INDEX

A acidic solutions 468 reaction with phosphorus halides acidity constants (Ka) 478 See also 686–7 absolute temperature 320 Henderson–Hasselbalch equation reaction with thionyl chloride 686 absolute uncertainty in measurements 112 buffer solutions 490–1 solubility 436 absorption spectrum 165 determining 480 structural formulae for various 56–7 acceptor stems 782 values for weak monoprotic acids at aldehydes 683, 690, 691–2, 734 accessible electrons See valence electrons 25 °C 479 condensed structural formula 58–9 accuracy of measurement 109 acidophiles 458–9 aldopentoses 739 acetals 742 acids See also conjugate acids; monoprotic aldoses 734, 737 acetic acid and vapour pressure 291 acids; strong acids; weak acids algebraic equations 84–7 acetone of alcohols 684 aliphatic amines 694, 702–3 boiling point and structure 262–3 amino acids 758 nomenclature 695–6 dipolar forces 262 balancing equations for redox reaction with nitrous acid 708 acetylene 616 reactions 519 aliphatic carboxylic acids 710 acetylsalicylic acid 660 binary 487–8 nomenclature 713–14 achiral molecules 663, 667 Brønsted–Lowry definitions 460–6 aliphatic hydrocarbons 590 See also acid anhydrides 711 commonly found in nature 463 alkanes nomenclature 716 commonly used in laboratories 462 alkadienes 626 acid halides 710 contributing factors to strength 487 alkali metals 25 nomenclature 716 diprotic 464, 774 alkaline batteries 542 acid ionisation constants (pKa) insects’ defence mechanisms 474 alkaline dry cells 542 acidity of αβ-ammoniumχσδλπρ groupsµνγ ε 759 polyprotic 464, 774 alkaline earth metals 25 acids 478–9 reaction with amines 704–8 alkaline regions 495–6 amines 702 redox reactions in 518–20 alkaline solutions 468 amino acids 759 strength of 472–4 alkaloids 705 interpreting 480 strength of amines 702 alkanamines 695 selected alcohols in aqueous triprotic 464 alkanes 590, 591–609 See also saturated solution 684 actinoids 24 hydrocarbons side-chain carboxyl groups 759 activation (Ea) 571, 572 balancing combustion reactions 630–2 values for weak monoprotic acids at activators 771 boiling point 261, 603–4, 681 25 °C 479 actual yields 148 conformation 593–5 acid–base indicators 493, 497–9 acyclic alkanes 60 constitutional isomerism 64–6 common 498 acyclovir 780–1 conversion from alkenes 646–7 nature’s own 499–500 acyl groups 710 cycloalkanes 595–603 acid–base reactions 123–4, 460 addition to the carbon–carbon double density 604 alkenes 637 bonds 632 high-molar-mass 604 conjugate acid–base pairs 464–6 adenine 773, 778 identifying parent chain 61 conjugate bases for Brønsted–Lowry adenosine 5′-triphosphate (ATP3-) 774–5 isomeric 604–7 acids 465 adhesive forces 289 IUPAC guidelines 62–4 identifying conjugate acid–base pairs agricultural fertilisers 366, 368 molecular and condensed structural in 465–6 air pollution and equilibrium 394–5 formulae 592 predicting equilibria 701 alanine 707, 762 nomenclature 60–4, 592 acid–base reactions in water 467–74 Fischer projections 756 physical properties of 603–9 autoprotolysis of water 467–9 COPYRIGHTEDalcohols 665, 677–93 MATERIALreactions of 630–2 pH 469–72 acid-catalysed dehydration 687 solubility 681 strength of 472–4 acid-catalysed dehydration to alkanolates 685 acid–base titrations 493–9 alkenes 687–90 alkatrienes 626 acidic region 495 basicity of 684–5 alkenes 590, 609–30 alkaline region 495–6 boiling point and solubility 681 acid-catalysed hydration 640–1 calculating endpoint 496 classifiying 680 addition of bromine and chlorine equivalence points 495 conversion to haloalkanes 685–7 644–5 initial pH 495 ester formation 692–3 alcohol conversion by strong acid–base titrations 494–7 acid ionisation constants (pKa) 684 dehydration 687–90 acid-catalysed dehydration naming guidelines 677–9 characteristics of addition alcohols 687–90 physical properties of 680–1 reactions 632 three-step 689 preparation from alkenes 682 cis–trans isomers 611–12 two-step 689–90 preparation from haloalkanes 682–3 describing cis–trans isomers 617–19 acid-catalysed hydration 640–1 preparation of 682–3 electrophilic addition reactions 633–48 alkenes 682, 687–90 production from reducing carbonyl enthalpy of hydrogenation 646–8 mechanism of 643 compounds 683 isomers 688 acidic natural environments 458 reaction with active metals 685 low-molar-mass 610, 617 acidic regions 495 reaction with hydrohalic acids 685–6 nomenclature 614–17

Index 823

BMIndex 823 4 May 2015 1:16 PM alkenes (continued) ammonia gases, acid–base reactions atomic force microscopes 11 physical properties of 628–9 461–2 atomic mass 19–21 production into alcohol 682 ammonium dichromate 513 calculating averages from isotopic reactions of 632–48 αβ-ammoniumχσδλπρ groupµνγ ε ionisation abundances 21–2 reducing to form alkanes 646–7 constants 759 of isotopes 20 shapes of 611–13 ammonium ion buffers and pH 491–2 ranges and conventional masses 21 specifying configuration usingE,Z amorphous solids 297–8 atomic mass unit (u) 19 system 622–3 amount of substance 132 atomic numbers (Z) 18 stabilities of 646–8 amphiprotic compounds 462 atomic orbitals 157, 174, 181 tri-and tetrasubstituted amplitude 158 hybridisation processes 241–6 configurations 619–20 orbital overlaps 240 atomic radii 199–201 two-step mechanisms in electrophilic amylase, structures 768 trends in 200–1 addition reactions 635–7 amylopectin 745 atomic theories 11–15 vision and colour detection in amylose 745 atomisation enthalpy (∆atH) 341 eyes 612–13 analogous forces 260 atoms 7 ways to designate configuration 617–23 angle strain 597 absorption and emissions spectra 162–4 alkoxides 685 anhydrous 37 colours and sizes to represent 46 alkyl groups, nomenclature, formulae and aniline 696, 706, 707–8 composition 19 abbreviations 61 animal fats 748, 749 counting 136 alkylamines 695 anionic surfactants 436–7 early history 12 alkynes 590, 609 anions 7–8 electrons in 26–7 nomenclature 616–17 anode reactions 542 excited states 163 physical properties of 628–9 anodes 525–7, 538 ground states 163 shapes of 611–13 anomeric carbons 738 and light 162–3 alpha particles 17 anomers 739 lone pairs 38 amides 711–12 anti addition 645 magnetic properties of 196–7 hydrogen bonds 765 anti selectivity 645 spectra 164–6 nomenclature 716–17 antibiotics and resistant strains of structures 15–21 amines 693–709 bacteria 718 Aufbau principle 186, 191, 193 amide formation 708–9 anti-cancer drugs 668 Australian Institute of Sport 308 boiling point and solubility 697–8 anticodon 782 autoionisation of water 467 classifiying 694–5 antisense strands 783 autoprotolysis constant of water preparation from haloalkanes 698–9 antiviral drugs 780–1 (Kw) 467–9 reaction with acids 704–8 apatites 297 at various temperatures 468 reaction with bases 700–4 apoenzymes 769 autoprotolysis of water 467–9 separation and purification of 706 aqueous solutions, electrolysis in 538–40 determining if blood is acidic or strength of bases 703–4 arenes 590, 610, 649 basic 468–9 synthesis of arylamines 699 arginine and basicity 760 Avogadro constant (NA) 132–3, 136, 270 use in pharmacological drugs 705–6 , phase changes 300 axial bonds 598, 740 αβ-aminoχσδλ acidsπρ µνγ755ε arithmetic operations 80–4 axial hydrogen atoms 598 αβ-ammoniumχσδλπρ groupµνγ ε ionisation constants additions 81 interconversions 599 (pKa) 759 division and fractions 80–1 axial positions 229 amino acids 755–61 divisions 82 axial–axial interactions 599–600 20 common acids found in multiplications 80, 82 azide ions 699 proteins 756–7 percentages 82–4 azimuthal quantum numbers (l) 174 acid–base properties 758–9 subtractions 81 azo compounds 708 acidic side chains 757 aromatic amines 694, 702–3 assessing structural variations 757–8 base and acid strengths 702 chirality 755 nomenclature, molecular and condensed B acid ionisation constants (pKa) 759 structural formulae 696 balanced chemical equations 126, 128–32 L-amino acids 756 physical properties of 698 combustion of methane 630 non-polar side chains 756 reaction with nitrous acid 707–8 guidelines for 128 polar side chains 757 aromatic carboxylic acids 710 ball-and-stick models amino sugars 738 nomenclature 714 aldehydes and ketones 58 ammonia (NH3) 366, 368 aromatic compounds 648–52 alkanes 591, 593 calculating Kc from equilibrium drawing resonance structures 652–3 ammonia 227 concentrations 403–5 resonance strengths 652 butan-2-ol 665 derivatives 693 aromatic dicarboxylic acids, chlorine pentafluoride 231, 232 equilibrium constant expression nomenclature 714 chlorine trifluoride 230 (Kc) 381–2 aromatics 589 cyclohexane 598 formation of 556 Arrhenius, Svante 460, 571 methane 45, 227 phase diagrams 304–5 Arrhenius equation 573 methanol 677 tetrahedral geometry 227 aryl groups 649 napthalene 293 various representations of 47 aspirin 660 See also acetylsalicylic acid phosphorus pentachloride 229, 230

824 Index

BMIndex 824 4 May 2015 1:16 PM propane 46 blood sugar 737 burettes 493 sulfur hexafluoride 231, 232 boat conformations 598–9 butan-1-ol sulfur tetrafluoride 229, 230 conversion from chair boiling point 681 triiodide ion 230 conformations 599 nomenclature 678 water 227 Bohr, Niels 166–7 butan-2-ol 665–6 tetrafluoride 232 boiling point elevation (∆Tb) 448 nomenclature 678 Balmer, Johann 166 boiling points See also normal boiling points representations of 668–9 band (metallic solids) 296 alcohols 681 superimposed mirror images 666 barometers 268 alkanes 603–4, 681 butane 64, 127, 662 base ionisation constants (pKb) amines 697–8 boiling point 262–3 amines 702 effect of atmospheric pressure on 291 combustion 123, 126 bases 478–9 increasing temperature of water 356 line structures 44 values for weak bases at 25 °C 479–80 nonvolatile solutes 447 structures 591 bases 93 See also conjugate bases; strong selected chemical substances 300 structures for 262–3 bases; weak bases bomb calorimeters 326–7 butane-1,2,3-triol 673–4 of alcohols 684–5 bond-breaking processes 48 butane-1,4-diol, boiling point 681 amines 700–4 bond energies 211, 237–8 by-products 148 amino acids 758 bond enthalpies 340–4 Brønsted–Lowry definitions 460–6 at 25 °C 342 C common 97 calculating reaction enthalpies 343–4 caesium, 296 commonly found in nature 463–4 bond lengths 211, 235–7 Cahn–Ingold–Prelog (CIP) rules 620 commonly used in laboratories 462–3 for common chemical bonds 236 calcium 420 diprotic 464 bond-making processes 48 calcium carbide, molar mass 275–6 monoprotic 464 bond polarities 236 calcium compounds of marine polyprotic 464 bonding orbitals 240 organisms 441–2 redox reactions in 520–1 bonds See also covalent bonds; double calorimeters 324 strength of 472–4 bonds; free electrons; ionic bonds; bomb 326–7 strength of amines 702, 703–4 single bonds; triple bonds simple constant 329–30 basic solutions 468 See also alkaline bound 173 Calvin–Benson cycle 515 solutions depicting 39 capillary action 289 basicity constants (Kb) 478 fundamentals of 210–14 car industry’s fuel cell development amines 701 boron, atomic mass ranges and 546 values for weak bases at 25 °C 479–80 conventional masses 21 carbocations 689 batteries 540–6 See also fuel cells; boron trifluoride primary (1°) 636 galvanic cells sp2 hybrid orbitals 244–5 secondary (2°) and tertiary (3°) 636, 12-volt 540, 541 trigonal planar geometry 226 637, 638 dry cell 542–3 Bose–Einstein condensate 258 stability 637–40 lead storage 540–1 bound electrons and quantised stability of alkyl 638 modern high-performance 543–5 levels 173 structural representations 637 Bayer Chemicals 660 boundaries 320 carbohydrates 673, 734–47 Becquerel, Antoine, Henri 15 boundary surface diagrams 178 monosaccharides 734–41 benzene 438, 609, 648 Boyle, Robert 269 carbon Kekulé structures 649–50 Boyle’s Law 269–70 atomic mass ranges and conventional orbital overlaps 650 Bragg, Sir William Henry 215 masses 21 phase changes 300 Bragg, Sir William Lawrence 215 standard states 335 resonance energies 651–2 bridged bromonium ions 645 structural formula 39 resonance models 651 bridged halonium ions 645 carbon dioxide 208, 226 structures 649–52 bromine balanced chemical equations valence bond theories 650 addition to alkenes 644–5 129–30 benzoic acid 293, 714 addition to cycloalkenes 645 dipole moments 234 beryl 297 atomic mass ranges and conventional fire extinguishers 277 beryllium hydride masses 21 impact on coral reefs 402–3 linear geometry and Lewis boiling point 258 multiple bonds 249–50 structure 225–6 phase changes 300 phase diagrams 304 sp hybrid orbitals 245–6 1-bromo-2-chloro-1-fluoroethene 619 supercritical 302 binary acids 487–8 Brønsted, Johannes 460 carbon tetrachloride 234 binary compounds Brønsted–Lowry definition of acids and boiling point 258 chemical formulae guidelines 35 bases 460–6, 633 carbonates and solubility product nomenclature for nonmetallic 51–2 Büchner, Eduard 769 (Ksp) 440 oxidation numbers 510–11, 512 buffer solutions 488–93 carbonyl compounds 683 binary hydrogen compounds 266–7 calculating pH 489–92 carbonyl groups 734 biocatalysts 577–8 calculating pH of ammonia/ammonium carboxyl groups 710 biochemistry 5, 732 ion buffer 491–2 acidity of 758–9 biodiesels 137 preparing with predetermined pH 492–3 acidity of side-chain 759

Index 825

BMIndex 825 4 May 2015 1:16 PM carboxylic acids 59–60, 683, 690, 710–18 reaction reversibility 370 drawing 602–3 acid halides, acid anhydrides and reactions at equilibrium 369–73 polyenes 626–8 lactones 716 reactions not at 373–4 cis–trans system 617–19 amides 711–12, 716–17 relationship between Gibbs energy clathrate 266 esters 711 and 385–7 closed systems 320 lactams 716–17 chemical formulae 34–7 cochineal 499 nomenclature 713–18 binary compound guidelines 35–6 codeine 705, 706 577–9 calculating mole ratios from 137–8 coding strands 783 See also sense strands catalysts compounds 35 coenzymes 769 chemical equilibrium 393 determining 138–40 coffee cup calorimeters 329–30 effect on reaction rates 563 ionic compounds 36–7 cohesive forces 289 effect on reactions 577 chemical kinetics See kinetics combustion reactions 326 catalytic converters 395 chemical reactions 122–5 balancing 630–2 catalytic cycles 580 mechanistic arrows 48–9 octane 354 catalytic hydrogenation 646 mole ratios 143–5 rocket fuels 345 catalytic reductions 646 chemical species 6–7 common ionic effect 444–5 catenation properties 38 chemical symbols 18 common ions 445 cathode rays 16 chemical thermodynamics 318–21 See competing reactions 148 cathode reactions 542 also enthalpy (H); entropy (S) compound molecules 7 cathodes 525–7, 538 calculating heat capacity 323–4 compounds 8, 35 cathodic protection 535, 536 choosing right rocket fuels 345 calculating amounts of elements in 137–8 cations 7–8, 195–6 denoting changes in 320–1 various representations of common 47 electron configurations 195–6 equations 331–2 comproportionation reactions 541 cell potential (E cell) 528–9 See also equations manipulation 333 concentration of solutions 424–9 electrochemical potentials first law of thermodynamics 321–7 accuracy of 426 cell reactions 524 Hess’s law 332–5 calculating 425–6 electrolysis in aqueous solutions 539 important equations 385 diluting 427–9 lead storage batteries 541 second law of thermodynamics equations 424 cellulose 745, 746–7 352–5 preparing solution of known Chadwick, James 18 chemical volcanoes 513 concentration 426–7 Chain, Ernst 718 chemiluminescence 124 concentration ratios 491 chair conformations 597–8 chemistry’s broad scope and concentration tables 397, 481 conversion to boat conformations 599 applications 4–6 guidelines for 399–400 dissaccharides 742, 744 chiral molecules 662–76 condensation 259 monosaccharides 740–1 amino acids 755 condensation points 301 showing axial and equatorial in biological environments 674–5 condensed structural formulae 39–40 bonds 598 carbohydrates 734 alcohols 57 chalcogens 25 DNA 777 aldehydes and ketones 58–9 Chanteau, Stephanie 44 enantiomerism 664–70 alkanes 591 charge neutralisation processes 48–9 chlorine configurational isomers 612 Charles, Jacques-Alexandre-Cesar 270 addition to alkenes 644–5 conformationally locked isomers 600–1 Charles’ Law 270 atomic mass ranges and conventional conformations 593 chemical equations 14, 125–7 See also masses 21 alkanes 593–5 balanced chemical equations mass numbers and abundance 20 boat 598–9 chemical equilibrium 368 chlorine pentafluoride 231 chair 597–8 adding catalysts 393 chlorine trifluoride 229–30 cycloalkanes 597–601 adding inert gases at constant chlorofluorocarbons (CFCs) 579 conformers 593, 594 volumes 392 chloroform, dipole moments 234 conjugate acid–base pairs 464–6 adding/removing products or chromates and solubility product identification in acid–base reactants 388–90 (Ksp) 440 reactions 465–6 and air pollution 394–5 chromic acid 690 relative strengths in 480–1 calculating equilibrium concentrations chromium mass number and conjugate acids 464, 484, 489 from initial concentrations 400–10 abundance 20 conjugate bases 464, 465, 475, 478, calculating Kc from equilibrium chymotrypsin 674–5 480–1, 484, 489, 491–2, 495 concentrations 396–400 cis configurations 765 constitutional isomers 594, 604, 662 changing pressure in gaseous cis isomers 45, 612, 617 alkanes 64–6 reactions 390–3 cis-1,2-dimethylcyclopentane 601, 602 line structures 66 changing temperature of reaction cis-but-2-ene 612 physical properties of 606 mixtures 393 enthalpy of hydrogenation 647 recognising 65–6 changing volume of systems 390–2 cisplatin 569–70 cooling jackets technology 307–8 effect of removing product 390 11-cis-retinal 612 copper how systems establish 373 cis–trans isomers electron density plots 179 Le Châtelier’s principle 388 alkenes 611–12 reaction with silver nitrate 523 predicting shifts in 393–4 cycloalkanes 601–3, 664 reaction with zinc 522–3

826 Index

BMIndex 826 6 May 2015 1:50 PM coral reefs and impact from carbon Davisson, Clinton 171 dispersion forces 259, 260–1 See also dioxide 402–3 d-block elements 24 See also transition instantaneous dipole-induced dipole core electrons 190 metals forces Corey, Robert 765 melting points 296–7 disproportionation reactions 541 corrosion 534–6 paramagnetic properties 197 dissaccharides 742–5 environmental 536 de Broglie equation 171 3-D structures 744–5 coulomb (C) 523 de Broglie, Louis 170–1 Haworth projections and chair Coulomb’s law 210 degenerates 181 conformations 742, 744 covalent bonds 7, 8, 26, 208, 210 dehydration processes 687–90 dissociations 124 characteristic features of 211 Democritus 12 difference from dissolution 449 network solids 295 denaturation process, proteins 771–2 ionic compounds 430–1 properties of 233–9 denaturation processes 574 dissolution process 423, 430 covalent compounds 37 deoxyribonucleic acid (DNA) 692, 733, difference from dissociation 449 Crick, Francis HC 777 775 equilibrium constants 433 CrimTrac agency 785 3′ and 5′ ends 776 disulfide bonds 767–8 critical point 302 applications in crime solving 784–5 divisions, exponents 95 critical pressure 302 complementary base sequence 778–9 d-monosaccharides 736 critical temperature (Tc) 302 enzyme-substrate complex and UV DNA See deoxyribonucleic acid (DNA) C-terminal amino acids 763 radiation effect on 578 DNA fingerprinting 784–5 cyanidium caldarium 458–9 hydrogen bonding in 265 DNA ligase 780 cyclic amides and nomenclature 717 See monosaccharide components 773 DNA polymerase 779–80 also lactams primary structure of single- DNA profiling 784–5 cyclic hydrocarbons 595 stranded 775–6 double bonds 217, 248, 609 cycloalkanes 60, 595–603 replication of 779–80 depicting 39 cis–trans isomers 601–3, 664 secondary structure of double- qualitative tests for 644 conformation 597–601 sided 777–8 restricted rotations in 611–12 general formula for 596 tertiary structure (supercoiled ways of designating orientation 617–23 nomenclature 596–7 structures) 779 double helix structures of DNA 777–8 cycloalkenes three-dimensional structures 47–8 drug metabolism half lives 569–70 addition of bromine and chlorine 644 detergents 752–4 dry cell batteries 542–3 bridged halonium ions intermediates and dextrose 737 dynamic equilibrium 368 anti selectivity 645 diamagnetic atoms 197 cis–trans isomers nomenclature 626–8 diamonds 556 E dienes, trienes and polyenes 626–8 structural model 295, 563 E,Z system 617, 619–23 nomenclature 623–8 synthetic 563 assigning priorities in 620–1 cyclobutane 596 diastereomers 662, 663–4, 673 priority rules 620 cyclohexane 596 diatomic molecules 212 specifying configuration of alkenes chair conformations 597–8 diaxial interactions 599–600 in 622–3 conformational isomers 600–1 dienes, trienes and polyenes 626–8 eclipsed conformations 594 interconversion from chair to boat diethy ether eclipsed interaction strain 597 conformation 599 phase changes 300 effective nuclear charge (Zeff) 183 cyclohexanol 678 vapour pressure 291 Einstein, Albert 161, 162 cyclopentane 596 dilution of solutions 427–9 electrochemical changes 525 dimensional analysis 105–8 electrochemical potentials 524, 528 D dimethyl oxalate, structural formula 293 electrochemistry 507, 525 d,l system 736 1,2 dimethylcyclopentane 45 electrolysis 318, 319, 537–40 d orbitals 184 2,2-dimethylpropane, boiling point 261 in aqueous solutions 538–40 boundary surface diagrams 181 dinitrogen tetroxide (N2O4) sodium chloride 537–8 electron density plots 180–1 calculating Kc from equilibrium electrolysis cells 537 Daimler Chrysler and fuel cell concentrations 396–7 electrolytic cells 537 development 546 equilibrium mixture compositions compared with galvanic cells 538 d-aldohexoses 736, 737 371 electrolytic conduction 526 d-aldotetroses 736 reactions at equilibrium 369–71 electromagnetic radiation 158 d-aldotrioses 736 diols 679 electromagnetic spectra 160 Dalton (Da) 19 dipeptides 762 electron configurations 190–8 Dalton, John 13 dipolar forces 259, 262–3 See also atoms’ magnetic properties 196–7 Dalton’s atomic theory 13–14 dipole–dipole forces electron−electron repulsions 193–4 Dalton’s law of partial pressures 280 dipole moments 233–5 excited states 197 dark reactions 514–15 See also Calvin– effect on boiling points 262 ion configurations 195–6 Benson cycle predicting 234–5 orbitals with nearly equal data dipole–dipole forces 259, 260 energies 194–5 extrapolation processes 89 dipole-induced dipole forces 259, 260 electron density pictures 178 graphical representations 87–93 diprotic acids 464, 774 electron density plots 178 interpolation processes 88 diprotic bases 464 electron spin 175

Index 827

BMIndex 827 4 May 2015 1:16 PM electron transfer reactions See redox sp hybrid orbitals 246, 248 erythrose 673 reactions sp2 hybrid orbitals 245, 247 esters 683, 711 electronegativities 209, 212–14 sp3 hybrid orbitals 244 formation of 692–3 between carbon and hydrogen 603 enthalpy, standard change 331–2 inorganic acids 693 effect on acid strength 487 enthalpy (H) 328–45 nomenclature 716 between and carbon 680 bond enthalpies 340–4 triglycerides 748 between oxygen and hydrogen 680 Hess’s law 332–5 ethane, phase changes 300 electron−electron repulsions 193–4 standard change 331–2 ethane electronic conduction 526 standard enthalpy of combustion eclipsed conformation 594 ο electronic transitions 163 (∆cH ) 339–40 Lewis structures 591 electrons 7, 157 See also free electrons; standard enthalpy of formation staggered conformation 593 ο geometry (∆f H ) 335–9 ethanol in atoms 26–7 enthalpy of hydrogenation for boiling point 681 bound 173 alkenes 646–8 determining empirical formula kinetic energy 161 entropy (S) 346–51 141–2 lone pairs 38, 218, 226, 227 effect on spontaneous reactions 355 limiting and excess reagents 146 order of filling orbitals 187 number of particles, effect on 350 nomenclature 678 physical data 18 physical state factors 349–50 phase changes 300 properties of 170–2 predicting 351 production of 682 shielding 183–5 statistical probability of determining reaction rates 570 states of 163 direction of heat flow 346–8 solubility 435, 436, 681 unequal sharing 211–14 temperature factors 349 structural formula 39 electrophiles 633 volume factors 348–9 as sustainable fuel alternative 641–2 electrophilic addition reactions environmental corrosion 536 various representations of 47 alkenes 633–48 environmental disasters 208 ethene 609 mechanism of 639–40 enzyme kinetics 577–9 addition of hydrogen halides 634 two-step mechanisms 635–7 enzymes 577–8, 732–3, 769–71 See also industrial and commercial elemental analysis 138 biocatalysts importance 610 elementary reactions 575 distinguishing between multiple bonds 247–8 elements 7 enantiomers 675 nomenclature 614, 617 emission spectra 165–6 DNA 779–80 shape of 611 and hydrogen 182 nomenclature 771 ethyl stearate 137–8 empirical formulae 137–43 properties of 771 ethylene glycol 679 calculating amounts of elements in equatorial bonds 598, 600, 740 ethyne 609, 616 See also acetylene compounds 137–8 equatorial hydrogen atoms 598 gas stoichiometry 284–5 calculating percentage composition from interconversions 599 multiple bonds 248–9 chemical analysis 138–9 equatorial positions 229 nomenclature 617 calculating theoretical percentage from equilibrium arrows 368 Euler’s number 97 chemical analysis 139–40 equilibrium constant expression excess reagents 146 determining 140–3 (Kc) 370–2, 374–5 excited-state configurations 163, 197–8 guidelines for 141 adding chemical equilibria 379–80 exothermic processes 124, 308, 329, 339, emulsifying agents 753 calculating equilibrium 354–5, 393, 572 enantiomers 662–3, 664–70 concentrations 400–10 enthalpy of hydrogenation 647 alanine 756 calculating from equilibrium exponents 93–5 how enzymes distinguish between concentrations 396–400 decreasing by factor of three 96 675 changing direction of equilibrium 378 increasing by factor of two 95 representing complicated organic converting from Kp 377–8 logarithms 95–9 molecules 668–70 converting into Kp 376–7 multiplication 94–5 stereocentres 668–70 heterogeneous reactions 382–4 extensive property 324–5 endothermic processes 124, 308, 329, magnitude of 380 extrapolation processes 89 355, 393, 572–3 multiplying coefficients by a factor 379 gas–liquid solutions 433 relationship between position of F endpoints 493 equilibrium and 381 f orbitals 181 calculating strong acid and base equilibrium constant expression (Kp) Faraday, Michael 648 titrations 496 converting from Kc 376–7 fats 750 energy, quantisation 166–8 converting into Kc 377–8 rancidification 752 energy diagrams gases 374–5 fatty acids 748–9 electrophilic addition reactions 637 relationship between Kc and 375–8 amount in saturated and two-step reactions 572, 576–7 equilibrium constants 370 See also unsaturated 751 energy level diagrams 168–70, 191 autoprotolysis constant of water (Kw) reduction of chains 751–2 helium 182 calculating 372–3 fatty-acid methyl esters (FAME) hydrogen 182 gases 433 138–9 methane (CH4) 242 equivalence points 493, 495 See also f-block elements 24, 188 multi-electrons 184 stoichiometric points paramagnetic properties 197

828 Index

BMIndex 828 4 May 2015 1:16 PM fireworks galactose 743 general organic nomenclature 67–8 colour and electron Galvani, Luigi 524 genetics and chemistry 5 configurations 197–8 galvanic cells geometry ο redox reactions 509 cell potential (E cell) 529 features of molecular 238–9 first law of thermodynamics 321–7 compared with electrolytic cells 538 linear electron pairs 225–6 determining heat loss or gain 323–7 processes in 525–7 octahedral electron pairs 231–2 gases 322–3 redox reactions 522–8 optimum types for electron pairs 225 heat 322 setting up 524–5 peptide bonds 764–5 heat capacity 323–6 summary of components and tetrahedral electron pairs 227 first-order rate laws 566–8, 570 processes 527 trigonal bipyramidal electron half-lives (t½) 567–8 galvanic corrosion 536 pairs 228–30 radioactive decay of iodine 567 galvanisation process 535 trigonal planar electron pairs 226 Fischer, Emil 736, 762 garnierite 297 Gerlach, Walter 175 Fischer projections gas constants 270 germanium mass numbers and alanine 756 gas discharge tubes 16 abundance 20 converting to Haworth projections 739 gas mixtures 279–83 Germer, Lester 171 d-aldotrioses, tetroses, pentoses, Dalton’s law of partial pressures 280 Gibbs energy (G) 352–5 hexoses 736 describing 280–3 relationship between equilibrium monosaccharides 735 limiting reagents in 285–6 and 385–7 Fleming, Sir Alexander 718 mole fractions (x) 281 glass 297 See also silicon dioxide Florey, Sir Howard 718 gas stoichiometry 283–8 (SiO2) fluoresce 754 mole conversions 286–7 αβ-d-glucopyranoseχσδλπρµνγ εconformations 740 (F2) 212 summary of conversions 287 αβ-d-glucopyranoseχσδλπρµνγ ε addition to alkenes 644 gas volume chair conformations 741 boiling point 260, 266 calculating 271–2 conformations 740 dispersion forces 261 relationship between amount and 270 Haworth projections 741 unequal sharing of electron density 212 relationship between pressure and αβ-d-glucoseχσδλπρ 739µνγ ε Food Standards Australia and New 269–70 αβ-dχσ-glucoseδλπρ µνγ739ε Zealand 83 relationship between temperature d-glucose 737 formal charges 218–19 and 270 converting from Fischer to Haworth ways to minimise 221 gaseous solutions 431–2 projection 739 Franklin, Rosalind 777 gases 8, 268–79 glucose 737 See also dextrose free electrons 173, 183 adding inert gases at constant combustion reactions 331 properties of 171 volumes 392 converting line structures 42–3 free radicals 580 calculating pressure 272–3 InChI identifiers 55 freezing point depression (∆Tf) 448 calculating volume 271–2 line structures 40–1 water (H2O) 449 changing pressure in reactions 390–3 melting point 293 freezing points determining density 276–8 mole ratios in chemical reactions calculating using colligative determining molar mass 274–6 143–4 property 447–8 entropy 348–9 reaction to form lactic acid 334 lowering temperature of water 356 equilibrium constant expression structural formula 293 normal 259 (Kp) 374–5, 376–8 thermochemical equations 337 salt solutions 450 first law of thermodynamics 322–3 various representations 32–3 frequency (v) 158 graphical representations of d-glyderaldehyde 736 wavelengthαβχσδλ ( )πρ conversionsµνγ ε 159–60 experiments 87–9 glyceraldehyde 734 αβ-dχσ-fructofuranoseδλπρµνγ ε 740 ideal gas equation 270–4 reactions 675 d-fructose 737, 739 laws 269–70 stereoisomerism 735 fructose 740 phase changes 122, 301, 391 glycerol 679 fuel cells 545–6 relationship between volume and glycogen 746 fuel industry, sustainable amount 270 glycols 679 alternatives 137–9, 641–2 relationship between volume and glycosides 742 functional groups 590 See also alkanes; pressure 269–70 glycosidic bonds 742, 744, 745–6 alkynes relationship between volume and gold foil experiments 16–17 alcohols 56–7 temperature 270 Gouldsmit, Samuel 175 aldehydes and ketones 58–9 solubilities of common gases in grape sugar 737 carboxylic acids 59–60 water 432 graphite 544, 556 common 56 standard enthalpy of formation standard states 335 ο nomenclature 54–60 (∆fH ) 341 structural model 295, 563 furanoses 739 gas–liquid solutions graphs 87–93 conformations 740 effect of temperature and pressure interpreting 91–3 on 434 linear relationships 87 G ocean health 451–2 x–y 87 Gabriel synthesis 699 solubilities of common gases in greenhouse effect 120 d-galactose 737 water 432–5 greenhouse gases 265–6

Index 829

BMIndex 829 4 May 2015 1:16 PM ground-state configurations 163, 186 Hess’s law 332–5, 338 ethanol 681 conditions of 187 calculating bond enthalpies 341–3 molecular solids 293–4 helium 191 heterocyclic amines 694 hydrogen chloride gases 461 groups 24 heterocyclic aromatic amines 694 hydrogen cyanide 474 guanidine 704 base and acid strengths 702 basicity 760 nomenclature 773 applied electric fields and alignment guanine 773 physical properties of 698 of 233 heterogeneous catalysts 577 boiling point 266–7 H heterogeneous equilibrium 382 Lewis structure 217 Haber–Bosch process 368 heterogeneous reactions hydrogen halides, electrophilic addition half-cells 524 equilibrium constant expression reactions 633–7 calculating potential 531–2 (Kc) 382–4 hydrogen sulfide 209 half-equations 516–17 reaction rates 562 bonding in hybrid orbitals 243–4 half-lives (t½) hexane, solubility 435, 436 hydrogenation processes 285–6 calculating 567–8 high-molar-mass alkanes 604 hydrogen–oxygen fuel cells 545–6 first-order rate laws 567–8 holoenzymes 769 hydrohalic acids 685 reaction rates 561 homogeneous catalysts 577 hydrolysis, maltose 771 second-order rate laws 569–70 homogeneous equilibrium 382 hydrometers 541 half-reactions homogeneous reactions 382 hydronium ions 460 electrolysis in aqueous solutions 538 reaction rates 562 hydroxide ions 460 standard reduction potentials at Hund’s rule 193–4, 197 hydroxides and solubility product 25 °C 530–1 hybrid overlaps 241–6, 611 (Ksp) 440 halides and solubility product (Ksp) 440 bonding of carbon dioxide 249–50 hydroxyl groups 677 haloalkanes 682–3 hydrogen sulfide (H2S) 243–4 nomenclature 679 conversion of alcohols to 685–7 summary of valence 246 hypertonic and hypotonic solutions effect conversion to amines 698–9 hybrid orbitals 241–50, 650 on red blood cells 451 halogens 25 sp 245–6 addition to alkenes 645 sp2 244–5 I boiling point 260 sp3 241–3 ibuprofen 663 oxoacids 488 hydrates 37 active and inactive enantiomers 671–2, halonium ions 645 hydration of ions 437 675 hardening of fatty acids 751–2 polar molecules 438 ideal gas equations 270–4 Haworth, Sir Walter Norman 738 hydrocarbons 60, 589 See also immiscible liquids 435 Haworth projections saturated hydrocarbons; unsaturated improper fractions 81 converting from Fischer hydrocarbons inaccessible electrons See core electrons projections 739 classes of 590 InChI 55 dissaccharides 742, 744 constitutional isomers 604–5 induced fit models 578, 771 monosaccharides 738–40 cyclic hydrocarbons 595 inductive effects 638, 759 health sciences and benefits of hydrochloric acid reaction with sodium infixes and nomenclature 67 chemistry 5 hydroxide 329–30 inhibitors 577 heat 320 hydrogen initiators 633 determining 326–7 activity series of metals 531 inorganic acids 692, 693 first law of thermodynamics 322–7 atomic mass ranges and conventional inorganic compounds internal energy of food 326–7 masses 21 binary compounds nomenclature 53 heat capacity 323–6 atomic orbitals 181 drawing Lewis structures 218–20 calculating heat from temperature binary compounds nomenclature 53 ionic compounds nomenclature change, mass and specific heat and ball-and-stick 53–4 325–6 model 35 nomenclature processes 51–4 determining 324–5 DNA 265 nonmetallic binary compounds heat of reaction at constant pressure electron configurations 191 nomenclature 51–2 (qp) 328 electron density plots 179 space-filling models 52 helicases 780 emission spectrum 165, 166, 182 insects’ defence mechanisms 474 helium energy level diagrams 169, 182 insoluble solutes 438, 439 chemical formula and ball-and-stick energy levels 167–8 instantaneous dipole 260 model 35 fundamentals of bonding in 210–14 instantaneous dipole-induced dipole electron configurations 191 generating fuel from 546 forces 259 emission spectrum 182 interaction energy 211 instantaneous rate of change of energy level diagrams 182 orbital overlaps 241 concentration 558–9 hemiacetals 738–40 requirements for bonding 263–4 insulin 764, 768 hemicelluloses 746 hydrogen bonds 260, 263–5 integral membrane proteins 769 hemiketals 738 3-D structures 267 intensity (light) 158 Henderson–Hasselbalch equation between amide groups 765 intensive property 325 491–2 aqueous ethanol 436 intercalation processes 544 herpes infections 781 effect of intermolecular 697–8 intermolecular forces 258–68

830 Index

BMIndex 830 4 May 2015 1:16 PM International Bureau of Weights and ketoses 734 water 227 Measures 115 common 737 xenon tetrafluoride 232 International Chemical Identifier kilogram, international prototype L-glyceraldehyde 736 (InChI) 55 101, 115 light International Union of Pure and Applied kilojoule (kJ) 320 absorption and emissions spectra Chemistry (IUPAC) 25, 51, 696 See kinetic energy 258 162–4 also nomenclature kinetics 554–5, 556 atomic spectra 164–6 alcohol naming guidelines 677–8 enzymes 577–9 calculating emission energies 163–4 alkanes naming guidelines 62–3 characteristics of 158–70 first 10 alkanes 592 L energy of 161–2 prefixes for carbon atoms 60 αβ-lactamχσδλ πρantibioticsµνγ ε 718 particle properties 160–2 interpolation processes 88 lactams 711 properties 158–60 iodine nomenclature 716–17 light reactions 514 addition to alkenes 644 lactase 743 like-dissolves-like rule 436, 437 boiling point 260 lactic acid 743 limiting reagents 145–8 dispersion forces 261 lactones 711 in gas mixtures 285–6 sublimation (deposition) 300 nomenclature 716 limonene’s enantiomers 672 ion–dipole interactions 263 lactose line structures ionic bonds 208, 214–16 Haworth projection and chair aldehydes and ketones 58 ionic compounds conformations 742 alkanes 591 chemical formulae 36–7, 54 intolerance 743 constitutional isomers 66 empirical formulae 142 lagging strands 780 converting 42–3 lattice energies 216 L-amino acids 756 glucose 40–1 liquid–solid solutions 437 The Lancet 668 guidelines for 40 nomenclature 53–4 lanthanoids 24 See also rare earth isoprene 41–2 solution stoichiometry 430–1 elements Nanoputians series 44 ionic product (Qsp) 444 lattice energies 215–16 napthalene 293 ionic solids 292, 297 ionic compounds 216 linear alkylbenzenesulfonates (LAS) 754 ionisation energy (Ei) 182, 183, 201–2 Lavoisier, Antoine 12 linear geometries 611 ions 7–8 law of conservation of mass 12, 14 for two sets of electron pairs 225–6, configurations 195–6 law of definite proportions 12–13, 14 238 hydration 437 law of multiple proportions 14–15 lipid bilayers 769 iron, corrosion 534, 535 Le Châtelier, Henri 388 lipids 732, 748–54 See also triglycerides iron oxide hydroxide 535 Le Châtelier’s principle 388, 395, 687 naturally occurring 748 isobutane 662 lead storage batteries 540–1 liquid hydrogen 345 isoelectronic ions 195 leading strands 780 liquid oxygen 345 isolated systems 320 Leclanché, George 542 liquid solutions 432–8 isomeric alkanes 604–7 Leclanché cells 542 gas–liquid 432–5 physical properties of 606 Leucippus 12 liquid–liquid 435–7 isomers 662 See also constitutional Lewis, Gilbert Newton 217, 633 liquid–solid 437–8 isomers Lewis acids 633, 636 liquid–liquid solutions 435–7 configurational 612 Lewis bases 633 liquids 8, 289–91 conformationally locked 600–1 Lewis structures 216–24, 239–40 condensed phases 9 distinguishing between 39 ammonia 227 phase changes 122 relationships between 664 beryllium hydride 225–6 properties of 289–90 representations of 45 boron trifluoride 226 vapour pressure 290–1 isoprene 610 building 217–21 liquid–solid solutions 437–8 line structures 41–2 carbon dioxide 226 lithium isotonic solutions 450 carbonyl groups 734 atomic mass ranges and conventional effect on red blood cells 451 carboxyl groups 710 masses 21 isotopes 18 chlorine pentafluoride 231 electron configurations 191 medical 22, 23 chlorine trifluoride 229 lithium aluminium hydride 683 IUPAC See International Union of Pure and conventions for 217 lithium ion cells 544–5 Applied Chemistry (IUPAC) drawing guidelines 217 l-monosaccharides 736 ethane 591 lock-and-key models 578 J methane 227, 591 logarithms methanol 677 exponents 95–9 joules (J) 320, 523 nitrite ions 226 graphs 98–9 phosphorus pentachloride 228–9 types of 469–70 K resonance structures 221–4 uncertainties and significant figures Kekulé, August 649 sulfur hexafluoride 231 in 113 Kekulé structures 649–50, 651 sulfur tetrafluoride 229 low-molar-mass alkenes 610 ketones 683, 690, 691, 734 tertiary (3°) carbocation 637 nomenclature 617 condensed structural formula 58–9 triiodide ion 230 Lowry, Thomas 460

Index 831

BMIndex 831 4 May 2015 1:16 PM M metals 25 mole ratios 491 activity series 531 molecular compounds and formulae 142 magnesium corrosion 534–6 molecular equations 127 atomic mass ranges and conventional reaction with oxygen 508 molecular formulae 34, 140, 142 masses 21 reactions with alkenes 646 oxidation numbers representation 511 gas stoichiometry 287–8 methane 60 molecular solids 292–4 ionisation energy (E ) 202 i 3-D structural formulae 45 molecules 7 magnesium oxide 509 atomisation equation 341 diatomic 212 magnetic properties of atoms 196–7 balanced equations for combustion 630 line structures 44 magnetic quantum numbers (m ) 175 l phase changes 300 moles 132–6 main reactions 148 sp3 hybrid orbitals 241–3 calculating amounts of elements from maltose 742, 743–4 tetrahedral geometry 227 compounds 137–8 hydrolysis 771 various representations 34 gas stoichiometry 286–7 manometers 269 various representations of 47 ratios from chemical formulae 137–8 marine organisms methane hydrates 265–6 ratios in chemical reactions 143–5 calcium compounds and solubility methanol monophosphoric esters 774 products 441–2 chemical equilibrium 375 monoprotic acids 464 defence mechanisms 474 Lewis and ball-and-stick models 677 K and pK for weak acids at 25 C 479 poisonous proteins 772 a a ° monoprotic bases 464 Markovnikov, Vladimir 634 solubility 681 monosaccharides 734–41 Markovnikov’s rule 634–5, 637–40, 682 standard enthalpy of formation ο cyclic structures 738–41 Mars Climate Orbiter 100 (∆fH ) 343 Fischer projections 735, 737 mass numbers (A) 18 methoxyethane 263 nomenclature 737 mass percentage compositions boiling point and structure 262–3 physical properties of 738 calculating empirical formula methoxymethane structural formula 39 stereoisomerism 735 from 141–2 methyl group conformations 599–600 morphine 705 calculating from chemical 4-methylcyclopent-2-enone 669 analysis 138–9 4-methylpent-2-ene 617 mRNA See messenger RNA (mRNA) calculating theoretical percentage from 2-methylpropan-2-ol 678 multi-electrons chemical analysis 139–40 2-methylpropane 64 energy level diagrams 184 matter dipolar forces 262 ionisation energy (Ei) 202 classifying 8–10 line structures 40 orbital energies 181–2 interconverting 9 2-methylpropene shielding 183 physical properties of states 9 carbocation 638 multiple bonds 246–50 specifying states of 127 nomenclature 617 ethene 247–8 states of 258 metric systems See SI (Système ethyne 248–9 McBride, William 668 International) units multiplication, exponents 94–5 measurement Meyer, Julius Lothar 23, 156 accuracy 109 micelles 753 N precision 109, 110 Michaelis–Menten mechanisms 578 naming systems See nomenclature uncertainties and significant Millikan, Robert 16 NanoBalletDancer 44 figures 109–15 mineral oils 604 NanoKid 44 mechanistic arrows 48–9 mirror planes 667 naproxen 675 medical isotopes 22, 23 miscible liquids 435 napthalene 293 melting points 292 mixtures 9 sublimation (deposition) 300 alkanes 604 molal (b) concentration 446–7 National Aeronautics and Space amines 698 molality See molal (b) concentration Administration (NASA) 100 metals 296 molar concentration 446 National Measurement Institute molecular solids 293–4 molar enthalpy of fusion (∆fusH) 300 (NMI) 115 network solids 295 molar enthalpy of sublimation natural logs 97 selected chemical substances 300 (∆subH) 300 natural mineral formations 420 silicon dioxide 297–8 molar enthalpy of vaporisation negative catalysts 577 See also inhibitors sodium 296 (∆vapH) 299, 301 negative polarities 526 triglycerides 750, 751 molar heat capacity of selected substances emission spectrum 166 Mendeleev, Dmitri Ivanovich 23, 156 at 25 °C 325 net ionic equations 431 meniscus 289 molar masses (M) 133–4 balancing redox reactions 516–28 mercury calculating amount from mass 134 network solids 292, 295 emission spectrum 166 calculating mass from amount 135 neutral solutions 468 phase changes 300 determining of unknown gas 274–6 neutrons, physical data 18 messenger RNA (mRNA) 782–4 molar solubility (s) 442 Newman projections base sequences 783–4 calculating from solubility product cyclohexane 598 transcription process 783 (Ksp) 443–4 ethane 593, 594 metal catalysts 699 molarity (c) of solutions 446 nicad batteries 543 metallic solids 292, 295–7 mole fractions (x) 281 –cadmium storage cells 543 See metalloids 25 solutions 447 also nicad batteries

832 Index

BMIndex 832 4 May 2015 1:16 PM nickel–metal hydride batteries 543–4 nuclear medicine 567 2s orbitals nitrate ions resonance structures 221 nucleic acids 775 See also depictions of 178 nitration 699 deoxyribonucleic acid (DNA) electron density plots 183 nitrite ions 226 secondary structure 777–8 radius and nuclear charge 179 nitrogen tertiary structure 779 3s orbitals electron density plots 179 atomic mass ranges and conventional nucleons 18 order of reactions 565 masses 21 nucleophiles 633, 682 organic chemistry 633 oxidation numbers 511–12 nucleophilic substitution 682 organic compounds and functional groups phase diagrams 304 nucleoside diphosphates 774 nomenclature 54–60 solubility in water versus pressure 434 nucleoside monophosphates 774–5 organic molecules, drawing line nitrogen dioxide 395 nucleosides 773–5 structures 40–3 equilibrium constants 385–6 nomenclature 774 osmosis 450–1 equilibrium mixture compositions 371 nucleotides 774 osmotic pressure 450–1 reactions at equilibrium 369–71 structural formula 775 polysaccharides 745 resonance structures 223–4 nucleus 17 oxalates and solubility product (Ksp) 440 nitroglycerin 692 nuclides 18 oxalic acid 714 nitrous acids and reaction with aromatic nutrition information oxaliplatin 569–70 amines 707–8 calculating 78–9 oxidants 508 Nobel Prizes 215 expressing energy in SI 104–5 oxidation numbers 509–16 See also winners in chemistry 4–6, 16–17 interpreting graphs 91–3 oxidation states noble gases 25 using graphs to demonstrate 89–91 assigning numbers in redox configurations 191–2 working out energy per serving 86–7 reactions 513 nodes 179 working out percentage of daily exceptions to the rule 512 nomenclature 51–68 recommended intakes 83–4 rules for assigning 510–12 alcohols 677–9 symbols to represent 511 alkanes 60–6 use in analysing redox reactions 515 alkenes 614–16 O oxidation processes 508, 538 alkynes 616–17 ocean health and thermal pollution activity series of metals 531 amines 695–7 451–2 alkanes 630 carboxylic acid derivatives 716–18 octahedral geometries 46 silver–copper cells 525–6 carboxylic acids 712–15 six sets of electron pairs 231–2, 234, oxidation states 510 cycloalkenes 623–8 239 oxidising agents 508, 690 enzymes 771 octane, combustion reactions 354 oxoacids 487–8 general organic 67–8 octane ratings 139 oxoanions inorganic compounds 51–4 oils 750 nomenclature guidelines 54 monosaccharides 736–7 rancidification 752 resonance structures 222–3 nucleosides 774 oligopeptides 763 oxonium ions 642–3, 684 number prefixes 52 oligosaccharides 742–5 oxygen organic compounds 54–68 Open Pool Australian Light Water Reactor atomic mass ranges and conventional rules for 51 (OPAL) 22, 23 masses 21 nonbonded interaction strain 599 open systems 320 phase changes 300 nonmetallic binary compounds 51–2 opioid analgesics 705 reactions with metal 508 common roots 52 optical brighteners 754 solubility in water versus pressure nonmetals 25 orbital overlaps 240–1 434 non-polar covalent bonds 603 benzene 650 standard states 335 non-polar molecules 208 cis–trans isomers 611 ozone depletion 579–80 solubility 435, 438 conventions for model 241 non-SI units 104–5 tertiary (3°) carbocation 637 pressure 269 orbitals 178 See also d orbitals; hybrid P nonspontaneous reactions 318, 355, orbitals p orbitals 180, 186 532–4 electron distributions 178–81 paraffin wax 604 nonspontaneous redox reactions 507 energies 181–5 paramagnetic atoms 197 nonvolatile solutes 445 filling order of 186–9 parent chains 61 boiling point 447 with nearly equal energies 194–5 particles and effect on entropy (S) 350 norepinephrine 704, 705 p orbitals 180, 181 parts per billion (ppb) 282 normal boiling points 258 s orbitals 180, 195 parts per million (ppm) 282 periodic trends in binary hydrogen sizes 179 pascal (Pa) 269 compounds 267 various depictions of 178–9 passivation technique 535 selected elements 259 1s orbitals Pasteur, Louis 769 normal freezing points, selected boundary surface diagrams 179 Pauli, Wolfgang 176 elements 259 electron density plots 179, 183 Pauli exclusion principle 176, 186, 193, N-substituted primary amines 697 See 2p orbitals 197 also secondary amines; tertiary amines boundary surface diagrams 180 Pauling, Linus 212, 213, 650, 764, 765 N-terminal amino acids 763 electron density plots 183 Pauling scale 212, 213, 603

Index 833

BMIndex 833 4 May 2015 1:16 PM p-block elements 24, 188 general form 302 effect in gaseous reactions 390–3 diamagnetic properties 197 interpreting 308–9 effect on gas–liquid solubility 434–5 penicillin 711, 717, 718 nitrogen and carbon dioxide 304 effect on phase changes 301 pentan-1-ol, boiling point 681 predicting state of matter 306–7 osmotic 450–1 pentane silicon dioxide 310 relationship between volume and boiling point 261 water 303–4 269–70 electron density model 603 phenols 708 vapour 290–1 line structures 44 boiling point 258 primary (1°) carbocations 636 structures 591 phenylalanine 782 primary (1°) structures 764, 770 pentapeptides 762 phosphorus halides 685 primary alcohols 680, 682 d-pentoses 736 phosphorus pentachloride 228–9 acid-catalysed dehydration 687 penultimate carbons 736 photoelectric effect 160–1 oxidation of 690–2 peptide bonds 762 energy balance for 162 reaction with hydrohalic acids 686 geometry 764–5 photons 161, 167 two-step acid-catalysed peptides 762–4 properties of 171 dehydration 689–90 structures 763–4 photosynthesis 513–15 primary amines percentage by mass 138 photosystems I and II (PS I and base and acid strengths 702 percentage uncertainty in PSI II) 514 physical properties of 698 measurements 112 phthalimide ions 699 preparation from haloalkanes 699 percentage yields 148–9 physical state, entropy 349–50 primary cells 540 periodic table of the elements 23–5 planar structures, peptide bonds 764–5 primase 780 in block form 187 Planck’s constant (h) 161, 172 principal quantum numbers (n) 173–4 development of 156–7 planes of symmetry 667 See also mirror products 122, 368, 556 electronegativities 213 planes adding/removing in equilibrium ionisation energy (Ei) increases 201 plasma 258 388–90 modern 24–5 pnictogens 25 effect of removing 390 naming processes 25 pOH of solutions 469, 470 rates of formation 559 radii of atoms 199 polar covalent bonds 212 propan-1-ol relationship between sectors of table and polar molecules 680 boiling point 681 ground-state configurations 188 hydration 438 nomenclature 678 structures 186–9 solubility 435–6 solubility 681 periods 24 polarisability 260 structural formula 263 petrolatum 604 polarity, alcohols 680 propan-2-ol 667 petroleum industry 588–9 polyenes line structures 42 pH 469–72 drawing cis–trans isomers 627–8 nomenclature 678 ammonia/ammonium ion buffer 491–2 naming cis–trans isomers 626–7 propane balance in nature 459 polymers 633, 755 balanced chemical equations for blood 488–9 polynucleotides 776 combustion 130–1 calculating 470–2 polypeptides 763 ball-and-stick models 46 calculations in buffer solutions 489–92 structures 764 Newman projection 594–5 initial 495 polyprotic acids 464, 774 space-filling models 47 nature’s own indicators 499–500 polyprotic bases 464 staggered conformation 594–5 strong acid and base solutions 476–7 polysaccharides 742, 745–7 structures 591 strong acid–base titrations 494–6 polyunsaturated triglycerides 751 propane-1,3-diol and vapour pressure 291 value of common aqueous solutions 472 positive catalysts 577 propanoic acids 482–4 weak acid and base solutions 481–2 positive polarities 526 propene 610 weak acid–strong base titrations 497 potassium dichromate, preparing solution addition of hydrogen halides 634 weak base–strong acid titrations 497 by dilution 427–8 carbocation 637 pH meters 472 potassium sulfate, electrolysis 538–9 nomenclature 614, 617 pharmaceuticals potential difference 523 shape of 611 anti-cancer drugs 669 galvanic cells 525 proper fractions 81 early development 660–1 potential energy diagrams 571–3 propylene glycol 679 enantiomerism in drugs 668 powers of numbers 93 propyne 616 opioid analgesics 705–6 precision of measurements 109, 110 proteins 763 See also enzymes phase, light 158–9 preferred axes 174 denaturation process 771–2 phase change material (PCM) 307–8 prefixes poisonous 772 phase changes 122, 298–310 common SI units 103 primary (1°) structures 764, 770 development of cooling jackets 307–8 nomenclature and class of quaternary (4°) structures 769, 770 gases 391 compounds 67–8 secondary (2°) structures 765–7, 770 for selected substances 300 pressure (p) 268–9 structures 764–9 phase diagrams 302–7 calculating 272–3 tertiary (3°) structures 767–8, 770 aqueous solution of nonvolatile calculating pressure–volume proton transfer reactions 467 solutes 447 variations 273–4 protons 17 constructing 304–5 Dalton’s law of partial pressures 280 physical data 18

834 Index

BMIndex 834 4 May 2015 1:16 PM Proust, Joseph Louis 12 reaction rates 556–61 d-ribose 739–40 public health promotion and chemistry 6 average rate of consumption 558 ribosomal RNA (rRNA) 781–2 pure substances 9 catalysts and effect on 563 ribosomes 781–2 pure water 468 concentration–time profile of RMIT University 307–8 pH of 469 reactions 557 RNA See ribonucleic acid (RNA) purine bases 773, 777 effect of temperature on 563 rocket fuels 345 pyranoses 739 half-lives (t½) 561 Röntgen, Wilhelm 15 conformations 740 measuring concentrations over rusting See corrosion Pyrex® 298 time 557–8 Rutherford, Ernest 16–18 See also gold pyridinium chlorochromate (PCC) 691–2 nature of reactants and effect on reaction foil experiments pyrimidine bases 773, 777 rates 562 rate laws 564–70 S Q relationship between substrate and 579 s orbitals 180, 195 quadratic equations 482 temperature and effect on 563 salbutamol 706 calculating pH using 484–6 temperature factors in 571–5 salicylic acid 660, 714 qualitative analysis 126 reagents 685, 690 salt bridges 526 redox reactions 26–7, 506–7 quantisation of energy 166–8, 173–7 Sanger, Frederick 764 acidic solutions 518–20 quantitative analysis 126 saponification process 752 alcohols 690–2 quantum mechanics 172, 176 saturated fatty acids 749, 751 assigning oxidation numbers 513 quantum numbers 173–7 saturated hydrocarbons 60, 590, 591 See balancing equations in acidic quarks 18 also alkanes solutions 519 quaternary (4°) structures 768–9, 770 saturated solutions 423, 444–5 balancing net ionic equations 516–28 quotients 80–1 saturation curves 579 basic solutions 520–1 s-block elements 24 R electrolysis 537–40 diamagnetic properties 197 galvanic cells 522–8 scanning tunnelling microscopes 11, 171 R,S systems 672, 736 identifying 509 scientific notations 110 racemates 663, 668 oxidation numbers 509–16 second law of thermodynamics 352–5 racemic mixtures See racemates photosynthesis 513–15 predicting temperatures at which radioactivity 18 predicting outcome of 533–4 reactions occur 353–4 radionuclides 18 spontaneous and nonspontaneous 532–4 secondary (2°) carbocations 636, 637, Ramakrishnan, Venkatraman 782 using oxidation numbers to 638 rare earth elements 24, 297 analyse 515 secondary (2°) structures 765–7, 770 rate constants 565 reducing agents 508, 683, 699, 772 αβ-helixχσ δλpatternsπρµνγ 765–6ε rate laws 564–70, 575–6 reductants 508 αβ-pleatedχσδλπρ sheetµνγ ε766–7 electrophilic addition reactions 637 reduction potentials (Ered) 528, 529–33 secondary alcohols 680, 682 first-order 566–8 reduction processes 508, 538 acid-catalysed dehydration 687 second-order 568–70 oxygen in water 534 oxidation of 690–2 zero-order 570 silver–copper cells 525–6 reaction with hydrohalic acids 686 rate-determining steps 576 reduction–oxidation reactions See redox three-step acid-catalysed rate-limiting steps 576 reactions dehydration 689 rates of reaction 559 regioselective reactions 634, 637–40 secondary amines effect of temperature on 573–4 relaxation process 198 base and acid strengths 702 estimating initial 559–61 replication forks 780 nomenclature 697 reactants 122, 123, 368, 556 resonance models physical properties of 698 adding/removing in equilibrium aromatic compounds 652–3 secondary cells 540, 543–4 388–90 benzene 651 second-order rate laws 568–70 chemical nature and effect on reaction resonance structures 221–4 half-lives (t½) 569–70 rates 561–2 dinitrogen oxide 223–4 seesaw shapes 229, 238 concentration and effect on 562 oxoanions 222–3 semiconductors 25 physical nature and effect on reaction peptide bonds 764 sense strands 783 rates 562 reverse osmosis 446 serine 762 rates of consumption 559 reversible reactions 126 serylalanine 762 reaction rates over time 557 rhodopsin 612–13 shielding 183–5 reaction coordinates 571 ribbon models SI (Système International) units 101–4 reaction intermediates 572 double-stranded DNA 777 chemical thermodynamics 320, 348 reaction mechanisms 575–9 haemoglobin 768 common chemistry 102 catalysts 577 salivary amylase 768 common prefixes 103–4 enzyme kinetics 577–9 ribonucleic acid (RNA) 692, 775, 781–4 deriving 103 reaction quotient expression (Qc) 373 messenger RNA (mRNA) 782–4 pressure (p) 269 gases 374–5 monosaccharide components 773 seven base 101 predicting how systems change ribosomal RNA (rRNA) 781–2 standard enthalpy of reaction ο 374 transfer RNA (tRNA) 782 (∆rH ) 331 reaction quotients (Q) 373, 389 types found in Escherichia coli 781 sigmaαβχσ ( )δλ bondsπρµ νγ211ε

Index 835

BMIndex 835 4 May 2015 1:16 PM significant figures in calculations 112–14 quantification of 439–45 stereocentres significant figures in measurements relationship between solubility product 3-D structures 668–70 109–15 and 442–4 molecules with more than one 672 rules for 111 solubility products (Ksp) 439 molecules with two 673–4 silica See silicon dioxide (SiO2) calculating from solubility data 442–3 naming 671–2 silicon calculating molar solubility 443–4 rules for configuration 672 atomic mass ranges and conventional comparing values of 441 stereoisomers 673 masses 21 relationship between solubility drawing 670–1 chemical formula and ball-and-stick and 442–4 monosaccharides 734–5 model 35 selected slightly soluble salts at types of 662 structural model 295 25 °C 440 stereoviews 47–8 silicon carbide 295 solutes 423 steric strain 599, 600 See also nonbonded silicon dioxide 295 nonvolatile 445 interaction strain melting point 297–8 solution stoichiometry 150, 424–31 Stern, Otto 175 phase diagram 310 applications of 429–30 Stern−Gerlach magnetic field silver bromide ionic compounds 430–1 experiment 175 calculating solubility 442–3 solutions 422 stoichiometric coefficients 126, 368 solution stoichiometry 429–30 calculating molality (b) 446–7 stoichiometric points 493 silver–copper cells 524 colligative properties 445–52 stoichiometry 126, 143–50 See also gas anode and cathode changes 525–6 molarity (c) 446 stoichiometry cell reactions 532 solvation 437 calculating product masses from reduction potentials (Ered) 529 solvents 423 chemical reactions 144–5 simple constant calorimeters 329–30 Sørensen, Søren 469 limiting reagents 145–8 single bonds 217 sp hybrid orbitals 245–6, 611 percentage yields 148–89 depicting 39 sp2 hybrid orbitals 244–5 solution 150 strength of 652 sp3 hybrid orbitals 241–3 strong acids 475–7 See also strong bases skeletal models for cyclohexane 598 space-filling models 46–7 calculating endpoint 496 slow-release drugs 555 acid–base reactions 461 electrical conductivity 473 soaps 752–4 cis–trans isomers 612 pH calculations 476–7 sodium inorganic compounds 52 and strong base titrations 494–7 colour and electron specific heat calculations 325–6 strong bases 473, 475–7 configurations 197–8 specific heat capacity 325 calculating endpoint 496 emission spectrum 166 spectator ions 431 pH calculations 476–7 melting point 296 spin quantum numbers (ms) 175 and strong acid titrations 494–7 sodium 4-dodecylbenzenesulfonate 754 spontaneous reactions 318, 348, 352–5, structural formulae 37–44 sodium bicarbonate 532–4 amines 698 calculating decomposition 339 common 319 condensed 39–40, 57 thermal decomposition 350, 382–3 effects of standard enthalpy and entropy cycloalkenes 626 sodium borohydride 683 changes on 355 dimethyl oxalate 293 sodium chloride gaseous solutions 431 glucose 293 electrolysis 537–8 staggered conformations 593 4-methylpent-2-ene 617 ο hydration of ions 437 standard cell potentials (E cell) 528–33 subatomic particles 18 structural representations 215 standard enthalpy of combustion sublimation (deposition) 300 ο sodium hydroxide reaction with (∆cH ) 339–40 subscripts, when to use 37 hydrochloric acid 329–30 standard enthalpy of formation substituents 61 ο sodium lauryl sulfate 436–7 (∆fH ) 335–9 substrates 577–8, 771 sodium oxide 298 calculating enthalpy of reaction 338 sucrose 742, 771 sodium-vapour lamps emission selected gases at 25 °C 341 conversion into glucose and energies 163–4 selected substances at 25 °C 335–6 fructose 573–4 solid wedges 45 standard enthalpy of reaction decomposition in acidic solutions ο solids 8, 292–8 (∆rH ) 331–2 568 characteristics of different 292 effect on spontaneous reactions 355 decomposition in stomach 564–5 condensed phases 9 standard Gibbs energy change first-order rate laws 566 effect of crushing 562 (∆G ο ) 354–5 initial rates of reaction 559–61 phase changes 122 standard hydrogen electrodes (SHEs) use in nuclear medicine 567 solubility 530 suffixes in nomenclature and class of alcohols 681 standard reduction potentials compounds 67 amines 697–8, 706 common mistakes 529 sulfates and solubility product (Ksp) 440 gas–liquid solutions 432–5 values for half-reactions at 25 °C sulfonic acids 692 impact of temperature on 438 530–1 sulfur oxygen in water and oceans 452 standard states 331–2 atomic mass ranges and conventional polar and non-polar molecules starch 745 masses 21 435–6 state functions 333 chemical formula and ball-and-stick properties of 423 Steitz, Thomas A 782 model 35

836 Index

BMIndex 836 4 May 2015 1:16 PM sulfur dioxide 509–10 thermodynamic temperature 320 See also trisaccharides 742 mass composition 14 absolute temperature tropical fats 750 sulfur hexafluoride 234 thermodynamics See chemical 3-D structural formulae 46 thermodynamics U octahedral geometry 231 thermometers, degree of precision 110 Uhlenbeck, George 175 sulfur tetrafluoride 229 thiol groups 767–8 ultraviolet radiation 160 sulfur trioxide mass composition 14 thionyl chloride 685, 686 uncertainties in calculations 112–14 supercoiling formations 779 Thomson, George 171 uncertainties in measurements 109–15 superconductors 297 Thomson, JJ 16 unequal electron sharing 212–14 supercritical fluids 258, 301–2 three-dimensional structures 45–8, 178–9 units 100–8 superscripts 93 See also powers of butan-2-ol 665 chemical thermodynamics 320 numbers formulae 45–6 consequences of inconsistent use surface tension 289 hydrogen bonding 267 of 100 surroundings 320 propan-2-ol 667 dimensional analysis 105–8 symproportionation reactions 541 stereocentres 669–70 ® non-SI 104–5 syn addition 646 Taxol 669 SI (Système International) 101–4 systems 320 threose 673 unleaded petrol, calculating theoretical thymidine 773, 774 percentage composition from chemical T thymine 778 formulas 139–40 Taxol® 669 tin mass numbers and abundance 20 unsaturated fatty acids 749, 751 temperature tin plating 535 unsaturated hydrocarbons 590, 610 See cooking eggs 574–5 titrants 493 also arenes effect on conformers 594 titration curves uridine 773, 774 effect on gas–liquid solubility 434 preparing buffer solution with effect on reaction mixtures 393 predetermined 492–3 V effect on reaction rates 563, 571–5 strong base with strong acid 494–6 valence bond theories 239–50, 650 effect on solubility 438 weak acid–strong base titrations 497 valence electrons 189–90, 208 entropy 349 weak base–strong acid titrations 497 valence-shell-electron-pair repulsions impact on solubility of oxygen in water/ torsional strain 597, 599 See also (VSEPR) theory 225–32, 611 ocean 452 eclipsed interaction strain limitations of 232 relationship between volume and 270 Tour, James 44 vaporisation 259 template strands 783 See also antisense trans configurations, peptide bonds 765 vapour pressure 290–1 strands trans isomers 45, 601, 644 Vaseline® 604 tert-butyl cations 636 trans-1,2-dimethylcyclopentane 601, 602 vegetable oils 748, 749 tert-butyl group conformations 600 trans-but-2-ene 612 viscosity 290 tertiary (3°) carbocations 636, 637, 638 enthalpy of hydrogenation 647 vision and colour detection in eyes tertiary (3°) structures 767–8, 770 transcription process 783 612–13 tertiary alcohols 680, 685 trans-fats 751–2 voltmeters 524 acid-catalysed dehydration 687 transfer RNA (tRNA) 782 volts (V) 523, 525 resistance to oxidation 690, 691 transition metals 24 volume, effect of change in three-step acid-catalysed catalysts 651 equilibrium 390–2 dehydration 689 configuration of ions 195 volumetric flasks 425 tertiary amines oxidation numbers 511 base and acid strengths 702 reactions with alkenes 646 nomenclature 697 transition states 571–2 W physical properties of 698 triacylglycerols 748 water (H2O) See also pure water tertiary butyl cations 636 triatomic polar molecules 209 acid–base reactions 460–2, 467–74 tetrahedral geometry 591 triglycerides 732, 748–54 acid-catalysed hydration 640–1 electron pairs 227, 238 physical properties of 750–1 atom-level representations 7 molecular solids 294 polyunsaturated 751 autoprotolysis 467–8 network solids 295 structures 750 boiling point 267 tetrapeptides 762 trigonal bipyramid geometry 238–9 critical point 302 thalidomide 664, 668 electron pairs 228–30 geometry 227, 294 thallium, atomic mass ranges and trigonal planar geometry for electron lowering freezing point and increasing conventional masses 21 pairs 226, 238 boiling point 356 theoretical yields 148 2,3,4 trihydroxybutanal 673 molal freezing point depression theory of resonance 650 triiodide ions 230 constant 449 thermal pollution 452 triols 679 phase changes 299, 300 thermochemical equations 331–2, 336 trioses 734–5 phase diagrams 303–4 rules for manipulating 333 tripeptides 762 states of 256–7 standard enthalpy of combustion triple bonds 217, 609, 611 structure of ice 267 ο (∆cH ) 339–40 depicting 39 triple point 304 standard enthalpy of formation triple points 303, 304 vapour pressure 291 ο (∆fH ) 336–7 triprotic acids 464 various representations of 47

Index 837

BMIndex 837 4 May 2015 1:16 PM Watson, James D 777 Kb and pKb at 25 °C 479–80 Z Watson–Crick model 777 simplifying assumptions 482 wave patterns 171 and strong acid titrations 497 zero-order rate laws 570 zinc wavelengthαβχσδλ ( )πρ 158,µνγ 172ε weak polyprotic acids 758 frequency (v) conversions 159–60 white phosphorus, melting point reaction with copper ions 522–3 weak acids 461, 478–86 295 reaction with silver nitrate 527–8 calculating pH in 481–2 Wilkins, Maurice 777 zinc–copper cells 524 calculating pH values from zinc–manganese dioxide cells 542 zwitterions 755, 760–1 Ka value 482–4 X electrical conductivity 473 xenon tetrafluoride 232 K and pK at 25 C 479 a a ° x-rays 15–16 simplifying assumptions 482 x–y graphs 87 and strong base titrations 497 weak bases 461, 462, 473, 478–86 amines 700 Y calculating pH in 481–2 Yonath, Ada E 782

838 Index

BMIndex 838 4 May 2015 1:16 PM BMIndex 839 4 May 2015 1:16 PM BMIndex 840 4 May 2015 1:16 PM BMIndex 841 4 May 2015 1:16 PM BMIndex 842 4 May 2015 1:16 PM