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Chapter 2

Thermodynamics of Combustion


Properties of Mixtures

The thermal properties of a pure substance are described by quantities including
internal energy, u, enthalpy, h, specific heat, cp, etc. Combustion systems consist of
many different gases, so the thermodynamic properties of a mixture result from a
combination of the properties of all of the individual gas species. The ideal gas law
is assumed for gaseous mixtures, allowing the ideal gas relations to be applied to
each gas component. Starting with a mixture of K different gases, the total mass, m,
of the system is


mi ;



where mi is the mass of species i. The total number of moles in the system, N, is


Ni ;



where Ni is the number of moles of species i in the system. Mass fraction, yi, and
mole fraction, xi, describe the relative amount of a given species. Their definitions
are given by


and xi 



where i ¼ 1,2,. . .,K. By definition,

yi ¼ 1



xi ¼ 1:


S. McAllister et al., Fundamentals of Combustion Processes,
Mechanical Engineering Series, DOI 10.1007/978-1-4419-7943-8_2,
# Springer Science+Business Media, LLC 2011



2 Thermodynamics of Combustion

With Mi denoting the molecular mass of species i, the average molecular mass, M,
of the mixture is determined by
Ni Mi X
M¼ ¼ i
xi M i :
From Dalton’s law of additive pressures and Amagat’s law of additive volumes
along with the ideal gas law, the mole fraction of a species in a mixture can be found
from the partial pressure of that species as
Pi Ni Vi
¼ ¼ ¼ xi ;


where Pi is the partial pressure of species i, P is the total pressure of the gaseous
mixture, Vi the partial volume of species i, and V is the total volume of the mixture.
The average intrinsic properties of a mixture can be classified using either a molar
base or a mass base. For instance, the internal energy per unit mass of a mixture, u,
is determined by summing the internal energy per unit mass for each species
weighted by the mass fraction of the species.
mi ui X
u¼ ¼
y i ui ;
where U is the total internal energy of the mixture and ui is the internal energy per
mass of species i. Similarly, enthalpy per unit mass of mixture is

y i hi

and specific heat at constant pressure per unit mass of mixture is
cp ¼


yi cp;i :


A molar base property, often denoted with a ^ over bar, is determined by the sum
of the species property per mole for each species weighted by the species mole
fraction, such as internal energy per mole of mixture
u^ ¼
xi u^i ;

enthalpy per mole of mixture
h^ ¼


xi h^i ;

2.2 Combustion Stoichiometry


and entropy per mole of mixture
s^ ¼


xi s^i :


Assuming constant specific heats during a thermodynamic process, changes of energy,
enthalpy, and entropy of an individual species per unit mass are described as follows:
Dui ¼ cv;i ðT2  T1 Þ


Dhi ¼ cp;i ðT2  T1 Þ


Dsi ¼ cp;i ln

Ri ln


Pi,1 and Pi,2 denote the partial pressures of species i at state 1 and state 2, respectively.
Ri is the gas constant for species i (Ri ¼ R^u =Mi ¼ universal gas constant/molecular
mass of species i). The overall change of entropy for a combustion system is
DS ¼


mi Dsi :


A summary of the thermodynamic properties of mixtures is provided at the end
of the chapter.


Combustion Stoichiometry

For a given combustion device, say a piston engine, how much fuel and air should
be injected in order to completely burn both? This question can be answered by
balancing the combustion reaction equation for a particular fuel. A stoichiometric
mixture contains the exact amount of fuel and oxidizer such that after combustion is
completed, all the fuel and oxidizer are consumed to form products. This ideal
mixture approximately yields the maximum flame temperature, as all the energy
released from combustion is used to heat the products. For example, the following
reaction equation can be written for balancing methane-air combustion  

CH4 þ ? O2 þ N2 ! ?CO2 þ ?H2 O þ ?N2 ;
where air consisting of 21% O2 and 79% N2 is assumed.1 The coefficients associated
with each species in the above equation are unknown. By balancing the atomic

These coefficients are called the reaction stoichiometric coefficients. This is done here to simplify the calculations of the heat of reaction and flame temperature later in the chapter. Ca Hb Og . For instance. the balanced reaction equation reads: CH4 þ 2ðO2 þ 3:76N2 Þ ! 1CO2 þ 2H2 O þ 7:52N2 : (2. N. Using this procedure we can determine all the coefficients. with air can be expressed as     b g b b g Ca Hb Og þ aþ  ðO2 þ3:76N2 Þ!aCO2 þ H2 Oþ3:76 aþ  N2 : (2. The first method develops the stoichiometry of combustion using the general principle of atomic balance. O) is the same in the products and the reactants. Examples are given here for a fuel mixture containing 95% methane and 5% hydrogen. multiply the individual stoichiometry equations by the mole fractions of the fuel components and add them: .52 mol of air and its molecular mass is 28.18 2 Thermodynamics of Combustion abundance on both the reactant and product sides. H. In this text. Combustion stoichiometry for a general hydrocarbon fuel. the reactions are balanced using 1 mol of fuel. one can find the coefficient for each species. hence the product side should also have 1 mol of C atoms.96 kg/kmol.11) Note that on the reactant side there are 2·(1 + 3. There are two typical approaches for systems with multiple fuels.76) or 9. The above formula is for a single-component fuel and cannot be applied to a fuel consisting of multiple components. 0:95CH4 þ 0:05H2 þ 1:925ðO2 þ 3:76N2 Þ ! 0:95CO2 þ 1:95H2 O þ 7:238N2 : The other method of balancing a fuel mixture is to first develop stoichiometry relations for CH4 and H2 individually: CH4 þ 2ðO2 þ 3:76N2 Þ ! CO2 þ 2H2 O þ 2  3:76N2 H2 þ 0:5ðO2 þ 3:76N2 Þ ! H2 O þ 0:5  3:76N2 Then. The coefficient of CO2 is therefore unity. we have 1 mol of C atoms. let’s determine the coefficient for CO2: on the reactant side. For stoichiometric methane combustion with air.12) 4 2 2 4 2 The amount of air required for combusting a stoichiometric mixture is called stoichiometric or theoretical air. making sure that the total number of each type of atom (C.

Equivalence Ratio: Normalizing the actual fuel-air ratio by the stoichiometric fuelair ratio gives the equivalence ratio. in the range of 0.05–0. 2.2 Combustion Stoichiometry 19 0:95  fCH4 þ 2ðO2 þ 3:76N2 Þ ! CO2 þ 2H2 O þ 2  3:76N2 g 0:05  fH2 þ 0:5ðO2 þ 3:76N2 Þ ! H2 O þ 0:5  3:76N2 g )0:95CH4 þ 0:05H2 þ 1:925ðO2 þ 3:76N2 Þ ! 0:95CO2 þ 1:95H2 O þ 7:238N2 2.13 becomes  mf  Mf ¼ . f <1 is a lean mixture. ma (2. f. fuels are often combusted with an amount of air different from the stoichiometric ratio. Most hydrocarbon fuels have a stoichiometric fuel-air ratio. f. Similar to f.2. the mixture is described as fuel lean.07. is given by f ¼ mf .2. The range of f is bounded by zero and 1. f ¼ 1 is a stoichiometric mixture. and f >1 is a rich mixture. If excess air is used.a (2. respectively. For a stoichiometric mixture.15) The subscript s indicates a value at the stoichiometric condition. Eq.1 Methods of Quantifying Fuel and Air Content of Combustible Mixtures In practice. as AFR ¼ 1/f. the mixture is described as fuel rich. For instance. An alternative . the stoichiometric AFR of gasoline is about 14. For most hydrocarbon fuels. Note that equivalence ratio is a normalized quantity that provides the information regarding the content of the combustion mixture.14) where Mf and Mair (~28. If less air than the stoichiometric amount is used. fs. f¼ f mas Nas NO2s ¼ ¼ ¼ fs ma Na NO2.7. For this reason.13) where mf and ma are the respective masses of the fuel and the air. The air-fuel ratio (AFR) is also used to describe a combustible mixture and is simply the reciprocal of FAR. it is convenient to quantify the combustible mixture using one of the following commonly used methods: Fuel-Air Ratio (FAR): The fuel-air ratio. 14–20 kg of air is needed for complete combustion of 1 kg of fuel. fs ¼  ma stoichiometric ða þ b4  2gÞ  4:76  Mair (2. the range of f is bounded by zero and 1 corresponding to the limits of pure air and fuel respectively.84 kg/kmol) are the average masses per mole of fuel and air.

4 0.1 with their graphic relations. the products of combustion include many different % of excess air Equivalence ratio. φ fuel air ratio (mass) fuel air ratio (mass) Table 2.3 0. Lambda is the ratio of the actual air-fuel ratio to the stoichiometric air-fuel ratio defined as AFR 1=f 1 1 ¼ ¼ ¼ AFRs 1=fs f =fs f l¼ (2.1 0 0 2 4 6 8 10 Equivalence ratio.5 fs = 0.4 0. Percent Excess Air: The amount of air in excess of the stoichiometric amount is called excess air. φ 400 300 fs = 0.4 s 0.1 Relations among the three variables for describing reacting mixtures f (fuel air ratio by mass) f (equivalence ratio) %EA (% of excess air) f 1f f ¼ fs  f f¼ %EA ¼ 100 f f s 100  fs f ¼ 100 1  f =fs %EA þ 100 f¼ %EA ¼ 100 %EA þ 100 f =fs 0.0.5 f = 0.5 Fuel air ratio (mass) . is defined as   ma  mas ma %EA ¼ 100 ¼ 100 1 mas mas (2. lambda is less than 1.1 0.5 2.0 Equivalence ratio.20 2 Thermodynamics of Combustion variable based on AFR is frequently used by combustion engineers and is called lambda (l).5 Fuel air ratio (mass) Equivalence ratio. φ 10 8 6 4 2 0 −100 0 100 200 300 400 % of excess air 400 300 200 100 0 −100 % of excess air 0. lambda is greater than 1.2 0.2 0.16) Lambda of stoichiometric mixtures is 1.0. For rich mixtures. f.1 0 0 200 400 % of excess air 10 fs = 0.5 1. Converting between quantification methods: Given one of the three variables (f.05 0.4 0.0.3 0. the other two can be deduced as summarized in Table 2.3 0.2 0. and %EA). In general.05 8 6 4 2 0 0 0. %EA.05 200 100 0 −100 0 0.05 0.17) For example. The percent excess air.2 0. a mixture with %EA ¼ 50 contains 150% of the theoretical (stoichiometric) amount of air. φ 0.1 0.3 0. for lean mixtures.0 1.

1 f¼ 100 !f¼ 100 þ %EA 1þ 1 a a þ b4  2g  (2.18) b 3:76 b g b g 1 a þ  N2 þ a þ   1 O2 aCO2 þ H2 O þ 2 f 4 2 4 2 f In terms of %EA. The ratio of mole fractions between CO2 and O2 is xCO2 a %EA a   ¼  ! ¼  b g %EA b g xCO2 100 xO2 aþ  aþ  4 2 100 4 2 xO2 or using Table 2. the corresponding global equation can be written as   1 b g a þ  ðO2 þ 3:76N2 Þ ! f 4 2     a b 3:76 b g 1 CO2 þ H2 O þ a þ  N2 þ 1  Ca Hb Og f 2f f 4 2 f Ca Hb Og þ (2. If the products are assumed to contain only unburned fuel and major combustion products. N2.2 Combustion Stoichiometry 21 species in addition to the major species (CO2. Often additional information on the products is needed for complete balance of the chemical reaction. the global equation for lean combustion fb1 is   1 b g a þ  ðO2 þ 3:76N2 Þ ! Ca Hb Og þ f 4 2      (2. O2). assuming that the products contain major species only (complete combustion) and excess air.21) .2.20) xCO2 xO 2 For rich combustion (f>1). H2O. and other species formed by the degradation of the fuel.19) b %EA b g b g %EA aCO2 þ H2 O þ 3:76 þ 1 a þ  N2 þ a þ  O2 2 100 4 2 4 2 100 C a Hb Og þ The amount of excess air can be deduced from measurements of exhaust gases. unburned fuels. However. and the balance of the stoichiometric equation requires the use of thermodynamic equilibrium relations. we replace f by  100 and the result is %EA þ 100   %EA b g þ 1 a þ  ðO2 þ 3:76N2 Þ ! 100 4 2      (2. the products may contain CO.

(b) fs ¼ Example 2. Hence. . A saturation table for steam gives the saturation temperature at this water pressure ffi 53 C. free ambient air is preferred.300 lb.3 kPa Solution: The first step is writing and balancing the stoichiometric reaction equation.7 US gallons) of gasoline? Solution: We will use isooctane C8H18 to represent gasoline.2 How many kg (lb) of air are used to combust 55.7 kg (6 lb).5 L (~14.22 2 Thermodynamics of Combustion Example 2. for transportation applications. This is a lot of weight if it must be carried. 2.84 kg/kmol ¼ 0:066 One gallon of gasoline weighs about 2. determine: (a) (b) (c) (d) the mole fraction of fuel the fuel-air ratio the mole fraction of H2O in the products the temperature of products below which H2O starts to condense into liquid at 101. Using Eq.2 kPa. The required air weighs about 40/fs  610 kg  1.     18 18 C8 H18 þ 8 þ  0 ðO2 þ 3:76N2 Þ ! 8CO2 þ 9H2 O þ 3:76 8 þ  0 N2 4 4 C8 H18 þ 12:5ðO2 þ 3:76N2 Þ ! 8CO2 þ 9H2 O þ 3:76  12:5  N2 From here: (a) xC8 H18 ¼ NC8 H18 1 ¼ 0:0165 ¼ NC8 H18 þ Nair 1 þ 12:5  4:76 Mf 114 ¼ 0:066 ¼ ða þ b4  2gÞ  4:76  Mair 12:5  4:76  28:96 N H2 O 9 (c) xH2 O ¼ ¼ 0:141 ¼ N CO2 þ N H2 O þ N N2 8 þ 9 þ 3:76  12:5 (d) The partial pressure of water is 101 kPa  0.141 ¼ 14.1 Considering a stoichiometric mixture of isooctane and air.12. The total fuel thus weighs about 40 kg (88 lb). The stoichiometric fuel-air ratio is fs ¼ Mf b 4 ða þ  g 2Þ  4:76  Mair 114 kg=kmol ¼ ð8 þ 18=4  0Þ  4:76  28.

%EA ¼ 100 a 7  ¼ 0:667 ! %EA ¼ b g xCO2 ð7 þ 16=4  0Þð0:084=0:088Þ aþ  4 2 xO 2 ¼ 66:7 Next we use the relations given in Table 2. The value of the LHV can be calculated from the HHV by subtracting the amount of energy released during the phase change of water from vapor to liquid as LHV ¼ HHV  NH2O. the value of total heat release is denoted as the lower heating value (LHV).1 to convert %EA to f and l 2.084 and xO2 ¼ 0. Solution: To avoid condensation of water inside the instruments.P MH2O hfg Nfuel Mfuel (MJ/kg). The mole fractions measured under dry conditions will be larger than at real conditions since water is removed. additional energy (equal to the latent heat of vaporization) can be extracted and the total energy release is called the higher heating value (HHV). The amount of heat release from combustion of the fuel will depend on the phase of water in the products. Determine the %EA. measurements of exhaust gases are taken on a ‘dry’ mixture that is obtained by passing the exhaust gases through an ice bath so that most water is condensed.3 kPa). Measurements of dry exhaust give mole fractions of CO2 and O2 as xCO2 ¼ 0. Further removal of water can be done with desiccants. as both xCO2 and xO2 are increased by the same factor. and l.22) .088.3 Heating Values 23 Example 2. (2.3 f¼ 100 100 ¼ ¼ 0:6 %EA þ 100 66:7 þ 100 l¼ 1 ¼ 1:67 f Heating Values Heating values of a fuel (units of kJ/kg or MJ/kg) are traditionally used to quantify the maximum amount of heat that can be generated by combustion with air at standard conditions (STP) (25 C and 101.3 In a model “can-combustor” combustion chamber. When the water vapor is condensed to liquid. If water is in the gas phase in the products. equivalence ratio f. However.2. this will not impact the relation deduced above. n-heptane (C7H16) is burned under an overall lean condition.

1 Enthalpy of Formation In combustion processes. has units of MJ/kg.92 MJ/kmol.3.P is the number of moles of water in the products. A departure from standard conditions is accompanied by an enthalpy change. 2.24 2 Thermodynamics of Combustion where NH2O. Dh^oi . and N2. It follows from above that the heating value of the fuel is the difference in the enthalpies of the reactants and the products. quantifies the chemical bond energy of a chemical species at standard conditions.44 MJ/kg ¼ 43. have enthalpies of formation of zero. Elements in their most stable forms.p ¼ HR  Hp : (2. with HP and HR denoting the respective total enthalpies of products and reactants. In combustion literature. Suppose reactants with 1 kmol of fuel enter the inlet of a control volume at standard conditions and products leave at the exit. in combustion systems.23) The negative value of Qrxn. has units of MJ/kmol. A maximum amount of heat is extracted when the products are cooled to the inlet temperature and the water is condensed. Dh^oi . The enthalpy of formation of a substance is the energy needed for the formation of that substance from its constituent elements at STP conditions (25 C and 1 atm). the change of enthalpy of an ideal gas is described by the sensible enthalpy. H2. The molar base enthalpy of formation.3. Dh^oi .1. Conservation of energy for a constant pressure reactor. reactants are consumed to form products and energy is released. the LHV is normally called the enthalpy or heat of combustion (QC) and is a positive quantity. However. 2. and the mass base enthalpy of formation. Latent heat for water at STP is hfg ¼ 2.p indicates heat transfer out of the system to the surroundings. For thermodynamic systems without chemical reactions. such as C(graphite). the evaluation of the enthalpies is not straightforward because the species entering the system are different than those coming out due to chemical reactions. Enthalpies of formation of commonly encountered chemical species are tabulated in Table 2. with the subscript p indicating that the value was calculated at constant pressure. .1 Determination of HHV for Combustion Processes at Constant Pressure A control volume analysis at constant pressure with no work exchanged can be used to theoretically determine the heating values of a particular fuel. O2. Qrxn. This energy comes from a rearrangement of chemical bonds in the reactants to form the products.2. gives  Qrxn.p ¼ QC.p is often referred to as the enthalpy of reaction or heat of reaction. The standard enthalpy of formation. The enthalpy of reaction is related to the enthalpy of combustion by Qrxn.

12 277.25 201.3 kPa.2.1.73 +52. 101. is thus the sum of the sensible enthalpy and the enthalpy of formation:2 h^i ¼ Dh^oi þ h^si (2. h^i .28 84.29 +33.52 110. 2. To where the subscript i refers to species i. 101. Note that the sensible enthalpy of any species is zero at standard conditions.53 74.23 259.02 Dh^o (MJ/kmol) +217. An amount of heat produced in the reaction is transferred 2 When phase change is encountered.83 393. the enthalpy of formation of CO2 is determined by reacting 1 kmol of C(graphite) with 1 kmol of O2 at 25 C at a constant pressure of 101. The ‘absolute’ or ‘total’ enthalpy.10 +249.54 238.522 kJ (heat out) Fig. the total enthalpy needs to include the latent heat. T0 denotes the standard temperature (25 C).3 Heating Values 25 Table 2.00 +226. flows out of this reactor at 25 C as sketched in Fig. 1 kmol of CO2. 2. The product.2 Enthalpy of formation of common combustion species Species Dh^o (MJ/kmol) Species H2O (g) CO2 CO CH4 C3H8 C7H16 (g) (n-heptane) C8H18 (g) (isooctane) CH3OH (g) (methanol) CH3OH (l) (methanol) C2H6O (g) (ethanol) C2H6O (l) (ethanol) 241.79 +90.3 kPa ZT c^p ðTÞdT.43 235. For instance.1 Constant-pressure flow reactor for determining enthalpy of formation 1 kmol C C + O2 → CO2 1 kmol O2 @ 25°C.46 +715.68 126. h^i ¼ Dh^oi þ h^si þ h^latent . .99 +472.15 H N NO NO2 O OH C (g) C2H2 (acetylene) C2H4 (ethylene) C2H6 (ethane) C4H10 (n-butane) Q = −393.3 kPa h^si ¼ CV 1 kmol CO2 @ 25°C.19 +39. and ^ indicates that a quantity is per mole.71 224.87 104.24) One way to determine the enthalpy of formation of a species is to use a constantpressure flow reactor.

p at STP. The amount of excess air used will not affect  Q0rxn.R Dh^oi.26) i Usually excess air is used in such a test to ensure complete combustion. such as O.P " ¼ i X i Ni.27) .P h^si.R Dh^oi.3. the enthalpy formation of NO is Dh^oNO ¼ +90.R  i X Ni. H. the amount of heat transfer from the constant-pressure reactor to the surroundings is defined as the heating value.P Dh^oi. we can now evaluate the enthalpies of the reactants and products.52 MJ/kmol.R h^si.R  X # Ni. Unless the reactant mixtures are heavily diluted.2 Evaluation of the Heat of Combustion from a Constant-Pressure Reactor Using the conservation of energy equation (2.p ¼ X Ni. therefore the enthalpy formation of CO2 is negative Dh^oCO2 ¼ 393. O2 and N2. The enthalpy of formation is not negative for all chemical species.1. R Dh^oi. Inserting the expression for the total enthalpy.R þ h^si.   X   X Qrxn:p ¼ HR  Hp ¼ Ni. the enthalpy of formation is positive.P Dh^oi.29 MJ/kmol. the water in the products at STP normally will be liquid.P þ i X i Ni.23).26 2 Thermodynamics of Combustion out of this system. For most unstable or “radical” species. 2. The sensible enthalpies of common reactants and products can be found in Appendix 1. meaning that energy is needed to form NO from its elements.R  i X Ni. When the products are cooled to the same conditions as the reactants. and CH3. HHV is determined: HHV ¼ Q0rxn. N. p : Nfuel Mfuel The negative sign in front of Q0rxn. This means that CO2 at 25 C contains less energy than its constituent elements C(graphite) and O2.P Dh^oi. At STP the sensible enthalpy terms drop out for both reactants and products and the heat release is  Q0rxn.P (2.25) i where Ni is the number of moles of species i.P . (2.3 Assuming that water in the products is liquid. which have zero enthalpy of formation. (2. For instance.P þ h^si.R  Ni.p ensures that HHV is positive.

the total internal energy of the reactants. conservation of energy yields  Qrxn. UR.v ¼ UR  UP ¼ X Ni.28) Because of the combustion process.R R^u T0 i (2. HHV for combustion processes is calculated as HHV ¼ Q0rxn.32) .29) Ni.3.3 Heating Values 2.P  X i Ni.P X  i Ni. the same type of accounting must be used to include the change in chemical bond energies.R Dh^oi.R  i X Ni.R R^u T0 ¼ HR  ¼ X i Ni.R R^u T0  " X i X Ni.v ¼ UR  Up (2. Note that relation h ¼ u + pv is mass based and the corresponding molar base relation is h^ ¼ u^ þ R^u T. At STP (T ¼ T0 ¼ 25 C).R  i ¼ X Ni.P  i X # Ni.P  P i Nfuel Mfuel i  Ni.31) Therefore.R R^u T0 i The total internal energy of products is evaluated in a similar manner: UP ¼ X Ni.P Dh^oi.30) i Using the internal energy relations.R R^u T0 .P R^u T0 ! Ni. inside the closed system is UR ¼ HR  PV X Ni.P þ i X i Ni. (2.v   P Ni.R Dh^oi.R Dh^oi.R  X i (2.P R^u T0 (2.2 27 Determination of HHV for Combustion Processes from a Constant-Volume Reactor A constant-volume reactor is more convenient than the constant-pressure reactor to experimentally determine the HHV of a particular fuel. The internal energy will be evaluated by using its relation to enthalpy.P Dh^oi. we can re-express the heat release at constant volume in terms of enthalpies as Q0rxn.2.P Dh^oi. For a closed system.

2 Bomb calorimeter . 2.P  Ni.3. the fuel and air are often enclosed in an explosive-proof steel container (see Fig.2).p is !   X X b g ^ ^ þ  1 R^u T0 Ni.R Ru T0 ¼ DN Ru T0 ¼ (2. Conservation of energy gives UP  UR ¼ Q0rxn. The vessel is then submerged in water or another liquid that absorbs the heat of combustion. 2. 2. therefore normally no distinction is made between the heat of reaction at constant pressure or constant volume. CaHbOg. For a general fuel. The heat capacitance of the vessel plus the liquid is then measured using the same technique as other calorimeters.v is to make sure that HHV is positive. The fuel is burned with sufficient oxidizer in a closed system.33) 4 2 i i and is usually small in comparison to HHV.2. A constant-volume analysis of the bomb calorimeter data is used to determine the heating value of a particular fuel. the difference between –Qrxn. The negative sign in front of Q0rxn.34) Thermocouple Stirrer Igniter Insulated container filled with water Reaction chamber (bomb) Sample cup Fig.1 Experimental Determination of HHV: The Bomb Calorimeter To experimentally measure the heating value of a fuel.28 2 Thermodynamics of Combustion where Nfuel is the number of moles of fuel burned and Mfuel is the molecular mass of the fuel. The closed system is cooled by heat transfer to the surroundings such that the final temperature is the same as the initial temperature. The standard conditions are set for evaluation of heating values.v (2.v and –Qrxn. whose volume does not change during a reaction. Such an instrument is called a bomb calorimeter.

The amount of heat transfer is estimated by  Q0rxn.P Q0rxn.3 Heating Values 29 Because the final water temperature is close to room temperature.3 X Ni.P  i P  Ni. i where Nfuel is the number of moles of fuel burned and Mfuel is the molecular weight of the fuel. we start out with 1 mol of H2 and 0. the water in the combustion products is usually in liquid phase. The bomb calorimeter can also measure the enthalpy of formation of a chemical species.5 mol of O2.v þ DN R^u T0 Ni.steel þ mwater  cp.P  i 2. namely H2O. Therefore the measurement leads to the HHV from a constant-volume combustion process as described by Eq. 2. Dh^i.32: ( HHV ¼ Q0rxn. These element species have zero enthalpy of formation. In a bomb calorimeter. Example 2.36) where DN ¼ X Ni.4 A table of thermodynamic data gives the enthalpy of formation for liquid water as Dh^H0 2 OðlÞ ¼ 285.P ¼ Q0rxn.v  X Ni.0 kJ of heat transfer out of the reacted mixture. Estimate the error of the enthalpy measurement.R Dh^i.P .35) where DT is the temperature change of the water and the steel container. (2. to determine enthalpy of formation of H2O.R ¼ 0: i The only product is the species of interest. if the final temperature of the combustion products is higher than the reactants by only a few degrees (<10 C).P (2. The negative sign in front of Q0rxn. A bomb calorimeter burning 1 mol of H2 with O2 measures 282. therefore X 0 Ni. .8 kJ/mol.P  X i ! )   Ni.R : i Representative HHV Values Listed in Table 2.v ¼ ðmsteel  cp.v ensures that HHV is positive.2.3 are higher heating values of some common and less common fuels.v þ  P Ni. For instance. the error is negligible. We therefore can write the 0 enthalpy of formation of H2O.3.water ÞDT. as 0 Dh^i.R R^u T0 i ¼ Ni.R R^u T0 = Nfuel Mfuel .

7 Propanol 33.5 Ethane 51.400 16.690 8.35 Butane 49.30 2 Thermodynamics of Combustion Solution: We start out with the combustion stoichiometry H2 ðgÞ þ 0:5O2 ðgÞ ¼ H2 OðliqÞ.800 12.900 19.220 2.000–14. 0 Dh^H2 OðlÞ ¼ Q0rxn.3 Paraffin 46 Diesel 44.400 21. DN ¼ 1:5 ðChange in moles of gas in the mixtureÞ Applying the ideal gas approximation to the energy balance with Q0rxn.8  285.5 Hydrazine 19.8 Coal 15–27 Wood 15 Peat 6–15 Methanol 22.270 382 622 4.5 Gasoline 47.03%.8 ¼ 0.500 9.100 kJ/mol 286 890 1.0 kJ.9 Propane 50.560 2. since the P-V work (1. more heat is given off if the reaction is carried out at constant pressure.500 18.8 Methane 55.5 .900 22.9 Benzene 41.900 14.5 mol of gases in the reactants would contribute to Dh^H0 2 OðlÞ .100 23.300 8.368 2.300 ~4.480 200–350 300 726 1.000 6.020 1.400 19.5R^u T0 ) due to the compression of 1.7 Ethanol 29. In this case.v ¼ 282.6 Acetylene 49. this difference is only about 1–2% of the enthalpy of formation.7)/285. The enthalpy of formation for gaseous H2O is obtained by adding the latent heat to Dh^H0 2 OðlÞ : Dh^H0 2 OðgÞ ¼ Dh^H0 2 OðlÞ þ h^fg ¼ 241:88 kJ/mol.900 20.500 2.370 12.877 ~5.v þ DN R^u T0 .200 393.8 BTU/lb 61.3 Heat values of various fuels Heating value Fuel MJ/kg Hydrogen 141. Table 2.500–6.8 Ammonia 22. ¼ 282:0 kJ/mol  1 mol þ ð1:5 mol  8:314 J/mol  K  298K  0:001 kJ/JÞ ¼ ð282:0  3:72ÞkJ ¼ 285:7 kJ The error is (285.800 14.300 3.0 Carbon 32.500 21.000 9.4 Hexamine 30. However.700 20.

5 The heat released by 1 mol of sugar in a bomb calorimeter experiment is 5.4 Adiabatic Flame Temperature One of the most important features of a combustion process is the highest temperature of the combustion products that can be achieved.37) where HP ðTP Þ ¼ X Ni. DN ¼ 0. or adiabatic flame temperature. will be presented.R ½Dh^oi.3 is a graphic explanation of how the adiabatic flame temperature is determined. work is zero and the enthalpy of combustion equals the heat transfer: 5.R h^i. Under this idealized condition.4 Adiabatic Flame Temperature 31 where h^fg ¼ 43:92 kJ/mol: Example 2.R þ h^si.2.1 Constant-Pressure Combustion Processes An adiabatic constant-pressure analysis is used here to calculate the adiabatic flame temperature. the enthalpy of the product mixture .P h^i.P ¼ i X Ni. 2.648 kJ/mol.R ¼ X Ni. the methodology used to calculate the maximum temperature. Therefore.P þ h^si. Solution: The balanced chemical reaction equation is C12 H22 O11 ðsÞ þ 12O2 ðgÞ ¼ 12CO2 ðgÞ þ 11H2 OðliqÞ Since the total number of moles of gas is constant (12) in the products and reactants.4.R ðTR Þ: i Figure 2. 2.P ðTP Þ i and HR ðTR Þ ¼ X i Ni.P ½Dh^oi. In the next two sections. At the initial reactant temperature. (2. conservation of energy is: HP ðTP Þ ¼ HR ðTR Þ. Calculate the enthalpy of combustion per mole of sugar. The temperature of the products will be greatest when there are no heat losses to the surrounding environment and all of the energy released from combustion is used to heat the products.648 kJ/mol.

An equilibrium state solver takes into account dissociation of products at high temperature. 3.R ðTR Þ i (2.p þ X i X ) Ni.P ðTP Þ ¼  i X Ni.3 Graphical interpretation of adiabatic flame temperature is lower than that of the reactant mixture.R i Ni. making it more accurate than the first two methods.P  i ¼ Q0rxn. Finding the equilibrium state using computer software (such as Cantera).P ðTP Þ ¼ X i Ni.P h^si.P Dh^oi.R ðTR Þ i Rearranging yields X ( Ni.R h^si.32 2 Thermodynamics of Combustion HR (T) HR (TR) = Hp (TP) Enthalpy HR (TR) Ο x Energy Release Ο HP(T) HP (TR) Reactant Temperature Adiabatic Flame Temperature Temperature.R ðTR Þ þ X Ni. average cp From conservation of energy.R Dh^oi. Method 1: Constant. The energy released from combustion is used to heat up the products such that the condition HP ðTP Þ ¼ HR ðTR Þ is met.P ½Dh^oi.R h^si. Hp ðTp Þ ¼ HR ðTR Þ. An iterative enthalpy balance. 2. T Fig. which can be expressed as X Ni. Three different methods can be used to obtain TP: 1.R þ h^si.R ½Dh^oi. 2. The first two methods can be performed manually if complete combustion is considered and provide only quick estimates.38) . The task is finding the product temperature given the enthalpy of reactants.P þ h^si. Using an average cp value.

(2.R ðTR Þ (2.P(TP)  cˆpi (TP  T0) with cˆpi  constant.R and P i Ni.p c^pi are assumed to be approximately equal.R h^si.R ðTR Þ Pi TP ¼ T0 þ Ni.P ¼ Q0rxn.R  i X Ni. therefore  Q0rxn.R ðTR Þ P ¼ Ni.R ðTR Þ.R c^p i.38 represents i the difference of sensible enthalpy between TR and T0 (25 C) for the reactant mixture. the above equation reduces to (as sensible enthalpies of reactants are zero at T0) TP ¼ T0 þ LHV  Nfuel  Mfuel P : Ni.R ðTR  T0 Þ P  TR  T0 Ni.p  TR þ P Ni.R Dh^oi.P c^pi  c^p ðTP  T0 Þ X i Ni.P c^pi i When reactants enter the combustor at the standard conditions.p ¼ X Ni.P c^pi i Q0rxn.R h^si. Ni.39) i Note that water in the products is likely in gas phase due to the high combustion temperature.P c^pi i 4 P i Ni.R h^si. in Eq.P c^pi (2.R h^si.41) i LHV  Nfuel  Mfuel P ¼ TR þ . Ni.2. 2.P c^pi P i i Ni.4 Adiabatic Flame Temperature 33 with  Q0rxn. With the assumption that the sensible enthalpy can be approximated by hˆsi.p þ X i Ni.P : (2.p ¼ LHVNfuelMfuel ¼ LHVmf when the fuel is P completely consumed.P c^pi i where the following approximation has been applied4 P i Ni.R c^p i.42) . The second term. we have ðTP  T0 Þ X Ni.P Dh^oi.40) i Rearranging the equation one finds TP as P Q0rxn.p þ Ni.

i. 2.34 2 Thermodynamics of Combustion The above procedure is general and can be applied to any mixture. reactants and the standard temperature.R  (TR – T0).. cp. the products have a total mass of mf + ma.P ¼ Q0rxn.P TP ffi T0 þ (2. so the accuracy of this approach depends on the value selected for the specific heat cˆp. Similarly.e. Similarly. mfb ¼ mf since there is enough air to consume all the fuel in a lean mixture.4. for the rich mixtures one gets fr1 Tp ¼ TR þ fs  LHV fs  LHV ¼ TR þ ð1 þ f Þ cp.R ¼ mfb LHV þ Hs.P cp.P ð1 þ f  fs Þ cp. the flame temperature peaks at the stoichiometric ratio. By mass conservation. the the reactants and products.p þ Hs. sensible enthalpy of the reactants is estimated by Hs. fs ¼ 0. where cp.P ¼ cp ðTÞ. As expected. Method 2: Iterative enthalpy balance A more accurate approach is to find the flame temperature by iteratively assigning the flame temperature Tp until Hp(Tp)  HR(TR).43) where cp. respectively. f. where mfb is the amount of fuel burned.R. As such. where cp.058 for methane). where fs is the stoichiometric fuel/air ratio by mass.R  cp.g. If the heating value of a fuel is given.P is an average value of specific heat evaluated at the average temperature of  where T ¼ ðTp þ TR Þ=2.R ¼ cp ðTÞ. From conservation of energy.44) Note that fs is very small for hydrocarbon fuels (e. Then the adiabatic flame temperature is calculated for a lean mixture as fb1 mf  LHV þ ðma þ mf Þ cp.R ¼ (ma + mf ) cp. i.e.R ðTR  T0 Þ ðma þ mf Þ cp. The enthalpy of reactants is assumed given.P  (TP – T0). for lean combustion as shown in Fig. Therefore. the product (flame) temperature increases almost linearly with equivalence ratio. The sensible enthalpy of the products is approximated by Hs.P f  LHV f  fs  LHV ¼ TR þ ¼ TR þ ð1 þ f Þ cp.R is an average value of specific heat evaluated at the average temperature of  where T ¼ ðTR þ T0 Þ=2. In rich combustion. a mass-based analysis for the same control volume can be conducted.P is used in deriving the second line.. cp. ma.P (2. the flame temperature decreases with f..P ¼ (ma + mf ) cp.P ð1 þ f  fs Þ cp. for f>1. Hs. The initial mixture consists of fuel and air with mf and ma. Note that the specific heat is a function of temperature. the amount of fuel burned (with air.P mf  LHV mf =ma  LHV  TR þ ¼ TR þ ðma þ mf Þ ð1 þ mf =ma Þ cp. The enthalpy of products can be expressed in the following form . ma) is mfb ¼ ma fs . the limiting factor is the amount of air available. For fb1.P equals the amount of heat released from combustion plus the sensible enthalpy of the reactants. Hs. For rich combustion (f > 1).

R h^si.P Dh^oi. 2. .2. This method.P ½Dh^oi.R ðTR Þ (2.R i Next.4 Comparison of flame temperatures with different approaches HP ðTP Þ ¼ X Ni. The product temperature can be estimated by linear interpolation.R ðTR Þ i Ni.P þ X i Ni. still assumes complete combustion to the major products. φ 10 Fig. we guess a higher flame temperature.P h^si. 2H2O ↔2H2 + O2. we rearrange the above equation to find an expression for the sensible enthalpy of the products as X i X i X i Ni.P h^si. For example. one evaluates Hp(Tp1) from tables such as those in Appendix 3.P ðTP Þ ¼ HR ðTR Þ ¼ i X Ni.4 Adiabatic Flame Temperature 35 2500 Estimate with constant cp Temperature (K) 2000 Enthalpy balance 1500 Simulated flame 1000 Equilibrium 500 0 0.P ðTP Þ ¼ X X Ni. If Hp(Tp1) < HR(TR).R  i Ni.p þ X X X Ni. Method 3: Equilibrium State (Free software: Cantera.R ðTR Þ: i With an initial guess of flame temperature.R h^si.R h^i.45) i Ni. although more accurate.P h^si.P þ i X Ni. One repeats this process until the two closest temperatures are found such that Hp(Tf1) < HR(TR) < Hp(Tf2).P ðTP Þ ¼ Q0rxn.R Dh^oi. Tp2. Commercial software: Chemkin) Dissociation5 of products at high temperature (T > 1.500 K at ambient pressure) can take a significant portion of energy from combustion and hence the product 5 Dissociation is the separation of larger molecules into smaller molecules.P ðTP Þ ¼ Ni.P þ h^si.P h^i.R þ i Ni.P Dh^oi.1 1 Equivalence Ratio. Tp1.R Dh^oi.P h^si.P ¼ i X Ni.

2. Also included are the results from a flame calculation using a detailed. Predicted adiabatic flame temperatures of a methane/air mixture at ambient pressure using these methods are compared in Fig.76 i ¼ Dh^oH2 þ 0:5Dh^oO2 þ 1:88Dh^oN2  1  Dh^oH2O ¼ 0 þ 0 þ 0  1 mol  ð241:88 kJ/molÞ ¼ 241:88 kJ N2(g)) ! . which has a residence time of less than 1 s. One reason for the deviation is the assumptions made about product species in the rich mixtures. forward and backward reaction rates of any chemical reaction steps are balanced. 3) if infinite time is available for chemical reactions.P i (O2(g) +3. the rich mixture equilibrium temperatures are lower than those from the flame calculation.36 2 Thermodynamics of Combustion temperature is lower than that calculated with only major components as products. In addition. and N2. Estimate the adiabatic flame temperature of a constant-pressure reactor burning a stoichiometric mixture of H2 and air at 101. even without knowledge of the chemical kinetics. or temperature. By constraining certain variables such as constant pressure and enthalpy. Visible deviations arise near stoichiometric conditions and become larger in richer mixtures. For rich mixtures at the equilibrium state. the chemical equilibrium state is often used in combustion engineering as a reference point for chemical kinetics (the subject of Chap.R  Ni.p ¼ Ni.4 for a range of equivalence ratios. Cantera) are preferred for this task.P Dh^oi. Computer programs (such as STANJAN. On the lean side.3 kPa and 25 C at the inlet. H2O. the chemical equilibrium state can be determined by minimizing the Gibbs free energy.R Dh^oi. the results from the detailed flame model calculations are closest to reality. unburned O2. Chemkin. Example 2. as hand calculations are time consuming. as real flames have finite residence times and generally do not reach equilibrium. non-equilibrium flame model. At this ideal state.6. 2.5 H2O (g) þ 1. Because the conversion of CO into CO2 releases a large amount of energy. pressure. Among the methods. The equilibrium flame temperature is expected to be lower than the temperatures estimated with Method 1 or Method 2. CO is preferred over CO2 due to the deficiency in O2.88 N2(g) X X Q0rxn.4. as the major products are CO2. The equilibrium state determines the species concentrations and temperature under certain constraints such as constant enthalpy. the results agree reasonably well among all methods. Solution: The combustion stoichiometry is H2(g) þ 0.2 Comparison of Adiabatic Flame Temperature Calculation Methods The presented methods of estimating adiabatic flame temperature will produce different values from each other.

H2 Oð1.p þ i X HP ðTP Þ ¼ HR ðTR Þ X X Ni.88·56.253 K.O ðTR Þ 2 H2 2 2 2 O2 2 2 þ NN2 Dh^oN2 þ NN2 h^s.69 + 1.000 K 2.1 MJ .H2 O ðTP Þ þ 0 þ 1:88  h^s.000 K.i i ð241:88 þ 0ÞkJ=mol ð0:047 þ 1:88  0:035Þ kJ/mol  K 2.31 ¼ 3.N2 ðTR Þ 1  Dh^0H2 O þ h^s.230 K. By doing this procedure.R Dh^oi. Method 2: Iterative enthalpy balance: X Ni.223 K to evaluate the specific heats.N2 ðTP Þ ¼ 0 þ 0 þ 0 þ 0 þ 0 þ 0 Dh^0H2 O þ h^s.p h^si.2.83 + 98. 500 KÞ ¼ 0:0467 kJ/mol  K and c^p (average) at 1.R ðTR Þ i i i NH2 O Dh^oH2 O þ NH2 O h^s.p þ Ni. let’s pick TP ¼ 2. the calculated flame temperature becomes Tp ~ 2.500 KÞ ¼ 0:0350 kJ/mol  K: P Q0rxn.88·74.148 K + 298 K)/ 2 ~ 1.500 K HP(TP) (MJ) 241.p Dh^oi.6 MJ 241.96 + 1.R þ Ni. Using the new average temperature of 1.500 K was too high. we obtain TP ~ 2.14 ¼ 63.4 Adiabatic Flame Temperature 37 Method 1: Assuming a constant c^p.223 K.83 + 72.R h^si.H ðTR Þ þ NO Dh^o þ NO h^s. The average temperature is now Tave ¼ 1.H2 O ðTP Þ þ NN2 Dh^oN2 þ NN2 h^s. For this case.N2 ð1.H2 O ðTP Þ þ 1:88  h^s.275 K.148 K ¼ 300 þ The average temperature of the products and reactants is now (2.N2 ðTP Þ ¼ NH Dh^o þ NH h^s. indicating that the initial assumption of Tave ¼ 1. c^p.R h^si.R ðTR Þ Pi Tp ¼ T0 þ Ni. TP (K) 2.500 K. We now plug in the value for the heat of formation of water and use thermodynamic property tables to evaluate the sensible enthalpy terms. This new average temperature can be used to calculate the specific heats and the process should be continued until the change in the average temperature is on the order of 20 K.p ðTp Þ ¼ Ni.p c^p.N2 ðTP Þ ¼ 0: The first step is to guess the product temperature.

5%) of H2 existing in the products due to the dissociation of H2O at high temperature. we can use linear extrapolation (or interpolation if we bracketed the real value): TP  2. The equilibrium mole fractions are listed below Mole fractions Species H2 O2 N2 H2O xreactant 0. This 41 K difference is about 1.5563 0 xproduct 0.0153 0.p ¼ LHV of H2 at constant pressure Q0rxn.P Dh^oi. consider combustion of 1 mol of gaseous hydrogen with 0.000 K.500  2.0079 0. If radicals.425. and H2O are the only species in the system.7 The space shuttle burns liquid hydrogen and oxygen in the main engine.000 K was too low. For more accuracy. and O.R  X Ni.R Dh^oi.3 kPa. Determine the adiabatic flame temperatures using the average cp method.500 K which resulted in a much smaller remainder. Solution: The combustion stoichiometry is H2ðgÞ þ 0:5O2ðgÞ ! H2 OðgÞ  Q0rxn.2958 0.500 K . 500 0 þ 3:1 ¼ 2.5 mol of gaseous O2 at 101. implying that TP ~ 2. To estimate the maximum flame temperature. are also included in the products. equilibrium temperature is 2. The process was repeated with a higher guess of TP ¼ 2.P ¼ Dh^oH2 þ 0:5Dh^oO2  1Dh^oH2O i ¼ 0 þ 0  1 molð241:88 kJ/molÞ ¼ 241:88 kJ Guessing a final temperature of about 3.526K Method 3: Cantera.p ¼ X i Ni.38 2 Thermodynamics of Combustion Our initial guess of TP ¼ 2. the equilibrium temperature drops to 2. Example 2.1479 0.000 3:1 þ 63:6 TP ¼ 2. we use average specific heats evaluated at 1. such as H.1 K.384 K because additional dissociation occurs. Results of the above three methods agree with each other within 100–200 K which is less than 12% of the flame temperature.3286 Note that there is a small amount (~1.6478 0. Assume H2. OH. O2.500 K.7% of the flame temperature.

to compute the equilibrium temperature with only three species H2.2.6667 0. we get X ¼ 0.800 K we get Tp ¼ 300 K þ 0:66  241:88 kJ=mole 3. Let’s find out how much fuel is not burned by considering the following stoichiometric reaction: H2 ðgÞ þ 0:5O2 ðgÞ ! X  H2 þ 0:5X  O2 þ ð1  XÞ  H2 OðgÞ The mole fraction of H2 in the products is xH2 ¼ X X ¼ : X þ 0:5X þ 1  X 0:5X þ 1 With xH2 ¼ 0. Species H2 O2 H2O Reactant 0. That is. such as Chemkin.P c^pi i 241:88 kJ=mol ¼ 300 K þ 0:047 kJ/mol  K 5. The mole fractions of these three before reaction and after combustion are listed below. What is the main reason for such a BIG discrepancy? The estimated temperature is well above 2. a new estimate based on c^p at 1.2915. about 30% of the products is H2.3333 0 Product 0. the dissociation is very significant.600 K. 822 K Discussion: This temperature is evidently much higher than the NASA reported value of ~3.3412.5628 As seen in the table. If we estimate c^p at 1.7 K. H2(g) þ 0.2915 0. If we assume 66% of fuel is burned.4 Adiabatic Flame Temperature 39 P Q0rxn.R ðTR Þ Pi TP ¼ T0 þ Ni.000 K and one expects a substantial dissociation of H2O back to H2 and O2. O2.514:7 K: 0:04966 kJ/mole  K .500 K leads to Tp ¼ 300 K þ 0:66  241:88 kJ=mol 3.1457 0.p þ Ni.700 K 0:047 kJ/mol  K that is in much better agreement with the equilibrium result. and H2O. Now we use Cantera or a commercial software program.R h^si.5 O2 (g) ↔ H2O (g). The predicted adiabatic flame temperature drops to 3508.

note that their values for enthalpy of formation are positive.675 K. latent heat of vaporization 212. the total energy required is then 8. cp ~ 0.84 kJ/mol and 12.5O2.0510 0. (2) for O2. boiling temperature ¼ 183 C. Species H2 O2 H2O OH O H Reactant 0.5809 0. the predicted equilibrium temperature drops to 3.8 C.3333 0 0 0 0 Product 0.26 kJ/kg-K. and O take some energy to form. 2. the pressure needs to be taken into consideration as the combination of radicals occurs faster at higher pressures.5·12.5 Chapter Summary The following shows the relations among different thermodynamics properties expressed in terms of mass fractions and mole fractions.0143 0.076 K. Because the space shuttle engine operates at 18.94 MPa is 3.0296 The energy needed to vaporize liquid H2 and O2 and heat them from their boiling temperatures to 25 C are estimated to be 8.747 psi.0336 0.84 þ 0. latent heat of vaporization 445.3 kJ/mol.1503 0.7 kJ/kg.1005 0. the radicals OH.7 kJ/kg.1077 0. ~186 atm) at 100% power.12 kJ/kg-K.832  148 K or ~3.3 kJ/(0.92 kJ/mol (energy ¼ latent heat + sensible energy from boiling point to STP).3333 0 0 0 0 Product 0. H. we estimate the space shuttle main engine temperature is 3. With H2 þ 0. boiling temperature ¼ 252.0330 0. cp ~ 4.049 kJ/mol-K) ¼ 148 K. and O in the products. The temperature drop due to this process is about ~15. With this.6667 0. .7051 0.94 MPa (2.4 K and the mole fractions are listed below. The predicted equilibrium temperature at 18.0771 Evidently.6667 0. H.1169 0. OH.40 2 Thermodynamics of Combustion If we include additional species.832. The following information is used for estimating energy to vaporize H2 and O2: (1) for H2. The table below shows the mole fractions of each species in this case. Species H2 O2 H2O OH O H Reactant 0.92 or about 15.

s (kJ/kg-K) K P s j  hj j¼1 Specific heat at constant pressure cp(kJ/kg-K) K P yj  cpj j¼1 Specific heat at constant volume cv (kJ/kg-K) K P yj  cvj j¼1 Internal energy of mixture. . yi. xi Mi – K P xj M j j¼1 Mixture molecular mass.2. h (kJ/kg) K P yj  h j j¼1 Entropy of mixture.5 Chapter Summary Property Species densityri (kg/m3) 41 Mass fraction. yi ryi Mole fraction xi xi Mi rP K xj Mj j¼1 Mole fraction. Enthalpy of reaction or heat of reaction: Energy that must be supplied in the form of heat to keep a system at constant temperature and pressure during a reaction. M (kg/kmol) K P K P 1 yj =Mj j¼1 Internal energy of mixture. u^ (kJ/kmol) M K P yj  uj j¼1 Enthalpy of mixture. h^ (kJ/kmol) M K P M K P yj  hj M K P yj  sj M K P j¼1 1 M 1 M 1 M xj  u^j j¼1 K P xj  h^j j¼1 K P xj  s^j j¼1 K P xj  c^pj j¼1 K P xj  c^vj j¼1 K P xj  u^j K P xj  h^j K P xj  s^j j¼1 yj  cpj j¼1 Specific heat at constant volume c^v (kJ/kmol-K) 1 M K P j¼1 j¼1 Specific heat at constant pressure c^p (kJ/kmol-K) 1 M j¼1 j¼1 Entropy of mixture. xi [] yi =Mi K P – yj =Mj j¼1 Mass fraction. u (kJ/kg) K P yj  u j j¼1 Enthalpy of mixture. ^s (kJ/kmol-K) xj Mj j¼1 K P xj  c^pj j¼1 yj  cvj K P xj  c^vj j¼1 Definitions Enthalpy of combustion or heat of combustion: Ideal amount of energy that can be released by burning a unit amount of fuel.

Ca Hb Og     b g b b g Ca Hb Og þ a þ  ðO2 þ 3:76N2 Þ ! aCO2 þ H2 O þ 3:76 a þ  N2 4 2 2 4 2 Variables to quantify combustible mixtures m Fuel/air ratio by weight: f ¼ maf m For stoichiometric mixture: fs ¼ masf f mas Equivalence ratio: f ¼ fs ¼ ma 1=f AFR Normalized air/fuel ratio l ¼ AFR ¼ 1=f ¼ f =f1 s ¼ f1 s s Percent of excess air     ðma  mas Þ ma 1 1 ¼ 100  1 ¼ 100 %EA ¼ 100 mas f mas Global equation for lean combustion fb1   1 b g a þ  ðO2 þ 3:76N2 Þ Ca Hb Og þ f 4 2      b 3:76 b g b g 1 a þ  N2 þ a þ   1 O2 ! aCO2 þ H2 O þ 2 f 4 2 4 2 f in terms of l   b g Ca Hb Og þ l a þ  ðO2 þ 3:76N2 Þ 4 2     b b g b g ! aCO2 þ H2 O þ 3:76  l  a þ  N2 þ ðl  1Þ a þ  O2 2 4 2 4 2 Global equation for rich combustion f>1with the assumption that products contain unburned fuel   1 b g a þ  ðO2 þ 3:76N2 Þ Ca Hb Og þ f 4 2     a b 3:76 b g 1 H2 O þ a þ  N2 þ 1  ! CO2 þ Ca Hb Og f 2f f 4 2 f Enthalpy of formation (heat of formation) determined by bomb calorimeter Q0rxn.R ¼ þ  1 4 2 i i Dh^oi ¼ .v þ DN  R^u T0 Ni.P X X b g DN ¼ Ni. Combustion stoichiometry for a general hydrocarbon fuel.42 2 Thermodynamics of Combustion Enthalpy of formation or heat of formation: Heat of reaction per unit of product needed to form a species by reaction from the elements at the most stable conditions.P  Ni.

R ðTR Þ i P TP ¼ T0 þ Ni.P Dh^i.P MH2O hfg .v is the heat released from a constant-volume reactor where the products and reactants are at STP.2. Heating values at STP (T0) from a constant-volume reactor P HHV ¼ i o Ni.440kJ=kg Nfuel Mfuel Heating values at STP (T0) determined from a constant-pressure reactor P HHV ¼ i Ni.P ðTP Þ HP ðTP Þ ¼ i i Trial and error of TP such that HP(TP) matches HR(TR) .R  P i o Ni.R Dh^i.P ¼ Ni.R Dh^i.P þ h^si.P c^pi i or if mixture is not stoichiometric: mass-base analysis using LHV and f f b 1 TP ¼ TR þ f  LHV f  fs  LHV ¼ TR þ ð1 þ f Þ cp ð1 þ f  fs Þ cp f > 1 TP ¼ T R þ fs  LHV fs  LHV ¼ TR þ ð1 þ f Þ cp ð1 þ f  fs Þ cp Method 2: Enthalpy Balance HP ðTP Þ ¼ HR ðTR Þ X X Ni.p  i P  Ni.P ½Dh^oi. hfg ¼ 2.P h^i.R  o P i Ni.R h^si.5 Chapter Summary 43 where Q0rxn.P o Nfuel Mfuel Adiabatic flame temperature for reactants at standard conditions Method 1: Estimate based on average c^p values P Nfuel Mfuel LHV þ Ni.P þ  P Ni.P c^pi i TP  TR þ Nfuel Mfuel LHV P Ni.R R^u T0 i ðMJ=kgÞ Nfuel Mfuel LHV ¼ HHV  NH2O.P Dh^i.

but is this really a good idea? We’re going to compare a blend of ethanol (70% ethanol and 30% gasoline by volume) to gasoline.i : mi cv. if you need to get 100 kW of power from an engine.2) mixture.5 is 250 MJ/kmol.3 There has been a lot of interest about replacing gasoline with ethanol.200 K. Assume complete combustion. (c) Using an average cp for the products at 1. and fuel/air ratio. equivalence ratio.26 H15.i i¼1 2.5 is 114. 2. The mass flow rate of methane is 1.2 with the assumption of complete combustion. (a) Determine the mole fractions of CO2 and O2 in the exhaust for an engine with normalized air/fuel ratio l ¼ 1. 2. (b) The enthalpy of formation of C8.4 Gasoline is assumed to have a chemical composition of C8. Determine the LHV of gasoline in terms of MJ/kg. estimate the adiabatic flame temperature at constant pressure of 1 atm for the lean (l ¼ 1. how much CO2 are you emitting in g/s? How does this compare to the same engine running a stoichiometric mixture of 100% gasoline and air? 2.5. The exhaust gas temperature was measured to be 500 C and approximately . show that the mixture temperature and pressure at two different states are related to the respective pressures as T2 ¼ T1  ðg1Þ=g P2 P1 where K P g¼ i¼1 K P mi cp. The molecular mass of C8.15 kg/h. Calculate the lower heating value (LHV) of a 70% ethanol/30% isooctane mixture in terms of kJ/mol of fuel.1 Consider an isentropic combustion system with a total of K species.62 kg/kmol. Assuming constant specific heats.2 Measurements of exhaust gases from a methane-air combustion system show 3% of oxygen by volume (dry base) in the exhaust.26 H15.26 H15. Assuming complete combustion. determine the excess percentage of air. How does this compare to the tabulated value for gasoline (isooctane)? Assuming a 20% thermal efficiency. how much of each fuel (in mol/ s) do you need? If you have a stoichiometric mixture of the ethanol/gasoline blend and air in your 100 kW engine.5 A mixture of methane gas and air at 25 C and 1 atm is burned in a water heater at 150% theoretical air.44 2 Thermodynamics of Combustion Exercises 2.

. (b) Measurements indicate a maximum flame temperature of about 3.7 A space heater burns propane and air with intake temperature at T0 ¼ 25 C and pressure at 1 atm (see Fig.300 K. 2. 2. Assume that the entire system is at P ¼ 1 atm and complete combustion occurs in both the heater and in the exhaust section. 2. Compare with the result from (a) and discuss the main reasons for the discrepancy.5).. (b) With the assumption of constant specific heats for the gases..Exercises 45 Q Additional propane Q 3-way catalyst heater Station 1 T1 = 500K Station 2 T2 T0 φ = 0.6 An acetylene-oxygen torch is used in industry for cutting metals. In order to use a 3-way catalyst for exhaust treatment. estimate the temperature at station 2.5 Exercise 2. (a) Estimate the maximum flame temperature using average specific heat cp. T ¼ 25 C and P ¼ 1 atm.7 1 atm. T2. determine the amount of heat generated from burning of 1 kg of methane.e.5). additional propane is injected into the exhaust to consume all the remaining oxygen in the exhaust such that the gases entering the catalyst contain only CO2.e. and N2 only at station 1. (a) Draw a schematic of the water heater and name its most important elements.0. O2. (c) Calculate the temperature of the hot water if the heat exchanger were to have an efficiency of 1. H2O.8. perfect heat transfer. and N2 at station 2. The exhaust gases exit at temperature T1 ¼ 500 K and contain CO2. The specific heat can be approximated by that of N2 at 700 K as c^p ¼ 30:68 kJ=kmol  K. Note that the propane at the injection station is at the same conditions as heater inlet. H2O. The combustible mixture enters the heater at an equivalence ratio f ¼ 0. i. 2.8 Fig. Determine the injection rate of propane into the exhaust between station 1 and station 2 (see Fig. The volumetric flow rate of cold water (at 22 C) to the heater is 4 L/min. 2. (b) Using Cantera. (a) The volumetric flow rate of propane entering the heater is 1 L/min. i.

2. 2.9 Consider the combustion chamber in a jet engine at cruising altitude.7. H2O. Qloss Fig.46 2 Thermodynamics of Combustion Fuel: Tfuel = 25°C Pfuel = 1 atm Air: Tair = 427°C Pair = 1 atm Products .6.25. (b) If the mass flow rate of fuel is 1 kg/s. In the main combustor. (a) Determine the minimum O2 pressure inside the bomb necessary to allow complete combustion of the solid carbon. H2O. all of which enter the afterburner. CO2. (a) Write the stoichiometric chemical reaction for the fuel with air. O2 and N2. are combusted with pure oxygen in a 500 cm3 bomb calorimeter initially at 300 K. C(s). the gases exiting the afterburner are CO.6 Exercise 2. H2O. (b) When the bomb is cooled back to its initial temperature of 300 K. O2 and N2. In the afterburner.75. what is the mass flow rate of air? (c) What is the rate of heat loss from the combustion chamber if 10% of the LHV (heat of combustion) of the fuel is lost to surroundings? (d) What is the temperature of the products? (e) How does the temperature change if we burn fuel rich (f > 1)? How about fuel lean (f < 1)? (Hint: Easiest to show with a plot) 2. The products of the main combustor are CO2. After the carbon is placed inside the bomb.8 Two grams of solid carbon. the chamber is evacuated and then filled with gaseous oxygen from a pressurized tank. A schematic of this system is shown in Fig. determine the pressure inside the bomb. hexane is burned with air at an equivalence ratio of f ¼ 0. The intake conditions are as indicated in Fig. The entire system is .10 An afterburner is a device used by jet planes to increase thrust by injecting fuel after the main combustor.9 2. 2. For simplicity. the combustor is operated at 1 atm of pressure and burns a stoichiometric (f ¼ 1) mixture of n-heptane (C7H16) and air. and CO2 only. In the afterburner the hexane reacts with the excess O2 from the main combustor to form CO. Combined with the products of the main combustor. 2. additional hexane is injected such that the equivalence ratio is f ¼ 1.

.7). and the pressure everywhere is atmospheric. N2 Afterburner CO. 2.000 K. Determine the temperature of the exhaust gases at each stage (Fig. The inlet temperature of the hexane and air is 20 C. 2.10 insulated. O2. O 2 . CO2. N2 T2 = ? hexane T = 20oC Fig. H2O.Exercises 47 air T = 20oC hexane T = 20oC main combustor T1 = ? CO2. H2O.7 Exercise 2. Note: An approximate answer is sufficient and it can be assumed that the specific heats for the gases are constant and approximately equal to that of N2 at 1.

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