Chapter6 Solutions

1
Chapter 6 Solutions

PROBLEMS
Instructors note: You should inform your students to find the fractional change in
the limiting current density below. With the information as given without the
change in red, they cannot find a specific exact number.
6.1 Determine the fractional change in the mass transfer limiting current density for the
cathode of a PEFC between an uncompressed and a 20% compressed DM. The fuel cell
is operating at 80C on fully humidified cathode air flow at 1 atm pressure. The
uncompressed DM is 300 m thick with a porosity of 70%. Assume there is no flooding
on the catalyst layer or in the DM.
Soln:
Since for an unflooded electrode, the mass transfer limiting current density is linearly
proportional to the effective diffusivity, we simply have to calculate the change in the
effective diffusivity in this case to determine the change.
( )
( )
1
1
1
eff
|
|
o

Where :
t
t t
*
= o
=0.2 for 20% strain
So
( )
( )
( )
( )
( )
( )
1 1 1 0.7
1 =1 1 0.625
1 0.8 0.8
eff
| |
|
o

= = =

Assuming a Bruggeman correlation is appropriate and the tortuosity is the same, the
fractional gas-phase diffusivity change for the case of 10% strain is:
1.5
1.5
1.5 1.5
0.625
0.844
0.7
eff
compressed eff
eff
uncompressed
D D
D D
|
|
= = =

So the limiting current density would decrease by about 15% under the compression,
based solely on gas-phase transport.
2

6.2 Discuss the various methods of flow humidification and identify the strengths and
weaknesses of each approach.
Method Advantages Disadvantages
Sparging - active Simple for lab use. Easy
to purchase or build.
Too large and inefficient
for practical application in
systems.
Direct liquid injection
active
Precise metering of liquid
injected, based on
developed technology.
Requires a pump, an item
that can break.
Membrane humidifier
active
Developed technology, no
moving parts, reliable.
Impossible to control level
of humidification, large
volume, relatively
expensive.
Internal recirculation -
passive
Requires no parts, perfect
for portable applications,
only a reconfiguration of
the flow channel directions
to be counter current.
Can not achieve complete
humidification for extreme
conditions. Internal
humidity gradients are
harmful for long-term
performance.
Embedded particles Pt-
passive
This can also reduce
crossover losses
Additional Pt in system is
costly and can reduce
lifetime.

3

6.3 Do some reading and find out how the relative humidity of a flow of gas can be
measured in a fuel cell. Is there a robust, inexpensive sensor that is readily available?
Soln:
There are several different methods to measure humidity. Some are listed below. The
accurate measurement and calibration of a humidity gage is a difficult engineering
problem.
Method Physical principle Comments
Sling
Psychrometers
Measures the wet and dry bulb
temperature on two probes (one is
moist) to determine humidity. RH
can be found from the difference
in the temperatures and a
psychrometric chart.
Old versions required rotational
motion of the wet probe (thus the
name sling psychrometer. Some
new digital versions do not. Difficult
to insert into a flow stream, and
cannot handle droplets. Inconvenient
but accurate results.
Resistance
Hygrometer

Senses humidity by means of
sensors (usually a polymer
electrolyte membrane) whose
electrical resistance is affected by
moisture.
More convenient than
psychrometers, these cannot handle
liquid droplets on the gage. Difficult
cannot handle droplets.
Capacitance
Hygrometer
Senses humidity by means of
sensors whose electrical
capacitance is affected by
moisture.
More convenient than
psychrometers, these cannot handle
liquid droplets on the gage. Difficult
cannot handle droplets.
Chilled mirror
dewpoint
meters
Use chilled mirror and laser to
detect condensation on mirror.
Temperature of the mirror is
controlled to maintain equilibrium
between evaporation and
condensation on the mirror, and
the dewpoint temperature is
known.
The most precise instruments
available.
Other methods There are several other old and
new methods to attempt humidity
measurement that can be found.
Some new versions involve advanced
electronic approaches, some involve
calibrate hair curling
4

6.4 Calculate the net rate of water vapor uptake into an air cathode flow at the given
conditions for a 250-cm
2
fuel cell operating at 1.2 A/cm
2
. Compare the cathode uptake to
the water generation. What drying rate would the anode have to share to obtain a steady
state?
Cathode Condition Inlet Outlet
RH 0.5 1.0
Temperature 80
o
C 80
o
C
Pressure 3.2 atm 2.7 atm
Stoichiometry 2.0 -

Soln:
The water uptake:

Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 47.12
3.2 101.325
0.50 47.12
1
3.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .
=
Where the P
sat
values were calculated at 80
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.2 250
2.0
0.21 4 96485

=0.007403mol/s
, 2 ,
0.50 47.12
0.007403
3.2 101.325
0.50 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.00058 mol/s
4
,
1.2 250
15.55 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.2 250
1 0.003702
0.21 4 96485
mol
s
=

5

( )
( )
,
, 2 ,
,
1.0 47.12
0.003702
2.7 101.325
0.00077
1.0 47.12
1
1
2.7 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

Comparing the inlet and outlet water flow with generation in the cathode:
, 2 , , 2 , ,
0.00077 0.0058 0.001555 0.001365 mol /s
v H O out v H O in w gen
n n n = =
(negative if flooding)
This is the rate that the anode must pick up extra moisture to maintain a cell balance.

6.5 Derive Eq. (6.16), assuming a transient buildup or dryout of water can occur.
Soln:
We can start with Eq. 6.15:
( ) ( )
( ) ( )
O2 O2
, ,
O2,in,dry O2,in,dry
, ,
H2 H2
, ,
H2,in,dry H2,in,dry
,
, ,
1
4 4
1 1
1
2 2

1 1
out c in c
out c in c
out a in a
slugs out
out a in a
iA iA
F y y F
iA iA
F y y F
n

_ _
_ _

_ _
_ _
| | | | | |
| | |
| | |
\ . \ . \ .
+

| | | | | |
| | |
| | |
\ . \ . \ .
+

, , ,
2
a slugs out c
iA
n
F
+ =

If the stoichiometry is constant and, and we divide by iA/2F from each term:
( ) ( )
( ) ( )
, ,
O2 O2
O2,in,dry O2,in,dry
, ,
H2 H2
, ,
H2,in,dry H2,in,dry , , , ,
, ,
1
2 2
1 1
1
1
2 1 1
out c in c
out c in c
out a in a
slugs out a slugs out c
out a in a
y y
y y n n
iA F
_ _

_ _

_ _
_ _
| | | |

| |
| |
\ . \ .
+

| |
|
|
+ | |
\ .
+ =
|

\ .

Which is Eq. 6-16. Students may start earlier in the derivation to get to 6-15.
6

Instructors note: You may wish to inform students in 6.6 that it may be impossible
to balance on inlet RH alone here so they are not confused when this is what they
solve for.
6.6 For the fuel cell in problem 6.4, determine the inlet relative humidity that would
achieve a global balance, assuming all uptake occurs in the cathode and there are no
water slugs at this balanced condition. Can the fuel cell be balanced with a change in the
inlet RH alone? Assume zero net water drag.
Soln:
RH ? 1.0
Temperature 80
o
C 80
o
C
Stoichiometry 2.0 -

The water uptake:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
47.12
3.2 101.325
47.12
1
3.2 101.325
in
in
others
v H O in
in
RH
n
n
RH
| |
\ .
=
| |
\ .

Where the Psat values were calculated at 80
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.2 250
2.0
0.21 4 96485

=0.007403mol/s
, 2 ,
47.12
0.007403
3.2 101.325
47.12
1
3.2 101.325
in
v H O in
in
RH
n
RH
| |
\ .
=
| |
\ .
=
( )
, 2 ,
0.001076
1 0.145324
in
v H O in
in
RH
n
RH
=

4
,
1.2 250
15.55 10
2 96485
w gen
iA mol
n
nF s
= = =

7

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.2 250
1 0.003702
0.21 4 96485
mol
s
=

( )
( )
,
, 2 ,
,
1.0 47.12
0.003702
2.7 101.325
0.00077
1.0 47.12
1
1
2.7 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

Comparing the inlet and outlet water flow with generation in the cathode, assuming all
uptake is at the cathode and there must be a balance (and the net drag is zero):
( )
, 2 , , 2 , , , 2 ,
0.001076
0.00077 0.001555 0.001555
1 0.145324
in
v H O out v H O in w gen v H O in
in
RH
n n n n
RH
= + = + = +

Solving for RH
in
, we have a negative number..thus, the fuel cell cannot be balanced on
the inlet cathode RH alone in this problem!
8

6.7 For the fuel cell in problem 6.4, determine the exit temperature that would achieve a
global balance, assuming all uptake occurs in the cathode and there are no water slugs at
this balanced condition. If the exit temperature is not changed, what is the total volume of
liquid water that must exit a 100-fuel-cell stack in 1 h to maintain a balance at these
conditions?
Soln:
RH 0.5 1.0
Temperature 80
o
C ?
o
C
Stoichiometry 2.0 -

Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 47.12
3.2 101.325
0.50 47.12
1
3.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .
=
Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.2 250
2.0
0.21 4 96485

=0.007403mol/s
, 2 ,
0.50 47.12
0.007403
3.2 101.325
0.50 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.00058 mol/s
4
,
1.2 250
15.55 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.2 250
1 0.003702
0.21 4 96485
mol
s
=

9

( )
( )
( )
( )
, ,
, 2 ,
, ,
1.0
0.003702
2.7 101.325
1.0
1 1
2.7 101.325
out
out g sat out g sat out
others
t out
v H O out
t out
p T p T
n
p
n
p T p T
p
|
|
| | | |

| |
\ . \ .
= =
| | | |

| |
\ . \ .

( )
( )
,
, 2 , , 2 , ,
,
1.0
0.003702
2.7 101.325
0.00058 0.001555
1.0
1
2.7 101.325
g sat out
v H O out v H O in w gen
g sat out
p T
n n n
p T
| |
\ .
= + = +
| |
\ .

Solving for the P
g
and relating it to the temperature via Excel, you can show:
T
exit
=99.79
o
C at a balance
If the exit temperature is not changed, what is the total volume of liquid water that must
exit a 100-fuel-cell stack in 1 h to maintain a balance at these conditions?
Assuming all the uptake is at the cathode, and the net drag is zero, so the anode plays no
part in the water balance, we can solve for the net accumulation in the cathode if the exit
temperature is not changed.
If we do the same procedure at 80
o
C, we will see the following:
, 2 ,
1.0 47.12
0.003702
2.7 101.325
0.00077
1.0 47.12
1
2.7 101.325
v H O out
mol
n
s
| |
|
| |
\ .
= =
|
| |
\ .
\ .

The net balance then is:
4
, 2 , , , 2 ,
0.00058 15.55 10 0.00077 0.001365
v H O in w gen v H O out
mol
n n n
s
| |
+ = + =
|
\ .

Of accumulation (flooding). Note that if we took the anode into account, there would be
a different result.
In a 100 cell stack for 1 hour, we would end up with (after looking up density of liquid
water at 80
o
C):
3
3
min
0.001365 60 60 18 972 0.091
min
water
mol s kg kg
V m
s hr mol m
| | | | | | | | | |
= =
| | | | |
\ . \ . \ . \ . \ .

That is 91 liters of water, not an insignificant amount.
10

6.8 Calculate the net rate of water vapor uptake into an air cathode flow at the given
conditions for a 320 cm
2
fuel cell that is operating at 1.0 A/cm
2
. If the net transport
coefficient of water from the anode to the cathode is -0.2, calculate the net rate of water
storage in the fuel cell at this condition. What would happen over time to the fuel cell
performance and operating parameters in the accompanying table?
Cathode/Anode Condition Inlet Outlet
RH 0.5/1.0 1.0/1.0
Temperature 80
o
C 80
o
C
Pressure 3.2 /3.2 atm 2.6/2.8 atm
Stoichiometry 2.0/1.5 -

Soln:
Cathode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 47.12
3.2 101.325
0.50 47.12
1
3.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .
=
Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 320
2.0
0.21 4 96485

=0.007897mol/s
, 2 ,
0.50 47.12
0.007897
3.2 101.325
0.50 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.000619 mol/s
4
,
1.0 320
16.58 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.0 320
1 0.003948
0.21 4 96485
mol
s
=

11

( )
( )
,
, 2 ,
,
1.0 47.12
0.003948
2.6 101.325
0.00086
1.0 47.12
1
1
2.6 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

Anode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
1.0 47.12
3.2 101.325
1.0 47.12
1
3.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .

o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 320
1.5
2 96485
=0.002487mol/s
, 2 ,
1.0 47.12
0.002487
3.2 101.325
1.0 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.000423 mol/s
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 320
0.5 0.000829
2 96485
mol
s

( )
( )
,
, 2 ,
,
1.0 47.12
0.000829
2.8 101.325
0.000165
1.0 47.12
1
1
2.8 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

For the cathode, the balance is:
, , 2 , , 2 ,
0.2
0.001658 0.000619 0.00086 0.000754
drag w gen v H O in v H O out
I mol
n n n n
F s
| |
+ + = + + = +
|
\ .

of accumulation. Since it is positive it is flooding
For the anode, the balance is:
, 2 , , 2 ,
0.2
0.000423 0.000165 0.000921
drag v H O in v H O out
I mol
n n n
F s
| |
+ = + =
|
\ .

of accumulation
12

The net result for the cell is flooding at a total rate of:
0.001675 mol/s
Over time, on both the anode and cathode, water would accumulate until slugs are
formed, and blown out of the cell or begin to reduce performance. Instability of the
performance could also result. Essentially, the cell would flood, with all the ramifications
that come with flooding.
6.9 For the fuel cell in Problem 6.8, what exit temperature of the fuel cell would be
needed to achieve a water balance in this condition, assuming all other parameters remain
the same?
RH 0.5/1.0 1.0/1.0
Temperature 80
o
C ?
o
C

Soln:
Cathode:
From Problem 6.8:
, 2 ,
0.50 47.12
0.007897
3.2 101.325
0.50 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.000619 mol/s
4
,
1.0 320
16.58 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
( )
1.0 320
1 0.003948
0.21 4 96485
mol
s
=

13

( )
( )
,
, 2 ,
,
1.0 47.12
0.003948
2.6 101.325
0.00086
1.0 47.12
1
1
2.6 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

Anode:
, 2 ,
1.0 47.12
0.002487
3.2 101.325
1.0 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.000423 mol/s
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 320
0.5 0.000829
2 96485
mol
s

( )
( )
( )
( )
, ,
, 2 ,
, ,
1.0
0.000829
2.8 101.325
1.0
1 1
2.8 101.325
out
others
t out
v H O out
t out
p T p T
n
p
n
p T p T
p
|
|
| | | |

| |
\ . \ .
= =
| | | |

| |
\ . \ .

( )
( )
,
, , 2 , , 2 ,
,
1.0
0.003948
2.6101.325
0.2
0.001658 0.000619
1.0
1
2.6101.325
g sat out
c g sat out
p T
dn I
n n n n
dt F p T
| |
\ .
= + + = + +
| |
\ .

( )
( )
,
, 2 , , 2 ,
,
1.0
0.000829
2.8101.325
0.2
0.000423
1.0
1
2.8101.325
g sat out
a g sat out
p T
dn I
n n n
dt F p T
| |
\ .
= + = +
| |
\ .

( )
( )
( )
( )
, ,
, ,
1.0 1.0
0.003948 0.000829
2.6101.325 2.8101.325
0 0.001658 0.000619 0.000423
1.0 1.0
1 1
2.6101.325 2.8101.325
g sat out g sat out
a c g sat out g sat out
p T p T
dn dn
dt dt p T p T
| | | |

| |

\ . \ .
= = + +
| | | |

| |

\ . \ .

Solving, we find P
sat
=96,245 Pa and therefore T
exit
(on anode and cathode) 98.71
o
C =for
a balance.
14

Instructors Note: When solved, the cell will not balance on any RH of the anode
and cathode at an exit temperature of 80
o
C. Please assign the changes in red below.
6.10 For the fuel cell in Problem 6.8, can the inlet RH of the fuel cell be changed to
achieve a water balance in this condition, assuming all other parameters remain the same?

RH ?/? 1.0/1.0
Temperature 80
o
C 80
o
C
Soln:
Lets see if it will be dry at 0/0 RH on the anode and cathode:
Cathode:
From Problem 6.8:
, 2 ,
0.0 47.12
0.007897
3.2 101.325
0.50 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.0 mol/s
4
,
1.0 320
16.58 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
= ( )
1.0 320
1 0.003948
0.21 4 96485
mol
s
=

( )
( )
,
, 2 ,
,
1.0 47.12
0.003948
2.6 101.325
0.00086
1.0 47.12
1
1
2.6 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

15

Anode:
, 2 ,
0 47.12
0.002487
3.2 101.325
0 47.12
1
3.2 101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.0 mol/s
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 320
0.5 0.000829
2 96485
mol
s

( )
( )
,
, 2 ,
,
1.0 47.12
0.000829
2.8 101.325
0.000165
1.0 47.12
1
1
2.8 101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

, , 2 , , 2 ,
0.2
0.001658 0.0 0.00086
c
dn I
n n n n
dt F
= + + = + +

, 2 , , 2 ,
0.2
0.0 0.000165
a
dn I
n n n
dt F
= + = +

0.000165 0.001658 0.00086 0.00063
a c
dn dn mol
dt dt s
| |
+ = + =
|
\ .

So there is a net flooding situation here, even with zero inlet RH on both sides. In
practice, this cell would actually be a pretty poor performer, due to the drying at the inlet
more than the flooding at the exit. There would be a large gradient in moisture content
across the cell, leading to low overall performance and enhanced degradation. Having a
mild temperature gradient would be more helpful.
16

Instructors note: Please note the text changes in red below in Prob. 6.11:
6.11 For a 100-cm
2
fuel cell at 1 A/cm
2
operation, with a net drag coefficient of 0.1, and
the other conditions shown in the accompanying table, solve for the cathode
stoichiometry that must be used to achieve a water balance with no liquid water ejection
from the fuel cell.
RH 0.5/1.0 1.0/1.0
Temperature 65
o
C 70
o
C
Pressure 1.2 /1.1 atm 1/1 atm
Stoichiometry ?/1.2 -

Soln:
Cathode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 24.87
1.2 101.325
0.50 24.87
1
1.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .

Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 100
0.21 4 96485
c

4
,
1.0 100
5.18 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.0 100
1
0.21 4 96485
c

( )
( )
( )
,
, 2 ,
,
1.0 100 1.0 30.99
1
0.21 4 96485 1101.325
1.0 30.99
1
1
1101.325
out
out g sat out
others
c
t out
v H O out
out g sat out
t out
p T
n
p
n
p T
p
|
|
| |
| |
|
|

\ . \ .
= =
| | | |

|
|

\ .
\ .

17

Where the P
sat
o
C.
Anode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
1.0 24.87
1.1 101.325
1.0 24.87
1
1.1 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .

Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 100
1.2
2 96485
=0.0006218mol/s
, 2 ,
1.0 30.99
0.0006218
1101.325
1.0 30.99
1
1101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.0001786 mol/s
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 100
0.2 0.0001036
2 96485
mol
s

( )
( )
,
5
, 2 ,
,
1.0 30.99
0.0001036
1101.325
4.567 10
1.0 30.99
1
1
1101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|

| |
| |
|
|
\ . \ .
= = =
| | | |

|
|

\ .
\ .

Where the P
sat
o
C.
( )
4
, , 2 , , 2 ,
1.0100 0.50 24.87 1.0100 1.0 30.99
1
0.1 0.21 4 96485 1.2101.325 0.21 4 96485 1101.325
5.18 10
0.50 24.87 1.0 30.
1 1
1.2101.325
c c
c
dn I
n n n n
dt F

| | | |

| |

\ . \ .
= + + = + + +
| |

|
\ .

99
1101.325
| |
|
\ .

5
, 2 , , 2 ,
0.1
0.0001786 4.567 10
a
dn I
n n n
dt F
= + = +

18

( )
5 4
1.0100 0.50 24.87 1.0100 1.0 30.99
1
0.21 4 96485 1.2101.325 0.21 4 96485 1101.325
0 0.0001786 4.567 10 5.18 10
0.50 24.87 1.0 30.99
1 1
1.2101.325 1101.325
c c
a c
dn dn
dt dt

| | | |

| |

\ . \ .
= = + +
| | |

|

\ . \

|
|
.
Solving, we find
c
=2.96

Instructors note: See change in problem related to change in 6.11 below in red.
6.12 For the fuel cell in problem 6.11 and the conditions shown in the table for problem
6.11, solve for the cathode exit temperature that must be used to achieve a water balance
with no liquid water ejection from the fuel cell. What would happen to the net drag
coefficient if the anode humidity at the inlet were reduced? Assume
c
=2.5
RH 0.5/1.0 1.0/1.0
Temperature 65
o
C ?
o
C
Pressure 1.2 /1.1 atm 1/1 atm

Soln:
Cathode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 24.87
1.2 101.325
0.50 24.87
1
1.2 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .

Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 100
2.5 0.00308
0.21 4 96485
mol
s
| |
=
|

\ .

19

, 2 ,
0.50 24.87
1.2 101.325
0.00351
0.50 24.87
1
1.2 101.325
in
others
v H O in
n
mol
n
s
| |
|
| |
\ .
= =
|
| |
\ .
\ .

4
,
1.0 100
5.18 10
2 96485
w gen
iA mol
n
nF s
= = =

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=( )
1.0 100
2.5 1 0.00185
0.21 4 96485
mol
s
| |
=
|

\ .

( )
( )
( )
( )
, ,
, 2 ,
, ,
1.0
0.00185
1101.325
1.0
1 1
1101.325
out
others
t out
v H O out
t out
p T p T
n
p
n
p T p T
p
|
|
| | | |
| |
\ . \ .
= =
| | | |

| |
\ . \ .

Anode:
Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
1.0 24.87
1.1 101.325
1.0 24.87
1
1.1 101.325
in
others
v H O in
n
n
| |
\ .
=
| |
\ .

o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 100
1.2
2 96485
=0.0006218mol/s
, 2 ,
1.0 30.99
0.0006218
1101.325
1.0 30.99
1
1101.325
v H O in
n
| |
\ .
=
| |
\ .
=0.0001786 mol/s

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=

1.0 100
0.2 0.0001036
2 96485
mol
s
= =

20

( )
( )
( )
( )
, ,
, 2 ,
, ,
1.0
0.0001036
1101.325
1.0
1 1
1101.325
out
others
t out
v H O out
t out
p T p T
n
p
n
p T p T
p
|
|
| | | |

| |
\ . \ .
= =
| | | |

| |
\ . \ .

( )
( )
,
4
, , 2 , , 2 ,
,
1.0
0.00185
1101.325
0.1
5.18 10 0.00351
1.0
1
1101.325
g sat out
c g sat out
p T
dn I
n n n n
dt F p T
| |
|
\ .
= + + = + + +
| |
\ .

( )
( )
,
, 2 , , 2 ,
,
1.0
0.0001036
1101.325
0.1
0.0001786
1.0
1
1101.325
g sat out
a g sat out
p T
dn I
n n n
dt F p T
| |
\ .
= + = +
| |
\ .

( )
( )
( )
( )
, ,
4
, ,
1.0 1.0
0.00185 0.0001036
1101.325 1101.325
0 0.0001786 5.18 10 0.00351
1.0 1.0
1 1
1101.325 1101.325
g sat out g sat out
a c g sat out g sat out
p T p T
dn dn
dt dt p T p T
| | | |
| |

\ . \ .
= = + +
| | | |

| |

\ . \ .

Solving, we find P
sat
=35,379 Pa and therefore T
exit
(on anode and cathode) 73.09
o
C =for
a balance.
The net drag coefficient would decrease, and possibly become negative, if the anode
humidity at the inlet were reduced since the concentration gradient would pull water from
the cathode to the anode through the MEA.
21

6.13 The problem of unintentional crossover, or the bypass phenomenon, can be reduced
in several ways. A few ways we can design a flow channel with reduced crossover to an
adjacent channel include increased compression, decreased DM porosity, and increased
land width. Discuss the trade-offs associated with these approaches.
Method Advantages Disadvantages
Increased
compression
Will decrease in-plane
crossover, may decrease
contact resistance.
Entire stack dimensions
will decrease slightly
Decreases reactant flow to the catalyst
layer under the lands, can decrease
performance beyond the elastic limit for
compression of the materials, can cause
damage to the MEA.
Decreased
DM porosity
crossover without possible
over-compression or
damage. Reduces liquid
water storage during
operation in the DM
Decreases reactant flow to the catalyst
layer under the lands, reducing
unflooded performance.
Increased
land width
crossover without possible
over-compression or
damage.
Increased liquid water storage under
lands in operation, greater tendency to
flood in general, possible dead zones
under center of land where reactant does
not get to catalyst layer. Heavier stack.

22

Instructors note: Please see the added note and cross-outs in red below in 6.14
before assigning with modification.
6.14 At 0.2 A/cm
2
, a DMFC has a net drag coefficient of 4.0, no hydraulic permeation
effects, and an electro-osmotic drag coefficient of 3.0, calculate the water crossover and
equivalent power lost per day for a 10 M methanol solution DMFC at idle in the anode of
a 10-cell, 10-cm
2
/cell DMFC stack.
Soln:
From Eq. 6.51,
( )
3 ,
A
c a r
CH OH drag cap c a
C i
n DA A P
x F l
kk
A
= + A
A

And for the net drag:
,
2
net a c
H O d
iA
n
F
o
= =
, , ,
2 2 2 2 2 2
net a c drag diff perm gas perm cap temp
H O H O H O H O H O H O
n n n n n n
= + + + +

Then at 0.2 A/cm
2 c a
C
DA
x
A
=
iA
F
. Plugging in numbers we have:
c a
C
DA
x
A
=
0.2 10
10 0.000207 17.909
96,485
cells
watera c
watera c
mol mol
s day

| | | |
= =
| |
\ .
\ .

3
3
for comparison:
18 1000
17.909 0.323
998,000 1
watera c
mol g m L L
day mol g m day
| | | |
| | | |
=
| | | |
\ . \ .
\ . \ .

23

6.15 Determine the ideal net water drag transfer coefficient for a hydrogen fuel cell so
that external humidification is not needed. How would you design the electrode and
diffusion media structure to achieve this goal?
Soln:
From Eq. 6.30,
,
2
net a c
H O d
iA
n
F
o
=
Where the net drag coefficient represents the total transport of water to the cathode.
For a hydrogen fuel cell, the net water produced on the cathode is
2
2
H O
iA
n
F
=
So that if 0.5
d
o = , then all water produced on the cathode would be transported to the
anode, and there would be no need to balance water production on the cathode with flow,
the membrane would be moisturized. Note that there would still need to be water
removal from the anode, so that this would not eliminate water management concerns,
but it would keep the most moisture in the membrane at all times.
To achieve this goal, we could make the anode much dryer than the cathode to pull the
generated water to the anode. In terms of the electrodes and diffusion media structure, a
more hydrophilic structure on the anode, or a more water absorbing (lower EW) structure
on the anode compared to the cathode could be used to redistribute the produced water
toward the anode.
24

6.16 Determine the global anode oxidation and cathode reduction reactions for trioxane,
formaldehyde, and ethanol.
Soln:
For all of the alcohol based fuel cells, the cathodic reaction is the same as a hydrogen air
fuel cell, and the anode reaction is fuel +water electrons+protons+CO
2
. We just have
to balance out the numbers:
Trioxane:
Anode:
C
3
H
6
O
3
+3H
2
O 3CO
2
+12e
-
+12H
+

Cathode:
2H
+
+2e
-
+1/2O
2
H
2
O
Overall:
C
3
H
6
O
3
+3O
2
3CO
2
+3H
2
O

Formaldehyde:
Anode:
CH
2
O

+H
2
O CO
2
+4e
-
+4H
+

Cathode:
2H
+
+2e
-
+1/2O
2
H
2
O
Overall:
CH
2
O

+O
2
CO
2
+H
2
O

Ethanol:
Anode:
C
2
H
5
OH

+3H
2
O 2CO
2
+12e
-
+12H
+

Cathode:
25

2H
+
+2e
-
+1/2O
2
H
2
O
Overall:
C
2
H
5
OH

+3O
2
2CO
2
+3H
2
O

6.17 Would the best possible diffusion media used in the anode of the DMFC be
hydrophobic or hydrophilic? Why?
Soln:
In the anode of the DMFC, you need the liquid solution to reach the anode surface. In
general, a hydrophilic anode diffusion media is preferred. There must be some provision
for removal of the CO2 bubbles, in which case some hydrophobic pores would be useful,
but in general a hydrophilic DM will work better.
26

6.18 Consider a typical DMFC operating system. On the anode side, a 2 M solution of
methanol (2 mol of methanol per liter of solution) is circulated into the anode and then
pumped back into the fuel tank. Some of the methanol in the solution is being consumed
at the anode, and 100 mA/cm
2
equivalent is being consumed at the cathode via
crossover. The water generated at the cathode or transported to the cathode by
drag/diffusion is condensed and pumped back into the anode tank, along with all effluent
from the anode. Write a symbolic expression to solve for the required mass flow rate of
pure methanol back into the anode mix to maintain molarity of the mixture as constant.
(Hint: the water produced at the cathode is being added to the mixture, and some of the
methanol is being consumed, so the mixture will become more diluted with time unless a
stream of pure methanol is added to balance the mass loss.)
Anode
Cathode
Water, Methanol in
Dry air in
Water, Methanol out
Moist air out
Condenser and pump
All water in + generated + left over methanol back to anode
Dry air to ambient
Pure
MEOH
?
3
=
OH CH
m

Soln:
This problem is essentially a conservation of mass on water and methanol. Lets take a
look at the methanol in the flow stream, in terms of conservation of molar rate of change
in the methanol stored in the fuel flow.
3
injected
CH OH rxn x over
dn iA iA
n
dt nF nF

= +
Where we seek to find
injected
m , which is
3 injected CH OH
n MW
This would simply be the consumption of the methanol if the product water was not
being added to the mixture. Since this added water is going in, we will have to add in
more methanol to keep the molarity constant. This also means the total volume of the fuel
mixture will be continually increasing. We are not considering the ramifications of that
here, but practically, there would have to be a periodic dumping of the mixture. The
molar water generation rate is:
27

2
2
H O rxn
dn iA iA
dt nF F
= =
Note we are assuming all the moisture is recovered into the liquid phase and pumped
back to the anode flow. Some will likely go out of the cathode in the vapor phase. We
are also assuming complete reaction of the CH3OH that crosses over to the cathode,
which is a reasonable assumption for low levels of crossover.
To keep the same molarity, we need to keep the same molar ratio, so:
2
3
1=constant
H O
CH OH
dn
dt
dn
dt
=
or
3
2
1
injected
CH OH rxn x over
H O rxn
dn iA iA
n
dt nF nF
dn iA
dt nF
+
= =

, 2 , 3
injected
rxn H O rxn CH OH x over
iA iA iA
n
nF nF nF

= + + =
, 2 , 3
0.1
2 6 6
rxn H O rxn CH OH x over
iA iA A
F F F

+ +
2 0.1
3 6
injected
iA A
n
F F
= +
This can be rearranged a bit more. The crossover is assumed to be independent of
current.

Instructors Note: Change the second bullet point in 6.19 to counter-current flow, as
seen below in red.
6.19 For an isothermal neat hydrogen fuel cell at moderate current density with adequate
cathode flow stoichiometry, sketch the current distribution from inlet to exit for the
following cases:
- 50% RH inlet anode, 50% RH inlet cathode, concurrent flow
- 50% RH inlet cathode, 50% RH inlet anode, counter-concurrent flow
28

Soln:
In the first case, the actual flow in the anode is higher than in the cathode, even if they
have the same stiochiometry, due to the dilution from air as the assumed oxidant carrier.
This we expect the current density to follow the moisture content in the anode, and
increase from the beginning of the cell, to a point where they may (or may not) be
flooding depending on the operating conditions. See Example 6.7

Distance from Inlet
C
u
r
r
e
n
t

D
e
n
s
i
t
y
Possible flooding

Cathode
Anode

In the second case, it is merely the reverse of the first and the current should look the
same. In later printings of the book, the intended problem of counter-current flow is
included:
50% RH inlet cathode, 50% RH inlet anode, counter-concurrent flow
Distance from Inlet
C
u
r
r
e
n
t

D
e
n
s
i
t
y

Anode
Cathode

29

In this case, the flow on both sides is dry, but the cathode is more dry due to the higher
flow rate, even at the same RH. Therefore the performance increased toward the middle
where the moisturization of both sides is maximum. The location of the peak is difficult
to know without more data as it depends on the flow rate in the cathode and the water
generation rate, which will work to move the peak in opposite directions toward the ends.

6.20 Determine the relationship between the required water at the anode (water
stoichiometry) and the fuel stoichiometry for a dimethyl ether (DME) fuel cell in
symbols. What are the consequences on performance of so much water required at the
anode inlet? What can be done to engineer this situation?
Soln:
DME undergoes the following global anode oxidation and cathode reduction reactions:
(CH
3
)
2
O + 3H
2
O 2CO
2
+ 12H
+
+ 12e
-
Anode
12H
+
+ 12e
-
+ 3O
2
6H
2
O Cathode
The anode DME stoichiometry can therefore be shown as:
DME
12
DME
Fn
iA
=

where i is the current density and A is the superficial electrode area. Since water is also a
reactant, we can define a water anode stoichiometry as well:
2
H2O
4
H O
Fn
iA
=

Considering an anode DME and water vapor flow mixture, the water stoichiometry is
related to the DME stoichiometry through thermodynamics of psychrometric mixtures:

, , H2O, del
H2O
H2O, req
1 1
1 12 1

3
4
Rx
dme dme
t a sat t a sat
Rx
iA
P P RH F P P RH n
iA
n
F

( (
( (

= = =

where RH is the relative humidity of the anode gas mixture, P
t,a
is the anode inlet total
pressure, and P
sat
is the thermodynamic saturation pressure of the mixture. A plot of the
relationship between DME and water stoichiometry is shown in the figure below:
30

DME Stoichiometry
0 5 10 15 20
W
a
t
e
r

S
t
o
i
c
h
i
o
m
e
t
r
y
0
2
4
6
8
10
3 atm, 80
o
C
3 atm, 100
o
C
1.7 atm, 80
o
C
1.7 atm, 100
o
C
1 atm, 80
o
C
1 atm, 100
o
C

Plot of DME fuel cell inlet stoichiometry versus fuel cell inlet water stoichiometry as a
function of operating pressure and temperature, assuming fully humidified anode inlet
flow.

What are the consequences on performance of so much water required at the anode inlet?
With no net drag of water to the anode, the operating temperature and RH must be very
high, which will restrict the DME mole fraction and limit the anode performance via
mass limitations.
What can be done to engineer this situation?
The system could be engineered to have a net water flux toward the anode, by
engineering the operating conditions (dryer anode vs cathode) or the materials (more and
hygroscopic anode (lower EW) and hydrophilic diffusion media to store and hold water.

31

6.21 Assume a 100-cm
2
fuel cell anode exit at 100% RH,
a
= 1.5 at 1 A/cm
2
and a
cathode exit of 80%,
c
= 2.5 at 1 A/cm
2
, 363 K, 1 atm back pressure throughout. What
is the total combined relative humidity of the exit flow? That is, if the anode and cathode
exit flow were mixed, what is the resulting RH? This concept of total humidity can be
useful when evaluating the expected performance and flooding criteria. That is, if total
RH >100%, then some liquid buildup and slug ejection will occur.
Soln:
Lets consider the flow to be mixed:
( )
,
v
g sat
y P
RH
P T
= and
, 1 , 2
, 1 , 1
v flow v flow
v
v
total total f total f
n n
n
y
n n n
+
= =
+

The temperature is 363 K (90
o
C), P
sat
=69.971 kPa from correlation in book solved. P=1
atm throughout.
On the cathode:
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 100
1.5 0.001851
0.21 4 96485
mol
s
=

( )
( )
,
, 2 ,
,
0.8 69.971
0.001851
1101.325
0.002285
0.8 69.971
1
1
1101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
| |
\ . \ .
= = =
|
| | | | \ .
|
|

\ .
\ .

On the anode:
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
=
1.0 100
0.5 0.000259
2 96485
mol
s

( )
( )
,
, 2 ,
,
1.0 69.971
0.000259
1101.325
0.000578
1.0 69.971
1
1
1101.325
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
mol
n
s p T
p
|
|
| |
| |
|
|
| |
\ . \ .
= = =
|
| | | | \ .
|
|

\ .
\ .

Now lets mix them, we expect a RH somewhere between the 80% at the cathode and
100% at the anode, but biased toward the cathode, since the overall flowrate there is so
much higher:
32

, 1 , 2
, 1 , 1
0.002285 0.000578
0.5757
0.002285 0.001851 0.000578 0.000259
v flow v flow
v
v
total total f total f
n n
n
y
n n n
+
+
= = = =
+ + + +

Plugging in:
( )
,
0.5757 101.325
0.834
69.971
v
g sat
y P
RH
P T
= = =
So the answer is in the range we expect. Note the dominance of the cathode flow in
controlling the overall mixed humidity of the flow. The cathode flow is diluted via air,
and usually has a higher stoichiometry to account for this.

6.22 Calculate the percent change in effective diffusivity for a gas flowing through an
uncompressed DM and a DM compressed to 10 and 20% strain, assuming the tortuosity
remains the same.
Soln:
From Error! Reference source not found., we see a normal uncompressed porosity is
around 0.8. Then, assuming the compressed strain is 10-20% on the DM, we can
calculate from Eq. [6-1]:
( )
( )
1
1
1
eff
|
|
o

Where :
t
t t
*
= o =0.1 or 0.2 for 10 and 20% strain, respectively

So
( )
( )
( )
( )
( )
( )
1 1 1
1 1 = or 1
1 0.9 0.8
eff
| | |
|
o

= =
for 10 and 20% strain, respectively.

Assuming a Bruggeman correlation is appropriate and the tortuosity is the same, the
fractional gas-phase diffusivity change for the case of 10% strain is:
33

( )
( )
1.5
1.5
1
1
0.9
eff
compressed
eff
uncompressed
D
D
|
|
| |
|
\ .
=
Which for an average DM with 80% porosity =0.958. A decrease in about 4%.
For 20% strain:
( )
( )
1.5
1.5
1
1
0.8
eff
compressed
eff
uncompressed
D
D
|
|
| |
|
\ .
=

Which for an average DM with 80% porosity =0.907. A decrease in about 9%.
The plot below is a general solution for a wide range of initial porosities:
0
0.2
0.4
0.6
0.8
1
1.2
0.5 0.6 0.7 0.8 0.9 1
C
o
m
p
r
e
s
s
e
d
t
o
U
n
c
o
m
p
r
e
s
s
e
d
D
i
f
f
u
s
i
v
i
t
y
R
a
t
i
o
InitialPorosity
20%strain
10%strain

34

20%stain 10%strain
initialporosity Percentagechange
0.9 0.958624039 0.981538756
0.89 0.954011579 0.979471633
0.88 0.949301966 0.977359034
0.87 0.944492132 0.975199443
0.86 0.93957888 0.972991278
0.85 0.934558875 0.970732885
0.84 0.929428641 0.968422534
0.83 0.924184553 0.966058414
0.82 0.918822825 0.963638631
0.81 0.913339507 0.961161199
0.8 0.907730472 0.958624039
0.79 0.901991407 0.956024969
0.78 0.896117804 0.9533617
0.77 0.890104948 0.950631831
0.76 0.883947907 0.947832838
0.75 0.877641515 0.944962068
0.74 0.871180367 0.942016733
0.73 0.864558796 0.938993898
0.72 0.857770864 0.935890471
0.71 0.850810343 0.932703197
0.7 0.843670699 0.929428641
0.69 0.836345074 0.92606318
0.68 0.828826268 0.922602989
0.67 0.821106712 0.919044024
0.66 0.813178455 0.91538201
0.65 0.805033133 0.911612423
0.64 0.796661947 0.907730472
0.63 0.788055635 0.903731075
0.62 0.779204444 0.899608846
0.61 0.7700981 0.89535806
0.6 0.760725774 0.890972638

6.23 What is the effect of reactant dilution on water vapor uptake? That is, will a 50%
mixture of hydrogen and nitrogen at the anode pick up more, less, or the same moisture
as a pure hydrogen feed?
Soln:
The water uptake is a function of the saturation pressure, which is a unique function of
temperature only. The particular gas that water is evaporating into or condensing from
has no effect. Many people think that the vapor pressure of a substance is measured into
air, and therefore the ambient gas may have an effect, but the saturation pressure is an
equilibrium of phases of a substance, so that the other gas-phases present, if non-reacting,
have no effect.
Instructors Note: See clarification in red in prob 6.24
6.24 Compare hydraulic permeability to drag and diffusion in a polymer electrolyte.
Under what cases would each mode dominate water transport?
Soln:
Mode of transport Cases where mode would dominate
Hydraulic permeability Large pressure difference between
anode and cathode side and low current
35

.
2 ,
cap c a
r
H O cathode
P
kk
n
l

A
=

Electro-osmotic drag
F
iA
n n
d O H
=
2

High current with fully humidified flow
Diffusion
2
2 2
H O
H O h O NF
C
n D A
x
c
=
c

Large difference in flow humidity
values between anode and cathode

Instructors Note: See clarification in red in prob 6.25
6.25 For a direct methanol anode reaction, 1 mol of water is reacted per mole of
methanol. Determine the molarity of a 1 : 1 molar ratio DMFC solution at room
temperature. This is the desired design molarity of the solution at the anode electrode.
Soln:
CH
3
OH+H
2
OCO
2
+6e
-
+6H
+
Molarity of a solution is defined to be the number of moles of solute divided by the
number of liters of solution. =Moles per liter of solvent (moles Methanol per Liter of
Water)
3
2 3
1
CH OH
H O CH OH
moles
M
L
+
=

1 mole of methanol, MW, Methanol (CH
3
OH =32 g/mol) 1000 L =1 m
3
, =790 kg/m
3

36

3
5 3
3
32
1 4.05063 10 0.0405
790,000
CH OH
g
mole
mole m L
g
m
= = =

1 mole of water, MW =18 g/mol), =990 kg/m
3
(from tables at ~room temp)
2
3
18
1 0.01804
998,000
H O
g
mole
mole L
g
m
= =

So the ratio of these has to be 1:1 until there is 1 L of solution, or:
0.0405 0.01804 1
0.05854 1
17.08
a a
a
a
+ =
=
=

So a perfectly balanced inlet molar concentration would be a 17.08M solution.
Comment: If there was any net drag to or from the anode of water, this would change the
ideal inlet concentration.
Open-Ended Problem
6.26 Can you think of a way to actually monitor the solution molarity? That is, is there a
way to make some sort of gauge to measure the molarity of a methanol solution? How
would you do this in practice? (Hint: There are several ways to achieve this, think of
what property variation there would be between different molarity solutions.)
Soln:
There are several ways to achieve this, some have been developed and patented for
DMFC applications. The table below lists some of the ways and principles of operation.
In general, when developing a sensor, you look for some physical parameter that changes
as a result of what you are measuring and exploit this. The list below is non-exhaustive.

Gage Type Physical Principle
Density The density of a MEOH-Water mixture
37

changes with molarity, thus a density gage
(there are many ways to do this) can be
used
Electrochemical The open circuit voltage of a fuel cell will
change with the solution molarity. A very
small anode/air cathode fuel cell can be
used and the OCV monitored. Once
calibrated, the OCV can be used as a
measure of the molarity
Vapor pressure The total vapor pressure of the
methanol/water mixture will change with
temperature and molarity

38

Computer Problems
6.27 Program the gas-phase water balance for a H2 PEFC in Excel or other computer
language or workbook software you are comfortable with. Assume the net drag to the
cathode is zero (i.e., electro-osmotic drag = diffusion and hydraulic drag is zero). Is this
cell flooding or drying? Hint:This zero-net drag assumption is generally valid (globally,
at least) for thin membranes and means that all water generated must be removed by the
cathode flow, that is, you can ignore the anode here. Complete the following:
(a) Calculate the mass flow rate of water into an air cathode at RH = 50%, 80C, 3.2 atm
pressure, and stoichiometry of 2.6 at 1 A/cm
2
for a 100-cm
2
cell. Check your computed
solution with a hand calculation.

Inlet
( )
( )
,
, 2 ,
,
1
in
in g sat in
others
t in
v H O in
in g sat in
t in
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
, 2 ,
0.50 47.12
324.240
0.50 47.1
1
324.245
in
others
v H O in
n
n
| |
|
\ .
=
| |
|
\ .

Where the P
sat
o
C.
nF y
iA
n
in others
dry in, reactant,
in reactant,
= =
1.0 100
2.6
0.21 4 96485

=0.003208 mol/s
, 2 ,
0.50 47.12
0.003208
324.240
0.50 47.1
1
324.245
v H O in
n
| |
|
\ .
=
| |
|
\ .
=0.000251 mol/s
(b) Calculate the mass flow rate of water out of the same air cathode at RH = 100%,
80C, 3.1 atm exit pressure. Check your computed solution with a hand calculation.
o
C.

( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
= =
( )
( )
,
, 2 ,
,
1
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
39

1.0 100
1.6
0.21 4 96485

=0.001974 mol/s
, 2 ,
1 47.12
0.001974
314.107
1 47.12
1
314.107
v H O out
n
| |
|
\ .
=
| |
|
\ .
=0.000348 mole/s
(c) One way to balance the water in the cell is to use the heat generated by the cell to
tailor the cooling channels and provide a desired outlet temperature. Calculate the exit
temperature of the cathode required to balance the water with this cell, assuming the exit
RH is 1.
o
C.
Assume: All the water transport is in the cathode flow only.
P
sat
values from Appendix A-10
4
,
100
5.18215 10
2 96485
w gen
iA mol
n
nF s
= = =

The vapor uptake at the exit must match the generated flow +the inlet flow, taking into
consideration the consumed oxygen:
( )
( )
,
, 2 ,
,
1
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
=
( )
( )
( )
( )
( )
6
1
0.001974
3.1101.325 8.11 10
1 0.00658 1
1
3.1101.325
sat
sat
sat sat
P T
P T
mol
P T s P T
| |
|

\ .
=
| |
\ .

Balancing,
( )
( )
6
6.28 10
1 0.00318
sat
sat
P T
mol
P T s

Arranging a little:
We can solve for Psat and then determine the appropriate temperature by interpolation (or
by using a Goal seek function in an Excel Program)
I get: 96.2
o
C (students will get slightly different answers using the equations for P
sat
in
Ch 3 and Appendix. This is too large a temperature gradient for a stack, in general. A
40

better approach might be to reduce the inlet RH from 50%, induce some flow through the
anode (which we are neglecting here), or increase the flow rate a bit.
(d) Another way to balance the water in the cell is to tailor the exit pressure of the cell.
Calculate the exit pressure required to balance the water with this cell, assuming the exit
RH is 1. If this is not possible with the given cathode stoichiometry, what cathode
stoichiometry will get the job done?
Not possible with pressure dropeven a 1 Pa exit is still flooded.
Assuming the exit is 3.1 atm, 80
o
C
4
,
100
5.18215 10
2 96485
w gen
iA mol
n
nF s
= = =

, 2 ,
0.50 47.12
0.003208
324.240
0.50 47.1
1
324.245
v H O in
n
| |
|
\ .
=
| |
|
\ .
=0.00251 mol/s
4
, , , 2 ,
5.18215 10 0.00251
w out w gen v H O in
mol mol
n n n
s s
= + = +

The vapor uptake at the exit must match the generated flow +the inlet flow, taking into
consideration the consumed oxygen:
( )
, reactant,in
reactant,in,dry
1
others out
iA
n
y nF
=
( )
100
1 0.001233 0.0011233
0.21 4 96485
c c
mol
s
=

( )
( )
,
, 2 ,
,
1
out
out g sat out
others
t out
v H O out
out g sat out
t out
p T
n
p
n
p T
p
|
|
| |
|
\ .
=
| |
|
\ .
( )
4
, , , 2 ,
1 47.17
0.001233 0.0011233
3.1101.325
5.18215 10 0.00251
1 47.17
1
3.1101.325
c
w out w gen v H O in
mol mol
n n n
s s
| |

|
\ .
= = + = +
| |
\ .

Solving, we have to have a cathode stoich of 6.08, and the water is balanced.
41

(e) Another way to balance the water is to tailor the inlet RH. Calculate the inlet RH
required to balance the water with this cell, assuming the exit RH is 1. If this is not
possible with the given cathode stoichiometry, what cathode stoichiometry will get the
job done?
Going back to the cathode stoich of 2.6 and our computer program or analytical approach
above, the inlet RH would be below zero, which is not feasible. In this operating
condition, the reduction of the inlet RH to zero is not enough, and something else (e.g. a
temperature gradient or flow rate increase) must be applied.
Instructors note: See the change below in problem 6.28.
6.28 Expand your program in Problem 6.27 to include a net drag coefficient and the
effects of anode flow. For the same cathode conditions as problem 6.27, (a) and (b),
determine the anode/cathode (assume they are the same) exit temperature needed to
balance the water generated. The flow of humidified hydrogen into the anode is at
RH=100%, 80C, 3.2 atm pressure, and stoichiometry 1.5 at 1 A/cm
2
for a 100-cm
2
cell.
The anode flow leaves at 3.1 atm and 100% RH at the chosen exit temperature. Plot the
required exit temperatures of the anode and cathode as a function of net drag coefficient.
Soln:
This problem is solved with my computer program that calculates all of the above.
Similarly to other problems solved in this chapter, if the anode and cathode exit
temperature are the same, the value of 97.8
o
C will balance the entire cell. If the anode
and cathode temperatures can be maintained differently, then a separate exit temperature
spread for each net drag coefficient can be found. The anode exit temperature
requirement will increase, and the cathode exit temperature will decrease, with
decreasing net drag coefficient.

Instructors note: Note the change in wording in red below.
6.29 Apply the program developed in Problem 6.27 to a direct methanol fuel cell. There
will be no uptake by the anode, and the cathode must remove all water to prevent
flooding. The flow of a 5 M methanol solution into the anode is at 60C, 1 atm pressure,
and stoichiometry 1.5 at 0.2 A/cm
2
for a 100-cm
2
cell. The anode flow leaves at 1 atm.
The cathode flow enters at 0% RH and leaves at 100% RH. The cathode flow enters at
1.2 atm and leaves at 1 atm.
42

(a) Plot Determine the required cathode flowrate stoichiometry at 60C to avoid slug
formation in the cathode for a net drag coefficient of 3.0.
Soln:
For this you could use the hydrogen fuel cell program and just calculate on the cathode,
like we did in Problem 6.27. The solution is the same. Here though, we need to remove
3iA/F of water with just the cathode flow due to the high net drag:
At 60
o
C, we have to have a cathode stoich of 2.72 for the water to be balanced.
(b) Plot Determine the required cathode flowrate stoichiometry at 80C to avoid slug
formation in the cathode for a net drag coefficient of 3.0.
o
C, we have to have a cathode stoich of 1.49, and the
water is balanced.
(c) Plot Determine the required cathode flowrate stoichiometry at 90C to avoid slug
formation in the cathode as a function of net drag coefficient.
o
C, we have to have a cathode stoich of 1.19, and the
water is balanced. This is likely not enough to satisfy the mass transport requirements.
Thus, even with a DMFC with a liquid anode and high net transport to the cathode, at this
high temperature, the membrane will be dry due to the high temperature flow at the
cathode.

Chapter6 Solutions

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter6 Solutions

Uploaded by

Copyright:

Available Formats

1

= o =0.1 or 0.2 for 10 and 20% strain, respectively

for 10 and 20% strain, respectively.

You might also like