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1. ADVANCED
CHEMISTRY 1
Philip Matthews
B
&
&
CAMBRIDGE
UNIVERSITY PRESS

2. Contents
Acknowledgements
How to use this book
PHYSICAL CHEMISTRY
1 Elements, atoms and electrons: basic
ideas
1.1 Dalton's atomic theory
1.2 Evidence for atoms
1.3 Cathode rays
1.4 Millikan's experiment
1.5 Electric Charge is quantised
2 Energy levels
2.1 Energy changes
2.2 Energy levels
2.3 Max Planck and energy levels
2.4 Light energy
3 Atoms and the nucleus
3.1 A plum pudding
3.2 How the nucleus was discovered
3.3 The discovery of protons
3.4 Moseley and atomic number
3.5 Discovery of neutrons
3.6 A comparison of electrons, protons and
neutrons
3.7 Isotopes
3.8 Atomic mass units
3.9 Relative atomic and molecular masses
3.10 Einstein's equation
3.11 Binding energy
3.12 Mass defect and mass excess
4 Discovery of radioactivity
4.1 The discovery of radioactivity
4.2 New elements
4.3 Some properties of radiation
4.4 Units of radioactivity
4.5 Nuclear reactions
4.6 Artificially prepared elements
4.7 A sad ending
pagex
xi
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9.2
9.3
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10.1
10.2
10.3
11
11.1
11.2
11.3
11.4
Radioactive decay 28
Detection of radiation 28
Half-lives 29
The radioactive decay law 31
Decay schemes 31
Nuclear energy 34
Discovery of nuclear energy 34
Fission reactions 34
Nuclear power 35
Fusion reactions 37
Nuclear weapons 38
Applications of radioactivity 41
Industrial uses of radioactivity 41
Medical uses of radioactivity 42
Radiocarbon dating 42
Chemical applications 43
Bohr's model of the atom 46
Energy levels of the hydrogen atom 46
How to calculate the ionisation energy of
hydrogen 47
What are Orbitals? 48
What are stationary states? 48
Ground and excited states 49
The hydrogen atom spectrum 51
Balmer's formula for the hydrogen atom 51
Bohr's explanation 51
Other lines in the hydrogen spectrum 51
Waves and particles 54
Experimental evidence about the nature
of light 54
What is wave—particle duality? 56
de Broglie's equation 56
Schrödinger's theory of the atom 58
Schrödinger's theory of the hydrogen
atom 58
What do the quantum numbers teil us? 59
Different types of orbital 59
Wavefunctions and what they mean 60

3. 11.5 The shapes of orbitals
11.6 The spin quantum number
12 The aufbau method and electron
structures
12.1 What is the aufbau method?
12.2 More about orbital energies
12.3 Filling orbitals - the importance of energy
12.4 The Pauli exclusion principle
12.5 Hund's rule
12.6 Background to Hund's rule
12.7 The aufbau method in action
13 Electron structures, ionisation
energies and shielding
13.1 What is shielding?
13.2 Ionisation energies down a Group
13.3 Ionisation energies across a Period
13.4 How ionisation energies are linked to
Groups in the Periodic Table
14 Bonding in molecules: valence bond
theory
14.1 Valence bond theory
14.2 Dot-and-cross diagrams for diatomic
molecules
14.3 Dot-and-cross diagrams for triatomic and
quadratomic molecules
14.4 Dot-and-cross diagrams for hydrocarbons
14.5 Showing bonds by lines
14.6 Bonding in oxoanions
14.7 Resonance structures
15 Coordinate bonding
15.1 What is coordinate bonding?
16 Molecular orbital theory
16.1 Wavefunctions can be positive or
negative
16.2 How wavefunctions can be combined
16.3 Bonding and antibonding orbitals using s
orbitals
16.4 Bonding and antibonding orbitals using p
orbitals
16.5 Energies of bonding and antibonding
orbitals
16.6 Molecular orbitals for homopolar
diatomic molecules
16.7 Molecular orbitals for heteropolar
diatomic molecules
16.8 Molecular orbitals for hydrocarbons
17 Shapes of molecules
17.1 Molecular modeis
17.2 Electron repulsion theory
17.3 The isoelectronic rule
17.4 Hybridisation
18 Ionic bonding
18.1 Covalent substances have some ionic
character
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18.2
18.3
18.4
18.5
18.6
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19.1
19.2
19.3
19.4
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20.1
20.2
20.3
20.4
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20.5
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21.1
21.2
21.3
21.4
21.5
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22.1
22.2
22.3
22.4
22.5
22.6
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23.1
23.2
23.3
23.4
23.5
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24.1
24.2
24.3
24.4
24.5
24.6
24.7
24.8
24.9
25
25.1
Ionic substances have some covalent
character 101
Other evidence that a substance contains
ions 102
Which elements make ionic Compounds? 103
Why do ionic Compounds exist? 103
Ionic Compounds and electron structures 104
Polar molecules and polar bonds 107
What is a polar molecule? 107
Polar bonds and electronegativities 107
Polar molecules and dipole moments 108
Polarisability 111
Intermolecular forces 113
Where are intermolecular forces found? 113
What causes intermolecular forces? 113
Dispersion forces and polarisability 114
Intermolecular forces are also produced
by permanent dipoles 114
Some words of warning 114
Hydrogen bonding 117
What is hydrogen bonding? 117
Evidence for hydrogen bonding 117
Intermolecular and intramolecular
hydrogen bonding 119
Hydrogen bonding in biochemistry 120
Hydrogen bonding in solids 120
Metallic bonding 122
How can you recognise a metal? 122
What is the band structure of metals? 122
Why do metals conduct electricity? 123
Semiconductors 123
Why do metals conduct heat? 126
Metal atoms exist in a sea of electrons 126
The three states of matter 128
The three states of matter 128
How do we know that gases are disorderly? 129
Differences in properties of solids, liquids
and gases 129
The potential energy curve for two
neighbouring molecules 130
Some remarkable substances 130
Three types of spectroscopy 136
Emission and absorption spectra 136
Electronic spectroscopy 136
Vibrational spectroscopy 136
Rotational spectroscopy 136
Translations 138
Electromagnetic waves 138
The electric field and electrons 139
The magnetic field and electrons 139
Selection rules 140
Visible spectroscopy 142
Why does copper(n) sulphate Solution
lookblue? 142
IV Contents

4. 25.2 The visible spectrum of copper(n)
sulphate Solution
25.3 How does a visible light spectrometer
work?
25.4 What happens to the photons absorbed
by copper(n) sulphate Solution?
25.5 Why vibrations are important in visible
spectra
26 Ultraviolet spectroscopy
26.1 The ultraviolet spectrum of alkenes
26.2 The ultraviolet spectrum of arenes
26.3 The ultraviolet spectrum of aldehydes
and ketones
27 Vibrational spectroscopy
27.1 Why is vibrational spectroscopy useful?
27.2 What are group frequencies?
27.3 Making sense of vibrational spectra
27.4 Vibrational spectra can teil us about the
strengths of bonds
28 Nuclear magnetic resonance
28.1 The importance of nuclear spin
28.2 The patterns in an n.m.r. spectrum
28.3 Why do protons appear in different
places in the spectrum?
28.4 N.m.r. spectra can teil us how many
protons are present
28.5 Not only hydrogen atoms can show up in
n.m.r.
29 Mass spectrometry
29.1 What are mass spectrometers?
29.2 The design of a mass spectrometer
29.3 The whole number rule and Standards of
mass
29.4 Mass spectra and isotopes
29.5 Calculating relative atomic masses from
mass spectra
29.6 What are fragmentation patterns?
29.7 The effect of isotopes in a molecule's mass
spectrum
30 X-ray diffraction
30.1 What causes X-ray diffraction?
30.2 More about diffraction
30.3 Bragg's equation
30.4 Different types of X-ray diffraction
experiment
30.5 Explanation of powder photographs
30.6 The arrangement of planes in crystals
30.7 The arrangements of individual atoms
31 Crystallography
31.1 What is crystallography?
31.2 The dosest packing of atoms
31.3 Structures that are not close-packed
31.4 Coordination numbers
31.5 Metal crystals
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32.1
32.2
32.3
32.4
32.5
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33.1
33.2
33.3
33.4
33.5
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34.1
34.2
34.3
35
35.1
35.2
35.3
35.4
35.5
36
36.1
36.2
36.3
36.4
37
37.1
37.2
37.3
37.4
37.5
37.6
38
38.1
38.2
38.3
39
39.1
39.2
39.3
39.4
40
40.1
Unit cells 179
The seven crystal Systems 179
The fourteen Bravais lattices 179
What are unit cells? 179
Radius ratio rules 184
The number of atoms or ions in a unit
cell 185
Sizes of atoms, ions and molecules 188
How can we estimate the size of an
atom? 188
Metallic and covalent radii 188
Van der Waals radii 189
Ionic radii 190
Bondlengths 191
Real and ideal gases 193
The gas laws 193
Real gases and the van der Waals
equation 195
How good is the van der Waals equation? 196
Kinetic theory of gases 200
What is the kinetic theory of gases? 200
The pressure of an ideal gas 200
The connection between energy and
temperature 201
The spread of energies in a gas 202
Kinetic theory and Avogadro's theory 203
Chemistry and gases 205
Gay-Lussac's law of combining volumes 205
Avogadro's theory 205
Dalton's law of partial pressures 206
Graham's law of diffusion 206
The mole 209
What is the mole? 209
How to work with moles of Compounds 210
Moles and equations 210
Moles and balancing equations 211
The empirical formula and molecular
formula of a Compound 212
Percentage compositions 213
Molar masses of gases and liquids 216
Measuring the molar mass of a gas 216
Measuring the molar mass of a soluble
gas 217
Measuring the molar mass of a volatile
liquid 218
Moles and titrations 221
Standard Solutions 221
The concentration of a Solution 223
Concentration and molarity 224
How to do calculations involving
concentrations 224
Four types of titration 227
Acid-base titrations 227
Contents v

5. 40.2 Redox titrations
40.3 Titrations involving iodine
40.4 Silver nitrate titrations
41 Oxidation numbers and oxidation
states
41.1 What are oxidation and reduction
reactions?
41.2 What are oxidation numbers?
41.3 Oxidation numbers of elements in
covalent Compounds
41.4 Oxidation numbers of elements in ions
41.5 Rules for assigning oxidation numbers
41.6 Oxidation states
41.7 Using oxidation numbers with equations
41.8 Half-equations
42 Energy changes
42.1 Energy changes and chemical bonds
42.2 Energy changes and energy diagrams
42.3 Exothermic and endothermic reactions
43 Enthalpy
43.1 What is enthalpy?
43.2 Enthalpy and Standard states
43.3 Enthalpy and State functions
43.4 Hess's law
44 Standard enthalpies
44.1 Standard enthalpy of an dement
44.2 Standard heats of formation
44.3 Standard heats of combustion
44.4 Enthalpy changes when substances break
apart
44.5 Bond energies and average bond energies
44.6 Heats of hydrogenation
45 Calculations using Hess's law
45.1 Using heats of formation
45.2 Impossible reactions
46 Lattice energies
46.1 What is meant by lattice energy?
46.2 The Born-Haber cycle
46.3 What do lattice energies teil us?
47
47.1
47.2
47.3
47.4
48
48.1
48.2
48.3
Enthalpy changes in Solutions
Heats of neutralisation
Hydration energies
Heats of Solution
Enthalpies of formation of ions in
Solution
Internal energy
What is internal energy?
Taking account of work
Measuring internal energy with a bomb
calorimeter
49 Entropy
49.1 A first look at entropy
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49.2
49.3
49.4
49.5
49.6
49.7
49.8
49.9
49.1(
49.1
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50.1
50.2
50.3
50.4
50.5
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51.1
51.2
51.3
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52.1
52.2
52.3
52.4
52.5
52.6
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53.1
53.2
53.3
53.4
53.5
53.6
53.7
53.8
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54.1
54.2
54.3
55
55.1
The Boltzmann distribution 281
More about energy levels 281
Entropy changes and mixing of gases 282
Entropy and disorder 283
Reversible and irreversible changes 285
Some changes are spontaneous, some are
not 285
Entropy and reversible changes 286
Entropy and non-reversible changes 286
49.10 Standard entropies 288
49.11 Calculating entropy changes 289
Free energy 291
What is free energy? 291
Standard free energies 293
Free energy values do not teil us how fast
a reaction will occur 294
Free energy changes under non-standard
conditions 294
Ellingham diagrams and the extraction of
metals 295
Equilibrium and free energy 299
What is the effect of concentration and
pressure on free energy? 299
What is the connection between free
energy and equilibrium? 300
Equilibrium and equilibrium constants 301
Chemical equilibrium 304
Equilibrium constants 304
Equilibrium constants and their units 305
Are equilibrium constants really
constant? 306
How does temperature affect an
equilibrium reaction? 306
How can the connection between
equilibrium constants and temperature
be made more exact? 307
Pressure can change the proportions of
reactants and products at equilibrium 308
Some equilibrium reactions 314
What this unit is about 314
The bismuth trichloride—water reaction 314
The chromate(vi)-dichromate(vi) reaction 314
The iodine—iodine trichloride reaction 314
The iodine—triiodide reaction 315
The nitrogen dioxide-dinitrogen
tetraoxide reaction 315
The decomposition of ammonium salts 315
Reactions involving complex ions 315
Measuring equilibrium constants 318
How can equilibrium constants be
measured? 318
The ester equilibrium 318
The hydrogen iodide equilibrium 320
Equilibria between phases 323
What is a phase? 323
vi Contents

6. 55.2 How to interpret a phase diagram
55.3 The phase diagram of sulphur
55.4 The phase diagram of helium
56 Chromatography
56.1 What is chromatography?
56.2 Paper chromatography
56.3 Thin layer chromatography (TLC)
56.4 Column chromatography
56.5 Ion exchange chromatography
56.6 Gas-liquid chromatography (GLC)
56.7 High pressure liquid chromatography
(HPLC)
57 Polymorphism and allotropy
57.1 What is polymorphism?
57.2 What is allotropy?
58 Equilibrium between a solid and
liquid
58.1 What happens when a liquid freezes?
58.2 Cooling curves
58.3 Cooling curves for mixtures
59 Solubility of salts in water
59.1 The solubility of a solid in water
59.2 Fractional crystallisation
59.3 Crystals that contain water of
crystallisation
59.4 Saturated and supersaturated Solutions
60 Explaining solubilities
60.1 Why is water a good solvent for ionic
crystals?
60.2 Entropy changes are important when a
crystal dissolves
60.3 The sizes of the ions in a crystal are
important in explaining solubilities
60.4 Why is water a good solvent for many
covalent substances?
60.5 Covalent liquids often dissolve covalent
solids
60.6 Volume changes when solids dissolve
61 Mixtures of liquids
61.1 What is the difference between miscible
and immiscible liquids?
61.2 Raoult's law and ideal Solutions
61.3 Solutions that do not obey Raoult's law
61.4 Why are there deviations from Raoult's
law?
61.5 Why do some liquids mix and others
not?
62 Competition between solvents
62.1 Solvent extraction
62.2 Solvent extraction is an equilibrium
process
62.3 Partition coefficients
62.4 Why do some results not fit the partition
law?
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63.1
63.2
63.3
63.4
63.5
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64.1
64.2
64.3
64.4
64.5
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65.1
65.2
65.3
65.4
65.5
65.6
65.7
65.8
65.9
65.10
65.11
65.12
65.13
65.14
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66.1
66.2
66.3
66.4
66.5
66.6
66.7
66.8
66.9
66.10
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67.1
67.2
67.3
67.4
363
Distillation 365
The boiling points of mixtures 365
How distillation works 366
Industrial distillation 368
Does distillation always work? 369
Steam distillation 370
Solubility product 373
What is a solubility product? 373
Using solubility products to calculate
solubilities 373
The common ion effect 375
Solubility products teil us when a
precipitate will be made 375
Using solubility products in chemical
analysis 376
Colligative properties 379
What are colligative properties? 379
Why does a solute influence the vapour
pressure of water? 379
Elevation of boiling point 379
How to make use of the boiling point
constant 380
Depression of freezing point 381
Osmotic pressure 382
Methods of measuring osmotic pressure 382
How might we explain osmosis? 383
How to calculate molar masses from
osmotic pressure experiments 383
Some examples of osmosis 384
Abnormal molar masses 384
Calculating the degree of dissociation
from abnormal molar masses 385
The thermodynamic explanation of
colligative properties 386
Raoult's law and solids in Solution 387
Electrochemical cells 389
How an equilibrium is set up between a
metal and Solution 389
The Standard hydrogen electrode 390
Standard electrode potentials 390
Combining half-cells 391
How to work out cell reactions 392
A quick way of writing cells 393
The anode and cathode in a cell 393
More about salt bridges 393
The electrochemical series 394
Some useful cells 395
Cells and concentration changes 400
How cell e.m.f.s change with
concentration 400
How to work out equilibrium constants
from cell e.m.f.s 401
Concentration cells 403
pH and the glass electrode 404
68 Corrosion 408
68.1 An example of corrosion 408
Contents vn

7. 68.2 The rusting of iron
68.3 How does a layer of zinc prevent iron
rusting?
68.4 Why does tin protect iron from corrosion?
69 Cells and thermodynamics
69.1 The link between free energy and cell
e.m.f.s
69.2 Calculating Standard e.m.f.s from free
energy values
69.3 Calculating free energy values from
Standard e.m.f.s
70 Redox potentials
70.1 Standard redox potentials
70.2 Predicting redox reactions
70.3 Predicting reactions in the laboratory
from redox potentials
70.4 Redox titrations
71 Redox Charts
71.1 What is a redox chart?
71.2 How to use redox charts
71.3 What is disproportionation?
72 Electrolysis
72.1 What is an electric current?
72.2 What happens during electrolysis?
72.3 Examples of electrolysis
72.4 How to calculate the mass of a substance
liberated in electrolysis
72.5 Why is electrolysis used in industry?
73 Conductivity of Solutions
73.1 How do we measure conductivity?
73.2 Molar conductivities
73.3 Molar conductivities and the degree of
dissociation
73.4 How individual ions contribute to
conductivities
73.5 How can we make use of conductivity
measurements?
74 Acids and bases
74.1 Early ideas about acids
74.2 Acids give hydrogen ions in Solution
74.3 The Brensted theory of acids and bases
74.4 The Lewis theory of acids and bases
75 Strong and weak acids
75.1 What is the difference between strong
and weak acids?
75.2 Conjugate acids and bases
75.3 The ionic produet of water
75.4 Acid dissociation equilibrium constants
75.5 What makes an acid strong?
75.6 What is the connection between pH and
PKa?
75.7 Base dissociation constants and p/Cb
75.8 How to work out the degree of
dissociation of a weak acid
409 75.9 How to work out the pH of a weak acid 450
75.10 Buffer Solutions 450
Neutralisation and titrations 455
Salt hydrolysis 455
Salts of a strong acid and a strong base 455
Salts of a strong acid and a weak base 455
Salts of a weak acid and a strong base 455
Salts of a weak acid and a weak base 456
Endpoints in titrations depend on the
strength of the acid and base 456
Indicators 456
Rates of reactions 459
Why do we study the rates of reactions? 459
What makes reactions take place? 459
What can prevent reactions taking place? 460
How can we make reactions go faster? 461
Two theories of reaction rates 465
Collision theory 465
More about the activation energy 466
Catalysts and activation energy 467
Transition State theory 467
Measuring the rates of reactions 471
An example of measuring a rate 471
Six ways of measuring rates 472
Measuring the rates of very fast reactions 476
Rate laws 480
What is a rate law? 480
How can we discover the rate law? 481
Quick ways of finding the rate law 482
The contribution of individual Orders to
the overall rate law 484
Reaction mechanisms 487
What is a reaction mechanism? 487
Bonds can break in two ways 487
The slowest Step in a reaction governs the
rate 488
Free radical reactions 489
Mechanisms of the hydrolysis of
halogenoalkanes 490
The influence of catalysts 491
The kinetics of enzyme reactions 492
INDUSTRIAL CHEMISTRY
The chemical industry 497
Why is the chemical industry important? 497
The stages in producing a new produet 498
The economics of produetion 499
Cash flow in the produetion cycle 500
Running a chemical plant 501
Designing a chemical plant 502
Energy and mass balances 502
82.8 Continuous and batch processing 503
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76
76.1
76.2
76.3
76.4
76.5
76.6
76.7
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77.1
77.2
77.3
77.4
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78.1
78.2
78.3
78.4
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79.1
79.2
79.3
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80.1
80.2
80.3
80.4
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81.1
81.2
81.3
81.4
81.5
81.6
81.7
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443
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449
82
82.1
82.2
82.3
82.4
82.5
82.6
82.7
449
vm Contents

8. 83
83.1
83.2
83.3
83.4
Chemical processes
Examples of modern chemical
manufacture
Manufacture of sulphuric acid
The Haber process for the manufacture of
ammonia
The manufacture of nitric acid
506
506
506
508
510
84 The chlor-alkali industry 512
84.1 What is the chlor-alkali industry? 512
84.2 The production of chlorine and sodium
hydroxide 512
84.3 The ammonia-soda (Solvay) process 514
85 The extraction of metals 518
85.1 The methods of extraction 518
85.2 Extracting the noble metals 518
85.3 Reducing sulphide ores 520
85.4 Reducing an oxide ore
85.5 The extraction of reactive metals
86 The oil industry
86.1 Why is the oil industry important?
86.2 Catalytic re-forming
86.3 Catalytic cracking
86.4 Thermal cracking
Appendix A The laws of thermodynamics
Appendix B Table of ionisation energies
Appendix C Table of atomic masses
Appendix D Values of some universal
constants
Bibliography
Examination questions
Answers to examination questions
Subject index
Index of names
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521
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525
526
527
528
533
535
536
538
539
540
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559
569