ME F414 Fuel Cell Science and Technology: Tribeni - Roy@pilani - Bits-Pilani - Ac.in

ME F414
Fuel Cell Science and Technology
Dr. Tribeni Roy

Instructor-in-charge
tribeni.roy@pilani.bits-pilani.ac.in
9/14/2021 63
Brief overview of last class
• Thermodynamic potentials
• Heat potential of fuel
• Work potential of fuel
9/14/2021 64
Relationship between Gibbs Free Energy and Electrical Work
For a constant-temperature, constant-pressure process (dT, dp = 0) this

reduces to T = 200 K and p = 1 atm
T = 400 K and p = 5 atm
Valid for different values of temperature and pressure as long as these
values are not changing during the reaction
9/14/2021 65
Relationship between Gibbs Free Energy and Voltage
• The potential of a system to perform electrical work is

measured by voltage (also called electrical potential)
• The electrical work done by moving a charge Q, measured in

coulombs, through an electrical potential difference E in volts
• If the charge is assumed to be carried by electrons, then
• Thus, the Gibbs free energy sets the magnitude of the reversible
voltage for an electrochemical reaction
9/14/2021 66
Relationship between Gibbs Free Energy and Voltage
For example, in a hydrogen–oxygen fuel cell, the reaction has a

Gibbs free-energy change of –237 kJ/mol under standard-state
conditions for liquid water product. The reversible voltage generated
by a hydrogen–oxygen fuel cell under standard-state conditions is
thus
is the standard-state reversible voltage and is the standard-state free-energy change

for the reaction
9/14/2021 67
Standard Electrode Potentials: Computing Reversible Voltages
• Standard electrode potential tables compare the standard-state

reversible voltages of various electrochemical half reactions
relative to the hydrogen reduction reaction
• In these tables, the standard-state potential of the hydrogen

reduction reaction is defined as zero, thus making it easy to
compare other reactions.
Selected List of Standard Electrode Potentials
9/14/2021 68
• To find the standard-state voltage produced by a complete

electrochemical system, we simply sum all the potentials in the
circuit
• The standard-state potential of the hydrogen–oxygen fuel cell is

determined by
9/14/2021 69
• For a set of coupled half reactions, how do we know which

reaction will spontaneously proceed as the reduction reaction
and which reaction will proceed as the oxidation reaction?
• The answer is found by comparing the size of the electrode

potentials for the reactions
• Because electrode potentials really represent free energies,

increasing potential indicates increasing “reaction strength”
9/14/2021 70
A direct methanol fuel cell uses methanol ( ) as fuel instead of

hydrogen. Calculate the standard-state reversible potential for a direct
methanol fuel cell
• Thus, the net cell potential for a methanol fuel cell is +1.199 V;
almost the same as for a H2–O2 fuel cell
• E0 values are independent of reaction amounts

9/14/2021 71
Predicting reversible voltage of a fuel cell
under non-standard state conditions
• Standard-state reversible fuel cell voltages (E0 values) are only
useful under standard-state conditions (room temperature,
atmospheric pressure, unit activities of all species)
• Fuel cells are frequently operated under conditions that vary

greatly from the standard state
• High-temperature fuel cells operate at 700–10000C, automotive

fuel cells often operate under 3–5 atm of pressure, and almost all
fuel cells cope with variations in the concentration (and
therefore activity) of reactant species
• We will study variation of reversible fuel cell voltages with

temperature, pressure and concentration
9/14/2021 72
Reversible Voltage Variation with Temperature
9/14/2021 73
• Considering ET as the reversible cell voltage at an arbitrary
temperature T, at constant pressure
• for a chemical reaction is positive, ET will increase with

temperature
• is negative, then ET will decrease with temperature
• For most fuel cell reactions is negative; therefore, reversible

fuel cell voltages tend to decrease with increasing temperature
9/14/2021 74
ME F414
Fuel Cell Science and Technology
Dr. Tribeni Roy

Instructor-in-charge
tribeni.roy@pilani.bits-pilani.ac.in
9/14/2021 75
Brief overview of last class
• Bridging thermodynamics with electrochemistry
• Predicting reversible voltages under standard and non-standard

conditions
9/14/2021 76
Reversible Voltage Variation with Pressure
• Like temperature effects, the pressure effects on cell voltage
may also be calculated starting from the differential
expression for the Gibbs free energy
9/14/2021 77
• The variation of the reversible cell voltage with pressure is

related to the volume change of the reaction
• If the volume change of the reaction is negative (if fewer

moles of gas are generated by the reaction than consumed, for
instance), then the cell voltage will increase with increasing
pressure
• Le Chatelier’s principle: Increasing the pressure of the system

favors the reaction direction that relieves the stress on the
system
9/14/2021 78
• Usually, only gas species produce an appreciable volume

change. Assuming that the ideal gas law applies:
where represents the change in the total number of moles of gas upon reaction. If
is the number of product moles of gas and is the number of reactant moles of
gas, then = –
• Pressure, like temperature, turns out to have a minimal effect

on reversible voltage
9/14/2021 79
Reversible Voltage Variation with Concentration: Nernst Equation
• To understand how the reversible voltage variation with

concentration, we need to introduce the concept of chemical
potential
• Chemical potential measures how the Gibbs free energy of a

system changes as the chemistry of the system changes
• Each chemical species in a system is assigned a chemical

potential
9/14/2021 80
where is the chemical potential of species i in phase α and expresses how

, ,
much the Gibbs free energy of the system changes for an infinitesimal increase in the
quantity of species i (while temperature, pressure, and the quantities of all other species
in the system are held constant).
• When we change the amounts (concentrations) of chemical

species in a fuel cell, we are changing the free energy of the
system
• This change in free energy in turn changes the reversible

voltage of the fuel cell
9/14/2021 81
• Understanding chemical potential is key to understanding how

changes in concentration affect the reversible voltage
• Chemical potential is related to concentration through activity a:
where is the reference chemical potential of species i at standard-state conditions

and is the activity of species i
9/14/2021 82
9/14/2021 83
• Consider an arbitrary chemical reaction placed on a molar
basis for species A in the form
• On a molar basis for species A, for this reaction may be

calculated from the chemical potentials of the various species
participating in the reaction (assuming a single phase):
9/14/2021 84
• Recognizing that the lumped standard-state chemical

potential terms represent the standard-state molar free-
energy change for the reaction, , the equation can be
simplified to a final form
• van’t Hoff isotherm – tells how the Gibbs free energy of a

system changes as a function of the activities (read
concentrations or gas pressures) of the reactant and product
species
9/14/2021 85
 If a reaction involves 2Na+, the activity of Na+ must be raised to the power of 2 (e.g., a2Na+)
 Only chemical species that are actually participating as reactants or products in the
electrochemical reaction appear in the Nernst equation
9/14/2021 86
• The Nernst equation outlines how reversible electrochemical

cell voltages vary as a function of species concentration, gas
pressure, and so on
• This equation is the centerpiece of fuel cell thermodynamics
• We replace the activities of hydrogen and oxygen gases by their

unitless partial pressures ( , )
9/14/2021 87
• If the fuel cell is operated below 100∘C, so that liquid water is
produced, we set the activity of water to unity ( )
• It is apparent that pressurizing the fuel cell in order to

increase the reactant gas partial pressures will increase the
reversible voltage
• If we operate a room temperature H2–O2 fuel cell on 3 atm pure

H2 and 5 atm air, thermodynamics predicts a reversible cell
voltage of 1.254 V
9/14/2021 88

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ME F414

Fuel Cell Science and Technology

Dr. Tribeni Roy

• Heat potential of fuel

• Work potential of fuel

For a constant-temperature, constant-pressure process (dT, dp = 0) this

• The potential of a system to perform electrical work is

• The electrical work done by moving a charge Q, measured in

• If the charge is assumed to be carried by electrons, then

For example, in a hydrogen–oxygen fuel cell, the reaction has a

is the standard-state reversible voltage and is the standard-state free-energy change

• Standard electrode potential tables compare the standard-state

• In these tables, the standard-state potential of the hydrogen

• To find the standard-state voltage produced by a complete

• The standard-state potential of the hydrogen–oxygen fuel cell is

• For a set of coupled half reactions, how do we know which

• The answer is found by comparing the size of the electrode

• Because electrode potentials really represent free energies,

A direct methanol fuel cell uses methanol ( ) as fuel instead of

• E0 values are independent of reaction amounts

• Fuel cells are frequently operated under conditions that vary

• High-temperature fuel cells operate at 700–10000C, automotive

• We will study variation of reversible fuel cell voltages with

• for a chemical reaction is positive, ET will increase with

• is negative, then ET will decrease with temperature

• For most fuel cell reactions is negative; therefore, reversible

Dr. Tribeni Roy

• Bridging thermodynamics with electrochemistry

• Predicting reversible voltages under standard and non-standard

• The variation of the reversible cell voltage with pressure is

• If the volume change of the reaction is negative (if fewer

• Le Chatelier’s principle: Increasing the pressure of the system

• Usually, only gas species produce an appreciable volume

• Pressure, like temperature, turns out to have a minimal effect

• To understand how the reversible voltage variation with

• Chemical potential measures how the Gibbs free energy of a

• Each chemical species in a system is assigned a chemical

where is the chemical potential of species i in phase α and expresses how

• When we change the amounts (concentrations) of chemical

• This change in free energy in turn changes the reversible

• Understanding chemical potential is key to understanding how

• Chemical potential is related to concentration through activity a:

where is the reference chemical potential of species i at standard-state conditions

• On a molar basis for species A, for this reaction may be

• Recognizing that the lumped standard-state chemical

• van’t Hoff isotherm – tells how the Gibbs free energy of a

• The Nernst equation outlines how reversible electrochemical

• This equation is the centerpiece of fuel cell thermodynamics

• We replace the activities of hydrogen and oxygen gases by their

• It is apparent that pressurizing the fuel cell in order to

• If we operate a room temperature H2–O2 fuel cell on 3 atm pure

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