Engineering Chemistry I (for BPUT)

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Cover Contents Preface Roadmap to the Syllabus Chapter 1: Structuere and Bonding 1.1 Introduction to Quantum Mechanics 1.2 Planck’s Quantum Theory (1900) 1.3 Einstein’s Unidirectionality of Light (1905) 1.4 Photoelectric Effect (1888) 1.5 Bohr’s Atomic Model (1913) 1.6 Hydrogen Spectrum 1.6.1 Ritz–Rydberg Principle 1.7 de Broglie Equation 1.7.1 Bohr’s Theory Versus de Broglie Equation 1.8 Uncertainty Principle (1927) 1.8.1 Significance of Uncertainty Principle 1.8.2 Comparison Between Orbit and Orbital 1.9 Wave Mechanics 1.9.1 Wave Function (y) 1.9.2 Significances of y and y2 1.9.3 Schrödinger Wave Equation A Particle in a Box: Time-independent Schrödinger’s Equation in a One-dimensional System Significance of Eqs. (1.16) Through (1.20) 1.9.4 Eigen Values, Eigen Functions and Eigen Value Equation Eigen Values Eigen Functions Eigen Value Equation 1.9.5 Applications of Schrödinger’s Equation 1.10 Interpretation of Wave Functions 1.10.1 Born Interpretation of Wave Function y 1.11 Molecular Orbital Theory of Diatomic Molecules 1.11.1 Linear Combination of Atomic Orbitals to Form Molecular Orbitals in the Light of Schrödinger’s Wave Equation 1.11.2 Formation of Bonding Molecular Orbital (Involving s-Orbitals) 1.11.3 Formation of Anti-bonding Molecular Orbital (Involving s-Orbitals) 1.11.4 Formation of Molecular Orbitals Involving s-Orbitals 1.11.5 Formation of Molecular Orbitals Involving p-Orbitals Formation of IIBMO and IIABMO Bond Order 1.11.6 Molecular Orbitals of Heteroatomic Molecules 1.11.7 Summary of MOT 1.11.8 Differences Between AO and MO 1.12 Metallic Bonding 1.12.1 Electron Sea Model/Free Electron Model 1.12.2 Conditions for the Formation of Metallic Bond 1.12.3 Characteristics of Metallic Bond and Properties of Metals 1.12.4 Molecular Orbital Theory or Band Theory of Metals 1.12.5 Conductors, Semiconductors and Insulators 1.13 Superconductors and Superconductivity 1.13.1 Low Temperature Superconductivity (LTSC) 1.13.2 High Temperature Superconductivity (HTSC) 1.13.3 Properties of Superconductors 1.13.4 Applications of Superconductors 1.14 Review Questions 1.15 Multiple Choice Questions Answers Chapter 2: Phase Rule 2.1 Introduction 2.2 Phase, Component and Degree of Freedom 2.2.1 Phase (P) 2.2.2 Components (C) 2.2.3 Degree of Freedom (F) 2.3 Derivation of Phase Rule 2.3.1 Merits of Phase Rule 2.3.2 Limitations of Phase Rule 2.4 One-Component Systems 2.4.1 Water System Significances of Areas Between the Lines AOC, AOB and BOC Critical Point, Point A 2.4.2 Application of Clapeyron’s Equation to Water System 2.4.3 Polymorphism and Allotropy Polymorphism Allotropy 2.4.4 Sulphur System 2.5 Two-component Systems and Condensed Phase Rule 2.5.1 Transition or Peritectic or Meritectic Temperature and Incongruent Melting Point 2.5.2 Eutectic Systems 2.5.3 Applications of Eutectic Systems 2.5.4 Non-eutectic Composition 2.5.5 Significance of Eutectic Point 2.5.6 Binary Eutectic Systems 2.5.7 Bismuth–Cadmium System (Bi–Cd) 2.5.8 Silver–Lead System (Ag–Pb System) 2.5.9 Iron–Carbon System (Fe–C System) 2.5.10 Phase Diagram of Fe–C System 2.6 Review Questions 2.7 Multiple Choice Questions Answers Chapter 3: Solid State 3.1 Introduction 3.2 Types of Solids 3.2.1 Crystalline Solids Metallic Crystal Non-metallic Crystal 3.2.2 Amorphous Solids 3.3 Crystal System 3.4 Space Lattice 3.5 Unit Cell and Type 3.5.1 Types of Unit Cell 3.6 Type, Crystal Systems 3.7 Bravais Lattices 3.8 Crystallographic Planes and Directions (Miller Indices) 3.8.1 Inter-planar Spacing 3.9 Analysis of a System 3.9.1 Atomic Radius 3.9.2 Number of Atoms per Unit Cell 3.9.3 Co-ordination Number 3.9.4 Length of Unit Cell and Density of an Element Mathematical Calculations Calculation of Mass of Unit Cell General Formula 3.9.5 Atomic Packing Factor (Packing Fraction or Density of Packing) 3.10 Closed Packed Structure 3.10.1 Hexagonal Close-Packed (HCP) 3.10.2 Cubic Close-Packed (CCP) or Face-Centred Cubic (FCC) 3.10.3 Body-Centred Cubic 3.11 Ionic Solids 3.11.1 Ionic Compound of Type AB Sodium Chloride (Rock Salt) Type Structure Cesium Chloride (CsCl Type) Zinc Blende (ZnS) Type Structure: (ZnS) Calcium Fluoride [Fluorite] (CaF2 Type) Anti-fluorite Structure (Li2-O) Type [Na2O] Type Wurtzite Structure 3.12 Defects in Crystals 3.12.1 Stoichiometric Defects Schottky Defect Frenkel Defects 3.12.2 Non-stoichiometric Defects 3.13 Cubic, Octahedral and Tetrahedral Holes 3.13.1 Radius Ratio 3.14 Review Questions 3.15 Multiple Choice Questions Answers Chapter 4: Chemical Kinetics 4.1 Introduction 4.2 Types of Chemical Reactions 4.2.1 Spontaneous Reactions/Instantaneous Reactions 4.2.2 Slow Reactions 4.2.3 Moderate Reactions 4.3 Rate of Reactions 4.4 Rate Constant of a Reaction 4.5 Factors Affecting the Rates of Chemical Reactions 4.5.1 Concentration of Reactants 4.5.2 Nature of Reactants and Products 4.5.3 Surface Area of Reactants 4.5.4 Temperature 4.5.5 Presence of Catalyst In Exothermic Reactions In Endothermic Reactions 4.5.6 Exposure to Radiations 4.6 Molecularity of a Reaction 4.6.1 Characteristics of Molecularity 4.7 Order of a Reaction 4.7.1 Characteristics of Order of Reaction 4.7.2 Differences Between Molecularity and Order of Reaction 4.8 Zero-order Reactions 4.8.1 Illustration of Zero-order Reaction 4.9 First-order Reactions 4.9.1 Expression for Rate Constant of a First-order Reaction 4.9.2 Graphical Determination of First-order Rate Constant (k1) 4.9.3 Half-life Period of First-order Reactions 4.9.4 Average Life Period 4.9.5 Pseudo First-order Reactions 4.9.6 Measurement of Rate Constant of First-order Reaction 4.9.7 Exercises 4.10 Second-order Reactions 4.10.1 Derivation of Expression for the Rate Constant of a Second-order Reaction 4.10.2 Graphical Determination of Second-order Rate Constant (k2) Involving One Reactant 4.10.3 Graphical Determination of Second-order Rate Constant (k2) Involving Two Different Reactants 4.10.4 Half-life Period of Second-order Reactions 4.11 Fractional-order Reactions 4.12 Units of Rate Constants of Different Order Reactions 4.13 Methods for Determination of Order of Reactions 4.13.1 Use of Integral Rate Equation 4.13.2 Graphical Method 4.13.3 Half-life Period Method 4.13.4 Ostwald’s Isolation Method 4.14 Theories of Reaction Rates 4.14.1 Collision Theory 4.14.2 Model Problems 4.14.3 Limitations of Collision Theory 4.14.4 Theory of Absolute Reaction Rates or Transition State Theory or Activated Complex Theory 4.14.5 Activated Complex and Energy of Activation 4.14.6 Comparison Between Collision Theory and Transition State Theory 4.15 Review Questions 4.16 Multiple Choice Questions Chapter 5: Catalysis 5.1 Introduction 5.2 Types of Catalysts 5.2.1 Positive Catalysts 5.2.2 Negative Catalysts 5.2.3 Auto-catalysts 5.3 Promoters 5.4 Characteristics of Catalytic Reactions 5.5 Catalytic Poisoning 5.5.1 Temporary Poisoning 5.5.2 Permanent Poisoning 5.5.3 Theory Behind Catalytic Poisoning 5.5.4 Auto-catalytic Poisoning 5.6 Induced Catalysis 5.7 Types of Catalysis 5.7.1 Homogeneous Catalysis Theories of Homogeneous Catalysis 5.7.2 Heterogeneous Catalysis Theories of Heterogeneous Catalysis 5.7.3 Enzyme Catalysis Characteristics of Enzyme Catalysis Mechanism and Kinetics of Enzyme Catalysed Reactions Michaelis and Menten Mechanism 5.8 Review Questions 5.9 Multiple Choice Questions Answers Chapter 6: Electrochemistry 6.1 Introduction 6.2 Electrochemical Cells (Galvanic Cell) 6.2.1 Salt Bridge 6.3 Types of Electrodes 6.3.1 Gas Electrode Construction 6.3.2 Oxidation–Reduction Electrode Quinhydrone Electrode 6.3.3 Metal–Metal-ion Electrode 6.3.4 Amalgam Electrode 6.3.5 Metal–Insoluble Salt Electrode Calomel Electrode 6.4 Electromotive Force and its Measurement 6.5 Free Energy Change and Electrical Work 6.6 Nernst Equation 6.7 Standard Electrode Potentials 6.7.1 Using the Table of Standard Electrode Potentials 6.7.2 Electrode Potential and Stoichiometry 6.7.3 Displacement Reactions 6.8 Combining Standard Electrode Potential to Determine the Cell Potential 6.9 Calculation of the EMF of Galvanic Cells 6.10 Applications of EMF Measurement 6.10.1 Evaluation of Thermodynamic Functions 6.10.2 Determination of pH of Solution Hydrogen Electrode Calculation of ER (EHydrogen electrode) Advantages of Hydrogen Electrode Disadvantages of Hydrogen Electrode Quinhydrone Electrode Advantages of Quinhydrone Electrode Disadvantages of Quinhydrone Electrode Glass Electrode Advantages of Glass Electrode Disadvantages 6.11 Electrochemical Energy Sources 6.11.1 Dry Cells 6.11.2 Secondary Cells Electrode Reactions 6.11.3 Fuel Cells Electrode Reaction Advantages of Fuel Cell Over Electrochemical Cell 6.12 Review Questions 6.13 Multiple Choice Questions Answers Chapter 7: Thermochemistry 7.1 Introduction 7.1.1 Thermochemical Standard State 7.2 Heat of Reaction (Kirchoff’s Equation) 7.2.1 Physical States of the Reactants and Products 7.3 Heat of Formation 7.4 Heat of Combustion 7.5 Heat of Neutralization 7.6 Heat of Solution 7.6.1 Integral Heat of Solution 7.6.2 Differential Heat of Solution 7.7 Heat of Hydration Important Points 7.8 Bond Energy 7.8.1 Factors Affecting Bond Energy 7.8.2 Application of Bond Energies 7.9 Hess’s Law of Constant Heat Summation Experimental Verification Another Way 7.9.1 Application of Hess’s Law 7.10 Born–Haber Cycle (Born–Haber Cycle Lattice Energy) 7.10.1 Born–Haber Cycle of an Ionic Crystal 7.11 Review Questions 7.12 Multiple Choice Questions Answers Chapter 8: Thermodynamics 8.1 Introduction 8.1.1 What Is Thermodynamics and Why Is It Useful? 8.1.2 Basic Definitions Needed to Describe Thermodynamics Systems 8.1.3 State of a System 8.1.4 Changes in a State 8.2 Perfect Differential 8.2.1 What is a Perfect Differential? 8.2.2 How to Prove Exact Differential? 8.3 Internal Energy and the First Law of Thermodynamics 8.3.1 First Law of Thermodynamics 8.3.2 Consequences of the First Law of Thermodynamics 8.4 Work and Heat 8.4.1 Work 8.4.2 Heat Characteristics of Heat Unit of Work 8.5 Heat Capacities and Enthalpy 8.6 Some Important Thermodynamic Derivations 8.7 Limitations of the First Law of Thermodynamics 8.8 Heat Engine 8.8.1 Carnot Cycle/Carnot Heat Engine 8.8.2 Efficiency of a Heat Engine 8.9 Second Law of Thermodynamics 8.9.1 Kelvin–Planck Statement 8.9.2 Clausius Statement 8.10 Concept of Entropy 8.10.1 Reversible and Irreversible Changes 8.10.2 Physical Meaning of Entropy 8.10.3 Entropy and Disorder 8.10.4 Absolute Entropies 8.10.5 Standard Entropies of Substances 8.10.6 Effect of Temperature, Volume and Concentration on the Entropy 8.10.7 Entropy Change Accompanying Change of Phase From Solid Phase to Liquid Phase From Liquid Phase to Vapour Phase 8.10.8 Some Mathematical Formulae 8.10.9 Direction of Spontaneous Change 8.11 Free Energy—The Gibbs Function More About the Gibbs Free Energy 8.11.1 Gibbs Function: Is It Free? Is It Energy? 8.11.2 Standard Gibbs Free Energy 8.11.3 Free Energy of a Gas: Standard States 8.12 Gibbs–Helmholtz Equation 8.12.1 Gibbs–Helmholtz Equation in Terms of Energy and Enthalpy Change 8.12.2 Gibbs–Helmholtz Interim of Work Function 8.12.3 Application of Gibbs–Helmholtz Equation 8.13 Free Energy and Equilibrium 8.13.1 Approaching Equilibrium: Free Energy Can Only Fall 8.13.2 Difference Between ΔGº and ΔG 8.13.3 Equilibrium Constant 8.13.4 Equilibrium and Temperature 8.14 Some Important Thermodynamic Derivations 8.14.1 Maxwell Relationship 8.15 Review Questions 8.16 Multiple Choice Questions Answers Index