COm

82 C6COd Caition

TABLE 3.2
Adiabatic Flame Temperatures (K) of Selected Fuels with Air at 1 atm:
Reactants Initially at 298 K
Equivalence ratio, F

0.8 1.0 1.2

Fuel
Gaseous Fuels
2020 2250 2175
Methane
2040 2265 2200
Ethane
2045 2270 2210
Propane
2150 2355 2345
Octane
Liquid Fuels
2050 2275 2215
Octane
2040 2265 2195
Cetane
No. 2 fuel oil 2085 2305 2260

Methanol 1755 1975 1810

Ethanol 1935 2155 2045

Solid Fuel (Dry)

Bituminous coal 1990 2215 2120
1960 2185 2075
Lignite
Wood 1930 2145 2040
RDP 1960 2175 2085
Solid Fuels (25% Moisture)
1760 1990 1800
Lignite
Wood 1480 1700 1480

RDF 1660 1885 1695

Refuse-derivedfuel

reactants. The procedure is shown in the following examples. For complex fuel
the enthalpy of formation is first calculated from the heating value as shown in
Example 3.8. Adiabatic flame temperatures for various representative fuels are

shown in Table 3.2.

Example 3.13

Find the adiabatic flame temperature of carbon monoxide burning with 50%
excess air at 25°C and 1 atm. Neglect dissociation. The complete reaction is

CO+(O, +3.76 N,) CO +0.25 O +2.82 N

 Thermodynamics of Combustion 83

Solution

The energy equation (Equation 3.68) for this reaction is

h a075h+a+2.82 a Jreact

A +0.25 h +a+2.82 h+ai

JCO2
N Jprod

where the subscript s reters to the sensible enthalpy. The reactants are at the
oround state, and as a result the sensible enthalpies for the reactants is 0. From
Appendix C,

Ahco -110.50 MI/kgmol

Aheo= -393.51 M/kgmol

Aho, = 0 M/kgmol

Ah =0 MI/kgmol

Substituting and simplifying.

(0-110.53)= [hco -393.52)+ 0.25 ho,, +0.282 h

From above, the left hand side of the equation (LHS) is equal to -110.53. The
solution process is then to guess a temperature that balances the energy equa-
ton by making the right hand side of the equation (RHS) equal the LHS. Using
Appendix C and guessing T=2000 K,

RHS = (91.45-393.52)+0.25(59.20)+2.82(56.14) = -128.95

Guess T= 2100 K,

RHS =(97.50-393.52)+0.25(62.99)+2.82(59.75)= -111.78

Guess T 2200 K,

-94.42
KHS=(103.57-393.52)+0.25(66.80)+2.82(63.37)
=

Thus, interpolation the adiabatic flame temperature is 2107 K.

is 2084 .
en dissociation is included the adiabatic flame temperature
5ociation always educes the flame temperature.
 Combus
Second tdition
84
On

Example 3.14

coal was
combusted th
with 50% excess
50o
bituminous
L. air
In Example
3.5, 100 kg were 5.833 kgmol CO, 2.778
mol H{O,
1 atm. The
products 3.8 it was found
at 25°C
and
and 37.303 kgmol
N2. In Example adisnat the
3.307 kgmol O, bituminous coal
is -1079 kl/kg. Find the flame
formation of this with 50% excess air at
heat of bituminous coal burned and
temperature of this
dissociation and neglect the
ash.
1 atm. Neglect

Solution the energy equation becom

mes
as in Example 3.13,
process
Following the
same

this becomes
For 100 kg of coal

hcos-395,520) k
100 kgcoal
-1079 K|=5,83 kgmolco|
Kgcoal kgmoko
ho-241,830) k
+2.78kgmolh;o| kgmolo

k
+ 3.31 kgmolo: ho kgmolos,
+37.30 kgmol, | hN,
k
kgmoha

Solving iteratively using data from Appendix C,

Right Hand Side
Left Hand Side T (K)
1900 -137,000 kJ
-107,900 kJ
2000 58,700 kJ
-107,900 kJ

Thus, by interpolation the adiabatic flame temperature is 1915 .

As a further simplification, when only an approximate answer is desircu,

enthalpy of the combustion products may be obtained from an average speenc ie

Then the energy equation becomes

3.70
map (T-T.)+ LHV]+me,(T-Ts) =
(m, +m )e,(Tam-16) .
Thermodynamics o f Combustion 85

abatic
adiaba flame temperature and assuming that the air and fuel enter
for the
olving
reference
temperature of 25°C =77°
the
at
+ LHv
T fameo 1+ (3.71)
f Cp

heat of the products. The specific heat of N, may be

ohere C. is the average specific
approximation.
sed in this 3.71 it that adiabatic flame temperature is a func-
can be seen
Erom Equation
when comparing one fuel
ion of both
fuel-air ratio and lower heating value. Hence,
value alone does not necessarily imply a higher
stoi-
with another, a larger heating
because the stoichiometric fuel-air ratio must also
be
-hiometric flame temperature
value of natural
For example, carbon monoxide has one-third the heating
onsidered. several hundred degrees higher
the stoichiometric fiame temperature is
as, and yet
much lower fuel-air ratio.
ecause has a
it

Example 3.15

of carbon monoxide burning with 50%

Estimate the adiabatic flame temperature
excess air at 25°C and
1 atm using Equation 3.71.

Solution
the complete reaction is
From Example 3.13

+0.25 O2+2.82 Na
CO+(O, +3.76 N) ->CO2

The fuel-air ratio is

nM 28
90.2704
f, nairls)Mair 0.75(4.76)(29)
mair(s)

From Table 2.2,

LHVcO=10,100 kl/kg
we choose to
that the will be approximately 2200 K,
flame temperature
WIng
Use the value of caN. at 1000 K. From Appendix C,
2

32.7 k kgmol1.17k
kg K
1G
.
ANDA
Cp,N2 kgmol K 28 kg
/CENTRAL)
86
Combustion Engineering, Second
Eiti t

Substituting into Equation 3.71,

(0.270 10,100 K. KE=2133 K

flame = 298*|
1+0.270 kg 1.17k 2133 K
Thus Tiame 2133 K. This compares favorably to fame2107 K, which was ohtois
in
Example 3.13 using a more complete formulation. The adiabatic flamefene
ture for CO combustion with 50% excess air including dissociation is tempera
2084 K.
this method is only approximate, it can provide a quick estimate of the Vhie
flame temperature.
adiahaaic

3.7 PROBLEMS
1. Calculate (a) the stoichiometric fuel-air ratio by weight of octane (CH,
(b) the kg of octane in one cubic meter of a stoichiometric mixture of octane
and air at 300 K and1 atm, and () the weight ofthe stoichiometric octane
and air mixture at 27°C and 1 atm.
2. Wood charcoal is used as a cooking fuel in many developing countries.
Generally this is locally produced, low quality wood charcoal produced at
low temperature. A combustion engineer is working on designing a forced
air, charcoal cookstove with 1500 W of cooking power. To ensure that there
is sufficient air to ensure complete combustion while maintaining the stove
air. The
temperature high, the stove should be designed to have 10% excess
stove does not condense the water in the combustion products. The ultimate

analysis of thelocally produced charcoal is 92% C, 6% O, and 2% H (wt)

and the higher heating value is 30 MJ/kg. Determine (a) the lower heating
airflow rate in
value of the charcoal and (b) assuming 50% efficiency, the
L/min at standard temperature and pressure.
4000 rpm, and eacn
3. A 4-cylinder, 4-stroke automobile engine is running at
mixture of octane
cylinder has a displacement of 0.65 L. A stoichiometric volumetric efn
and air at 20°C and 1 atm is drawn into the engine. The useu
mass of octane
ciency at wide open throttle is 85%. Calculate (a) the the liters per
in per minute, and (c)
per minute, (b) the volume of air drawn
hour of octane used by the engine. The volumetric efficiency is the mass o

of charge with vouine

charge ingested per intake event divided by the mass to that
to the displacement of the cylinder at density equal 0
equal
charge entering the port. air
4. To form a stoichiometric mixture of 27°C n-octane vapor and air, tnca

1S brought in at 1 atmosphere and temperature 1, and mixed l a f e T

isobaric and calculate A
lquid. ASsume the process is adiabatic and
The octane liquid is brought in at 25°C. Use the data in Appendiee
and B. hane

5. An engineer, Pat, calculated the stoichiometric fuel-air raio 1 * and

and dry air. Pat then did an experiment on a burner with roo a
 and flame temperatures
16 CHAPTER 1 Chemical thermodynamics
1.4 FLAME TEMPERATURE CALCULATIONSS
1.4.1 ANALYSIS
examines the equation for the flame temperature (Eqn
(1.l)), one can make
anone
If interesting observation. Given the values in Table 1.1 and the realization that
each mole of the reactant fuel, one can see that
many moles of product form for
the sum of the molar heats of the products will be substantially greater than the
sum of the molar heats of the reactants; that is
m (AH),> J
AH)|
react
prod
Consequently, it would appear that the flame temperature is determined not by the
specific reactants, but only by the atomic ratios and the specific atoms that are intro-
duced. It is the atoms that determine what products will form. Only ozone and acet-
ylene have positive molar heats of formation high enough to cause a noticeable
variation (rise) in flame temperature. Ammonia has a negative heat of formation
low enough to lower the final flame temperature. One can normalize for the effects
of total moles of products formed by considering the heats of formation per gram
(Ah); these values are given for some fuels and oxidizers in Table 1.1. The variation
of (Ah) among most hydrocarbon fuels is very small. This fact will be used later in
correlating the flame temperatures of hydrocarbons in air.
One can draw the further conclusion that the product concentrations are als0
functions only of temperature, pressure, and the C/H/O ratio and not the original
source of atoms. Thus, for any C-H-O system, the products will be the same
that is, they will be CO2, H20, and their dissociated products. The dissociation re-
actions listed earlier give some of the possible 'new' products. A more complete list
would be
CO2,H0, Cco,H2,O2,OH,H,O, O3, C,CH4
For a C-H-0-N system, the following could be added:
N2,N, NO, NO2, N20, NH3, NO*,¬
Nitric oxide has a very low ionization potential and could ionize at flame temper
tures. For a normal composite solid propellant containing C-H-0-N-CI-Al.
many more products would have to be considered. In fact if one lists all the possio
number of products for this system, the solution to the problem becomes more a
cult, requiring the use of computers and codes for exact results. However, knowle
of thermodynamic equilibrium constants and kinetics allows one to eliminate may
possible product species. Although the computer codes listed in Appendix I esscu
sion
tially make it unnecessary to eliminate any product species, the following discuss thout
gives one the opportunity to estimate which products can be important u
running any computer code.
 1.4 Flame Temperature Calculations 17
Consider a C-H-0-N system. For an
overoxidized case, an excess of oxygen
converts all the carbon and hydrogen
present to CO2 and H20, and the following re-
actions among species exists:
COCO+502, Qp=-283.2 kJ
H20H2+02, , = -242.2 kJ
H20H+OH, Qp -284.5 kJ
where the Q, values are calculated at 298 K. This
heuristic postulate is based upon the
fact that at these temperatures and at least 1%
pressures dissociation takes place. The
pressure enters into the calculations through Le Chatelier's principle that the
rium concentrations will shift with the equilib-
pressure. The equilibrium constant,
independent of pressure, can be expressed in a form that contains the pressure.although
A vari-
ation in pressure shows that the molar quantities change. Since the reactions noted
above are quite endothermic, even small concentration
If one
changes must be considered.
initially assumes that certain products of dissociation are absent and calculates
a temperature that would indicate 1% dissociation of the
species, then one must reeval-
uate the flame temperature by including in the product mixture the products of disso
ciation; that is, one must indicate the presence of CO, H2, and OH as
products.
Concern about emissions from power plant sources has raised the level of interest
in certain products whose concentrations are much less than 1%, even though such
concentrations do not affect the temperature even in a minute way. The major
pollutant of concern in this regard is nitric oxide NO. To make an estimate of the
amount of NO found in a system at equilibrium, one would use the equilibrium
reaction of formation of NO
Na +0No
As a rule of thumb, any temperature above 1700 K gives sufficient NO to be of
concern. The NO formation reaction is pressure insensitive, so there is no need to
specify the pressure.
I f in the overoxidized case 72 > 2400 K at P = 1 atm or 72> 2800 K at
P 2 0 atm, the dissociation of O2 and H2 becomes important; namely
H22H, ,=-436.6 kJ
O20, O= -499.0 kJ
Although these dissociation reactions are written to show the dissociation of l mol of
the molecule, recall that the Kpf values are written to show the formation of 1 mol of
tne radical. These dissociation reactions are highly endothermic, and even very small
are H and O atoms.
products
percentages can affect the final temperature. The new
18 CHAPTER 1 Chemical thermodynamics and flame temperatures
Actually, the presence of O atoms could be attributed to the dissociation of wato
this higher temperature according to the equilibrium step at
H20H2 +0, Qp =-498.3 kJ
Since the heat absorption is about the same in each case, Le
Chatelier's principle
indicates a lack of preference in the reactions
leading to O. Thus in an overoxidized
lame, water dissociation introduces the species H2. O2, OH,
H, and O.
At even higher temperatures, the nitrogen begins to take part in the reactions
affect the system and
to thermodynamically. At T> 3000 K, NO forms
mostly from the
reaction
N +O2=NO, Qp =-90.5 kJ
rather than
N2 +H2O?NO +H2, Qp=-332.7 kJ
IfT2> 3500 K at P =1 atm or T> 3600 K at 20 atm, N2 starts to
another highly endothermic reaction:
dissociate by
Na2N, Op=-946.9 kJ
Thus the complexity in solving for the flame temperature depends on the number of
product species chosen. For a system whose approximate temperature range is
known, the complexity of the system can be reduced by the approach discussed
earlier. Computer programs and machines are now available that can handle the
most complex systems, but sometimes a little thought allows one to reduce the
complexity of the problem attain a better understanding of the results.
Equation (1.11) is now examined closely. If the n; values (products) total a num-
ber 4, one needs (u +1) equations to solve for the ni values and T2. The energy
equation is available as one equation. Furthermore, one has a mass balance equation
for each atom in the system. If there are a atoms, then (4 - a) additional equations
are required to solve the problem. These (4 a ) equations come from the equilib
must
rium equations, which are basically nonlinear. For the C-H-0-N system one
in which
simultaneously solve five linear equations and (u -4) nonlinearequations terms
it is present in
one of the unknowns, T2, is not even present explicitly. Rather,
is a difficult one to solve and
of the enthalpies of the products. This set of equations
codes.
can be done only with moderm computational
nitric acid taking place at a pressure
Consider the reaction between octane and
stoichiometric equation is written as
P as an example. The
+nH,oH20+ nH,H2
ncHi CgH18 +nHNO, HNO3-nco,CO2
+nN, N2 +nOHOH +nNONO
+ncoCO+no,O2
+noO+ncCsolid + nuH
 Calculations 1 19
9
Temperature
1.4 Flame
no
expression,
this general
explicitly for balance
mixture ratio is not specified new mass
Since the and u = 11. Thus the
to eliminate products
effort is made
equations (a
=
4) are
NH =
2nH, + 21H,0 +noH t HH
+no+nNO
+nco +nOH
No= 2no, +nH,0 + 2nco,
NN =
2nN, +nNO
Nc =nco, +nco+nc
where
NH = 18nc;H18 nHNO
No = 3HNo,
Nc = 8nC;H8
NN = nHNO3
needed would be
The seven (4 -
a
-
4 =
7) equilibrium equations
C+O2CO2, Kpt=nco,/no, i)
-1/2
i)
Ha+0Hh0, K,=(nH,o/ma.P/
+1/2
(ii)
C+0co, K-(rco/)(P/E»)
Kp1 =nOH/n (iv)
Ha+0
2 OH,
nNO
o+NNO, K» (v
)/2
(vi)
00,
no
HhH = 1/2
(vii)
n these equationsn includes only the gaseous products; that is, it does not
include nc. One determines nc from the equation for Nc.
The reaction between the reactants and products is considered irreversible, so
Lhat only the products exist in the system being analyzea. Thus, if the reactants
were H2 and O2, H2 and O2 would appear on the product side as well. In dealing
20 CHAPTER 1 Chemical
thermodynamics and flame
temperatures
with the equilibrium reactions, one
and O2. They are
ignores the molar quantities
given or known of the
quantities."The amounts of H2 and ctants
rea.
Ha
uct mixture would be unknowns. This O2 in the
point should be
though it isobvious. It is one of the major sources
considered carefiull
flame temperature problems of error in even
by hand. first
There are various mathematical attempts to solve
solve
merical methods [4,6,7). The most approaches for solving these
commonly used equations by
McBride [4] described in Appendix I. program is that of Gordon nu.
As mentioned earlier, to and
solve
composition, one must consider a explicitly for the temperature T2 and the
equations, (4 a) nonlinearproduct
mass balance
librium equations, and an -
energy equation in which one of the equi
even
explicitly present. Since numerical unknowns T2 is not
on
computers, the procedures are used to solve
the problem
with respect to thermodynamic functions are represented in terms of power series
In the
temperature.
general iterative approach, one first determines
the
the product equilibrium
composition at an
initially assumed value of the state for
pressure, and then checks to see whether the
one temperature and
Chemical equilibrium is energy equation is satisfied.
usually described by either of two
formulations-equilibrium constants or minimization of free equivalent
simple problems as determining the decomposition energy. For such
temperature of a
lant having few exhaust
products or examining the variation of a monopropel
specific species
with temperature or it is most convenient to deal with
pressure, equilibrium
constants. For complex problems, the
problem reduces to the same number of
interactive equations whether one uses equilibrium constants or minimization
of free energy. However, when one uses equilibrium constants, one encounters
more computational bookkeeping, more numerical difficulties with the use of
components, more difficulty in testing for the presence of some condensed
species, and more difficulty in extending the generalized methods to conditions
that require nonideal equations of state [4,6,8].
The condition for equilibrium may be described by any of several thermo-
such the minimization of the Gibbs or Helmholtz free en-
dynamic functions, as
ergy or the maximization of entropy. If one wishes to use temperature an
free
pressure to characterize thermodynamic state, one finds that the Gibbs
a
and are
inasmuch as temperature pressure
energy is most easily minimized, min-
Helmholtz free energy is most easily
its natural variables. Similarly, the and volume
state is characterized by temperature
mized if the thermodynamic
(density) I4]. and comp
used procedure for temperature
As stated, the most commonly of Gordon and McBriae
versatile computer program
sition calculations is the and a descen
the minimization of the Gibbs free energy technique similar
[4], who use
iteratively. A
method to solve the equations
Newton-Raphson
equilibrium
constants are used is show
when
method for solving the equations
in Ref. [7]