Oxidation state periodic trends

Chemical properties of element 111 were predicted through the use of the Periodic Table, DF calculations and some more qualitative theories [164]. The results indicate that element 111 will be like Au(III) with little tendency to show stable 1+ or 2+ oxidation states. The trend to an increase in the higher oxidation states, 3+ and 5+, was attributed to relativistic effects. The possibility of 111 was suggested. 

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. 

The ranking is consistent with the three trends for determining A nature of the ligands, oxidation state of the metal, and position of the metal in the periodic table. 

Comments on some trends and on the Divides in the Periodic Table. It is clear that, on the basis also of the atomic structure of the different elements, the subdivision of the Periodic Table in blocks and the consideration of its groups and periods are fundamental reference tools in the description and classification of the properties and behaviour of the elements and in the definition of typical trends in such characteristics. Well-known chemical examples are the valence-electron numbers, the oxidation states, the general reactivity, etc. As far as the intermetallic reactivity is concerned, these aspects will be examined in detail in the various paragraphs of Chapter 5 where, for the different groups of metals, the alloying behaviour, its trend and periodicity will be discussed. A few more particular trends and classification criteria, which are especially relevant in specific positions of the Periodic Table, will be summarized here. 

The subject of this chapter is the periodicity of the aqueous chemistry of the elements of the s-block (Groups 1 and 2) and the p-block (Groups 11-18) of the Periodic Table. Modified Latimer diagrams summarize the chemistry of all the elements, and some volt-equivalent diagrams are given to represent the inter-relations between various oxidation states of the elements. Explanations of some trends in redox chemistry are discussed in detail. 

Predict the aqueous solution chemistry of element 114. What is the expected oxidation state By extrapolating periodic table trends, estimate the first ionization potential of element 114 [see Nash and Bursten (1999)]. 

These points are well illustrated by comparing Cu, Ag and Au with respect to the relative stabilities of their oxidation states. Although few compounds formed by these elements can properly be described as ionic, the model can quite successfully rationalise the basic facts. The copper Group 1 Id is perhaps the untidiest in the Periodic Table. For Cu, II is the most common oxidation state Cu(I) compounds are quite numerous but have some tendency towards oxidation or disproportionation, and Cu(III) compounds are rare, being easily reduced. With silver, I is the dominant oxidation state the II oxidation state tends to disproportionate to I and III. For gold, III is the dominant state I tends to disproportionate and II is very rare. No clear trend can be discerned. The relevant quantities are the ionization energies Iu l2 and A the atomisation enthalpies of the metallic substances and the relative sizes of the atoms and their cations. These are collected below / and the atomisation enthalpies AH%tom are in kJ mol-1 and r, the metallic radii, are in pm. 

Covalent oxides at high oxidation states and high electronegativities form the strongest acids. For this skill, note that the periodic trends for acid and base strength of the oxide of an element follows the same pattern we ve seen before. 

The oxides of the Group 15 elements clearly exemplify two important trends that are manifest to some extent in all main groups of the Periodic Table (1) the stability of the higher oxidation state decreases with increasing atomic number, and (2) in a given oxidation state the metallic character of the elements, therefore the basicity of the oxides, increases with increasing atomic number. Thus Pm and Asra oxides are acidic, Sb111 oxide is amphoteric, and Bim oxide is strictly basic. 

Bismuth (Z = 83) is the heaviest stable element in group 15 (VA) of the periodic table (see Periodic Table Trends in the Properties of the Elements). The Bi isotope, which is 100% abundant, has a 9/2 nuclear spin. Bi, an alpha emitter is used in nuclear medicine as a radiotherapeutic agent. Bismuth has two stable oxidation states Bi(V), corresponding to complete loss of the valence electrons, and Bi(III), a lower oxidation state that retains two valence electrons. Both oxidation states are diamagnetic. The latter is more stable and more common since Bi(V) has a large reduction potential ... 

The concept of an atom s oxidation state see Oxidation Number) can provide fundamental information about the stmcture and reactivity of the compound in which the atom is found. In fact, it can be argued that oxidation states provided the basis for Medeleev s initial organization of the periodic table. For the main group elements, the relative stability of lower oxidation states within a given group increases as the atomic number increases. This trend in the periodic table see Periodic Table Trends in the Properties of the Elements) is generally attributable to the presence of an inert s pair see Inert Pair Effect) caused by relativistic effects see Relativistic Effects). 

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