Transition elements ionic compounds

Reference has been made already to the existence of a set of inner transition elements, following lanthanum, in which the quantum level being filled is neither the outer quantum level nor the penultimate level, but the next inner. These elements, together with yttrium (a transition metal), were called the rare earths , since they occurred in uncommon mixtures of what were believed to be earths or oxides. With the recognition of their special structure, the elements from lanthanum to lutetium were re-named the lanthanons or lanthanides. They resemble one another very closely, so much so that their separation presented a major problem, since all their compounds are very much alike. They exhibit oxidation state -i-3 and show in this state predominantly ionic characteristics—the ions. 

Attempts to classify carbides according to structure or bond type meet the same difficulties as were encountered with hydrides (p. 64) and borides (p. 145) and for the same reasons. The general trends in properties of the three groups of compounds are, however, broadly similar, being most polar (ionic) for the electropositive metals, most covalent (molecular) for the electronegative non-metals and somewhat complex (interstitial) for the elements in the centre of the d block. There are also several elements with poorly characterized, unstable, or non-existent carbides, namely the later transition elements (Groups 11 and 12), the platinum metals, and the post transition-metal elements in Group 13. 

The redox behaviour of Th, Pa and U is of the kind expected for d-transition elements which is why, prior to the 1940s, these elements were commonly placed respectively in groups 4, 5 and 6 of the periodic table. Behaviour obviously like that of the lanthanides is not evident until the second half of the series. However, even the early actinides resemble the lanthanides in showing close similarities with each other and gradual variations in properties, providing comparisons are restricted to those properties which do not entail a change in oxidation state. The smooth variation with atomic number found for stability constants, for instance, is like that of the lanthanides rather than the d-transition elements, as is the smooth variation in ionic radii noted in Fig. 31.4. This last factor is responsible for the close similarity in the structures of many actinide and lanthanide compounds especially noticeable in the 4-3 oxidation state for which... 

The Niccolite Structure. The substances which crystallize with the niccolite structure (B8) are compounds of transition elements with S, Se, Te, As, Sb, Bi, or Sn. The physical properties of the substances indicate that the crystals are not ionic, and this is substantiated by the lack of agreement with the structural rules for ionic crystals. Thus each metal atom is surrounded by an octahedron of non-metal atoms but these octahedra share faces, and the edges of the shared faces are longer than other edges (rather than shorter, as in ionic crystals). Hence we conclude that the bonds are covalent, with probably some metallic character also. 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

The systematic investigation of the chemistry of the transition elements began in the nineteenth century, and it rapidly became apparent that many of the compounds were somewhat different from those with which chemists were then familiar. There was a clear difference between the behaviour of simple ionic compounds such as sodium chloride and typical transition-element compounds such as FeCl2-4H20. It was also obvious that the compounds did not resemble the typically covalent compounds of organic chemistry. It was considered that many of the compounds formed by transition metals were of a complex constitution, and they were accordingly known as complexes. 

The variations in ionic radii of the transition elements of the 4th period serve to exemplify the arguments needed to rationalize similar variations in the other transition series. Figure 7.3 includes a plot of the radii of the 2 + ions of those transition elements of the 4th period that form them. The plot includes the radius of the Ca2+ ion, which represents the beginning of the series but has no 3d electrons, as also has the Zn2+ and Ga3+ ions (both 3d10) at the end of the series. The radii are those of octahedrally coordinated ions as they are found in crystalline compounds, the counter-ions (i.e. the ions of opposite charge) being situated at the vertices of an octahedron, as shown in Figure 7.4. 

Although there is no space to develop a detailed discussion of the solubilities of compounds of the transition elements, the general insolubility of their + 2 and + 3 hydroxides is important. The rationale underlying their insolubility can be summarized (i) the hydroxide ion is relatively small (152 pm ionic radius) and the ions of the +2 and +3 transition metals assume a similar size if their radii are increased by 60-80 pm, and (ii) the enthalpy of hydration of the hydroxide ion (—519 kJ mol ) is sufficiently negative to represent a reasonable degree of competition with the metal ions for the available water molecules, thus preventing the metal ions from becoming fully hydrated. Such effects combine to allow the lattice enthalpies of the hydroxides to become dominant. 

In general, it is observed that the charges on simple positive ions are limited to a maximum of three even if an inert gas configuration is not reached. Thus the elements of the transition series all may lose two electrons (the s electrons are lost first) to give dipositive ions in ionic compounds, and a number of them give -1-3 ions. Similarly, as a rule, the lanthanide... 

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