Lecture 1

September 27, 2021

Electrochemical thermodynamics

• Overview of principles covered in the course

• Calculating ΔG, ΔH, ΔS
• Thermodynamic efficiency

1
 Working Principle of a Fuel Cell

• 2 chemical reactions
- Fuel is consumed, H2O (or CO2) + electric
current is created

• 2 electrodes
- Anode : oxidation reaction
- Cathode: reduction reaction

• Electrolyte
- Transports ions
- Many different types → defines the fuel cell

2
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
1 out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

1. Fuel – thermodynamically favorable reaction

Favorability determined by ΔG of reaction 3
 Working Principle of a Fuel Cell
e- e-

2
excess water
fuel out + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

2. Electrode surface – transport planar

Diffusion through porous electrode porous
4
patterned
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out 3 + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in
3. Electrode material and structure – kinetics
Pt Material catalytic activity
Ni Surface area
Pd Geometry 5
Reactivity
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
4 out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in
4. Electrode-electrolyte interface – kinetics, transport
Adsorption-reaction-desorption mechanism
Surface concentration for diffusion vs. convection systems
6
stationary electrode rotating disc electrode
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
out
5
H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in
Defines the type of fuel
5. Electrolyte – transport, thermodynamics
cell: Salt carbonates,
Diffusion
KOH, phosphoric acid,
Redox properties for electron transfer
PEM, metal oxide
Operating temperature 7
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
6 out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

6. Electrode-electrolyte interface
8
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
7 out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

7. Electrode material
9
 Working Principle of a Fuel Cell
e- e-

8
excess water
fuel out + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

8. Electrode surface
10
 Course Syllabus
1. Electrochemical Thermodynamics and Its
Applications to Energy Devices

2. Electrochemical Kinetics

3. Transport Phenomena

4. Applications to Real Electrochemical Systems

11
 Working Principle of a Fuel Cell
e- e-

excess water
fuel out + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

Fuel + Oxidant = Products

12
Step 1: Thermodynamics
 Differentiating Among Different
Electrochemical Processes
“Thermodynamics is the study of energy change from one
state to another.”
Spontaneous Non-spontaneous
reactions (ΔG <0) reactions (ΔG >0)

• Fuel cells • Batteries (charging)

• Batteries • Electrolysis
• Corrosion • Electroplating
• Electrosynthesis
• Electrowinning
• Electrorefining
13
 Significance of ΔG

• Related to the H and S

ΔG° = ΔH ° – TΔS °
• ΔG : Related to energy production (or
consumption)
• ΔH : Total heat content of a system (internal
energy + product of pressure and volume);
energy required to create a system and make
room for it by displacing its environment and
establishing volume and pressure
• TΔS : Heat/energy that is released

14
 “Heat” release/absorption:
ΔH vs. ΔS
In our thermo course, we were taught:
• ΔH: “the thermodynamic quantity that states the total heat content of the system,
which is the sum of all internal process in a closed system”.
• So we considered endo/exothermic processes as total “heat” absorbing/releasing.

This is still correct, but in this course:

• We view ΔH as total potential chemical energy (such as energy stored in bond
formation).
• If all the potential chemical energy for a reaction went into electrical work and
there was no heat transfer, there would be no entropy change; ΔG = ΔH and
ΔS=0.
• When we refer to “heat”, we are only referring to “unavailable” heat and not
the heat of formation that contributes to internal energy (chemical bonds).

ΔG: spontaneous vs. non-spontaneous

ΔH: endothermic vs. exothermic
ΔS: heat released vs. absorbed (i.e. unavailable heat)
15
1Lindiwe Khotseng. Fuel Cell Thermodynamics. DOI: http://dx.doi.org/10.5772/intechopen.90141
 Example 1.1 Methanol Fuel Cell

CH3OH (l) + 3/2 O2 (g) → CO2 (g) + 2H2O (l)

CH3OH CO2

Fuel Cell

O2 H2O

a. What is the ΔG° (298 K, 1 atm)?

b. Is this reaction spontaneous?
c. Is heat absorbed or released?

16
Example 1.1 Methanol Fuel Cell
Solutions (a-c)

CH3OH (l) + 3/2 O2 (g) → CO2 (g) + 2H2O (l)

17
 Thermodynamic Efficiency (ηth)

Generalized definition of efficiency

useful energy
ηth =
Total available energy

For a fuel cell, this means

ΔG°
ηth =
ΔH°

For a fuel cell, ηth is the efficiency at which chemical energy is

converted to electrical energy

18
 Example 1.1 Methanol Fuel Cell
Solutions (d)

CH3OH (l) + 3/2 O2 (g) → CO2 (g) + 2H2O (l)

CH3OH CO2

Fuel Cell

O2 H2O

a. What is the ΔG° (298 K, 1 atm)?

b. Is this reaction spontaneous?
c. Is heat absorbed or released?
d. What is the thermodynamic efficiency?

19
Effect of Temperature on Efficiency for
(Constant ΔH and ΔS)
ΔG
ΔG = ΔH – TΔS ηth =
ΔH

We can define a characteristic temperature at which the

fuel cell delivers only heat (entropic heat). It is the
temperature where ΔG = 0 (TΔG=0)
ΔH°
0= ΔH° – TΔG=0ΔS° TΔG=0 =
ΔS°
20
 Example 1.1 Methanol Fuel Cell

CH3OH (l) + 3/2 O2 (g) → CO2 (g) + 2H2O (l)

CH3OH CO2

Fuel Cell

O2 H2O

a. What is the ΔG° (298 K, 1 atm)?

b. Is this reaction spontaneous?
c. Is heat absorbed or released?
d. What is the thermodynamic efficiency?
e. At what temperature does the fuel cell only deliver heat?
(assume no change in ΔH° and ΔS°)
21
Example 1.1 Methanol Fuel Cell
Solutions (e)

22
 Effect of Temperature on Efficiency for
(Variable ΔH and ΔS)
ΔG° ΔH° - TΔS° ΔS°
ηth = = = 1-T
ΔH° ΔH° ΔH°
Effect of increasing temperature on ΔH and ΔS (no longer
STP conditions of 273 K, 1 atm) in Example 1.1

T, |ΔH| (ΔH°< 0)
ΔH = ΔH° + Cp(T2-T1)

Heat
capacity

T2 T, |ΔS| (ΔS°< 0)
ΔS = ΔS° + Cpln 23
T1
 Effect of Phase Transitions

Enthalpy (ΔHvap) and entropy Enthalpy (ΔHfus) and entropy

(ΔSvap) of vaporization are (ΔSfus) of fusion are positive
positive

ΔHvap , ΔSvap > 0 ΔHfus , ΔSfus > 0

e.g., energy is required for

liquid → vapor transition
(vapor is a higher energy state)
• For a product in a reaction, that means extra energy is
required for the transition to a higher energy state
• For a reactant in a reaction, that means that the reaction is
supplied with a higher energy state 24
 Effect of Phase Changes
(Gas vs. Liquid)
ΔG = ΔH – TΔS
liquid → gas
ΔHf° : more negative less negative

ΔSf° : less positive more positive

ΔH ΔS ΔG
(-) (+) (-)
(+) (-) (+)
Temperature
(+) (+) (-,+) plays a key
role in
(-) (-) (-,+) determining
spontaneity

25
 Example 1.2 Using Other Fuels
Solutions (a-c)
CO2 (g) + H2O (l) → O2 (g) + H2 (g) + CO

CO2 O2

Electrochemical Cell CO

H2O H2

a. What is the ΔG° (298 K, 1 atm)?

b. Is this reaction spontaneous?
c. Is heat absorbed or released?
d. What is the thermodynamic efficiency?

26
 Thermodynamic Efficiency (ηth)

Generalized definition of efficiency

useful energy
ηth =
Total available energy

For an electrolyzer, this means

ΔH°
ηth =
ΔG°

Relationship is inverted compared to a fuel cell because

electrical energy (ΔG°) is converted into chemical energy
(ΔH°)
27
 Example 1.2 Using Other Fuels
Solutions (d)
CO2 (g) + H2O (l) → O2 (g) + H2 (g) + CO

CO2 O2

Electrochemical Cell CO

O2 H2

a. What is the ΔG° (298 K, 1 atm)?

b. Is this reaction spontaneous?
c. Is heat absorbed or released?
d. What is the thermodynamic efficiency?

28
 Defining Cell Potential (E°)

ΔG° is not directly measureable. How does it relate to a

measureable parameter for a fuel cell?

ΔG° = -z F E°

# e- transferred Faraday’s constant:

per mole product 9.6 x 104 C/mol e-

29
 Opening up the black box…
e- e-
ΔG° = -z F E°

excess water
fuel out + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in

30
 Opening up the black box…
e- e-

excess water
fuel out + heat
out

H 2O
H+
e-
O2
H+
H2

fuel in
(H2) air in
Oxidation half-reaction (anode) Reduction half-reaction (cathode)
31
H2(g) → 2H+ + 2e- 1/2O2 (g) + 2e- +2H+(g)→ H2O(l)
 Opening up the black box…

ΔG° is not directly measureable. How does it relate to a

measureable parameter for a fuel cell?

ΔG° = -z F E°

# e- transferred Faraday’s constant:

per mole product 9.6 x 104 C/mol e-

Oxidation half-reaction (anode) Reduction half-reaction (cathode)

H2(g) → 2H+ + 2e- 1/2O2 (g) + 2e- +2H+(g)→ H2O(l)

E° = E°oxidation + E°reduction
32