Stable oxidation states

The tendency of elements of higher atomic number to retain the s electrons as an inert pair is also encountered in Group IV, and in this case it is found that for lead the most stable oxidation state is + 2, achieved by loss of two p electrons. 

The oxidation state -1-4 is predominantly covalent and the stability of compounds with this oxidation state generally decreases with increasing atomic size (Figure 8.1). It is the most stable oxidation state for silicon, germanium and tin, but for lead the oxidation state +4 is found to be less stable than oxidation state +2 and hence lead(IV) compounds have oxidising properties (for example, see p. 194). 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

The abihty of iron to exist in two stable oxidation states, ie, the ferrous, Fe ", and ferric, Fe ", states in aqueous solutions, is important to the role of iron as a biocatalyst (79) (see Iron compounds). Although the cytochromes of the electron-transport chain contain porphyrins like hemoglobin and myoglobin, the iron ions therein are involved in oxidation—reduction reactions (78). Catalase is a tetramer containing four atoms of iron peroxidase is a monomer having one atom of iron. The iron in these enzymes also undergoes oxidation and reduction (80). 

The most common oxidation states and the corresponding electronic configurations of osmium ate +2 and + (t5 ), which ate usually octahedral. Stable oxidation states that have various coordination geometries include —2 and 0 to +8 (P] The single most important appHcation is OsO oxidation of olefins to diols. Enantioselective oxidations have also been demonstrated. 

Most of the free-radical mechanisms discussed thus far have involved some combination of homolytic bond dissociation, atom abstraction, and addition steps. In this section, we will discuss reactions that include discrete electron-transfer steps. Addition to or removal of one electron fi om a diamagnetic organic molecule generates a radical. Organic reactions that involve electron-transfer steps are often mediated by transition-metal ions. Many transition-metal ions have two or more relatively stable oxidation states differing by one electron. Transition-metal ions therefore firequently participate in electron-transfer processes. 

As in the preceding transition-metal groups, the refractory behaviour and the relative stabilities of the different oxidation states can be explained by the role of the (n — l)d electrons. Compared to vanadium, chromium has a lower mp, bp and enthalpy of atomization which implies that the 3d electrons are now just beginning to enter the inert electron core of the atom, and so are less readily delocalized by the formation of metal bonds. This is reflected too in the fact that the most stable oxidation state has dropped to +3, while chromium(VI) is strongly oxidizing ... 

By heating the metal with appropriate oxides or carbonates of alkali or alkaline earth metals, a number of mixed oxides of Ru and Os have been made. They include NasOs Og, LifiOs Og and the ruthenites , M Ru 03, in all of which the metal is situated in octahedral sites of an oxide lattice. Ru (octahedral) has now also been established by Ru Mdssbauer spectroscopy as a common stable oxidation state in mixed oxides such as Na3Ru 04, Na4Ru2 07, and the ordered perovskite-type phases M Ln Ru Og. 

There is a very marked contrast in this oxidation state between cobalt on the one hand, and the two heavier members of the group on the other. For cobalt it is one of the two most stable oxidation states, whereas for the others it is of only minor importance. 

Oxidation states found only in solids are given in brackets numbers in bold indicate the most stable oxidation states in aqueous solution. Colours refer to aqueous solutions ... 

This is the only oxidation state which, with the possible exception of Pa, is displayed by all actinides. From U onwards, its resistance to oxidation in aqueous solution increases progressively with increase in atomic number and it becomes the most stable oxidation state for Am and subsequent actinides (except No for which the f " configuration confers greater stability on the +2 state). 

Unsubstituted bisphthalocyanines 2 are formed in the presence of several elements which exist in a stable oxidation state of + III or +IV such as titanium, zirconium, hafnium, indium and most of the lanthanide and actinide elements. 

Metal atoms with a stable oxidation state of + IV are known to form unsubstituted bis(phthalo-cyanines) 9,10. They can be prepared by the reaction of a metal phthalocyanine, or an appropriate metal salt, and an alkali-metal phthalocyanine. 

The complexation of Pu(IV) with carbonate ions is investigated by solubility measurements of 238Pu02 in neutral to alkaline solutions containing sodium carbonate and bicarbonate. The total concentration of carbonate ions and pH are varied at the constant ionic strength (I = 1.0), in which the initial pH values are adjusted by altering the ratio of carbonate to bicarbonate ions. The oxidation state of dissolved species in equilibrium solutions are determined by absorption spectrophotometry and differential pulse polarography. The most stable oxidation state of Pu in carbonate solutions is found to be Pu(IV), which is present as hydroxocarbonate or carbonate species. The formation constants of these complexes are calculated on the basis of solubility data which are determined to be a function of two variable parameters the carbonate concentration and pH. The hydrolysis reactions of Pu(IV) in the present experimental system assessed by using the literature data are taken into account for calculation of the carbonate complexation. 

The thermodynamically stable oxidation state of a metal in a given environment is a function of the prevailing oxidation potential. The value of the potential is given by the Nemst equation, which is described in Chapter 5 for the generic reduction half-cell ... 

Transition metal oxides show a broad structural variety due to their ability to form phases of varying metal to oxygen ratios reflecting multiple stable oxidation states of the metal ions... 

Except for the elements at the ends of the rows, each transition metal can exist in several different oxidation states. The oxidation states displayed by the 3d transition metals are shown in Table 20-1. The most important oxidation states are highlighted in the table. The most common oxidation state for the 3d transition metals is +2, known for all the elements except Sc. Chromium, iron, and cobalt are also stable in the +3 oxidation state, and for vanadium and manganese the -H4 oxidation state is stable. Elements from scandium to manganese have a particularly stable oxidation state corresponding to the loss of ah the valence electrons configuration). 

In terms of gross features of mechanism, a redox reaction between transition metal complexes, having adjacent stable oxidation states, generally takes place in a simple one-equivalent change. For the post-transition and actinide elements, where there is usually a difference of two between the stable oxidation states, both single two-equivalent and consecutive one-equivalent changes are possible. 

Belouzov-Zhabotinsky reaction [12, 13] This chemical reaction is a classical example of non-equilibrium thermodynamics, forming a nonlinear chemical oscillator [14]. Redox-active metal ions with more than one stable oxidation state (e.g., cerium, ruthenium) are reduced by an organic acid (e.g., malonic acid) and re-oxidized by bromate forming temporal or spatial patterns of metal ion concentration in either oxidation state. This is a self-organized structure, because the reaction is not dominated by equilibrium thermodynamic behavior. The reaction is far from equilibrium and remains so for a significant length of time. Finally,... 

The known oxidation states of americium are +2, +3, +4, +5, and +6. However, the stable oxidation states are +3 and +4 the common oxidation state is +3, in which state, the behavior of americium and... 

Cr3+ and Cr6+ are the most stable oxidation states of chromium, but with the only difference that while +3 oxidation state is cationic where as the +6 oxdation state is oxoanionic. However, the other oxidation states of +1, +2, +4 and +5 are also known for chromium, especially in aqueous solution at different pH. Inter-conversion of these oxidation states too is very frequent. With this view, an attempt is made here to examine the effect of ultrasound on the inter-convertibility of chromium among various oxidation states in aqueous solutions. The details of this study is reported in the literature [36]. 

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