Redox/reduction potentials actinide ions

Control of the particle valence/conduction band oxidation/reduction potential is not only achieved through a judicious choice of particle component material band edge redox thermodynamics of a single material are also affected by solution pH, semiconductor doping level and particle size. The relevant properties of the actinide metal are its range of available valence states and, for aqueous systems, the pH dependence of the thermodynamics of inter-valence conversion. Consequently, any study of semiconductor-particle-induced valence control has to be conducted in close consultation with the thermodynamic potential-pH speciation diagrams of both the targeted actinide metal ion system and the semiconductor material. 

Reduction potentials for the actinide elements are shown in Fig. 14.6. These show formal potentials, defined as the measured potentials relative to the hydrogen ion/hydrogen couple taken as zero volts. The redox potentials are corrected to unit concentration of the reactants, but are not corrected for activity. The measured potentials were determined by electrochemical cells, equilibria, and enthalpy of reaction measurements. The potentials for add solution were... 

Note that AG° q has a liquid-phase standard state of 1 moI/L, and we can use a gas-phase standard state of either 1 atm or 1 mol/L, as long as we use the same convention for the oxidized and reduced forms. Often the 1 mol/L standard state is used. There are several sources of uncertainties in the calculations of reduction potentials, and we will comment on them by scanning the published literature on actinide elements, for which the most studied redox systems are actinyl aqua ions, with the exception of one study on Pu(VII)/Pu(VIII) [172], The first comment is that redox potentials are defined with respect to the standard hydrogen electrode corresponding to the following half-equation... 

The oxidation-reduction behavior of plutonium is described by the redox potentials shown in Table I. (For the purposes of this paper, the unstable and environmentally unimportant heptavalent oxidation state will be ignored.) These values are of a high degree of accuracy, but are valid only for the media in which they are measured. In more strongly complexing media, the potentials will change. In weakly complexing media such as 1 M HClOq, all of the couples have potentials very nearly the same as a result, ionic plutonium in such solutions tends to disproportionate. Plutonium is unique in its ability to exist in all four oxidation states simultaneously in the same solution. Its behavior is in contrast to that of uranium, which is commonly present in aqueous media as the uranyl(VI) ion, and the transplutonium actinide elements, which normally occur in solution as trlvalent... 

The standard electrode potentials, E, for such reduction reactions are related to the free energy change for the process by equation 5.3. Since some elements may exist in a number of different oxidation states, it is possible to construct electrode potential diagrams, sometimes called Latimer diagrams, relating the various oxidation states by their redox potentials. Examples are shown in Figure 5.6 for aqueous solutions of some first-row d-block metals and for some actinides in 1 mol dm acid. In cases where the reduction involves oxide or hydroxide ions bound to... 

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