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© Simple ideal gas theory predicts that the
specific heat of a gas is not a function of its
temperature or pressure.
© While the latter implication is effectively
true in practice, the specific heat of a gas
does increase with temperature above about
100ë
100 ë. This effect arises because molecules
have vibrational (internal) energy as well as
kinetic energy due to the motion of the
complete molecule.


© Gmpirical equations which allow the
calculation of specific heats as a function
of temperature have been in use for some
time. A polynomial expression is normally
used, with either fractional or integer
powers.
© A straightforward integer power series is
most convenient:
CP = a[0] + a[1]t +a[2]t2 + a[3]t3 +««..
© Values for the coefficients for the
polynomials for some gases are given in
(next slide and second slide).
Table 4.2 (next slide).
Where 9.9739 e-4 means 9.9739 Î 10-4
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© 6n the case of the above values, the data was
obtained in the temperatures range 25-
25-
2,000ë
2,000 ë and the polynomials should not be
used outside these limits.
© por hand calculations, tables of specific heats
are a more useful formulation and Table 4.3
(next slide)
slide) gives values for the common
combustion gases over a typical range of
temperatures for combustion in boilers.
© Straightforward linear interpolation should
be used for intermediate temperatures
temperatures..

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© While this method is not a particularly efficient
algorithm, it is stable and will generally converge to
within 5ë
5ë in four iterations.
© Gxample 1:
pind the adiabatic flame temperature for a
stoichiometric methane/air flame if the initial
temperature of the fuel and air is 10ë
10ë. Take the net
calorific value of methane as 50.14 MJ/kg.
© Solution:
The first step is to evaluate, for 1 kg fuel, the mass
of each of the reactants and products. These steps
have been covered in previous chapters and the result
can be summarized thus:

 
© Yeactants Products
1 kg CH4 2.75 kg CO2
4 kg O2 2.25 kg H2O
13.17 kg N2 13.17 kg N2
The initial temperature of the reactants is 10ë
10ë and the value of
HY is the sensible heat in the reactants (ref. 25ë
25ë):
HY = (10-
(10-25){1Ô
25){1ÔCPCH4 + (4Ô
(4ÔCPO2) + (13.17Ô
(13.17ÔCPN2)}
© The mean temperature of the reactants over the interval is
17.5ë
17.5 ë. At this temperature the values of the specific heats are:
CH4 2.23 kJ/kg/K
O2 0.92
N2 1.04
so HY = -293.9 kJ/kg methane


©
iving HP = CV + HY =50,144 ² 293.9 = 49,850 kJ/kg
This value of HP represents the sensible heat in the
combustion products above the reference
temperature of 25ë, i.e.
49,850 = (tf - 25) {(13.17Ô
{(13.17ÔCPN2) + (2.25Ô
(2.25ÔCPH2O) + (2.75Ô
(2.75ÔCPCO2)}
© To solve this equation by trial and error requires an
initial guess for the flame temperature.
6f we assume 1,575ë, the mean temperature of the
products above 25ë is (1,575 + 25)/2, i.e. 800ë.

‰
© The specific heats of nitrogen, water vapor
and carbon dioxide at this temperature are
N2 1.18 kJ/kg/K
H2O 2.33
CO2 1.26
so the energy equation is
49,850 = (tf-
25){(13.17Î
25){(13.17 Î1.18)+(2.25
1.18)+(2.25ÎÎ2.33)+(2.75
2.33)+(2.75ÎÎ1.26)}
tf=2,081
=2,081ë
ë
© The new mean temperature of the products is
(2,081+25)/2=1,053ë
(2,081+25)/2=1,053 ë
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© The specific heats are now:
N2 1.22 kJ/kg/K
H2O 2.50
CO2 1.30
solving the energy equation for the third time gives:
tf = 1,998ë
1,998ë
© The mean temperature of the products now becomes
(1,998+25)/2=1,012ë
(1,998+25)/2=1,012 ë giving
N2 1.22 kJ/kg/K
H2O 2.48
CO2 1.30
A further evaluation of the energy equation gives
tf = 2,001ë
2,001ë #

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© Values of the predicted adiabatic flame


temperature for hydrocarbon fuels are
affected by the following factors:
(1) the calorific value (and chemical
composition) of the fuel;
(2)the
(2) the air
air--to-
to-fuel ratio at which
combustion takes place; and
(3)the
(3) the initial temperature (preheat) of
the air and fuel.
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© 6t would be expected that the higher the
calorific value of the fuel the higher the final
flame temperature produced.
The picture is, however, not quite as simple as
this since the chemical composition of the
fuel also plays a part.
© por example, natural gas has a carbon-
carbon-to-
to-
hydrogen ratio of around 3.1 and a calorific
value of 54 MJ/kg (gross). A typical coal, on
the other hand, has a carbon-
carbon-to-
to-hydrogen
ratio of around 18.0 and a calorific value of
33.3 MJ/kg.

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© puels with a higher proportion of hydrogen
will generate more water vapor in their
combustion products; a glance at Table 4.3
shows that water vapor has a higher specific
heat than the other combustion products,
which will lower the adiabatic flame
temperature.
© The adiabatic flame temperature for a
number of common hydrocarbon fuels are
given before in Table 4.1. 6n each case
combustion is stoichiometric and the initial
temperature of the air and fuel is 25ë
25ë.

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© 6t can be seen that there is quite a
small variation in the calculated flame
temperature, given the wide variation
between the calorific values of these
fuels.
© The ´conformityµ is due to the effect
of the hydrogen in the fuel discussed
above.

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© Any excess air will increase the mass of flue
gas relative to the mass of fuel, with a
corresponding reduction in temperature.
© With sub-
sub-stoichiometric air supply the flame
temperature will also fall, as although the
mass of flue gas is reduced, the effective
calorific value of the fuel is also reduced by
an amount equivalent to the calorific value of
the carbon monoxide which is present in the
flue gas.

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© The net calorific value of carbon
monoxide is 10.11 MJ/kg.
© Next slide (pig.
(pig. 4.2)
4.2)
6t shows the temperature calculated
for a natural gas flame as a function of
the excess air ratio, and demonstrates
the effects described above
above..


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© Very high flame temperature can be achieved
by oxygen enrichment of the flame, as the
mass of flue gas is considerably reduced.
© Oxygen flames are used in a number of
process applications, in particular welding, but
the temperatures in oxygen-
oxygen-enriched flames
are so high that dissociation effects
(discussed later) are highly significant.


Ñ
© Common sense (and equation (2)) suggest that
preheating the air will increase the final
temperature of the flame.
© This is a useful feature because by increasing
the temperature difference between the flue
gas and the heat extracting fluid, greater
heat transfer will be obtained for the same
fuel input rate.


© This will result in an increase in the
thermal efficiency of the plant.
© An example of the effect of preheat on
the adiabatic temperature of a natural
gas flame at 5% excess air is shown in
pig. 4.3 (next slide).

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© 6n practice, there are a number of reasons
why the actual flame temperature will be
lower than the value predicted by this
procedure.
© The most significant of these is that at the
high temperature achieved in flames the
combustion products will ´dissociateµ back
into reactants or other higher reactive
species: this process is accompanied by an
absorption of energy, hence reducing the
actual flame temperature.

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