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(BQ) Part 2 book Inorganic chemistry has contents: The group 17 elements, the group 18 elements, organometallic compounds of s and pblock elements, dBlock chemistry general considerations, dBlock metal chemistry The second and third row metals,...and other contents.
Black plate (468,1) Chapter 16 The group 17 elements TOPICS & Occurrence, extraction and uses & & Physical properties Oxides and oxofluorides of chlorine, bromine and iodine & The elements & Oxoacids and their salts & Hydrogen halides & Aqueous solution chemistry & Interhalogen compounds and polyhalogen ions 13 14 15 16 17 H 18 He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Ga Ge As Se Br Kr Rb Sr In Sn Sb Te I Xe Cs Ba Tl Pb Bi Po At Rn Fr Ra d-block 16.1 Introduction The group 17 elements are called the halogens Fluorine, chlorine, bromine and iodine The chemistry of fluorine, chlorine, bromine and iodine is probably better understood than that of any other group of elements except the alkali metals This is partly because much of the chemistry of the halogens is that of singly bonded atoms or singly charged anions, and partly because of the wealth of structural and physicochemical data available for most of their compounds The fundamental principles of inorganic chemistry are often illustrated by discussing properties of the halogens and halide compounds, and topics already discussed include: electron affinities of the halogens (Section 1.10); valence bond theory for F2 (Section 1.12); molecular orbital theory for F2 (Section 1.13); electronegativities of the halogens (Section 1.15); dipole moments of hydrogen halides (Section 1.16); bonding in HF by molecular orbital theory (Section 1.17); VSEPR model (which works well for many halide compounds, Section 1.19); application of the packing-of-spheres model, solid state structure of F2 (Section 5.3); ionic radii (Section 5.10); ionic lattices: NaCl, CsCl, CaF2 , antifluorite, CdI2 (Section 5.11); lattice energies: comparisons of experimental and calculated values for metal halides (Section 5.15); estimation of fluoride ion affinities (Section 5.16); estimation of standard enthalpies of formation and disproportionation, illustrated using halide compounds (Section 5.16); halogen halides as Brønsted acids (Section 6.4); energetics of hydrogen halide dissociation in aqueous solution (Section 6.5); solubilities of metal halides (Section 6.9); common-ion effect, exemplified by AgCl (Section 6.10); stability of complexes containing hard and soft metal ions and ligands, illustrated with halides of Fe(III) and Hg(II) (Section 6.13); redox half-cells involving silver halides (Section 7.3); non-aqueous solvents: liquid HF (Section 8.7); non-aqueous solvents: BrF3 (Section 8.10); reactions of halogens with H2 (Section 9.4, equations 9.20–9.22); hydrogen bonding involving halogens (Section 9.6) Black plate (469,1) Chapter 16 Occurrence, extraction and uses In Sections 10.5, 11.5, 12.6, 13.8, 14.7 and 15.7 we have discussed the halides of the group 1, 2, 13, 14, 15 and 16 elements respectively Fluorides of the noble gases are discussed in Sections 17.4 and 17.5, and of the d- and f-block metals in Chapters 21, 22 and 24 In this chapter, we discuss the halogens themselves, their oxides and oxoacids, interhalogen compounds and polyhalide ions Astatine Astatine is the heaviest member of group 17 and is known only in the form of radioactive isotopes, all of which have short half-lives The longest lived isotope is 210 At (t12 ¼ 8:1 h) Several isotopes are present naturally as transient products of the decay of uranium and thorium minerals; 218 At is formed from the b-decay of 218 Po, but the path competes with decay to 214 Pb (the dominant decay, see Figure 2.3) Other isotopes are artificially prepared, e.g 211 At (an a211 emitter) from the nuclear reaction 209 83 Bi(a,2n) 85 At, and may 469 be separated by vacuum distillation In general, At is chemically similar to iodine Tracer studies (which are the only sources of information about the element) show that At2 is less volatile than I2 , is soluble in organic solvents, and is reduced by SO2 to Atÿ which can be coprecipitated with AgI or TlI Hypochlorite, ½ClOÿ , or peroxodisulfate, ½S2 O8 2ÿ , oxidizes astatine to an anion that is carried by ½IO3 ÿ (e.g coprecipitation with AgIO3 ) and is therefore probably ½AtO3 ÿ Less powerful oxidizing agents such as Br2 also oxidize astatine, probably to ½AtOÿ or ½AtO2 ÿ 16.2 Occurrence, extraction and uses Occurrence Figure 16.1 shows the relative abundances of the group 17 elements in the Earth’s crust and in seawater The major APPLICATIONS Box 16.1 Flame retardants The incorporation of flame retardants into consumer products is big business In Europe, the predicted split of income in 2003 between the three main categories of flame retardants is shown in the pie chart opposite The halogenbased chemicals are dominated by the perbrominated ether ðC6 Br5 Þ2 O (used in television and computer casings), tetrabromobisphenol A, Me2 Cf4-ð2;6-Br2 C6 H2 OHÞg2 (used in printed circuit boards) and an isomer of hexabromocyclodecane (used in polystyrene foams and some textiles) Concerns about the side-effects of bromine-based flame retardants (including hormone-related effects and possible production of bromodioxins) are now resulting in their withdrawal from the market Phosphorus-based flame retardants include tris(1,3dichloroisopropyl) phosphate, used in polyurethane foams and polyester resins Once again, there is debate concerning toxic side-effects of such products: although these flame retardants may save lives, they produce noxious fumes during a fire Many inorganic compounds are used as flame retardants; for example Sb2 O3 is used in PVC, and in aircraft and motor vehicles; scares that Sb2 O3 in cot mattresses may be the cause of ‘cot deaths’ appear to have subsided; Ph3 SbðOC6 Cl5 Þ2 is added to polypropene; borates, exemplified by: Br O Br O O Br O Br B are used in polyurethane foams, polyesters and polyester resins; ZnSnO3 has applications in PVC, thermoplastics, polyester resins and certain resin-based gloss paints Tin-based flame retardants appear to have a great potential future: they are non-toxic, apparently producing none of the hazardous side-effects of the widely used phosphorusbased materials [Data: Chemistry in Britain (1998) vol 34, June issue, p 20.] Further reading C Martin (1998) Chemistry in Britain, vol 34, June issue, p 20 – ‘In the line of fire’ R.J Letcher, ed (2003) Environment International, vol 29, issue 6, pp 663–885 – A themed issue of the journal entitled: ‘The state-of-the-science and trends of brominated flame retardants in the environment’ Black plate (470,1) 470 Chapter 16 The group 17 elements APPLICATIONS Box 16.2 Iodine: from cattle feed supplements to catalytic uses The annual output of iodine is significantly lower than that of chlorine or bromine, but, nonetheless, it has a wide range of important applications as the data for 2001 in the US show: of soil and drinking water is low; iodized hen feeds increase egg production Iodine is usually added to feeds in the form of ½H3 NCH2 CH2 NH3 I2 , KI, CaðIO3 Þ2 or CaðIO4 Þ2 Uses of iodine as a disinfectant range from wound antiseptics to maintaining germ-free swimming pools and water supplies We have already mentioned the use of 131 I as a medical radioisotope (Box 2.3), and photographic applications of AgI are highlighted in Box 22.13 Among dyes that have a high iodine content is erythrosine B (food redcolour additive E127) which is added to carbonated soft drinks, gelatins and cake icings Na+ O– I I [Data: US Geological Survey] The major catalytic uses involve the complex cis½RhðCOÞ2 I2 ÿ in the Monsanto acetic acid and Tennessee– Eastman acetic anhydride processes, discussed in detail in Section 26.4 Application of iodine as a stabilizer includes its incorporation into nylon used in carpet and tyre manufacture Iodized animal feed supplements are responsible for reduced instances of goitre (enlarged thyroid gland) which are otherwise prevalent in regions where the iodine content O CO2– Na+ I O I Erythrosine B (58% iodine; max ¼ 525 nm) natural sources of fluorine are the minerals fluorspar ( fluorite, CaF2 ), cryolite (Na3 ½AlF6 ) and fluorapatite, (Ca5 FðPO4 Þ3 ) (see Section 14.2 and Box 14.12), although the importance of cryolite lies in its being an aluminium ore (see Section 12.2) Sources of chlorine are closely linked to those of Na and K (see Section 10.2): rock salt (NaCl), sylvite (KCl) and carnallite (KClÁMgCl2 Á6H2 O) Seawater is one source of Br2 (Figure 16.1), but significantly higher concentrations of Brÿ are present in salt lakes and natural brine wells (see Box 16.3) The natural abundance of iodine is less than that of the lighter halogens; it occurs as iodide ion in seawater and is taken up by seaweed, from which it may be extracted Impure Chile saltpetre (caliche) contains up to 1% sodium iodate and this has become an important source of I2 ; brines associated with oil and salt wells are of increasing importance Extraction Fig 16.1 Relative abundances of the halogens (excluding astatine) in the Earth’s crust and seawater The data are plotted on a logarithmic scale The units of abundance are parts per billion (1 billion ¼ 109 ) Most fluorine-containing compounds are made using HF, the latter being prepared from fluorite by reaction 16.1; in 2001, %80% of CaF2 consumed in the US was converted into HF Hydrogen fluoride is also recycled from Al manufacturing processes and from petroleum alkylation processes, and re-enters the supply chain Difluorine is strongly oxidizing and must be prepared industrially by Black plate (471,1) Chapter 16 Physical properties and bonding considerations electrolytic oxidation of Fÿ ion The electrolyte is a mixture of anhydrous molten KF and HF, and the electrolysis cell contains a steel or copper cathode, ungraphitized carbon anode, and a Monel metal (Cu/Ni) diaphragm which is perforated below the surface of the electrolyte, but not above it, thus preventing the H2 and F2 products from recombining As electrolysis proceeds, the HF content of the melt is renewed by adding dry gas from cylinders CaF2 þ H2 SO4 ÿÿ CaSO4 þ 2HF " ð16:1Þ conc We have already described the Downs process for extracting Na from NaCl (Figure 10.1) and this is also the method of manufacturing Cl2 (see Box 10.4), one of the most important industrial chemicals in the US The manufacture of Br2 involves oxidation of Brÿ by Cl2 , with air being swept 471 through the system to remove Br2 Similarly, Iÿ in brines is oxidized to I2 The extraction of I2 from NaIO3 involves controlled reduction by SO2 ; complete reduction yields NaI Uses The nuclear fuel industry (see Section 2.5) uses large quantities of F2 in the production of UF6 for fuel enrichment processes and this is now the major use of F2 Industrially, the most important F-containing compounds are HF, BF3 , CaF2 (as a flux in metallurgy), synthetic cryolite (see reaction 12.43) and chlorofluorocarbons (CFCs, see Box 13.7) Figure 16.2a summarizes the major uses of chlorine Chlorinated organic compounds, including 1,2-dichloroethene and vinyl chloride for the polymer industry, are hugely important Dichlorine was widely used as a bleach in the paper and pulp industry, but environmental legislations have resulted in changes (Figure 16.2b) Chlorine dioxide, ClO2 (an ‘elemental chlorine-free’ bleaching agent), is prepared from NaClO3 and is favoured over Cl2 because it does not produce toxic effluents.† The manufacture of bromine- and iodine-containing organic compounds is a primary application of these halogens Other uses include those of iodide salts (e.g KI) and silver bromide in the photographic industry (although this is diminishing with the use of digital cameras, see Box 22.13), bromine-based organic compounds as flame retardants (see Box 16.1), and solutions of I2 in aqueous KI as disinfectants for wounds Iodine is essential for life and a deficiency results in a swollen thyroid gland; ‘iodized salt’ (NaCl with added Iÿ ) provides us with iodine supplement We highlight uses of iodine in Box 16.2 16.3 Physical properties and bonding considerations Table 16.1 lists selected physical properties of the group 17 elements (excluding astatine) Most of the differences between fluorine and the later halogens can be attributed to the: inability of F to exhibit any oxidation state other than ÿ1 in its compounds; relatively small size of the F atom and Fÿ ion; low dissociation energy of F2 (Figures 14.2 and 16.3); higher oxidizing power of F2 ; high electronegativity of fluorine Fig 16.2 (a) Industrial uses of Cl2 in Western Europe in 1994 [data: Chemistry & Industry (1995) p 832] (b) The trends in uses of bleaching agents in the pulp industry between 1990 and 2001; ClO2 has replaced Cl2 Both elemental chlorine-free and totally chlorine-free agents comply with environmental legislations [data: Alliance for Environmental Technology, 2001 International Survey] The last factor is not a rigidly defined quantity However, it is useful in rationalizing such observations as the anomalous physical properties of, for example, HF (see Section 9.6), † For a discussion of methods of cleaning up contaminated groundwater, including the effects of contamination by chlorinated solvent waste, see: B Ellis and K Gorder (1997) Chemistry & Industry, p 95 Black plate (472,1) 472 Chapter 16 The group 17 elements Table 16.1 Some physical properties of fluorine, chlorine, bromine and iodine Property F Cl Br I Atomic number, Z Ground state electronic configuration Enthalpy of atomization, Áa H o (298 K) / kJ molÿ1 ‡ Melting point, mp / K Boiling point, bp / K Standard enthalpy of fusion of X2 , Áfus H o (mp) / kJ molÿ1 Standard enthalpy of vaporization of X2 , Ávap H o (bp) / kJ molÿ1 First ionization energy, IE / kJ molÿ1 ÁEA H1 o (298 K) / kJ molÿ1 à Áhyd H o (Xÿ , g) / kJ molÿ1 Áhyd S o (Xÿ , g) / J Kÿ1 molÿ1 Áhyd Go (Xÿ , g) / kJ molÿ1 Standard reduction potential, E o ðX2 =2Xÿ Þ / V Covalent radius, rcov / pm Ionic radius, rion for Xÿ / pm Ãà van der Waals radius, rv / pm Pauling electronegativity, P [He]2s2 2p5 79 53.5 85 0.51 6.62 1681 ÿ328 ÿ504 ÿ150 ÿ459 þ2.87 71 133 135 4.0 17 [Ne]3s2 3p5 121 172 239 6.40 20.41 1251 ÿ349 ÿ361 ÿ90 ÿ334 þ1.36 99 181 180 3.2 35 [Ar]3d 10 4s2 4p5 112 266 332 10.57 29.96 1140 ÿ325 ÿ330 ÿ70 ÿ309 þ1.09 114 196 195 3.0 53 [Kr]4d 10 5s2 5p5 107 387 457.5 15.52 41.57 1008 ÿ295 ÿ285 ÿ50 ÿ270 þ0.54 133 220 215 2.7 ‡ For each element X, Áa H o ¼ 12  Dissociation energy of X2 ÁEA H1 o (298 K) is the enthalpy change associated with the process XðgÞ þ eÿ ÿÿ Xÿ ðgÞ % ÿðelectron affinity); see Section 1.10 Ãà Values of rion refer to a coordination number of in the solid state à the strength of F-substituted carboxylic acids, the deactivating effect of the CF3 group in electrophilic aromatic substitutions, and the non-basic character of NF3 and ðCF3 Þ3 N Fluorine forms no high oxidation state compounds (e.g there are no analogues of HClO3 and Cl2 O7 ) When F is attached to another atom, Y, the YÿF bond is usually stronger than the corresponding YÿCl bond (e.g Tables 13.2, 14.3 and 15.2) If atom Y possesses no lone pairs, or has lone pairs but a large rcov , then the YÿF bond is much stronger than the corresponding YÿCl bond (e.g CÿF versus CÿCl, Table 13.2) Consequences of the small size of the F atom are that high coordination numbers can be achieved in molecular fluorides YFn , and good overlap of " atomic orbitals between Y and F leads to short, strong bonds, reinforced by ionic contributions when the difference in electronegativities of Y and F is large The volatility of covalent F-containing compounds (e.g fluorocarbons, see Section 13.8) originates in the weakness of the intermolecular van der Waals or London dispersion forces This, in turn, can be correlated with the low polarizability and small size of the F atom The small ionic radius of Fÿ leads to high coordination numbers in saline fluorides, high lattice energies and highly negative values of Áf H o for these compounds, as well as a large negative standard enthalpy and entropy of hydration of the ion (Table 16.1) Worked example 16.1 Saline halides For the process: Naþ ðgÞ þ Xÿ ðgÞ ÿÿ NaXðsÞ " o values of ÁH (298 K) are ÿ910, ÿ783, ÿ732 and ÿ682 kJ molÿ1 for Xÿ ¼ Fÿ , Clÿ , Brÿ and Iÿ , respectively Account for this trend Fig 16.3 The trend in XÿX bond energies for the first four halogens The process above corresponds to the formation of a crystalline lattice from gaseous ions, and ÁH o (298 K) % ÁU(0 K) The Born–Lande´ equation gives an expression for ÁU(0 K) assuming an electrostatic model and this is appropriate for the group metal halides: LAjzþ jjzÿ je2 1ÿ ÁUð0 KÞ ¼ ÿ 4p"0 r0 n Black plate (473,1) Chapter 16 Physical properties and bonding considerations 473 NaF, NaCl, NaBr and NaI all adopt an NaCl structure, therefore A (the Madelung constant) is constant for this series of compounds The only variables in the equation are r0 (internuclear distance) and n (Born exponent, see Table 5.3) The term ð1 ÿ 1nÞ varies little since n varies only from for NaF to 9.5 for NaI The internuclear distance r0 ¼ rcation þ ranion and, since the cation is constant, varies only as a function of ranion Therefore, the trend in values of ÁU(0 K) can be explained in terms of the trend in values of ranion ÁUð0 KÞ / ÿ constant þ ranion ranion follows the trend Fÿ < Clÿ < Brÿ < Iÿ , and therefore, ÁU(0 K) has the most negative value for NaF Self-study exercises What is meant by ‘saline’, e.g saline fluoride? [Ans see Section 9.7] The alkali metal fluorides, MgF2 and the heavier group metal fluorides adopt NaCl, rutile and fluorite structures, respectively What are the coordination numbers of the metal ion in each case? [Ans see Figures 5.15, 5.18a and 5.21] Given the values (at 298 K) of Áf H o (SrF2 ,s) ¼ ÿ1216 kJ molÿ1 and Áf H o (SrBr2 ,s) ¼ ÿ718 kJ molÿ1 , calculate values for Álattice H o (298 K) for these compounds using data from the Appendices Comment on the relative magnitudes of the values [Ans SrF2 , ÿ2496 kJ molÿ1 ; SrBr2 , ÿ2070 kJ molÿ1 ] Fig 16.4 (a) The structure of ½IðpyÞ2 þ (determined by X-ray crystallography) from the salt ½IðpyÞ2 ½I3 Á2I2 [O Hassel et al (1961) Acta Chem Scand., vol 15, p 407]; (b) A representation of the bonding in the cation Colour code: I, gold; N, blue; C, grey oxidation states down the group; this is well exemplified among the interhalogen compounds (Section 16.7) NMR active nuclei and isotopes as tracers Although F, Cl, Br and I all possess spin active nuclei, in practice only 19 F (100%, I ¼ 12) is used routinely Fluorine19 NMR spectroscopy is a valuable tool in the elucidation of structures and reaction mechanisms of F-containing compounds; see case studies and and the discussion of stereochemically non-rigid species in Section 2.11 Self-study exercises In each example, use VSEPR theory to help you In Section 15.3, we pointed out the importance of anion, rather than cation, formation in group 15 As expected, this is even more true in group 16 Table 16.1 lists values of the first ionization energies simply to show the expected decrease down the group Although none of the halogens has yet been shown to form a discrete and stable monocation Xþ , complexed or solvated Iþ is established, e.g in ½IðpyÞ2 þ (Figure 16.4), ½Ph3 PIþ (see Section 16.4) and, apparently, in solutions obtained from reaction 16.2 Et2 O I2 þ AgClO4 ÿÿÿÿ AgI þ IClO4 " ð16:2Þ The corresponding Br- and Cl-containing species are less stable, though they are probably involved in aromatic bromination and chlorination reactions in aqueous media The electron affinity of F is out of line with the trend observed for the later halogens (Table 16.1) Addition of an electron to the small F atom is accompanied by greater electron–electron repulsion than is the case for Cl, Br and I, and this probably explains why the process is less exothermic than might be expected on chemical grounds As we consider the chemistry of the halogens, it will be clear that there is an increasing trend towards higher In the solution 19 F NMR spectrum (at 298 K) of [BrF6 ]þ [AsF6 ]ÿ , the octahedral cation gives rise to two overlapping, equal intensity : : : quartets (J(19 F79 Br) ¼ 1578 Hz; J(19 F80 Br) ¼ 1700 Hz) What can you deduce about the nuclear spins of 79 Br and 80 Br? Sketch the spectrum and indicate where you would measure the coupling constants [Ans see R.J Gillespie et al (1974) Inorg Chem., vol 13, p 1230] The room temperature 19 F NMR spectrum of MePF4 shows a doublet (J ¼ 965 Hz), whereas that of [MePF5 ]ÿ exhibits a doublet (J ¼ 829 Hz) of doublets (J ¼ 33 Hz) of quartets (J ¼ Hz), and a doublet (J ¼ 675 Hz) of quintets (J ¼ 33 Hz) Rationalize these data, and assign the coupling constants to 31 P–19 F, 19 F–19 F or 19 F–1 H spin–spin coupling [Ans MePF4 , trigonal bipyramidal, fluxional; [MePF5 ]ÿ , octahedral, static] See also end-of-chapter problems 2.32, 2.34, 13.12, 14.13, 14.20b, 15.12 and 16.9, and self-study exercises after worked examples 13.1 and 15.2 Artificial isotopes of F include 18 F (bþ emitter, t12 ¼ 1:83 h) and 20 F (bÿ emitter, t12 ¼ 11:0 s) The former is the longest lived radioisotope of F and may be used as a radioactive Black plate (474,1) 474 Chapter 16 The group 17 elements RESOURCES, ENVIRONMENTAL AND BIOLOGICAL Box 16.3 Bromine: resources and commercial demand World reserves of bromine in seawater, salt lakes and natural brine wells are plentiful The major producers of Br2 draw on brines from Arkansas and Michigan in the US, and from the Dead Sea in Israel, and the chart below indicates the extent to which these countries dominate the world market Environmental issues, however, are likely to have a dramatic effect on the commercial demand for Br2 We have already mentioned the call to phase out some (or all) bromine-based flame retardants (Box 16.1) If a change to other types of flame retardants does become a reality, it would mean a massive cut in the demand for Br2 The commercial market for Br2 has already been hit by the switch from leaded to unleaded motor vehicle fuels Leaded fuels contain 1,2C2 H4 Br2 as an additive to facilitate the release of lead (formed by decomposition of the anti-knock agent Et4 Pb) as a volatile bromide 1,2-Dibromoethane is also used as a nematocide and fumigant, and CH3 Br is a widely applied fumigant for soil Bromomethane, however, falls in the category of a potential ozone depleter (see Box 13.7) and its use will be phased out in industrialized countries by 2005, and in developing countries by 2015 Further reading B Reuben (1999) Chemistry & Industry, p 547 – ‘An industry under threat?’ [Data: US Geological Survey] tracer The 20 F isotope has application in F dating of bones and teeth; these usually contain apatite (see Section 14.2 and Box 14.12) which is slowly converted to fluorapatite when the mineral is buried in the soil By using the technique of neutron activation analysis, naturally occurring 19 F is converted to 20 F by neutron bombardment; the radioactive decay of the latter is then monitored, allowing the amount of 19 F originally present in the sample to be determined The synthesis of F2 cannot be carried out in aqueous media because F2 decomposes water, liberating ozonized oxygen (i.e O2 containing O3 ); the oxidizing power of F2 is apparent from the E o value listed in Table 16.1 The decomposition of a few high oxidation state metal fluorides generates F2 , but the only efficient alternative to the electrolytic method used industrially (see Section 16.2) is reaction 16.4 However, F2 is commercially available in cylinders, making laboratory synthesis generally unnecessary 420 K K2 ½MnF6 þ 2SbF5 ÿÿÿÿ 2K½SbF6 þ MnF2 þ F2 " 16.4 The elements Difluorine Difluorine is a pale yellow gas with a characteristic smell similar to that of O3 or Cl2 It is extremely corrosive, being easily the most reactive element known Difluorine is handled in Teflon or special steel vessels,† although glass (see below) apparatus can be used if the gas is freed of HF by passage through sodium fluoride (equation 16.3) NaF þ HF ÿÿ Na½HF2 " ð16:3Þ Difluorine combines directly with all elements except O2 , N2 and the lighter noble gases; reactions tend to be very violent Combustion in compressed F2 ( fluorine bomb calorimetry) is a suitable method for determining values of Áf H o for many binary metal fluorides However, many metals are passivated by the formation of a layer of nonvolatile metal fluoride Silica is thermodynamically unstable with respect to reaction 16.5, but, unless the SiO2 is powdered, the reaction is slow provided that HF is absent; the latter sets up the chain reaction 16.6 SiO2 þ 2F2 ÿÿ SiF4 þ O2 " SiO2 þ 4HF ÿÿ SiF4 þ 2H2 O " † See for example, R.D Chambers and R.C.H Spink (1999) Chemical Communications, p 883 – ‘Microreactors for elemental fluorine’ ð16:4Þ 2H2 O þ 2F2 ÿÿ 4HF þ O2 " ð16:5Þ ð16:6Þ Black plate (475,1) Chapter 16 The elements Cl Br I 475 Intramolecular distance for molecule in the gaseous state / pm Intramolecular distance, a / pm Intermolecular distance within a layer, b / pm Intermolecular distance between layers / pm 199 228 267 198 227 272 332 331 350 374 399 427 Fig 16.5 Part of the solid state structures of Cl2 , Br2 and I2 in which molecules are arranged in stacked layers, and relevant intramolecular and intermolecular distance data The high reactivity of F2 arises partly from the low bond dissociation energy (Figure 16.3) and partly from the strength of the bonds formed with other elements (see Section 16.3) Charge transfer complexes Dichlorine, dibromine and diiodine Dichlorine is a pale green-yellow gas with a characteristic odour Inhalation causes irritation of the respiratory system and liquid Cl2 burns the skin Reaction 16.7 can be used for small-scale synthesis, but, like F2 , Cl2 may be purchased in cylinders for laboratory use MnO2 þ 4HCl ÿÿ MnCl2 þ Cl2 þ 2H2 O " oxidized to high oxidation states; converted to stable salts containing I in the þ1 oxidation state (e.g Figure 16.4) ð16:7Þ conc Dibromine is a dark orange, volatile liquid (the only liquid non-metal at 298 K) but is often used as the aqueous solution ‘bromine water’ Skin contact with liquid Br2 results in burns, and Br2 vapour has an unpleasant smell and causes eye and respiratory irritation At 298 K, I2 forms dark purple crystals which sublime readily at bar pressure into a purple vapour In the crystalline state, Cl2 , Br2 or I2 molecules are arranged in layers as represented in Figure 16.5 The molecules Cl2 and Br2 have intramolecular distances which are the same as in the vapour (compare these distances with rcov , Table 16.1) Intermolecular distances for Cl2 and Br2 are also listed in Figure 16.5; the distances within a layer are shorter than 2rv (Table 16.1), suggesting some degree of interaction between the X2 molecules The shortest intermolecular XÁÁÁÁX distance between layers is significantly longer In solid I2 , the intramolecular IÿI bond distance is longer than in a gaseous molecule, and the lowering of the bond order (i.e decrease in intramolecular bonding) is offset by a degree of intermolecular bonding within each layer (Figure 16.5) It is significant that solid I2 possesses a metallic lustre and exhibits appreciable electrical conductivity at higher temperatures; under very high pressure I2 becomes a metallic conductor Chemical reactivity decreases steadily from Cl2 to I2 , notably in reactions of the halogens with H2 , P4 , S8 and most metals The values of E o in Table 16.1 indicate the decrease in oxidizing power along the series Cl2 > Br2 > I2 , and this trend is the basis of the methods of extraction of Br2 and I2 described in Section 16.2 Notable features of the chemistry of iodine which single it out among the halogens are that it is more easily: A charge transfer complex is one in which a donor and acceptor interact weakly together with some transfer of electronic charge, usually facilitated by the acceptor The observed colours of the halogens arise from an electronic transition from the highest occupied à MO to the lowest unoccupied à MO (see Figure 1.23) The HOMO–LUMO energy gap decreases in the order F2 > Cl2 > Br2 > I2 , leading to a progressive shift in the absorption maximum from the near-UV to the red region of the visible spectrum Dichlorine, dibromine and diiodine dissolve unchanged in many organic solvents (e.g saturated hydrocarbons, CCl4 ) However in, for example, ethers, ketones and pyridine, which contain donor atoms, Br2 and I2 (and Cl2 to a smaller extent) form charge transfer complexes with the halogen à MO acting as the acceptor orbital In the extreme, complete transfer of charge could lead to heterolytic bond fission as in the formation of ½IðpyÞ2 þ (Figure 16.4 and equation 16.8) 2py þ 2I2 ÿÿ ½IðpyÞ2 þ þ ½I3 ÿ " ð16:8Þ Solutions of I2 in donor solvents, such as pyridine, ethers or ketones, are brown or yellow Even benzene acts as a donor, forming charge transfer complexes with I2 and Br2 ; the colours of these solutions are noticeably different from those of I2 or Br2 in cyclohexane (a non-donor) Whereas amines, ketones and similar compounds donate electron density through a lone pair, benzene uses its -electrons; this is apparent in the relative orientations of the donor (benzene) and acceptor (Br2 ) molecules in Figure 16.6b That solutions of the charge transfer complexes are coloured means that they absorb in the visible region of the spectrum (%400–750 nm), but the electronic spectrum also contains an intense absorption in the UV region (%230–330 nm) arising from an electronic transition from the solventÿX2 occupied bonding MO to a vacant antibonding MO This is the socalled charge transfer band Many charge transfer complexes can be isolated in the solid state and examples are given in Black plate (476,1) 476 Chapter 16 The group 17 elements Fig 16.6 Some examples of charge transfer complexes involving Br2 ; the crystal structure of each has been determined by X-ray diffraction: (a) 2MeCNÁBr2 [K.-M Marstokk et al (1968) Acta Crystallogr., Sect B, vol 24, p 713]; (b) schematic representation of the chain structure of C6 H6 ÁBr2 ; (c) 1,2,4,5-ðEtSÞ4 C6 H2 ÁðBr2 Þ2 in which Br2 molecules are sandwiched between layers of 1,2,4,5-ðEtSÞ4 C6 H2 molecules; interactions involving only one Br2 molecule are shown and H atoms are omitted [H Bock et al (1996) J Chem Soc., Chem Commun., p 1529]; (d) Ph3 PÁBr2 [N Bricklebank et al (1992) J Chem Soc., Chem Commun., p 355] Colour code: Br, brown; C, grey; N, blue; S, yellow; P, orange; H, white Figure 16.6 In complexes in which the donor is weak, e.g C6 H6 , the XÿX bond distance is unchanged (or nearly so) by complex formation Elongation as in 1,2,4,5ðEtSÞ4 C6 H2 ÁðBr2 Þ2 (compare the BrÿBr distance in Figure 16.6c with that for free Br2 , in Figure 16.5) is consistent with the involvement of a good donor; it has been estimated from theoretical calculations that ÿ0.25 negative charges are transferred from 1,2,4,5-ðEtSÞ4 C6 H2 to Br2 Different degrees of charge transfer are also reflected in the relative magnitudes of Ár H given in equation 16.9 Further evidence for the weakening of the XÿX bond comes from vibrational spectroscopic data, e.g a shift for ðXÿXÞ from 215 cmÿ1 in I2 to 204 cmÿ1 in C6 H6 ÁI2 ) Ár H ¼ ÿ5 kJ molÿ1 C6 H6 þ I2 ÿÿ C6 H6 ÁI2 " C2 H5 NH2 þ I2 ÿÿ C2 H5 NH2 ÁI2 " Ár H ¼ ÿ31 kJ mol ÿ1 ð16:9Þ Figure 16.6d shows the solid state structure of Ph3 PÁBr2 ; Ph3 PÁI2 has a similar structure (IÿI ¼ 316 pm) In CH2 Cl2 solution, Ph3 PÁBr2 ionizes to give ½Ph3 PBrþ Brÿ and, similarly, Ph3 PI2 forms ½Ph3 PIþ Iÿ or, in the presence of excess I2 , ½Ph3 PIþ ½I3 ÿ The formation of complexes of this type is not easy to predict: the reaction of Ph3 Sb with Br2 or I2 is an oxidative addition yielding Ph3 SbX2 , 16.1; Ph3 AsBr2 is an As(V) compound, whereas Ph3 AsÁI2 , Me3 AsÁI2 and Me3 AsÁBr2 are charge transfer complexes of the type shown in Figure 16.6d.† † For insight into the complexity of this problem, see for example: N Bricklebank, S.M Godfrey, H.P Lane, C.A McAuliffe, R.G Pritchard and J.-M Moreno (1995) Journal of the Chemical Society, Dalton Transactions, p 3873 Black plate (477,1) Chapter 16 Hydrogen halides X Ph 477 16.5 Hydrogen halides Sb Ph The nature of the products from reaction 16.10 are dependent on the solvent and the R group in R3 P Solid state structure determinations exemplify products of type [R3 PI]þ [I3 ]ÿ (e.g R ¼ n Pr2 N, solvent ¼ Et2 O) and ½ðR3 PIÞ2 I3 þ ½I3 ÿ (e.g R ¼ Ph, solvent ¼ CH2 Cl2 ; R ¼ i Pr, solvent ¼ Et2 O) Structure 16.2 shows the ½ði Pr3 PIÞ2 I3 þ cation in ½ðR3 PIÞ2 I3 ½I3 All the hydrogen halides, HX, are gases at 298 K with sharp, acid smells Selected properties are given in Table 16.2 Direct combination of H2 and X2 to form HX (see equations 9.20– 9.22 and accompanying discussion) can be used synthetically only for the chloride and bromide Hydrogen fluoride is prepared by treating suitable fluorides with concentrated H2 SO4 (e.g reaction 16.11) and analogous reactions are also a convenient means of making HCl Analogous reactions with bromides and iodides result in partial oxidation of HBr or HI to Br2 or I2 (reaction 16.12), and synthesis is thus by reaction 16.13 with PX3 prepared in situ R3 P þ 2I2 ÿÿ R3 PI4 CaF2 þ 2H2 SO4 ÿÿ 2HF þ CaðHSO4 Þ2 Ph X (16.1) ð16:10Þ " " ð16:11Þ 2HBr þ H2 SO4 ÿÿ Br2 þ 2H2 O þ SO2 ð16:12Þ conc + iPr iPr " 368 pm conc P iPr I I PX3 þ 3H2 O ÿÿ 3HX þ H3 PO3 292 pm " X ¼ Br or I ð16:13Þ iPr I I I Some aspects of the chemistry of the hydrogen halides have already been covered: P iPr iPr (16.2) Clathrates Dichlorine, dibromine and diiodine are sparingly soluble in water By freezing aqueous solutions of Cl2 and Br2 , solid hydrates of approximate composition X2 Á8H2 O may be obtained These crystalline solids (known as clathrates) consist of hydrogen-bonded structures with X2 molecules occupying cavities in the lattice An example is 1,3,5ðHO2 CÞ3 C6 H3 Á0:16Br2 ; the hydrogen-bonded lattice of pure 1,3,5-ðHO2 CÞ3 C6 H3 was described in Box 9.4 A clathrate is a host–guest compound, a molecular assembly in which the guest molecules occupy cavities in the lattice of the host species Table 16.2 liquid HF (Section 8.7); solid state structure of HF (Figure 9.8); hydrogen bonding and trends in boiling points, melting points and Ávap H o (Section 9.6); formation of the ½HF2 ÿ ion (Section 8.7; equation 9.26 and accompanying discussion); Brønsted acid behaviour in aqueous solution and energetics of acid dissociation (Sections 6.4 and 6.5) Hydrogen fluoride is an important reagent for the introduction of F into organic and other compounds (e.g reaction 13.38 in the production of CFCs) It differs from the other hydrogen halides in being a weak acid in aqueous solution (pKa ¼ 3:45) This is in part due to the high HÿF bond dissociation enthalpy (Table 6.2 and Section 6.5) At high concentrations, the acid strength increases owing to the stabilization of Fÿ by formation of ½HF2 ÿ , 16.3 (scheme 16.14 and Table 9.4) Selected properties of the hydrogen halides Property HF HCl HBr HI Physical appearance at 298 K Melting point / K Boiling point / K Áfus H o (mp) / kJ molÿ1 Ávap H o (bp) / kJ molÿ1 Áf H o (298 K) / kJ molÿ1 Áf Go (298 K) / kJ molÿ1 Bond dissociation energy / kJ molÿ1 Bond length / pm Dipole moment / D Colourless gas 189 293 4.6 34.0 ÿ273.3 ÿ275.4 570 92 1.83 Colourless gas 159 188 2.0 16.2 ÿ92.3 ÿ95.3 432 127.5 1.11 Colourless gas 186 207 2.4 18.0 ÿ36.3 ÿ53.4 366 141.5 0.83 Colourless gas 222 237.5 2.9 19.8 þ26.5 þ1.7 298 161 0.45 Black plate (919,1) Index ferrocene/ferrocenium reference electrode, 731 ferroelectric materials, 152, 599ÿ600, 656, 824 ferromagnetic coupling, 610, 629 ferromagnetic materials, 584, 608, 619 ferromagnetism, 352, 584 ferrous see iron(II) fertilizers nitrogenous, 278(B), 280(B), 357, 388, 395(B), 396, 416(B), 460 phosphate, 388, 395(B), 421(B) potassium-based, 259 fibreglass, 314(B), 826 fibres, 826 inorganic, 826ÿ7 fibrous sulfur, 439, 440 fire-resistant materials, 425 firework ingredients, 277, 278, 296, 389, 486 first order kinetics ligand substitution reactions, 773 radioactive decay, 56 first order rate constant, 56 FischerÿTropsch reaction, 803ÿ4 catalysts for, 756, 803 Fischer-type carbene complexes, 729 five-coordinate molecules d-block metal compounds, 544 fluxionality, 72, 528 rearrangements in, 73, 73(F), 528 shape(s), 45(F), 46(T), 541(T) see also pentagonal planar ; squarepyramidal ; trigonal bipyramidal molecules flame photometry, 261 flame retardants, 296, 341, 469(B), 640 boron-based, 296 halogen-based, 469(B), 471, 474(B) phosphorus-based, 389, 469(B) tin-based, 341, 389, 469(B) flame tests, 261, 279 flash photolysis, applications, 771(B), 778(B) flavours, extraction of, 231(B) flue gas desulfurization processes, 278(B) fluorescence, lanthanoid complexes, 746 fluoride acceptors, 157, 222, 224, 225, 405, 409, 440, 485 fluoride affinities, 157 fluorinating agents, 224, 409, 448, 477, 480, 481, 496, 624 fluorine abundance of isotope(s), 875 in biological systems, 830 bonding in, 391 extraction of, 470ÿ1 ground state electronic configuration, 18(T), 28ÿ9, 33, 42, 472(T), 880 occurrence, 470 physical properties, 472(T), 878, 879, 880, 883, 884, 887 radioisotopes, 473ÿ4 term symbols for, 573(B) see also difluorine fluorine bomb calorimetry, 474 fluorine nitrate, 417 fluorine-19 NMR spectroscopy, 72, 473 fluorite (CaF2 ) lattice, 149, 470 fluoro bridges, 364, 410, 451, 478, 496, 604, 655, 659 fluoroapatite, 387, 423(B), 470, 474 fluorocarbons, 361, 471 fluorosulfonic/fluorosulfuric acid, 223ÿ4, 450, 461 physical properties, 218(F), 223ÿ4 self-ionization of, 224 as solvent, 223ÿ4, 442 fluorosulfates, 450 fluorous biphasic catalysts, 798 fluorspars, 149, 277, 470, 814 fluxes, brazing/soldering, 296 fluxionality, 72ÿ3 in cyclopentadienyl complexes, 507 in d-block organometallic compounds, 713, 726, 726(F), 736 in organometallic compounds, 528, 530 in p-block compounds, 407, 507 food preservatives, 457, 459(B) fool’s gold, 432ÿ3 formamide dielectric constant, 215(T) transfer of ions to (from water), 216 formic acid hydrogen bonding in, 245, 245(F) structure, 245(F) four-centre two-electron bonding interactions, 702 four-coordinate molecules d-block metal compounds, 543ÿ4, 543(F) shape(s), 45(F), 46(T), 541(T) see also disphenoidal ; square planar ; tetrahedral molecules fourteen-coordinate molecules, f -block metal compounds and complexes, 758 francium, 257, 261, 875, 881 FranckÿCondon principle, 780 franklinite, 820 Frasch process, 433, 433(F) free energy, see also Gibbs energy Frenkel defects, 158ÿ9, 814 experimental observation of, 159 freons, 361 frequency doubling (in lasers), 744(B) FriedelÿCrafts catalysts, 281, 290, 655 FriedelÿCrafts reactions, 228, 307, 309, 310ÿ11 frontier orbitals for hexahydrohexaborate(2ÿ) ion, 329(B) see also HOMO; LUMO FrostÿEbsworth diagrams, 204ÿ8, 206(F), 207(F) for chromium in aqueous solution, 207, 207(F) interpretation of, 206ÿ8, 208(WE) limitations, 206 for manganese in aqueous solution, 205ÿ6, 206ÿ7, 206(F) for nitrogen in aqueous solution, 207ÿ8, 207(F), 399(WE) for phosphorus in aqueous solution, 207ÿ8, 207(F), 208(WE) relationship to potential diagrams, 205ÿ6 FTIR (Fourier transform infrared) spectroscopy, 800(B) fuel cells, 239, 240ÿ1(B) first obervation, 240(B) use in motor vehicles, 240ÿ1(B) Fuller, Richard Buckminster, 348 fullerenes, 1, 348ÿ53 C60 , 348 cycloaddition reaction, 353 ene-like nature, 350 halogenation reactions, 350, 350(F) oxo compounds, 350 reactivity, 349ÿ53 structure, 348, 349(F) 919 C70 , 348 structure, 349, 349(F) C120 , 353 halides, 350, 351(F) Isolated Pentagon Rule (IPR) for, 348 occurrence, 339 organometallic derivatives, 725, 725(F) production of, 348 reactivity, 349ÿ53 structures, 348, 349(F) fullerides, 270(B), 352ÿ3 structure, 352(F) superconducting salts, 352, 817 fuller’s earth, 374(B) fulminates, 380 fumaric acid hydrogen bonding in, 248(B) hydrogenation of, 799, 800(F) fumigants, 474(B) fundamental absorptions (in IR spectra), 92 fungicides, 460, 521(B), 596, 636, 638 furnace-lining bricks, 284(B) fused salts see molten salts g-radiation, 55 penetrating power of, 55(F) gadolinium abundance of isotope(s), 875 ground state electronic configuration, 18(T), 742(T), 881 physical properties, 24(F), 742(T), 745(T), 881 gadolinium(III) complexes, 74(B), 750 gadolinium hydrides, 749 galena, 210, 339, 433 gallaborane, 303ÿ4 reactions, 304 structure, 303ÿ4, 304(F) gallium abundance of isotope(s), 875 appearance of metal, 300 extraction of, 294 ground state electronic configuration, 18(T), 297(T), 880 lattice structure, 136 occurrence, 293, 294 physical properties, 134, 135(T), 297(T), 877, 879, 880, 884 radioisotopes, 324 reactivity, 301 in semiconductors, 144, 296 structure of metal, 136 worldwide production of, 295(F) gallium arsenide, 402 compared with silicon as a semiconductor, 514(B) demand for, 294, 296 doping of, 824 ternary GaAs1 ÿ x Px , 823 thin films, 823 uses, 296, 341(B), 389, 402, 514(B), 820(T), 823 gallium(I) bromide, 312 in synthesis of multinuclear gallium compounds, 312ÿ13 in synthesis of organogallium compounds, 516 gallium cage compounds, 322 gallium(I) chloride, 312, 313 gallium cyclopentadienyl complexes, 517 galliumÿgallium triple bond, 516 Black plate (920,1) 920 Index gallium hydrides, 253, 302, 303ÿ4, 303(F) see also digallane gallium nitride, 318, 820(T) gallium organometallic compounds, 514ÿ18, 516(WE) gallium oxides and hydroxides, 317 gallium trialkyls, 514ÿ15 gallium triaryls, 515 gallium trihalides, 303, 311 galvanic cells, 193ÿ4 cell potentials, 194 redox reactions in, 192 galvanized steel, 139ÿ40, 201(B), 596 gas detectors/sensors, 341, 375(B), 600(B), 687(B), 820(T) gas hydrates, 355(B) gas mantles, 756 gas masks, 340(B) gasoline, synthesis of, 803, 807 Gemini missions, 240(B) gemstones, 275ÿ6, 296, 339, 346(B) artificial, 652 geometrical isomerism in dinitrogen difluoride, 49, 405 in platinum(II) complexes, 687, 688(B) geometrical isomers, 48ÿ9, 549 IR spectroscopy, 549, 550(F) NMR spectroscopy, 550(B) platinum(II) complexes, 549, 550(F) gerade (subscript on symmetry label), 558(B) germanates, 373, 375, 375(F) germane, 219, 247(F), 355 germanium abundance, 339(F) abundance of isotope(s), 875 bond enthalpy terms, 343(T) ground state electronic configuration, 18(T), 342(T), 881 lattice structure, 149, 152 physical properties, 342(T), 877, 879, 881, 884 reactions, 353, 364 as semiconductor, 143, 341 structure, 149 uses, 341 germaniumÿcarbon bonds, 344 germanium cyclopentadienyl complexes, 520 germaniumÿgermanium bonds, 344 germanium–germanium double bonds, 520ÿ1 germanium halides, 364 germanium halohydrides, 356 germanium organometallic compounds, 520ÿ1 germanium oxides, 373, 375 germanium sulfides, 377(T), 378 germanium tetraalkyls and tetraaryls, 520 germanium Zintl ions, 358 structure, 359, 359(F) germides, 360ÿ1 germylenes, 520 getters in vacuum tubes, 278 Gibbs energy of activation, 765, 787(B) for catalysis, 787 for self-exchange reactions, 780ÿ1 Gibbs energy change on complex formation, 183, 185 for dissolution of ionic salts in aqueous solution, 175ÿ6 plots against oxidation state, 205, 206(F), 207(F) relationship with enthalpy and entropy, 169 equilibrium constant(s), 169, 175, 194 on transfer of ions from water to organic solvent, 215ÿ16 Gibbs energy profiles catalysed reactions, 787(F) ligand substitution reactions, 765 gibbsite, 316 Gillespie, R.J., 43 glass fibres, 314(B), 826 glasses, 296, 314(B), 340, 341, 369ÿ70, 434 pigments in, 627, 627(B), 638 globular proteins, 831 glucose pen meter, 731(B) glutamic acid, 831(T) glyceraldehyde, as chiral reference compound, 96(B) glycine, 831(T) glycoproteins, 833 goethite, 595, 619, 619(B) gold, 689ÿ94 abundance of isotope(s), 875 ground state electronic configuration, 18(T), 650(T), 881 metal, 689ÿ90 and nitric acid, 416 occurrence, extraction and uses, 647, 648 oxidation states, 540(T), 689ÿ90 physical properties, 135(T), 650(T), 881, 884 recycling of, 690(B) gold carbonyl, structure, 712 gold complexes, 543(F) gold(I) complexes, 694 gold(III) complexes, 690ÿ1 gold(I) cyano compounds, 694 gold(I) fluoride, 692 gold mixed-valence compounds, 691 gold(III) oxide, 690 gold(III) phosphino complexes, 691 gold trihalides, 690 Gouy balance, 579 Graham’s law of effusion, 61 gram magnetic susceptibility, 580(B) graphite compared with boron nitride, 317 intercalation compounds, 263, 345, 347ÿ8 production of, 339 reactivity, 345 salts, 347 structure, 345, 348(F) uses, 340, 340(F), 345 Gra¨tzel cell, 341(B) gravimetric analysis, 324, 632 common-ion effect in, 178 Greek letters, listed, 864 green chemistry, 228(B), 386(B), 786 Green Chemistry (RSC journal), 228(B) ‘green’ fuel, 239, 240(B) green solvents, 229, 230 GreenÿTaube experiment, 775 green vitriol, 622 greenhouse gases, 355(B), 367(B), 456(B) greenockite, 648 grey cast iron, 138(B) grey tin, 136, 137(WE), 143, 149 Grignard reagents, 509ÿ10 enantiomerically pure, 510 examples of use, 511ÿ12, 514, 524, 526, 527 preparation of, 509 ground state, of hydrogen atom, 16 ground state electronic configuration(s), 16ÿ17, 17, 21 d-block metals, 18(T), 536, 597(T), 650(T), 880, 881 determination of, 17, 21ÿ2(WE) f -block metals, 18(T), 742(T), 881, 882 listed for elements, 18(T), 880ÿ2 notation(s), 16, 17, 30, 31 p-block elements, 18(T), 297(T), 342(T), 389(T), 435(T), 472(T), 495(T), 880, 881 s-block elements, 18(T), 260(T), 278(T), 880, 881 see also aufbau principle ground state trans-influence, 688(B), 768 group 1, 257ÿ74 abundance, 257 acetylides, 261 amalgams, 263 amides, 219, 261 amido complexes, 271ÿ2 appearance of metals, 261 atomic spectra, 96, 96(B), 261 azides, 400 carbonates, 265ÿ6 compared with group 2, 289(T) complex ions in aqueous solution, 268ÿ71 extraction of metals, 257ÿ9 flame tests, 261 fullerides, 270(B), 352ÿ3 ground state electronic configurations, 18(T), 260(T), 880, 881, 882 halates, 486 halides, 145(B), 157, 263ÿ4, 478 lattice energies, 157, 264(T) radius ratios, 145(B) solubilities in water, 176(T), 264 structures, 148ÿ9 hydrated ions, 171ÿ2, 177(T), 267ÿ8 hydrides, 237, 251ÿ3, 263 hydrogencarbonates, 265ÿ6 hydroxides, 167, 265 intercalation compounds, 263, 347 IUPAC-recommended name, 21(T) NMR active nuclei, 68(T), 260(T), 261 non-aqueous coordination chemistry, 271ÿ2 occurrence, 257 organometallic compounds, 504ÿ7 oxides, 264ÿ5 oxoacid salts, 265ÿ6 ozonides, 265, 439 perhalates, 487 peroxides, 264 phosphates, 421 phosphides, 402 physical properties, 135(T), 146(F), 259ÿ61, 260(T), 877, 879, 880, 881, 882, 883, 884 radioactive isotopes, 60(B), 261 reactivity of metals, 238, 261ÿ3 solutions of metals in liquid ammonia, 219, 220 suboxides, 265 superoxides, 264ÿ5 uses, 259 see also caesium; francium; lithium; potassium; rubidium; sodium group 2, 275ÿ92 abundance, 276(F) alkoxy complexes, 288, 289(F) amido complexes, 288, 289(F) appearance of metals, 279 carbonates, 174(T), 286 compared with group 1, 289(T) Black plate (921,1) Index group cont compared with group 13, 289(T) complex ions in aqueous solution, 287ÿ8 coordination complexes, 283, 288 extraction of metals, 276ÿ7 flame tests, 279 ground state electronic configurations, 18(T), 278(T), 880, 881, 882 halides, 280ÿ3 lattice energies, 157 hydrides, 254ÿ5, 279 hydroxides, 173, 285ÿ6 IUPAC-recommended name, 21(T) metallocenes, 510, 526 organometallic compounds, 507, 509ÿ11 oxides, 173, 283ÿ5 oxoacid salts, 286 pernitrides, 401ÿ2 peroxides, 285 phosphides, 402 physical properties, 135(T), 146(F), 278ÿ9, 278(T), 877, 879, 880, 881, 882, 884 radioactive isotopes, 275, 279 reactivity of metals, 238, 279 solutions of metals in liquid ammonia, 219, 220, 279 sulfates, 286, 460 uses, 277ÿ8 see also barium; beryllium; calcium; magnesium;radium; strontium group 3, 597ÿ8, 651 abundance, 594(F), 646(F) ground state electronic configurations, 880, 881, 882 occurrence, extraction and uses, 371, 593, 645 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 882, 884 see also scandium; ytterium group 4, 598ÿ601, 652ÿ4 abundance, 594(F), 646(F) ground state electronic configurations, 880, 881 halides, 230 occurrence, extraction and uses, 593, 645ÿ6 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also hafnium; titanium; zirconium group 5, 602ÿ5, 654ÿ8 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 occurrence, extraction and uses, 593ÿ4, 646 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also niobium; tantalum; vanadium group 6, 606ÿ11, 658ÿ66 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 occurrence, extraction and uses, 594, 646 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also chromium; molybdenum; tungsten group 7, 611ÿ17, 666ÿ71 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 occurrence, extraction and uses, 594ÿ5, 646ÿ7 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also manganese; rhenium; technetium group 8, 617ÿ24, 671ÿ9 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 Mo¨ssbauer spectroscopy, 73ÿ5, 74(T) occurrence, extraction and uses, 138(B), 595, 647 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also iron; osmium; ruthenium group 9, 624ÿ30, 679ÿ84 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 occurrence, extraction and uses, 595ÿ6, 647 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also cobalt; iridium; rhodium group 10, 630ÿ4, 684ÿ9 abundance, 594(F), 646(F) carbonyls, physical properties, 709(T) ground state electronic configurations, 880, 881 occurrence, extraction and uses, 596, 647 physical properties, 135(T), 597(T), 650(T), 878, 880, 881, 884 see also nickel; palladium; platinum group 11, 634ÿ9, 689ÿ94 abundance, 594(F), 646(F) carbides, 357 ground state electronic configurations, 880, 881 halides, 199ÿ202 solubilities in water, 176(T) solubility in water, 176, 176(T) Mo¨ssbauer spectroscopy, 74(T), 75 occurrence, extraction and uses, 596, 647ÿ8 physical properties, 135(T), 597(T), 650(T), 690, 690(T), 878, 880, 881, 884 see also copper; gold; silver group 12, 639ÿ41, 694ÿ7 abundance, 594(F), 646(F) ground state electronic configurations, 880, 881 lattice structures, 135, 135(T) occurrence, extraction and uses, 596ÿ7, 648 physical properties, 135(T), 597(T), 650(T), 695(T), 878, 880, 881, 884 see also cadmium; mercury; zinc group 13, 293ÿ337 abundance, 294(F) appearance of elements, 299ÿ300 aqua ions, 322 compared with group 2, 289(T) coordination complexes, 323ÿ4 electron-deficient borane clusters, 293, 326ÿ34 elements, 299ÿ301 extraction of elements, 293ÿ4 ground state electronic configurations, 18(T), 296ÿ7, 297(T), 880, 881 halides, 307ÿ13 hydrides, 301ÿ7 hydroxides, 314ÿ15, 316 lattice structures, 134, 135(T) 921 metal borides, 324ÿ5 nitrides, 317ÿ19 nitrogen-containing compounds, 317ÿ22 NMR active nuclei, 68(T), 297(T), 299 occurrence, 293 organometallic compounds, 253, 259, 511ÿ18 oxidation states, 297 oxides, 173ÿ4, 313, 316, 317 oxoacid salts, 322 oxoacids/oxoanions, 314ÿ15, 316ÿ17 physical properties, 135(T), 296ÿ9, 297(T), 877, 879, 880, 881, 884 reactivity of elements, 301 redox reactions in aqueous solution, 322ÿ3 structures of elements, 135(T), 136, 300ÿ1 uses of elements and compounds, 295ÿ6 see also aluminium; boron; gallium; indium; thallium group 14, 338ÿ84 abundance, 339(F) allotropes of carbon, 345ÿ53 aqueous solution chemistry, 381 bonding considerations, 343ÿ4 cation formation, 342 compounds with metals, 357ÿ61 elements, 342ÿ54 extraction of elements, 339 ground state electronic configuration, 18(T), 342, 880, 881 halides, 361ÿ5 structures, 363, 364ÿ5, 365(WE) halohydrides, 356 hydrides, 354ÿ5 intercalation compounds, 345ÿ8 ionization energies, 342, 342(T) lattice structures, 135(T), 136 metallocenes, 525, 526ÿ7 Mo¨ssbauer spectroscopy, 74(T), 344 nitrogen-containing compounds, 379ÿ81 NMR active nuclei, 68(T), 342(T), 344 occurrence, 338ÿ9 organometallic compounds, 344(B), 376ÿ7, 476, 518ÿ27 oxidation states, 338 oxides, 174, 365ÿ70, 373, 375ÿ6 oxoacids and salts, 368, 370ÿ3, 373ÿ5, 381 physical properties, 135(T), 342ÿ5, 342(T), 877, 879, 880, 881, 884 reactivity of elements, 345, 349ÿ53, 353, 353ÿ4(WE) structures of elements, 136, 149, 150(F), 345, 348ÿ9, 348(F), 353 sulfides, 377ÿ9 uses, 339ÿ41 see also carbon; germanium; lead; silicon; tin group 15, 385ÿ431 abundance, 387(F) aqueous solution chemistry, 428ÿ9 bonding considerations, 390ÿ1 compounds with metals, 401ÿ3 double bond formation, 527 elements, 392ÿ4 extraction of, 387 ground state electronic configuration, 18(T), 24, 880, 881 halides, 403ÿ5, 406ÿ11 redox chemistry, 411(WE) hydrides, 394ÿ401 bond enthalpies, 394(WE) NMR active nuclei, 68(T), 389(T), 391 Black plate (922,1) 922 Index group 15 cont occurrence, 386ÿ7 organometallic compounds, 476ÿ7, 527ÿ30 oxides, 174, 412ÿ15, 417ÿ19 oxoacids, 415ÿ17, 419ÿ24 oxohalides of nitrogen, 405ÿ6 physical properties, 135(T), 389ÿ92, 389(T), 877, 879, 880, 881, 883, 884 radioactive isotopes, 57, 391ÿ2 reactivity of elements, 392ÿ4 recommended name, 21(T) sulfides, 426ÿ8 thermochemical data, 389(T), 390(WE) uses, 387ÿ9 see also antimony; arsenic; bismuth; nitrogen; phosphorus group 16, 432ÿ67 abundance, 433(F) aqueous solution chemistry, 464ÿ5 bonding considerations, 436ÿ7 charge transfer complexes, 531 compounds with nitrogen, 462ÿ4 elements, 437ÿ42 extraction of elements, 433 ground state electronic configuration, 18(T), 880, 881 halides, 448ÿ53 hydrides, 170, 442ÿ6 see also water isotopes as tracers, 437 IUPAC-recommended name, 21(T), 432 NMR active nuclei, 68(T), 435(T), 437 occurrence, 432ÿ3 organometallic compounds, 530ÿ2 oxides, 453ÿ7 oxoacids and salts, 457ÿ62 physical properties, 434ÿ6, 435(T), 877, 879, 880, 881, 883, 884 polymeric compounds, 446ÿ8 representation of hypervalent compounds, 436 uses, 433ÿ4 see also oxygen; polonium; selenium; sulfur; tellurium group 17, 468ÿ91 abundance, 470(F) aqueous solution chemistry, 488ÿ9 bonding considerations, 471ÿ3 charge transfer complexes, 475ÿ7 clathrates, 477 elements, 474ÿ5 extraction of elements, 470ÿ1 ground state electronic configuration, 880, 881, 882 hydrogen halides, 477ÿ8 interhalogen compounds, 479ÿ82 isotopes as tracers, 473 IUPAC-recommended name, 21(T), 468 metal halides, 478ÿ9 NMR active nuclei, 68(T), 473 occurrence, 469ÿ70 oxides, 448, 483ÿ4 oxoacids and salts, 485ÿ7 oxofluorides, 484ÿ5 physical properties, 146(F), 472(T), 878, 879, 880, 881, 882, 883, 884 polyhalide anions, 483 polyhalogen cations, 482 reactions with dihydrogen, 242 uses, 471 see also astatine; bromine; chlorine; fluorine; iodine group 18, 492ÿ502 abundance of elements, 493, 493(F) compounds, 157, 496ÿ501 crystalline structures, 134 extraction of elements, 493 ground state electronic configuration, 18(T), 880, 881, 882 halides, 496ÿ9, 501 ionization energies, 158(F) IUPAC-recommended name, 21(T), 492 NMR active nuclei, 68(T), 495 occurrence, 493 oxides (of xenon), 499 oxofluorides, 499 oxofluoro complexes, 499, 501 physical properties, 135(T), 158(F), 494ÿ6, 495(T), 878, 880, 881, 882 uses, 493ÿ4 see also argon; helium; krypton; neon; radon; xenon group theory, 79 groups (in periodic table), 20, 20(F) IUPAC-recommended names, 21(T) Grove, William, 240(B) Grubbs’ catalysts, 730, 789 advantages, 789ÿ90 example of use, 790 guanineÿcytosine base-pairs (in DNA), 250, 252(F) Guignet’s green, 608 gypsum, 276, 278(B), 286, 287(B) uses (in US), 287(B) gypsum plasters, 287(B) earliest use, 287(B) H NMR spectroscopy see proton NMR spectroscopy HaberÿBosch process, 416, 801(T) Haber process, 238, 395ÿ6, 804ÿ5 catalysts, 395, 396, 801(T), 804, 805 haem group, 837, 838(F) haem-iron proteins, 837ÿ9 haematite, 138(B), 296, 595, 619 haemerythrin, 841ÿ3 haemocyanins, 839ÿ41 haemoglobin, 831, 837ÿ9 binding of carbon monoxide, 366, 839 ribbon representation, 838(F) hafnium, 652ÿ3 abundance of isotope(s), 875 ground state electronic configuration, 18(T), 650(T), 881 metal, 652 occurrence, extraction and uses, 645ÿ6 oxidation states, 540(T), 652 physical properties, 135(T), 650(T), 881, 884 hafnium borohydrides, 547, 548(F) hafnium(IV) complexes, 652 hafnium halides, 652, 653 hafnium hydrides, 251 hafnium nitride, 402(B) hafnium(IV) oxide, 652 hafnium(IV) oxo-complexes, 652 half-cells/reactions, 193ÿ4 in potential diagrams, 203ÿ4, 205(WE) sign of standard reduction potentials for, 195 standard reduction potentials listed, 196(T), 885ÿ7 half-life, of radioisotopes, 56, 57, 57(T), 60(B), 61, 64, 65 half-sandwich complexes, 735, 761 halides, 478ÿ9 f -block metal, 757, 758 group 1, 157, 263ÿ4 group 2, 157, 280ÿ3 group 3, 598, 651 group 4, 230, 598ÿ9, 601, 652, 652ÿ3 group 5, 604, 605, 654ÿ5, 656, 656ÿ7 group 6, 606, 607, 608, 659, 662, 663, 665 group 7, 614ÿ15, 667, 669 group 8, 618ÿ19, 622ÿ3, 673, 675, 676 group 9, 624, 627, 679, 680 group 10, 631, 684, 686 group 11, 156ÿ7, 174(T), 176(T), 199ÿ202, 635, 638, 690, 691, 692 group 12, 640, 695, 696 group 13, 307ÿ13 group 14, 361ÿ5 group 15, 403ÿ5, 406ÿ11 redox chemistry, 411(WE) group 16, 448ÿ53 group 18, 496ÿ9, 501 lanthanoid, 749 MXn -to-MXn þ transition, 299(B) halite, 148 halogen-based flame retardants, 469(B), 471, 474(B) halogen oxides, 483ÿ4 halogen oxofluorides, 484ÿ5 halogens, 21(T), 468 see also group 17 halohydrides, group 14, 356 hapticity of ligands, 503(B), 700 hard cations and ligands, 187ÿ8 examples, 188(T), 651, 656, 681, 756, 757 hard and soft acids and bases (HSAB) principle, 187ÿ8 ‘hard’ water, 286 hassium, 62(T) health risks, radioactive isotopes, 60(B) heavier d-block metals, 536, 645ÿ99 heavy water see deuterium oxide Heck reaction, 228, 722(B) Heisenberg’s uncertainty principle, HeitlerÿPauling bonding model, 26 helium abundance of isotope(s), 875 atomic interactions in, 16 extraction of, 493 ground state electronic configuration, 17, 18(T), 21ÿ2(WE), 31, 495(T), 880 liquid, 493ÿ4, 495 nuclei, 55 see also -particles occurrence, 493 physical properties, 24(F), 135(T), 158(F), 495(T), 878, 880 synthesis by nuclear fusion, 62 term symbol for, 573(B) uses, 493ÿ4, 494, 494(B) heme, see haem hemihydrate, 286 hemimorphite, 596 henicosahedron, 334, 334(F) herbicides, manufacture of, 733(B) Hess’s Law of constant heat summation, applications, 155, 156(WE), 169, 298ÿ9(WE), 354(WE), 394(WE), 435(WE) Black plate (923,1) Index heterogeneous catalysis commercial applications, 801(B), 802ÿ7 alkene polymerization, 802 catalytic converters, 805ÿ6 Contact process for SO3 production, 805 FischerÿTropsch reaction, 803ÿ4 Haber process, 804ÿ5 zeolites as catalysts, 806ÿ7 examples, 801(B) organometallic cluster models, 807ÿ8 surfaces and interactions with adsorbates, 799, 801ÿ2 heterogeneous catalysts, 239, 243ÿ4, 340(B), 341, 396, 647 meaning of term, 786 heteroleptic complex, 233 heteronuclear diatomic molecules, molecular orbital theory, 41ÿ3 heteronuclear NMR spectra, 71(F) types, 71 heteronuclear spinÿspin coupling, 67(B), 69ÿ72, 70, 70(F), 71, 71(F) heteropoly blues, 661 heteropolyanions, 602, 660ÿ2 hexaammine complexes, reduction of, 202 hexaaqua ions, 171, 180 reduction of, 202 hexadentate ligands, 184(T) hexafluorosilicate ion, 363ÿ4 hexagonal bipyramid, 547(F) hexagonal bipyramidal molecules d-block metal compounds, 547, 547(F), 695 f -block metal compounds and complexes, 758 hexagonal close-packed (hcp) lattice, 132 interstitial holes in, 133ÿ4, 402 unit cell, 133(F) hexahalides, metal, 478 closo-hexahydrohexaborate(2ÿ) ion bonding in, 329(B) factors affecting reactivity, 331 halogenation of, 331 oxidation of, 331 preparation of, 327 reactions, 330ÿ1 structure, 326(F), 327, 328(WE) synthesis of, 327 hexamethyltungsten, 545(F), 725 hex-1-ene, hydrogenation of, 798 high-spin complexes, 544, 555, 560, 566, 574(WE), 771, 772 Co(IV), 624 Co(III), 624, 627 Co(II), 628, 777, 780 Cr(II), 609, 777 electronic spectra, 574 Fe(IV), 617 Fe(III), 620 Fe(II), 622, 764 magnetic moments, 581(T), 581(WE), 582(T), 583 Mn(III), 614 Mn(II), 616 thermodynamic aspects, 585 high-temperature superconductors, 324, 352, 389, 633(B), 635, 817ÿ19, 817(T) precursors, 288 structures, 152, 352(F), 817ÿ18 HIPIP (high potential protein), 848 histamine, 840(B) histidine, 831(T) Hittorf’s phosphorus, 392ÿ3, 392(F), 393 HMPA (hexamethylphosphoramide), 271 lithium complexes with, 271 holmium abundance of isotope(s), 875 ground state electronic configuration, 18(T), 742(T), 881 physical properties, 742(T), 745(T), 745ÿ6(WE), 881 holmium organometallic compounds, 755 HOMO (highest occupied molecular orbital), 43, 44(F) in borane clusters, 329(B) homogeneous catalysis advantages and disadvantages, 791 alkene (olefin) metathesis, 789ÿ90 industrial applications, 722(B), 791ÿ7 alkene hydrogenation, 722(B), 791ÿ3 hydroformylation (Oxo-process), 722(B), 795ÿ6, 797(T) Monsanto acetic acid synthesis, 722(B), 793ÿ4 TennesseeÿEastman acetic anhydride process, 722(B), 794, 795(F) homogeneous catalysts, 239, 243, 683 development of, 797ÿ9 examples, 722(B) meaning of term, 786 homoleptic complex, 233 homonuclear covalent bond, 27 homonuclear diatomic molecules bond dissociation energies, 28, 35(T) ground state electronic configurations, 35(F) meaning of term, 27 molecular orbital theory, 29ÿ36 valence bond theory, 27ÿ9 homonuclear spinÿspin coupling, 66ÿ7(B) homopolyanions, 602 hops extraction, 231(B), 232 hormite clays, 374(B) hostÿguest compounds, 355(B), 477 HREELS (high resolution electron energy loss spectroscopy), 800(B) HSAB (hard and soft acids and bases) principle, 187ÿ8 Hund’s rules, 21, 574(B) applications, 555, 745 limitations, 573(B) hybrid orbitals, 100ÿ5 for d-block metal complexes, 556(T) hydrated proton(s), 163, 236 hydrates, 236 hydration, 171 thermodynamics, 176ÿ7, 589 hydration energy, 175 hydration enthalpy, 176ÿ7 first row d-block metal M2þ ions, 586, 587(F) hydration entropy, 176ÿ7 hydration isomers, 548 d-block metal compounds, 548 hydration shell of ion, 170ÿ2 hydrazine, 397ÿ8 bonding in, 391 as Brønsted base, 169 production of, 392, 397 structure, 169, 398, 398(F) uses, 226(B), 397 hydrazinium salts, 397ÿ8 hydrazoic acid, 400 hydride ion, 237 hydride ligands, 702ÿ3 923 hydrides anomalous properties, 246, 247(F) binary, 251ÿ5 of d-block metals, 598 of d-block elements, 254 d-block metal, reactions, 723 group 2, 279 group 11, 638 group 12, 640 group 13, 301ÿ7 group 14, 354ÿ5 group 15, 394ÿ401 bond enthalpies, 394(WE) group 16, 170, 442ÿ6 lanthanoid, 749 of p-block elements, 253ÿ4, 301ÿ7, 354ÿ5, 394ÿ401 trends in physical properties, 246, 247(F) polar and non-polar bonds in, 244 of s-block elements, 237, 251ÿ3, 254, 263, 279 see also binary hydrides; covalently bonded ; interstitial metal ; polymeric ; saline hydrides hydrido carbonyl complexes, preparation of, 702, 723 hydrido complexes, d-metal, 254, 668, 707 hydroamination, catalysts, 752(B) hydrocarbons boiling points, 355(F) catalytic reforming of, 801(T), 803 compared with other group 14 hydrides, 354 production from methanol, 807 production of, 803ÿ4 hydrochloric acid, 163ÿ4 hydrocyanic acid, 380 hydroformylation process, 244, 795ÿ6 catalysts for, 722(B), 789, 795, 797ÿ8, 797(T) effect of ligand bite angle, 789 hydrogen, 236ÿ56 abundance of isotope(s), 875 ground state electronic configuration, 16, 17, 18(T), 42 isotopes, 237ÿ8 metallic character, 239(B) physical properties, 24(F), 877, 879, 880, 883, 884 term symbol for, 573(B) see also dihydrogen; protium hydrogen-2 see deuterium hydrogen-3 see tritium a-hydrogen abstraction, 721ÿ2 hydrogen atom, 236 Bohr radius, emission spectra, 4ÿ5 ground state, 16 solutions of Schro¨dinger wave equation for, 11(T) hydrogen azide, 400 reactions, 400 structure, 400(F) hydrogen bonding, 244ÿ50, 250(WE) in beryllium compounds, 287(F) in biological systems, 250, 252(F), 842ÿ3 in carboxylic acids, 244ÿ5, 248(B) in group oxoacid salts, 266, 268(F) in group 15 compounds, 394, 421 in ½H5 O2 þ , 236, 237(F), 247, 249(F) in hydrogen peroxide, 442 in ice, 163, 244 Black plate (924,1) 924 Index hydrogen bonding cont intermolecular, 162 IR spectroscopy, 246ÿ7 by nitrogen, 391, 394 in non-aqueous solvents, 216, 218, 221 in phosphoric acid, 421 in solid state structures, 247ÿ50, 248(B) hydrogen bond(s), 244ÿ6 meaning of term, 244 hydrogen bridges see bridging hydrogen atoms hydrogen bromide physical properties, 477(T) thermodynamic data, 170(T) hydrogen chloride aqueous solution, 163ÿ4 physical properties, 477(T) thermodynamic data, 170(T) hydrogen cluster (in hydrogenase), 849, 849(F) hydrogen cyanide, 380 bonding in, 105ÿ6, 105(F), 250 equilibrium constants, 164(B) in plants, 379(B) reactions, 380 hydrogen difluoride anion bonding in, 123, 124(F) structure, 221(B), 247, 249(F) hydrogen disulfide, 446 hydrogen economy, 238 b-hydrogen elimination, 721 hydrogen fluoride, 477ÿ8 anomalous properties, 246, 247(F) bond dissociation enthalpy, 170(T), 245(T), 477 bonding in, 42 dipole moment, 40 liquid, as solvent, 221ÿ2 physical properties, 218(F), 221, 477(T) production of, 277, 471 solid state structure, 247, 249(F) thermodynamic data, 170(T) hydrogen halides, 167, 477ÿ8 dissociation in aqueous solution, 169ÿ70 production of, 242, 477 hydrogen iodide physical properties, 477(T) thermodynamic data, 170(T) hydrogen ion, 236 see also proton hydrogen migration, 721 hydrogen nomenclature for oxoacids, 168(B) hydrogen peroxide, 442ÿ5 bonding in, 391 physical properties, 443(T), 887 production of, 442, 442(F) reactions, 442, 444ÿ5 redox reactions, 444(WE) structure, 27(F), 443, 443(F) uses, 443 hydrogen selenide, 445 dissociation in aqueous solution, 170 physical properties, 247(F), 445(T) hydrogen storage vessels, 240(B), 251, 647, 749 hydrogen sulfide, 445 dissociation in aqueous solution, 170 extraction of sulfur from, 433 occurrence, 445 physical properties, 247(F), 445(T) production of, 445 structure, 82(F) hydrogen telluride, 445 dissociation in aqueous solution, 170 physical properties, 247(F), 445(T) hydrogen-like species, orbital energies, 13 hydrogen-transfer agent(s), 350 hydrogenase enzymes, 624 hydrogenases, 847, 848ÿ9 hydrogenating agents, 306 hydrogenation of alkenes, 626, 678, 722(B), 724, 791ÿ3, 798 of fumaric acid, 799, 800(F) of unsaturated fats, 239 hydrogenation catalysts, 239, 242, 243ÿ4, 596, 626, 647, 678, 752(B), 791ÿ3 hydrogensulfate(1ÿ) ion, 167 hydrolysis, in aqueous chemistry, 172 hydrophobic zeolites, 372 hydrosilylation, catalysts, 752(B) hydrothermal method of synthesis, 375 hydrothermal oxidation, 232 hydroxide ion, 163 hydroxides, 167 as bases, 167 group 1, 167, 226 group 2, 174(T), 285ÿ6 group 3, 651 group 8, 174(T), 619, 623 group 9, 627 group 10, 631 group 11, 635 group 12, 640, 695, 696 group 13, 314ÿ15, 316 lanthanoid, 750 hydroxo-bridged species, 172, 287, 429, 608, 609(F), 842 hydroxyapatite, 387, 423(B) hydroxylamine, 169, 399 hydroxylamine oxidoreductase, 853 hygroscopic substances d-block metal compounds, 605, 612, 622 group halides, 283 meaning of term, 283 p-block metal compounds, 364, 399, 464, 484 hyperconjugation in boron hydrides, 304 negative, 356 hypervalent molecules, 104, 120 hypho-cluster, 326, 328 hypochlorites, 485 cyanides treated by, 647(B) as oxidizing agents, 469, 485 hypochlorous acid, 485, 488 anhydride, 483ÿ4 as weak acid, 167 hypofluorous acid, 485 hypohalites, 485ÿ6 hypohalous acids, as weak acids, 485, 488 hypoiodous acid, 489 hyponitrous acid, 415 hypophosphoric acid, 420ÿ1, 420(T) hypophosphorous acid, nomenclature, 168(B), 420(T) I (interchange) mechanism, 765 Ia (associative interchange) mechanism, 765 ice density, 163 hydrogen bonding in, 162ÿ3, 163(F), 244 structure, 162ÿ3, 163(F) icosahedral molecules borane cluster compounds, 330(F) borohydride ions, 87(F) boron allotropes, 300(F) icosahedral point group, 86 icosahedron, 330(F) Id (dissociative interchange) mechanism, 765 identity operator (E), 82, 83ÿ4(WE) ilmenite, 593, 599, 600(B) imperfections in surfaces, 801, 801(F) improper rotation axis (Sn ), 82, 83(F) incandescent gas mantles, 756 indirect band gap semiconductors, 514(B) indium abundance of isotope(s), 875 appearance of metal, 300 extraction of, 294ÿ5, 295 ground state electronic configuration, 18(T), 297(T), 881 lattice structure, 136 occurrence, 293, 294 physical properties, 24(F), 135(T), 297(T), 877, 879, 881, 884 reactivity, 301 structure of metal, 136 uses, 296 indium(I) chloride, 313 indium cyclopentadienyl complexes, 518 indium hydride, adducts, 305 indium nitride, 318 indium organometallic compounds, 514ÿ18 indium oxides and hydroxides, 317 indiumÿtin oxide, 296, 317(B) indium trialkyls, 514ÿ15 indium triaryls, 515 indium trihalides, 311 induced-dipoleÿinduced-dipole interactions, 155 industrial processes BASF acetic acid process, 793, 794(T) Bayer process, 293ÿ4 Contact process for SO3 production, 455, 459, 805 Czochralski process, 143(B), 821 Downs process, 257ÿ8 Frasch process, 433, 433(F) HaberÿBosch process, 416 Haber process, 238, 395ÿ6 MobilÿBadger process (for alkylation of aromatics), 807 Mond process, 596 Monsanto acetic acid process, 470(B), 721, 722(B), 793ÿ4, 794(T) MTG process, 807 MTO process, 807 Oxo-process (for hydroformylation of alkenes), 795ÿ6 Pilkington process, 341 Raschig process, 397 Rochow process, 518 Sasol process, 803 Shell Higher Olefins Process, 797 silicon purification, 143(B) Solvay process, 266, 267(F), 277, 283 steel manufacture, 138(B) TennesseeÿEastman acetic anhydride process, 470(B), 722(B), 794, 795(F) Wacker process, 787ÿ8, 788(F) zone melting, 143(B) inert gases see group 18 inert pair effect stereochemical, 48 thermodynamic, 279, 297, 298(B), 299(B), 322, 364, 517, 694 Black plate (925,1) Index infinite dilution, 165 infrared see IR inner orbital complexes, 557(B) inner quantum number, 15(B), 572(B) inner-sphere mechanism, 777ÿ9 inner transition elements, 535, 741 see also f -block metals insecticides, 296(B), 389, 607 insulation fibreglass, 314(B) insulators band theory for, 142 ionic solids as, 131 intercalation compounds, 263, 345, 347ÿ8 interchange mechanism, 765 interhalogen compounds, 479ÿ82 bonding in ions, 482 physical properties, 480(T) structures, 479, 481ÿ2, 481(T) intermediate, meaning of term, 765 intermediate hydrides, 255 intermetallic compounds, 140ÿ1 intermolecular hydrogen bonding, 162 internal dihedral angle, in group 16 compounds, 443(F), 446, 448 internal energy change, relationship to enthalpy change, 23(B) internuclear distance, 27, 144, 237 interstitial alloys, 139ÿ40 interstitial atoms, in cage structures, 702, 718 interstitial carbides, 357 interstitial holes, 133ÿ4, 139 interstitial metal hydrides, 240(B), 702 interstitial metal nitrides, 401 intramolecular bond parameters, determination of, 7(B) intramolecular transfers, of alkyl group, 721 intrinsic defects, 813 intrinsic semiconductors, 143 crystal structures, 152 inverse spinels, 316(B), 619 inversion centre absence in chiral molecules, 97 g and u symmetry labels, 30(B), 558(B) in octahedron, 121(F) reflection through, 82 iodates, 486 iodic acid, 486 iodinating agent(s), 480 iodine abundance of isotope(s), 875 in biological systems, 471, 830 ground state electronic configuration, 18(T), 472(T), 881 occurrence, 470 physical properties, 472(T), 878, 879, 881, 883, 884, 886 radioisotopes, 60(B), 470(B) uses, 470(B), 471 see also diiodine iodine-containing charge transfer complexes, 475, 476, 477 iodine heptafluoride, 479, 480(T), 481(T) iodine monobromide, 480, 480(T) iodine monochloride, 480, 480(T) iodine monofluoride, 480 iodine pentafluoride, 479, 480(T), 481(T) self-ionization of, 481 iodine trichloride, 481(T) dimer, 479, 481 iodine trifluoride, 480(T), 481(T) ionÿdipole interaction, 171 ion exchange lanthanoids separated by, 747, 748(F) water purified by, 286, 443(B) ion-exchange resins, 265 aqueous group ions adsorbed on, 268 ion-pair, isolated, coulombic attraction in, 152ÿ3 ion propulsion system, 494(B) ionÿsolvent interactions, 215 ionic bonds, 26 ionic charge, stabilities of complexes affected by, 186 ionic complexes, 557(B) ionic lattices, 146ÿ52 ionic liquids, 227ÿ30 applications, 229ÿ30 ionic mobilities, non-aqueous solvents, 218, 223 ionic radii, 144ÿ5 listed for various elements, 145(B), 177(T), 877ÿ8 d-block metals, 878 f -block metals, 742(T) p-block elements, 177(T), 877ÿ8 s-block elements, 177(T), 877 periodic trends, 145ÿ6, 146(F) ratios, 145(B) in silicates, 370(F) see also under individual elements, physical properties ionic salts solubilities, 174ÿ8 transfer from water to organic solvent, 215ÿ16 ionic size, 144ÿ6 stabilities of complexes affected by, 186 ionic solids electrical conductivity in, 815ÿ17 structures, 146ÿ52 ionization, thermodynamics, 23, 296ÿ7, 588 ionization energy, 23ÿ4 d-block metals, 24(F), 537, 690(T), 695(T), 880, 881 first row M2þ ions, 589(F) and electronegativity, 37 first, 23, 24(F) of hydrogen, listed for elements, 24(F), 880ÿ2 paucity of data for d-block metals, 689 second, 23 successive ionizations, 23 third, 23 trends, 23, 24(F), 259, 279, 296ÿ7, 342, 537, 689, 695 units, 6, 23 see also under individual elements, physical properties ionization isomers, 548 d-block metal compounds, 548 ions, notation, 162(N) ipso-carbon atom of phenyl ring, 512 IR spectrometer, 94 IR spectroscopy, 90ÿ4 bending modes, 91(F), 92, 92(F) bent triatomic molecules, 92 d-block metal carbonyls, 701, 702(F), 702(T), 722 degrees of vibrational freedom, 90ÿ1 deuterium exchange reactions, 63ÿ4, 63(WE) effect of hydrogen bonding, 246ÿ7 fundamental absorptions, 92 925 isomers distinguished by, 548, 549, 550(F) linear triatomic molecules, 92 selection rule for IR active mode, 91, 550(F) stretching modes, 91(F), 92, 92(F) XY3 molecules, 92ÿ3 XY4 molecules, 93 iridium, 679ÿ84 abundance of isotope(s), 875 ground state electronic configuration, 18(T), 650(T), 881 metal, 679 occurrence, extraction and uses, 647 oxidation states, 540(T), 679 physical properties, 135(T), 650(T), 881, 884 iridium(III) ammine complexes, 681 iridium-based catalysts, 794 iridium carbonyl cluster anion, structure, 714(F) iridium carbonyls physical properties, 709(T) structures, 713, 713(F), 716(WE) synthesis of, 710 iridium(I) complexes, 683ÿ4 iridium(II) complexes, 682ÿ3 iridium(III) complexes, 681ÿ2 iridium(IV) complexes, 680 iridium(II), dinitrogen complexes, 677 iridium(IV), halo salts, 680 iridium(V), halo salts, 679 iridium(III), hexaaqua cation, 680 iridium(III), hexachloro salts, 681 reactions, 681 iridium(IV), hexachloro salts, 680 reactions, 680 iridium hexafluoride, 679 iridium(V), hydrido complexes, 679 iridium organometallic compounds, 683ÿ4, 725 iridium-osmium alloy, 647 iridium(III), oxalato complexes, 681 iridium(IV) oxide, 680 iridium pentafluoride, 679 iridium tetrafluoride, 680 iridium trichoride, reactions, 681(F) iridium trihalides, 680 iron, 617ÿ24 abundance, 594(F) abundance of isotope(s), 875 analytical determination of, 601 in biological systems, 595, 830, 831(T), 832ÿ5, 837ÿ9, 841ÿ3 commercial production of, 138(B) corrosion/rusting of, 201(B), 617 ground state electronic configuration, 18(T), 597(T), 880 metal, 595, 617 minerals, 138(B), 595 occurrence, extraction and uses, 138(B), 595 oxidation states, 540(T), 617 phase diagram, 136(F) physical properties, 135(T), 597(T), 878, 880, 884, 885, 886 polymorphism, 139 recycling of, 138ÿ9(B) standard reduction potentials, 196(T), 205(WE), 538(WE), 885 transport and storage in mammals, 832ÿ5 iron(III), acetylacetonate complexes, 179, 180, 180(F), 621 iron-based catalysts, 239, 396, 722(B), 801(T), 803, 804, 805 Black plate (926,1) 926 Index iron carbonyl hydride physical properties, 734(T) preparation of, 702 iron carbonyls physical properties, 709(T) reactions, 710, 711, 719, 722, 723, 728 structures, 75(F), 712, 712(F), 713 synthesis of, 710 uses, 710(B) iron(II) complexes, 623ÿ4 outer-sphere redox reactions, 779, 780, 780(T) water exchange reaction, 772 iron(III) complexes, 620ÿ1 outer-sphere redox reactions, 779, 780, 780(T) iron(IV) complexes, 618 iron-containing proteins, 837ÿ9, 841ÿ3, 847ÿ51 iron deficiency (in body), 595, 623(B) iron dihalides, 622 iron garnets, 619 iron(III), hexaammine ion, 621 iron(III), hexaaqua ion, 172, 619, 620 reduction of, 202 iron(III), hexacyano ion, 620 iron(II), hydrido complex anion, 254, 254(F) iron(II) hydroxide, 174(T), 623 iron(III) hydroxide, 174(T), 619 iron-57 (Mo¨ssbauer) spectroscopy, 73ÿ5, 623, 851 ironÿmolybdenum protein (in nitrogenase), 850ÿ1, 850(F) iron(III) nitrate, 620 iron(III), nitrosyl complex, 412, 771(B) iron organometallic compounds, 725, 736, 737 see also ferrocene; iron carbonyls iron(III), oxalate ion, as chiral species, 97(WE) iron(II) oxide, 623, 814, 817 standard Gibbs energy of formation, 210(F) iron(III) oxide, 595, 619, 833 iron pentacarbonyl, 49 iron(III) perchlorate, 620 iron(III), porphyrinato complexes, 621 iron powder, manufacture of, 710(B) iron pyrites, 432ÿ3, 595, 623 iron silicide, 358 iron(II) sulfamate, 181(B) iron(II) sulfate, 622 iron(III) sulfate, 620 iron(II) sulfide, 174(T), 617, 623 iron-sulfur proteins, 847ÿ51 model studies, 851 see also ferredoxins; hydrogenases; nitrogenases; rubredoxins iron supplements, 623(B) iron trihalides, 618ÿ19 irrational susceptibility, 579 IrvingÿWilliams series, 587ÿ8 isocyanic acid, 380 isoelectronic molecules, 43 isoelectronic relationships, boron phosphate, 313(WE) isoform II, 836(F) isolated ion-pair, coulombic attraction in, 152ÿ3 Isolated Pentagon Rule (for fullerenes), 348 isolobal principle, 329(B), 358, 714 applications, 716 isomer shift (in Mo¨ssbauer spectroscopy), 75 isomerism in d-block metal complexes, 547ÿ52 see also stereoisomerism; structural isomerism isomerization of alkenes, 722(B), 795 in octahedral complexes, 774, 775(F), 776 isopolyanions, 602 isostructural species, 43 isotactic polymers meaning of term, 802(N) production of, 734(B), 802 isotope dilution analysis, 65 isotope exchange reactions, 63, 770, 777 isotopes abundance, 875ÿ6 applications, 63ÿ5 artificially produced, 57ÿ8, 741 mass number ranges listed, 875ÿ6 meaning of term, 2, naturally occurring, 386, 875ÿ6 isotopic enrichment, 65, 68 isotopic labelling, 64, 386, 770 applications, 770 ITO (indiumÿtin oxide), 296, 317(B) IUPAC definitions, chiral molecules, 95(N) IUPAC nomenclature, 20ÿ1, 21(T) actinoids/lanthanoids, 17(N), 741(N) chiral compounds, 96(B) cis/trans (E/Z) isomers, 49(N) didentate ligands, 183(N) group 15 trihydrides, 394(T) oxoacids, 167, 168(B), 420(T), 458(T) semi-metals, 338(N) transition elements, 21, 535 transuranium elements, 62(T) jÿj coupling, 572(B) JahnÿTeller distortions, 545, 561ÿ2, 563(F), 574 in chromium compounds, 609, 610, 772 in copper compounds, 574, 636, 637, 772 in gold compounds, 691 in manganese compounds, 614, 615 JahnÿTeller theorem, 562 jewellery alloys, 139 Jørgensen, Sophus Mads, 625(B) Josephson junctions, 819 Jupiter, fluid hydrogen in core, 239(B) kaolinite, 374(B) Kapustinskii equation, 158, 285(WE) a-Keggin anions, 660, 661, 661(F) reduction of, 661 Kel-F polymer, 361 Kepert model, 541ÿ2 definition, 542 limitations, 542 kernite, 293, 296, 315 kinetic isotope effect, 64, 237 kinetic trans-effect, 688(B), 768 kinetically inert substances, 238, 260, 319, 343, 385, 626, 663, 685, 764, 779 kinetically labile complexes, 764 kinetics, radioactive decay, 56ÿ7, 56(WE) kinks on metal surfaces, 801, 801(F) Kipp’s apparatus, 445 Kirchhoff’s equation, 23(B) Koopmans’ theorem, 116(B) Kotani plots, 584 Kroto, Harry, 1, 348 krypton abundance, 493, 493(F) abundance of isotope(s), 875 extraction of, 493 ground state electronic configuration, 17, 18(T), 21ÿ2(WE), 495(T), 881 physical properties, 24(F), 135(T), 158(F), 495(T), 878, 881 uses, 494 krypton difluoride, 492, 501 solid state structure, 497(F) Kyoto Protocol, 367(B) l notation for chiral molecules, 551(B), 551(B) l notation for chiral molecules, 96(B), 551(B) laccase, 844ÿ5 lactoferrin, 833 lacunary anions, 661ÿ2 lamellar compounds, 345 Lande´ splitting factor, 581 Langmuir, Irving, 26 lanthanide, see lanthanoid lanthanoid contraction, 137, 536, 649, 743 lanthanoids, 645, 741 borides, 324 carbides, 749 colours of aqua complexes, 745(T) complexes, 750ÿ1 luminescence, 746 as NMR shift reagents, 751(B) electronic spectra, 744ÿ5, 745ÿ6(WE) endohedral metallofullerenes, 353 ground state electronic configurations, 17, 18(T), 742(T), 881 halides, 749 hydrides, 749 hydroxides, 750 IUPAC nomenclature, 17(N), 741(N) magnetic moments, 745, 745(T), 746(WE) metals, 748ÿ9 nitridoborates, 318 occurrence, 747 organometallic compounds, 751ÿ5 oxidation states, 743, 749 oxides, 750 physical properties, 742(T), 881 separation of, 747, 748(F) lanthanum abundance of isotope(s), 875 ground state electronic configuration, 18(T), 650(T), 742(T), 881 occurrence, extraction and uses, 645 oxidation state, 540(T) periodic table classification, 645, 741 physical properties, 135(T), 650(T), 742(T), 745(T), 881, 884, 885 lanthanum carbide, 357 lanthanum(III) complexes, 750(F) lanthanum hydroxide, 750 lanthanumÿnickel alloy, 749 lanthanum organometallic compounds, 755 lapis lazuri, 446(B) Laporte-forbidden transitions, 571, 574(WE), 616 Laporte selection rule, 538, 571 LAPS (Lewis acid pigment solubilization) technique, 311(B) large cations with large anions, 270(B), 711(B) lasers, 744(B) Black plate (927,1) Index Latimer diagrams, 204 relationship to FrostÿEbsworth diagrams, 205ÿ6 see also potential diagrams lattice defects, 158ÿ9, 813ÿ15 lattice energy, 152 applications, 157ÿ8 in BornÿHaber cycle, 155, 156(F), 156(WE) calculated vs experimental values, 156ÿ7 estimated by electrostatic model, 152ÿ5 estimates using Kapustinskii equation, 158, 285(WE) for first row d-block metal dichlorides, 586, 586(F) group halides, 264(T) trends, 299(B) lattice enthalpy change, 155, 177 lattice structures, 131, 146ÿ52 ‘laughing gas’, 412 lawrencium, 62(T) ground state electronic configuration, 18(T), 742(T), 882 longest lived isotope, 755(T) mass number range, 876 oxidation state(s), 743(T) physical properties, 882 synthesis of, 61 laws and principles BeerÿLambert Law, 571, 576 Curie Law, 583 Graham’s law of effusion, 61 Hess’s Law of constant heat summation, 155, 156(WE), 298ÿ9(WE) Le Chatelier’s principle, 172, 178 Pauli exclusion principle, 21 see also rules laxative/purgative, 277, 460 layer structures, 151 d-block metal complexes and compounds, 614, 615, 632, 633(F), 653, 659, 660(B), 663, 680 metal halides, 478 p-block compounds, 263(F), 314, 317, 318(F), 345, 348(F), 371ÿ2, 378, 816 lazurite, 446(B) LCAOs (linear combinations of atomic orbitals), 29 Le Chatelier’s principle, 172, 178 lead abundance, 339(F) abundance of isotope(s), 876 bond enthalpy terms, 343(T) extraction of, 210, 339 ground state electronic configuration, 18(T), 342(T), 881 minerals/ores, 210, 339 physical properties, 135(T), 342(T), 877, 879, 881, 884, 886 reactivity, 353 recycling of, 339(B) structure, 135(T), 136 toxicity, 344(B) uses, 341 lead-206, 56(F), 57(T) lead-210, 56(F), 57(T) lead-214, 56(F), 57(T) lead(II) acetate, 381 lead(IV) acetate, 381 leadÿacid storage battery, 339(B), 341, 381 lead(II), aqua ion, 381 lead(II) azide, 400 lead cyclopentadienyl complexes, 525, 525(F) lead dihalides, 365 lead-free solders, 296, 344(B), 389 lead halides, 365 lead hydride, 355 lead(II) iodide, solubility in water, 174(T), 175(WE) lead organometallic compounds, 524ÿ6 lead oxides, 341, 375ÿ6, 381 lead(II) sulfate, 341, 381 lead(IV) sulfate, 381 lead sulfide, 378 solubility in water, 174(T), 378ÿ9(WE) lead tetraalkyls and tetraaryls, 259, 344(B), 474(B), 518, 524 lead tetrachloride, 365 lead Zintl ions, 358 leaded motor fuels, 342(F), 344(B), 474(B), 518, 524 leaving group effect on reaction rates, 773, 779 in electron-transfer processes, 779 in substitution reactions, 764 Leclanche´ cell, 595, 595(F) LEDs (light-emitting diodes), 296, 514(B), 820(T) dependence of colour on composition, 823(T) LEED (low-energy electron diffraction), 7(B), 800(B) lepidocrocite, 595, 619, 619(B) leucine, 831(T) levelling effects of non-aqueous solvents, 217, 219 Lewis, G.N., 26 Lewis acid pigment solubilization, 311(B) Lewis acid(s), 171 beryllium dichloride, 281ÿ2(WE) beryllium hydroxide, 285 boron compounds, 307, 313, 314 as catalysts, 313, 652 d-block metal halides, 599, 652 group 13 compounds, 313, 314 group 13 halides, 307 group 13 organometallics, 513 group 14 halides, 364 group 14 organometallic compounds, 523, 525 group 15 halides, 224, 407, 411 as metal centres in complexes, 188(T) reactions in ionic liquids, 229 Zn(II)-containing enzymes, 854ÿ8 Lewis base(s), 171 donation of electrons to Lewis acid, 179 ligands as, 179, 180 as ligands in complexes, 188(T) phosphine as, 397 reaction of group 13 hydrides, 303 water as, 171ÿ2 Lewis structures, 26ÿ7 LFER (linear free energy relationship), 773 LFSE (ligand field stabilization energy) changes on oxidation of chromium and vanadium, 589 Co(III) vs Co(II) complexes, 626 octahedral compared with tetrahedral systems, 586(F), 587 and spinel structures, 587 thermochemical and spectroscopic values, 586 trends, 585ÿ6 LGO (ligand group orbital) approach to bonding, 107ÿ12 927 for bent triatomic molecules, 109ÿ12 for d-block metal octahedral complexes, 567(B) for linear triatomic molecules, 107ÿ9 Libby, W.F., 64 ligand field stabilization energies, trends, 585ÿ6 ligand field theory, 570, 586 ligand group orbital meaning of term, 107 see also LGO approach ligand substitution in d-block metal carbonyls, 719, 722 in d-block metal complexes, 764ÿ6 in octahedral complexes, 769ÿ77 effect of entering ligand, 773 effect of leaving ligand, 773 stereochemistry, 774 in square planar complexes, 766ÿ9 ligands abbreviations, 184(T) denticity, 183, 184(T) hapticity, 503(B), 700 meaning of term, 179 nucleophilicity, 769 structures, 184(T) light speed of, 4, 53, 873 see also UV radiation; visible light light-induced reactions, 242 lime see calcium oxide limestone, 276, 278(B) Lindqvist structure, 660, 661(F) linear free energy relationship, 773 linear molecules, 45(F), 46(T) d-block metal compounds, 543, 628, 638, 694, 696 [I3 ]ÿ ion, 483 interhalogen ions, 481(T) Kepert model, 542 molecular orbital approach to bonding, 107ÿ9 orbital hybridization for, 101ÿ2, 104, 105ÿ6, 556(T) orbital interactions in, 119, 120(F) point groups, 85ÿ6 symmetry properties, 86(F) vibrational modes, 92 xenon difluoride, 46(WE), 92(WE), 124, 125(F), 496(T) linear molecules, d-block metal compounds, 712 linkage isomerism, in d-block metal complexes, 682 linkage isomers, 549 d-block metal complexes, 549 Lipscomb, W.N., 124, 124(N), 327(N) liquid air, fractional distillation of, 392, 493 liquid ammonia, 217, 218ÿ21 physical properties, 218, 218(F), 218(T) reactions in, 218ÿ19, 261 redox reactions in, 221 self-ionization of, 217, 218 solutions of d-block metal compounds/complexes, 621, 685, 693, 694 of lanthanoids, 749 of s-block metals, 219ÿ20, 279, 722 liquid dihydrogen, storage of, 240(B) liquid dinitrogen tetraoxide, 217, 225ÿ7 acidÿbase behaviour in, 226 reactions in, 226ÿ7 Black plate (928,1) 928 Index liquid gases, boiling points, 242(T), 387, 389(T), 495(T), 817 liquid helium, 493ÿ4, 495, 495(T), 817 liquid hydrogen, boiling point, 242(T), 817 liquid hydrogen fluoride, 221ÿ2 acidÿbase behaviour in, 221ÿ2 electrolysis in, 222 liquid range, 218(F) physical properties, 221 self-ionization of, 221 liquid nitrogen, 387ÿ8, 389(T), 817 liquid ranges, solvents, 218(F) liquid sulfur dioxide, 217ÿ18 as solvent, 441, 454 lithal, 253 litharge, 376 lithium abundance of isotope(s), 876 amido complexes, 271ÿ2, 272(F) appearance of metal, 261 compared with magnesium, 260, 288, 289ÿ90 extraction of metal, 258 flame colour, 261 ground state electronic configuration, 18(T), 31, 260(T), 880 in liquid ammonia, 219, 221(T) NMR active nuclei, 68(T), 260(T), 505 nuclear binding energy, 53ÿ4(WE) occurrence, 257 physical properties, 24(F), 135(T), 259, 260(T), 877, 879, 880, 883, 884, 885 production of, 229, 258 reactions, 262 term symbol for, 573(B) see also dilithium lithium alkyls, 505ÿ7 structure, 505(F), 506(F) lithium aluminium hydride, 253, 259, 281(B), 306 lithium amide, 261 lithium carbonate, 259, 265, 266, 290 lithium cobaltate (mixed oxide), uses, 262(B), 625 lithium complexes, 268, 271ÿ2 lithium-containing crown ether complexes, 268 lithium fluoride, 264, 290 lithium halides, 145(B), 264, 264(T) lithium hydride, 251, 252(T) lithium hydroxide, 167, 290 lithium-ion battery, 262(B), 625, 816 lithiumÿiron sulfide battery, 262(B) lithium niobate (mixed oxide), 655, 816 thin films, 825 uses, 824(T) lithium nitrate, 290 lithium nitride, 259, 263, 263(F), 290, 816 electrical conductivity, 816(F) solid state structure, 263(F) lithium oxide, 264, 290 lithium ozonide, 265 lithium perchlorate, 290 lithium peroxide, 264, 265, 290 lithium tetrahydridoaluminate(1ÿ), 253, 259, 281(B), 306 lithium tetrahydroborate(1ÿ), 303, 303(F) lobes, atomic orbital, 13, 14(F) localized bonds, 100, 116 two-centre two-electron bond, 28 localized -bonds, 100, 102 London dispersion forces see dispersion forces lone pair(s) of electrons, 26 effect on bonding, 391, 437 effect on dipole moments, 40 in hybrid orbitals, 103 stereochemical effects, 46, 48, 449, 452, 526 stereochemically inactive, 46 low-spin complexes, 544ÿ5, 555, 560, 566, 764 Co(II), 629 Co(III), 625, 626, 769, 777 Co(IV), 624 Cr(II), 581(WE) Cu(IV), 634 Fe(II) and Fe(III), 620, 623 Ir(III), 681, 769 Mn(II), 617 Mn(III), 615 Ni(III) and Ni(IV), 630, 631 octahedral complexes, 560ÿ1, 561(T) Pd(IV), 684 Pt(IV), 684 Rh(III) and Rh(VI), 679, 680, 681, 769 Ru(II), Ru(III) and Ru(IV), 674, 676, 678 low-temperature baths, 367, 368(T), 388(T) LS coupling, 572(B) lubricants, 314, 317, 340, 345, 660(B), 663 luminescence, lanthanoid complexes, 746 LUMO (lowest unoccupied molecular orbital), 43, 44(F) in borane clusters, 329(B) in boron hydride adducts, 304(WE) lunar rock, 593, 623, 645 lutetium abundance of isotope(s), 876 ground state electronic configuration, 17, 18(T), 742(T), 881 physical properties, 742(T), 745(T), 881 lutetium(III) complexes, 750 lutetium organometallic compounds, 751, 753, 755 Lyman series, 4, 4(F), 5(F) lysine, 831(T) lysozyme, 459(B) m prefix (for bridging atoms), meaning of notation, 172(N) macrocyclic complexes, 186 macrocyclic effect, 186 macrocyclic ligands, 220, 268ÿ71, 288 in d-block metal complexes, 629ÿ30, 639 in d-block metal complexes, 546, 546(F) and Kepert model, 542 see also crown ethers; cryptands; porphyrins Madelung, Erwin, 153 Madelung constants, 153, 154, 158 listed for various lattice types, 154(T) for spinels, 587 magic acid, 224 MAGLEV (magnetic-levitation) trains, 819 magnesia, 284(B) milk of, 277 magnesite, 276 magnesium abundance of isotope(s), 876 compared with lithium, 260, 288, 289ÿ90 extraction of, 276 ground state electronic configuration, 18(T), 278(T), 880 physical properties, 135(T), 278(T), 877, 879, 880, 884, 885 reactivity, 279 recycling of, 276(B) uses, 277 magnesiumÿaluminium alloys, 276(B), 277, 277(F) magnesium(II), aqua species, 288 magnesium boride, 324 structure, 819, 819(F) superconducting properties, 819 magnesium bromide, 283 magnesium carbide, 279, 357 magnesium carbonate, 290 solubility in water, 174(T), 286 thermal stability, 283, 286, 290 magnesium fluoride, 282, 290 magnesium halides, 282ÿ3 magnesium hydroxide, 285ÿ6, 290 solubility in water, 174(T) magnesium nitrate, 290 magnesium nitride, 290 magnesium organometallic compounds, 509ÿ10 magnesium oxide, 157, 192, 284, 284(F), 290 melting point, 284(F) uses, 284(B) magnesium perchlorate, 281(B), 290 magnesium peroxide, 285, 290 magnesium silicide, 358 magnesium sulfate, 277, 281(B), 286, 460 magnetic moments, 579 of actinoids, 746 of lanthanoids, 745, 745(T), 746(WE) spin and orbital contributions to, 581ÿ3 see also effective magnetic moment magnetic quantum number, magnetic recording tapes, 608, 619 magnetic resonance imaging, 74(B), 493 magnetic spin quantum number, 15 magnetic susceptibility, 579, 580(B) experimental determination of, 579ÿ80, 628 units, 580(B) magnetically dilute systems, 584 magnetite, 138(B), 296, 316(B), 595, 619 magnets, 747(B) Magnus’s green salt, 687ÿ8 main group elements, 21 malachite, 596 malolactic fermentation, 459(B) manganate(VII) ion, 204, 612 colour, 538, 539 electronic transitions in, 571(T) manganate(IV) salts, 614 manganate(V) salts, 613 manganate(VI) salts, 613 manganate(VII) salts, 612 reactions, 612ÿ13 manganese, 611ÿ17 abundance, 594(F) abundance of isotope(s), 876 analytical determination of, 612 in biological systems, 614, 830, 831(T) FrostÿEbsworth diagram, in aqueous solution, 205ÿ6, 206ÿ7, 206(F) ground state electronic configuration, 18(T), 597(T), 880 metal, 611ÿ12 minerals, 151, 594ÿ5 occurrence, extraction and uses, 594ÿ5 oxidation states, 540(T), 611 physical properties, 135(T), 597(T), 878, 880, 884, 885, 887 polymorphism, 136 potential diagram, 204(F) Black plate (929,1) Index manganese cont standard reduction potentials, 196(T), 204, 885 structure, 135ÿ6 manganese(III), acetylacetonate complexes, 615 manganese(II) carbonate, 616 manganese carbonyl physical properties, 709(T) reactions, 711, 723 structure, 712, 712(F) manganese carbonyl derivatives, reactions, 720 manganese carbonyl hydride physical properties, 734(T) preparation of, 723 manganese(II) complexes, 616ÿ17 water exchange reaction, 772 manganese(III) complexes, 615 manganese(IV) complexes, 614 manganese dihalides, 616 manganese(II), hexaaqua ion colour, 538 electronic transitions in, 571(T), 574(WE) manganese(III), hexaaqua ion, 615 manganese(III), hexacyano ion, 615 manganese(II) hydroxide, solubility of, 201 manganese(III) hydroxide, solubility of, 201 manganese(II) ions, oxidation of, 201ÿ2 manganese nitride, 233 manganese organometallic compounds, 725 see also manganese carbonyl; manganocene manganese(II) oxide, 616, 816 manganese(III) oxide, 615 manganese(IV) oxide, 614 manganese(VII) oxide, 612 manganese(V) oxochloride, 613 manganese(VI) oxochloride, 613 manganese(VII) oxohalides, 612 manganese(II) sulfate, 616 manganese tetrafluoride, 613 manganese trifluoride, 614ÿ15 manganocene, 731 many-electron atoms, 16ÿ17 marble, 276 Marcus, Rudolph A., 780(N) MarcusÿHush theory, 780ÿ1 applications, 781, 781ÿ2(WE), 844 Marsh test, 397(B) martensitic stainless steels, 140(B) mass defect, 53 mass number, conservation in nuclear reactions, 57, 59 mass spectrometry, isotopes, matches, component compounds, 389, 427, 486 matrix isolation, carbonyls prepared by, 710 medical applications drugs, 623, 623(B), 647, 648, 689(B), 791 imaging, 74(B), 493, 593, 647, 671(B) iron supplements, 623(B) radioisotopes, 61(B), 470(B), 647, 671(B) Meissner effect, 817 meitnerium, 62(T) melting points, 137 d-block metals, 135(T), 597(T), 646, 650(T) group metal oxides, 284(F) group 18 elements, 135(T) metallic elements, 135(T) p-block hydrides, 246, 247(F), 394(T) zinc halides, 640(F) see also under individual elements, physical properties membrane (electrolysis) cell, 266(B) Mendele´ev, Dmitri, 17 mendelevium, 62(T) ground state electronic configuration, 18(T), 742(T), 882 longest lived isotope, 755(T) mass number range, 876 oxidation state(s), 743(T) physical properties, 882 mer-isomers, 49, 549 mercury, 694ÿ5, 695ÿ7 abundance of isotope(s), 876 extraction of, 648 ground state electronic configuration, 18(T), 650(T), 881 lattice structures, 135 melting point, 134, 135(T) metal, 694ÿ5 NMR active nuclei, 68(T), 835 occurrence, 648 oxidation states, 540(T), 694ÿ5 physical properties, 24(F), 648(B), 695(T), 881, 884 potential diagram, 696 reactivity, 694 toxicity, 648(B) uses, 648(B) mercury(I), disproportionation of, 696ÿ7 mercury(I) chloride, 696, 697 mercury(II) complexes, 696 mercury(I) compounds, 696ÿ7 mercury-containing metallothioneins, 835 mercury dihalides, 695ÿ6 solubility in water, 696(F) mercury (electrolysis) cell, 266(B) mercury(I) halides, 696, 697 mercury(I) nitrate, 697 mercury(II) nitrate, 648(B) mercury(II) oxide, 696 mercury polycations, 695 mesityl substituents, 343, 344 meta-antimonites, 424 meta-arsenites, 422 metaboric acid, 314, 314(F) metal borides, 324 structures, 325(T) metal carbonyls see d-block metal carbonyls metal films, deposition of, 823ÿ4 metal halides energetics, 478ÿ9(WE) structures, 478 metalÿmetal multiple bonds bonding, 610, 611(F) chromium, 610ÿ11 molybdenum, 664, 665ÿ6 osmium, 676 rhenium, 670 ruthenium, 679 tungsten, 664, 665 metallacyclopropane ring, 704 metallic bonding, 131 metallic elements, solid state structures, 131ÿ6 metallic hydrides, 251, 749 metallic radii, 136ÿ7 and coordination number, 137 listed for various elements, 135(T), 877ÿ8 d-block metals, 135(T), 597(T), 878 f -block metals, 742(T) 929 p-block elements, 135(T), 877ÿ8 s-block elements, 135(T), 877 trends for s- and d-block metals, 536(F) see also under individual elements, physical properties metallocenes, 507, 731ÿ2, 755, 761 group 2, 510, 526 group 14, 525 coparallel and tilted C5 rings in, 526ÿ7 see also chromocene; cobaltocene; ferrocene; manganocene; nickelocene; thorocene; uranocene; vanadocene; zirconocene metalloenzymes, 595, 596, 614, 831, 831(T), 843, 844, 854ÿ9 metallofullerenes, endohedral, 353 metalloproteins, 831ÿ2, 847ÿ51 electron transfer in, 782 metallothioneins, 835ÿ7, 836(F) metals bonding in, 141 resistivity, 141, 141(F) ‘metaphosphoric acid’, 422 metastable state, 345 metastable technetium isotope, 61(B) metathesis reactions, 254 see also alkene (olefin) metathesis metavanadates, 603ÿ4, 603(F) meteorites, 593 methaemerythrin, 843 methanation process, 801(T) methane anomalous properties, 247(F) bonding in, 103, 103(F), 115ÿ16 compared with silane, 343, 354 as greenhouse gas, 367(B) release from sea deposits, 355(B) sources, 367(B) vibrational modes, 94(F) methane hydrates, 355(B) methanofullerenes, 352 methanoic acid see formic acid methanol conversion to alkenes or gasoline, 807 dielectric constant, 215(T) production of, 239, 807 transfer of ions to (from water), 216 methionine, 831(T) methyl viologen, as quenching agent, 678 methylaluminoxane catalysts, 734(B) 1-methyl-3-ethylimidazolium cation, 230 methylhydrazine, 226(B) methyllithium, species present in solution, 505(F), 505(T) S-metolachlor (herbicide), 733(B) Meyer, Lothar, 17 mica(s), 151, 293, 371 microporous materials, 340(B) microstates, 573(B), 576ÿ7 table(s), 573(B), 577(T) milk of magnesia, 277 Miller indices, 801(N) Mingos cluster valence electron count, 716 see also total valence electron counting schemes minus (ÿ) notation for chiral molecules, 96(B), 551(B) mirror images, non-superposability in enantiomers, 95, 95(F) mirror plane, 80ÿ1 mispickel, 387 mitochondria, 845 Black plate (930,1) 930 Index mitochondrial electron-transfer chain, 845ÿ7, 853 mixed metal oxides, 152, 316ÿ17, 316(B) antimonates, 424 cobalt compounds, 624ÿ5 electrical conductivity, 816, 816(F) Hf and Zr compounds, 655ÿ6 iron compounds, 617, 618, 619 nickel compounds, 631 titanium compounds, 599 uranium compounds, 757 mixed-valence complexes/compounds cobalt(III/II) oxide, 624 gold compounds, 691 palladium complexes, 684, 685 platinum complexes, 685ÿ6 ruthenium complexes, 676, 678ÿ9 uranium oxide, 757 mixing of orbitals, 33ÿ4, 571 MobilÿBadger process (for alkylation of aromatics), 807 MOCVD (metalÿorganic chemical vapour deposition) technique, 514, 821, 824 models and theories band theory, 141ÿ2 Bohr model of atom, 5ÿ6, 298(B) crystal field model, 557 DewarÿChattÿDuncanson model, 701, 704 electrostatic model for ionic lattices, 152ÿ5, 156 HeitlerÿPauling bonding model, 26 HundÿMulliken bonding model, 26 JahnÿTeller theorem, 562 Kepert model, 541ÿ2 Koopmans’ theorem, 116(B) molecular orbital (MO) theory, 26, 29ÿ36 quantum theory, 3ÿ6 RutherfordÿBohr model of atom, valence bond (VB) theory, 26, 100ÿ7 valence-shell electron-pair repulsion (VSEPR) theory, 43, 45ÿ6, 46ÿ7(WE) moderators (in nuclear reactors), 60, 237 modulus, (mathematical) meaning of term, 153(N) molality, aqueous solutions, 165, 166 molar extinction coefficient, 571 typical values for various electronic transitions, 571(T) molar magnetic susceptibility, 579 experimental determination of, 579ÿ60, 579ÿ80 units, 580(B) molarity aqueous solutions, 165, 166 water, 162(WE) mole, meaning of term, molecular (covalent) hydrides, 253ÿ4 molecular dipole moments, 40, 40ÿ1(WE) molecular orbital diagrams cyclopentadienyl complexes, 508(B) for d-block metal complexes -bonding, 566ÿ7, 568(F) -bonding only, 565ÿ6, 566(F) for diatomic molecules, 31(F), 32(F), 34(F), 42(F), 44(F), 142(F) group 16 halide ions, 453(F) partial diagrams, 119, 120(F), 121(F), 124(F), 125(F), 127(F), 566(F), 568(F) for polyatomic molecules, 113(F), 114(F), 120(F), 121(F), 125(F), 127(F), 329(B), 453(F) polyatomic species, 107 for triatomic molecules, 108(F), 111(F) molecular orbital (MO) theory, 26 applications, 29ÿ33, 261(WE), 329(B) diatomic molecules heteronuclear molecules, 41ÿ3 homonuclear molecules, 29ÿ33, 261(WE) rules for, 29 molecular orbital theory for boron hydrides, 124ÿ7, 328, 329(B) compared with valence bond theory, 116ÿ17 for d-block metal octahedral complexes, 564ÿ70 diatomic molecules, 35(WE) ligand group orbital approach, 107ÿ12, 117ÿ19 objective use of, 119ÿ27 polyatomic molecules, 107ÿ19 molecular orbitals, 29 highest occupied (HOMO), 43, 44(F), 329(B) lowest unoccupied (LUMO), 43, 44(F), 304(WE), 329(B) mixing of, 33ÿ4, 571 parity of, 30(B), 558(B) /à orbitals, 32 /à orbitals, 30 molecular shape geometrical isomerism, 48 VSEPR theory, 43, 45ÿ8 molecular symmetry, 79ÿ99 molecular wires, 729(B) molluscs, oxygen transport proteins, 839ÿ41 molten salts, 227 applications, 227, 258 reactions in, 229ÿ30 as solvents, 227 molybdates(VI), 660 molybdenite, 433, 646, 660(B) molybdenum, 658ÿ66 abundance of isotope(s), 876 in biological systems, 646, 830, 831(T) ground state electronic configuration, 18(T), 650(T), 881 metal, 658ÿ9 occurrence, extraction and uses, 646 oxidation states, 540(T), 658ÿ9 physical properties, 135(T), 650(T), 881, 884 molybdenum carbonyl physical properties, 709(T) reactions, 719, 723 structure, 712 synthesis of, 710 molybdenum carbonyls, reactions, 735 molybdenum(III) complexes, 664 molybdenum(IV) complexes, 663 molybdenum(V) complexes, 662ÿ3 molybdenum(VI) complexes, 662 molybdenum dihalides, 665 molybdenum(IV), halo complexes, 663 molybdenum hexafluoride, 659 bonding in, 104 molybdenumÿiron protein (in nitrogenase), 850ÿ1, 850(F) molybdenumÿmolybdenum multiple bonds, 664, 665ÿ6 molybdenum organometallic compounds, 705(F), 725, 730, 735ÿ6, 736(F) see also molybdenum carbonyl molybdenum(IV) oxides [Mo3 (m3 -O)(m-O)3 (H2 O)9 ]4þ , 663(F) MoO2 , 663 molybdenum(VI) oxide, 660 molybdenum(VI) oxohalides, 659 molybdenum pentahalides, 662 molybdenum peroxo complexes, 444(F), 662 molybdenum(IV) sulfide, 660(B), 663 molybdenum tetrahalides, 663 molybdenum trihalides, 663 ‘molybdic acid’, 660 monazite, 645, 747 lanthanoids extracted from, 747 thorium extracted from, 748 Mond process, 596 Monel metal, 596, 630 monobasic acids, 166, 167, 169 monocapped octahedral molecules d-block metal compounds/complexes, 545, 546(F), 656 xenon heptafluoride anion, 498, 498(F) monocapped octahedron, 546(F) monocapped square-antiprismatic molecules, Zintl ions, 359(F) monocapped trigonal bipyramid see bicapped tetrahedron monocapped trigonal prism, 546(F) monocapped trigonal prismatic molecules d-block metal compounds/complexes, 545ÿ6, 546(F), 652, 653(F), 656, 665 orbital hydridization for, 556(T) monochromatic radiation in polarimetry, 96 in X-ray diffraction, 146(B) monoclinic sulfur, 439 monodentate ligands, 183, 184(T), 305 complexes with, factors affecting stabilities, 186ÿ8 monolayer on catalyst surface, 801 monooxygenases, 722, 843 monotopic elements, Monsanto acetic acid process, 793ÿ4 catalysts used, 470(B), 722(B), 793, 794 compared with BASF process, 794(T) reactions steps, 721, 799 montmorillonite, 374(B) Montreal Protocol, 266(B), 362(B) mordants, 316 Mo¨ssbauer spectroscopy, 73ÿ5 Fe-57 spectroscopy, 73ÿ5, 623, 851 Sn-119 spectroscopy, 344 suitable nuclei, 74(T), 344 motor vehicle airbags, 259, 388, 392 motor vehicle catalytic converters, 646(B), 647, 802, 805ÿ6 motor vehicles, fuel cells in, 240ÿ1(B) Mount St Helens eruption, 456(B) MOVPE (metal organic vapour phase epitaxy) technique, 514 MRI (magnetic resonance imaging) scanners, 74(B), 493, 593, 646, 819 MTG (methanol-to-gasoline) process, 807 MTO (methanol-to-olefins) process, 807 Mulliken electronegativity values, 37ÿ8, 38(F) multilayer heterojunction bipolar transistor wafer, 823 multinuclear NMR spectroscopy, 66ÿ73, 301ÿ2(WE) multiple bonds in polyatomic molecules, valence bond approach, 105ÿ7 see also metalÿmetal multiple bonds multiplicity of NMR spectroscopic signal, 69ÿ70 Black plate (931,1) Index myoglobin, 831, 837ÿ9 n-type semiconductors, 144, 375(B), 378, 823 N-donor ligands, 183, 184(T) [N5 ]þ ion, 400ÿ1 [NAD]þ , 845 [NAD]þ /NADH couple, 846(F), 847 nanosecond flash photolysis, 778(B) nanotubes, 353 dihydrogen absorbed in, 240(B) naphthalide salts, as reducing agents, 711 Naproxen, 792, 793 NASICON (sodium super-ionic conductors), 816 electrical conductivity, 816(F) National Institute of Standards and Technology, caesium clock, 260(B) native gold, 647, 648 native platinum, 647 Natta, Giulio, 512(B) natural abundance of isotopes, 68(T), 74(T), 875ÿ6 naturally occurring radioactive nuclides, 55ÿ7 abundance, 875ÿ6 half-lives, 57(T) nature see biological systems nearest-neighbour atoms in close-packed lattices, 132, 134, 135 Ne´el temperature, 584ÿ5 negative catalyst, 786 negative hyperconjugation, 356 neodymium abundance of isotope(s), 876 ground state electronic configuration, 18(T), 742(T), 881 physical properties, 742(T), 745(T), 881 neodymium(III) complexes, 751 neodymium lasers, 744(B) neodymium organometallic compounds, 753, 755 neon abundance, 493(F) abundance of isotope(s), 876 extraction of, 493 ground state electronic configuration, 18(T), 21ÿ2(WE), 495(T), 880 physical properties, 24(F), 135(T), 158(F), 495(T), 878, 880 term symbols for, 573(B) uses, 494 nephelauxetic effect, 578, 578ÿ9(WE) neptunium, 62(T) ground state electronic configuration, 18(T), 742(T), 882 longest lived isotope, 755(T) mass number range, 876 metal, 756 oxidation state(s), 743(T) physical properties, 742(T), 882 potential diagram, 758(F) synthesis of, 748 Nernst equation, 194, 197, 198, 198(WE), 211 nerve gases, 388(B) Nessler’s reagent, 696 neutrino, 55 neutron activation analysis, 474 neutron diffraction ionic lattices studied by, 146 and magnetic moments, 585 metal hydrides studied by, 703 neutron(s), 1ÿ2 high-energy, bombardment by, 57 penetrating power of, 55(F) properties, 2(T), 53 ‘slow’/thermal, bombardment by, 57ÿ8 Nicalon fibres, 827 nickel, 630ÿ4 abundance, 594(F) abundance of isotope(s), 876 analytical determination of, 632 in biological systems, 830, 831(T) ground state electronic configuration, 18(T), 597(T), 880 metal, 630 occurrence, extraction and uses, 596 oxidation states, 540(T), 630 physical properties, 135(T), 597(T), 878, 880, 884, 885 recycling of, 596(F) nickel(II) acetylacetonate complexes, 631 nickel arsenide, 402 structure, 403(F) nickel-based catalysts, 239, 596, 630, 797, 801(T) nickel cadmium (NiCd) battery, 596, 631, 648 electrochemical reactions, 596 nickel carbonyl reactions, 711 structure, 712 nickel carbonyls physical properties, 709(T) reactions, 711 synthesis of, 710 nickel complexes, 185, 186, 564 bonding in, 557 formation of, 182(WE) nickel(II) complexes, 632ÿ3 ligand substitution reactions, 773 racemization of, 776 water exchange reaction, 772 nickel(I) compounds, 634 nickel(II) compounds, 631ÿ2 nickel(III) compounds, 631 nickel(IV) compounds, 630ÿ1 nickel dihalides, 631 nickel(II), hexaammine ion, 632 absorption spectra, 576(F) nickel(II), hexaaqua ion, 631 absorption spectra, 576(F) ligand substitution reactions, 773 stepwise stability constants (H2 O displaced by NH3 ), 588(F) nickel(II), hydrido complex anion, 254 nickel(IV), hydrido anion, 254, 254(F) nickel(III) hydrous oxide, 631 nickel(II) hydroxide, 631 nickelÿmetal hydride battery, 251(B), 596 nickel organometallic compounds, 728(F) see also nickel carbonyl; nickelocene nickel(II) oxide, 631, 816, 817 standard Gibbs energy of formation, 210(F) as thin film, 820(T) nickel(II) oxide, doping with Li2 O, 814, 814(F) nickel(II) pentacyano anion, 632 nickel silver, 596 nickel(II) sulfide, 631 nickel(II) tetracyano anion, 632 nickel tetrafluoride, 630 nickel trifluoride, 630ÿ1 nickelocene, 731 reactions, 731(F) nido-clusters, 326, 326(F), 328, 359, 403(WE), 716(WE) 931 night-storage radiators, 284(B) nine-coordinate molecules d-block metal compounds, 547, 651 f -block metal compounds and complexes, 750, 756, 758 see also tricapped trigonal prismatic nineteen-electron complexes, 731 niobates, 655, 820(T), 824(T), 825 niobite, 646 niobium, 654ÿ8 abundance of isotope(s), 876 ground state electronic configuration, 18(T), 650(T), 881 metal, 654 occurrence, extraction and uses, 646 oxidation states, 540(T), 654 physical properties, 135(T), 650(T), 881, 884 niobium(IV) complexes, 656 niobium(V) complexes, 656 niobium hydrides, 251 niobium(IV) oxide, 656 niobium(V) oxide, 655 niobium(V) oxohalides, 655 niobium pentahalides, 654ÿ5 niobium subhalides, 657ÿ8, 658(WE) niobium tetrahalides, 656 niobiumÿtitanium superconductors, 593, 646, 819 niobium trihalides, 656ÿ7 nitrate ion bonding in, 106ÿ7(WE), 120, 121(F), 417 structure, 417, 418(F) test for, 412, 771(B) nitrate salts, 416ÿ17 removal from waste water, 417(B) nitrato ligands, 226ÿ7 nitric acid, 167, 416ÿ17 acid anhydride, 415 basic behaviour in non-aqueous solvents, 217, 223 commercial demand, 416(B) manufacture of, 416, 801(T) nomenclature, 168(B) structure, 417, 418(F) nitric oxide see nitrogen monoxide nitric oxide transport protein, 840(B) nitrides, 401ÿ2 boron nitrides, 317ÿ19 of d-block metals, 401, 402(B), 598, 606 of p-block elements, 317ÿ19 of s-block elements, 259, 263, 290 nitrido bridges, 674ÿ5 nitridoborates, 318 nitrite salts, 388, 415 removal from waste water, 417(B) nitrogen abundance, 387(F) abundance of isotope(s), 876 bond enthalpy terms, 390(T) fixing of, 386ÿ7, 847, 850 FrostÿEbsworth diagram, in aqueous solution, 207ÿ8, 207(F), 399(WE) ground state electronic configuration, 18(T), 28, 103, 389(T), 880 liquid, 387, 388(T) occurrence, 386ÿ7 physical properties, 24(F), 389(T), 877, 879, 880, 883, 884 reaction(s) with, hydrogen, 243, 387, 395ÿ6 term symbols for, 573(B) uses, 387ÿ8 see also dinitrogen Black plate (932,1) 932 Index nitrogen difluoride radical, 405 nitrogen dioxide, 414ÿ15 equilibrium with dinitrogen tetraoxide, 414 physical properties, 412(T) structure, 414(F) nitrogen fixation, 850 nitrogen fluorides, 404(T), 405 nitrogen halides, 403ÿ5 dipole moments in, 404(WE) nitrogen monoxide, 412ÿ13 in biological systems, 413(B), 840(B) physical properties, 412(T) reversible bonding to [Fe(H2 O)6 ]2þ , 412, 771(B) see also nitrosyl ligand; nitrosyl radical nitrogen oxides, 412ÿ15 see also NOx emissions nitrogen oxoacids, 415ÿ17 nitrogen oxohalides, 405ÿ6 nitrogenÿselenium compounds, 464 nitrogenÿsulfur compounds, 462ÿ4 nitrogen tribromide, 404 nitrogen trichloride, 404, 404(T) nitrogen trifluoride, 40, 404, 404(T) nitrogen triiodide, 405 nitrogenases, 850ÿ1 Fe protein in, 850 FeMo protein in, 850ÿ1, 850(F) nitrogenous fertilizers, 278(B), 357, 388, 395(B), 396, 416(B), 460 nitroglycerine, 388 nitronium ion, 217(N) nitrophorin, 840(B) nitroprusside, 623 nitrosyl anion, 415 nitrosyl complexes, 412, 570, 771(B) nitrosyl halides, 405 nitrosyl ion, 217, 413 nitrosyl ligands, 623ÿ4 binding to Fe(III) in nitrophorin, 840(B) displacement of CO by, 723 valence electron count for, 569ÿ70, 570, 708, 723 nitrosyl radicals, environmental effects, 805 nitrous acid, 167, 415ÿ16 acid anhydride, 413 nomenclature, 168(B) nitrous oxide see dinitrogen monoxide nitryl cation, 415 nitryl halides, 405 nitryl ion, 217 NMR active nuclei d-block metals, 68(T), 649, 651, 702, 835 group 1, 68(T), 260(T), 261 group 13, 68(T), 297(T), 299 group 14, 68(T), 342(T), 344 group 15, 68(T), 389(T), 391 group 16, 68(T), 435(T), 437 group 17, 68(T), 473 group 18, 68(T), 495 NMR spectroscopy, 66ÿ73, 66(B) applications t-butyllithium, 505ÿ6(WE) d-block metal carbonyls, 701ÿ2 electron-transfer processes, 778(B) geometrical isomers, 549, 550(B) metallothioneins, 835 p-block compounds, 70ÿ2 s-block compounds, 68, 261, 505ÿ6(WE) chemical shifts, 66(B), 68ÿ9 and isotope abundance, 66(B), 68, 68(T) lanthanoid shift reagents, 751(B) multiplicity of signal, 69ÿ70, 505ÿ6(WE) non-binomial multiplets, 71, 506(WE) nuclear spinÿspin coupling in, 66ÿ7(B), 69ÿ72, 70, 70(F), 71, 71(F) nuclei suitable for, 66(B), 68, 68(T) proton-decoupled, 71, 71(F) resonance frequencies, 66(B) signals broadening of, 66(B), 68 multiplicity, 66ÿ7(B), 69ÿ70, 70, 72 relative integrals, 66(B) satellite peaks, 72, 72(F), 550(B) solvents for, 66(B) spectral windows, 68 standard references, 66(B), 68(T) see also boron-11; carbon-13; fluorine-19; oxygen-17; phosphorus-31; proton ; thallium-205; tin-119 NMR spectroscopy nobelium, 62(T) ground state electronic configuration, 18(T), 742(T), 882 longest lived isotope, 755(T) mass number range, 876 oxidation state(s), 743(T) physical properties, 882 noble gas electronic configuration(s), 21ÿ2(WE), 24 noble gases, 21(T), 492 see also group 18 nodal planes, atomic orbital, 13, 14(F) nomenclature actinoids/lanthanoids, 17(N), 20, 741(N) boranes, 328(B) chiral complexes and compounds, 96(B), 551(B) cis/trans (E/Z) isomers, 49(N) coordination complexes, 253(N), 503(B) crown ethers, 268 cyclopentadienyl complexes, 503(B) group 15 trihydrides, 394(T) hybrid orbitals, 101, 102, 103 oxidation states, 193 oxoacids, 167, 168(B) of halogens, 485(T) of phosphorus, 420(T) of sulfur, 458(T) periodic table, 20ÿ1, 21(T) Stock, 193 substitution mechanisms, 765(N) transuranium elements, 62(T) zeolites, 373(N) non-aqueous media, 214ÿ35 acidÿbase behaviour in, 216ÿ17 applications, 181(B), 218 dielectric constants listed, 215(T) differentiating effects, 217 group complexes in, 271ÿ2 levelling effects, 217, 219 non-close-packed lattices, 134 non-crossing rule, 575 non-stoichiometric compounds, 814, 815, 816 2,5-norbornadiene, 705 normal modes of vibration, 90ÿ1, 91(F) normalization factors, 28 see also wavefunctions notation bridging atoms, 172(N) chiral molecules, 96(B), 551(B) concentration, 162(N), 766(N), 771(B) crystal field theory, 558(B), 562(B) crystal planes, 801(N) doubly degenerate orbital, 558(B) electronic transitions, 562(B) ground state electronic configuration, 16, 17, 30, 31 ions, 162(N), 766(N) standard reduction potentials, 197(B) triply degenerate orbital, 558(B) wavefunctions, 12(B) NOx emissions, 413, 414(B) environmental effects, 414(B) sources, 413, 414(B), 806(F) see also nitrogen oxides nuclear binding energy, 53ÿ5 nuclear charge effective, 17, 19(B), 22, 23, 34(F), 36, 41, 144 see also atomic number nuclear emissions, 55 nuclear fission, 58ÿ61 balancing equations, 59(WE) energy production by, 60 nuclear fuel reprocessing, 61, 181(B), 218, 481, 677 nuclear fusion, 62ÿ3 nuclear magnetic resonance see NMR nuclear power, 59(B), 60ÿ1 as percentage of electricity in various countries, 59(B) nuclear reactors Chernobyl disaster, 60(B) control rods, 60, 296, 645 coolants, 259 fuel-rod cladding, 645 heat-transfer agents, 494 moderators, 60, 237 nuclear spin quantum number, 68 listed for various NMR active nuclei, 68(T) listed for various nuclei, 68(T) nuclear transformations, 55ÿ6, 57ÿ8 nuclei bombardment by high-energy particles, 57 bombardment by ‘slow’/thermal neutrons, 57ÿ8 nucleon, average binding energy per, 54ÿ5 nucleophilicity discrimination factor, 769 determination of, 769, 770(F) listed for square planar Pt(II) complexes, 771(T) for square planar Pt(II) complexes, 770(F) nucleophilicity parameter, 769 nucleophilicity sequence for substitution, 769 nucleus of atom, nuclides nomenclature for, radioactive, 55ÿ7 Nyholm, R.S., 43 octadecahedral molecules, borane cluster compounds, 330(F) octahedral clusters boranes, 326, 326(F), 328(WE), 330(F) bonding in organometallic clusters, 714 carbaboranes, 333, 333(WE) metal carbonyl, 713, 713(F), 714(F) molybdenum, 665 niobium, 657 tantalum, 657 tungsten, 665 zirconium, 653 octahedral complexes As(V), 409 base-catalysed hydrolysis, 774ÿ6 Cd(II), 695 Black plate (933,1) Index octahedral complexes cont Co(II) and Co(III), 625(B), 626, 628 Cr(III), 557, 608 crystal field stabilization energies, 560ÿ1, 561(T) Cu(II), 637 dissociative mechanisms, 772 distortion of, 545, 561ÿ2 Fe(II) and Fe(III), 254, 557, 620, 621, 623ÿ4, 624 Hg(II), 696 Ir(IV), 680 isomerization in, 775(F), 776 Kepert model, 542 lanthanoid, 751 Mg(II), 283 Mn(II) and Mn(III), 615, 616 Mo(IV) and Mo(V), 662, 663 molecular orbital theory for, 564ÿ70 Nb(V), 656 Ni(II), 557, 631, 632 Os(II), 254 osmium, 673, 673ÿ4, 675 Pd(IV), 684 Pt(IV), 254, 684, 685 racemization of, 776ÿ7 relationship to square planar complexes, 562, 563(F) rhenium, 668, 669, 670 ruthenium, 254, 673, 673ÿ4, 675 Sc(III), 598 substitution reactions, 769ÿ77 Ta(IV), 656 technetium, 668, 669, 670 Ti(III), 601 U(VI), 758 V(III), 605 W(IV) and W(V), 662, 663 Y(III), 651 Zn(II), 641 Zr(IV), 652 octahedral crystal field, 558ÿ60 energy level diagram, 575(F) splitting of d orbitals in, 559(F), 563(F) octahedral holes in close-packed lattices, 133ÿ4, 139, 401 octahedral molecules, 45(F), 46(T), 48, 87(F) Al(III) fluoride complexes, 309ÿ10 bismuth halides, 411 d-block metal compounds, 544ÿ5, 605, 667, 679, 712, 713 geometrical isomers, 48ÿ9, 625(B) group 16 halides and ions, 452 group 17 oxoacids, 487 group 17 oxoacids and salts, 487 interhalogen ions, 481ÿ2, 481(T) NMR spectroscopy, 70 orbital hybridization for, 104, 556(T) orbital interactions in, 120ÿ3 point groups, 86 relationship to trigonal prismatic molecules, 545, 625(B) telluric acid, 462 xenon hexafluoride, 496(T) octahedralÿpentagonal bipyramidal conversion, changes in CFSE, 772(T) octahedral point group, 86 octahedralÿsquare planar interconversions, 632 octahedralÿsquare-based pyramidal conversion, changes in CFSE, 772(T) octahedralÿtetrahedral interconversions, 628, 629 octahedron, 330(F) relationship to trigonal prism, 545 octane number, increasing, 801(T), 807 oct-1-ene, hydroformylation of, 795 octet rule, 36, 36(WE) see also eighteen-electron rule olefin see alkene oleum, 455, 461 solution of boric acid in, 223 see also sulfuric acid oligomerization of alkenes, 797 olivine, 276, 371 Onnes, H Kamerlingh, 817 opacifiers (in ceramics and paints), 341, 652, 820 optical activity, 95 optical isomers, 95, 549, 552 optical properties, yttrium hydrides, 253(B) optoelectronic devices, 296, 514(B), 820(T), 824(T) orbital basis set, 32 orbital energies, hydrogen-like species, 13 orbital hybridization, 100ÿ5 sp hybridization, 101ÿ2, 104, 105(F), 106 sp2 hybridization, 102ÿ3, 104, 105 sp3 hybridization, 103, 103(WE), 104 sp2 d hybridization, 104 sp3 d hybridization, 104 sp3 d hybridization, 104 orbital interaction diagrams see molecular orbital diagrams orbital mixing, 33ÿ4 orbital quantum number, 9, 15(B), 572(B) ores, extraction of elements from, 138(B), 210 organoaluminium compounds, 511ÿ14 organoantimony compounds, 527ÿ30 organoarsenic compounds, 527ÿ30 organobarium compounds, 510 organoberyllium compounds, 507, 509(F) organobismuth compounds, 527ÿ30 organoboranes, 303(F), 321, 511 organocalcium compounds, 510 organogallium compounds, 514ÿ18, 516(WE) organogermanium compounds, 520ÿ1 organoindium compounds, 514ÿ18 organolanthanoid complexes, 751ÿ5 uses, 752(B) organolead compounds, 259, 344(B), 474(B), 524ÿ6 organolithium compounds, 505ÿ7 organomagnesium compounds, 509ÿ10 organomercury compounds, transmetallation of, 509 organometallic compounds, 42, 338, 503ÿ34, 700ÿ40, 751ÿ5, 759ÿ61 of actinoids, 759ÿ61 of d-block metals, 700ÿ40 Z nomenclature, 503(B) effect of bulky substituents on stability, 343, 519, 521, 523 of group elements, 504ÿ7 of group elements, 507, 509ÿ11 of group 13 elements, 259, 511ÿ18 of group 14 elements, 344(B), 376ÿ7, 476, 518ÿ27 of group 15 elements, 476ÿ7, 527ÿ30 of group 16 elements, 530ÿ2 of lanthanoids, 751ÿ5 meaning of term, 503, 700 of p-block elements, 511ÿ32 933 reactions, 719ÿ23 of s-block elements, 504ÿ11 organoselenium compounds, 530ÿ1 organosilicon compounds, 376ÿ7, 518ÿ20 organosilicon hydrides, 519ÿ20(WE) organostrontium compounds, 510, 510ÿ11(WE) organotellurium compounds, 530ÿ1 organothallium compounds, 514ÿ18 organotin compounds, 521ÿ4, 523ÿ4(WE) uses, 518, 521(B) organotin halides, 521ÿ2, 523ÿ4(WE) reactions, 522(F) organotin(IV) hydrides, 523 Orgel diagrams, 575, 575(F), 576(F) orpiment, 387, 428, 433 orthoboric acid, 314, 314(F) see also boric acid orthoclase, 370, 372 orthometallation, 680, 681(F), 720 orthonitrates, 417 orthoperiodic acid, 487 orthophosphoric acid, nomenclature, 168(B), 420(T) orthorhombic sulfur, 439 orthovanadates, 603 ‘osmic acid’, 672 osmiridium, 647 osmium, 671ÿ8 abundance of isotope(s), 876 ground state electronic configuration, 18(T), 650(T), 881 metal, 671 NMR active nuclei, 651 occurrence, extraction and uses, 647 oxidation states, 540(T), 671 physical properties, 135(T), 650(T), 881, 884 osmium carbonyl cluster anions, structures, 714, 714(F) osmium(II), carbonyl complexes, 671 osmium carbonyls as catalysts, 799 physical properties, 709(T) reactions, 711, 720, 723 structures, 712, 712(F), 713, 714, 714(F), 716, 716(WE) synthesis of, 710 osmium(II) complexes, 677ÿ8 osmium(III) complexes, 676 osmium(IV) complexes, 675 osmium(V) complexes, 673ÿ4 osmium(VI) complexes, 672 osmium(VII) complexes, 672 osmium(II), dinitrogen complexes, 677 osmium(III), halo complexes, 676 osmium(IV), hexafluoro anion, reactions, 675(F) osmium(II), hydrido anion, 254, 676 osmium, imido compounds, 672 osmium organometallic compounds, 730 see also osmium carbonyls osmiumÿosmium triple bond, 676 osmium(IV) oxide, 673 osmium(VIII) oxide, 672 osmium oxofluorides, 671 osmium pentahalides, 673 osmium tetrahalides, 673 osmium trihalides, 675 outer orbital complexes, 557(B) outer-sphere mechanism, 777, 779ÿ82 testing for, 780ÿ1, 781ÿ2(WE) ... increased (see Figure 16 .2) 2KClO3 ỵ 2H2 C2 O4 K2 C2 O4 ỵ 2ClO2 ỵ 2CO2 ỵ 2H2 O 16:43ị " 2NaClO3 ỵ SO2 ỵ H2 SO4 2NaHSO4 ỵ 2ClO2 " 16:44ị Despite being a radical, ClO2 shows no tendency to dimerize... [He]2s2 2p5 79 53.5 85 0.51 6. 62 1681 328 504 150 459 2. 87 71 133 135 4.0 17 [Ne]3s2 3p5 121 1 72 239 6.40 20 .41 125 1 349 361 90 334 ỵ1.36 99 181 180 3 .2 35 [Ar]3d 10 4s2 4p5 1 12 266 3 32 10.57 29 .96... 1s2 4 .2 10 [He]2s2 2p6 24 .5 27 0.34 18 [Ne]3s2 3p6 84 87 1. 12 36 [Ar]3d 10 4s2 4p6 116 120 1.37 54 [Kr]4d 10 5s2 5p6 161 165 1.81 86 [Xe]4f 14 5d 10 6s2 6p6 20 2 21 1 0.08 1.71 6.43 9.08 12. 62