AME513 Principles of Combustion PDF

AME 513 
 
Principles of Combustion 
"
Paul Ronney!
Fall 2012!
Administrative details"
  Instructor: Prof. Paul Ronney!
Office: OHE 430J!
Phone: (213) 740-0490!
Email: ronney@usc.edu!
Website: http://ronney.usc.edu!
Office hours: Mondays 1 pm – 4 pm!
  Teaching assistant: Ning Liu!
Office: RRB 207; Lab: RRB 111!
Phone: (213) 740-5361 !
Email: ningl@usc.edu!
Office hours: Tuesdays 1 pm – 4 pm!
  Grader: Thada Suksila!
Email: suksila@usc.edu!
  Grading: 30% homework, 30% midterm, 40% final!
  7 homework assignments; 10 points per day late penalty;
lowest HW grade dropped!
AME 513 - Fall 2012 - Lecture 1 - Introduction 2
• 1
Administrative details"
  References!
  PDRʼs lecture notes!
  Prof. Egolfopoulosʼs lecture notes (to be distributed)!
  Steven R. Turns, An Introduction to Combustion: Concept and
Applications, 3rd Edition, 2012
http://www.mhprofessional.com/product.php?isbn=0073380199!
  Optional supplemental material!
  Combustion Theory, Forman A Williams, 2nd Edition, Addison-
Wesley, 1985!
  Combustion, Flames, and Explosions of Gases, Bernard Lewis and
Guenther von Elbe, 3rd Edition, Academic Press, 1987!
  Combustion, Irvin Glassman and Richard Yetter, 4th Edition,
Academic Press, 2008!
Tentative course outline"

  Introduction (1 week)!
  Building blocks of combustion!
  Chemical thermodynamics (2 weeks)!
  Chemical kinetics (3 weeks)!
  Transport phenomena (1 week)!
  Combining the building blocks!
  Conservation equations (1 week)!
  Premixed flames (3 weeks)!
  Non-Premixed flames (3 weeks)!
• 2
Helpful handy hints"
  Download lectures from website before class!
  Each lecture includes!
  Outline!
  Examples!
  Summary!
… make use of these resources!
  Bringing your laptop allows you to add notes & download
files from course website as necessary!
  If you don’t have Powerpoint, you can download a
free powerpoint viewer from Microsoft’s website!
  … but if you don’t have the full Powerpoint and Excel, you
won’t be able to open the imbedded Excel spreadsheets!
  Please ask questions in class - the goal of the lecture is to
maintain a 2-way Socratic dialogue on the subject of the
lecture!
AME 513 
 
"
Lecture 1!
Introduction: Why combustion?!
• 3
Outline"
  Why study combustion?
  What do we want to know?
  Types of combustion processes
  Premixed
  Nonpremixed
  Alternatives to combustion for transportation vehicles
  Brief history of internal combustion engines
  “Bonus” material (on your own…)
  Review of thermodynamics
  Engineering scrutiny
Why study combustion?"

  > 80% of world energy production results from combustion
of fossil fuels
  Energy sector accounts for 9% of US Gross Domestic
Product
  Our continuing habit of burning things and our quest to find
more things to burn has resulted in
  Economic booms and busts
  Political and military conflicts
  Global warming (or the need to deny its existence)
  Human health issues
• 4
US energy flow, 2010, units 1015 BTU/yr"
Each 1015 BTU/yr = 33.4 gigawatts

http://www.eia.gov/totalenergy/data/annual/diagram1.cfm
What do we do with combustion?"

  Power generation (coal, natural gas)
  Transportation (land, air, sea vehicles)
  Weapons (rapid production of high-pressure gas)
  Heating
  Lighting
  Cooking (1/3 of the world’s population still uses biomass-
fueled open fires)
  Hazardous waste & chemical warfare agent destruction
  Production of new materials, e.g. nano-materials
  (Future?) Portable power, e.g. battery replacement
  Unintended / undesired consequences
  Fires and explosions (residential, urban, wildland, industrial)
  Pollutants – NOx (brown skies, acid rain), CO (poisonous),
Unburned HydroCarbons (UHCs, photochemical smog),
formaldehyde, particulates, SOx
  Global warming from CO2 & other products
• 5
What do we want to know?"
  From combustion device
  Power (thermal, electrical, shaft, propulsive)
  Efficiency (% fuel burned, % fuel converted to power)
  Emissions
  From combustion process itself
  Rates of consumption
»  Reactants
»  Intermediates
  Rates of formation
»  Intermediates
»  Products
  Global properties
»  Rates of flame propagation
»  Rates of heat generation (more precisely, rate of conversion of
chemical enthalpy to thermal enthalpy)
»  Temperatures
»  Pressures
Why do we need to study combustion?"

  Chemical thermodynamics only tells us the end states - what
happens if we wait forever and a day for chemical reaction
to occur
  We need to know how fast reactions occur
  How fast depends on both the inherent rates of reaction and
the rates of heat and mass transport to the reaction zone(s)
  Chemical reactions + heat & mass transport = combustion
  Some reactions occur too slowly to be observed, e.g.
2 NO → N2 + O2
has an adiabatic flame temperature of 2650K but no one has
ever made a flame with NO because reaction rates are too slow!
  Chemical reaction leads to gradients in temperature,
pressure and species concentration
  Results in transport of energy, momentum, mass
  Combustion is the study of the coupling between
thermodynamics, chemical reaction and transport processes
• 6
Types of combustion"
  Premixed - reactants are intimately mixed on the molecular
scale before combustion is initiated; several flavors
  Deflagration
  Detonation
  Homogeneous reaction
  Nonpremixed - reactants mix only at the time of combustion -
have to mix first then burn; several flavors
  Gas jet (Bic lighter)
  Liquid fuel droplet
  Liquid fuel jet (e.g. Kuwait oil fire, candle, Diesel engine)
  Solid (e.g. coal particle, wood)
Type! Chemical Heat / mass Momentum Thermo-
reaction! transport! transport! dynamics!
Deflagration" ✔" ✔" ✗" ✔"
Detonation" ✗" ✗" ✔" ✔"
Homogeneous reaction" ✔" ✗" ✗" ✔"
Nonpremixed flames" ✗" ✔" ✗" ✗

Deflagrations"
  Subsonic propagating front sustained by conduction of heat from
the hot (burned) gases to the cold (unburned) gases which raises
the temperature enough that chemical reaction can occur; since
chemical reaction rates are very sensitive to temperature, most of
the reaction is concentrated in a thin zone near the high-
temperature side!
  May be laminar or turbulent!
  Temperature increases in convection-diffusion zone or preheat
zone ahead of reaction zone, even though no heat release occurs
there, due to balance between convection & diffusion!
  Reactant concentration decreases in convection-diffusion zone,
even though no chemical reaction occurs there, for the same
reason!
  How can we have reaction at the reaction zone even though
reactant concentration is low there? (See diagram…) Because
reaction rate is much more sensitive to temperature than reactant
concentration, so benefit of high T outweighs penalty of low
concentration!
• 7
Schematic of deflagration "
Reaction zone
2000K Direction of propagation
Product Speed relative to unburned gas = SL
concentration Temperature
Reactant
concentration
300K
Distance from reaction zone

Convection-diffusion zone
! ≈ "/SL = 0.3 - 6 mm
Turbulent premixed flame experiment in a

fan-stirred chamber ( Flame thickness (δ) ~ α/SL"
http://www.mech-eng.leeds.ac.uk/res- (α = thermal diffusivity)"
group/combustion/activities/Bomb.htm)"
Premixed flames - detonation"

  Supersonic propagating front sustained by heating via shock wave!
  After shock front, need time (thus distance = time x velocity) before
reaction starts to occur ( induction zone )!
  After induction zone, chemical reaction & heat release occur!
  Pressure & temperature behavior coupled strongly with supersonic/
subsonic gasdynamics!
  Ideally only M3 = 1 Chapman-Jouget detonation is stable !
! ! !! !(M = Mach number = Vc; V = velocity, !
! ! !! !! c = sound speed = (γRT)1/2 for ideal gas)!
Heat release Induction

zone zone
CJ detonation :
Temperature 1/ 2 1/ 2
$ H(" 2 #1) ' $ H(" 2 #1) '
Pressure
M1 M1 = &1+ ) +& )
% 2" ( % 2" (
Shock
q
H= (heat release parameter)
3 2 1 RT1
M=1 M<1 M>1
q = CP (T3t # T2t ) = fQR
P t decreases across shock

AME 513
P t decreases in heat release zone
- Fall 2012 - Lecture 1 - Introduction 16
T t constant across shock T t increases in heat release zone
!
• 8
Premixed flames - homogeneous reaction"
  Model for knock in premixed-charge engines!
  Fixed mass (control mass) with uniform (in space) T, P and
composition!
  No propagation in space but propagation in time!
  In laboratory, can heat the chamber to a certain T and measure reaction
time, or compress mixture (increases P & T, thus reaction rate) will
initiate reaction!
Reactant concentration
Temperature
Time
Non-premixed or diffusion flames"

  Reaction zone where fuel & O2 fluxes in stoichiometric proportion
  Generally mixed is burned - mixing slower than chemical reaction
  No inherent propagation rate (flame location determined by
stoichiometric location)
  No inherent thickness (δ = mixing layer thickness ~ (α/Σ)1/2)
(Σ = strain rate)
  Unlike premixed flames with characteristic propagation rate SL and
thickness δ ~ α/SL that are almost independent of Σ
Candle
Kuwait
Diesel engine Oil fire Forest fire
• 9
Reaction zone
2000K
Product
Oxygen concentration Fuel
concentration
300K 300K
Convection-diffusion zone Distance from

reaction zone
!δ≈ ("/#)
(ατ)
1/2
1/2
Diesel engine combustion"

 Two extremes!
 Droplet combustion - vaporization of droplets is slow, so droplets burn
as individuals!
 Gas-jet flame - vaporization of droplets is so fast, there is effectively a jet
of fuel vapor rather than individual droplets!
 Reality is in between, but in Diesels usually closer to the gas jet with
extras – regions of premixed combustion!
Flynn, P.F, R.P. Durrett, G.L. Hunter, A.O. zur Loye, O.C. Akinyemi, J.E. Dec, C.K. Westbrook,
SAE Paper No. 1999-01-0509.
• 10
Alternative #1 - external combustion"
  Examples: steam engine, Stirling cycle engine!
  Use any fuel as the heat source!
  Use any working fluid (high γ, e.g. helium, provides better efficiency)!
  Heat transfer, gasoline engine!
  Heat transfer per unit area (q/A) = k(dT/dx)!
  Turbulent mixture inside engine: k ≈ 100 kno turbulence !
! !≈ 2.5 W/mK!
  dT/dx ≈ ΔT/Δx ≈ 1500K / 0.02 m!
  q/A ≈ 187,500 W/m2!
  Combustion: q/A = ρYfQRST = (10 kg/m3) x 0.067 x (4.5 x 107 J/kg) x
2 m/s = 60,300,000 W/m2 - 321x higher!!
  CONCLUSION: HEAT TRANSFER IS TOO SLOW!!!!
  That s why 10 large gas turbine engines ≈ large (1 gigawatt) coal-
fueled electric power plant!
k = gas thermal conductivity, T = temperature, x = distance, ρ = density, Yf =

fuel mass fraction, QR = fuel heating value, ST = turbulent flame speed in
engine !
Alternative #2 - Electric Vehicles (EVs)"

  Why not generate electricity in a large central power plant
and distribute to charge batteries to power electric motors?!
  Chevy Volt Li-ion battery – 10.3 kW-hours usable capacity,
435 pounds = 1.88 x 105 J/kg !
  Gasoline (and other hydrocarbons): 4.3 x 107 J/kg!
  Even at 30% efficiency (gasoline) vs. 90% (batteries),
gasoline has 76 times higher energy/weight than batteries! !
  1 gallon of gasoline ≈ 457 pounds of batteries for same
energy delivered to the wheels!
  Other issues with electric vehicles!
  "Zero emissions ??? - EVs export pollution!
  50% of US electricity is by produced via coal at 40%
efficiency – virtually no reduction in CO2 emissions!
  Battery replacement cost ≈ $8000 ≈ 80,000 miles of gasoline
driving (@ $3.50/gal, 35 mpg)!
  Environmental cost of battery materials!
  Possible advantage: make smaller, lighter, more streamlined
cars acceptable to consumers!
• 11
Zero emission electric vehicles"
Alternative #3 - Hydrogen fuel cell"

  Ballard HY-80 Fuel cell engine !
!(power/wt = 0.19 hp/lb)!
  48% efficient (fuel to electricity)!
  MUST use hydrogen (from where? !
!H2 is an energy carrier, not a fuel)!
  Requires large amounts of platinum !
!catalyst - extremely expensive!
  Does NOT include electric drive system !
!(≈ 0.40 hp/lb thus fuel cell + motor !
!at ≈ 90% electrical to mechanical efficiency)!
  Overall system: 0.13 hp/lb at 43% efficiency (hydrogen)!
  Conventional engine: ≈ 0.5 hp/lb at 30% efficiency (gasoline)!
  Conclusion: fuel cell engines are only marginally more efficient, much
heavier for the same power, and require hydrogen which is very difficult
and potentially dangerous to store on a vehicle!
  Prediction: even if we had an unlimited free source of hydrogen and a
perfect way of storing it on a vehicle, we would still burn it, not use it in
a fuel cell"
• 12
Hydrogen storage"
  Hydrogen is a great fuel!
  High energy density (1.2 x 108 J/kg, ≈ 3x hydrocarbons)!
  Much faster reaction rates than hydrocarbons (≈ 10 - 100x at same T)!
  Excellent electrochemical properties in fuel cells!
  But how to store it???!
  Cryogenic (very cold, -424˚F) liquid, low density (14x lower than water)!
  Compressed gas: weight of tank ≈ 15x greater than weight of fuel!
  Borohydride solutions!
»  NaBH4 + 2H2O → NaBO2 (Borax) + 3H2!
»  (mass solution)/(mass fuel) ≈ 9.25 !
  Palladium - Pd/H = 164 by weight!
  Carbon nanotubes - many claims, few facts…!
  Long-chain hydrocarbon (CH2)x: (Mass C)/(mass H) = 6, plus C atoms
add 94.1 kcal of energy release to 57.8 for H2!!
  MORAL: By far the best way to store hydrogen is to attach it to carbon
atoms and make hydrocarbons, even if you re not going to use the
carbon as fuel!!
Alternative #4 - solar"
  Arizona, high noon, mid summer: solar flux ≈ 1000 W/m2!
  Gasoline engine, 20 mi/gal, 60 mi/hr, thermal power = (60 mi/hr / 20
mi/gal) x (6 lb/gal) x (kg / 2.2 lb) x (4.3 x 107 J/kg) x (hr / 3600 sec) =
97 kilowatts !
  Need ≈ 100 m2 collector ≈ 32 ft x 32 ft - lots of air drag, what about
underpasses, nighttime, bad weather, northern/southern latitudes,
etc.?!
Do you want to drive one of these every day (but never at night?)
• 13
Alternative #4 - solar"
  Ivanpah solar thermal electric generating station!
  400 MW maximum power, ≈ 48 MW annual average (small compared
to coal or nuclear, 1,000 MW)!
  3 towers, each 460 ft tall!
  6 mi2, 17,000 mirrors !
  $2.2 billion = $46/watt vs. $2/watt for conventional coal or natural
gas power plants !
Alternative #5 - biofuels"
  Essentially solar energy – “free” (?)!
  Barely energy-positive; requires energy for planting, fertilizing,
harvesting, fermenting, distilling!
  Very land-inefficient compared to other forms of solar energy –
life forms convert < 1% of sunʼs energy into combustible material!
  Currently 3 subsidies on US bio-ethanol vehicle fuel: !
  45¢/gal (≈ 67¢/gal gasoline) !
! tax credit to refines!
  54¢/gal tariff on sugar-based !
! ethanol imports!
  Requirement for 10% ethanol !
! in gasoline!
  Displaces other plants – not !
!necessarily “carbon neutral”!
  Uses other resources - arable !
!land, water – that might !
!otherwise be used to grow food!
!or provide biodiversity (e.g. in !
!tropical rain forests)!
• 14
Alternative #6 - nuclear"
  High energy density
  U235 fission: 8.2 x 1013 J/kg ≈ 2 million x hydrocarbons!
  Radioactive decay much less, but still much higher than
hydrocarbon fuel
  Carbon neutral
  Not practical for vehicles but…
Ford Nucleon concept car (1958)
Edison2 vehicle"
  http://www.edison2.com!
  Won X-prize competition for 4-passenger vehicles (110 MPG)!
  Key features - Very low weight (830 lb), very aerodynamic,
very low rolling resistance!
  Engine: 1 cylinder, 40 hp, 250 cc, turbocharged ICE!
  Ethanol fuel (high octane rating, allows high compression
ratio thus high efficiency)!
  Rear engine placement reduces air drag due to radiator!
  Beat electric vehicles despite unfair advantage in US EPA
MPG equivalency: 33.7 kW-hr electrical energy = 1 gal, same
as raw energy content !
!of gasoline (44 x 106 !
!MJ/kg) – doesnʼt "
"account for fuel "
"burned to create "
"the electrical energy!"
• 15
History of automotive engines"
  1859 - oil discovered at Drake s
Well, Titusville, Pennsylvania (20
barrels per day) - 40 year supply!
  1876 - premixed-charge 4-stroke
engine – Nikolaus Otto!
  1st “practical” ICE!
  4-stroke, overhead valve,
crankshaft!
  Power: 2 hp; Weight: 1250
pounds; fuel: coal gas (CO + H2)!
  Comp. ratio = 4 (knock limited),
14% efficiency (theory 38%)!
  Today CR = 9 (still knock limited),
30% efficiency (theory 55%)!
  In 136 years, the main efficiency
improvement is due to better fuel!

  1897 - nonpremixed-charge engine - Diesel
- higher efficiency due to!
  Higher CR (no knocking)!
  No throttling loss - use fuel/air ratio to
control power!
  1901 - Spindletop Dome, east Texas -
Lucas #1 gusher produces 100,000 barrels
per day - ensures that 2nd Industrial
Revolution will be fueled by oil, not coal
or wood - 40 year supply!
  1921 - tetraethyl lead anti-knock additive
discovered at General Motors!
  Enabled higher CR (thus more power,
better efficiency) in Otto-type engines!
• 16
  1938 – oil discovered at Dammam, Saudi Arabia (40 year
supply)!
  1952 - A. J. Haagen-Smit, Caltech!
!
NO + UHC + O2 + sunlight → NO2 + O3!

(from exhaust) (brown) (irritating)!
!
! !(UHC = unburned hydrocarbons)!
  1960s - emissions regulations!

  Detroit won t believe it!
  Initial stop-gap measures - lean mixture, EGR, retard spark!
  Poor performance & fuel economy!
  1973 & 1979 - energy crises due to Middle East turmoil!
  Detroit takes a bath, Asian and European imports increase!

  1975 - Catalytic converters, unleaded fuel!
  More aromatics (e.g., benzene) in gasoline - high octane but
carcinogenic, soot-producing!
  1980s - Microcomputer control of engines!
  Tailor operation for best emissions, efficiency, ...!
  1990s - Reformulated gasoline!
  Reduced need for aromatics, cleaner (?)!
  ... but higher cost, lower miles per gallon!
  Then we found that MTBE pollutes groundwater!!!!
  Alternative oxygenated fuel additive - ethanol - very attractive
to powerful senators from farm states!
• 17
  2000’s - hybrid vehicles!
  Use small gasoline engine operating at maximum power
(most efficient way to operate) or turned off if not needed!
  Use generator/batteries/motors to make/store/use surplus
power from gasoline engine!
  Plug-in hybrid: half-way between conventional hybrid and
electric vehicle!
  2 benefits to car manufacturers: win-win!
»  Consumers will pay a premium for hybrids!
»  Helps to meet fleet-average standards for efficiency & emissions!
  Do fuel savings justify extra cost? Consumer Reports study:
only 1 of 7 hybrids tested showed a cost benefit over a 5 year
ownership if tax incentives were removed!
»  Dolly Parton: You wouldnʼt believe how much it costs to look
this cheap !
»  Paul Ronney: You wouldn’t believe how much energy some
people spend to save a little fuel
  2010 and beyond
  ???!
Practical alternatives to the status quo"

  Conservation!!
  Combined cycles: use hot exhaust from internal combustion
engine to heat water for conventional steam cycle - can
achieve > 60% efficiency but not practical for vehicles - too
much added volume & weight!
  Natural gas!
  4x cheaper than electricity, 2x cheaper than gasoline or diesel for
same energy!
  Somewhat cleaner than gasoline or diesel, but no environmental
silver bullet!
  Low energy storage density - 4x lower than gasoline or diesel!
• 18
Practical alternatives to the status quo"
  Fischer-Tropsch fuels - liquid hydrocarbons from coal or
natural gas
  Coal or NG + O2  CO + H2  liquid fuel
  Competitive with ≈ $100/barrel oil
  Cleaner than gasoline or diesel
  … but using coal increases greenhouse gases!
Coal : oil : natural gas = 2 : 1.5 : 1
  Could use biomass (e.g. agricultural waste) instead of coal or
natural gas as “energy feedstock”
  But really, there is no way to decide what the next step is until
it is decided whether there will be a tax on CO2 emissions
  Personal opinion: most important problems are (in order of
priority)
  Global warming
  Energy independence
  Environment
Summary - Lecture 1"

  Combustion is the interaction of thermodynamics, chemical
reaction and heat/mass/momentum transport, but which is/
are most important depends on the situation
  Combustion is ubiquitous in our everyday lives and will
continue to be for our lifetimes
  Many advantages of fossil fuels over other energy sources
  Cheap (?), plentiful (?), clean (?)
  Energy/weight of fuel itself
  Power/weight of engines
  Materials costs (e.g. compared to fuel cells)
  The most important distinction between flames is premixed
vs. non-premixed, i.e. whether the reactants are mixed before
combustion
• 19
Discussion point"
Our current energy economy, based primarily on fossil
fuel usage, evolved because it was the cheapest
system. Is it possible that itʼs also the most
environmentally responsible (or “least environmentally
irresponsible”) system?!
Review of thermodynamics (1)"

  1st Law of Thermodynamics (conservation of
energy) - you can’t win !
  2nd Law of Thermodynamics - you can’t break
even !
  Equation of state (usually ideal gas law) - you
can’t even choose the game !
• 20
Review of thermodynamics (2)"
  1st Law of Thermodynamics for a control mass, i.e. a fixed mass
of material (but generally changing volume)!
! !dE = δQ - δW !
E = energy contained by the mass - a property of the mass!
Q = heat transfer to the mass!
W = work transfer to or from the mass (see below)!
d vs. δ = path-independent vs. path-dependent quantity!
  Control mass form useful for fixed mass, e.g. gas in a piston/
cylinder!
  Each term has units of Joules!
  Work transfer is generally defined as positive if out of the control
mass, in which case - sign applies, i.e. dE = δQ - δW; If work is
defined as positive into system then dE = δQ + δW!
  Heat and work are NOT properties of the mass, they are energy
transfers to/from the mass; a mass does not contain heat or work
but it does contain energy (E)!
Review of thermo (3) - heat & work"

  Heat and work transfer depend on the path, but the internal
energy of a substance at a given state doesn t depend on how
you got to that state; for example, simple compressible
substances exchange work with their surroundings according to
δW = + PdV (+ if work is defined as positive out of control mass)!
  For example in the figure below, paths A & B have different ∫ PdV
and thus different work transfers, even though the initial state 1
and final state 2 are the same for both!
!!
2
P A
B
1
V 42
AME 513 - Fall 2012 - Lecture 1 - Introduction
• 21
Review of thermo (4) - heat & work"
  What is the difference between heat and work? Why do we need to
consider them separately?!
  Heat transfer is disorganized energy transfer on the microscopic
(molecular) scale and has entropy transfer associated with it!
  Work transfer is organized energy transfer which may be at either the
microscopic scale or macroscopic scale and has no entropy transfer
associated with it!
  The energy of the substance (E) consists of !
  Macroscopic kinetic energy (KE = 1/2 mV2)!
  Macroscopic potential energy (PE = mgz)!
  Microscopic internal energy (U) (which consists of both kinetic
(thermal) and potential (chemical bonding) energy, but we lump them
together since we can t see it them separately, only their effect at
macroscopic scales!
  If PE is due to elevation change (z) and work transfer is only PdV
work, then the first law can be written as!
! !dU + mVdV + mgdz = δQ - PdV!
!
V = velocity, V = volume, m = mass, g = gravity!
Review of thermo (5) - types of energy"
Energy
Energy contained by a substance (E) Energy transfers to/from a substance
Macroscopic Heat transfer (Q)

Disorganized
Has associated entropy transfer
Microscopic only
Work transfer (W)

Potential energy (PE) Organized
Has NO associated entropy transfer
Kinetic energy (KE) Microscopic or macroscopic
Microscopic (U)
Lump KE and PE together
• 22
Review of thermo (6) - 1st law for CV"
  1st Law of Thermodynamics for a control volume, a fixed volume
in space that may have mass flowing in or out (opposite of control
mass, which has fixed mass but possibly changing volume):!
dE ! ! v2 v2
= Q ! W + m! in (hin + in + gzin ) ! m! out (hout + out + gzout )
dt 2 2
  E = energy within control volume = U + KE + PE as before!
  Q˙ ,W˙ = rates of heat & work transfer in or out (Watts)!
  Subscript in refers to conditions at inlet(s) of mass, out to outlet
(s) of mass!
  m˙ = mass flow rate in or out of the control volume!
!   h ≡ u + Pv = enthalpy!
  Note h, u & v are lower case, i.e. per unit mass; h = H/M, u = U/M, V =
v/M, etc.; upper case means total for all the mass (not per unit mass)!
!
  v = velocity, thus v2/2 is the KE term!
  g = acceleration of gravity, z = elevation at inlet or outlet, thus gz is
the PE term!
  Control volume form useful for fixed volume device, e.g. gas
turbine!
  Most commonly written as a rate equation (as above)!
Review of thermo (7) - 1st law for CV"

  Note that the Control Volume (CV) form of the 1st Law looks
almost the same as the Control Mass (CM) form with the addition
of m˙ (h+ v2/2 + gz) terms that represent the flux of energy in/out of
the CV that is carried with the mass flowing in/out of the CV!
  The only difference between the CV and CM forms that isn t
obvious is the replacement of u (internal energy) with h = u + Pv!
!   Where did the extra Pv terms come from? The flow work needed
to push mass into the CV or that you get back when mass leaves
the CV!
• 23
Review of thermo (8) - steady flow"
  If the system is steady then by definition!
  d[ ]/dt = 0 for all [properties], i.e. ECV, MCV, h, v, z!
  All fluxes, i.e. m˙ , Q˙ ,W˙ are constant (not necessarily zero)!
  Sum of mass flows in = sum of all mass flows out (or m˙ in = m˙ out
for a single-inlet, single-outlet system) (if we didn t have this
condition
! then the mass of the system, which is a property of
the system, would not be constant)! !
  In this case (steady-state, steady flow) the 1st Law for a CV is!
) # 2 2 & ,
0 = Q˙ " W˙ + m˙ +(hin " hout ) + %v in 2 " v out 2 ( + (gzin " gzout ).
* $ ' -
Review of thermo (9) - conservation of mass"

  For a control mass!
!m = mass of control mass = constant (wasn t that easy?)!
  For a control volume!
dmCV
= " m˙ i # " m˙ j
dt all inlets all outlets
!(what accumulates = what goes in - what goes out)!

!
!
!
• 24
Review of thermodynamics (10) - 2nd law"
  The 2nd Law of Thermdynamics states!
The entropy (S) of an isolated system always increases or remains
the same!
  By combining !
  2nd law!
  1st Law!
  State postulate - for a system of fixed chemical composition, 2
independent properties completely specify the state of the system!
  The principle that entropy is a property of the system, so is additive!
it can be shown that !
Tds = du + Pdv!
Tds = dh - vdP!
!These are called the Gibbs equations, which relate entropy to other
thermodynamic properties (e.g. u, P, v, h, T)!
!
Review of thermodynamics (11) - 2nd law"

  From the Gibbs equations, it can be shown for a control mass!
#Q
dS "
T
= sign applies for a reversible (idealized; best possible) process!
> applies if irreversible (reality)!
T is the temperature on the control mass at the location where the heat is
! transferred to/from the CM!
  And for a control volume!
dSCV Q!
+ m! in sin " m! out sout !
dt T
!SCV is the entropy of the control volume; if steady, dSCV/dt = 0!
  These equations are the primary way we apply the 2nd law to the
energy conversion systems discussed in this class!
  Work doesn t appear anywhere near the 2nd law - why? Because
there is NO entropy transfer associated with work transfer, whereas
there IS entropy transfer associated with heat transfer!
• 25
Review of thermo (12) - equations of state"
  We ll only consider 2 equations of state in this course!
  Ideal gas - P = ρRT (P = pressure, ρ = 1/v = density, T = temperature
(absolute), R = gas constant = ℜ/Mmix, ℜ = universal gas constant
(8.314 J/mole-K), Mmix = molecular weight of gas mixture)!
  Incompressible fluid - ρ = constant!
  Definition of specific heats (any substance)!
$ #h ' $ #u ' C
CP " & ) ;CV " & ) ;* " P
% #T ( P % #T (V CV
  For ideal gases - h = h(T) and u = u(T) only (h and u depend only
on temperature, not pressure, volume, etc.), thus for ideal gases!
! dh du dh du
CP = ;CV = ;h = u + Pv = u + RT; = + R " CP = CV + R
dT dT dT dT
  From dh = CPdT, du = CvdT, the Gibbs equations and P = ρRT we
can show that (again for an ideal gas only)!
! #T & #P & #T & #V & ! #P & #V &
S2 " S1 = CP ln% 2 ( " Rln% 2 ( = CV ln% 2 ( + Rln% 2 ( = CV ln% 2 ( + CP ln% 2 (
$ T1 ' $ P1 ' $ T1 ' $ V1 ' $ P1 ' $ V1 '
Review of thermo (13) - isentropic relations"

  Recall from the 2nd Law, dS ≥ δQ/T!
  If a process is reversible dS = δQ/T, and if furthermore the process
is adiabatic δQ = 0 thus dS = 0 or S2 - S1 = 0 (isentropic process)
then the previous relations for S2 - S1 can be written as !
( )1
" T2 % " P2 % ( " T2 % " v1 %( )1 " P2 % " v1 %(
$ '=$ ' ; $ '=$ ' ; $ '=$ '
# T1 & # P1 & # T1 & # v 2 & # P1 & # v 2 &
!Isentropic processes are our favorite model for compression and
expansion in engines!
  But remember these relations are valid only for !
!   Ideal gas!
  Constant specific heats (CP, CV) (note that since for an ideal gas CP =
Cv + R and R is a constant, if any of CP, Cv and γ = CP/Cv are constant
then the other two must be constant also)!
  Reversible adiabatic (thus isentropic) process!
(Still very useful despite all these restrictions…)!
• 26
Engineering scrutiny 1. Smoke test"
See http://ronney.usc.edu/AME101F011/AME101-F11-LectureNotes.pdf
(Chapters 2 & 3) for more details!
!
  Equivalent in building electronics: turn the power switch on

and see if it smokes!
  For analysis: check the units - this will catch 90% of your
mistakes !
  Example: I just derived the ideal gas law as Pv = R/T,
obviously units are wrong!
  Other rules!
  Anything inside a square root, cube root, etc. must have units
that is a square (e.g. m2/sec2) or cube, etc.!
  Anything inside a log, exponent, trigonometric function, etc.,
must be dimensionless!
  Any two quantities that are added together must have the
same units!
Engineering scrutiny 2. Function test"
  Equivalent in building electronics: does the device do what it

was designed it to do, e.g. the red light blinks when I flip
switch on, the bell rings when I push the button, etc.!
  For analysis: does the result gives sensible predictions?!
  Determine if sign (+ or -) of result is reasonable, e.g. if
predicted absolute temperature is –72 K, obviously it s
wrong!
  Determine whether what happens to y as x goes up or down
is reasonable or not. For example, in the ideal gas law, Pv =
RT:!
  At fixed v, as T increases then P increases – reasonable!
  At fixed T, as v increases then P decreases – reasonable!
  Etc.!
• 27
Engineering scrutiny 2. Function test"
  Determine what happens in the limit where x goes to

special values, e.g. 0, 1, ∞ as appropriate!
  Example: entropy change (S2 - S1) of an ideal gas!
#T & #P &
S2 " S1 = CP ln% 2 ( " Rln% 2 (
$ T1 ' $ P1 '
  For T2 = T1 and P2 = P1 (no change in state) then S2 – S1 = 0 or
S2 = S1!
  Limit of S2 = S1, the allowable changes in state are!
! R ( )1
" T2 % " P2 % CP "P % (
$ '= $ ' = $ 2'

# T1 & # P1 & # P1 &
which is the isentropic relation for ideal gas with constant
specific heats!
! 55
AME 513 - Fall 2012 - Lecture 1 - Introduction
Engineering scrutiny 3. Performance test"
  Equivalent in building electronics: how fast, how

accurate, etc. is the device!
  For analysis: how accurate is the result?!
  Need to compare result to something else, e.g. a
careful experiment, more sophisticated analysis,
trusted published result, etc.!
  Example, I derived the ideal gas law and predicted Pv =
7RT - passes smoke and function tests, but fails the
performance test miserably (by a factor of 7)!
• 28
AME 513 
 
"
Lecture 2
Chemical thermodynamics I – 1st Law
Outline"
  Fuels - hydrocarbons, alternatives
  Balancing chemical reactions
  Stoichiometry
  Lean & rich mixtures
  Mass and mole fractions
  Chemical thermodynamics
  Why?
  1st Law of Thermodynamics applied to a chemically reacting
system
  Heating value of fuels
  Flame temperature
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 2
• 1
Fuels & air"
  Usually we employ hydrocarbon fuels, alcohols or coal
burning in air, though other possibilities include H2, CO, NH3,
CS2, H2S, etc.
  For rocket fuels that do not burn air, many possible oxidizers
exist - ASTE 470, 570 & 572 discuss these
  Why air?
  Because it s free, of course (well, not really when you think of
all the money we’ve spent to clean up air)
  Air ≈ 0.21 O2 + 0.79 N2 (1 mole of air) or 1 O2 + 3.77 N2 (4.77
moles of air)
  Note for air, the average molecular weight is
0.21*32 + 0.79*28 = 28.9 g/mole
thus the gas constant = (universal gas constant / mole. wt.)
= (8.314 J/moleK) / (0.0289 kg/mole) = 287 J/kgK
  Also ≈ 1% argon, up to a few % water vapor depending on the
relative humidity, trace amounts of other gases, but we’ll
usually assume just O2 and N2
Hydrocarbons"
  Alkanes - single bonds between carbons - CnH2n+2, e.g. CH4, C2H6
H H H H H H
H C H H C C H H C C C H
H H H H H H
methane ethane propane
  Olefins or alkenes - one or more double bonds between carbons
H H H H H H
C C H C C C C C C C
H H H H H H H H H
ethene or propene or 1, 3 butadiene
ethylene propylene
  Alkynes - one or more triple bonds between carbons - higher
heating value than alkanes or alkenes due to strained
(endothermic) bonds than alkanes or alkenes, also very reactive
H C C H
ethyne or
acetylene
• 2
Hydrocarbons"
  Aromatics - one or more ring structures
H H
H C C H
H H H
H H C C C
C C C C
C H C C C H C C C H
H C H
H C C
C C C C H
H H
H H H H
benzene toluene napthalene
  Alcohols - contain one or more OH groups
H H H
H C OH H C C OH
H H H
methanol ethanol
Biofuels"
  Alcohols - produced by fermentation of food crops (sugars or
starches) or cellulose (much more difficult, not an industrial
process yet)!
  Biodiesel - convert vegetable oil or animal fat (which have very
high viscosity) into alkyl esters (lower viscosity) through
transesterification with alcohol
Methyl linoleate
Generic ester structure (R =

any organic radical, e.g. C2H5)
Ethyl stearate
Methanol + triglyceride Glycerol+ alkyl ester

Transesterification process
• 3
Practical fuels"
  All practical fuels are
BLENDS of hydrocarbons and
sometimes other compounds
  What distinguishes fuels?
  Flash point - temperature
above which fuel vapor
pressure is flammable when
mixed with air
  Distillation curve - temp.
range over which molecules
evaporate
  Relative amounts of paraffins
vs. olefins vs. aromatics vs.
alcohols
  Amount of impurities, e.g.
sulfur
  Structure of molecules -
affects octane number
(gasoline) or cetane number
(Diesel)
Gasoline - typical composition"
Benzene
Toluene
J. Burri et al., Fuel, Vol. 83, pp. 187 - 193 (2004)
• 4
Practical fuels - properties"
  Values NOT unique because
  Real fuels are a mixture of many molecules, composition varies
  Different testing methods & definitions
Property Jet-A Diesel Gasoline

Heating value (MJ/kg) 43 43 43
Flash point (˚C) (T at which vapor 38 70 -43
makes flammable mixture in air)
Vapor pressure (at 100˚F) (psi) 0.03 0.02 8
Freezing point (˚C) −40 -38 -40
Autoignition temperature (˚C) (T at 210 240 260
which fuel-air mixture will ignite
spontaneously without spark or flame)
Density (at 15˚C) (kg/m3)# 810 850 720
Practical fuels - properties"
http://www.afdc.energy.gov/afdc/pdfs/fueltable.pdf
• 5
Practical fuels"
 What doesn’t distinguish one fuel from another?
 Energy content (except for fuels containing alcohols, which are
lower)
 Examples
 Gasoline - low-T distillation point, easy to vaporize, need high
octane number; reformulated gasoline contains alcohols
 Diesel - high-T distillation point, hard to vaporize, need LOW
octane number for easy ignition once fuel is inject
 Jet fuel - medium-T distillation point; need low freezing T since it
will be used at high altitude / low T
Stoichiometry"
  Balancing of chemical reactions with known (assumed) products
  Example: methane (CH4) in air (O2 + 3.77N2)
CH4 + a(O2 + 3.77N2) → b CO2 + c H2O + d N2
(how do we know this know this set is reasonable? From 2nd
Law, to be discussed later)
Conservation of C, H, O, N atoms:
nCH4(1) + nO2(0) + nN2(0) = nCO2(b) + nH2O(0) + nN2(0)
nCH4(4) + nO2(0) + nN2(0) = nCO2(0) + nH2O(2c) + nN2(0)
nCH4(0) + nO2(2a) + nN2(0) = nCO2(2b) + nH2O(c) + nN2(0)
nCH4(0) + nO2(0) + nN2(3.77*2a) = nCO2(0) + nH2O(0) + nN2(2d)
Solve: a = 2, b = 1, c = 2, d = 7.54
CH4 + 2(O2 + 3.77N2) → 1 CO2 + 2 H2O + 7.54 N2
or in general
Cx H y + (x + y 4)(O2 + 3.77N 2 ) " xCO2 + (y 2)H 2O + 3.77(x + y 4)N 2

!
• 6
Stoichiometry"
  This is a special case where there is just enough fuel to combine
with all of the air, leaving no excess fuel or O2 unreacted; this is
called a stoichiometric mixture
  In general, mixtures will have excess air (lean mixture) or excess
fuel (rich mixture)
  This development assumed air = O2 + 3.77 N2; for lower or higher %
O2 in the atmosphere, the numbers would change accordingly
Stoichiometry"
  Fuel mass fraction (f)
fuel mass nfuel M fuel 1"(12x +1y)
f= = =
total mass nfuel M fuel + nO2 M O2 + nN2 M N2 1"(12x +1y)+ (x + y 4)"(32+ 3.77" 28)
ni = number of moles of species i, Mi = molecular weight of species i
! For the specific case of stoichiometric methane-air (x = 1, y = 4),

f = 0.0550; a lean/rich mixture would have lower/higher f
  For stoichiometric mixtures, f is similar for most
hydrocarbons but depends on the C/H ratio = x/y, e.g.
  f = 0.0550 for CH4 (methane) - lowest possible C/H ratio
  f = 0.0703 for C6H6 (benzene) or C2H2 (acetylene) - high C/H ratio
  Fuel mole fraction Xf
fuel moles n fuel 1
Xf = = =
total moles n fuel + nO + n N 1+ (x + y 4)
2 2
which varies a lot depending on x and y (i.e. much smaller

for big molecules with large x and y)
! 14
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1
• 7
Stoichiometry"
  Fuel-to-air ratio (FAR)
fuel mass fuel mass (fuel mass)/(total mass) f
FAR = = = =
air mass total mass - fuel mass 1 - (fuel mass)/(total mass) 1 - f
and air-to-fuel ratio (AFR) = 1/(FAR)
  Note also f = FAR/(1+FAR)
!   Equivalence ratio (φ)
FAR (actual mixture)
"=
FAR (stoichiometric mixture)
φ < 1: lean mixture; φ > 1: rich mixture
  What if we assume more products, e.g.
! CH4 + ?(O2 + 3.77N2) → ? CO2 + ? H2O + ? N2 + ? CO
In this case we have 4 atom constraints (1 each for C, H, O, and N
atoms) but 5 unknowns (5 question marks) - how to solve?
Need chemical equilibrium (discussed later) to decide how much
C and O are in the form of CO2 vs. CO
Fuel properties"
Fuel Heating value, QR (J/kg) f at stoichiometric
Gasoline 43 x 106 0.0642

Methane 50 x 106 0.0550
Methanol 20 x 106 0.104
Ethanol 27 x 106 0.0915
Coal 34 x 106 0.0802
Paper 17 x 106 0.122
Fruit Loops 16 x 106 Probably about the same as paper
Hydrogen 120 x 106 0.0283
U235 fission 83,140,000 x 106 1
Pu239 fission 83,610,000 x 106 1
2H + 3H fusion 339,00,000 x 106 2H : 3H =1:1
• 8
Chemical thermodynamics - introduction"
  Besides needing to know how to balance chemical reactions,
we need to determine how much internal energy or enthalpy
is released by such reactions and what the final state
(temperature, pressure, mole fractions of each species) will
be
  What is highest temperature flame? H2 + O2 at φ = 1? Nope,
T = 3079K at 1 atm for reactants at 298K
  Probably the highest is diacetylnitrile + ozone
C4N2 + (4/3)O3 → 4 CO + N2
T = 5516K at 1 atm for reactants at 298K
  Why should it? The H2 + O2 system has much more energy
release per unit mass of reactants, but still a much lower
flame temperature

  The problem is that the products are NOT just H2O, that is, we
don t get
H2 + (1/2)O2 → H2O
but rather
H2 + (1/2)O2 → 0.706 H2O + 0.062 O2 + 0.184 H2
+ 0.094 H + 0.129 OH + 0.040 O
i.e. the water dissociates into the other species
  Dissociation does 2 things that reduce flame temp.
  More moles of products to soak up energy (1.22 vs. 1.00)
  Energy is required to break the H-O-H bonds to make the other species
  Higher pressures will reduce dissociation - Le Chatelier’s principle:
When a system at equilibrium is subjected to a stress, the system shifts
toward a new equilibrium condition in such as way as to reduce the
stress
(more pressure, less space, system responds by reducing number

of moles of gas to reduce pressure)
• 9
  Actually, even if we somehow avoided dissociation, the H2 -
O2 flame would be only 4998K - still not have as high a flame
temp. as the weird C4N2 flame
  Why? H2O is a triatomic molecule - more degrees of freedom
(DOFs) (i.e. vibration, rotation) than diatomic gases; each
DOF adds to the molecule s ability to store energy
  So why is the C4N2 - O3 flame so hot?
  CO and N2 are diatomic gases - fewer DOFs
  CO and N2 are very stable even at 5500K - almost no dissociation
  O3 decomposes exothermically to (3/2)O2
Chemical thermodynamics - goals"

  Given an initial state of a mixture (temperature, pressure,
composition), and an assumed process (constant pressure,
volume, or entropy, usually), find the final state of the
mixture
  Three common processes in engine analysis
  Compression
»  Usually constant entropy (isentropic)
»  Low P / high V to high P / low V
»  Usually P or V ratio prescribed
»  Usually composition assumed frozen - if it reacted before
compression, you wouldn t get any work out!
  Combustion
»  Usually constant P or v assumed
»  Composition MUST change (obviously…)
  Expansion
»  Opposite of compression
»  May assume frozen (no change during expansion) or equilibrium
composition (mixture shifts to new composition after expansion)
• 10
Chemical thermo - assumptions"
  Ideal gases - note many flavors of the ideal gas law
•  PV = nℜT
•  PV = mRT
•  Pv = RT
•  P = ρRT
P = pressure (N/m2); V = volume (m3); n = number of moles of gas;
ℜ  = universal gas constant (8.314 J/moleK); T = temperature (K)
m = mass of gas (kg); R = mass-specific gas constant = ℜ/M
M = gas molecular weight (kg/mole); v = V/m = specific volume (m3/kg)
ρ = 1/v = density (kg/m3)
  Adiabatic
  Kinetic and potential energy negligible
  Mass is conserved
  Combustion process is constant P or V (constant T or s
combustion isn’t very interesting!)
  Compression/expansion is reversible & adiabatic
(⇒ isentropic, dS = 0)
Chemical thermodynamics - 1st Law"

  1st Law of thermodynamics (conservation of energy),
control mass: dE = δQ - δW
  E = U + PE + KE = U + 0 + 0 = U
  δW = PdV
  Combine: dU + PdV = 0
  Constant pressure: add VdP = 0 term
  dU + PdV + VdP = 0 ⇒ d(U+PV) = 0 ⇒ dH = 0
  Hreactants = Hproducts
  Recall h ≡ H/m (m = mass), thus hreactants = hproducts
  Constant volume: PdV = 0
  dU + PdV + VdP = 0 ⇒ d(U) = 0
  Ureactants = Uproducts, thus ureactants = uproducts
  h = u + Pv, thus (h - Pv)reactants = (h - Pv)products
  Most property tables report h not u, so h - Pv form is useful
  New twist: h or u must include BOTH thermal and chemical
contributions!
• 11
  Enthalpy of a mixture (sum of thermal and chemical terms)
n
• H = " n i h˜ i ; h˜ i = enthalpy of i per mole of i = [ h˜ (T) # h˜ 298 ]i + $h˜ of ,i
i=1
(n (no subscripts) = number of species; n i = number of moles of i)
• [ h˜ (T) " h˜ 298 ]i = enthalpy to raise i from temperature of 298 to T (thermal enthalpy)
!
! • "h˜ of ,i = enthalpy of formation of i at 298K & 1 atm, i.e. enthalpy change resulting
from formation of i from its elements in their standard state (chemical enthalpy)
!
Note "h˜ o = 0 for elements in their standard state, e.g. O (gas), C(solid)
f ,i 2
n
• m = mass of mixture = " n i M i ; M i = molecular weight of i

i=1
! Combine all these to form

n
! H
$ n ([h˜ (T) " h˜
i 298 i ] + #h˜ of ,i )
i=1
! h= = n
m
$n M i i
i=1

  Note we can also write h as follows
n n
H
$ ni [h˜ (T) " h˜298 ]i + #h˜ of ,i
( ) $ nn ([h˜ (T) " h˜
i
T
298 i] + #h˜ of ,i )
i=1 i=1
h= = n = n
m ni
$n M i i $n Mi
i=1 i=1 T
ni Moles of i
= = Mole fraction of i = X i
nT Total moles of all gases
!
n
H
$ X ([h˜ (T) " h˜
i 298 i ] + #h˜ of ,i )
! h= = i=1
n
m
$X M i i
i=1
U H " PV H " mRT

u= = = = h " RT
m m m
  Use these boxed expressions for h & u with h = constant (for constant P
combustion) or u = constant (for constant V combustion)
! AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 24
• 12
  Examples of tabulated data on h(T) - h298, Δhf, etc.
(double-click table to open Excel spreadsheet with all data for CO,
O, CO2, C, O2, H, OH, H2O, H2, N2, NO at 200K - 6000K)
CO O2 CO2
Molecular weight = 28.01054 g/mole Molecular weight = 31.99879 g/mole Molecular weight = 44.00995 g/mole
!hfo (kJ/mole) -110.541 !hfo (kJ/mole) 0.000 !hfo (kJ/mole) -393.522
T s h-h_298 T s h-h_298 T s h-h_298

K J/mole-K kJ/mole K J/mole-K kJ/mole K J/mole-K kJ/mole
200 185.916 -2.858 200 193.376 -2.866 200 199.865 -3.414
298 197.543 0.000 298 205.033 0.000 298 213.685 0.000
300 197.723 0.054 300 205.213 0.054 300 213.915 0.067
400 206.125 2.975 400 213.765 3.029 400 225.225 4.008
500 212.719 5.929 500 220.589 6.088 500 234.814 8.314
600 218.204 8.941 600 226.346 9.247 600 243.199 12.916
700 222.953 12.021 700 231.363 12.502 700 250.663 17.761
800 227.162 15.175 800 235.814 15.841 800 257.408 22.815
900 230.957 18.397 900 239.827 19.246 900 263.559 28.041
1000 234.421 21.686 1000 243.475 22.707 1000 269.215 33.405
1100 237.609 25.033 1100 246.818 26.217 1100 274.445 38.894
1200 240.563 28.426 1200 249.906 29.765 1200 279.307 44.484
1300 243.316 31.865 1300 252.776 33.351 1300 283.847 50.158
1400 245.889 35.338 1400 255.454 36.966 1400 288.106 55.907
1500 248.312 38.848 1500 257.969 40.610 1500 292.114 61.714
1600 250.592 42.384 1600 260.337 44.279 1600 295.901 67.580
1700 252.751 45.940 1700 262.575 47.970 1700 299.482 73.492
1800 254.797 49.522 1800 264.701 51.689 1800 302.884 79.442
1900 256.743 53.124 1900 266.726 55.434 1900 306.122 85.429
2000 258.600 56.739 2000 268.655 59.199 2000 309.210 91.450
2100 260.370 60.375 2100 270.504 62.986 2100 312.160 97.500
2200 262.065 64.019 2200 272.278 66.802 2200 314.988 103.575
2300 263.692 67.676 2300 273.981 70.634 2300 317.695 109.671
2400 265.253 71.346 2400 275.625 74.492 2400 320.302 115.788
2500 266.755 75.023 2500 277.207 78.375 2500 322.808 121.926

  Example: what are h and u for a CO2-O2-CO at 10 atm, 2500K
with XCO = 0.0129, XO2 = 0.3376, XCO2 = 0.6495?
Pressure doesn t affect h or u but T does; from the tables:
M CO = 0.02801; M O2 = 0.03200; M CO2 = 0.04401 kg /mole
"h˜ of ,CO = #110.541; "h˜ of ,O2 = 0; "h˜ of ,CO2 = #393.522 kJ /mole
[ h˜ (2500) # h˜ 298 ]CO = 75.023; [ h˜ (2500) # h˜ 298 ]O2 = 78.375; [ h˜ (2500) # h˜ 298 ]CO2 = 121.926 kJ /mole
n
$ X ([h˜ (T) " h˜

i 298 i ] + #h˜ of ,i ) 0.0129(75.023 "110.541) + 0.3376(78.375 + 0) + 0.6495(121.926 " 393.522) kJ /mole
i=1
h= n =
! 0.0129(0.02801) + 0.3376(0.03200) + 0.6495(0.04401) kg /mole
$X M i i
i=1
kJ J
h = "3784 = "3.784 % 10 6
kg kg
n
& 0.03975 kg
R= ; M = $ X i M i = 0.0129(0.02801) + 0.3376(0.03200) + 0.6495(0.04401) =
M i=1
mole
8.314J
0.03975 kg 209.2J
'R= =
moleK mole kgK
6 J 209.2J J
u = h " RT = "3.784 % 10 " (2500K) = "4.307 % 10 6
kg kgK kg

!
• 13
  Final pressure (for constant volume combustion)
"
PV = mRT, R = ; " = universal gas constant = 8.314 J/moleK
M n
"
Total mass i=1
ni M i
M (for mixture) = = n
Total moles
! " ni
i=1
Constant volume combustion : V = constant, m = constant

n (products)
! P
"n i
Tproducts
! Combine : products = i=1
n (reactants)
Preactants Treactants
"n i
i=1
!
Chemical thermo - heating value"

  Constant-pressure energy conservation equation (no heat
transfer, no work transfer other than PdV work)
n (reactants) n (products)
$ ni [h˜ (T) " h˜298 ]i + #h˜ of ,i

( ) $ n ([h˜ (T) " h˜
i 298 i ] + #h˜ of ,i )
i=1 i=1
hreactants = n (reactants) = hproducts = n (products)
$n M i i $n M i i
i=1 i=1
Denominator = m = constant, separate chemical and thermal terms:
n (reactants) n (products) n (products) n (reactants)
# n i [ h˜ (T) " h˜ 298 ]i "

( ) # ni [h˜ (T) " h˜298 ]i
( ) # n $h˜ i
o
f ,i " # n $h˜ i
o
f ,i
! i=1 i=1 i=1 i=1
n (reactants) = n (products)
#n M i i #n M i i
i=1 i=1
  Term on left-hand side is the negative of the total thermal enthalpy

change per unit mass of mixture; term on the right-hand side is
! the chemical enthalpy change per unit mass of mixture
• 14
  By definition, CP ≡ (∂h/∂T)P
  For an ideal gas, h = h(T) only, thus CP = dh/dT or dh = CPdT
  If CP is constant, then for the thermal enthalpy
h2 - h1 = CP(T2 - T1) = mCP(T2 - T1) /m
  For a combustion process in which all of the enthalpy release by
chemical reaction goes into thermal enthalpy (i.e. temperature
increase) in the gas, the term on the left-hand side of the boxed
equation on page 27 can be written as
# n i [ h˜ (T) " h˜ 298 ]i "

( ) # n ([h˜ (T) " h˜
i 298 i ] )
i=1 i=1
mCP (Treactants " Tproducts )
n (reactants) =
m
#n M i i
i=1
where CP is the constant-pressure specific heat averaged

(somehow) over all species and averaged between the product
and reactant temperatures
!
!

  Term on right-hand side of boxed equation on page 27 can be re-
written as
n (products) n (reactants) n (products) n (reactants)
n fuel M fuel
" ni#h˜ of ,i $ " ni#h˜ of ,i " ni#h˜ of ,i $ " n #h˜i
o
f ,i
i=1 i=1 i=1 i=1
n (reactants)
= f
n fuel M fuel n fuel M fuel
"n M i i
i=1
  Last term is the chemical enthalpy change per unit mass of fuel;
define this as -QR, where QR is the fuel’s heating value
n (products) n (reactants)
! % ni$h˜ of ,i # % n $h˜ i
o
f ,i
i=1 i=1
QR " #
n fuel M fuel
  For our stereotypical hydrocarbons, assuming CO2, H2O and N2 as
the only combustion products, this can be written as
! x # $h of ,CO2 + (y 4) # $h of , H 2O "1# $h of , fuel " (x + y 4)$h of ,O2

QR = "
1# M fuel

!
• 15
Chemical thermo - flame temperature"
  Now write the boxed equation on page 27 (conservation of energy
for combustion at constant pressure) once again:
n (reactants) n (products) n (products) n (reactants)
# n i [ h˜ (T) " h˜ 298 ]i "

( ) # n ([h˜ (T) " h˜
i 298 ]i ) # n $h˜i
o
f ,i " # n $h˜i
o
f ,i
i=1 i=1 i=1 i=1
n (reactants) = n (reactants)
#n M i i #n M i i
i=1 i=1
mCP (Treactants " Tproducts )

  We ve shown that the left-hand side =
m
! and the right-hand side = -fQR; combining these we obtain
Tproducts = Treactants + fQR /CP
  This is our simplest estimate of ! the adiabatic flame temperature
(Tproducts, usually we write this as Tad) based on an initial
temperature (Treactants, usually written as T∞) thus
! (constant pressure combustion,
Tad = T" + fQR /CP T-averaged CP)

  This analysis has assumed that there is enough O2 to burn all the
fuel, which is true for lean mixtures only; in general we can write
QR
Tad = T" + f burnable
CP
where for lean mixtures, fburnable is just f (fuel mass fraction)
whereas for rich mixtures, with some algebra it can be shown that
# 1" f &
! f burnable = f stoichiometric % (
$1" f stoichiometric '
thus in general we can write
Q
Tad = T" + f R (if f # f stoichiometric )
! CP
% 1$ f ( QR
Tad = T" + f stoichiometric ' * (if f + f stoichiometric )
&1$ f stoichiometric ) CP
!
• 16
  For constant-volume combustion (instead of constant pressure),
everything is the same except u = const, not h = const, thus the term on
the left-hand side of the boxed equation on page 27 must be re-written as
$n (reactants) ' $n (products) '
& # n i [ h˜ (T) " h˜ 298 ]i " (PV ) reactants) " & # n i [ h˜ (T) " h˜ 298 ]i " (PV ) products)
( ) ( )
% i=1 ( % i=1 (
n (reactants)
#n M i i
i=1
The extra PV terms (= mRT for an ideal gas) adds an extra mR(Tproducts-
Treactants) term, thus
! mCP (Tproducts " Treactants ) mCP (Tproducts " Treactants ) " mR(Tproducts " Treactants )
#
m m
= (CP " R)(Tproducts " Treactants ) = Cv (Tproducts " Treactants )
which means that (again, Tproducts = Tad; Treactants = T∞)
Tad = T" + fQR /Cv (constant volume combustion, T-averaged CP)
which is the same as for constant-pressure combustion except for the Cv
! instead of CP
!

  The constant-volume adiabatic flame (product) temperature on the
previous page is only valid for lean or stoichiometric mixtures; as
with constant-pressure for rich mixtures we need to consider how
much fuel can be burned, leading to
QR
Tad = T" + f (if f < f stoichiometric )
Cv
$ 1# f ' QR
Tad = T" + f stoichiometric & ) (if f > f stoichiometric )
%1 # f stoichiometric ( Cv
  Note that the ratio of adiabatic temperature rise due to
combustion for constant pressure vs. constant volume is
!
(Tad " T# ) constant v CP
= =$
(Tad " T# ) constant P CV
  In practice, one can determine CP by working backwards from a
detailed analysis; for stoichiometric CH4-air, f = 0.055, QR = 50 x
! 106 J/kg, constant-pressure combustion, Tad = 2226K for T∞ =
300K, thus CP ≈ 1429 J/kg-K (for other stoichiometries or other
!
fuels CP will be moderately different)
!
!
• 17
Example of heating value"
  Iso-octane/air mixture:
C8H18 + 12.5(O2 + 3.77N2) → 8 CO2 + 9 H2O + 12.5*3.77 N2
n (products) n (reactants)
% n $h˜ i
o
f ,i # % n $h˜ i
o
f ,i
i=1 i=1
QR " #
n fuel M fuel
=#
(8$h˜ o
f ,CO 2 + 9$h˜ of , H 2O + 12.5(3.77)$h˜ of ,N 2 # 1$h˜ of ,C 8 H18 + 12.5$h˜ of ,O 2 + 12.5(3.77)$h˜ of ,N 2
) ( )
1MC 8 H18
=#
(8 moles)(#393.5 kJ/mole) + 9(#241.8) + 12.5(3.77)(0)) # (1(#250.0) + 12.5(0) + 12.5(3.77)(0))
(1 mole)(0.114 kg/mole)
7
= 44,500 kJ/kg = 4.45 x 10 J/kg
Comments on heating value"

  Heating values usually computed assuming that due to
reaction with air all C → CO2, H → H2O, N → N2, S → SO2, etc.
  If one assumes liquid water, the result is called the higher
heating value; if one (more realistically) assumes gaseous
water, the result is called the lower heating value
  Most hydrocarbons have similar QR (4.0 - 4.5 x 107 J/kg) since
the same C-C and C-H bonds are being broken and same C-O
and H-O bonds are being made
  Foods similar - on a dry weight basis, about same QR for all
  Fruit Loops™ and Shredded Wheat™ have same heating
value (110 kcal/oz = 1.6 x 107 J/kg) although Fruit Loops™ is
mostly sugar whereas Shredded Wheat™ has none (the above
does not constitute a commercial endorsement)
  Fats slightly higher than starches or sugars
  Foods with (non-digestible) fiber lower
• 18
Comments on heating value"
  Acetylene is higher (4.8 x 107 J/kg) due to C-C triple bond
  Methane is higher (5.0 x 107 J/kg) due to high H/C ratio
  H2 is MUCH higher (12.0 x 107 J/kg) due to heavy C atoms
  Alcohols are lower (2.0 x 107 J/kg for methanol, CH3OH) due
to useless O atoms - add mass but no enthalpy release
Example of adiabatic flame temperature"

  Lean iso-octane/air mixture, equivalence ratio 0.8, initial temperature
300K, average CP = 1400 J/kgK, average Cv = 1100 J/kgK:
Stoichiometric: C8H18 + 12.5(O2 + 3.77N2) → 8 CO2 + 9 H2O + 12.5*3.77 N2
FAR (actual mixture, " = 0.8) f /(1# f " =0.8 )

"= = " =0.8 = 0.8
FAR (stoichiometric mixture, " = 1) f " =1 /(1# f " =1 )
n fuelM fuel
f" =1 = n (reactants)
$n M i i
i=1
(1 mole C 8 H18 )(0.114 kg/mole)
=
(1 mole C 8 H18 )(0.114 kg/mole) + (12.5 mole O 2 )(0.032 kg/mole) + (12.5 * 3.77 mole N 2 )(0.028 kg/mole)
= 0.06218
! FAR" =1 = f" =1 /(1# f " =1 ) = 0.06218 /(1# 0.06218) = 0.06630
f" =0.8 /(1# f " =0.8 )
" = 0.8 : = 0.8 % f" =0.8 = 0.0504
0.06630
Tad = T& + fQR /CP = 300K + (0.05054)(4.45 '10 7 J /kg) /(1400J /kgK) = 1906K (const. P)
Tad = T& + fQR /CV = 300K + (0.05054)(4.45 '10 7 J /kg) /(1100J /kgK) = 2345K (const. V)

!
• 19
  Many fuels, e.g. hydrocarbons, when chemically reacted with oxygen
or other oxidizing agents, will release a large amount of enthalpy
  This chemical energy or enthalpy is converted into thermal energy or
enthalpy, thus in a combustion process the product temperature is
much higher than the reactant temperature
  Only 2 principles are required to compute flame temperatures
  Conservation of each type of atom
  Conversation of energy (sum of chemical + thermal)
… but the resulting equations required to account for changes in
composition and energy can look formidable
  The key properties of a fuel are its heating value QR and its
stoichiometric fuel mass fraction fstoichiometric
  The key property of a fuel/air mixture is its equivalence ratio (φ)
  A simplified analysis leads to
Tad = T" + fQR /CP (constant pressure)
Tad = T" + fQR /CV (constant volume)

!
• 20
AME 513 
 
"
Lecture 3
Chemical thermodynamics II – 2nd Law
Outline"
  Why do we need to invoke chemical equilibrium?
  Degrees Of Reaction Freedom (DORFs)
  Conservation of atoms
  Second Law of Thermodynamics for reactive systems
  Entropy of an ideal gas mixture
  Equilibrium constants
  Application of chemical equilibrium to hydrocarbon-air
combustion
  Application of chemical equilibrium to compression/
expansion
AME 513 - Fall 2012 - Lecture 3 - Chemical Thermodynamics 2 2
• 1
Why do we need chemical equilibrium?"
  (From lecture 2) What if we assume more products, e.g.

1CH4 + 2(O2 + 3.77N2) → ? CO2 + ? H2O + ? N2 + ? CO
In this case how do we know the amount of CO vs. CO2?
  And if if we assume only 3 products, how do we know that
the preferred products are CO2, H2O and N2 rather than
(for example) CO, H2O2 and N2O?
  Need chemical equilibrium to decide - use 2nd Law to
determine the worst possible end state of the mixture
Degrees of reaction freedom (DoRFs)"

  If we have a reacting soup of CO, O2, CO2, H2O, H2 and OH,
can we specify changes in the amount of each molecule
independently? No, we must conserve each type of atom (3
in this case)
  Conservation of
C atoms: nCO + nCO2 = constant
O atoms: nCO + 2nCO2 + 2nO2 + nH2O + nOH = constant
H atoms: 2nH2O + 2nH2 + nOH = constant
  3 equations, 6 unknown ni’s ⇒ 3 degrees of reaction freedom
(DoRFs)
  # of DoRFs = # of different molecules (n) - # of different
elements
  Each DoRF will result in the requirement for one equilibrium
constraint
• 2
Conservation of atoms"
  Typically we apply conservation of atoms by requiring that
the ratios of atoms are constant, i.e. the same in the reactants
as the products
C atoms: nCO + nCO2 = constant
O atoms: nCO + 2nCO2 + 2nO2 + nH2O + nOH = constant
H atoms: 2nH2O + 2nH2 + nOH = constant
nC X CO + X CO2
= = constant
nO X CO + 2X CO2 + 2X O2 + X H 2O + X OH
nC X CO + X CO2
= = constant
n H 2X H 2O + 2X H 2 + X OH
  Specifying nO/nH also would be redundant, so the number of
atom ratio constraints = # of atoms - 1
!   What are these constants? Depends on initial mixture, e.g.
for stoichiometric CH4 in O2, nC/nO = 1/4, nC/nH = 1/4
2nd law of thermo for reacting systems"

  Constraints for reacting system
  First law: dE = δQ - δW = δQ - PdV
  Second law: dS ≥ δQ/T
  Combine: TdS - dU - PdV ≥ 0 for any allowable change in the
state of the system
  For a system at fixed T and P (e.g. material in a piston-cylinder
with fixed weight on top of piston, all placed in isothermal bath:
d(TS-U-PV) ≥ 0, or per unit mass d(Ts-u-Pv) ≥ 0
  Define Gibbs function g ≡ h - Ts = u + Pv - Ts
  Thus for system at fixed T and P: d(-g) ≥ 0 or dg ≤ 0
  Thus at equilibrium, dg = 0 or dG = 0 (g or G is minimum) and for
each species i
!G
" µi = 0 µi = chemical potential of species i
!ni
  Similarly, for system at fixed U and V (e.g. insulated chamber of
fixed volume): ds ≥ 0, at equilibrium ds = 0 or dS = 0 (s is
maximum)
• 3
Entropy of an ideal gas mixture"
  Depends on P AND T (unlike h and u, which depend ONLY on T)
A B C A B C A, B, C
 P = Pref P = Pref P = Pref  P ≠ Pref P ≠ Pref P ≠ Pref  P ≠ Pref
(1) (2) (3)

  (1) Start with gases A, B and C at temperature n
T and Po = 1 atm
S = SA + SB + SC = nA !!sA (T ) + nB !!sB (T ) + nC !!sC (T ) = " ni !!sio (T )
o o o
i=1
S = total entropy of all gases;ni = moles of species i; n = number of species

!!sio (T ) = entropy per mole of i at any temperature T & ref. pressure = 1 atm
  (2) Raise/lower each gas to pressure P ≠ 1 atm (same P for all)
!SA = nA $%C! P ln (T2 T1 ) " # ln ( P2 P1 )&' = nA $%C! P ln (T T ) " # ln ( P Pref )&' = "nA # ln ( P Pref )
n n n n
S = ( ni !!sio (T ) " ( ni # ln ( P Pref ) = ( ni $%!!sio (T ) " # ln ( P Pref )&' = ( ni !!sio (T ) " nT # ln ( P Pref )
i=1 i=1 i=1 i=1

  (3) Now remove dividers, VA  VA + VB + VC (V = volume)
!SA = nA #$C! P ln (T2 T1 ) + " ln (V2 V1 )%& = nA #$C! P ln (T T ) + " ln ((VA +VB +VC ) VA )%&
= nA " ln (( nA + nB + nC ) nA ) = 'nA " ln ( nA nT );recall X A ( nA nT = mole fraction of A
n n n
S = ) ni !!sio (T ) ' nT " ln ( P Pref ) ' ) "ni ln ( ni nT ) = ) ni #$!!sio (T ) ' " ln Xi %& ' nT " ln ( P Pref )
i=1 i=1 i=1
  Can also combine Xi and P/Pref terms using partial pressures Pi;
for an ideal gas mixture Xi = Pi/P, where (as above) P without
subscripts is the total pressure = ΣPi
n n
S = ( ni $%!!sio (T ) " # ln Xi &' " nT # ln ( P Pref ) = ( ni $%!!sio (T ) " # ln Xi " # ln ( P Pref )&'
i=1 i=1
n
= ( ni $%!!s (T ) " # ln ( Pi Pref )&'
i
o
i=1
• 4
  Most useful form - entropy per unit mass (m), since mass is
constant:
n n
S
( n $%!!s (T ) " # ln X &' " n # ln ( P P ) ( X $%!!s (T ) " # ln X &' " # ln ( P P )
i i
o
i T ref i i
o
i ref
i=1 i=1
s= = n
= n
m
(n M i i (X M i i
i=1 i=1
ℜln(P/Pref) - entropy associated with pressure different from 1 atm -

P > Pref leads to decrease in s
ℜXiln(Xi) - entropy associated with mixing (Xi < 1 means more than 1
specie is present - always leads to increase in entropy
since -Xiln(Xi) > 0)
  Denominator is just the average molecular weight
  Units of s are J/kgK
Equilibrium of an ideal gas mixture"

  How to use this result? dG = 0 means there are n equations of the
form ∂G/∂ni = 0 for n unknown species concentrations!
  Break system into multiple sub-systems, each with 1 DoRF, e.g..
for a chemical reaction of the form
νAA + νBB → νCC + νDD
e.g. 1 H2 + 1 I2 → 2 HI
A = H2, νA = -1, B = I2, νB = -1, C = HI, νC = 2, D = nothing, νD = -0
conservation of atoms requires that
dnA dn dn dn
= ! B = C = D = k (k = any constant, + or -)
!A !B !C !D
  G = H – TS, where
n n
H = ! ni h!i (T ); h!i (T ) = [ h(T
! ) " h! ] + #h! o ; S = ! n %#!s o (T ) " $ ln ( P P )'
298 i f ,i i& i i ref (
i=1 i=1
n n
G = H " TS = ! ni %&h!i (T ) " T#!s (T ) + $T ln ( Pi Pref )'( = ! ni %&#g!io (T ) + $T ln ( Pi Pref )'(
i
o
i=1 i=1
where #g!io (T ) ) h!i (T ) " T#!sio (T ) is the Gibbs function for pure i at temp. T & P = Pref
• 5
n # %
dP
dG = )'!g!io (T )dni + "T ln ( Pi Pref ) dni + ni "T i + ni d #$!g!io (T )%&( = 0
i=1 $ Pi &
n n
1st term: ) !g!io (T )dni = k )! i !g!io (T ), e.g. 2!g! HI
o
(T ) *1!g! Ho 2 (T ) *1!g! Io2 (T )
i=1 i=1
, 2 /
n , n !i /
2nd term: ) "T ln ( Pi Pref ) dni = k"T ln . + ( Pi Pref ) 1, e.g. k"T ln .
( PHI Pref ) 1
. P P 1 P P 11
i=1 - i=1 0 - ( H 2 ref ) ( I2 ref ) 0
n n
dPi dP "T n
3rd term: ) ni "T = "T ) ni i = ) dPi = 0 since P = constant
i=1 Pi i=1 ni P P i=1
n
4th term: ) ni d #$!g!io (T )%& = 0 since T = constant
i=1
n , n !i /
n
!i # n %
2 k )! i !g!io (T ) + k"T ln . + ( Pi Pref ) 1 = 0 2 + ( Pi Pref ) = exp '* )! i !g!io (T ) "T (
i=1 - i=1 0 i=1 $ i=1 &
n
# n % )! i # n %
or in terms of mole fractions'+ Xi! i ( ( P Pref ) i=1 = exp '* )! i !g!io (T ) "T (
$ i=1 & $ i=1 &

2'1'1
! X2 $ ! P $
For example ## 1 HI 1 && ## && = exp *+' ( 2(g! HI
o
(T ) '1(g! Ho 2 (T ) '1(g! Io2 (T )) )T ,-
" X H 2 X I2 % " Pref %
It is fairly inconvenient to work with the exp[-g/RT] terms, but we can

tabulate for every species its equilibrium constant Ki, i.e. the value of
this term for the equilibrium of the species with its forming elements
in their standard states, e.g.
K HI = exp $%! ( "g! HI
o
(T ) ! 0.5"g! Ho 2 (T ) ! 0.5"g! Io2 (T )) #T &'
So in general for a reaction of the form νAA + νBB → νCC + νDD
! +! D '! A '! B
XC! C X D! D ! P $C K C! C K D! D
# && =
X A! A X B! B #" Pref % K A! A K B! B
n
Xi = mole fraction of i; note( Xi =1
i=1
P = total pressure, Pref = reference pressure = 1 atm

K i = equilibrium constant of i (from tables) = function of T only (not P)
• 6
Equilibrium constants"
  Examples of tabulated data on K - (double-click table to open
Excel spreadsheet with all data for CO, O, CO2, C, O2, H, OH, H2O,
H2, N2, NO at 200K - 6000K)
  Note K = 1 at all T for elements in their standard state (e.g. O2)
CO O2 CO2
Molecular weight = 28.01054 g/mole Molecular weight = 31.99879 g/mole Molecular weight = 44.00995 g/mole
!h f o (kJ/mole) -110.541 !hfo (kJ/mole) 0.000 !hfo (kJ/mole) -393.522
T h-h_298 Keq T h-h_298 Keq T h-h_298 Keq

K kJ/mole (no units) K kJ/mole (no units) K kJ/mole (no units)
200 -2.858 3.567E+25 200 -2.866 1.000E+00 200 -3.414 8.148E+94
298 0.000 1.190E+16 298 0.000 1.000E+00 298 0.000 1.395E+61
300 0.054 9.085E+15 300 0.054 1.000E+00 300 0.067 5.248E+60
400 2.975 1.360E+11 400 3.029 1.000E+00 400 4.008 3.678E+43
500 5.929 1.664E+08 500 6.088 1.000E+00 500 8.314 1.764E+33
600 8.941 1.854E+06 600 9.247 1.000E+00 600 12.916 2.265E+26
700 12.021 7.334E+04 700 12.502 1.000E+00 700 17.761 2.662E+21
800 15.175 6.416E+03 800 15.841 1.000E+00 800 22.815 5.295E+17
900 18.397 9.701E+02 900 19.246 1.000E+00 900 28.041 7.065E+14
1000 21.686 2.067E+02 1000 22.707 1.000E+00 1000 33.405 3.439E+12
1100 25.033 5.870E+01 1100 26.217 1.000E+00 1100 38.894 4.454E+10
1200 28.426 2.050E+01 1200 29.765 1.000E+00 1200 44.484 1.190E+09
1300 31.865 8.382E+00 1300 33.351 1.000E+00 1300 50.158 5.548E+07
1400 35.338 3.886E+00 1400 36.966 1.000E+00 1400 55.907 4.013E+06
1500 38.848 1.991E+00 1500 40.610 1.000E+00 1500 61.714 4.119E+05
1600 42.384 1.106E+00 1600 44.279 1.000E+00 1600 67.580 5.622E+04
1700 45.940 6.577E-01 1700 47.970 1.000E+00 1700 73.492 9.700E+03
1800 49.522 4.136E-01 1800 51.689 1.000E+00 1800 79.442 2.037E+03
1900 53.124 2.728E-01 1900 55.434 1.000E+00 1900 85.429 5.043E+02
2000 56.739 1.876E-01 2000 59.199 1.000E+00 2000 91.450 1.437E+02
2100 60.375 1.333E-01 2100 62.986 1.000E+00 2100 97.500 4.612E+01
2200 64.019 9.767E-02 2200 66.802 1.000E+00 2200 103.575 1.644E+01
2300 67.676 7.350E-02 2300 70.634 1.000E+00 2300 109.671 6.406E+00
2400 71.346 5.656E-02 2400 74.492 1.000E+00 2400 115.788 2.702E+00
2500 75.023 4.443E-02 2500 78.375 1.000E+00 2500 121.926 1.222E+00
Chemical equlibrium - example"

  For a mixture of CO, O2 and CO2 (and nothing else, note 1 DoRF
for this case) at 10 atm and 2500K with C:O = 1:3, what are the
mole fractions of CO, O2 and CO2?
1 CO2 ⇔ 1 CO + .5 O2
X CO1 X O2 .5 "10 atm %1+.5(1 KCO1KO2 .5 0.0444311.5
$ ' = = = 0.0364 (chem. equilibrium)
X CO2 1 # 1 atm & KCO2 1 1.2221
X CO + X O2 + X CO2 = 1 (sum of mole fractions = 1)
nC X CO + X CO2 1
= = (conservation of atoms)
nO X CO + 2X O2 + 2X CO2 3
  3 equations, 3 unknowns: XCO2 = 0.6495, XO2 = 0.3376, XCO = 0.0129

  At 10 atm, 1000K: XCO2 = .6667, XO2 = 0.3333, XCO = 2.19 x 10-11
!   At 1 atm, 2500K: XCO2 = 0.6160, XO2 = 0.3460, XCO = 0.0380
  With N2 addition, C:O:N = 1:3:6, 10 atm, 2500K: XCO2 = 0.2141, XO2
= 0.1143, XCO = 0.0073, XN2 = 0.6643 (XCO2/XCO = 29.3 vs. 50.3
without N2 dilution) (note still 1 DoRF in this case)
  Note high T, low P and dilution favor dissociation
• 7
Chemical equlibrium"
  How do I know to write the equilibrium as
1 CO2 ⇔ 1 CO + .5 O2
and not (for example)
2 CO + 1 O2 ⇔ 2 CO2
For the first form
1+.5(1 2+1(2
X CO1 X O2 .5 " P % KCO1KO2 .5 X CO 2 X O2 1 " P % KCO 2KO2 1
$ ' = ) $ ' =
X CO2 1 $# Pref '& KCO2 1 X CO2 2 $# Pref '& KCO2 2
2(2(1
X CO2 2 " P % KCO2 2
) $ ' =
X CO 2 X O2 1 $# Pref '& KCO 2KO2 1
which is the appropriate expression of equilibrium for the 2nd

form - so the answer is, it doesn t matter as long as you re
!
consistent
Chemical equlibrium - hydrocarbons"

  Reactants: CxHy + rO2 + sN2 (not necessarily stoichiometric)
  Assumed products: CO2, CO, O2, O, H2O, OH, H, H2, N2, NO
  How many equations?
  10 species, 4 elements ⇒ 6 DoRFs ⇒ 6 equil. constraints
  4 types of atoms ⇒ 3 atom ratio constraints
  Conservation of energy (hreactants = hproducts) (constant pressure
reaction) or ureactants = uproducts (constant volume reaction)
n
  "X i =1 n (products)
"n
i=1 i
  Pressure = constant or (for const. vol.) Pproducts i=1
Tproducts
= n (reactants)
  6 + 3 + 1 + 1 + 1 = 12 equations Preactants Treactants
  How many unknowns? "n i
i=1
!   10 species ⇒ 10 mole fractions (Xi)
  Temperature
  Pressure
  10 + 1 + 1 = 12 equations
!
• 8
  Equilibrium constraints - not a unique set, but for any set
  Each species appear in at least one constraint
  Each constraint must have exactly 1 DoRF
  Note that the initial fuel molecule does not necessarily appear in the set
of products! If the fuel is a large molecule, e.g. C8H18, its entropy is so
low compared to other species that the probability of finding it in the
equilibrium products is negligible!
  Example set (not unique)
1+.5)1 1 0.5
1 .5
X CO X O2 # P & {KCO (T)} {KO2 (T)}
CO2 " CO + 0.5O2 ; % ( =
X CO2 1 %$ Pref (' {KO (T)}
1
2
H 2O " H 2 + 0.5O2 ; etc.

0.5H 2 " H
0.5O2 " O
H 2O " 0.5H 2 + OH
0.5N 2 + 0.5O2 " NO

  Atom ratios
nC x X CO + X CO
= = 2
nO 2r X CO + 2X CO + 2X O + X H O + X OH + X O + X NO
2 2 2
nC x X CO + X CO2
= =
n H y 2X H 2O + 2X H 2 + X OH + X H
nC x X + X CO2
= = CO
n N 2s 2X N 2 + X NO
  Sum of all mole fractions = 1
n
"X i = X CO + X CO2 + X O2 + X O + X H 2O + X H 2 + X OH + X H + X N 2 + X NO = 1
i=1
!
  Conservation of energy (constant P shown)
! $ ni [h˜ (T) " h˜298 ]i + #h˜ of ,i

( ) $ n ([h˜ (T) " h˜
i 298 i ] + #h˜ of ,i )
i=1 i=1
hreactants = n (reactants) = hproducts = n (products)
$n M i i $n M i i
i=1 i=1
• 9
  This set of 12 simultaneous nonlinear algebraic equations looks
hopeless, but computer programs (using slightly different
methods more amenable to automation) (e.g. GASEQ) exist
  Typical result, for stoichiometric CH4-air, 1 atm, constant P

  Most of products are CO2, H2O and N2 but some dissociation (into
the other 7 species) occurs
  Product γ is much lower than reactants - affects estimation of
compression / expansion processes using Pvγ relations
  Bad things like NO and CO appear in relatively high concentrations
in products, but will recombine to some extent during expansion
  By the time the expansion is completed, according to equilibrium
calculations, practically all of the NO and CO should disappear, but
in reality they don t - as T and P decrease during expansion,
reaction rates decrease, thus at some point the reaction becomes
frozen , leaving NO and CO stuck at concentrations MUCH
higher than equilibrium
• 10
Adiabatic flame temp. - hydrocarbons"
3500
Initial temperature T! = 300K CH4-air (const. P)
Initial pressure = 1 atm C3H8-air (const. P)
C8H18-air (const. P)
3000
H2-air (const. P)
Adiabatic Flame Temp. (K) CH4-O2 (const. P)
CH4-air (const. V)
2500
2000
1500
1000
500
0
0 0.5 1 1.5 2 2.5 3
Equivalence ratio
Adiabatic flame temp - hydrocarbons"

  Adiabatic flame temperature (Tad) peaks slightly rich of
stoichiometric - since O2 is highly diluted with N2, burning
slightly rich ensures all of O2 is consumed without adding a
lot of extra unburnable molecules
  Tad peaks at ≈ 2200K for CH4, slightly higher for C3H8, iso-
octane (C8H18) practically indistinguishable from C3H8
  H2 has far heating value per unit fuel mass, but only slightly
higher per unit total mass (due to heavy air), so Tad not that
much higher
  Also - massive dissociation as T increases above ≈ 2400K,
keeps peak temperature down near stoichiometric
  Also - since stoichiometric is already 29.6% H2 in air (vs. 9.52%
for CH4, 4.03% for C3H8), so going rich does not add as many
excess fuel molecules
  CH4 - O2 MUCH higher - no N2 to soak up thermal energy
without contributing enthalpy release
  Constant volume - same trends but higher Tad
• 11
Compression / expansion"
  Compression / expansion processes are typically assumed
to occur at constant entropy (not constant h or u)
  Use sreactants = sproducts constant for compression / expansion
instead of hreactants = hproducts or ureactants = uproducts
  All other relations (atom ratios, ΣXi = 1, equilibrium
constraints) still apply
  Three levels of approximation
  Frozen composition (no change in Xi s), corresponds to
infinitely slow reaction
  Equilibrium composition (Xi s change to new equilibrium),
corresponds to infinitely fast reaction (since once we get to
equilibrium, no further change in composition can occur)
  Reacting composition (finite reaction rate, not infinitely fast or
slow) - more like reality but MUCH more difficult to analyze
since rate equations for 100 s or 1000 s of reactions are
involved
  Which gives most work output?
  Equilibrium - you re getting everything the gas has to offer;
recombination (e.g. H + OH → H2O) gives extra enthalpy
release, thus more push on piston or more kinetic energy of
exhaust
  Frozen - no recombination, no extra heat release
  Reacting - somewhere between, most realistic
• 12
  Example - expansion of CO2-O2-CO mixture from 10 atm, 2500K to 1
atm in steady-flow control volume (e.g. nozzle) or control mass (e.g
piston/cylinder)
  Initial state (mixture from lecture 2 where h was calculated):
XCO = 0.0129, XO2 = 0.3376, XCO2 = 0.6495, T = 2500 , P = 10 atm
h = -3784 kJ/kg, u = -4397 kJ/kg
o
"˜sCO (T) = 266.755 J /moleK ;"˜sOo2 (T) = 277.207 J /moleK;"˜sCO
o
2
(T) = 322.808 J /moleK
s=
+X CO ( "˜sCO
o
(
# $ln X CO ) + X O2 "˜sOo2 # $ln X O2 + X CO2 "˜sCO
o
2
) (
# $ln X CO2 # $ln(P /Pref ) )
X CO MCO + X O2 MO2 + X CO2 MCO2
(.0129)(266.755 " 8.314 ln(.0602)) + (0.3376)(277.207 " 8.314 ln(0.3376)) + (0.6495)( 322.808 " 8.314 ln(0.6495)) " 8.314 ln(10 /1)
s=
(.0129)(0.028) + (0.3376)(0.032) + (0.6495)(0.044)
s = 7382 J /kgK
!
  Expand at constant entropy to 1 atm, frozen composition:
T = 1738K, XCO = 0.0129, XO2 = 0.3376, XCO2 = 0.6495, ,
h = -4795 kJ/kg, u = -5159 kJ/kg, s = 7381J/kgK
  Work done (control volume, steady flow)
= hbefore - hafter = +1011 kJ/kg
  Work done (control mass) = ubefore - uafter = +762 kJ/kg
  Expand at constant entropy to 1 atm, equilibrium composition:
T = 1794K, XCO = 0.00022, XO2 = 0.3334, XCO2 = 0.6664
(significant recombination)
h = -4811 kJ/kg, u = -5184 kJ/kg, s = 7382 J/kgK
  Work done (control volume, steady flow) = +1027 kJ/kg
(1.6% higher)
  Work done (control mass) = 787 kJ/kg (3.3% higher)
  Moral: let your molecules recombine!
• 13
  In order to understand what happens to a chemically reacting
mixture if we wait a very long time, we need to apply
  1st Law of Thermodynamics (conservation of energy) - but this
doesn t tell us what the allowable direction of the reaction is; A
→ B or B → A are equally valid according to the 1st Law
  2nd Law of Thermodynamics (increasing entropy) - invokes
restrictions on the direction of allowable processes (if A → B is
allowed then B → A isn t)
  Equilibrium occurs when the worst possible end state is
reached; once this point is reached, no further chemical
reaction is possible unless something is changed, e.g. T, P,
V, etc.
  The statements of the 2nd law are
  ds ≥ 0 (constant u & v, e.g. a rigid, insulated box)
  dg = d(h - Ts) ≤ 0 (constant T and P, e.g. isothermal piston/
cylinder)

  The application of the 2nd law leads to complicated looking
expressions called equilibrium constraints that involve the
concentrations of each type of molecule present in the
mixture
  These equilibrium constraints are coupled with conservation
of energy, conservation of each type of atom, and the ideal
gas law (or other equations of state, not discussed in this
class) to obtain a complete set of equations that determine
the end state of the system, e.g. T, P and composition of the
combustion products
• 14
AME 513 
 
"
Lecture 4
Chemical kinetics I – Basic Concepts
Outline"
  Law of Mass Action (LOMA)
  Kinetic theory of gases as applied to chemical reactions
  Homogeneous reaction
  Well-stirred reactor
  Chain branching
  H2 – O2 reaction
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 2
• 1
Law of Mass Action (LoMA)"
  First we need to describe rates of chemical reaction
  For a chemical reaction of the form
νAA + νBB → νCC + νDD
e.g. 1 H2 + 1 I2 → 2 HI
A = H2, νA = 1, B = I2, νB = 1, C = HI, νC = 2, D = nothing, νD = 0
the Law of Mass Action (LoMA) states that the rate of reaction
d # [A] & d # [B] & d # [C] & d # [D] & " "
$ ' = $ ' = ) $ ' = ) $ ' = )k f [ A] A [ B] B
dt % " A ( dt % " B ( dt % " C ( dt % " D (
[ i ] = concentration of molecule i (usually moles per liter)
kf = forward reaction rate constant
  How to calculate [ i ]?
!   According to ideal gas law, the total moles of gas per unit volume (all
molecules, not just type i) = P/ℜT
  Then [ i ] = (Total moles / volume)*(moles i / total moles), thus
[ i ] = (P/ℜT)Xi (Xi = mole fraction of i)
  Minus sign on d[A]/dt and d[B]/dt since A & B are being depleted
  Basically LoMA states that the rate of reaction is proportional to the
number of collisions between the reactant molecules, which in turn is
proportional to the concentration of each reactant
Collision rate"
  How to estimate kf? Chemical reaction requires
  Collision between molecules
  Enough kinetic energy; call this the “activation energy Ea
  Luck (“steric factor”, p) – e.g. orientation at time of collision
  How many collisions does a molecule undergo per unit time?
  Molecule of diameter σ & speed c will sweep out an effective volume
per unit time = πσ2c (Why diameter not radius? Molecules collide
when center-to-center spacing is 2r = σ)
  (Molecules per unit volume) * (Volume swept per unit time) ~
Frequency of collisions = [A]πσ2c
  Multiply by [A] to get collisions per unit volume per unit time = [A]
[A] πσ2c
  Kinetic theory of gases give mean molecular speed (c) & number of
collisions per unit volume (V) per unit time for A & B (ZAB):
2
8kT Z "" +" B % 8kT m m
c= ! AB = [ A ] [ B ] ! $ A ' ; µ( A B
!µ V # 2 & !µ m A + mB
k = Boltzmann’s const. = 1.38 x 10-23 J/K = R/NAvogadro; m = mass of 1 molecule
• 2
Collision rate"
  On a mole (rather than molecule) basis
2
Z AB / N Avo ! " + " B $ 8 ( kN Avo ) T
= [ A / N Avo ] [ B / N Avo ] ! N Avo # A &
V " 2 % ! ( µN Avo )
Z! AB ( ! *( ! *
2
! " + " B $ 8,T ( ! *( ! * 2
' = ) A+) B+ ! N Avo # A & = A B N Avo (! A + ! B ) 2! RT
V " 2 % ! M ) +) +
  Example: how often do N2 molecules collide at 298K & 1 atm?

σ = 3.61 x 10-10 m, mass = 4.65 x 10-26 kg (µN2-N2 = 2.32 x 10-26 kg)
[ N 2 ] = N Avogadro ( P !T ) =
(6.02 "10 23
/ mole) (101325N / m 2 )
=
2.46 "10 25
(8.314J / moleK ) (298K ) m3
2
* -
Z AB # 2.46 "10 25 &# 2.46 "10 25 & , 2 (3.61"10 m ) / 8 (1.38 "10 )23 J / K ) ( 298K )
)10
1.66 "10 35 coll
=% (% (! , /
=
V $ m 3
'$ m 3
' + 2 . ! ( 2.32 "10 )26
kg) m 3s
Z AB 1 1.66 "10 35 coll m3 2 molecules 1.35 "1010

Collisions per molecule = = 3 25
=
V [ N2 ] ms 2.46 "10 molecules coll s
  At 2200K, ZN2-N2 = 4.98 x 109/s; typical time for hydrocarbon

oxidation ≈ 10-3 s, thus each molecule collides ≈ 5 x 106 times!
Energy distribution"
  Maxwell-Boltzman distribution: f = # of molecules with KE of
E, per unit energy 2 E
f ( a) = a exp (!a );a "
! kT
  Zero probability of zero or infinite KE (a = E/kT = 0 or ∞); peak
probability at a = 0.5
  Fraction of molecules with Ea/kT greater than some value β

2 "a
! f (a)da = erf ( a ) " !
e a
1
# 0.9
2 exp(-a)
! f (a)da = 1" erf ( ) " +
!
" e" " 0.8
0.7 ∫f(a)d(a) = fraction of
"
0.6 molecules with KE > E/kT
#
2 0.5
Limit " $ # ! f (a)da = " e" "
! 0.4
"
0.3
  Textbook uses exp(-β) not 0.2 f(a)
(2 / ! ) " e!" - similar trends 0.1
but not technically correct! 0

0 1 2 3 4 5 6
a = E/kT
• 3
Energy distribution"
  Ea = “activation energy” representing the energy barrier that
must be overcome for reaction
  E is not enthalpy of reaction Δhf (or heating value QR); in
general there is no relation between E & Δhf - E affects
reaction rates whereas Δhf & QR affect end states (e.g. Tad),
though Δhf & QR affect reaction rates indirectly by affecting T
Total Kinetic Activation

Energy energy energy energy (E)
A+B A+B
Potential Enthalpy
energy of reaction
C+D
Unsuccessful collision
Successful collision
Time
Diary of a collision
Reaction rate"
  So finally the reaction rate expression should be the
combination of collision rate (ZAB/V), energy (Ea) and steric
“luck” (p) factors
!
d[ A] " Z! % +" ) +%
= ! # AB & # * f (a)da& { p}
dt $ V ' $+ Ea /(T '+
+" 0 E 3 2 Ea !(Ea +%
= ! ,- A! ./,- B! ./ N Avo (! A + ! B ) 2! RT #1! erf 2
2
{ $+
} a
5+
1 (T 4 ! (T
e
(T )
& { p}
'+
d ,- A! ./
= -,- A! ./,- B! ./ N Avo (! A + ! B ) 2Ea M AB e ( a
2 !E (T )
Large Ea (T {erf ( ) 61} : dt
p
mole
2
3 , mole . , 1 . 2 J/mole , -[-] . 1 , 1 . m2 1 1
Check units: m = 7 3 8 7 8 m -[-]e /[-] 9 = 7 3 8 m 2 2 9 = OK
s - m / - mole / kg/mole s -m / s s s
2 +" 0 E 3 2 Ea !(Ea (T ) +%
Note also k f = pN Avo (! A + ! B ) 2! RT #1! erf 2 a
5+ e &
+$ 1 (T 4 ! (T +'
2 !( Ea (T )
Large Ea (T : k f : pN Avo (! A + ! B ) 2Ea M AB e
• 4
Reaction rate"
  Compare to book example
2 +) # E & 2 Ea !(Ea "T ) +-
k f = pN Avo (! A + ! B ) 2! RT *1! erf % a
(+ e .
+, $ "T ' ! "T +/
Ea 31600J / mol +) # E & 2

a Ea !(Ea "T ) +-
= = 1.900; *1! erf % (+ e . = 1.384
"T (8.314J / moleK ) ( 2000K ) ,+ $ "T ' ! "T /+
"
R= ; M = molecular weight based on reduced mass
M
8.314J / moleK
= (16)(2) / (16 + 2) = 1.778 = 0.01778kg / mole 0 R = = 4677J / kgK
0.01778kg / mole
# 6.02 110 23 & 2 4677J
( (3.05 110 m + 2.827 110 m ) 2!
!10 !10
k f = p% 2000K (1.384)
$ mole ' kgK
m3
= 2.21110 9 ( p)
mole s
# cm 3 & m 3 2 m3
Using values from Table 4.1, k f = %1.5 110 7 ( 6 3 ( 2000K ) exp (!1.384) = 1.50 110
7
$ mole s ' 10 cm mole s

1.50 110 7
0 p= = 0.0068 vs. 0.075 from textbook example
2.21110 9
Comments on LoMA"
  In practice, terms other than exp(-β) are treated as expendable; reaction rate
constant kf expressed in Arrhenius form; for E per mole not per molecule:
k f = Z T n exp !Ea ( "T )

Z = pre-exponential factor, n = another (nameless) constant, Ea = activation
energy (cal/mole); ℜ = gas constant = NAvogadrok; working backwards, units of Z
must be (moles per liter)1-νA-vB/(K-nsec)
  With 3 parameters (Z, n, E) any curve can be fit!
  The exponential term causes extreme sensitivity to T for E/ℜ >> T!
1 E/R = 1000K 1
E/R = 3000K
E/R = 10000K
E/R = 20000K
0.8
0.1
exp(-E/RT)
exp(-E/RT)
0.6
0.01
0.4
0.001
0.2
E/R = 1000K
E/R = 3000K
0.0001 E/R = 10000K
0 E/R = 20000K
0 2000 4000 6000 8000 1 10

4
10-5
Temperature (K) 0 2000 4000 6000 8000 1 104
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I

Temperature (K) 10
• 5
Comments on LoMA"
  The full reaction rate expression (omitting over-wiggles) is then
1 d[A] 1 d[B]
( )
!A !B
= = !Z "# A$% "# B$% T a exp !E
! A dt ! B dt &T
  The H2 + I2 → 2HI example is one of few where reactants →
products occurs in a single step; most fuels go through many
intermediates during oxidation - even for the simplest
hydrocarbon (CH4) the standard mechanism
http://www.me.berkeley.edu/gri_mech/ includes 53 species and
325 individual reactions!
  The only likely reactions in gases, where the molecules are far
apart compared to their size, are 1-body, 2-body or 3-body
reactions, i.e. A → products, A + B → products or
A + B + C → products
  In liquid or solid phases, the close proximity of molecules makes
n-body reactions plausible
Comments on LoMA"
  Recall that the forward reaction rate is
d # [A] & d # [B] & d # [C] & d # [D] & " "
$ ' = $ ' = ) $ ' = ) $ ' = )k f [ A] A [ B] B
dt % " A ( dt % " B ( dt % " C ( dt % " D (
  Similarly, the rate of the reverse reaction can be written as
d # [C] & d # [D] & d # [A] & d # [B] & " "
$ ' = $ ' = ) $ ' = ) $ ' = )k b [C ] C [ D] D
! dt % " C ( dt % " D ( dt % " A ( dt % " B (
kb = backward reaction rate constant
  At equilibrium, the forward and reverse rates must be equal, thus
! +! D )! A )! B
! !
k f [C ] C [ D ] D
!
XP k X ! C X ! D # P & C D A B XC! C X D! D # P Pref &
! +! )! )! C
= ;[ ]i = i " f = C! A D! B % ( = ! A ! B %% ((
kb [ A ]! A [ B ]! B !T kb X A X B $ !T ' X A X B $ Pref !T '
! +! D )! A )! B ! +! D )! A )! B
k # !T & X !C X ! D # P &C
C
K C! C K D! D
" f %% (( = C! A D! B %% (( =
kb $ Pref ' X A X B $ Pref ' K A! A K B! B
This ties reaction rate constants (kf, kb) and equilibrium constants (Ki s) together
• 6
Homogeneous reaction"
  Given a homogeneous system (T, P, [ ] same everywhere at
any instant in time, but may change over time), how long will
it take for the mixture to react (explode?)
  Model for knocking in premixed-charge piston engines
  As reaction starts, heat is released, temperature increases,
overall reaction rate Ω increases, heat is released faster, T
rises faster, Ω increases faster, … <BOOM>
  Simple analysis - assumptions
  Single-step reaction νAA + νBB → νCC + νDD
  Excess of B (example: lean mixture with A = fuel, B = oxygen)
  νA = νB = 1
  Adiabatic, constant-pressure or constant-volume, ideal gas,
constant CP and CV
  Constant mass
  Energy equation (constant volume) - if all fuel consumed
CV (Tad ! T" ) = fQR = #$Y f (t = 0) !Y f (t = ")%&QR (Yf = fuel mass fraction)
So at any instant in time
CV (T (t) ! T" ) = #$Y f (0) !Y f (t)%&QR
where Yf(t) is the instantaneous fuel mass fraction (at t = 0, no fuel
consumed, T = initial temperature = T∞; at t = ∞, Yf = 0, all fuel consumed, T
= Tad); then
[ fuel]" M fuel [ fuel](t)M fuel
Y f (t = 0) = f = $ Y f (t) =
#" #"
QR M fuel {[ fuel]" % [ fuel](t)}
$ CV (T(t) % T" ) = (Eq. 1)
#"
(this simply says that there is a linear relationship between the amount of
fuel consumed and the temperature rise) (If constant pressure CV  CP)
  Since we assumed νA = νB = 1, where A = fuel, B = oxygen
!
d[A] d[ fuel] d[B] d[Ox]
= = = " [Ox]# - [Ox](t) = [ fuel]# - [ fuel](t) (Eq. 2)
dt dt dt dt

!
• 7
  Reaction rate equation (assume n = 0)
d[A] # # % "E ( d[ fuel] % "E (
= "ZT n [ A] A [ B] B exp' *+ = "Z [ fuel](t)[Ox ](t)exp' * (Eq. 3)
dt & $T ) dt & $T(t) )
  Combine Eqs. 1, 2, 3, non-dimensionalize:
d! "1 % " !$ %
! = !! $ !1+ ! ' exp $ '
d" ## & # 1+ H (1! ! ) &
[ fuel](t) [ fuel](t) E [ fuel])
!( = ;$ ( ; " ( tZ[ fuel]) ;# ( <1
[ fuel](t = 0) [ fuel]) *T) [Ox])
QR M fuel [ fuel]) fQR CV (Tad ! T) ) Tad
H( = = = !1
%)CV T) CV T) CV T) T)
  Notes on this result
  ϕ is the equivalence ratio for our special case νA = νB = 1; only
valid for lean mixtures since we assumed surplus of A = fuel
  Get pressure from P(t) = ρ∞RT(t); if constant pressure equation
are exactly the same except Tad is the constant-P value
  Equation looks scary but just a 1st order nonlinear ordinary
differential equation - integrate to find ε(τ) (amount of product
formed as a function of time) for various ϕ (stoichiometry), β
(activation energy), initial temp. (T∞), H (heat release)
  Initial condition is ε = 1 at τ = 0
  What do we expect?
  Since reaction rate is slowest at low T, reaction starts slowly
then accelerates
  Induction time (e.g. time to reach 90% completion of reaction,
ε = 0.1) should depend mostly on initial temperature T∞, not final
temperature Tad since most of the time needed to react is before
self-acceleration occurs
  Very different from propagating flames where SL depends mostly
on Tad not T∞ because in for flames there is a source of high T
(burned gases) to raise gas T to near Tad before reaction started;
in the homogeneous case no such source exists
  This means that the factors that affect flame propagation and
homogeneous reaction are very different
• 8
  Double-click chart to edit or change parameters
  Case shown: ϕ = 0.7, β = 10, H = 6
  Note profile and time to ignite depend strongly on β, much less on
ϕ and H
epsilon = Fuel / initial fuel Oxygen Temperature

1.6
1.4
1.2
0.8
0.6
0.4
0.2
0
0.0E+00 5.0E+01 1.0E+02 1.5E+02 2.0E+02 2.5E+02 3.0E+02 3.5E+02 4.0E+02 4.5E+02
Dimensionless time
  In case of real chemistry, besides the thermal acceleration
mechanism there is also a chemical or chain branching
acceleration mechanism, e.g. for H2-O2
H + O2 → OH + O (only way to break O=O bond directly)
H2 + OH → H + H2O
O + H2 → OH + H etc.
where 1 radical (H, OH, O) leads to 2, then 4, then 8, …
radicals
  In the case above, the net reaction would be
2 H2 + O2 → H + OH + H2O
which shows the increase in the radical pool
  This chain branching mechanism leads to faster runaway
than thermal runaway since 2x > e-a/x for sufficiently large x
  H can also be removed from the system via
H + O2 + M → HO2 + M (M = any molecule)
  H can also be removed from the system via
H + wall → H(wall); H(wall) + H(wall) → H2(wall) → H2(gas)
• 9
  But at the beginning there is no H – how to get it?
H2 + O2 → HO2 + H (mostly this: Δh = 55 kcal/mole )
H2 + M → H + H + M (slower since Δh = 104 kcal/mole - too big)
O2 + M → O + O + M (Δh = 119 kcal/mole - even worse)
(M = any molecule)
  What happens to HO2?
HO2 + H2 → HOOH + H (HOOH = H2O2 = hydrogen peroxide)
HO2 + HO2 → HOOH + O2 (radical-radical – is it more important?)
HOOH + M → 2OH (chain branching if H + O2 → OH + O ineffective)
  Which chain-branching route is more important, H or HO2?
H + O2 → OH + O; d[O2]/dt = -1016.7[H][O2]T-0.8e-16500/RT
[ ]: mole/cm3; T: K; R: cal/moleK; t: sec
Depends on P2 since [ ] ~ P, strongly dependent on T
H + O2 + M → HO2 + M; {M = any molecule}
d[O2]/dt = -1015.2[H][O2][M]T0e+1000/RT for M = N2
(higher rate for CO2 and especially for H2O)
Depends on P3, nearly independent of T
  Rates equal ( crossover ) when
[M] = 101.5T-0.8e-17500/RT
  Ideal gas law: P = [M]RT thus
P = 103.4T0.2e-17500/RT (P in atm)
⇒  crossover at 950K for 1 atm, higher T for higher P, thus at
low T / high P, H + O2 → OH + O branching does not occur;
relatively inactive HO2 forms:
H + O2 + M → HO2 + M
HO2 + wall → HO2(wall)
2 HO2(wall) → H2(wall) + 2 O2(wall)
H2(wall) + 2 O2(wall) → H2 + 2 O2
 Causes “2nd explosion limit” of

H2 – O2 system in vessel with
constant-T walls
• 10
  What causes 2 other limits??? Rules:
  H, OH, O more reactive than HO2
  When radicals hit wall, they may adsorb and be converted to
stable species
  Radical concentrations small, thus radical-radical reactions
unlikely (but maybe HO2 + HO2 … homework problem!)
  Reaction rates vary with pressure (P)
» Collisions (of any molecule) with wall ~ P1 (P = pressure)
» Bimolecular reactions (e.g. H + O2 → OH + O) ~ P2
» Trimolecular reactions (e.g. H + O2 + M → HO2 + M ) ~ P3
  First limit
  H + O2 → OH + O dominates H + O2 + M → HO2 + M
  As P↑, molecule-wall collisions increase more slowly than
molecule-molecule collisions, thus probability of radicals
reaching wall and being converted to stable species decreases –
chain branching can occur - explosion
  As T↑, branching rates (e.g. H + O2 → OH + O) increase (high Ea)
thus impact of loss at walls decreases – explosion
  Third limit
  HO2 is not a stable species, just much less active a radical
compared to H, OH, O
  Again, as P↑, molecule-wall collisions increase more slowly than
molecule-molecule collisions, thus probability of HO2 reacting in
gas phase to produce HOOH before reaching wall and being
converted to stable species decreases – chain branching can
occur – explosion
HO2 + H2 → HOOH + H or HO2 + HO2 → HOOH + O2
HOOH + M → 2 OH
OH + H2 → HOH + H
H + O2 + M → HO2 + M
and the cycle continues
• 11
  Example of ignition time for real fuels at engine-like T & P
  Low T (1000/T > 1): VERY different times for different fuels, dominated
by slow breakdown rate of fuel molecule
  High T: Similar times because H + O2 → OH + O branching rather than
fuel molecule breakdown (except for toluene which is hard to crack )
  Note ignition time increases with increasing T for 750 < T < 900K
(negative effective activation energy!)
Well-stirred reactor"
  The homogeneous-reaction example was for time-dependent
behavior of a fixed mass with no flow; what about the opposite
(steady, fixed volume, with flow in/out)?
  Assume reactants and products are perfectly stirred, i.e. as soon as
reactants flow into the reactor, they are completely mixed with
products (constant T, P and composition throughout reactor)
  Again will have low fuel + high T or high fuel + low T in reactor
  Energy balance; ( )R = in reactor
! P (TR ! T" )
( Mass of A burned per unit time) QR = thermal enthalpy rise in reactor = mC
TR ! T"
! A,"
YA,"QR = CP (Tad ! T" ) # ( Mass of A burned per unit time) = mY
Tad ! T"
mass of A burned mass of fuel burned moles of fuel burned
Also, = volume
time moles of fuel burned time $ volume
d[A] & !E ) T !T
= MA VR = M AVR Z [ A ] R [ B ] R exp ( ! A," R " (Eq. 1)
+ = mY
dt R ' %TR * Tad ! T"
moles A moles A mass A total mass 1 1
Note [ A ] R = = = YA,R ! R ; [ B ] R = YB,R ! R
volume A mass A total mass volume A M A MB
• 12
  But how to find YA,R and YB,R? Mass balance on A
Mass A burned per unit time = (total mass flow)(change in mass fraction A) = m! (YA,! "YA,R )
CP (TR " T! ) YA,! T "T T "T
YA,! "YA,R = = CP (TR " T! ) = YA,! R ! # YA,R = YA,! ad R
QR CP (Tad " T! ) Tad " T! Tad " T!
1 ! Y T "T
Then since [ A ] R = YA,R ! R , finally [ A ] R = R A,! ad R (Eq. 2)
MA M A Tad " T!
  Mass balance on B: since one B molecule is consumed for every A
YB,! "YB,R = ! (YA,! "YA,R ) ! ; ! = stoichimetric oxygen to fuel mass ratio; YB,! = YA,!! / "
YA,!! $ 1 CP (Tad " T! ) CP (TR " T! ) '
# YB,R = " ! (YA,! "YA,R ) # YB,R = ! & " )
" %" QR QR (
! CP $ 1 ' $ 1 TR " T! '
# YB,R = & (Tad " T! ) " (TR " T! )) = ! YA,! & " )
QR % " ( % " Tad " T! (
1 ! "Y $ 1 T " T '
Then since [ B ] R = YB,R ! R , finally [ B ] R = R A,! & " R ! ) (Eq. 3)
MB M B % # Tad " T! (
  Finally (really finally this time!) combining Eqs. 1, 2, 3
M AVR Z Tad " T! $ "E '

m! = [ A] R [ B] R exp & )
YA,! TR " T! % #TR (
M AVR Z Tad " T! ! RYA,! Tad " TR ! R" YA,! * 1 TR " T! - $ "E '
m! = , " / exp & )
YA,! TR " T! M A Tad " T! M B + # Tad " T! . % #TR (
! R2VR" YA,! Z Tad " TR * 1 TR " T! - $ "E '
m! = , " / exp & )
MB TR " T! + # Tad " T! . % #TR (
PR2VR! YA,! Z Tad2 Tad " TR * 1 TR " T! - $ "E '
m! = 2 2 2 , " / exp & )
R M BTad TR TR " T! + " Tad " T! . % #TR (
m! 1 1" TR * 1 TR " ! - $ "# ' PR2VR! YA,! Z T T E
= 2 , " / exp & ); m! ref 0 2 ;TR 0 R ;" 0 ! ; # 0
!
mref TR TR " ! + " 1" ! . % TR ( R M BTad 2
Tad Tad #Tad
  Equation for reactor temperature TR as a function mass flow rate for

varying values of the properties in the reference mass flow, heat
release parameter (ε) and dimensionless activation energy (β)
• 13
  Very low flow – plenty of time, nearly complete reaction, TR ≈ Tad
  Very high flow – not enough time, very little reaction, TR ≈ T∞
  Results show classical Z-shaped response with hysteresis
  Upper – “extinction” branch – when mass flow increased too much,
reactor “extinguishes” due to insufficient residence time – TR drops to
lowest branch
  Lower – “ignition” branch – when mass flow decreased enough, reactor
“ignites” due to adequate residence time, TR rises to highest branch
1 1
Dimensionless reactor Temp. TR
0.9 0.9
Dimensionless reactor Temp. TR

0.8 0.8
0.7 0.7
0.6 0.6
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 β = 3, ε = 0.2, φ = 1 0.1 β = 5, ε = 0.2, φ = 1
0 0
1.E-05 1.E-04 1.E-03 1.E-02 1.E-01 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04 1.E-03
Mass flow Mass flow
  Middle branch generally unstable
  Small increase in mass flow for momentarily fixed TR (thus
reaction rate) will increase reactant leakage, thus decrease T,
moving reaction rate still lower, eventually dropping to lower
branch
  Opposite for small decrease in mass flow (jump to upper branch)
  Upper and lower branches stable – e.g. increase in mass flow
decreases TR and takes you back to same branch
  Results very sensitive to β
  As β increases, extinction point rises to higher T, i.e. closer to Tad
  At realistic values of β, curve spans many decades of mass flow
– never looks like textbook plots
  β of 3 and 5 plotted – not realistic, should be 10 or more for
hydrocarbon oxidation
  Weak effects of ε and φ

  Who cares about this? Can use this apparatus to study
kinetics and obtain estimates of reaction rate parameters Z
and E, especially by measuring mass flow at extinction

• 14
Summary"
  Chemical reaction require a collision; collision rates
determined by kinetic theory of gases
  Reaction requires adequate kinetic energy (exp(-Ea/RT) term)
and steric (luck) factor, resulting in ZTnexp(-Ea/RT) expression
with 3 adjustable parameters Z, n, Ea
  Chemical kinetic systems for realistic fuels are comprised of
100s or 1000s of individual reactions, but some general rules
(e.g. regarding T and P effects) expected
  Much information can be deduced from well-characterized
experiments (e.g. constant P, T vessel)
  Reaction rates + thermodynamics can be used to describe
model systems, e.g. (time-dependent) homogeneous reaction
or (steady-state) Well-Stirred Reactor
• 15
AME 513 
 
"
Lecture 5
Chemical kinetics II – Multistep mechanisms
Outline"
  Analytical solution for 1-step reaction
  Irreversible
  Reversible
  Steady-state approximation
  Pressure effects – Lindemann mechanism
  Spreadsheet-level modeling
  Partial equilibrium approximation
  Online chemical kinetics calculator
AME 513 - Fall 2012 - Lecture 5 - Chemical Kinetics II 2
• 1
1-step irreversible reaction"
  First consider 1 single (irreversible) reaction:
A+B→C+D (forward reaction, rate constant kf)
d [ A]
= !k f [ A ] [ B ]
dt
But [A] and [B] are not independent, any decrease in [A] results in
an identical decrease in [B] and increase in [C] & [D]; for a
stoichiometric excess of [B], i.e. [B]o > [A]o
[ A ] o ! [ A ] = [ B ] o ! [ B ] " [ B ] = ([ B ] o ! [ A ] o ) + [ A ]
d [ A] d [ A]
" = !k f [ A ] {([ B ]o ! [ A ]o ) + [ A ]} " !k f dt = 2
dt [ A ] + ([ B ] o ! [ A ] o ) [ A ]
# [ A] &
" !k f ([ B ]o ! [ A ]o ) t = ln %% ( + Constant
(
$ [ A ] + ([ B ] o ! [ A ] o ) '
# [ A] & # & # A &
t = 0 : [ A ] = [ A ]o " Constant = ! ln %% o(
" !k f ([ B ]o ! [ A ]o ) t = ln %%
[ A] ( ! ln % [ ]o (
( ( % B (
$ [ B ]o ' $ [ A ] + ([ B ] o ! [ A ] o ) ' $ [ ]o '
( )
!k f [ B ]o ![ A ]o t
"
[ A] = e (1! [ A]o [ B]o )
[ A]o 1! ([ A]o [ B]o ) e!k ([B] ![ A] )t f o o
1-step reversible reaction"

  Now consider 1 single (but reversible) reaction:
A+B→C+D (forward reaction, rate constant kf)
C+D→A+B (reverse reaction, rate constant kb)
d [ A]
= !k f [ A ] [ B ] + kb [C ] [ D ]
dt
[ A ] o ! [ A ] = [ B ] o ! [ B ] = [C ] ! [C ] o = [ D ] ! [ D ] o
" [ B ] = [ B ] o ! [ A ] o + [ A ] ; [C ] = [C ] o + [ A ] o ! [ A ] ; [ D ] = [ D ] o + [ A ] o ! [ A ]
d [ A]
" = !k f [ A ] {[ B ]o ! [ A ]o + [ A ]} + kb {[C ]o + [ A ]o ! [ A ]}{[ D ]o + [ A ]o ! [ A ]}
dt
1 d [ A] 2 d [ A]
" = [ A ] + a [ A ] + b " ( kb ! k f ) dt = 2
where
(kb ! k f ) dt [ A] ! a [ A] + b
k f ( [ B ] o ! [ A ] o ) + kb ( 2 [ A ] o + [ C ] o + [ D ] o ) kb ( [ A ] o + [ C ] o ) ( [ A ] o + [ D ] o )
a# ;b #
(k b ! kf ) (k b ! kf )
$ a 2 + 4b + a + 2 A '
" ( kb ! k f ) t = !
1
ln &
[ ] ) + Constant
a + 4b % a + 4b ! a ! 2 [ A ] )(
2 & 2
• 2
  Initial condition: t = 0, [A]= [A]o
# a 2 + 4b + a + 2 A &
t = 0, [ A ] = [ A ]o ! ( kb " k f ) (0) = "
1
ln %
[ ]o ( + Constant
a + 4b $ a + 4b " a " 2 [ A ]o ('
2 % 2
# a 2 + 4b + a + 2 [ A ]o &(
1
! Constant = ln %
a 2 + 4b %$ a 2 + 4b " a " 2 [ A ]o ('
# a 2 + 4b + a + 2 [ A ]o a 2 + 4b " a " 2 [ A ] &(
1
! ( kb " k f ) t = ln %
a 2 + 4b %$ a 2 + 4b " a " 2 [ A ]o a 2 + 4b + a + 2 [ A ] ('
  In general the algebra horrendous but consider special case
[A]o = [B]o, [C]o = [D]o = 0
2
2kb [ A ]o kb [ A ] o 2 kb k f [ A ] o
[ A ] o = [ B ] o , [C ] o = [ D ] o = 0 ! a = " ;b = " ; a 2 + 4b =
kb " k f kb " k f kb " k f
a 2 + 4b + a + 2 [ A ]o 1" k f kb
! =
a 2 + 4b " a " 2 [ A ]o 1+ k f kb

# a 2 + 4b + a + 2 A 1" k f kb &
! ( kb " k f ) t =
(k b " kf )
ln %
[ ] (
2 kb k f [ A ]o %$ a 2 + 4b " a " 2 [ A ] 1+ k f kb ('
) [ A ] k k "1 + [ A ] ,
!t=
1
ln +
f (
b ) o.
2 kb k f [ A ] o +
* [ A ] k f k (
b +1 " [ A)] .
o-
) [ A] k f kb "1 + [ A ]o ,
Check #1: [ A ] = [ A ]o ! t =
1
ln +
o ( ) .= 1
ln [1] = 0 OK
2 kb k f [ A ] o + [ A ] o
* ( )
k f kb +1 " [ A ]o .- 2 kb k f [ A ]o
Check #2: As t / 0, need to approach equilbrium concentration [ A ]eq
[ A ]o
t / 0 ! [ A] ( )
k f kb +1 " [ A ]o / 0 ! [ A ]eq =
k f kb +1
At equilbrium forward & reverse rates are equal, i.e.
"k f [ A ] [ B ] = "kb [C ] [ D ] ! "k f [ A ] [ A ] = "kb ([ A ]o " [ A ]) ([ A ]o " [ A ])
2 2
! "k f [ A ] = "kb ([ A ]o " [ A ]) ! k f kb [ A ] = [ A ]o " [ A ] ! [ A ] =
[ A ]o = [ A ]eq OK
k f kb +1
• 3
1.2 12
kf = 10, kb = 1, [A]o = 1
Concentration of A
Concentration of A
10
0.8 [A]eq = 0.240 8
0.6 6
0.4 4 kf = 1, kb = 10, [A]o = 10

0.2 2
[A]eq = 7.60
0 0
0 0.5 1 1.5 0 0.05 0.1 0.15 0.2
Time Time
Steady-state approximation - concept"

  These calculations are tedious, need some simplifications to
handle more complex reaction mechanisms!
  Consider a two-step reaction with very reactive radical N
O + N2 → NO + N (rate constant k1)
N + O2 → NO + O (rate constant k2)
  Net production of N: d [ N ] dt = k1 [O ] [ N 2 ] ! k2 [ N ] [O2 ]
  The steady-state approximation assumes d[N]/dt ≈ 0, i.e.
d [N ] d [N ] k [O ] [ N 2 ]
k1 [O ] [ N 2 ] >> ;k2 [ N ] [O2 ] >> ! [N ] " 1
dt dt k2 [O2 ]
in which case
d [ NO ] k [O ] [ N 2 ]
= k1 [O ] [ N 2 ] + k2 [ N ] [O2 ] = k1 [O ] [ N 2 ] + k2 1 [O2 ] = 2k1 [O] [ N 2 ]
dt k2 [O2 ]
  Does NOT imply [N] = constant, only that [N] varies slowly
compared to its production & consumption rates individually
  When valid? Typically when a rapidly-reacting intermediate (N
in this case) is produced by a slow reaction (O + N2 → NO + N)
• 4
Lindemann (1922) - P effects on decomposition"
  Unimolecular decomposition of A (e.g. H2O2 + M → 2 OH)

A + M → A* + M (rate constant k1f; A* = activated state of A)
A* + M → A + M (rate constant k1b; k1f/k1b = Kequilibrium = KA/KA*)
A* → B (rate constant k2)
  Steady state assumption for A* yields
d !" A* #$ k [ A] [ M ] d [ B] k k [ A] [ M ]
= k1 f [ A ] [ M ] % k1b !" A* #$[ M ] % k2 !" A* #$ & 0 ' !" A* #$ & 1 f ' = k2 !" A* #$ = 2 1 f
dt k1b [ M ] + k2 dt k1b [ M ] + k2
  “Apparent” overall reaction rate: find keff such that d[A]/dt =
-d[B]/dt (i.e. rate of consumption of reactant A = rate of
production of product B):
d !" A* #$ k [ A] [ M ]
= k1 f [ A ] [ M ] % k1b !" A* #$[ M ] % k2 !" A* #$ & 0 ' !" A* #$ & 1 f
dt k1b [ M ] + k2
d [ A] d [ B] k1 f [ M ]
' = %keff [ A ] = % ' keff =
dt dt 1+ ( k1b k2 ) [ M ]
  Note at low P ([M] small): keff → k1f[M] ~ P1;
high P: keff → k1fk2/k1b ~ P0 (falloff in rate at high P)
Steady-state approx. – chain branching"

  Overall reaction A2 + B2 → 2AB
A2 + M → A + A + M (rate constant k1, chain initiation)
A + B2 → AB + B (rate constant k2, chain branching)
A2 + B → AB + A (rate constant k3, chain branching)
A + B + M → AB + M (rate constant k4, chain termination)
  Steady state assumption for A and B:
d [ A] 2k [ A ] [ M ] + k3 [ A2 ] [ B ]
= 2k1 [ A2 ] [ M ] ! k2 [ A ] [ B2 ] + k3 [ A2 ] [ B ] ! k4 [ A ] [ B ] [ M ] " 0 # [ A ] " 1 2
dt k2 [ B2 ] + k4 [ B ] [ M ]
d [ B] k2 [ A ] [ B2 ]
= k2 [ A ] [ B2 ] ! k3 [ A2 ] [ B ] ! k4 [ A ] [ B ] [ M ] " 0 # [ B ] "
dt k3 [ A2 ] + k4 [ A ] [ M ]
k2 [ A ] [ B2 ] k2 [ A ] [ B2 ]
# 2k1 [ A2 ] [ M ] ! k2 [ A ] [ B2 ] + k3 [ A2 ] ! k4 [ A ] [M ] " 0
k3 [ A2 ] + k4 [ A ] [ M ] k3 [ A2 ] + k4 [ A ] [ M ]
2
$& k [ A ] [ M ] (& $& k k [ A ]2 (& k [ A ] [ M ] $& 4k k [ B ] (&
[ A] !% 1 2 ) [ A] ! % 1 3 2 ) = 0 # [ A] = 1 2 %1+ 1+ 2 3 22 )
'& k2 [ B2 ] *& &' k2 k4 [ B2 ] &* 2k2 [ B2 ] &' k1k4 [ M ] &*
• 5
Steady-state approx. – chain branching"
  Text states that k1 & k4 should be much smaller than k2 & k3
since k2 & k3 are radical-molecule reactions - what’s wrong
with that statement?
  Anyway if the 2nd term inside the square root is >> 1 then
k1k3 d [ B2 ] k k k [B ]
[ A] ! [ A2 ] " ! # [ A2 ] 1 2 3 2
k2 k4 [ B2 ] dt k4
  Rate of [B2] consumption increases with k1, k2, k3 but

decreases with k4 due to loss of A and B radicals
2
  Note that the requirement 4k2 k3 [ B2 ] k1k4 [ M ] >> 1 always breaks
down at sufficiently high P since [B2] ~ P but [M]2 ~ P2, thus
steady-state assumption for this reaction mechanism fails at
high enough P
Excel spreadsheet model"

  OK is this for real? Create Excel spreadsheet model and
compare “exact” solutions using Euler’s method to advance
solution from time step t to t+Δt: f(t+Δt) ≈ f(t) + {df(t)/dt}Δt, e.g.
df (t) d [ A]
f (t + !t) " f (t) + !t # [ A ]t+!t " [ A ]t + !t
dt dt t
d [ A]
= 2k1 [ A2 ] [ M ] $ k2 [ A ] [ B2 ] + k3 [ A2 ] [ B ] $ k4 [ A ] [ B ] [ M ]
dt
# [ A ]t+!t " [ A ]t + ! [ A ]t = [ A ]t + {2k1 [ A2 ] [ M ] $ k2 [ A ] [ B2 ] + k3 [ A2 ] [ B ] $ k4 [ A ] [ B ] [ M ]} !t
Euler’s method very simple not very stable or accurate – use

e.g. 4th order Runge-Kutta when Euler fails (actually Euler’s
method gives the first term in the 4th order Runge-Kutta)
  Spreadsheet inputs: k1 – k4; initial concentrations of A2, B2, A,
B, AB, M; Δt
  Outputs: concentrations vs. time; time to reach 90%
completion of reaction to AB; time to peak [A]; time to peak
[B]; validity of steady-state approximation (rates of formation
& destruction of A > 10x net rate of change of [A])
• 6
Excel spreadsheet model – baseline case"
  k1 = 0.01, k2 = 2, k3 = 1, k4 = 1
  Time = 0: [A2] = 1, [B2] = 1, [M] = 10, [A] = [B] = [AB] = 0
2 0.1
1.8 0.09
Minor (radical) species (A, B)

Major species (A2, B2, AB)
1.6 0.08
1.4 0.07
A2 B2 AB
1.2 0.06
A B
1 0.05
0.8 0.04
0.6 0.03
0.4 0.02
0.2 0.01
0 0
0 5 10 15 20 25 30 35
Time
Validity of steady-state approximation"

  Approximation invalid initially when no radical pool exists
  Also invalid when reactants A2 & B2 have been depleted
significantly thus k2[A][B2] & k3[B][A2] are not large
2
1.8
1.6
1.4 Steady state OK? (1 = yes, 0 = no)

1.2 Steady state [A] / Actual [A]
0.8
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35
Time
• 7
Excel spreadsheet model - results"
  Radical (A, B) concentrations are much lower than major
(stable) species (A2, B2, AB)
  Radical pool builds quickly to peak, reaches steady-state,
then decreases slowly as reactants are consumed
  Product AB follows mirror-image of reactants A2 & B2,
showing that steady-state exists, radical concentrations shift
quickly as reactant concentrations shift
  How do changes in input parameters affect reaction time
(90% of AB formed)? For 10% increase in parameter (in case
of [A], [B], [AB], added 0.1 to initial mixture), % change in
reaction time:
Property k1 k2 k3 k4 [M] [A2] [B2] [A] [B]
% change -6 -4 -2 2 -4 36 -11 -17 -8
k1, k2, k3 increases overall reaction rate, k4 decreases rate

due to loss of radicals; adding [A] decreases rate more than
adding [B] due to bottleneck of initiation A2 + M → 2A + M
Partial equilibrium approximation"

  Analogous to steady-state approximation, but applies to a
single (reversible) reaction rather than a single species
  Requires both forward and reverse rates to be fast compared
to net rate, e.g. for A + B2  AB + B
k1 f [ A ] [ B2 ] >> k1 f [ A ] [ B2 ] ! k1b [ AB ] [ B ] ;k1b [ AB ] [ B ] >> k1 f [ A ] [ B2 ] ! k1b [ AB ] [ B ]
  Example: for reactants A2, B2, product A2B, radicals A, B, AB

A + B2 → AB + B Rate constant k1f
AB + B → A + B2 Rate constant k1b
B + A2 → AB + A Rate constant k2f
AB + A → B + A2 Rate constant k2b
AB + A2 → A2B + A Rate constant k3f
A2B + A → AB + A2 Rate constant k3b
A + AB + M → A2B + M Rate constant k4 (NOT in partial equil.)
[ AB] [ B] ! K AB K B " K ; [ AB] [ A] ! K AB K A " K ; [ A2 B] [ A] ! K A B K A " K 2
eq,1 eq,2 eq,3
[ A] [ B2 ] K A K B 2
[ B] [ A2 ] K B K A [ AB] [ A2 ] K AB K A
2 2
• 8
Partial equilibrium approximation"
  Combining these results to solve for radical species A, B, AB
3
K eq,1K eq,2 [ A2 ] [ B2 ] K eq,3 K eq,1K eq,3 [ A2 ] [ B2 ]
[ A] = ; [ B] = ; [ AB ] = K eq,1K eq,2 [ A2 ] [ B2 ];
[ A2 B] [ A2 B]
  Then the product formation rate is
3
d [ A2 B ] K eq,1K eq,2 [ A2 ] [ B2 ] K eq,3
= k4 [ A ] [ AB ] [ M ] = k4 K eq,1K eq,2 [ A2 ] [ B2 ] [ M ]
dt [ A2 B]
2
K eq,1K eq,2 K eq,3 [ A2 ] [ B2 ] [ M ]
= k4
[ A2 B]
  Obviously cannot apply at t = 0 since [A2B] = 0, but early on,
before [A2] and [B2] depletion is significant,
2
[ A2 B] ! 2k4 K eq,1K eq,2 K eq,3 [ A2 ] [ B2 ] [ M ] t t1/2 behavior
Online chemical kinetics calculator"

  What if the mechanism is more complex or less stable?
http://navier.engr.colostate.edu/~dandy/code/code-5/index.html
  Chemical mechanisms for H2-O2, CH4-O2 and a few others
  Input page simple except for need to choose by trial & error:
  Total integration time (long enough to see fuel consumption &
product formation)
  Time interval (Δt) (small enough to resolve transients)
  Output format hard to feed into to Excel!
• 9
Online chemical kinetics calculator"
  Typical example - stoich. H2-O2, T = 850K, P = 1 atm, near 3rd
explosion limit, above 2nd limit so mole fractions of H, O, OH
very small, ≈ 10-9
  Similar to schematic A2 + B2 results
1 0.007
Mole fraction HO2 and H2O2

0.9
Mole fraction H2 and H2O
0.006
0.8
0.7 0.005
0.6 H2
0.004
0.5 H2O
HO2 x 100 0.003
0.4
H2O2
0.3 0.002
0.2
0.001
0.1
0 0
0 20 40 60 80 100
Time (seconds)
Summary"
  Chemical kinetic systems for realistic fuels are comprised of
many individual reactions, resulting in coupled Ordinary
Differential Equations in terms of the concentrations of
reactants [A], [B], [C], [D], … of the form
d # [A] & d # [B] & d # [C] & d # [D] & " "
$ ' = $ ' = ) $ ' = ) $ ' = )k f [ A] A [ B] B
dt % " A ( dt % " B ( dt % " C ( dt % " D (
  Analytical solution of these equations is impossible for all but
the simplest cases
!   Techniques exist for simplifying these large sets of equations
  Steady-state (for one species)
  Partial equilibrium (for one reversible reaction)
  Many others…
  Simplifying methods exploit the fact that some reactions (e.g.
radical + stable species) are typically faster than others (e.g.
chain initiation, 3-body recombination, radical + radical) and
so adjust to changing concentrations on a shorter time scale
• 10
AME 513 
 
"
Lecture 6
Chemical kinetics III – real fuels
Outline"
  Experimental methods
  Types of reaction
  CO-O2
  Hydrocarbons
  NOx
  Flame inhibition
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 2
• 1
Experimental methods"
  Constant volume vessel
  Heat evacuated vessel to some temperature, inject reactants
quickly (shorter than reaction time scale), see if it reacts
explosively or just slowly
  Ideally constant T & P
  Not well-defined limit, depends on injection / mixing time ~ d2/D
(d = vessel dimension, D = diffusivity) being much faster that
reaction, only useful for conditions with “slow” reaction
  For gases, both mass D and thermal D ~ 1/P, so characteristic
reaction time required for explosion varies with P!
  Wall effects crucial (radical sink)
  Only yields global properties (e.g. overall reaction rates)
  Well-stirred reactor
  Well defined limits
  Must be certain that mixing of fresh reactants with products
already in reactor is much shorter than residence time in reactor
  Typically need very large mass flows to study flame-like
conditions since reaction time scale ~ 10-3 s in flame
  Only yields global properties
  Plug-flow reactors
  Flow reactants down a preheated tube (usually constant T),
measure species at varying distances along tube (~ time)
  Can obtain data on observing evolution of individual species,
not just global properties, thus infer elementary reaction rates
  Laminar or turbulent flow
  Only useful for “slow” reactions (low temperature, not flame-like
conditions) (tens of milliseconds)
  Need to address issue of axial dispersion of reactants
  Shock tube
  Pass shock wave through mixture, watch evolution of species
  Step-like change in T and P, well defined, nearly homogeneous
  Can obtain data on individual reactions
  Amenable to quantitative laser diagnostics
  Only useful for “fast” reactions (few ms)
• 2
  Laminar flame
  “Simple” setup – measure burning velocity SL
  Obviously applicable to “real” flame chemistry
  Flames are very thin (< 1mm), hard to probe inside to measure
species evolution
  Interaction with transport via convection and diffusion –
compare results with computations using detailed flame models
  Not a sensitive instrument – overall reaction rate ~ SL1/2
Types of reactions"
  Global reaction
  Example: CH4 + 2O2 → CO2 + 2 H2O
  NOT an actual reaction that occurs
  No relation between order of reaction (3 in this example) and
actual pressure effect on reaction rate
  Chain initiation
  Example: H2 + M → H + H + M
  Break stable molecule into radical(s)
  High Ea – endothermic, must break strong bond
  High Z (i.e. not very orientation sensitive)
  Not needed in flames, where radical source (products) exists
  Chain branching
  Example: H + O2 → OH + O
  Use radical to create more radical
  High Ea - endothermic, must break strong bond, but also make
a bond, so not as high as chain initiation
  Moderate Z (somewhat orientation sensitive)
• 3
Types of reactions"
  Chain propagation or “shuffle” reaction
  Example: OH + H2 → H2O + H
  Use radical + stable molecule to create another pair
  Moderate Ea – may be nearly thermo-neutral
  Moderate Z (somewhat orientation sensitive)
  Chain termination
  Example: H + OH + M → H2O + M
  Recombine radicals into stable molecules (usually products)
  Low or zero Ea – exothermic, no activation barrier
  Need 3rd body to absorb enthalpy and conserve momentum
  Moderate Z (may be orientation sensitive)
  Schematic multi-step mechanism (e.g. Hautman et al, 1981)
C3H8 → 1.5 C2H4 + H2 (Initial breakdown of fuel)
C2H4 + O2 → 2 CO + 2 H2 (C2H4 = surrogate for radicals)
2H2 + O2 → 2 H2O (oxidation of H2)
2CO + O2 → 2 CO2 (oxidation of CO)
Reaction rates crazy (see Turns, p. 158) – sometimes order of
reaction is negative – causes problems as concentration → 0
H 2 – O 2"
  Simulate explosion limits using online chemistry calculator
  Use time to 50% H2 consumption as measure of explosion limit
  Diffusion time ~ P so scale accordingly, e.g. at 10 atm, allow
10x more time than at 1 atm
  Results for t at 1 atm = 25 s close to experiments (Fig. 5.1)
  Second limit independent of time (vessel size & walls material)
  Second limit where branching vs. recombination rates ≈ same
10000
H + O2 → OH + O =
1000 t at 1 atm = 1 second H + O2 + M → HO2 + M
t at 1 atm = 25 seconds when P = 103.4T0.2e-17500/RT
Pressure (torr)
H + O2 rates equal
100
10
1
400 450 500 550 600 650 700
Explosion temperature (˚C)
• 4
CO – O2"
  H2-O2 already discussed – 3 explosion limits
  CO MUCH different because no chain branching and no
“shuffle” reaction to create product
CO + O2 → CO2 + O Very slow, but needed as source of O
O2 + M → O + O Very high activation energy, even slower
CO + M → C + O + M No way! C=O is strongest chemical bond!
CO + O + M → CO2 + M Creates product but removes radicals
  As a result, pure CO – O2 oxidation is extremely slow!
  Early experiments showed widely varying results because of
contamination with water; with any hydrogen source
CO + OH → CO2 + H Shuffle reaction to create CO2
H + O2 → OH + O Regenerate OH plus another O
Neither are fast, but better than alternatives!
  Stoich. CO + O2, 1 atm, 1500K, time to consume 50% of CO:
  No H2O: 1.03 s; 1 ppm H2O: 0.27 s; 10 ppm: 0.038 s;
  100 ppm 0.0043 s; 1,000 ppm 0.00080 s; 10,000 ppm 0.00023 s
CO – O2"
  Case shown: const. T = 1000K, P = 1 atm, CO:H2:O2 = 1:1:10
  To a good approximation, H2-O2 acts as infinitely fast (i.e.
steady-state) radical source for CO
  CO does not affect H2-O2 process, CO reaction just too slow
  50% H2 consumption in ≈ 400 µs, ≈ same with or without CO
• 5
CO – O2"
  Explosion limit experiments show 2nd-limit behavior, even
with “dry” CO – not really dry
  CSU homogeneous kinetics model (next page) does not!
Dickens et al., 1964

Gordon and Knipe, 1955
CO – O2"
  Unlike classical experiments, CSU homogenous kinetics
calculator predicts that dry CO has only a single limit – but
CSU site does not include O3 which may be important
  With H2O addition, behavior is very similar to H2-O2 with
offset to higher T - CO is a “parasite” on the OH source
10000
1000
Pressure (torr)
100
CO (Dry)
10 CO (1% H2O)
H2-O2
1
400 600 800 1000 1200 1400
• 6
Hydrocarbon – O2"
  Hydrocarbons inhibit their own oxidation, because they react

with radicals more readily than O2 reacts with radicals
  Once an H atom is removed from fuel, e.g.
C3H8 + O2 → C3H7• + HO2•
then the fuel radical can lose another H to form an alkene, e.g.
C3H7• + O2→ C3H6 + HO2•
thus alkenes are a key intermediate in alkane oxidation
  Nearly all of fuel must be consumed before radical pool
needed to consume CO can build up
  CO oxidation is the last step
  β-scission – fuel molecule breaks apart 1 C-C bond away from
C missing an H atom (avoids having to move an H atom to an
adjacent C atom)
  This stuff only matters at “low” temperatures (<1500K) where
H + O2 branching is inhibited by the hydrocarbons; at higher
temperatures, H + O2 branching is sufficiently rapid
Hydrocarbon – O2"
• 7
Hydrocarbon – O2"
  Hydrocarbons have no 1st or 2nd explosion limit; instead of H +
O2 + M → HO2 + M being the dominant recombination
reaction, it’s CH4 + H → CH3 + H2, which has same pressure
dependence as the branching reaction H + O2 → OH + O
  C-H bonds stronger in CH4 than C3H8, thus higher explosion T
10000
H2-O2
CH4-O2
1000
C3H8-O2
Pressure (torr)
100
10
1
400 500 600 700 800 900 1000
Hydrocarbon oxidation"
  Start with fuel molecule RH, where R is an organic radical , e.g.
propane without an H H H H H H H
H C C C• + H• = H C C C H
H H H H H H
propyl radical propane
  Abstract an H atom from RH
RH + O2 → R• + HOO•
  Add an O2 to R•
R• + O2 → ROO•
  Produce peroxides with O-O single bond (half as strong as O=O
double bond (120 kcal/mole vs. 60 kcal/mole), much easier to break)
ROO• + RH → R• + ROOH or HOO• + RH → R• + HOOH
  Break O-O single bond, create chain branching process
ROOH + M → RO• + •OH or HOOH + M → HO• + •OH
  Newly created radicals generate more organic radicals
RH + •OH → R• + HOH or RH + RO• → R• + ROH
  Note that rate of reaction will be sensitive to rates of H atom removal
from fuel molecule RH
• 8
  Rate of H atom removal depends on strength of C-H bond, which
in turn depends on how many other carbons are bonded to that C
- stronger bond, slower reaction, less knock
H H C C
H C H H C C H C C H C C
H H H C
methane primary C-H bond secondary C-H bond tertiary C-H bond
105 kcal/mole 98 kcal/mole 95 kcal/mole 93 kcal/mole
  Examples: n-heptane: 6 primary, 12 secondary C-H bonds

2, 2, 4 trimethy pentane: 15 primary, 2 secondary, 1 tertiary
H H H
H H H H H H H
H C H H H
H C C C C C C C H
H C C C C C H
H H H H H H H
n-heptane H C H C H
primary secondary tertiary H H H H H H

2, 2, 4 trimethylpentane
(iso-octane)
  Does this small difference in bond strength matter? YES
because activation energy is high
  If we use bond strength as a measure of activation energy
(dangerous in general, but ok here…) then at a typical 900K
Ωmethane : Ωprimary : Ωsecondary : Ωtertiary
exp(-Emethane/ℜT) : exp(-Eprimary/ℜT) : exp(-Esecondary/ℜT) : exp(-Etertiary/ℜT)
≈ exp(-105,000 cal/mole/(1.987 cal/mole-K)(900K)) :
exp(-98000/1.987*900) : exp(-95000/1.987*900) : exp(-93000/1.987*900)
≈ 1 : 50 : 268 : 820
  As a result, fuels with mostly primary C-H bonds will
decompose much more slowly than isomers with more
secondary & tertiary C-H bonds – higher octane number in
gasoline-type fuels
• 9
  How to make CO? RO• formed by cleavage of O-O bond in
peroxide then enter aldehyde route
RO• + M → R’HCO + H + M, e.g. C2H5O• + M → CH3HCO + H + M
  Aldehydes have weakest C-H bond (≈87 kcal/mole) thus
R’HCO + M → R’CO• + H• + M, e.g. CH3HCO + M → CH3CO + H• + M
R’HCO + O2 → R’CO• + HO2•, e.g. CH3HCO + O2 → CH3CO• + HO2•
  Aldehydes also have weak C-C bond thus
R’CO• + M → R’ + CO + M, e.g. CH3CO• + M → CH3• + CO + M
  Somewhat roundabout but easiest way to make CO, still takes
a “long” time, see flow reactor result – first aldehydes CH2O
and C2H4O form, then CO rises as aldehydes decompose
  Larger hydrocarbons also have negative temperature coefficient
(NTC) behavior at low T (below H + O2 branching)
  NTC especially prevalent in rich mixtures – reaction rate decreases
with increasing T
  R• + O2 → ROO• is very reversible due to weak R-O bond
  Equilibrium favors dissociation (ROO• → R• + O2) at higher T, so
ROO• won’t stick around long enough to make ROOH
  At higher temperatures HOO• + RH → R• + HOOH forms peroxides,
lessening the need for ROO•
  (HOOH reaction has higher Ea than ROO• + RH → R• + ROOH
because the former is more exothermic; C-O bond strength 86 vs
111 kcal/mole for H-O, thus HOOH reaction more dominant at higher
temperature)
  Also forms “cool flames” – exothermic propagating waves that
don’t consume all reactants because of NTC shut-down – no longer
“homogeneous” reaction
  Negative temperature coefficient behavior not seen in calculations
because no ROOH chemistry in CSU model
• 10
Hydrocarbon – O2"
Hewitt and Thornes, 1937

C3H8-O2, φ = 5, 0.6 liter vessel
(Note T and P axes are flipped)
Chemical fire suppressants"

  Key to suppression is removal of H atoms
H + HBr → H2 + Br
H + Br2 → HBr + Br
Br + Br + M → Br2 + M
--------------------------------
H + H → H2
  Why Br and not Cl or F? HCl and HF too stable, 1st
reaction too slow
  HBr is a corrosive liquid, not convenient - use CF3Br
(Halon 1301) - Br easily removed, remaining CF3 very
stable, high CP to soak up thermal enthalpy
  Problem - CF3Br very powerful ozone depleter - banned!
  Alternatives not very good; best ozone-friendly chemical
alternative is probably CF3CH2CF3 or CF3H
  Other alternatives (e.g. water mist)
• 11
Chemical fire suppressants"
Agent Name Boiling % volume Relative ODF*,** Mass inert /

point required for effectiveness mass propane
(K) total fire on mass required for
suppression in basis total fire
air* suppression
CF3Br Halon-1301 215 2.9 432.10 13 2.44
CF3CH2CF3 HFC-236fa 272 5.6 851.20 0 4.89
CF3H HFC-23 188 12.6 882.00 0 5.48
CF3CHClF HCFC-124 262 6.7 994.95 0.03 5.79
CF2HCl HCFC-22 230 11.6 1003.40 0.055 6.16
CF3CFH2 HFC-134a 247 10.5 1071.00 0 6.49
CF3CFHCF3 HFC-227ea 293 6.3 1071.00 0 6.20
C2F6 FC-116 195 7.8 1076.40 0 6.33
CF3CHF2 HFC-125 225 9.4 1128.00 0 6.76
C3F8 FC-218 235 6.1 1146.80 0 6.63
C4F10 FC-31-10 275 5 1190.00 0 6.80
CF4 FC-14 145 13.8 1214.40 0 7.64
CF3CHCl2 HCFC-123 300 7.5 1237.50 0.02 7.26
*
Source: National Research Council, Fire suppression substitutes and alternatives to
Halon for U. S. Navy applications, National Academy Press, Washington, D. C., 1997.
**
ODF = Ozone depletion factor relative to CFCl2 = 1
Zeldovich mechanism for NO formation"

 Extremely high activation energy due to enormous strength
of N≡N bond (≈ 220 kcal/mole)
O + N2 → NO + N
N + O2 → NO + O
N + OH → NO + H
  Reaction (1) is limiting; Z1exp(-E1/ℜT) < Z2exp(-E2/ℜT) except
for T > 3394K
 1 NO molecule formed from (1) yields 2 NO molecules
 Assuming steady-state for N, partial equilibrium for O, OH, H,
with O2, Heywood (1988) shows:
%116,000 cal/mole ( #1/ 2
" NO = 8x10#16 T exp' *P (T in K, P in atm, " in sec)
& $T )
  T = 2200K, P = 1 atm: τNO = 0.59 second
  By comparison, time scale for chemical reactions in flame front
≈ 0.001 second for stoichiometric hydrocarbon-air
!
 Thus, Zeldovich NO occurs in the burned gases downstream
of the flame front, not in the flame front itself
• 12
Summary"
 Real fuels have very complex chemistry, not just 1 or 2 steps
 Need chain branching for fast reaction
 Hydrogen, CO, hydrocarbons dominated by
  Initiation – H2 + M → H + H + M, RH + M → R + H + M
  Branching
» Typically H + O2 → OH + O at high T / low P
» Peroxide path (with HOOH or ROOH) at low T / high P where
H atoms are lost due to recombination
  Recombination - H + O2 + M → HO2 + M
  Radical termination at walls in explosion vessel
  CO oxidation
  Requires CO + OH → CO2 + H
  Parasitic on H2 – O2 mechanism since CO + OH relatively slow
  Hydrocarbons
  Inhibit their own oxidation due to RH + H → R + H2
  Decomposition rate depends on C-H bond strength
  First fuel decomposes, generates radical pool, generates CO
then oxidizes it
Midterm exam"
 October 19, 9:00 – 10:30 am
 Covering lectures 1 - 6
 Open books / notes / calculators
 Laptop computers may be used ONLY to view .pdf versions
of lecture notes – NOT .pptx versions
  Note .pdf compilation of all lectures:
http://ronney.usc.edu/AME513F12/AME513-F12-AllLectures.pdf
  GASEQ, Excel spreadsheets, CSU website, etc. NOT ALLOWED
 Followed by lecture 10:45 am – 11:50 am
• 13
Midterm exam – topics covered"
  Heating value
  Flame temperatures
  Equilibrium
»  Degrees of reaction freedom
»  Equilibrium constraints
  Compression/expansion
  Chemical kinetics
  Law of mass action, collision theory
  Arrhenius form of reaction rate expression
  Coupling with thermodynamics
»  Adiabatic constant-volume reaction
»  Constant-pressure Well-Stirred Reactor
  Multistep reactions
» Single-step irreversible & reversible
» Steady-state & partial equilibrium approximations
  Kinetics of real fuels
»  H2 – O2
»  CO – O2
»  Hydrocarbons – O2
Midterm exam – types of problems"

  Property values will be given if needed
  Heating value
  Equilibrium
 Chemical kinetics
  Exact solution (for very simple chemistry!)
  Steady state or partial equilibrium
  How would an explosion limit plot change if
» Wall conditions changed
» New species affecting certain reactions added
  “Most likely” reaction steps (similar to Turns 5.7)
  General - how would QR, Tad, reaction rates, homogenous
explosion time, WSR blowout, etc. be affected by
  Ronney Fuels, Inc. – new fuel or additive
  Planet X – different atmosphere (pressure, temperature, etc.)
• 14
AME 513 
 
"
Lecture 7
Conservation equations
Outline"
  Conservation equations
  Mass
  Energy
  Chemical species
  Momentum
AME 513 - Fall 2012 - Lecture 7 - Conservation equations 2
• 1
Conservation of mass"
  Cubic control volume with sides dx, dy, dz
  u, v, w = velocity components in x, y and z directions
" ! ( !v) %
$ !v + dy ' dxdz
# !y &
" ! ( ! u) %
( !u) dydz $ !u + dx ' dydz
dy # !x &
dx
( !v) dxdz
  Mass flow into left side & mass flow out of right side
# " ( ! u) &
m! left = !uA = !u(dydz) m! right = ! % !u + dx ( dydz
$ "x '
  Net mass flow in x direction = sum of these 2 terms
# " ( ! u) & " ( ! u)
m! x = !udydz ! % !u + dx ( dydz = ! dxdydz
$ "x ' "x
Conservation of mass"
  Similarly for y and z directions
" ( !v) " ( ! w)
m! y = ! dxdydz; m! z = ! dxdydz
"y "z
  Rate of mass accumulation within control volume
!m ! ( !V ) !!
= = dxdydz;V = volume
!t !t !t
  Sum of all mass flows = rate of change of mass within
control volume
" ( ! u) " ( !v) " ( ! w) "!
!! dxdydz ! ! dxdydz ! ! dxdydz = dxdydz
"x "y "z "t
"! $ " ( !u) " ( ! v ) " ( ! w ) ' "! ! !
# = !& + + )# + * + ( !u ) = 0
"t % "x "y "z ( "t
!
Note u = velocity vector = uiˆ + viˆ + wiˆ
x y z
iˆx , iˆy , iˆz = unit vectors in x, y, z directions
• 2
Conservation of energy – control volume"
  1st Law of Thermodynamics for a control volume, a fixed volume
in space that may have mass flowing in or out (opposite of control
mass, which has fixed mass but possibly changing volume):
dE ! ! v2 v2
= Q ! W + m! in (hin + in + gzin ) ! m! out (hout + out + gzout )
dt 2 2
  E = energy within control volume = U + KE + PE as before
  Q˙ ,W˙ = rates of heat & work transfer in or out (Watts)
  Subscript in refers to conditions at inlet(s) of mass, out to outlet
(s) of mass
  m˙ = mass flow rate in or out of the control volume
!   h ≡ u + Pv = enthalpy
  Note h, u & v are lower case, i.e. per unit mass; h = H/M, u = U/M, V =
v/M, etc.; upper case means total for all the mass (not per unit mass)
!
  v = velocity, thus v2/2 is the KE term
  g = acceleration of gravity, z = elevation at inlet or outlet, thus gz is
the PE term
Conservation of energy"
  Same cubic control volume with sides dx, dy, dz
  Several forms of energy flow
  Convection
  Conduction
  Sources and sinks within control volume, e.g. via chemical
reaction & radiative transfer = q’’’ (units power per unit volume)
  Neglect potential (gz) and kinetic energy (u2/2) for now
  Energy flow in from left side of CV
"T # "T &
E! left = m! left h + qleft = !uAh ! kA = !uh(dy)(dz) ! (dy)(dz) % k (
"x $ "x '
  Energy flow out from right side of CV
" ! ( ! u) % " !h % " !T ! ) !T , %
E! right = m! right h + qright = $!u + dx '(dy)(dz)$h + dx ' ( (dy)(dz)$k + + k . dx '
# !x & # !x & # !x !x * !x - &
/ !h ! ( ! u) ! ( !u) !h 2 " !T ! ) !T , %2
= 0 !uh + !u dx + h dx + ( dx ) ( $k + +* k .- dx'3 (dy)(dx)
1 !x !x !x !x # !x !x !x &4
  Can neglect higher order (dx)2 term

• 3
  Net energy flux (Ex) in x direction = Eleft – Eright
) "h " ( !u) " # "T &,
E! x = *!!u ! h + % k (- (dy)(dz)(dx)
+ "x "x "x $ "x '.
  Similarly for y and z directions (only y shown for brevity)
) !h ! ( ! v ) ! # !T &,
E! y = * ! v + h " % k (- (dx)(dz)(dy)
+ !y !y !y $ !y '.
  Combining Ex + Ey
+) "h "h " # "T & " # "T & # " ( !u) " ( ! v) &+-
E! x + E! y = *!!u ! ! v + % k ( + % k ( ! h % + (. (dx)(dz)(dy)
+, "x "y "x $ "x ' "y $ "y ' $ "x "y '+/
! ! ! ! ! !
{ ( ) ( )}
= !! u 0 1h ! h1 0 ( !u ) + 1 0 k 1T (dx)(dz)(dy)
  dECV/dt term
!ECV !#$m ( h " P ! )%& !( !V ) ' !h ! ( P ! ) * - !! P !! !h !(P !) 0
= = (h " P ! ) + !V ) " , = .h " +! "! 1V
!t !t !t ( !t !t + / !t ! !t !t !t 2
- !P !! 0
3 !! P !! ! "P 3 - !!
!h !h !P 0
= .h " + ! " ! !t 2 !t 1 V = .h + ! " 1 (dx)(dy)(dz)
3 !t ! !t !t ! 3 / !t !t !t 2
/ 2
  dECV/dt = Ex + Ey + heat sources/sinks within CV
" !! !h % ! ! ! ! ! !
{ ( ) (
! (dx)(dz)(dy)
#h + ! & (dx)(dy)(dz) = (! u ) *h ( h* ) ( !u ) + * ) k *T + q'''
$ !t !t '
) }
" !! ! ! % , !h ! ! / ! !
$ !t ' - !t 0
( !
+ h # + * ) ( !u )& + ! . + u ) *h 1 ( * ) k *T = q''' ) ( )
  First term = 0 (mass conservation!) thus (finally!)
$ !h ! ! ' ! !
(
! & + u " #h
% !t
))( * # " (k#T ) = q'''
!
  Combined effects of unsteadiness, convection, conduction

and enthalpy sources
  Special case: 1D, steady (∂/∂t = 0), constant CP (thus ∂h/∂T =
CP∂T/∂t) & constant k:
dT k d 2T !
q'''
u ! 2
=
dx !CP dx ! CP
• 4
Conservation of species"
  Similar to energy conservation but
  Key property is mass fraction of species i (Yi), not T
  Mass diffusion ρD instead of conduction – units of D are m2/s
  Mass source/sink due to chemical reaction = Miωi (units kg/m3s)
which leads to
$ !Y ! ! ' ! !
! & i + u " #Yi ) * # " ! D#Yi = M i!! i
( ) ( )
% !t (
  Special case: 1D, steady (∂/∂t = 0), constant ρD
dYi d 2Y M !!
u ! D 2i = i i
dx dx "
  Note if ρD = constant and ρD = k/CP and there is only a single
reactant with heating value QR, then q’’’ = -QRMiωi and the
equations for T and Yi are exactly the same!
  k/ρCPD is dimensionless, called the Lewis number (Le) –
generally for gases D ≈ k/ρCP ≈ ν, where k/ρCP = α = thermal
diffusivity, ν = kinematic viscosity (“viscous diffusivity”)
Conservation equations"
  Combine energy and species equations
$ !Yi ! ! ' ! ! M !! $ !Y ! ! ' ! ! ! M !!
&%
!t
( )(
( )
" % !t ( Le
(
+ u " #Yi ) * D# " #Yi = i i + & i + u " #Yi ) * # " #Yi = i i ) "
( )
$ !T ! ! ' k ! ! M i!! iQR T * T T * T, ! Yi
( )
&% + u " #T )( * ( )
! =*
# " #T = q''' ; Let T! = ,
= ,Y =
!t ! CP " CP Yi,,QR / CP Tad * T, Yi,,
$ !T! " " ' ! ! !i $ !Y! " " ' ! ! !i
+ & + u " #T!
% !t
( ))( * !# " (#T" ) = * M"Y! ;
i
& + u " #Y!
% !t
( !
))( * Le # " ( #Y" ) =iM!
"Y
i,, i,,
$ ! T! + Y! '
! ! (
+ u " # T" + Y"
) ! !
) * !# " # T" + Y" = 0
Add species & energy equations for Le = 1: &
&% !t
( ( ))
)(
( ( ))
  T! + Y! is constant, i.e. doesn’t vary with reaction but
  If Le is not exactly 1, small deviations in Le (thus T) will have
large impact on ω due to high activation energy
  Energy equation may have heat loss in q’’’ term, not present in
species conservation equation
• 5
Conservation equations - comments"
  Outside of a thin reaction zone at x = 0
dT k d 2T m!
! = 0; !u = = constant; 2nd order O.D.E
dx !uCP dx 2 A
Boundary conditions upstream of reaction zone: x = 0,T = Tad ; x " #,T " T#
!k k
$ T (x) = T# + (Tad ! T# ) e! x/! ; ! %
=
"uCP "# SLCP
Boundary conditions downstream of reaction zone: x = 0,T = Tad ; x " !#,T " Tad
$ T (x) = Tad = constant
  Temperature profile is exponential in this convection-
diffusion zone (x ≥ 0); constant downstream (x ≤ 0)
  u = -SL (SL > 0) at x = +∞ (flow in from right to left); in
premixed flames, SL is called the burning velocity
  δ has units of length: flame thickness in premixed flames
  Within reaction zone – temperature does not increase despite
heat release – temperature acts to change slope of
temperature profile, not temperature itself
Schematic of deflagration (from Lecture 1) "

Reaction zone
Product Speed relative to unburned gas = SL
Reactant
concentration
300K
! ≈ "/SL = 0.3 - 6 mm
  Temperature increases in convection-diffusion zone or preheat

zone ahead of reaction zone, even though no heat release occurs
there, due to balance between convection & diffusion
  Temperature constant downstream (if adiabatic)
  Reactant concentration decreases in convection-diffusion zone,
even though no chemical reaction occurs there, for the same
reason
• 6
Conservation equations - comments"
  In limit of infinitely thin reaction zone, T does not change but
dT/dx does; integrating across reaction zone
0+
0+
dT 0+
d 2T 0+
!
q''' 0+ dT $ 0+
!
q'''
" u dx dx ! " ! dx 2
dx = " "C dx # uT ]0! ! ! &% = "
dx 0! 0! "CP
dx
0! 0! 0! P
' dT dT * !
q''' 0+
0+
! Adx 0+ q'''dV
q''' !
# !) ! ,= " dx = " ="
( dx x=0+ dx x=0! + 0! k 0! kA 0! kA
' dT dT * ! R
mQ " S AC (T ! T ) (T ! T )
#) ! ,=! = ! - L P ad - = ! ad -
( dx x=0+ dx x=0! + kA kA #
  Note also that from temperature profile:

T (x) = T! + (Tad " T! ) e" x/! (x # 0)%' * dT dT - (T " T )
&), " / = " ad !
T (x) = Tad = constant (x $ 0) (' + dx x=0+ dx x=0" . !
  Thus, change in slope of temperature profile is a measure of
the total amount of reaction – but only when the reaction
zone is thin enough that convection term can be neglected
compared to diffusion term
Conservation of momentum"
  Apply conservation of momentum to our control volume
results in Navier-Stokes equations:
!
"u ! ! ! ! ! !
( )
! + ! u ! " u = #"P + ! g + µ" 2 u
"t
or written out as individual components
"u "u "u " P % " 2u " 2 v (

! + !u + ! v =- +! gx +µ ' 2 + 2 * (x momentum)
"t "x "y "x & $x $y )
"v "v "v " P % " 2u " 2 v (
! + !u + ! v =- +! gy +µ ' 2 + 2 * (y momentum)
"t "x "y "y & $x $y )
  This is just Newton’s 2nd Law, rate of change of momentum =
d(mu)/dt = Σ(Forces)
  Left side is just d(mu)/dt = m(du/dt) + u(dm/dt)
  Right side is just Σ(Forces): pressure, gravity, viscosity
• 7
AME 513 
 
"
Lecture 8
Premixed flames I: Propagation rates
Outline"
  Rankine-Hugoniot relations
  Hugoniot curves
  Rayleigh lines
  Families of solutions
  Detonations
  Chapman-Jouget
  Others
  Deflagrations
AME 513 - Fall 2012 - Lecture 8 - Premixed flames I 2
• 1
Rankine-Hugoniot relations"
  What premixed flame propagation speeds are possible in 1D?
  Assumptions
  Ideal gas, steady, 1D, constant area, constant CP, Cv, γ ≡ CP/Cv
  Governing equations
  Equations of state: P = ! RT;h2 ! h1 = CP (T2 ! T1 )
  Mass conservation: m! / A = !1u1 = ! 2 u2
  Navier-Stokes, 1D, no viscosity:
!u !P m!
!u + = 0, !u = = const. " !u 2 + P = const " P1 +!1u12 =P2 +!2 u 22
!x !x A
  Energy conservation, no work input/output:
h1 + u12 / 2 + q = h2 + u22 / 2
q = heat input per unit mass = fQR if due to combustion
  Mass, momentum, energy conservation eqns. can be
combined yielding Rankine-Hugoniot relations:
! " P2 "1 % 1 " P2 %" "1 % q u2 ! u1 (u "1
$ !1' ! $ !1'$ +1' = ; = = !1
! !1 # P1 "2 & 2 # P1 &# "2 & RT1 u1 u1 "2
1D momentum balance - constant-area duct "
Coefficient of friction (Cf)
Wall drag force Velocity u Velocity u + du

Cf " pressure P pressure P + dP
1 #u 2 $ (Wall area) density ! density !
2 duct area A duct area A
mass flux = !uA mass flux = !uA
d(mu)
! Forces = ! dt
!
! Forces = PA " (P + dP)A " C (1 / 2 !u )(Cdx)
f
2
d(mu)
! ! = mu
= ! mu ! " m(u
! + du) Thickness dx,
dt circumference C,
wall area Cdx
! + C f (1 / 2 !u 2 )Cdx = 0
Combine: AdP+mdu
! = const; m! = !uA # P + !u 2 = const
If C f = 0 : AP+mu
# P1 + !1u12 = P2 + !2 u22
• 2
Hugoniot curves"
  Defines possible end states of the gas (P2, ρ2, u2) as a
function of the initial state (P1, ρ1, u1) & heat input (q/RT1)
(≈ 31 for stoich. hydrocarbon-air, ≈ 43 for stoich. H2-air)
  2 equations for the 3 unknowns (P2, ρ2, u2) (another unknown
T2 is readily found from ideal gas law P2 = ρ2RT2)
  For every initial state & heat input there is a whole family of
solutions for final state; need one additional constraint – how
to determine propagation rate u1?
100 20
H=0 18 H=0
H = 35 16 H = 35
14
10
12
P!/P1
P2/P1
10
8
1
6
4
2
0.1 0
0.1 1 10 0 1 2 3 4 5 6 7 8 9 10
!1/!2 !1"!2
Hugoniot curves"
  In reference frame at rest with respect to the unburned gases
  u1 = velocity of the flame front
  Δu = u2 – u1 = velocity of burned gases
  Combine mass & momentum:
P1 +!1u12 =P2 +!2 u 22 ; !u = m! / A = const.
2 2
! P1 +
( m! / A) = P2 +
( m! / A) !
P2 " P1 # m! &
= "% (
2
1 !1 1 !2 1 !2 "1 !1 $ A'
  Thus, straight lines (called Rayleigh lines) on P vs. 1/ρ (or
specific volume, v) plot correspond to constant mass flow
  Note Rayleigh lines must have negative slope
  Entropy – another restriction on possible processes (S2 ≥ S1)
T2 P P ! RT "
S2 ! S1 = CP ln ! R ln 2 ; 2 = 2 2 ;CP = R
T1 P1 P1 !1RT1 " !1
!"
S !S # P ! & " !1 P2 1 P2 ! P #! &
" 2 1 = ln % 2 1 ( ! ln = ln ! ln 2 ;S2 ) S1 " 2 ) % 1 (
CP $ P1 !2 ' " P1 " P1 !1 P1 $ !2 '
• 3
  H = 0: shock Hugoniot – only P2/P1 > 1 (thus ρ1/ρ2 < 1) is
possible; P2/P1 < 1 would result in decrease in entropy
  H ≠ 0, P2 ≈ P1
  Usual “weak deflagration” branch where
!u ! T q fQ
= 1" 1 = 1" 2 < 0; T2 = T1 + = T1 + R = Tad (P=const.)
u1 !2 T1 " R / (" "1) CP
  Burned gases at T = Tad move away from front
  u1 = SL = laminar burning velocity (if perfectly flat, 1D, laminar);
depends on transport properties and reaction rates
  For turbulent flames, u1 = ST (depends additionally on turbulence
properties)
  H ≠ 0, P2 > P1 - detonations
!u !
= 1" 1 > 0
u1 !2
  Can’t determine T2/T1 as simply as with weak deflagrations
  Burned gases move in same direction as front
  Out of all possible choices, how to determine u1?
  Above D: strong detonations (M2 < 1)
  D – B: weak detonations (M2 > 1) (point B: mass flow = ∞)
  B – C: impossible (mass flow imaginary, see Rayleigh line discussion)
  C – E: weak deflagrations (M2 < 1) (point C: mass flow = 0)
  Below E: strong deflagrations (M2 > 1)
5
F H=0
H=2
4
D
3
!"#!$%
2 B
C
1
A E
0
0 1 2 3
!$#!"%
• 4
Detonation velocities - calculation"
  From Hugoniot relation
! +1 P2
1+
"
! P2 "1 % "
1 P % " " % q d ( P2 P1 ) ! !1 P1
$ !1' ! $ 2 !1'$ 1 +1' = (Eq. 1) ( = (Eq. 2)
! !1 # P1 "2 & 2 # P1 &# "2 & RT1 d ( "1 "2 ) 1! +1 "1
!
! !1 "2
  From Rayleigh2 line
P2 ! P1 " m! % 2
= ! $ ' = ! ( !1u1 ) (
1 !2 !1 !1 # A&
2
P2 P1 !1 (! u ) ! u2 M 2c2 M 2" RT1
= ! 1 1 = ! 1 u12 = ! 1 = ! 1 1 = ! 1 = !" M12 (Eq. 3)
!1 !2 !1 P1!1 P1 RT1 RT1 RT1
d ( P2 P1 )
( = !! M12 (Eq. 4)
d ( !1 !2 )
  From mass conservation
2 2 P2 P1
!1u1 = !2 u2 ! ( !1u1 ) = ( !2 u2 ) ! M12 = M 22 (Eq. 5)
!1 !2
Chapman-Jouget detonation"
  5 equations, solve for the 5 unknowns M1, M2, P2/P1, ρ1/ρ2
and d(P2/P1)/d(ρ1/ρ2) at the tangency point where the
slopes d(P2/P1)/d(ρ1/ρ2) are equal on the Hugoniot curve &
Rayleigh line:
1/2 1/2
" ( q RT1 ) (! 2 !1) % " ( q RT1 ) (! 2 !1) %
M1 = $1+ ' +$ ' ; M2 = 1
# 2! & # 2! &
  This is called the Chapman-Jouget detonation (path is A 
F  D) - why is it the most probable detonation speed?
Heat release Induction
zone zone
Temperature
M1
Pressure
Shock
3 2 1
M=1 M<1 M>1
AME P513 - Fallacross

t decreases 2012shock
- Lecture 8 - Premixed
P t decreases flames
in heat release zone I 10
T t constant across shock T t increases in heat release zone
• 5
Chapman-Jouget detonation"
  Consider structure of detonation – shock followed by
reaction zone, because shock requires only a few
collisions to complete whereas reaction requires 106s
  If subsonic behind reaction zone, expansion waves can
catch up to front and weaken shock, slowing it down (why
are expansion waves more prevalent than compression
waves? To be discussed in class…) which results in
smaller M1 thus larger M2
  Can’t achieve weak detonations (M2 > 1) with this
structure because you can’t transition from M < 1 to M > 1
with heating in a constant-area frictionless duct (Rayleigh
flow)
  So CJ detonation (M2 = 1) is the only stable detonation –
mostly borne out by experiments
Deflagrations - burning velocity"

  Recall P2 ≈ P1
  How fast will the flame propagate? Simplest estimate based on the
hypothesis that
Rate of heat conducted from hot gas to cold gas (i) =
Rate at which enthalpy is conducted through flame front (ii) =
Rate at which heat is produced by chemical reaction (iii)
Reaction zone
Speed relative to unburned gas = SL
Product
Reactant
concentration
300K
! ≈ "/SL = 0.3 - 6 mm
• 6
  Estimate of i
Conduction heat transfer rate = -kA(ΔT/δ)
k = gas thermal conductivity, A = cross-sectional area of flame
ΔT = temperature rise across front = Tproducts - Treactants
δ = thickness of front (unknown at this point)
  Estimate of ii
Enthalpy flux through front = (mass flux) x Cp x ΔT
Mass flux = ρuA (ρ = density of reactants = ρ∞, u = velocity = SL)
Enthalpy flux = ρ∞CpSLAΔT
  Estimate of iii
Heat generated by reaction = QR x (d[fuel]/dt) x Mfuel x Volume
Volume = Aδ
QR = CPΔT/f
Fuel mass (Mass fuel / volume)
f = =
Total mass (Mass total / volume)
(Moles fuel / volume)(mass fuel / moles fuel) [F]" M fuel
= =
(Mass total / volume) #"
[F]∞ = fuel concentration in the cold reactants

!

  Combine (i) and (ii)
  δ = k/ρCpSL = α/SL (δ = flame thickness) (same as Lecture 7)
  Recall α = k/ρCp = thermal diffusivity (units length2/time)
  For air at 300K & 1 atm, α ≈ 0.2 cm2/s
  For gases α ≈ ν (ν = kinematic viscosity)
  For gases α ~ P-1T1.7 since k ~ P0T.7, ρ ~ P1T-1, Cp ~ P0T0
  For typical stoichiometric hydrocarbon-air flame, SL ≈ 40 cm/s,
thus δ ≈ α/SL ≈ 0.005 cm (!) (Actually when properties are
temperature-averaged, δ ≈ 4α/SL ≈ 0.02 cm - still small!)
  Combine (ii) and (iii)
SL = (αω)1/2
ω = overall reaction rate = (d[fuel]/dt)/[fuel]∞ (units 1/s)

  With SL ≈ 40 cm/s, α ≈ 0.2 cm2/s, ω ≈ 1600 s-1
  1/ω = characteristic reaction time = 625 microseconds
  Heat release rate per unit volume = (enthalpy flux) / (volume)
= (ρCpSLAΔT)/(Aδ) = ρCpSL/k)(kΔT)/δ = (kΔT)/δ2
= (0.07 W/mK)(1900K)/(0.0002 m)2 = 3 x 109 W/m3 !!!
  Moral: flames are thin, fast and generate a lot of heat!
• 7
  More rigorous analysis (Bush & Fendell, 1970) using Matched
Asymptotic Expansions
  Convective-diffusive (CD) zone (no reaction) of thickness δ
  Reactive-diffusive (RD) zone (no convection) of thickness δ/β(1-ε)
where 1/[β(1-ε)] is a small parameter
  T(x) = T0(x) + T1(x)/[β(1-ε)] + T2(x)/[β(1-ε)]2 + …
  Collect terms of same order in small parameter
  Match T & dT/dx at all orders of β(1-ε) where CD & RD zones meet
1/2
" 2! Ze! " % " 1.344 ! 3(1! ! ) % E T
SL = $$ ' 1+
2' $ '; " ( ,! ( *
# ( " (1! # )) & # " (1! ! ) & )Tad Tad
  Same form as simple estimate (SL ~ {αω}1/2, where ω ∼ Ze-β is
an overall reaction rate, units 1/s), with additional constants
  Why β-2 term on reaction rate?
  Reaction doesn’t occur over whole flame thickness δ, only in thin
zone of thickness δ/β
  Reactant concentration isn’t at ambient value Yi,∞, it’s at 1/β of
this since temperature is within 1/β of Tad

  What if not a single reactant, or Le ≠ 1? Mitani (1980)
extended Bush & Fendell for reaction of the form
! A A + ! B B ! products;!! = ZYA! A YB! B exp ("Ea / #T ) resulting in
1/2
# !B &
! " # A +# B !1 # A (# B # A ) 1 1
%
SL = % 2! Ze YA," G (
! A +! B +1
Le !! A
Le !! B (
$ ( " (1! # )) A B '
"
!B
G) !A
* y ( y + a) e! y dy ; a ) " (1! # )($ !1) / LeB ; $ = equivalence ratio
0
  Recall order of reaction (n) = νA+ νB

  Still same form as simple estimate, but now β-(n+1) term since n
may be something other than 1 (as Bush & Fendell assumed)
  Also have LeA-νA and LeB-νB terms – why? For fixed thermal
diffusivity (α), for higher LeA, DA is smaller, gradient of YA
must be larger to match with T profile, so concentration of A
is higher in reaction zone
• 8
  How does SL vary with pressure?
d[A] ! !
= !k f [ A ] A [ B ] B ~P! A P! B ~P! A +! B ~P n (for example A = fuel, B = oxidant)
dt
1 d[A]
"! ~ ~ P !1P n ~ P n!1
[A]" dt
Thus SL ~ {αω}1/2 ~ {P-1Pn-1}1/2 ~ P(n-2)/2
  For typical n = 2, SL independent of pressure
  For real hydrocarbons, working backwards from
experimental results, typically (e.g. stoichiometric CH4-air) SL
~ P-0.4, thus n ≈ 1.2
  This suggests more reactions are one-body than two-body,
but actually observed n is due to competition between two-
body H + O2 branching vs. 3-body H + O2 + M which
decelerates reaction
Deflagrations - temperature effect"

  Since Zeldovich number (β) >> 1
Tad "!! E
!! =
!! (Tad ) " T T =Tad "Tad
For typical hydrocarbon-air flames, E ≈ 40 kcal/mole
ℜ = 1.987 cal/mole, Tf ≈ 2200K if adiabatic
⇒ β ≈ 10, at T close to Tf, ω ~ T10 !!!
⇒ Thin reaction zone concentrated near highest temp.
∴ In Zeldovich (or any) estimate of SL, overall reaction rate Ω
must be evaluated at Tad, not T∞
⇒  How can we estimate E? If reaction rate depends more
on E than concentrations [ ], SL ~ {αω}1/2 ~ {exp(-E/ℜT)}1/2
~ exp(-E/2ℜT) - Plot of ln(SL) vs. 1/Tad has slope of -E/2ℜ
  If β isn t large, then ω(T∞) ≈ ω(Tad) and reaction occurs
even in the cold gases, so no control over flame is
possible!
  Since SL ~ ω1/2, SL ~ (Tβ)1/2 ~ T5 typically!
• 9
Burning velocity measurement"
  Many techniques, all attempt to determine the speed of the
unburned gases relative to the flame front or vice versa
(since that’s the definition of SL)
  Counterflow very popular (e.g. Prof. Egolfopoulos)
Deflagrations – burning velocities"
≈ 2200K
SL
≈ 40 cm/s Tad
or
Tad
SL
≈ 1500K
≈ 5 cm/s
! ≈ 0.5 !=1 !≈2

Lean Stoichio-
Fuel %
Rich
limit metric limit
Schematic of flame temperatures and

Real data on SL (CH4-air, 1 atm)
laminar burning velocities
• 10
Deflagrations - summary"
  These relations show the effect of Tad (depends on fuel &
stoichiometry), α (depends on diluent gas (usually N2) & P),
ω (depends on fuel, T, P) and pressure (engine condition)
on laminar burning rates
  Re-emphasize: these estimates are based on an overall
reaction rate; real flames have 1000 s of individual
reactions between 100 s of species - but we can work
backwards from experiments or detailed calculations to get
these estimates for the overall reaction rate parameters
• 11
AME 513 
 
"
Lecture 9!
Premixed flames II: Extinction, stability,
ignition!
Outline"
  Flammability limits!
  Chemical considerations!
  Aerodynamics (i.e. stretch effects)!
  Lewis number!
  Heat losses to walls!
  Buoyancy!
  Radiative heat losses!
  Flame instabilities!
  Flame ignition!
  Simple estimate!
  Effects of Lewis number!
  Effects of ignition source!
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 2
• 1
Flammability / extinction limits"
  Too lean or too rich mixtures won t burn - flammability limits!
  Even if mixture is flammable, still won t burn in certain
environments!
  Small diameter tubes!
  Strong hydrodynamic strain or turbulence!
  High or low gravity!
  High or low pressure!
  Understanding needed for combustion engines & industrial
combustion processes (leaner mixtures ⇒ lower Tad ⇒ lower
NOx); fire & explosion hazard management, fire suppression, ... !
Flammability limits - basic observations"

  Limits occur for mixtures that are thermodynamically
flammable - theoretical adiabatic flame temperature (Tad) far
above ambient temperature (T∞)!
  Limits usually characterized by finite (not zero) burning velocity
at limit"
  Models of limits due to losses - most important prediction:
burning velocity at the limit (SL,lim) - better test of limit
predictions than composition at limit!
• 2
Premixed-gas flames – flammability limits"
SL
or Tad
Lean limit (1)

Lean limit (2)
Tad
SL
Same thing on
Small % change rich side too!
in fuel % at limit
SL,lim(1)
Large % change
in S L at limit
SL,lim(2)
Lean Rich
limit
Stoichio- limit Fuel %
metric
2 limit mechansims, (1) & (2), yield similar fuel % and Tad at limit
but very different SL,lim
Flammability limits in vertical tubes"

  Most common apparatus - vertical tube (typ. 5 cm in diameter)!
  Ignite mixture at one end of tube, if it propagates to other end,
it s flammable !
  Limit composition depends on orientation - buoyancy effects"
Upward propagation Downward propagation!
• 3
Chemical kinetics of limits"
  Recall crossover of H + O2  OH + O vs. H + O2 + M  HO2 + M at low T –
but this just means that at low Tad, flame will propagate very slowly due to
absence of this branching route
  Computations show no limits without losses – no purely chemical criterion
(Lakshmisha et al., 1990; Giovangigli & Smooke, 1992) - for steady planar
adiabatic flames, SL decreases smoothly towards zero as fuel
concentration decreases (domain sizes up to 10 m, SL down to 0.02 cm/s)
  …but as SL decreases, d increases - need larger computational domain or
experimental apparatus
  Also more buoyancy & heat loss effects as SL decreases ….
Giovangigli &
Smooke, 1992
Left: H2-air
Right: CH4-air
Chemical kinetics of limits"

!
!
!
!
!
!
!
!
!
!
!
!
!
Ju, Masuya, Ronney (1998)!
Ju et al., 1998
• 4
Aerodynamic effects on premixed flames"
  Aerodynamic effects occur on a large scale compared to the transport
or reaction zones but affect SL and even existence of the flame!
  Why only at large scale?!
  Re on flame scale ≈ SLδ/ν (ν = kinematic viscosity) !
  Re = (SLδ/α)(α/ν) = (1)(1/Pr) ≈ 1 since Pr ≈ 1 for gases!
  Reflame ≈ 1 ⇒ viscosity suppresses flow disturbances!
  Key parameter: stretch rate (Σ)!
1 dA
"# (A = flame area)
A dt
  Generally Σ ~ U/d!
U = characteristic flow velocity!
d = characteristic flow length scale!
! !
Aerodynamic effects on premixed flames"

  Strong stretch (Σ ≥ Ω ~ SL2/α or Karlovitz number Ka ≡ Σα/SL2 ≥ 1)
extinguishes flames!
  Moderate stretch strengthens flames for Le < 1!
! Thermal diffusivity of the bulk mixture (" )
Le !
Mass diffusivity of scarce reactant into the bulk mixture (D)
" 1%
!! = " $1! '
# Le &
SL/SL(unstrained, adiabatic flame)!
Buckmaster &
Mikolaitis,
1982a!
ln(Ka)!
• 5
Lewis number tutorial"
  Le affects flame temperature in curved (shown below) or
stretched flames!
  When Le < 1, additional thermal enthalpy loss in curved/stretched
region is less than additional chemical enthalpy gain, thus local
flame temperature in curved region is higher, thus reaction rate
increases drastically, local burning velocity increases!
  Opposite behavior for oppositely curved flames!
Direction of Unburned gas

propagation
Fuel Fuel
diffusion Heat Heat diffusion
diffusion diffusion
Flame
front
Burned gas
TIME SCALES - premixed-gas flames"

  Chemical time scale!
tchem ≈ δ/SL ≈ (α/SL)/SL ≈ α/SL2!
!α = thermal diffusivity [typ. 0.2 cm2/s], !
!SL = laminar flame speed [typ. 40 cm/s]

  Conduction time scale!
tcond ≈ Tad/(dT/dt) ≈ d2/16α!
d = tube or burner diameter

  Radiation loss time scale!
trad ≈ Tad/(dT/dt) ≈ Tad/(Λ/ρCp) (Λ = radiative loss per unit volume)

Optically thin radiation: Λ = 4σap(Tad4 – T∞4) !
ap = Planck mean absorption coefficient [typ. 2 m-1 at 1 atm]!
⇒  Λ ≈ 106 W/m3 for HC-air combustion products

⇒  trad ~ P/σap(Tad4 – T∞4) ~ P0, P = pressure!
  Buoyant transport time scale!
t ~ d/V; V ≈ (gd(Δρ/ρ))1/2 ≈ (gd)1/2

(g = gravity, d = characteristic dimension)

Inviscid: tinv ≈ d/(gd)1/2 ≈ (d/g)1/2 (1/tinv ≈ Σinv)

Viscous: d ≈ ν/V ⇒ tvis ≈ (ν/g2)1/3 (ν = viscosity [typ. 0.15 cm2/s])!
• 6
Time scales (hydrocarbon-air, 1 atm)"
TTiim
mee ssccaallee S
Stto
oiicchh.. ffllaam
mee L
Liim
miitt ffllaam
mee
C
Chheemmiissttrryy ((ttcchheemm)) 00..0000009944 sseecc 00..2255 sseecc
o
orr d
diiffffu
ussiio onn ((ttddiiffff))
B
Buoyant, invviisscciid
u o y a n t , i n d ((ttiinnvv)) 00..007711 sseecc 00..007711 sseecc
B
Buoyant, viscous ((ttvviiss))
u o y a n t , v i s c o u s 00..001122 sseecc 00..001100 sseecc
C
Coonnddu uccttiioon n ((ttccoonndd)),, d
d == 55 ccmm 00..9955 sseecc 11..44 sseecc
R
Raaddiiaattiio
on n ((ttrraadd)) 00..1133 sseecc 00..4411 sseecc
  Conclusions!
  Buoyancy unimportant for near-stoichiometric flames!
(tinv & tvis >> tchem)!
  Buoyancy strongly influences near-limit flames at 1g!
(tinv & tvis < tchem)!
  Radiation effects unimportant at 1g (tvis << trad; tinv << trad)!
☞  Radiation effects dominate flames with low SL !
(trad ≈ tchem), but only observable at µg!
  Small trad (a few seconds) - drop towers useful!
  Radiation > conduction only for d > 3 cm!
  Re ~ Vd/ν ~ (gd3/ν2)1/2 ⇒ turbulent flow at 1g for d > 10 cm

Flammability limits due to losses"

  Golden rule: at limit! Heat loss rate per unit volume 1
"
Heat generation rate per unit volume #
  Why 1/β not 1? T can only drop by O(1/β) before extinction - O
(1) drop in T means exponentially large drop in Ω, thus
exponentially!small SL. Could also say heat generation occurs
only in δ/β region whereas loss occurs over δ region!
! 2000
Adiabatic flame
1500
Temperature (K)
Non-adiabatic flame
1000
Convective-diffusive zone, O( !)
500 Reactive-diffusive zone, O( !/")
Convective-loss zone
0
-0.2 0 0.2 0.4 0.6 0.8 1
Spatial coordinate (cm)
• 7
  Heat loss to walls!
  tchem ~ tcond ⇒ SL,lim ≈ (8β)1/2α/d at limit !
!or Pelim ≡ SL,limd/α ≈ (8β)1/2 ≈ 9!
  Actually Pelim ≈ 40 due to temperature averaging - consistent
with experiments (Jarosinsky, 1983)!
  Upward propagation in tube!
  Rise speed at limit ≈ 0.3(gd)1/2 due to buoyancy alone (same as
air bubble rising in water-filled tube (Levy, 1965))!
!Pelim ≈ 0.3 Grd1/2; Grd = Grashof number ≡ gd3/ν2!
  Causes stretch extinction (Buckmaster & Mikolaitis, 1982b):!
!tchem ≈ tinv or 1/tchem ≈ Σinv!
! $ g# 2 '1/ 4 $ * $ T '$
! " SL,lim = f (Le)& , 1 ''
) ; f (Le) = exp& &1+ )&1+ ))
! % d ( % 4 % Tad (% Le ((
!Note f(Le) < 1 for Le < 1, f(Le) > 1 for Le > 1 - flame can survive at
lower SL (weaker mixtures) when Le < 1!
!
Difference between S and SL"

Mass conservation: if SL = constant
A S Approach speed of
!! SAtube = !! SL A flame " flame = unburned gas
Atube SL S ≈ 0.3(gd)1/2
A flame S 0.3 gd 0.3 1/4 SL

At
! limit: = = 1/4
= Gr SL SL
Atube SL # g" &
2 f
! f% ( SL SL
! $ d ' SL SL
⇒  long flame skirt at high Gr or with
small f (low Lewis number, Le)! SL SL
(but note SL not really constant over Burned
gas
flame surface!)!
SL
S
SII SL !∞ /!ad
Flame
S II front
Tube walls
Flow pattern in flame-front
fixed reference frame
• 8
  Downward propagation – sinking layer of cooling gases
near wall outruns & suffocates flame (Jarosinsky et
al., 1982)!
  tchem ≈ tvis ⇒ SL,lim ≈ 1.3(gα)1/3!
  Pelim ≈ 1.65 Grd1/3!
  Can also obtain this result by equating SL to sink rate of
thermal boundary layer = 0.8(gx)1/2 for x = δ

  Consistent with experiments varying d and α (by varying
diluent gas and pressure) (Wang & Ronney, 1993) and g (using
centrifuge) (Krivulin et al., 1981)!
Flammability limits in vertical tubes"
Buoyancy-induced
flame stretch
Cooling
combustion products near
wall cause sinking boundary
layer
Direction of flame
propagation
Direction of flame
Flame propagation
front
Tube walls Tube walls
Upward propagation Downward propagation!
• 9
Flammability limits in tubes"
5
10
Le=0.17 Le=1.73
Le=0.3 Le=1.86
Le=0.71 Le=2.02
Peclet number at limit

4
10 Le=0.86 Le=2.17
Le=0.96 Le=2.76
Le=1.46 Le=3.2
3
10
2
10
Pe = 40
1/2
Pe = 0.28 Ra
w
1
10 2 3 4 5 6 7 8 9 10
10 10 10 10 10 10 10 10 10
Rayleigh number
Upward propagation - Wang & Ronney, 1993!
Flammability limits in tubes"
4
10
Le=0.17 Le=1.97
Le=0.27 Le=2.19
Le=0.71 Le=2.38
Peclet number at limit
Le=0.96 Le=3.22
Le=1.47 Le=3.34
3
10 Le=1.74 Le=3.57
Le=1.88
2
10
Pe = 40
1/3
Pe = 1.7 Ra
w
1
10
2 3 4 5 6 7 8 9
10 10 10 10 10 10 10 10
Rayleigh number
Downward propagation - Wang & Ronney, 1993!
• 10
Flammability limits – losses - continued…"
  Big tube, no gravity – what causes limits?!
  Radiation heat loss (trad ≈ tchem) (Joulin & Clavin, 1976;
Buckmaster, 1976)! 1 1.2$%kad
SL,lim =
"#C p Tad
!! ! !!
  What if not at limit? Heat loss still decreases SL, actually 2
possible speeds for any value of heat loss, but lower one
generally unstable!
!
S (burning velocity)
1
S 2 ln S 2 = "Q; 0.8
SL(non"ad ) 0.6
S# ,
SL(ad )
0.4
$%& 2
Q# 2
0.2 Flammability
limit
k(Tad " T' )SL(ad )
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Q (heat loss)
! AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 21
Flammability limits – losses - continued…"

  Doesn t radiative loss decrease for weaker mixtures, since
temperature is lower? NO!!
Heat loss rate T2
Impact of heat loss ~ ~ "E / #T $ as T %
Heat release rate e
  Predicted SL,lim (typically 2 cm/s) consistent with µg

experiments (Ronney, 1988; Abbud-Madrid & Ronney, 1990)!
!
• 11
Reabsorption effects"
  Is radiation always a loss mechanism?!
  Reabsorption may be important when aP-1 < d!
  Small concentration of blackbody particles - decreases SL
(more radiative loss)!
  More particles - reabsorption extend limits, increases SL!
2.50 4.2
Pressure
Maximum pressure (atm)

Burning velocity (cm/s)
4.1
2.25
Burning velocity 4
2.00 3.9 Abbud-Madrid &

Ronney (1993)
3.8
1.75
3.7
1.50 3.6
0 2 4 6 8
Mass of particles in chamber (g)
Reabsorption effects on premixed flames"

  Gases – much more complicated because absorption coefficient
depends strongly on wavelength and temperature & some radiation
always escapes (Ju, Masuya, Ronney 1998)!
  Absorption spectra of products different from reactants!
  Spectra broader at high T than low T!
  Dramatic difference in SL & limits compared to optically thin!
1000 CO2 1300K

Absorption coefficient (m-1 atm-1 )
300K
100
10
0.1
100 H2 O 1300K
300K
10
0.1
1000 10000
Wavenumber (cm-1 )
• 12
Stretched flames - spherical"
  Spherical expanding flames, Le < 1: stretch allows flames to exist
in mixtures below radiative limit until flame radius rf is too large &
curvature benefit too weak (Ronney & Sivashinsky, 1989)!
1 dA 1 d 2 drf dS 2S
!" = 2
A dt 4#rf dt
4#rf2 =
r f dt
($
dR
)
+ S 2 lnS 2 =
R
%Q
  Adds stretch term (2S/R) (R = scaled flame radius; R > 0 for Le < 1;
R < 0 for Le > 1) and unsteady term (dS/dR) to planar steady
equation!
  Dual limit: radiation at large rf, curvature-induced stretch at small rf
(ignition limit)!
Stretched flames - spherical"

!
80
!
Dimensionless radius (R)
Q = 0.36
70
!
60
! Q = 0.4
! 50
! 40 Q = 0.42
! 30
Q = 0.45
! 20
Q = 0.5
!
10
!
0
! 0 20 40 60 80 100
! Dimensionless time !( )
Theory (Ronney & Sivashinsky, 1989) ! ! !!
!
! ! ! !Experiment!
! ! ! (Ronney, 1985)!
!
• 13
Stretched counterflow or stagnation flames"
  Mass + momentum conservation, 2D, const. density (ρ)!
!u !u !u 1 ! P " ! 2u ! 2u %
+ u + v =- +gx +µ $ 2 + 2 ' (x momentum)
!t !x !y " !x # !x !y &
!v !v !v 1 ! P " ! 2v ! 2v %
+ u + v =- +gy +µ $ 2 + 2 ' (y momentum)
!t !x !y " !y # !x !y &
!u !v
+ =0 (mass conservation)
!x !y
! (u, v = velocity components in x, y directions)!
!!
!admit an exact, steady (∂/∂t = 0) solution which is the same with or without
viscosity (!!!): !!
! u=!x,
! v=-!y,!P = Po + ! (g
! x x + gy y)! Σ = rate of strain (units s-1)!
  Similar result in 2D axisymmetric (r, z) geometry:!
! ur = -"r /2, uz = "z
!Very simple flow characterized by a single parameter Σ, easily
implemented experimentally using counter-flowing round jets…!

!
Stretched counterflow or stagnation flames"

  Σ = duz/dz – flame located where uz = SL!
  Increased stretch pushes flame closer to stagnation
plane - decreased volume of radiant products!
  Similar Le effects as curved flames!
Fuel/Oxidizer
Flame
zx
Flame
r
Fuel/Oxidizer
• 14
Premixed-gas flames - stretched flames"
  Stretched flames with radiation (Ju et al., 1999): dual limits,
flammability extension even for Le >1, multiple solutions
(which ones are stable?)!
Premixed-gas flames - stretched flames"

  Dual limits & Le effects seen in µg experiments, but evidence for
multivalued behavior inconclusive!
! !Guo et al. (1997)!
• 15
Stability of premixed flames"
  Many types, e.g.!
  Thermal expansion (Darrieus-Landau, DL) – always occurs due
to lower density of products than reactants!
  Rayleigh-Taylor (buoyancy-driven, RT) – upward propagating
flames unstable (more dense reactants on top of products),
downward propagating stable!
  Diffusive-thermal (DT) (Lewis number, already discussed)!
  Viscous fingering (Saffman-Taylor, ST) in confined geometries
when viscous fluid (e.g. oil) displaced by less viscous fluid (e.g.
water) – occurs in flames because products are more viscous
than reactants!
Effects of thermal expansion"

 Darrieus-Landau instability - causes infinitesimal wrinkle in
flame to grow due simply to density difference across front
Williams, 1985!
Bernoulli:!
P+1/2ρu2 = const!
Aflame ↓, u ↑, P ↓!
Aflame↑, u↓, P↑!
FLOW →!
Aflame ↓, u ↑, P ↓! Aflame↑, u↓, P↑!
• 16
Apparatus for studying flame instabilities"
Lexan sheets
Aluminum plate
Unburned gas
Flame front
Spark
electrodes Burned gas Video camera
(3 pairs)
Partial pressure
gas mixing system
Mixing chamber
Spark Exhaust
generator manifold
Oxidizer
Diluent
Fuel
Exhaust Ball
valve
Computer
  Aluminum frame sandwiched between Lexan windows!

  40 cm x 60 cm x 1.27 or 0.635 or 0.32 cm test section!
  CH4 & C3H8 fuel, N2 & CO2 diluent - affects Le, Peclet #!
  Upward, horizontal, downward orientation!
  Spark ignition (3 locations, ≈ plane initiation)!
  Exhaust open to ambient pressure at ignition end - flame
propagates towards closed end of cell!
Results - video - baseline case, DL-dominated"
6.8% CH4-air, horizontal, 12.7 mm cell!

• 17
Upward propagation – RT enhanced"
6.8% CH4-air, upward, 12.7 mm cell!

Downward propagation – RT suppressed"

!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
6.8% CH4-air, downward, 12.7 mm cell!
• 18
High Lewis number"
!
3.0% C3H8-air, horizontal, 12.7 mm cell (Le ≈ 1.7)!
Low Lewis number"

!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
8.6% CH4 - 32.0% O2 - 60.0% CO2, horizontal, 12.7 mm cell (Le ≈ 0.7)!
• 19
Horizontal, but ST not DL dominated"
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
9.5% CH4 - 90.5% air, horizontal, 3.1 mm cell!
Ignition - basic concepts"

  Experiments (Lewis & von Elbe, 1987) show that a minimum energy
(Emin) (not just minimum T or volume) required to ignite a flame!
  Emin lowest near stoichiometric (typ. 0.2 mJ) but minimum shifts to
richer mixtures for higher HCs (why? Stay tuned…)!
  Prediction of Emin relevant to energy conversion and fire safety
applications!
Minimum ignition energy (mJ)
• 20
Basic concepts"
  Emin related to need to create flame kernel with dimension (δ) large
enough that chemical reaction (Ω) can exceed conductive loss rate
(α/δ2), thus δ > (α/ω)1/2 ~ α/(αω)1/2 ~ α/SL ~ δ !
  Emin ~ energy contained in volume of gas with T ≈ Tad and radius ≈
δ ≈ 4α/SL !
4$ 3 4$ k (T ' T )
" E min # % &C p (Tad ' T( ) # 0.3 % 3 &(C p (Tad ' T( ) # 34) (2 ( ad 3 (
3 3 SL
Successful
ignition
Unsuccessful Initial profile
Initial profile
ignition
! Later
TEMPERATURE
TEMPERATURE
!
Still later
Later
Still later
SL
DISTANCE DISTANCE
Predictions of simple Emin formula"

  Since α ~ P-1, Emin ~ P-2 if SL is independent of P!
  Emin ≈ 100,000 times larger in a He-diluted than SF6-
diluted mixture with same SL, same P (due to α and λ
differences)!
  Stoichiometric CH4-air @ 1 atm: predicted Emin ≈ 0.010
mJ ≈ 30x times lower than experiment (due to chemical
kinetics, heat losses, shock losses …)!
  … but need something more (Lewis number effects):!
  10% H2-air (SL ≈ 10 cm/sec): predicted Emin ≈ 0.3 mJ = 2.5 times
higher than experiments!
  Lean CH4-air (SL ≈ 5 cm/sec): Emin ≈ 5 mJ compared to ≈ 5000mJ
for lean C3H8-air with same SL - but prediction is same for both!
• 21
Lewis number effects"
  Ok, so why does min. MIE shift to richer mixtures for higher HCs?!
  Leeffective = αeffective/Deffective!
  Deff = D of stoichiometrically limiting reactant, thus for lean mixtures
Deff = Dfuel; rich mixtures Deff = DO2!
  Lean mixtures - Leeffective = Lefuel!
  Mostly air, so αeff ≈ αair; also Deff = Dfuel!
  CH4: DCH4 > αair since MCH4 < MN2&O2 thus LeCH4 < 1, thus Leeff < 1!
  Higher HCs: Dfuel < αair, thus Leeff > 1 - much higher MIE!
  Rich mixtures - Leeffective = LeO2!
  CH4: αCH4 > αair since MCH4 < MN2&O2, so adding excess CH4
INCREASES Leeff!
  Higher HCs: αfuel < αair since Mfuel > MN2&O2, so adding excess fuel
DECREASES Leeff!
  Actually adding excess fuel decreases both α and D, but
decreases α more!
Const1 Const 2 Const 3
" eff = " mix ~ ;DO2 ~ +
M mix M mix MO 2
Effect of spark gap & duration"

  Expect optimal ignition duration ~ ignition kernel time scale ~ RZ2/α!
  Duration too long - energy wasted after kernel has formed and
propagated away - Emin ~ t1!
  Duration too short - larger shock losses, larger heat losses to
electrodes due to high T kernel !
  Expect optimal ignition kernel size ~ kernel length scale ~ RZ!
  Size too large - energy wasted in too large volume - Emin ~ R3!
  Size too small - larger heat losses to electrodes!
Sloane & Ronney, 1990 Kono et al., 1976
Detailed chemical model
1-step chemical model
• 22
Effect of flow environment"
  Mean flow or random flow (i.e. turbulence) (e.g. inside IC engine
or gas turbine) increases stretch, thus Emin!
Kono et al., 1984 DeSoete, 1984

Effect of ignition source"

  Laser ignition sources higher than sparks despite lower heat losses,
less asymmetrical flame kernel - maybe due to higher shock losses with
shorter duration laser source? !
Minimum ignition energy (mJ)
10
ps laser
ns laser
Lewis & von Elbe
Sloane & Ronney
Ronney
Kingdon & Weinberg
0.1
4 5 6 7 8 9 10 11 12
Mole percent CH4 in air
Lim et al., 1996
• 23
AME 513 
 
"
Lecture 10
Premixed flames III: Turbulence effects
Motivation"
  Study of premixed turbulent combustion important because
  Turbulence increases mean flame propagation rate (ST) and
thus mass burning rate (= ρ ST Aprojected)
  If this trend increased ad infinitum, arbitrarily lean mixtures
(low SL) could be burned arbitrarily fast by using sufficiently
high u’ ...but too high u' leads to extinction - nixes that idea
  Even without forced turbulence, if the Grashof number
gd3/ν2 is larger than about 106 (g = 103 cm/s2, ν ≈ 1 cm2/s ⇒
d > 10 cm), turbulent flow will exist due to buoyancy
  Examples
 Premixed turbulent flames
» Gasoline-type (spark ignition, premixed-charge) internal combustion
engines
» Stationary gas turbines (used for power generation, not propulsion)
 Nonpremixed flames
» Diesel-type (compression ignition, nonpremixed-charge) internal
combustion engines
» Gas turbines
» Most industrial boilers and furnaces
AME 514 - Fall 2012 - Lecture 10 - Premixed flames III 2
• 1
Turbulent burning velocity"
  Models of premixed turbulent combustion don t agree with
experiments nor each other!
Bray (zero heat release) Pope & Anand (zero heat release)
(large heat release) (large heat release)
Turbulent Burning Velocity (ST /SL )

30
Sivashinsky
25
Yakhot
20
15 Experiment
x (Re =1,000)
T
10
Gouldin (Re =1,000)
T
5
0
0 10 20 30 40 50
Turbulence Intensity (u'/SL )
Basics of turbulence"
  Good reference: Tennekes: A First Course in Turbulence
  Job 1: need a measure of the strength of turbulence
  Define turbulence intensity (u ) as rms fluctuation of
instantaneous velocity u(t) about mean velocity ( u)
'1 T 2 * '1 T *
(u') 2 " limT #$ ) & (u(t) % u ) dt, ; u " limT #$ ) & u(t)dt,
(T 0 + (T 0 +
2.2 !
Large u'
Small u'
2.1
!
Velocity
1.9
1.8
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Time
• 2
  Job 2: need a measure of the length scale of turbulence
  Define integral length scale (LI) as
 A measure of size of largest eddies
 Largest scale over which velocities are correlated
 Typically related to size of system (tube or jet diameter, grid
spacing, …)
# [ u(x) % u ][ u(x + r) % u ]
LI (x) " $ 0
A(x,r)dr; A(x,r) "
u'(x)u'(x + r)
Here the overbars denote spatial (not temporal) averages
 A(r) is the autocorrelation function at some time t
 Note A(0) = 1 (fluctuations around the mean are perfectly
! correlated at a point)
 Note A(∞) = 0 (fluctuations around the mean are perfectly
uncorrelated if the two points are very distant)
 For truly random process, A(r) is an exponentially decaying
function A(r) = exp(-r/LI)
  In real experiments, generally know u(t) not u(x) - can define
time autocorrelation function A(x,τ) and integral time scale τI
at a point x
$
" I (x) # % 0 A(x, " )d" ; A(x, " ) #
[ u(x,t) & u (x)][ u(x,t + " ) & u (x)]
u'(x) 2
Here the overbars denote temporal (not spatial) averages
  With suitable assumptions LI = (8/π)1/2u τI
  Define integral scale Reynolds number ReL ≡ u LI/ν (recall ν
! = kinematic viscosity)
  Note generally ReL ≠ Reflow = Ud/ν; typically u ≈ 0.1U, LI ≈
0.5d, thus ReL ≈ 0.05 Reflow
  Turbulent viscosity νT
  Molecular gas dynamics: ν ~ (velocity of particles)(length
particles travel before changing direction)
  By analogy νT ~ u LI or νT/ν = C ReL; C ≈ 0.061
  Similarly, turbulent thermal diffusivity αT/α ≈ 0.042 ReL
• 3
Turbulent burning velocity"
  Experimental results shown in Bradley et al. (1992) smoothed
data from many sources, e.g. fan-stirred bomb
Bradley et al. (1992)"

  Compilation of data from many sources
= ST/SL!
= u /SL
• 4
Characteristics of turbulent flames"
  Most important property: turbulent flame speed (ST)
  Most models based on physical models of Damköhler (1940)
  Behavior depends on Karlovitz number (Ka)
Mean strain rate due to turbulence u'3 /15" LI

Ka ! !
Mean chemical rate (!! ) SL2 / #
u'3 /15"LI % (2
$1/ 2 u' u' LI Defined using cold-
Ka = 2
= 0.157Re L ' * ; Re + gas viscosity ν
S L /# & SL ) "
  Low Ka: Huygens propagation, thin fronts that are wrinkled by
turbulence but internal structure is unchanged
!   High Ka: Distributed reaction zones, broad fronts
Characteristics of turbulent flames"

Burned gas Burned
Burnedgas
gas
SL
SL SL
SL !
Unburned gas Kolmogorov Unburned gas Kolmogorov
Integral Integral
scale eddy scale eddy
scale scale
eddy eddy
TP TP
Temperature
Temperature
TR TR
Distance or time Distance or time
"Thin" flame "Distributed" flame

(Re » 1, Ka « 1) (Re » 1, Ka » 1)
• 5
Turbulent combustion regimes"
  Comparison of flamelet and distributed combustion (Yoshida,
1988)
Flamelet: temperature is Distributed: significant

either T∞ or Tad, never probability of temperatures
between, and probability of between T∞ or Tad, probability
product increases through the of intermediate T peaks in
flame! middle of flame!
Estimates of ST in flamelet regime"

  Damköhler (1940): in
Huygens propagation
Duct boundary;
regime, flame front is duct cross-section
wrinkled by turbulence area = AL
but internal structure and Flame surface SL

SL are unchanged area AT
  Propagation rate ST due SL Flame surface
area = duct
only to area increase via ST cross-section
area = AT
wrinkling:
ST/SL = AT/AL SL
= SL
SL
SL
SL
• 6
Estimates of ST in flamelet regime"
  Low u /SL: weakly wrinkled flames
  ST/SL = 1 + (u /SL)2 (Clavin & Williams, 1979) - standard for
many years
  Actually Kerstein and Ashurst (1994) showed this is valid only
for periodic flows - for random flows ST/SL - 1 ~ (u /SL)4/3
  Higher u /SL: strongly wrinkled flames
  Schelkin (1947) - AT/AL estimated from ratio of cone surface
area to base area; height of cone ~ u /SL; result
2
ST SL " 1+ (2u' /SL ) " 2 ( u' /SL ) at high u' /SL
  Other models based on fractals, probability-density functions,
etc., but mostly predict ST/SL ~ u /SL at high u /SL with the
possibility of bending or quenching at sufficiently high Ka ~
!
(u /SL)2, e.g. Yakhot (1988):
" (u' S )2 %
'! (
L u'/ SL )
ST SL ! exp $$ 2'
at high u'/ SL
# ( ST SL ) & ln (u'/ SL )
Effects of thermal expansion"

  Byckov (2000):
% #2 2
(
ST ' 4" 3 (1+ 2( ST SL ) ) (u$ SL ) *; " + ,- > 1
= exp' 2*
SL 2
,f
' " + 1+ 2" (" #1)( ST SL )#2 + 8" 2 ( ST SL )#2 ( ST SL ) *
[ ]
& )
  Same as Yakhot (1988) if no thermal expansion (θ = 1)
  Also says for any θ, if u /SL = 0 then ST/SL = 1; probably not true
! 50
Front propagation rate (S / S )
L
T
40
30
20
! = 1 (Yakhot)
! = 2
10 ! = 4
! = 8
0
0 20 40 60 80 100
Turbulence intensity (u'/S )
L
• 7
ST in distributed combustion regime"
  Much less studied than flamelet combustion
  Damköhler (1940):
ST !
! !T DT ! ! DT = "T ScL
SL ! L DL DL "L ScT
! 0.061Re L ScL ! A Re L
ScT
A ≈ 0.25 (gas); A ≈ 6.5 (liquid)

  Assumption ωT ≈ ωL probably not valid for high β; recall
Tad "!! E
!! =
!! (Tad ) " T T =Tad RTad
…but probably ok for small β
  Example: 2 equal volumes of combustible gas with E = 40 kcal/mole, 1
volume at 1900K, another at 2100K
ω(1900) ~ exp(-40000/(1.987*1900)) = 3.73 x 104
ω(2100) ~ exp(-40000/(1.987*2100)) = 1.34 x 104
Average = 2.55 x 104, whereas ω(2000) = 2.2 x 104 (16% difference)!
∴ Averaging over ±5% T range gives 16% error!
• 8
AME 513 
 
"
Lecture 11
Non-premixed flames I: 1D flames
Outline"
  Flat flames
  Liquid droplets
  Stretched flames
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 2
• 1
Non-premixed or diffusion flames"
  Inherently safer – no mixing of fuel and oxidant except at time/
place combustion is desired
  Slower than premixed – need to mix AND burn, not just burn
  Simplest approach to determining properties: mixed is
burned - chemical reaction rates faster than mixing rates
  No inherent propagation rate (unlike premixed flames where SL
~ [αω]1/2)
  No inherent thickness δ (unlike premixed flames where
thickness ~ α/SL) - in nonpremixed flames, determined by
equating convection time scale = δ/u = τ to diffusion time scale
δ2/α ⇒ δ ~ (ατ)1/2 where τ is a characteristic flow time scale (e.g.
d/u for a jet, where d = diameter, u = velocity, LI/u for turbulent
flow, 1/Σ for a counterflow etc.)
  Burning must occur near stoichiometric contour where reactant
fluxes are in stoichiometric proportions (otherwise surplus of
one reactant)
  Burning still must occur near highest T since ω ~ exp(-E/RT) is
very sensitive to temperature (like premixed flames)
Reaction zone
2000K
Product
Oxygen concentration Fuel
concentration Temperature concentration
300K 300K
Convection-diffusion zone Distance from

reaction zone
!δ≈ ("/#)
(ατ)1/2
1/2
• 2
Diesel engine combustion"
 Two limiting cases
 Droplet combustion - vaporization of droplets is slow, so droplets
burn as individuals
 Gas-jet flame - vaporization of droplets is so fast, there is
effectively a jet of fuel vapor rather than individual droplets
 Reality is in between, but in Diesels usually closer to the gas jet
with extras – regions of premixed combustion
Flynn, P.F, R.P. Durrett, G.L. Hunter, A.O. zur Loye, O.C. Akinyemi, J.E. Dec, C.K. Westbrook,
SAE Paper No. 1999-01-0509.
1D planar steady nonpremixed flame"

  1D flame, convection from left to right, unknowns Tf, xf
  ρu = const. (mass conservation); assume ρD & k/CP = const.
Flame temperature T = Tf
YF,0
T
Fuel (F) Yox,L
!u Temperature (T)
TF,0
Oxidizer (O)
Tox,L
Reaction zone x = xf
Fuel boundary x = 0 Oxidizer boundary x = L
2
dT k dT dYF d 2YF
Fuel side: u ! = 0; u ! D =0
dx !CP dx 2 dx dx 2
dT k d 2T dY d 2Yox
Oxidizer side: u ! 2
= 0; u ox ! D =0
dx !CP dx dx dx 2
• 3
  Fuel, oxidizer mass fractions
dYF d 2YF
u ! DF = 0; boundary conditions YF = YF,0 at x = 0, YF = 0 at x = x f
dx dx 2
dY d 2Yox
u ox ! Dox = 0; boundary conditions Yox = Yox,0 at x = L, Yox = 0 at x = x f
dx dx 2
1! e F ( f ) 1! e ox ( f )
(u/D ) x!x (u/D ) x!x
" YF = YF,0 ; Y ox = Yox,0

1! e ( F ) f 1! e ox ( f )
! u/D x (u/D ) L!x
uL ! ! x ! M Y
Define Pe = , Leox = , LeF = , x! = , S = ox ox F,0
! Dox DF L ! F M F Yox,0
PeLe x! ! x! x! ! x!
YF 1! e F ( f ) Yox 1! e ox ( f )
PeLe
" = ! ; =
YF,0 1! e!PeLeF x f Yox,0 1! e PeLeox (1! x! f )
  … but how to determine flame location xf?
  Note S is the ratio of mass of oxidizer stream to mass of fuel
stream needed to make a stoichiometric mixture of the two
  Also frequently used in analyses is the stoichiometric mixture
fraction Zst = 1/(1+S) = mass fraction of fuel stream in a
stoichiometric mixture of fuel and oxidant streams

  For reaction νFFuel + νoxOx  products, ratio of fuel to oxidizer
mass fluxes due to diffusion must be in stoichiometric ratio =
νFMF/νoxMox for (but opposite directions, hence - sign) at x = xf:
dYF "FMF dY
! DF =! ! Dox ox
dx x=x f ! " ox M ox dx x=x f +
!(u/DF ) x f ( ) ! u/D x
DFYF,0 e u (u/DF ) x f ! F M F DoxYox,0 e ox f u (u/Dox ) x f
" e = ! e
1! e ( F ) f DF ! ox M ox 1! e(u/Dox )( L!x f ) Dox
! u/D x
YF,0 ! M Yox,0
" !(u/DF ) x f
=! F F
1! e ! ox M ox 1! e u/Dox )( L!x f )
(
(
" S 1! e
(u/Dox )( L!x f )
) = ! (1! e ) !(u/DF ) x f
" S (1! e ( )
) = ! (1! e )
(uL/! )(! /Dox ) 1!x f /L !(uL/! )(! /DF )( x f /L )
" S (1! e ) = ! (1! e ) " S ! Se (

PeLeox (1! x! f ) !PeLeF x! f PeLeox 1! x! f ) !PeLeF x! f
= !1+ e
PeLeox (1! x! f ) !PeLeF x! f
" Se +e = S +1
• 4
  Not solvable for xf in closed form but look at special cases…
  Special case #1: weak convection (Pe  0, exp(Pe) ≈ 1 + Pe,
throw out terms of order Pe2)
PeLeox (1! x! f ) !PeLeF x! f
Se +e ( )
= S +1 " S 1+ PeLeox (1! x! f ) +1! PeLeF x! f # S +1
!1 !1
$ LeF ' $ ! M Y Le '
SPeLeox (1! x! f ) # PeLeF x! f " x! f # &1+ ) " x f = L &&1+ F F ox,0 F ))
% SLeox ( % ! ox M ox YF,0 Leox (
  Special case 2: LeF = Leox= 1
Pe 1! x!
Se ( f ) + e f = S +1 " ( Se Pe +1) e f = S +1
!Pe!x !Pe!x
1+ S
!Pe!x f
"e =
1+ Se Pe
  Special case 3: Pe  ∞
PeLeox (1! x! f ) !PeLeF x! f 1 $ 1+ S '
Se +e = S +1 " 1! x! f # ln & )
PeLeox % S (

  Energy equation:
dT k d 2T
Fuel side: u ! = 0; BCs: T = TF,0 at x = 0, T = Tf at x = x f
dx !CP dx 2
dT k d 2T
Oxidizer side: u ! = 0; BCs: T = Tox,0 at x = L, T = Tf at x = x f
dx !CP dx 2
  Solutions
1! e( )
u/! x
1! e Pe!x
Fuel side: T (x) = TF,0 + (Tf ! TF,0 ) (u/! ) x f
= TF,0 + (Tf ! TF,0 ) Pe!x
1! e 1! e f
(u/! )( x!x f ) Pe x! ! x!
1! e 1! e ( f )
Oxidizer side: T = Tf ! (Tf ! Tox,0 ) (u/! )( L!x f )
= Tf ! (Tf ! Tox,0 ) Pe 1! x!
1! e 1! e ( f )
• 5
  Matching: heat release = (fuel flux to reaction zone) x (fuel
heating value) = conductive heat flux away from reaction
zone on both sides
dYF dT dT
!QR ! DF =k !k "
dx x=x f ! dx x=x f ! dx x=x f +
k (Tf ! TF,0 ) u (u/! ) x f k (Tf ! Tox,0 ) e (

!(u/DF ) x f ! u/! ) x f
QR ! DFYF,0 e u (ux/DF ) u (u/! ) x f
!(u/DF ) x f
e =! e ! e
1! e( ) f ! 1! e ( f )
u/! x (u/! ) L!x
1! e DF !
!QRYF,0 !CP (Tf ! TF,0 ) !CP (Tf ! Tox,0 )
" !(u/DF ) x f
= !
1! e ( ) f 1! e ( f )
! u/! x (u/! ) L!x
1! e
QRYF,0 CP Tf ! TF,0 Tf ! Tox,0
" !(uL/! )(! /DF )( x f /L )
= !(uL/! )( x f /L )
! ! (!uL/! )( x f /L )
1! e( )e
uL/
1! e 1! e
Q Y CP Tf ! TF,0 T !T
" R F,0!PeLeF x! f
= !Pe!x f
! f Pe ox,0 !Pe!x
1! e 1! e 1! e e f

  Can solve explicitly for Tf if you’re desperate
QRYF,0 CP Tf ! TF,0 T !T Tf TF,0 Tf Tox,0
!PeLeF x! f
= !Pe!x f
! f Pe ox,0 !Pe!x f
= !Pe!x f
! !Pe!x f
! Pe !Pe!x f
+ !Pe!x
1! e 1! e 1! e e 1! e 1! e 1! e e 1! e Pee f
QRYF,0 CP TF,0 Tox,0
!PeLeF x! f
+ !Pe!x f
! !Pe!x
Tf = 1! e 1! e 1! e Pee f
1 1
!Pe!x
! !Pe!x
1! e f 1! e Pee f
1 T!F,0 T!ox,0
!PeLeF x! f
+ !
1! e Pee f ; T! " CPT
!Pe!x f !Pe!x
or T!f = 1! e 1! e
1 1 YF,0QR
!Pe!x
! !Pe!x
1! e f 1! e Pee f
• 6
  Special case 1: Pe  0
QRYF,0 CP Tf ! TF,0 Tf ! Tox,0 QRYF,0 CP Tf ! TF,0 Tf ! Tox,0
!PeLeF x! f
= ! " = !
1! e 1! e
!Pe!x f
1! e Pee
!Pe!x f
1! (1! PeLeF x! f ) 1! (1! Pe!x f ) 1! (1+ Pe) (1! Pe!x f )
QRYF,0 CP Tf ! TF,0 T ! Tox,0 QY x!
" = ! f " R F,0 = (Tf ! TF,0 ) + (Tf ! Tox,0 ) f
PeLeF x! f Pe!x f Pe (!1+ x! f ) CP LeF 1! x! f
!1
% LeF ( QY SLeox
Recall that as Pe # 0, x! f $ '1+ * " R F,0 = (Tf ! TF,0 ) + (Tf ! Tox,0 )
& SLeox ) CP LeF LeF
QR LeF (Tf ! TF,0 ) Leox (Tf ! Tox,0 ) ! ox M ox
" = +
CP YF,0 Yox,0 !FMF
LeF % QRYF,0 ( SLeox
or Tf = ' + TF,0 * + Tox,0
SLeox + LeF & CP LeF ) SLeox + LeF
  Dependence on Pe disappears (as expected)
  Behavior same on fuel and oxidant side except for stoichiometric
scaling factor νoxMox/νFMF (also expected)
  Decreasing Le has same effect as increasing reactant
concentration (!) – completely unlike premixed flame where planar
steady adiabatic flame temperature is independent of Le

  Special case #2: LeF = Leox = 1
QRYF,0 CP Tf ! TF,0 T !T !Pe!x 1+ S
!Pe!x f
= !Pe!x f
! f Pe ox,0
!Pe!x f
,e f =
1! e 1! e 1! e e 1+ Se Pe
1+ S
QRYF,0 !Pe!x 1!
1! e f 1+ Se Pe
" = (Tf ! TF,0 ) ! (Tf ! Tox,0 ) Pe !Pe!x f
= (Tf ! TF,0 ) ! (Tf ! Tox,0 )
CP 1! e e 1+ S
1! e Pe
1+ Se Pe
QY 1+ Se Pe !1! S
" R F,0 = (Tf ! TF,0 ) ! (Tf ! Tox,0 ) = (Tf ! TF,0 ) + (Tf ! Tox,0 ) S
CP 1+ Se Pe ! e Pe ! Se Pe
QRYF,0
+ (TF,0 + STox,0 )
Q T ! T T ! T ! M CP
" R= f F,0
+ f ox,0 ox ox or Tf =
CP YF,0 Yox,0 ! F M F 1+ S
  When LeF = Leox = 1, convection (contained in Pe = uL/α)

does not affect Tf at all!
• 7
  Super special case 2a: LeF = Leox = 1 AND TF,0 = Tox,0 = T∞:
QR Tf " T# Tf " T# ! ox M ox YF,0 QR
! = + ! Tf = +T
CP YF,0 Yox,0 ! F M F ! ox M ox YF,0 CP #
1+
! F M F Yox,0
To interpret the YF,0/(…) term, consider stoichiometric mixture
of fuel and oxidizer streams:
YF,0 kg fuel, 1 kg total mixture from fuel side
! mass of oxidant $ ! M
Need mass of oxidant = YF,0 # & = YF,0 ox ox kg oxidizer
" mass of fuel %stoichiometric !FMF
! ox M ox
YF,0
mass of oxidant !FMF
Total mass of oxidizer stream needed = = kg of oxidizer stream
Yox,0 Yox,0
mass of fuel YF,0 YF,0
Mass fraction of fuel in this total mixture = f = = =
total mass ! ox M ox YF,0 ! ox M ox
YF,0 1+
!FMF Yox,0 ! F M F
1+
Yox,0
QR
' Tf = f + T( - adiabatic flame temperature of stoichiometric mixture of fuel stream + oxidant stream
CP

  Special case 3: Pe  ∞
!PeLeF x! f
= !Pe!x f
! =
Pe !Pe!x f
" ! Pe(1! x! f )
1! e 1! e 1! e e 1! 0 1! 0 1! e
Le
1 & 1+ S ) & 1+ S ) ox
Recall as Pe # $ :1! x! f % ln ( + " Pe (1! x! f ) = ln ( +
PeLeox ' S * ' S *
QRYF,0 Tf ! Tox,0
" = (Tf ! TF,0 ) ! Leox
;
CP 1! ((1+ S ) S )
If Leox = 1,
QRYF,0 Q
= (Tf ! TF,0 ) + S (Tf ! Tox,0 ) " R =
(Tf ! TF,0 ) + (Tf ! Tox,0 ) ! ox M ox
CP CP YF,0 Yox,0 !FMF
  As Pe (convection effects) increase, effects of LeF & Leox on

flame temperatures decrease
• 8
  Much of our understanding of nonpremixed flames is
contaminated by the facts that
  Leox (O2 in air) ≈ 1
  We live in a concentrated fuel / diluted oxidizer world (S >> 1);
we already showed that for Leox ≈ 1, at high Pe, flame
temperature is unaffected by Pe or LeF
  Consider low Pe: for CH4/air
! M Y (2)(32) 1
S = ox ox F,0 = = 17.2 >> 1
! F M F Yox,0 (1)(16) 0.233
For Pe ! 0, S >> 1, Leox " 1:
LeF # QRYF,0 & SLeox 1 #Q Y &
Tf = % + TF,0 ( + Tox,0 " % R F,0 + TF,0 LeF ( + Tox,0
SLeox + LeF $ CP LeF ' SLeox + LeF S $ CP '
QRYF,0 ( 5 )10 J / kg) (1)
7
" " 35, 700K >> TF,0

CP 1400J / kgK
* LeF doesn't affect Tf significantly
  Similar trend for Pe  -∞ (homework problem…)
Basic structure of nonpremixed flame"

  The inevitable Excel spreadsheet … (Pe = 3, S = 1 shown)
1.2
YF/Yfo Yox/Yox,0
1 Tf/DT (fuel side) Tf/DT (ox side)
0.8
0.6
0.4
0.2
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
• 9
Droplet combustion"
  Heat from flame conducted to fuel surface, vaporizes fuel,
fuel convects/diffuses to flame front, O2 diffuses to flame
front from outside, burning occurs at stoich. location
  As fuel burns, droplet diameter dd(t) decreases until dd = 0
or droplet may extinguish before reaching dd = 0
  Experiments typically show dd(0)2 - dd(t)2 ≈ Kt
Tf
[Oxygen]
df = 2rf
[Fuel]
Temperature
dd = 2rd Td
T!
Droplet
surface
Flame front
Droplet combustion"
Marchese et al. (1999), space experiments, heptane in O2-He

• 10
Droplet combustion"
  Analysis similar to 1D planar flame with specified mass flux
but need to use 1D steady spherical version of convection-
diffusion conservation equations for Yf, Yox and T
!! ! ! 1 d
Mass conservation: + " # ( ! u ) = 0 $ 2 ( r 2 ! u) = 0
!t r dr
$ m! = 4" r 2 !u = constant
% !h ! ! ( ! ! ! ! ! !
( ) (
Energy conservation: ! ' + u # "h * + " # k "T = q'''
& !t )
) ! $ !CP u # "T + k " # "T = 0
dT k d , 2 dT /
$ ! CP u + .r 1=0
dr r 2 dr - dr 0
% !Y ! ! ( ! ! ! ! ! !
Species conservation: ! ' i + u # "Yi * + " # ! D"Yi = M i#! i $ !u # "Yi + " # ! D"Yi = 0
( ) ( ) ( )
& !t )
dYi ! D d , 2 dYi /
$ !u + .r 1=0
dr r 2 dr - dr 0
Droplet combustion"
  Unknowns
  Flame temperature Tf and flame location rf (as with flat flame)
  Fuel mass flux mdot = ρuA = ρdud(4πrd2) from droplet surface
(expressed in Pe in the following analysis) (new)
»  Note that mdot must be constant, but the fuel mass flow is not; the
fuel disappears by r = rf, but the total mass flow (i.e. of inert and
products) must be constant out to r = ∞
  Fuel concentration at droplet surface YF,d or stoichiometric
parameter S (new)
  2 more unknowns, so need 2 more equations (total of 4)
»  Reactant diffusive fluxes into flame sheet in stoichiometric
proportions (as with flat flame)
»  Fuel enthalpy flux into flame sheet = thermal enthalpy flux out (by
heat conduction) (as with flat flame)
»  Energy balance at droplet surface (new)
»  Mass balance at droplet surface (new)
• 11
Droplet combustion"
  Fuel side (rd ≤ r ≤ rf)
dYF ! DF d " 2 dYF %
' = 0, m! = 4! r "u = constant
2
!u ! 2 $r
dr r dr # dr &
dY d " dY % " P
mC r
( PeLeF F = $ r! 2 F ' where Pe ) , r! )
d!r d!r # d!r & 4! krd rd
dYF dYF d!r
( PeLeFYF + C1 = r! 2 ( =
d!r PeLeFYF + C1 r! 2
ln ( PeLeFYF + C1 ) 1
( = ! + C2 ( YF = C1' + C2' e!PeLeF /r!
PeLeF r!
Boundary Conditions: r = rd (!r = 1),YF = YF,d and r = rf (!r = r!f ),YF = 0
!PeLeF /r!f
( YF (!r ) =
(
YF,d e ! e!PeLeF /r! ) ; dY
F PeLeF YF,d e
=!
!PeLeF /r!
!PeLeF /r!f !
e ! e!PeLeF d!r r! 2 e !PeLe /
F fr
! e!PeLeF
dYF Y e!PeLeF YF,d dY PeLeF YF,d
= !PeLeF !PeLeF,d
F / r!f
= !PeLeF PeLeF (1!1/ r!f )
; F = !
d!r r!=1 e ! e!PeLeF e !1 d!r r!=!rf r!f2 e!PeLeF (1!1/rf ) !1
  Note similarities to planar case, but now due to r2 factors in conservation
equations we have exp(-Pe/r) terms instead of exp(-Pe*x) terms
Droplet combustion"
  Oxygen side (r ≥ rf)
Yox = C1' + C2' e!PeLeox /r!
Boundary Conditions: r = rf (!r = r!f ),Yox = 0 and r! " #,Yox = Yox,#
!PeLe /r!
e!PeLeox /r! ! e ox f
dY PeLeox e!PeLeox /r!
$ Yox (!r ) = Yox,# !PeLeox /r!f
; ox = Yox,# !
1! e d!r r! 2 1! e!PeLeox /rf
dYox PeLeox Yox,# dY
= PeLeox /r!f
; F =0
d!r r! =!rf r!f2
e !1 d!r r!=#
!PeLeox /r!f
Yox (!r ) 1! PeLeox / r! ! e & PeLeox )1
Note as r!f " #: % !PeLeox /r!f
= 1! ( +
Yox,# 1! e ' 1! e!PeLeox /r!f * r!
!PeLeox /r!f Yox (!r ) r!
Generally Pe = O(1), Leox = O(1), r!f >> 1 $ 1! e % 1 / r!f $ % 1! f
Yox,# r!
d & 2 dYox )
Same form as convection-free solution to (r +=0
dr ' dr *
$ At large r!, convection term u ~ 1 / r! 2 " 0 faster than diffusion term
• 12
Droplet combustion"
  Temperature (rd ≤ r ≤ rf)
dT k d " 2 dT % dT d " 2 dT %
' = 0, m! = 4" r !u ( Pe = $ r!
2
! CP u ! 2 $r '
dr r dr # dr & d!r d!r # d!r &
dT
( PeT + C1 = r 2 ( T = C1' + C2' e!Pe/r ; BCs: r! = 1,T = Td and r! = r!f ,T = T f
dr
!Pe/r!f
( T (!r ) =
(T f (
! Td ) e!Pe/r! ! T f e!Pe ! Td e ) ; dT = Pe (T ! T ) e f d
!Pe/r!
!Pe/r!f !Pe/r!f
e !e !Pe
d!r r! 2
e! e!Pe
dT
= Pe
(Tf ! Td ) e!Pe = Pe
T !T
f d dT
;
Pe (T f ! Td )
= 2
!Pe/r!f !
dr r! =1 e !e !Pe
e
Pe(1!1/r!f )
!1 dr r! =!rf r!f 1! e!Pe(1!1/rf )
  Temperature (r ≥ rf)
dT
PeT + C1 = r! 2 ! T = C1' + C2' e"Pe/r! ; BCs: r! # $,T = T$ and r! = r!f ,T = T f
d!r
"Pe/r!f
! T (!r ) =
(T " T e ) " (T " T ) e
f $ f $
"Pe/r!
;
dT Pe (T f " T$ ) e
=" 2
"Pe/r!
"Pe/r!f "Pe/r!f
1" e d!r r! 1" e
"Pe/r!f
dT Pe (T f " T$ ) e Pe (T f " T$ ) dT
=" 2 "Pe/r!f
= " 2 Pe/r!f ; =0
d!r r! =!rf r!f 1" e r!f e "1 d!r r!=$
Droplet combustion"
  As with flat flame, stoichiometric balance at flame sheet is
dY ! M dY
! DF F = ! F F " Dox ox
d!r r!=!rf ! ! ox M ox d!r r!=!rf +
PeLeF YF,d ! M PeLeox Yox,"
! DF = ! F F " Dox
!rf2 e!PeLeF (1!1/r!f ) !1 ! ox M ox !
rf2
e
PeLeox /r!f
!1
1 ! F M FYox," 1 1 1
!PeLeF (1!1/r!f )
=! PeLeox /r!f
= ! PeLeox /r!f
e !1 ! ox M oxYF,d e !1 Se !1
PeLeF (1/r!f !1) PeLeox /r!f
#e + Se = 1+ S
Looks very similar to flat-flame case… but again note 1/r terms vs.
x in flat-flame case, plus Pe and S are unknowns (since mass flux
and YF,d are unknown) (and of course flame location rf is unknown)
  Special case: LeF = Leox = 1
!Pe/r!f e!Pe + S
e = (Eq. 1)
1+ S
• 13
Droplet combustion"
  As with flat flame, energy balance at flame sheet is
dYF dT dT
!QR ! DF =k !k "
d!r d!r r! =!rf ! d!r r! =!rf +
PeLeF YF,d Pe (Tf ! Td ) Pe (Tf ! T# )

!QR ! DF ! =k 2 ! +k 2 !
r!f2 e!PeLeF (1!1/rf ) !1 r!f 1! e!Pe(1!1/rf ) r!f e Pe/rf !1
!QR ! DF
k YF,d
=k
(Tf ! Td ) + k (Tf ! T# )
!PeLeF (1!1/r!f ) !Pe(1!1/r!f ) Pe/r!
!CP DF e !1 1! e e f !1
YF,d QR CP
=
(T f !T d ) +
(T f ! T# )
!PeLeF (1!1/r!f ) !Pe(1!1/r!f ) Pe/r!f
1! e 1! e e !1
Again looks similar to flat-flame case…
  Special case: LeF = 1
!Pe/r!
YF,d QR e f ! e!Pe
= (Tf ! Td ) + (Tf ! T" ) !Pe/r!
(Eq. 2)
CP 1! e f
Droplet combustion"
  New constraint #1 - conductive heat flux to droplet surface
= enthalpy needed to vaporize the mass flux of fuel
dT dT " P Lv
mC L
k ( 4! rd2 ) " v!
= mL = = Pe v
dr r! =1 d!r r! =1 4! krd CP CP
T "T Lv Pe 1"1/r! CP (Tf " Td )
! Pe f
Pe(1"1/r!f )
d
= Pe ! e ( f ) = 1+ (Eq. 3)
e "1 CP Lv
  New constraint #2 - mass balance at droplet surface: mass
flow from droplet into gas (fuel only) = rate of fuel
convected into gas + rate of fuel diffused into gas
dYF ! P
mC k dY
m! = !! DF A ! F,d "
+ mY (1!YF,d ) = ! F
dr r=rd 4! rd k "CP DF d!r r! =1
Y
F,d PeLeF (1!1/r!f ) YF,d
" PeLeF (1!YF,d ) = PeLeF PeLeF (1!1/r!f )
"e !1 =
e !1 1!YF,d
!PeLeF (1!1/r!f )
" YF,d = 1! e (Eq. 4)
• 14
Droplet combustion"
  4 equations for 4 unknowns:
e"Pe + S "Pe
YF,d QR "e
Eq. 1 + Eq. 2 ! = (Tf " Td ) + (Tf " T# ) 1+ S"Pe
CP e +S
1"
1+ S
YF,d QR $Q $ S ' '
! = (Tf " Td ) + (Tf " T# ) S ! YF,d && R " && )) (Tf " T# ) )) = Tf " Td (Eq. 5)
CP % CP % YF,d ( (
S ! M
1 ox ox F,d Y ! M
Note = = ox ox - all known quantities!
YF,d YF,d ! F M FYox,# ! F M FYox,#
e"Pe + S CP (Tf " Td ) CP (Tf " Td ) S
Eq. 1 + Eq. 3 ! e Pe
1+ S
= 1+
Lv
!
Lv
=
1+ S
(ePe +1) (Eq. 6)
$Y ' 1+ S 1+ (YF,d S )
Eq. 1 + Eq. 4 ! YF,d = & F,d ) S = 1" e"Pe "Pe ! = e Pe (Eq. 7)
% S ( e +S 1" S (YF,d S )
CP (Tf " Td ) S $ 1+ (YF,d S ) ' 1
Eq. 6 + Eq. 7 ! = && +1)) ! YF,d = (Eq. 8)
Lv 1+ S % 1" S (YF,d S ) ( 1+ Lv CP (Tf " Td )
Droplet combustion"
CP (Tf " Td ) #Q # S & &
Eq. 5 + Eq. 8 ! % R " %% (( (Tf " T) ) (( = Tf " Td
CP (Tf " Td ) + Lv %$ CP $ YF,d ' '
(QR " Lv ) CP + ( S YF,d ) (T) " Td ) (QR " Lv ) CP + Td + ( S YF,d ) T)
! Tf " Td = or Tf = (Eq. 9)
1+ S YF,d 1+ S YF,d
Finally have one unknown isolated!
QRYF,0 CP + (TF,0 + STox,0 ) QR CP + TF,0 / YF,0 + ( S / YF,0 ) Tox,0
Compare to Le = 1 planar flame Tf = =
1+ S 1+ ( S / YF,0 )
1
Eq. 8 + Eq. 9 ! YF,d =
Lv 1+ ( S YF,d )
1+
CP (QR " Lv ) CP + ( S YF,d ) (T) " Td )
! YF,d =
(QR " Lv ) + ( S YF,d ) CP (T) " Td ) (Eq. 10)
(QR + Lv (S YF,d )) + (S YF,d ) CP (T) " Td )
QR " Lv
1+
Reality check: YF,d =
( S YF,d ) CP (T) " Td ) < 1 since QR " Lv < QR + Lv ( S YF,d ) - OK
QR + Lv ( S YF,d )
1+
( YF,d ) CP (T) " Td )
S
• 15
Droplet combustion"
  So finally we can calculate the mass burning rate (Pe) in
terms of known properties
# &
% (
# 1+ (YF,d S ) & % 1+ (YF,d S ) (
Eq. 7 + Eq. 10 ! Pe = ln %% (( = ln %
$ 1"Y F,d ' % 1" ( R v ) ( F,d ) P ( ) d ) ((
Q " L + S Y C T " T
% (Q + L ( S Y ) ) + ( S Y ) C (T " T ) (
$ R v F,d F,d P ) d '
# ! M &
QR %Yox,) F F ( + CP (T) " Td )
QR (YF,d S ) + CP (T) " Td ) $ ! ox M ox '
! Pe = ln (1+ B); B * = (Eq. 11)
Lv Lv
! P
mC dr
Pe * = ln (1+ B), m! = ! d ud Ad = ! d d 4" rd2
4! krd dt
drd CP dr k k
! !d 4" rd2 = ln (1+ B) ! rd d = ln (1+ B) ! rd drd = ln (1+ B) dt
dt 4" krd dt ! d CP ! d CP
rd2 dd2 k
= = ln (1+ B) t + C; initial condition dd = dd (0) at t = 0
2 8 ! d CP
8k
! dd2 (0) " dd2 (t) = ln (1+ B) t FINALLY!
! d CP
Droplet combustion"
  Comments
  (8k/ρdCP)ln(1+B) is called the burning rate constant – units length2/
time
  k/ρdCP is NOT the thermal diffusivity because ρd is the droplet
density, not gas density!
  B is called the Transfer Number – ratio of enthalpy generated by
combustion to enthalpy need to vaporize fuel; typical values for
hydrocarbons ≈ 10, much lower for methanol (≈ 3)
  Enthalpy release (QR) appears only inside a ln( ), thus changing Tf
hardly affects burning rate at all - why? The more rapidly fuel is
vaporized, the more rapidly the fuel vapor blows out, thus the harder
it is for heat to be conducted back to the fuel surface
  In fact since you can’t change k, ρd or CP significantly in fuel/air
combustion, only the droplet diameter affects burning time
significantly (time ~ 1/dd2)
  Flame temperature almost same as plane flame with adjusted
enthalpy release QR – Lv vs. QR
  Can also use this formula for mdot even if no combustion (just
evaporation of a cold droplet in a hot atmosphere) – set QR = 0
  Nothing in expression for Pe, Tf, rf or YF,d depend on pressure
• 16
Droplet combustion"
  What about flame radius rf?
e"Pe + S Pe # # 1" S (Y S ) &&
"Pe/r!f
Eq. 1 + Eq. 7 ! e = ! r!f = = ln(1+ B) ln %% (1+ S ) %% F,d
+ S ((((
1+ S # 1+ S & $ 1+ (YF,d S ) ''
ln % "Pe ( $
$e +S'
rf d f ln(1+ B) ln(1+ B)
! r!f = = = =
rd dd ln (1+ (YF,d S )) # ! M &
ln %1+Yox,) F F (
$ ! ox M ox '
  df/dd is constant and doesn’t even depend on transport

properties, just thermodynamic properties!
  As expected, as Yox,∞ decreases (more diluted oxidizer),
flame moves farther out (less fuel flux)
  Also fuel mass fraction at droplet surface YF,d
!FMF
B "Yox,#
1+ (YF,d S ) B " (YF,d S ) ! ox M ox
Eq. 7 + Eq. 11 ! = e ln(1+B) ! YF,d = =
1" S (YF,d S ) 1+ B 1+ B
  Since usually YF,d/S << 1 (see example), YF,d ≈ B/(1+B)
which is only slightly less than 1
Droplet combustion"
  Comment on T and Yox profiles for r  ∞
#Pe/r!f #Pe/r!f
As r ! " : T (!r ) =
(T # T e ) # (T # T ) e
f " f "
#Pe/r!
!
(T # T e ) # (T # T ) (1# Pe / r!)
f " f "
#Pe/r!f #Pe/r!f
1# e 1# e
T # T Pe 1
= T" + f #Pe/"r!f ~
1# e r! r!
T f # T" Pe r!
Also since typically r!f >> 1, = T (!r ) ! T" + = T" + (T f # T" ) f
1# (1# Pe / r!f ) r! r!
$ 1 PeLeox ' $ r!f '
Similarly Yox (!r ) = Yox," &1# ) and for r!f >> 1,Yox (!r ) ! Yox," &1# )
% 1# e#PeLeox /r!f r! ( % r! (
  This is identical to pure diffusion in spherical geometry:

d ! 2 dT $ C d ! 2 dYox $ C
#r & = 0 ' T (r) = C1 + 2 ; #r & = 0 ' Yox (r) = C1 + 2
dr " dr % r dr " dr % r
rf
BCs T = Tf at r = rf ,T = T( at r = ( ' T (r) = T( + (Tf ) T( )
r
! rf $
BCs Yox = 0 at r = rf ,Yox = Yox,( at r = ( ' Yox (r) = Yox,( #1) &
" r%
so diffusion dominates convection at large r
• 17
Droplet combustion"
  Example for typical fuel (heptane, C7H16) in air
8k Q (Y S ) + CP (T" ! Td ) YF,d ! M 1(100)
dd2 (0) ! dd2 (t) = ln (1+ B) t; B = R F,d ; = Yox," F F = 0.233 = 0.0662
! d CP Lv S ! ox M ox 11(32)
B=
( 4.46 #10 7
J / kg) ( 0.0622 ) + (1400J / kgK ) ( 298K ! 371.5K )
= 8.40
3.18 #10 5 J / kg
8k 8 ( 0.026W / mK )
Burning rate constant ln (1+ B) = ln (1+ 8.40 )
! d CP ( 680kg / m 3 ) (1400J / kgK )
= 4.9 #10 !7 m 2 / s = 0.49mm 2 / s
df ln(1+ B) ln(1+ 8.40)
Flame diameter = = = 35.0
dd ln (1+ (YF,d S )) ln (1+ 0.0662 )
(QR ! Lv ) CP + Td + ( S YF,d ) T"
Flame temperature T f =
1+ S YF,d
=
( 4.46 #10 7
! 3.18 #10 J / kg) (1400J / kgK ) + 371.5K + (1 / 0.0662 ) (298K )
5
= 2266K
1+1 / 0.0662
B ! (YF,d S ) 8.40 ! 0.0662
Fuel mass fraction at droplet surface YF,d = = = 0.887
1+ B 8.40 +1
Droplet combustion"
  What if Le ≠ 1?
Eq. 1: e
PeLeF (1/r!f !1)
+ Se
PeLeox /r!f
= 1+ S; Eq. 2:
YF,d QR CP
=
(Tf ! Td ) + (Tf ! T" )
!PeLeF (1!1/r!f ) !Pe(1!1/r!f ) Pe/r!
1! e 1! e e f !1
Pe 1!1/r! CP (Tf ! Td )
Eq. 3: e ( f ) = 1+
!PeLeF (1!1/r!f )
; Eq. 4: YF,d = 1! e
Lv
YF,d 1! e PeLeF (1/r!f !1) YF,d Y 1
Eq. 1 # YF,d = PeLeox /r!f
or PeLeF (1/r!f !1)
= F,d PeLeox /r!f (Eq. A)
S e !1 1! e S e !1
Y 1! e PeLeF (1/r!f !1) !PeLeF (1!1/r!f ) Pe/r! 1/Leox
Eq. A + Eq. 4 # F,d PeLeox /r!f = 1! e # e f = (1+ (YF,d S )) (Eq. B)
S e !1
Pe 1!1/r!
Eq. 3 # Tf ! Td = ( Lv CP ) e ( f ) !1 ( ) (Eq. C)
Eq. 2 + Eq. A + Eq. C #
(QR CP ) (YF,d S )
=
( Lv (Pe 1!1/r!
CP ) e ( f ) !1
!Pe(1!1/r!f )
) + (L v ( Pe 1!1/r!
CP ) e ( f ) !1 + Td ! T"
Pe/r!f
)
1+ (YF,d S ) !1 1! e e !1
• 18
Droplet combustion"
!
QR
=
(
Pe 1"1/r!
e ( f ) "1
! +
Pe 1"1/r!
) (
e ( f ) "1 + (CP Lv ) (Td " T# )
Pe/r!
)
Lv 1" e"Pe(1"1/rf ) e f "1
Pe "Pe/r!f Pe "Pe/r!f
=
(e e "1) + (e e )
"1 + (CP Lv ) (Td " T# )
"Pe Pe/r!f Pe/r!f
1" e e e "1
"Pe/r!f Pe/r!f "Pe/r!f
!
QR
=
e Pee ( e ) (
"1 + e Pee )
"1 + (CP Lv ) (Td " T# )
=
e Pe "1+ (CP Lv ) (Td " T# )
Pe/r!f Pe/r!f
Lv e "1 e "1
QR
! e Pe =
Lv (
(1+ (YF,d S ))
1/Leox
) +1" (C P Lv ) (Td " T# )
! Pe = ln (1+ B'); B' $

(
QR (1+ (YF,d S ))
1/Leox
)
"1 + CP (T# " Td )
Lv
QR (YF,d SLeox ) + CP (T# " Td )
Note for (YF,d S ) << 1, B' %
Lv
Droplet combustion"
!1/Leox Leox ln (1+ B')
r!f = Pe ln (1+ (YF,d S )) " r!f =
ln (1+ (YF,d S ))
# &
(1+ B')
(
Pe 1!1/r! !Pe/r!
)
Tf ! Td = ( Lv CP ) e ( f ) !1 = ( Lv CP ) e Pee f !1 = ( Lv CP ) % (
% 1+ Y S 1/Leox (
$( ( F,d ) )
!1 (
'
)
QR ! Lv ) 1/Leox , ) 1/Leox , QR ! Lv
CP +*
(1+ (YF,d S )) !1.- + T/ + +*(1+ (YF,d S )) !1.-Td C + Td + T/ (S YF,d ) Leox
P
Tf = 1/Le
0
(1+ (YF,d S )) ox 1+ ( S YF,d ) Leox
LeF /Leox
YF,d = 1! e
!PeLeF (1!1/r!f )
= 1! e!PeLeF e
!PeLeF /r!f
= 1!
(1+ (Y F,d S ))
LeF
(1+ B')
  Same as previous results when Leox = 1
  LeF doesn’t affect burning rate (Pe), rf or Tf at all, only YF,d!
  For decreasing Leox
  B’ (thus Pe) increases, but not much because of ln(1+B’) term
  rf decreases because of Leox term; increasing B’ inside ln( )
term has less effect
  Tf increases because of (1/Le) exponent
• 19
Droplet combustion"
  The d2-law assumes no buoyant or forced convection, but
in most applications there is likely to be significant flow;
one relation for the effect of flow on burning rate is
2 2 4 Nu k 0.555Re1/2
d Pr
1/ 3
[d(0)] " [ d(t)] = Kt;K = ln(1+ B); Nu = 2 + 1/ 2
# l CP
[
1+ 1.232 (Re d Pr 4 / 3 ) ]
Red = Droplet Reynolds number = ud(t)/ν
Nu = Nusselt number based on droplet diameter
! u = droplet velocity relative to gas
Pr = Prandtl number = ν/α
ν = kinematic viscosity
α = thermal diffusivity = k/ρCp
  Reduces to the previous result for u = 0 (thus Re = 0)
1D stretched flame"
  Simple counterflow, fuel at x = +∞, oxidant at x = -∞, u = -Σx,
again assume ρD & k/CP = constant
Fuel + inert
  Stagnation plane (u = 0) at x = 0, but
flame may be on either side of x = 0
depending on S, LeF & Leox
  Somewhat similar to plane
unstretched case but this
configuration is easy to
obtain experimentally x=0
  Model for local behavior of
flame in turbulent flow field
(“laminar flamelet” model)
Oxidant + inert
• 20
1D stretched flame"
  Species conservation:
dYF d 2Y dY d 2Y
!u ! ! D 2F = 0 " -#x F ! ! Le 2F = 0;
dx dx dx dx
x dYF 1 d 2YF
Let x! =
2! / #
" x! +
d!x 2LeF d!x 2
= 0 " YF ( x! ) = C1erf LeF x! + C2 ( )
2 a !t 2
Recall erf (a) =
! 0
$ e dt
Fuel side boundary conditions: x! = x! f ,YF = 0; x! = %,YF = YF,%
" YF ( x! ) =
( (
YF,% erf )
LeF x! ! erf ( LeF x! f )) ; dY F
=
2 LeF YF,%e
!LeF x! 2f
1! erf ( LeF x! f ) d!x x! = x! f ! 1! erf ( LeF x! f )

Oxidizer side boundary conditions: x! = x! f ,Yox = 0; x! = !%,Yox = Yox,!%
" Yox ( x! ) = !
( (
Yox,% erf Leox x! ! erf ) ( Leox x! f )) ; dY ox
=!
2 Leox Yox,%e
!Leox x! 2f
1+ erf ( Leox x! f ) d!x x! = x! f ! 1+ erf ( Leox x! f )
1D stretched flame"
  Energy equation:
dT d 2T dT d 2T
!uCP ! k 2 = 0 " -#x ! " 2 = 0;
dx dx dx dx
x dT 1 d 2T
Again let x! = " x! + = 0 " x! = C1erf ( x! ) + C2
2" / # d!x 2 d!x 2
Fuel side boundary conditions: x! = x! f ,T = Tf ; x! = $,T = TF,$
! x! 2f
(T f ! TF,$ ) erf ( x! ) + TF,$erf ( x! f ) ! Tf dT 2 (Tf ! TF,$ ) e
" T ( x! ) = ; =
erf ( x! f ) !1 d!x x! = x! f # erf ( x! f ) !1
Oxidizer side boundary conditions: x! = x! f ,T = Tf ; x! = !$,T = Tox,!$
! x! 2f
(T f ! Tox,!$ ) erf ( x! ) + Tox,!$erf ( x! f ) + Tf dT 2 (Tf ! Tox,!$ ) e
" T ( x! ) = ; =
erf ( x! f ) +1 d!x x! = x! f # erf ( x! f ) +1
• 21
1D stretched flame"
 Stoichiometric balance condition at flame sheet is the same
as always
dYF "FMF dY
! DF =! ! Dox ox
d!x x! = x! f ! " ox M ox d!x x! = x! f +
!LeF x! 2f !Le x! 2
2 LeF YF,!e "FMF 2 Leox Yox,!e ox f
! DF =+ ! Dox
# 1! erf ( LeF x! f ) " ox M ox # 1+ erf Leox x! f ( )
!LeF x! 2f !Leox x! 2f
DF LeF YF,!e " M Y Yox,!e
! = F F ox,!
Dox Leox 1! erf LeF x! f (
" ox M oxYF,! 1+ erf Leox x! f ) ( )
!S
Leox !( LeF !Leox ) x! 2f 1! erf
e =
( LeF x! f )
LeF 1+ erf ( Leox x! )
f
1! erf ( x! f ) ! 1! S $
If LeF = Leox = 1 then S = ! x! f = erf !1 # &
1+ erf ( x! f ) " 1+ S %
1D stretched flame"
 Energy balance condition is the same as always
dYF dT dT
!QR ! DF =k !k
dx x=x f ! dx x=x f ! dx x=x f +
!LeF x! 2f ! x! 2 ! x! 2f
2 (Tf ! TF,# ) e 2 (Tf ! Tox,!# ) e
f
2 LeF YF,#e
" !QR ! DF =k !k
" 1! erf ( LeF x! f ) ! erf ( x! f ) !1 ! erf ( x! f ) +1
!LeF x! 2f ! x! 2f ! x! 2f
"
YF,#QR !CP DF
LeF
e
=
(T f ! TF,# ) e
+
(T f ! Tox,!# ) e
CP k 1! erf ( LeF x! f ) 1! erf ( x! f ) erf ( x! f ) +1
(1!LeF ) x! 2f Tf ! TF,# T ! Tox,!#
YF,#QR 1 e
" = + f
CP LeF 1! erf ( LeF x! f ) 1! erf ( x! f ) 1+ erf ( x! f )
1! S
YF,#QR 1! erf ( x! f ) 1!
If LeF = Leox = 1 then = (Tf ! TF,# ) + (Tf ! Tox,!# ) = (Tf ! TF,# ) + (Tf ! Tox,!# ) 1+ S
CP 1+ erf ( x! f ) 1+
1! S
1+ S
QRYF,0
+ (TF,0 + STox,0 )
Y Q CP
" F,# R = (Tf ! TF,# ) + (Tf ! Tox,!# ) S or Tf =
CP 1+ S
• 22
1D stretched flame"
 For S = 1, LeF = Leox = 1, flame located at stagnation plane
 For S > 1 (oxidizer more diluted than fuel), flame moves
toward oxidizer boundary – need steeper gradient of oxidizer
 S or Zst = 1/(1+S) has significant effect on flame behavior; for
flame on oxidizer side, radicals (mostly formed on fuel side
because of lower bond strengths of C-H & C-C compared to
O=O) are convected away from flame sheet, so flames are
weaker even for same Tf
1.5
Flame location (xf)
0.5
-0.5
-1
-1.5
0.01 0.1 1 10 100
Stoichiometric parameter (S)
1D stretched flame"
  Temperature & species profiles are error functions
  For S = 1, profiles are symmetric about x = 0; convection (u) is small
& behavior similar to unstretched flame at low Pe, decreasing either
Le increases Tf
  For S > 1, flame lies on oxidizer side of stagnation plane; strong
effect of convection - flame temperature is drastically affected by
Le, decreasing LeF moves flame closer to x = 0 & increases Tf but
opposite trend for Leox
2500 1 2500 1
S=1
S = 15
2000 0.8 2000 0.8
T
Temperature (K)
1500 0.6
Temperature (K)
1500 T 0.6 Yf/Yf,∞

Y/Y∞
Y/Y∞
Yf/Yf,∞ Yox/Yox,-∞
1000 Yox/Yox,-∞ 0.4 1000 0.4
500 0.2 500 0.2
0 0
0 0
-2 -1 0 1 2
-2 -1 0 1 2
Scaled coordinate (x) Scaled coordinate (x)
• 23
AME 513 
 
"
Lecture 12
Non-premixed flames II: 2D flames, extinction
Outline"
  Jet flames
  Simple models of nonpremixed flame extinction
AME 513 - Fall 2012 - Lecture 12 - Nonpremixed flames II 2
• 1
Axisymmetric jet – boundary layer flow "
  Assumptions: steady, axisymmetric, constant density, zero
mean axial (x) pressure gradient
  Boundary layer approximation – convective transport (of
momentum or species) only in axial (x) direction, diffusion
only in radial (r) direction
  Jet momentum J = constant (though kinetic energy is not,
nor is mass flow since entrainment occurs)
! !
! " $u 1 $ ( rur ) !u ! ! ! !P ! !
Continuity : ! " u = 0 # x +
$x r $r
(
= 0; Momentum : + u " ! u = %
!t
) "
+ g + #! 2 u
$u $u # $ & $ux ) $Y $Y D $ & $Y )

# x % momentum : ux x + ur x + (r + = 0; Fuel : ux F + ur F + F ( r F + = 0
$x $r r $r ' $r * $x $r r $r ' $r *
Cr 3J
Let $ = ;C = ! e = ( "ue A) ue = "ue2 4% re2 (Axial momentum at jet exit)
; J = mu
x 16%# 2 "
$ $$ $ %Cr $ %$ $ $ $$ $ C $
= = 2 = , = =
$x $x $$ x $$ x $$ $r $r $$ x $$
Axisymmetric jet – boundary layer flow "

!ux 1 ! ( rur ) !u C ! (!ur )
Continuity : + =0" x = 2
!x r !r !! ! !!
!ux !u " ! $ !ux ' $ !u ' !u C! ! $ !ux '
x # momentum : ux + ur x + &r ) = 0 " & ur # x ) x + &! )=0
!x !r r !r % !r ( % C ( !! x !! % !! (
Eventually leads to :
#2 #1 #2
3J 1 $ !2 ' ux (x, r) 3 $ x ' $ ! 2 ' 2u r
ux (x, r) = &1# ) " = Re & ) & 1# ) ;Re * e e
16#"$ x% 4( ue 8 % re ( % 4( "
#1
3J 1 ! (1# ! / 4) 3 $ x ' ! (1# ! / 4)
2 2
u (x, r)
ur = 2
" r = & )
16#$ x (1+ ! 2 / 4) ue 4 % re ( (1+ ! 2 / 4)2
#1 #2 #1
#2
3re ue $ x ' $ ! 2 ' Y (x, r) 3 $ x ' $ ! 2 '
YF (x, r) = & ) &1# ) " F = Re & ) &1# )
2D % re ( % 4( YF,e 4 % re ( % 4(
  On the axis (r = 0 thus η = 0), both ux & YF decay as 1/x
  Off axis, the jet spreads ~ η ~ r/x, i.e. linearly
  This allows us to use “simple” scaling to estimate flame
lengths…
• 2
Nonpremixed-gas flames - laminar gas-jet flames"
  Flame height (Lf) scaling estimated by equating time for
diffusion of O2 to jet centerline tD
tD ~ d2/Dox, d = stream tube diameter, Dox = oxygen diffusivity
to convection time (tC) for fuel to travel from jet exit to end
of flame at Lf
tC ~ Lf/u
  The problem arises that d is not necessarily the same as the
jet exit diameter de = 2re – if the flow accelerates or
decelerates (i.e. u changes), to conserve mass d must change
  For the simplest case of constant u, d:
d2/D ~ Lf/ue ⇒ Lf ~ ued2/D or Lf/de ~ Ude/D
Gases: D ≈ ν ⇒ Lf/de ~ Ude/ν = Red
  Which is consistent with experimental data for laminar,
momentum-controlled jets
100 Sunderland et al. (1g)

Sunderland et al. (µg, 1 atm)
Sunderland et al. (µg, 0.5 atm)
Cochran and Masica (µg)
Bahadori et al. (µg)
j
L /d
Bahadori & Stocker (µg)

10
f
1 10 100 1000
Reynolds number (Re)
• 3
  For buoyancy-controlled jets, the flow accelerates
u ~ (gLf)1/2, g = acceleration of gravity
and to conserve volume flow, the stream tube diameter
must decrease
u(πd2/4) = constant = ue(πde2/4), thus d ~ de(ue/u)1/2 (round jet)
ud = constant = uede, thus d ~ de(ue/u) (slot jet)
and thus for laminar, buoyancy-controlled round-jet flames
tC ~ Lf/u, tD ~ d2/Dox, u ~ (gLf)1/2, d ~ de(ue/u)1/2
Lf/u ~ d2/Dox, thus Lf/(gLf)1/2 ~ de2(ue/u)/Dox ~ de2(ue/(gLf)1/2)/Dox
Lf ~ uede2/Dox – same as momentum-controlled, consistent with
experiments shown on previous slide
but for laminar, buoyancy-controlled slot-jet flames
tC ~ Lf/u, tD ~ d2/Dox, u ~ (gLf)1/2, d ~ de(ue/u)1
Lf/u ~ d2/Dox, thus Lf/(gLf)1/2 ~ de2(ue/u)2/Dox ~ de(ue2/(gLf)1)/Dox
Lf ~ (ue4de4/gDox2)1/3 – very different from momentum-controlled!
Nonpremixed-gas flames - gas-jet flames"

  Also if jet is turbulent, D ≠ constant, instead D ~ u’LI ~ ud
  Example for round jets, momentum controlled
tC ~ Lf/u, tD ~ d2/Dox, Dox ~ ud
Lf/u ~ d2/Dox, thus Lf/u ~ de2/(ud)
Lf ~ de– flame length doesn’t depend on exit velocity at all –
consistent with experiments shown on next slide
  Also high ue ⇒ high u’ ⇒ Ka large - flame lifts off near base
  Still higher ue - more of flame lifted
  When lift-off height = flame height, flame blows
off (completely extinguished)
Lifted flame (green =

fuel; blue = flame)
• 4
Nonpremixed-gas flames - gas-jet flames"
  Summary of jet flame scaling
  Always equate diffusion time to convection time
»  Diffusion time ~ d2/Dox, d = stream tube diameter, Dox = oxygen
diffusivity)
»  Convection time ~ Lf/u
  Volume conservation (2 choices)
» uede2 ~ u(Lf)d(Lf)2 (round jet)
» uede ~ u(Lf)d(Lf) (slot jet)
  Buoyancy effects (2 choices)
» Buoyant flow: u(Lf) ~ (gLf)1/2
» Nonbuoyant: u(Lf) = u(0) = constant
  Turbulence effects (2 choices)
» Laminar: Dox = molecular diffusivity= constant
» Turbulent: Dox ~ u’LI ~ u(Lf)d(Lf)
  Total of 2 x 2 x 2 possibilities!
Burke-Schumann (1928) solution"

  Axisymmetric flow of a fuel & annual oxidizer with equal u
  Overventilated if ratio of mass flow of fuel to oxidizer is <
stoichiometric ratio, otherwise underventilated
  Burke-Schumann solution is essentially a boundary layer
approximation – assume convection only in streamwise
direction, diffusion only in radial
direction – valid at high Pe = urj/D
!YF 1 ! # !Y &
!u " % r! D F ( = 0
!x r !r $ !r '
  Solution rather complicated (Eq. 9.55)
but flame height involves only
  Dimensionless coordinate ~ xD/urj2
  Stoichiometric coefficient to identify
flame location
• 5
Flame widths at 1g and µg"
 Note Lf ≈ same at 1g or µg (microgravity) for round jet, but
flame width greater at µg because tjet larger
 µg flame width ~ (Dtjet)1/2 - greater difference at low Re due
to axial diffusion (not included in aforementioned models)
& stronger buoyancy effects
10
o
w/d
Sunderland et al. (1g)

Sunderland et al. (µg, 1 atm)
1 Sunderland et al. (µg, 0.25 atm)
Cochran and Masica
Bahadori et al.
10 100 1000
Reynolds number (Re)
Flame lengths at 1g and µg"

 Low Re: depends Froude number (Fr = ue2/gde)
 1g (low Fr): buoyancy dominated, teardrop shaped
 µg (Fr = ∞): nearly diffusion-dominated, morelike a spherical
droplet flame
 High Re: results independent of Fr
do = 3.3 mm, Re = 21 ! ! !d = 0.42 mm, Re = 291!

Sunderland et al. (1999) - C2H6/air
• 6
Nonpremixed flame extinction"
  Up till now, we’ve assumed “mixed is burned”(infinitely fast

chemical reaction) – but obviously nonpremixed flames can
be extinguished due to finite-rate chemistry
  Generic estimate of extinction condition
  Temperature in reaction zone is within 1/β of Tf
  Reactant concentration in reaction zone is 1/β of ambient value
  Thickness of reaction zone is 1/β of transport zone thickness
!1
# d [ Fuel ] &
Reaction time scale ~ [ Fuel ]!" % (
$ dt '
!1 !1
# [ Fuel ] [Ox ] !E/)T f & # [Ox ] !E/)T f &
= [ Fuel ]!" % Z !" +"
e ( = %Z +"
e (
$ ! ! ' $ !2 '
11 [Ox ]+" e!E/)T ; Ox = !Yox,+"
Residence time ~ + !* ~ Z [ ]+"
!* !2 M ox
Z !Yox,+" !E/)T f
+ e , 1 at extinction
* M ox " 3
Nonpremixed flame extinction"
  For a stretched counterflow flame, for a reaction that is first

order in fuel and O2, Liñán (1974) showed that the Damköhler
number (Da) at extinction (which contains the stretch rate Σ)
is given by
Daext ! e $%(1" # ) " (1" # ) + 0.26 (1" # ) + 0.055 (1" # ) &'

2 3 4
3
* T - Y
x 2f ! Z e" " E S "1
Da ( 8! e ,, f // F,")
2 3
;" ( a # (
T
+ ox,") . S (1+ S ) M ox 0 " RT f S +1
which has the same functional form as estimated on the

previous slide (in particular the Z/Σ and e-β/β3 terms)
• 7
Final exam"
 December 17, 11:00 am – 1:00 pm, ZHS 159
 Cumulative but primarily covering lectures 7 - 12
 Open books / notes / calculators
 Laptop computers may be used ONLY to view .pdf versions
of lecture notes – NOT .pptx versions
  Note .pdf compilation of all lectures:
http://ronney.usc.edu/AME513F12/AME513-F12-AllLectures.pdf
  GASEQ, Excel spreadsheets, CSU website, etc. NOT ALLOWED
  Homework #4 must be turned in by Friday 12/14 at 12:00
noon (NOT 4:30 pm!), solutions will be available at that time
where you drop off homework
Midterm exam – topics covered"

  Conservation equations
  Mass
  Energy
  Chemical species
  Momentum
  Premixed flames
  Rankine-Hugoniot relations
  Detonations
  Deflagrations
» Propagation rates
» Flammability limits, instabilities, ignition
  Nonpremixed flames
  Plane unstretched
  Droplet
  Counterflow
  Jet
  Extinction
• 8
Midterm exam – types of problems"
  Premixed flames (deflagrations and/or detonations)
  Propagation rates
  Ignition or extinction properties
  Nonpremixed flames – mixed is burned in first
approximation
  Flame location
  Jet flame length scaling
  Extinction limit
  General - how would burning rate, flame length, extinction limit,
etc. be affected by
  Ronney Fuels, Inc. – new fuel or additive
  Planet X – different atmosphere (pressure, temperature, etc.)
• 9

AME513 Principles of Combustion PDF

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AME 513

AME 513 - Fall 2012 - Lecture 1 - Introduction 2

AME 513 - Fall 2012 - Lecture 1 - Introduction 3

Tentative course outline"

AME 513 - Fall 2012 - Lecture 1 - Introduction 4

AME 513 - Fall 2012 - Lecture 1 - Introduction 5

AME 513 - Fall 2012 - Lecture 1 - Introduction 7

Why study combustion?"

AME 513 - Fall 2012 - Lecture 1 - Introduction 8

Each 1015 BTU/yr = 33.4 gigawatts

AME 513 - Fall 2012 - Lecture 1 - Introduction 9

What do we do with combustion?"

AME 513 - Fall 2012 - Lecture 1 - Introduction 10

AME 513 - Fall 2012 - Lecture 1 - Introduction 11

Why do we need to study combustion?"

AME 513 - Fall 2012 - Lecture 1 - Introduction 12

AME 513 - Fall 2012 - Lecture 1 - Introduction 13

AME 513 - Fall 2012 - Lecture 1 - Introduction 14

Distance from reaction zone

Turbulent premixed flame experiment in a

AME 513 - Fall 2012 - Lecture 1 - Introduction 15

Premixed flames - detonation"

Heat release Induction

P t decreases across shock

AME 513 - Fall 2012 - Lecture 1 - Introduction 17

Non-premixed or diffusion flames"

Convection-diffusion zone Distance from

AME 513 - Fall 2012 - Lecture 1 - Introduction 19

Diesel engine combustion"

AME 513 - Fall 2012 - Lecture 1 - Introduction 20

k = gas thermal conductivity, T = temperature, x = distance, ρ = density, Yf =

AME 513 - Fall 2012 - Lecture 1 - Introduction 21

Alternative #2 - Electric Vehicles (EVs)"

AME 513 - Fall 2012 - Lecture 1 - Introduction 23

Alternative #3 - Hydrogen fuel cell"

AME 513 - Fall 2012 - Lecture 1 - Introduction 24

AME 513 - Fall 2012 - Lecture 1 - Introduction 25

AME 513 - Fall 2012 - Lecture 1 - Introduction 27

Ford Nucleon concept car (1958)

AME 513 - Fall 2012 - Lecture 1 - Introduction 29

AME 513 - Fall 2012 - Lecture 1 - Introduction 30

AME 513 - Fall 2012 - Lecture 1 - Introduction 31

History of automotive engines"

AME 513 - Fall 2012 - Lecture 1 - Introduction 32

NO + UHC + O2 + sunlight → NO2 + O3!

! !(UHC = unburned hydrocarbons)!

 1960s - emissions regulations!

AME 513 - Fall 2012 - Lecture 1 - Introduction 33

History of automotive engines"

AME 513 - Fall 2012 - Lecture 1 - Introduction 34

Practical alternatives to the status quo"

AME 513 - Fall 2012 - Lecture 1 - Introduction 36

AME 513 - Fall 2012 - Lecture 1 - Introduction 37

Summary - Lecture 1"

AME 513 - Fall 2012 - Lecture 1 - Introduction 38

AME 513 - Fall 2012 - Lecture 1 - Introduction 39

Review of thermodynamics (1)"

AME 513 - Fall 2012 - Lecture 1 - Introduction 40

AME 513 - Fall 2012 - Lecture 1 - Introduction 41

Review of thermo (3) - heat & work"

V = velocity, V = volume, m = mass, g = gravity!

AME 513 - Fall 2012 - Lecture 1 - Introduction 43

Review of thermo (5) - types of energy"

AME 513 

  1960s - emissions regulations!

  Equivalent in building electronics: turn the power switch on

  Equivalent in building electronics: does the device do what it

  Determine what happens in the limit where x goes to

  Equivalent in building electronics: how fast, how

  Alcohols - contain one or more OH groups