Periodic Table oxidation states

In this oxidation state the titanium atom has formally lost its 3d and 4s electrons as expected, therefore, it forms compounds which do not have the characteristics of transition metal compounds, and which indeed show strong resemblances to the corresponding compounds of the lower elements (Si, Ge, Sn, Pb) of Group IV—the group into which Mendeleef put titanium in his original form of the periodic table. 

These elements formed Group IIB of Mendeleef s original periodic table. As we have seen in Chapter 13, zinc does not show very marked transition-metaf characteristics. The other two elements in this group, cadmium and mercury, lie at the ends of the second and third transition series (Y-Cd, La-Hg) and, although they resemble zinc in some respects in showing a predominantly - - 2 oxidation state, they also show rather more transition-metal characteristics. Additionally, mercury has characteristics, some of which relate it quite closely to its immediate predecessors in the third transition series, platinum and gold, and some of which are decidedly peculiar to mercury. 

Ground-state electronic configuration is ls 2s 2p 3s 3p 3i 4s. Manganese compounds are known to exist in oxidation states ranging from —3 to +7 (Table 2). Both the lower and higher oxidation states are stabilized by complex formation. In its lower valence, manganese resembles its first row neighbors chromium and especially iron ia the Periodic Table. Commercially the most important valances are Mn, Mn ", or Mn ". ... 

Zirconium [7440-67-7] is classified ia subgroup IVB of the periodic table with its sister metallic elements titanium and hafnium. Zirconium forms a very stable oxide. The principal valence state of zirconium is +4, its only stable valence in aqueous solutions. The naturally occurring isotopes are given in Table 1. Zirconium compounds commonly exhibit coordinations of 6, 7, and 8. The aqueous chemistry of zirconium is characterized by the high degree of hydrolysis, the formation of polymeric species, and the multitude of complex ions that can be formed. 

Meta/ Oxides. The metal oxides aie defined as oxides of the metals occurring in Groups 3—12 (IIIB to IIB) of the Periodic Table. These oxides, characterized by high electron mobiUty and the positive oxidation state of the metal, ate generally less active as catalysts than are the supported nobel metals, but the oxides are somewhat more resistant to poisoning. The most active single-metal oxide catalysts for complete oxidation of a variety of oxidation reactions are usually found to be the oxides of the first-tow transition metals, V, Cr, Mn, Fe, Co, Ni, and Cu. 

No entirely satisfactory explanation of these observations has been devised, though they are paralleled by the similar reluctance of other elements following the completion of the 3d subshell to achieve their highest oxidation states — see particularly Se (p. 755) and As (p. 552) immediately preceding Br in the periodic table. The detailed kinetics of several oxidation reactions involving aqueous solutions of Br04 ... 

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 formation of several oxidation states is typical of the elements on the right side of the periodic table. We have already discussed in Chapter 19 the fact that chlorine can exist in the + 1, +3, +5, and +7 oxidation states as well as in the — 1 state. In its compounds, chlorine is most often found in the — 1 state. This preponderance of — 1 compounds shows that elemental chlorine behaves as an oxidizing agent in most of its reactions. 

To devise a periodic table of configurations of bonded atoms we would be obliged to focus on perhaps the highest oxidation state or the lowest oxidation state. Such decisions would not appear to... 

Compared to the sum of covalent radii, metal-silicon single bonds are significantly shortened. This phenomenon is explained by a partial multiple bonding between the metal and silicon [62]. A comparison of several metal complexes throughout the periodic table shows that the largest effects occur with the heaviest metals. However, conclusions drawn concerning the thermodynamic stability of the respective M —Si bonds should be considered with some reservation [146], since in most cases the compared metals show neither the same coordination geometries nor the same oxidation states. 

The chemistry of plutonium is unique in the periodic table. This theme is exemplified throughout much of the research work that is described in this volume. Many of the properties of plutonium cannot be estimated accurately based on experiments with lighter elements, such as uranium and neptunium. Because massive amounts of plutonium have been and are being produced throughout the world, the need to define precisely its chemical and physical properties and to predict its chemical behavior under widely varying conditions will persist. In addition to these needs, there is an intrinsic fundamental interest in an element with so many unusual properties and with so many different oxidation states, each with its own chemistry. 

The known oxidation states of plutonium present a 5f -series, starting from f1 [Pu(VII)] up to f5 [Pu(III)]. But contrary to the 4f - and 5f series across the period table, where the properties can be described by some smooth varying parameters, changing of the oxidation states influences the electronic properties drastically. Due to the large range of available oxidation states plutonium represents a favorable element among the actinides to study these effects. 

In a different set of experiments solutions of Pu(III) or Pu(VI) in H2O (Ar saturated, pH adjusted to 7, 2 x 10-5 M in Pu) were irradiated in the ANL 60Co-y source at a position where the dose was 1 megarad/hr (Jj) 1 mM H2O2 produced/hr. Cation exchange column behavior was used in an attempt to identify Pu oxidation states, see Table III. The results obtained after an irradiation of 1 hr. were indistinguishable from the "blank", i.e. a solution not subjected to irradiation. The irradiation for a 24 hr. period failed to demonstrate a marked increase in the amount of Pu(IV) produced that could be ascribed to the effects of radiolysis. 

This chapter and the following two chapters survey the properties of the elements and their compounds in relation to their locations in the periodic table. To prepare for this journey through the periodic table, we first review the trends in properties discussed in earlier chapters. We then start the journey itself with the unique element hydrogen and move on to the elements of the main groups, working from left to right across the table. The same principles apply to the elements of the d and f blocks, but these elements have some unique characteristics (mainly their wide variety of oxidation states and their ability to act as Lewis acids), and so they are treated separately in Chapter 16. 

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