TEXTBOOK OF PHYSICAL CHEMISTRY

By JOSHUA HERNANDEZ

CONTENTS 1 SOME FUNDAMENTAL CHEMICAL CONCEPTS 1 1 INTRODUCTION 1 2 DEFINITIONS OF SOME CHEMICAL TERMS 1 3 STATES OF MATTER 1 4 NATURE OF INTERMOLECULAR FORCES 1 5 CHEMICAL AND PHYSICAL PROPERTIES 1 6 MEASUREMENTS (FORCE, PRESSURE, ENERGY AND TEMPERATURE) QUICK RECAP FUNDAMENTAL LAWS OF CHEMISTRY PROBLEMS MULTIPLE CHOICE QUESTIONS 2 GASEOUS STATE INTRODUCTION 2 1 THE LAWS GOVERNING THE IDEAL GAS BEHAVIOUR 2 2 THE COMBINED GAS LAW AND THE GAS EQUATION 2 3 NUMERICAL VALUES OF R 2 4 DALTON’S LAW OF PARTIAL PRESSURE 2 5 GRAHAM’S LAW OF DIFFUSION 2 6 THE KINETIC THEORY OF IDEAL GASES 2 7 DEDUCTION FROM KINETIC THEORY 2 8 THE DISTRIBUTION OF MOLECULAR VELOCITIES 2 9 THE MEAN FREE PATH OF GAS MOLECULES 2 10 VISCOSITY 2 11 DEGREES OF FREEDOM AND THEIR APPLICATION TO EQUIPARTITION OF ENERGY 2 12 LAW OF EQUIPARTITION OF ENERGY 2 13 THE SPECIFIC HEATS OF GASES 2 14 THE BAROMETRIC FORMULA (VERTICAL DISTRIBUTION) 2 15 REAL GASES 2 16 CAUSES OF DEVIATIONS 2 17 MODIFICATION OF THE IDEAL GAS EQUATION 2 18 EXPLANATION OF BEHAVIOUR OF REAL GASES FROM VAN DER WAALS EQUATION 2 19 OTHER EQUATIONS OF STATE LIST OF FORMULAS 3 LIQUIDS 3 1 LIQUIDS AND THE CRITICAL PHENOMENA 3 2 EXPERIMENTAL DETERMINATION OF CRITICAL CONSTANTS 3 3 CONTINUITY OF STATE 3 4 VAN DER WAALS EQUATION AND THE CRITICAL PHENOMENA 3 5 THE LAW OF CORRESPONDING STATES 3 6 LIQUEFACTION OF GASES 3 7 STRUCTURE OF LIQUIDS 4 PROPERTIES OF LIQUIDS 4 1 VAPOUR PRESSURE 4 2 BOILING POINT 4 3 SURFACE TENSION 4 4 VISCOSITY OF LIQUIDS 5 THE SOLID STATE 5 1 INTRODUCTION 5 2 CRYSTALLINE STATE 5 3 TYPES OF SOLIDS 5 4 PROPERTIES OF SOLIDS 5 5 CRYSTALLOGRAPHY 5 6 SPACE LATTICE 5 7 CRYSTAL SYSTEMS 5 8 PACKING OF ATOMS IN CLOSE-PACKED STRUCTURE 5 9 BRAGG’S LAW 5 10 EXPERIMENTAL METHODS OF X-RAY DIFFRACTION 5 11 DEFECTS IN SOLIDS 5 12 HEAT CAPACITIES OF SOLIDS 6 THERMODYNAMICS 6 1 INTRODUCTION 6 2 THERMODYNAMIC TERMS 6 3 MATHEMATICAL TECHNIQUES 6 4 STATE FUNCTIONS AND EXACT DIFFERENTIALS 6 5 THE EQUIVALENCE OF HEAT AND WORK 6 6 ENERGY AND THE CONSERVATION OF ENERGY (THE FIRST LAW OF THERMODYNAMICS) 6 7 INTERNAL ENERGY (E) 6 8 WORK, HEAT AND ENERGY CHANGES 6 9 PRESSURE VOLUME WORK 6 10 REVERSIBILITY AND MAXIMUM WORK 6 11 HEAT CONTENT (ENTHALPY) 6 12 HEAT CAPACITIES AT CONSTANT VOLUME AND CONSTANT PRESSURE 6 13 HEAT CAPACITY RELATIONSHIPS 6 14 THE INTERNAL ENERGY OF AN IDEAL GAS (THE JOULE EXPERIMENT) 6 15 EFFECT OF PRESSURE AND TEMPERATURE ON HEAT CAPACITIES OF IDEAL GASES 6 16 HEAT CAPACITY–TEMPERATURE RELATIONSHIPS 6 17 ISOTHERMAL PROCESS 6 18 ADIABATIC PROCESS 6 19 WORK OF EXPANSION IN REVERSIBLE ADIABATIC PROCESS 6 20 JOULE-THOMSON EFFECT 7 THERMOCHEMISTRY 7 1 INTRODUCTION 7 2 STANDARD STATE AND THE SIGN CONVENTION FOR HEAT TRANSFER 7 3 HEAT OF REACTION 7 4 THE LAWS OF THERMOCHEMISTRY 7 5 HEAT OF FORMATION 7 6 HEAT OF SOLUTION 7 7 HEAT OF NEUTRALIZATION 7 8 HEAT OF FORMATION OF IONS IN SOLUTION 7 9 HEAT OF COMBUSTION 7 10 VARIATION OF HEAT OF REACTION WITH TEMPERATURE 7 11 THE TEMPERATURE OF FLAMES 7 12 BOND ENERGIES IMPORTANT TERMS AND FORMULAS 8 ENTROPY: THE SECOND LAW OF THERMODYNAMICS 8 1 SPONTANEOUS PROCESSES 8 2 THE SECOND LAW OF THERMODYNAMICS 8 3 THE CARNOT CYCLE 8 4 ENTROPY 8 5 ENTROPY CHANGE IN A REVERSIBLE PROCESS 8 6 ENTROPY CHANGE IN AN IRREVERSIBLE PROCESS 8 7 ENTROPY AND THE SECOND LAW (MOLECULAR INTERPRETATION OF ENTROPY) 8 8 DEPENDENCE OF ENTROPY ON VARIABLES OF A SYSTEM 8 9 ENTROPY CHANGES FOR AN IDEAL GAS 8 10 ENTROPY OF MIXING FOR IDEAL GASES 8 11 ENTROPY AND CHANGE OF STATE 8 12 ENTROPY CHANGE IN CHEMICAL REACTIONS 8 13 STATISTICAL APPROACH TO ENTROPY 8 14 DETERMINATION OF ENTROPIES OF SUBSTANCES (THE THIRD LAW OF THERMODYNAMICS) 9 FREE ENERGY FUNCTIONS 9 1 CRITERION OF EQUILIBRIUM 9 2 FREE ENERGY AND BOILING POINTS 9 3 PROPERTIES OF HELMHOLTZ FREE ENERGY (A) 9 4 PROPERTIES OF GIBBS FREE ENERGY (G) 9 5 THE GIBBS–HELMHOLTZ EQUATION 9 6 MAXWELL RELATIONS 9 7 THERMODYNAMIC EQUATION OF STATE 9 8 CLAPEYRON EQUATION 9 9 CLAUSIUS–CLAPEYRON EQUATION 9 10 CHEMICAL POTENTIAL 9 11 THE GIBBS–DUHEM EQUATION 9 12 APPLICATIONS OF CHEMICAL POTENTIAL 9 13 ACTIVITIES AND ACTIVITY COEFFICIENTS 10 CHEMICAL EQUILIBRIUM 10 1 REVERSIBLE PROCESSES 10 2 THE LAW OF MASS ACTION 10 3 THERMODYNAMIC DERIVATION OF THE EQUILIBRIUM CONSTANT 10 4 EQUILIBRIUM CONSTANTS EXPRESSED IN DIFFERENT UNITS 10 5 RELATIONSHIP BETWEEN KP AND KC 10 6 PROPERTIES OF EQUILIBRIUM CONSTANTS, KP AND KC 10 7 THE LE-CHATELIER–BRAUN PRINCIPLE 10 8 EFFECT OF INERT GAS (A GAS WHICH DOES NOT ENTER INTO THE REACTION) ON EQUILIBRIUM 10 9 TYPES OF CHEMICAL EQUILIBRIA 10 10 APPLICATION OF LAW OF MASS ACTION TO HOMOGENEOUS GASEOUS EQUILIBRIA 10 11 DEGREE OF DISSOCIATION FROM DENSITY MEASUREMENTS 10 12 COMBINATION OF EQUILIBRIA 10 13 HOMOGENEOUS EQUILIBRIA IN LIQUID SYSTEMS 10 14 EQUILIBRIA IN HETEROGENEOUS SYSTEMS 10 15 VARIATION OF EQUILIBRIUM CONSTANT WITH TEMPERATURE 10 16 VARIATION OF EQUILIBRIUM CONSTANT WITH PRESSURE 11 PHASE EQUILIBRIA 11 1 INTRODUCTION 11 2 DEFINITIONS OF VARIOUS TERMS INVOLVED IN THE PHASE RULE 11 3 DETERMINATION OF DEGREES OF FREEDOM WITHOUT THE HELP OF PHASE RULE 11 4 DEDUCTION OF PHASE RULE 11 5 CLAPEYRON EQUATION FOR CONSTRUCTION OF PHASE DIAGRAM 11 6 APPLICATIONS OF THE PHASE RULE 11 7 THE SULPHUR SYSTEM 11 8 TWO-COMPONENT SYSTEMS 11 9 COMPOUNDS FORMING SOLID SOLUTIONS 11 10 THREE-COMPONENT SYSTEMS 12 SOLUTIONS 12 1 INTRODUCTION 12 2 TYPES OF SOLUTIONS 12 3 MODES OF EXPRESSING COMPOSITION (CONCENTRATION) OF SOLUTIONS 12 4 SOLUTION OF GASES IN LIQUIDS 12 5 HENRY’S LAW AND RAOULT’S LAW 12 6 MIXTURES OF TWO LIQUIDS 12 7 THE IDEAL SOLUTION AND RAOULT’S LAW 12 8 NON-IDEAL (REAL) SOLUTIONS OF MISCIBLE LIQUIDS 12 9 RELATIONSHIP BETWEEN THE COMPOSITION OF A SOLUTION AND THE COMPOSITION OF THE VAPOUR ABOVE IT 12 10 BOILING POINT DIAGRAMS OF BINARY MISCIBLE LIQUID MIXTURES 12 11 FRACTIONAL DISTILLATION OF BINARY MISCIBLE LIQUID MIXTURES 12 12 THE FRACTIONATING COLUMN 12 13 AZEOTROPIC MIXTURES 12 14 COMPLETELY IMMISCIBLE LIQUIDS: STEAM DISTILLATION 12 15 PARTIALLY MISCIBLE LIQUID PAIRS 12 16 VAPOUR PRESSURE CURVES AND DISTILLATION OF PARTIALLY MISCIBLE LIQUID PAIRS 12 17 SOLUTIONS OF SOLIDS IN LIQUIDS 12 18 THE SOLUBILITY CURVE 12 19 DISTRIBUTION OF A SOLUTE BETWEEN TWO NON-MISCIBLE SOLVENTS (THE NERNST DISTRIBUTION LAW) 12 20 THERMODYNAMIC DEDUCTION OF DISTRIBUTION LAW 12 21 APPLICATIONS OF THE DISTRIBUTION LAW 13 COLLIGATIVE PROPERTIES OF SOLUTIONS 13 1 INTRODUCTION 13 2 VAPOUR PRESSURE LOWERING OF THE SOLVENT 13 3 BOILING POINT ELEVATION OF SOLUTIONS 13 4 FREEZING POINT DEPRESSION OF SOLUTIONS 13 5 OSMOSIS AND OSMOTIC PRESSURE 13 6 DIALYSING MEMBRANES 13 7 DONNAN MEMBRANE EQUILIBRIA 13 8 MEASUREMENT OF OSMOTIC PRESSURE 13 9 RELATION BETWEEN VARIOUS COLLIGATIVE PROPERTIES 13 10 COLLIGATIVE PROPERTIES OF SOLUTIONS CONTAINING TWO OR MORE SOLUTES 13 11 COLLIGATIVE PROPERTIES OF SOLUTIONS OF ELECTROLYTES 14 ELECTROCHEMISTRY 14 1 INTRODUCTION 14 2 OHM’S LAW AND ELECTRICAL UNITS 14 3 ELECTROLYTIC CONDUCTION 14 4 FARADAY’S LAWS AND ELECTROCHEMICAL EQUIVALENTS 14 5 ELECTROLYTIC CONDUCTANCE 14 6 EQUIVALENT AND MOLAR CONDUCTANCE 14 7 EXPERIMENTAL DETERMINATION OF EQUIVALENT CONDUCTANCE 14 8 APPLICATION OF CONDUCTANCE MEASUREMENTS 14 9 THEORIES OF STRONG ELECTROLYTES 14 10 TRANSFERENCE NUMBERS 14 11 METHODS FOR THE DETERMINATION OF TRANS­PORT NUMBERS 14 12 ABNORMAL TRANSFERENCE NUMBERS 15 IONIC EQUILIBRIA 15 1 OSTWALD’S DILUTION LAW 15 2 CONCEPTS OF ACIDS AND BASES 15 3 HARD AND SOFT ACIDS AND BASES 15 4 IONIZATION CONSTANTS OF ACIDS AND BASES 15 5 IONIZATION OF WATER (IONIC PRODUCT OF WATER) 15 6 THE PH SCALE 15 7 COMMON ION EFFECTS 15 8 BUFFER SOLUTIONS 15 9 HYDROLYSIS 15 10 HYDROGEN ION (ACID BASE) INDICATORS 15 11 COMPLEX ION EQUILIBRIA (INSTABILITY CONSTANT) 15 12 THE SOLUBILITY PRODUCT 16 ELECTROCHEMICAL CELLS 16 1 INTRODUCTION 16 2 MEASUREMENT OF EMF USING POTENTIOMETER 16 3 SIGN CONVENTIONS 16 4 REVERSIBLE ELECTRODE PROCESSES 16 5 NERNST EQUATION 16 6 NERNST THEORY OF ELECTRODE-POTENTIAL 16 7 REFERENCE ELECTRODE 16 8 ELECTRODES FOR THE MEASUREMENT OF PH 16 9 CONCENTRATION CELLS 16 10 LIQUID JUNCTION POTENTIAL 16 11 POTENTIOMETRIC TITRATIONS 16 12 FUEL CELLS 16 13 POLAROGRAPHY 16 14 THE CORROSION OF METALS 17 CHEMICAL KINETICS 17 1 INTRODUCTION 17 2 REACTION RATE 17 3 ORDER AND MOLECULARITY OF A REACTION 17 4 FIRST ORDER REACTIONS 17 5 SECOND ORDER REACTIONS 17 6 REACTIONS OF THE THIRD ORDER 17 7 ZERO ORDER REACTIONS 17 8 EFFECT OF TEMPERATURE ON REACTION VELOCITY 17 9 ENERGY OF ACTIVATION 17 10 COLLISION THEORY OF REACTION RATES 17 11 THE TRANSITION-STATE THEORY OF REACTION RATES 17 12 THE COLLISION THEORY OF UNIMOLECULAR REACTIONS 17 13 KINETIC THEORY OF TERMOLECULAR REACTIONS 17 14 COMPLEX REACTIONS 17 15 CHAIN REACTIONS 17 16 BRANCHING CHAINS, EXPLOSIVE REACTIONS 17 17 INFLUENCE OF IONIC STRENGTH 17 18 KINETICS IN CHEMICAL ENGINEERING 18 CATALYSIS 18 1 INTRODUCTION 18 2 GENERAL CHARACTERISTICS OF CATALYZED REACTIONS 18 3 TYPES OF CATALYSIS 18 4 ENZYME CATALYSIS 18 5 THEORIES OF CATALYSIS 18 6 CATALYTIC POISONING 18 7 AUTOCATALYSIS 18 8 EXAMPLES OF CATALYTIC PROCESSES 19 COLLOIDS 19 1 INTRODUCTION 19 2 CLASSIFICATION OF COLLOIDS 19 3 METHODS OF PREPARATION OF COLLOIDAL SOLUTIONS 19 4 PURIFICATION OF COLLOIDAL SOLUTIONS 19 5 PROPERTIES OF COLLOIDS 19 6 PRECIPITATION OF COLLOIDS BY ELECTROLYTES 19 7 THE STABILISATION OF THE COLLOIDAL STATE 19 8 EMULSIONS 19 9 GELS 19 10 APPLICATIONS OF COLLOIDS 19 11 ADSORPTION 19 12 ADSORPTION OF GASES BY SOLIDS 19 13 TYPES OF ADSORPTION 19 14 ADSORPTION ISOTHERMS 19 15 EXPLANATION OF TYPE I ISOTHERM 19 16 TYPE II–V ISOTHERMS 19 17 ADSORPTION FROM SOLUTION 19 18 APPLICATIONS OF ADSORPTION 20 ATOMIC STRUCTURE 20 1 INTRODUCTION 20 2 THE ELECTRICAL NATURE OF THE ATOM 20 3 THE CHARGE-TO-MASS RATIO OF AN ELECTRON 20 4 THE CHARGE ON THE ELECTRON 20 5 MODELS OF ATOMIC STRUCTURE 20 6 RUTHERFORD’S NUCLEAR MODEL OF THE ATOM 20 7 ATOMIC NUMBER 20 8 THE NUCLEAR CHARGE 20 9 ATOMIC APECTRA 20 10 BOHR MODEL OF ATOM