THE THERMODYNAMICS OF

ELECTROCHEMICAL SYSTEMS

CHE2615
 The Chemical Potential and the Electric
Potential
• The propensity of a substance to contribute to a system’s
energy is called Chemical Potential (m)
• When the substance is a charged particle we must include
the response of the particle to an electrical field in
addition to its Chemical Potential. We call this
Electrochemical Potential.
m𝑖 = m𝑖,𝑐ℎ𝑒𝑚 + 𝑧𝐹φ
𝒛 = charge on the particle
m𝒊,𝒄𝒉𝒆𝒎 = 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒑𝒂𝒓𝒕 𝒐𝒇 𝒕𝒉𝒆 𝒄𝒉𝒆𝒎𝒊𝒄𝒂𝒍 𝒑𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍
𝑭 = Faraday’s constant (96485 C /mol)
𝝋 = electric potential (field under consideration)

• These are perhaps the most fundamental measures of

thermodynamics.
 Chemical Potential
• Chemical potential (or electrochemical potential if it is
charged) is the measure of how all the thermodynamic
properties vary when we change the amount of the
material present in the system.
• The Gibbs “chemical potentials” for component A for
example, may be defined in a multiplicity of ways
depending on what conditions are held constant as
follows: Here we see that the
chemical potential describes
how the free energy (Gibbs
or Helmholtz) and the
enthalpy and internal energy
all vary with changes in the
amount of the material in
the system.
• The first equality is the one generally used in defining the
“chemical potential” in that experiments may easily be
designed wherein the temperature and pressure are
maintained constant.
• It is inconvenient to conduct experiments at constant
volume and temperature and It is indeed difficult to
conceive of ways to conduct experiments either at
constant entropy and volume or at constant entropy and
pressure.
• Since the energy, entropy, heat content, Helmholtz
energy, and Gibbs energy are defined only by differential
equations, we can determine only differences of these
quantities between two states of a system containing the
same quantity of matter.
 Gibbs Free Energy
• The free energy function is the key to assessing the way in
which a chemical system will spontaneously evolve.
• Because the chemical potentials depend on composition
(pressure and temperature), the Gibbs energy of a mixture
may change when these variables change
This expression is the
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑖 𝑑𝑛𝑖 fundamental equation of
chemical thermodynamics

𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑖 𝑑𝑛𝑖

dG   m i dni constant T
constant P
 Partial molar Gibbs energies
• Partial molar Gibbs energy is simply the chemical potential
• The chemical potential μJ of substance J at some
composition:
 G 
 
μJ =  
 nJ  p,T,n’


nJ is the amount (the number of moles) of J

n’ the amounts of all other substances
• The total Gibbs energy G of the mixture (A & B)
G = nA μA + nB μB
• where μA and μB are the chemical potentials at the
composition of the mixture.
• That is, the chemical potential of a substance in a
mixture is the contribution of that substance to the total
Gibbs energy of the mixture.
 The Gibbs-Duhem equation
 nJ dmJ = 0
J

• The change of Gibbs energy G of the mixture (A & B)

dG = mAdnA + mBdnB + nAdmA + nBdmB
• At constant pressure and temperature,
dG = mAdnA + mBdnB

nAdmA + nBdmB = 0
• The chemical potentials of a mixture cannot change
independently: in a binary mixture, if one increases the
other must decrease.
 Gibbs Function and Work
• Start with the First Law of Thermodynamics and some
standard thermodynamic relations. We find

dU  dq  dw dq = T dS
dw  PdV  dwelectrical

dU  T dS  PdV  dwelectrical dHP  dU P  PdV

dGT  dHT  T dS
 dUT,P  PdV  T dS
 T dS  PdV  dwelectrical  PdV  T dS dGT,P  dwelectrical
And therefore, the Gibbs function identifies the amount of
work we can extract electrically from a system.
 THE CELL POTENTIAL

• Cell potential (V) (1 V = 1 J C-1 s) is the potential

difference between the two electrodes
• When the cell potential is large, a given number of
electrons travelling between the electrodes can do a
large amount of work;
• When the cell potential is small, the same number of
electrons can only do a small amount of work.
• A cell in which the overall reaction is at equilibrium can
do no work, and then the cell potential is zero.
 Gibbs and the Cell Potential
• Here we can easily see how this Gibbs function relates to
a potential.
welectrical  V Q
since Q  nF
 nF E
• We identify work which is negative with work which is
being done by the system on the surroundings.
• And negative free energy change is identified as defining
a spontaneous process.
GT, P  welectrical  n F E
• Note how a measurement of a cell potential directly
calculates the Gibbs free energy change for the process.
 The maximum amount work:
• The maximum non-expansion work, in which the current
context is electrical work, that a system (the cell) can do
is given by
we,max = G (at constant T and P)
• It follows that, to draw thermodynamic conclusions from
measurements of the work a cell can do, we must ensure
that the cell is operating reversibly, for only then is it
producing maximum work.
• Since the reaction Gibbs energy is a property relating to a
specified composition of the reaction mixture, to make
use of ∆rG we must ensure that the cell is operating
reversibly at a specific, constant composition.
• Both these conditions are achieved by measuring the cell
potential when it is balanced by an exactly opposing
source of potential so that the cell reaction occurs
reversibly, the composition is constant, and no current
flows: in effect, the cell reaction is poised for change, but
not actually changing.
• The resulting potential difference is called the zero-
current cell potential E (electromotive force or emf of
the cell)
• Relation between E and rG :

n F E = rG

Faraday’s constant F = 96485 C mol-1

 Chemical Potential and Activity

• How does chemical potential change with

activity?
m  m  R T ln a
• Integration of the expressions for the
dependence of amount of material on the
Gibbs function, leads to the following
relationship:
 Reaction Quotient
wA  xB  yC  zD
• In order to analyze a chemical process mathematically,
we form this reaction quotient.
y z
aC a D
Q w x
a A aB
• It always has products in the numerator and reactants in
the denominator
• It explicitly requires the activity of each reaction
participant.
• each term is raised to the power of its stoichiometric
coefficient.
 Simplifying Approximations
• Leave out terms involving solids, pure liquids, and
solvents

• Solutes appear as the concentration (in M).

• Gases appear as the partial pressure (in atm).

REACTION QUOTIENT IS UNITLESS.

• But its value does depend upon the chosen reference
state.
 Concentration Dependence
• How does Gibbs free energy change with activity
(concentration)?
• Same dependence as with the chemical potential. We
have

G  G  R T ln a
• When we apply this to a reaction, the reaction quotient
comes into to play, giving us

G  G  R T ln Q
 Equilibrium
G  G  R T ln Q
• When all participants have unit activity (a=1), then Q=1
and ln Q = 0.
G  G
• Reaction proceeds, Q changes, until finally ∆G = 0. The
reaction stops. This is equilibrium.

0  G  R T ln Q *

 G   RT ln Q *
Q  Keq
*

• This special Q* (the only one for which we achieve this

balance) is renamed Keq, the equilibrium constant.
• The chemical potential of a single charged
species cannot be measured, since charged
particles cannot easily be added to a system
without adding ions of the opposite charge at the
same time.
 ELECTROCHEMICAL CELLS
• Redox reactions involving reduction half cell
reaction and oxidation half cell reaction
• Consider the overall reaction

𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
𝑐 𝑑
𝑜
(𝑎𝑐 ) (𝑎 𝑑 )
∆𝐺 = ∆𝐺 + 𝑅𝑇𝑙𝑛
(𝑎𝑎 )𝑎 (𝑎𝑏 )𝑏

∆𝐺 < 0
∆𝐺 𝑜 < 0
19
 Nernst equation 0

𝑜
∆𝐺 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙 and ∆𝐺0 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙
𝑐 𝑑
𝑜 (𝑎 𝑐 ) (𝑎 𝑑 )
−𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙 + 𝑅𝑇𝑙𝑛
(𝑎𝑎 )𝑎 (𝑎𝑏 )𝑏
𝑅𝑇 (𝑎 ) 𝑐 (𝑎 )𝑑
𝑜 𝑐 𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑛
𝜈𝑒 𝐹 (𝑎𝑎 )𝑎 (𝑎𝑏 )𝑏
𝑅𝑇 (𝑎 ) 𝑐 (𝑎 )𝑑
𝑜 𝑐 𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 2.3026 𝑙𝑜𝑔
𝜈𝑒 𝐹 (𝑎𝑎 )𝑎 (𝑎𝑏 )𝑏

At T 298.15 K: F = 96485 C/mol

0.05916 (𝑎 ) 𝑐 (𝑎 )𝑑
𝑜 𝑐 𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔
𝜈𝑒 (𝑎𝑎 )𝑎 (𝑎𝑏 )𝑏 20
 Standard potentials
• It is not possible to measure the
contribution of a single electrode, we may
define the potential of one of the electrodes
as having a zero potential and then assign
values of others

*Standard hydrogen electrode (SHE):

Pt | H2(g) | H+(aq) at all temperatures

The Standard Hydrogen Electrode

Eo (H+/H2) half-cell = 0.000 V

e-

H2 (g) at 1 atm

(H+ (aq) = 1.0 M

Pt electrode
*Standard potential E0 of another couple
may be assigned by constructing a cell in
which it is the right-hand electrode and the
standard hydrogen electrode is left-hand
electrode
• e.g.

Pt | H2(g) | H+(aq)||Ag+(aq) | Ag(s)

𝐸 𝑜 (Ag+ / Ag) = 0.80 V at 25oC

Similarly, 𝐸 𝑜 (AgCl / Ag, Cl-) = 0.22 V

 The standard potential of a cell in
terms of reduction potentials
*Standard potential of a cell formed from any two
electrodes can be calculated by taking the difference of
their standard potentials. e.g.

Ag(s) | Ag+(aq) || Cl-(aq) | AgCl(s) | Ag(s)

is equivalent to two cells joined back-to-back:

Ag(s) | Ag+(aq) || H+(aq)| H2(g) | Pt

Pt | H2(g) | H+(aq)|| Cl-(aq) | AgCl(s) | Ag(s)

The overall potential of the composite cell:

𝑜
𝐸𝑐𝑒𝑙𝑙 =𝐸 𝑜 (AgCl/Ag, Cl-) - 𝐸 𝑜 (Ag+ / Ag) = - 0.58 V
Example
Consider the following cell reaction at 25oc and
1 bar
Pt(s)|H2(g)1bar|H+ (aq)||HBr(0.01)|AgBr(s)|Ag(s)
Given that:
AgBr s + 𝑒 − → 𝐴𝑔 𝑠 + 𝐵𝑟 − 𝑎𝑞 𝐸 𝑜 = 0.073 𝑉
1
𝐻2 g + 𝑒 − → 𝐻 + 𝑎𝑞 𝐸 𝑜 = 0.0 𝑉
2

a) Calculate the mean ion coefficient of HBr

using the DHLL
b) Determine the emf of the cell and compare
this with the measured emf of 0.3127V
25
a) HBr aq → 𝐻+ (𝑎𝑞) + 𝐵𝑟 − (𝑎𝑞)
This is a 1:1 electrolyte, thus;

I=c
log 𝛾± = − 0.509 𝑧+ 𝑧− √𝐼

log 𝛾± = − 0.509 1x − 1 √(0.01)

log 𝛾± = − 0.0509

𝛾± = 10−0.0509 = 0.8894
b) Cell reaction
Red. Rxn:

AgBr s + 𝑒 − → 𝐴𝑔 𝑠 + 𝐵𝑟 − 𝑎𝑞 𝐸 𝑜 = 0.073 𝑉

Oxd. Rxn:

1
𝐻 g → 𝐻+ 𝑎𝑞 + 𝑒 − 𝐸 𝑜 = 0.0 𝑉
2 2
------------------------------------------------------
Overall cell rxn:
1
𝐻 g + AgBr s → 𝐻 + 𝑎𝑞 + 𝐵𝑟 − 𝑎𝑞 + 2𝐴𝑔 𝑠
2 2

𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 − 𝐸𝑜𝑥
𝑜
𝐸𝑐𝑒𝑙𝑙 = 0.073 − 0 = 0.073𝑉
 𝑣𝐻+ 𝑣 −
𝑜 0.05916 (𝑣𝐻 + 𝑎 𝐻 + ) (𝑣𝐵𝑟 − 𝑎𝐵𝑟 − ) 𝐵𝑟
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 1
𝜈𝑒
(𝑎𝐻2 )2

1 (𝑐 𝛾 − )1
𝑜 0.05916 (𝑐 𝛾 𝐻 + ) 𝐵𝑟
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑜𝑔 1
1
𝑃 2
𝑃𝑜
𝑜 0.05916
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 𝑐 2 𝛾±2
1

0.05916
𝐸𝑐𝑒𝑙𝑙 = 0.073 𝑉 − log(0.01)2 (0.8894)2
1

𝐸𝑐𝑒𝑙𝑙 = 0.073 𝑉 − (−0.24266)

𝐸𝑐𝑒𝑙𝑙 = 0.3138 𝑉
a) ZnCl2 aq → Zn2+ (aq) + 2Cl− (aq)
This is a 1:2 electrolyte, thus;

I = 3c
log 𝛾± = − 0.509 𝑧+ 𝑧− √𝐼

log 𝛾± = − 0.509 2x − 1 √3(0.000772)

log 𝛾± = − 0.048991

𝛾± = 10−0.048991 = 0.89332
b) Cell reaction
Red. Rxn:

2AgCl s + 2𝑒 − → 2𝐴𝑔 𝑠 + 2𝐶𝑙 − 𝑎𝑞 𝐸 𝑜 = 0.2223𝑉

Oxd. Rxn:

Zn g → 𝑍𝑛2+ 𝑎𝑞 + 2𝑒 − −𝐸 𝑜 = −(−0.7626) 𝑉
------------------------------------------------------
Overall cell rxn:
Zn g + 2AgCl s → 𝑍𝑛2+ 𝑎𝑞 + 2𝐶𝑙 − 𝑎𝑞 + 2𝐴𝑔 𝑠
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑒𝑑 − 𝐸𝑜𝑥
𝑜
𝐸𝑐𝑒𝑙𝑙 = 0.2223 − (−0.7626) = 0.9849𝑉
 0.05916
𝐸𝑐𝑒𝑙𝑙 = 𝑜
𝐸𝑐𝑒𝑙𝑙 − log(𝑣𝑍𝑛2+ 𝑎𝑍𝑛2+ )𝑣𝑍𝑛2+ (𝑣𝐶𝑙− 𝑎𝐶𝑙− )𝑣𝐶𝑙−
𝜈𝑒

𝑜 0.05916
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log(𝑐 𝛾𝑍𝑛2+ )1 (2𝑐𝛾𝐶𝑙− )2
2

𝑜 0.05916
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 4𝑐 3 𝛾±3
2
0.05916
𝐸𝑐𝑒𝑙𝑙 = 0. 9849 𝑉 − log(0.000772)3 (0.89332)3
2

𝐸𝑐𝑒𝑙𝑙 = 0. 9849 𝑉 − (−0.26273)

𝐸𝑐𝑒𝑙𝑙 = 1.2476 𝑉

c) Measured emf is 1.2475 V

Example 3
Consider the cell reaction below:

Pt(s)|H2(g)1bar|H + (aq)||HBr(0.01)|AgBr(s)|Ag
(s)
If the emf of of the cell is 0.3127 V and EoR
=0.073 V, determine the mean activity
coefficient of HBr

32
 0.05916
E cell  E o
 log m 2  2
ne
cell

( E  E cell ) n e
o
log m   
2 2 cell

 0.05916
( E cell  E ocell )n e
2lo    2 log m
 0.05916
(0.3127  0.0711) Vx 1
2lo    2 log 0.01
 0.05916V

 4.08384 4000
 0.08384
lo    0.04192
2
   10 0.04192  0.90799
33
Example 4

Consider a cell in Example 2 with a

measured emf 1.2475V.
Determine mean activity coefficient of
0.000772M ZnCl2.

34
 0.05916
E cell  E o
 log 4m 3  3
ne
cell

( E  E cell )n e
o
log m   
3 3 cell

 0.05916
( E cell  E ocell )n e
3lo    log 4  3 log m
 0.05916
(1.2475  0.9849) V x 2
3lo    log 4  3 log 0.000772
 0.05916V

   8.8776   0.60206 9.3371

 0.14253
lo    0.04751
3
   10 0.04751  0.89637
35
Thermodynamic properties from emf
measurements
Fundamental thermodynamic equations

𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 + 𝜇𝑖 𝑑𝑛𝑖

𝜕(∆𝐺)
= −∆𝑆
𝜕𝑇

∆𝐺 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙
𝑜
∆𝐺 𝑜 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙

𝜕𝐸𝑐𝑒𝑙𝑙
𝜈𝑒 𝐹 = ∆𝑆
𝜕𝑇
𝑜
𝜕𝐸𝑐𝑒𝑙𝑙
𝜈𝑒 𝐹 = ∆𝑆 𝑜
𝜕𝑇
 ∆𝐺 = ∆𝐻 − 𝑇∆𝑆

∆𝐻 = ∆𝐺 + 𝑇∆𝑆

𝜕𝐸𝑐𝑒𝑙𝑙
∆𝐻 = −𝜈𝑒 𝐹𝐸𝑐𝑒𝑙𝑙 + 𝑇𝜈𝑒 𝐹
𝜕𝑇

𝜕𝐸𝑐𝑒𝑙𝑙 −1
𝐽
𝜈𝑒 𝐹 in V 𝐾 𝑎𝑛𝑑 𝑉 =
𝜕𝑇 𝐶

Similar expression
∆𝐻 𝑜

∆𝑆 𝑜
Temperature coefficients
• The measurement of emf values at various
temperatures provides a very convenient
method of obtaining thermodynamic values
for chemical reactions
2 3
T T T
Ecell = a+b +c +d + …
K K K
2
𝜕Ecell T T
= b + 2c + 3d +⋯
𝜕T K K

Similarly
o 2
𝜕Ecell T T
= b + 2c + 3d +⋯
𝜕T K K
Example
The EAg/AgCl(s)/Cl- at various T are shown
below
a) Calculate Eo at 25oC
b) Determine the temperature coefficient
of the cell at 25oC
T(K) Eo V
283.15 0.2314
288.15 0.2286
298.15 0.2224
303.15 0.2191
308.15 0.2115 39
 o T T 2
a) Ecell, Ag/AgCl/Cl− = a+b
K
+c
K

Use quadratic regression (QUAD)

a)= -1.35359
b)= 0.011432
c) = -2.0611 x 10−5
( b)
(a )
2
T 5  T 
E Ag AgCl Cl (V)   1.3535  0.01143   2.061x10  
K K
At 298.15 K
2
 298.15 K  5  298.15 
E Ag AgCl Cl (V)   1.3535  0.01143   2.061x10  
 K   K 
 0.2227 V

41
( b)
2
T T
E Ag AgCl Cl (V )   1.3535  0.01143   2.061 
K K
At 298.15 K
2
T T
E Ag AgCl Cl (V )   1.3535  0.01143   2.061 
K K
E 5  T 
( ) P  0.01143 2 (2.061x10 ) 
T K
E 5  298.15 K 
( ) P  0.01143 2 (2.061x10 ) 
T  K 
 8.597 x10 4 V K 42
At 25 C the emf and E / T of the cell
o

Pb(s) PbCl 2 (s), KCl, AgCl (s) Ag

are 0.4902V and  1.86 x10 4 V K 1 respectively.
The silver electrodeis the cathode.
(a ) Write the cell reaction
(b) Calculate G and H of the reaction :
Pb(s)  2AgCl (s)  PbCl 2 2Ag (s)
(c)Compare with the data provided

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(a )
Re d rxn : 2AgCl (s)  2e  2Ag (s)  2Cl  (aq )
Oxd.rxn : Pb(s)  Pb2 (aq )  2e 
Cell rxn : 2AgCl (s)  Pb(s)  2Ag (s)  PbCl 2 (s)

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( b)
G   n e FE cell
 2 x 96485C mol1x 0.4902J C 1
 9.4594 x104 J mol

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(c)
2AgCl (s)  Pb(s)  2Ag (s)  PbCl 2 (s)
G rxn   f
n G o

Pr oducts
 f
n G o

reac tan ts

H rxn   f
n H o

Pr oducts
 f
n H o

reac tan ts

G rxn  1xnG of , PbCl2 ( s )  2nG of ,AgCl

 [1x  314.0  _ 2(109.79)]103 J mol1  9.442x104 J mol1
H rxn  1xnH of , PbCl2 (s )  2nH of ,AgCl
H rxn  [1x  359.2  2(127.07)]103 J mol1  1.0506 x105 J mol1

46