Properties transition elements

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

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 three series of elements arising from the filling of the 3d, 4d and 5d shells, and situated in the periodic table following the alkaline earth metals, are commonly described as transition elements , though this term is sometimes also extended to include the lanthanide and actinide (or inner transition) elements. They exhibit a number of characteristic properties which together distinguish them from other groups of elements ... 

The total lanthanide contraction is of a similar magnitude to the expansion found in passing from the first to the second transition series, and which might therefore have been expected to occur also in passing from second to third. The interpolation of the lanthanides in fact almost exactly cancels this anticipated increase with the result, noted in preceding chapters, that in each group of transition elements the second and third members have very similar sizes and properties. 

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... 

There are two immediate questions we ask about the transition elements once we know where they are in the periodic table (1) Why do we consider these elements together (2) What is special about their properties These questions are closely related because they both depend upon the electron configurations of the atoms. What, then, is the electron configuration we might expect for these elements ... 

In the sixth-row transition elements (lan-thanum through mercury) there is an additional complication. There are seven 4f orbitals which are very close in energy to the 5d orbitals. Putting electrons into these 4f orbitals means there will be fourteen additional elements in this row. These fourteen elements are almost identical in many chemical properties. We will discuss them in the next chapter. 

What properties do we actually find for the transition elements What kinds of compounds do they form How can the properties be interpreted in terms of the electron populations of the atoms ... 

Table 22-III. some properties of fourth-row transition elements...

What properties of the transition elements are consistent with their being classified as metals ... 

The elements in Groups 3 through 11 are called the transition metals because they represent a transition from the highly reactive metals of the s block to the much less reactive metals of Group 12 and the p block (Fig. 16.1). Note that the transition metals do not extend all the way across the d block the Group 12 elements (zinc, cadmium, and mercury) are not normally considered to be transition elements. Because their d-orbitals are full, the Group 12 elements have properties that are more like those of main-group metals than those of transition metals. Just after... 

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. 

In the papers referred to above it is pointed out that the mechanical properties of the transition elements and the distances between atoms in metals and intermetallic compounds are well accounted for by these considerations. In the following sections of the present paper a discussion is given of the number of valence electrons by the Brillouin polyhedron method, and it is shown that the calculations for the filled-zone alloys such as the 7-alloys provide further support for the new system of metallic valences. 

The transition elements comprise groups 3 to 12 and are found in the central region of the standard periodic table, an example of which is reproduced on the endpaper. This group is further subdivided into those of the first row (the elements scandium to zinc), the second row (the elements yttrium to cadmium) and the third row (the elements lanthanum to mercury). The term transition arises from the elements supposed transitional positions between the metallic elements of groups 1 and 2 and the predominantly non-metallic elements of groups 13 to 18. Nevertheless, the transition elements are also, and interchangeably, known as the transition metals in view of their typical metallic properties. 

Silicon-transition metal chemistry is a relatively new area. The work of Hein and his associates (1941) on Sn—Co derivatives established the possibility of forming bonds between a Group IVB metal and a transition element 139), but it was another fifteen years before CpFe(CO)2SiMej 203), the first of many silyl derivatives, was synthesized. The interest in these compounds derives from (1) comparison with the corresponding alkyl- and Ge-, Sn-, and Pb- transition metal (M) complexes, including the role of ir-back-bonding from filled d orbitals of M into empty d orbitals on Si (or other Group IVB metal), and (2) expectation of useful catalytic properties from such heteronuclear derivatives. 

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