Hydrogen, electrode oxidation

Fig. 6. Band edge positions of several semiconductors ia contact with an aqueous electrolyte at pH 1 ia relation to the redox (electrode) potential regions (vs the standard hydrogen electrode) for the oxidation of organic functional groups (26,27).

Other Coordination Complexes. Because carbonate and bicarbonate are commonly found under environmental conditions in water, and because carbonate complexes Pu readily in most oxidation states, Pu carbonato complexes have been studied extensively. The reduction potentials vs the standard hydrogen electrode of Pu(VI)/(V) shifts from 0.916 to 0.33 V and the Pu(IV)/(III) potential shifts from 1.48 to -0.50 V in 1 Tf carbonate. These shifts indicate strong carbonate complexation. Electrochemistry, reaction kinetics, and spectroscopy of plutonium carbonates in solution have been reviewed (113). The solubiUty of Pu(IV) in aqueous carbonate solutions has been measured, and the stabiUty constants of hydroxycarbonato complexes have been calculated (Fig. 6b) (90). 

The concept of the fuel cell, that is, a cell in which inert electrodes immersed in an electrolyte could he intimately contacted with a reacting fuel (e.g., hydrogen) and oxidant (e.g., air) and so generate an electric current, was demonstrated in 1839 by Grove and intensively studied by him during the next decade. 

Metals in practice are usually coated with an oxide film that affects the potential, and metals such as Sb, Bi, As, W and Te behave as reversible A//A/,Oy/OH electrodes whose potentials are pH dependent electrodes of this type may be used to determine the solution s pH in the same way as the reversible hydrogen electrode. According to Ives and Janz these electrodes may be regarded as a particular case of electrodes of the second kind, since the oxygen in the metal oxide participates in the self-ionisation of water. 

According to Sato et al.,6,9 the barrier-layer thickness is about 1.5 to 1.8 nm V-1, and increases to 3 nm around the oxygen-evolution potential. In Fig. 5, the scale of the electrode potential, Vrhe, is that of the reversible hydrogen electrode (RHE) in the same solution. The electrode potentials extrapolated from the linear plots of the potentials against the film thickness suggested that the potential corresponding to the barrier thickness equal to zero is almost equal to 0.0 V on the RHE scale, independent of the pH of the solution, and approximately agrees with the equilibrium potential for the oxide film formation of Fe or Fe. Therefore it is concluded that the anodic overpotential AE applied from the equilibrium potential to form the oxide film is almost entirely loaded with the barrier portion. 

Any inert metallic component of an electrode is written as the outermost component of that electrode in the cell diagram. For example, a hydrogen electrode constructed with platinum is denoted H+(aq) H2(g) Pt(s) when it is the right-hand electrode in a cell diagram and Pt(s) H2(g) H+(aq) when it is the left-hand electrode. An electrode consisting of a platinum wire dipping into a solution of iron(II) and iron(III) ions is denoted either Fe3+(aq),Fe2 (aq) Pt(s) or Pt(s) Fe3+(aq),Fe2+(aq). In this case, the oxidized and reduced species are both in the same phase, and so a comma rather than a line is used to separate them. Pairs of ions in solution are normally written in the order Ox,Red. 

Fig. 17. Cyclic voltammogram of the water-soluble Rieske fragment from the bci complex of Paracoccus denitrificans (ISFpd) at the nitric acid modified glassy carbon electrode. Protein concentration, 1 mg/ml in 50 mM NaCl, 10 mM MOPS, 5 mM EPPS, pH 7.3 T, 25°C scan rate, 10 mV/s. The cathodic (reducing branch, 7 < 0) and anodic (oxidizing branch, 7 > 0) peak potentisds Emd the resulting midpoint potential are indicated. SHE, standEU d hydrogen electrode.

Figure 8.31. Principle of a Polymer Electrolyte Membrane (PEM) fuel cell. A Nation membrane sandwiched between electrodes separates hydrogen and oxygen. Hydrogen is oxidized into protons and electrons at the anode on the left. Electrons flow through the outer circuit, while protons diffuse through the...

The areas bounded by solid lines correspond to regions of thermodynamic stability of certain substances that are named in the diagram. This stability is relative. The dashed line a in the diagram corresponds to the equilibrium potential of the hydrogen electrode. Metallic zinc, for which the reaction lines are below the line for the hydrogen electrode, can be oxidized while hydrogen is evolved (see Section 2.4.1). 

An important eonelusion was that the best catalyst is not the alloyed one as expected, nor the mixture of Pt/XC 72 and Ru/XC 72 powders, but one eonsisting of a dispersion of Pt colloid and Ru colloid on the same carbon support, i.e., the Pt + Ru/XC 72 eatalyst. The latter leads to higher current densities for the eleetro-oxidation of methanol than the other catalysts with the same atomic ratio for potentials lower than 0.5 V versus a reversible hydrogen electrode (RHE) (Fig. 11.3). This result... 

Figure 18.6 Energetics of the ORR at the heme/Cu site of CcO the enzyme couples oxidation of ferroc3ftochrome c (standard potential about —250 mV all potentials are listed with respect to a normal hydrogen electrode) to reduction of O2 (standard potential at pH 7 800 mV). Of the 550 mV difference, only 100 mV is dissipated to drive the reaction 220 mV is expanded to translocate four protons from the basic matrix compartment to the acidic IMS (inter-membrane space). In addition 200 mV is converted into transmembrane electrostatic potential as ferroc3ftochrome is oxidized in the IMS, but the charge-compensating protons are taken from the matrix. The potentials are approximate.

Eor formic acid oxidation, 182 Eor methanol oxidation, 189, 350-351 Eor oxygen reduction, 18-20, 276-277, 297, 364-365, 522, 534, 538 Theoretical Standard Hydrogen Electrode, 58-60, 101... 

The hydrogen electrode can be used to measure pH values over the whole pH region. However, it is not applicable to reducing or oxidizing media or... 

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