Standard reaction enthalpy from cell potential

A fascinating point, especially to physical chemists, is the potential theoretical efficiency of fuel cells. Conventional combustion machines principally transfer energy from hot parts to cold parts of the machine and, thus, convert some of the energy to mechanical work. The theoretical efficiency is given by the so-called Carnot cycle and depends strongly on the temperature difference, see Fig. 13.3. In fuel cells, the maximum efficiency is given by the relation of the useable free reaction enthalpy G to the enthalpy H (AG = AH - T AS). For hydrogen-fuelled cells the reaction takes place as shown in Eq. (13.1a). With A//R = 241.8 kJ/mol and AGr = 228.5 under standard conditions (0 °C andp = 100 kPa) there is a theoretical efficiency of 95%. If the reaction results in condensed H20, the thermodynamic values are A//R = 285.8 kJ/ mol and AGR = 237.1 and the efficiency can then be calculated as 83%. 

When the pH is specified, each biochemical half reaction makes an independent contribution to the apparent equilibrium constant K for the reaction written in terms of reactants rather than species. The studies of electochemical cells have played an important role in the development of biochemical thermodynamics, as indicated by the outstanding studies by W. Mansfield Clarke (1). The main source of tables of ° values for biochemical half reactions has been those of Segel (2). Although standard apparent reduction potentials ° can be measured for some half reactions of biochemical interest, their direct determination is usually not feasible because of the lack of reversibility of the electrode reactions. However, standard apparent reduction potentials can be calculated from for oxidoreductase reactions. Goldberg and coworkers (3) have compiled and evaluated the experimental determinations of apparent equilibrium constants and standard transformed enthalpies of oxidoreductase reactions, and their tables have made it possible to calculate ° values for about 60 half reactions as functions of pH and ionic strength at 298.15 K (4-8). 

The double-layer corrected deal enthalpy of activation, (AH ), obtained from the slope of a plot of — R In k against temperature at a given nonisoAermal cell potential ( 12.3.7.1) is approximately equal to the activation enthalpy, AH, for the elementary reaction at that potential . Also, the real activation enthalpy, (AHJ), , obtained from the temperature dependence of the double-layer corrected standard rate constant, k rr> can be identified approximately with the intrinsic barrier , AG. Therefore, from Eqs. (n) and (o) ... 

Equations 20.176 and 20.179 emphasise the essentially thermodynamic nature of the standard equilibrium e.m.f. of a cell or the standard equilibrium potential of a half-reaction E, which may be evaluated directly from e.m.f. meeisurements of a reversible cell or indirectly from AG , which in turn must be evaluated from the enthalpy of the reaction and the entropies of the species involved (see equation 20.147). Thus for the equilibrium Cu -)-2e Cu, the standard electrode potential u2+/cu> hence can be determined by an e.m.f. method by harnessing the reaction... 

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