2. Understanding Corrosion | |
2.5.2 Derivation of Nernst Equation |
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Consider a general reaction for a galvanic cell such as:
lL + mM
qQ + rR ……… (1)
Where l, m, q and r are the number of
moles of L, M, Q and R respectively.
The corresponding change in Gibb's free
energy ∆G for the reaction above is given by the difference in molal
free energy of products and reactants.
∆G = ∆G° (products) - ∆G°
(reactants) ……………… (2)
Where ∆G° is standard free
energy, ∆G is free energy change.
So: ∆G
= (qGQ + rGR ) – (lGL + mGM )
…………………… (3)
If each substance is in standard state;
∆G°
= (qG°Q + rG°R ) – (lG°L + mG°M
) ……………… (4)
But from Vanhoff Isotherm, we have
GA
= G°A + RT ln aA
……………………………………. (5)
Where aA
= Activity of the substance,
T = Absolute temperature,
And R = Gas constant.
Activity of a substance is defined as pressure
in atmospheres for gases, and is adequately approximated by concentration C;
in gram equivalents per liter for many relatively dilute corrosive solutions.
Activity Coefficient = CA
rA
Substituting (4) from (5):
∆G - ∆G° = (qGQ - qG°Q
) + (rGR - rG°R ) – (lGL - lG°L
) – (mGM - mG°M ) .....(5')
Using this equation (5'):
∆G - ∆G° = RT ln aR + RT ln aQ – RT ln aL
– RT ln aM
∆G - ∆G° = RT ln [ (aqQ arR ) / ( amM alL
)] ……… (6)
∆G
- ∆G° = RT ln [ (aproducts) / (areactants)]
……… (7)
But we have ∆G
= - nFE
∆G
- ∆G° = - nF (E - E°)
= RT ln [(aproducts) / (areactants)]
E
- E° = - {RT/nF} ln [ (aproducts) / (areactants)
So, we get the
NERNST EQUATION as:
E = E° - {RT/nF} ln [ (aproducts) / (areactants)]
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