Nernst Equation, Equlibrium and Potential

By S.E. Van Bramer, 2/22/98

Starting with the Nernst Equation for the equlibrium; Ox + n e- <--> Red :

R .T . C ox
E cell E std_cell ln Typical form of Nernst Equation
n. F C red

n .F C ox Rearange
E cell E std_cell . ln
R .T C red

.
C ox E cell E std_cell . n F
R .T
e Gives the ratio of oxidized to
C red reduced form of redox pair.

.
C ox ( ∆E ) . n F
R .T
e Reduced variables to ∆E, the
C red difference between the equlibrium
potential and the applied potential.

This function describes how the equlibrium ration of oxidized and reduced form depend upon the applied potential.
Notice that
if ∆E = 0 Where the applied potential is the same as the standard cell potential. Then the exponent is
0, so the ratio of Cox/Cred = 1. This is the conditions for the standard state.

If ∆E > 0 Where the applied potential is positive of Eo. Now the exponent is greater than 0 so the ratio of
C ox/Cred >1. The concentration of the oxidized form is greater than the concentration of the reduced form. This is
consistent with the half reaction because an applied potential positive of Eo pulls e-'s off and causes oxidation.

If ∆E < 0. Where the applied potential is negative of Eo. Now the exponent is less than 0 so the ratio of
C ox/Cred < 1. The concentration of the oxidized form is less than the concentration of the reduced form. This is
consistent with the half reaction because an applied potential negative of Eo pushes e-'s on and causes reduction.

nernst.mcd 1 S.E. Van Bramer

3/1/99 svanbram@science.widener.edu
 Now let's take a graphical look at this function.

Look at a range of applied potentials for a reaction with 1 electron exchanged:

∆E 0.4 .volt , 0.39 . volt .. 0.4 .volt n 1

Some Constants for electrochemistry:

8.31441 .joule .K .mole 298 .K 96484.6 .coul .mole

1 1 1
R T F

The functions to describe α (the ratio of oxidzied over reduced) and the concentration of
each species (assuming a total concentration of 1.

.
∆E . n F
R .T 1
α ( ∆E , n ) e C red( ∆E , n ) C ox( ∆E , n) 1 C red( ∆E , n)
1 α ( ∆E , n )

Nernst Relationships
1

C red ( ∆E , n )
Concentration

C ox ( ∆E , n ) 0.5

0
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential
a

Nernst Relationships
0

ln C red ( ∆E , n )
Concentration

ln C ox ( ∆E , n ) 10

15

20
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential

nernst.mcd 2 S.E. Van Bramer

3/1/99 svanbram@science.widener.edu
 Now, let's see what happens if the number of electrons changes: n 2

Nernst Relationships
1

C red ( ∆E , n )
Concentration

C ox( ∆E , n ) 0.5

0
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential
a

Nernst Relationships
0

10

ln C red ( ∆E , n )
Concentration

ln C ox ( ∆E , n ) 20

30

40
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential

n 3

nernst.mcd 3 S.E. Van Bramer

3/1/99 svanbram@science.widener.edu
 Now, let's see what happens if the number of electrons changes: n 3

Nernst Relationships
1

C red( ∆E , n )
Concentration

C ox( ∆E , n ) 0.5

0
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential
a

Nernst Relationships
0

20
ln C red ( ∆E , n )
Concentration

ln C ox ( ∆E , n )

40

60
0.4 0.3 0.2 0.1 0 0.1 0.2 0.3 0.4
∆E
Cell Potential

nernst.mcd 4 S.E. Van Bramer

3/1/99 svanbram@science.widener.edu