Transition elements third series

Transition Elements Third Series—Period 6, Groups 4 to 12... 

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. 

As mentioned above, some chemistry of a few heavier elements is also of concern in the development of the geosphere and of living systems as we shall see later. A striking case is the chemistry of molybdenum (Mo) and tungsten (W), which we take here with vanadium (V). The first two elements are in the second and third series of transition metals and all three are found in higher combining ratios and with a greater preference for S rather than O, W less so than Mo (the... 

Figure 4.93 illustrates some aspects of the break in the vertical trend of atomic orbital energies es and for early, middle, and late transition elements, showing the contrasting behavior of third-series versus first- and second-series elements. The... 

Upon comparison of the k< m exchange rate of the Tc(V) system with that of the Re(V), the significant increase in reactivity (ca. 3 orders of magnitude) is very prominent and not necessarily indicative of an associative activation. It is, however, possible that the Tc(V) hydroxo complex might be very reactive via an associative pathway, since it is known that the Tc(V) center much more readily accepts electron density than does the corresponding Re(V) complexes (55). The greater ease by which coordination sphere expansion can occur in third-row d-series transition elements such as W(IV) and Re(V) (not very easily... 

Ruthenium also belongs to the platinum group, which includes six elements with similar chemical characteristics. They are located in the middle of the second and third series of the transition elements (groups 8, 9, and 10). The platinum group consists of ruthenium, rhodium, palladium, osmium, iridium, and platinum. 

As the first element in the third series of the transition elements, hafnium s atomic number ( jHf) follows the lanthanide series of rare-earths. The lanthanide series is separated out of the normal position of sequenced atomic numbers and is placed below the third series on the periodic table ( La to 7,Li). This rearrangement of the table allowed the positioning of elements of the third series within groups more related to similar chemical and physical characteristics—for example, the triads of Ti, Zr, and Hf V, Nb, andTa and Cu, Ag, and Au. 

Osmium is found in group 8 (VIII) of the periodic table and has some of the same chemical, physical, and historical characteristics as several other elements. This group of similar elements is classed as the platinum group, which includes Ru, Rh, and Pd of the second transition series (period 5) and Os, Ir, and Pt of the third series of transition metals (period 6). 

Mercury is located in group 12 (IIB) below Zn and Cd. Even though mercury is at the end of the third series of transition elements, it is not always considered one of the transition elements. 

This chapter consists of a description of the ions formed in aqueous solutions by the transition elements - the d-block elements - and a discussion of the variations of their redox properties across the Periodic Table from Group 3 to Group 12. There is particular emphasis on the first transition series from scandium to zinc in the fourth period, with summaries of the solution chemistry of the second (Y to Cd) and third (Lu to Hg) series. The d-block ions in solution are those restricted solely to aqua complexes of cations, e.g. [Fe(H20)f,]" +, and the various oxocalions and oxoanions formed, e.g. V02+ and MnCXj". Oxidation states that are not well characterized are omitted or referred to as such. 

Each d subshell consists of five orbitals and can accommodate 10 electrons, so each transition series consists of 10 elements. The first series extends from scandium through zinc and includes many familiar metals, such as chromium, iron, and copper. The second series runs from yttrium through cadmium, and the third series runs from lanthanum through mercury. In addition, there is a fourth transition series made up of actinium through the recently discovered and as yet unnamed element 112. 

From left to right across the first transition series, melting points increase from 1541°C for Sc to a maximum of 1910°C for V in group 5B, then decrease to 420°C for Zn (Table 20.1, Figure 20.2). The second- and third-series elements exhibit a... 

FIGURE 20.3 Atomic radii (in pm) of the transition elements. The radii decrease with increasing atomic number and then increase again toward the end of each transition series. Note that the second- and third-series transition elements have nearly identical radii. 

The atomic radii of the second- and third-series transition elements from group 4B on are nearly identical, though we would expect an increase in size on adding an entire principal quantum shell of electrons. The small sizes of the third-series atoms are associated with what is called the lanthanide contraction, the general decrease in atomic radii of the /-block lanthanide elements between the second and third transition series (Figure 20.4). 

The densities of the transition metals are inversely related to their atomic radii (Figure 20.5). The densities initially increase from left to right across each transition series and then decrease toward the end of each series. Because the second-and third-series elements have nearly the same atomic volume, the much heavier third-series elements have unusually high densities 22.6 g/cm3 for osmium and 22.5 g/cm3 for iridium, the most dense elements. 

In contrast with the difluorides, the distribution of trifluorides extends to the third series of the transition metals, where iridium and gold trifluorides are fully characterized. In the second series, trifluorides are known for the elements from niobium to rhodium, with the exception of technetium, and in the first series, from titanium to cobalt. All the trifluorides have been characterized structurally, with earlier reports based on X-ray powder-diffraction data, since the compounds were not prepared in single-crystal form until more recently, when high-temperature, crystal-growth techniques became available. 

In the third transition series the 4/ shell is complete and has spherical symmetry and angular effect. Any effect must be due to the radial part of the appropriate wave functions. Thus so far as the effects on the third series of transition elements are concerned the second implication that the contraction is due to the angular part of the 4/ wave functions does not appear to be convincing. 

By the lUPAC (International Union of Pure and Applied Chemistry) definition, a transition metal is an element, an atom of which contains an incomplete d shell, or that gives rise to a cation with an incomplete d shell. Transition metals have a total of nine atomic orhitals, but only some of these are used for bonding to ligands. Coordination number denotes the number of donor atoms associated with the central atom and dictates the shape, or stereochemistry, of the coordination complex. The most common coordination numbers for the first transition metal series are four (tetrahedral and square-planar) and six (octahedral). Metals in the early second and third series are larger and thus can have higher coordination numbers, forming more stmcturally complex molecules. 

Another major classification of the elements in terms of the periodic table is shown in Figure 1.7. Three areas are defined and named the main group elements, the transition elements, and the inner transition elements. The main group elements are the simplest to learn abont, and they will be stndied first. The transition elements inclnde some of the most important elements in onr everyday lives, such as iron, nickel, chrominm, zinc, and copper. The transition elements are often divided into four rows of elements, called the first, second, third, and fourth transition series. The elements of the fourth transition series except for actinium (Ac), and those of the main group elements above 112, are artificial they are not found in nature. The two inner transition series fit into the periodic table in periods 6 and 7, right after lanthanum (La) and actinium (Ac), respectively. The inner transition elements include a few important elements, including uranium and plutonium. The first series of inner transition elements is called the lanthanide series, after lanthanum, the element that precedes... 

The analytical chemistry of the transition elements see Transition Metals), that is, those with partly filled shells of d (see (f Configuration) or f electrons see f-Block Metals), should include that of the first transition period (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) and that of the second transition series (Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, and Ag). The third transition series embraces Hf, Ta, W, Re, Os, Ir, Pt, and An, and although it formally begins with lanthanum, for historical reasons this element is usually included with the lanthanoids (rare-earth elements) see Scandium, Yttrium the Lanthanides Inorganic Coordination Chemistry Rare Earth Elements). The actinoid elements see Actinides Inorganic Coordination Chemistry) are all radioactive see Radioactive Decay) and those with atomic number see Atomic Number) greater than uranium (Z = 92) are artificial the analytical chemistry of these elements is too specialized to consider here. 

---