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Theory
Before considering SOFC’s it is useful to clarify the theory and notation which will be
used in the electrochemical analysis. Consider a generalised chemical reaction at
equilibrium:
Where, all species are assumed to be uncharged. Using the concept of chemical
potential [2] this reaction can be represented as:
∑υ Mi
i i =0 (2)
Where, the υi are the stoichiometric coefficients, positive for RHS and negative for
LHS (an arbitrary convention) and Mi the mass of the reactants and products.
Thermodynamic theory shows that the condition for equilibrium of this reaction is:
∑υ µi
i i =0 (3)
Now, if some of the species are charged, the condition for equilibrium is changed and
it can be shown to be [2]:
∑υ (µ
i
i i + zi FΦ = 0) (4)
µ (T , p ) = µ 0 (T ) + RT ln p p (5)
o
By convention p0=1 bar. Hence µ 0 (T ) is the chemical potential per mole of a perfect
gas at a pressure of 1 bar. It is a function of temperature only.
In mixtures of perfect gases, the chemical potential of each species is independent and
its pressure dependency governed by its partial pressure, that is:
µ i (T , pi ) = µ io (T ) + RT ln pi p (6a)
o
µ i (T , pi ) = µ io (T ) + RT ln p p + RT ln ( xi ) (6b)
o
1
O2 + 2e − ⇔ O 2− (7)
2
is in equilibrium. Hence:
1
( ) (
µ O + 2 µ e − − FΦ C = µ O 2− − 2 FΦ E
2 2
) (8)
ΦC − Φ E =
1
2F
( 1
2 µ O + 2µ e − µ O
2
− 2− ) (9)
H 2 + O 2− ⇔ H 2O + 2e − (10)
is at equilibrium. Hence:
2
( 2− )
µ H + µ O − 2 FΦ E = µ H O + 2 µ e − FΦ A2
( − ) (11)
ΦA − ΦE =
1
2F
(
µ H 2 O + 2 µ e − − µ H 2 − µ O 2− ) (12)
The electric potential difference between the cathode and anode is, therefore:
ΦC − Φ A =
1
2F
(
µ H 2 + 12 µ O2 − µ H 2O ) (13)
Assuming all gases behave as ideal gases, each of the chemical potentials terms in
equation (13) can be written in the form of equation (6b) giving:
( )
RT xH 2 xO22 RT p
1
1 o o o
+
ΦC − Φ A = µ H 2 + 2 µ O2 − µ H 2O +
1
ln ln (14)
2F 2 F xH 2O 4 F po
Now introducing the Gibbs Function for a chemical reaction, which is defined as the
change in chemical potential from reactants to products; and taking advantage of the t
incomplete
References:
[1] J.B. Young, Thermodynamics and Kinetics of Fuel Cells (Notes), Cambridge
University Engineering Dept., 17/11/2001.