GRADUATE PHYSICAL CHEMISTRY (VOLUME - I)

Size: px

Start display at page:

Download "GRADUATE PHYSICAL CHEMISTRY (VOLUME - I)"

Opal Quinn
5 years ago
Views:

PURI l SHARMA l PATHANIA S GRADUATE PHYSICAL CHEMISTRY (VOLUME - I) (for B.Sc. Ist year students of U.P. (Unified)and other Indian Universities) (Strictly as per UGC curriculum) Dr.

1 PURI l SHARMA l PATHANIA S GRADUATE PHYSICAL CHEMISTRY (VOLUME - I) (for B.Sc. Ist year students of U.P. (Unified)and other Indian Universities) (Strictly as per UGC curriculum) Dr. B.S. LARK Former Professor and Head, Department of Chemistry, Guru Nanak Dev University, AMRITSAR (Pb.) Future for WINNERS VISHAL PUBLISHING CO. JALANDHAR - DELHI

2 CONTENTS 1. MATHEMATICAL CONCEPTS Logarithms and Logarithmic Functions 1.1. Common and Natural Logarithms 1.2. Laws of Logarithms 1.3. Log Tables 1.4. Antilogarithms and Antilogarithm Tables 2. Curve Sketching, Linear Graphs and Slopes 2.1. Curves and Slopes 2.2. Inclination of a Line and The Slope of a Line 2.3. Drawing The Graphs of Linear Equations 3. Calculus 3.1. Conceptual Dialogue 1: Differentiation 3.2. Steps for ab Initio Differentiation 3.3. Differentiation Rules 3.4. Differentials (Derivatives) dy/dx i.e.,f (x) of Some Functions 3.5. Succesive or Higher Order Differentiation 3.6. Maximum and Minimum 4. Partial Differentiation 4.1. Higher Order Partial Derivatives 4.2. The Euler Reciprocal (Reciprocity) Relation 4.3. The Euler Chain Relation (The Cyclic Rule) 4.4. Miscellaneous Problems of Partial Derivation 5. Integration 5.1. Definite Integrals 5.2. Methods of Integration 6. Factorial Notation 7. Permutations and Combinations 7.1. Fundamental Principal of Counting/ Association 7.2. Permutations 7.3. Permutations for N Objects Taken All at a Time ( n P n ) 7.4. Permutations of n Objects Out of Which R are To Be Selected n P r 7.5. Conceptual Corrolary 7.6. Combinations 7.7. Permutations : (Various Formulae) 7.8. Combinations : (Various Formulae) 7.9. Diagonals of a Polygon 8. Probability 1 (B). COMPUTERS Introduction 1.1. Type of Computers 1.2. Classification 2. Development of Computers 3. Algorithms and Flow Charts 4. Different Components of a Computer 5. Hardware and Software 6. The Binary Number Systems 7. Decimal to Binary Conversion 8. Other Number Systems 9. Conversion of a Number From any Other System to Decimal System 10. Octal to Binary Conversion 11. Binary Arithmetic 12. Programming Algorithm Flow Charts Introduction to Computer Programming Languages 13. Operating Systems Batch Operating Systems Personal Computer Operating Systems The UNIX Operating System Microkernel Based Operating System 2. THE GASEOUS STATE The Kinetic Molecular Theory of Gases 1.1. Postulates of Kinetic Molecular Theory 1.2. Justification for The Postulates 1.3. Pressure of an Ideal (or Perfect) Gas- Kinetic Gas Equation 2. Kinetic Energy and Temperature 3. Derivation of Gas Laws

3 3.1. Boyle s Law 3.2. Charle s Law 3.3. Avogadro s Law 3.4. The Ideal Gas Equation 3.5. Graham s Law of Diffusion 3.6. Dalton s Law of Partial Pressures 4. Thermal Motion of The Molecules 5. Real Gases 5.1. Deviations of Real Gases From Ideal Behaviour and Compressibility Factor 5.2. Compressibility of Various Gases 5.3. Effect of Temperature on Deviations from Ideal Behaviour 5.4. Explanation for The Deviations 6. The van der Waals Equation of State 6.1. Correction due to Volume of Gas Molecules 6.2. Correction Due to Intermolecular Forces of Attraction 6.3. Calculation of the Correction Factor, p van der Waals Gas Equation for One Mole of A Real Gas 6.5. van der Waals Gas Equation for n Moles of a Gas 6.6. Units For The van der Waals Constants 6.7. Significance of van der Waals Constants 6.8. Discussion of The van der Waals Equation 7. Other Equations of State 7.1. Dieterici Equation 7.2. Berthelot Equation 7.3. Clausius Equation 7.4. Radlich-Kwong Equation 7.5. The Virial Equation of State 8. Critical Constants of a Gas 8.1. Determination of Critical Constants 8.2. The P-V Isotherms of Carbon Dioxide 8.3. Continuity of State 8.4. Isotherms of van der Waals Gas and Co- Relations Between Critical Constants and van der Waals Constants 8.5. Critical Compressibility Factor 8.6. Determination of van der Waals Constants a and b From Critical Data 9. The Principle of Corresponding States and Reduced Equation of State 10. Molecular Velocities Maxwell s Law of Distribution of Molecular Velocities Effect of Temperature on Distribution of Molecular Velocities Types of Molecular Velocities Collision Diameter Collision Number Collision Frequency Collision Frequency Between Unlike Molecules Number Density of an Ideal Gas (n*) Mean Free Path Coefficient of Viscosity and Mean For Path of a Gas 11. Liquefaction of Gases The Joule-Thomson Effect Linde s Apparatus Adiabatic Expansion Involving Mechanical Work Liquefaction of Helium Applications of Liquefied Gases 3. THE LIQUID STATE Intermolecular Forces 2. Nature of Molecules and Dipole Moment 2.1. Polar and Non Polar Molecules 2.2. Heteronuclear Diatomic Molecules 2.3. Direction of Dipole Moment 2.4. Polar, Non-Polar and Ionic Molecule 2.5. Percentage Ionic Character 2.6. Dipole Moments of Halogen Acids 2.7. Bond Moments and Dipole Moments of Polyatomic Molecules 2.8. Diploe Moment and cis- trans- Isomerism 3. Mixing of Molecules and Intermolecular Interactions 3.1. Induced Dipole-Induced Dipole Interaction 3.2. Dipole-Induced Dipole Interaction 3.3. Dipole-Dipole Interaction 4. Similarity of Various Interactive Energies 5. Repulsive Forces

4 6. Hydrogen Bonding (H-Bonding) 6.1. Types of H-Bonding 6.2. Consequences of H-Bonding 7. Unusual Behaviour of Water 7.1. Water in Solid State (Ice) is Lighter Than in Liquid State (Water) 7.2. Density of Water 7.3. Characteristic Properties of Water 8. Effect of Unusual Behaviour of Water 9. Miscellaneous Problems 10. Some Other Weak Intermolecular Forces Hydrophobic Interactions Aromatic Interactions Interactions Involving Ions 11. Structure of Liquids Structure of Liquids and Structural Differences Between Solids, Liquids and Gases Hole Theory of Liquids The Free Volume in a Liquid Radial Distribution Function Structure of Simple Liquids 4. SOLID STATE Introduction 2. Difference Between Crystalline and Amorphous Solids 3. Size and Shape of Crystals : Interfacial Angles 3.1. Law of Constancy of Interfacial Angles 4. Symmetry in Crystal Systems 4.1. Plane of Symmetry ( n ) 4.2. Axis of Symmetry (C n ) 4.3. Centre of Symmetry (I) 4.4. Rotation Reflection Axis of Symmetry (S n ) 4.5. Rotation Inversion Axis of Symmetry 5. Elements of Symmetry of A Cubic Crystal 5.1. Law of Constancy of Symmetry 6. Point Groups 7. Space Lattice and Unit Cell 8. Bravais Lattices 9. Seven Crystal Systems 10. Density of Cubic Crystals 11. Law of Rational Indices 12. Lattice Planes and Their Designation Weiss Indices Miller Indices 13. Interplanar Spacing in a Crystal System Lattice Planes of The Cubic System Inter Planar Distance Ratios 14. X-Ray Diffraction Laue Method 15. The Bragg Equation Derivation of The Bragg Equation 16. Experimental Methods 17. Powder Method, The Debye Scherrer Method 18. N Values for Simple Cubic (PRIMITIVE P) Lattice 19. bcc (I) Lattice sc vs. bcc Lattice Prior Knowledge of a fcc Lattice 20. Analysis of Powder Diffraction Pattern of NaCl Ions Per Unit Cell/Density of The Crystal 21. Powder Pattern of Potassium Chloride 22. Crystal Structure of Cesium Chloride 5. LIQUID CRYSTALS Liquid Crystals (Mesomorphic State) 2. Discovery of The Phenomenon 3. Some Terms and Definitions 4. Characteristics and Shapes of Mesogens 5. Order in Liquid Crystals 5.1. Order Parameter (S) 5.2. Variation of Order Parameter S with Temperature 6. Types of Mesomorphism 6.1. Thermotropic Mesomorphism 6.2. Lyotropic Mesomorphism 6.3. Metallotropic Mesomorphism 7. Vapour Pressure Temperature Diagrams 8. Thermography

5 9. Classification of Thermotropic Liquid Crystals 9.1. Smectic Liquid Crystals 9.2. Nematic Liquid Crystals 10. Molecular Arrangements in Various States of Liquid Crystals Smectic LC s Nematic LC s Normal Liquids Liquid Crystals in Daily Life 11. Compounds Exhibiting Both Smectic and Nematic Characters 12. Cholesteric Liquid Crystals 13. Disc-Shaped Liquid Crystals 14. Polymer Liquid Crystals 15. Polymorphism in Thermotropic Liquid Crystals 16. The Melting of Nematic Crystals 17. Pressure-Induced Mesomorphism 18. Thermochromic Liquid Crystals (TLC) 19. Liquid Crystal Display (LCD) and Seven Segment Cell 20. Difference Between Solids/Liquids and Liquids Crystals 21. Applications of Liquid Crystals 6. COLLOIDAL STATE Introduction 1.1. Colloidal Systems 2. Classification of Colloids 2.1. Classification Based Upon Nature of Interaction Lyophilic Colloids 2.2. Lyophobic Colloids 2.3. Lyophobic vs. Lyophillic Sols 2.4. Classification Based Upon Manner of Aggregation Dispersion Colloids Macromolecular Colloids Association Colloids Micelles 3. True Solutions, Colloidal Solutions and Suspensions 4. Preparation of Colloidal Solutions 4.1. Lyophilic Sols 4.2. Lyophobic Sols Dispersion Methods Colloid Mill Methods Ultrasonic Generators Electrical Dispersion Preptization Condensation Methods Double Decomposition Oxidation 5. Purification of Colloidal Solutions 5.1. Dialysis 5.2. Ultra-Filtration 6. General Properties of Colloidal Systems 6.1. Heterogeneous Character 6.2. Diffusibility 6.3. Filterability 6.4. Visibility 6.5. Colligative Properties 6.6. Optical Properties 6.7. The Brownian Movement 7. Some Specific Properties of Hydrophobic Colloidal Systems 7.1. Electrical Properties 7.2. The Origin of Charge on Colloidal Particles 7.3. Both Positive and Negative Sols 7.4. Charge on The Colloidal Particle Through Ionization of Colloidal Material 7.5. Electrical Double Layer 8. Stability of Colloids 8.1. Stability of Lyophobic Colloids 8.2. Stability of Lyophilic Colloids 9. Coagulation of Colloidal Sols 9.1. By The Action of Electrolytes Hardy-Schulze rule 9.2. Flocculation Value 9.3. Departures From Hardy Schulze Rule 9.4. Amount of Coagulant and Nature of Coagulation 9.5. Coagulation of Lyophilic Sols 9.6. Lyotropic or Hofmeister Series 9.7. By The Mutual Action of Sols 9.8. By Presistent Dialysis

6 9.9. Coagulation By Mechanical Means 10. Protective Colloids Gold Number 11. Electrokinetic Properties Electrophoresis, Experimental Set Up Electrophoretic Mobility Electro Osmosis 12. Emulsions (Liquids in liquids) Classification Identification of The Type of an Emulsion Emulsifiers Applications of Emulsions 13. Liquids in Solids (GELS) Preparation of Gels Elastic and Non Elastic Gels Syneresis 14. Thixotropy Pectization Applications 15. Colloidal Electrolytes Properties of Aqueous Solutions of Colloidal Electrolytes 16. Importance and Application of Colloids 7. CHEMICAL KINETICS Chemical Kinetics 2. Rate of Reaction 2.1. Following Reaction Rate Instantaneous rate Rate determination through physical property 2.2. Expressing Reaction Rates 3. Factors Influencing Rates of 3.1.Effect of The Nature of Reactants and Products 3.2.Effect of Concentration 3.3.Effect of Temperature 3.4.Effect of Catalyst 3.5.Effect of Surface Area of Reactants 3.6.Effect of Radiation 3.7.Effect of Pressure 3.8.Ultrasound Assisted 3.9. Effect of Solvents Orientation Effect Kinetic Isotopic Effect (KIE) 4. Significance of Velocity Constant or Rate Constant 5. Order of A Reaction 5.1. One Reactant Only 5.2. Two Reactants 5.3. Three Reactants 5.4. Fractional Order of Various Order 6. Zero Order 6.1. Some Heterogeneous Zero Order 6.2. Rate Equation For Zero Order 6.3. Units of k Graphical Representation of Zero Order 6.5. of Kinetic Data of Zero Order 7. First Order 7.1. Some Characteristics of I Order 7.2. Units of k Examples of First Order 7.4. Completed Fraction of I st Order Reaction 7.5. of Kinetic Parameters of I st Order 8. Second Order 8.1. Case I. - When There is Only One Reactant 8.2. Case II. When There are Two Different Reactants 8.3. Units of k Examples of Second Order 9. Third Order 10. of Higher Orders 11. Half-Life Time of a Reaction t 1/2 For A First Order Reaction Reactant Left After n Half Lives For A First Order Reaction t 1/2 For A Second Order Reaction

7 11.4. t 1/2 For A Third Order Reaction t 1/2 of Zero Order Dependence of t 1/2 Upon Initial Concentration of A Single Reactant (A ) 12. Methods For Determining The Order of A Reaction The Use of Differential Rate Expressions. Hit and Trial Method The Use of Integral Rate Expressions Graphical Method The Half-Life Method Ostwald s Isolation Method 13. Molecularity of A Reaction Order and Molecularity of Simple Order and Molecularity of Complex 14. Radioactive Decay Units of k Amount of Radioactive Substance Left Amount of Radioactive Substance Left in Terms of t 1/ Half Lives of Some Radioactive Isotopes Average Life 15. Experimental (Instrumental) Methods to Study Kinetics Optical Methods Spectroscopic Method Electrical Conductivity Method Potentiometric Method 16. Effect of Temperature on Reaction Rates Concept of Activation Energy Effect of Catalyst Calculation of Energy of Activation, The Arrhenius Equation 17. Theories of Reaction Rates Simple Collision Theory Based Upon Hard Sphere Model, Between Dissimilar Molecules Collision Theory of Bimolecular Between Similar Molecules Comparison of The Experimental and Theoretical k 2 Values Activated Complex Theory (ACT) of Bimolecular Eyring Equation for in Solution Comparison of The ACT with Collision Theory The Lindemann Theory of Unimolecular 18. Scope of Chemical Kinetics 8. CATALYSIS Catalysis 2. Auto-Catalysis 3. Promoters 4. Negative Catalysts 5. General Characteristics of Catalytic 6. Types of Catalysis 7. Theories of Homogeneous Catalysis 7.1. Formation of Reactive Intermediate 7.2. Acid-Base Catalysis 8. Enzyme Catalysis 8.1. Enzyme 8.2. Significance of k m and v max 9. Heterogeneous Catalysis 9.1. Heterogeneous Catalysis Involving Solid Reactants 9.2. Heterogeneous Catalysis Involving Liquid Reactants 9.3. Heterogeneous Catalysis Involving Gaseous Reactants 10. Theories of Heterogeneous Catalysis The Chemical Theory The Adsorption Theory 11. Miscellaneous Examples of Catalysts Lindlar Catalyst Adam s Catalyst Palladium Catalyst Ziegler-Natta Catalyst, Karl Ziegler and Giulio Natta Catalytic Converters Phase Transfer Catalysis and Catalyst Aliquat-336

χ A = P A Gen. Chem. II Exam I review sheet (Ch. 10, 11, 13, 14) Ch. 10 Gases behave physically similarly.

χ A = P A Gen. Chem. II Exam I review sheet (Ch. 10, 11, 13, 14) Ch. 10 Gases behave physically similarly. Gen. Chem. II Exam I review sheet (Ch. 10, 11, 13, 14) Ch. 10 Gases behave physically similarly. KMT (Kinetic Molecular Theory): particles in a gas: are in constant rapid motion are tiny compared to the