P.A. Cox - Inorganic chemistry (793955), страница 64
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(1987) The Electronic Structure and Chemistry of Solids, Oxford University Press, Oxford, UK.Müller, U. (1993) Inorganic Structural Chemistry, Wiley, Chichester, UK.Smart, L. and Moore, E. (1996) Solid State Chemistry, 2nd edn., Chapman and Hall, London, UK.Wells, A.F. (1985) Structural Inorganic Chemistry, 5th edn., Clarendon Press, Oxford, UK.West, A.R. (1984) Solid State Chemistry and its Applications, Wiley, Chichester, UK.Section EBurgess, J. (1978) Metal Ions in Solution, Ellis Horwood, Chichester, UK.Jensen, W.B.
(1980) The Lewis Acid-Base Concepts: An Overview, Wiley, New York, USA.Gutmann, V. (1968) Coordination Chemistry in Nonaqueous Solution, Springer, Berlin, Germany.Section F, G, H, IChriste, K.O. (2001) A Renaissance in Noble Gas Chemistry, Angewandte Chemie International Edition, vol. 40, pages 1419–21.Cotton, F.A. and Wilkinson, G. (1988) Advanced Inorganic Chemistry, 5th edn., Wiley, New York, USA.Elsenbroich, Ch.
and Salzer, A. (1992) Organometallics: A Concise Introduction, 2nd edn., VCH, Weinheim, Germany.Greenwood, N.N. and Earnshaw, A. (1997) Chemistry of the Elements, 2nd edn., Butterworth-Heinemann, Oxford, UK.Kettle, S.F.A. (1998) Physical Inorganic Chemistry: A Coordination Chemistry Approach, Oxford University Press, Oxford, UK.Nicholls, D. (1974) Complexes and First-Row Transition Elements, Macmillan, London, UK.Seabourg, G.T. and Loveland, W.D. (1990) The Elements Beyond Uranium, Wiley-Interscience, New York, USA.Section JCox, P.A.
(1989) The Elements: Their Origin, Abundance and Distribution, Oxford University Press, Oxford, UK.Cox P.A. (1995) The Elements on Earth: Inorganic Chemistry in the Environment, Oxford University Press, Oxford, UK.Kaim, W. and Schwederski, B. (1994) Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life, Wiley, Chichester, UK.Thompson, D. (1995) Insights into Speciality Inorganic Chemicals, Royal Society of Chemistry, London, UK.Thompson, R. (1995) Industrial Inorganic Chemicals: Production and Uses, Royal Society of Chemistry, London, UK.Williams, R.J.P. and Frausto de Silva, J.J.R. (1991) The Biological Chemistry of the Elements: The Inorganic Chemistry of Life, ClarendonPress, Oxford, UK.APPENDIX ITHE ELEMENTS 1–103A periodic table of elements can be found in Appendix II.APPENDIX IITHE PERIODIC TABLE OF ELEMENTSINDEX18-electron rule, 210, 237–238, 241abundance, 253–255acceptor 89;see also acidacceptor number, 126acid anydride, 171acid dissociation constant, see acidity constantacid, 26, 265–266, 270Brønsted, 114, 127, 129–132, 151, 178hard/soft, 90, 134, 197, 200, 209, 217Lewis, 89–91, 126, 147, 154, 200Lux-Flood, 127acidity constant, 130–132activation energy, 32, 120, 267adsorption, 267alkalide, 191alkyl migration, 242Allred-Rochow electronegativity, 21alternation effect, 148alumina, 201aluminosilicate, 201amalgam, 197, 264ambidentage ligand, 226ammonia, 56, 63–65, 118, 161–162, 265ammonium ion, 52, 162amphoterism, 132, 139, 171, 194, 200analysis, 45–47aromaticity 82associative mechanism, 228–229atmosphere, 258atomic mass, 2atomic number, 2, 12atomic orbital, 6–7, 9, 67–70, 211atomic radius, 8, 16, 27, 109aufbau principle, 13autoionization, 127autoprotolysis, 127azide, 164band model, 120–122bandgap, 121base, 26, 89–91Brønsted, 98, 127, 129–131hard/soft, 90, 127, 134Lewis, 89–91, 126, 131Lux-Flood, 127benzene 82bleach, 178, 266body-centred cubic structure, 100Bohr radius, 8boiling point, 92–93, 150bond angle, 39, 58, 77bond energy, see bond enthalpybond enthalpy, 85–88, 149, 151, 208bond length, 39, 49, 91, 88bond order, 69, 71bond polarity, 23–24, 73, 94bond stretching frequency, 47, 88, 236borane, 83, 153Born model, 125Born-Haber cycle, 116Born-Lande equation, 117building up principle, 13cadmium ioidide structure, 104, 110carbon cycle, 272carbon monoxide, 54, 74, 235–238carbonate, 53, 113, 119, 138, 159, 195, 265, 273carbonyl compound, 235–238carbonyl insertion, 242catalyst, 32, 114, 143, 161, 242, 267–270center of symmetry; see inversion centerceramic reaction, 43cesium chloride structure, 96, 104, 190CFC, 274chalcogen, 15, 173–176chalcogenide, 15, 110, 174;see also sulfidechalcophile, 173, 220, 256–257charge transfer transition, 231, 233β-hydride elimination, 240back donation, 235, 240281282INDEXchelate, 135, 227chimie douce, 115cis-platin, 263close packing 99–101, 105cluster compound 81, 83, 113, 225cobalamin, 262color, 122, 231–233complex, 133–136, 139, 142donor-acceptor, 89–91, 154non-transition metal, 191, 197, 246transition metal, 210–214, 217, 222, 224–238conduction band, 120conjugate acid, 129conjugate base, 129conjugate-base mechanism, 229coordination compound, 37, 39;see also complexcoordination geometry, 39, 56–60, 103–104, 219, 223, 224coordination number, 27, 39, 91, 103–105, 109, 146, 224corundum structure, 201covalent bond, 22–24, 51–86, 101, 111covalent solid, see polymeric solidcrown ether, 135cryptand, 135, 191crystal structure, 95–115;see also ionic solid, polymeric solidcrystalline solid, 49, 95Curie law, 233cyanide, 159, 212–213cyclopentadienyl compound, 83, 205, 240, 250, 269dπ-pπ bond, 146d-d transition, 231–232dative bond, 89degeneracy, 8, 11, 69, 211deltahedron, 83deuterium, 3, 152Dewar-Chatt-Duncanson model, 240diagonal relationship, 188, 189diamagnetism, 10diamond, 101, 157diborane, 55, 79, 154dielectric constant 94, 122, 125, 139dihedral axis, 63exchange reaction 42dipole moment, 23, 65, 94disproportionation, 118, 143, 179, 198, 216dissociation energy, 71;see also bond enthalpydissociative mechanism, 228–229donor number, 126donor, 89;see also baseeffective atomic number; see 18-electron ruleeffective nuclear charge, 11, 16–19, 21electride, 191electrochemical cell, 140electrode potential, 140–142, 186, 190, 200, 215–217electrolysis, 36, 177, 190, 194, 264electron affinity, 19, 116, 170electron configuration, 9, 13, 27, 69–61, 210, 213, 245electron deficiency, 54, 153electron number, 239electron spin, 10, 17, 20, 70, 213, 232electron transfer reaction, 230electronegativity, 21–24, 26, 121, 188empirical formula, 37, 46enantiomer, 227endothermic reaction, 30enthalpy, 30–31, 85–87, 92, 116–119entropy, 31, 92, 126, 131, 134, 135equilibrium constant, 31;see also acidity constant,formation constant, Gibbsfree energyessential element, 259exchange energy, 11, 208;see also spin-pairing energyexchange reaction 42exclusion principle, see Pauli exclusion principleexothermic reaction, 30explosive, 164, 171, 179extraction of elements, 35–36face-centred cubic structure, 99Faraday constant, 140Fermi level 120fertilizer, 164, 266fingerprinting, 45–49fluxional molecule, 48fluorite structure, 104formal charge, 53formation constant, 133, 197frontier orbital, 75Frost diagram, 142, 162, 179, 200, 216, 250Gibbs free energy, 31, 125, 137, 140INDEXGignard reagent, 195glass, 95, 266graphite, 102, 114, 157Haber process, 161, 268half-life, 3, 152, 181, 189, 193, 246, 248halide, 26, 58, 104, 110, 127, 178complex, 113, 134, 178, 197structure, 104–111, 178, 190, 195, 197, 200hapticity, 239hard acid/base, 90;see also acid,baseheme, 261Hess’ law, 30, 85, 116heteropolar bond, 23heteropolymetallate, 223high-spin complex, 213HOMO, 75, 90homopolar bond, 23H?ckel theory, 82Hund’s first rule, 11, 17, 70hybridization, 73, 77hydrazine, 162hydride, 26, 129, 150hydroformylation, 268hydrogen bond, 79, 93, 151hydrogen electrode, 140, 143hydrogen peroxide, 171, 266hydrogenation, 268hydrothermal reaction, 43, 114, 257hydroxide, 130, 132, 138, 139, 170hypervalence, see octet expansioninfrared, 47, 236inner-sphere mechanism, 230insertion compound, 114insulator, 120inter pair effect, 188, 202intercalation compound, 114interhalogen compound, 179intermolecular force, 92–94interstitial, 97, 122inversion center, 62, 69, 231ion exchange, 114, 246, 266ionic conductor, 122–123, 201, 270ionic radius 108–110, 118, 138–139, 186, 190, 209, 246ionic solid, 19, 23–24, 98, 121, 170, 178energy, 116–119283structure, 103–100, 170, 190, 194–195ionization energy, 8, 10, 16–19, 116, 118, 186, 209, 246Irving-Williams series, 117isoelectronic principle, 52, 112, 146, 155isomerism, 164, 222–223isopolymetallate, 223isotope 2, 152, 203, 248, 255, 263Jahn-Teller distortion, 214, 219Kapustinskii equation, 118kinetic stability, 30, 143, 228kinetics, see rate of reactionKoopmans’ theorem, 10Kroll process, 220lanthanide, 245–247lanthanide contraction, 245Latimer diagram, 142lattice energy, 116–119, 138, 186layer structure, 106, 110, 197LCAO approximation, 68–70Le Chatelier’s principle 32lead-acid battery, 203Lewis acid/base, see acid, baseLewis structure, 51ligand, 133;see also complexligand exchange, 228ligand field splitting, 211–214, 232ligand field stabilization energy, 213, 216, 217, 220, 224, 229lithophile, 220, 256London dispersion, see van der Waals’ forcelone-pair, 52;see also non-bonding electronlow-spin complex, 213, 222, 229, 234LUMO, 75, 90macrocycle, 135, 191Madelung constant, 117magnetic susceptibility, 233Marcus theory, 230mass spectrometry, 47metal-metal bond, 112, 188, 198, 202, 205, 223, 225, 234, 237metal-rich compound, 112, 180metallic element, 26, 101metallic solid, 22, 26, 97, 101metallocene, 240;see also cyclopentadienyl compound284INDEXmetalloid, 27metalloprotein, 261–261metathesis, 42microporous solid, 114mineral 96, 256–258mixed-valency compound 202, 222, 247molar mass, 2molecular formula, 37, 47molecular orbital diagram, 69, 73–74, 82, 90, 212molecular orbital, 67–84molecular solid, 92, 97Mond process, 236Monsanto process, 242Moseley’s law, 13Mulliken electronegativity, 21multicentre bond, 76, 82;see also three-centre bondmultiple bond, 28, 52–54, 71, 78, 86–88, 101, 146, 158, 163,170nephelauxetic effect, 232Nernst equation, 141neutron, 1, 49, 249, 254nickel arsenide structure, 104, 111,nitrogen fixation, 262, 273noble gas, 15, 101, 181nomenclature, 38–39, 150, 171, 225non-bonding electron, 52, 56–60, 73–75, 86, 89, 204non-crystalline solid, 95non-stoichiometry, 96, 114–115, 220non-metallic element, 26, 101, 145–148nuclear fission, 249nuclear fusion, 152, 254nuclear magnetic resonance, 3, 48nucleus, 1–3, 248, 254octahedron, 57, 62, 103–105, 211–213octet expansion, 52, 146octet rule, 27, 52, 145optical absorption, 48, 121, 231optical activity, 63, 227optical isomer, 227orbital approximation, 9, 67orbital energy, 10, 13;see also molecular orbital diagramorganometallic compound, 191, 195, 197, 201, 205, 239–244,250, 268outer-sphere mechanism, 230oxidation number, see oxidation stateoxidation state, 34–35, 38–40, 118–119, 141–142oxidation, 33–36, 269;see also redox reactionoxidative addition, 238, 242oxide bronze, 115oxide, 27, 170acid/base properties, 27, 127, 131, 170complex, 113, 170structure, 103–105, 113–115, 170, 190, 219, 223oxidizing agent, 33, 141, 147, 164, 179oxoacid, 27, 34, 131, 163, 170, 175, 178oxoanion, 26, 113, 147, 163, 170, 175, 178, 216, 219, 223oxocation, 163, 249ozone, 169π acceptor, 212, 235–238, 241π donor, 212π orbital, 70, 74, 78, 235, 241paramagnetism, 10, 70, 233–234Pauli exclusion principle, 10, 13, 17, 56, 69Pauling electronegativity, 21, 87Pauling’s rules, 132penetration, 11periodic table, 12–19, 25–28, 186perovskite structure, 113, 115peroxide, 34, 171, 190, 238, 262peroxoacid, 172, 266pH, 130, 136, 139, 216photosynthesis, 261, 272pK, see acidity constantplatinum metal, 209pnictide, 165pnictogen, 165point group, 61–65polarity, see bond polarity, dipole moment, solventpolarizability 93, 110, 139polyanion, 112, 147, 205polybasic acid, 129, 132polycation, 147, 176, 180, 198polymeric solid, 22, 98, 101, 106, 170, 194polymerization, 91, 146, 178,, 223, 242, 269polymorphism, 96polynuclear complex, 225, 237polyprotic acid, 129, 132precipitation, 43, 258principal axis, 63protolysis, 129–132proton, 1INDEXquantum number, 6, 10, 16radial probability distribution, 7, 11radioactive decay series, 3–4, 249radioactivity, 3, 152, 177, 181, 189, 193, 246, 248–249, 263radius-ratio rules, 109RAM, see atomic massrare earth, 246rate of reaction, 32, 143, 228–230reaction mechanism, 228–230redox reaction, 33–36, 140–143, 230reducing agent, 33, 141, 147, 190reduction, 33–36;see also redox reactionreductive elimination, 238, 242reflection plane, 61–63relativistic effect, 19resonance, 53, 79, 82, 132, 146rhenium troxide structure, 104, 107rocksalt structure, 104, 190, 194, 219rotation axis, 61–62rutile structure, 104Rydberg constant, 8σ donor, 212σ orbital, 68–70Schr?dinger’s equation, 5, 9screening, 11, 13selection rule, 231semiconductor, 121–123, 201Schönflies notation, 63–64siderophile, 256silica, 95, 159silicate, 106, 113, 159, 257soap, 266soft acid/base, 90–91;see also acid, basesolid, 22–23, 95–123;see also ionic solid, metallic solid, polymeric soliddefects, 122–124electronic properties, 115, 120–123synthesis, 43, 115solubility product, 137solubility, 125, 137–139, 189, 195, 204, 258solvation, 125, 133solvation energy, 125, 134, 138, 189solvent leveling, 131solvent system, 127, 180solvent, non-aqueous, 43, 125–128, 139, 162, 176, 180, 190solvolysis, 127spectrochemical series, 212spectroscopy, 8, 12–13, 45–48, 231–233, 236sphalerite structure, 104spin-only formula, 233spin-pairing energy, 213spinel structure, 201, 220standard state, 31steric number, 57–60, 146stoichiometric formula, 37, 46stoichiometry, 27, 37, 39, 96, 103suboxide, 191sulfide, 110, 138, 174, 196, 220, 257sulfuric acid, 127, 129, 175, 265, 268, 273superacid, 176superoxide, 171, 190, 262symmetry, 61–66symmetry operation, 61–65symmetry element, 61–65synergic effect, 235syngas, 268synthesis, 41–44, 115, 151, 154, 158, 166, 174, 181, 242tetrahedron, 57, 64, 103, 214thermochemical radius, 118thermodynamics, 29–32;see also enthalpy, entropy, Gibbs free energythree-centre bond, 54, 76, 78–80, 181toxicity, 260, 263trace element, 261–262trans effect, 229trans influence, 229transactinide element, 249transuranium element, 248–252trigonal bipyramid, 57–58tritium, 152Trouton’s rule, 92tungsten bronze, 97, 115, 121Union-Carbide process, 268unit cell, 96–97vacancy, 97, 122valence band, 120–121valence structure, 51–55valency, 39, 145van der Waals’ force, 91, 110, 117Vaska’s compound, 238VSEPR model, 56–60, 146, 180, 182285286INDEXWade’s rules, 83, 205water, 39, 43, 56, 77, 125–144, 152, 271–273wavefunction, see atomic orbital, molecular orbitalWerner complex, 224Wilkinson’s catalyst, 269X-ray, 12–13, 48–49Zeise’s salt, 240zeolite, 114, 266, 270Ziegler-Natta catalyst, 269zinc blende structure, 104Zintl compound, 112, 160, 202.
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