Reversible potential

Cell Volta.ge a.ndIts Components. The minimum voltage required for electrolysis to begin for a given set of cell conditions, such as an operational temperature of 95°C, is the sum of the cathodic and anodic reversible potentials and is known as the thermodynamic decomposition voltage, is related to the standard free energy change, AG°C, for the overall chemical reaction,... 

Electrorefining. Electrolytic refining is a purification process in which an impure metal anode is dissolved electrochemicaHy in a solution of a salt of the metal to be refined, and then recovered as a pure cathodic deposit. Electrorefining is a more efficient purification process than other chemical methods because of its selectivity. In particular, for metals such as copper, silver, gold, and lead, which exhibit Htfle irreversibHity, the operating electrode potential is close to the reversible potential, and a sharp separation can be accompHshed, both at the anode where more noble metals do not dissolve and at the cathode where more active metals do not deposit. 

In electro deposition, the reduced form of the metal is the elemental form M, x = 0, and there is no chelated M in solution. Neglecting activity coefficients, the reversible potential is... 

Chlorine dioxide gas is a strong oxidizer. The standard reversible potential is determined by the specific reaction chemistry. The standard potential for gaseous CIO2 in aqueous solution reactions where a chloride ion is the product is —1.511 V, but the potential can vary as a function of pH and concentration (26) ... 

Corrosion occurs even if the two reactants involved are not at standard conditions. In this case the nonstandard equiUbrium potential for each reaction, often referred to as the reversible potential, can be calculated from the Nemst equation. Additional information on thermodynamic aspects of corrosion can be found in Reference 10. 

Steel coated with tin (tinplate) is used to make food containers. Tin is more noble than steel therefore, well-aerated solutions will galvanically accelerate attack of the steel at exposed areas. The comparative absence of air within food containers aids in preserving the tin as well as the food. Also the reversible potential which the tin-iron couple undergoes in organic acids serves to protect exposed steel in food containers. 

By means of a resistance in the circuit the spontaneous corrosion reaction can be made to proceed at a predetermined rate, and the rate can be measured by means of an ammeter A. At the same time the potentials of the individual electrodes can be measured by means of a suitable reference electrode, a Luggin capillary and high-impedance voltmeters and Kj. At equilibrium there is no net transfer of charge (/ = A = 0). the e.m.f. of the cell is a maximum and equals the difference between the reversible potentials of the two electrodes... 

Meta Flade potential (V, M. S.H.E.) Comparison with reversible potential of the eauiUbrium specified... 

Even discounting the case of aluminium, which is usually covered by protective oxide films, it is evident from Table 1.23 that the quantitative connection between the galvanic corrosion rate of the more active member of the couple and the difference of reversible potentials of the two metals, is non-existent. 

These considerations show the essentially thermodynamic nature of and it follows that only those metals that form reversible -i-ze = A/systems, and that are immersed in solutions containing their cations, take up potentials that conform to the thermodynamic Nernst equation. It is evident, therefore, that the e.m.f. series of metals has little relevance in relation to the actual potential of a metal in a practical environment, and although metals such as silver, mercury, copper, tin, cadmium, zinc, etc. when immersed in solutions of their cations do form reversible systems, they are unlikely to be in contact with environments containing unit activities of their cations. Furthermore, although silver when immersed in a solution of Ag ions will take up the reversible potential of the Ag /Ag equilibrium, similar considerations do not apply to the NaVNa equilibrium since in this case the sodium will react with the water with the evolution of hydrogen gas, i.e. two exchange processes will occur, resulting in an extreme case of a corrosion reaction. 

A metal when immersed in a solution of its cations may take up the reversible potential corresponding with the M exchange process, but whether or not this occurs in practice will depend on the magnitude of its exchange current density in relation to any others that are possible due to other exchange processes in the solution under consideration. In oxygenated solution the and 02 0H equilibria provide possible alterna-... 

The self-discharge process has made experimental determination of the reversible potential of the Ni(OH)2/NiOOH couple very difficult. A major advance was the realization by Bourgault and Conway... 

Upon an increase of the anodic reverse potential finally up to 8 V versus Li the cyclic voltammogran corresponding to Fig. 9 remains unchanged, showing that the passivating layer at the electrode also protects the solvents (PC and DME) from being oxidized. Subsequent deposition and dissolution of lithium at the passivated electrodes remains possible when the electrode is passivated but the cycling efficiency decreases. 

Inward Rectification refers to decreased conductance upon membrane depolarization. In classical inward rectifier K+ channels, rectification is strong and currents rapidly decline at membrane potentials positive to the reversal potential, in contrast to other Kir channels in which rectification is weak and currents decline only gradually at potentials positive to the reversal potential. 

As in chemical systems, however, the requirement that the reaction is thermodynamically favourable is not sufficient to ensure that it occurs at an appreciable rate. In consequence, since the electrode reactions of most organic compounds are irreversible, i.e. slow at the reversible potential, it is necessary to supply an overpotential, >] = E — E, in order to make the reaction proceed at a conveniently high rate. Thus, secondly, the potential of the working electrode determines the kinetics of the electron transfer process. 

The potential [Pg.159]

It is important to note for a later section that a simple dependence of the cathodic current (or anodic current) on the concentration C o(C r) is obtained if the experiment is carried out at constant electrode potential [see equations (10) and (11)] but not if the experiment is carried out at constant overpotential since the value of the reversible potential depends on the ratio of C o/C a in solution [see equation (19)]. The significance of is, however, exact. 

The major effect of an increase in temperature on the actual electron transfer process is to increase A , and hence to enhance the reversibility of the electrode process. The reversible potential is, however, itself temperature dependent, and... 

The formation of an ion will have a negative A F and hence electrode reactions which produce an anion or a cation from a neutral substrate wiU be favoured by an increase in pressure. That is, the reversible potential for the reaction... 

A difficulty in the analysis of reactions suspected to take place with concerted movement of atoms lies in the irreversibility of most of the processes and the consequent impossibility of characterizing rates at the reversible potential. An approach which has been suggested is the comparison of the substituent effects of appropriate electrode reductions and homogeneous reactions as in the example (Marcus, 1968)... 

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