Electrochemical Thermodynamics

First some terms

A) Chemical ReversibilityConsider the reaction O+ne-R
If we make the potential more positive
R O+ne- Thus the reaction is chemically reversible. If new reactions happen when we
change the potential or reaction products are unstable, the reaction is chemically irreversible.
Chemical reversibility says nothing about energy.
B) Thermodynamic Reversibility

Potential

Eeq

O/R

If we start at the equilibrium potential, an infinitesimal change in potential

will cause a reaction. An infinitesimal change in potential in the opposite
direction will reverse the reaction. Chemically irreversible reactions cannot
be thermodynamically reversible.

C) Practical reversibility: get close enough to thermodynamic reversibility that we can use
reversible, thermodynamic expressions to model the system.
Free energy and electromotive force
In electrochemistry, our most important thermodynamic variable is Go. Lets illustrate the
meaning of free energy change by examining the reaction
Zn+ 2AgCl Zn2+ + 2 Ag + 2 ClWe will perform this reaction three ways (thought experiment)
1) Mix Zn and AgCl- allow an infinitesimal reaction to take place with all reactants in their
standard state. We do this in a calorimeter and find
Ho=heat=-233 kJ/mole Zn reacted. Heat is liberated from this reaction.
2) Prepare Zn and Ag/AgCl electrodes, and allow the electrons to pass between them through a
resistor. We proceed with the entire
apparatus in a calorimeter (including the
resistor) and get
Ag
calorimeter
Ho=heat=-233 kJ/mole Zn reacted
AgCl
Zn
Zn2+

3) Now suppose we put one calorimeter around the resistor (determines the heat QR) and one
around the solution (determines the heat in
the cell, QC). We find of course that that
Calorimeter 2, QR

+ = 233 .
Ag
Calorimeter 1 However, as we increase the resistance,
AgCl
| | increases and | | decreases. As R
QC
Zn
Zn2+
approaches , approaches -43 kJ per
mole of Zn reacted and approaches 190 kJ/mole of Zn. In fact, the useful work (free energy) is that through the resistor. Thus
, =
= = ( + ) =

(1)

The maximum work we can get out of the cell is -190 kJ/mole Zn reacted. (Instead of liberating
heat, we could do electrical work by replacing the resistor with something else.)
At infinite resistance, E across the electrode =ENernst=Eeq=Erxn
G|=recoverable work= charge passed x reversible potential difference
G|=nF|E| where n is the number of moles of electrons per mole of Zn in this case.

Potential

Now the potential difference between the electrodes is the reversible difference. Thus we only
need to change the potentially infinitesimally positive to move the reaction in one direction and
infinitesimally negative to go in the opposite direction.
Consider the reaction Fe3++e- Fe2+ shown at the left. We
dont have to move the potential to -0.77 to start reduction. It
can start at potentials just negative of 0.77.

In contrast, G, changes sign when we move the potential from

infinitesimally above equilibrium to infinitesimally below
equilibrium. In one case charge may pass from + to potential,
and in the other case, charge will pass from to + potential. In
one case we can do work and in one case, we have to do work.

0.77

Fe3+/Fe2+

Hence, although the equilibrium potential is the same for the reaction in both directions, the
work that we can do has different signs for the two directions of the reaction. Thus, we only
have one potential for the electrode, but we need two G values, one for each direction of the
reaction.
To account for the change in G with the direction of the reaction, we invent the term
electromotive force and assign it to a reaction. Lets illustrate this with an example. Although
the electrode potential doesnt change with the reaction direction, the electromotive force does.
Lets illustrate with an example

AgCl +e- Ag + Cl- Eo=0.2223

Zn2+ +2e- Zn

Eo=-0.7628

We have two possible directions for a full cell.

(A) 2 AgCl + Zn Zn2+ +2Ag +2 ClSchematically we let the right electrode be the one at which reduction occurs.
Zn/Zn2+(a=1), Cl-(a=1)/AgCl/Ag
EMF= Eoright-Eoleft
Erxn=EMF=0.2223-(-0.7628)=0.9851
This is a galvanic cell as the reaction is spontaneous. For spontaneous reaction, E>0.
(B) Zn2+ +2Ag +2 Cl- 2 AgCl + Zn
Ag/AgCl/Cl-(a=1), Zn2+(a=1)/Zn
Erxn=EMF= Eoright-Eoleft=-0.7628-0.2223=-0.985 V
In this case, Erxn is negative, so the reaction is not spontaneous. This would be an electrolytic
cell. We have to do work to make the reaction occur. We would have to put a battery between
the electrodes to make the reaction occur.

and

(2)

For example A, G is negative and the reaction is spontaneous.

For example B, G is positive and the reaction is not spontaneous.
The origin of electrode potentials
Lets briefly look at the origin of the electrical potentials and why a particular reaction is
spontaneous. The Zn electrode is relatively easy to comprehend. When we put the Zn electrode
in a solution containing Zn2+ with an activity of 1, most likely initially a very small amount of Zn
gets oxidized. This leaves behind a negative charge on the Zn electrode and leads to a negative
potential. After a very short time, the energy of the electrons in Zn is high enough (due to the
negative charge) that these electrons are in equilibrium with the Zn2+ in solution. (With the
negative charge on the electrode, addition of more electrons to the electrode and formation of
Zn2+ is no longer favorable.) Note that for this electrode, the standard potential is relatively
negative (Zn2+ +2e- Zn, Eo=-0.7628).
What about the Ag/AgCl electrode. Supposing we have a silver wire that we contact with AgCl
in a solution containing Cl- with a=1. Ag+ is easier to reduce than Zn2+. Thus in this case, the
Ag electrode likely donates a few electrons to AgCl to create more Ag. This creates a positive

charge on the electrode until the energy of the electrons is in equilibrium with the AgCl. Hence
the electrode has a relatively positive potential (AgCl +e-
Ag + Cl- Eo=0.2223).
eNow consider operating the cell with a resistor in the
external circuit as show in the figure. The electrons have a
higher energy in the Zn than in the Ag electrode so they flow
Ag
+
from the Zn electrode to the Ag electrode. When electrons
+
+ AgCl can flow from left to right, there is no longer equilibrium, so
+
Zn
we see oxidation of Zn and reduction of AgCl. Note that
+
with an infinite resistor, current does not flow, so we just
2+
have the equilibrium situation.
Zn , Cl
To reverse the current flow, we would have to put a battery (or a potentiostat) in place of the
resistor, and the battery would have to have a potential that exceeds the equilibrium potential to
cause current to flow. However, the potential drop between the Zn and Ag electrodes need only
differ infinitesimally for the reaction to change direction. The battery potential only needs to
exceed the electrode potential difference infinitesimally.
In general, the more negative the electrode potential, the easier the metal is to oxidize. With this
example, we are oxidizing Zn and reducing AgCl so the reaction is spontaneous. In the opposite
direction the reaction is not spontaneous.
How electrode potentials vary with the concentration of species in solution
For a reaction at constant pressure and temperature, the equilibrium condition is dG=0. If we
hold temperature and pressure constant and allow a reaction to proceed to the extent of reaction
dan infinitesimal number of moles of a reactant with a stoichiometric coefficient of 1), then

= ( )

,,

(3)

In this equation, i represents a particular product or reactant and is the stoichiometric

coefficient of the species in the reaction.

We define = ( )

,,

as the chemical potential. This terms shows how dG will change

with the addition or removal of an infinitessimal amount of a particular species. For a singlephase system this is sufficient for determining equilibrium conditions. However, when there are
charged species and phases with different electrical potentials (and a charge transfer reaction),
we have to take into account the electrical potentials. We use a to show that we are taking
electrical potential into account.

= ( )

,,

= +

(3a)
(4)

This accounts for the effect of electrical potential differences on the energies of charged species
in different phases denotes a specific phase). To give this some intuitive sense, if a phase has
a specific potential, we change the work we need to do to bring an ion into that phase.
Properties of electrochemical potential
1) = for uncharged species. ( denotes a specific phase)
2) = +

is the standard state chemical potential and is the activity.

3) For a pure phase = (activity =1)

4) For electrons in metals, = . In this case we do not need an activity correction
because the concentration of electrons in a metal is essentially constant.
Deriving the Nernst Equation for a specific cell

Au

Au
Salt
bridge

Ag

Zn
Zn2+, NO3-

Ag+, NO3-

Using the chemical potentials, lets deduce the

Nernst equation. Remember our convention, take
potentials as right minus left. is the potential in a
phase

S2

S1

= ( ) + ( 2 ) + ( 2 1 ) + ( 1 ) + ( )
We need to evaluate each of the differences on the right side of the equation. Consider
first . The only species that can transfer between these phases is the electron. Thus,
at equilibrium (open circuit) the electrochemical potential of the electrons must be the same in
the two metals (otherwise electrons would move between the metals and current would flow).
=
=
=

A similar situation occurs for . By analogy

We will assume that the junction potential between the two solutions is negligible. We use a salt
bridge to minimize junction potentials. Thus, 2 1 0. We return to this in the next set
of lecture notes.
Next, lets consider 2 . Here we have equilibrium between Zn2+ in solution and the
electrons in Zn.
2+ + 2
At equilibrium (zero current)
2
2

=
+ 2 2
2+ + 2+ + 2

2
2

2+ + 2
2+
=
+
2
2

Similarly, we can consider 1 . You can show

1

+

Now that we have all the individual terms, we can combine them

= =

+2+ +2
+

2 2+

+0+

1+

1 +

Noting that some terms cancel, e.g. = , and combining the appropriate terms give

2
1

+
2+ + 2 2+

2+
+
(
2)
1
2
+

When the activities of all species are 1, we get Eo.

=1

Thus,
=

= + 2 (

2 2+

2
1
+

2
1

+
2+ + 2 2+

Why do I need to know about chemical potentials?

I suppose you could just remember the rules for the Nernst equation

=

+ where is the stoichiometric coefficient in the chemical

reaction (positive for reactants and negative for products in this case).
However, the chemical potentials show the origins of the Nernst equation and they also give us
certain intuitions. For example suppose we connect a copper and Ag rod. Is there an electrical
potential drop between the rods, and can we measure it? The
Au
Au
first question is whether there is an electrical potential drop
between Cu and Ag. The answer is yes, presuming that
Cu

Ag

. In general the chemical potential of electrons

depends on the metal.

Now, can we measure this potential? The answer to this question is no. All voltmeters must
have two wires with identical leads to measure electrical potential. In the case in the picture,

= ( ) + ( ) + ( )

=
+
+
=0

The potential drops at the different interfaces will cancel, so we cannot measure this electrical
potential difference. The reason we get electrical potential differences in electrochemistry is
electrons do not enter solution and ions do not enter electrodes. The origins of potential
differences are not solely electrons, so interfacial potential drops do not cancel.
Review of sign conventions
We report Eo values with respect to the normal hydrogen electrode (NHE) (working electrodeNHE), with the working electrode formally on the right. Remember, we measure potential as
right minus left. For example, for Ag/Ag+ the cell for determining E0 is
Pt/H2(a=1)/H+(a=1)/Ag+(a=1)/Ag
If we measure the potential difference, we find that the Ag electrode is 0.799 V positive of the Pt
one. Thus, we say that the reduction potential (or standard electrode potential) of Ag/Ag+ is
0.799 V. The more positive the potential, the more positive charge we have on the electrode.

This likely means a small amount of Ag+ was reduced to make the charge on the electrode more
positive than that on Pt. The positive potential says that for this cell, reduction of Ag+ is
spontaneous. (Positive potentials indicate a reaction is spontaneous.) Electrons can flow from Pt
to Ag to reduce Ag+. The EMF for Ag oxidation is -0.799 V. Thus oxidation is not spontaneous.
For an arbitrary combination of half cells, we still have
=
If we look at this for the following cell
Cu/Cu2+(a=1)/Ag+(a=1)/Ag
we can use Eo values as all species are at their standard state (if not at standard state, we need to
use the Nernst equation to determine E). Thus, formally for this cell we have

= /
+ /2+ = ((=1) ,(=1) ) ((=1) ,(=1) )

= (=1) (=1)
Note that the NHE cancels out. Thus, is the actual voltage different between Ag and Cu
with no current flowing.
Remembering these points can help us avoid errors when converting from one reference
electrode to another. For example, suppose we make a measurement of -0.302 V with respect to
a Ag/AgCl electrode (E=0.197 V versus NHE for saturated KCl in the electrode). How do we
convert the -0.302 V to a number versus the NHE. We simply note what all the potentials mean.
0.302 = /
0.197 = /
= ( / ) + (/ ) = 0.302 + 0.197
= 0.105

Summing half cells

When we use half cells to create a full cell, we simply have Eright-Eleft with reduction formally on
the right, but when we use half cells to create another half cell, we have to be more careful
because the NHE potential will not cancel in this case. Consider the following case
(1) Fe3+ + e- Fe2+ Eo=0.770 V

(2) Fe2+ + 2e- Fe Eo= -0.409 V

(3) Fe3+ + 3e- Fe Eo=?
We add (1) and (2) to get (3). However, if we add Eo values we get
(,()/() , ) + (,()/(0) , )
= ,()/() + ,()/(0) 2,
This is not what we want. We instead have to resort to using G values. G is a state function
and is additive for full and half reactions, whereas E is not additive for half reactions. For the
above reactions (1)-(3) we have
1 = 1 = (0.770)
2 = 22 = (0.409)
3 = 33 = 3(? )
3 = 1 + 2 = 1 + 22
3 = 33 = 1 + 22
3

1 + 22 1 + 22 0.770 + 2(0.409)
=
=
=
= 0.016
3
3
3

The same G procedure will work for full cells, but why not just subtract Eo values (right minus
left). Dont forget if the activities are not 1, we have to use the Nernst equation rather than just
Eo.
Formal Potentials
So far, we have talked about the Nernst equation in terms of activities. Unfortunately, when we
prepare a solution we usually know its concentration, not its activity. Consider the reaction
Cu2+ + e- Cu+
Relative to the NHE
2+

= +

However, this equation isnt useful if I only know the concentrations and not activities. We
define the activity coefficient , where = [ ]. The brackets represent concentration.
Substituting the expression into the Nernst equation, we get

 2+ [2+ ]
2+ [2+ ]

= +

= +

+ [+ ]
+
[+ ]

Setting = +

2+
+

, we get
= +

[2+ ]

[+ ]

This equation is often simpler to use than the one with activities, but we have to know , which
depends on the conditions of the reaction. will depend on the concentration of supporting
electrolytes in the solution.