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3. Specific Heats of Gases

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 100 . This effect arises because molecules have vibrational (internal) energy as well as kinetic energy due to the motion of the complete molecule.

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A straightforward integer power series is most convenient: CP = a[0] + a[1]t +a[2]t2 + a[3]t3 +««.9739 × 10-4 3 . Empirical equations which allow the calculation of specific heats as a function of temperature have been in use for some time. (next Where 9. Values for the coefficients for the polynomials for some gases are given in slide). A polynomial expression is normally used. with either fractional or integer powers.. Table 4.2 (next slide and second slide).9739 e-4 means 9.

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the data was obtained in the temperatures range 25252. In the case of the above values.000 and the polynomials should not be used outside these limits. tables of specific heats are a more useful formulation and Table 4.3 (next slide) gives values for the common slide) combustion gases over a typical range of temperatures for combustion in boilers. 6 . be used for intermediate temperatures. Straightforward linear interpolation should temperatures. For hand calculations.

Take the net calorific value of methane as 50.While this method is not a particularly efficient algorithm. the mass of each of the reactants and products. it is stable and will generally converge to within 5 in four iterations. These steps have been covered in previous chapters and the result can be summarized thus: 7 .14 MJ/kg. Solution: The first step is to evaluate. for 1 kg fuel. Example 1: Find the adiabatic flame temperature for a stoichiometric methane/air flame if the initial temperature of the fuel and air is 10 .

17 CPN2)} (10The mean temperature of the reactants over the interval is 17.04 so HR = -293.92 N2 1.5 .9 kJ/kg methane 8 .25 kg H2O 13.17 kg N2 13. At this temperature the values of the specific heats are: CH4 2.75 kg CO2 4 kg O2 2.17 kg N2 The initial temperature of the reactants is 10 and the value of HR is the sensible heat in the reactants (ref.23 kJ/kg/K O2 0. Reactants Products 1 kg CH4 2. 25 ): HR = (10-25){1 CPCH4 + (4 CPO2) + (13.

575 .850 kJ/kg This value of HP represents the sensible heat in the combustion products above the reference temperature of 25 .575 + 25)/2. If we assume 1.e.75 CPCO2)} To solve this equation by trial and error requires an initial guess for the flame temperature.25) {(13. i. Giving HP = CV + HR =50.25 CPH2O) + (2. 49.17 CPN2) + (2. i. the mean temperature of the products above 25 is (1.9 = 49. 9 .e.144 ² 293. 800 .850 = (tf .

17×1.26)} tf=2.18)+(2.75×1.33)+(2.053 10 .33)+(2.18)+(2.25×2.33 CO2 1. The specific heats of nitrogen.850 = (tf25){(13.081 The new mean temperature of the products is (2. water vapor and carbon dioxide at this temperature are N2 1.26 so the energy equation is 49.081+25)/2=1.25×2.18 kJ/kg/K H2O 2.75× 25){(13.17×1.

48 CO2 1.30 solving the energy equation for the third time gives: tf = 1.001 # 11 .012 giving N2 1.50 CO2 1.22 kJ/kg/K H2O 2.The specific heats are now: 1.998 The mean temperature of the products now becomes (1.998+25)/2=1.30 A further evaluation of the energy equation gives tf = 2.22 kJ/kg/K N2 H2O 2.

and (3)the (3) the initial temperature (preheat) of the air and fuel. 12 .5. (2)the air-to(2) the air-to-fuel ratio at which combustion takes place. Calculated Adiabatic Flame Temperatures 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.

The picture is.CALORIFIC VALUE It would be expected that the higher the calorific value of the fuel the higher the final flame temperature produced. For example. 13 .1 and a calorific value of 54 MJ/kg (gross). on the other hand. however.3 MJ/kg. not quite as simple as this since the chemical composition of the fuel also plays a part.0 and a calorific value of 33. A typical coal. has a carbon-to-hydrogen carbon-toratio of around 18. natural gas has a carbon-tocarbon-tohydrogen ratio of around 3.

a glance at Table 4. Fuels with a higher proportion of hydrogen will generate more water vapor in their combustion products. In each case combustion is stoichiometric and the initial temperature of the air and fuel is 25 . 14 . which will lower the adiabatic flame temperature.1. The adiabatic flame temperature for a number of common hydrocarbon fuels are given before in Table 4.3 shows that water vapor has a higher specific heat than the other combustion products.

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. It 15 . The ´conformityµ is due to the effect of the hydrogen in the fuel discussed above.

with a corresponding reduction in temperature. 16 . 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.AIR-TOAIR-TO-FUEL RATIO Any excess air will increase the mass of flue gas relative to the mass of fuel. With sub-stoichiometric air supply the flame subtemperature will also fall.

2) It shows the temperature calculated for a natural gas flame as a function of the excess air ratio. The net calorific value of carbon monoxide is 10. and demonstrates the effects described above. 4. 4.2) (Fig. Next slide (Fig. above.11 MJ/kg. 17 .

air fuel ratio .

Oxygen flames are used in a number of process applications. Very high flame temperature can be achieved by oxygen enrichment of the flame. 19 . as the mass of flue gas is considerably reduced. but the temperatures in oxygen-enriched flames oxygenare so high that dissociation effects (discussed later) are highly significant. in particular welding.

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.PREHEAT Common sense (and equation (2)) suggest that preheating the air will increase the final temperature of the flame. 20 .

3 (next slide). 4. 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 Fig. 21 .

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hence reducing the actual flame temperature. 23 . In practice. 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. there are a number of reasons why the actual flame temperature will be lower than the value predicted by this procedure.

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