Cells with Gaseous Electrodes

The cell:

contains a gas with a fixed oxygen pressure in one electrode and the M/MO2 metal-metal oxide couple in the other. The overall cell reaction is:

Using Eq (10.8) for the chemical potential of O2, the form of Eq (10.6) for this cell is:

AG = gMO2 - gM - (gO2 + RT ln pO2 )= AGo - RT lnpo2

Applying this result to Eq (10.5a) with z = 2 and noting that from Eq (9.33b),

AGo = RTln(pO2 ) , the oxygen potential of the MO2/M couple, gives the cell EMF:

Equation (10.14) provides a means of determining the free energy of formation of MO2 by finding the oxygen pressure in the gaseous electrode, pO2, at which s = 0.

Other examples of solid-state electrochemical cells with a gaseous electrode are given in Problems 10.9 and 10.10.

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