Redox potential diagram for

The redox-potential diagram for the donor-Ru(bpy)3 -MV triad system in Figure 5 is helpful in understanding the sequence of electron transfer events in these composites. Although excitation of the sensitizer is always the initial step in the overall process, there are several possible pathways for subsequent reactions. Transient absorbance measurements on the donor-sensitizer and... 

The redox potential diagram in eq. 1 illustrates that the effect of optical excitation is to create an excited state which has enhanced properties both as an oxidant and reductant, compared to the ground state. The results of a number of experiments have illustrated that it is possible for the excited state to undergo either oxidative or reductive electron transfer quenching (2). An example of oxidative electron transfer quenching is shown in eq. 2 where the oxidant is the alkyl pyridinium ion, paraquat (3). 

Figure 5 Redox predominance diagrams for iron (a) and manganese (b) boundaries represent the standard reduction potential for reduction of the (thermodynamically-stable) species above the boundary to the (thermodynamically-stable) species below the boundary. If the redox predominance regions of two species (e.g., the gray regions of Fe + and Mn04 ) do not overlap along the y-axis when the two diagrams are superimposed, reaction between the two species is thermodynamically favored...

The potential diagram for indium in acidic solution (pH = 0) is given below with standard redox potentials given in V ... 

Figure 8 The predominance diagram (Pourbaix diagram) indicating the pH-redox potential interaction for manganese species in aqueous solution. The dotted lines indicate the thermodynamic water stability region. The full lines correspond to 1 mol I concentration of species in the liquid phase, the dashed lines to 10 molconcentration.

Oxidation state-potential diagrams for nonmetallic and transition metal elements provide an interesting framework for analyzing the highly varied results obtained for redox reactions involving as many as nine oxidation states. So many different products and stoichiometries are obtained from the reduction of nitric acid that early work seeking patterns of reaction was abandoned after many years of frustrating effort. 

Because of the complexity of the redox reactions, they cannot be conveniently presented in a Pourbaix pH-potential diagram. For battery applications, the revised diagram given by Silverman [80] is more correct than that found in the Pourbaix Atlas [81]. The diagram is shown in Figure 5.5. 

The diagram gives regions of existence, i.e. for a particular combination of pH and redox potential it can be predicted whether it is thennodynamically favourable for iron to be inert (stable) (region A), to actively dissolve (region B) or to fonn an oxide layer (region C). 

Ladder diagrams can also be used to evaluate equilibrium reactions in redox systems. Figure 6.9 shows a typical ladder diagram for two half-reactions in which the scale is the electrochemical potential, E. Areas of predominance are defined by the Nernst equation. Using the Fe +/Fe + half-reaction as an example, we write... 

The ladder diagram for this system is shown in Figure 11.24a. Initially the potential of the working electrode remains nearly constant at a level near the standard-state potential for the Fe UFe redox couple. As the concentration of Fe + decreases, however, the potential of the working electrode shifts toward more positive values until another oxidation reaction can provide the necessary current. Thus, in this case the potential eventually increases to a level at which the oxidation of H2O occurs. 

A comprehensive list of standard potentials is found in Ref. 7. Table 2-3 gives a few values for redox reactions. Since most metal ions react with OH ions to form solid corrosion products giving protective surface films, it is appropriate to represent the corrosion behavior of metals in aqueous solutions in terms of pH and Ufj. Figure 2-2 shows a Pourbaix diagram for the system Fe/HjO. The boundary lines correspond to the equilibria ... 

As may be seen from the potential-pH diagram " (Fig. 6.3) platinum is immune from attack at almost all pH levels. Only in very concentrated acid solutions at high redox potentials (i.e. under oxidising conditions) is there a zone of corrosion. This accounts for the solubility of platinum in aqua regia. Platinum is also prone to complex-ion formation, and this can lead... 

It is considered useful to include here the potential-pH diagram for some redox systems related to oxygen (Fig. 2.1) [4]. Lines 11 and 33 correspond to the (a) and (b) dashed lines bounding the stability region of water, as depicted in all the subsequent Pourbaix diagrams. 

The potential-pH diagram for the system tellurium-water at 25 °C is given in Fig. 2.4. It was constructed by using the following homogeneous and heterogeneous (solid/liquid, gas/liquid) equilibria, involving redox and non-redox processes, in which all of the above-referred dissolved substances of tellurium, as well as the solid ones, participate ... 

The analysis of thermodynamic data obeying chemical and electrochemical equilibrium is essential in understanding the reactivity of a system to be used for deposition/synthesis of a desired phase prior to moving to experiment and/or implementing complementary kinetic analysis tools. Theoretical and (quasi-)equilibrium data can be summarized in Pourbaix (potential-pH) diagrams, which may provide a comprehensive picture of the electrochemical solution growth system in terms of variables and reaction possibilities under different conditions of pH, redox potential, and/or concentrations of dissolved and electroactive substances. 

The idea that the cathode potential with respect to ]lt(H20)/Pt-0Hads determines the value of the pre-exponential factor in the ORR rate expression was inspired by a comment by Andy Gewirth (Urbana) in his talk in Leiden, pointing to the value of Pourbaix diagrams for understanding ORR electrocatalysis. Indeed, the information on these ORR-mediating and facilitating M/M-OH surface redox systems is to be found in Pourbaix s Atlas. 

Table 2.1 states the redox relations at standard conditions. Extended information on the distribution of the redox pairs — still under equilibrium conditions but under varying redox potential and pH — is given in a Pourbaix diagram. Figure 2.4 is an example of such a diagram for the binary sulfur and oxygen system in water at 1 atm and 25°C with the sum of the concentrations of... 

As can be seen from the energy level structure diagram, the relative position of the HOMO and LUMO levels are not less important than the energy gap between them, since they control the possibility of charge injection. At this point, however, note, that a MO scheme is often used for illustration, but more properly the total energy states of the molecules and their radical cations and anions that may be subjected to electronic rearrangement have to be considered. Bearing this in mind, the measured values of redox potentials can be translated into the molecular orbital picture. 

Figure 5. An oxidation state diagram for Mo, Cr, Fe and Mn. For Mo and Cr, N = III for Fe and Mn, N = II. Potentials are given at standard states in acid solution relative to the hydrogen electrode. On such a diagram, die slope between any two points equals the redox potential. In conh ast to most other metals, multiple Mo oxidation states are accessible over a small range of potentials. Note also that Mo is oxidized to Mo(VI) at relatively low potential (similar to Fe(III). Figure modified after Frausto da Silva and Williams (2001).

Fig. 10-26. Energy diagram for a cell of photoelectrolytic decomposition of water consisting of a platinum cathode and an n-type semiconductor anode of strontium titanate of which the Fermi level at the flat band potential is higher than the Fermi level of hydrogen redox reaction (snao > epM+zHj) ) he = electron energy level referred to the normal hydrogen electrode ri = anodic overvoltage (positive) of hole transfer across an n-type anode interface t = cathodic overvoltage (negative) of electron transfer across a metallic cathode interface.

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