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 ADVANCED
CHEMISTRY 1
Philip Matthews

B&&
CAMBRIDGE
UNIVERSITY PRESS
 Contents

Acknowledgements pagex 5 Radioactive decay 28

How to use this book xi 5.1 Detection of radiation 28
5.2 Half-lives 29
5.3 The radioactive decay law 31
5.4 Decay schemes 31
PHYSICAL CHEMISTRY
6 Nuclear energy 34
1 Elements, atoms and electrons: basic 6.1 Discovery of nuclear energy 34
ideas 3 6.2 Fission reactions 34
1.1 Dalton's atomic theory 3 6.3 Nuclear power 35
1.2 Evidence for atoms 5 6.4 Fusion reactions 37
1.3 Cathode rays 6 6.5 Nuclear weapons 38
1.4 Millikan's experiment 6
1.5 Electric Charge is quantised 7 7 Applications of radioactivity 41
7.1 Industrial uses of radioactivity 41
2 Energy levels 9 7.2 Medical uses of radioactivity 42
2.1 Energy changes 9 7.3 Radiocarbon dating 42
2.2 Energy levels 9 7.4 Chemical applications 43
2.3 Max Planck and energy levels 11
2.4 Light energy 11 8 Bohr's model of the atom 46
8.1 Energy levels of the hydrogen atom 46
3 Atoms and the nucleus 13 8.2 How to calculate the ionisation energy of
3.1 A plum pudding 13 hydrogen 47
3.2 How the nucleus was discovered 13 8.3 What are Orbitals? 48
3.3 The discovery of protons 14 8.4 What are stationary states? 48
3.4 Moseley and atomic number 15 8.5 Ground and excited states 49
3.5 Discovery of neutrons 15
3.6 A comparison of electrons, protons and 9 The hydrogen atom spectrum 51
neutrons 16 9.1 Balmer's formula for the hydrogen atom 51
3.7 Isotopes 17 9.2 Bohr's explanation 51
3.8 Atomic mass units 17 9.3 Other lines in the hydrogen spectrum 51
3.9 Relative atomic and molecular masses 18
3.10 Einstein's equation 18 10 Waves and particles 54
3.11 Binding energy 20 10.1 Experimental evidence about the nature
3.12 Mass defect and mass excess 21 of light 54
10.2 What is wave—particle duality? 56
4 Discovery of radioactivity 23 10.3 de Broglie's equation 56
4.1 The discovery of radioactivity 23
4.2 New elements 24 11 Schrödinger's theory of the atom 58
4.3 Some properties of radiation 24 11.1 Schrödinger's theory of the hydrogen
4.4 Units of radioactivity 25 atom 58
4.5 Nuclear reactions 25 11.2 What do the quantum numbers teil us? 59
4.6 Artificially prepared elements 26 11.3 Different types of orbital 59
4.7 A sad ending 27 11.4 Wavefunctions and what they mean 60
11.5 The shapes of orbitals 61 18.2 Ionic substances have some covalent
11.6 The spin quantum number 63 character 101
18.3 Other evidence that a substance contains
12 The aufbau m e t h o d and electron ions 102
structures 66 18.4 Which elements make ionic Compounds? 103
12.1 What is the aufbau method? 66 18.5 Why do ionic Compounds exist? 103
12.2 More about orbital energies 66 18.6 Ionic Compounds and electron structures 104
12.3 Filling orbitals - the importance of energy 67
12.4 The Pauli exclusion principle 67 19 Polar molecules and polar bonds 107
12.5 Hund's rule 68 19.1 What is a polar molecule? 107
12.6 Background to Hund's rule 68 19.2 Polar bonds and electronegativities 107
12.7 The aufbau method in action 68 19.3 Polar molecules and dipole moments 108
19.4 Polarisability 111
13 Electron structures, ionisation
energies and shielding 71 20 Intermolecular forces 113
13.1 What is shielding? 71 20.1 Where are intermolecular forces found? 113
13.2 Ionisation energies down a Group 71 20.2 What causes intermolecular forces? 113
13.3 Ionisation energies across a Period 72 20.3 Dispersion forces and polarisability 114
13.4 How ionisation energies are linked to 20.4 Intermolecular forces are also produced
Groups in the Periodic Table 73 by permanent dipoles 114
20.5 Some words of warning 114
14 Bonding in molecules: valence bond
theory 77 21 Hydrogen bonding 117
14.1 Valence bond theory 77 21.1 What is hydrogen bonding? 117
14.2 Dot-and-cross diagrams for diatomic 21.2 Evidence for hydrogen bonding 117
molecules 78 21.3 Intermolecular and intramolecular
14.3 Dot-and-cross diagrams for triatomic and hydrogen bonding 119
quadratomic molecules 78 21.4 Hydrogen bonding in biochemistry 120
14.4 Dot-and-cross diagrams for hydrocarbons 79 21.5 Hydrogen bonding in solids 120
14.5 Showing bonds by lines 79
14.6 Bonding in oxoanions 80 22 Metallic bonding 122
14.7 Resonance structures 80 22.1 How can you recognise a metal? 122
22.2 What is the band structure of metals? 122
15 Coordinate bonding 84 22.3 Why do metals conduct electricity? 123
15.1 What is coordinate bonding? 84 22.4 Semiconductors 123
22.5 Why do metals conduct heat? 126
16 Molecular orbital theory 87 22.6 Metal atoms exist in a sea of electrons 126
16.1 Wavefunctions can be positive or
negative 87 23 The three states of matter 128
16.2 How wavefunctions can be combined 87 23.1 The three states of matter 128
16.3 Bonding and antibonding orbitals using s 23.2 How do we know that gases are disorderly? 129
orbitals 87 23.3 Differences in properties of solids, liquids
16.4 Bonding and antibonding orbitals using p and gases 129
orbitals 88 23.4 The potential energy curve for two
16.5 Energies of bonding and antibonding neighbouring molecules 130
orbitals 89 23.5 Some remarkable substances 130
16.6 Molecular orbitals for homopolar
diatomic molecules 90 24 Three types of spectroscopy 136
16.7 Molecular orbitals for heteropolar 24.1 Emission and absorption spectra 136
diatomic molecules 91 24.2 Electronic spectroscopy 136
16.8 Molecular orbitals for hydrocarbons 92 24.3 Vibrational spectroscopy 136
24.4 Rotational spectroscopy 136
17 Shapes of molecules 95 24.5 Translations 138
17.1 Molecular modeis 95 24.6 Electromagnetic waves 138
17.2 Electron repulsion theory 95 24.7 The electric field and electrons 139
17.3 The isoelectronic rule 96 24.8 The magnetic field and electrons 139
17.4 Hybridisation 97 24.9 Selection rules 140

18 Ionic bonding 101 25 Visible spectroscopy 142

18.1 Covalent substances have some ionic 25.1 Why does copper(n) sulphate Solution
character 101 lookblue? 142

IV Contents
25.2 The visible spectrum of copper(n) 32 Unit cells 179
sulphate Solution 142 32.1 The seven crystal Systems 179
25.3 How does a visible light spectrometer 32.2 The fourteen Bravais lattices 179
work? 143 32.3 What are unit cells? 179
25.4 What happens to the photons absorbed 32.4 Radius ratio rules 184
by copper(n) sulphate Solution? 144 32.5 The number of atoms or ions in a unit
25.5 Why vibrations are important in visible cell 185
spectra 144
33 Sizes of atoms, ions and molecules 188
26 Ultraviolet spectroscopy 146 33.1 How can we estimate the size of an
26.1 The ultra violet spectrum of alkenes 146 atom? 188
26.2 The ultraviolet spectrum of arenes 147 33.2 Metallic and covalent radii 188
26.3 The ultraviolet spectrum of aldehydes 33.3 Van der Waals radii 189
and ketones 147 33.4 Ionic radii 190
33.5 Bondlengths 191
27 Vibrational spectroscopy 149
27.1 Why is vibrational spectroscopy useful? 149 34 Real and ideal gases 193
27.2 What are group frequencies? 151 34.1 The gas laws 193
27.3 Making sense of vibrational spectra 151 34.2 Real gases and the van der Waals
27.4 Vibrational spectra can teil us about the equation 195
strengths of bonds 155 34.3 How good is the van der Waals equation? 196

35 Kinetic theory of gases 200

28 Nuclear magnetic resonance 157
35.1 What is the kinetic theory of gases? 200
28.1 The importance of nuclear spin 157
35.2 The pressure of an ideal gas 200
28.2 The patterns in an n.m.r. spectrum 158
35.3 The connection between energy and
28.3 Why do protons appear in different
temperature 201
places in the spectrum? 158
28.4 N.m.r. spectra can teil us how many 35.4 The spread of energies in a gas 202
35.5 Kinetic theory and Avogadro's theory 203
protons are present 158
28.5 Not only hydrogen atoms can show up in
n.m.r. 36 Chemistry and gases 205
159
36.1 Gay-Lussac's law of combining volumes 205
36.2 Avogadro's theory 205
29 Mass spectrometry 161 36.3 Dalton's law of partial pressures 206
29.1 What are mass spectrometers? 161 36.4 Graham's law of diffusion 206
29.2 The design of a mass spectrometer 161
29.3 The whole number rule and Standards of 37 The m o l e 209
mass 162 37.1 What is the mole? 209
29.4 Mass spectra and isotopes 164 37.2 How to work with moles of Compounds 210
29.5 Calculating relative atomic masses from 37.3 Moles and equations 210
mass spectra 164 37.4 Moles and balancing equations 211
29.6 What are fragmentation patterns? 164 37.5 The empirical formula and molecular
29.7 The effect of isotopes in a molecule's mass formula of a Compound 212
spectrum 165 37.6 Percentage compositions 213
30 X-ray diffraction 168 38 Molar masses of gases and liquids 216
30.1 What causes X-ray diffraction? 168 38.1 Measuring the molar mass of a gas 216
30.2 More about diffraction 168 38.2 Measuring the molar mass of a soluble
30.3 Bragg's equation 169 gas 217
30.4 Different types of X-ray diffraction 38.3 Measuring the molar mass of a volatile
experiment 169 liquid 218
30.5 Explanation of powder photographs 170
30.6 The arrangement of planes in crystals 171 39 Moles and titrations 221
30.7 The arrangements of individual atoms 172 39.1 Standard Solutions 221
39.2 The concentration of a Solution 223
31 Crystallography 174 39.3 Concentration and molarity 224
31.1 What is crystallography? 174 39.4 How to do calculations involving
31.2 The dosest packing of atoms 174 concentrations 224
31.3 Structures that are not close-packed 176
31.4 C oordination numbers 176 40 Four types of titration 227
31.5 Metal crystals 176 40.1 Acid-base titrations 227

Contents v
40.2 Redox titrations 227 49.2 The Boltzmann distribution 281
40.3 Titrations involving iodine 229 49.3 More about energy levels 281
40.4 Silver nitrate titrations 230 49.4 Entropy changes and mixing of gases 282
49.5 Entropy and disorder 283
41 Oxidation numbers and oxidation 49.6 Reversible and irreversible changes 285
states 234 49.7 Some changes are spontaneous, some are
41.1 What are oxidation and reduction not 285
reactions? 234 49.8 Entropy and reversible changes 286
41.2 What are oxidation numbers? 235 49.9 Entropy and non-reversible changes 286
41.3 Oxidation numbers of elements in 49.10
49.1( Standard entropies 288
covalent Compounds 235 49.11
49.1 Calculating entropy changes 289
41.4 Oxidation numbers of elements in ions 236
41.5 Rules for assigning oxidation numbers 237 50 Free energy 291
41.6 Oxidation states 237 50.1 What is free energy? 291
41.7 Using oxidation numbers with equations 238 50.2 Standard free energies 293
41.8 Half-equations 240 50.3 Free energy values do not teil us how fast
a reaction will occur 294
42 Energy changes 243 50.4 Free energy changes under non-standard
42.1 Energy changes and chemical bonds 243 conditions 294
42.2 Energy changes and energy diagrams 244 50.5 Ellingham diagrams and the extraction of
42.3 Exothermic and endothermic reactions 245 metals 295

43 Enthalpy 247 51 Equilibrium and free energy 299

43.1 What is enthalpy? 247 51.1 What is the effect of concentration and
43.2 Enthalpy and Standard states 248 pressure on free energy? 299
43.3 Enthalpy and State functions 249 51.2 What is the connection between free
43.4 Hess's law 250 energy and equilibrium? 300
51.3 Equilibrium and equilibrium constants 301
44 Standard enthalpies 252
44.1 Standard enthalpy of an dement 252 52 Chemical equilibrium 304
44.2 Standard heats of formation 252 52.1 Equilibrium constants 304
44.3 Standard heats of combustion 253 52.2 Equilibrium constants and their units 305
44.4 Enthalpy changes when substances break 52.3 Are equilibrium constants really
apart 255 constant? 306
44.5 Bond energies and average bond energies 255 52.4 How does temperature affect an
44.6 Heats of hydrogenation 256 equilibrium reaction? 306
52.5 How can the connection between
45 Calculations using Hess's law 259 equilibrium constants and temperature
45.1 Using heats of formation 259 be made more exact? 307
45.2 Impossible reactions 260 52.6 Pressure can change the proportions of
reactants and products at equilibrium 308
46 Lattice energies 263
46.1 What is meant by lattice energy? 263 53 Some equilibrium reactions 314
46.2 The Born-Haber cycle 263 53.1 What this unit is about 314
46.3 What do lattice energies teil us? 265 53.2 The bismuth trichloride—water reaction 314
53.3 The chromate(vi)-dichromate(vi) reaction 314
47 Enthalpy changes in Solutions 271 53.4 The iodine—iodine trichloride reaction 314
47.1 Heats of neutralisation 271 53.5 The iodine—triiodide reaction 315
47.2 Hydration energies 273 53.6 The nitrogen dioxide-dinitrogen
47.3 Heats of Solution 273 tetraoxide reaction 315
47.4 Enthalpies of formation of ions in 53.7 The decomposition of ammonium salts 315
Solution 274 53.8 Reactions involving complex ions 315

48 Internal energy 276 54 Measuring equilibrium constants 318

48.1 What is internal energy? 276 54.1 How can equilibrium constants be
48.2 Taking account of work 276 measured? 318
48.3 Measuring internal energy with a bomb 54.2 The ester equilibrium 318
calorimeter 277 54.3 The hydrogen iodide equilibrium 320

49 Entropy 279 55 Equilibria b e t w e e n phases 323

49.1 A first look at entropy 279 55.1 What is a phase? 323

vi Contents
55.2 How to interpret a phase diagram 323 63 Distillation 365
55.3 The phase diagram of sulphur 324 63.1 The boiling points of mixtures 365
55.4 The phase diagram of helium 324 63.2 How distillation works 366
63.3 Industrial distillation 368
56 Chromatography 327 63.4 Does distillation always work? 369
56.1 What is chromatography? 327 63.5 Steam distillation 370
56.2 Paper chromatography 328
56.3 Thin layer chromatography (TLC) 330 64 Solubility product 373
56.4 Column chromatography 330 64.1 What is a solubility product? 373
56.5 Ion exchange chromatography 331 64.2 Using solubility products to calculate
56.6 Gas-liquid chromatography (GLC) 331 solubilities 373
56.7 High pressure liquid chromatography 64.3 The common ion effect 375
(HPLC) 332 64.4 Solubility products teil us when a
precipitate will be made 375
57 Polymorphism and allotropy 335 64.5 Using solubility products in chemical
57.1 What is polymorphism? 335 analysis 376
57.2 What is allotropy? 336
65 Colligative properties 379
58 Equilibrium b e t w e e n a solid and 65.1 What are colligative properties? 379
liquid 340 65.2 Why does a solute influence the vapour
58.1 What happens when a liquid freezes? 340 pressure of water? 379
58.2 Cooling curves 341 65.3 Elevation of boiling point 379
58.3 Cooling curves for mixtures 341 65.4 How to make use of the boiling point
constant 380
59 Solubility of salts in water 345 65.5 Depression of freezing point 381
59.1 The solubility of a solid in water 345 65.6 Osmotic pressure 382
59.2 Fractional crystallisation 346 65.7 Methods of measuring osmotic pressure 382
59.3 Crystals that contain water of 65.8 How might we explain osmosis? 383
crystallisation 346 65.9 How to calculate molar masses from
59.4 Saturated and supersaturated Solutions 347 osmotic pressure experiments 383
65.10 Some examples of osmosis 384
60 Explaining solubilities 349 65.11 Abnormal molar masses 384
60.1 Why is water a good solvent for ionic 65.12 Calculating the degree of dissociation
crystals? 349 from abnormal molar masses 385
60.2 Entropy changes are important when a 65.13 The thermodynamic explanation of
crystal dissolves 350 colligative properties 386
60.3 The sizes of the ions in a crystal are 65.14 Raoult's law and solids in Solution 387
important in explaining solubilities 351
60.4 Why is water a good solvent for many 66 Electrochemical cells 389
covalent substances? 351 66.1 How an equilibrium is set up between a
60.5 Covalent liquids often dissolve covalent metal and Solution 389
solids 352 66.2 The Standard hydrogen electrode 390
60.6 Volume changes when solids dissolve 352 66.3 Standard electrode potentials 390
66.4 Combining half-cells 391
61 Mixtures of liquids 355 66.5 How to work out cell reactions 392
61.1 What is the difference between miscible 66.6 A quick way of writing cells 393
and immiscible liquids? 355 66.7 The anode and cathode in a cell 393
61.2 Raoult's law and ideal Solutions 355 66.8 More about salt bridges 393
61.3 Solutions that do not obey Raoult's law 356 66.9 The electrochemical series 394
61.4 Why are there deviations from Raoult's 66.10 Some useful cells 395
law? 357
61.5 Why do some liquids mix and others 67 Cells and concentration changes 400
not? 357 67.1 How cell e.m.f.s change with
concentration 400
62 Competition b e t w e e n solvents 362 67.2 How to work out equilibrium constants
62.1 Solvent extraction 362 from cell e.m.f.s 401
62.2 Solvent extraction is an equilibrium 67.3 Concentration cells 403
process 362 67.4 pH and the glass electrode 404
62.3 Partition coefficients 363
62.4 Why do some results not fit the partition 68 Corrosion 408
law? 363 68.1 An example of corrosion 408

Contents vn
68.2 The rusting of iron 409 75.9 How to work out the pH of a weak acid 450
68.3 How does a layer of zinc prevent iron 75.10 Buffer Solutions 450
rusting? 409
68.4 Why does tin protect iron from corrosion? 410 76 Neutralisation and titrations 455
76.1 Salt hydrolysis 455
69 Cells and thermodynamics 412 76.2 Salts of a strong acid and a strong base 455
69.1 The link between free energy and cell 76.3 Salts of a strong acid and a weak base 455
e.m.f.s 412 76.4 Salts of a weak acid and a strong base 455
69.2 Calculating Standard e.m.f.s from free 76.5 Salts of a weak acid and a weak base 456
energy values 412 76.6 Endpoints in titrations depend on the
69.3 Calculating free energy values from strength of the acid and base 456
Standard e.m.f.s 413 76.7 Indicators 456

70 Redox potentials 415 77 Rates of reactions 459

70.1 Standard redox potentials 415 77.1 Why do we study the rates of reactions? 459
70.2 Predicting redox reactions 416 77.2 What makes reactions take place? 459
70.3 Predicting reactions in the laboratory 77.3 What can prevent reactions taking place? 460
from redox potentials 416 77.4 How can we make reactions go faster? 461
70.4 Redox titrations 417
78 Two theories of reaction rates 465
71 Redox Charts 420 78.1 Collision theory 465
71.1 What is a redox chart? 420 78.2 More about the activation energy 466
71.2 How to use redox charts 420 78.3 Catalysts and activation energy 467
71.3 What is disproportionation? 422 78.4 Transition State theory 467

72 Electrolysis 426 79 Measuring the rates of reactions 471

72.1 What is an electric current? 426 79.1 An example of measuring a rate 471
72.2 What happens during electrolysis? 427 79.2 Six ways of measuring rates 472
72.3 Examples of electrolysis 428 79.3 Measuring the rates of very fast reactions 476
72.4 How to calculate the mass of a substance
liberated in electrolysis 430 80 Rate laws 480
72.5 Why is electrolysis used in industry? 431 80.1 What is a rate law? 480
80.2 How can we discover the rate law? 481
73 Conductivity of Solutions 433 80.3 Quick ways of finding the rate law 482
73.1 How do we measure conductivity? 433 80.4 The contribution of individual Orders to
73.2 Molar conductivities 434 the overall rate law 484
73.3 Molar conductivities and the degree of
dissociation 435 81 Reaction mechanisms 487
73.4 How individual ions contribute to 81.1 What is a reaction mechanism? 487
conductivities 435 81.2 Bonds can break in two ways 487
73.5 How can we make use of conductivity 81.3 The slowest Step in a reaction governs the
measurements? 436 rate 488
81.4 Free radical reactions 489
74 Acids and bases 439 81.5 Mechanisms of the hydrolysis of
74.1 Early ideas about acids 439 halogenoalkanes 490
74.2 Acids give hydrogen ions in Solution 439 81.6 The influence of catalysts 491
74.3 The Brensted theory of acids and bases 440 81.7 The kinetics of enzyme reactions 492
74.4 The Lewis theory of acids and bases 441

75 Strong and w e a k acids 443

75.1 What is the difference between strong I N D U S T R I A L CHEMISTRY
and weak acids? 443
75.2 Conjugate acids and bases 443 82 The chemical industry 497
75.3 The ionic produet of water 444 82.1 Why is the chemical industry important? 497
75.4 Acid dissociation equilibrium constants 445 82.2 The stages in producing a new produet 498
75.5 What makes an acid strong? 446 82.3 The economics of produetion 499
75.6 What is the connection between pH and 82.4 Cash flow in the produetion cycle 500
PKa? 448 82.5 Running a chemical plant 501
75.7 Base dissociation constants and p/Cb 449 82.6 Designing a chemical plant 502
75.8 How to work out the degree of 82.7 Energy and mass balances 502
dissociation of a weak acid 449 82.8 Continuous and batch processing 503

vm Contents
83 Chemical processes 506 85.4 Reducing an oxide ore 520
83.1 Examples of modern chemical 85.5 The extraction of reactive metals 521
manufacture 506
83.2 Manufacture of sulphuric acid 506 86 The oil industry 525
83.3 The Haber process for the manufacture of 86.1 Why is the oil industry important? 525
ammonia 508 86.2 Catalytic re-forming 526
83.4 The manufacture of nitric acid 510 86.3 Catalytic cracking 527
86.4 Thermal cracking 528
84 The chlor-alkali industry 512
Appendix A The laws of thermodynamics 533
84.1 What is the chlor-alkali industry? 512
84.2 The production of chlorine and sodium Appendix B Table of ionisation energies 535
hydroxide 512 Appendix C Table of atomic masses 536
Appendix D Values of some universal
84.3 The ammonia-soda (Solvay) process 514
constants 538
Bibliography 539
85 The extraction of metals 518 Examination questions 540
85.1 The methods of extraction 518 Answers to examination questions 558
85.2 Extracting the noble metals 518 Subject index 559
85.3 Reducing sulphide ores 520 Index of names 569