PHYSICAL CHEMISTRYPhysical Chemistry RL Madan Former Principal, Government College, Panchkula & Former Head, Chemistry Department Government Post Graduate College Faridabad, Haryana McGraw Hill Education (India) Private Limited NEW DELHI ‘McGraw Hill Education Offices New Delhi New York St Louis San Francisco Auckland Bogota Caracas Kuala Lumpur Lisbon London Madrid Mexico City Milan Montreal San Juan Santiago Singapore Sydney Tokyo TorontoAbout the Author Ma RL Madan has about 35 years of experience in teaching chemistry at the undergraduate level. After obtaining a PhD in Chemistry, he began his teaching career at Government Postgraduate College, Gurgaon. Thereafter, he has held positions of Head of Chemistry Department at Government Postgraduate College, Faridabad, and Principal, Government College Panchkula and Tigaon (Faridabad). Prof. Madan has done extensive research work in the areas of adsorption and surface science at the Chemistry Department of Indian Institute of Technology, New Delhi. He did postdoctoral work for studies on polymers at Prague University, Czech Republic, under a UNESCO fellowship. He has also been awarded a fellowship by the Swedish Institute for Research Work on Superconductivity at Stockholm University, Sweden. Prof. Madan has authored several best-selling books on chemistry.Physical Chemistrya McGraw Hill Education (India) Private Limited Published by McGraw Hill Education (India) Private Limited P-24, Green Park Extension, New Delhi 110 016 Physical Chemistry Copyright ©2015 by McGraw Hill Education (India) Private Limited. No part of this publication may be reproduced or distributed in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise or stored in a database or retrieval system without the prior written permission of the publishers. The program listings (if any) may be entered, stored and executed in a computer system, but they may not be reproduced for publication. This edition can be exported from India only by the publishers, McGraw Hill Education (India) Private Limited. Print Edition: 978-12-5906-254-4 12-5906-254-6 EBook Edition: ISBN (13 digit): 978-93-3290-136-0 ISBN (10 digit): 93-3290-136-8 Managing Director, McGraw Hill Education (India) Private Limited: Kaushik Bellani Head—Higher Education (Publishing and Marketing): Vibha Mahajan Senior Publishing Manager (SEM & Tech. 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This work is published with the understanding that McGraw Fill Education (India) and its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought.‘Typeset at Tej Composers, WZ 391, Madipur, New Delhi 110 063. eBook Conversion by DigiConv Technologies, C-240, 1st Floor, Pandav Nagar, Delhi - 110092. www.digiconv.comDedicated to the Memory of My Loving Mother Late Mrs janki Devi Who made me what I am and to whom I owe a lotForeword Chemistry has made a significant impact on society and is intimately linked to the well- being of humankind. The rate of advancement of basic sciences is so high that academicians look forward for strategies to cope with those advancements. Physical chemistry provides a decent bridge between mathematical sciences and experimental sciences. The present textbook is a sincere effort in this direction. This book provides a unified approach to the study of chemistry for undergraduate (Pass and Honours) students. The text is well illustrated with examples from surrounding environments which will help students grasp the concepts easily. There are several highlights of this book. The chapter dealing with mathematical concepts and computers will provide a powerful tool to students in understanding the basic concepts and solve numerical problems in shorter time. Partial differentiation and integration needs special mention in this regard. Incorporation of computers and introducing analog and digital devices will provide a good basic platform to understanding physical chemistry Biographical sketches of some scientists relevant to particular topics will surely enthuse students. Liquid state, colloidal state chemical kinetics and thermodynamics have been written especially in a systematic, lucid and comprehensible style. Learning objectives have been given exhaustively in each chapter of the book. Sufficient examples have been given at the end of each chapter, along with summary for quick revision, key relations, question bank including multiple-choice questions and general questions so that students can evaluate their learning potential themselves. The level of text material in each chapter is sufficient to escalate this book to international standard. I am sure this book will procure the author and publishers a good name in the market. The hard work done by the author is commendable and deserves to be congratulated. I wish huge success to this book. NK Sandle Prof. Department of Chemistry, Indian Institute of Technology (IIT), DelhiContents Preface 1. Basic Concepts 1.1 Introduction 1.2 Systems of Measurement 1.3. Massand Weight 14 Volume 1.5 Scientific Notation 1.6 Uncertainty 17 Dimensional Analysis Summary Exercises Short-Answer Questions General Questions 2. Mathematical Concepts and Computers 21 Introduction to Mathematical Concepts 2.2 Logarithmic Relations 2.3 Curve Sketching 2.4 Linear Graphs and Calculation of Slopes 2.5 Differentiation 2.6 Maxima and Minima 2.7 Partial Differentiation 2.8 Integration 2.9 Definite Integral 2.10 Factorials 2.11 Permutations and Combinations 2.12 Probability 2.13 Mutually Exclusive Events 2.14 Introduction to Computers 2.15 Components of a Computer 2.16 Hardware and Software 2.17 Binary System 2.18 Binary Arithmetic 2.19 Operating System 2.20 Computer Programming SummaryExercises General Questions 3. Gaseous State 3.1 Introduction 3.2 Kinetic Theory of Gases 3.3 Maxwell Distribution of Velocities 3.4 Most Probable Velocity (a), Average Velocity (v) and Root Mean Square (RMS) Velocity (u) 3.5 Degree of Freedom 3.6 Principle of Equipartition of Energy 3.7. _ Collision Diameter, Collision Number, Collision Frequency and Mean Free Path 3.8 Viscosity of Gases 3.9 The Barometric Formula 3.10 Ideal Gas and Real Gas 3.11 Critical Phenomenon 3.12 Liquefaction of Gases Summary Exercises General Questions 4. The Liquid State 4.1 Introduction 4.2 Vapour Pressure of a Liquid 43 Surface Tension of a Liquid 44 Determination of Surface Tension 4.5 Parachor 4.6 — Viscosity 4.7 Rheochor 48 Refractive Index 4.9 Liquid Crystals Summary Exercises Short Answer Questions General Questions 5. The Solid State 5.1 Introduction 5.2 Types of Solids 5.3 Types of Crystals 5.4 Space Lattice and Unit Cell of a Crystal 5.5 Packing of Particles in a Crystal 5.6 Radius Ratio 5.7 Number of Atoms in a Unit Cell for Simple Cubic, FCC and BCC Structures 5.8 Fundamental Laws of Crystallography 5.9 Miller Indices 5.10 Isomorphism and Polymorphism eaae Point Groups and Space Groups 5.12 Investigation of Internal Structure of a Solid by X-Ray Diffraction SummaryExercises General Questions 6. Colloidal State Introduction Classification of Colloids Micelles Preparation of Colloidal Solutions Properties of Sols (Colloidal Solutions) Protective Colloids and Gold Number Emulsions Gels Various Methods to Determine the Size of Colloidal Particles 6.10 Applications of Colloids Summary Key Equations Exercises General Questions 7. Chemical Kinetics Introduction Factors Affecting Rate of a Reaction Molecularity of a Reaction Rate Law and Rate Constant Zero-Order Reaction First-Order Reaction Radioactive Decay as a First-Order Phenomenon Second-Order Reaction Third-Order Reaction 7.10 Relations between Half-Life Period and Order of a Reaction Formulation of Mechanism of a Reaction 7.12 Methods for the Determination of Order of a Reaction 7.13 Complications in the Determination of Order of Reaction 7.14 Surface Reactions 7.15 Chain Reactions 7.16 Temperature Dependence and Arrhenius Equation 7.17 Collision Theory of Reaction Rates 7.18 Transition State Theory or Theory of Absolute Reaction Rates or Theory of Activated Complex Formation 7.19 Experimental Methods of Chemical Kinetics Summary Key Equations Exercises General Questions 8. Catalysis 8.1 Introduction 8.2. General Characteristics of Catalysed Reactions 8.3 Theories of Catalysis 8.4 Important Features of Solid Catalysts 8.5 Shape-Selective Catalysis by Zeolites 8.6 Homogeneous Catalysis 8.7 Heterogeneous Catalyis8.8 Enzyme Catalysis 8.9 Autocatalysis Summary Key Relations Short-Answer Questions General Questions 9. Thermodynamics-I 9.1 Introduction 9.2 Joule’s Law 9.3 Calculation of Values of w, q, AU and AH in Adiabatic Expansion of an Ideal Gas Summary Key Relations Exercises Short-Answer Questions General Questions 10. | Thermochemistry 10.1 Introduction 10.2 Latest Sign Conventions for Q or AH, AU and W 10.3 Heat of Reaction (or Enthalpy of Reaction) 10.4 Standard State 10.5 Different Kinds of Heat (or Enthalpy) of Reaction 10.6 Hess’s Law of Constant Heat Summation 10.7 Bond Enthalpy or Bond Energy 10.8 Variation of Heat of Reaction with Temperature—Kirchhoff’s Equation Summary Key Relations Exercises Short-Answer Questions General Questions 11, Themodynamics-II 11.1 Introduction 11.2 Carnot Cycle 11.3. Thermodynamic Scale of Temperature 11.4 Concept of Entropy 11.5 Entropy Change for an Ideal Gas Under Different Conditions 11.6 — Entropy Change on Mixing of Ideal Gases 11.7 Helmholtz Free Energy 11.8 Gibbs Free Energy (or Gibbs Energy) 11.9 Criteria for Feasibility or Spontaneity of a Process 11.10 Maxwell Relationships 11.11 Gibbs-Helmholtz Equation Summary Key Relations Exercises Short-Answer Questions General Questions 12. Themodynamics-III 12.1 Third Law of Thermodynamics13. 14, 12.2 Statements of Third Law of Thermodynamics 12.3. Residual Entropy 12.4 Partial Molar Properties (Open Systems) 12.5. Clausius-Clapeyron Equation 12.6 Fugacity and Activity Summary Key Relations Exercises Short-Answer Questions General Questions Chemical Equilibrium 13.1 Introduction 13.2 The State of Chemical Equilibrium 13.3 Law of Mass Action 13.4 Applications of Equilibrium Constant 13.5 Partial Molar Quantities 13.6 Free-Energy Change as a Criterion of Spontaneity 13.7 Thermodynamic Derivation of the Law of Chemical Equilibrium 13.8 Van’t Hoff Reaction Isotherm 13.9 Relation between K, and K,. 13.10 _ Van’t Hoff Equation for Temperature Dependence of Equilibrium Constant (Van’t Hoff Reaction Isochore) 13.11 Le-Chatelier’s Principle 13.12 Clausius-Clapeyron Equation 13.13 Hammett Equation Summary Exercises Short-Answer Questions General Questions Phase Equilibria and Phase Rule 14.1 Introduction 14.2 Explanation of the Terms 14.3 Equilibrium 14.4 Thermo dynamic Derivation of Phase Rule 14.5 Different Techniques for the Determination of Transition Point 14.6 Phase Diagram 14.7 Phase Diagram of the Water System 14.8 Solid-Liquid Phase Transition 14.9 Phase Diagram of Carbon Dioxide System 14.10 Phase Diagram of Sulphur System 14.11 Two-Component Systems 14. Types of Two-Component Systems Involving Solid-Liquid Equilibria 14.13 Experimental Determination of Phase Diagram of Two Component Systems 14.14 Study of Some Two-Component Systems 14.15 Freezing Mixtures 14.16 Phase Diagram of Magnesium-Zinc System 14.17 Phase Diagram of Ferric Chloride-Water Systems15. 16. 14.18 Phase Diagram of NaySO4 —H 0 System 14.19 Sodium Chloride—Water System 14.20 Phase Diagram of Copper Sulphate-Water System Summary Exercises Short-Answer Questions General Questions Distribution Law 15.1 Nernst Distribution Law—Introduction 15.2 Thermodynamic Derivation of Distribution Law 15.3 _ Modification in Distribution Law in Case of Change in Molecular State 15.4 Applications of Distribution Law 15.5 Studying Chemical Equilibrium Involving Formation of Complex Compounds 15.6 Utility of Distribution Law in the Process of Extraction 15.7 _ General Formula for Amount of Substance Left Unextracted and Volume of Extracting Liquid used Each Time 15.8 Determination of Degree of Hydrolysis from Distribution Law Summary Key Relations Exercises Short-Answer Questions General Questions Electrochemistry-I 16.1 Introduction 16.2 Electrical Resistance and Electrical Conductance 16.3. Measurement of Electrolytic Conductance, Speci Conductivity, Equivalent Conductivity and Molar Conductivity 16.4 Numerical Problems on Specific, Equivalent and Molar Conductivities 16.5 Effect of Dilution on Specific Conductance and Equivalent Conductance 16.6 Arrhenius Theory of Ionisation 16.7 Ostwald Dilution Law 16.8 — Variation of Conductivity with Concentration of Strong Electrolytes (Debye-Huckel-Onsagar Equation) 16.9 Kohlrausch’s Law 16.10 Anomalous Behaviour of Strong Electrolytes Debye-Huckel Theory 16.11 Migration of Ions and Transport Number 16.12 Hittorf’s Theoretical Device—Change in Concentration 16.13 Transport Number 16.14 Moving Boundary Method for the Determination of Transport Numbers 16.15 Conductometric Titrations Summary Key Relations Exercises Short-Answer Questions17. 18. General Questions Electrochemistry-I 17.1 Buffer Solution—Introduction 17.2. Henderson Equation for the pH of a Buffer Mixture 17.3 Buffer Capacity and Buffer Index 17.4 Neutralization Phenomenon 17.5 Salt Hydrolysis 17.6 Hydrolysis Constant and Degree of Hydrolysis 17.7 Expressions for the Hydrolysis Constant, Degree of Hydrolysis and pH of Solutions of Salts of Strong Acid and Weak Base 17.8 Expressions for the Hydrolysis Constant, Degree of Hydrolysis and pH of Solution of a Salt of Weak Acid and Strong Base 17.9 _ Expressions for Hydrolysis Constant, Degree of Hydrolysis and PH of Solutions of Salts of Weak Acid and Weak Base Summary Key Relations Exercises Short-Answer Questions General Questions Electrochemistry-III 18.1 Electrochemical Cell 18.2 Electrolytic Cell 18.3 Schematic Representation of an Electrochemical Cell 18.4 Emfofa Cell 18.5 Weston Standard Cell 18.6 Reversible Cell 18.7 Irreversible Cell 18.8 Types of Electrodes 18.9 Relationship between Electrical Energy and Chemical Energy 18.10 Expressions for AG, AH and AS in Terms of Temperature Coefficient of the Emf 18.11 Measurement of Electrode Potentials of Zinc Electrode and Copper Electrode 18.12 Reference Electrodes 18.13 Electrochemical Series 18.14 Activity and Activity Coefficient of Electrolytes 18.15 — Nemst Equation for Measuring Emf of a Cell 18.16 Nernst Equation for Single Electrode Potential 18.17 Electrode Potential of Reduction-Oxidation Electrode 18.18 Calculation of Equilibrium Constant (K) from Nernst Equation 18.19 Irreversible Electrode Processes 18.20 Concentration Cells 18.21 Emf of Electrode Concentration Cell without Transference 18.22 Emf of Electrolyte Concentration Cells without Transference 18.23 Emf of an Electrolyte Concentration Cell with Transference 18.24 Liquid Junction Potential 18.25 Determination of Activity and Activity Coefficient from Emf Measurement 18.26 Applications of emf Measurements 18.27 _ Different Types of Electrodes in Practical Use19. 18.28 Determination of pH or H* Concentration of a Solution by emf Measurement 18.29 Potentiometric Titrations 18.30 Corrosion 18.31 Electrochemical Theory of Corrosion 18.32 Methods of Prevention of Corrosion Summary Key Relations Exercises Short-Answer Questions General Questions Atomic Structure and Quantum Mechanics 19.1 Introduction 19.2 Classical Mechanics 19.3. Black Body and Black-Body Radiations 19.4 Kirchhoff’s Law of Black-Body Radiations 19.5 Spectral Distribution of Black-Body Radiation 19.6 Planck’s Radiation Law 19.7 Photoelectric Effect 19.8 Heat Capacity of Solids 19.9 Quantum Mechanics 19.10 Bohr’s Model of Atom 19.11 De Broglie Hypothesis (Dual Nature of Matter and Radiations) 19.12 Heisenberg’s Uncertainty Principle 19.13 The Compton Effect 19.14 Sinusoidal Wave Equation 19.15 Schrodinger Wave Equation 19.16 Born’s Interpretation and Significance of Wave Function () 19.17 Normalised and Orthogonal Wave Functions 19.18 Operators 19.19 Postulates of Quantum Mechanics 19.20 Derivation of Schrodinger Wave Equation Based on the Postulates of Quantum Mechanics 19.21 Particle in a One-Dimensional Box 19.22 Calculation of Expectation Values using Wave Function 19.23 Particle in a Three-Dimensional Box 19.24 Concept of Degeneracy 19.25 Schrodinger Wave Equation in Terms of Polar (Spherical) Coordinates 19.26 Separation of Variables 19.27 Expressions for Angular Spherical Wave Functions 19.28 Expression for the Radial Wave Function 19.29 Quantum Numbers from Schrodinger Wave Equation 19.30 Concept of Orbital 19.31 Shapes of Orbitals Summary Key Relations Exercises Short-Answer Questions General Questions20. 21. Quantum Mechanics and Chemical Bonding 20.1 Quantum Mechanics and Chemical Bonding 20.2 Valence Bond Theory 20.3 Molecular Orbital Theory 20.4 Physical Picture of Bonding and Antibonding Wave Functions 20.5 Variation of Electron Probability Density Along Internuclear Axis in Bonding and Antibonding Molecular Orbitals 20.6 Formation of Molecular Orbitals from Atomic Orbitals 20.7 Concept of 0, o*, 77, 7* Orbitals and their Characteristics 20.8 Formation of Hy Molecule 20.9 Hybridisation 20.10 Quantum Mechanical Principles of Hybridisation 20.11 Calculation of the Coefficients of Atomic Orbitals in different Hybrid Orbitals 20.12 Comparison of Valence Bond (VB) Molecular Orbital (MO) Models Summary Key Relations Exercises Short-Answer Questions General Questions Spectroscopy 21.1 Introduction 21.2 Rotational, Vibrational and Electronic Energies of Molecules 21.3. Molecular Spectroscopy Versus Atomic Spectroscopy 21.4 Absorption and Emission Spectroscopy 21.5 Types of Molecular Energies and Born-Oppenheimer Approximation 21.6 Types of Molecular Spectra 21.7. Selection Rules for Rotational and Vibrational Spectra 21.8 Width and Intensities of the Spectral Lines 21.9 Degrees of Freedom 21.10 Pure Rotational Spectra of Diatomic Molecules 21.11 Nonrigid Rotor (Qualitative Description) 21.12 Isotopic Effect 21.13 Vibrational Spectra of Diatomic Molecules (Infrared Spectra) 21.14 Vibrational Energy of an Anharmonic Oscillator (Morse Equation) 21.15 — Vibrational-Rotational Spectra Obtained for a Diatomic Molecule Taking it as Anharmonic Oscillator 21.16 — Applications of Study of Infrared Spectrum 21.17 Vibrational Frequencies of Functional Groups 21.18 Introduction 21.19 _ Rotational-Vibrational Raman Spectra of Diatomic Molecules 21.20 Introduction 21.21 Born-Oppenheimer Approximation in Relation to Electronic Spectra of Molecules 21.22 Potential Energy Curve and Frank-Condon Principle 21.23 Electronic Transition in 9, 77, and n Molecular Orbitals Exercises22. 23. 24, Short-Answer Questions General Questions Photochemistry 22.1 Introduction 22.2 Differences between Thermochemical and Photochemical Reactions 22.3. Lambert’s Law of Transmission of Light 22.4 Beer’s Law 22.5 Laws of Photochemistry 22.6 Quantum Efficiency or Quantum Yield 22.7 Some Examples of Photochemical Reaction 22.8 Luminescence 22.9 _ Excitation of Electrons (Jablonski Diagram) 22.10 Photosensitisation 22.11 Photochemical Equilibrium Summary Key Relations Exercises Short-Answer Questions General Questions Physical Properties and Molecular Structure Introduction bal 5 Optical Activity 23.3 Measurement of Optical Activity 23.4 — Cause of Optical Activity in a Compound 23.5 Dipole Moment 23.6 Polarisation of Molecules (Induced Polarisation) 23.7 Dipole Moment and Structure of Molecules 23.8 Magnetic Susceptibility 23.9 Explanation of Diamagnetism and Paramagnetism 23.10 Determination of the Magnetic Moment of a Paramagnetic Substance 23.11 Applications of Magnetic Susceptibility Measurement Summary Key Relations Exercises Short-Answer Questions General Questions Liquid Liquid Mixtures 4.1 Introduction 3 2. Expressing Concentration of Solutions 24.3. Raoult’s Law 24.4 Henry’s Law 24.5 Duhem-Margules Equation 24.6 Completely Soluble Liquids 24.7 Vapour Pressure Composition Diagram for Ideal Solutions 24.8 Vapour Pressure Composition Curves for Non-Ideal Solutions (Derivation from Ideal Behaviour) 24.9 Principle of Distillation of Binary Miscible Liquids 24.10 Distillation of Binary Miscible Solutions25. 26. 24.11 Azeotropes 24.12 Immiscible Liquids 24.13 Steam Distillation 24.14 Partially Miscible Liquids 24.15 Effect of Impurities on Consolute Temperature (Critical Solution Temperature) Summary Key Relations Exercises Short-Answer Questions General Questions Dilute Solutions and Colligative Properties 25.1 Introduction 25.2 Determination of Vapour Pressure of a Liquid by Manometric Method 25.3. Determination of Lowering of Vapour Pressure of the Solvent 25.4 Relation between the Relative Lowering of Vapour Pressure and the Molecular Mass of the Solute (Raoult’s Law) 25.5 Osmosis Phenomenon 25.6 Van’t Hoff Relation between the Osmotic Pressure of a Solution and Molecular Mass of the Solute 25.7 Van’t Hoff Theory of Dilute Solution Taking the Example of Osmosis 25.8 Determination of Osmotic Pressure 25.9 Theories of Osmosis 25.10 Elevation in Boiling Point 25.11 Relation between Elevation in Boiling Point of Solution and Molecular Mass of Solute 25.12 Depression in Freezing Point 25.13 Relation between Depression in Freezing Point and Molecular Mass of the Solute 25.14 Van’t Hoff Factor Summary Key Relations Exercises Short-Answer Questions General Questions Adsorption 26.1 Introduction 26.2 Physical Adsorption and Chemical Adsorption 26.3 Adsorption Isotherm 26.4 Freundlich Adsorption Isotherm 26.5 Langmuir Theory of Adsorption 26.6 Bet Equation 26.7 Adsorption by Solids from Solutions 26.8 Gibbs Adsorption Equation 26.9 Applications of Gibbs Adsorption Equation 26.10 Applications of Adsorption Summary Key Relations27. 28. Exercises Short-Answer Questions General Questions Polymers 27.1 Introduction 27.2 Terms used in Relation to Polymers 27.3. Natural and Synthetic Polymers 27.4 Number Average and Mass- Average Molecular Masses 27.5 Methods for the Determination of Molecular Masses 27.6 Step Polymerisation Summary Key Relations Exercises Short-Answer Questions General Questions Nuclear Chemistry 28.1 Isotopes 28.2 Fundamental Particles of the Nucleus 28.3 Natural Radioactivity 28.4 Artificial Disintegration or Transmutation of Elements 28.5 Q Value of Nuclear Reactions 28.6 Nuclear Fission 28.7 Nuclear Fusion 28.8 Applications of Radioactivity 28.9 Tracer and Tracer Technique 28.10 Applications of Tracer (Radio Isotopes) Technique 28.11 Design of Nuclear Reactor 28.12 Soddy’s Group-Displacement Law Summary Key Relations Exercises Short-Answer Questions General QuestionsPreface I feel immensely pleased to present Physical Chemistry to the teaching fraternity and the students. Physical chemistry is the study of macroscopic, atomic, sub-atomic and particulate phenomena in chemical systems. It applies the principles, practices and concepts of motion, energy, force, time, thermodynamics, quantum chemistry, statistical mechanics and equilibrium. Physical chemistry, a branch of chemistry, is a core subject at undergraduate science and technology course curricula of different universities and autonomous institutes in the country. In the study of this subject for the above courses, a number of books by foreign authors are widely used as reference books. The teaching fraternity in India was feeling the need of a textbook written in a simple language and an interesting manner which could be grasped even by an average student. The present book has been written in response to the aspirations of the teaching community and the students. Target Audience This book covers the syllabus of Physical Chemistry for the students of BSc I, I and IIL (Pass and Honours or Major and Minor) of different Indian Universities. Students of other undergraduate professional courses having physical chemistry as a major subject may also use this book. The only prerequisite is that the students must possess a basic knowledge of chemistry of 11 and 12" standard to utilize this book. A basic knowledge of mathematics is also expected. Salient Features > Covers all important topics—Gaseous State, Liquid State, Solid State, Colloidal State, Chemical Kinetics, Catalysis, Thermodynamics, Chemical Equilibrium, Phase Equilibria, Distribution Law, Electrochemistry, Atomic Structure and Wave Mechanics, Chemical Bonding and Wave Mechanics, Spectroscopy, Photochemistry, Physical Properties and Molecular Structure, Liquid Solutions, Dilute Solutions, Adsorption, Polymers and Nuclear Chemistry > Latest IUPAC notations and SI units used } Principles and laws explained in the simplest possible way> Analogies from daily life used to clarify difficult points > Concept explanation through more than 1200 step-wise solved problems > Numerical problems for practice > Applications and case studies like applications of equilibrium constant, cases to understand structure of liquid crystals and how they flow > More than 500 line, phase, and real-time illustrations Prologue on mathematical concepts Key words and Key relations provided in the summary Concept boxes to highlight important facts that are asked in examinations Special features such as interesting facts, common pitfalls, key terms interspersed Subject index provided for quick location of terms, laws, theories, etc. + Over 450 solved examples covering all types of problems in different chapters More than 800 review questions Over 400 objective-type questions About the Book The style of the book is such that it encourages students to understand physical chemistry rather than leam it by rote memorization. Simple and comprehensible language has been used to explain the principles involved in different topics. The opening chapter, Basic Concepts, acquaints the students with different systems and units of physical quantities. As recommended by IUPAC and CGPM, SI system of measurement and units of physical quantities have been followed by and large, although CGS system has been retained in some problems. This is because questions in some university papers still appear in CGS units. IUPAC has recommended changes in the names of certain terms, for example, conductivity in place of specific conductance, and Gibbs energy in place of Gibbs free energy. This has been highlighted in the chapters on electrochemistry and thermodynamics. Readers can refer to the Table of Content to know more about the topics covered in this book. Biographical sketches of scientists are given to inspire and stimulate the minds of students towards the subject. Analogies from daily life have been chosen to explain intricate points. Historical developments leading to the establishment of different theories and laws have found due place in the book. How the different principles of physical chemistry come to the rescue of people in difficult situations has been explained with the help of interesting pictures. Although this part is non-evaluative, it makes the subject exciting and easily understandable. The text is supported by a large number of solved examples and problems for practice. Learning Objectives given at the beginning of each chapter give the detailed contents of the chapter. Summary provided at the end of a chapter lists the important information in brief for last-minute revision before the examination. Also given in the summary are Key Points and Key Relations, which are required in solving numerical problems. Exercises consist of two parts, objective evaluation and subjective evaluation. As per the latest recommendation on the setting of question papers, multiple-choice questions, fill-in-the-blanks questions, short-answer questions and general (long-answer) questions have been provided to prepare the students to face examinations boldly. Online Learning Center The text is accompanied by an Online Learning Center, which can be accessed at https://www.mhhe.com/madan/pcl. This includes objective-type questions, concept boxes, and answers to unsolved problems. Acknowledgements I express my thanks and regards to my mentor and Ph. D. guide Prof. N. K. Sandle, Department of chemistry, Indian Institute of Technology (IIT), New Delhi for providing me inspiration and support during the preparation of the book. I thank all the reviewers who read the initial manuscript and gave commendable suggestions, some of which have been incorporated in the text. Their names are given below: Rabinarayan Birla Institute of Technology and Science (BITS), Pilani, Panda Rajasthan KM Gardakar —_ Shivaji University, Kolhapur, Maharashtra PH Parsania Saurashtra University, Rajkot, Gujarat V Kannapan University of Madras, Chennai, Tamil Nadu — alakshmi University of Madras, Chennai, Tamil Nadu Sasmita Dash Annamalai University, Chidambaram, Tamil Nadu Swarnalakshmi Guru Nanak College, Chennai, Tamil Nadu I place on record the efforts made by Ms Renu upadhayay, Mr Anuj Srivastava and other staff of McGraw Hill Education to ensure the smooth publication of the book. Readers are welcome to send constructive criticism and feedback to me at rattanlal.madan@gmail.com RL Madan Publisher’s Note McGraw Hill Education (India) invites suggestions and comments from you, all of which can be sent to info.india@mheducation.com (kindly mention the title and author name in the subject line). Piracy-related issues may also be reported.Basic Concepts 1 LEARNING OBJECTIVES Acquaint with different systems of measurement of different quantities Understand how we gradually shifted from the British system to the metric system Know the seven basic physical quantities and their units Learn in detail about the units of the seven physical quantities Differentiate between mass and weight Write very large or very small numbers in scientific notation Carry out arithmetical calculations using exponential notation Differentiate between precision and accuracy Define significant figures and learn the rules for deciding significant figures in different kinds of numbers Leam addition, subtraction, multiplication and division ofsignificantfigures Learn conversion of units from one system to another through dimensional analysis 1.1 INTRODUCTION A. substance is associated with physical properties and chemical properties. Some examples of physical properties are colour, odour, smell, density, melting point and boiling point. These properties can be measured without the substance undergoing decomposition or association. Observation of a chemical property requires a chemical change to occur. Chemical properties of a substance include acidic or basic nature, combustibility, etc. We require some parameters to assess certain properties. For example, properties like length, width, area, volume, etc., are quantitative in nature. That is, they are associated with definite values. Any quantitative measurement is represented by a number followed by units in which it is measured. It is absurd to say that a particular substance measures 6—in length we need to specify whether it is 6 cm or 6 m. When we say it is 6 m long, we mean it measures 6 units on the scale of metre. I SYSTEMS OF MEASUREMENT In scientific studies and research, two different systems of measurement have been in use. These are the English System and the Metric System. The metric system originated in France in the late eighteenth century and is more convenient to use because it is based on the decimal systemof numbers. Before 1960, both the systems of measurement were being used by the scientific community. Some parts of the globe preferred the English system because they were used to it. Greater proportion of the scientific population advocated a switch to the metric system because it was more convenient and hence more scientific. The metric system is called the International System of Units (called Le Systems International d’ Unites in French and abbreviated as SI units). Historically, this system was established by the 11"* General Conference on Weights and Measures (Conference General des Poides at Measures in French and abbreviated as CGPM). The CGPM is an intergovernmental treaty organization created by a diplomatic treaty known as Meter Convention which was signed in Paris in 1875. As a consequence of serial meetings of the international scientific community, it was agreed in 1960 to adopt SI units for scientific experimentation and studies, although both the units continue to be used in textbooks. We have been rather slow in adopting SI units in our works. The SI system has seven base units pertaining to seven fundamental quantities as listed in Table 11. Table 1.1 Seven basic physical quantities and their units Length | metre m Mass m kilogram kg Time c second s Electric current r ampere A Thermodynamic t kelvin K temperature Amount ofthe substance n mole mol Luminous intensity ly candela cd SI base units are separately defined as under: 1. Metre The metre is the length of the path travelled by light in vacuum during a time interval of 1299792458 of a second. 2. Kilogram The kilogram is equal to the mass of the international prototype of the kilogram. 3. Second The second is the duration of 9192631770 periods of radiation corresponding to the transition between the two hyperfine levels of the ground state of the caesium-133 atom 4. Ampere The ampere is that constant current which, if maintained in two straight parallel conductors of infinite length, of negligible circular cross section,and placed 1 metre apart in vacuum would produce between these conductors a force equal to 2 x 1077 newton per metre of length. a . Kelvin The Kelvin is the 1/273.16 fraction of the thermodynamic temperature of the triple point of water. 6. Mole The mole is the amount of substance which contains as many elementary entities are there are atoms in 0.012 kilogram of carbon-12. Its symbol is mol. The elementary entities must be specified and may be one of atoms, molecules, ions, electrons or other specified particles. 7. Candela The candela is the luminous intensity, in a given direction, of a source that emits monochromatic radiations of 540 = 10'2 hertz frequency and that has a radiant intensity in that direction of 1/683 watt per steradian. The SI system allows the use of prefixes to indicate the multiples or submultiples of a unit as given below in Table 1.2. In fact, this is the strength of the SI system because it is based on decimal system (multiples or submultiples of 10) Table 1.2 Prefixes in SI system 10-24 yocto y 10 deca da 102! zepto z 102 hecto h 10-18 atto a 103 kilo k 40715 femto f 10° mega M 40712 pico - 109 siga c 10-9 nano a 10!2 tera T 1076 micro H 1015 peta e 1073 milli m 10'8 exa EB 1072 centi e 102! zeta Z 1073 deci d 1024 yotta y The other physical quantities such as speed, acceleration, volume, density, pressure, force, etc., can be derived from the basic seven units. 1.3 MASS AND WEIGHTMass of a substance is the amount of matter present in it while weight is the force exerted by gravity on an object. The mass of a substance is constant whereas the weight may vary from place to place due to change in gravitational force. The mass of a substance can be determined accurately in the laboratory by using an analytical balance. Presently, we have the electronic top- weighing balance which directly gives the mass of the substance correct up to three or four decimal places depending upon the precision of the balance used. The SI unit of mass is one kg. However, its 10> multiple (1 kg = 1000 g), that is gram, is used more frequently for weighing small amounts of chemicals that are used in chemical reactions. Physical quantity measured Base unit Sl abbreviation —_— reat fa ~\ kelvin K @ apace A 9 candela ed Fig 1.1 Seven base units 1.4 VOLUME The unit of volume is (length)?, As the SI unit of length is metre, the SI unit of volume is (metre)? or m. In chemical laboratories, we use smaller volumes for experimentation. Hence, volumes are often denoted in cm? or dm? units. Litre (L) which is not an SI unit is used for the measurement of volumes of liquids. 1 L = 1000 mL and 1000 cm? = 1 dm? Thus, 1L = 1 dm? = 1000 mL = 1000 cm? Volumes of liquids or solutions are measured with the help or graduated cylinders, burettes, pipettes, etc.