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Lecture 8
Thermodynamics Relevant for Fuel Cells
Thermodynamics :
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Closed system
Open system
E = U + KE +PE
H = Q W
H= U + pV
H.enthalpy
p= pressure of fluid
V = volume of fluid
Piston cylinder
Steam turbine
U. internal energy
(total intrinsic energy of a substance,
associated with microscopic movement, i.e.
kinetic energy and interactions between
particles on atomic scale, i.e. chemical and
potential energy)
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-E
+E
An irreversible process does generate entropy ( e.g. heat loss from friction,
or heat transfer through a finite temperature difference)
If the temperature gradient is made infinitesimally small
(at the expense of the heat transfer rate!), the process approaches a reversible one.
Entropy, a property or point function, is based on this reversible heat transfer:
dS = (Q/T)rev
After integration: S = Qrev/T0
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Ssurroundings = Qsurroundings / T0
Stotal = (Sproducts Sreactants)system + (Qsurroundings / T0)
Thermodynamic Potentials
First and second law can be used to set up a number of rules governing how
energy can be transferred from one form to another.
These rules are called thermodynamic potentials.
dU =TdS -pdV
reversible heat transfer
(dU/dS)v = T
mechanical work
(dU/dV)S = -p
Lets define a new thermodynamic potential, the Gibbs free energy, G(T,p)
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Enthalpy H
Thermodynamic potential that is a function of S and p can be obtained by
transforming U with respect to V
by definition, we call this new thermodynamic potential H, Enthalpy
H = U (dU/dV)S V
Since (dU/dV)s = -p, one gets H = U + pV
Through differentiation, one obtains dH = dU +pdV + Vdp
Knowing that dU = TdS pdV gives
dH = TdS + Vdp
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Internal energy, U
Enthalpy, H = U + pV
+pV
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Heat engines
Operate in closed system (no mass flow) on cycle:
1. Heat input from external high-T source
2. Partial conversion of heat to work ( e.g. in turbine)
3. Rejection of waste heat to low-T sink (e.g. condenser with cooling water)
initial and final states are identical, thus: Q - W = E = 0
Wnet (net work) = net heat = Qin- Qout
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Carnot cycle
Thermal efficiency, th = Wnet/Qin= (Qin-Qout)/Qin = 1-Qout/Qin
Maximum work is achieved when all processes are conducted reversibly
as proposed for idealized cycle by Carnot:
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T
Q in
1
TH
Wnet
TL
Q out
S1 =S4
3
S
S2 =S3
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Work potential is the amount of useful work that the steady flow device can perform as it changes
from initial T and P to dead state T0, P0
Since it is an open system with mass flow, we must account for both internal energy and flow work of the mass
by using enthalpy, H
dH = -Q W ( note: minus signs because system rejects heat and does work)
WCarnot = (1- T0/T) Qin, Carnot = Qin, Carnot T0dSin, Carnot
Qin, Carnot = WCarnot + T0dSin, Carnot
But. equation should be written in terms of the system, not just the Carnot cycle heat engine
Heat leaving the system, Qout, system , = heat entering the heat engine, Qin, Carnot
EXERGY
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Efficiencies
Thermal efficiency of heat engine, thermal = Wnet / Qin
thermal, Carnot = 1 TL / TH
note: TL is usually fixed at ambient condition; efficiency is thus determined by TH
However, to get to high T, the fuel loses some of its chemical energy to irreversible
processes:
for example, in adiabatic combustion of methane with excess air, ~35% of the work
potential of the fuel is used up to change the temperature of the molecules involved
Cengel and Boles, Thermodynamics: An Engineering Approach, 3rd ed, WCB/McGraw-Hill, Boston, 1998
Example:
Steam turbine operating at TH = 700 K
Water leaving at 350 K
thermal, Carnot = 1 TL / TH = 1- 350/700 = 0.5 ( 50 % efficiency)
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Fuel cell
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G = H - TS
change in Entropy
(disorder)
Lets determine how much heat energy and electric energy can be generated
in a hydrogen fuel cell under ideal conditions:
H2 + O2
H 2O
130.547
O2
205.033
H2O (l)
69.92
S = 69.92-0.5*205.033-130.547= -163.14
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Lets determine how much heat energy and electric energy can be generated
in a hydrogen fuel cell under ideal conditions:
H2 + O2
H 2O
(298
130.547
O2
205.033
H2O (l)
69.92
S = 69.92-0.5*205.033-130.547= -163.14
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where n = 2 electrons
Lets assume we have a PEM fuel cell with 100 cm2 electrode area
operating at cell voltage Vcell =0.7 V
and a cell current icell =0.6 amp/cm2 ( i.e. 60 amps)
P total = P electrical + P thermal
P thermal = P total - P electrical
= ( V ideal x icell) (Vcell x icell)
= (Videal Vcell) x icell
= ( ____ - _____) x ( ______ )
P thermal = __________ W ( _______ %)
P total
= __________ W
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Lets assume we have a PEM fuel cell with 100 cm2 electrode area
operating at cell voltage Vcell =0.7 V
and a cell current icell =0.6 amp/cm2 ( i.e. 60 amps)
P total = P electrical + P thermal
P thermal = P total - P electrical
= ( V ideal x icell) (Vcell x icell)
= (Videal Vcell) * icell
= (1.23- 0.7)V * ( 60 A )
P total
= 73.8 W
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