Professional Documents
Culture Documents
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!
• 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!
• 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
Principles of Combustion
"
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
• 4
US energy flow, 2010, units 1015 BTU/yr"
• 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
• 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
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
• 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
Candle
Kuwait
Diesel engine Oil fire Forest fire
AME 513 - Fall 2012 - Lecture 1 - Introduction 18
• 9
Reaction zone
2000K
Product
Oxygen concentration Fuel
concentration Temperature
concentration
300K 300K
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!
• 11
Zero emission electric vehicles"
• 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?)
AME 513 - Fall 2012 - Lecture 1 - Introduction 26
• 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)!
AME 513 - Fall 2012 - Lecture 1 - Introduction 28
• 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…
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!
• 16
History of automotive engines"
1938 – oil discovered at Dammam, Saudi Arabia (40 year
supply)!
1952 - A. J. Haagen-Smit, Caltech!
!
• 17
History of automotive engines"
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
???!
AME 513 - Fall 2012 - Lecture 1 - Introduction 35
• 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
• 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?!
• 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)!
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!
!
Energy
• 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)!
AME 513 - Fall 2012 - Lecture 1 - Introduction 45
• 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 ).
* $ ' -
• 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)!
!
• 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 '
AME 513 - Fall 2012 - Lecture 1 - Introduction 51
• 26
Engineering scrutiny 1. Smoke test"
See http://ronney.usc.edu/AME101F011/AME101-F11-LectureNotes.pdf
(Chapters 2 & 3) for more details!
!
• 27
Engineering scrutiny 2. Function test"
! 55
AME 513 - Fall 2012 - Lecture 1 - Introduction
• 28
AME 513
Principles of Combustion
"
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
• 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
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
• 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)
Benzene
Toluene
• 4
Practical fuels - properties"
Values NOT unique because
Real fuels are a mixture of many molecules, composition varies
Different testing methods & definitions
http://www.afdc.energy.gov/afdc/pdfs/fueltable.pdf
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 10
• 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)
• 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"
• 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
• 9
Chemical thermodynamics - introduction"
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
• 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)
• 11
Chemical thermodynamics - 1st Law"
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
! H
$ n ([h˜ (T) " h˜
i 298 i ] + #h˜ of ,i )
i=1
! h= = n
m
$n M i i
i=1
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
• 12
Chemical thermodynamics - 1st Law"
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
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
Chemical thermodynamics - 1st Law"
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
! P
"n i
Tproducts
! Combine : products = i=1
n (reactants)
Preactants Treactants
"n i
i=1
!
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 27
$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 M i i #n M i i
i=1 i=1
• 14
Chemical thermo - heating value"
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 (reactants) n (products)
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
• 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 M i i #n M i i
i=1 i=1
!
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 32
• 16
Chemical thermo - flame temperature"
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
!
AME 513 - Fall 2012 - Lecture 2 - Chemical thermodynamics 1 33
!
!
• 17
Example of heating value"
Iso-octane/air mixture:
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
• 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
$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
Summary - Lecture 2"
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
Principles of Combustion
"
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
• 1
Why do we need chemical equilibrium?"
• 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
• 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
i=1
!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
Entropy of an ideal gas mixture"
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
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 ) + $T ln ( Pi Pref )'(
i
o
i=1 i=1
where #g!io (T ) ) h!i (T ) " T#!sio (T ) is the Gibbs function for pure i at temp. T & P = Pref
• 5
Equilibrium of an ideal gas mixture"
n # %
dP
dG = )'!g!io (T )dni + "T ln ( Pi Pref ) dni + ni "T i + ni d #$!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 &
• 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
• 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 $# Pref '& KCO 2KO2 1
"X i =1 n (products)
"n
i=1 i
Pressure = constant or (for const. vol.) Pproducts i=1
Tproducts
= n (reactants)
6 + 3 + 1 + 1 + 1 = 12 equations Preactants Treactants
How many unknowns? "n i
i=1
! 10 species ⇒ 10 mole fractions (Xi)
Temperature
Pressure
10 + 1 + 1 = 12 equations
!
• 8
Chemical equlibrium - hydrocarbons"
Equilibrium constraints - not a unique set, but for any set
Each species appear in at least one constraint
Each constraint must have exactly 1 DoRF
Note that the initial fuel molecule does not necessarily appear in the set
of products! If the fuel is a large molecule, e.g. C8H18, its entropy is so
low compared to other species that the probability of finding it in the
equilibrium products is negligible!
Example set (not unique)
1+.5)1 1 0.5
1 .5
X CO X O2 # P & {KCO (T)} {KO2 (T)}
CO2 " CO + 0.5O2 ; % ( =
X CO2 1 %$ Pref (' {KO (T)}
1
2
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)
n (reactants) n (products)
$n M i i $n M i i
i=1 i=1
• 9
Chemical equlibrium - hydrocarbons"
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
• 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
• 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
Compression / expansion"
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
Compression / expansion"
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
!
Compression / expansion"
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
Summary - Lecture 3"
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)
• 14
AME 513
Principles of Combustion
"
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
• 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
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
• 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
A+B A+B
Potential Enthalpy
energy of reaction
C+D
Unsuccessful collision
Successful collision
Time
Diary of a collision
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 7
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 +/
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:
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
• 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
Homogeneous reaction"
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
Homogeneous reaction"
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
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 15
Homogeneous reaction"
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
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 16
• 8
Homogeneous reaction"
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
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
Homogeneous reaction"
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
Homogeneous reaction"
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
Homogeneous reaction"
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
• 10
Homogeneous reaction"
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
Homogeneous reaction"
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
Homogeneous reaction"
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
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 24
• 12
Well-stirred reactor"
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! (
Well-stirred reactor"
Finally (really finally this time!) combining Eqs. 1, 2, 3
• 13
Well-stirred reactor"
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
Well-stirred reactor"
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
AME 513 - Fall 2012 - Lecture 4 - Chemical Kinetics I 28
• 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
Principles of Combustion
"
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
• 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
• 2
1-step reversible reaction"
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
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-step reversible reaction"
1.2 12
kf = 10, kb = 1, [A]o = 1
Concentration of A
Concentration of A
10
0.6 6
0 0
0 0.5 1 1.5 0 0.05 0.1 0.15 0.2
Time Time
• 4
Lindemann (1922) - P effects on decomposition"
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
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
• 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
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
AME 513 - Fall 2012 - Lecture 5 - Chemical Kinetics II 13
1.8
1.6
0.8
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35
Time
AME 513 - Fall 2012 - Lecture 5 - Chemical Kinetics II 14
• 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
• 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
• 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
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)
AME 513 - Fall 2012 - Lecture 5 - Chemical Kinetics II 19
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
AME 513 - Fall 2012 - Lecture 5 - Chemical Kinetics II 20
• 10
AME 513
Principles of Combustion
"
Lecture 6
Chemical kinetics III – real fuels
Outline"
Experimental methods
Types of reaction
CO-O2
Hydrocarbons
NOx
Flame inhibition
• 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
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 3
Experimental methods"
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
Experimental methods"
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
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 7
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)
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 8
• 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!
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
Explosion temperature (˚C)
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 12
• 6
Hydrocarbon – O2"
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
Explosion temperature (˚C)
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 15
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
AME 513 - Fall 2012 - Lecture 6 - Chemical Kinetics III 16
• 8
Hydrocarbon oxidation"
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
Hydrocarbon oxidation"
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
Hydrocarbon oxidation"
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
Hydrocarbon oxidation"
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"
• 11
Chemical fire suppressants"
• 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"
Chemical thermodynamics
Stoichiometry
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
• 14
AME 513
Principles of Combustion
"
Lecture 7
Conservation equations
Outline"
Conservation equations
Mass
Energy
Chemical species
Momentum
• 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
AME 513 - Fall 2012 - Lecture 7 - Conservation equations 3
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
• 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
• 3
Conservation of energy"
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
AME 513 - Fall 2012 - Lecture 7 - Conservation equations 7
Conservation of energy"
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'''
!
• 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
AME 513 - Fall 2012 - Lecture 7 - Conservation equations 11
300K
Convection-diffusion zone
! ≈ "/SL = 0.3 - 6 mm
• 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 #
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
• 7
AME 513
Principles of Combustion
"
Lecture 8
Premixed flames I: Propagation rates
Outline"
Rankine-Hugoniot relations
Hugoniot curves
Rayleigh lines
Families of solutions
Detonations
Chapman-Jouget
Others
Deflagrations
• 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
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
AME 513 - Fall 2012 - Lecture 8 - Premixed flames I 5
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
Rankine-Hugoniot relations"
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?
Rankine-Hugoniot relations"
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
!"#!$%
2 B
C
1
A E
0
0 1 2 3
!$#!"%
AME 513 - Fall 2012 - Lecture 8 - Premixed flames I 8
• 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
• 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
Reaction zone
2000K Direction of propagation
Speed relative to unburned gas = SL
Product
concentration Temperature
Reactant
concentration
300K
Convection-diffusion zone
! ≈ "/SL = 0.3 - 6 mm
• 6
Deflagrations - burning velocity"
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
• 7
Deflagrations - burning velocity"
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
AME 513 - Fall 2012 - Lecture 8 - Premixed flames I 15
• 8
Deflagrations - burning velocity"
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
• 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)
≈ 2200K
SL
≈ 40 cm/s Tad
or
Tad
SL
≈ 1500K
≈ 5 cm/s
• 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
Principles of Combustion
"
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!
• 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, ... !
• 2
Premixed-gas flames – flammability limits"
SL
or Tad
Lean Rich
limit
Stoichio- limit Fuel %
metric
2 limit mechansims, (1) & (2), yield similar fuel % and Tad at limit
but very different SL,lim
• 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
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!
! !
" 1%
!! = " $1! '
# Le &
SL/SL(unstrained, adiabatic flame)!
Buckmaster &
Mikolaitis,
1982a!
ln(Ka)!
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 10
• 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!
Flame
front
Burned gas
• 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
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)
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 14
• 7
Flammability limits due to losses"
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!
!
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 15
Tube walls
Flow pattern in flame-front
fixed reference frame
• 8
Flammability limits due to losses"
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)!
Buoyancy-induced
flame stretch
Cooling
combustion products near
wall cause sinking boundary
layer
Direction of flame
propagation
Direction of flame
Flame propagation
front
• 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
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
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
• 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)
• 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
4.1
2.25
Burning velocity 4
1.50 3.6
0 2 4 6 8
Mass of particles in chamber (g)
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)!
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…!
!
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 27
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?)!
• 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!
Williams, 1985!
Bernoulli:!
P+1/2ρu2 = const!
Aflame ↓, u ↑, P ↓!
Aflame↑, u↓, P↑!
FLOW →!
• 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
• 17
Upward propagation – RT enhanced"
• 18
High Lewis number"
!
3.0% C3H8-air, horizontal, 12.7 mm cell (Le ≈ 1.7)!
• 19
Horizontal, but ST not DL dominated"
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
9.5% CH4 - 90.5% air, horizontal, 3.1 mm cell!
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 39
• 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
• 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
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 43
• 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!
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
AME 513 - Fall 2012 - Lecture 9 - Premixed flames II 46
• 23
AME 513
Principles of Combustion
"
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)
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 )
AME 514 - Fall 2012 - Lecture 10 - Premixed flames III 3
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
AME 514 - Fall 2012 - Lecture 10 - Premixed flames III 4
• 2
Basics of turbulence"
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)
Basics of turbulence"
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
= ST/SL!
= u /SL
AME 514 - Fall 2012 - Lecture 10 - Premixed flames III 8
• 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)
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
• 5
Turbulent combustion regimes"
Comparison of flamelet and distributed combustion (Yoshida,
1988)
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 )
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
• 8
AME 513
Principles of Combustion
"
Lecture 11
Non-premixed flames I: 1D flames
Outline"
Flat flames
Liquid droplets
Stretched flames
• 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
• 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.
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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 6
• 3
1D planar steady nonpremixed flame"
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
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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 7
!(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 )
• 4
1D planar steady nonpremixed flame"
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 (
• 5
1D planar steady nonpremixed flame"
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 +
• 6
1D planar steady nonpremixed flame"
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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 13
• 7
1D planar steady nonpremixed flame"
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
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
• 8
1D planar steady nonpremixed flame"
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
1.2
YF/Yfo Yox/Yox,0
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"
• 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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 24
• 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!=$
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 25
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 +
!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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 31
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 '
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! (
• 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# )
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
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 38
• 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
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
" Yox ( x! ) = !
( (
Yox,% erf Leox x! ! erf ) ( Leox x! f )) ; dY ox
=!
2 Leox Yox,%e
!Leox x! 2f
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)
AME 513 - Fall 2012 - Lecture 11 - Nonpremixed flames I 45
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)
Yf/Yf,∞ Yox/Yox,-∞
1000 Yox/Yox,-∞ 0.4 1000 0.4
0 0
0 0
-2 -1 0 1 2
-2 -1 0 1 2
Scaled coordinate (x) Scaled coordinate (x)
• 23
AME 513
Principles of Combustion
"
Lecture 12
Non-premixed flames II: 2D flames, extinction
Outline"
Jet flames
Simple models of nonpremixed flame extinction
• 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
• 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
AME 513 - Fall 2012 - Lecture 12 - Nonpremixed flames II 5
1 10 100 1000
Reynolds number (Re)
• 3
Nonpremixed-gas flames - laminar gas-jet flames"
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!
AME 513 - Fall 2012 - Lecture 12 - Nonpremixed flames II 7
• 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!
• 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
10 100 1000
Reynolds number (Re)
AME 513 - Fall 2012 - Lecture 12 - Nonpremixed flames II 11
• 6
Nonpremixed flame extinction"
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
• 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
• 8
Midterm exam – types of problems"
Premixed flames (deflagrations and/or detonations)
Flame temperature
Propagation rates
Ignition or extinction properties
Nonpremixed flames – mixed is burned in first
approximation
Flame temperature
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