ADVANCED CHEMISTRY 1 Philip Matthews E CAMBRIDGE i: UNIVERSITY PRESSContents Acknowledgements How 10 use this book PHYSICAL CHEMISTRY 1 Elements, atoms and electrons: basic ideas Dalton’s atomic theory Evidence for atoms, Cathode rays Millikan’s experiment lectric charge is quantised Energy levels Energy changes Energy levels Max Planck and energy levels Light energy Atoms and the nucleus 1 Aplum pudding ‘2. How the nucleus was discovered 3. The discovery of protons 4 Moseley and atomic num 5 6 Discovery of neutrons A comparison of electrons, protons and neutrons. 37 38 its 3.9. Relative atomic and molecular masses 3. 3 3 .10 Einstein's equation -I1 Binding energy 2. 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 Antificially prepared elements 4.7. Asad ending age x 10.2 103 u Wa Radioactive decay Detection of radiation Half-lives The radioactive decay law Decay schemes Nuclear energy Discovery of nuclear energy Fission reactions Nuclear power Fusion reactions Nuclear weapons Applications of radioactivity Industrial uses of radioactivity ‘Medical uses of radioactivity Radiocarbon dating Chemical applications Bohr’s model of the atom Energy levels of the hydrogen atom How to calculate the ionisation energy of hydrogen What are orbitals? What are stationary states? Ground and excited states The hydrogen atom spectrum Balmer’s formula for the hydrogen atom Bohtr’s explanation Other lines in the hydrogen spectrum Waves and particles Experimental evidence about the nature of light What is wave-particle duality? de Broglie’s equation Schrddinger’s theory of the atom Schrodinger’s theory of the hydrogen atom ‘What do the quantum numbers tell us? Different types of orbital Wavefunctions and what they mean Contents 28 28 29 31 34 34 35 37 4a 42 42 a 46 47 43. 49 51 51 31 51 54 54 36 36 582 121 122 3 4 125 126 127 BA 2 3. ba 14d 14.2 143, 144 145 146 147 15 15.1 16 16.1 16.2 16.3 164 16.5 16.6 16.7 16.8 7 1d 17.2 173, 74 18 18.1 ‘The shapes of orbitals The spin quantum number ‘The aufbau method and electron structures What is the aufbau method? ‘More about orbital energies Filling orbitals — the importance of energy ‘The Pauli exclusion principle Huné’s rule Background to Hund’s rule ‘The aufbau method in action Electron structures, ionisation energies and shielding What is shielding? Ionisation energies down a Group Tonisation energies across a Period How ionisation energies are linked to Groups in the Periodic Table Bonding in molecules: valence bond theory Valence bond theory Dot-and-cross diagrams for diatomic molecules Dot-and-cross diagrams for triatomic and quadratomic molecules Dot-and-cross diagrams for hydrocarbons ‘Showing bonds by lines Bonding in oxoanions Resonance structures Coordinate bonding What is coordinate bon 82 Molecular orbital theory Wavefunctions can be positive or nega How wavefunctions can be combined Bonding and antibonding orbitals using s orbitals Bonding and antibonding orbitals using p orbitals Energies of bonding and antibonding orbitals ‘Molecular orbitals for homopolar diatomic molecules Molecular orbitals for heteropolar diatomic molecules Molecular orbitals for hydrocarbons Shapes of molecules Molecular models Flectron repulsion theory ‘The isoelectronic rule Hybridisation Tonic bonding Covalent substances have some ionic character Contents 7 1 mn 2 B 7 78 78 29 79 80 80 a4 87 87 87 87 8s 89 °0 1 92 95 95 96 97 101 101 18.2 18.3 18.4 18.5 186 19 191 19.2 193, 4 20 20.1 20.2 203 20.4 20.5 21 211 212 213 223 224 22.6 2B 2 23.2 23 BA 24 24.1 24.2 24.3 244 245 24.6 24.7 24.8 24.9 25 23.1 Tonic substances have some covalent character Other evidence that a substance contains ions Which elements make ionic compounds? Why do ionic compounds exist? Ionic compounds and electron structures Polar molecules and polar bonds What is a polar molecule? Polar bonds and electronegativi Polar molecules and dipole moments Polarisability Intermolecular forces Where are intermolecular forces found? What causes intermolecular forces? Dispersion forces and polarisability Intermolecular forces are also produced by permanent dipoles Some words of wan Hydrogen bonding What is hydrogen bonding? Evidence for hydrogen bonding Intermolecular and intramolecular hydrogen bonding Hydrogen bonding in biochemistry Hydrogen bonding in solids Metallic bonding How can you recognise a metal? What is the band structure of metals? Why do metals conduct electricity? Semiconductors Why do metals conduct heat? ‘Metal atoms exist in a sea of electrons The three states of matter ‘The three states of matter How do we know that gases are disorderly? Differences in properties of solids, liquids and gases ‘The potential energy curve for two neighbouring molecules Some remarkable substances Three types of spectroscopy Emission and absorption spectra Electronic spectroscopy Vibrational spectroscopy Rotational spectroscopy ‘Translations Electromagnetic waves ‘The electric field and electrons ‘The magnetic field and electrons Selection rules Visible spectroscopy Why does copper(tt) sulphate solution look blue? 101 102 103 103, 104, 107 107 107 108 Mt 13 113 113. 14 a 4 17 117 17 119 120 120 122 122 122 123, 123, 126 126 128 128 9 129 Bo Bo 136 136 Be 136 136 Bs 138 19 139 140 142 14225.2 25.3 25.4 25.5 26 26.1 26.2 263 27 27.1 272 273 27.4 28 28.1 28.2 283 28.4 28.5 29 29.1 29.2 29.3 29.4 29.5 29.6 29.7 30 30.1 30.2 30.3 304 30.5 30.6 30.7 31 Bld 312 313 314 313 The visible spectrum of copper) sulphate solution, How does a visible light spectrometer work? What happens to the photons absorbed by copper(it) sulphate solution? Why vibrations are important in visible spectra Ultraviolet spectroscopy The ultraviolet spectrum of alkenes The ultraviolet spectrum of arenes The ultraviolet spectrum of aldehydes and ketones Vibrational spectroscopy Why is vibrational spectroscopy useful? What are group frequencies? Making sense of vibrational spectra Vibrational spectra can tell us about the strengths of bonds Nuclear magnetic resonance The importance of nuclear spin The patterns in an nam. spectrum Why do protons appear in different places in the spectrum? Nam. specira can tell us how many protons are present Not only hydrogen atoms can show up in nmr. Mass spectrometry What are mass spectrometers? ‘The design of a mass spectrometer The whole number rule and standards of Mass spectra and isotopes Calculating relative atomic masses from mass spectra What are fragmentation patterns? The effect of isotopes in a molecule’s mass spectrum, X-ray diffraction What causes X-ray diffraction? More about diffraction Brage’s equation Different types of X-ray diffraction experiment Explanation of powder photographs ‘The arrangement of planes in crystals ‘The arrangements of individual atoms Crystallography What is crystallography? ‘The closest packing of atoms Structures that are not close-packed Coordination numbers Metal crystals 142 143 144 laa 146 146 47 147 49 49 151 151 155 157 137 158 158. 158 159 161 161 ll 162 164 164 164 165 168 168 169 169 170 171 172 1” 174 174 176 176 176 32 32.1 32.2 323 324 325 3 33.1 33.2 333 334 33.5 34 34.1 34.2 343 35 35.1 35.2 35.3 354 35.5 36 36.1 36.2 363 364 37 37.1 37.2 373. 374 375 37.6 38 38.1 38.2 383 39 39.1 39.2 39.3, 39.4 40 40.1 Unit cells ‘The seven crystal systems ‘The fourteen Bravais lattices What are unit cells? Radius ratio rules The number of atoms or ions in a unit cell Sizes of atoms, ions and molecules How can we estimate the size of an atom? Metallic and covalent radii Van der Waals radii Ionic radii Bond lengths Real and ideal gases ‘The gas laws Real gases and the van der Waals ‘equation How good is the van der Waals equation? Kinetic theory of gases Whaat is the kinetic theory of gases? The pressure of an ideal gas ‘The connection between energy and temperature ‘The spread of energies in a gas Kinetic theory and Avogadro's theory Chemistry and gases Gay-Lussac’s law of combining volumes Avogadro's theory Dalton’s law of partial pressures Graham's law of diffusion The mole ‘What is the mole? How to work with moles of compounds ‘Moles and equations ‘Moles and balancing equations ‘The empirical formula and molecular formula of a compound Percentage compositions Molar masses of gases and liquids ‘Measuring the molar mass of a gas Measuring the molar mass of a soluble gas Measuring the molar mass of a volatile liquid Moles and titrations Standard solutions The concentration of a solution Concentration and molarity How to do calculations involving concentrations Four types of titration Acidbase titrations Contents 179 179 179 179 184 185 188 188 188. 189 190 191 193 193 195 196 200 200 200 201 202 203 205 205 205, 206 206 209 209 210 210 211 212 213, 216 216 217 218 221 221 223 224 224 227 22740.2 403 40.4 4l 34 44 44.1 44.2 443 444 445 44.6 45 45.1 45.2 46 46.1 46.2 46.3 47 47.1 47.2 473 47.8 48 48.1 48.2 483 49 49.1 Redox titrations Titrations involving iodine Silver nitrate titrations Oxidation numbers and oxidation states What are oxidation and reduction reactions? What are oxidation numbers? Oxidation numbers of elements in covalent compounds ‘Oxidation numbers of elements in ions Rules for assigning oxidation numbers Oxidation states Using oxidation numbers with equations Half-equations Energy changes Energy changes and chemical bonds Energy changes and energy diagrams Exothermic and endothermic reactions Enthalpy What is enthalpy? Enthalpy and standard states Enthalpy and state functions Hess's law Standard enthalpies Standard enthalpy of an element Standard heats of formation Standard heats of combustion Enthalpy changes when substanc apart Bond energies and average bond energies Heats of hydrogenation s break Calculations using Hess’s law Using heats of formation Impossible reactions Lattice energies ‘What is meant by lattice energy? The Born-Haber cycle What do lattice energies tell us? 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 Entropy A first look at entropy Contents 227 229 20 234 234 235 235 236 237 237 238 240 243 243 245 247 247 248, 249 250 252 252, 252 253 255 255 256 259 259 260 263 263 263 265 271 271 273 273 274 276 276 276 277 279 279 49.2 493 49.4 49.5 49.6 49.7 ‘The Boltzmann distribution More about energy levels Entropy changes and mixing of gases, Entropy and disorder Reversible and irreversible changes Some changes are spontaneous, some are not 49.8 Entropy and reversible changes 49.9 Entropy and non-reversible changes 49.10 Standard entropies 49.11 Calculating entropy changes 50 Free energy 50.1 What is free energy? 50.2 Standard free energies 50.3 Free energy values do not tell us how fast, a reaction will occur 50.4 Free energy changes under non-standard conditions 50.5 Ellingham diagrams and the extraction of metals 51 Equilibrium and free energy 51.1 What is the effect of concentration and pressure on free energy? 51.2. What is the connection between free energy and equilibrium? 51.3. Equilibrium and equilibrium constants 52 Chemical equilibrium 52.1 Equilibrium constants 52.2 Equilibrium constants and their units 52.3 Are equilibrium constants really constant? How does temperature affect an equilibrium reaction? How can the connection between equilibrium constants and temperature be made more exact? Pressure can change the proportions of reactants and products at equilibrium 52.4 52.5 52.6 53 Some equilibrium reactions 53.1 What this unit is about 53.2 The bismuth trichloride-water reaction 53.3 The chromate(v}~dichromate(vi) reaction 53.4 The iodine-iodine trichloride reaction 53.5 ine-triiodide reaction 53.6 itrogen dioxide tetraoxide rea ‘The decomposition of ammonium salts Reactions involving complex ions 53.7 53.8 54 Measuring equilibrium constants 54.1 How can equilibrium constants be measured? ‘The ester equilibrium ‘The hydrogen iodide equilibrium 54.2 54.3 55 Equilibria between phases 55.1 What isa phase? 281 281 282 283 235 285 286 286 288 289 291 291 293, 204 294 295 299 209 300 301 304 304 305 306 306 307 308 314 314 314 314 314 315 315, 315, 315, 318 318 318, 320 323 32355.2 55.3 55.4 56 36.1 56.2 36.3 56.4 56.5 56.6 36.7 57 57.1 57.2 58 58.1 58.2 583 39. 59.1 59.2 59.3 39.4 60 60.1 60.2 60.3 60.4 60.5 60.6 61 61.1 61.2 613 614 62 62.1 62.2 62.3 624 How to interpret a phase diagram ‘The phase diagram of sulphur ‘The phase diagram of helium Chromatography What is chromatography? Paper chromatography Thin layer chromatography (TLC) Column chromatography on exchange chromatography Gas-liquid chromatography (GLC) High pressure liquid chromatography (HPLC) Polymorphism and allotropy ‘What is polymorphism? What is allotropy? Equilibrium between a solid and liquid What happens when a liquid freezes? Cooling curves Cooling curves for mixtures Solubility of salts in water The solubility of a solid in water Fractional crystallisation Crystals that contain water of crystallisation Saturated and supersaturated soluti Explaining solubilities Why is water a good solvent for ionic crystals? Entropy changes are important when a exystal dissolves The sizes of the ions in a crystal are important in explaining solubilities Why is water a good solvent for many covalent substances? Covalent liquids often dissolve covalent ‘Volume changes when solids dissolve Mixtures of liquids What is the difference between miscible and immiscible liquids? Raoult’s law and ideal solutions Solutions that do not obey Raoult’s law Why are there deviations from Raoult’s law? Why do some liquids mix and others not? Competition between solvents Solvent extraction Solvent extraction is an equili process Partition coefficients Why do some results not fit the partition law? 323 324 324 327 327 328 330 330 331 331 332 335, 335 36 340 340 341 341 345 345 346 346 347 349 349 350 351 351 352 352 355 359 356 362 362 363 363 63 63.1 63.2 633 63.4 63.5 64.1 642 64.3 64.4 645 6 63.1 65.2 65.5 65.6 65.7 65.8 65.9 65.10 65.11 65.12 65.13 65.14 66 66.1 66.2 66.3 66.4 66.5 66.6 66.7 66.8 66.9 66.10 o7 ont 673 ora 68 68.1 Distillation The boiling points of mixtures How distillation works Industrial distillation Does distillation always work? Steam distillation Solubility product ‘What is a solubility product? Using solubility products to calculate solubilities The common ion effect Solubility products tell us when a is in chemical analysis Colligative properties What are colligative properties? Why does a solute influence the vapour pressure of water? Elevation of boiling point How to make use of the boiling point constant Depression of freezing point Osmotic pressure Methods of measuring osmotic pressure How might we explain osmosis? How to calculate molar masses from osmotic pressure experiments Some examples of osmosis ‘Abnormal molar masses Calculating the degree of dissociation from abnormal molar masses The thermodynamic explanation of colligative properties Raoult’s law and solids in solution Electrochemical cells How an equilibrium is set up between a metal and solution The standard hydrogen electrode Standard electrode potentials Combining half-cells How to work out cell reactions A quick way of writing cells ‘The anode and cathode in a cell More about salt bridges ‘The electrochemical s Some useful cells les Cells and concentration changes How cell e.m.f.s change with concentration How to work out equilibrium constants from cell ems Concentration cells pH and the glass electrode Corrosion An example of corrosion Contents 365 365 366 368 369, 370 373 373, 373 375 375, 376 379 379 379 379 380 381 382 382 383 383 384 384 385 386 387 389 389 390 390 391 302 393 393 393, 394 395 400 401 403 404 408 408 vil68.2 683 68.4 0 69.1 69.2 693 70 70.1 70.2 703 704 1 ma 712 13 2 Ra 72.2 723 72.4 725 B Ba B2 BS BA 74. 74.1 74.2 743 74.4 7 751 752 3 734 15 73.6 73.7 73.8 vill The rusting of iron How does a layer of zinc prevent iron rusting? Why does tin protect iron from corrosion? Cells and thermodynamics The link between free energy and cell ems Calculating standard e.m.f. from free energy values Calculating free energy values from standard ems Redox potentials Standard redox potentials Predicting redox reactions Predicting reactions in the laboratory from redox potentials Redox titrations Redox charts What is a redox chart? How to use redox charts What is disproportionation? Electrolysis What is an electric current? What happens during electrolysis? Examples of electrolysis How to calculate the mass of a substance liberated in electrolysis Why is electrolysis used in industry? Conductivity of solutions How do we measure conductivity? Molar conductivities ‘Molar conductivities and the degree of dissociation How individual ions contribute to conductivities How can we make use of conductivity measurements? Acids and bases Early ideas about acids Acids give hydrogen ions in solution The Bronsted theory of acids and bases The Lewis theory of acids and bases Strong and weak acids What is the difference between strong, and weak acids? Conjugate acids and bases The ionic product of water Acid dissociation equilibrium constants What makes an acid strong? ‘What is the connection between pH and DK? Base dissociation constants and pk, How to work out the degree of dissociation of a weak acid Contents 409 409 410 42 412 412 413 41s 415 416 416 417 420 420 420 422 426 426 427 428 430 431 433 433 434 435 435 436 439 439 39 440 441 443 443 443 44a 445 446 448 449 449 75.9 How to work out the pH of a weak acid 75.10 Buffer solutions 76 Neutralisation and titrations 76.1 Salt hydroly: 76.2 Salts of a strong acid and a strong base 76.3 Salts of a strong acid and a weak base 76.4 Salts of a weak acid and a strong base 76.5 Salts of a weak acid and a weak base 76.6 Endpoints in titrations depend on the strength of the acid and base Indicators 76.7 77 Rates of reactions 77.1. Why do we study the rates of reactions? 77.2 What makes reactions take place? 77.3 What can prevent reactions taking place? 77.4 How can we make reactions go faster? 78 Two theories of reaction rates 78.1 Collision theory 78.2 More about the activation energy 78.3. Catalysts and activation energy 78.4 Transition state theory 79 Measuring the rates of reactions 79.1. An example of measuring a rate 79.2 Six ways of measuring rates 79.3, Measuring the rates of very fast reactions 80 Rate laws 80.1 What isa rate law? 80.2 How can we discover the rate law? 80.3 Quick ways of finding the rate law 80.4 The contribution of individual orders to the overall rate law 81 Reaction mechanisms 81.1 What isa reaction mechanism? 81.2 Bonds can break in two ways 81.3. The slowest step in a reaction governs the rate Free radical reactions Mechanisms of the hydrolysis of halogenoalkanes ‘The influence of catalysts The kinetics of enzyme reactions INDUSTRIAL CHEMISTRY 82 The chemical industry 82.1. Why is the chemical industry important? 82.2 The stages in producing a new product 82.3 The economics of production 82.4 Cash flow in the production cycle 82.5 Running a chemical plant 82.6 Designing a chemical plant 82.7. Energy and mass balances 82.8 Continuous and batch processing. 450 450 455 455 455 455 455 456 456 456 459 459 459 460 461 465 465 466 467 467 an 471 472 476 480 481 482 484 487 487 487 488 439 490 491 492 497 497 498 499 500 501 502 502 50383 83.1 83.2 33.3 83.4 a4 84.1 84.2 84.3 85 85.1 85.2 35.3 Chemical processes Examples of modem chemical manufacture Manufacture of sulphuric acid ‘The Haber process for the manufacture of ammonia ‘The manufacture of nitric acid The chlor-alkali industry What is the chlor-alkali industry? The production of chlorine and sodium hydroxide The ammonia-soda (Solvay) process ‘The extraction of metals ‘The methods of extraction Extracting the noble metals Reducing sulphide ores 506 506 506 508 510 512 512 512 514 sis 518 518 520 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, coments 520 521 525 525 526 527 528 533 535 536 338 539 540 558 559 569,