Table of Contents
Preface v
Acknowledgements vii
1 Atomic Structure and the Periodic Table 1
1.1 The Subatomic Particles of Matter 1
1.1.1 Behaviour in an electric field/magnetic field 1
1.1.2 Isotopes 3
1.1.3 Relative masses of an element 4
1.2 Orbitals and Quantum Numbers 6
1.2.1 The nature of electron 6
1.2.2 Shapes of orbitals 10
1.3 Electronic Configurations 12
1.3.1 Rules used in working out electronic configuration 12
1.3.2 Electronic configuration of transition elements 15
1.3.3 Anomalous electronic configurations 16
1.4 Ionisation Energies 16
1.4.1 Factors influencing the magnitude of ionisation energies 17
1.5 Periodic Table: Trend in Ionisation Energy 22
1.6 Periodic Table: Trend in Atomic Radii 24
2 Chemical Bonding 29
2.1 Metallic Bonding 29
2.1.1 Physical properties of metals 30
2.2 Ionic Bonding (or Electrovalent Bonding) 31
2.2.1 Guidelines for drawing dot-and-cross diagrams 34
2.2.2 Physical properties of ionic compounds 35
2.3 Covalent Bonding 39
2.3.1 Covalent bond formation 40
2.3.2 Dative Covalent bond (coordinate bond) 42
2.3.3 Factors affecting strength of covalent bond 44
2.3.4 Shapes of molecules - The VSEPR model 46
2.3.5 Using the Hybridisation Model to understand shape 52
2.3.6 Delocalised bonding/resonance 56
2.4 Intermediate Bond Types 58
2.4.1 Covalent character in ionic bonds 58
2.4.2 Ionic character in covalent bonds 60
2.5 Physical Properties of Covalent Compounds 62
2.5.1 Properties of giant covalent compounds 62
2.5.2 Properties of simple covalent compounds 64
2.6 Intermolecular Forces of Attraction 64
2.6.1 Instantaneous dipole-induced dipole (id-id) interactions 65
2.6.2 Permanent dipole-permanent dipole (pd-pd) interactions 67
2.6.3 Hydrogen bonding 70
2.7 Summary of Chemical Bonding: Putting it all Together 74
3 Ideal Gas and Gas Laws 81
3.1 Gas Laws 82
3.1.1 Boyle's law 82
3.1.2 Charles' law 83
3.1.3 Gay-Lussac's law 84
3.1.4 Avogadro's law 84
3.1.5 The ideal gas law 88
3.1.6 Further manipulations of the ideal gas equation 90
3.1.7 Dalton's Law of Partial Pressure 91
3.1.8 Types of mathematical problems involving the gas laws 95
3.2 Kinetic Theory of Gases 96
3.2.1 Graphical plots representing ideal behaviour 97
3.2.2 Deviation from ideal gas behaviour 100
3.2.3 Nature of gas 103
4 Chemical Thermodynamics 109
4.1 Energy Changes in Chemical Reactions 110
4.1.1 Standard enthalpy changes 113
4.1.2 Calculating enthalpy changes from experimental data 117
4.1.3 Calculation of enthalpy changes using Hess' Law 122
4.1.4 Constructing energy cycles 123
4.1.5 Born-Haber cycle and Hess' law 127
4.1.6 Constructing Born-Haber cycles 129
4.1.7 Energetics involving aqueous ionic compounds 133
4.2 Entropy 135
4.2.1 What is entropy? 137
4.2.2 Factors affecting entropy of a chemical system 138
4.2.3 Predicting the spontaneity of a reaction 141
4.2.4 Relationship between ΔG$$$, ΔH$$$, ΔS$$$ and temperature 142
5 Reaction Kinetics 147
5.1 Qualitative Analysis of Reaction Rates 147
5.1.1 Factors affecting reaction rates 150
5.2 Quanlitative Analysis of Reaction Rates 155
5.2.1 Rate of reaction 155
5.2.2 The rate equation (Rate law) 159
5.2.3 Experimental methods used to determine order of reaction 164
5.3 Rate Equation and Reaction Mechanism 182
5.4 Transition State Theory 184
5.5 Catalysis 187
5.5.1 Homogeneous catalysis 187
5.5.2 Heterogeneous catalysis 188
5.5.3 Autocatalysis 190
5.5.4 Enzymes (biological catalysts) 191
6 Chemical Equilibria 197
6.1 Reversible Reactions 197
6.2 Equilibrium Systems 199
6.3 Equilibrium Constants Kc and Kp 200
6.3.1 Writing Kc or Kp for heterogeneous equilibria 204
6.3.2 Calculations involving Kc 205
6.3.3 Calculations involving Kp 208
6.4 Le Chatelier's Principle 211
6.4.1 Effect of concentration changes 211
6.4.2 Effect of pressure changes 214
6.4.3 Effect of temperature changes 220
6.4.4 Effect of temperature changes on the value of the equilibrium constant 222
6.4.5 Effect of catalyst 223
6.5 The Haber Process 226
7 Ionic Equilibria 231
7.1 The Brønsted-Lowry Theory of Acids and Bases 232
7.2 Conjugate Acid-Base Pairs 234
7.3 The pH Scale 234
7.4 The Dissociation Constant of Water, Kw 235
7.5 Strength of Acids 240
7.6 Acid Dissociation Constant Ka and pKa 241
7.7 Strength of Bases 246
7.8 Base Dissociation Constant Kb and pKb 247
7.9 Complementary Strengths of a Conjugate Acid-Base Pair 249
7.10 Hydration and Hydrolysis 251
7.10.1 Classifying type of salt based on strengths of acid and base that form it 253
7.10.2 Hydrolysis of high charge density cations 255
7.11 Buffer Solutions 256
7.11.1 How does an acidic buffer work 256
7.11.2 How does an alkaline buffer work 258
7.11.3 The role of buffer in controlling pH in blood 259
7.11.4 Calculating pH of buffer solutions 260
7.12 Acid-Base Indicators 263
7.13 Acid-Base Titrations 266
7.13.1 Titration curve of a strong acid-strong base titration 268
7.13.2 Titration curve of a weak acid-strong base titration 269
7.13.3 Titration curve of a strong acid-weak base titration 276
7.13.4 Titration curve of a weak acid-weak base titration 278
7.13.5 Titration curve of a polybasic acid-strong base titration 280
7.13.6 Titration curve of a carbonate-strong acid titration (Double-Indicator Method) 281
7.13.7 Titration curve of a mixture of weak acids-strong base titration 286
7.13.8 Back-titration 288
7.14 Solubility Product Ksp 290
7.14.1 Solubility and Ksp 291
7.14.2 Ionic product and Ksp 293
7.14.3 Common ion effect 295
7.14.4 Solubility in qualitative analysis 297
8 Redox Chemistry and Electrochemical Cells 303
8.1 Rules for Assignment of Oxidation States 307
8.2 Balancing Redox Equations 310
8.3 Redox Titrations 313
8.3.1 Manganate(VII) titrations 314
8.3.2 Dichromate(VI) titrations 315
8.3.3 Iodine-thiosulfate titrations 316
8.4 Redox Reactions and Electricity 318
8.4.1 Electrode potential 319
8.4.2 Experimental set-up of half-cells 322
8.4.3 Information obtained from the standard electrode potential 325
8.4.4 Describing cell components using conventional notation 328
8.4.5 Calculating standard cell potential 330
8.4.6 Using $$$ to predict feasibility of a reaction 332
8.4.7 Effect of concentration changes on $$$ value 335
8.4.8 Effect of ligands on $$$ value 337
8.5 Types of Electrochemical Cells 338
8.6 Electrolysis 341
8.6.1 Faraday's laws of electrolysis 342
8.6.2 Selective discharge of ions 345
8.6.3 Industrial uses of electrolysis 347
9 The Periodic Table - Chemical Periodicity 357
9.1 Atomic Structure and Period 3 Elements 359
9.1.1 Trend in atomic radius 359
9.1.2 Trend in ionic radius 359
9.1.3 Trend in first ionisation energy (1st I.E.) 362
9.1.4 Trend in electronegativity 363
9.2 Structure, Bonding and Period 3 Elements 364
9.2.1 Variation in melting points and boiling points 364
9.2.2 Variation in electrical conductivity 365
9.3 Oxides and Chlorides of Period 3 Elements 366
9.3.1 Oxides of Period 3 elements 369
9.3.2 Chlorides of Period 3 elements 373
10 Chemistry of Groups 2 and 7 381
10.1 Atomic Structure and Group Trends 381
10.1.1 Trend in atomic radius 381
10.1.2 Trend in ionic radius 382
10.1.3 Trend in 1st I.E. 382
10.1.4 Trend in electron affinity 382
10.1.5 Trend in electronegativity 383
10.1.6 Trend in metallic character 383
10.2 Physical Properties of Group 2 Elements 384
10.3 Chemical Properties of Group 2 Elements 384
10.3.1 Reaction with water 386
10.3.2 Reaction with oxygen 387
10.4 Thermal Stability of Group 2 Compounds 387
10.5 Some Uses of Group 2 Elements and Their Compounds 391
10.6 Properties of Beryllium 391
10.7 Solubility of Group 2 Compounds 394
10.8 Physical Properties of Group 7 Elements 397
10.8.1 Melting point, boiling point and volatility 397
10.8.2 Colour 398
10.8.3 Solubility in water 399
10.8.4 Solubility in organic solvent 399
10.8.5 Trend in bond energy 400
10.9 Chemical Properties of Group 7 Elements 400
10.9.1 Displacement reaction of halogens 402
10.9.2 Reaction with thiosulfate 403
10.9.3 Reaction with alkali 406
10.9.4 Reaction with hydrogen 408
10.10 Hydrogen Halides 409
10.10.1 Thermal stability of hydrogen halides 410
10.10.2 Acidity of hydrogen halides 411
10.10.3 Reaction of halides with concentrated acid 411
10.10.4 Distinguishing tests for halide ions 413
10.11 Industrial Uses and Environmental Impact of Group 7 Elements and Their Compounds 415
10.11.1 Fluorine and its compounds 415
10.11.2 Chlorine and its compounds 415
10.11.3 Bromine and its compounds 415
11 Introduction to Transition Metals and Their Chemistry 421
11.1 Writing Electronic Configuration 422
11.2 Physical Properties of Transition Metals 425
11.2.1 Trend in atomic radius 425
11.2.2 Trend in ionic radius 426
11.2.3 Trend in first ionisation energy 427
11.2.4 Trend in melting and boiling points 428
11.2.5 Trend in electrical conductivity 429
11.2.6 Trend in density 429
11.3 Chemical Properties of Transition Metals 430
11.3.1 Variable oxidation states 430
11.3.2 Catalytic properties 434
11.3.3 Formation of complexes 437
11.3.4 The property of colour 444
11.3.5 Ligand exchange reactions 451
11.3.6 Selected reactions of some transition metals and their compounds 458
Index 465
