260 Spring 2004 PDF
260 Spring 2004 PDF
260 Spring 2004 PDF
WHY ?
WHAT ?
Few Examples:
IGCC, fuel reforming and synthesis
Fuel Cells, fueling the fuel cell, FC3
Hydrogen Economy: generation and storage
Photoelectricity
HOW ?
ource: International Energy Agency
The Terawatt
TheChallenge
ENERGY REVOLUTION
14 Terawatts (4 TW in US)
R. Smalley*
(The
Terawatt
Challenge)
Rice University
50
45
B
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H
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0.5%
C
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ENERGY
WATER
FOOD
ENVIRONMENT
POVERTY
TERRORISM & WAR
DISEASE
EDUCATION
DEMOCRACY
POPULATION
2003
O
il
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
50
45
40
35
30
25
20
15
10
5
0
2050
Source: Internatinal Energy Agency
40
Carbon free
sources to
stabilize
CO2
30 -- 60 Terawatts
35
30
25
20
15
10
5
H
yd
ro
el
ar
ec
,
w
tr
ic
in
d,
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B
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s
/F
is
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on
as
Fu
si
on
C
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O
il
TW
50
40
30
CO2 free
--
20
-10
0
2000
2020
2040
2060
2080
2100
YEAR
Wigley, Richels and Edmonds, ppmv of CO2, pre-industrial concentration is 350 ppmv
Global Temperature!
CO2 emission
reduction:
Improve plant
efficiency
Use low C fuels
Use pure H2
Sequester CO2!
RENEWABLES
The public may copy and use this information without charge, provided that this Notice and any statement of authorship are
reproduced on all copies. Neither the Government nor the University makes any warranty, express or implied, or assumes any
liability or responsibility for the use of this information. Courtesy of Los Alamos National Lab. Used with permission.
Basic Energy Needs for the Hydrogen Economy, May 2003, DOE
Especially for mobile applications, fuel cells may work with a reformer
(although direct methanol cells are also under development)
The Mobile
Storage Problem:
puzzle!
GMs HyWire
Basic Energy Needs for the Hydrogen Economy, May 2003, DOE
NaBH 4 + 2H 2O catalysis
4H 2 + NaBO2
OR 66 gH2/L compared to 70 g/L liquid H2 and 23 g/L gas (at 350 bar).
Basic Energy Needs for the Hydrogen Economy, May 2003, DOE
Q@120C
2 I2 +SO2 +2H2O2HI+H2SO2
+Q@800950C
2H2SO4
2SO2 +2H2O+O2
+Q@450C
2 2HII2 +H2
Thermochemical Cycle
850 C
2 H 2O +Q
@
2 H 2 + O 2
50%
Capture/conversion + Electrolysis
G (Spring)
From matter and Energy (1912) by Frederick Soddy Noble Prize in Chemistry, 1921.
Isentropic process
Combined cycles
Gas mixtures: Molar and mass fractions, molecular weight, partial pressure
Internal energy, enthalpy and ehthropy.
Chemical Equilibrium
Constant U,V constraints: Maximization of entropy
Constant T,P constraints: Minimization of gibbs free energy
The fundamental equation
The chemical potential
Law of mass action
Equilibrium constant
Endothermic and exothermic reactions
Fuel reforming
Steam reforming
Water gas shift
Fuel reforming
Steam reforming
Water gas shift
Conservation of charge
Chemical kinetics
Activation energy
Ozone reaction
Pollutants in combustion
1) CO formation: partial equilibrium approximation
2) NO formation: Zeldovich, thermal mechanism
3) Dependence of CO consumption and NO formation on temperature.
Heterogeneous Kinetics
Adsorption, surface reaction and desorption
Catalytic chain
Example: Catalytic converter
Introduction to Electrochemistry
Current, reaction rate, electrochemical equilibrium
Butler-Volmer equation
Over potential
1) Ohmic overpotential
2) Activation overpotential
3) Mass transfer overpotential
Transfer coefficient
1) Changes in the free energies
2) Changes in the forward and backward reaction rates
Butler-Volmer Equation
Cell voltage profile for PEM: Cathode activation, cell resistance, anode
activation and mass transport
Oxygen reduction
Multistep mechanisms
Transport equation
Fouriers law
Ficks law
Flames in SI engines
Knock
Brayton cycle
Coal gasification
CO2 capture
Fission reaction
Hydrogen characteristics
Availability
Component irreversibility
Irreversibility analysis for a feed pump and the primary heat exchanger
Electrolysis
-
Limiting current
Photovoltaics
-
Opportunity
Market segments
Cost
Fuel cell
- History
-
Types
Leading organizations
Electricity failure from approximately 1:30PM and the class was dismissed.
The 90% capacity factor means the plant on average over a long time (like a year) will operate 90% of the
time.
Problem 2 This problem illustrates the concept of specific work, the effect of fluid
density on the work required for its compression and the effect of intercooling as a
means to reduce the work needed for compressing gases.
2.1 Find the pressure at which intercooling should be performed to achieve the greatest
reduction in the work needed by a two-stage compressor of air from atmospheric pressure
and temperature to 100 atmospheres. The air can be assumed to behave as an ideal gas,
with temperature independent specific heat. Assume that each stage of the compression is
isentropic and that the intercooling occurs at constant pressure returning the air to its
initial temperature prior to entering the second stage.
2.2 What is the work supplied per unit mass of air being compressed?
2.3 What would be the work needed per unit mass if no intercooling was applied?
2.4 Compare the work above to the work needed to compress a unit mass of liquid water
from one to 100 atmospheres. You may ignore the density and temperature changes of
water during the compression.
2.5 What values would you expect for the actual compressor work in parts 2.2 and 2.3 if a
practical device of reasonable size would be used instead of the ideal ones?
Problem 3 This problem introduces the concept of total energy efficiency of a
transportation system.
According to Faradys Law, the heat formation of a molecule, H, can also be expressed
as an electrochemical potential:
U = - H/ ne F,
where ne is the number of electrons participating in the chemical bonding and F is the
Farady constant = 96,485 Coulomb/mol.
Only a fraction of the energy of formation is available for reversible energy conversion,
which is determined by the Gibbs free energy, G.
To produce hydrogen from water by electrolysis, H has to be invested ( in this case 286
kJ/mol at 25 C) .
However, when hydrogen combines in a fuel cell with oxygen to produce water, only the
reversible energy G is obtained (237kJ/mol). Since two electrons participate in the
bonding of a hydrogen molecule, the theoretical voltage that can be produced in a fuel
cell is 1.23 volts. In reality, there are losses due to resistance to ion motions and
polarization at the electrode interfaces, so that the actual voltage obtained is much less in
practice, about 0.7 volts.
3.1 What is the power-plant to wheels efficiency of a fuel cell powered transportation
system, if the hydrogen is produced by electricity with a thermal- to electrical power
conversion efficiency in the plant is 0.5?
3.2 What should the internal combustion engine (ICE) efficiency of the cars to allow the
conventional transportation power system to have the same energy utilization efficiency
as the electrolysis/fuel cell system? You may assume that the energy efficiency of
gasoline and diesel manufacturing plants (i.e. refinery) is 96%.
3.2 If the hydrogen is obtained by methane steam reformation, which currently has 0.7
energy efficiency, what would the answers to questions 3.1 and 3.2 be?
Homework I Solution
Problem 1
1.1
Natural Uranium : X (g/yr)
Enriched Uranium :Y (g/yr)
Discarded Uranium: Z (g/yr)
Mass Conservation: X=Y+Z
Mass Conservation of U-235:
0.71X=4.4Y+0.25Z
Eq.(1)
Eq.(2)
Eq.(3)
Hence, we lose almost 90% of the natural uranium in the enrichment process.
Since U-235 in the enriched Uranium is 4.4/100*Y, we can represent the used Uranium
for fission from the natural Uranium as
4.4/100*0.111X=0.004877X.
Eq.(4)
Hence, only 0.4877% of the natural Uranium is actually used for fission.
Then, power can be represented as
0.004877X* rankine * nuclear *1MW-day/g=1000MW*365 day* capacity
where rankine =0.35, nuclear =0.95 and capacity =0.9. Then, we get X=2.026*108
g/yr=202.6 ton/yr=0.56ton/day.
1.2
Average daily amount of coal used: X (kg/day)
X* steam *27800BTU/kg*1J/9.48*10-4BTU*1day/(24*3600sec) =1000*106 W* capacity
where steam =0.471. Then, we get X=6.04*106kg/day=5640 ton/day.
1.3
Area for the flat panel : X (cm2)
500cal/(cm2 day)/(0.239cal/J)* conv *X*1day/(24*3600sec)=1000*106W
where conv =0.12. Then, X=3.441*1011cm2. Also, total area required is 2X=68.8km2.
Problem 2
2.1
P1=1atm, T1=300K Isentropic compression I P2,T2
P2,T2 Intercooling P2=P2,T2=T1=300
P2,T2 Isentropic compression II P3=100atm,T3
In the compressions I and II, T and P have the following relationships
P2 T2
=
P1 T1
k /( k 1)
P T
and 3 = 3
P2 T1
k /( k 1)
Eq. (5)
w = c p (T3 T1 ) + c p (T2 T1 )
Eq.(6)
( k 1) / k
P
+ 3
P2
( k 1) / k
Eq.(7)
By differentiating w by P2 , we get
P2 = P1 P3 =10atm.
2.2
From Eq. (5), we get T2=T3=579K. Using Eq. (6) and cp~1kJ/kg K at T~450K, we get
558kJ/kg.
2.3
P1=1atm, T1=300K Isentropic compression P2=100atm,T2
Using Eq. (5) again, we get T2=1118K. Using w = c p (T3 T1 ) and cp~1.1kJ/kg K at
T~700K, we get w = 900kJ/kg.
It is clear that intercooling reduces the work required for compression significantly.
2.4
w=vdP=0.001m3/kg*(10130kPa-101.3kPa)=10kJ/kg.
The compression work of liquids is typically 1-2% of that of gases.
2.5 Assuming c ~0.7-0.9, work in 2.2 and 2.3 should increase by 10-40%.
Problem 3
3.1
3.2
ICE =0.344
Without considering the refinery efficiency of fuels, it becomes
ICE =0.330
(4)
What is the Second Law efficiency of the power cycle, without sequestration?
Calculate the molar fuel/air ratio in this case.
Calculate the work transfer in the separation and liquefaction steps of CO2.
The total sequestration work is the sum of both. First assume that both
gaseous separation and liquefaction are ideal, i.e. both require the minimum
work. (Use attached T-s diagram of CO2 for calculation)
If the Second Law efficiencies of both steps are 80%, what is the fraction of
sequestration work of the power cycle work? Note that the Second law
(5)
(6)
efficiency for separation and liquefaction is the ratio between the minimum
work required and the actual work required.
What thermodynamic processes should be used in liquefaction to achieve
ideal minimum work? Why are these ideal minimum work processes difficult
to achieve in practice?
What processes would you use instead in liquefaction, and why do they
require more work? How would you modify these more practical liquefaction
process to bring them closer to the ideal processes, and what additional cost is
needed to achieve those modifications?
II.
It has been proposed (see attachment) that separating nitrogen from air before
burning is perhaps more economical, since in this case the products of combustion are
only CO2 and O2. Repeat the calculations for the separation and liquefaction work, and
compare the results with the first case. Note that in this case, some of O2 is circulated in
the cycle to keep the maximum temperature at 1300 C. Separating N2 before combustion
may have some emissions benefits.
III.
Yet another proposal is to burn in air, at atmospheric pressure, but use a catalytic
combustion unit so that the products of combustion in this case are limited to
CO2+N2+H2. Next CO2 is separated isothermally at the products temperature, and the
H2+N2 mixture is used in a fuel cell to produce electricity directly. Calculate the total
sequestration work in this case, and compare with the previous two cases..
(Courtesy of Prof. Steven Penoncello, Professor of Mechanical Engineering. Used with permission.)
Homework II Solution
(1) The efficiency in the ideal case (Carnot cycle) is:
ideal =1-(300K)/(273K+1300K)=0.81.
0.5
II =
= 0.62
0.81
k /(k 1)
and T2 = T1 + (T2 s T1 ) /
c
Note that
T 2
T2
T2
H R = h of ,C6 H 6 + c p ,C6 H 6 dT + 7.5 c p , O2 dT + 3.76 c p , N 2 dT
To
To
To
From Gibbs free energy change, we get a different value of the maximum work:
wmax = G = h + Ts =3131MJ/kmol+300(6 sCO 2 +3 s H 2O -7.5 sO 2 - sC 6 H 6 )
=3131MJ/kmol+300(6moles*0.214MJ/kmol+3moles*0.189MJ/kmol-7.5moles*0.205MJ/kmol 0.173MJ/kmol)=3173MJ/kmol.
and
T3
T3
T3
H p = 6 h of ,CO2 + c p ,CO2 dT + 3 h of , H 2O + c p , H 2O dT + 3.76 7.5 c p , N 2 dT .
To
To
To
While computing the above two expressions, keep in mind that c p is a function of
temperature.
In the mixing process
To
T2
T2
H R (T2 ) = X c p ,O2 dT + 3.76 c p , N 2 dT
To
T
o
and
T4
T4
T4
H P (T4 ) = 6 h of ,CO2 + c p ,CO2 dT + 3 h of , H 2O + c p , H 2O dT + X c p ,O2 dT +
To
To
To
3.76 (7.5 + X ) c p , N 2 dT
T4
To
we get X =16.78.
(3)
6CO2+24.28*3.76N2+
16.78O2
T=300K,
P=1atm
24.28*3.76N2+
16.78O2
6CO2 (gas)
T=300K,
P=1atm
W = nCO 2 ((hCO 2, 2 hCO 2,1 ) T ( sCO 2, 2 sCO 2,1 )) + n N 2 ((hN 2, 2 hN 2,1 ) T ( s N 2, 2 s N 2,1 ))
+ nO 2 ((hO 2, 2 hO 2,1 ) T ( sO 2, 2 sO 2,1 ))
= RT (nCO 2 log(
1
) + (n N 2 + nO 2 ) log(
))
X CO 2,1
1 X CO 2
,1
= 58.6 MJ
Required work for separation: 58.6MJ/kmol of C6H6 (3.7% of the work produced in
the cycle)
6CO2 (gas)
T1=300K,
P1=1atm
6CO2 (liquid)
T2=300K,
P2=100atm
(4) II =
Hence, 25% increase of the sequestration work (149.1MJ/kmol of C6H6 and 9.5% of
the work produced in the cycle.)
(5) Since no entropy should be generated in the process to minimize the required
work, the temperature of the device should be regulated to be the same as that of
environment (Isothermal compression). Note that work is supplied for separation and
hence should be removed in the form of heat to the environment to keep the
temperature constant. To reject heat while maintaining the temperature requires this
process to occur very slowly.
(6) Instead of using isothermal compression, one can consider isentropic compression
and heat rejection in a real situation. As we learned from problem II in Homework I,
one can reduce the required work using intercooling. If one uses a large number of
intercoolings and compressors, one can bring these compression and heat rejection
processes closer to the ideal isothermal process. However, this will increase the
capital cost of the plant. Using 3 compressors as shown below, the required work is
72.6MJ/kmol of C6H6 (20% increase over the isothermal work)
State 1
T1=300K, P1=1atm, h1=810kJ/kg
State 2 (Isentropic compression 1)
P2=6atm, S2=S1, h2=920kJ/kg
State 3 (heat rejection)
T3=300K, P3=6atm, h3=805kJ/kg
State 4 (Isentropic compression 2)
P4=30atm, S4=S3, h4=910kJ/kg
State 5 (heat rejection)
T5=300K, P5=30atm, h5=780kJ/kg
State 6 (Isentropic compression 3)
P6=100atm,S6=S5, h6=840kJ/kg
State 7 (heat rejection)
T7=300K, P7=100atm, h7=560kJ/kg
II.
In combustion process, this has only O2 and C6H6 in the reactant:
C 6 H 6 + XO2 6CO2 + 3H 2 O + ( X 7.5)O2
110.56*3.76N2+
110.56O2
T=300K,
P=1atm
110.56*3.76N2
110.56O2
T=300K,
P=1atm
6CO2+103.06O2
T=300K,
P=1atm
6CO2
103.06O2
T=300K,
P=1atm
III.
Combustion (adiabatic, p=1atm)
6CO2+6*3.76N2+
3H2
6CO2
T=2342K,
P=1atm
T=2342K,
P=1atm
6CO2
T=2342K
P=1atm
6CO2
T=300K
P=1atm
However, as we saw in class, this is a reversible reaction and at any state, the mixture, in
general, is composed on CH4, H2O, CO, CO2, H2. The mixture composition depends
strongly on the temperature.
(1)
(2)
Calculate the heat transfer to the reformer per unit mass of the mixture.
(3)
Since the reformed gas contains, besides H2, CO, we will use it in a Solid
Oxide fuel cell, which itself is maintained at 1100 K, and is supplied, besides
the reformed gases, with air at 1100 K. Calculate the maximum electrical
work transfer from the fuel cell, per unit mass of the reformer mixture, and the
heat transfer to the cell from an environment maintained at 1100 K.
(4)
Calculate the maximum EMF for this cell (open circuit voltage), knowing that
for each molecule of H2 or CO consumed, the anode produces two electrons.
The curve in the next page shows the impact of the temperature at the reformer exit on
the composition of the reformed gases. It was obtained using EQUIL, starting with one
mole of CH4 and two moles of water in the liquid form.
HW 3 SOLUTION
1.
Qreforming
H1
Reformer
CH4+2H2O(L)
300K
H2
CO,CO2,H2,H2O,CH4
T=1100K
Using Equil one can calculate the mole fractions of the final stage and enthalpies of
the initial and final stages. In the "Gas Chemistry input" (chem.inp) file in Equil, you
need to specify CO, CO2, H2, H2O and CH4. Also, you need to supply "Surface
chemistry input" for H2O in liquid form.1 An example of input files is as follow:
Gas Chemistry Input
ELEMENTS C H O END
BULK
H2O(L)
END
Application Input
REAC CH4 1
REAC H2O(L) 1
TP
PRES 1
TEMP 300
CNTN
END
REAC CH4 1
REAC H2O(L) 1
TP
PRES 1
TEMP 1100
END
Using the above input files, you will get the following answer:
You should not put H2O(L) in the "Gas Chemistry input". The gas chemistry input is for gases only.
**************************************************************
*
CHEMKIN Collection Release 3.7
*
*
EQUIL Application
*
*
CHEMKIN INTERFACE FOR STANJAN
*
* Copyright 1997-2002 Reaction Design. All Rights Reserved.
*
**************************************************************
INITIAL STATE:
EQUILIBRIUM STATE:
P (atm)
1.0000E+00
T (K)
3.0000E+02
V (cm3/gm)
4.7205E+02
H (erg/gm)
-1.2410E+11
U (erg/gm)
-1.2458E+11
S (erg/gm-K)
6.2814E+07
W (gm/mol)
1.7358E+01
Mol Fractions
H2
0.0000E+00
CO2
0.0000E+00
CH4
3.3333E-01
H2O
0.0000E+00
H2O(L)
6.6667E-01
GAS PHASE
Mols
W (gm/mol)
V (cm3/gm)
Mol Fractions
CO
H2
CO2
CH4
H2O
1.3448E-05
3.3621E-06
3.3333E-01
1.2061E-02
6.5459E-01
1.0000E+00
1.6043E+01
1.5345E+03
0.0000E+00
0.0000E+00
0.0000E+00
1.0000E+00
0.0000E+00
1.0000E+00
3.0000E+02
4.8916E+02
-1.2380E+11
-1.2429E+11
6.3889E+07
1.7358E+01
1.0362E+00
1.6112E+01
1.5279E+03
1.1463E-13
3.8935E-05
9.7337E-06
9.6503E-01
3.4919E-02
1.9638E+00
1.0000E+00
REAC CH4 1
REAC H2O(L) 2
TP
PRES 1
TEMP 1100
Reached end of input ...
Constant temperature and pressure problem.
MIXTURE:
INITIAL STATE:
EQUILIBRIUM STATE:
P (atm)
1.0000E+00
T (K)
1.1000E+03
V (cm3/gm)
1.7327E+03
H (erg/gm)
-5.6216E+09
U (erg/gm)
-7.3773E+09
S (erg/gm-K)
4.8881E+07
W (gm/mol)
1.7358E+01
Mol Fractions
CO
0.0000E+00
H2
0.0000E+00
CO2
0.0000E+00
3.3333E-01
CH4
0.0000E+00
H2O
6.6667E-01
H2O(L)
GAS PHASE
Mols
1.0000E+00
W (gm/mol)
1.6043E+01
V (cm3/gm)
5.6263E+03
Mol Fractions
CO
0.0000E+00
H2
0.0000E+00
CO2
0.0000E+00
CH4
1.0000E+00
H2O
0.0000E+00
BULK PHASE: BULK1
Mols
2.0000E+00
Mol Fractions
H2O(L)
1.0000E+00
1.0000E+00
1.1000E+03
8.6517E+03
-4.4884E+10
-5.3651E+10
1.9509E+08
1.0432E+01
1.5953E-01
6.3843E-01
3.9961E-02
8.4767E-04
1.6123E-01
0.0000E+00
4.9915E+00
1.0432E+01
8.6522E+03
1.5953E-01
6.3843E-01
3.9961E-02
8.4767E-04
1.6123E-01
0.0000E+00
0.0000E+00
CO
CO2
H2
H2O
Mole fractions
8.48e-4
0.16
0.04
0.638
0.161
Number of moles/
(per kg mixture of
CH4 and 2H2O)
0.08
15.4
3.8
61.3
15.5
2.
Qreforming=H2-H1
Qreforming=7.910MJ/(kg mixture of CH4 and 2H2O)
3.
Air,
T=1100K
Qcell
Fuel cell
CO,CO2,H2,H2O,CH4
T=1100K
H2O+CO2+N2
T=1100K
Wmax
Required O2 in the cell per one mole of mixture after reformer can be calculated as
CH4
8.48e-4
O2
Required
8.48e-4*2
CO
H2
0.16
0.638
0.16/2
0.638/2
Total
0.4
Hence, 0.4 mole of O2 and 0.4*3.76=1.504 mole of N2 is required in the cell per one
mole of mixture. In terms of mass, 5.25kg of air is required per kg of (CH4+2H2O)
To calculate G , we use Equil again and an example of input files is as follow:
Gas Chemistry Input
ELEMENTS C H O N END
Application Input
REAC CO 0.16
REAC H2 0.638
REAC O2 0.4
REAC N2 1.504
PT
PRES 1
TEMP 1100
END
INITIAL STATE:
1.0000E+00
1.1000E+03
4.0094E+03
1.3874E+08
-3.9238E+09
1.0306E+08
2.2513E+01
5.5099E-02
1.3775E-02
2.9203E-04
1.3775E-01
2.1971E-01
5.5444E-02
5.1793E-01
EQUILIBRIUM STATE:
1.0000E+00
1.1000E+03
3.4593E+03
-3.1069E+10
-3.4574E+10
9.3398E+07
2.6092E+01
1.1214E-04
8.0049E-02
1.0086E-16
8.7922E-13
4.4343E-04
3.1913E-01
6.0027E-01
4.
Mole fractions after reformer
CH4
CO
CO2
H2
H2O
Mole fractions
8.48e-4
0.16
0.04
0.638
0.161
Number of moles/
(per kg mixture of
CH4 and 2H2O)
0.08
15.4
3.8
61.3
15.5
of H2 and CO)=168J/mol
H2O <=> H+ + OH(a) Use the Table 4.1 in the Lecture Note Electrochemical Energy Conversion and
Storage to define two half cell reactions for the above reaction and calculate the
electrochemical potential of the reaction under standard conditions.
(b) Calculate the molalities of H+ and OH- in deionized water at 298K from the Gibbs
free energy of reaction. Show calculation step by step.
2. An exhaust gas analyzer uses an electrochemical solid state cell (sensor) to measure
oxygen concentrations in the exhaust. This cell consists of a solid-state electrolyte
zirconium dioxide (ZrO2) with yttria (Y2O3) that provides oxygen ion conduction in the
cell, and Pt electrodes used for anode and cathode, depicted as,
Homework IV Solution
1. For an overall reaction of
H2O <=> H+ + OH(a) Use the Table 4.1 in the Lecture Note Electrochemical Energy Conversion and
Storage to define two half cell reactions for the above reaction and calculate the
electrochemical potential of the reaction under standard conditions.
H2O+e- <-> 1/2H2+OH- -0.828Volt
0 volt
1/2H2 <-> H+ + eH2O <->H++OH-
(Anode)
(Cathode)
-0.828Volt
(b) Calculate the molalities of H+ and OH- in deionized water at 298K. Show calculation
step by step and state all assumptions made.
Note that is related to mole fractions of H+ and OH- by the following equations
assuming that the activity coefficients of the species are 1:
a + a + m + m
Gro
)
Eq. 1 H OH = H H OH OH = K p (T , P) = exp(
aH 2Ol
RT
1
Assuming H + = OH = 1 ,
mH + mOH
= K p (T , P) = exp(
Gro
)
RT
1
Eq.2 nF = Gro .
From Eqs. 1 and 2, one can get Kw=[H+][OH-]=1.0x10-14 at 298K. If pH=7, then
[H+]=[OH-]=1.0x10-7. Then, the molalities (mH+ and mOH-) and molarities ([H+] and [OH]) of H+ and OH- are identical, which is equal to 1.0x10-7mole per 1000g water.
The molality is the number of moles of solute present in 1000 grams of water while molarity is the
number of moles of solute present in one liter of water. Note that 1000 grams is equivalent to one
liter of water.
2. An exhaust gas analyzer uses an electrochemical solid state cell (sensor) to measure
oxygen concentrations in the exhaust. This cell consists of a solid-state electrolyte
zirconium dioxide (ZrO2) with yttria (Y2O3) that provides oxygen ion conduction in the
cell, and Pt electrodes used for anode and cathode, depicted as,
O2 + 4e <=> 2O2(a) Please write the governing equation for the cell potential as a function of
pressures, Peg and Pair.
If one assumes that Peg >Pair and Peg and Pair are the partial pressure of O2 in the
exhaust and the air, respectively, the potential generated by partial pressure difference
is as follow:
Peg
RT
log(
)
nF
Pair
Note that Pt electrodes in the air acts as a cathode due to higher partial pressure of O2.
Also, it is assumed that the activity coefficients are 1.
(b) What would the cell voltage be when the partial pressure of oxygen in the exhaust gas
is 0.02atm?
State all assumptions made in answering (a) -(b)
If we assume T=300K, Pair=0.21atm, then we get
= 8.314 300 /(4 96485) log(0.02 / 0.21) =15.2mV
(b) What is the maximum amount of work that such a cell would produce?
Note that concentration of Cu2+ changes from 3.5 to (3.5+1)/2=2.25 in the
concentration cell and from 1 to 2.25 in the dilute cell.
If we define X is the change in the molal values in the concentrated solution and
assume that the activity coefficient of Cu2+ is 1 or does not change within the range
between 1 to 3.5 molal, we get
mCu 2+
RT
Dilute
=
log(
)=
nF
mCu 2+
Conc
Since X changes from 0 to 1.25.
Work =- G = nF = RT
1.25
1+ X
2H++2e- -> H2
Electrode 2 reaction (Cathode, 3.5molal solution)
Cu2+ +2e- -> Cu(s)
Potential between two electrodes can calculated as
2
aH + aCu( s )
RT
nF
2 96485C / mol
PH 2 aCu 2+
Hence, one can get value by measuring .
K C1
m3
131667
=
(0.001987T ) 2
mol
30620 1
1
exp
R T 298
KC2 =
103943
9834 1
1
exp
R
T 298
2
31400 1
1 m 3 1
s
k f ,1 = 0.933 exp 2.5
R
330 T
mol
18000 1
1
m 3
k f , 2 = 0.636 exp
R
300 T
mol
s
28956
1
1
s 1
R
325 T
Write down the reaction rate equations for the three reactions.
Write down the formation rates for each species in terms of the time rate of
change of its molar concentration.
Integrate these equations for p = 1, 10 and 100 atm, at temperatures in the
given range, take T = 320, 340, 360 and 380 K.
Use these results to determine the impact of the pressure on the concentration
of methanol in the products. Can you explain this trend form the reaction
equations?
Use the results to determine the optimum operating conditions for maximizing
methanol production in terms of p, T and residence time.
How much heat transfer is required in your optimum case to keep the
Integrating the differential equations is most easily done using Matlab ordinary
differential equations solver, Sungbae will post an example on how to do that.
Problem #2
Consider the electrode reaction O + e = R. Under the conditions that bulk concentrations
[O]*=[R]*=1mM, ko= 10-6cm/s, and =0.3.
1. Calculate the exchange current density, jo=io/A in microamps/cm2.
2. Draw a current density overpotential curve for this reaction for currents up to
600 microamps/cm2 anodic and cathodic. Neglect mass transfer effects.
3. Draw log j vs. a curves for the current ranges in question 2.
Homework V solution
Problem 1.
1. The reaction rate equations for the three reactions are as follow:
k b ,1 = k f ,1 / K C1
k b,2 = k f , 2 / K C 2
Rr ,3 = k f ,3 [CH 3 OH ]
Note that you should consider backward reactions in the first two reactions.
4. Increasing the pressure raises the mole fraction of CH3OH when T 340, but does not
have a significant effect after T 360. It is due to the following reasons:
1) In the first reaction, which generates CH3OH, the forward reaction favors higher
pressure since the number of moles decreases during the forward reaction. Thus, by
increasing the pressure of the reactor, the concentration of CH3OH increases more
rapidly.
2) After T 360, even at low pressure, the first reaction is sufficiently fast. So
increasing the pressure does not help. Also, note that the concentration of CH3OH
drops back to almost zero with time due to the third reaction (dissociation of
CH3OH) indicating that the third reaction becomes active after T 360.
5. The maximum mole fraction of CH3OH one can obtain is ~33% at T=340K and P=10100atm with a residence time less than 1msec.
6. The mole concentration changes at T=340K, P=10atm and residence time=1msec are
as follow:
Before the
reactor
(mol/m3)
After the
reactor
(mol/m3)
CO
H2
CH3OH H2O
CO2
CH2O
Total
71.5
167
47.6
71.5
357.3
0.0
25.8
70.6
47.1
72.0
0.3
215.8
From the first law of the thermodynamics one can get Q as follow:
Q = H 2 H 1 = ni hi ni hi =-6.5MJ
P
Since this Q is with 357.3 mole of inlet mixture, one can get Q& as follow:
Q& = 6.5MJ / 357.3moles 300moles / s = 5.4 Mwatt
Problem 2.
1.
*
j o = io / A = k o [O ] F = 10 6 cm / s 10 3 mol / 1000cm 3 96485Coulomb / mol = 9.65 10 2 A / cm 2
2 and 3. Using the Butler-Volmer equation, you can get the following figures
e-
Cathode
Anode
e-
Proton Exchange
Membrane
H2
H+
H+
Carbon Supported
Pt Particles
H2O
H2O
H+
H+
H2O
H2O
O2/Air
Nafion type
membrane
H2O
Carbon Supported
Pt Particles
1) Calculate the equilibrium fuel cell voltage under the operating conditions.
2) Develop an analytical expression that relates the fuel cell operating voltage to the
current density obtainable from the fuel cells by considering ohmic and activation
overpotentials across the cell. Plot the effect of ohmic and activation
overpotentials to the fuel cell voltage loss as a function of current density in
mA/cm2 in the range from 0 to 2A/cm2.
3) Plot the second law efficiency of the fuel cell (see equation 2.7 in lecture note on
electrochemical thermodynamics (electrochemLecturenote1.pdf)) and the power
density in W/cm2 as a function of current density in mA/cm2.
Please state all assumptions clearly.
HOMEWORK VI Solution
1)
One can get the equilibrium fuel cell voltage from the following equation:
Gr (T , P )
=
Eq.(1)
ne F
Note that Gr is the function of T and P. Using Equil, one can get
Gr (T = 353K , P = 150kPa) =230kJ/(mole of H2). Using Eq.(1), we get
230kJ / mole
= 1.19Volt
=
2 * 96485C / mole
2)
i
/A
a ,cathode = RT ln( o ,cathode )
ne F
i/ A
io ,anode / A
RT
ln(
)
i/ A
(1 )ne F
i
= i R = R A
A
cell = r a ,cathode- a ,anode
a ,anode =
3)
sec ond =
i 1
1
i
i
H& r / A = hr
= 284kJ / mol
= 1.47 10 3 (W / m 2 )
A 2F
2 96485C / mol A
A
W& out = current density x cell potential (W/m2)
athena % chemkin
Figure 4 Gas_equil.inp
identified by its chemical symbol and its number of moles in the mixture.
after END keyword. Therefore, if CNTN is used, one can get more than one
END signifies the end of the keywords for a particular equil calculation.
7) Also, you can generate your own file and name it ****.inp instead of
Gas_equil.inp file.
8) Once chem..inp and Gas_equil.inp files are ready, you can calculate the
equilibrium conditions. Click the run button and the program will start computing
the equilibrium conditions.
9) After the computation is finished, click view the button of equil.out. You will see
the following text.
EQUIL: Chemkin interface for Stanjan-III
CHEMKIN-III Version 3.20, 2000/09/11
DOUBLE PRECISION
WORKING SPACE REQUIREMENTS
PROVIDED REQUIRED
INTEGER 579 579
REAL 2052 2052
CHARACTER 34 34
CKLIB: CHEMKIN-III GAS-PHASE CHEMICAL KINETICS LIBRARY,
DOUBLE PRECISION Vers. 5.31 2000/10/02
Copyright 1995, Sandia Corporation.
The U.S. Government retains a limited license in this software.
KEYWORD INPUT
REAC H2 2
REAC O2 1
REAC N2 3.76
HP
TEMP 300
TEST 2000
PRES 1
CNTN
END
Constant pressure and enthalpy problem.
EQUIL: Chemkin interface for Stanjan-III
CHEMKIN-III Version 3.20, 2000/09/11
DOUBLE PRECISION
WORKING SPACE REQUIREMENTS
PROVIDED REQUIRED