Theory of Combustion - YIN-Chungen

Course Notes
FACE9 – Theory of Combustion
Theory of Combustion
FACE 9
Fall 2004
• Examination date: PE course

• Lecturer: Chungen Yin
Pon 101, room 4
chy@iet.aau.dk
• Course homepage: http://www.iet.aau.dk/~chy and/or to Lasse
MM1. Combustion and Thermochemistry

MM2. Chemical Kinetics
MM3. Premixed Flames: Laminar vs. Turbulent
MM4. Diffusion Flames: Laminar vs. Turbulent
MM5. Burning of Solid Fuels
Textbook:
Stephen R. Turns. ”An Introduction to Combustion – Concepts and Applications”.

(2nd edition), McGraw-Hill, 2000 ISBN 0-07-116910-5
2
MM1: Combustion and Thermochemistry
Contents
· Ideal-gas behavior
▫ Equation of state
▫ Calorific equation of state
▫ Ideal-gas mixture
▫ Reactant & product mixtures: Stoichiometry; Equivalence ratio
· Enthalpy
▫ Absolute enthalpy; Enthalpy of formation
▫ First law of thermodynamics
▫ Enthalpy of reaction; Heating values
▫ Adiabatic flame temperature
· Chemical equilibrium
▫ Second law of thermodynamics
▫ Chemical equilibrium principle
▫ Full equilibrium products of combustion
· Ideal-gas behavior
◦ Combustion: ”Rapid oxidation generating heat, or both light and heat; also slow
oxidation accompanied by relatively little heat and no light”
◦ ”Ideal gas is the system where interaction is absent (i.e., zero potential energy)”.
◦ High temperatures associated with combustion generally result in sufficiently low

densities for the Ideal Gas Behaviour to hold.
▫ Equation of state
P V = N Ru T ⇔ P V = m RT ⇔ P v = RT ⇔ P = ρ RT
Ru : universal gas constant, = 8315 J/(kmol - K)
v : specific volume, m 3 / kg
R : specific gas constant, R = Ru /MW ( MW is gas molecular weight)
▫ Calorific equations of state

◦ The internal energy u is a function of temperature T,
du = cv dT u : specific internal energy, J / kg cv : constant − volume specific heat, J /( kg ⋅ K )
◦ The enthaply h is also a function of temperature T,
d h = c p dT
h : specific enthalpy, J / kg. (h = u + P v)
c p : constant − pressure specific heat, J /( kg ⋅ K ). (c p = cv + R )
4
◦ The specific heats (of gas) are generally functions of temperature: in general, the more
FACE9 – Theory of Combustion complex the molecule, the greater its molar specific heats.
- 3 components of internal energy:

translational, vibrational & rotational;
- Diatomic molecule:
not only translational but also
vibrational & rotational contributions.
- Monatomic molecule:
only translational kinetic energy;
▫ Ideal-gas mixtures
Ni mi
xi = xi : mole fraction of species i Yi = Yi : mass fraction of species i
N tot mtot
Yi = xi MWi / MW mix xi = Yi MW mix / MWi

1
MWmix : mixture molecular weight, kg / kmol , MWmix = ∑ xi MWi = ∑ (Yi / MWi )
i
i
▫ Reactant & product mixtures
◦ Stoichiometry: The stoichiometric quantity of oxidizer is just that amount needed to
completely burn a quantity of fuel.
C x H y + a (O 2 + 3.76 N 2 ) → x CO 2 + ( y / 2) H 2O + 3.76a N 2
m  4.76 a MWair
( A / F )stoic =  air  = a = x+ y/4
 mfuel stoic 1 MWfuel
◦ Equivalence ratio: commonly used to indicate quantitatively whether a fuel-oxidizer mixture

is rich, lean, or stoichiometric.
( A / F )stoic ( F / A) Φ > 1 : fuel rich mixtures

Φ= =
(A/ F) ( F / A)stoic Φ < 1 : fuel lean mixtures
◦ Percent excess air

(1 − Φ)
% excess air = × 100%
Φ
6
· Enthalpy
▫ Absolute enthalpy = Enthalpy of formation + Sensible enthalpy change
◦ Enthalpy of formation: associated with chemical bonds;
◦ Sensible enthalpy change: associated only with T.
hi (T ) = h fo,i (Tref ) + ∆ hs ,i (Tref )

123 1424 3 14243 Tref = 25 °C
Absolute enthalpy Enthalpy of formation Sensible enthalpy Standard-state:
at temperature T at standard reference change in going from Pref = P o = 1 atm
state (Tref , P 0 ) Tref to T
◦ Convention: Enthalpies of formation are zero for the elements in their naturally occuring state
at the reference state temperature and pressure.
◦ Interpretation: Formation enthalpy— net change in enthalpy associated with breaking chemical
bonds of the standard state elements & forming new bonds to create species of interest.
- To form O atoms at standard states

requires the breaking of a rather strong
chemical bond O=O. The bond energy
for O2 at standard-state is 498390
kJ/kmolO2, so the enthalpy of formation of
O atom is half the value.
- At T=4000K, an additional sensible
enthalpy contributes to the absolute
enthalpy.
▫ First law of thermodynamics — Energy conservation

◦ First law for Fixed mass (i.e., a System): No mass flow across the bounaries
&
Q + W& = dE
{ { 12/3
dt
Instantaneous rate Instantaneous rate Instantaneous time

of heat transferred of work done rate of change of
into system on the system system energy
If neglecting potential & kinetic energy, the energy in the system (E) consists of:
- Internal Energy (U): thermal energy due to translation, rotation and vibration of molecules;
- Chemical Energy: chemical bonds between atoms in molecules.
◦ First law for open systems with mass flow across the bounaries of Control Volume
Two additional terms:

(1) Energy (incl. Internal & Kinetic & Potential energy) convected in and/or out due to the flow
(2) Work done to move the fluid across the boundaries.
Q& + W& + m& (ei − eo ) + m& ( Pi vi − Po vo ) = dE / dt

14444 4244444 3
additional terms
e= + 1 v2 +
u{ 2
gz
{ h= u{ + P
{v
internal energy { internal energy
kinetic energy potential energy flow work
For steady flow with 1 stream flowing in & 1 stream flowing out of CV, the energy
Equation may be simplified to (if neglect the potential energy for gas flows):
Q& cv + W& cv = m& ( ho − hi ) + m& ( 12 v o2 − 12 vi2 )

8
▫ Enthalpy of combustion & Heating value
◦ Enthalpy of reaction (i.e., Enthalpy of combustion)
qcv = ho − h i = hprod − hreac

∆hR ≡ qcv = hprod − hreac

∆H R = H prod − H reac = ∑ Ni hi − ∑ Ni hi
prod reac
( H = N h = m h)
◦ Heating value (i.e., heat of combustion): The difference between the energy needed to
break the bonds in the reactants and the energy released in the formation of the bonds in the
products. Numerically equal to the enthalpy of reaction, but with opposite sign.
- Upper or Higher heating value, HHV: the heat of combustion calculated assuming that
all of the water in the products has condensed to liquid;
- Lower heating value, LHV: corresponds to the case where none of the water is assumed
to condense.
- Latent heat vaporization, hfg: the heat required in a constant-pressure process to
completely vaporize a unit mass of liquid at a given temperature. (equal the heat released
when vapor is condensed to liquid).
h fg (T , P ) ≡ hvapor (T , P ) − hliquid (T , P )
∆H c ≡ − ∆H R = H reac − H prod = ∑ N i hi − ∑ N i hi
reac prod
9
◦ Example: 1 kg liquid fuel undergoing combustion in air

- Formation enthalpy, Absolute enthalpy, Enthalpy of vaporization
- LHV and HHV of a fuel at different states.
Absolute
Enthalpy, h h(v ) (T )
kJ/kg Fuel
h(l ) (T )
HHV
h fg , fuel
(vapor fuel) Product
298 K LHV
(vapor fuel)
T
h of (v )
HHV
h of (l )
LHV (liquid fuel)
(liquid fuel) h fg , H 2O
(per kg fuel)
10
▫ Adiabatic flame temperature
◦ Constant-pressure adiabatic flame temperature: If a fuel-air mixture burns
adiabatically at constant pressure, the absolute enthalpy of the reactants at initial state equals
the absolute enthalpy of the product at the finial state (in furnace or gas-turbine combustor).
H reac (Tinit , P) = H prod (Tad , P )
- Demand the knowledge of the composition of combustion product. At typical flame

temperatures, the products dissociate and the mixture comprises many species.
- Dissociation causes a lowering of Tad since more energy is tied up in chemical bonds
(enthalpies of formation) at the expense of the sensible enthalpy.
h ( kJ / kg mix )
Ti Tad
T
hreac = hprod
◦ Constant-volume adiabatic flame temperature: e.g., in an ideal Otto-cycle analysis.
U reac (Tinit , Pinit ) = U prod (Tad , Pf ) ⇔ H reac − H prod − V ( Pinit − Pf ) = 0
H reac − H prod − Ru ( N reacTinit − N prodTad ) = 0

- For the same initial conditions, constant-volume combustion results in much higher
temperatures than for constant-pressure combustion due to “pressure forces doing no work
when the volume is fixed.”
11
· Chemical equilibrium
▫ Second law of thermodynamics
◦ ”The entropy of the universe (i.e., System plus its surroundings) increases during any
spontaneous process”.— Energy spontaneously disperses from being localized to becoming
spread out if it is not hindered.
Example 1: A rock (system) will fall if it is lift up and let go freely (surroundings = air+ground).
When rock falls down and cooled Kinetic Energy (Air motion)
Potential Energy
back to its initial temperature after Sound Energy (Compressed Air)
Localized in system (Rock) it hits the ground Heating Air & Ground
◦ Entropy: ”the uselessness of the energy of the universe”.

Example 2: 10 tons of high-temperature & high-pressure steams + A river of cold water
- Spontaneous process: they will become warm water if mixing them together;
- Usefulness of energy: Before mixing, the steams of high-T & P can be used to generate a
lot of electricity (very useful!). After mixing, although the total energy keeps unchanged, the
energy of the universe is much less useful: they can not be used for power generation at all.
- The entropy, i.e., the uselessness of the energy of the universe, will always increase in any
spontaneous process until an equilibrium state is reached (stop changing).
◦ The 2nd law in entropy ( dS )U ,V , m ≥ 0 The equality holds only for equilibrium state.
Just measures the spontaneous dispersal of energy: How much
∆S =" Energy dispersed" / T energy is spread out in a process as a function of temperature.
The 2nd law for a fixed energy system of fixed mass and volume (i.e., no heat or work interaction) is not
particularly useful since more frequently, one need to calculate the composition of a mixture at a given
temperature, pressure and stoichiometry — Gibbs free energy
◦ The 2nd law in Gibbs free energy G ≡ H − TS : (dG )T , P , m ≤ 0

12
▫ Chemical equilibrium principle
◦ Gibbs free energy for a mixture of ideal gases
Gmix = ∑ Ni gi,T ≡ ∑ Ni [ gio,T + RuT ln(Pi / P o )]

g i ,T : the Gibbs function for the i − th species
g io,T : the Gibbs functionon of the pure species at the standard − state pressure (i.e., Pi = P o )
g io (T ) ≡ g of ,i (T ) +
1
424 3 ∑
α j g oj (T )
j elements
Gibbs function
of formation
α j : stoichiometric coefficients of elements j required to form 1mole of the compound
Pi = xi P P : pressure of the mixture, which does not necessarily equal 1atm (= P o )
i i ∑ i
∑ dNi [ gio,T + RuT ln(Pi / Po )] = 0
d (ln P ) = dP / P dP = 0
dGmix = 0 i   → (at equilibrium)
◦ Chemical Equilibrium Expression:

a A + b B +L ⇔ eE + f F +L dN A = −κ ⋅ a dN B = −κ ⋅ b L dN E = +κ ⋅ e dN F = +κ ⋅ f L
[ ]
( P / P o ) e ⋅ ( PF / P o ) f ⋅ etc
− (e g Eo ,T + f g Fo,T + L) − (a g Ao ,T + b g Bo ,T + L) = Ru T ln E
14444444442444444444 3 ( PA / P o ) a ⋅ ( PB / P o ) b ⋅ etc
Standard−state Gibbs function change, ∆GTo =∑ Prod −∑ React 14 444 4244444 3
Equilibrium constant, K p
∆GTo = (e g of ,E + f g of ,F + L) T − (a g of ,A + b g of ,B + L) T (Standard-state Gibbs function change)

o e o f
( PE / P ) ⋅ ( PF / P ) ⋅ etc
Kp = (Equilibrium constant)
( PA / P o ) a ⋅ ( PB / P o ) b ⋅ etc
∆GTo = − RuT ln K p or K p = exp(− ∆GTo /( RuT ))
13
▫ How to calculate full equilibrium products of combustion
◦ Assuming no dissociation: i.e., ignore some minor species in combustion product;

◦ Adiabatic flame temperature & Composition of combustion products can be obtained by

solving the equations (principles) simultaneously:
- The first law of thermodynamics: by which Adiabatic Flame Temperature can be
obtained if the composition of combustion products is given.
- Chemical equilibrium principle: which provides equations on the composition of
combustion products at given mixture temperature and pressure.
- Conservation of elements (i.e., atom-conservation): which provides additional equations
on composition to close the problem.
At given temperature & pressure, the composition of combustion products can be obtained from
the combination of the latter two rules.
◦ Principle of Le Chatelier: Any system initially in a state of equilibrium when subjected

to a change (e.g., increasing pressure or temperature) will shift in composition in such a
way as to minimize the change.
CO 2 ⇔ CO + 12 O 2 − Q
- Increasing the pressure suppresses the dissociation of CO2 into CO and O2; (shift in fewer-
moles direction to lower pressure)
- Increasing the temperature at a fixed pressure promotes the dissociation. (shift in the
endothermic direction to lower temperature)
14
MM2: Chemical Kinetics
Contents
· Global vs. Elementary reactions
· Elementary reaction rates

▫ Bimolecular reactions
▫ Arrhenius equation
▫ Other elementary reactions
· Rates of reaction for multistep mechanisms

▫ Net production rate
▫ Relation between rate coefficients and equilibrium constants
▫ Steady-state approximation
▫ Partial equilibrium approximation
▫ Chain and chain-branching reactions (3 explosion limits in H2-O2 system)
15
· Global vs. Elementary reactions

▫ Global reactions — ”Black-box” approach
◦ 1mol fuel + a mols oxidizer to form b moles combustion products
F + a Ox → b Pr
[X i ]: the molar concentration (kmol / m 3 )

d [X F ]
ω& F ≡ = −kG (T ) ⋅ [X F ] n ⋅ [X Ox ] m of the i th species in the mixture.
dt
◦ Global reaction rate kG (T ) : generally not a constant, but a strong function of T.
◦ Reaction order: exponents n & m relate to the reaction order.

- the reaction is nth order with respect to the fuel, mth order with respect to the oxidizer,
and (n+m)th order overall;
- For global reactions, n and m are not necessarily integers;
- For elementary reactions, reaction orders will always be integers.
▫ Elementary reactions
◦ Intermediate species: unrealistic to believe a oxidizer molecules simultaneously
collide with 1 single fuel molecule to form b product molecules, since this would require
breaking several bonds and subsequently forming many new bonds.
2H 2 + O 2 → 2H 2O (Global reaction)
 H 2 + O 2 → HO 2 + H (1)
 H + O → OH + O (2)
 2
(Important elementary reaction)
 OH + H 2 → H 2 O + H (3)
 H + O 2 + M → HO 2 + M (4)

16 L
Q: Why is the global reaction highly improbable? Why is the 1st reaction likely to be an
elementary reaction? (based on simple molecules collision)
H2 : H−H O2 : O=O
H 2O : H−O−H HO 2 : H−O−O
A: (1) For the global reaction to occur, two H2 molecules must simultaneously collide
with one O2 molecule in the appropriate orientation, e.g.,
H H
O=O
H H
In addition, 1 double bond and 2 single bonds must be broken and 4 single
bonds must be formed.
Based on the chance of the molecules colliding correctly and the appropriate
bonds being broken and formed, it is apparent that the global reaction is highly
improbable.
(2) For the 1st reaction to occur, one H2 molecule must collide with one O2 molecule
(with fairly general orientation), e.g.,
H−H O=O
In addition, only 1 single bond must be broken, 1 double bond must be

transformed to a single bond, and one single bond must be formed.
The probability of the molecules colliding correctly and the appropriate bonds
being broken and formed is relatively large, indicating this reaction could be an
elementary reaction.
In order for a reaction to occur, the molecules must collide in an appropriate
17 orientation and the proper bonds must be broken and formed.
· Elementary reaction rates

▫ Bimolecular reactions: Most elementary reactions in combustion are bimolecular
A+B→C+D
d [A ]
= −kbimolec [A ] [B] [A ], [B]: the molar concentration (kmol/m 3 ) of A and B, respectively
dt
◦ Reaction order & rate
- All elementary bimolecular reactions are overall second order, being first order with respect
to each of the reacting species;
- The rate coefficient, k bimolec , again is a function of T, but has a theoretical basis.
◦ Collision theory:
 No. of collisions between 
d [A ]  all A and all B molecules  
Probability that a 
 kmol of A 
− =  ⋅ collision leads to  ⋅  
dt Unit volum e × unit time    No. of A molecules
   reaction  144424443
144444244444 
3
1 4 4 4 2 4 4 43 3rd term = Constant
2nd term
1st term
1st term depends on 3 factors:
- Number of A & B molecules, i.e., their molar concentrations. So, the first term ~ [A][B];
- Mean traveling speed of the molecules v , which is T-dependent, v ~ T 1/ 2 ;
- Diameters and mass of A and B molecules.
2nd term depends on 2 factors, it can be expressed as a product of the two factors:
- An energy factor, exp(− E / RuT ) , which expresses the fraction of collisions that occur with an
energy above the threshold level necessary for reaction, E, or activation energy;
- A geometrical or steric factor, p, that takes into account the geometry of collision between
A and B. e.g., OH + H → H 2O , a reaction is more likely if H atom strikes the O side of OH
18 rather than the H side, since the product’s bond: H-O-H.
▫ Arrhenius equation
d [A ]
− ∝ C1 T 1 / 2 [A ][B]⋅ C2 p exp( − E / RuT ) ⋅ 1 / N AV
dt 14 4244 3 14442444 3 123
1st term 2nd term 3rd term
- Arrhenius equation: The bimolecular rate coefficient kbimolec can be expressed by
d [A]
= −kbimolec [A] [B]
dt
k (T ) = A exp( − E / Ru T ) (Arrhenius form)
A : pre − exponential factor (or frequency factor), a constant, including all the units for rate coefficient.
1/ 2
But from the derivation based on collision theory, A is not strictly constant but A ~ T .
- Arrhenius plots of log k ~ 1 / T for experimental data are used to get the two parameters.
- Three-parameter function form for the rate coefficient, kbimolec:

k (T ) = A T b exp( − E / RuT )
▫ Other elementary reactions (Unimolecular & Termolecular reactions)

◦ Unimolecular reactions: a single species to form one or two product species
A→B or A→B+C
◦ Termolecular reactions: involve three reactant species. General form:
A+B+M→C+M
M may be any molecule and is frequently referred to as a third body.
19
· Rates of reaction for multistep mechanisms

▫ Net product rate
kf
A+B⇔ C+D k f , k r : the elementary forward and reverse rate coefficients, respectively
kr
◦ Net product rate of species A:
d [A ]
= −k f [A ] [B] + kr [C] [D]
dt
▫ Relation between rate coefficients and equilibrium constants

◦ Why?
- Measuring rate coefficients of elementary reactions is a difficult task, which possess a rather
large degree of uncertainty. The more reliable rate coefficients often known no better than
within a factor of two;
- Equilibrium constants, which are based on thermodynamic measurements or calculations,
are very accurate and precise in most cases.
◦ How?
- For equilibrium condition, A+B=C+D, the Net Production Rate of species A must be zero, as
well as other species;
− k f [A ] [B] + kr [C] [D] = 0 ⇔
[C] [D] = k f
[A ] [B] kr
- The equilibrium constant based on partial pressures for an arbitrary equilibrium reaction:
( P / P o )c ( P / P o ) d L
Kp = C o a D o b c, d , a, b (superscripts) : the stoichiometric coefficients
( PA / P ) ( PB / P ) L
- Define an equilibrium constant based on molar concentration, Kc
Kc =
[ ] [ ]
C c D dL N P
[ ] [ ]
A a B bL
Molar concentration X i = i = i [ ]
20 V RuT
◦ What?
K p = K c ( RuT / P o )c + d +L− a −b −L K c = K p (for a bimolecular reaction)
k f (T )
= K c (T )
k r (T )
▫ Steady-state approximation
◦ In many combustion systems, highly reactive intermediate species, e.g., radicals, are formed.
◦ Physically, after a rapid initial buildup in concentration, the radical is destroyed as rapidly as it
formed, so its rate of formation and rate of destruction are equal. This situation typically
occurs when the reaction forming the intermediate species is slow, while the reaction
destroying the intermediate is very fast. Thus the concentrations of the radical are quite
small comparing with reactants and products.— Apply Steady-state approximation to
intermediates or radicals.
◦ Example: Formation of nitric oxide, where the reactive intermediate of interest is N atom.
 O + N → k1
NO + N Slow (rate limiting)
2
 k2
 N + O 2 → NO + O Extremely fast
- Net production rate of N atom:
d [N ]
= k1[O] [N 2 ] − k2 [N ] [O 2 ]
dt
- After a rapid transient allowing the buildup of N atoms to some low concentration, the 2
terms on the right-hand-side become equal. The steady-state concentration of N atoms:
[N] ss = k1[O] [N 2 ]
k2 [O 2 ]
21
▫ Chain and chain-branching reactions

◦ Chain reactions
- involve the production of a radical species that subsequently reacts to produce another
radical. This radical, in turn, reacts to produce yet another radical.
- this sequence of events, or chain reaction, continues until a reaction involving the formation
of a stable species from two radicals break the chain.
◦ A hypothetical chain mechanism

A 2 + B 2 → 2AB (global reaction)
(1) Chain-initiation reaction:

k1
A 2 + M → A+A+M M : may be any molecule & frequently referred to as a "Third Body"
(2) Chain-propagating reactions involving the free radicals A and B are,
k
A + B2 →
2
AB + B
k
B + A 2 →
3
AB + A
(3) Chain-terminating reaction:
k
A + B + M →
4
AB + M
◦ Chain-branching reactions
- involve the formation of two radical species from a reaction that consumes only one radical.
The existence of a chain-branching step in a chain mechanism can have an explosive effect.
- With chain branching, radical species concentration could build up geometrically, causing
the rapid formation of products. The rate of the chain-initiation step does not control the
overall reaction rate any more. Instead, the rates of radical reactions dominate.
- explosion behavior of mixtures of H2 and O2 is a result of chain-branching steps.
22
◦ H2-O2 system: 3 explosion limits (an example)
2H 2 + O 2 → 2H 2O (global reaction)
(1) Chain-initiation reaction:

 H2 + M → H + H + M (very high temperatures) (1)
 H + O → HO + H (other temperatures) (2)
 2 2 2
(2) Chain-propagating reactions involving the free radicals (O, H & OH):
 H + O 2 → O + OH (3)
 O + H → H + OH (4) Fast reaction in both forward and reverse directions
2
 H + OH → H O + H (5)
 2 2
 O + H 2 O → OH + OH (6)
(3) Chain-terminating reactions involving the free radicals (O, H & OH):
 H + H + M → H2 + M (7)
 O + O + M → O 2 + M (8)
 H + O + M → OH + M (9) Slow reaction

 H + OH + M → H 2 O + M (10)
(4) Include reactions involving radical HO2 & species H2O2 to complete the mechanism:
H + O 2 + M → HO 2 + M (11) - Chain term inating reaction at low T & middle P

- Active at high pressures
 HO 2 + H → OH + OH (12)

M HO 2 - involved chain sequence
 HO 2 + H 2 → H 2 O 2 + H (13)
 H 2 O 2 + OH → H 2 O + HO 2 (14)

 H 2 O 2 + H → H 2 O + OH (15) H 2 O 2 − involved chain sequence
23  M
3 explosion limits
(if follow a vertical line, say at 500C)
- 1st explosion limit: Mean-free path becomes
short enough for O, H & OH radicals to react
with other species before destroyed at walls.
At low pressures: molecular mean-free path is
long enough for O, H, & OH radicals to reach & be
destroyed by walls before reacting with other

3000 species, resulting in the quenching of the chain-
propagating reactions and no explosion occurs.
As the pressure increases: molecular mean-
free path decreases and the O, H, & OH radicals
begin to react with other species. At some
pressure (e.g., ~1.5mmHg for 500C), the chain-
propagating reactions prevail over wall radical
destruction and the mixture can explode.
- 2nd explosion limit: HO2 radical destruction
at walls.
As pressure is increased past the 1st explosion
limit, reaction (11) begins to compete with (3) for
50 H atoms. HO2 radical is relatively inactive and can
reach walls & be destroyed. At some pressure
(e.g., ~50mmHg for 500C), the former prevails
over the latter, which effectively quenches the H
radicals and terminates the explosion process.
- 3rd explosion limit: Mean-free path becomes
short enough for HO2 radical to react with
other species before being destroyed at alls.
At higher pressure (e.g., ~3000mmHg for
500C), the mean-free path becomes short enough
1.5 for HO2 radicals to react with other species, e.g.,
reactions (12)-(13), before being destructed at
walls. Reaction (13) adds a chain-branching step
which opens up the H2O2 chain sequence.
24
▫ Partial equilibrium approximation
◦ Many combustion processes simultaneously involve both fast and slow reactions such
that the fast reactions are rapid in both the forward and the reverse directions.
Treating fast reactions as if they were equilibrated simplifies chemical kinetics
by eliminating the need to write rate equations for the radical species involved.
Example: The 3 fast chain-propagating reactions in H2-O2 combustion system: R3, R4 &
R5. Derive the algebraic relations for the radicals [O], [H] & [OH] in terms of
kinetic rate coefficients, Kc’s (or kf’s, kr’s), and the molar concentrations of
reactants and products, [H2], [O2] & [H2O].
[Solution] RR3 f = RR3r
⇔ k3 f [H ][O 2 ] = k3r [OH ][O]
⇔ K c, 3 =
[OH][O] = k3 f
[H][O 2 ] k3r
K c, 4 =
[OH][H] = k4 f K c, 5 =
[H 2O][H ] = k5 f
[O][H 2 ] k4r [OH ][H 2 ] k5r
 [O 2 ] [H 2 ]
 [O ] = K c, 3 K c, 5 [H O]
 2
 1/ 2
2 [O 2 ] [H 2 ] 
  3
⇒  [H ] = K c, 3 K c, 4 K c, 5



 [H 2O] 2 

(
 [OH ] = K c, 3 K c, 4 [O 2 ] [H 2 ] )
1/ 2

- Major advantage: Eliminate production rates for the radicals.
- If add the slow reaction, R10, to the 3 fast reactions, then the production rate of H2O:
ω& H 2 O ≡ k10 [H ][OH][M ]
25
MM3: Premixed Flames: Laminar vs. Turbulent
Contents
· Two types of flames

▫ Premixed flames vs. Duffusion flames (i.e., nonpremixed flame)
· Laminar premixed flames

▫ Typical laminar flame structure
▫ Phenomena & problems (All related to flame speed & thickness)
- Ignition & quenching; Flammability
- Flame stability: Flashback & Liftoff & Blowoff
▫ Flame speed & thickness and influencing factors
· Turbulent premixed flames

▫ Basic concepts
- Length scales & time scales
- Turbulence Reynolds number & Damkohler number
▫ Three turbulent-flame regimes
▫ Turbulent flame stabilization
26
· Two type of flames
◦ Flame: ”A flame is a self-sustaining propagation of a localized combustion zone at
subsonic velocities.”
(1) Premixed flame

◦ Gaseous fuel and oxidizer are perfectly mixed before combustion;

◦ Rapid, essentially constant-pressure, exothermic reaction;
◦ Laminar premixed flames have a unique burning velocity for given fuel-oxidizer mixture;
Turbulence increases the burning velocity.
(2) Diffusion flame (i.e., Nonpremixed flame)

◦ Gaseous fuel and oxidizer streams are separated;
◦ Combust as they mix;
◦ Dominated by the mixing of reactants, which can be either laminar or turbulent;
◦ Reaction take place at interface between fuel and oxidizer.
Typical Bunsen-burner flame is a dual flame:

- a fuel rich premixed inner flame;
- a diffusion outer flame: resulted when CO & H2 products
from rich inner flame encounter ambient air.
27 (Premixed fuel & oxidizer)
· Laminar premixed flames

▫ Typical laminar flame structure
Cold reactants
zone Product zone
(little heat released) (Bulk of chemical energy released)
Fast- Slow-chemistry region
For stoichiometric hydrocarbon mixtures in ambient air:

◦ The flame is ~1 mm thick and moves at ~0.5 m/s;
◦ Pressure drop through the flame is very small: ~1 Pa;
◦ Temperature in reaction zone is high: 2200-2600 K;
◦ Density ratio of reactant to product: ~7;
◦ 2 sub-reaction zones: (1) Fast-chemistry (dominated by bimolecular reactions; destruction of fuel
molecules & creation of many intermediate species occur; blue in lean-flame due to CH & blue-green in
slightly-rich flame due to C2); (2) Slow-chemistry, dominated by three-body radical recombination
28 reactions & burnout of CO (via CO+OH= CO2+H).
◦ For the flame to remain stationary, the flame speed must equal the speed of the normal
component of unburned gas at each location
et
she
e
m
F la
Flame speed, SL
(burning velocity)
Flame speed (burning velocity)

Ignition point (moving toward unburned fuel) A thin layer of gasoline (stationary)
S L = vu sin α
It causes the essential conical character of the flame.

29
▫ Phenomena & problems

◦ Ignition & quenching criteria (Williams’ criteria)
- Criterion I – Ignition will only occur if enough energy is added to the gas to heat a slab
about as thick as a steadily propagating laminar flame to the adiabatic flame temperature;
- Criterion II – The rate of liberation of heat by chemical reactions inside the slab must
approximately balance the rate of heat loss from the slab by thermal conduction.
◦ Ways to extinguish a flame

- Flame passing through narrow passgeways;
Quenching distance: the critical diameter of a circular tube where a flame extinguishes,
rather than propagates, which is very dependent on flame thickness.
- Addition of diluents;
- Blowing flame way from the reactants, dependent on flame speed.
◦ Flammability limits
- Theoretical: A flame will propagate only within a range of mixture concentrations between
lower and upper limits of flammability (the leanest mixture – the richest mixture);
- Practical: Experimental flammability limits are also related to heat losses from the system;
Due to radiation from high-temperature

combustion products to lower-temperature
environment, flame cools. The cooling creates
a negative temperature gradient at the rear of
the flame zone.
Then heat is lost by conduction from the
flame proper.
When sufficient heat is removed, the flame
ceases to propagate.
30
◦ Flashback & liftoff (balance between flame speed and unburned mixture velocity)
- Flashback— flame enters & propagates in

burner tube without quenching.
Operation in area to the left of flashback-
zone line results in flashback. Flashback-free
operation (right) – Higher velocity;
The least tolerance to flashback @ slightly

rich stoichiometries — where maximum
laminar flame speed occur. (effect of
stoichiometry on laminar flame speed)
The flashback stability of natural gas (CH4)
is much greater than manufactured gas, as a
Due to soot formation in rich flame result of high flame speed for H2 in the latter.
(effect of species on laminar flame speed)
Natural gas - Liftoff— flame is not attached to burner

tube, rather than, stabilized at some
distance from the tube.
Depend on local flame & flow properties
near the edge of burner port;
At low flow velocity: flame edge is close to
burner lip— attached;
At increased velocity: cone angle of flame
decrease (=1/sin(SL/vu)), the edge of flame
displaced a small distance downstream;
Further increase in velocity: flame edge
jumps to a downstream position far from
burner lip — lifted; … then blowoff.
Decreased heat & radical loss to burner tube
vs. Increased dilution with ambient fluid.
Greater stability to lifting of manufactured
gas flame than natural gas flame — due to
high flame speed for H2.
31 Manufactured gas (containing H2)
▫ Flame speed & thickness and the influencing factors

◦ Major assumptions:
- 1D, constant-area, steady flow;
- Kinetic & potential energies, viscous shear work, and thermal radiation are all neglected;
- Small pressure difference across the flame is neglected: thus the pressure is constant;
- Diffusion of heat and mass are governed by Fourier’s and Fick’s laws, respectively;
α k
- Lewis number, thermal/mass diffusivity, is 1 to simplify energy equation, Le ≡ = =1;
D ρ cpD
- Individual species specific heats are all equal and constant;
- Fuel and oxidizer form products in a single-step exothermic reaction;
- Fuel is completely consumed at the flame;
- Reaction is confined to the second half of the flame thickness, δ / 2 < x < δ .
1 kg Fuel + ν kg Oxidizer → (ν + 1) kg Products
32
◦ Mass conservation equation
m& ′′ = ρ v x = ρu S L = constant
& ′′ , then S L will be obtained.
If we can solve the mass burning rate m
◦ Energy conservation equation

dT d  dT 
m& ′′c p
1424 dx
3
+
dx 
(− ρ ⋅ D ⋅ c p )
dx 
= − h of ,i m& i′′′
14243 ∑
144424443 by chemical reaction
by convection /volume by diffusion per unit volume
( )
= − h of , F m& F′′′ + h of ,Ox (ν m& F′′′ ) − h of , Pr (ν + 1) m& F′′′
( )
= −m& F′′′ h of , F + ν h of ,Ox − (ν + 1) h of , Pr ≡ −m& F′′′ ∆hc
3
m& F′′′ : the reaction rate (per unit volum e), = ω& F × MWF , kg /( s ⋅ m ), (dependent on tempera ture)
∆hc : heat of combustion of the fuel
dT 1 d  dT  m& ′′′ ∆h
m& ′′ − k =− F c
dx c p dx  dx  cp
(1) Integrate the energy conservation equation over − ∞ < x < +∞

dT / dx = 0 ∞
T =T k dT ∆hc
m& ′′ T T =Tb −
u c p dx dT / dx = 0
=−
cp ∫ m& F′′′ dx
−∞
δ δ Tb
∆hc linear between dx & dT ∆hc δ ∆hc δ
m& ′′ (Tb − Tu ) = −
cp ∫ m& F′′′ dx   → = −
cp ∫ m& F′′′
Tb − Tu
dT = −
c p Tb − Tu ∫ m& F′′′ dT
0 0 Tu
∆hc ⋅ δ
m& ′′ (Tb − Tu ) = − m& F′′′ (1)
cp
33
& ′′, δ )
Eqn(1) gives a relation between ( m (i.e., ( S L , δ ) ).
& F′′′ = ω& F MWF ≡ −k (T ) ⋅ [X F ] n ⋅ [X Ox ] m ⋅ MWF

! Attention in calculating the average reaction rate, m
Since assuming reaction takes place in 2nd half flame thickness, use mean temperature
in δ / 2 < x < δ to evaluate the rate coefficient, k (T ) , in Arrhenius equation.
(2) Integrate the energy conservation equation over − ∞ < x ≤ δ / 2 for the 2nd equation.
dT / dx = (T −Tu ) / δ δ /2
T = (T +T ) / 2 k dT b
∆hc
m& ′′ T T =T u b
u
−
c p dx dT / dx = 0
= −
cp ∫
m& F′′′ dx = 0
− ∞
14442444 3
reaction occurs in 2nd half
m& ′′ δ / 2 − k / c p = 0 (2)
! Attention in calculating all the properties: Since conduction occurs over entire flame
thickness while not only in 2nd half where reaction is confined, both conductivity & specific
heat should be based on the mean temperature over the entire flame thickness.
& ′′, δ ) can be solved, then ( S L , δ ) will be solved:

From (1) & (2), ( m
1/ 2
 m& ′′′ 
S L = − 2α (ν + 1) F 
 ρu  α ≡ k /( ρu c p ) thermal diffusivity
δ = 2α / S L
34
◦ Influence of different factors on flame speed & thickness
1 −1 k (T ) 0.75
~Tu P ; ~T
k (T ) ρu
→α ∝ TuT 0.75 P −1
c p (T )
α≡     where T ≡ 0.5(Tu + Tb )
ρu c p (T )
k (T ) ~ exp( − E / R T ); [ X ]= P /( R Tb )
m& F′′′ ρu ∝ (Tu P −1 ) k (T )[X ] n     ub    u  → ∝ (Tu P −1 ) exp( − E / RuTb ) P n / Tbn
1424 3 1424 3 n : overall reaction order
1/ ρu ω&
m& F′′′ ρ u ∝ TuTb− n P n −1 exp( − E / RuTb )
S L ∝ T 0.375TuTb− n / 2 exp( − E / 2 RuTb ) P ( n − 2) / 2
δ ∝ T 0.375Tbn / 2 exp( + E / 2 RuTb ) P − n / 2
- Strong temperature dependence of laminar flame speed;

- Pressure dependence of laminar flame speed: depend on the reaction order n;
- Equivalence-ratio dependence of laminar flame speed;
- Fuel type;
- ……
35
◦ Effect of temperature on flame speed
◦ Effect of pressure on flame speed

Theory indicates a dependency on reaction order;
Experimental measurements generally show a

negative dependence of pressure
36
◦ Effect of equivalence ratio
Except for very rich mixtures, the primary

effect of equivalence ratio on flame speed
for similar fuels is a result of how this
parameter affects flame temperature.
one would expect flame speeds to be a

maximum at a slightly rich mixture and
fall off on either side.
Flame thickness shows the inverse

trend, having a minimum near
stoichiometric.
37
◦ Effect of fuel type

- Roughly speaking, the flame velocities of

C3-C6 hydrocarbons all follow the same
trend as a function flame temperature.
- C2H4 and C2H2 have flame velocities
greater than the C3-C6 group, while CH4
lies somewhat below.
- H2’s maximum flame speed is many times
greater than that of C3H8, because (1)
the thermal diffusivity of pure H2 is many
times greater than the hydrocarbon fuels;
(2) the mass diffusivity of hydrogen is
much greater than for the hydrocarbons;
(3) the reaction kinetics for H2 are very
rapid since the relatively slow step
CO → CO 2 that is a major factor in
hydrocarbon combustion is absent.
38
· Turbulent premixed flame
▫ Basic concepts
◦ Turbulent flow increases the flame propagation, but no evidence that turbulence
substantially alters the chemistry.
◦ No practical universal method to predict turbulent flame behavior.

◦ 3 kinds of turbulent-flame regimes:
- Wrinkled laminar-flame regime;
- Distributed-reaction regime;
- Flamelets-in-eddies regime.
◦ Turbulent flame speed

m& m& : reactant flow rate; ρu : unburned gas density; A : time − averaged flame area
St =
A ρu
◦ ′ = (u ′) 2 + (v ′) 2 + ( w′) 2
Turbulent intensity v rms
◦ Turbulent length scales — Integral scale & Kolmogorov scale

l0 − integral scale, i.e., the largest eddy scale 0.25
 ν 3l0 
lk − Kolmogorov microscale, i.e., the smallest eddy scale, =  
 ( v′ ) 3 
 rms 
′ l0
v rms
◦ Turbulence Reynolds number Re l0 =
ν
◦ Damkohler number: a characteristic flow (mixing) time / a characteristc chemical time
′
" eddy turnover time" for the largest eddies l 0 / v rms
Da ≡ =
chemical reaction time δ L / SL
39
▫ Three turbulent-flame regimes

δL ≤ lK Wrinkled laminar-flame regime
The reaction zone thickness is much thinner than the

smallest scale of turbulence: the turbulent motion can only
wrinkle or distort the thin laminar flame zone.
l0 > δ L > l K Flamelets-in-eddies regime
parcels of
unburned gas
Kolmogorov microscale l K
= (100, 1, 0.01)
Laminar flame thickness δ L
Largest eddy scale l l0 < δL Distributed-reaction regime
= 0 (1, 10000)
Laminar flame thickness δ L All turbulent motion scales smaller than reaction zone
Turbulent intensity v′rms thickness, then transport in reaction zone is governed by
= (0.01, 1, 100, 10000)
40 Laminar flame speed S L both molecular processes and turbulence.
◦ Wrinkled laminar-flame regime
- Chemical reactions occur in thin sheets (thinner than Kolmogorov scale);
- Damkohler number always greater than 1 — Fast chemistry (comparing with fluid mixing);
- Flame becomes wrinkled— flame area larger than laminar flme;
- Flame speed less dependent on laminar burning velocity & thus less on fuel/air or fuel type;
- Flame speed: 3~5 times laminar burning velocity.
◦ Distributed-reaction regime
- Difficult to achieve in a practical device: require simultaneously small integral length scale
(l0) & large turbulent intensity — very high velocity in small passages (huge pressure loss &
less sustainable flame)
- Damkohler number always less than 1 — Slow chemistry (comparing with fluid mixing);
- Many pollution formation reactions are slow & occur in distributed regions;
- Difficult to handle: transport in reaction zone governed by both molecules & turbulence.
◦ Flamelets-in-eddies regime
- Characterized by moderate Damkohler numbers & high turbulence intensity (v rms ′ / S L >> 1 );
- Of particular interest: some practical combustion devices operate in this regime;
- Follow the ideas that support eddy-breakup model — (1) burning zone consists of parcels
of unburned gas & almost fully burned gas; (2) combustion rate determined by the rate at
which parcels of unburned gas are broken down into smaller ones (create sufficient interfacial
area between unburned mixture & hot gases to enable reaction); (3) thus chemical reaction rates
play no role in determining burning rate while turbulent mixing rates controlled.
41
▫ Methods to turbulent flame stabilization

◦ Low-velocity bypass ports
◦ Refractory burner tiles
◦ Bluff-body flame-holders
◦ Swirl or jet-induced recirculating flows
◦ Rapid increase in flow area creating recirculating separated flow
Creation of a strong recirculation zone of hot products close to the burner throat
(1) ignites unburned gases; (2) provides a zone where local turbulent flame speed match local
flow velocity
42
MM4: Diffusion Flames: Laminar vs. Turbulent
Contents
· Laminar diffusion flames

▫ Laminar constant-density jets
▫ Laminar jet flame
- Flame contour: Temperature, species mass fractions & velocity field
- A few important features: Flame surface, soot, length vs. initial condition
▫ Theoretical analysis
- Conserved scalars: Mixture fraction
- Flame length and its dependence on flowrate & stoichiometry
· Turbulent diffusion flames

▫ Flame shape and size — Flame length
▫ Flame holding and stability — Liftoff & blowout
43
· Laminar diffusion flame

▫ Laminar constant-density jet (nonreacting)
◦ Why – much in common with laminar jet flame; easier to describe mathematically.
Still air
Fuel jet
ρ e , ve
Y F ,e ≡ 1
◦ Potential core – the effects of viscous shear & diffusion have not yet to be felt; both
the velocity and nozzle-fluid mass fraction remain unchanged from their nozzle-exit
values and are uniform in this core.
◦ The initial jet momentum is conserved: The jet velocity decreases, while larger and
larger amount of air is entrained into the jet as it proceeds downstream.
◦ The mass of “fuel” issuing from the nozzle is conserved.
? Detailed velocity and fuel mass-fraction field in the jet.
44
◦ Assumptions
- Uniform fluid density throughout the flow field, ρ ( r , x ) = ρ e = constant ;
- Species molecular transport is by simple binary diffusion governed by Fick’s law;
- Momentum & species diffusivities are constant & equal, i.e., Schmidt number Sc ≡ ν / D = 1 ;
- Only radial diffusion of momentum and species is important; axial diffusion is neglected. (it
implies that the solution only applies some distance downstream of the nozzle exit).
◦ Governing equations
∂ v x 1 ∂ (vr r )
- Mass conservation equation + =0
∂ x r ∂r
∂vx ∂v 1 ∂  ∂vx 
- Axial momentum conservation equation v x + vr x = ν r 
∂x ∂r r ∂ r  ∂ r 
∂YF ∂Y 1 ∂  ∂YF 
- Species conservation equation v x + vr F = D r 
∂x ∂r r ∂ r  ∂ r 
YOx = 1 − YF
◦ Boundary conditions
- Along the jet centerline: (1) no source/sink of fluid; (2) Symmetry condition;
v r (0, x ) = 0; ∂ v x (0, x ) / ∂r = 0; ∂Y F (0, x ) / ∂r = 0
- At large radius: (1) stagnant fluid; (2) no fuel present;
v x (∞, x) = 0; YF (∞, x ) = 0
- At jet exit: uniform axial velocity & fuel mass fraction at nozzle mouth and zero elsewhere.
v x (r ≤ R, 0) = ve ; YF (r ≤ R, 0) = YF , e = 1; v x (r > R, 0) = 0; YF (r > R, 0) = 0
45
◦ Solution
v x / ve = 0.375 × Re j × ( x / R) −1 × (1 + ξ 2 / 4) −2 valid for ( x / R) ≥ 0.375 Re j
0 .5 ξ3 Re j : Jet Reynolds number, Re j ≡ ρ eve R / µ

 3J e  1 ξ− 4
vr =   1
 3ρ J  2 1 r
 16π ρ e  x (1 + ξ 2 ) 2
ξ : contain similarity variable r/x, ξ =  e e 

4  16 π  µ x
YF = 0.375 × Re j × ( x / R ) −1 × (1 + ξ 2 / 4) −2
J e : Jet initial momentum flow , J e = ρ e ve2 π R 2
- Centerline velocity decay (Centerline mass fraction of fuel): more rapid decay at low Rej
- Spread rate: the ratio of the jet half width (i.e., the radial location where the jet velocity
decays to one-half of its centerline value) to the axial distance: High-Rej jets are narrow.
- Spread angle: the angle whose tangent is the spread rate;
Dimensionless centerline fuel mass fraction, YF,0/1
Diffusion becomes more & more important

in comparison with initial jet convection
with decrease of Rej
r1 / 2 2.97 α ≡ tan −1 (r1 / 2 / x)

=
x Re j
Relative importance of (1) Radial diffusion vs (2) Initial jet axial convection.
46
▫ Laminar jet flame
Φ (r = 0, x = L f ) = 1
Oxidizer diffuses inward
Fuel diffuses outward
◦ Flame surface: Locus of points where the equivalence ratio equals unity.
High-temperature zone occurs in an angular region until flame tip is reached.
◦ Two offsetting effects in upper regions of a vertical flame: (1) Buoyancy accelerates flow &
narrows flame (mass conservation); (2) Narrowing flow increases fuel concentration gradient,
enhancing diffusion. They cancels in predicting flame length for circular- (& square-) pot nozzle.
◦ Soot formation: For hydrocarbon flames, soot present (typically orange or yellow flame);
Formed on fuel side in reaction zone, consumed in oxidizing region (e.g., flame tip); If soot can
not be consumed out, then soot “wing” may appear — Smoke.
◦ Relationship between flame length & initial conditions: L f ~ QF / YF , stoic .
47
▫ Theoretical analysis of laminar jet flame

◦ Why need conserved scalars?
- For a three-”species” system: 1 kg Fuel + ν kg Oxidizer → (ν + 1) kg Products
In flame analysis, the assumption is always made: “Inside flame zone, only fuel and
products exist; beyond the flame, only oxidizer and products exist”;
- Closed problem: 5 equations for 5 unknowns;

5 Equations: 1 Mass conservation;
1 Axial momentum conservation;
2 Species conservation (1 for fuel, YF , & 1 for oxidizer, YOx):
∂ ∂ ∂ ∂Y
(rρ v x Yi ) + (rρ v r Yi ) − (rρ D i ) = 0
∂x ∂r ∂r ∂r
1 Energy conservation (based on mixture temperature):
 ∂ c p dT 
∂
( ∫
rρ v x c p dT +) ( ∫
∂ ∂ 
rρ vr c p dT −  rρα) =0
∫
∂x ∂r ∂r  ∂r 
 
5 Unknowns: vr ( r , x ), v x ( r , x ), T ( r , x ), YF ( r , x ), YOx ( r , x )
YPr ( r , x) = 1 − YF ( r , x) − YOx (r , x)
- Major difficulties
Some BCs necessary to solve fuel & oxidizer species & energy equations must be specified
at the flame, whose location is not yet known before solving the problem. e.g.,
∂Yi  C1 when r ≤ r f ( x ) (inside flame sheet)
= due to the discontinuity at flame sheet.
∂r  C2 when r > r f ( x) (outside flame sheet)
- Solution: Use of conserved scalars to rewrite the governing equations

Use of conserved scalars can eliminate the boundary-condition (BC) dilemma, which
require BCs only along flame axis, far from flame & at nozzle exit plane.
48
◦ What is a conserved scalar?
- It is any scalar property that is conserved through the flow field
{ + ν kg Oxidizer
1 kg Fuel 1424 3 → (ν + 1) kg Products
1424 3
Cm H n O2 + N 2 CO2 + H 2O
For example, the element mass fraction of (C+H) is a conserved scalar, since elements
(C+H) are neither created nor destroyed by chemical reaction (just change in form:
originate from Fuel & after reaction also exist in products)
The mixture enthalpy, h, is also a conserved scalar in the flow field when there are no
sources (or sinks) of thermal energy (i.e., radiation into/out of the flow; viscous dissipation)
T
h≡ ∑ Yi hof ,i + ∫T ref
c p dT
- Mixture fraction, f
Mass of elements originating from Fuel stream
f ≡
Mass of mixture
For the above three-”species” reaction: all (C+H) originates from the fuel stream.
f = ({
1) YF
{
+ ({ 1 )
ν +1
YPr
{
+ ({
0) YOx
{
kg (C + H) kg Fuel kg (C + H) kg products kg (C + H) kg oxidizer
kg Fuel kg mixture kg products kg mixture kg oxidizer kg mixture
 1  1 at fuel stream
⇔ f = YF +   YPr 
ν +1 f =0 far from the flame (all are oxidizer)
 (0, 1) inside & beyond the flame
Particularly useful For diffusion flames;

For premixed flames: uniform f everywhere assuming same diffusivity for all species.
49
◦ How to eliminate the BC dilemma by using mixture fraction?

- 4 Equations for 4 unknowns (instead of 5 equations for 5 unknowns)
4 Equations: 1 Mass conservation; (same as before)
1 Axial momentum conservation; (same as before)
1 Mixture-fraction equation (instead of 2 species conservation!):
∂ ∂ ∂ ∂f
(rρ v x f ) + (rρ vr f ) − (rρ D ) = 0
∂x ∂r ∂r ∂r
1 Energy equation (based on absolute enthalpy!):
∂ ∂ ∂ ∂h
(rρ v x h) + (rρ vr h) − (rρα ) = 0
∂x ∂r ∂r ∂r
4 Unknowns: v r ( r , x ), v x ( r , x ), h ( r , x ), f ( r , x )
- Boundary conditions: No need to use BC at flame sheet for both Mixture-fraction & Energy
equations thanks to no discontinuities in f & h at the flame sheet.
∂f (0, x) / ∂r = 0 (symmetry)

BCs for mixture fraction =  f (∞, x) = 0 (no fuel in oxidizer)
 f (r ≤ R, 0) = 1; f (r > R, 0) = 0 (top − hat exit profile)
 ∂h(0, x) / ∂r = 0

BCs for absolute enthalpy =  h(∞, x) = hOx,∞
 h(r ≤ R, 0) = h ; h(r > R, 0) = h
 F ,e Ox,∞
h−h
Under assumption α = D , if we use a dimensionless mixture enthalpy h* = h −Ox ,∞
F , e hOx , ∞
then h* = f : thanks to totally same equation & boundary condition for them.
3 equations for 3 unknowns in fact!!
- Once f(r,x) is solved, the flame sheet is easily located by f = f stoic ≡ 1 .

ν +1
- Remaining problems: Find state relations to get species (Yi, T) from f.
50
◦ How to get state relationships?
- Take inside-the-flame as an example
{ + ν kg Oxidizer
(1 + a) kg Fuel 1424 3 → (ν + 1) kg Products
1424 3 + a kg Fuel
{
Cm H n O2 + N 2 CO2 + H 2O Cm H n
α 1 (1 + ν ) 1+α
f = 1× + × =
(1 + ν ) + α 1 + ν (1 + ν ) + α (1 + ν ) + α
α
YF =
(1 + ν ) + α
f − ν 1+1 f stoic = 1 f − f stoic
ν +1
⇔ YF = 1
   → =
1 − ν +1 1 − f stoic
- State relationships
 YF = ( f − f stoic ) /(1 − f stoic )


Inside the flame ( fstoic < f ≤ 1)  YOx = 0
 YPr = (1 − f ) /(1 − fstoic )
 YF = 0

At the flame ( f = f stoic )  YOx = 0
 YPr = 1
 YF = 0

Outside the flame (0 ≤ f < fstoic )  YOx = 1 − f / fstoic
 YPr = f / f stoic
The mixture temperature can also be determined from mixture fraction.

See Eqns (9.51a)~(9.51c) (P327) for Inside flame, At flame & Outside flame, respectively.
51
- The simple and closed-form state relationships are based on the use of only 3 species
(fuel, oxidizer & products) and greatly simplified thermodynamics;
Simplified-state relationships for species mass fraction
Simplified-state relationships for mixture temperature
- For complex mixtures, state relationships are frequently based on equilibrium, partial
equilibrium methods, or experiments — the idea behind the use of mixture fraction is same.
52
◦ Flame length
- Once mixture fraction, f(r,x), is solved, then the flame length will be obtained.
- Various correlations exist from different assumptions.
(1) Effects of flowrate & geometry

In all these conditions: Buoyancy-controlled flame L f ∝ (QF ) n (n > 0)
Linear dependence of flame

length on flowrate for circular port
Somehow greater-than-linear
dependence for the slot burners.
At same flowrate: The more

narrow the slot burner ports (h/d
increasing), the significantly
shorter the flame becomes.
Short flame frequently desired

in design.
Increased surface area of jet, thus radial diffusion

becomes more important, resulting shorter flames.
Predicted flame lengths for circular & slot burners having equal port areas
53
Pure fuel from nozzle (2) Factors affecting stoichiometry

(C4H10)
L f ∝ S n (n > 0)
(C3H8)  moles ambient fluid 
S : molar stoichiometric ratio, =  
 moles nozzle fluid  stoic
(C2H6)
[Example]: Pure fuel from nozzle, ambient fluid is air.

(CH4)
C x H y + a (O 2 + 3.76 N 2 ) → x CO 2 + ( y / 2) H 2 O + 3.76a N 2
( x + y / 4) y
xO2 x+ 4 y
S= = 1
= 4.76( x + 4 )
1
1+ 3.76
Fuel + air (0% ~ 80%)

from nozzle
Decreased S Increased xO2, thus decreased S
54
· Turbulent diffusion flame
▫ General observations
◦ Shape & color
- Turbulent diffusion jet flames visually have brushy edges
- Turbulent diffusion hydrocarbon flames generally are more luminous than

the premixed ones since some soot is usually present within the flame.
- The width of the “flame zone” increases with downstream distance: large
high-temperature region at flame tip.
◦ Influence of initial jet diameter & fuel flowrate on the flame size
- At low flowrate (laminar flame): Flame height independent of jet diameter; only on flowrate;
- Transitional regime: Flow rate increases, turbulence begins to affect flame height;
- Fully turbulent flame (after transitional regime): (1) flames (local minimum) shorter than
their laminar counterparts; (2) Further increase in flowrate, flame lengths either keep
constant, or increase at decreasing rates – due to “increased jet convection & mixing rate
(radial diffusion)”; (3) Significant dependence of flame length on initial diameter.
55
▫ Flame length
◦ Simplified analysis
- Same as Laminar flame analysis: 4 equations for 4 unknowns by using Mixture Fraction;
- Difference lies on:
(1) time-averaged variables (v r , v x , f , h ) replace instantaneous ones (v r , v x , h, f ) ;
(2) turbulent transport properties (ν t , Dt , α t ) replace their molecular counterparts (ν , D, α ) .

- By assuming turbulent viscosity, mass diffusivity and thermal diffusivity are all same, then
one turbulent model is required to obtain the turbulent viscosity.
- Calculated results:
(1) Predicted flame length is about 45 nozzle diameters;
(2) Flame aspect ratio (flame length/width) is about 11:1, which is somehow greater than
experimental values of ~7:1 for hydrocarbon jet flames (neglecting density fluctuations is
probably the most serious oversimplification).
δ f /2
hf Calculated mixture-fraction distribution using

Prandtl’s mixing-length model (for turbulent
viscosity) applied to a jet flame
56
◦ Factors affecting flame length
- For vertical flames created by a fuel jet issuing into a still environment, 4 primary factors:
(1) Relative importance of initial jet momentum flux vs. buoyant forces on the flame, Fr f ;
(2) Stoichiometry, f s;
(3) Ratio of nozzle fluid to ambient gas density, ρ e / ρ ∞ ;
(4) Initial jet diameter, d j .
ve f s1.5
Fr f : Flame Froude number, ≡ ∆T f
∆T f : characteristic temperature rise
ρ
( ρ e )0.25 ( T g d j )0.5 resulting from combustion
∞ ∞
- Increased mixing, produced from buoyancy-induced motion, results in relatively shorter

flames in comparison with the non-buoyant case: “one expects the non-buoyant flame
height to decrease & the normal gravity flame height to increase”.
57
(C3H8)
(CH4)
1
- The smaller the stoichiometric mixture fractions ( f s ≡ ν +1 ), the longer the flames.
because the larger amount of air to be entrained per kg fuel.
- Increasing the density of the nozzle fluid produces the same effect as increasing the nozzle
diameter.
58
▫ Liftoff and blowout
- At sufficiently low flowrates: attached flame — flame quite close to burner tube outlet;
- At increased flowrates: liffoff — no continuous flame close to the burner port. Should be
avoided so that stable flame keeps close to the burner, allowing for positive ignition by a
spark/pilot flame at burner and assuring a controlled flame position;

- Further increase in flowrates: blowout — flame blows out. Should be avoided.
Universal blowout stability curve
◦ For a fixed fuel, blowout velocities increase with jet diameter

That is why it is hard to blow out oil-well fires.
59
MM5: Burning of Solid Fuels

Contents
· Heterogeneous reactions
· Burning of carbon
▫ Overview
▫ One-film model
▫ Two-film model
· Burning of coal
60
· Heterogeneous reactions
▫ Overall process of gas-solid reactions
1. Transport of reactant molecule to solid surface by convection and/or diffusion;

2. Adsorption of the reactant molecule on the surface;

3. Elementary reaction steps (complex physical chemistry). Instead, three “rate laws”
could be used, as a result of how strongly the reactant and/or product molecules are
adsorbed on the surface:
◦ If the reactant molecules A is weakly adsorbed, then reaction rate is proportional to the
gas-phase concentration of A adjacent to the surface,
ℜ = k (T ) ⋅ [ A ]
◦ If A is strongly adsorbed, then reaction rate is independent of the gas-phase concentration
of A,
ℜ = k (T )
◦ If the reactant molecules A is weakly adsorbed, while the product molecules B is strongly
absorbed, then reaction rate is proportional to the concentration ratio of A immediately
adjacent to the surface,
ℜ = k (T ) ⋅
[A]
[B ]
4. Desorption of product molecules from the surface;
5. Transport of product molecules away from the surface by convection and/or diffusion.
61
· Burning of carbon
▫ Overview
◦ Carbon attacked by either O2, CO2 or H2O, undergoing 4 global reactions at its surface;
◦ The principal product at carbon surface is CO;
◦ CO diffuses away from the surface and reacts with inward-diffusing O2 by global homogeneous
reaction: CO+1/2O2 = CO2;
◦ In principle, carbon oxidation problem could be solved by species, energy and mass
conservation equations (defining all of the elementary reactions), together with appropriate
boundary conditions;
◦ Difficulties: Carbon surface is porous and the detailed nature of the surface changes as carbon
reaction proceeds — Intraparticle diffusion plays a major role sometimes.
◦ Simplified models rely on the global reactions and usually assume the surface is impervious to
diffusion — One-film, two-film or continuous film models.
62
▫ One-film model
◦ No flame in the gas phase and maximum temperature occurs at carbon surface;
◦ At particle surface: Carbon reacts kinetically with O2 to produce CO2. In general, this reaction
choice is not particularly good since CO is the preferred product at combustion temperatures.
This assumption eliminates the problem of how and where CO oxidizes into CO2.
◦ How to evaluate (1) mass burning rate of carbon m
& C ; (2) carbon surface temperature Ts ; (3)
mass fractions of O2 and CO2 at carbon surface?
63
◦ Overall mass & species conservation
(No gas-phase reactions at all)
Gas phase consists of O2, CO2 and

inert gas.
O2 diffuses inward, reacting with

surface to form CO2, which then
diffuses outward.
The inert gas forms a stagnant layer.
′′ = m& net
m& C ′′ = m& CO
′′ − m& O
′′
2 2
1 kg C + ν I kg O 2 → (ν I + 1) kg CO 2 32 = 2.664
ν I = 12 m& O2 = ν I m& C m& CO2 = (ν I + 1) m& C m& i = Ai m& i′′
dYO2
Fick’s law of diffusion: ′′
m& O ′′ + m& CO
= YO2 (m& O ′′ ) − ρD
{2 142dr
144 42 2 444 32
mass flow
43
mass flow of O 2 mass flow of O 2 associated
of O 2 per associated with bulk
unit area with molecular diffusion
flow per unit area per unit area
 1 + YO2 ,∞ / ν I 
⇒ m& C = 4π rs ρ D ln 
 1 + YO , s / ν I  (Derived from mass-transfer alone)
 2 
if B is small, then ln(1+ B ) ≈ B YO2 ,∞ − YO2 , s YO2 ,∞ − YO2 , s ∆Y
 → m& C = 4π rs ρ D × = ≡
ν I + YO2 , s  ν I +YO2 , s  Rdiff
 4π r ρ D 
64  s 
◦ Surface kinetics
Carbon reaction rate (in kg/s ⋅ m 2 ) : m& C [

′′ , s = k c (T ) O2,s ⋅ MWC ] (O2 weakly adsorbed at carbon surface)
kc = A exp( − E A / RuTs )
[O2, s ] = MW
MW
mix P
RT
YO2 , s
O2 u s
MWC ⋅ MWmix P
′′ , s = 4π rs2 ⋅ A exp( − E A / Ru Ts ) ⋅
m& C = As m& C × YO2 , s ≡ K kin × YO2 , s
MWO 2 Ru T s
YO2 , s − 0 ∆Y
m& C = ≡ (Derived from chemical kinetics)
(1 / K kin ) Rkin
◦ Circuit analog
YO2 ,∞
m& C =
Rdiff + Rkin
ν I + YO2 , s
Rdiff ≡
(4π rs ) ⋅ ρ D
1 ν I ⋅ RuTs
Rkin = ≡
K kin ( 4π rs2 ) ⋅ A exp(− E A / RuTs ) ⋅ P ⋅ MWmix
65
Rkin 1 1 ν I ⋅ Ru ⋅ ρ D
= × × Ts exp( E A / RuTs ) ×
Rdiff rs P A ⋅ MWmix ⋅ (ν I + YO2 , s )
66
◦ Energy conservation
=0 (steady state)
m& C hC + m& O2 hO2 − m& CO2 hCO2 = Q& s −i + Q& s − f + Q& rad
1444442444443 {
= m& C × ∆hC =0
dT
m& C ∆hC = − k g As + ε s Asσ (Ts4 − Tsurr
4
) ⇒ Ts
dr r
s
67
▫ Two-film model
(CO & CO2) (CO2 & O2)

CO + (1/2) O2 = CO2
C + CO2 = 2CO
◦ Somehow more realistically capture the chemical & physical process in carbon combustion;
◦ Two gas films: one interior to flame sheet & one exterior;
◦ Carbon surface attacked by CO2 and reacted into CO by C+CO2 = 2CO;
◦ CO produced at particle surface diffuses outward and is consumed at a flame sheet where CO
meet an inward-diffusing O2 flow in stoichiometric proportions; thus both CO and O2 are zero at
flame sheet;
◦ Method to obtain mass burning rate of carbon is similar with one-film model.
68
· Burning of coal (biomass or other solid fuels)
▫ May burn in the different ways due to the heterogeneous nature & the wide variation
in composition;
Proximate analysis Ultimate analysis
Fixed carbon C
H
Volatiles
O
Moisture
N
There are still some other minor or
Ash S trace elements, such as Cl, Hg, ...
▫ General scheme:
◦ 1st stage: Moisture driven off;
◦ 2nd stage: Evolution of the volatiles;

The volatiles may burn homogeneously in gas phase or at solid particle surface.
Particle may swell and become porous as volatiles released during this stage.
◦ 3rd stage: Reaction of char & mineral matter.

After devolatilization, the material left is char and mineral matter. Char burns in the
same way as carbon; mineral matter is transformed into ash, slag, and fine
particulate fume in various proportions. The porous structure of char could be quite
important in actual process.
69

Theory of Combustion - YIN-Chungen

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Course Notes

FACE9 – Theory of Combustion

• Examination date: PE course

MM1. Combustion and Thermochemistry

MM2. Chemical Kinetics

MM3. Premixed Flames: Laminar vs. Turbulent

MM4. Diffusion Flames: Laminar vs. Turbulent

MM5. Burning of Solid Fuels

Stephen R. Turns. ”An Introduction to Combustion – Concepts and Applications”.

◦ High temperatures associated with combustion generally result in sufficiently low

▫ Calorific equations of state

du = cv dT u : specific internal energy, J / kg cv : constant − volume specific heat, J /( kg ⋅ K )

◦ The enthaply h is also a function of temperature T,

- 3 components of internal energy:

Yi = xi MWi / MW mix xi = Yi MW mix / MWi

◦ Equivalence ratio: commonly used to indicate quantitatively whether a fuel-oxidizer mixture

( A / F )stoic ( F / A) Φ > 1 : fuel rich mixtures

◦ Percent excess air

hi (T ) = h fo,i (Tref ) + ∆ hs ,i (Tref )

- To form O atoms at standard states

▫ First law of thermodynamics — Energy conservation

Instantaneous rate Instantaneous rate Instantaneous time

Two additional terms:

Q& + W& + m& (ei − eo ) + m& ( Pi vi − Po vo ) = dE / dt

Q& cv + W& cv = m& ( ho − hi ) + m& ( 12 v o2 − 12 vi2 )

qcv = ho − h i = hprod − hreac

∆hR ≡ qcv = hprod − hreac

◦ Example: 1 kg liquid fuel undergoing combustion in air

H reac (Tinit , P) = H prod (Tad , P )

- Demand the knowledge of the composition of combustion product. At typical flame

◦ Constant-volume adiabatic flame temperature: e.g., in an ideal Otto-cycle analysis.

U reac (Tinit , Pinit ) = U prod (Tad , Pf ) ⇔ H reac − H prod − V ( Pinit − Pf ) = 0

H reac − H prod − Ru ( N reacTinit − N prodTad ) = 0

◦ Entropy: ”the uselessness of the energy of the universe”.

◦ The 2nd law in Gibbs free energy G ≡ H − TS : (dG )T , P , m ≤ 0

Gmix = ∑ Ni gi,T ≡ ∑ Ni [ gio,T + RuT ln(Pi / P o )]

◦ Chemical Equilibrium Expression:

∆GTo = (e g of ,E + f g of ,F + L) T − (a g of ,A + b g of ,B + L) T (Standard-state Gibbs function change)

▫ How to calculate full equilibrium products of combustion

◦ Assuming no dissociation: i.e., ignore some minor species in combustion product;

◦ Adiabatic flame temperature & Composition of combustion products can be obtained by

◦ Principle of Le Chatelier: Any system initially in a state of equilibrium when subjected

· Global vs. Elementary reactions

· Elementary reaction rates

· Rates of reaction for multistep mechanisms

· Global vs. Elementary reactions

[X i ]: the molar concentration (kmol / m 3 )

◦ Reaction order: exponents n & m relate to the reaction order.

In addition, only 1 single bond must be broken, 1 double bond must be

· Elementary reaction rates

- Arrhenius equation: The bimolecular rate coefficient kbimolec can be expressed by

- Three-parameter function form for the rate coefficient, kbimolec:

▫ Other elementary reactions (Unimolecular & Termolecular reactions)

· Rates of reaction for multistep mechanisms

▫ Relation between rate coefficients and equilibrium constants

▫ Chain and chain-branching reactions

of a stable species from two radicals break the chain.

◦ A hypothetical chain mechanism

(1) Chain-initiation reaction:

(1) Chain-initiation reaction:

H + O 2 + M → HO 2 + M (11) - Chain term inating reaction at low T & middle P

destroyed by walls before reacting with other

MM3: Premixed Flames: Laminar vs. Turbulent