Electronic entropy electrostatic field

The standard electrode potential convention is a different approach from that normally taken with thermodynamic quantities related to chemical change in electron number for gas-phase molecules and ions. Ionization potentials and electron affinities are referenced to the electrostatic zero potential energy of the infinitely separated electron in a field-free vacuum." The electron itself is conventionally treated as an ideal gas (the thermal electron convention) or as a subatomic particle with no heat capacity or entropy (the ion convention). lonization/electron attachment enthalpies under the two conventions differ by 1.48kcalmoU at 298 K," while the corresponding free energies under the two conventions are only equal at 0 K and 297 K. ... 

Ji is the electron flux vector, C is the electrochemical potential acting on the electron flux, and Js represents the total entropy density flux vector. We choose this expression, rather than a version based on Eq. (6.1.29), because we wish to treat separately the effects of temperature and of electrochemical potential. The latter involves aU the contributions associated with temperature gradients, electron density gradients, and the externally imposed electrostatic field. It is expedient to introduce a current density vector as = e Ti- Then, along one dimension, we adopt i) = T 3s T + -V( /e) as our dissipation function. For this unidirectional flow pattern, the... 

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