxide: Calcination and Roasting 305
17.6 Smelting: Flux and Slag 307
17.7 Isolation of Metals through Reduction of Metal Ores 308
Carbon Reduction of Oxides of Metals in Furnace and Ellingham Diagram; Reduction by H2 at
High Temperature; Displacement by Metal in Solution: Cementation in Hydrometallurgy; Reduction
by a More Electropositive Metal at High Temperature; Self-reduction Method; Electrolytic
Reduction Method; Different Reduction Processes for Metal Extraction; Special Techniques of
Metal Extraction: Extraction and Refining of Nickel by Mond’s Process; Special Techniques of
Metal Extraction: Hydrometallurgical Extraction of Silver; Special Technique of Metal Extraction:
Hydrometallurgical Extraction of Gold; Special Technique of Metal Extraction: Extraction of
Titanium and Zirconium; Extraction Procedure (Summary) of Different Metals

17.8 Hydrometallurgy and Biomining Technology 325

Hydrometallurgy vs. Pyrometallurgy and Basic Steps of Hydrometallurgy; Leaching of Ores and
its Chemistry; Leach Solution: Concentration and Purification; Recovery of the Metal from the
Concentrated and Purified Leach Liquor; Chemistry of Leaching of Sulfide Ores of Copper, Nickel,
Zinc and Cobalt; Electrolysis of Aqueous Solution of Metal Salts for the Recovery of the Metal –
Hydrometallurgical Approach; Biomining and Biomineral Technology: Metal Extraction by
Bioleaching
xvi Fundamental Concepts of Inorganic Chemistry

17.9 Purification and Refining of Metals After their Extraction from Ores 339
Physical Methods of Purification of Metals; Chemical Methods of Purification of Metals;
Electrolytic Refining of Metals — A Special Chemical Method of Purification

17.10 Physico-Chemical Methods of Separation and Purification of Metals 347

Solvent Extraction (i.e. Liquid-Liquid Extraction) of Metals; Quantitative Treatment of Solvent
Extraction (i.e. Liquid-Liquid Extraction); Characteristic Features of Ion Exchange Resins and
Ion Exchange Process (i.e. Ion Exchange Chromatography); Application of Ion Exchange
Chromatography for Purification and Separation of Metal Ions; Chelating Resins to Bind the Metal
Ions; Chromatographic Method: Separation and Purification of Metal Ions
Exercise XVII 377

Bibliography B1–B2

Appendices A1–A10

Appendix I: Units and Conversion Factors A1

Appendix II: Some Physical and Chemical Constants A4
Appendix III: Wavelength and Colours A5
Appendix IV: Names, Symbols, Atomic Numbers and Atomic
Weights of the Elements A6
Appendix V: Some Useful Mathematical Relationships A8

Index I1–I7