INDEX

acidic regions reaction to form esters 835 A strong acid–strong base/strong base–strong absolute temperatures 299 reaction with acid anhydrides 1031 absolute uncertainties 35, 37–8 acid 473–4 reaction with acid chlorides 1031 absorbance (A) of light 575 weak acid–strong base/weak base–strong reaction with active metals 828 absorption spectra 127–8 acid 476 reaction with carboxylic acid accuracy of measurement 32–3 acidic solutions 437 derivatives 1031–2 acetaldehydes 945 alcohols 827 reaction with carboxylic acids 1028–31 acetals 955, 957–8 redox reactions in 501–3 reaction with esters 1031 as carbonyl-protecting groups 959 thiols 846–7 reaction with phosphorus halides 830 formation of 958, 993–5 acidity constants (Ka) 447 See also reaction with thionyl chlorides 830 acetic acids 433, 464, 466 Henderson–Hasselbalch equation from reduction of carbonyl compounds 826 in buffer solutions 467–8 secondary (2°) 823 Ka 447–8 esters 1010 determining values 449 solubility 1018 speciation diagrams 478 acidophiles 430 structural formula 55–6 vapour pressure variations 262 acids 432 See also diprotic acids; monoprotic tertiary (3°) 823 acids; strong acids; weak acids aldehydes 770, 833 acetones 1 13 boiling points 248–9 amino acids 1066–8 H-NMR and C-NMR spectra 913 calculating vapour pressure 413 bond enthalpies 461 acid-catalysed hydrations 956–8 electron density models 948 common 433 addition of alcohols 955–9 industrial uses 949 dissociation in aqueous solutions at 25° 462 addition of Grignard reagents 953–4 acetophenones 949, 950, 970 maximum strength 465 addition of carbon nucleophiles 955 acetylenes 716 molecular basis of strength 461–5 aliphatic 949 achiral compounds 761, 765, 772 See also oxoacids 462–4 aromatic 949 meso compounds polyprotic 433, 447, 479 boiling points 1018 achiral enols 970 strengths of 441–2 catalytic reductions 965 achiral isomers 773 superacids 465, 482 formation of imines 960–1 acid anhydrides 835, 1012 triprotic 461 formation of oximes and hydrazones 962 hydrolysis 1032, 1035 actins 1060 formation of tetrahedral carbonyl addition nomenclature 1016 actinoids 16, 548, 602 intermediates 951, 966 reaction with alcohols 1031, 1032 activation energies (Ea) 665, 666, 667 a-halogenation 970–1 reaction with ammonia and amines calculating from two rate constants 670 from hydration of alkynes 950–1 1036, 1037 second-order decomposition of nitrogen industrially important 949 acid chlorides 835, 1012, 1028, 1042 dioxide 668–70 IR spectra 889–90 hydrolysis 1032, 1035 activities 355, 523 metal hydride reductions 964–5 reaction with alcohols 1031, 1032 actual yields 98 nomenclature 947 reaction with ammonia and amines acyclic alkanes 58 nucleophilic acyl additions 1027 1036, 1037 acyl groups 1012 oxidation to carboxylic acids 967–8, 1020 acid halides 746 acyl halides 746 See also acid halides from ozonolysis of alkenes 950 formation of 1028 structure and bonding 1012 position of keto–enol equilibrium 969 nomenclature 1016 acylation of aromatic compounds 742, 746–7 preparation from oxidation of alcohols structure and bonding 1012 addition to the carbon–carbon double bond 723 950 adducts 481, 556 reaction to form 2 alcohols 826 acid ionisation constants (pKa) 448 ° alcohols in dilute aqueous solutions 827 drawing structures 483 reaction with addition of Grignard amines 855 adenines 739 reagents 951–5 a-ammonium groups 1067 adenosine diphosphates (ADP) 526, 631, 634 reduction to 1° alcohols 826, 964, 966 aromatic carboxylic acids 1024 adenosine triphosphates (ATP) 526, 31, 634 reductive amination of 962, 964 a-carboxyl groups 1067 amount of glucose in 988 solubility 948, 1018 carboxylic acids 1023–5 chair conformations 991 structural formula 56–7 interpreting 449 adhesive forces 260 structures 944 ionisable groups of amino acids 1067 adiabatic processes 300 alditols 995–6 phenols 839 adipic acids 1014 d-aldohexoses 988 phosphoric acids 623 agricultural chemicals 163 aldopentoses 990 side-chain caryboxyl groups 1067 agricultural fertilisers 622, 633 aldoses 986 acid–base indicators 472 COPYRIGHTEDAir Canada 26 MATERIALaldotetroses 988–9 pKa 479 air pollution and ways to reduce 372 aldotrioses 986, 988 colours of acid and base forms 480 airbags 498 aliphatic aldehydes 949 common 481 airconditioning, working principles behind 331 aliphatic amines 847 how they work 479–80 alanines 858, 1063 nomenclature 848–9 selecting best indicators 480–1 d-alanines 1065 aliphatic carboxylic acids 1012 acid–base reactions 432 Alcoa 605 nomenclature 1014 carboxylic acids 1023–5 alcohols 822–7, 1014 solubility 1018 group 13 620 1H-NMR spectrum 910 aliphatic dicarboxylic acids 1014 phenols 840 acid-catalysed dehydration to alkenes aliphatic hydrocarbons 698 See also alkanes acid–base reactions in water 436–42 831–3 alkadienes 720 acid–base titrations 472–81 acidity of 827 alkali metals 17 amino acids 1068 from addition of Grignard reagents to alkaline batteries 534 glycines 1069 carbonyl compounds 826–7 alkaline earth metals 17 strong acid–strong base 472–4 basicity of 827 alkaline regions weak acid–strong base 474–7 boiling points 948, 1018 strong acid–strong base/strong base–strong weak base–strong acid 474–7 functional groups 822 acid 474 acid–catalysed halogenations 970 IR spectrum 888 weak acid–strong base/weak base–strong acid–catalysed hydrations oxidation to form aldehydes 950 acid 477 aldehydes and ketones 956–8 physical properties 824–5 alkaloids 848 alkenes 728–30 preparation from alkenes 825 alkanes 698–711 aromatic compounds 744 preparation from haloalkanes 826 13C-NMR spectrum 909 mechanisms of additions 729 primary (1°) 823 boiling points 247, 708–9, 824

Index I-1141

BMIndex I-1141 1 June 2015 9:06 AM alkanes (continued) amines 847–53 anti selectivity 731 condensed and molecular formulae 699 1H-NMR spectrum 912 antibodies 1060 conformation 700–1 pKa at 25° 855 antibonding molecular orbitals 206, 208 constitutional isomerism 61–2 pKb at 25° 854–5 antibonding orbitals 265–6 formation from reduction of alkenes 731–2 basicity of 854–7 anti-cancer agents 560 high-molar mass 709 determining class of 848 anti-cancer drugs 781, 1000 IHD 876 IR spectra 889 anticoagulants 1019 IR spectrum 886–7 physical properties 851–2 antifreeze 410 isomeric 709–10 preparation from haloalkanes 852–3 anti-inflammatory drugs 781 NMR spectrum 908–9 reaction of aromatic amines with nitrous antimony 607, 610, 622, 623 nomenclature 58–63, 699, 702–3 acids 859–61 nomenclature 564 physical properties 708–11 reaction to form amides 861 valence electrons 149 reactions of 722–3 reaction with carboxylic acid apatites 266, 608, 635 structures 698, 699 derivatives 1036 aprotic solvents 805, 806, 834 alkanolates 828 reactions with acids 857–61 aqua regia 520 alkenes 698, 711, 1038 separation and purification of 857–8 arenes 698, 711–12, 734 1H-NMR spectrum 909–10 synthesis from carboxylic acids 1039 argentites 486 13C-NMR spectrum 910 synthesis into arylamines 853 argon 618 acid-catalysed dehydration from synthesis by reductive amination 963–4 close-packed structures 277 alcohols 831–3 use in pharmaceuticals 859 phase change data 268 acid-catalysed hydrations 728–30 a-amino acids 1062, 1063 Argyle diamond mine 696 addition of bromine and chlorine 730–3 d-amino acids 1065 aromatic aldehydes 949 addition of hydrogen halides 724–8 amino acids 628, 630, 1060, 1062–74 See also aromatic amines 847 addition to the carbon–carbon double peptides; polypeptides; proteins pKa and pKb at 25° 855 bond 723 pKa 1067 reaction with nitrous acids 859–61 characteristic addition reactions to 723 acidic groups 1066–8 solubility 852 cis–trans configurations 717 analysis based on charge 1073 aromatic carboxylic acids 1012 cis–trans isomers 713 analysis of 1075–6 acidity of 1024 configuration usingE,Z system 719 basic groups 1068 nomenclature 1015 designating configurations 717–19 electrophoresis 1071–3 aromatic compounds 734–42 E,Z systems 718–19 isoelectric points 1070–1 acylation 746–7 electrophilic addition reactions 723–33 in meteorites 1066 alkylation 745–6 IHD 876 other common 1065 bromination 743 IR spectrum 886, 887 pH 1069–70 chlorination 743 low-molar-mass 712, 717 protein-derived 1063–4 electrophilic aromatic substitutions 742–7 nomenclature 716–22 ratios of undissociated acids compared with Friedel–Crafts acylation 949–50 ozonlysis of 950 conjugate base 1070 aromatic dicarboxylic acids 1015 physical properties 722 separation of mixture based on aromatic hydrocarbons 734 See also benzenes preparation into alcohols 825 charges 1073–4 IR spectrum 889 reactions of 723–33 sequence analysis 1076 nomenclature 739–42 reduction to form alkanes 731–2 structural variations 1063 resonance energies 737 relative stabilities 732–3 titration of 1068–9 aromatic ketones 949 shapes of 712–13 4-aminobutanoic acids (GABA) 1065 aromatic properties 734, 738–9 alkoxides 828 b-amino alcohols 955 Hückel’s criteria 738 alkoxy groups 842 amino sugars 989 Arrhenius, Svante 432, 665 alkyl carbocations, order of stability 727 ammonia 184, 350, 482 Arrhenius equation 667–70 alkyl groups 59–60 calculating pH of ion buffers 468 arsanes 622 alkyl halides 724, 792–3 catalytic formation of 681 L-ascorbic acids 997 alkylamines 849 changing equilibrium 368–9 arsenic 610, 622 alkylation of aromatic compounds 742, 745–6 HSAB principle 486 arsenic acids 623 alkylbenzenes 1020 periodic trends in boiling points 251 arsenous acids 623 alkynes 2, 698, 711 phase diagrams 271–2 aryl grignards 952 hydration of 950–1 reaction with carboxylic acid aryl groups 734 IHD 876 derivatives 1036–7 ascorbic acids 478 IR spectrum 886, 887 structures 48 aspirins 882, 1031 low-molar-mass 717 ammonium acetates 458 association processes 423 nomenclature 716–22 ammonium chlorides 228 astatines 615 physical properties 722 ammonium formates 458 asthma and treatments for 820 reactions of 733 a-ammonium group pKa 1067 AstraZeneca 779 shapes of 712–13 ammonium hydrogen phosphates 633 asymmetric synthesis 781 alloys 402 ammonium ions buffer and pH 468 atmospheric gases 218, 252 effect of weak acids on 466–7 amorphous solids 286–7 atmospheric pollutants 632 alpha particles 9–10 amount of substance 85 atom efficiency 99 aluminium 288, 486, 603 amperes (A) 27, 531 atomic force microscopes (AFMs) 8 ccp structures 276 amphiprotic compounds 434 atomic mass 12–13 ground-state electron configuration 150 amplitude of light waves 120, 121 atomic mass unit (u) 12–13 See also Dalton (Da) ionisation energies (Ei) 158 amylopectins 1002 atomic nuclei spin 894–5 melting points 604 amyloses 1002 atomic numbers (Z) 11, 159 aluminium oxide (alumina) 288 angle strains 703 atomic orbital models 142–3 aluminosilicates 603, 621 anhydrous 41 atomic radii 155–7 ambidentate ligands 559 anilines 740, 849, 857–8 calculating using crystal structure data 285–6 amide bonds 1014 anionic surfactants 397 trends in 156–7 amides See also cyclic amides anions 4, 159, 160, 282, 519, 551 atomic spectra 127–8 carboxylic acids 1013 as Lewis bases 482 atomic theories 4–7 formation from amines 861 stability 161 atomisation enthalpy (∆atH) 319 formation from esters 1037 anodes 508, 509, 529 atoms 2, 4, 11, 47 hydrolysis 1034–6 lead storage batteries 532–3 axial positions 185 IR spectra 890–1 reaction in dry cells 534 characteristics of 120 nomenclature 1016 anomeric carbons 990 donor 551 reductions 1039 anomers 990 electron clouds 484 resistance to alcohols 1032 interconversions 993 electrons in 18–19 resistance to ammonias 1036 anti additions 731 equatorial positions 185

I-1142 Index

BMIndex I-1142 1 June 2015 9:06 AM formal charge 179 benzenes 398–9, 711–12, 734–8 halogens 246 ground and excited states 126 1H-NMR spectrum 911 helium 616 imaging and manipulating 8 alkylation 745–6 isomeric alkanes 710 magnetic properties 154–5 Friedel–Crafts acylation 746–7 nonvolatile solutes 411, 414 single, double and triple bonds 42 IR spectra 888–90 solvents 411 structures 7–13 Kekulé’s structure 734–5, 736 thiols 846 Aufbau principle 145–8, 149, 151, 155, 159, nitration 744 Boltzmann constant 324 206, 208, 572 nomenclature 739–40 bomb calorimeters 307 Australian Synchrotron 124–5, 885 phase change data 268 bond angles of alkenes and alkynes 712–13 autoionisation of water 436 resonance energies 736–7 bond-breaking processes 49 autoprotolysis constant of water (Kw) 437 resonance structures 735–6 bond energies 172–3 autoprotolysis of water 436–8 sulfonation 744 oxygen 209 equations for 449–50 valence bond theory 735 trends in 193, 210–11 suppressing 446–7 benzoic acids 263–4, 740, 1010 bond enthalpies 318–21, 323 average rate of consumption 643–4 association processes 423 binary acids 461 Avogadro constant (NA) 85, 176, 227 nomenclature 1015 and Hess’s law 319–21 Avogadro’s law 222 separation from benzyl alcohols 1025–6 selected averages at 25° 320 axial bonds 704 benzol[a]pyrenes 741–2 bond lengths 172–3 axial ligands 557, 558 benzyl alcohols 836 for common chemicals 191 axial–axial interactions 706 1H-NMR spectrum 900 covalent bonds 191–3 azimuthal quantum numbers (l) 136–7 benzyl groups 740 factors influencing 192 azo compounds 860 benzylamine spectrum 912 oxygen 209 benzylic carbon oxidation 1020, 1022 selected nitrogen compounds 631 B benzylic hydrogens 1020 bond-making processes 49 baking soda beryls 266 bonding See also covalent bonding; hydrogen calculating decomposition 317 berylliums 163 bonding decomposition 327, 358 beryllium hydrides 183 between atoms 42 balanced chemical equations 82, 352 sp hybrid orbitals 201–2 carboxylic acids 1012 ball-and-stick models 47 beryllium oxides 288 fundamentals of 172 aldehydes and ketones 56 beta radiation 658 ionic 176–7 cycloalkanes 704 bidentate ligands 553–4, 557 single, double and triple 177 dimethyl ether 842 bn at 25° 566 transition metal complexes 569–73 ethanes 700 nomenclature 551 unequal electron sharing 173–4 methanethiols 845 bimolecular reactions 671, 800 bonding molecular orbitals 205 methanols 822 BINAP-catalysed asymmetric synthesis 781 bonding orbitals 196 naphthalenes 263 binary acids boric acids 620 Balmer, Johann 128 bond enthalpies 461 boric oxides 620 barium sulfates 390 strengths of 462 boron 13, 63, 486, 602 barometers 220 binary compounds 40 reactivity of compounds 619–20 Bartlett, Neil 617 ionic compounds 53–4 valence-electron configurations 603, 619 base ionisation constants (pKb) 448 nomenclature 52–3 boron carbides 289 amines 854–5 solubility 106 boron nitrides 288, 289 guanidine group of arginines 1068 binary hydrogen compounds 251 boron trifluorides 484 imidazole group of histidines 1068 biocatalysts 681 sp2 hybrid orbitals 200–1 base-catalysed reactions, amides 1034 biochemistry Bose–Einstein condensate 220 base-catalysed tautomerism 969 importance of hydrogen bonds 250 bosutnib 64 bases 432 See also strong bases; weak bases use of x-ray diffractions in 286 bound electrons 135–6 amines 854–7 biofuels 984–5 measuring stability 159 common 433 biogeochemical cycles of nature 626–36 boundaries 300 diprotic 434 nitrogen cycle 630–2 boundary surface diagrams 140 maximum strength 465 oxygen cycle 627–8 1s orbital 141 monoprotic 434 phosphorus cycle 632–5 d orbitals 142 polyprotic 434, 447 sulfur cycle 628–9 p orbitals 141 strengths of 441–2 bismuth 607, 610, 622, 623 bovine spongiform encephalopathy (BSE) 1084 basic solutions 437 bismuth subsalicylates 610–11 Boyle, Robert 221 alcohols 827 bismuthanes 622 Boyle’s law 221 redox reactions in 503–4 black phosphorus 610 b-pleated sheet patterns 1078, 1081 basicity constants (Kb) 447 Bloch, Felix 894 polypeptides 1079 batteries 532–7 See also fuel cells; blood Brady’s reagents 962 galvanic cells clot prevention 552 Bragg, William Henry 3, 176, 284 dry cells 533–5 determining if basic or acidic 437–8 Bragg, William Lawrence 2–3, 176, 284 internal energy (U) 303 pH in 471 Bragg equation 284–5 lead storage 532–3 blood sugar 988, 998 Brand, Hennig 17, 608 modern high-performance 535–6 bn See cumulative formation constants (bn) breathalysers 538 bauxite 603, 604, 606 boat conformations bridged chloronium ions 743 bcc lattice 279–80 cycloalkanes 704–5 bridged halonium ions 731 Becquerel, Henri 7 interconversions from chair 705–6 bromic acids 626 Bednorz, Georg 290 body-centred cubic (bcc) lattice 279–80 bromide salts 401 Beer–Lambert law 578, 916–17 Bohr, Niels 128–9 bromido ligands 559 Beer’s law 578, 916–17 Bohr magnetons (mB) 578 bromination b-elimination 797, 807–10 boiling point elevations (DTb) 414–16 alkenes 723 compared with nucleophilic boiling points 245 See also normal boiling aromatic compounds 743 substitutions 811 points benzenes 735 comparing E1 and E2 reactions 809 alcohols 824 haloalkanes 794–7 E1 reactions 808 alkanes 247, 708–9, 824 bromines 13 E2 reactions 809, 833 amines 851 addition to alkenes 730–3 mechanisms of 808–10 binary hydrogen compounds 251 applications of 615 predicting products of 807–8 bismuth 610 boiling points 245 predicting reaction mechanisms 809–10 carbonyl groups 948 intermolecular forces 241, 242 bending vibrations 883, 886 carboxylic acids 1018 isotope abundance 880 benzaldehydes 740 ethers 843 phase change data 268 benzanoic acids 1010 gallium 606 vapour pressure 261

Index I-1143

BMIndex I-1143 1 June 2015 9:06 AM bromobenzenes 743 carbon 13 catalytic hydrogenations 731–2 1-bromo-2-chloro-1-fluorenes 718 cycle 635–6 catalytic reductions 731–2 bromocyclohexanes 797 prefixes for chain lengths of 1 to 10 58 alkenes 736 bromomethanes 615 pure forms of 696 catenation properties 42, 603 Brønsted, Johannes 432 standard states 315 cathode rays 9 Brønsted–Lowry acids 442, 612 carbon dioxides 183, 72, 620, 635 cathodes 508, 509, 529 Brønsted–Lowry acids and bases atmospheric concentrations 252 dry cell batteries 534 432–5, 482 calculating amount produced 318 nicad batteries 535 conjugate acid–base pairs 434–5 levels in Earth’s atmosphere 348 reaction in dry cells 534 bronze 402, 607 molecular speed distributions 225 cathodic protection 526 buffer solutions 466–72 probable speeds 226 cations 4, 160, 282 Ka 467–8 supercritical 269 configurations 153 in biological systems 471 triple points 270–1 stability 161 calculating pH 466–70 use in fire extinguishers 236 ccp structures 276, 280 calculating pH change in 470 carbon monoxides 213, 372, 620 Celsius 300 preparing solution with predetermined in biological systems 582–3 cell diagrams 509, 525–6 pH 469 a-carbons 968 copper and hydrogen 513 burettes 472 racemisation of 970 silver–copper cells 510 but-2-enes 713, 717, 725 carbon tetrachlorides 189–90, 245 cell potentials (Ecell) 511 butan-1-ols 396 carbonates 164, 585 calculating effect of concentration on 523–4 butan-2-ols Ksp at 25° 404 calculating equilibrium constants from 522 enantiomers 766 carbonation of Grignard reagents 1020–1 predicting 517–18 specific rotations ([a]) 777 carbon–halogen bonds 790–1 relationship between concentration, Gibbs structure and mirror images 763–4 carbonic acids 382, 620, 635, 840 energy and 520–6 butanals 949 carbonyl groups See also aldehydes; ketones cell reactions 506 1H-NMR spectrum 913 addition of alcohols 955–9 electrolysis of potassium sulfates 529–30 boiling points 948 addition of ammonia, amines and related fuel cells 537 butane 62, 268, 760 compounds 959–64 lead storage batteries 533 boiling points 248–9 addition of other carbon nucleophiles 955 nickel–metal hydride (NiMH) batteries 535 chemical equations 82 boiling points 948 predicting 517–18 reaction rates 648–9 electron density model 951 cellulose 984, 1002–3 structures 699 molecular vibrations 883 structures of plant walls 1003 butane-1,2,3-triol stereocentres 771 physical properties 948 ceramics 287–9 butanoic acids reactions with addition of Grignard applications of advanced 289 boiling points 1018 reagents 951–5 piezoelectric 289 IR spectrum 890 structure and bonding 943 superconductors 289–90 by-products 98 carborane acids 465 CFSE 571–2 a-carboxyl group pKa 1067 Chadwick, James 10 C carboxyl groups 1012 chair conformations 703–4 13C-NMR spectroscopy 894 nomenclature 1014 cyclohexane 704 13C-NMR spectrum 906–8 reductions 1038 d-glucopyranose 992 aldehydes and ketones 913 carboxylic acid derivatives d-glucose 995 alkanes 909 hydrolysis 1032–6 interconversions 705–6 alkenes 910 reaction with alcohols 1031–2 maltose 1001 benzenes 911–12 relative reactivities of 1042 monosaccharides 991–2 chemical shifts 907 carboxylic acids 57–8, 833, 835 chalcocites 589, 611 citric acids 907 1H-NMR spectrum 913 chalcogens 17 cadmium 266 acid halide formations 1028 chalcopyrites 486, 589 caesium 265 acid–base reactions 1023–5 Chanteau, Stephanie 46 caesium chlorides 283 base reactions 1025–6 charge neutralisation processes 49–50 ’cage’ ligands See hexadentate ligands boiling points 948 Charles, Jacques-Alexandre-César 221 Cahn–Ingold–Prelog (CIP) rules 718 carbonation of Grignard reagents 1020–1 Charles’ law 221 calaverites 486 esters 1013 chelate complexes 551 calcites 775, 776 formation of hydrolysis of nitriles 1021 chelate effect 565–8, 959 calcium 163 hydrolysis of derivatives to form 1021–2 chelate rings 551 oxidation number 497 IR spectrum 890–4 chelating ligands 551 calcium carbides 237–8 nomenclature 945, 1013–15 chemical equations 6, 82 determining molar mass 234–5 nucleophilic acyl substitutions 1026–7 balancing 83–4 calcium carbonates odiferous properties 1018 butane 82 calculating pH 440 oxidation of alkylbenzenes 1020 chemical equilibrium 350, 356 decomposition 339 oxidation of primary alcohols and adding catalysts to 371 levels in marine environments aldehydes 1020 adding inert gases at constant volume 370 348 oxidisation processes 967–8 adding/removing products or reactants calcium chlorides 163 physical properties 1017–19 367–8 calcium oxides 163, 164, 588 reaction with alcohols 1028–31, 1032 calculating equilibrium concentrations from calcium silicates 588 reaction with ammonia and amines 1036 initial concentrations 376–80 calorimeters 306 reduction into primary alcohols 826 calculating Kc from equilibrium Campbell Microanalytical Laboratory reductions 1038 concentrations 373–5 88 structural formula 57–8 changing direction of 355 candelas 27 structure and bonding 1012 changing pressure in gaseous reactions capillary action 260 synthesis of amines from 1039 368–70 capsaicin 837 use of its derivatives in medicine 1019 changing temperature in reaction car industry and sustainable fuel carnosines 1062 mixtures 370–1 alternatives 537 carnotites 585 and Gibbs energy diagrams 359–62 carbanions 952 cassiterites 607 and Gibbs energy 337–9 carbocations 725 catalysis 680, 1060 how systems change to establish 353–4 order of stabilities of alkyl 727 catalysts 680–4 Le Châtelier’s principle 366–7 relative stabilities 726–8, 803 chiral inorganic 781 manipulating constant expressions 355–6 carbohydrates 984 See also disaccharides; effect on equilibrium 371 mixture compositions for nitrogen dioxide monosaccharides; oligosaccharides effect on reaction rates 647 and dinitrogen tetroxides 352 chair conformations 992 catalytic converters 372, 632, 681 multiplying coefficients by a factor 355–6 carbolic acids 836 See also phenols catalytic cycles 679 reversibility of reactions 351

I-1144 Index

BMIndex I-1144 1 June 2015 9:06 AM selected substances at 25° 335 chromates, Ksp at 25° 404 condensed structural formulae 43 simplifying approximations in chromic acids 833, 967 alkanes 699 calculations 380–1 chromium 12, 265, 590–1 configurational isomers 713 chemical formulae ground-state electron configuration 152–3 conformationally locked isomers in determining 90–1 chymotrypsins 778 cycloalkanes 706 mole ratios from 89–90 cinnabars 486, 592, 611 conformations See also boat conformations; molecules 40–1 cis alkenes 713 chair conformations chemical kinetics 640–1, 664–71 cis isomers 46, 560 alkanes 700–1 chemical reactions 4, 82 4-methylpent-2-ene 717 cycloalkanes 703–8 Gibbs energy diagrams 360–2 achiral 773 eclipsed 700 mechanistic arrows in 49–50 cis–but-2-enes 713 envelope 703 ο mole ratios in 94–5 enthalpy of hydrogenation (DfH ) 733 monosaccharides 991–2 stoichiometry 93–4 cis–cyclooctenes 720 potential energy difference between 700 chemical shifts cis–1,2-dimethylcyclohexanes 732 staggered 700 13C-NMR spectrum 907 cis–1,2-dimethylcyclopentanes 762 conformers 700 alcohols 910 cisplatins 560 conjugate acid–base pairs 434–5 aldehydes and ketones 913 11-cis-retinal 714, 961 identifying pairs in Brønsted–Lowry alkanes 909 cis–trans isomers 560 reactions 435 alkenes 909 alkenes 713 relative strengths 450 amines 912 configurations in alkenes 717 conjugate acids 434 average values of hydrogen atoms 902 cycloalkanes 707–8 conjugate bases 434 carboxylic acids 913 cycloalkenes 720–1 determining Brønsted–Lowry acids 435 correlation chart for 1H-NMR 901 drawing 708 constant pressure calorimeters 308, 309–10 correlation chart for carbon functional polyenes 721 constitutional isomers 760, 968 See also groups 907 citric acids 1010 tautomers esters 913–14 13C-NMR spectrum 907 alkanes 61–2, 709–10 identifying isomers using data from 902–3 citronella 942 boiling points 846 chemical symbols 11 citrulines 1065 drawing 63 chemical thermodynamics 296–7, 298–9 See Claude, Georges 616 equivalent hydrogen atoms 899 also enthalpy (H); entropy (S) closed systems 300 recognising 62–3 first law 302–8 close-packed structures of solids 274–7 Coomassie Brilliant Blue 1072 heat and temperature concepts 299–300 cobalt ion oxidation states 549 coordinate bonds 556 important equations 364 codeine 850–1, 857 coordination chemistry 556 reversible processes 336 coffee cup calorimeters 308 coordination complexes 481 second law 327–8, 331 cohesive forces 260 coordination compounds 556 state functions 301 colchicines 917 coordination isomers 559 third law 328–30 cold fusion and flawed experiments 311 copper 265, 402, 589–91, 607 chiral drugs 779, 780–1 collagen 1060 electrolysis 612 chiral inorganic catalysts 781 colligative properties of solutions 410–23 electron density plots 140 chiral isomers 773 boiling point elevation and freezing point by-products 612 chiral ketos 970 depression 414–16 ground-state electron configuration 153 chiral ligands 781 estimating freezing points using 415 reaction with silver nitrates 506 chirality 760, 764 measuring solute dissociations 420–3 reaction with zinc 505 amino acids 1062–3 mole fractions (x) 411 specific heats and molar heat capacities in biological world 778–9 osmosis and osmotic pressure 416–20 at 25° 305 carbohydrates 986 Raoult’s law 411–12 using crystal structure data to calculate detecting properties in laboratories 775–8 solutions with more than one volatile radius 285–6 chitins 989 component 413–14 copper acetate complex 552 chlor–alkali processes 613 collision theory 664–71 core electrons 148 chloric acids 626 activation energies 665 Corey, Robert 1077 chloride salts 401 molecular orientation factors in 664–5 correlation tables 883–4 chlorination temperature factors 667–70 corrosion 526–7 aromatic compounds 743 colour wheels 574 mechanisms of 527 haloalkanes 794–7 colours methods to protect against 527 chlorine dioxides 625 detection in human eyes 714–15 Coudamin® 1019 chlorine pentafluorides 187–8 transition metal complexes 574–8 coulombs (C) 506, 531 chlorine trifluorides 179–80, 186 combustion reactions 92–3, 306, 318, 332 Coulomb’s law 172 chlorines 12, 13, 241 common ionic effects 407 coumarin 1019 addition to alkenes 730–3 calculating molar solubilities (s) 407–8 counterions 556, 559 disproportionation reactions 614–15 common ions 407 nomenclature 564 free radicals 679 common logarithms 521, 523 covalent bonding 4, 172, 264, 556 industrial and commercial applications complementary colours 575 bond lengths 191–3 613–14 complex splitting patterns 903 characteristics of 173 intermolecular forces 242 complexes 549 dipole moments 189–90 oxides of 625 compounds 4, 48 enthalpies 320 shielding 895 calculating amount of elements within in p-block elements 626 chloroacetic acids 459–60 89–90 properties of 189–95 chloroauric acids 520 unsystematic names 50 of solids 263 2-chlorobutanes 725 comproportionation reactions 533 using energy stored in 194 chloroethanes 724 concentration valence bond theory 196–205 chloroethenes 613 calculating effect on cell potentials 523–4 Creutzfeldt Jakob disease (CJD) 1084 chlorofluorocarbons (CFCs) 678–9, 792 relationship between cell potential, Gibbs Crick, Francis 286 chloroforms 189–90 energy and 520–6 critical points 269 nomenclature 793 of solutions 100–5 critical pressures 269 2-chloro-2-methylpropanes 726 units of 31 critical temperatures (Tc) 269 1-chloropropanes 726 using Nernst equation to determine 524–5 cryolites 604, 605 1-chloropropane spectrum 905 concentration cells 525–6 crystal field splitting energy (CFSE) 571–2 2-chloropropanes 724, 726 concentration tables 373–4 crystal field theory, bonding in octahedral 2-chlorotoluene and 4-chlorotoluene summary of 375 coordination complexes 570–2 spectra 912 condensation 245, 260 crystal lattices 277–9, 285 chlorous acids 626 phosphates 634 crystalline defects 287 cholesterol 775 condensation points 268 crystalline solids 279

Index I-1145

BMIndex I-1145 1 June 2015 9:06 AM C-terminal amino acids 1074 detergents 1048, 1072 disproportionation reactions 533, 569, 584 See cubic close-packed (ccp) structures 276, 280 deuterium 11 also dismutations cubic structures 279–81 dextrorotatory compounds 776, 777 chlorines 614–15 cumulative formation constants (bn) dextrorotatory enantiomers 987 dissociation reactions 106, 420–3 565, 567–8 dextrose 988 compared with dissolutions 421 cuprites 589 diabetes and management 998 diprotic acids 635–6 Curie, Marie 612 diagrams, Gibbs energy change (DG) 302 dissolution processes 392 Curtis, Neil 555 dialysing membranes 416 compared with dissociations 421 cyanidium caldarium 430 dialysis 416 gas–liquid solutions 394, 395 cyanohydrins 955 diamagnetism 154, 548, 578 disubstituted benzenes nomenclature 740 cyclic acetals 959 transition metal complexes 570 disulfide bonds 1079 cyclic amides 1013, 1017 See also lactams diamonds 264, 279, 642, 696 disulfides 847 cyclic ethers 842 metastability of 671 DNA 250, 286, 835 cyclic hemiacetals 956, 990, 993 properties of 288 effect of radiation on 175 cyclic hydrocarbons 702, 719–20 diastereomers 760, 761–2, 771 enzyme–substrate complex (E.S) 682 nomenclature 719–20 diatomic molecules 173, 241 stereoviews 48–9 cycloalkanes 58, 702 heteronuclear 211–12 UV damage to 682 cis–trans isomers 707–8 homonuclear 210–11 2,4-DNP test 962 See also Brady’s reagents conformationally locked isomers 706 diaxial interactions 706 Dobson units (DU) 678 conformations 703–8 diazenes 631 donor atoms 551 IHD 876 diazonium salts 859–60 donor covalent bonds 556 nomenclature 702–3 dibromobenzenes 734, 735 L-DOPA 781 cycloalkenes dichlorine heptaoxides 625 doped semiconductors 287 addition of bromine and chlorine 730 dichlorine monoxides 625 double bond equivalents 876 See also index of cis–trans isomers 720–1 1,1-dichloroethane 898, 899 hydrogen deficiency (IHD) nomenclature 719–20 1,2-dichloroethane 613, 899 double bonds 177 cyclobutane structural formula 702 dichloromethane 834 designating orientation of groups 717 cyclohexane-1,3-diols 774 diethyl ethers enthalpies 320 cyclohexanes 703–4 boiling points 948 nomenclature 719 disubstituted derivatives 774 IR spectrum 888 restricted rotations 713 interconversions of chair to boat valence bond theory 203 phase change data 268 conformations 705–6 downfield positions 897 vapour pressure variations 262 mass spectrum 878 dry cell batteries 533–5 differential rate laws 649–55 See also rate structural formula 702 dry ice 268 cyclohexenes 797 laws sublimation 267 1,2-cyclopentanediols 773 calculating rate constant from data 651 dynamic equilibrium 350, 362, 402 cyclopentanes 773 calculating reaction rates from rate structural formula 702 laws 654–5 E cyclopentene IR spectrum 887 concentration and time data 650, 651 determining exponents of 653 eclipsed conformations 700 cysteines 628, 629 eclipsed interaction strains 703 cytochromes 1081 determining order of reactions 650 method of initial rates 651 effective concentrations 523 See also activities relationship between order of reaction and effective nuclear charge (Zeff) 144 D change in concentration 654 effusion processes 228 D,L systems 987 diffractometers 285 Eigler, Don 8 d orbitals 141, 548, 549 diffusion processes 228 Einstein, Albert 123 boundary surface diagrams 142 dimensional analysis 30–2 electrical conductivity of strong and weak degeneracy 570–1 acids 442 dimers 423, 1017 electron energies and distribution in free electrochemical changes 507 3,3-dimethylbutan-1-ol spectrum 910 transitional metal ions 570 electrochemical potentials 506, 511 See also 1,2-dimethylcyclohexene 732 DaimlerChrysler 537 cell potentials (Ecell) Dalton (Da) 12 1,2 dimethylcyclopentane 559 electrochemical reactions 531–2 Dalton, John 6 cis–trans isomers 707–8 electrochemistry 495, 507, 569 Dalton’s atomic theory 6–7 isomers 46 electrode reactions Dalton’s law of partial pressures 231–2 dimethyl ethers 482 lead storage batteries 532–3 dative bonds 556 boiling points 844 nicad batteries 535 daughter ions 879 structural formula 43 electrolysis 298, 528–31 Davisson, Clinton 133 structures 842 aluminium purification 603–4 Davy, Humphry 630 2,4 dimethylhexane 60 in aqueous solutions 529–31 d-block elements 16, 156, 161, 265–6, 548, 2,2-dimethylpropane boiling points 247 calculations related to 532 602 See also transition metals 2,2-dimethylpropanol-1-ol spectrum 910 chromium 591 d–d transitions 574, 577, 578 dimethyl sulfides 629 predicting products in 530–1 DDT 798 dinitrogen oxide resonance structures 181–2 purification of copper 589–90, 612 de Broglie equation 133, 135 dinitrogen tetroxides refining process 586 de Broglie, Louis 133 decomposition 350–1, 360–1, 373 electrolysis cells 528–31, 604 decane equilibrium mixture compositions 352 compared with galvanic cells 528–9 boiling points 247 Gibbs energy diagrams 361 fluorines 613 IR spectrum 886–7 predicting equilibrium shifts 371 electrolytic cells 528 degenerate energy levels 142–3 diols 823 electrolytic chor–alkali processes 614 degenerate orbitals 570–1, 572 dipeptides 1074 electrolytic conductions 508 degrees of saturation 876 dipolar forces 246, 247–9, 263 electromagnetic radiation 120, 121–2, 881 dehydration 831–3 dipole moments 189–90 applications of 124 L-dehydroascorbic acids 997 dipole–dipole forces 246 See also dipolar and skin cancers 175 dehydrogenation 807 forces electromagnetic spectrum 122 delocalised bonds 196, 263 dipole-induced dipole forces 246 electromotive forces 507 ® Demerol 851 diprotic acids 434, 623, 624, 635 electron affinity (Eea) 159–60 Democritus 4 Ka 447 changes with atomic numbers 159 denaturation processes 1082 titrations and equivalence points 478 electron configurations 149–55 density of isomeric alkanes 710 diprotic bases 434 heteronuclear diatomic molecules 211 b-2-deoxy-d-ribofuranose 990–1 disaccharides 999–1002 octahedral transition metal complexes 572 depositions 267 three-dimensional structures 1001–2 shorthand 151 desalination plants 417, 418 dismutations 584 electron density distributions, nitrogen deshielding effects 895, 897 dispersion forces 246–7, 263 compounds 631

I-1146 Index

BMIndex I-1146 1 June 2015 9:06 AM electron density models racemic mixtures 778 for heterogeneous systems 358–9 aldehydes 944 resolution of 780 manipulating 355–6 carbonyl groups 948, 951 specific rotations a( ) 777 writing expressions for 354 methanethiols 845 endergonic reactions 333 equilibrium constant expression (Kp) for pentanes 708 endothermic reactions 308, 323, 332–3, gases 354–5 electron density pictures 139–40 370, 372 equilibrium constants (K) 350–9, 521–2 electron density plots 139 gases in organic solvents 393 calculating 364–5 copper 140 potential energy diagrams 666 calculating temperatures not at 25° 365–6 d orbitals 145 predicting 371 calculating from cell potentials 522 hydrogen 140 endpoints 472 magnitude of 356 s and p orbitals 144, 145 energy See quantisation of energy predicting acid–base reactions 854 electron paramagnetic resonance (EPR) 917 energy changes and dissociation of acids in equivalence points 472 See also stoichiometric electron spin 137 aqueous solutions at 25° 462 points electron spin resonance (ESR) 916, 917 energy diagrams diprotic acids 478 electron transfer reactions See redox reactions conformational analysis of ethane 701 strong acid–strong base/strong base–strong electronegativities 174 hydrogen halides addition to alkenes 726 acid 474 electron–electron interactions 143 SN1 reactions 802 weak acid–strong base/weak base–strong electron–electron repulsions 143, 144, SN2 reactions 801 acid 477 152, 576 two-step exothermic reactions 672–3 equivalent hydrogen atoms 897–9 effect on ionisation energies 158 two-step intermediates 666 Ertl, Gerhard 681 electronic conductions 508 energy level diagrams erythritols 995 electronic factors 829 designating orbitals in 149 erythroses 770 electronic structures 628 helium 143 Escher, MC 278 electronic transitions 19, 126, 574 hydrogen 131, 143 ESR 915, 917 hydrogen 142–3 light 130–2 esterases 780 representations of 130 multi-electron systems 144 esters See also Fischer esterifications; lactones; transition metal complexes 578 sp hybrid orbitals 202, 204 transesterifications electrons 9, 10, 18–19 sp2 hybrid orbitals 200, 203 of acetic and benzanoic acids 1010 depictions of orbitals 139–40 sp3 hybrid orbitals 198, 200 carboxylic acids 1013 effect of nuclear charge 143 sulfur 152 chemical shifts 913–14 effect of other electrons 143 enols 950, 968, 971 conversion into 3° alcohols 827 equations for 134 achiral and chiral 970 hydrolysis 1032–5 geometry 195 forms of 969–70 of inorganic acids 835 linear geometry 183 enthalpy (H) 299, 308–23 IR spectrum 890 lone pairs 42, 178 bond enthalpies 318–21, 323 methanethiols 841–2 multi-electron systems 143 denoting changes in 300–1 nomenclature 1016 octahedral geometry 187–8 dissociation of acids in aqueous solutions reaction with alcohols 1031, 1032 one-electron system 142 at 25° 462 reaction with ammonia and amines optimum geometry for pairs 182 flawed measurements and experiments 311 1036, 1037 orbital electron distributions 139–42 gas–liquid solutions 393 reaction with Grignard reagents 1040–1 orbital energies 142–5 Hess’s law 312–14, 316 reduction into 1° alcohols 826 orbital sizes 140–1 standard enthalpy of formation 314–18 reductions 1038 properties of 132–5 standard enthalpy of reaction 310–12 ethane-1,2-diamine 766 quantisation of energy 135–9 enthalpy diagrams 317 ethanes restrictions on quantum numbers 138 sodium chloride lattice enthalpy 321 energy diagrams 701 shapes for five sets of pairs 187 solids dissolving in liquid 399 phase change data 268 ο shapes for six sets of pairs 188 enthalpy of hydrogenation (DfH ) alkenes staggered conformations 700 tetrahedral geometry 184 732–3 ethanethiol boiling points 846 trigonal bipyramidal geometry 185–7 enthalpy of solution (DsolH) 399–400 ethanols 65–6, 396, 464, 797 trigonal planar geometry 183 aqueous sodium bromide 401 pKa 827 unequal sharing of 173–4 group 1 metal halides at 25° 400 as alternative fuel and sustainability 984–5 wave patterns 133 enthalpy change (DH) 267, 268 boiling points 844 ο wavelength (l) 134 entropy (S) 299, 323–7 calculating DrG 334–5 electron-withdrawing groups 856, 1024 denoting changes in 300–1 hydrogen bonds in aqueous 397 electrophiles 482, 723 and entropy change 324–5 limiting reagents 96–8 electrophilic addition reactions to alkenes factors affecting 325–7 metabolism in body 663 723–33 predicting algebraic sign of 327 molecular vibrations 883 electrophilic aromatic substitution and probability 323–4 phase change data 268 reactions 742–7 envelope conformations 703 production of 825 electrostatic forces of solids 263 enzyme catalysis 681 relative acidities 838 elemental analysis 88, 90 enzyme inhibitors 684 specific heats and molar heat capacities elemental fluorines 612–13 enzyme kinetics 681–4 at 25° 305 elemental gases 252 induced fit hypothesis 682 structural formula 43 elemental nitrogen 608 lock-and-key hypothesis 682 structures 48, 825 elemental oxygen enzyme-catalysed oxidations 722 ethenes 711, 712 importance in biosphere 628 enzymes 681 See also biocatalysts; bonding 202–3 reaction rates 654–5 esterases orbital overlaps 203 elementary reactions 671, 672, 681 distinguishing between enantiomers 778 ethers 842–5 elements 4, 17–18 enzyme–substrate complex (E.S) 681 IR spectrum 888 emission spectrum 127–8 DNA 682 nomenclature 842–3 hydrogen 131 EPR 917 physical properties 843–4 empirical formulae 87–93 equatorial bonds 704 reactions of 844–5 calculating from percentage composition 92 methyl groups 706 ethoxide ions 797 determining 91–3 equatorial ligands 557, 558 ethyl acetates 1029 en ligands 566, 567, 766 equilibrium See chemical equilibrium ethyl benzoate spectrum 911 enantiomers 758, 760, 762–75 equilibrium arrows 350 ethyl butanoate IR spectrum 891 a-amino acids 1063 equilibrium constant expression (Kc) 351–2 4-ethyl-3,6-dimethyloctane 701 analgesics 851 calculating equilibrium concentrations 2-ethyl-3-methylpent-1-ene 716 asymmetric synthesis 781 376–80 ethylene glycols 823 complicated organic molecules 766–8 calculating from equilibrium ethylenediamines 551, 563 See also ethane- geometries of inorganic 765–6 concentrations 373–5 1,2-diamine how enzymes distinguish between 778 compared with position of equilibrium 357 enantiomers 766

Index I-1147

BMIndex I-1147 1 June 2015 9:06 AM ethylenediaminetetraacetic acids formaldehydes 944, 949 gas stoichiometry 237–41 (H4EDTA) 551–2 nomenclature 945 determining partial pressures 240–1 ethynes 65–6, 711, 716 treatment for urinary tract infections 963 ethyne production 237–8 bond angles 712–13 formic acids 449 mole conversions 239–40 bonding 203–5 Franklin, Rosalind 286 gaseous solutions 392 industrial production 237–8 free atoms 4 gases See also real gases non-hybrid overlaps 204 free electrons 136 Avogadro’s law 222 eugenols 836 equations for 134 Boyle’s law 221 Euston, Robert 779 free induction decay (FID) 896 calculating tank pressure 222–3 excess reagents 96 free radicals 679, 794, 917 Charles’ law 221 excited states 16, 19, 126 freezing point depression (DTf) 414–16 condensation points 268 ο configurations 155 calculating molar mass 415–16 Df H at 25° 319 exergonic reactions 333 estimating for salt solutions 421 effect of change in pressure on equilibrium in exothermic reactions 308, 309–10, 318, 370, using colligative properties to estimate 415 reactions 368–70 624, 666 freezing points, nonvolatile solutes 414 effect of compressing quantity into smaller ammonia 370 frequency (v) volume 230 catalytic reductions 736 electromagnetic radiation 122, 881 effect of doubling molecules in fixed energy diagrams 672–3 light 120 volume 230 gases in water 393 wavelength conversion 121 elemental 252 hydrogen halides addition to alkenes frequency factors 668 ideal gas equations 222–4 725–6 Friedel–Crafts acylation 746, 949–50 increase in entropy (S) 325 methanol 321 Friedel–Crafts alkylation 745, 746 ionisation energies (Ei) 157 octane 332 b-d-fructofuranose 991 molar masses 229 writing thermochemical equations for d-fructose 988 molecular energy distributions 226–7 312 fructose 991 molecular speeds of 224–6 explosives 194 fuel cells 537–8 phase reactions with fast, reversible extensive properties 305 breathalysers 538 steps 673–4 E,Z systems fuel industry, alternative fuels 537 pressure (p) 220–1 alkenes 718–19 functional groups 54–7 rates of gas movement 228–9 assigning priorities in 719 alcohols 822 relationship between speed and energy 226–7 carboxylic acids 1012–13, 1016 reversible reactions 336 F characteristic IR vibrational frequencies solubilities in water 393 f orbitals 142, 148, 548 884 standard states 301 fac isomers 561 common 55 writing expressions for Kp 354–5 face-centred cubic structures 280, 281 identifying using IR spectroscopy 884 gas–liquid solutions 393–6 sodium chloride 282–3 interconversion of 1042–3 gemstones 546 facial isomers 561 order of precedence for nomenclature 947 geraniols 834 Faraday, Michael 531, 734 selective reduction of 1040 Gerlach, Walter 137 Faraday constant 520 thiols 845 germanium 12, 607, 620 Faraday’s law 531–2 furan 739 Germer, Lester 133 fats 1045, 1046 furanoses 990 Gibbs, Joseph Willard 299 fatty acids 1044 Gibbs energy change (DG) 520–1 f-block elements 16, 156, 161 G calculating 521 feldspars 621 GABA 1065 and spontaneity 302 ferritins 583 Gabriel synthesis 853 Gibbs energy diagrams 359–62 ferrochromes 590 d-galactosamine 989 chemical reactions 360–2 ferromagnetism compared with d-galactose 988 hypothetical reactions 361 paramagnetism 580 galena 486, 611 phase changes 359–60 fingerprint regions 883 gallium 486, 606, 620 Gibbs energy (G) 296, 299, 328, 332–9 fingerprinting identification research 885 gallium arsenides 610 denoting changes in 300–1 fireworks and redox reactions 496–7 Galvani, Luigi 506 equilibrium 337–9 first law of thermodynamics 302–8 galvanic cells 504–11 predicting outcome of reactions 362 heat capacity and specific heat 304–6 compared with electrolytic cells 528–9 relationship between cell potential, volume first-order rate laws 655–9, 671 copper–silver nitrate reactions 506 and 520–6 concentration–time calculations 656 notation and cell reactions 509–10 relationship between constant and equilibrium determining order of reactions 657–8 predicting cell reaction and potential constants 362–6 half-life reactions 658–9 517–18 and work 336–7 kinetics for reactions 664 processes in 507–11 glass 286–7 Fischer, Emil 987, 1028, 1074 reduction potentials 511–20 d-glucitol 995 Fischer esterifications 1028–31 setting up 506–7 d-gluconate 996 reversibility of reactions 1029 standard reduction potentials 514 a-d-glucopyranose 988, 990, 991 Fischer projections 987 using Nernst equations 523 b-d-glucopyranose 990, 991, 993 aldotrioses, tetroses, pentoses and zinc–copper reactions 505 chair conformations 991 hexoses 988 galvanisation processes 527 Haworth projections 993 a-amino acids 1063 gamma rays 122 d-glucopyranose 992 converting to Haworth structures 990 garnierites 266 d-glucosamine 989 Fleischmann, Martin 311 gas density d-glucose 988 flotation processes 586 determining minimum temperature for hot air chair conformations 995 fluorines 251, 730, 790, 791 See also balloons to rise 236–7 converting Fischer projection to Haworth elemental fluorines effect on frequency of molecular structure 990 boiling points 246 collisions 237 enzyme–catalysed oxidations 996–7 compounds formed between platinum features of 235–6 oxidation 996 and 617 practical applications of 236 glucose 986 See also dextrose dispersion forces 246 gas discharge tubes 9 chemical reactions 94–5 electron affinity (Eea) 159 gas mixtures enantiomers 761 intermolecular forces 242 Dalton’s law of partial pressures 231–2 melting points 264 molecule bonding 173, 627 determining density 235–7 glucose oxidase 998 shielding 895 determining molar mass 234–5 d-glucuronic acids 996–7 use in pharmaceuticals 798 determining pressures and mole d-glyceraldehyde 987 fluorite structures 283 fractions 232–3 l-glyceraldehydes 987 fluoroapatites 633 homogenous mixtures 231 (R)- and (S)-glyceraldehydes 986–7 formal charge of atoms 179 limiting reagents 238–9 glycine, titrations 1069, 1070

I-1148 Index

BMIndex I-1148 1 June 2015 9:06 AM b-1,4-glycosidic bonds 1002 amines 912 effect on poisonous proteins 1084 glycogens 1002 benzenes 911–12 treatment for jellyfish stings 1085 glycols 823 carboxylic acids 913 heat capacities 304–6 glycosides 993–5 1-chloropropane 905 heat of reaction at constant volume (qv) 306 structural formula 994–5 correlation chart for chemical shifts 901 H4EDTA 551–2 a-1,4-glycosidic bonds 1001, 1002 determining structural formula from number Heisenberg, Werner 135 See also uncertainty a-1,6-glycosidic bonds 1002 of signals in 899 principle glycosidic bonds 999, 1001, 1002 with integration for benzyl alcohols 900 helium See also liquid helium gold 402, 486, 592 with lines of integration of tert-butyl electron configurations 149 calculating heat absorption from temperature acetate 900 emission spectrum 143 change 305–6 toluene 911 ionisation energy (Ei) 143 ccp structures 277 1,1,2-trichloroethane 904 liquid 268 extraction processes 567–8, 586 Haber–Bosch process 350, 608, 681 molecular orbitals (MOs) 206–7 specific heats and molar heat capacities haem groups 582 superfluidity 616 at 25° 305 haematites 587 a-helix patterns 1078, 1081 gold foil experiment 9–10 haemoglobins 582, 1060, 1079–80, 1081 hemiacetals 955–6, 989 gold hydroxide, limiting reagents 97–8 haems 1080 conversion to acetals 957–8 Gouldsmit, Samuel 137 half-cell reactions in dry cells 534 formation of 956–7 grape sugars 988 half-cells 506 hemicelluloses 1003 grapefruit mercaptans 846 calculating potentials 514–15 hemiketals 956 graphites 264, 536, 642, 696 cell diagrams 513 Henderson–Hasselbalch equation 468, 476, specific heats and molar heat capacities Nernst equation 525 1069 at 25° 305 half-equations 500 Henry’s law 395–6 standard states 315 half-life reactions Héroult, Paul 605 greenhouse gases 252 first-order 658–9 hertz (Hz) 881 Grignard, Victor 951–2 second-order 661–2 Hess’s law 312–14, 316 Grignard reagents 826–7, 951–5, 959 zero-order 663 and bond enthalpies 319–21 addition of carbon dioxide to form carboxylic halic acids 625 dissociation of acids in aqueous acids 954–5 halide ions 551, 797 solutions 461 addition to aldehydes 953–4 halides 161 and lattice enthalpies 323 addition to formaldehydes 953 Ksp at 25° 404 standard enthalpy of formation 317 addition to ketones 953–5 structures 283 heteroatoms 842 carbonations 1020–1 Hall, Charles 605 heterocyclic amines 847 reaction with esters 1040–1 Hall–Héroult process 603, 605 heterocyclic aromatic amines 847, 1068 reaction with protic acids 952–3 a-haloaldehydes 970 pKa and pKb at 25° 855 ground states 19, 126, 145 haloalkanes 724, 791 solubility 852 conditions for 146 b-elimination 807–10 heterocyclic compounds 738 electron configurations 150 chlorination and bromination 794–7 heterogeneous catalysts 680, 681 group 13 elements 602–6 leaving groups 804 heterogeneous equilibrium 358 HSAB principle 486 nomenclature 792–4 heterogeneous reactions 647 hydride anions 620 nucleophilic substitution compared with Kc 358–9 reactivity of compounds 619–20 b-elimination 810–12 heterolytic cleavages 461 valence-electron configurations 602 nucleophilic substitutions 799–806, heteronuclear diatomic molecules 211–12 group 14, oxoacids 463 829–30 hexadentate ligands 554, 555 group 14 elements 606–8 preparation into alcohols 826 hexagonal close-packed (hcp) structures 276, 281 oxidation states 606 preparation into amines 852–3 hexagonal geometry reactivity of compounds 620–2 principal reactions of 797 face-centred cubic arrangements 281 valence-electron configurations 606 reactions with hydrohalic acids 828–30 solids 275–6 group 15 elements 608–12 SN1 versus E1 reactions 810 hexanes 58, 397, 399 carbon cycle 635–6 SN2 versus E2 reactions 811 mass spectrum 878 nitrogen cycle 630–2 structures 803–4 hexanoic acid molecular vibrations 883 oxoacids 463 haloforms 793 6-hexanolactams 1017 phosphorus cycle 632–5 halogenated methanes 793 hexoses 988 reactivity of compounds 622–3 halogenated organic compounds 798 hexylresorcinols 836 group 16 elements 611–12 a-halogenations 970–1 high resolution mass spectrometry 879 nomenclature 624 halogenations 793 determining molecular formula from 880 oxidation states 624 of alkanes 793 highly acidic environments 430 oxoacids 463 aromatic compounds 742 high-molar mass alkanes 709 oxygen cycle 627–8 halogens 17, 161, 241–2 high-molar mass amine solubilities 852 reactivity of compounds 623–5 oxoacids 464 high-spin configurations 572, 573, 579 sulfur cycle 628–9 pharmaceutical drugs containing 798 high-temperature superconductors (HTS) 290 group 17 elements 612–15 a-haloketones 970–1 Hinshelwood, Cyril 667 composition of concentrated hydrohalic halonium ions 731 histidines 1068 acids 625 halous acids 625 histidine ligands 583 oxidation states 625 hard Lewis acids 484, 486, 603, 606, 608 homogeneous catalysts 680 oxoacids 463, 625–6 ranking 485 homogeneous reactions 358, 647 reactivity of compounds 625–6 hard Lewis bases 484 homolytic cleavages 461 group 18 elements 616–19 ranking 485 homonuclear diatomic molecules 210–11 compounds of 617 hardening process of oils 1046 honey and antibacterial properties 1000 group theory 570–1 hard–soft acid–base principle (HSAB) 485–6 HSAB principle 485–6 guanidines 857 hashed wedges 47 Hückel, Erich 738 pKb 1068 Haworth, Sir Walter Norman 990 Hund’s rule 152, 154, 155, 206, 208, 572 guanidinium ions 857 Haworth projections hybrid orbitals 197–202 See also sp hybrid gypsum 486 b-d-glucopyranose 993 orbitals; sp2 hybrid orbitals; sp3 hybrid d-glucopyranose 992 orbitals H maltose 1001 hybridisation of atomic orbitals 735 1H-NMR spectroscopy 894 monosaccharides 990–1 hydrate isomers 559 1H-NMR spectrum 896–7 hcp structures 276, 281 hydrates 41 alcohols 910 head lice treatments 798 hydration 723, 728 alkanes 909 heat 299–300 hydration enthalpies 399 alkenes 909–10 denaturation process 1082 group 1 metal halides at 25° 400 aldehydes 913 determining 306–8 hydration of ions 398, 505

Index I-1149

BMIndex I-1149 1 June 2015 9:06 AM hydrazines 631 hydrophobic properties 1018 insulin 998 and pH 453–4 hydroxide ions 432, 551 polypeptide chains 1079 hydrazinium chloride, pH 457–8 hydroxides, Ksp at 25° 404 integral membrane proteins 1082 hydrazones 962 hydroxyapatites 635 integrated rate laws 649–50, 655–64 hydride anions 620 a-hydroxycarboxylic acids 955 first-order 655–9, 671 hydride ions 964 hydroxyl groups 822, 825 kinetics for reactions 664 hydrobromic acids 625 nomenclature 823 second-order 659–62, 671 hydrocarbons 58 See also saturated 4-hydroxypentanals 989–90 zero-order 662–4, 671 hydrocarbons; unsaturated hydrocarbons hyperconjugations 727 integration technique 899–901 calculating IHD 876 hypertonic solutions 419 integration values 906 classes of 698 hyperventilation 382 intensity of light 120 cyclic 702 hypochlorite ions 614 intensive properties 305 hydrochloric acids 433, 625 hypohalous acids 625 intercalation processes 536 hydrochlorination 723 hypotonic solutions 419 interconversions, functional groups 1042–3 hydrochlorofluorocarbons (HFCs) 792 intermolecular forces 245–51 hydrofluoric acids 625 I balance between kinetic energies and a-hydrogens 968 ibuprofen, enantiomers in 768–9, 778 241–2 hydrogens 13 ice jackets 274 dispersion forces 246–7 average values of chemical shifts 902 ideal gas equations 222–4, 229–30 strength indicators for 245 electron configurations 149 applications of 234–7 internal energy (U) 299 electron density plots 140 compared with van der Waals equation chemical reactions 302 electronic transitions 142–3 244 complete discharge of batteries 303 emission patterns 128 ideal gases 222, 229–30 denoting changes in 300–1 emission spectrum 143 ideal solutions 412 International Bureau of Weights and energy levels of 129–30 IHD 876–7 Measures 27, 39 interaction energies 173 ilmenites 266, 589 International Union of Pure and Applied ionisation energy (Ei) 143 imidazoles 739, 1068 Chemistry (IUPAC) 17, 50, 516 See also molecular orbitals (MOs) 205–6 imines 960–1 nomenclature molecular speed distributions 225 immiscible liquids 396 naming alkanes 59–61 molecule bonding 172 index of hydrogen deficiency (IHD) 876–7 order of precedence of functional orbital overlaps 197 indium 486, 606 groups 947 oxidation numbers 498 oxidation numbers 603 publications by 51 probable speeds 226 oxidation states 620 interstitial holes 282 writing (Kc) for 354 indoles 739 intramolecular covalent bonds 246 hydrogen bonding 246, 264, 423, 825 induced fit hypothesis 682 iodine-131 658–9 in aqueous ethanol 397 inductive effects 727 iodine 241, 267 carboxylic acids 1017–18 industrial chemicals 163, 164 applications of 615 effect on boiling points 844 inert pair effect 620 boiling points 246 importance in biochemistry 250 inert transition metal complexes 568–9 deficiency in diets 615 peptides 1078 infixes and meanings 65 intermolecular forces 242 polypeptides 1080 infrared (IR) spectrum 883 ion configurations 153–4 primary and secondary amines 851 alcohols 888 ion pairs 421 requirements for formation 249–50 aldehydes 889–90 ion–dipole interactions 249, 398 of solids 263 alkanes 886–7 ion-exchange chromatography 1076 hydrogen bromides 625 alkenes 887 ionic bonding 176–7 hydrogen chlorides 625 alkynes 887 ionic compounds 53–4, 174 reaction in water 434 amines 889 lattice energies 176–7 reaction with gaseous ammonia 436 aromatic hydrocarbons 889 like-dissolves-like rule 398 relative acidities 838 benzene 888–90 nomenclature and chemical formulae for hydrogen cyanides 204–5 carboxylic acids 890–4 common polyatomic 54 hydrogen fluorides 178, 212, 625 determining compound from molecular solubility 106 bonding 173–4 formula and 892 structures 282 dipole moments 189 esters and amides 890–1 ionic products (Qsp) 407 periodic trends in boiling points 251 ethers 888 ionic salts hydrogen halides interpreting 886, 893 quantifying solubilities 402–3 addition to alkenes 724–8 limitations of 894 solubility versus temperature 401 mechanisms of additions 727–8 infrared (IR) spectroscopy 881–5 ionic solids 263, 266 hydrogen iodides 625 characteristic vibrational frequencies of structures 281–3 concentration–time profile of functional groups 884 ionisation energies (Ei) 143 decomposition 647–8 correlation tables 883–4 gaseous atoms 157 estimating initial rate of reactions 644–6 fingerprinting identification 885 helium 144 rate law 649 molecular vibrations 883 irregularities in 158 second-order half-lives 661–2 vibrational spectrum 882 magnesium 158 hydrogen peroxides 623–4 infrared active 883 nitrogen oxides 212 hydrogen selenides 624 infrared radiation 881 ionisation isomers 559 hydrogen sulfate ions, conjugate bases 435 infrared spectrophometers 882 ions 4 See also common ions hydrogen sulfides 624 inhibitors 680 chemical periodicity 160–4 hydrogen tellurides 624 initial pH hydration 398 hydrogenation 238–9, 723 strong acid–strong base/strong base–strong sizes of 160 hydrogenators 239 acid 473 stoichiometry of solutions 106–10 hydrogen–oxygen fuel cells 537 weak acid–strong base/weak base–strong IR spectrum See infrared (IR) spectrum hydrohalic acids 828 acid 475 iridium 592 hydroiodic acids 625 initial rates 648 iron 586–8 hydrolysis 1021–2 inorganic acids 835 bcc lattice 279–80 amides 1034–6 inorganic compounds nomenclature 52–4 corrosion 526 carboxylic acids 1032–6 inorganic phosphates 631, 632, 634, 635 specific heats and molar heat capacities polypeptides 1075–6 inorganic reagents 613 at 25° 305 hydrometers 533 inorganic stereoisomers 781 iron ores 587 hydronium ions 184–5, 432 insoluble properties 399 iron oxide reduction 588 hybrid orbitals 198–9 instantaneous dipoles 246 iron–porphyrin complexes 582 hydrophilic properties 1018 instantaneous rate of change of isobutanes 760 hydrophobic interactions 1080 concentration 644 isobutyl cations 726

I-1150 Index

BMIndex I-1150 1 June 2015 9:06 AM isoelectronic ions 153, 627 kidney stones 409 chlorine fluorides 179–80 relationships between 160 kilograms 27, 39 chlorine pentafluorides 187–8 trends in sequence 160 kilojoules (kJ) 300 chlorine trifluorides 186 isoelectronic points (pI) 1070–1 kinetic energy distributions, reaction mixture at conventions for 177–8 isolated systems 300 varying temperatures 667 dimethyl ethers 842 isomeric cresols 836 kinetic energy (Ekinetic) 123, 665 ethenes 202 isomers 43, 760 See also cis isomers; cis– average energy and temperature 227 hydronium ions 184–5 trans isomers; constitutional isomers; balance between intermolecular attractive methane 184 trans isomers forces and 241–2 methanethiols 845 configurational 713 equations for 224 methanols 822 conformationally locked 706 speed and 226–7 nitric oxides 630 fac and mer 561 Knowles, William 781 oxygen 207 identifying using chemical shift data 902–3 krypton 163, 617, 618 phosphorus pentachlorides 185 relationships among 762 Ksp See solubility products (Ksp) sulfur compounds 629 transition metal complexes 559–60 sulfur dioxides 178–9 using IR spectrum to distinguish L sulfur hexafluorides 187 between 884 labile transition metal complexes 568–9 sulfur tetrafluorides 186 isopentyl acetates’ IHD 877 lactams 1013 sulfur–oxygen bonds 192 tertiary carbocations 725 isophthalic acids 1020 lactic acids, determining Ka and pKa 454–5 isoprenes 712 lactones 1013 triiodide ions 186 2-isopropyl-5-methyl-cyclohexanols 775 nomenclature 1016, 1017 xenon oxides 618–19 isotonic solutions 419 use in medicine 1019 xenon tetrafluorides 188 isotopes 11, 12, 14 lactose 999 ligands 481, 549, 551–5 IUPAC See International Union of Pure and L-amino acids 1065 chiral 781 Applied Chemistry (IUPAC) lanthanoids 16, 548, 602 See also rare earth effect on colours 576 elements en 566, 567, 766 J LAS 1048 identifying 554–5 joules (J) 300, 506 laser light 118–19 in transition metal complexes 553 lattice energies 161, 323 ligand-to-metal charge transfer (LCMT) ionic compounds 176–7 transitions 577, 578 K lattice enthalpies light 120–32 K See acidity constants (K ) a a and Hess’s law 321 absorbance (A) 575 Kamerlingh-Onnes, Heike 290 potassium iodide 399–400 absorption and emission spectra 126–7 Kb See basicity constants (Kb) lattice points 277 atomic spectra 127–8 Kc See equilibrium constant expression (Kc) lattices 277 calculating energy 123 Kekulé’s, August 734 laughing gas 630 See also nitrous oxides effect of polarising filters on 776 Kekulé’s structure 734–5, 736, 838 Lavoisier, Antoine 5, 611, 696 energy level diagrams 130–2 kelvin (K) 27, 300 law of conservation of mass 4, 6 particle properties 122–6 Kendrew, John C 1080 law of definite proportions 4, 5, 6 plane-polarised 776 keratin 1060 law of multiple proportions 7 quantisation of energy 128–30 ketals 956 LCMT transitions 577, 578 wave-like properties of 120–2 keto–enol tautomerism 968–71 Le Châtelier, Henri 366 like-dissolves-like rule 396, 397, 398, 604 acid and base catalysed 969 Le Châtelier’s principle 366–7, 681, 831 limestone 486, 588 a-halogenation 970–1 leaching processes 586, 592 limiting reagents 96–8 racemisation of 970 lead 608 in gas mixtures 238–9 d-2-ketohexoses 988 oxidation numbers 622 Lindemann, Fredrick Alexander 667 ketones 733, 833, 834 Lindlar catalysts 733 13 oxidation states 606 C-NMR spectrum 913 oxides 621–2 line of integration 899 acid–catalysed hydrations 956–8 specific heats and molar heat capacities line structures 43–6 addition of Grignard reagents 953–5 at 25° 305 converting 44–5 addition of carbon nucelophiles 955 lead iodide molar solubilities (s) 405–6 naphthalenes 263 aromatic 949 lead storage batteries 532–3, 621 linear alkylbenzenesulfonates (LAS) 1048 catalytic reductions 965 lead sulfates 621 linear geometry 183, 195 drawing structural formulae 946 leaving groups 804 hybrid orbitals 202 formation of imines 960–1 Leclanché, George 534 Link, Dr Karl 1019 formation of oximes and hydrazones 962 Leclanché cells 534 linkage isomers 559 formation of tetrahedral carbonyl addition Leucippus 4 linoleic acids 1044, 1045 intermediates 951, 966 levomethorphans 851 lipids 1043 a-halogenation 970–1 levorotatory compounds 776, 777 liquefied petroleum gas (LPG) 268 hemiketals 956 levorotatory enantiomers 987 liquid helium 289, 616 from hydration of alkynes 950–1 Lewis, Gilbert Newton 177, 481 liquid nitrogen 289, 608 industrially important 949 Lewis acid–base reactions 481–6, 556 liquid nitroglycerin 194 IR spectrum 889–90 HSAB principle 485–6 liquid solutions 392–401 ketals 956 transition metal complexes 549 gas–liquid 393–6 metal hydride reductions 964–5 Lewis acids 481, 551, 620 See also hard liquid–liquid 396–7, 398–401 nomenclature 945–7 Lewis acids liquid–liquid solutions 396–7, 398–401 nucleophilic acyl additions 1027 nomenclature 482 liquids 260–2 from oxidation of 2° alcohols 950 recognising 482–3 standard states 301 oxidation to carboxylic acids 968 soft 484, 485 vapour pressure 261–2 from ozonolysis of alkenes 950 Lewis adducts See adducts Lister, Joseph 836 position of keto–enol equilibrium 969 Lewis bases 481, 797 See also hard Lewis lithium 13, 150 preparation from Friedel–Crafts bases; ligands; nucleophiles; lithium aluminium hydrides 826, 964, acylation 949–50 recognising 482–3 1038, 1039 reaction to form 3° alcohols 826 soft 484, 606, 608 lithium chlorides 302, 303 reduction to 2° alcohols 826, 964, 966 Lewis structures 177–82 lithium ion cells 536 reductive amination of 962, 964 aldehydes and ketones 944 Litvinenko, Alexander 612 solubility of low-molar-mass 948 ammonia 184 LIX® reagents 962 structural formula 56–7 beryllium hydrides 183 local magnetic fields 895 structure and bonding 944 boron trifluorides 183 localised bonds 196 ketoses 986 carbon dioxides 183 lock-and-key hypothesis 682 ketotrioses 986 carbon suboxides 620 logarithms 37, 521 Kevlar™ 289 carboxyl groups 1012 lone pairs of electrons 42, 178

Index I-1151

BMIndex I-1151 1 June 2015 9:06 AM low-molar mass alcohols nomenclature 822 mercury 265, 266, 586 molal concentrations 410 See also molality (b) low-molar mass aldehydes, solubilities 948 applications of 592 molal freezing point depression constants low-molar mass alkenes 717, 723 emission patterns 128 (Kf) 414, 420 low-molar mass amine solubilities 852 nomenclature 564 molality (b) 410–11 low-molar mass anhydrides 1032 phase change data 268 molar concentrations 410 See also molarity (c) low-molar mass ethers nomenclature 842 meridional isomers 561 molar enthalpy of fusion (DfusH) 267 low-molar mass ketone solubilities 948 meso compounds 772, 774 molar enthalpy of sublimation (DsubH) 267 low-molar-mass alkenes 712 metal cations 266, 483 molar enthalpy of vaporisation (DvapH) 267 low-molar-mass alkynes 717 metal hydrides 535 molar mass (M) 85–6 Lowry, Thomas 432 reductions 964–5 alcohols 824 low-spin configurations 572, 573, 579 metallic solids 263, 265–6 alkanes 824 lysines 961 metalloenzymes 583–4 calculating amount from 86 lysozymes 1081 metalloids 17, 161–2, 603, 619 calculating mass from amount 87 oxoacids 463 comparing mass of compounds with 879 M metalloproteins 581–2 determining 234–5 macrocyclic ligands 555 metallurgy 584–5, 587, 589 from osmotic pressure (p) 420 mad cow disease 1084 metals 17, 161, 163, 602, 741 See also alloys gases 229 magnesium 13 catalysts 732 in units 31 hcp structures 277 close-packed structures 277 using freezing point depression data to hard acids 486 ionisation energies (Ei) 158 calculate 415–16 magnesium alkoxides 959 melting points 265 molar solubilities (s) 403 magnetic levitation trains 290 oxidation numbers 497 calculating from Ksp 405–6 magnetic moment (m) 578 with permanent magnetism 580 calculating using common ion effects 407–8 magnetic nanoparticles 581 reaction with oxidising acids 519 molarity (c) 100, 410 magnetic quantum numbers (ml) 137 soft acids 486 mole conversions 239–40 magnetic resonance imaging (MRI) 875 solid solutions of 402 mole fractions (x) 232–3, 411 magnetism of superconductors 289–90 meteorites and amino acids 1066 molecular beam apparatus and magnetites 587 methaemoglobins 582 experiments 225–6 main-group metals 548 methane 184, 432–3, 620 molecular energy distributions malachites 589 atomisation enthalpy (DatH) 319 gases 226–7 malic acids 1010 boiling points 247 sulfur hexafluorides 227 maltose 1001 calculating pressures using van der Waals and molecular equations 83 manganese 148, 581, 588 ideal gas equations 244 molecular formulae 40, 91 d-mannitol 995 close-packed structures 277 alkanes 699 d-mannosamine 989 combustion reactions 723 determining from high resolution mass manometers 220–1 molecular speed distributions 225 spectra 880 Manuka honey and antibacterial phase change data 268 molecular ions 878 properties 1000 probable speeds 226 molecular mass measurements 878 margarine production 238–9, 1046 sp3 hybrid orbitals 197–9 molecular models, gas solubilities 393 marine environments and health 248 structures 40, 48 molecular orbital diagrams 206–7 Markovnikov, Vladimir 724 methanols 396, 397 carbon monoxides 213 Markovnikov’s rule 724, 728, 825, 950–1 acidity of 827 hydrogen 206 Mars Climate Orbiter 26 boiling points 851 hydrogen fluorides 212 mass numbers (A) 11 standard enthalpy of formation 320–1 nitrogen oxides 211 mass percentage compositions structures 822 oxygen 209 calculating from chemical analysis 90 writing expressions for Kp 354–5 molecular orbital theory 196, 205–13 calculating theoretical 91 methenamines 963 molecular orbitals (MOs) 205–7 mass spectrometry 90, 877–80, 914 methionines 628, 629 effect of orbital mixing 210–11 isotope abundance and mass of common menthols 775 hydrogen 205–6 elements 880 methoxyethane boiling points 248–9 oxygen 207–10 isotopes 879–80 methyl acetate spectrum 897 molecular oxygen 967, 998 matter 4 methyl ethyl ketones (MEK) 945, 949 molecular solids 263–4 physical states and effect on entropy (S) 326 methyl groups, equatorial bonds 706 molecular speeds specifying states of 82–3 methyl isobutyl ketones (MIBK) 949 effect on pressure 229–30 states of 220 methylamine boiling points 851 gases 224–6 Maxwell–Boltzmann distributions 667–8 4-methylbenzylidine camphor 917 molecular vibrations 883 McBride, William 758 methylcyclohexanols 729, 774 molecularity 671 measurements 1-methylcyclohexene 728, 909 molecules 4 See also diatomic molecules early development in 26 3-methylcyclopentanol 773 chemical formulae 40–1 precision and accuracy 32–3 4-methylcyclopent-2enone 767 moles 27, 85–7 rounding multi-step calculations 36–7 3-methylpentane 60 ratios from chemical formulae 89–90 mechanistic arrows in chemical reactions 4-methylpent-2-ene cis isomers 717 ratios in chemical reactions 94–5 49–50 2-methylpropane 62, 760 molybdenites 611 medical diagnostic tools 874–5 boiling points 248 molybdenum disulfide oxidation numbers 498 melting points 245 See also normal melting 2-methylpropanoic acid spectrum 913 monatomic gases 616 points metres 27 monodentate ligands 551, 553 alkanes 709 metric systems See SI (Système International) bn at 25° 566 bismuth 610 units geometry 558 gallium 606 Meyer, Julius Lothar 15 monoprotic acids 433, 623 group 13 elements 604 micelles 1047 determining Ka and pKa 454–5 ionic compounds 176 Michaelis constant 683–4 speciation diagrams 479 isomeric alkanes 710 Michaelis–Menten equation 683 monoprotic bases 434 metallic solids 265–6 Michaelis–Menten mechanism 682 d-monosaccharide 987–9 network solids 264 microfibrils 1003 l-monosaccharides 987–9 red phosphorus 610 Millikan, Robert 9 monosaccharides 986–9 triglycerides 1046 mines and spontaneous reactions 641 amino sugars 989 white phosphorus 610 mirror planes 765 conformations 991–2 Mendeleev, Dmitri Ivanovich 15, 606 miscible liquids 396, 397 cyclic structures 989–93 meniscuses 260 mixed-valence compounds 622 d-and l-, 987–9 menthone, IR spectrum 890 MLCT transitions 578 determining structure of reaction mer isomers 561 molal boiling point elevation constants products 996 mercaptans 845 (Kb) 414 Fischer projections 987

I-1152 Index

BMIndex I-1152 1 June 2015 9:06 AM formation of glycosides 993–5 nitric acids 433, 463, 519, 835 transition metal complexes 562–5 interconversions 992–3 conjugate bases 435 writing formula from coordination mutarotations in 992–3 industrial production of 622 compound 565 nomenclature 988 nitric oxides 372, 519–20, 600, 630 non-1-ene 722 oxidation to aldonic acids (reducing nitriles 1021 nonbonded interaction strains 704 sugars) 996 nitrite ions 183, 551, 630 nonmetallic binary compounds 52–3 oxidation to uronic acids 996–7 nitrogen 13 See also elemental nitrogen; liquid nonmetals 17, 161, 164, 619 physical properties 989 nitrogen oxidation numbers 497 reduction to alditols 995–6 bond lengths 631 oxoacids 463 stereoisomers 986–7 calculating solubility using Henry’s nonoxidising acids 518–20 monosubstituted benzenes nomenclature law 395–6 nonpolar molecules 396 739–40 classifying 162 nonpolar solvents 399 Monsanto process 781 compounds 622 nonreducing sugars 999 Montreal Protocol 679 cycle 630–2 nonspontaneous reactions 298, 363 morphine 850–1 Earth atmospheric gas 218 nonvolatile solutes 410 MRI 875 oxidation numbers 519 boiling points 411, 414 Müller, Alex 290 phase diagrams 271 norepinephrines 857 multi-electron systems, orbital energies solubility in water versus pressure 394 normal boiling points 245, 262 144 specific heats and molar heat capacities normal freezing points 245 multiple bonds 202–5 at 25° 305 normal melting points 245 multiplets (m) 903 triple points 270–1 Noyori, Ryoji 781 multiplicity (splitting patterns) 904, 906 valence electrons 149 N-substituted primary amines 849–50 Murchison Meteorite 1066 nitrogen dioxides 372, 519 N-terminal amino acids 1074 mutarotations 992–3 calculating equilibrium constants 364 nucleophilic substitutions 797, 971 myoglobins 582, 1079–80 equilibrium mixture compositions 352 nucleophilicity 802–3 myosins 1060 second-order decomposition 668–70 nuclear magnetic resonance 894–5 nitrogen monoxides 519 nuclear magnetic resonance (NMR) N nitrogen oxides 211 spectrometers 896–7 (n + 1) rule 904–6 atmopheric pollutant 632 nuclear magnetic resonance (NMR) N-acetyl-d-glucosamines 989 ionisation energy (Ei) 212 spectroscopy 894–908 naltrexones 851 nitrogenase 608 (n + 1) rule 904–6 naming systems See nomenclature nitroglycerins 600, 835 alkanes 908–9 Nanoputians series 46 nitronium ions 744 chemical shifts 901–3 naphthalenes 264, 267, 741 nitrosamines 861 common terms in 897 structures 263 nitrosyl chloride decomposition rates 660 determining integration values 901 resonance structures 737–8 nitrous acids 463 equivalent hydrogen atoms 897–9 naproxens 778 reaction with aromatic amines 859–61 shielding 895–6 asymmetic synthesis 781 nitrous oxides 630 signal areas 899–901 resolution of (R,S) 780 calculating equilibrium constants not signal splitting 903–6 1 National Aeronautics and Space Administration at 25° 365–6 solving H-NMR spectral problems 914–15 (NASA) 26 decomposition 663 nuclei 10, 120 National Measurement Institute (NMI) 39 NMR spectrometers 616 nucleic acids 630 native-PAGE 1072 Nobel, Alfred 194 nucleophiles 482, 797 natural logarithms 521 noble gases 17, 616 common samples and their relative nd orbitals, transition metal complexes configurations 151 effectiveness 803 550 nodes 140, 205 nature of 802–3 negative catalysts 680 See also inhibitors nomenclature 50–1 nucleophilic acyl substitutions 1026–7, 1032, negative polarities 508 acid anhydrides and acid halides 1016 1038, 1042 neon 616 alcohols 822–3 nucleophilic substitutions 799–806, 826, 1021 close-packed structures 277 aldehydes and ketones 944–7 analysis of reactions 805–6 electron configurations 150–1 aliphatic amines 848–9 compared to b-elimination reactions 811 emission patterns 128 aliphatic carboxylic acids 1014 determining products of 799–800 specific heats and molar heat capacities alkanes 58–63, 699, 702–3 ethers 845 at 25° 305 alkenes and alkynes 716–22 mechanisms of 800–2 Nernst, Walter 523 amides and lactones 1016–17 predicting reaction products and Nernst equation 522–5 carboxyl groups 1014 mechanisms 806 net ionic equations 107–8, 520 carboxylic acids 1013–15 SN1 and SN2 comparisons 805 balancing for redox reactions 500–4 coordination complexes 564–5 SN1 reactions 801–2 network solids 263–5 cycloalkanes 702–3 SN2 reactions 800–1, 829–30 neutral atoms 120 cycloalkenes 719–20 nucleus–nucleus repulsions 172–3 neutral radicals 879 disubstituted benzenes 739–40 nuclides 11 neutral solutions 437 drug molecules 64 neutrons 10 elements in periodic table 17–18 O Newman projections esters and lactones 1016–17 observed rotations 776 alkanes 700, 701 ethers 842–3 oct-1-yne IR spectrum 887 cycloalkanes 704 general organic 65–6 octahedral geometry 47, 187–8, 190, 195, N-glycosides 994 group 16 hydrides 624 576, 625 nicad batteries 535 haloalkanes 792–4 octahedral holes 282 NiCd 535 inorganic compounds 52–4 octahedral transition metal complexes 557–8 nichromes 590 Lewis acids 482 changes in energies of d orbitals 571 nickel–cadmium storage cells 535 ligands 551 with cis–trans isomers 560 nickel–metal hydride (NiMH) batteries low-molar mass alcohols 822 colour properties 578 535 monosaccharides 988 crystal field theory of bonding 570–2 nicotinamide adenine dinucleotides monosubstituted benzenes 739–42 electron configurations 572, 573 (NAD+) 739 organic compounds 54–66 low- and- high-spin configurations 572 ninhydrins 1073 phenyl groups 945 magnetism 579 nitinols 402 phosphorus 622 orientation of orbitals in respect to ligands 571 nitrate anion resonance structures 180–1 polysubstituted benzenes 740–2 octanoic acids 833 nitrate fertilisers 622, 681 prioritising order of precedence for functional octyl methoxycinnamates 917 nitration groups 947 oils 1045, 1046 amines 853 secondary and tertiary amines 849–50 Olah, George 465 aromatic compounds 742, 744 thiols 845 oleic acids 1044, 1045

Index I-1153

BMIndex I-1153 1 June 2015 9:06 AM oleoresin capsicum sprays 837 oxidising agents 496, 519–20, 833 group 16 611–12, 623–6 oligopeptides 1074 aldehydes 967–8 group 17 612–15 oligosaccharides 999 biological 739 group 18 616–19 one-electron system orbital energies 144 blood glucose monitors 998 reactivities of 482 Open Pool Australian Light Water Reactor group 14 621 PCC 834–5, 950 (OPAL) 14 group 15 622 pentan-1-ol 396, 888 open systems 300 group 16 625 pentane opioid analgesics 850–1 group 17 612, 625 boiling points 247, 948 optical activities 775–8 group 18 618 electron density models 708 optical brighteners 1048 industrial 624 structures 699 orbital energies 142–5 oximes 962 pentanoic acids 65–6 orbital mixing 210–11 oxoacids 462–4 pentapeptides 1074 orbital overlap models group 16 624 pentoses 988 alkenes 713 group 17 625–6 penultimate carbons 987 benzenes 735 groups 14 and 15 622 peptide bonds 1074 tertiary carbocations 725 of nonmetals and metalloids 463 geometry 1077 orbital overlaps 196–7 phosphorus 623 peptides 1061, 1074, 1075 constructive and destructive 208 strengths of 463 Pepto-Bismol 610 conventions for model 197 oxoanions 54, 181, 585 perbromic acids 626 ethenes 203 oxonium ions 729 percentage by mass 90 ethynes 204 oxo-processes 949 percentage compositions, calculating empirical orbitals 19, 136, 137 See also hybrid orbitals oxygen 13 See also molecular oxygen; ozone formula from 92 depictions 139–40 bond length and energy 209 percentage uncertainties 35, 38 filling sequence 148 compounds of 611 percentage yields 98–9 with nearly equal energies 152–3 cycle 627–8 perchloric acids 626 order of filling with electrons 146 Earth atmospheric gas 218 perhalic acids 625 size of 140–1 molecular orbitals (MOs) 207–10 periodic table of the elements 15–18 order of reaction 648 paramagnetism 209 anion stability 161 relationship between change in concentration phase change data 268 atomic radii 155–7 and 654 solubility in water versus pressure 394 Aufbau principle and order of orbital organic chemistry 481–2 specific heats and molar heat capacities filling 145–8 isotope abundance and mass of common at 25° 305 in block form 147 elements 880 standard states 315 cation stability 161 organic compounds 712 oxygen evolving complex (OEC) 581 electronegativities of elements 174 equivalent hydrogen atoms 898 ozone 611, 624, 950 elements named after scientists 18 halogenated 798 depletion 678–9, 792 ionisation energies (Ei) 157 nomenclature 54–66 determining rate laws for decomposing Mendeleev’s original 616 organic molecules, function as ligands 555 676–7 metals, nonmetals and metalloids 161–2 organic phosphates 634, 635 resonance structures 627–8 modern 16–17 organic photovoltaics 790 units of measurement 678 original table in German 16 organic reagents 613 ozone-depleting chemicals 615 p-block elements 163–4 organochlorine insecticides 798 rows and blocks showing relationship organomagnesium compounds 951–2 P between table and ground-states 147 organometallic compounds 555, 951–2 p orbitals 141, 147–8, 548, 602 s-block elements 162–3 ornithines 1065 PAGE 1071–2 valence electrons 148–9 ortho positions 741, 838 PAHS 741–2 periods 16 osmium 592 pairing energy (P) 572 peroxydisulfuric acids 624–5 osmometers 419 palladium 311 peroxysulfuric acids 624–5 osmosis 416–20 applications of 592 Perutz, Max F 1080 osmotic membranes 416 deactivated 733 petrolatum 709 osmotic pressure (p) 417–20 palmitic acids 1044, 1045 pewter 607 calculating 419 para positions 741, 838 pH 438–43 See also initial pH calculating molar mass from 420 paraffin wax 709 amino acid charges 1069–70 Ostwald, Wilhelm 622 paraffins 793 calculating 440 Ostwald process 622 paramagnetism 154, 548, 578 calculating ammonia/ammonium ion oxalates, Ksp at 25° 404 compared with ferromagnetism 580 buffers 468 oxalic acids 1014 liquid oxygen 209 calculating change in buffer solutions 470 oxidation numbers 497–9, 628 transition metal complexes 570 calculating for buffer solutions 466–70 exceptions to the rule 498 parent chains 58–9 calculating salt solutions of weak acids and group 13 602–3 parent ions 878 bases 455–8 how to represent 498 partial hydrogenation 1046 calculating strong acids and bases 444–5 lead 622 partial pressure calculating weak acids and bases 450–5 use in analysing redox reactions 499 determining 240–1 determining dune lakes’, 439 oxidation processes 496, 529 gas mixtures 231–2 effects of hyperventilation on blood 382 phenols 841 using Raoult’s law 413 initial 473 1° and 2° alcohols 833–5 particles and effect on entropy (S) 327 measuring diluted strong acid thiols 847 parts per billion (pbm) 233 solutions 446–7 oxidation states 497 See also oxidation numbers parts per million (ppm) 233 phenols 841 common states and configurations for pascal (Pa) 221 predicting how salt affects 458 transition metal complexes 550 Pascal’s triangle 904 preparing buffer solution with determining transition metal passivation processes 526 predetermined 469 complexes 556–7 Pauli, Wolfgang 138 testing swimming pools and soil 443 group 13 620 Pauli exclusion principle 138, 145, 146, 155, values of common aqueous solutions 441 group 14 606, 621 206, 208, 572, 576 pH meters 441 group 16 624 Pauling, Linus 174, 735, 1077–8 pH test kits 443 group 17 625 Pauling scale of electronegativity 174 pH test papers 441 phosphorus 622, 632 p-block elements 16, 156, 161–2, 163–4, pharmaceutical drugs oxidation/reduction potentials 512 600–1, 602–19 containing halogens 798 oxides 584–5, 587 bonding in 626–7 enantiomers in 761, 1019 acid–base characteristics 620 group 13 602–6, 619–20 single enantiomer drugs 779 group 14 621 group 14 606–8, 620–2 synthesising chiral drugs 780–1 oxidising acids 518–20 group 15 608–12, 622–3 use of amines in 859

I-1154 Index

BMIndex I-1154 1 June 2015 9:06 AM phase change materials 274 polycyclic aromatic hydrocarbons propenes 65–6, 712 phase changes 266–73 (PAHs) 741–2 propofols 997 calculating equilibrium temperature polydentate ligands 551 propylene glycols 823 for 338–9 bn at 25° 566 propynes 716 Gibbs energy diagrams 359–60 geometry 558 proteins 1060, 1062, 1074 phase diagrams 269–73 stereoisomerism in 561 common amino acids found in 1064 practical applications of 274 polyene cis–trans isomers 721 denaturation process 1082–5 selected substances 268 polyfunctional compounds 820 denaturing agents and modes of action 1082 water 266–7 polyhedral structures 603 1° structure 1075–6, 1083 phase diagrams 269–73 polymers 723, 1062 2° structures 1077–8, 1083 aqueous solution of nonvolatile solutes 414 polypeptides 1074 3° structures 1078–81, 1083 characteristics of 269–70 1° structure 1075–6 4° structures 1081–2, 1083 constructing 271–2 2° structures 1077–8 three-dimensional structures 1077–82 interpreting 272–3 4° structures 1081–2 protic acids 952–3 silicas 273 three-dimensional structures 1077–82 protic solvents 804, 805, 810 water 270 polyphosphates 634 protium 11 phase of light waves 121 polyprotic acids 433, 447, 479 proton transfer reactions 436 phenolphthaleins 480 polyprotic bases 434, 447 protons 10 phenols 245, 740, 741, 835–42 polysaccharides 999, 1002–3 Proust, Joseph Louis 5 acid–base reactions 840 polysubstituted benzenes nomenclature 740–2 Purcell, Edward 894 acidity levels of 839 polyunsaturated triglycerides 1046 pure silicas 286 See also quartz acidity of 838–9 Pons, Stanley 311 pure water 437 ester formations 841–2 positive catalysts 680 pOH of 438 oxidation processes 841 positive polarities 508 PVCs (polyvinylchlorides) 613 phenoxide ions 842 post-transition metals 548 pyranoses 990 phenyl groups 740 potassium 149, 163 Pyrex® 287 nomenclature 945 potassium iodide lattice enthalpies 399–400 pyridines 738, 830 phospate anion resonance structures 181 potassium sulfate electrolysis 529–30 pyridinium chlorochromate (PCC) 834–5, 950 phospate condensation 634 potential difference 506 pyrimidines 738 phospates 164 potential energy diagrams 665 pyrites 611 phosphanes 622 endothermic reactions 666 pyrophosphoric acids 634 phosphate diesters 635 potential energy (PE) 665 pyrroles 739 phosphate esters 635 precipitates 408–9 phosphate fertilisers 633 precision of measurement 32–3 Q phosphate monoesters 635 pre-exponential factors 668–70 quadratic formulae in equilibrium phosphates 632 preferred axes 136–7 products 459–60 inorganic 631, 632, 634, 635 prefixes common SI units 28 qualitative analysis 82 organic 634, 635 prefixes for chain lengths of 1 to 10 carbon quantisation of energy 19, 128–30, 135–9 phosphoric acids 479, 623, 633–4, 835 atoms 58 quantitative analysis 82 phosphorus 608–10 pressure (p) See also osmotic pressure ( ) p quantum mechanics 19 black 610 calculating 222–3 quantum numbers 136–9 cycle 632–5 calculating volume–pressure variations quarks 11 elemental nitrogen 609 223–4 oxidation states 622, 632 effect on equilibrium change in gaseous quartets (q) 903 oxides 622 reactions 368–70 quartz 286, 621 red 609 effect on gas solubility 395 quinones 841 white 264, 608, 609 effect on real gas behaviours 243 phosphorus halides 828 gases 220–1 R phosphorus pentachlorides 185 molecular speed effect on 229–30 R,S systems 768–70 phosphorus trichlorides 482 van der Waals equation 243–4 assigning configurations to photochemical smog 632 vapour 261–2 stereocentres 769–70, 987 photoelectric effect 122–3, 126 relationship between volume and 221 racemic mixtures 778, 779, 802 photons 123, 134 pressure–volume work 303 blood thinning drugs 1019 photosynthesis 581, 636 pre-transition metals 548 radiation 122 piezoelectric ceramics 289 Priestley, Joseph 611 radical cations 878 pig iron 588 primary (1°) alcohols 823, 824 radical substitution reactions 794 pKa See acid ionisation constants (pKa) acid–catalysed dehydration 831 determining products of 796 pKb See base ionisation constants (pKb) addition of Grignard reagents to radicals 794 See also free radicals pKw 439 formaldehyde 953 radioactive isotopes 14 Planck, Max 19 oxidation processes 833–5 calculating half-lives 659 Planck’s constant (h) 123, 881 oxidation to carboxylic acids 1020 first-order decay 658 plane-polarised light 775–6, 986 preparation from haloalkanes 826 radioactivity 11 measuring rotation of 776–7 reaction with hydrohalic acids 828–30 radio–frequency radiation 895 planes of symmetry 765 See also mirror planes primary (1°) amines 847 radionuclides 11 plasma 220 primary carbon atoms 55 Radom, Leo 465 platinum 486, 592, 617 primary cells 532 radon 229, 618 pnictogens 17 primitive cubic structures 279 Raoult’s law 411–12, 413 pOH of solution 438–9 principal quantum numbers (n) 136 rare earth elements 16, 266 polar covalent bonds 173–4 products 4, 82, 516 rate coefficients 648 polar molecules 396, 843 effect of addition/removal from rate constants 648 See also rate coefficients dipole moments 189 equilibrium 367–8 calculating activation energy from 670 hydration process 398 rates of formation 644 calculating from rate data 651 polar stratospheric clouds (PSC) 679 promethiums 548 rate laws 647–9, 671 polarimeters 776, 777, 779 propan-1-ols 396, 397 differential 649–55 polarisability properties 246 boiling points 249 integrated 655–64 electron clouds 484 propan-2-ol, structures and mirror images 765 rate of reactions Polaroid™ 775 propanes 268 compared to rates of consumption and rates polonium 279, 612, 624 structures 699 of formation 644 polyacrylamide gel electrophoresis 1071–2 three-dimensional structures 47 estimating initial 644–6 polyatomic anions 266, 551, 607, 612 propane-1,3-diol, vapour pressure rate-determining step 672–4 polyatomic cations 612 variations 262 mechanisms with fast, reversible steps polyatomic oxoanions 164 propanoic acids and pH 452–3 673–4

Index I-1155

BMIndex I-1155 1 June 2015 9:06 AM rate-limiting step 672 naphthalenes 737–8 selenous acids 463, 625 rates of consumption of reactants 644 nitrate anions 180–1 semiconductors 17, 287, 610, 612 rates of formation of products 644 nitrite ions 630 semipermeable membranes 416 reactants 4, 82, 516 ozone 627–8 sepulchrate ligands 555 chemical nature and effect on reaction peptide bonds 1077 serylalanines 1074 rates 646 phenols 838 Sharpless, Barry 781 concentrations and effect on reaction phosphate anions 181 SHE 513, 516 rates 647 phosphorus 632 shielding effect 144–5, 156, 895–6, 897 effect of addition/removal from respiration processes 628 on ionisation energies 158 equilibrium 367–8 reverse osmosis 410 SI (Système International) units 26–9, 881 physical nature and effect on reaction desalination plants 417, 418 common prefixes for 28 rates 646–7 reversible reactions 82, 98, 336 gas constants 30 rates of consumption 644 equilibrium 351 non-SI units 29–30 reacting fractions 667 heterogeneous systems 358 seven base 26 reaction coordinates 665 rhodopsin 714–15, 961 units commonly used in Chemistry 27 reaction intermediates 666, 674 ribbon models side-chain caryboxyl group’s pKa 1067 reaction mechanisms 650, 671–9 haemoglobins 1081 sigma (s) bonds 173 rate-determining steps 672–4 myoglobins 583, 1080 signal splitting 903–6 steady-state approximation 674–7, 679 a-d-ribofuranose 990–1 aldehydes 913 reaction quotient expression (Qc) 353 RMIT 274 multiplicity and relative intensities of peak reaction quotients (Q) 353, 522, 523 RNA 835 in 904 reaction rates 640–1, 642–6 Röntgen, Wilhelm 7 significant figures 33–8 average rate of consumption 643–4 root-mean-square speed 228, 229 in calculations 35–6 calculating from rate laws 654–5 Rosenberg, Barnett 560 logarithms 37 concentration–time profiles 642–3 rotten egg gas See hydrogen sulfides rules for 34 effect of catalysts on 680 rubidium 149 silanes 620 factors affecting 646–7 ruby lasers 131–2 silicas 264, 286, 621 See also pure silicas; initial rate 648 rusting process See corrosion silicon dioxides measurements of concentrations over Rutherford, Ernest 2, 9–10, 618 See also gold phase diagrams 273 time 643 foil experiment silicates 164 rate laws 647–9 rutiles 486, 589 silicic acids 622 relationships within 648–9 silicons 13, 264 real gases S purifying and refining 606–7 deviations from ideal behaviour 243 s orbitals 548 silicon carbides 264, 288 halogens 241–2 ground-state configurations 153 silicon dioxides 273, 621 properties of 242–3 size of radius 141 silicon nitride applications 289 van der Waals equation 243–4 salbutamols 820, 857 silver 265, 402 red blood cells, effect of hypo, hyper and salt bridges 508 applications of 591–2 isotonic solutions on 419 salt linkages 1081 ccp structures 277 red phosphorus 609 Sanger, Frederick 1075 specific heats and molar heat capacities redox potentials 512 saponification 1033, 1047 at 25° 305 redox reactions 19 sarcophagines 555 silver bromides in acidic solutions 501–3 Sargeson, Alan 555 Ksp 404–5 balancing net ionic equations 500–4 saturated calomel electrodes (SCE) 516 solution stoichiometry 105–6 in basic solutions 503–4 saturated fatty acids 1044, 1045 silver nitrates and Ksp 402–3 galvanic cells 504–11 saturated hydrocarbons 58, 698 See also silver–copper cells 507, 508 identifying 496–7 alkanes calculating standard cell potentials 514–15 predicting outcome 517 oxidation of 723 cell diagrams 510 shipwrecks 494 saturated solutions 392 silver-mirror tests 967, 996 spontaneous and nonspontaneous 516–18 Sayers, Dorothy L 779 silver/silver chloride electrodes 516 using oxidation numbers to analyse 499 s-block elements 16, 156, 162–3, 602 single bonds 177, 556 redox reagents 582 scanning tunnelling microscopes (STMs) 8 enthalpies 320 reducing agents 496, 620, 826, 964, SCE 516 p-block elements 626 1038, 1082 Scheele, Carl Wilhelm 611 singlets (s) 903, 907, 910, 912 reducing sugars 996, 999 scheelites 266 skeletal models, cycloalkanes 704 reduction potentials (Ered) 511–20, 621 See Schrödinger equation 136 slag 588 also oxidation/reduction potentials; redox Scoville scale 837 slightly soluble salts 402–3 potentials scrapie 1084 kidney stones 409 reduction processes 496, 529 SDS PAGE 1072 Ksp at 25° 404 reduction–oxidation reactions See redox second law of thermodynamics 327–8, 331 soaps 1047 reactions secondary (2°) alcohols 823, 824 sodium reductions acid-catalysed dehydration 831, 832–3 biochemical and industrial applications carboxylic acids 1038–40 addition of Grignard reagents to 162–3 fatty-acid chains 1046 aldehydes 954 emission patterns 128 reductive amination reactions 964 oxidation processes 833–5, 950 melting points 265 red-violet ions 575 preparation from haloalkanes 826 sodium 4-dodecylbenzenesulfonates 1048 Reed, Christopher 465 reaction with hydrohalic acids 828 sodium acetates 466 reference compounds 876, 896 secondary (2°) amines 847 sodium azides 498 refractories 288 pKa and pKb at 25° 855 sodium bicarbonate See baking soda repeating patterns, crystal lattices and unit nomenclature 849–50 sodium borohydrides 826 cells 278 reaction with nitrous acids 861 sodium bromides 401 resonance energies solubility 852 sodium carbonates 163 aromatic compounds 739 secondary carbon atoms 55 sodium chlorides 176, 613 aromatic hydrocarbons 737 secondary cells 532, 535 calculating pH 456–7 benzenes 736–9 second-order rate laws 659–62, 671 dissociation reactions 420–1 resonance for nuclei of spin 895 concentration–time calculations 660 electrolysis of molten 528–31 resonance signals 898 half-life reactions 661–2 face-centred cubic structures 282–3 resonance stabilisation 464 kinetics for reactions 664 internal energy (U) 303 resonance structures 180–2 rate constants 661 lattice enthalpies 321, 323 amines 856 seconds 27 reaction in water 398 benzenes 735–6 selenic acids 463, 625 sodium D lines 777 dinitrogen oxides 181–2 selenium 612, 624 sodium dodecyl sulphate (SDS-PAGE) 1072

I-1156 Index

BMIndex I-1156 1 June 2015 9:06 AM sodium hydroxide 163 space-filling models 47–8 stereoisomers See also diastereomers; enantiomers calculating pH 440 nonmetallic binary compounds 53 a-amino acids 1063 sodium lauryl sulfates 397 speciation diagrams cyclohexane-1,3-diol 774 sodium pyrophosphates 634 dissociation of acids in aqueous drawing 767–8 sodium sulfates 163 solutions 478–9 inorganic 781 sodium triphosphates 634 specific heat capacities (c) 305 monosaccharides 986–7 sodium-vapour street lights 126–7, 155 specific heats 305 transition metal complexes 559–60, 561–2 soft Lewis acids 484, 606, 608 specific rotations a( ) 777 stereospecific reactions 730, 732 soft Lewis bases 484, 485 spectator ions 107 stereoviews 48–9 solar energy alternatives 790 spectrochemical series 576, 578–9 steric factors 668, 829 solder 607 spectrophotometers 575 steric hindrances 803, 843 solid solutions 402 sperrylites 486 steric strains 704, 706 See also nonbonded solid wedges 47 sphalerites 586, 592 interaction strains solids 262–6 spin 19, 894–5 Stern, Otto 137 characteristics of different 263 spin down 19 Stern–Gerlach magnetic field experiment 138 close-packed structures 274–7 spin quantum numbers (ms) 137–8 stibanes 622 crystal lattices and unit cells 277–9 spin up 19 Stingose® 1085 crystalline defects 287 splitting patterns 903 stock solutions 103 cubic structures 279–81 1H-NMR spectrum 905 Stockholm Convention on Persistent Organic ionic 281–3 characteristics for common organic Pollutants 798 magnitude of forces on 262–3 groups 906 stoichiometric coefficients 82, 350 phase diagrams 273 spontaneous reactions 298, 642 stoichiometric points 472 standard states 301 definitions of 362 stoichiometry 81, 82, 89, 93–110 See also gas structures of ionic 281–3 determining direction of 363 stoichiometry; solutions stoichiometry using x-ray diffractions 284–6 effects of enthalpy and entropy changes chemical reactions 93–4 solubility products (Ksp) 402–9 on 333 electrochemical reactions 531–2 calculating from solubility data 404–5 galvanic cells 514, 516–18 mass calculations 95 predicting formation of precipitates 408–9 Gibbs energy change 302 summary of relationships 240 relationship with solubility 403–6 in lead batteries 533 straight-chain alkanes 58 slightly soluble salts at 25° 404 in mines 641 stretching vibrations 883, 886, 890 and solubilities for common electrolytes 406 predicting probability of direction of 324 strong acids 444–7 solubility properties 392 square planar transition metal complexes calculating pH in 444–5 amines 852 559–60 electrical conductivity 442 carboxylic acids, alcohols and crystal field theory applications 573 measuring pH of dilute 446–7 aldehydes 1018 d-orbital splitting diagram 573 strong acid–strong base titrations 472–4 common gases in water 393 square pyramidal transition metal titration curves 473 ethers 843 complexes 558–9 strong bases 442, 444–7 and Ksp for common electrolytes 406 staggered conformations 700 for b-elimination 807 monosaccharides 989 stainless steel 288, 402, 590 calculating pH in 444–5 quantification of 402–9 standard cell notations 509 strong base–strong acid titrations 472–4 ο solubility versus temperature for ionic standard cell potentials (Ecell) 511–12 titration curves 473 ο salts 401 standard enthalpy of combustion (DcH ) 318 strong-field ligands 576 ο soluble solutions 392 standard enthalpy of formation (DfH ) 314–18 structural formulae 41–6 solutes 100, 392 calculating atomisation enthalpy 319 alanines 858 solutions 100, 392 selected standard state gaseous atoms at 25° aldehydes 56–7 boiling point elevation and freezing point 319 carboxylic acids 57–8 depression 414–16 selected substances at 25° 315 cycloalkanes 702 colligative properties 410–23 thermochemical equations 315–16 dimethyl ether 43 concentration of 100–5 using Hess’s law 317 ethanols 43 ο molality (b) 410–11 standard enthalpy of reaction (DrH ) 310–12 glycosides 994–5 molarity (c) 410 thermochemical equations 313–14 imines 961 ο mole fractions (x) 411 standard entropy of formation (Df S ) 329–30 ketones 946 ο with more than one volatile standard entropy of reaction (DrS ) 329–30 1°, 2° and 3° alcohols 55 component 413–14 standard entropy (S ο) 328–30 three-dimensional 46–9 ο Raoult’s law 411–12 standard Gibbs energy change (DrG ) 333–5 structural isomers 559 solutions stoichiometry 100–10 calculating 333–4 structures See also Lewis structures; ο ο applications of 105–6 calculating from DrH and DrS 333–4 three-dimensional structures ο calculating involving ionic reactions 108–9 calculating from DfG 334–5 adducts 483 calculating involving unknown standard Gibbs energy of formation alkanes 698, 699 ο compounds 110 (Df G ) 334 amino acid selenocysteine 612 calculating ions in solution 107 ozone 628 a-amino acids 1062 calculating using net ionic equations 107–8 standard hydrogen electrodes (SHE) 513, 516 bidentate ligands 551 diluting 103–5 standard reduction potentials boron 619 equations for 101–2 common mistakes in 512 butan-2-ol 763–4 ions 106–10 determining 513–16 cisplatin 560 preparing known concentration 102–3 standard states of substances 301 diamond and graphite 265 preparing known concentration by starch 1002 electronic 628 dilution 104 state functions 301 elemental boron 603 solubility of common binary ionic statistical probabilities in entropy 323–4 group 17 oxoacids 625 compounds 106 steady-state approximation 674–7, 679 ionic solids 283 solvation 398 use in constructing rate laws 676–7 myoglobins and heamoglobins 1080 solvation enthalpies 399 steam burns 322 octahedral complex cis–trans isomers 560 solvents 100, 392, 399, 949 stearic acids 1044, 1045 organometallic compounds 555 boiling points 411 steel 586–8 oxoacids 462, 463–4 for nucleophilic substitutions 804–5 steel and production of 587–8 p-block elements 626 solvolysis reactions 801 stereocentres 765–6 peptide chains 1081 d-sorbitol 995 acyclic molecules with two 770–3 peptides 1062, 1075 sorbitols 995 assigning R, S configurations to peroxydisulfuric and peroxysulfuric Sørensen, Søren 438 stereocentres 769–70 acids 625 sp hybrid orbitals 201–2, 204 cyclic molecules with two 773–4 phosphoric acids 623 sp2 hybrid orbitals 200–1, 203 molecules with three or more 775 polydentate ligands 552 sp3 hybrid orbitals 197–9, 200 R,S systems 768–70 polypeptides 1075–81

Index I-1157

BMIndex I-1157 1 June 2015 9:06 AM structures (continued) terephthalic acids 1015 thymols 836 propan-2-ol 765 terminal carbons 42 thyroxines 1065 sulfur 611 termolecular reactions 671 tin 12, 606, 607, 608 superoxide dismutase (SOD) 584 terpenes 942 tin plating 526 transition metal complexes 549 tert-butyl acetate spectrum 900 tincture of iodine 100 styrenes 740 tert-butyl cations 725, 726 titanium subatomic particles 10 tert-butyl groups 706 applications of 590 sublimations 267 tertiary (3°) alcohols 823, 824 metallurgy 589 subscripts 41 acid-catalysed dehydration 831, 832–3 titanium carbides 288 substituents 58 addition of Grignard reagents to titanium dioxides (titania) 288 substrates (S) 681 ketones 954–5 titanium nitrides 288, 289 sucrose 986, 999 conversion from esters 827 titrants 472 suffixes and class of compounds 65 nomenclature 849–50 titration curves 472 sulfates, Ksp at 25° 404 resistance to oxidation 834 glycine 1069, 1070 sulfato ligands 559 tertiary (3°) amines 847 strong acid–strong base 473 sulfhydryl groups 845 pKa and pKb at 25° 855 strong base–strong acid 473 sulfides 585 solubilities 852 weak acid–strong base 475 sulfonation of aromatic compounds 742, 744 tertiary butyl cations 725 weak base–strong acid 475 sulfonic acids 835 tertiary carbon atoms 55 Tollen’s reagents 967–8, 996 sulfurs 13 tetraanion EDTA4-, 552 toluenes 740, 741 abundance of 611 tetradentate ligands 554 1H-NMR spectrum 911 applications of 612 tetrafluoroethene 613 conversion to 4-hydroxybenzoic acid 860 cycle 628–9 tetrahedral carbonyl addition intermediates IR spectrum 889 energy level diagrams 152 aldehydes and ketones 951, 966 torsional strains 703, 704 See also eclipsed oxidation numbers 628 carboxylic acids 1026–7, 1040 interaction strains sulfur dioxides 6, 178–9 tetrahedral geometry 184, 189–90, 197 Tour, James 46 calculating equilibrium constants 365 enantiomers 766 trans alkenes 733 law of multiple proportions 7 features of 195 trans isomers 46, 560, 713 removal from gaseous mixture 359 hybrid orbitals 202 chiral 773 sulfur hexafluorides 187 ice 251 trans-1,2-dibromocyclohexane 730 determining average molecular and molar ionic solids 283 trans-1,2-dimethylcyclopentane 762 kinetic energy 227 nucleophilic substitutions 802 trans-but-2-ene 713, 733 sulfur oxides 624 p-block elements 627 trans-cycloalkene 720 sulfur tetrafluorides 186 phosphorus oxides 633 trans-cyclooctene 720 sulfur trioxides 6, 7 transition metal complexes 549, 558 trans-dihalocycloalkanes 730 sulfuric acids 433–4, 464, 520, 612, 624, 629, tetrahedral holes 282, 283 transesterifications 1031 680, 835 tetrahedral transition metal complexes trans-fats 1046 sulfuryl chloride rate laws and constants 653 colour properties 578 transferrins 583 sunscreens 917 crystal field theory applications 573 transition metal complexes 556–81 superacids 465, 482 d-orbital splitting diagram 573 applications of 549 superconductors 266, 287 tetramethylsilane (TMS) 896 bn for monodentate and polydentate ligands high-temperature 290 tetrapeptides 1074 at 25° 566 magnetism 289–90 tetraprotic acids 634 bonding 569–73 supercritical fluids 220, 268–9 tetroses 986, 988 chelate effect 565–8 superfluids 616 thalidomide 758–9, 762 colour properties 570, 574–8 superoxide dismutase (SOD) 583, 584, 628 enantiomers 761 common states and configurations 550 superoxide electronic structures 628 thallium 13, 603, 620 coordination number 4 558, 573 surface active agents 397 theoretical yields 98 coordination number 5 558–9 surface tension 260 theory of resonance 735 coordination number 6 557–8 surfactants 397 thermal energy (RT) 229 determining d-electron configurations 550–1 surroundings 300 thermite reactions 95 determining oxidation states 556–7 sweetening agents 995 thermochemical equations 310, 312 See also disproportionation reactions 569 sylvites 486 Hess’s law electrochemical aspects 569 symproportionation reactions 533 for exothermic reactions 313–14 geometry 549, 558 syn additions 732 rules for manipulating 313 inert and labile complexes 568–9 synchrotron IR microscopy 885 standard enthalpy of formation 315–16 isomerism 559–60 systems 300 thermodynamic equilibrium constants 355 magnetism 570, 578–81 thermodynamic temperature 299–300 See also nd orbitals 550 T absolute temperature nomenclature 562–5 tartaric acids 1010 thioacetals 845 structures 552, 557–8 stereoisomers 772 thioesters 845 use in anti-cancer treatments 560 tautomerism 950, 968 thioethers 628, 845 writing formula from name of coordination tautomers 968 thiols 628, 820, 845–7 compounds 565 Taxol® 560, 767, 781 acidity of 846–7 transition metal ions in biological Teflon 613 nomenclature 845 systems 581–4 tellurium 612, 624 oxidation to disulfides 847 electron transfer proteins 584 tellurous acids 625 physical properties 846 metalloenzymes 583–4 temperature structures 845 transport and storage metalloproteins 582–3 autoprotolysis constant of water (Kw) 437 thionyl chlorides 828 transition metals 16, 548, 549–51 average kinetic energy and 227 thiosulfuric acids 624 applications of 590–2 calculating equilibrium temperature for phase third law of thermodynamics 328–30 colours from 546 change 338–9 Thompson, JJ 9 configurations 153 denoting changes in 300 Thomson, George 133 conversion process 586 effect on entropy (S) 325–6 three-centre, two electron bonds 619 magnetic behaviour 548 effect on equilibrium in reaction three-dimensional structures 46–9 See also metallurgy 587 mixtures 370–1 ball-and-stick models; space-filling models reduction process 586 effect on reaction rates 647 disaccharides 1001–2 refining process 586 effect on solubilities of solid solutes 401 ice 251 separation process 585–6 effect on viscosity 261 peptide bonds 1077 use in catalytic reductions 732 factor in collision theory 667–70 simplifying 767 transition states 665–6 intensity of steam 322 threoses 771 triacylglycerols 1043 relationship between volume and 221 threshold energies 665 triatomic molecules dipole moments 189

I-1158 Index

BMIndex I-1158 1 June 2015 9:06 AM 1,1,2-trichloroethane spectrum 904 orbital overlaps 196–7 wavelength (l) triglycerides 1043–8 summary of hybridisation schemes 202 electromagnetic radiation 122, 881 melting points 1046 valence electrons 148–9 frequency conversion 121 physical properties 1045–6 configurations 602, 603, 606, 619, 626 light 120 polyunsaturated 1046 valence-shell-electron-pair repulsion (VSEPR) ultraviolet absorption of conjugated structures 1045 theory 182–8, 558, 725 molecules 916 trigonal bipyramidal geometry alkenes and alkynes 712–13 wavenumbers (ν ) 882 185–7, 195 common mistakes in 188 weak acids 447–60, 626 trigonal planar geometry 183, 195 linear geometry 183 calculating pH 450–8 hybrid orbitals 202 octahedral geometry 187–8 effects on metal alloys 466–7 transition metal complexes 558–9 tetrahedral geometry 184 electrical conductivity 442 2,3,4-trihydroxybutanals 770–1 trigonal bipyramidal geometry 185–7 Ka and pKa at 25° 448 stereoisomers 771 trigonal planar geometry 183 situations when simplifying assumptions triiodide ions 186 van der Waals equation fail 458–60 triiodothyronine 1065 compared with ideal gas equations 244 solutions containing salt of 458 2,2,4-trimethylpentane spectrum 909 constants for gases 243–4 weak acid–strong base titrations 474–7 trinitroglycerine 194 van der Waals, Johannes 243 titration curves 475 triols 823 vanadium 265 weak bases 442, 447–60 trioses 986 vanillins 836, 837 calculating pH 450–8 tripeptides 1074 van’t Hoff equation 370, 401, 417 Kb and pKb at 25° 448 triple bonds 177, 627, 713 van’t Hoff factor (i), effect of concentrations situations when simplifying assumptions enthalpies 320 on 422 fail 458–60 nomenclature 716 van’t Hoff, Jacobus Henricus 370 solutions containing salt of 458 orbital overlaps 204–5 vaporisation 245 weak base–strong acid titrations 474–7 triple points 270 vapour pressure titration curves 475 triplets (t) 903, 906 effect of nonvolatile solutes on solvents 412 weak-field ligands 576 triprotic acids 434, 623, 632 ideal, two-component solution of volatile white phosphorus 264, 608, 633 speciation diagrams 479 compounds 413 melting points 610 triprotic binary acids 461 relationship with mole fractions 411 reactivity 609 trisaccharides 999 temperature effect on 261–2 Wilkins, Maurice 286 tropical oils 1045 of two volatile liquids 413 wine industry and chemical analysis 39 tungsten 265 venoms and treatments 1085 Wohwill process 520 nomenclature 564 vibrational infrared 882 work 303 valence electrons 149 viscosity of liquids 261 calculating maximum non-pV work 337 tungsten carbides 288 vitamin A 722, 961 and Gibbs energy (G) 336–7 tungsten hexafluoride molar mass 229 vitamin C 997 World Organization for Animal Health 1084 tyrosines 1065 voltmeters 506 volts (V) 506, 507 X U volume xenon 163, 618 Uhlenbeck, George 137 relationship between amount of gas and 222 xenon oxides 617, 618–19 ultraviolet (UV) radiation 122, 175 relationship between pressure and 221 xenon tetrafluorides 188 uncertainties 33–8 relationship between temperature and 221 x-ray crystallography 3, 176, 916, 917 in calculations 35–6 calculating volume–pressure variations x-ray diffractions 284–6 uncertainty principle 135 223–4 x-rays 122 unimolecular reactions 671, 801 effect on entropy (S) 325 xylene 740 unit cells 277–9 volumetric flasks 101 units 26, 29–30, 300 von Fraunhofer, Joseph 777 units of concentration 31 von Liebig, Justus 758 Y units of molar mass 31 yttrium barium copper oxide superconductors 287 universes 300 W unpaired electrons 154–5 warfarin 1019 Z a, b-unsaturated acids 955 water 48, 184, 396 See also autoprotolysis of Zaitsev’s elimination 807 unsaturated fatty acids 1044 water Zaitsev’s rule 807, 831, 833 unsaturated hydrocarbons 698, 711 See also as acid and base 432, 434 zeolites 621 alkenes; alkynes; arenes acid–base properties 623 zero order reactions 662 nomenclature 716–17 acid–base reactions in 436–42 zero-order rate laws 662–4, 671 unsaturation index See index of hydrogen addition to alkenes 728–30 kinetics for reactions 664 deficiency (IHD) critical points 269 Zewail, Ahmed H 640 upfield positions 897 effect on entropy 326 zinc 266 uranium isotopes 613 ice 258 applications of 592 urea molal freezing point depression hcp structures 277 calculating standard entropy of constants 420 oxidation 534 formation 329–30 normal boiling points 262 by-products 606 calculating standard Gibbs energy oxidation processes 581 reaction with copper ions 505 change 333–4 periodic trends in boiling points 251 reaction with silver nitrates 510–11 uronic acids 996–7 phase change data 268 zinc and hydrogen half cells 513 UV-B radiation 175 phase changes 266–7 zinc sulfide structure 283 UV/visible spectroscopy 916 reaction with carboxylic acid zinc–copper cells 507 red-violet ions 575 derivatives 1032–6 electrochemical potentials 506 specific heats and molar heat capacities zinc–manganese dioxide cells 534 V at 25° 305 zirconium carbides 288 valence bond theory 196–205, 944 structures of ice 251 zirconium oxides (zirconia) 288, 289 benzenes 735 triple points 270 zircons 266 hybrid orbitals 197–202 vapour pressure variations 262 zone refining processes 606–7 multiple bonds 202–5 Watson, James 286 zwitterions 449, 1062, 1069, 1071

Index I-1159

BMIndex I-1159 1 June 2015 9:06 AM BMIndex I-1160 1 June 2015 9:06 AM BMIndex I-1161 1 June 2015 9:06 AM BMIndex I-1162 1 June 2015 9:06 AM BMIndex I-1163 1 June 2015 9:06 AM BMIndex I-1164 1 June 2015 9:06 AM