Fuel Cells Thermodynamics

Fuel Cells Thermodynamics
Internal energy
The energy associated with microscopic movement and interaction between particles on the
atomic and molecular scale.
Entropy is determined by the number of possible microstates accessible to a system (the

number of possible ways of configuring a system)
For an isolated system
S = k log Ω
S:total entropy of the system;
K:Boltzmann’s constant;
O:number of possible microstates accessible to the system
Dr. Sanjeev Gautam & Narinder Paliwal (UICET, Panjab University, Chandigarh -160014, India)
First law
The law of conservation of energy
d (Energy)univ = d(Energy)system +d (Energy)surrounding = 0

d (Energy)system = -d (Energy)surrounding
Energy transfer between a closed system and its surrounding via heat(Q) and work (W)
dU = dQ –dW....................................................(T1)
Positive work is defined as work done by the system on the surroundings If there is only
mechanical work done by a system (eg. Expansion of a system by dV against a pressure, P)
(dW)mechanical=pdV
dU = dQ –dW
Second law
In a system, a process that occurs will tend to increase the total entropy of the universe.
dSuniv >= 0
For a reversible transfer of heat at contant pressure
dS=dQrev/T...................................................(T2)
Thermodynamic Potentials
How energy can be transferred from one form to

another!
Combining first Law (T1) and Second Law (T2)

dU = Tds - pdV
H2-O2 Fuel Cell
H2+1/2 O2 ---> H2O ; ΔGrxn=-273 kJ/mol H2
eg 5 mole of O2 is reacted , the extrinsic Gibbs free energy change
Intrinsic Gibb’s free energy of the reaction is -237 KJ/mol of H2
Intrinsic Gibb’s free energy of the reaction is -237 KJ/mol of H2
Some Important terms
Standard State
Because most thermodynamic quantities depend on T and p, we need a reference

state called as a standard state.
Room temperature(298.15K) and Pressure 1 bar=100kPa
Standard state condition are designated by a superscript zero,
Reversibility
•Reversible implies equilibrium

•E represents a reversible fuel cell voltage and V represents an operational ( nonreversible ) fuel
cell voltage
Heat Potential of a Fuel . Enthalpy
Temperature dependence of Enthalpy and Entropy

dH=TdS+Vdp
for a constant pressure process
dH=TdS = dU+dW
Max. energy that can be extracted –
enthalpy of reaction involving fuel
Calculating Reaction Enthalpies
enthalpy required to form 1 mole of chemical species ‘i’ at STP from the reference
species
Work potential of a fuel: Gibbs free energy
G=H-TS
dG = dH – TdS
Relationship between Gibbs free energy and Electrical Work
Relationship between Gibbs free energy and voltage
o Potential of a system to perform electrical work is measured by voltage (electrical
potential)
o Electrical work done by moving a charge Q ( coulombs) through an electrical potential
difference E(volts), Welec
Welec=EQ
If the charge is carried by electrons
Q = nF n: number of moles of electrons transferred ; F: Faraday constant
H2-O2 Fuel Cell
Standard Electrode Potentials: computing reversible voltage
Standard state electrode potential is standard state reversible voltages of various

electrochemical half reactions relative to the hydrogen reduction reaction.
o Since hydrogen rxn system in opposite direction -ve sign is added
o In a redox pair, rxn with higher potential would remain as it is, while direction of the other rxn
would change and hence the sign of Eo would change.
o Eo never changes even one require to multiply by a number to get correct stoichiometry
Standard Electrode Potential
F2(g) + 2H+ + 2e- 2HF(aq) +3.05 [10] H2AlO3- + H2O + 3e- Al + 4 OH- -2.33 [1]
Fc+ + e- Fc(s) +0.641 [13] H2BO3- + H2O + 3e- B + 4 OH- -1.79 [1]
2FeO42- + 5H2O + 6e- Fe2O3(s) + 10OH- +0.81 [9] H2PO2- + e- P + 2 OH- -1.82 [1]
[Fe(CN)6]2- + e- [Fe(CN)6]4- +0.36 2H2O + 2e- H2(g) + 2 OH- -0.8277 [1]
Fe(CN)64 + 6H+ +2e- Fe(s) + 6HCN(aq) -1.16 [9] HfO(OH)2 + H2O + 4e- Hf + 4 OH- -2.50 [1]
Fe(OH)2(s) + 2e- Fe(s) + 2OH- -0.89 [9] HfO2+ + 2 H+ + 4e- Hf + H2O -1.724 [1]
Fe2+ + 2e- Fe(s) -0.44 [5] Hg22+ + 2e- Hg(l) +0.85
Fe2O3(s) + 3H2O + e- 2Fe(OH)2(s) + 2OH- -0.86 [9] Hg2+ + 2e- Hg(l) +0.80
Fe3+ + 3e- Fe(s) -0.04 [9] Hg2+ + 2e- Hg2+ +0.91 [10]
Fe3+ + e- Fe2+ +0.77 HgO(s) + H2O + 2e- Hg(l) + 2OH- +0.0977
Fe3O4(s) + 8H+ + 8e- 3Fe(s) + 4H2O +0.085 [12] Ho2+ + 2e- Ho -2.1 [1]
FeO42- + 3e- + 8H+ Fe3+ + 4H2O +2.20 [16] Ho3+ + 3e- Ho -2.33 [1]
Fm2+ + 2e- Fm -2.30 [1] Ho3+ + e- Ho2+ -2.8 [1]
Fm3+ + 3e- Fm -1.89 [1] HPO32- + 2 H2O + 3e- P + 5 OH- -1.71 [1]
Fr+ + e- Fr -2.9 [1] 2HIO(aq) + 2H+ + 2e- I2(s) + 2H2O +1.44
Ga3+ + 3e- Ga(s) -0.53 2IO3- + 12H+ + 10e- I2(s) + 6H2O +1.20
Gd3+ + 3e- Gd -2.279 [1] IO3- + 5H+ + 4e- HIO(aq) + 2H2O +1.13
Ge(s) + 4H+ + 4e- GeH4(g) -0.29 I2(s) + 2e- 2I- +0.54 [5]
Ge4+ + 4e- Ge(s) +0.12 I3- + 2e- 3I- +0.53 [5]
GeO(s) + 2H+ + 2e- Ge(s) + H2O +0.26 In3+ + 3e- In(s) -0.34 [10]
GeO2(s) + 2H+ + 2e- GeO(s) + H2O -0.37 [IrCl6]2- + e- [IrCl6]3- +0.87[4]
2H+ + 2e- H2(g) 0.0000 =0 K+ + e- K(s) -2.931 [3]
La(OH)3(s) + 3e- La(s) + 3OH- -2.90 [3]
La3+ + 3e- La(s) -2.379 [3]
Li+ + e- Li(s) -3.0401 [3][4]
Predicting reversible voltage of a fuel cell under non-standard-state conditions
Reversible voltage variation with temperature
For molar reaction quantities
By integrating and Defining ET as the reversible cell voltage at T At cinstant p,
Assumed that ΔS does not change with Temperature; Otherwise temperature (through heat
capacity)Dependence of entropy change has to be considered
Reversible voltage variation Reversible voltage variation with
with pressure concentration
(dE/dP)T = - (? ng R T ) / nF p ; applying ideal gas law; ng – change in total no of moles of

gas upon rxn
Fuel cell efficiency
o Ideal efficiency of a fuel cell is limited by ΔG

o Real efficiency is lower than ideal efficiency because of non-ideal irreversible process
Ideal reversible fuel cell efficiency
If work is extracted from a chemical reaction,
For a fuel cell, the maximum amount of energy available to do work is given by Gibbs free energy.
Thus the reversible efficiency of a fuel cell is
At room temperature, H2-O2 Fuel Cell
(when liquid water is produce - higher heating value) ?hoLHV = 241 k J / mole - when water
vapour is produced
HHV:Higher heating value
H2-O2 fuel cell, if H2O(l) is product, it is HHV. If H2O(g) is product, it is LHV. Efficiency is
calculated based on HHV
Comparison with conventional heat/expansion engine
Real fuel cell efficiency
Two main reasons for decrease in

fuel cell efficiency:
o Voltage losses
o Fuel utilization
Voltage efficiency of the fuel cell
Ratio of the real operating voltage of the fuel cell (V) to the thermodynamically reversible voltage
of the fuel cell (E)
o Operating voltage depend on the current (i) drawn from the fuel cell:
o The lighter the current load, the lower the voltage
o Fuel cell are most efficient at low load
Fuel utilization efficiency of the fuel cell
Ratio of the fuel need by the cell to generate electric current and the total products to the fuel cell.
o The supply of fuel to a fuel cell is adjusted to the current

o FC is always supplied with just a bit more fuel than it need at any load
Stoichiometric factor, λ = 1 / efuel
o Constant stoiciometric, say 1.1 1.1 times the fuel require for 100% utilization
o Constant flow rate 110% of max fuel consumption
εreal = εthermo x εvoltage x εfuel

Fuel Cells Thermodynamics

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Fuel Cells Thermodynamics

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Fuel Cells Thermodynamics

Entropy is determined by the number of possible microstates accessible to a system (the

For an isolated system

S:total entropy of the system;

O:number of possible microstates accessible to the system

The law of conservation of energy

d (Energy)univ = d(Energy)system +d (Energy)surrounding = 0

For a reversible transfer of heat at contant pressure

How energy can be transferred from one form to

Combining first Law (T1) and Second Law (T2)

H2+1/2 O2 ---> H2O ; ΔGrxn=-273 kJ/mol H2

eg 5 mole of O2 is reacted , the extrinsic Gibbs free energy change

Intrinsic Gibb’s free energy of the reaction is -237 KJ/mol of H2

Intrinsic Gibb’s free energy of the reaction is -237 KJ/mol of H2

Because most thermodynamic quantities depend on T and p, we need a reference

Room temperature(298.15K) and Pressure 1 bar=100kPa

Standard state condition are designated by a superscript zero,

•Reversible implies equilibrium

Temperature dependence of Enthalpy and Entropy

Calculating Reaction Enthalpies

If the charge is carried by electrons

Q = nF n: number of moles of electrons transferred ; F: Faraday constant

Standard Electrode Potentials: computing reversible voltage

Standard state electrode potential is standard state reversible voltages of various

For molar reaction quantities

By integrating and Defining ET as the reversible cell voltage at T At cinstant p,

(dE/dP)T = - (? ng R T ) / nF p ; applying ideal gas law; ng – change in total no of moles of

o Ideal efficiency of a fuel cell is limited by ΔG

Ideal reversible fuel cell efficiency

If work is extracted from a chemical reaction,

HHV:Higher heating value

Real fuel cell efficiency

Two main reasons for decrease in

Fuel utilization efficiency of the fuel cell

o The supply of fuel to a fuel cell is adjusted to the current

εreal = εthermo x εvoltage x εfuel

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