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1.1 Stoichiometric flame
Compute the adiabatic flame temperature at constant pressure of stoichiometric methane burning with air using three classes of assumptions and methods: Table 1: Methods to evaluate adiabatic flame temperatures Method Number of reactions Assumptions on 0 1 2 3 1 1 1 n Constant and equal Constant Variable Variable Technique Analytic Analytic Tables of enthalpy Code
The reference temperature for thermodynamic data is chosen at Repeat the exercice for two inlet temperatures: first
K. K and second (a value
typical of gas turbines) K. For method 2, Annex in § 3 provides values of molar sensible enthalpies versus temperatures for all required species.
1.2 Lean flames
Compute the adiabatic flame temperature at constant pressure of lean methane-air flames as a function of equivalence ratio using method 1 in Table 1.
2.1 Stoichiometric flame
Methane and air react through: (1)
Writing Eq. however. The derivation is written here using molar quantities for convenience but it can also be written using mass quantities. the total enthalpy of state 1 is: (3) while the total enthalpy of state 2 is : (4) Writing that leads to: . These errors can only be suppressed by taking more species and reactions into account (see § 2.2005]. The mass stoichiometric ratio is . The enthalpy of moles of a given species is: (2) where is the molar heat capacity and is the heat of formation of one mole of species [Poinsot. it leads to neglecting dissociations (for example molecules being broken into and ) and to large errors on adiabatic flame temperatures.4). This is not a major problem to compute flame temperatures when they remain low enough. (1) implicitely assumes that all other chemical reactions are neglected. In the present case.1. The system goes from state 1 (unburnt) to state 2 (burnt) at constant pressure so that its total enthalpy is constant. using the fact that all pure species have zero formation enthalpies .with moles of for one mole of in air. At higher temperatures.
1986] or in thermodynamic tables [Stull. 2. 1985.1971]. Eq.1At this stage must be obtained from tables found in textbooks [Williams. This can be simplified depending now on the form used for the enthalpy changes versus temperatures.1. For the present flame: (6) which means that burning one mole of releases kJ.1 Method 0: analytic The easiest method to solve Eq. (5) is to assume that all heat capacities are constant and equal to a value . Eq. Solving Eq. (5) becomes: (7) or (8) The main issue is then to choose Here. since (for example ! Which gas and at which temperature should be used ? of at a 'reasonable' temperature so that dominates in fresh and burnt gas. Kuo.(5) where is the molar heat of reaction. (5) gives the adiabatic flame temperature . the K) can be taken: . (5) could also have been written directly by stating that the difference between the sensible enthalpies of states 2 and 1 was the heat of reaction .
Note that for this case. Cold reactant temperature K.K when when K. K 298. (5) is to assume that the heat capacities are constant: they do not depend on temperature (but they still depend on the species type ). the term is almost zero. In the present case.6 J/moleK 37. For gases such as or K) on the final flame temperature values of remember that low temperature must match usual thermodynamic predictions for diatomic gases: with so that J/moleK.6 41. the issue becomes to choose values for the heat capacities which change significantly with temperature and have been assumed to be constant here.1 32.3 34.8 K 2734 2398 Table 3: Adiabatic flame temperature of stoichiometric methane-air flames assuming constant heat capacities and evaluating them at an arbitrary temperature .1 54. K and K 2.0 J/moleK 33. This is far from the exact answer.1.1.4 J/moleK 29. Tables 2 (for and 3 (for K) show the influence of the temperature used to evaluate . Cold . Table 2: Adiabatic flame temperature of stoichiometric methane-air flames assuming constant heat capacities and evaluating them at an arbitrary temperature .15 1000 J/moleK 35. (5) becomes: (9) which is a simple linear equation in .2 J/moleK 29. The exact answer (to be determined in § 2.4) is K without dissociations and K with dissociations.2 Method 1: analytic A better method to solve for in Eq. Eq. since . Some arbitrariness is necessary.8 72.
(5) can be recast as: the sensible molar enthalpy of species (10) which is an implicit equation for given below.15 K 1000 K J/moleK 35. K K 298. Let us call: . A part of such tables is given in § 3: the table provides values of vs temperature for the main species. this analytic method works but it depends too strongly on the choice of at which heat capacities are evaluated to provide a quantitative and precise result.6 41.1 32. 2.1.1. A simple iterative method using tables for is (11) so that Eq.4 J/moleK 29.4) is and K with dissociations.3 Method 2: using Tables Solving Eq.6 J/moleK 37.8 K 3070 K 2703 K Obviously. Calling at temperature . (5) can be done without assuming that the heat capacities are constant if tables for the changes of sensible enthalpy are available.3 34.reactant temperature K. Removing the assumption of constant heat capacities is needed and can be achieved as described in the next section. Such tables may also be found in textbooks or in specialized books. The exact answer (to be determined in § 2.1 54.8 72.0 J/moleK 33. (10) becomes: (12) . Eq.2 J/moleK 29.
break molecules and diminish temperature. K is the solution. Reading and interpolating Table 4 shows that value obtained numerically in § 2. If the reactant temperature is of § 3: so that K is close to K.4. this is exactly the 2. Table 4 shows values of for main species in methane-air combustion. especially at high temperatures where dissociations take place.If the reactant temperature is K.1. Linear interpolation K which is exactly the value obtained numerically in K. is zero so that the equation to solve is for temperatures from to . T (K) 2200 2300 2400 2500 2600 743 790 834 879 923 Obviously the value of when between and K gives § 2. To obtain precise results for such cases. Here EQUIL was used to solve the previous problem (Table 5).1. Such codes can be bought or obtained as freewares from certain laboratories. This is generally not true. equilibrium codes are needed.4. Two sets of species: A simple chemistry case with only as main species A complex chemistry case taking into account dissociations through the species .1. methods presented in the previous section still assume that only one reaction is sufficient to describe the thermochemistry of the reaction. Again. Table 4: Sensible enthalpy K. the enthalpy of the fresh gases must be such that is read from the table .4 Method 3: using equilibrium codes Even though using thermodynamic tables removes ambiguities on the choice of heat capacities and allows to take into account variable with temperature and species type.
Reactant temperature Final flame temperature Final flame temperature Simple chemistry Complex chemistry 298. 2. not enough the present written: moles will be available to burn moles.2 Lean flames If the equivalence ratio is less than unity. The chemical reaction controlling methane-air combustion can then be (13) for lean flames where is a factor smaller than unity.15 K 600 K 2327 K 2547 K 2225 K 2367 K Results illustrate the importance of dissociations: when complex chemistry and dissociations are accounted for.1995].which are the species used in the GRI Mechanism [Frenklach. the effect of dissociation is much smaller and a simple estimate based on a limited number of species is sufficient. the final flame temperature goes down from K to K for K and from K to K for K. for lean and/or cool flames. Note that the kinetic reactions are NOT needed for equilibrium computations: only the list of species is required. However. Table 5: Adiabatic flame temperature of stoichiometric methane-air flames using an equilibrium code (EQUIL of the CHEMKIN package) and all species of GRI Mechanism [Frenklach.1995]. Dissociations are important and must be taken into account in the present example because the maximum temperatures are high (typically larger than K). The equivalence ratio of the reactant is (14) .
For the present case. The values of Eq. this equation gives . at K are used (see Table 2) so that assuming constant heat capacities. (15) becomes: (16) which gives as a function of equivalence ratio: (17) Figure 1: Variations of adiabatic flame temperature versus equivalence ratio for lean . Writing again that the enthalpy of leads to: (15 ) Knowing . we limit ourselves to the method 1.so that reactants is actually equal to the equivalence ratio is equal to the enthalpy of products .
For K) are 3.5 83.4 115.8 103.methane-air flames.9 142.6 88.1 74.2 0 12. Constant heat capacities Figure 1 displays variations of versus for the two cases stoichiometric flames.1 134.4 67 162.6 181.1 63.3 128.9 86. and K) and 3 ( K.5 0 8.1 0 9.5 191.9 82.3 78 81.4 152.1 104. the adiabatic values obtained in Table 2 ( recovered.1 74.7 66.2 110 References . Annex: enthalpy tables Table 5: Enthalpy differences combustion ( T (K) 298.6 109.8 93.7 70.6 172 78.9 for main species in methane-air ).4 70.15 600 2200 2300 2400 2500 2600 2700 0 13.3 122 99. 0 10.
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