Concentration and n

0.10

0.08 ●n=1
0.06

0.04 ○n=2
(E-Eφ')/V

■n=3
0.02

0.00

-0.02 At a ratio of conc’s =

-0.04 1 the equilibrium
-0.06
potential E is equal to
-0.08
the standard
potential.
-0.10
-4 -3 -2 -1 0 1 2 3 4

ln(Cox/Cred)

The standard potential is defined

at unit concentration (activity)
and standard temp and pressure.

The effect of pH on Equilibrium potential

The concentration of protons within a solution will effect

the redox chemistry of the half reaction.
Consider
O2 + 4e + 4H+ 2H2O

Increasing the concentration ACID

ALKALI of H+ will make it chemically
easier to drive the reaction to
the right. Conversely by
reducing the H+ concentration
the left is favoured.

This can be reflected through the Nernst equation.

1
 Consider H2/H+
H+ + e 1/2H2 (g) (Eφ = 0 V by definition)

E = E φ '+ RT
nF ln Cox
Cred

RT [H + ] As hydrogen gas is in its

E = 0+ ln ‘standard state’, this term
nF [ H 2 ]0.5
=1
RT
E= ln[ H + ] pH = − log10 [ H + ]
nF

2.3RT
E= ( − pH ) As we know n = 1
F

Note under standard conditions (for example in the

standard hydrogen electrode) [H+] = 1 mol dm-3 which has
a pH of ‘0’.

0.0

-0.2
If we raise the
pH (reducing the
H+ concentration)
E/V

-0.4
it will be more
-0.6
difficult to form
H2­. This is
-0.8
reflected in the
equilibrium
-1.0
potential of the
0 2 4 6 8 10 12 14 16 system.

pH

2
 Gradient
This plot has a gradient of 0.059 V at 298 K. It is
important to note that if we change the ratio of H+ to e’s
used in the system the gradient will also change.

2.3RT Here v is the number of

E = E φ '+ log10 [ H + ]v
nF protons and n the number
2.3RTv of electrons involved in
E = E φ '+ ( − pH ) the complete reaction.
nF
O2 + 4e + 4H+ 2H2O (Eφ’ = +1.223 V)

Here v = 4 and n = 4 so the v/n ration is 1. In this

case the gradient will be 0.059 V at 25 oC.

Consider,

ClO3- + 2H+ + e ClO2 + H2O (E φ’ = 1.175 V)

φ 2.3RT [ClO3− ][ H + ]2 This is a

E = E '+ log10
nF [ClO2 ][ H 2O ] concentration
dependent
2.3RT  [ClO3− ]  term. Not
E = E φ '+ log
 10 [ H + 2
] + log 
1F 
10
[ClO2 ]  affected by
pH.
2.3RTx 2  [ClO3− ] 
E = E φ '+  ( − pH ) + log10 
1F  [ClO2 ] 

We know have a ration of v/n = 2 hence in this case the

potential will move by –0.118 V per pH unit

3
 Reactions that are possible only at certain
pH’s
In this case we will have the situation that under
certain pH’s we will have a thermodynamically
favourable reaction at others we will not.
(*)NAD+ + H+ + 2e NADH (E’ = -0.32V) pH 7
V3+ + e V2+ (E φ’ = -0.255V)

Applying the same rules the reaction would be,

NADH + 2V3+ NAD+ + 2V2+ + H+ E = +0.065 V

This is a spontaneous reaction but how does pH affect

the thermodynamics?

Only ‘*’ will be pH dependent, v/n = 0.5 hence -0.030 V per

pH unit

Under acid conditions the reaction is non-spontaneous

0.6

0.4
NADH/NAD+
system (inverted)
0.2
E/V

0.0

Above pH 4 the
-0.2

-0.4 reaction is
0 2 4 6 8 10 12 14 16
spontaneous
pH
(release of
protons more
favourable).
V3+/V2+ constant

4
 + if produced v = number of protons

Overall Shift = Protons produced or consumed x v/n x 60 mV

- if consumed n = number of electrons

A + vH+ + ne B Consume H+

C + ne Dx- + vH+ Produces H+

Potential Limits in Water

1.4

1.2
2H2O O2 + 4e + 4H+ These two
reactions limit the
1.0

0.8

0.6 potential window in

0.4
water hence
E/V

0.2

0.0 materials with a

-0.2
redox potential
outside of the
-0.4

2H++2e H2
-0.6

-0.8 window will be

-1.0
0 2 4 6 8 10 12 14 thermodynamically
pH unstable

5
 Energy systems
We saw earlier that NADH ultimately reacts with
molecular oxygen in the cytochrome c system
NADH NAD+ + H+ + 2e (E’ = +0.32V) pH 7
1/2O2 + 2e + 2H+ H2O (E’ = +0.816 V) pH
7
E = 1.136 V
∆Gr = −nFE
∆Gr = −(2 × 96485 × 1.136)
∆Gr = −219 kJ mol-1 (based on NADH)
No coincidence that NADH/O2 system is almost at the
maximum potential window in water.

Corrosion
Many metals corrode spontaneously. This is an
electrochemical process.
In neutral solution:
O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq)EO2/OH- = 0.401 V

2 Fe(s) → 2 Fe2+(aq) + 4 e- EFe/Fe2+ = 0.440 V

2 Fe(s) + O2(g) + 2 H2O(l) → 2 Fe2+(aq) + 4 OH-(aq)

Ecell = 0.841 V

Hence this is a spontaneous process.

6
In this case the Iron Here the Zn is
metal ‘corrodes’ and sacrificed before the
forms Fe2(OH)3. Fe.