Irreversible thermodynamics comparison with reversible

Except for very electron-rich donors that yield stable, persistent radical cations, the ox values are not generally available.64 Thus the cation radicals for most organic donors are too reactive to allow the measurement of their reversible oxidation potentials in either aqueous (or most organic) solvents by the standard techniques.65 This problem is partially alleviated by the measurement of the irreversible anodic peak potentials E that are readily obtained from the linear sweep or cyclic voltammograms (CV). Since the values of E contain contributions from kinetic terms, comparison with the values of the thermodynamic E is necessarily restricted to a series of structurally related donors,66 i.e.,... 

The skills developed to produce the equilibrium diagram Figure A.l, are now applied anew. Neither hydrogen nor carbon monoxide occur as free substances in nature, where they are immediately oxidized. They must be made and stored, at thermodynamic and economic cost. The reversible thermodynamics are assessed below, using as the basis of calculation a notional, electrochemical, equilibrium, steam reformer. Figure A.4, for comparison with the alternative practical and irreversible combustion-driven reformers. 

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