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نظرية احتراق 3 ميكانيكا
نظرية احتراق 3 ميكانيكا
1
2021
1
CONTENTS
Chapter 1
Introduction
Chapter 2
Thermochemistry of Combustion
Chapter 3
Introduction to Mass Transfer
Chapter 4
Chemical Kinetics
Chapter 5
Laminar Premixed Flame
Chapter 6
Laminar Diffusion Flame
Chapter 7
Droplet Evaporation and Burning
2
Chapter 1
INTRODUCTION
4
refining and cement industries extensively use energy produced
by combustion. Many others industrial processes meet their
energy need by combustion include among others: boilers,
metal melting, metal heating, metal treating, glass melting,
glass treating, fluid heating, clay firing and drying. The
demand for energy in the industrial sector is expected to
continue to increase rapidly. Most of the energy (88%) is
produced by the combustion of fossil fuels like oil, natural gas,
and coal.
6
However, combustion has some downsides related to
environmental pollution. The major pollutants generated due to
combustion include unburned hydrocarbons, nitrogen oxides,
carbon monoxide, sulfur oxides and particulate matter. Primary
pollution concerns relate to specific health hazards, smog, acid
rain, global warming and ozone depletion.
8
Chapter 2
THERMOCHEMISTRY OF COMBUSTION
In this chapter, some basic relations for ideal gases and their
mixtures are perused as they are an integral part of combustion studying.
Several thermodynamics topics related to combustion and reacting system
are also discussed. Chemical equilibrium is developed and applied to
combustion product mixtures.
V mv nv (2.1a)
U mu nu (2.1b)
H mh nh (2.1c)
Where the symbols with overbar, e.g., u and h are molar based intensive
properties.
PV mRT (2.2a)
PV NR T (2.2b)
Pv RT (2.2c)
P RT (2.2d)
Where the specific gas constant R is related the universal gas constant Rµ
(=8315 J/lmol-K) and the molecular weight MW by
R R / MW (2.3)
01
The assumption of ideal gas appears appropriate for all combustion
systems considered as the temperatures associated with combustion
processes are high that results in low densities.
T
h(T ) href c p dT (2.6b)
Tref
00
u
cp ( )P (2.7b)
T
In general, the more complex the molecule, the greater its molar
specific heat is. The specific heats cv and cp are functions of temperature.
The more complex molecules have also greater temperature dependence.
Yi 1 (2.10a)
i
i 1 (2.10b)
i
Mass fractions and mole fractions can be converted from to another using
the following expressions
i Yi MWmix / MWi (2.11a)
01
Yi i MWi / MWmix (2.11b)
Where MWmix is the mixture molecular weight and can be calculated as:
For ideal gases, the mixture pressure is the sum of the constituent partial
pressures,
P Pi (2.13)
i
The partial pressure may be related to the mixture composition and total
pressure as:
Pi i P (2.14)
u mix Yi ui (2.15b)
i
02
pressures. The constituent specific entropies can be determined using
standard-state (Pref=Po=1 atm) values as:
Pi
si (T , Pi ) si (T , Pref ) R ln (2.17a)
Pref
Pi
si (T , Pi ) si (T , Pref ) R ln (2.17b)
Pref
dPsat h fg dTsat
2
(2.19)
Psat R Tsat
1W2 is the work done by the system on the surroundings in going from
state 1 to state 2,
E1 2 is the change in total system energy (sum of internal, kinetic
and potential energies) in going from state 1 to state 2.
For a control volume, fluid may flow across the boundaries, see
Fig. 2.1b. In the case of steady-state, steady-flow (SSSF), the first law
can be expressed as:
Q cv Wcv m
eo m
ei m
( Po vo Pi vi ) (2.22)
where
04
Q cv is the rate of heat transferred across the control surface from the
surroundings to the control volume
W cv is the rate of all work done by the control volume, including shaft
work, but excluding flow work,
m eo is the rate of energy flowing out of the control volume,
m ei is the rate of energy flowing into of the control volume,
( Po vo Pi vi ) is the rate of work associated with pressure forces where
m
fluid crosses the control surface, flow work
m is the rate of mass crossing the control volume,
e is the specific energy of the system.
Fig. 2.1 (a) Schematic of fixed-mass system with moving boundary above the piston.
(b) Control volume with fixed boundaries and steady state flow.
Considering that enthalpy is the sum of internal energy and flow work,
h u Pv (2.23)
and the total system energy is the sum of internal, kinetic and potential
energies,
05
1
E m(u 2 gz ) (2.24)
2
The first law for control volume can have the following form:
1
Q cv W cv m
[(ho hi ) ( o2 i2 ) g ( z o z i )]
2
(2.25)
or on a specific mass basis,
1
q cv w cv (ho hi ) ( o2 i2 ) g ( z o z i ) (2.26)
2
Where lower case letters are used to denote mass specific quantities.
06
2.3 REACTANT AND PRODUCT MIXTURES
2.3.1 Stoichiometry
a x y/4 (2.28)
where MWair and MWfuel are the molecular weights of air and fuel,
respectively. Table 2.1 reports stoichiometric air-fuel ratios for methane
07
and solid carbon. It is also reported the oxygen –fuel ratio for combustion
of H2 in pure O2. It is noted that (O/F)ratio much greater than one
for all systems.
A/F 12-18 Spark ignition
A/F 18-70 Diesel Engine
A/F 100-200 Gas turbine
( A / F ) stoic ( F / A)
(2.29)
(A/ F) ( F / A) stoic
The definition implies that
for fuel-rich mixtures, 1
for fuel-lean mixtures, 1 .
for a stoichiometric mixture, Φ = 1.
08
There are other different parameters used to define relative
Stoichiometry. Among others,
Percent stoichiometric is defined as
100%
%stoichiometric _ air
(2.30)
(1 )
%excess _ air *100%
(2.31)
Example 1.
Butane (C4H10) burns with air at an equivalence ratio of
0.75. Determine the number of moles of air required per mole of
fuel.
Solution
The following expression may be used to calculate the (A/F) stoich for a
hydrocarbon fuel of the form CxHy.
MWair
( A / F ) stoic 4.76a
MW fuel (aa)
Where a x y / 4 4 10 / 4 6.5
28.85
( A / F ) stoic 4.76 * 6.5 * 15.33
58.12
11
( A / F ) stoic 15.33
By definition ( A / F ) 20.44
0.75
MW fuel
( A / F ) molar ( AlF )
MWair
58.12
20.44 * 41.17 Mole air/mole fuel
28.85
Another solution
MW fuel ( AlF ) stoic MW fuel
( A / F ) molar ( AlF )
MWair MWair
Using the eqn. (aa), we can get
Example 2
Solution:
The complete stoichiometric combustion reaction for the described fuel
can be expressed as
10
C3 H 8 CH 4 7 * (O2 3.76 N 2 ) 4CO2 6H 2 O 26.32 N 2
11
Enthalpy of Formation and Absolute Enthalpy
o
The enthalpy of formation, h f ,i of a particular species,
The standard state is chosen as the most stable form of the element at
1 atm and 25 oC. For oxygen and Nitrogen the standard state is
gaseous O2 and N2.
hi (T ) h (Tref ) hs ,i
o
f ,i
12
Example
Determine the absolute enthalpy for the given mixture at
temperature of 1000 K, on both a mole basis (kJ/kmol) and a mass
basis (kJ/kg)
Species CO CO2 H2O N2 NO
No. of moles 0.095 6 7 34 0.005
Solution
Using the mole fraction definition
xi N i / N T
and using tables of thermodynamics properties of gases
hs ,i hi (T ) h fo,i
13
The molecular weight of mixture is required to determined hmix
MWmix xi MWi
=0.002*28.01+0.127*44.011+.147*18.016+0.7219*28.013
+0.0001*30.006
=28.52 kmol/kg
Then,
14
Enthalpy of Combustion and Heating Values
1 2
Qcv Wcv m [(ho hi ) ( o i2 ) g ( z o z i )]
2
15
The combustion process is assumed to be complete. A stoichiometric
mixture is considered where reactants enter and products exit, both
at standard state conditions (25 oC, 1 atm).
Figure 2.4 Enthalpy of combustion for stoichiometric methane air mixture with
water in the vapor state.
16
Example
The lower heating value of vapor n-decane (C10H22) is 44,597
kJ/kg at T=298 K. The enthalpy of vaporization of n-decane is 276.8
kJ/kg of n-decane. The enthalpy of vaporization of water at 298 K is
2442.2 kJ/kg of water. Determine the lower heating value of liquid n-
decane in kJ/kg. Determine also the higher heating value of vapor n-
decane at 298 K.
Solution
MWH 2O y / 2
HHVg LHVg h fg , H 2O *
MWC x H y
18.016 * 22 / 2
HHVg 44597 2442.2 *
142.284
=47999 kJ/kg n-decane
17
Figure 2.5 Different heating values
Example
Determine the enthalpy of formation in kJ/kmol for methane,
CH4, given the lower heating value of 50,016 kJ/kg at 298 K.
Solution
For 1 mole of CH4, the combustion equation can be written as
21
Adiabatic Flame Temperature
20
As most compilations or calculations of thermodynamic properties
provide values for enthalpy rather than internal energy, the above
equation can be rearranged to the following form:
PprodV N R T
prod
i u ad N prod RuTad
Thus,
Tini Tad
hreac hprod Ru ( )0
MWreac MWprod
where MW m / N and h H /m
21
Example
Determine the adiabatic flame temperature for constant-
pressure combustion of stoichiometric propane (C3H8)–air mixture
assuming reactants at 298 K, no dissociation of the products, and
constant specific heats evaluated at 1300 K. Also, determine the
adiabatic flame temperature for constant- volume combustion,
estimating the final pressure.
Solution
22
H react Ni hi
react
i f ,i hs, i)
N (
react
h o
= - 103,847 kJ
Tad 2357 K
23
We will evaluate the properties at a higher temperature; say 1500 K,
as the constant-volume adiabatic flame temperature is expected to be
quite higher than the constant-pressure adiabatic flame temperature.
H reac - 103,847 kJ
H prod 3 * [393,546 58.292 * (Tad 298)] 4 * [241,845
47.103 * (Tad 298)] 18.8 * [0 34.805 * (Tad 298)]
Tad 2846 K
The final pressure, Pf, may be calculated as
25
CHEMICAL EQUILIBRIUM
dS 0
It implies that composition of a system will spontaneously shift
toward the point of the maximum entropy when approaching from
either side, since dS is positive. Once the maximum entropy is
reached, no further change in composition is allowed, since this
would require the system entropy to decrease in violation of the
second law of thermodynamics. Mathematically, the condition of
equilibrium can be expressed as.
26
(dS mix )U ,V ,m 0
27
Tf
dT Pi
S i S (Tref ) c Ru ln o
o
i p ,i
Tref
T P
where the ideal-gas behavior is assumed and Pi is the partial pressure
of the ith species.
Gibbs Function
G H TS
(dG)T , P,m dH SdT TdS
(dG)T , P,m TdS
(dG)T , P,m 0 since dS 0
This inequality states that the Gibbs function always decreases
for spontaneous, isothermal, isobaric change of a fixed-mass system
28
in the absence of all work except boundary (-PdV) work. Therefore,
the Gibbs function attains the minimum in equilibrium, in contrast to
the maximum in entropy. Hence, at equilibrium
(dG)T , P,m 0
For a mixture of ideal gases, the Gibbs function for the ith species is
given by
Where g io,T is the Gibbs function of the pure species at the standard-
state pressure (i.e. Pi=Po) and Pi is the partial pressure. The standard
–state pressure, Po, by convention is taken to be 1 atm.
The Gibbs function for a mixture of ideal gases can be expressed as
31
dGmix 0
Or
dN [ gi
o
i ,T RuT ln( Pi / Po )] Ni d[ gio,T RuT ln( Pi / Po )] 0
aA bB ..... eE fF ......
dN A ka yy
dN B kb
.
.
dN E ke
dN F kF
30
Substituting Eqn. yy into Eqn. xx and canceling the proportionality
Constant k, it is obtained
The above equation can be rearranged and the log terms grouped
together to yield
31
Where the j are the stoichiometric coefficients of the elements required
to form one mole of the compound of interest. For example, the
coefficients are O 2 1 / 2 and C 1 for forming a mole of CO from O2
and C, respectively. The Gibbs functions of formation of the naturally
occurring elements are assigned values of zero at reference state.
o e o f
( PE / P ) ( PF / P ) .etc
Kp o a o b
( PA / P ) ( PB / P ) .etc
G RuT ln K p
o
T
Or
K p exp(G / RuT ) o
T ss
32
insight to this behavior can be obtained by recalling the definition of
G in terms of the enthalpy and entropy.
G H TS
o
T
o o
( H o / RuT ) ( S o / RuT )
Kp e .e
The last expression implies that the reaction tends to favor the
Example
Consider the equilibrium reaction O2 2O in a closed vessel
contains 1 mole of O2 when there is no dissociation. Calculate the
mole fraction of O2 and O for the following conditions:
A. T=2500 K, P=1.0 atm
B. T=2500 K, P=3.0 atm
Solution
Two equations are required to find the mole fractions, χO2 and χO.
The first equation is due to an equilibrium expression recognizing
that a=1 and b=2.
Evaluating the standard-state Gibbs function change at T=2500 K
33
GTo (bg of ,O ag of ,O 2 )T 2500K
(2 * 88203 1* 0)
=176206 kJ/kmol.
( PO / P o ) 2
Kp
( PO2 / P o )1
The equilibrium constant Kp can be rewritten in terms of mole
fractions.
( O )2
Kp ( P / P o
)
( O2 )1
( O )2
( P / P o
) exp( G o
T / RuT )
( O2 )1
176206
exp( )
8.315 * 2500
O2
( P / P o ) 0.9916
O 2
V1
34
The second equation can be obtained by equating the entire mole
fractions sum to unity
i
i 1
Or
O O 1
2 V2
T=2500 K T=2500 K
P=1 atm P=3 atm
χO2 0.3834 0.5671
χO 0.6166 0.4329
Example 2.8
Solution
35
36
or
37
38
41
Complex Systems
Full Equilibrium
The adiabatic flame temperature and the detailed composition
of the product of combustion can be obtained by solving
simultaneously the equations that represent the first law, complex
chemical equilibrium principles and atom conservation.
Major products of lean combustion are usually H2O, CO2, O2,
and N2; while for rich combustion, they are H2O, CO2, CO, H2 and
N2. It is interesting to indicate that the maximum flame temperature
occurs not at stoichiometric, but, rather, at slightly rich equivalence
ratio. This later is a consequence of the heat combustion, ΔHC, and
heat capacity of the products ( N prod .c p , prod ) . For equivalence ratios
40
with than ΔHC; while beyond (Tmax ) , ΔHC fall more rapidly than
does heat capacity.
Water-Gas Equilibrium
As indicated above, H2O, CO and H2 are major products for
rich combustion. Under these conditions the so-called water-gas shift
reaction must be taken into account. The reaction is described as
CO H 2 O CO2 H 2
The water-gas equilibrium is central to steam reforming in the
petroleum industry and gasification processes.
Pressure Effects
Pressure has a significant effect on dissociation with reactions
having changes in total number of moles. Increasing pressure results
in a decrease in CO2 and H2O dissociation. The trend is consistent
with Le Chatelier principle that states that any system initially in
equilibrium state when subjected to change will shift in composition in
such a way to minimize the change. For example, an increase in
pressure upon CO2 CO 1 / 2O2 reaction, this should cause a
shift to the CO2 side, i.e., in the direction to produce fewer moles.
For equimolar reactions, pressure has no effect.
41
Chapter 3
35
Mass Transfer Rate Laws
Fick's Law of Diffusion Fick's law describes the rate
at which one species, A, diffuses through the other, B. It is
on a mass basis
dYA
YA (m
m A
) DAB
m
" "
A
"
B
dx (3.1)
where:
m "A is the mass flux or the mass flow per unit area of
species A (kg/m2s)
"A m
YA (m B" ) is the mass flow of species A associated with bulk
flow per unit area (kg/m2s)
dYA
DAB is the mass flow of species A associated with
dx
molecular diffusion per unit area (kg/m2s)
ρ Density (kg/m3)
The mass flux is defined as the mass flow of species A per unit area
perpendicular to the flow:
35
"A m
m A/ A (3.2)
The second term on the right-hand-side is representing the diffusion
"A,diff , superimposed on the bulk flow
flux of species A, m
dYA
m "
A, diff DAB
dx (3.3)
DAB T 3/ 2
/P (3.5)
33
It is evident that that the diffusivity depends strongly on temperature
and inversely with pressure. The mass flux of species A, however,
depends on the product DAB , which has square-root temperature
dependence and is independent of pressure
DAB T 1/ 2
(3.6)
In many simplified analyses of combustion processes, the weak
temperature dependence is neglected and DAB is treated as constant.
Species Conservation
dm A
dt
[m A A]x [m A A]x x
A
m
x
Figure 3.1. Control volume for one dimensional analysis of conservation
of species A.
35
Referring to Fig. 3.1, species A flows into and out of the control volume
due to both of bulk flow and diffusion. Species A may be generated or
disappears due to chemical reaction. The net rate of change in the mass of
A within the control volume can be expressed as.
dmA,CV
[m A A]x [m A A]x x m AV
dt (3.7)
( YA ) dY
Ax AYA m DAB A
t dx x
dYA
AYA m DAB
m AAx
dx x x (3.8)
( YA ) dYA
YA m DAB A
m
t x dx
(3.9)
( YA )
For the case of steady flow where
t , Eqn. (3.9) becomes
35
d dYA
m A YA m A DAB 0
dx dx (3.10)
Stefan Problem
35
Stream mixture A-B
m "A
YA,i at interface
x=0
Liquid A
dYA
YA (m
m "
A
) DAB
m "
A
"
B
dx (3.1)
dYA
m YAm DAB
"
A
"
A
dx (3.12)
Rearranging and separating variable, we obtained
35
m A dYA
dx
DAB 1 YA (3.13)
m A
x ln[1 YA ] C
DAB , (3.14)
YA ( x 0) YA,i
m A x
YA ( x) 1 (1 YA,i ) exp( )
DAB (3.15)
56
DAB 1 YA ,
m A ln[ ]
L 1 YA , i (3.16)
Psat (Tliq,i ) MW A
Y A ,i (3.18)
P MWmix ,i
where the molecular weight of the mixture also depends on Psat.
56
heating the liquid, Ql, while the remainder causes the phase change.
The energy balance can be expressed as
Q g Ql m
(hvap hliq ) m
h fg (3.19)
56
Example 3.1
Consider water in a 25 mm diameter test tube into dry air at 1 atm
and 298 K. The distance from the water-air interface to the top of the
tube is L=15 cm. The mass fraction of the water vapor at the water
air interface is 0.0235 and the binary diffusivity for water vapor in air
is 2.6*10-5 m2/s.
Solution
Eqn. 3.16 can be applied to determine the mass flux since the
configuration represents the Stefan
DAB 1 YA ,
m A ln[ ]
L 1 YA , i
First it is required to determine the mean density of the mixture
P
mix , av
( Ru / MWmix , av )T
The average molecular weight may be given by
55
1
MWmix ,av ( M mix ,i M mix , )
2
Or
1
MWmix,av [1 / Y j ,i / MW j ,i 1 / Y j , / MW j , ]
2 j j
1
MWmix,av [1 /( 0.0235 / 18 0.9765 / 28.85) 1(1 / 28.85)]
2
=28.71 kg/kmol.
101325
mix, av
(8135 / 28.71) * 298
=1.2 kg/m3
55
= 0.495 *10-5 kg/m2s
H 2O * A
H 2O m
m
0.495 *10-5 * ( * 0.252 / 4)
=2.43*10-7 kg/s
The water vapor mass fraction is given by Eqn. 3.15
A x
m
YH 2O ( x) 1 (1 YH 2O ,i ) exp( )
DH 2O Air
0.495 *10-5 * 0.075
YH 2O ( L / 2) 1 (1 0.0235) exp( 5
)
1.2 * 2.6 *10
YH 2O (15 / 2) 0.01181
The fraction of the water mass flow that is contributed by bulk flow
and the fraction contributed by diffusion at x=L/2.
The fraction of the water mass flow that is contributed by bulk flow,
H 2O,bulk is given by
m
H 2O,bulk ( L / 2) YA ( L / 2)(m
m H" 2O ) A
53
H 2O,bulk (0.15 / 2) 0.01181* 0.495 *10-5 * (0.25)2 /4
m
=2.868*10-9 kg/s
dYA
m H 2O,diff DAB A
dx
The gradient of mass fraction at position x can be obtain
by differentiation of the following expression
A x
m
YH 2O ( x) 1 (1 YH 2O ,i ) exp( )
DH 2O Air
then,
dYH 2O ( x) A
(1 YH 2O,i )m A x
m
exp( )
dx DH O Air
2
DH 2O Air
55
= -0.1568 m-1
dYA
m H 2O,diff DAB A
dx
1.2 * 2.6 *105 * 0.1568 * ( * 0.252 ) / 4
=2.40*10-7 kg/s
Example 3.2
For the above example, consider that the interface vapor mass
fraction is unknown. Find the mass evaporation rate of the water
when the liquid water is at 20 oC, assuming equilibrium at the
interface.
Solution
At t=20 oC P=2.339 kPa, hfg=2454.1 kJ/kg
55
The interface mixture molecular weight can be determine as
MWmix,i x H 2O,i MWH 2O,i xair,i MWair,i
or
PH 2O,i P
MWmix,i MWH 2O,i (1 H 2O,i ) MWair,i
P P
2.339 2.339
MWmix ,i *18 (1 ) * 28.85
101,35 10135
=28.6 kg/kmol.
Thus,
2.339 18
YH 2O *
101.35 28.6
=0.0145
Then, the solution can be realized as described in the
above example.
dP h fg dT
P Ru / MW T 2
By integration
55
Psat h fg 1 1
exp[ ( )]
P Ru / MW T Tboil
Psat 2257 1 1
exp[ ( )]
1 8.135 / 18 293 373
Psat 2.62 kPa
55
Droplet Evaporation
Evaporating droplet
rS
r Y
(a)
Y
1.0
YS
Y
0 r
rS
(b)
Figure 3.3 Evaporation of a liquid droplet in a quiescent environment
56
vapor interface is denoted rs. Very far from the droplet
product D .
Evaporation Rate
The above assumptions reduce the case to Stefan's problem
while the change in coordinate system should be taken into
account. Overall mass conservation is expressed as
56
It is worthwhile to note that the mass flow rate is constant with
r while mass flux isn't. Species conservation is expressed as
dYA
m YA (m m ) DAB
"
A
"
A
"
B
dr (3.21)
dYA
m YAm DAB
"
A
"
A
dr (3.22)
Substituting Eqn. 3.20 into Eqn. 3.22, and rearranging to solve for
( m A ) , yields
evaporation rate, m
D AB dYA
m 4r 2
1 YA dr (3.23)
m dr dYA
4DAB r 2
1 YA
Integrating the 3.23 yields
m
ln[1 YA ] C
4DAB r (3.24)
(1 YA, )
m 4rs DAB ln
(1 YA, S
) (3.26)
1 Y A,
1 BY
1 Y A, S (3.27)
or
Y A, S Y A ,
BY
1 YA, S (3.28)
55
4rs DAB ln(1 BY )
m (3.29)
dmd
m
dt (3.30)
The droplet mass can be expressed in terms of droplet diameter,
D=2rS, and density, ρl,
md l D / 6 3
(3.31)
Substituting Eqn. 3.29 and Eqn. 3.31 and performing the
differentiation yields
dD 4 D AB
ln(1 BY )
dt l D (3.32)
55
dD 2 8DAB
ln(1 BY )
dt l (3.33)
dD 2
K
dt (3.35)
The droplet lifetime, td, can be determined by integrating Eqn. 3.35
which yields
td D / K 2
o (3.36)
A more general expression for the variation of D with time (t) is
D (t ) D Kt
2 2
o (3.37)
53
2
Equation 3.37 is known as the D LAW for droplet evaporation
which is also used to describe burning of fuel droplet.
D2
8DAB
Slope K ln( 1 BY )
Do2 l
t
0
tS
55
Example 3.3
Determine the influence of the ambient water vapor mole fraction on
the lifetimes of 50-μm diameter water droplets. The droplets are
evaporating in air at 1 atm. Assume the droplet temperature is 75 oC
and the mean air temperature is 200 oC. Use values of H O, 0.1,
2
Solution
Equation 3.36 can be used to estimate the droplet lifetime.
td D / K 2
o (3.36)
Tboil=100+273=373 K
P=101.35 kPa
hfg=2257 kJ/kg
MWH2O=18 kg/kmol.
DAB=2.2*10-5 m2/s @T=273 K
55
An integrated form of Clausius-Clapeyrion equation can be used to
estimate the saturation pressure at the liquid temperature
Psat h fg 1 1
exp[ ( )]
P Ru / MW T Tboil
Psat 2257 1 1
exp[ ( )]
1 8.135 / 18 (348 373
Psat=0.382 atm=38.72 kPa
Using steam table we may also find Psat=38.58 kPa at Tsat =75 oC.
0.382 0.382
*18 (1 ) * 28.85
1 1
=24.71 kg/kmol.
55
MWH 2O PH 2O MWH 2O
YH 2O H 2O * *
MWmix P MWmix
0.382 18
YH 2O *
1 24.71
=0.278
For χH2O,∞=0.1
18
YH 2O, 0.1*
(0.1*18 0.9 * 28.85)
=0.0648
Y A, S Y A ,
BY
1 YA, S
55
0.278 0.0648
1 0.278
=0.295
DAB T 3/ 2
/P (3.5)
Or
T2 3 / 2
DAB (T2 ) DAB (T1 )( )
T1
473 3 / 2 5
DAB (473) 2.2 *10 ( )
273
=5.017*10-5 m2/s
1
MWmix,av [ MWmix, S MWmix, ]
2
1
MWmix,av [24.71 0.1 *18 .9 * 28.85]
2
=26.24 kg/kmol.
56
The average density can be calculated by the ideal gas law
P
av
Ru / MWmix ,av )T
101325
(8135 / 26.24) * 473
=0.691 kg/m3
Thus,
K (8DAB / l ) ln( 1 BY )
(8 * 0.691* 5.017 *105 / 975) ln( 1 0.295)
=7.35*10-8 m2/s
td D / K 2
o
56
χH2O,∞ Y H2O,∞ BY K(m2/s) td (s)
0.1 0.0648 0.295 7.35*10-8 0.034
0.2 0.1349 0.1982 5.036*10-8 0.0496
0.3 0.211 0.0928 2.42*10-8 0.1033
56
Chapter 4
CHEMICAL KINETICS
38
Chapter 4
CHEMICAL KINETICS
F aOx b Pr (4.1)
d[ X F ]
kG (T )[ X F ] [ X Ox ]
n m
dt (4.2)
Where
38
[Xi] is the molar concentration of species i, in kmol./m3 or gmol/cm3
kG is the global rate coefficient which is a strong function of
temperature
Equation 4.2 indicates that 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 arise from curve-fitting
experimental data.
The global reaction is a simplified approach for solving some
problems. However, the approach tells nothing about what is actually
happening in the system from chemical point of view. In fact, for the
above reaction to be completed, many sequential processes can occur
involving many intermediate species.
For instance, to effect the global conversion of hydrogen and
oxygen to water
2H 2 O2 2H 2O (4.3)
H 2 O2 HO2 H (4.4)
H O2 OH O (4.5)
OH H 2 H 2O H (4.6)
H O2 M HO2 M (4.7)
38
During the uncompleted mechanism described above, many
radicals or free radicals (intermediate species) occur such as HO 2
(hydroperoxy), HO (hydroxyl), H and O. Free radicals are reactive
atoms or molecules that have unpaired electrons. The group of
elementary reactions necessary to express the details of an overall
reaction is called a reaction mechanism.
Bimolecular Reactions
A B C D (4.8)
d [ A]
kbimolec [ A][ B] (4.9)
dt
All elementary bimolecular reactions are overall second order, being
first with respect to each of the reacting species. The SI units for
kbimol. are m3/kmol-s.
The bimolecular rate coefficient can be expressed by empirical
Arrhenius form,
38
k( T ) A exp( EA / RuT ) (4.12)
d [ A]
kuni [ A] (4.15)
dt
38
At low pressures, the reaction becomes second order where it also
depends on the concentration of some molecules, M, with which the
reacting species may collide.
d [ A]
k[ A][ M ] (4.16)
dt
A B M C M (4.17)
d [ A]
kter [ A][ B][ M ] (4.18)
dt
Where M may be any molecule and is normally referred as a third
body.
33
RATES OF REACTION FOR MULTISTEP
MECHANISMS
k f1
H 2 O2 HO2 H (4.19)
k r1
kf2
H O2 OH O (4.20)
kr 2
kf3
OH H 2 H 2O H (4.21)
kr 3
kf4
H O2 M HO2 M (4.22)
kr 4
38
Where kfi and kri are the elementary foreword and reverse rate
coefficients, respectively, for the ith reaction. The net rate of
production of O2, for instance, is the sum of all the individual
elementary rates producing O2 minus the sum of all the rates
destroying O2, i.e.,
d [O2 ]
k r1[ HO2 ][ H ] k r 2 [OH ][O ]
dt
kr 4[ HO2 ][ M ] .....
k f 1[ H 2 ][O2 ] k f 2[ H ][O2 ]
k f 4[ H ][O2 ][ M ] ... (4.23)
Compact Notation
89
N N
ji X j ji X j
j 1 j 1 (4.24)
For i=1,,2,…..L
j Species i Reaction
1 O2 1 Eqn. (4.19)
2 H2 2 Eqn. (4.20)
3 H2O 3 Eqn. (4.21)
4 HO2 4 Eqn. (4.22)
5 O
6 H
7 OH
8 M
89
1 1 0 0 0 0 0 0
1 0 0 0 0 1 0 0
ji
0 1 0 0 0 0 1 0 (4.25a)
1 0 0 0 0 1 0 1
And
0 0 0 1 0 1 0 0
0 0 0 0 1 0 1 0
ji
0 0 1 0 0 1 0 0 (4.25b)
0 0 0 1 0 0 0 1
L
j ji qi for j=1,2,…,N (4.26)
i 1
where
and
89
N N
qi k fi [ X j ] kri [ X j ]
ji ji
(4.28)
j 1 j 1
kf
A B C D (4.29)
kr
d [ A]
k f [ A][ B] kr [C ][ D] (4.30)
dt
At equilibrium conditions the net time rates of species must be zero.
Thus, Eqn. 4.30 is reduced to
0 k f [ A][ B] kr [C ][ D] (4.31)
By rearranging
88
[C ][ D] k f (t )
(4.32)
[ A][ B] kr (t )
( PC / P o )c ( PD / P o ) d ....
Kp
( PA / P o ) a ( PB / P o )b .... (4.33)
[ X i ] i
reac
88
[ X i ] i
prod k f (T )
Kc
[ X i ] i k r (T )
reac
Example 4.1
CH 4 M CH3 H M
where the reverse reaction coefficient is given by
88
Solution
An algebraic expression for the forward rate coefficient, kf, can be
obtained using the following relation,
k f (T )
K p ( RuT / P o )
k r (T )
Substitute with
A2 B2 2 AB (4.37)
k1
A2 M A A M (4.38)
The chain propagating reactions involving free radicals A and B
k2
A B2 AB B (4.39)
k3
B A2 AB A (4.40)
k4
A B M AB M (4.41)
88
Chain-branching reactions involve formation of two
O H 2O OH OH (4.42)
Existence of a chain-branching step in a certain mechanism may
cause an explosive effect. In a system with chain branching, the
concentration of a radical species may be built up geometrically,
causing the rapid formation of the products. Chain-branching
reactions are responsible for a flame being self-propagating.
Steady-State Approximation
Many combustion mechanisms involve a highly reactive
intermediate radical for which the rate of formation is slow while the
reaction consuming is very fast. Under these conditions, the radical
concentration builds up for a short period, after that, the radical is
consumed as rapidly as it is created. Therefore, concentration of the
radical is quite small in comparison with those of reactants and
products. Analyses of such systems may be simplified by applying
the Steady-State Approximation.
A typical example of this system is zeldovich mechanism for
formation of nitric oxide, in which N atom is the reactive
intermediate of interest.
k1
O N 2 NO N (4.43)
83
k2
N O2 NO O (4.44)
Reaction 4.43 is rate limiting since it is slow whereas reaction 4.44 is
extremely fast. The net rate production of N radicals may be written as
d[ N ]
k1[O][ N 2 ] k 2 [ N ][O2 ] (4.45)
dt
k1[O][ N 2 ]
[ N ]ss
k 2 [O2 ] (4.46)
d [ N ]ss d k1[O][ N 2 ]
dt dt k 2 [O2 ] (4.47)
88
Example 4.2
As mentioned above, the Zeldovich mechanism is a famous
chain mechanism. It describes formation of nitric oxide from
atmospheric nitrogen at high temperature, i.e., thermal mechanism.
k1 f
O N 2 NO N (4.43)
k2 f
N O2 NO O (4.44)
For this mechanism, it was found that the second reaction is
much faster than the first. Therefore, the N-atom concentration may
be evaluated by applying the steady state approximation technique.
Moreover, O2 and O may be assumed in equilibrium since NO
formation is much slower than other reactions involving O2 and O.
O2 2O
The global mechanism is
kG
N 2 O2 2 NO
and NO formation rate is expressed as
d [ NO]
kG [ N 2 ]m [O2 ]n
dt
999
Determine kG, m and n using the elementary rate coefficients, etc,
from the detailed mechanism.
Solution
From the elementary reactions, one may express
d [ NO]
k1 f [ N 2 ][O] k 2 f [ N ][O2 ]
dt
d[ N ]
k1 f [ N 2 ][O] k2 f [ N ][O2 ]
dt
where reverse reaction rates are assumed negligible
k1 f [O][ N 2 ]
[ N ]ss
k 2 f [O2 ]
Substituting [N]ss into the above expression for d [ NO] / dt , yields
999
d [ NO]
2k1 f [ N 2 ][O]
dt
prod o
Kp
( Ru T / P )
[ X i ] i
react
[O]2 RuT 2 1
( o )
[O2 ] P
or
o 1 / 2
K pP
[O] [O2 ]
RuT
Therefore
1/ 2
d [ NO ] K pP o
2k1 f [ N 2 ][ O2 ] 1 / 2
dt RT
u
999
Comparing the above expression of NO formation rate with that of
global reaction, one can infer
K pP o 1 / 2
kG 2k1 f
Ru T
m 1
n 1/ 2
998
SOME IMPORTANT CHEMICAL
MECHANISMS
H2-O2 System
The hydrogen –oxygen system is important in its own right as,
for example, in rocket propulsion. It is also important as a subsystem
in the oxidation of hydrocarbons. The oxidation of hydrogen may be
outlined as follows.
H O2 O OH (H.3)
O H 2 H OH (H.4)
998
H 2 OH H 2O H (H.5)
O H 2O OH OH (H.6)
H H M H2 M (H.7)
O O M O2 M (H.8)
H O M OH M (H.9)
H OH M H 2O M (H.10)
H O2 M HO2 M (H.11)
becomes actives, then the following reactions and the reverse of H.2,
come into play:
HO2 H OH OH (H.12)
HO2 H H 2O O (H.13)
HO2 O O2 OH (H.14)
998
and
H 2O2 H H 2O OH (H.18)
H 2O2 M OH OH M (H.20)
998
reaction is the reaction of gaseous species at solid surfaces and is very
important in solid combustion and catalysis.
In a second region, where pressure is set between the first and
second limit, and temperature is greater than 400 oC, the mixture has
explosion feature. Under these conditions, the chain sequence H.3-
H.6 prevails over the radical destruction at the walls. Since
increasing pressure increases radical concentration linearly and
increases the reaction rate geometrically.
The mixture becomes again non-explosive while the pressure
goes above the second limit. This lack of explosion is a result of
competition for H atoms between the chain branching reaction H.3
and reaction H.11 which is an effective terminating step at low
temperature. Reaction H.11 is a chain terminating step because the
hydroperoxy radical, HO2, is relatively un-reactive at these
conditions, and consequently, it can diffuse to the wall to be
destroyed.
998
Figure 4.1. Explosion limits for a stoichiometric hydrogen-oxygen
mixture in a spherical vessel.
993
Carbon Monoxide Oxidation
Oxidation of carbon monoxide is extremely important either in
its own right or to the oxidation of hydrocarbon. Hydrocarbon
combustion simplistically can be characterized as a two-step process:
the first step involves the breakdown of the fuel to carbon monoxide,
with the second being the final oxidation of carbon monoxide to
carbon dioxide.
It is well known that CO oxidation is slow; however, presence
of small quantities of hydrogen containing species, H 2O or H2, can
have a tremendous effect on the oxidation rate. This is because the
CO oxidation step involving the hydroxyl radical is much faster than
the steps involving O2 and O.
Let water be the primary hydrogen-containing species, the
oxidation of carbon monoxide may be described by four steps.
CO O2 CO2 O (CO.1)
O H 2O OH OH (CO.2)
CO OH CO2 H (CO.3)
H O2 OH O (CO.4)
998
form OH and O through reaction CO.4. These radicals feed back into
the oxidation step (CO.3) and the first chain branching step (CO.2).
The key reaction of the mechanism is CO OH CO2 H (CO.3)
O H 2 OH H (CO.5)
OH H 2 H 2O H (CO.6)
999
The thermal or Zeldovich mechanism consists of two chain
reactions:
O N 2 NO N (N.1)
N O2 NO O (N.2)
N OH NO H (N.3)
O N 2 M N 2O M (N.4)
H N 2O NO NH (N.5)
O N 2O NO NO (N.6)
This mechanism becomes important in NO control strategies that
involve lean premixed combustion in gas turbines.
999
that finally form NO. For equivalence ratios less than about 1.2, the
Fenimore mechanism can be described as:
CH N 2 HCN N (N.7)
C N2 CN N (N.8)
NCO H NH CO (N.10)
NH H N H 2 (N.11)
N OH NO H (N.12)
For equivalence ratios richer than 1.2 the mechanism becomes much
more complex.
Hydrogen cyanide HCN
999
Chapter 5
113
The definition implies that the flame occupies a thin zone and
moves sub-sonically (deflagration wave). The flame is approximately
1 mm thick and moves at 0.5 m/s for stoichiometric hydrocarbon
mixtures at ambient air. Pressure drop through the flame is very
small, about 1 Pa, and temperature in the reaction zone is high (2200-
2600 K). It is also possible for combustion wave to propagate at
supersonic velocities that is called detonation.
u S L A u vu A bvb A (5.1)
114
where the subscripts u and b refer to the unburned and burned
gases, respectively. SL is the burning velocity (flame velocity) defined
as the velocity of the flame relative to the unburned reactant mixture.
Figure 5.2 (a) Bunsen burner schematic (b) Laminar flame speed
equals normal component of unburned gases, vu,n.
116
Bunsen-burner flame is a dual flame: a fuel rich premixed inner
flame surrounded by a diffusion flame. The shape of the flame is
determined by the combined effects of the velocity profile and heat
losses to the tube wall. For the flame to remain stationary, the flame
speed must equal the speed of the normal component of unburned
gases at each location. Thus,
S L vu sin (5.2)
Assumptions
1. One dimensional, constant area, steady flow.
2. Kinetic and potential energies, viscous shear work, and thermal
radiation are all neglected.
3. The small pressure drop across the flame is neglected, i.e., the
pressure is constant.
4. The Lewis number, Le, is unity. Where Lewis number is defined
as the ratio of thermal diffusivity to mass diffusivity, i.e.,
117
k
Le
D c p D (5.3)
equation.
5. Specific heats are assumed to be constant and equal for all
species.
6. The oxidation process is a single-step exothermic reaction.
7. The fuel is completely oxidized in the flame zone.
Conservation Laws
Conservations of mass, species and energy are applied to the
differential control volume illustrated in Fig. 5.3.
118
d ( x )
0 (5.4a)
dx
Or
x constant
m (5.4b)
Species Conservation
dm i
m i (5.5)
dx
Applying Fick's law yields
dYi
d [m Yi D ]
dx m i (5.6)
dx
is the mass production rate of species i per unit volume
where m
(kg/m3s).
Accordingly,
119
1 1
F m
m Ox
Pr
m
1 (5.8)
Fuel
dYF
d [ D ]
dYF dx m
m F (5.9a)
dx dx
Oxidizer
dYOx
d [ D ]
dYOx dx m
m F (5.9b)
dx dx
Products
dYPr
d [ D ]
dYPr dx - (1 )m
m F (5.9c)
dx dx
Energy Conservation
Using the first law of thermodynamics with considering the
assumptions given above, the following expression may be obtained
121
dT d dT
m c p i
[( Dc p ) ] h of ,i m
dx dx dx
(5.10a)
where:
dT
m c p is the rate of sensible enthalpy transported
dx
by convection per unit volume
d dT
[( Dc p ) ] is the rate of sensible enthalpy transported
dx dx
by diffusion per unit volume
h f ,i m i
o
is the rate of enthalpy production by
F hc
m
where hc is the heat of combustion of fuel. According to the
121
dT
d (k )
dT 1 dx m F hc
m
dx c p dx cp (5.10b)
u S L
m (5.11)
Solution
T ( x ) Tu (5.12a)
dT
( x ) 0
dx (5.12b)
T ( x ) Tb (5.12c)
dT
( x ) 0 (5.12d)
dx
122
For simplicity, a linear temperature profile over the flame thickness,
δ, is assumed as shown Fig. 5.4. Integrating Eqn. (5.10b), yields
dT / dx 0
k dT hc
m [T ]TT TTb dx m F dx
u
cp dT / dx 0 c p
(5.13)
By evaluating the limits, it becomes
123
hc
m (Tb Tu )
cp m dx
F
(5.14)
The limit on the right hand side can be changed from space to
dT Tb Tu
dx (5.15a)
or
dx dT
Tb Tu (5.15b)
hc T b
m (Tb Tu ) m F dT
c p (Tb Tu ) T u
(5.16)
Using the average reaction rate definition
T
1 u
m F m F dT
(Tb Tu ) T b
(5.17)
124
Equation (5.16) is simplified to
hc
m (Tb Tu ) m F
cp (5.18)
and
The algebraic Equation (5.18) involves two unknown m
δ, so it is required another equation to have a complete solution. This
may be realized through a reasonable assumption that considers the
fuel consumption occurs only in the high-temperature region. That is,
Tb Tu
T
2 (5.19)
and
Tb Tu
dT dx
(5.15b)
dT / dx(Tb Tu ) /
k dT hc
m [T ]T Tu m dx
T (Tb Tu ) / 2
dx F
cp dT / dx0 cp
125
/ 2 k / c p 0
m (5.20)
1/ 2
k (h )
m 2 2 c
m F
c p (Tb Tu ) (5.21)
and
1/ 2
m F
S L 2 (1 )
u (5.23)
126
1/ 2
2 u
(1 )m F (5.24a)
Or in terms of SL,
2 / S L (5.24b)
Example 5.1
Estimate the laminar flame speed of stoichiometric propane-air
mixture using the simplified theory expression. Use the given global
one-step reaction to estimate the mean reaction rate. The adiabatic
flame temperature of propane may be taken 2260 K.
d [C3 H 8 ] 15098
8.6 *1011 exp( )[C3 H 8 ]0.1[O2 ]1.65
dt T
Solution
The laminar flame speed is expressed as
1/ 2
F
m
S L 2 (1 )
u
F , and the
Thus, it is essential to evaluate the rate of fuel reaction, m
127
of the flame thickness, where chemical reaction is assumed to occur,
is given by
1 1
T [ (Tb Tu ) Tb ]
2 2
1 1
[ (2260 300) 2260]
2 2
=1170 K
1
YC H (YC H ,u YC H ,b )
3 8
2 3 8 3 8
1
(0.06015 0)
2
=0.0301
and
1
YO (YO ,u YO ,b )
2
2 2 2
1
(0.233(1 0.06015) 0)
2
=0.1095
128
Where A/F of a stoichiometric propane-air mixture is
1
1 15.625 and mass fraction of O2 in air is 0.233.
YC H
3 8
,u
P 101325
( Ru / MW )T (8315 / 29) *1770
=0.1997 kg/m3
d [C3H8 ] 15098
F 8.6 *1011 exp( )[C3H8 ]0.1[O2 ]1.65
dt T
0.1 1.65
15098 1.75 YC H YO
F 8.6 *10 exp(
11
) 3 8 2
T MWCH MW O
3 8 2
15098
8.6 *10 exp( 11
)(0.1997 )1.75 *
1770
0.1 1.65
0.301 0.1095
44 32
=-2.439 kmol/ m3s
129
F F * MWF
m
-2.439* 44
=107.3 kg/ m3s
1 1
Tt (Tb Tu ) (2260 300)
2 2
=1280 K
P 101325
u
( Ru / MW )Tu (8315 / 29) * 300
=1.18 kg/m3
Then
k (Tt ) 0.0809
u c p (Tt ) 1.18 *1186
=5.78*10-5 m2/s
Then, the laminar flame speed is
131
1/ 2
(2 * 5.78 *10 5 )(1 15.625)( 107.3)
SL
1 .18
=0.418 m/s=41.8 cm/s
131
5.3. FACTORS INFLUENCING FLAME
VELOCITY AND THICKNESS
5.3.1 Temperature
Using Eqns (5-23) and (5-24), the temperature dependencies of
flame speed, SL, and thickness, δ, may be inferred as
132
An empirical correlation of speed of laminar flame for stoichiometric
methane-air flames at 1 atm is given by Andrews and Bradley.
The correlation is presented in Fig. 5.5, along with data from other
investigators.
133
5.3.2 Pressure
1/ 2
F
m
S L 2 (1 )
u
It fits their data for pressure greater than 5 atm, see Fig. 5.6.
134
Figure 5.6 Effect of pressure on laminar flame speed of
stoichiometric methane-air mixture for Tu=16-27 oC.
135
Figure 5.7 Influence of equivalence ratio on the laminar flame speed
of methane-air mixtures at atmospheric pressure.
136
Figure 5.8 Flame thickness and quenching distance for methane –air
mixture at atmospheric pressure.
137
Figure 5.9 Relative flame speed for C1-C6 hydrocarbon fuels. The
reference flame speed is based on propane using the tube method.
Table 5.2 Laminar flame speeds for different pure fuels burning in air
(=1, P= 1 atm and Tu=room temperature)
Fuel Formula Laminar flame speeds, SL (cm/s)
Methane CH4 40
Ethane C2H6 43
Propane C3H8 44
Ethylene C2H4 67
Acetylene C2H2 136
Hydrogen H2 210
138
5.4. QUENCHING, FLAMMABILITY
AND IGNITION
139
aspect-ratio rectangular- slot burners, the quenching distance is
taken as the slot width. Tubes based quenching distances are
somewhat larger ( 30% ) than slit based ones.
Williams provides two criterions governing ignition and flame
extinction.
1. 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.
2. 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.
141
Fig. 5.10 Flame quenching in rectangular slot.
The heat loss from the flame slab to the wall can be obtained using
Fourier's law as
dT
Qcond kA
dx in gas (5.31)
at wall
where thermal conductivity, k, and the temperature gradient are
evaluated in the gas at wall. The area A is 2L , where δ the
adiabatic laminar flame thickness, L is slot length (perpendicular to
the page) and the factor 2 accounts for the flame being in contact
141
with wall on each side. The temperature gradient is assumed to be
linear and is expressed as
dT Tb Tw
dx d /b (5.32)
Tb Tw
(m F hc )(dL) k (2L) (5.33)
d /b
or
2kb(Tb Tw )
d 2
m F hc (5.34)
1/ 2
m F
S L 2 (1 )
u (5.23)
142
1/ 2
2 u
(1 )m F (5.24a)
d 2 b / S L (5.36a)
or
d b (5.36a)
143
Table 5.3 Quenching distances, flammability limits and minimum
ignition energies for various fuels
113
Example
Consider the design of a laminar-flow, adiabatic, flat flame
burner consisting of a square arrangement of a thin-walled tubes as
illustrated in the sketch. Fuel-air mixture flows through both the
tubes and the interstices between the tubes. It is desired to operate
the burner with stoichiometric methane-air mixture exiting the
burner tubes at 300 K and 4 atm. The quenching distance is
expressed as d 6 / S L for methane-air mixture. You may
consider that T
1.5
/ P.
114
Solution
A. For a flat flame to stabilize, the mean velocity of unburned
mixture must be equal the laminar flame speed at the design
temperature and pressure. Applying the correlation by Andrews and
Bradley for methane-air mixture, SL is given as
S L (300 K ) 43 * P 0.5
=43*(4)-0.5
=0.215 cm/s
, is expressed as
The mass flux, m
m
m / A u S L
P 5 *101325
u
( Ru / MWmix )Tu (8315 / 27.6)(300)
=5.61 kg/m3
Thus, the mass flux is
u S L 5.61* 0.215
m
115
1.21 kg/s - m
m 2
B. The diameter of the tube may be taken reasonably less than the
quenching distance to make the burner operate without danger of
flashback.
d 6 / S L
Thermal diffusivity should be obtained at the mean temperature.
1 1
Tt (Tb Tu ) (2260 300)
2 2
=1280 K
P 101325
u
( Ru / MW )Tu (8315 / 29) * 300
=1.18 kg/m3
Then
k (Tt ) 0.0809
u c p (Tt ) 1.18 *1186
=5.78*10-5 m2/s
116
The quenching distance at 1 atm, d1, is
d1= 1.61 mm
d / S L T 1.5 /( PS L )
T2 1.5 P1 S L,1
d 2 d1* ( ) ( )( )
T1 P2 S L,2
1 0.43
d 2 1.61 * (1) 1.5
( )( )
4 0.215
d2=0.805 mm
d design 0.65mm
117
To verify that the flow is laminar in the tube of the design diameter,
it is needed to determine Reynolds's number using air properties.
P 101325 * 4
u
( Ru / MW )Tu (8315 / 29) * 300
=4.72 kg/m3
then
u d design S L
Re
4.72 * 0.00065 * 0.215
15.89 *106
=41.5
The value of Reynolds's number is well blow the transient value, i.e,
the flow is laminar.
118
5.4.2 Flammability Limits
Example
A full propane cylinder from a camp stove leaks its contents of
0.5 kg into a (3.7*4.3*2.5) room at 20 oC and 1 atm. After a long time,
the fuel gas and room air are well mixed. Is the mixture in the room
flammable?
Solution:
From table 5.3, propane-air mixtures are flammable for
0.51<Φ<2.83. To solve the problem, one should obtain the
equivalence ratio of the mixture filling the room.
Assuming ideal gas behavior, the partial pressure of propane is
determined as
119
mC H ( Ru / MWC H )T
PC H 3 8 3 8
3 8
Vroom
0.5 * (8135 / 44) * 293
3.7 * 4.3 * 2.5
=680 Pa
PC H 680
C H 3 8
3 8
P 101325
=0.0067
and
= 97.21
The equivalence ratio of the mixture in the room is
121
5.4.3 Ignition
Spark ignition is the most common method used for ignition
since it is highly reliable and does not require a pre-existing flame.
Spark ignition is used in many devices including SI engines, gas
turbines; and different industrial, commercial, and residential
burners. This section is dedicated to discussion of minimum energy
concept.
121
dT
F hc 4Rcrit
m 3
/3 k 4Rcrit
2
dr Rcrit
(5.37)
dT (Tb Tu )
dr Rcrit Rcrit (5.38)
3k (Tb Tu )
2
Rcrit
m F hc (5.39)
122
Using the laminar flame speed and thickness expression, one can
obtain
Rcrit 6
SL (5.40)
The minimum ignition energy, Eign, is the energy required to heat the
gases of the critical volume to the flame temperature, Tb, then
Eign 61.6 b c p (Tb Tu )( )3
SL (5.42)
Using the ideal gas law b can be replaced to yield the final result:
c p Tb Tu 3
Eign 61.6 P( )( )( )
Rb Tb SL (5.43)
123
Pressure and Temperature Dependencies
2
EignP (5.44)
124
Table 5.4 Influence of temperature on ignition energies
125
FLAME STABILIZATION
126
127
Chapter 6
828
The region where chemical reaction occurs is generally quite
narrow. The high-temperature reaction zone occurs in an annular
region until the flame tip is reached.
For hydrocarbon flames, soot is frequently present, giving the
flame its typical orange or yellow appearance. In furnaces and
boilers, a certain amount of soot may be beneficial as a means of
increasing radiant heat transfer. However, in engines, soot causes
additional heat loss which is undesirable. The emission of soot
particulates to the atmosphere is undesirable as it may contain
condensed polycyclic aromatic hydrocarbons (PAHs), which have the
potential to cause cancer. Thus, soot emissions from stacks and
tailpipes need to be control.
Figure 6.2 Soot formation and destruction zone in laminar jet flames.
829
1. Formation of precursor species: Acetylene (C2H2) may be
considered a precursor species that causes the formation of
larger ring structures, PAHs.
2. Particle inception: It involves the formation of small particles of
critical size from growth by chemical means and coagulation.
3. Surface growth and agglomeration.
4. Particles oxidation. At some point, soot particles must pass
through an oxidizing zone of the flame. If all of soot particles are
oxidized, the flame is termed nonsooting, while incomplete
oxidation yields a sooting flame.
831
6.2 FLAME LENGTHS
Frf 1 Momentum-controlled
Frf 1 Buoyancy-controlled
Where I is the ratio of the actual initial momentum flow from the slot to
that of uniform flow
I J e, act / mF ve ,
If the flow is uniform, I=1, and for a fully developed, parabolic exit
velocity profile (for h>>b), I=1.5.
YF,Stoic is the stoichiometric fuel mass fraction.
Where a is the mean buoyant acceleration evaluated from
Tf
a 0.6 g ( 1) where g is the gravitational acceleration.
T
838
6.2.1 Circular-Port
The expressions are valid for momentum-controlled or buoyancy-
controlled.
Theoretical Expression
0.67
QF (T / TF ) T
L f ,thy
4D ln( 1 1 / S ) T f (6.2)
where
Experimental Expression
QF (T / TF )
L f , exp t 1330
ln( 1 1 / S ) (6.3)
where all quantities are evaluated in SI units. Note that the burner
diameter does not explicitly appear in either of these expressions.
832
6.2.2 Square-Port
Experimental Expression
QF (T / TF )
L f , exp t 1045
[inverf ((1 S ) 0.5 )]2
(6.5)
where inverf is the inverse error function. Values of the error function erf
are tabulated in Table 6.1. Again all quantities are in SI units.
833
1
,
4inverf [1 /(1 S )]
The
834
6.2.4 Slot Burner, Buoyancy Controlled
Theoretical Expression
2/9
9 4QF4 T4 T f
L f ,thy 2 4 4 (6.8)
8D ah TF T
Experimental Expression
3
QF4 T4
4
L f , exp t 2 *10 4 4 (6.9)
ah TF
Where a is the mean buoyant acceleration evaluated from
TF
a 0.6 g ( 1) (6.10)
T
where g is the gravitational acceleration. TF is the mean flame
temperature and may be assumed 1500 K.
3 3 2 / 3
4 L f ,B L f ,M
L f ,T L f ,M 1 3.38 1
L
9 f ,M L f ,B
835
(6.11)
where the subscripts M, B and T refer to momentum-controlled,
buoyancy-controlled and transient, respectively.
Example 6.1
It is desired to operate a square-port diffusion flame with a 50-
mm high flame in a laboratory. Determine the volumetric
flowrate required if the fuel is propane. Also, determine the heat
hc ) of the flame. What flowrate is required if
release ( m
methane is substituted for propane?
Solution
The following correlation is used to calculate the flame length for
square port
QF (T / TF )
L f , exp t 1045
[inverf ((1 S ) 0.5 )]2
(6.5)
For a certain flame length the corresponding fuel flow rate can be
determined using the above correlation.
The molar stoichiometric air-fuel ratio, S, is calculated as
S x y / 4 * 4.76
=(3+8/4)*4.76=23.8 kmol/kmol
836
Assuming that T TF 300 K and solving eqn 6.5 for QF,
yields
or
The propane density, at P=1 atm, T=300K) may be estimated using ideal
gas law and heat of combustion can be taken from Appendix B. Then, the
heat released rate is
Thus,
and
837
6.3 FACTORS AFFECTING FLAME LENGTH
838
6.3.2 Fuel Type
x y/4
S
O2 (6.13)
839
Figure 6.4 shows the flame length for different fuels relative to
methane calculated using Eqn. 6.3, assuming equal flowrate for all fuels.
The flame length increases as H/C ratio of the fuel decrease. This is less
significant for higher hydrocarbons. It is also noted that the carbon
monoxide and hydrogen flames are much smaller than the hydrocarbon
flames.
1 pri
S
pri (1 / S pure) (6.14)
841
where ψpri is the mole fraction of the stoichiometric requirement met by
the primary air, and Spure is the molar stoichiometric ratio associated with
the pure fuel.
848
6.3.4 Oxygen Content of Oxidizer
Figure 6.6 Effect of oxygen content in the oxidizer stream on flame length
842
6.3.5 Fuel Dilution with Inert gas
Diluting the fuel with an inert gas also reduces the flame length
and lessens soot formation down to the variation in the stoichiometric
ratio, S. For hydrocarbon fuels,
x y/4
S
1
O2 (6.15)
1 dil
843
Example 6.2
In a study of nitric oxide formation in laminar jet flames,
the propane fuel is diluted with N2 to suppress soot formation.
The nozzle fluid is 60 percent N2 by mass. The burner has a
circular port. The fuel, nitrogen and air are all at 298 K and 1
atm. Compare the flame lengths for the following two cases
Solution
To calculate the flame length, it is needed to determine the flame
temperature, Tf . As a first approximation the flame temperature may be
taken equal to the adiabatic flame temperature. The general
stoichiometric chemical balance is
C3 H8 N 2 5(O2 3.76 N 2 )
3CO2 4H 2O (18.8 ) N 2
The adiabatic flame temperature can be determined by equating the
enthalpy of the reactant to the enthalpy of the products.
844
103847 3 *[-393546 + 56.21* (Tad 289)]
4 *[241845 43.87 * (Tad 289)])
(18.8 ) * 33.71* (Tad 298
2335573 10046 *
Tad
(977.9 33.71* ) (AA)
YN 2 MWC3 H 8
(1 YN 2 ) MWN 2
1
S ( x y / 4) /[( ) O2 ] 4.76 * ( x y / 4) /(1 )
1 dil
845
1
S 4.76 * (3 * 8) /(1 )
4
=23.8
where 0
P 101325
f
( Ru / MWF )T (8315 / 44) * 300
=1.787 kg/m3
5 *106
m f
QF
f 1.787
=2.798*10-6 m3/s
Tad=Tf= 2388 K
846
Thus, the flame length is
=0.064 m =6.4 cm
YN 2 MWC3H8 0.6 44
*
(1 YN 2 ) MWN 2 (1 .6) 28
=2.36
Then,
1
S 4.76 * (3 * 8) /(1 2.38)
4
=7.041
847
To calculate the exit flowrate, the mean density of mixture must be
determined
1
MWmix 32.77
0.6 / 28 0.4 / 44
101325
f
(8315 / 32.77) * 300
=1.33 kg/m3
5 *106
m f
QF
f 1.33
=3.759*10-6 m3/s
848
3. The flowrate of the C3H8 in diluted flow is 5.10-6 kg/s.
849
Example 6.3
Design a natural-gas burner for a commercial cooking range that has a
number of circular arranged in a circle. The circle diameter are
constrained to be 160 mm. The burner must deliver 2.2 kW at full load
and operate with 40% primary aeration. For stable operation, the loading
of an individual port should not exceed 10 W per mm2 of port area. Also,
the full-load flame height should not exceed 20 mm. Determined the
number and the diameter of the ports.
Solution
Thus,
851
The primary aeration determines the flowrate of air premixed with fuel:
Thus,
858
and
852
A flame length of 19.8 mm meets the requirement of L f 20mm
where
853
Tf is the mean flame temperature, K
Example 6.1
In a study of nitric oxide formation in laminar jet flames, the
propane fuel is diluted with N2 to suppress soot formation. The nozzle
fluid is 60 percent N2 by mass. The burner has a circular port. The
fuel, nitrogen and air are all at 298 K and 1 atm. Compare the flame
lengths for the following two cases with the undiluted base case
F
(m 5.10 6 kg/s). What is the physical significance of your
results? Discuss.
C. The total flowrate of the diluted flow (C3H8+N2) is 5.10-6 kg/s.
D. The flowrate of the C3H8 in diluted flow is 5.10-6 kg/s.
Solution
To calculate the flame length, it is needed to determine the flame
temperature, Tf . As a first approximation the flame temperature
may be taken equal to the adiabatic flame temperature. The general
stoichiometric chemical balance is
C3 H8 N 2 5(O2 3.76 N 2 ) 3CO2 4H 2O (18.8 ) N 2
854
H reac (Ti , P) H prod (Tad , P)
-103847 kJ/kg
2335573 10046 *
Tad
(977.9 33.71* )
(AA)
YN MWC H
2 3 8
(1 YN ) MWN2 2
0.67
QF (T / TF ) T
Lf
4D ln( 1 1 / S ) T f
For Propane C3H8, the molar stoichiometric oxidizer-fuel ratio, S,
can be determined as
855
1
S 4.76 * (3 * 8) /(1 )
4
=23.8
where 0
P 101325
f
( Ru / MWF )T (8315 / 44) * 300
=1.787 kg/m3
5 *106
m f
QF
f 1.787
=2.798*10-6 m3/s
Tad=Tf= 2388 K
856
Thus, the flame length is
=0.064 m =6.4 cm
YN MWC H 0.6 44
2 3 8
*
(1 YN ) MWN2 2
(1 .6) 28
=2.36
Then,
1
S 4.76 * (3 * 8) /(1 2.38)
4
=7.041
857
To calculate the exit flowrate, the mean density of mixture must be
determined
1
MWmix 32.77
0.6 / 28 0.4 / 44
101325
f
(8315 / 32.77) * 300
=1.33 kg/m3
5 *106
m f
QF
f 1.33
=3.759*10-6 m3/s
858
m f / 0.6 5 *106 / 0.6
QF
f 1.33
=6.265*10-6 m3/s
Example 6.3
Design a natural-gas burner for a commercial cooking range that has a
number of circular arranged in a circle. The circle diameter is constrained
to be 160 mm. The burner must deliver 2.2 kW at full load and operate
with 40% primary aeration. For stable operation, the loading of an
individual port should not exceed 10 W per mm2 of port area. Also, the
full-load flame height should not exceed 20 mm. Determined the number
and the diameter of the ports.
Solution
859
Thus,
The primary aeration determines the flowrate of air premixed with fuel:
861
Where Z is the primary molar air-fuel ratio:
Thus,
and
868
The flame length is calculated as
862
Chapter 7
361
6. Fuel and oxidizer react in stoichiometric proportions at the flame
sheet. Chemical kinetics are assumed to be infinity fast, resulting
in an infinitesimal thin flame sheet.
7. The Lewis number, Le / D k g /( c pg D) , is unity.
Figure 7.1 Temperature and species profiles for simple droplet burning model
361
For given an initial droplet size and conditions far from the
droplet, i.e., the temperature, T∞, and the oxidizer mass fraction,
Yox,∞, the model analysis aims to yield expressions that allow us to
evaluate the following five parameters:
1. The droplet mass burning rate, m F .
2. The flame temperature, Tf.
3. The flame radius, rf.
4. The fuel vapor mass fraction at the droplet surface, YF , s .
Thus, five equations are needed to solve for the five unknowns. We
can derive five equations through
1. an energy balance at the droplet surface
2. an energy balance at the flame sheet
3. the oxidizer distribution in the outer region
4. the fuel vapor distribution in the inner region
5. phase equilibrium at the liquid-vapor interface expressed, for
example, by the clausius-Clapeyron relationship.
(7.1)
361
7.1.2 Species Conservation
Inner region Applying Fick’s law in the inner region where the fuel
vapor is the important diffusing species, we get
(7.2)
where the subscripts A and B denote fuel and products, respectively:
(7.3)
(7.4)
And the -operator in spherical coordinates is (..) d (..) / dr as
the only variations are in the r-direction. Thus, the Fick’s law is
(7.5)
The first-order ordinary differential equation must satisfy two
boundary conditions: at the droplet surface, liquid-vapor equilibrium
prevails, so
(7.6)
and at the flame, the fuel disappears, so
(7.7)
366
The general solution of Eqn. 7.5 is
(7.8)
where Z F 1 / 4D
Applying the droplet surface condition (Eqn. 7.6) to evaluate C1, we
obtain
(7.9)
Applying the flame boundary condition, a relation involving
the three unknowns YF,s, m F , and rf:
(7.10)
The combustion products mass fraction can be expressed as
(7.11)
Outer Region
(7.12)
361
Where ν is the stoichiometric (mass) ratio and includes any
nonreacting gases that may be a part of the oxidizer stream. This
relationship is illustrated in Fig. 7. 2. The vector mass fluxes in Fick’s
law are thus
(7.13)
(7.14)
(7.15)
Figure 7.2 Mass flow relationships at flame sheet. Note that the net mass
F
flow in both the inner and outer regions is equal to the fuel flowrate, m
361
with boundary conditions
(7.16)
(7.17)
Integrating Eqn. 7.15 yeilds
(7.18)
Applying the flame condition to eliminate C1 yields
(7.19)
Applying the condition at r (Eqn. 7.17), It is obtained an
F , and the flame radius,
algebraic relation between the burning rate, m
rf, i.e.,
(7.20)
The product mass distribution is
(7.21)
361
7.1.3 Energy Conservation
As the chemical reaction is confined to occur at the flame sheet, the
reaction rate is zero in the inner and outer zones. The energy equation
is then given by
(7.22)
(7.23)
(7.24)
(7.25)
For outer region
(7.26)
(7.27)
311
7.1.4 Temperature distributions
The general solution of the Eqn. 7.23 is
(7.28)
(7.28)
(7.29)
313
7.1.5 Energy Balance at droplet surface
Figure 7.3 Surface energy balance at droplet liquid-vapor interface (top) and
at flame sheet (bottom)
The conduction heat transfer rates and the enthalpy fluxes at the
surface of the evaporating droplet are shown in Fig. 7.3.
(7.30)
or
(7.31)
311
The heat conducted into the droplet interior, Q i l , can be handled in
several ways. One common approach is to model the droplet as
consisting of two zones: an interior region existing uniformly at its
initial temperature, T0; and a thin surface layer at the surface
temperature, Ts. For this so-called “onion-skin” model,
(7.32)
is the energy required to heat up from To to Ts the fuel that is
vaporized. For convenience, we define
(7.33)
So, for the onion model
(7.34)
(7.35)
and
311
(7.36)
where md is the mass of the droplet. Implementation of the lumped-
parameter model requires solving energy and mass conservation
equations for the droplet as a whole in order to obtain dTs/dt.
A third approach and the simplest, is to assume that the droplet
rapidly heats up to steady temperature, Ts. This, in effect, says the
thermal inertia of the droplet is negligible. With this assumption of
negligible thermal inertia,
(7.37)
The conduction heat transfer from the gas phase, Q i g , can be
evaluated by applying Fourier’s law and using the temperature
distribution in the inner region to obtain the temperature gradient, i.e.,
(7.38)
where
(7.39)
311
(7.40)
Referring to Fig. 7.3, the various energy fluxes at the flame sheet are
reported. Since flame temperature is the highest flame in the system,
311
heat is conducted both toward the droplet Q f i and away to infinity,
(7.41)
(7.42)
(7.43)
(7.44)
(7.45)
316
(7.46)
(7.47)
Considering that cpg is constant and Δhc is independent of temperature;
thus, we choose the flame temperature as a reference state to simplify
Eqn. 7.47.
(7.48)
Applying Fourier’s law at the two sides of the flame sheet, we can replace
Q f i and Q f , thus
(7.49)
311
(7.50)
(7.51)
h fg
A exp
RTboil
(7.52)
(7.53)
311
The fuel partial pressure can be related to the fuel mole fraction and mass
fraction as follows:
(7.54)
and
(7.55)
Substituting Eqns. 7.51 and 7.54 into Eqn. 7.55 yields
(7.56)
311
7.1.8 Summary and Solution
Table 7.1 summarizes the five equations that must be solved for the
F , r f , T f , Ts and YF , s . The system of nonlinear
five unknowns: m
(7.57)
(hc / ) c pg (T Ts )
Bo, q
qi l h fg (7.58)
4k g rs
m F ln( 1 Bo,q ) (7.59)
c pg
qi l h fg
Tf [Bo, q 1] Ts
c pg (1 ) (7.60)
311
ln[ 1 Bo,q ]
r f rs
ln[( 1) / ] (7.61)
Bo,q 1 /
YF ,s
Bo,q 1 (7.62)
YF , s PMW pr
Ts B
A(YF ,s MWF Y F ,s MW pr MWF
(7.63)
Where:
kg is the thermal conductivity
rs is the fuel droplet radius
cpg is the specific heat
qi-l is the heat conducted into the droplet interior
hfg is the latent heat of vaporization
ν is the stoichiometric mass ratio and includes any non-
reacting gases that may be a part of the oxidizer
stream.
P is the surrounding pressure
MW molecular weight
Δhc is the heat of combustion of fuel
313
A exp[ h fg / RTboil ]
B h fg / R
311
7.2 BURNING RATE CONSTANT AND DROPLET
LIFETIME
The droplet radius history can be obtained by writing a mass
balance at the droplet surface.
mass of the droplet decrease = rate at which the liquid is vaporized
dmd
m F (7.64)
dt
md lD3 / 6 (7.65)
dD 2
K (7.66)
dt
8k g
K ln( 1 Bo,q )
l c pg (7.67)
D 2 (t ) Do2 Kt (7.68)
td Do2 / K (7.69)
311
The D2 law is a good representation of experimental results after the
heat-up transient as shown in Fig. 7.4.
Figure 7.4 Experimental data for burning droplets illustrating D2 law behavior
after initial transient.
311
The properties cpg, kg, and ρl that appear in Eqn. 7.67 can be determined
as the following:
(7.68)
(7.69)
(7.70)
where
(7.71)
Example
Estimate the mass burning rate of a 1 mm diameter n-hexane droplet
burning in air at atmospheric pressure. Assume no heat is conducted
into the interior of the liquid droplet and that the droplet
temperature is equal to the boiling point. The ambient air
temperature is 298 K. Also, calculate the ratio of the flame radius to
droplet radius and flame temperature; and estimate the droplet
lifetime.
Solution
Using table B.1., the properties of n-hexane, C6H14, can be obtained
MW=86 kg/kmol Δhc=48696 kJ/kg
Tboil=69 oC=342 K hfg=335 kJ/kg
311
ρl=659 kg/m3 Tad=2273 K
4.76 * (6 14 / 4) * 86 / 28.85
=1 5.17
Thus, the transfer number can be calculated
(hc / ) c pg (T Ts )
Bo,q
qi l h fg
(48696 / 15.17) 1.189(298 342)
0 335
=9.426
316
4k g rs
m F ln( 1 Bo,q )
c pg
4 * 0.082 * 0.0005
ln( 1 9.426)
1189
=2.876*10-7 kg/s
qi l h fg
Tf [Bo, q 1] Ts
c pg (1 )
0 335
[15.17 * 9.426 1] 342
1.189(1 15.17)
=2816 K
311
8k g
K ln( 1 Bo,q )
l c pg
8 * 0.082
ln( 1 9.426)
659 *1189
=1.963*10-6 m2/s
311