Volume3B

Fundam

ental Co

ncepts o

f Inorganic C

hemistry

ThirdEdition

DasDas Asim K Das

Dedicated to Education

Volume 3BThird Edition

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Fundamental Concepts of

InorganicChemistry

3– 4–[Fe(CN) ] [Fe(CN) ]/6 6

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Fundamental Concepts of

Inorganic Chemistry

Volume 3BThird Edition

4819/XI, Prahlad Street, 24 Ansari Road, Daryaganj, New Delhi 110 002, IndiaE-mail: delhi@cbspd.com, cbspubs@airtelmail.in; Website: www.cbspd.com

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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 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 Equilibria.Volume 3B: Nonaqueous Solvents and Ionic Liquids; Redox Potentials, Formal Potentials and Applications; EMF Diagrams; Electroanalytical Techniques; Photoredox Reactions; Oscillating Reactions; Principles of Metallurgy and Refining and Purification of Metals; Different Techniques of Separation—Solvent Extraction, Ion Exchange and Chromatography.Volume 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 and Nitrosyls; Organometallics as Catalysts.Volume 7: Application of Metal Complexes in Analytical Chemistry and other Fields; Applications of Spectrophotometric Methods (IR, Raman, NMR, ESR, Mossbauer, UV-VIS, UV-PES); Theory of Errors and Statistical Treatment of Data.

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

Fundamental Concepts of

InorganicChemistry

Third Edition

Volume 3B

Contents at a Glance

1. Classical and Vector Models of Atom

2. Origin of the Quantum Theory

3. Fundamentals of Wave Mechanics

4. Wave Mechanical Model of Atom

5. Atomic Nucleus and its Structure

6. Radioactivity and Radiation Chemistry

7. Nuclear Reaction

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

Volume 1

9. Introduction to Chemical Bonding and Theories of Covalence—Valence BondTheory (VBT) and Molecular Orbital Theory (MOT)

10. Covalent Compounds—Characteristics, Structure and Reactivity

11. Hydrogen Bonding and Other Weaker Chemical Forces Including SupramolecularSystems

Volume 2

15. Nonaqueous Solvents

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

17. Metallurgy: Principles, Pyrometallurgy vs Hydrometallurgy—Extraction andPurification of Metals, Physicochemical Methods of Separation of Metals

Volume 3B

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

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

14. Acids and Bases and Ionic Equilibria in Aqueous Solutions

Volume 3A

Appendices (common to all three volumes)

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

Fundamental Concepts of

InorganicChemistry

Third Edition

CBS Publishers & Distributors Pvt Ltd

New Delhi • Bengaluru • Chennai • Kochi • Kolkata • MumbaiHyderabad • Jharkhand • Nagpur • Patna • Pune • Uttarakhand

Volume 3B

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

Professor, Department of ChemistryVisva Bharati University, Santiniketan 731235

West Bengal, India

Mahua DasMSc (CU), PhD (Visva Bharati)

Formerly Research AssociateDepartment of Chemistry

Visva Bharati University, Santiniketan 731235

West Bengal, India

Ankita DasMSc (Visva Bharati)

DST INSPIRE Research Fellow (IACS, Kolkata)

ISBN: 978-93-90709-12-0

Copyright © Authors and Publisher

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Disclaimer

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

Fundamental Concepts of

InorganicChemistry

Third Edition

Volume 3B

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 povertyjust to bring up us and to the memory of my second elder brother,

Late Pramatha Nath Das

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

Ramakirishna Mission Residential College, Narendrapur, Kolkata.

Asim K Das

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

A large number of exercises and problems essential for modern teaching have been incorporatedmeticulously at the end of each chapter to bridge the gaps, if any, in the understanding of the subject.Hope this earnest effort of Dr Das, a teacher of distinction, will receive well-deserved acclaim fromthe students and teachers of this subject.

Dr AV Saha DSc

Head of the Department of ChemistryRamakrishna Mission Residential College

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

Foreword

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

—Swami Vivekananda

We feel delighted to record the warm response which the first and second editions of the book hasreceived from the students and teachers throughout the country. We have incorporated all the aspectsof choice based credit system (CBCS) syllabus recently introduced in all universities and institutesand the suggestions received from the readers. In this edition, each chapter has been thoroughlyrevised, updated and rewritten to accommodate the recent views. In this enlarged version, scope ofthe book has been broadened by adding new topics and revisions of the earlier sections. In revisingthe book, we have taken all the measures to retain the basic features for which the earlier editionshave been so popular.

In preparing the manuscript, we have again freely consulted the original research papers, booksand reviews of the earlier authors and have borrowed their ideas whenever required. We are gratefuland 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 areextremely grateful to Mr SK Jain, Managing Director, CBS Publishers & Distrubutors, New Delhi,for his hearty support and encouragement. We are also thankful to Mr YN Arjuna, Senior VicePresident (Publishing, Editorial and Publicity), for his kind cooperation and suggestions. We are extremelythankful to the concerned DTP section for taking troubles in processing the manuscript.

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

Asim K DasMahua DasAnkita Das

Preface to the Third Edition

Jðkoku~ yHkrs Kkue~One who has shraddha acquires knowledge

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

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

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

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

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

Asim K Das

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

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

Preface to the First Edition

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

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 34Ion Electron Method of Balancing Redox Reactions; Oxidation Number and Rules for CalculatingOxidation Number; Oxidative Addition and Reductive Elimination Reaction; Equivalent Weightsof Oxidants and Reductants; Complementary and Noncomplementary Redox Reactions; Redoxand Acid-Base Reactions; Disproportionation and Comproportionation Reactions

16.2 Electrode Potentials: Standard Potentials 54Electrical 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 ElectrodePotential; Standard Electrode Potential: Nernst Equation: Stoichiometric Standard Potential andFormal Potential: Concept of pE; Sign Conventions of the Electrode Potentials; Types of ReversibleElectrode; Membrane Electrode and Ion Selective Electrode; Standard Electrode Potentials ofMetals and Electrochemical Series; Standard Reduction Potentials; Cell Representations and CellReactions and Function of Salt Bridges; Electrochemical Cells — Chemical Cells and ConcentrationCells; Reversible Chemical Cells: Cells with and without Transference: Galvanic vs. ElectrolyticCell: Ohmic Potential and Observed Cell

Contents

xiv Fundamental Concepts of Inorganic Chemistry

16.3 Formal (Conditional) Potentials 79

16.4 Effects of Different Factors on Electrode Potential: Application of such Effectsin Analytical Chemistry 82Effects of pH on Electrode Potentials due to the Participation of H+ or OH– in the ElectrodeProcess; 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 ofComplexation on Electrode Potentials; Chemistry of Aqua Regia and Dissolution of Noble Metals:Enhancement of Oxidisability of Metals through Complexation; Attack of Noble Metals by HFand 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 ofOxidisability of Metals through Complexation

16.5 Periodic Trends of Electrode Potential 110Variation of Standard Oxidation Potential of the Metals; Variation of Oxidising Power of theOxyanions in a Group

16.6 Function of Zimmermann-Reinhardt (Z-R) Solution (in Titrating Fe(II) byKMnO4 in the Presence of Chloride) 114

16.7 Instability of Some Species in Aqueous Solution 115

16.8 EMF Diagrams 119Latimer 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 170Basic Requirements of an Electrochemical Cell to Act as a Power Source; Representative Examplesof Primary and Secondary Cells; Some Representative Fuel Cells; Electrochemistry of Corrosion;Electrolytic Cell vs. Galvanic Cell: Electrolysis of Solutions and Electrodeposition; DecompositionVoltage of Electrolysis and Electrolytic Separation of Metals; Some Other Practical Applicationsof the Knowledge of Electrode Potential

16.15 Kinetic Factors in Electrode Process and Electron Transfer Reactions 190Importance of Kinetic Factors; Importance of Overpotential (in Electrode Process and CellPotential): Tafel Equation; Redox Reactions through Electron Transfer; Redox Reactions throughAtom Transfer

16.16 Photochemical Reactions: Photoredox Reaction and Photochemical Splittingof Water 194Some 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 222Polarographic Method of Analysis; Cyclic Voltammetry (CV); Amperometric Titration; CoulometricAnalysis

Solved Numerical Problems 255

Exercise XVI 274

Numerical Problems 283

Appendix 16A 287Chemistry of Explosives

Appendix 16B 291Chemical 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 297Chief Modes of Occurrence of Metals and Classification of Metals based on their Standard ElectrodePotentials; 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 300Earth’s Crust — Minerals and Ores; Sea-Water and Sea-Bed as the Sources of Metals; Classificationof 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 308Carbon Reduction of Oxides of Metals in Furnace and Ellingham Diagram; Reduction by H2 atHigh Temperature; Displacement by Metal in Solution: Cementation in Hydrometallurgy; Reductionby a More Electropositive Metal at High Temperature; Self-reduction Method; ElectrolyticReduction Method; Different Reduction Processes for Metal Extraction; Special Techniques ofMetal Extraction: Extraction and Refining of Nickel by Mond’s Process; Special Techniques ofMetal Extraction: Hydrometallurgical Extraction of Silver; Special Technique of Metal Extraction:Hydrometallurgical Extraction of Gold; Special Technique of Metal Extraction: Extraction ofTitanium and Zirconium; Extraction Procedure (Summary) of Different Metals

17.8 Hydrometallurgy and Biomining Technology 325Hydrometallurgy vs. Pyrometallurgy and Basic Steps of Hydrometallurgy; Leaching of Ores andits Chemistry; Leach Solution: Concentration and Purification; Recovery of the Metal from theConcentrated 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 byBioleaching

xvi Fundamental Concepts of Inorganic Chemistry

17.9 Purification and Refining of Metals After their Extraction from Ores 339Physical 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 347Solvent Extraction (i.e. Liquid-Liquid Extraction) of Metals; Quantitative Treatment of SolventExtraction (i.e. Liquid-Liquid Extraction); Characteristic Features of Ion Exchange Resins andIon Exchange Process (i.e. Ion Exchange Chromatography); Application of Ion ExchangeChromatography for Purification and Separation of Metal Ions; Chelating Resins to Bind the MetalIons; 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 AtomicWeights of the Elements A6

Appendix V: Some Useful Mathematical Relationships A8

Index I1–I7