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Solution Manual for Fuel Cell Fundamentals 3rd Edition by Ryan

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Book Title: Fuel Cell Fundamentals

Edition: 3rd Edition

Author: Ryan Ohayre

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 Fuel Cell Fundamentals
Solutions

Meagan Papac
Timothy P. Holme
Ryan O’Hayre
Suk Won Cha
Whitney Colella
Fritz B. Prinz

Solution companion to Fuel Cell Fundamentals, third edition.

Suggested grading schemes are given after the problem numbers.

1
Chapter 1 Solutions
Problem 1.1 (10 points) Possible answers include:
FC advantages over other power conversion devices:

1. Potentially higher efficiency.

2. Solid state components have no moving parts, giving higher reliability

and lower maintenance costs.

3. Silent operation.

4. Low emissions.

5. Fuel cells refuel rather than recharge, which could be faster.

Disadvantages:

1. Cost.

2. Low power density.

3. Problems of hydrogen storage, production, and transport.

4. Lower energy density for non-hydrogen fuels.

5. Temperature problems: PEMs can’t start in the cold, high tempera-

tures of SOFCs create materials, thermal cycling, and sealing
problems.

6. Water management issues in PEMs.

Applications:

1. Portable applications (such as laptops, cell phones, etc.) where their

fast refueling, silent operation, and independent scaling of fuel reser-
voir and power make fuel cells an attractive option.

2. Transportation applications where their low emissions and high effi-

ciency make fuel cells an attractive option.

3. Power generation applications where their silent operation, low emis-

sions, and high efficiency make fuel cells amenable to siting in cities for
distributed generation (DG) applications, reducing the cost of power
distribution and possibly making process heat available for combined
heating and power applications.

2
 Problem 1.2 (5 points) Fuel cells have lower power density than en-
gines or batteries, but can have large fuel reservoirs, so they are much better
suited to the high capacity/long runtime applications.

Problem 1.3 (10 points) You can easily tell which reactions are re-
duction and which are oxidation by finding which side of the reaction the
electrons appear on.
1. Cu → Cu2+ + 2e− Electrons are liberated, so this is an Oxidation
reaction.
2. 2H+ + 2e− → H2 Reduction
3. O2− → 12 O2 + 2e− Oxidation
4. CH4 + 4O2− → CO2 + 2H2 O + 8e− Oxidation
5. O2− + CO → CO2 + 2e− Oxidation
6. 2 O2
1
+ H2 O + 2e− → 2(OH)− Reduction
7. H2 + 2(OH)− → 2H2 O + 2e− Oxidation

Problem 1.4 (15 points) You can write full-cell reactions and then
split them into the half-cell reactions. You don’t need to be an expert chemist
to do this, just use the half-cell reactions given and make sure your equa-
tions balance with species number (e.g., that O is conserved) and charge
(e.g., electrons are conserved).
1. CO + 12 O2 → CO2 is a full-cell reaction common in SOFCs; the half-
cell reactions would be O2− + CO → CO2 + 2e− , which is an oxidation,
or anode, reaction, and 12 O2 + 2e− → O2− , which is a reduction, or
cathode reaction.
2. 2 O2 + H 2
1
→ H2 O is a full-cell reaction in SOFCs or PEMs, depending
on the circulating ion (O 2− or H+ , respectively). The half-cell reac-
tions would be: 12 O2 + 2e− + 2O+ → H2 O at the cathode of a PEM
and H2 → 2H+ + 2e− at the anode of a PEM; or 12 O2 + 2e− → O2−
at the cathode of an SOFC and O 2− + H2 → H2 O at the anode of
an SOFC.
3. Another full-cell reaction in an SOFC could be CH 4 + 2O2 → CO2 +
2H2 O with the half-cell reactions 8e − + 2O2 → 4O2− as the reducing,
or cathode reaction, and CH4 + 4O2− → CO2 + 2H2 O + 8e− as the
oxidizing, or anode reaction.

3
 4. To use the circulating ion (OH) − , you may construct the full-cell re-
action 12 O2 + H2 + H2 O → 2H2 O from the half-cell reactions H 2 +
2(OH)− → 2H2 O + 2e− as the oxidizing, or anode reaction, and
2 O2 + H2 O + 2e → 2(OH) as the cathode (reducing) reaction.
1 − −

Problem 1.5 (10 points) From Figure 1.7, H2 (l) has a higher volu-
metric energy density but lower gravimetric energy density than H 2 (g) at
7500 PSI. On a big bus, the gravimetric energy density is probably a greater
concern, so choose H2 (g). Other considerations that could affect the choice
include safety, the amount of hydrogen lost to boil-off, and the cost of liq-
uefaction versus compression.

Problem 1.6 (5 points)

1. Reactant transport–at high current density, there is a depletion effect.

Reactants cannot reach active sites quickly enough. The voltage loss
results from a lower concentration of reactants.(ηconc )

2. Electrochemical reaction–voltage loss from the sluggishness of the elec-

trochemical reaction (ηact )

3. Ionic conduction–resistance to ion flow in the electrolyte (ηohmic )

4. Product removal–in a PEM, water flooding blocks active reaction sites

(ηconc )

Problem 1.7 (20 points) First, we multiply the whole reaction by 2

because you cannot formally describe a bond in 12 O2 . We will later divide
by 2 at the end to find the energy of the reaction given. For the reaction
2H2 + O2 → 2H2 O, we form 2 O-H bonds in H2 O, so
E2∗H2 O = −2 ∗ 2 ∗ EO-H = −4 ∗ 460 kJ/mol
EO2 = + 494 kJ/mol
E2H2 = + 2 ∗ 432 kJ/mol
The energy released by the reaction is
1 1
(E2∗H2 O + EO2 + E2H2 ) = (−4 ∗ 460 + 494 + 2 ∗ 432) = −241 kJ/mol
2 2

The energy is negative because an energy input to the system is required to

break bonds.

4
 Problem 1.8 (20 points) You can see the benefits of the independent
scaling of the fuel reservoir and the fuel cell stack. For this problem, you
may compute the volume of the stack and the reservoir independently.
For the stack, you need to supply 30 kW with a fuel cell that supplies
power at 1 kW/L and 500 W/kg. Therefore, the volume needed is 30 kW ∗
1 kg
1 kW = 30 L and the weight is 30 kW ∗ 500 W = 60 kg.
1 L

For the fuel tank, you need to hold a quantity of fuel equal to
1 hr 3600 s
30 kJ/s ∗ ∗ ∗ 300 miles = 540 MJ
60 miles 1 hr
Note that 1 W = 1 J/s. Taking into account the 40% efficiency, you need
to hold an excess quantity of fuel, 540 MJ/0.40 = 1350 MJ. The hydrogen
is compressed to supply 4 MJ/L and 8 MJ/kg, so the fuel tank must be
1350 MJ ∗ 41MJL
= 337.5 L and 1350 MJ ∗ 81 MJ
kg
= 168.75 kg.
The entire system must occupy a volume Vsystem = Vtank + Vcell =
337.5 L + 30 L = 367.5 L and weighs Wsystem = Wtank + Wcell = 168.75 kg+
60 kg = 228.75 kg

Problem 1.9 (5 points) P = V I. See the figure.

Figure 1: Sketch of Voltage and Power as a function of current density for

the fuel cell described in problem 1.9.

5
 Problem 1.10 (20 points) Since the container can hold 900 L of H 2 in
the form of MH (i.e., LiH), we have a lot of H 2 stored in a relatively small
volume. Let’s convert 900 L to moles. H 2 density is 0.089 Lg .

0.089 g H2 1 mol H2
900 L ∗ ∗ = 40.05 mol H2
L 2g
We know that if H2 reacts to form water, a total energy of 244 kJ
mol can
be released. (Not all will be used by our fuel cell.)

244 kJ
40.05 mol ∗ = 9777.2 kJ in 900 L H2
mol
Next we convert kJ to Wh: [W ] = J
s ⇒ [W h] = [ Js ∗h] or [W h] = 3.6 [kJ]

1 Wh
9777.2 kJ ∗ = 2715.89 Wh
3.6 kJ
Energy
For volumetric energy density: V olume
 2
9
Vcontainer = π(r) (L) ⇒ π
2
(42.5) = 2703.73 cm3 or 2.7 L
2
2715.89 kWh kWh kWh
Energy Density = ≈1 or ≈ 0.92
2.7 L L L
Answer D

6
Chapter 2 Solutions
Problem 2.1 (6 points) When a gas undergoes a volume constriction,
possible configurations of the gas are removed. Entropy is a measure of
disorder—that is, the number of possible configurations a system can
assume—so the entropy of a gas in a smaller volume is lower (given that
the temperature of the gas remains constant—entropy is also a function of
temperature). Therefore, the entropy change is negative.

Problem 2.2 (6 points) G = H − T S, so for an isothermal reaction

(ΔT = 0), ΔG = ΔH − T ΔS.
(a) if ΔH < 0 and ΔS > 0, then ΔG < 0 and the reaction is
spontaneous.
(b) in this case, you cannot determine the sign of ΔG unless you are
given the temperature and the size of the changes in entropy and enthalpy.
(c) ΔH > 0 and ΔS < 0, so in this case, ΔG > 0 and the reaction is
non-spontaneous.
(d) again, you cannot make a determination from the information given.

Problem 2.3 (6 points) The reaction rate is determined by the acti-

vation barrier, and not by the overall energy change of the reaction. You
cannot determine which reaction proceeds faster.

Problem 2.4 (6 points) While the current scales with the amount of
reactants, the voltage does not. The thermodynamic potential comes from
the energy drop going from products to reactants, which does not scale with
reactant amount. Since E = −ΔG/nF , you can think of the scaling in n
cancelling the scaling in ΔG.

Problem 2.5 (6 points) The Nernst equation

RT Πaνprod
i

E = ET − ln
nF Πaνreact
i

shows that increasing the activity of the reactants decreases the argument
of the ln, which raises the reversible cell voltage (E) because the ln term is
negative. This, in essence, is Le’Chatlier’s principle.

Problem 2.6 (Not graded) When the reaction is in equilibrium, the

electrochemical potential of the system is everywhere zero. The electro-
chemical potential of electrons is simply the electrical potential. Electrons
on the products side see the electrical potential φP and on the reactants side
see the potential φR . Note that different species do not experience different

7
electrical potentials. Then, if Δφ is the difference in electrical potential from
one side to the other,
X X X
0= μ̃i dni = μoi dni + RT ln ai dni + nF Δφ
First, note that:
Q νi
X am n aprod
M aN
RT ln ai dni = RT (ln aM +ln aM −ln aA −ln aB ) = RT ln
m n 1 b
b
= RT ln Q νi
a A aB areact
Rearranging (2) and inserting the above result, you get
P o Q νi
μi dni RT aprod
Δφ = − − ln Q νi
nF nF areact
From the thermodynamic definition of chemical potential, μi ≡ ∂n ∂G
i
so that
Σμi dni = ΔG where the in this case denotes reference concentration. We
o o o
o
relate this term to E by − ΔG nF = E , but note that the
o o refers only to

reference concentration. The E term may still depend on temperature, so

o

we rename the quantity ET . Identifying E as the electrical potential across

the cell Δφ, we arrive at the Nernst equation (1).

Problem 2.7 (15 points) Yes, you can have a thermodynamic efficiency
greater than 1. We chose the metric of fuel cell efficiency to be ΔG/ΔH,
but it is in some sense an arbitrary choice.
To break the intuitive barrier against efficiencies greater than unity, con-
sider the efficiency of an electrolyzer, a device that makes hydrogen and
oxygen gas from water using electricity (this is the reverse of a fuel cell, and
may be used to generate hydrogen for some fuel cell applications). An elec-
trolyzer has an efficiency defined to be the ΔH of reaction (the output is the
useful heat energy of hydrogen), divided by the energy input ΔG. Therefore,
the efficiency of the electrolyzer is the inverse of fuel cell efficiency—so the
fuel cell at STP with an efficiency of 0.83, if ran in reverse as an electrolyzer,
would have an efficiency of 1/0.83, which is greater than 1.
For a fuel cell, consider the following example:  ≡ ΔG/ΔH. For an
isothermal reaction, ΔG = ΔH −T ΔS, so  = 1−T ΔH ΔS
. To get an efficiency
greater than 1, we can have ΔH negative and ΔS positive. The trick is
to use a solid or liquid reactant to make ΔS positive because solids and
liquids have very low entropy compared to gases. For the fuel cell reaction
C(s) + 12 O2 → CO at 298 K and 1 bar,
1
ΔS = SCO − SO2 − SC = 197.7 − 0.5 ∗ 205.1 − 5.7 (in J/mol ∙ K)
2
= 89.45 J/mol ∙ K

8
 1
ΔH = HCO − HO2 − HC = −110.5 − 0.5 ∗ 0 − 0 (in kJ/mol)
2
= −110.5 kJ/mol

then
 = 1 − T ΔH
ΔS
= 1 − (negative number) > 1

Problem 2.8 (not graded) The full-cell reaction for a DMFC is given
by 2.32, the half cell reactions are CH 3 OH + H2 O → 6H+ + CO2 + 6e−
and 32 O2 + 6e− + 6H+ → 3H2 O, so there are six electrons transferred per
methanol molecule.
(a)The methanol consumption is therefore

mol M eOH/s = i ∗ (mol M eOH)/C = i/(6 ∗ Na ∗ q) = i/6F

and the output mass flux, assuming the input flux is x mol/s, is vM eOH,out =
x − i/6F . The oxygen consumption is 32 as large as the methanol con-
sumption, and air is approximately 21% oxygen. Assuming the air input is
y mol/s, the air output is vair,out = y − 0.21 ∗ i/4F . The water output is
twice the methanol output. Assuming no water flows into the cell, the water
output is vH2 O,out = i/3F . The (molar) carbon dioxide output is equal to
the methanol consumption, so the output is vCO2 ,out = i/6F .
(b) The stoichiometric factor is the excess reactant delivered over that
required for operation at current i. λM eOH = 6F x/i and λair = 0.21y ∗4F/i.

Problem 2.9 (15 points) Assuming constant specific heats,

ΔH(T ) = ΔH o + cp (T − T o ) and ΔS(T ) = ΔS o + cp ln(T /T o ).
Find the temperature that satisfies:
X
ΔG(T ) = 0 = ΔH(T )−T ΔS(T ) = [ΔHio + cpi (T − T o ) − T (Sio + cpi ln(T /T o ))]

taking out the ΔH o and ΔS o ,

X
0 = ΔHrxn
o
− T ΔSrxn
o
+ [cpi (T − T o − T ln(T /T o ))]

or X
0 = ΔHrxn
o
− T ΔSrxn
o
+ (T − T o − T ln(T /T o )) c pi
Substituting numbers,

0 = −41.13 kJ/mol−T(−42.00 J/mol∙K)+(T −T o −T ln(T /T o ))(3.2 J/mol∙K)

A numerical solution (MATLAB or Excel or your graphing calculator work

fine) gives T ≈ 1020 K ≈ 747◦ C . The error of neglecting the dependence

9
of ΔS and ΔH on temperature led to an answer that was off by about
40 degrees in this case. A more sophisticated solution would include the
variance of cp with temperature, requiring an iterative solution or an expan-
sion for cp in terms of T .

Problem 2.10 (a) (10 points) Remember that the effect of temper-
ature enters into the first term of the Nernst equation. From the Nernst
equation, if the reactants and products are ideal,
 Q   Q νi 
RT (P/Po )νP P xνi i RT −ν x
E = ET − ln Q νi = ET − ln (P/Po ) ν P R QP νi i
nF (P/Po ) R R xi
ν nF R xi

In a reaction, the change in number of moles ΔnG = νP − νR . The temper-

ature dependent term is
ΔS
ET = E o + (T − To )
nF
For the voltages to be equal
E(T1 , P1 ) = E(T2 , P2 )
 Q νi 
ΔS RT1 ΔnG QP xi
E +
o
(T1 − To ) − ln (P1 /Po ) =
nF nF x νi
 QR iνi 
ΔS RT2 x
Eo + (T2 − To ) + ln (P2 /Po )ΔnG QP νi i
nF nF R xi

Canceling constant terms that appear on both sides of the equation and
solving for T2 ,
h Q νi i
ΔS
− R
ln (P /P ) ΔnG QP xi
nF nF 1 o ν i
R xi
T1 h Q ν i i = T2
ΔnG QP xνi
nF − nF ln (P2 /Po )
ΔS R
R x i
i

Simplifying for the H2 /O2 fuel cell with liquid water as product and for pure
components (xH2 = xO2 = 1) and dropping the Po , which is understood to
be 1 atm the expression simplifies to
ΔS + 1.5R ln P1
T1 = T2
ΔS + 1.5R ln P2
(b) (5 points) At STP, using the data from Appendix B,
ΔSrxn = SH2 O(l) − SH2 − 0.5SO2 = 69.95 − 130.86 − 0.5 ∗ 228.3
= −175.06 J/mol ∙ K

10
If P2 = P1 /10 then from the above expression,

ΔS + 1.5R ln P1 −175.06 + 1.5 ∗ 8.314 ∗ ln 1

T2 = T1 = 298
ΔS + 1.5R ln(P1 /10) −175.06 + 1.5 ∗ 8.314 ∗ ln(1/10)

Then T2 = 256 K . Note that at this temperature of −17◦ C, there will be

no H2 O(g) (so we shouldn’t use the ΔS for water vapor), but there will also
not be liquid water—the product will be ice! A full solution would use the
ΔS for liquid water down to 0◦ C and then the ΔS for ice below that.
To interpret the result, since ΔS is negative, the Nernst voltage decreases
with an increase in temperature. The decrease in pressure decreases the
Nernst voltage, so we must compensate by raising the Nernst voltage by
decreasing temperature; therefore, T2 < T1 .

Problem 2.11 (15 points) Two ways of attacking this problem yield
the same result. First, you could imagine a box with water, air, and hy-
drogen, and the reaction H2 + 12 O2 H2 O(l) is in equilibrium. To find
how much hydrogen is consumed by oxygen, find the equilibrium quantity
of hydrogen when oxygen is present. That is to say, find at what PH2 does
ΔGrxn = 0. From the Van’t Hoff isotherm
Πaνprod
i

ΔG = ΔGo + RT ln
Πaνreact
i

assuming air at the cathode (xO2 = 0.21):

a1H2 O 1
ΔG = ΔGo +RT ln = ΔGo +RT ln = ΔGo −RT ln(1)1.5 (xH2 )(0.21)0.5
1 0.5
a H2 a O2 (P/Po ) xH2 x0.5
1.5
O2

Solving for xH2 ,

ΔGo  
= ln (0.21)0.5 xH2
RT

   
1 ΔGo (−237 kJ/mol)
xH2 = exp = (2.18) exp = 5.41∙10−42
0.210.5 RT (8.314 J/mol ∙ K)(298 K)

so PH2 = 5.41 ∙ 10−42 atm.

Note that the partial pressure is very low, because it is very energetically
favorable for hydrogen to react with oxygen to form water.
The alternate way to solve the problem is to solve a concentration cell
where a voltage develops (1.23 V because it is a hydrogen/air system) but

11
E o = 0 because the concentration cell reaction is H 2 + O2 → H2 + O2 . In
this formulation, you solve the Nernst equation where the reactants have
activity 1 because they are pure:

RT PH2 /Po (0.21)0.5

1.23 = 0 − ln
nF 1
This gives the same equation:
 
1.23 ∗ nF
xH2 (0.21)0.5 = exp −
RT

Problem 2.12 (5 points) The efficiencies of each part multiply to give

the total efficiency of the cell:  = thermo V oltage f uel . For pure H2 /O2 at
STP, thermo = 0.83. We are given V , so V oltage = VE = 1.23 0.75
. We are given
λ, so f uel = λ = 1.1 . Therefore,
1 1

0.75 1
 = 0.83 ∗
1.23 1.1

 = 46%

Problem 2.13 (not graded) (a) The output flux of MeOH is vM eOH,out
= vM eOH,in − i/nF = 0.003 − 1000/(6 ∗ 96485) = 0.001 mol/s. The output
flux of air is vair,out = 0.03−0.21∗1000/(4∗96485) = 0.029 mol/s. vH2 O,out =
1000/(3∗96485) = 0.03 mol/s and vCO2 ,out = 1000/(6∗96485) = 0.02 mol/s.
(b) λM eOH = nF v/i = 6 ∗ 96485 ∗ 0.003/1000 = 1.7 and λair = 0.21 ∗
0.03 ∗ 96485 ∗ 4/1000 = 2.4.
(c) The methanol usage rate is i/nF = 1000/(6 ∗ 96485) = 0.0017 mol/s
so the power usage is 719.19 kJ/mol * 0.0017 mol/s = 1.24 kW. To find
the heat production, we need to know the efficiency. The electrical power
generated is Pe = i ∗ V = 1000 ∗ 0.3 = 300 W, and the rest of the energy
in the fuel is converted to heat. Therefore, the heat production rate is
1.24 kW − 300 W = Ph = 942 W .

Problem 2.14 (5 points)

Total power 1
Area = ⇒ 2000 W ∗ = 1333.3 cm2
Power per area 1.5 cm2
W

Answer b

12
 Problem 2.15 (10 points)
dQ dN dN i i
i= ⇒ i = nF ⇒ = ⇒N = (tf − ti )
dt dt dt nF nF
Using current density and area from 2.14, we can solve for current and use
that to find the number of moles of fuel.
N = mol e− 4000 A C ∗ 60min
sec
∗ 60 hrmin ∗ 24dayhr =1792.53 mol H2 in 24 hrs
(2 mol )(96400 )
H2 mol e−
We know that the reaction is: H 2 + 12 O2 → H2 O which means that we have
a 1:1 H2 to H2 O molar ratio. So we have 1792.52 moles of H 2 O. To
connect to L, we need atomic mass and density.
1792.53 mol H2 O 18 g 1 cm3
∗ ∗ = 32265.6 cm3 or 32.3 L
1 mol H2 O g

Answer c

Problem 2.16 (5 points) Le Chatelier’s principle tells us that the

reaction will favor the forward direction, increasing the thermodynamic
voltage.
Answer b

Problem 2.17 (10 points)

(a)
Electrode Reaction 1 Reaction 2
Cathode 2 O2
+ 2e− → O2− 2(O2 + 4e− ) → 2(2O2− )
1

Anode CO + O2− → CO2 + 2e− CH4 + 4O2− → 8e− + 2H2 O + CO2

Full Reaction 2 O2 + CO → CO2 CH4 + 2O2 → 2H2 O + CO2
1

(b)
Electrode Reaction 1 Reaction 2
Cathode 8e− + 2H2 O + 2CO2 → 4O2− + CH4 CO2 + 2e− → CO + O2−
Anode 4O2− → 8e− + 2O2 O2− → 2e− + 12 O2
Full Reaction 2H2 O + CO2 → 2O2 + CH4 CO2 → CO + 12 O2
Problem 2.18
(a) (5 points)
P 3000 W
A= ⇒ 1002 cm2
= 0.5 m2
j∗V (1 cm2 ∗ m2 )(0.6 V)
A

13
(b) (10 points) The heat generated is the difference between the power
put in and the generated electrical power.

Pheat = Pin − Pelec

λ | ΔH | i (1)(802, 000 mol JCH4 )(5000A)
Pin = = mol e−
nF (8 mol CH4 )(96485 mol e− )
C

Pelec = i ∗ V = 5000A ∗ 0.6V = 3000W

Pheat = Pin − Pelec = 5.2 kW − 3.0 kW = 2.2 kW

(c) (10 points) Rate of water production:

λi (1)(5000A) mol H2 O
νH 2 O = = = 0.013
(4 mol e− s
mol H2 O )(96485 mol e− )
nF C

Convert to moles per day:

mol H2 O 60 s 60 min 24 hr mol H2 O
0.013 ∗ ∗ ∗ = 1119.17
s 1 min 1 hr 1 day day
Use molecular weight to convert to volume:
18 g 1 cm3
VH2 O = 1119.17 molday
H2 O
∗ 1 mol H2 O ∗ 1 g ∗ 1 mL
1 cm3
∗ 1 L
1000 mL
VH2 O = 20.145 L

(d) (2 points) No.

20.145 day
L
 750 day
L
average consumption.

14
Chapter 3 Solutions
Problem 3.1 (a) (5 points) Reducing the potential raises the energy of
electrons in the electrode. To reduce their energy, electrons leave the
electrode, so the reaction proceeds faster in the forward direction.
(b) (5 points) Increasing the potential lowers the energy of electrons in
the electrode, so the reaction is biased in the forward direction.
(c) (5 points) We want to increase both reaction rates in the forward
direction. At the anode (H2 H+ + 2e− ) you want to draw electrons to
the electrode, so increase the potential. At the cathode
(2H+ + 2e− + 12 O2 H2 O) you want electrons to leave the electrode, so
reduce this potential. The overall voltage output falls from both effects.

Figure 2: Schematic of activation voltage losses for problem 3.1.

Problem 3.2 (5 points) Yes, it is possible to have a negative Galvani

potential at one electrode. It means that one half-cell reaction requires
energy input, and the other results in energy output. So long as the total
potential adds up to the measured full-cell potential, it is impossible to
know what each half-cell potential is!

Problem 3.3 (10 points) Alpha is the charge transfer coefficient. It

describes whether the “center of the reaction,” or peak of the reaction
activation barrier, falls nearer to one side of the reaction or the other. In
this figure, note that alpha does not change the final electrochemical
energy change, only the height of the peak in electrochemical energy.

15
 Figure 3: Schematic of different Galvani potentials, problem 3.2.

Figure 4: Effect of α on the electrochemical energy pathway for problem 3.3.

16
Problem 3.4 (5 points) The exchange current density is the current
density of the forward and reverse reactions at equilibrium (in an open
circuit).

Problem 3.5 (5 points) (a) The Tafel equation reads:

ηact = a + b log j
In the exponential regime, the Butler-Volmer equation simplifies to
RT RT
ηact = − ln jo + ln j
αnF αnF
Note: To convert between log and ln, use the conversion ln x = 2.3 log x.
The terms that go as a logarithm with current density are equal:
RT RT
b log j = ln j ⇒ b/2.3 =
αnF αnF
b = 2.3 αnF
RT

(b) Identifying the constant terms, we get

a = − αnF
RT
ln jo

Problem 3.6 (5 points) The full-cell reaction is CO + 12 CO2 → CO2 .

The half-cell reaction at the anode is O 2− + CO → CO2 + 2e− and at the
cathode is O2 + 4e− → 2O2− .

Problem 3.7 (5 points) The main job of a fuel cell catalyst is to be

able to form intermediate-strength bonds with reactants and products—
that is, to yield a low ΔGact . Also, it should have a long lifetime, which
means that it is resistant to poisoning and does not migrate or agglomerate
on the membrane. The requirements for an effective fuel cell catalyst-
electrode structure are: porosity, a high degree of interconnection between
the pores, a high effective catalyst area, high TPB density, high electronic
conductivity, and high exchange current density. It also must have a long
lifetime, meaning high mechanical strength and resistance to corrosion.
Ideally, it would also be cheap and easy to manufacture.

Problem 3.8 (not graded) From equation 3.51, using n = 1, j = 0 and

plugging in reactants and products, we find for the anode:
0.5
! ∗ ∗
! !
∗ C
CH ,i H + ,i Ce− ,i
0 = j0 0∗
2
eαF η/RT − 0∗ 0∗ e−(1−α)F η/RT
CH 2 ,i
C + C
H ,i e ,i −

17
and for the cathode
 ! !0.5 
∗ 0.25 C ∗ ∗ ∗
CO ,i e − ,i CH + ,i CH 2 O,i
0 = j0  0∗
2
0∗ C 0∗ eαF η/RT − 0∗ e−(1−α)F η/RT 
CO 2 ,i
C e− ,i H + ,i
CH 2 O,i

We introduce the shorthand f = F/RT and follow the same procedure as

in the text, we get next
 
∗,A ∗,A 0∗,A 0.5
CH + ,i C e− ,i C H2 ,i
ln  0∗,A 0∗,A ∗,A  = f ηA
CH + ,i Ce− ,i CH2 ,i

and  
∗,C 0.25 ∗,C ∗,C 0∗,C 0.5
CO 2 ,i
Ce− ,i CH + ,i CH 2 O,i
ln   = −f η C
0∗,C ∗,C
CO2 ,i Ce0∗,C
− ,i
0∗,C
CH + ,i CH 2 O,i

Next we use the definition of activity and subtract the two equations:
!  
∗,A ∗,A ∗,C 0.25 ∗,C ∗,C 0.5
a H + ∗ a e− (a ) ∗ a H + ∗ ae −
ln ∗,A 0.5
− ln  O2 ∗,C
 = f (η A + η C )
(aH2 ) a H2 O

Using η A + η C = E 0 − E, we find
!
RT (a∗,C
H2 O )
0.5
a∗,A
H+
a∗,A
e−
E=E − 0
ln − ln − ln
F (a∗,A 0.5 ∗,C 0.25
H2 ) (aO2 ) a∗,C
H+
a∗,C
e−

We multiply the second term by 22 to find the same formula as 3.63:

 ! ! 
∗,C ∗,A 2 ∗,A 2
RT a H2 O a H+
a e−
E = E0 − ln − ln − ln 
2F ∗,A ∗,C 0.5
a (a ) ∗,C
a + ∗,C
a−
H2 O2 H e

Problem 3.9 (not graded) (Note: the equation should have 1O 2 , not
2 O2 ) In general, for half cell reactions, equation 3.61 reads
1

Q ∗,C νi !
RT (a )
η =
C
ln Q P∗,C
nF (aR )νi
For the two sequential reactions, intermediates will cancel out, as shown
below: ! !
∗,C ∗,C ∗,C
RT a H O a H O a O
ηC = ln 2 2 2 2
2F (a∗,C+ )2 (a∗,C
− ) 2 a∗,C a ∗,C
H e O2 H 2 O2

18
The rest of the derivation follows the text.

Problem 3.10 (not graded)

(a) At equilibrium,
∗∗
CR CP∗∗ −(1−α)nf ηA
0= 0∗ e αnf ηA
− e
CR CP0∗

CP∗∗ ∗∗
CR
ln − (1 − α)nf η A = ln 0∗ + αnf ηA
CP0∗ CR
 ∗∗ 
CR CP0∗
−nf ηA = ln ∗
CR0∗ CP∗∗
 0∗ 
RT CR CP∗∗
ηA = ln ∗∗ ∗ C 0∗
nF CR P
(b) The Butler-Volmer equation is
 ∗ 
CR αnf (η0 +ηA ) CP∗ −(1−α)nf (η0 +ηA )
j = j0 0∗ e − 0∗ e
CR CP

Plugging in ηA from above,

"  0∗ #
∗
CR C C ∗∗ α C ∗  0∗
C C ∗∗ −(1−α)
0 0
P −(1−α)nf η
j = j0 0∗ e
αnf η
∗ R P
∗∗ ∗ C 0∗ − 0∗ e ∗ R P
∗∗ ∗ C 0∗
CR CR P C P C R P
 ∗ (C 0∗ )α (C ∗∗ )α 
−nf η 0 CP (CR )
CR ∗ 0∗ α−1 (C ∗∗ )α−1
αnf η 0
j = j0 e R P
0∗ (C ∗∗ )α (C 0∗ )α − e P
0∗ (C ∗∗ )α−1 (C 0∗ )α−1
CR R P C P R P
After much rearranging, this gives
 ∗ ∗ 
(CR
0∗ )α−1 (C ∗∗ )α
αnf η 0 CR −nf η 0 CP
j = j0 ∗∗ α−1 0∗ α e
P
∗∗ − e
(CR ) (CP ) CR CP∗∗

This is the Butler-Volmer equation again with a different j0 and defined

against the new reference concentrations CR
∗∗ and C ∗∗ .
P

Problem 3.11 (5 points) For reaction A, the net reaction rate in

2
mol/s ∙ cm2 is nF5∙2Acm2 = 2.5A/cm
2F = 1.30 ∙ 10−5 mol/s ∙ cm2 . For reaction B,
3A/cm 2
the net reaction rate is nF15∙5 cm
A
2 = 3F = 1.04 ∙ 10−5 mol/s ∙ cm2 .
Therefore, reaction A has a higher reaction rate.

Problem 3.12 (a) (2 points) P = IV = (1 A)(2.5 V ) = 2.5 W

19
(b) (2 points) By putting five cells together in series, you get an overall
voltage of 5(0.5 V ) = 2.5 V, the necessary voltage.
(c) (3 points) Note that when you stack cells together in series, the
current does not change. However, the amount of hydrogen required does
increase. One way to think of it is that when you are required to supply
2.5 W of power, you must supply 2.5 J/s of hydrogen, not just the 0.5 J/s
per cell. What is going on is that the first fuel cell uses 0.5 J/s of hydrogen
to raise the voltage of its cathode up to 0.5 V. When this cathode
connected to the anode of the next cell it is raised to a higher voltage, and
this cell uses 0.5 J/s of hydrogen to raise its output voltage, and so on.
The amount of hydrogen per cell is determined by the current by
ṄH2 = i/nF . The electric charge needed is
1 A ∙ 100 hrs. ∙ 3600
1 hr = 360, 000 C. Converting to moles of hydrogen,
s

360, 000 C/2F = 1.866 mol H2 . Converting to grams,

1.866 mol ∙ 1 2mol
g
= 3.73 g H2 per cell. So the fuel cell stack uses five times
that, 18.7 g H2
(d) (3 points) From the ideal gas law, V = nRT /P =
(1.866 × 5 mol)(0.08205 L ∙ atm/mol ∙ K)(298 K)/(500 atm) = 0.457 L.
V = 457 cm3 .
For storage in a metal hydride, the 5 wt.% hydrogen gives a storage
density of 10 g/cm3 ∙ 0.05 = 0.5 g/cm3 . To store 18.7 grams, you need a
volume of (18.7 g)/(0.5 g/cm3 ) = 37.3 cm3 . This is a significant
improvement over storage at 500 atm!
(e) (3 points) From part c above, the electric charge needed = 360,000 C.
Converting to moles of methanol, 360,000
6F
C
= 0.6219 mol CH3 OH.
Converting to grams: 0.6219 mol ∙ 132mol
g
= 19.9 g CH3 OH per cell. The
stack requires 99.5 g CH3 OH
1 cm3
Volume of liquid methanol: 99.5 g CH3 OH ∙ 0.79 g = 125.9 cm3

Problem 3.13 (10 points) The exchange current density is given by

∗
CR ΔG‡
jo = nF o∗ e− RT
CR

Grouping the preexponential terms into a constant that is temperature

independent,
ΔG‡
jo (T ) = Ce− RT

20