Lecture 2
October 04, 2021
Electrochemical Thermodynamics and Its Applications
to Energy Devices
Last lecture:
Spontaneous vs. non-spontaneous reactions
This lecture:
Establishing connection between ΔG and electrochemical
parameters
• Carnot, electrochemical, and conversion efficiencies
• Introduction to electrochemical concepts
• Using the Nernst equation for non-standard conditions
1
Thermodynamic Efficiency
ΔG = ΔH – TΔS
electrical chemical heat
energy energy released/absorbed
by the environment
ΔG ΔH
ηth,fuel cell = ηth,electrolysis =
ΔH ΔG
<1 >1
Dependence of fuel cell efficiency on temperature
ΔS T ΔH
ηth,fuel cell = 1 - T =1- where TΔG=0 =
ΔH TΔG=0 ΔS
2
Thermodynamic Efficiency
T=0K
ηth,fuel cell
T
ηth,fuel cell = 1 -
TΔG=0
0
Temperature
TΔG=0 3
How does fuel cell efficiency
compare to combustion?
The overall chemical reaction for hydrogen oxidation via a
fuel cell is similar to that of the combustion of hydrogen
H2 + ½ O2 → H2O
• Fuel cell efficiency is calculated based on electrical work
extracted from the system (ΔG).
• In a combustion engine, efficiency is calculated based on
the mechanical work extracted from the system when
heat is produced.
4
How does fuel cell efficiency
compare to combustion?
Reversible fuel cell Vs.
Reversible heat
Work is obtained from the engine
transport of electrons across Work is obtained from the
a potential difference and not expansion of volume as heat
from mechanical means. is generated.
Fuel cell as a control volume
Cell stack Mechanical
Byproduct heat power
electrical power
Input Output Input (heat) Output
(reactants) (exhaust) Reversible (waste heat)
Ideal Fuel
QH, TH heat engine QC, TC
μi,Ti, pi Cell μo,To, po
5
Carnot Efficiency of a Heat Engine
The Carnot Cycle is a theoretical thermodynamic cycle
proposed by Nicolas Leonard Sadi Carnot in 1824 that
provides an upper limit on the efficiency any classical
thermodynamic engine can achieve during the conversion
of heat into work.
Consider two systems at temperatures TH and TC
TH >TC
TH TC
6
Carnot Efficiency of a Heat Engine
The Carnot Cycle is a theoretical thermodynamic cycle
proposed by Nicolas Leonard Sadi Carnot in 1824 that
provides an upper limit on the efficiency any classical
thermodynamic engine can achieve during the conversion
of heat into work.
Consider two systems at temperatures TH and TC
TH >TC TH >Te> TC
Thermal
Heat transfer equilibrium
ΔG < 0 ΔG = 0
TH TC Te Te
7
Carnot Efficiency of a Heat Engine
Heat engine : work is extracted by Refrigerator or air conditioner : work
moving heat from a high temperature Vs. is put into the system to separate the
to low temperature source heat
Heat source Heat source
at TH at TH
QH QH
W W
Heat sink Heat sink
at TC at TC
QC QC
8
Carnot Efficiency of a Heat Engine
The net effect from the start point to the
finish point is that heat is transferred
from a high-temperature reservoir to a
low-temperature reservoir, and work is
heat
work extracted from the system as it changes
volume.
work The Carnot efficiency (ηCE) is
work
generally defined as
C Work extracted
ηCE=
Heat absorbed
work heat
9
Carnot Efficiency of a Heat Engine
|W1| + |W2| - |W3| - |W4|
ηCE = net work done by gas =
heat absorbed by gas |Q1|
Tc
ηCE= 1-
TH 10
Thermodynamic Efficiency
1
Tc
ηcarnot = 1 -
T
ηth,fuel cell
T = Tc
0
Temperature 11
Thermodynamic Efficiency
Fuel cells can offer higher theoretical
maximum efficiencies than heat engines !!
1
Tc
T=0K ηcarnot = 1 -
T
ηth,fuel cell
T
ηth,fuel cell = 1 -
TΔG=0
T = Tc
0
TBE Temperature 12
TΔG=0
Break-even Temperature
The break-even temperature (TBE) is the temperature at
which the Carnot efficiency (ηcarnot) is equal to the
thermodynamic fuel cell efficiency (ηth)
ηcarnot = ηth,fuel cell
Tc TBE
1- =1-
TBE TΔG=0
TBE = √ Tc ∙ TΔG=0
13
Conversion and Electrochemical
Efficiencies
For a fuel cell, we can calculate the maximum theoretical
thermodynamic efficiency of the cell assuming reaction
completion and no voltage losses
ΔG°
ηth,fuel cell =
ΔH°
But in practice, we do not achieve 100% conversion of reactants
into products. So we define a conversion efficiency (ηc)
Amount of fuel reacted
ηc =
Amount of fuel provided
Similarly, the measured cell potential is less than the
thermodynamic cell potential due to potential losses. So we
define an electrochemical efficiency (ηel)
E Measured potential
ηel = Calculated from ΔG
Ecell 14
What is potential?
Reduction potential is a measure of a tendency of a chemical
species to acquire electrons. Other names: Reduction-oxidation potential
Redox potential
Midpoint potential
The more positive the reduction potential, the more
favorable the reduction reaction
More thermodynamically
favored Based on the values provided in the
Standard Reduction table…
Au3+(aq) + 3e- → Au(s) E° = +1.50 V
Fe3+(aq) + e- → Fe2+(aq) E° = +0.77 V
15
What is potential?
Reduction potential is a measure of a tendency of a chemical
species to acquire electrons.
The oxidation potential is just the reverse reaction, which has
the opposite sign → (Eoxidation)reactionA = -(Ereduction)reactionA
Based on the values provided in the
Standard Reduction table…
More thermodynamically
favored Au3+(aq) + 3e- Au(s) E° = -1.50 V
Fe3+(aq) + e- Fe2+(aq) E° = -0.77 V
16
What is potential?
Reduction potential is a measure of a tendency of a chemical
species to acquire electrons.
The oxidation potential is just the reverse reaction, which has
the opposite sign → (Eoxidation)reactionA = -(Ereduction)reactionA
Ereduction Ereduction>0, reduction favored
Aox + ze- Ared
Eoxidation Ereduction<0
oxidation favored
Eoxidation>0
17
What is potential?
Reduction potential is measured relative to a reference
reaction (reference electrode).
vs. Standard Hydrogen Electrode (SHE)
Au3+(aq) + 3e- → Au(s) E° = +1.50 V
2H+(aq) + 2e- → H2(g) E° = 0.0 V
vs. Ag/AgCl/saturated KCl
Au3+(aq) + 3e- → Au(s) E° = +1.303 V
2H+(aq) + 2e- → H2(g) E° = -0.197 V
AgCl(s) + e- → Ag(s) +Cl- E° = 0.0 V
18
What is potential?
Absolute potential is the electrode potential of a metal measured with respect to a
universal reference system that neglects the metal-solution interface. It is the
difference in electronic energy between a point inside the metal of an electrode and
a point outside the electrolyte in which the electrode is submerged (an electron at
rest in vacuum).
The absolute potential is difficult to determine accurately, so the standard hydrogen
electrode (SHE) is typically used as a reference potential. The SHE is one of the
few systems for which the absolute potential has been accurately determined.
vs. vacuum (absolute potential)
Au3+(aq) + 3e- → Au(s) E° = +5.94 V
2H+(aq) + 2e- → H2(g) E° = +4.44 V
M+solution+ e-(g) → Mmetal E° = 0.0 V
Related to work
function of the metal 19
What is potential?
Reduction process of a species at an electrode
MO = Molecular Orbital
Electrode Solution Electrode Solution
e-
- Vacant MO
Potential
Energy level
of electrons
+ Occupied MO
A + e- → A- 20
What is potential?
Oxidation process of a species at an electrode
MO = Molecular Orbital
Electrode Solution Electrode Solution
- Vacant MO
Energy level
of electrons
Potential
+ Occupied MO
e-
A-→ A + e- 21
Where are the Electrochemical
Potential Losses?
e- e-
2 8
excess water
fuel out 3 + heat
1 4 6 7 out
5
H 2O
H+
e-
O2
H+
H2
fuel in
(H2) air in
Anodic overpotential, cathodic overpotential, ohmic losses resistances to
charge and mass transfer (covered later in the course) 22
Overall Efficiency
The overall efficiency (ηtotal) can be calculated as the
product of all the efficiencies in a system.
For a system with a given conversion and
electrochemical efficiency, the overall efficiency is
calculated as
ηtotal = ηth ∙ ηc ∙ ηel
Accounts for all
the voltage
losses
23
Example 1.3 Coupled Fuel Cell and
Electrolyzer
In a unit, the same cell serves as an electrolyzer (production then storage
of the formed hydrogen as a hydride) and a fuel cell (production of
electricity using the stored hydrogen).
H2
Electrolyzer Fuel cell
operating at operating at
-2.7 V +0.7 V e-
Given that both units operate at the same current density, a potential of 2.7
V is applied to the electrolysis cell and the fuel cell operates at a potential of
0.7 V.
(a) Determine whether the operating voltages are suitable to allow the
desired reactions to proceed. Comment on the heat flow of this system.
(a) Calculate the total electrochemical efficiency of the system considering
100% conversion efficiency.
24
Example 1.3 Coupled Fuel Cell and
Electrolyzer
How can we increase the voltage output of the fuel cell?
Fuel cell stack
25
Example 1.3 Coupled Fuel Cell and
Electrolyzer
How can we increase the voltage output of the fuel cell?
Arranging a fuel cell in series allows us increase the voltage
Fuel cell stack
Estack = Ecells x No. of cells 26
Thermoneutral Cell Potential in Water
Electrolysis
ΔG term TΔS term ΔH
Electrolysis term
Electric energy + Heat Fuel
Heat is needed to run an
Impractical!
electrolyzer
We can compensate for the heat required heat by adding
more electric energy to the system
The thermoneutral potential (Ethn) is the potential at which
the cell charge or discharge process puts out zero heat
ΔH = ΔG + TΔS TΔS
Ethn = Ecell -°
-z F -z F zF
ΔH
Where Ethn = - °
zF 27
Example 1.4 Thermoneutral Cell Potential
of Electrolysis Reaction
(a) What is the thermoneutral cell voltage of a water
electrolyzer run at STP?
(b) Explain how the reaction direction and heat flow changes
for operating voltages (E) below and above the
thermoneutral (Eth) and thermodynamic cell (Ecell)
voltages.
28
Thermoneutral Cell Potential in Water
Electrolysis
TΔS°
E°thn = E°cell -
zF
°
|E| < |Ethn|, need to add heat
|E| > |Ethn|, heat removed (more heat than needed)
Applied voltage
Cell will dissipate
heat from
overpotential
Ethn° 1.48 V
Cell will cool as it
absorbs heat
Ecell° 1.23 V
Not enough potential to
run non-spontaneous
reaction 29
Thermodynamic Cell Potentials at Non-
Standard Conditions
The Nernst Equation is an equation that relates the
reduction potential of an electrochemical reaction to the
standard electrode potential, temperature, and activities
(approximated by concentrations) of the chemical species
undergoing reduction and oxidation.
Reaction
quotient
[products]a
ΔG = ΔG° + RTln Q Q=
[reactants]b
-zF -zF
a,b = corresponding
stoichiometric coefficient
Ecell = E°cell,T - RT ln Q
zF
E°cell,T based on ΔG at
new temperature 30
Thermodynamic Cell Potentials at Non-
Standard Conditions
Standard conditions:
Activities (~concentrations) of solutes: 1 M
Pressure of gases: 1 atm
Temperature: 25 °C
Standard concentrations/pressures and standard temperature
Ecell = E°cell
Non-standard concentrations/pressures and standard temperature
Ecell = E°cell - RT ln Q
zF
Non-standard concentrations/pressures and non-standard temperature
Ecell = E°cell,T - RT ln Q
zF
Account for any changes in standard
potential with temperature (think heat
31
capacity calculations…)
Thermodynamic Cell Potentials at
Non-Standard Conditions
[products]a a,b = corresponding stoichiometric
Q=
[reactants]b coefficient
For the reversible reaction
[C]c[D]d
aA + bB cC + dD Q=
[A]a [B]b
Q is dimensionless
Activity (ai) is non-dimensional quantity
γi=1 γi = activity coefficient of species i
aCcaDd ci ci
Q= where a = γi ~ ci = concentration of species i
aAa aBb c0 c0
c0 = reference concentration (1 M)
For ideal or dilute solutions, activity can be approximated as concentration.
For ideal gases or gases at low pressure, activity can be approximated as pressure.
Note: Solids and pure liquids are not included in the calculation of Q, since their
activities are 1. 32
Thermodynamic Cell Potentials at
Non-Standard Conditions
[products] a
Reaction quotient (Q) does not Q=
include contributions from [reactants]b
solids in the reaction a,b = corresponding
stoichiometric coefficient
Under standard concentrations/pressures, the Nernst
equation simplifies to the standard cell potential
Ecell = E°cell,T - RT ln Q Q=1
zF
0
Ecell = E°cell,T
33
Thermodynamic Cell Potentials at
Non-Standard Conditions
Ecell = E°cell,T - RT ln Q
zF
• Account for any changes in standard Account for partial pressure
potential with temperature (think heat and concentration/dilution
capacity calculations…) effects, including inert gases
• Calculated from ΔG, so only reactants and water vapor, even when
and products taken into consideration. water is not a reactant/product
• Inert gases do not contribute.
34
Example 1.5 Solid Electrolyte Fuel Cell at
Non-standard Conditions
Solid oxide fuel cells (SOFCs) use a solid oxide or ceramic electrolyte to conduct
oxygen ions. They benefit from high efficiency, long-term stability, fuel versatility, low
emissions, and low costs. Common solid fuel oxides include yttria stabilized zirconia
(YSZ), scandia stabilized zirconia (ScSZ), and gadolinium doped ceria (GDC).
The challenge of these cells is that they require high
operating temperatures (>600 °C) to allow oxygen ion
transport to be sufficient for good performance.
Engineering SOFCs with high oxygen ion conductivity
at lower temperatures (even ~500 °C) is an active
area of ongoing research.
35
Example 1.5 Solid Electrolyte Fuel Cell at
Non-standard Conditions
In a solid electrolyte fuel cell utilizing YSZ as the solid
electrolyte, H2 and O2 are consumed at the anode and
cathode, respectively, according to the reactions:
H2(g) + O2- H2O(g) + 2e-
O2(g) + 4e- 2O2-
The cell is working at 800°C with pH2 = 80 kPa and pH2O = 20
kPa at the anode and pO2 = 100 kPa at the cathode.
Calculate
a) the thermodynamic cell potential (Ecell)
b) the thermodynamic efficiency (ηth) of the cell
36
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
37
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)
38
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 )
anode cathode 39
Analogies Between Chemical Reactivity
and Electrochemistry
ΔG =Σ ΔGproducts - Σ ΔGreactants
Ecell=Ereduction + Eoxidation
Activation (cathode) (anode)
energy =(Ereduction)cathode- (Ereduction)anode
(EA)
(kinetics)
reactants
Energy
ΔG
products
Reaction coordinate 40
Relationship Between Equilibrium
Constant (K), ΔG°, and E°cell
From Nernst Equation ΔG°
ΔG = ΔG° + RTln Q
At equilibrium,
ΔG=0 and Q= K
ΔG° = -RT ln K ΔG° = -zFE°cell
K E°cell
RT
E°cell = ln K
zF
E°reduction+E°oxidation
[products]a kforward
K = [reactants]b = (cathode) (anode)
kreverse
Concentrations @ equilibrium 41
Relationship Between Equilibrium
Constant (K), ΔG°, and E°cell
As the system approaches equilibrium
Q→K
ΔG° K E°cell Reaction @
standard
conditions
<0 >1 >0 forward reaction
spontaneous
0 1 0 @ equilibrium
>0 <1 <0 Reverse reaction
non-spontaneous
42
Thermodynamic Vs. Kinetic
Parameters
Thermodynamic Kinetic Parameters
Parameters
General Chemistry Equilibrium Constant Rate Constants
(K) (kforward, kreverse)
Electrochemistry Cell Potential (Ecell) Current (icathode, ianode)
or
Current density
(jcathode, janode)
• In chemistry, the relationship between K and the
rate constants, kforward (kf) and kreverse (kr) is simple.
kforward
K =
kreverse
• In electrochemistry, the relationship between
potential and current is more complex. 43
