260 Spring 2004 PDF

FUNDAMENTALS OF
ADVANCED ENERGY CONVERSION

2.996 & 2.994, Spring 04
A Ghoniem (IC), M Kazimi, Y Shao-Horn, J Tester
WHY ?
CO2, Terawatts, Needs and Sources,
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
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ENERGY
WATER
FOOD
ENVIRONMENT
POVERTY
TERRORISM & WAR
DISEASE
EDUCATION
DEMOCRACY
POPULATION
2003
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9.
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2050
Source: Internatinal Energy Agency
40
Carbon free
sources to
stabilize
CO2
30 -- 60 Terawatts
35
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*Noble prize, Chemistry, 1996
O
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Energy Sources and Demand
TW
50
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-Should be CO2 free

To limit CO2 to 450
30
CO2 free
--
20
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0
2000
2020
2040
2060
2080
2100
YEAR
Source: M.I. Hoffert et. al., Nature, 1998, 395, 881,
Wigley, Richels and Edmonds, ppmv of CO2, pre-industrial concentration is 350 ppmv
CO2 emissions and
Global Temperature!
CO2 emission
reduction:
Improve plant
efficiency
Use low C fuels
Use pure H2
Sequester CO2!
RENEWABLES
From Basic Research Need for a

Hydrogen Economy, Report of DOE BES
Workshop, May 13-15, 2003
FIGURE 1. GASIFICATION-BASED ENERGY PRODUCTION SYSTEM CONCEPTS
FIGURE 2. GASIFICATION-BASED ENERGY CONVERSION SYSTEM OPTIONS
(Courtesy of Prof. Wilson and Prof. Korakianitis. Used with permission.)
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.
Optimal Hydrogen Utilization: the Fuel Cell
Basic Energy Needs for the Hydrogen Economy, May 2003, DOE
How to Fuel the Fuel Cell Engine?
Especially for mobile applications, fuel cells may work with a reformer
(although direct methanol cells are also under development)
HYDROGEN & THE HYDROGEN ECONOMY
Energy carrier: must be produced, stored, transported & charged.
Like electricity: expensive to produce, transport, not easy to store.

Provides a good link with renewables or non-exhaustables.
Can be produced by:

Oxygen or steam Reforming of hydrocarbon, or,
Splitting water electrolytically or thermo-chemically.
Compression/liquefaction (20 K, 1 bar/293 K, 800 bar) energies are high.

Has low volumetric energy density (even in liquid form)
Storage: metal fiber tanks, cryogenic container, or in metal
hydrides (solids): through physical or chemical sorption.
The Mobile
Storage Problem:
Fuel Cell may be the
easiest piece of the
puzzle!
The Future of the Hydrogen Economy, Bright or Bleak

Eliasson (ABB) and Bossel (Fuel Cell Consultant), 2003
GMs HyWire
HYDROGEN STORAGE IN THE SOLID STATE
e.g., Sodium borohyrdride Cycle
NaBH 4 + 2H 2O catalysis
4H 2 + NaBO2
Typical fuel: 30% NaBH4+3%NaHO+67%H2, has 6.6%H2, all by wt.
OR 66 gH2/L compared to 70 g/L liquid H2 and 23 g/L gas (at 350 bar).
Nuclear Hydrogen Production
Q@120C
2 I2 +SO2 +2H2O2HI+H2SO2
+Q@800950C
2H2SO4
2SO2 +2H2O+O2
+Q@450C
2 2HII2 +H2
Thermochemical Cycle
for Hydrogen Production:

Sulfur-iodine process:
Non-electrolytic water splitting
850 C
2 H 2O +Q
@
2 H 2 + O 2
50%
Solar Hydrogen Production
Capture/conversion + Electrolysis
Basic Energy Needs for the Hydrogen Economy,

May 2003, DOE.
Spring 04, subject is offered as 2.996 (G) and 2.994 (U)
FUNDAMENTALS OF ADVANCED ENERGY CONVERSION
(2.60j, 2.62j,10.392j, 22.40j)
Perquisite: 2.006 or permission of instructor
G (Spring)
4-0-8 H-LEVEL Grad Credit,
A.F. Ghoniem (IC), M. Kazimi, Y. Shao-Horn, J. Tester.

Fundamentals of thermodynamics, chemistry, transport processes in energy sy stems.
Analysis of energy conv ersion in thermo-mechanical, thermo-chemical, electrochemical,
and photoelectric processes in existing and future power and transportation systems, with
emphasis on efficiency, environmental impact and performance. Systems utilizing fossil
fuels, hydrogen, nuclear and renewable resources, over a range of sizes and scales are
discussed. App lications include fuel reforming, hydrogen and synthetic fuel production,
fuel cells and batteries, combustion, catalysis, supercritical and combined cycles,
photovoltaics, etc. Energy storage and transmission. Optimal source utilization and fuellife cycle analysis.
From matter and Energy (1912) by Frederick Soddy Noble Prize in Chemistry, 1921.
The laws expressing the relations between energy and

matter are not solely of importance in pure science.
They necessarily come first.. In the whole record of
human experience, and they control, in the last resort,
the rise or fall of political systems, the freedom or
bondage of nations, the movements of commerce and
industry, the origin of wealth and poverty and the
physical welfare of the race. If this has been
imperfectly recognized in the past, there is no excuse,
now that these physical laws have become incorporated
into everyday habits of thought, for neglecting to
consider them first in questions relating to the future
2.996 Fundamentals of Advanced Energy Conversion Lecture Memo

Lecture number: 1
Date: February 4th, 2004
Needs: Terawatt challenge
Energy source and demand
CO2 emissions and global temperature
Thermal efficiencies of different turbines and combined cycles
Fuel cell: storage problem, storage in the solid state
Nuclear hydrogen production
Solar hydrogen production

Lecture number: 2
The first law of thermodynamics: Work and heat interactions

The stored energy
First law for an open system
The second law of thermodynamics: Entropy generation, efficiency
The combined statement of the first and second laws: Availability
Efficiency and second law efficiency

Lecture number: 3
Entropy in an open system
Isentropic process
Brayton cycles : Compressor and turbine efficiencies

Cycle efficiency, wnet
Recuperative cycle
Steam cycles : Conventional, superheating, reheat and regeneration cycle
Combined cycles
Gas mixtures: Molar and mass fractions, molecular weight, partial pressure
Internal energy, enthalpy and ehthropy.

Lecture number: 4
Mole, mole fraction, mass fraction, average molecular weight
Gas mixture: Partial pressure and volume

Internal energy, enthalpy and entropy
cp change with temperature
Entropy generation due to mixing
Separation of gases: CO2 sequestration

H2 production
Minimum work for separation (Ex. C6H6)
Reacting mixtures: Irreversibility

Endothermic and exothermic
Stoichiometry
Energy balance: Enthalpy of formation

Adiabatic flame temperature
IC engine: Introduction to Otto cycle

Lecture number: 5
Chemical thermodynamics: Adiabatic flame temperature

Enthalpy of reaction
Low and high heating values
Availability of a chemical reaction: Gibbs free energy, efficiency
Direct conversion: Fuel cell

Efficiency change with respect to operating temperature
Reactions in fuel cells
Electrolyzer
Indirect conversion: Carnot cycle efficiency

Internal combustion engine (SI)
Otto cycle efficiencies
1) Air standard cycle
2) Fuel/air cycle
3) Complete/incomplete combustions

Lecture number: 6
Date: February 23rd, 2004
Thermodynamics of a fuel cell

Maximum work, Ideal electric potential, and Nernest Equation
Efficiencies: first, second and fuel utilization
Change of the first law efficiency with changes in Temperature
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

Lecture number: 7
History of Thermodynamics: Thompson, Joule, Clausius, Carnot
Chemical potential in fuel cells
Review of Chemical Equilibrium

Constant U,V constraints: Maximization of entropy
Constant T,P constraints: Minimization of gibbs free energy
Law of mass action
Equilibrium constant
Endothermic and exothermic reactions
Fuel reforming
Steam reforming
Water gas shift
Introduction to a chemical equilibrium program(Equil).
Electrochemical energy conversion and storage

Readings, objective and scope

Lecture number: 8
Date: March 1st, 2004
Efficiency revisited: First law, second law, electrochemical, fuel efficiencies
Faradays law, Faradic efficiency
Basic operations of electrochemical cells: anode and cathode
Conservation of charge
Cell types: Galvanic, Equilibrium and Electrolytic
Pb-acid rechargeable battery
Complete cell diagram
Standard reference potential
The combined 1st and 2nd laws with generalized work

Lecture number: 9
Date: March 3rd, 2004
General equilibrium criteria
Gibbs-Faraday equilibrium equation
Derivation of the Nernst equation
Fugacity and activity
Fugacity of electrolyte solutions
Molality, Ionic strength

Lecture number: 10
Date: March 8th, 2004
Examples for cell potential calculations: H2/O2 and Zn/Cu cells
Review of Gibbs-Faraday equilibrium equation
Review of fugacity and activity
Nernst equation for ideal gases, liquid solutions and solids
Overall redox reaction in a galvanic cell
Chemical kinetics
Rate processes: chemical reaction rate, transport rate and flowrate

convection
Elementary, global and chain reactions.

Lecture number: 11
Power ratings of different applications
Chemical kinetics of H2 and O2 reaction
Reaction rate equation
Forward and backward reactions
Activation energy
Ozone reaction
Single step kinetics
Well stirred reactor: Governing equations, T-Q diagram, efficiency and

blowout

Lecture number: 12
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

Lecture number: 13
Power densities in IC engines, lithium batteries and fuel cells
Over potential
1) Ohmic overpotential
2) Activation overpotential
3) Mass transfer overpotential
Forward and backward reactions in a simple redox process
Standard activation energy for the anodic and cathodic reactions
Transfer coefficient
1) Changes in the free energies
2) Changes in the forward and backward reaction rates
Electrochemical reaction rate
Butler-Volmer Equation

Lecture number: 14
Cell voltage profile for PEM: Cathode activation, cell resistance, anode
activation and mass transport
Butler Volmer model :Tafel relationship
Example: Copper plating
Oxygen reduction
Multistep mechanisms
Introduction to mass transport

Lecture number: 16
Date: April 5th, 2004
Kinetic theory of gases

Rate of change of momentum
Mean free path
Molecular transport
Transport equation
Fouriers law
Ficks law
Species conservation equation
Energy conservation equation

Lecture number: 18
Flames in SI engines
Laminar and turbulent burning velocities
Microscopic flame structure
Two zone model
Dependency of Su on thermal diffusivity and characteristic time scale
Dependency of Su on equivalence ratio
Stratification and turbulence generation in engines
Knock

Lecture number: 19
Brayton cycle
Gas turbine combined cycle
Supercritical steam cycle
Coal gasification
Fuel cell/gas turbine cycle
CO2 capture
Nuclear power conversion: Boiling water reactor and pressurized water

reactor
Fission reaction
Neutron number vs atomic number and binding energy per neutron
Energy spectrum of fission neutrons
Supercritical water reactor
Gas cooled reactors
Multiple parameter optimization of a CO2 supercritical cycle to advanced

nuclear reactors.

Lecture number: 20
Hydrogen characteristics
Current and projected hydrogen powered cells
Projected effects of switching to hydrogen powered cars
Alternative ways of H2 production today and tomorrow
Nuclear technology in the hydrogen economy
Availability
Availability diagram for water
Component irreversibility

Lecture number: 21
Changes in the utilization factor with respect to turbine inlet pressure
Irreversibility analysis for a feed pump and the primary heat exchanger
Optimization of Supercritical CO2 Power Cycle

- Efficiencies of various cycles
- Various cycle losses
- Thermodynamic optimization process in
A simple Brayton cycle with recuperation
Brayton Cycles with Reheat Recompression
Brayton Cycle with Intercooling

Lecture number: 22
Electrolysis
-
Diffusion and migration
Limiting current
Applied voltage vs. current
Photovoltaics
-
Opportunity
Market segments
Cost
Solar panel and cell
Market share by technology
Crystalline silicon technology

Lecture number: 23
Date: May 3rd, 2004
Fuel cell
- History
-
Types
Advantages and disadvantages
Specific energy comparisons with heat engines
Leading organizations
Electricity failure from approximately 1:30PM and the class was dismissed.

Lecture number: 24
Date: May 5th, 2004
Proton Exchange Membrane Fuel Cells (PEMFC)

- Membrane Electrode Assembly (MEA) and components
- Catalyst layer structure
- MEA preparation method and structure
- Nafion membrane failure mechanism
- Coarsening of Pt particles
- PEMFC construction
- State of the art MEA performance
Solid Oxide Fuel Cells (SOFC)

- Electrochemical reactions
- SOFC materials
- SOFC planar design
- Siemens SOFC technology
- Technical challenges
- SOFC electrode performance
- Oxygen reduction process

Lecture number: 25
Date: May 10th, 2004
Battery types: Primary, secondary and reserve batteries

World battery production
Major considerations in battery selection
Fuel cell and battery voltages
Voltage profiles of common battery systems
Specific capacity of electrode materials
Alkaline Zn/MnO2 and lithium primary batteries
Battery design
Energy and power density of batteries
Secondary batteries (Lead acid, Ni-Cd, NiMH and Lithium batteries):
Advantages and disadvantages
Applications
Material degradation
Fundamentals of Advanced Energy Conversion

Spring 2004
Homework Set #1
Problem 1. The purpose of this problem is to familiarize you with the units of energy
and to compare some of the characteristics of various energy sources.
A 1000 MWe power plant is being planned for the rapidly expanding city of Las Vegas.
Consider three possible options for the plant: nuclear, coal and solar fueled. The total
system should have a capacity factor of 90%. Answer the following questions.
1.1 If an advanced nuclear power reactor is to be used, what amount of natural uranium
will be needed to fuel the plant annually? The thermal to electrical energy conversion
efficiency using a water-steam Rankine cycle with sub-critical pressure is 35%. The
nuclear to thermal energy conversion efficiency in the reactor is 95%, due to the
emissions of neutrinos which are not captured in the core. For simplicity assume U235 is the only fissionable material. By weight, U-235 constitutes 0.71% of natural
uranium, and the rest is U-238. The reactor fresh fuel requires a higher fraction of
U-235 (typically 4.4% in todays light water cooled reactors) which is obtained by
isotopic enrichment of the natural uranium. However, due to the energy intensity of
the operation of the enrichment plants when the U-235 fraction gets to be small, the
discarded uranium in the enrichment process (called uranium tails) has 0.25% U-235
fraction. The fission of one gram of U-235 produces 1 MW-day worth of nuclear
energy.
1.2 If the plant is to be of an advanced pulverized coal fired plant with a supercritical
water-steam Rankine cycle, what is the average daily amount of coal (in kg/day)
consumed to power the plant? Consult the notes from the first lecture (or other
sources) for the thermal efficiency of such plants. Assume the combustion of 1kg of
coal provides 27,800 Btu of energy (this is an average value, the real heat of
combustion varies with the type of coal). 1J = 9.48x10-4 Btu = 0.239cal.
1.3 If an advanced solar photovoltaic plant is to be used, with the best available solar
flux-to-electricity conversion efficiency of 12%, what is the total land area required to
provide the needed power? You may assume that the land needed is 2 times the flat
panel area. The daily total (direct and diffuse radiation) solar energy flux near the
city of Las Vegas has an annual average of 500 cal /cm2 per day. Assume that the
solar plant will have to also store sufficient energy during the day to meet an
equivalent demand at night.
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
Using Eqs. (1) and (2), we get

Y=0.1108X
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.
M.M. El-Wakil, Power Plant Technology, McGraw Hill, 2984, page 72
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)
Also, work can be represented as
w = c p (T3 T1 ) + c p (T2 T1 )
Eq.(6)
Using Eqs. (5) and (6), we get

P
w = c p T1 2
P1
( 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
thermal =0.5 : thermal efficiency

voltage =0.7/1.23=0.569 : Voltage drop
H 2 =237/286=0.829 : H2 to electric power conversion efficiency
tot = thermal * voltage * H 2 =0.236
3.2
tot =0.96* ICE

ICE =0.246
3.3
0.7* H 2 * voltage =0.330
0.330=0.96 ICE
ICE =0.344
Without considering the refinery efficiency of fuels, it becomes
ICE =0.330
MASSACHESUTS ISNTITUTE OF TECHNOLOGY

FUNDAMNETALS OF ADVANCED ENEFRGY CONVERSION
SPRING 04
HOMEWORK II
DUE DATE, FEBRARY 23, 2004
The rising atmospheric concentration of carbon dioxide, a product of hydrocarbon
combustion and a known green house gas, is a major environmental concern.
Means to reduce the rate of CO2 emission into the atmosphere include improving
energy conversion efficiency and using carbon free energy sources. Another way is
sequestration, that is to separate CO2 from the combustion products and store it in
some form away from the atmosphere. This technology is still in its infancy, but
effort to evaluate the energy penalty of sequestration, and potential long-term
success of storage is underway (see sequestration.mit.edu for more information and
some useful links). In this exercise, we will explore the energy penalty of CO2
sequestration from advanced power plants, using different separation strategies.
Consider a case in which benzene(C6H6) is used as a fuel, and calculate the total
separation and liquefaction work required in each of the following cases, as a fraction of
the available energy in the fuel, and of the work produced in the cycle without
sequestration.
Make the following assumptions:
(a) The maximum allowable cycle temperature is 1300 C. This is the temperature in
the combustor, achieved by burning the fuel stoichiometrically, and then mixing the
products with extra gases to reduce the temperature.
(b) The power cycle is an advanced combined cycle with efficiency 50%, based on the
total work produced without sequestration, and the fuel enthalpy of reaction.
(c) The products exit the cycle at 1 atm and 300 K.
(d) The environment is at 300 K and 1 atm.
(e) The final state of sequestered CO2 is liquid at 300 K and 100 atm.
I.
In the first design, it is suggested that we burn benzene in air, then remove CO2
from the products. The pressure ratio across the gas turbine compressor is 25, and the
compressor efficiency is 85%. Separate CO2 from the products in gaseous form first.
Next liquefy CO2.
(1)
(2)
(3)
(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.
Then, the second law efficiency becomes
0.5
II =
= 0.62
0.81
LHV of C6H6=40141kJ/kg=3131MJ/kmol (liquid) (Boiling point of C6H6 is 80 C)

Fuel per available energy is: 1kg/(40140kJ*0.81)=1kmol/2536MJ1
Fuel per work produced without sequestration: 1kg/20070kJ=1kmol/1565MJ.
(2)
Compression of air (assumptions: T1 =300K and P1 =1atm)
P T
From 2 = 2
P1 T1
k /(k 1)
and T2 = T1 + (T2 s T1 ) /
c
T2 =832K and P2 =25atm

In the combustion process (assumption: No CO and H2 generation)
C 6 H 6 + 7.5(O2 + 3.76 N 2 ) 6CO2 + 3H 2 O + 3.76 7.5 N

2
From H R (T2 = 832K ) = H p (T3 ) , we get T3 = 2878K
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
6CO2 + 3H 2 O + 3.76 7.5 N 2 + X (O2 + 3.76 N 2 ) 6CO2 + 3H 2 O + XO2 + 3.76(7.5 + X ) N 2

From H R (T3 ) + H R (T2 ) = H P (T4 = 1573K ) where
T3
T3
T3
H R (T3 ) = 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
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)
Separation work (Assume H2O is all liquid)
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
w = ((hCO 2, 2 hCO 2,1 ) T ( sCO 2, 2 sCO 2,1 ))

= (560kJ / kg 810kJ / kg ) 300 K * (3.3kJ / kgK 4.9kJ / kgK )
= 230kJ / kg of CO2
Since 6kmol(264kg) of CO2 is generated by 1kmol of C6H6, the required work for
liquefaction is 60.7MJ/kmol of C6H6 (3.9% of the work produced in the cycle)
Total sequestration work is 119.3MJ/kmol of C6H6 (7.6% of the work produced in
the cycle)
Ideal work
,
Actual work
Actual work = Ideal work / II = 1.25 Ideal work
(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
P4=30atm, S4=S3, h4=910kJ/kg
T5=300K, P5=30atm, h5=780kJ/kg
P6=100atm,S6=S5, h6=840kJ/kg
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
From H R (T2 = 832 K ) = H p (T3 = 1573K ) , we get X = 110.56.

Hence, in the initial separation of N2
110.56*3.76N2+
110.56O2
T=300K,
P=1atm
110.56*3.76N2
110.56O2
T=300K,
P=1atm
Required work for separation: 674.8MJ/kmol of C6H6 (Significant increase in work

due to the increase in the number of moles being separated)
However, if we do not throw out O2 after the turbine and circulate it, we only use
7.5moles of O2 instead of 110.56moles per 1 mole of C6H6. Hence, the required
work is
674.8MJ/kmol*7.5moles/110.56moles=45.8MJ/kmol of C6H6
One problem of circulating O2 is that we need to separate O2 from CO2 in the
product as follow:
6CO2+103.06O2
T=300K,
P=1atm
6CO2
103.06O2
T=300K,
P=1atm
The required work of this process is 58.0MJ/kmol of C6H6.
Total required work for separation is 45.8+58=103.8MJ/kmol of C6H6.
There is no change in the liquefaction work of CO2.
III.
Combustion (adiabatic, p=1atm)
C 6 H 6 + 6(O2 + 3.76 N 2 ) 6CO2 + 3H 2 + 6 * 3.76 N 2
From H R (T1 = 300K ) = H p (T2 ) , we get T2 = 2342 K

Separation (Const T)
6*3.76N2+3H2
6CO2+6*3.76N2+
3H2
6CO2
T=2342K,
P=1atm
T=2342K,
P=1atm
Required work for separation: 299MJ/kmol of C6H6 (Significant increase due to

increase in T)
For the liquefaction work, if we assume inlet temperature is 300K, then we get the same
required work (60.7MJ/kmol of C6H6). However, note that we may be able to use
extracted heat from CO2 since the temperature of the CO2 after the separator is 2342K.
The availability of CO2 can be calculated in the following process, assuming environment
temperature is 300K
6CO2
T=2342K
P=1atm
6CO2
T=300K
P=1atm
Wmax = H 1 H 2 To (S1 S 2 ) = 6moles * (112MJ / kmol 300K * 0.319 MJ / kmol)

= 97.8MJ
Hence, the total required work for sequestration is
(299-97.8+60.7)MJ/kmol of C6H6=262MJ/kmol of C6H6

SPRING 04
HOMEWORK III
DUE DATE, March 1, 2004
Most fuel cells run on pure hydrogen, or a mixture of inert gases and hydrogen, as a
fuel; and pure oxygen, or air as an oxidizer. Storing hydrogen requires either a
high-pressure tank, if kept in the gaseous phase, or a cryogenic tank, if maintained
in the liquid phase. Instead. One can start with another, easier to store fuel, e.g.,
methane CH4, reform that fuel to H2 and CO, and use this mixture in the cell. High
temperature solid oxide fuel cells are particularly suitable for processing such
mixture. In the homework, you will use a thermochemical properties code, EQUIL
to estimate the reforming requirements, and the cell efficiency.
The reforming process proposed here is a combined steam reforming and gas shift in one
step, that is:
CH 4 + 2H2O CO2 + 4H2 .
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)
Use EQUIL to determine the composition of the gas mixture as it exits a

reformer at T = 1100 K. Gaseous methane and liquid water enter the reformer
at 300 K. The reformer operates at atmospheric pressure.
(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
SPECIES CO H2 CO2 CH4 H2O END
Surface Chemistry Input
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.
*
**************************************************************
WORKING SPACE REQUIREMENTS

PROVIDED
REQUIRED
INTEGER
494
494
REAL
1281
1281
CHARACTER
37
37
Initializing CHEMKIN Gas-phase Library, a component of CHEMKIN Release 3.7.
This and All Other CHEMKIN Libraries are Copyright (C) 1997-2002 Reaction
Design.
Initializing SURFACE CHEMKIN Library, a component of CHEMKIN Release 3.7.
KEYWORD INPUT
REAC CH4 1
REAC H2O(L) 2
TP
PRES 1
TEMP 300
CNTN
END
Constant temperature and pressure problem.
Calling SUBROUTINE EQUIL
PROVIDED
REQUIRED
INTEGER
282
282
REAL
963
963
CHAR
6
6
MIXTURE:
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
BULK PHASE: BULK1

Mols
2.0000E+00
Mol Fractions
H2O(L)
1.0000E+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
CONTINUING TO NEW PROBLEM*******

KEYWORD INPUT
REAC CH4 1
REAC H2O(L) 2
TP
PRES 1
TEMP 1100
Reached end of input ...
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
Total CPUtime: 1 (seconds)

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
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
SPECIES CO CO2 CH4 O2 H2 H2O N2 END
Application Input
REAC CH4 8.48E-4
REAC CO 0.16
REAC CO2 0.04
REAC H2 0.638
REAC H2O 0.161
REAC O2 0.4
REAC N2 1.504
PT
PRES 1
TEMP 1100
END
Solutions are as follow:

Calling SUBROUTINE EQUIL
PROVIDED
REQUIRED
INTEGER
341
341
REAL
1196
1196
CHAR
7
7
MIXTURE:
P (atm)
T (K)
V (cm3/gm)
H (erg/gm)
U (erg/gm)
S (erg/gm-K)
W (gm/mol)
Mol Fractions
CO
CO2
CH4
O2
H2
H2O
N2
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
Total CPUtime: 2 (seconds)

Wmax = G = (H 2 TS 2 ) + (H 1 TS1 )
=-(-3.1069E+10-1100*9.3398E+07)+(1.3874E+08-1100* 1.0306E+08)
= 2.06x1010erg/gm=2.06MJ/(kg mixture)
We can get Wmax per unit mass of the reformer mixture by
Wmax =2.06MJ/(kg mixture)*(1kg+5.25kg)/ (kg mixture of CH4 and 2H2O)

=12.9MJ/(kg mixture of CH4 and 2H2O),
Qcell can be calculate from energy balance as
Qcell Wmax = H 2 H 1 =-6.66MJ/(kg mixture of CH4 and 2H2O)
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
If we represent Wmax per mole of H2 and CO used,
12.9MJ/(kg mixture of CH4 and 2H2O)* (kg mixture of CO and2H2)/(61.3+15.5 moles
of H2 and CO)=168J/mol
Voltage= 168*1000J/mol /(2*96485C/mol)=0.87Volt

SPRING 04
HOMEWORK IV
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.
(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,
Pt O2 (exhaust , peg ) ZrO2 + Y2O3 O2 (air , pair ) Pt

The electrode reaction that occurs at high temperature at both the anode-electrolyte and
cathode-electrolyte interfaces is
O2 + 4e <=> 2O2(a) Please derive the governing equation for the cell potential as a function of pressures,
Peg and Pair.
(b) What would the cell voltage be when the partial pressure of oxygen in the exhaust gas
is 0.02atm?
3. Consider an electrochemical cell with different concentration of aqueous CuCl2
solutions in each 1/2 cell. 3.5 molal CuCl2 on one side and 1 molal CuCl2 solution on the
other side separated by an ion conducting membrane permeable only to Cu+2 and Cl-1
ions. The electrodes are Pt coated with a thin film of copper metal.
(a) Initially will the cell produce a current against a resistive load? Explain.
(b) What is the maximum amount of work that such a cell would produce?
(c) What happens to the concentrations of ions in the cell after a period of time?
(d) Is there a way that you could modify this cell to determine the mean ionic activity of
CuCl2 as a function of concentration? (hint- Consider coupling the cell to a standard
hydrogen electrode via a salt bridge.
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. Mole fraction,
molality
Xi =
. State all assumptions made in answering questions 1-3.
molality + 1000 /18
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,
Pt O2 (exhaust , peg ) ZrO2 + Y2O3 O2 (air , pair ) Pt

The electrode reaction that occurs at high temperature at both the anode-electrolyte and
cathode-electrolyte interfaces is
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
3. Consider an electrochemical cell with different concentration of aqueous CuCl2

solutions in each 1/2 cell. 3.5 molal CuCl2 on one side and 1 molal CuCl2 solution on the
other side separated by a ion conducting membrane permeable only to Cu+2 and Cl-1 ions.
The electrodes are Pt coated with a thin film of copper metal.
(a) Initially will the cell produce a current against a resistive load? Explain.
A concentration cell produces a voltage as it attempts to reach equilibrium, which will
occur when the concentration in both cells are equal. To reach this point, Cu2+ ions in
the concentrated solution (3.5molal solution) are reduced while oxidation increases
Cu2+ in the dilute solution. However, oxidation of Cl-1 cannot occur since the standard
potential of Cl- is higher than that of Cu2+. Hence, released electrons from the anode
by Cu2+ oxidation can produce current passing through a resistive circuit. To satisfy
the local electroneutrality, Cl- should migrate from the concentration cell through the
membrane to the dilute cell. These reactions are represented as follow:
Electrode 1 reaction (Cathode, 3.5molal solution)
Cu2+ +2e- -> Cu(s)
cathode = 0.337V RT /(nF ) log(1/ Cu 2+ mCu 2+ ) where activity coefficient is equal to 1.
Note that Cl2(g) (Cl2(g)+2e- -> 2Cl- ) is not available and hence reduction of Cu2+
only occurs in the cathode.
Electrode 2 reaction (Anode, 1molal solution)
Cu(s) -> Cu2+ +2e anode = 0.337V RT /(nF ) log( Cu 2+ mCu 2+ )

Potential in the resistive load can be calculated as
[ 2+ m 2+ ]Dilute
[m 2+ ]Dilute
RT
RT
= cathode anode =
=
assuming the
log Cu Cu
log Cu
[ Cu 2+ mCu 2+ ]Conc
[mCu 2+ ]Conc
nF
nF
activity coefficients of Cu2+ ions in the dilute and concentrated solutions are the same.
Note that [mCu 2+ ]concentrated > [mCu 2+ ]Dilute and hence > 0 .
(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
log( 3.5 X )dX

0
Assuming T=300K, we get Work=1.47kJ/(mole of CuCl2)

(c) What happens to the concentrations of ions in the cell after a period of time?
Over a long period of time the potential will drop to zero when the concentrations of
Cu2+ become 1.25 molal in both cells. Also, Cl-1 ions will move to the dilute solution
to satisfy local electroneutrality (1.25 molal in both cells).
(d) Is there a way that you could modify this cell to determine the mean ionic activity
of CuCl2 as a function of concentration? (hint- Consider coupling the cell to a
standard hydrogen electrode via a salt bridge. State all assumptions made in
answering (a) -(d)
If the cathode of the cell is connected to the hydrogen electrode, we get the following
reaction:
Hydrogen electrode (Anode)
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
) = 0.337V 8.314 J /(mol K ) 300 K ln(1/ Cu 2+ )

O
ln(
=
nF
2 96485C / mol
PH 2 aCu 2+
Hence, one can get value by measuring .

SPRING 04
HOMEWORK V
Problem #1
In this problem, you will practice working with finite rate reaction equations in the
context of synthetic fuel production. Review the ozone chemistry example in the note
before working on this example. You will discover how operating conditions must be
selected carefully to maximize the yield of the desired chemical while minimizing others.
A catalytic reactor is used for the synthesis of methanol, CH 3OH , starting with water and
carbon monoxide that are produced from coal gasification. The catalyst in the reactor is
active at temperatures between 300 and 450 K. The reactor runs at isothermal conditions.
The important elementary reactions for the conversion of carbon monoxide and water
to methanol are:
(1) CO + 2H 2 CH 3OH
(2) CO + H 2O CO 2 + H 2
(3) CH 3OH H 2 + CH 2O
While these are, in principle, not elementary reactions, for the purpose of this analysis
they can be considered as if they were. These reactions take place in the gas phase, and
under isothermal conditions. The first two reactions are reversible, the third in an
irreversible dissociation of methanol that, if possible, should be avoided.
The feed gas into the reactor consists of 7/15 hydrogen, 1/5 carbon monoxide, 1/5 carbon
dioxide and 2/15 steam, all by volume. The total molar flow rate is 300 mol/s, the inlet
temperature of the feed gas ranges from 300 - 400 K, and the reactor pressure ranges
from 1 160 atm.
The objective of the following analysis is to find the conditions at which we can
maximize the production of methanol within the reactor, including the pressure,
temperature and residence time. The residence time is defined as the time the gas spends
within the reactor to reach the final state. The following data are provided for the
reactions:
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
k f ,3 = 0.244 exp 1.5
s 1
R

325 T
H of (CH 3OH ) = 201kJ / mol , c P ,CH 3OH =

44 J /(
mol
K )
H of (CH 2O) = 116kJ / mol , cP ,CH 2O =

35.5 J
/(mol K )
The activation energies in these expression are given in cal, and the universal gas
constant is R=1.987cal/mol K. Assume that the inlet gas and the reactor temperatures are
the same.
1.
2.
3.
4.
5.
6.
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
temperature constant within the reactor?
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 ,1 = k f ,1 [CO ][H 2 ] k b ,1 [CH 3 OH ]

2
Rr , 2 = k f , 2 [CO ][H 2 O ] k b , 2 [CO2 ][H 2 ]
Rr ,3 = k f ,3 [CH 3 OH ]
Note that you should consider backward reactions in the first two reactions.
2. The rates of formation of each species are as follow:

d [CO ]
= Rr ,1 Rr , 2
dt
d [H 2 ]
= 2 Rr ,1 + Rr , 2 + Rr ,3
dt
d [CH 3OH ]
= Rr ,1 Rr ,3
dt
d [H 2 O ]
= Rr , 2
dt
d [CO 2 ]
= R r ,2
dt
d [CH 2 O ]
= Rr , 3
dt
3.
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

SPRING 04
HOMEWORK VI
DUE DATE, April 5, 2004
Consider a single proton exchange membrane fuel cell operated at 80C with pure H2
and pure O2 inputs at 150kpa, in which Pt nanoparticles supported on carbon are
used as the electrocatalyst for hydrogen oxidation and oxygen reduction. The anode
and cathode electrode areas are 5cm2. The ohmic resistance across the fuel cell is
5 10 3 ohms. The exchange current densities for the rate determining steps of
oxygen reduction and hydrogen oxidation on Pt nanoparticles are 5x10-11A/cm2 and
1x10-3A/cm2, respectively.
Electrical Load
e-
Operating Temperature 80C
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
Membrane Electrode Assembly (MEA)
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 =
Assuming =0.5 , we get the following plot
3)
sec ond =
Wout W& out / A

=
H r H& r / A
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)
How to use CHEMKIN

1. To open a Chemkin Window
1) logon Athena
2) At the Athena prompt, type
athena % add chemkin
athena % chemkin
3) The following Chemkin window will pop up.
Figure 1 Chemkin window

4) Select an application from Chemkin window. The available applications and
their functions are described below:
Aurara: well stirred reactor simulation.

Creslaf: channel flow simulation.
Equil: equilibrium state calculation.
Oppdif: diffusion flame between two opposing nozzles.
Plug: Plug-flow chemical reactor simulation.
Premix: steady, laminar, one-dimensional premixed flame
simulation.
Senkin: predicts homogeneous gas-phase chemical kinetics in a
closed system with sensitivity analysis.
Shock: predicts the state of the products behind incident and
reflected shocks.
Spin: simulates one-dimensional rotating-disk.
Surftherm: analyzes the thermochemical and kinetic data in gasphase
and surface chemical reaction mechanisms.
In the next section, we describe how to use Equil. Other applications can be used in a
similar manner. However, there is one distinct difference between Equil and other
applications. Equil application doesnt use reaction mechanism data, however others use it.
2. How to Use Equil

Equil computes the chemical equilibrium state of an ideal gas or solution mixture.
1) Click the Equil button in the Chemkin window.
2) The window in Figure 2 appears.
Figure 2 Equil window
3) To calculate equilibrium state, one needs to generate two input files:

chem.inp and gas_equil.inp.
4) If you click the edit button in Gas Chemistry, you can view and edit
chem.inp file as shown in Figure 3. This chem.inp file contains elements
and species data.
Figure 3 Chem.inp file

5) You can generate your own file and name it ****.inp instead of chem.inp
file, but the file should be in the directory specified in the working directory. To
generate the ***.inp file, either use the text editor in
Athena or use a PC and send the file to Athena through FTP.
6) Next, you need to generate Gas_equil.inp. When you click the edit button
in Equil, you will see Figure 4.
Figure 4 Gas_equil.inp
REAC in Figure 4 stands for reactant; each line contains a reactant
identified by its chemical symbol and its number of moles in the mixture.
The reactants in the Figure 4 example are H2 , O2 and N2 . Their number of
moles is: 2, 1 and 3.76,respectively.
HP means constant enthalpy and pressure conditions. Other options are
available, e.g., EV, etc.
TEMP specifies the starting temperature (Units-K)
TEST specifies an estimate of the equilibrium temperature (Units-K)
PRES specifies the starting pressure (Units-atm)
CNTN is used to continue the computation in a different initial condition
after END keyword. Therefore, if CNTN is used, one can get more than one
solution. In Figure 4, the initial temperature (keyword TEMP) is changed
from 300 to 400.
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
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
PROVIDED REQUIRED
INTEGER 485 485

REAL 1810 1810
CHAR 9 9
STANJAN: Version 3.95, September 1993
W. C. Reynolds, Stanford Univ.
MIXTURE: INITIAL STATE: EQUILIBRIUM STATE:
P (atm) 1.0000E+00 1.0000E+00
T (K) 3.0000E+02 2.3902E+03
V (cm3/gm) 1.1772E+03 8.0794E+03
H (erg/gm) 2.6368E+07 2.6368E+07
U (erg/gm) -1.1665E+09 -8.1601E+09
S (erg/gm-K) 8.7862E+07 1.1079E+08
W (gm/mol) 2.0911E+01 2.4275E+01
Mol Fractions
H2 2.9586E-01 1.4689E-02
H 0.0000E+00 1.8294E-03
O2 1.4793E-01 5.6253E-03
O 0.0000E+00 6.1139E-04
OH 0.0000E+00 7.4783E-03
HO2 0.0000E+00 1.4207E-06
H2O 0.0000E+00 3.2410E-01
N2 5.5621E-01 6.4567E-01
H2O2 0.0000E+00 1.3816E-07
*************************CONTINUING TO NEW PROBLEM*************************
KEYWORD INPUT
REAC H2 2
REAC O2 1
REAC N2 3.76
HP
TEMP 400
TEST 2000
PRES 1
CNTN
END
P (atm) 1.0000E+00 1.0000E+00
T (K) 4.0000E+02 2.4406E+03
V (cm3/gm) 1.5696E+03 8.2699E+03
H (erg/gm) 1.4239E+09 1.4239E+09
U (erg/gm) -1.6651E+08 -6.9556E+09
S (erg/gm-K) 9.1881E+07 1.1137E+08
W (gm/mol) 2.0911E+01 2.4216E+01
Mol Fractions
H2 2.9586E-01 1.7373E-02
H 0.0000E+00 2.5222E-03
O2 1.4793E-01 6.5977E-03
O 0.0000E+00 8.6397E-04
OH 0.0000E+00 9.1448E-03
HO2 0.0000E+00 1.8246E-06
H2O 0.0000E+00 3.1940E-01
N2 5.5621E-01 6.4410E-01
H2O2 0.0000E+00 1.6602E-07
*************************CONTINUING TO NEW PROBLEM*************************
KEYWORD INPUT
REAC H2 2
REAC O2 1
REAC N2 3.76
HP
TEMP 500
TEST 2000
PRES 1
END
P (atm) 1.0000E+00 1.0000E+00
T (K) 5.0000E+02 2.4884E+03

V (cm3/gm) 1.9620E+03 8.4546E+03
H (erg/gm) 2.8378E+09 2.8378E+09
U (erg/gm) 8.4978E+08 -5.7288E+09
S (erg/gm-K) 9.5035E+07 1.1194E+08
W (gm/mol) 2.0911E+01 2.4150E+01
Mol Fractions
H2 2.9586E-01 2.0206E-02
H 0.0000E+00 3.3760E-03
O2 1.4793E-01 7.6135E-03
O 0.0000E+00 1.1825E-03
OH 0.0000E+00 1.0962E-02
HO2 0.0000E+00 2.2850E-06
H2O 0.0000E+00 3.1430E-01
N2 5.5621E-01 6.4236E-01
H2O2 0.0000E+00 1.9554E-07
Solving ODEs in MATLAB

To solve ODEs, one can use ode solvers in the Matlab, e.g., ode23tb. You can get help
by typing help ode23tb in the Matlab command window. As an example, consider the
following Van der Pol equation:
dx1
= x1 (1 x 22 ) x 2 ,
dt
dx 2
= x1 ,
dt
x1 (t = 0) =0 and x 2 (t = 0) = 0.25 .
Use the two m files attached to solve the above ODEs. Put both m files in the same
directory and execute the example.m file. Then you will get a time plot of x1 and x2.
Note that the van.m file contains information of the Van der Pol equation and the
example.m file specifies initial conditions, start and end integrations times and calls
van.m file to solve the ODEs.
1. example.m file
%%%start time
to=0;
%%%end time
tf=30;
%%%time step
step=0.5;
%%% initial conditions
xo=[0 0.25]';
%%% solve the odes
%%% t: time , x: output
[t,x]=ode23tb('van',[to:step:tf],xo);
%%% plot solutions
plot(t,x)
xlabel('time')
ylabel('value')
legend('x1','x2')
2. van.m file
function xdot=van(t,x)
xdot(1,1)=x(1)*(1-x(2)^2)-x(2);
xdot(2,1)=x(1);

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FUNDAMENTALS OF

ADVANCED ENERGY CONVERSION

CO2, Terawatts, Needs and Sources,

*Noble prize, Chemistry, 1996

Energy Sources and Demand

-Should be CO2 free

Source: M.I. Hoffert et. al., Nature, 1998, 395, 881,

CO2 emissions and

From Basic Research Need for a

FIGURE 1. GASIFICATION-BASED ENERGY PRODUCTION SYSTEM CONCEPTS

FIGURE 2. GASIFICATION-BASED ENERGY CONVERSION SYSTEM OPTIONS

(Courtesy of Prof. Wilson and Prof. Korakianitis. Used with permission.)

Optimal Hydrogen Utilization: the Fuel Cell

How to Fuel the Fuel Cell Engine?

HYDROGEN & THE HYDROGEN ECONOMY

Energy carrier: must be produced, stored, transported & charged.

Like electricity: expensive to produce, transport, not easy to store.

Can be produced by:

Compression/liquefaction (20 K, 1 bar/293 K, 800 bar) energies are high.

Storage: metal fiber tanks, cryogenic container, or in metal

hydrides (solids): through physical or chemical sorption.

Fuel Cell may be the

easiest piece of the

The Future of the Hydrogen Economy, Bright or Bleak

HYDROGEN STORAGE IN THE SOLID STATE

e.g., Sodium borohyrdride Cycle

Typical fuel: 30% NaBH4+3%NaHO+67%H2, has 6.6%H2, all by wt.

Nuclear Hydrogen Production

for Hydrogen Production:

Solar Hydrogen Production

Basic Energy Needs for the Hydrogen Economy,

Spring 04, subject is offered as 2.996 (G) and 2.994 (U)

FUNDAMENTALS OF ADVANCED ENERGY CONVERSION

(2.60j, 2.62j,10.392j, 22.40j)

Perquisite: 2.006 or permission of instructor

4-0-8 H-LEVEL Grad Credit,

A.F. Ghoniem (IC), M. Kazimi, Y. Shao-Horn, J. Tester.

The laws expressing the relations between energy and

2.996 Fundamentals of Advanced Energy Conversion Lecture Memo

Needs: Terawatt challenge

Energy source and demand

CO2 emissions and global temperature

Thermal efficiencies of different turbines and combined cycles

Fuel cell: storage problem, storage in the solid state

Nuclear hydrogen production

Solar hydrogen production

2.996 Fundamentals of Advanced Energy Conversion Lecture Memo

The first law of thermodynamics: Work and heat interactions

First law for an open system

The second law of thermodynamics: Entropy generation, efficiency

The combined statement of the first and second laws: Availability

Efficiency and second law efficiency

2.996 Fundamentals of Advanced Energy Conversion Lecture Memo

Entropy in an open system

Brayton cycles : Compressor and turbine efficiencies

Steam cycles : Conventional, superheating, reheat and regeneration cycle

2.996 Fundamentals of Advanced Energy Conversion Lecture Memo

Mole, mole fraction, mass fraction, average molecular weight

Gas mixture: Partial pressure and volume

Entropy generation due to mixing

Separation of gases: CO2 sequestration

Reacting mixtures: Irreversibility