2M TF Thermodynamics Sec.

5 2001-02

5. THERMODYNAMICS OF COMBUSTION
The relevant part of engel and Boles is Chapter 14, Chemical Reactions 5.1 INTRODUCTION

In 1M Thermodynamics and in the first parts of 2M Thermodynamics we have considered nonreacting thermodynamic systems only. Here, the analysis will be extended from non-reacting systems to reacting systems, i.e. the species composition will change during the thermodynamic process. In general, the known principles of conservation of mass and the first and second laws of thermodynamics can still be applied. However, conservation of mass needs to be extended to the principles of conservation of elements and the conservation of energy equation needs to include the effects of chemical energy associated with changes in chemical composition. Inclusion of these additional parameters will help us to determine the reactant and product species composition, their state, the heat released, the work done, the efficiency of the combustion process and its irreversibilities. In particular, the accurate product species composition that determines pollutant emissions from a combustion process has become increasingly important over the last two decades. 5.2 PROBLEM DESCRIPTION Reactants & T, p, n Products composition=? T=?, p=?

Reacting system

Combustion chamber
& Q = ?

heat exchanger
& Wpump
Non-reacting system pump

turbine

& Wturb,net

condenser

Fig 1: Combustion chamber and steam power cycle & Only non-reacting systems have been subject of previous lectures. The heat flow Q was assumed to be known and the thermodynamic analysis has focused on non-reacting system analysis. The next four lectures will discuss the reacting system and we will develop the tools of how to calculate the state of the products and the heat flow rate from the combustion chamber to the power generation cycle.

2M TF Thermodynamics Sec. 5 2001-02

5.3

CHEMICAL REACTIONS

Chemical bonds between the atoms of a molecule store chemical energy. During a combustion process the composition of the species changes (e.g. H2+0.5O2H2O), i.e. chemical bonds break up and new bonds are formed. During break-up chemical energy is released and some of the energy is bound in the newly formed chemical bonds. Generally, energy release and consumption do not balance and the reaction is said to be exothermic when energy is set free. The reaction is endothermic when energy is needed to drive the chemical process. How to account for chemical energies will be topic of section 5.5. For a reaction to take place, fuel and oxidiser need to be mixed on the molecular level in the right proportions. Mixtures of fuel and oxidiser can be called reactive mixtures. Extremely fuel rich or fuel lean mixtures will not burn. In addition, most reactive mixtures do not react automatically. The mixture must be brought locally above a certain ignition temperature (e.g. lighter, matches, spark plug) to start chemical reaction. E fuel Eactivation E products Fig. 2: Activation energy and energy release of a chemical reaction

The activation energy Eactivation must be provided to the system to trigger the onset of the chemical reaction. If E is negative, the reaction will proceed automatically until conversion of fuel and oxidiser into products is complete. When E is positive, the reaction is endothermic and it will stop if insufficient energy is provided to keep the reaction alive. 5.3.1 Fuels

For boilers, one main objective of the thermodynamic analysis of reactive systems is to calculate the heat flux from the combustion chamber to the heat exchanger. In gas turbine combustors, the aim is an enthalpy increase in the stream and in a reciprocating engine the work output due to increase pressure and temperature is the quantity of interest. Heat flux, change in enthalpy and work output can be associated with the energy release from the combustion process. The energy release strongly depends on destruction and formation of chemical bonds and hence, the chemical mechanisms and the fuel composition must be known. Reaction mechanisms usually have a large number of intermediate steps but in 2M we are only concerned with the overall result and will represent chemical reaction of fuel and oxidizer by one single (global) reaction step. Most commercial fuels are complex mixtures of a variety of chemical species. However, they can usually be represented adequately by higher order hydrocarbons. Hydrocarbons can be described by the chemical formula C Hy. Other fuels with oxygen content will be considered in Section x 5.11. Typical hydrocarbon fuels are listed in Table 1. Table 1: Simplified fuel compositions Gasoline (petrol) Diesel oil Ethanol Natural gas Approximated as Octane Dodecane Methane Chemical formula C8H18 C12H26 C2H5OH CH4

2M TF Thermodynamics Sec. 5 2001-02

5.3.2

Oxidiser

The most common oxidiser (sometimes called oxidant) is air since it is free and readily available. Air consists of mainly oxygen and nitrogen with some traces of carbon monoxide, Argon etc. The trace species and nitrogen do not react and can be grouped together as atmospheric nitrogen (AN). The molar composition of air can then be represented by 21% O2 and 79% AN. In general, all trace elements can be neglected and the simplified representation of air is 21% O2 and 79% N2 on a molar basis (nN2:nO2 = 79:21). The representation of air on a mass basis can then be written as (see Section 2 on Mixtures of Gases) Table 2: Conversion table (quantities per 100 kmol) ni (no. of kmol) O2 N2 total 21 79 100 Mi (molar mass) 32 28 mi = Mi ni (mass) 672 2212 2884 Yi= mi / m (mass fraction) 0.232 0.768 1.000

The composition of air on a mass basis is mO2:mN2 = 23.2:76.8. Pure oxygen (O2) is only used in special applications (e.g. rocket engines). Pure oxygen provides higher combustion temperatures since no energy is used for the heating of inert N2. Note: The assumption of inert N2 is not quite correct. At high temperatures some N2 will react to form nitrogen oxides (NO and NO2) and nitrous oxide (N2O). All these compounds are harmful pollutants and need to be considered in a detailed combustion analysis. However, reactions involving nitrogen are slow in comparison to the main reactions for the conversion of hydrocarbons into products and concentrations of NOx are generally in the range of ppm (parts per million). Concentrations of N2O are even smaller. These small quantities do hardly influence the global thermodynamic quantities and N2 can assumed to be inert for the present analysis. Conversion of N2 and oxygen into nitrogen oxides will be a topic of the combustion module in 3M Energy Engineering. 5.3.3 Products

Products of complete hydrocarbon combustion with air are CO2 and H2O. Complete combustion means that enough oxygen is provided to fully convert all fuel-carbon atoms into CO2 and all fuel-hydrogen atoms into H2O. If not enough oxygen is available during combustion some CO will form. Oxygen will leave the combustion chamber as a product if more oxygen is provided than needed for complete combustion. Note: Depending on the combustion process, fuel composition temperature, some species may dissociate into their elements. In particular, if exit temperatures are above 1500K, dissociation products like atomic H and O will form and the assumption of complete combustion with the only products being CO2 and H2O is not accurate. Detailed analysis of the combustion kinetics will be part of 3M Energy Engineering and 4M Combustion. The product analysis leads to the following definitions:

2M TF Thermodynamics Sec. 5 2001-02

5.3.4

Some Definitions

Stoichiometric Combustion: Stoichiometric combustion occurs when the minimum amount of air needed for complete combustion of fuel is available. The only products will be CO2, H2O and N2 .The latter does not take part in the reaction but cannot be ignored in the thermodynamics. Excess fuel (fuel rich mixture): Insufficient O2 supply will result in incomplete conversion of hydrocarbons to CO2 and some CO will form. Excess air (fuel lean mixture): All fuel is converted to CO2 and H2O. Excess O2 will leave the system. In reality, some excess air is needed due to imperfect mixing of fuel and air.

Obviously, the fuel composition and the proportion of fuel to oxidiser need to be known for a complete analysis of the combustion process. The fuel composition is uniquely given by the chemical formula. However, there are three common ways of how to express the proportion of fuel to oxidiser: & & & & 1. Air/fuel ratio (AFR) = m air m F , (sometimes FAR, = m F mair ) 2. Theoretical air: e.g. 150% theoretical air means 1.5 times that of stoichiometric combustion 3. Excess air: e.g. 50% excess air means the same as 150% theoretical air Now, the combustion equations can be written as 5.3.5 Combustion Equations:

Combustion of hydrocarbon fuel with pure oxygen: CxHy + nox O2 nCO2 CO2 + nH2O H2O + nO2 O2 + nCO CO + ... Combustion of hydrocarbon fuel with air: CxHy +nox (O2+79/21N2) nCO2 CO2 + nH2O H2O + nN2 N2 + nO2 O2 + nCO CO + Eq. (1)

Equations are typically written per kmol of fuel and nox depends on the proportion of fuel to air. 5.4 CONSERVATION EQUATIONS 5.4.1 Conservation of mass:

In a steady state combustion process as shown in Fig. 1 no mass is accumulated inside the & & combustion chamber, hence m = m . However, no conclusions can be drawn about the
products reactants

products composition. Therefore, the mass conservation analysis needs to be extended to the analysis of conservation of elements.

2M TF Thermodynamics Sec. 5 2001-02

5.4.2

Conservation of elements:

The number of atoms of each element j must be conserved, i. e.

products

n l

i i, j

reactants

n l

i i, j

Eq. (2)

with ni being the number of moles of species i and li,j being the number of atoms of element j in a molecule of species i. We obtain one equation for each element, e.g. 4 equations for hydrocarbon combustion with air. The four elements are C, H, O, N. The chemical reaction for stoichiometric hydrocarbon combustion with air can be written as CxHy + nox (O2+79/21N2) nCO2 CO2 + nH2O H2O + nN2 N2 Element conservation: C: x = 1nCO2 H: y = 2nH2O O: 2nox = 2nCO2+1nH2O N: 79/21nox = nN2 x elements of C in fuel, 1 element of C in CO2 y elements of H in fuel, 2 elements of H in H2O

The system has four unknowns (nox, nCO2, nH2O, nN2) and four equations and will therefore have a unique solution. Note: The number of moles is not conserved (e.g. 2H2+O2 2H2O) 5.4.3 Examples

Examples for lean and fuel rich mixtures will be calculated in the lecture. 5.5 ENERGY

Previous thermodynamic analysis has accounted for sensible and latent energy only. Sensible energy is associated with a change of state of a species (e.g. h = cp T). Latent energy is associated with a phase change of the species. However, molecules also possess chemical and nuclear energies. Nuclear energy will not be topic of this lecture and will not be discussed. Chemical energy is associated with chemical bonds between molecules. If a chemical reaction occurs, these bonds are broken and energy is released. New bonds form and this formation process is in general associated with consumption of energy, i.e. energy is bound in the newly formed molecular bonds. This change in chemical energy needs 1) to be quantified and 2) to be included in the overall energy balance. 5.5.1 Chemical Energy

Inclusion in the overall energy balance is relatively easy to achieve. Changes in specific internal energy of a particular species can be written as e = ht + ke + pe with ht = hc + hs ht, hc and hs denote the total enthalpy, chemical enthalpy and sensible enthalpy, respectively. We will see in Section 5.8 that latent heat can be included into the enthalpy of formation (for a definition of enthalpy of formation, see below). Note that by convention total enthalpy now means the total of sensible and chemical energy but it excludes kinetic and potential energies. This is unlike the use of the term total energy in the compressible flow theory. 5

2M TF Thermodynamics Sec. 5 2001-02

To evaluate the change in chemical energy, the experiment shown in Fig. 3 is conducted: & C, 25C, 1 atm nC = 1kmol/s
Combustion cooling

& CO2 , 25C, 1 atm nCO2 = 1 kmol/s

& O 2 , 25C, 1 atm nO2 = 1 kmol/s

& Q Fig 3: Steady flow combustion process Carbon (e.g. graphite that consists of 99% carbon atoms) and oxygen are fed into the combustion chamber at 25C and 1 atm. They react and form CO2 as product. The product is cooled to 25C & and the heat flow can be measured: Q = -393,520 kJ/s Neglecting kinetic and potential energy changes, First Law analysis of the combustion chamber yields Eq. (3) & & & & Q W = H out H in & & & H = n ht = mht with [ht ] = kJ/kg and [ht ] = kJ/kmol Note that enthalpy flows can be written as the product of mass flow multiplied by mass specific enthalpy ht (units kJ/kg) or as molar flow multiplied by mole specific enthalpy h t (unit kJ/kmol). ht and h t are related by h t = Mh t .No work is done, hence equation (3) results in & & & & Q = nCO2 h t ,CO2 nC h t ,C nO2 h t ,O2 & & nO & n Q = h t ,CO2 C h t ,C 2 h t ,O2 & & & nCO2 nCO2 nCO2 Eq. (4)

& & Q n CO2 =-393,520 kJ/kmolCO2 is a measure of the enthalpy difference between CO2 and its elements C and O2 at the same temperature T and p. This experiment leads to the following definitions:
Enthalpy of Formation: The enthalpy of formation of a substance, hf0, is defined as the heat evolved when one kmol of the substance is formed from its elements at their standard states. Standard State: The standard state is defined as 25C (298.15 K) and 1 atm. This is the reference state of a substance. By convention, each element in its standard state is assigned an enthalpy of zero (or has an enthalpy of formation of zero). The standard states of some elements are, e.g. H2(g), O2(g), N2(g), Hg(l), C(s,graphite). In particular the second part of the definition of standard state is of significance. Remember that in previous first law analyses of non-reacting systems only enthalpy differences have been used. However, in the presence of combustion, species are not conserved and representation of energy & & differences in the form of H = n (h(T2 ) h(T1 ) ) is no longer of any use. Therefore, absolute values of enthalpy are needed to solve equation (4). Applying above convention the absolute total enthalpy of any species i can be written as

2M TF Thermodynamics Sec. 5 2001-02

ht ,i (T ) = h f0,i + hi (T ) hi (T0 = 25C )

Eq. (5)

where the subscript s for sensible enthalpy has been dropped. Enthalpy at standard state reduces to enthalpy of formation. Deviations from the standard state can be associated with a change of state of species i and are accounted for by the second and third RHS terms. Hence, h 0 i accounts for f, chemical energies and h i (T) - h i (T0 ) accounts for changes in sensible energies. One of the major conclusions is that SFEE can be equally used for non-reacting and reacting processes when total enthalpies as defined in equation (5) are used. The use of total enthalpies automatically accounts for the presence of chemical reactions. If absolute enthalpy values need to be used, the enthalpy of formation must be known. If perfect gas assumptions do not hold, sensible energy changes must also be listed (i.e. hs cpT). Sensible enthalpies of some major species are given in Table 7 in the Data and Formula book. Table 3 of these notes gives enthalpies of formation of the most common species. Table 3: Enthalpies of formation at 25C and 1 atm (from engel and Boles) Substance Carbon Hydrogen Nitrogen Oxygen Carbon monoxide Carbon dioxide Water vapour Water (liquid) Hydrogen peroxide Ammonia Methane Acetylene Ethylene Ethane Propylene Propane n-Butane n-Octane vapour n-Octane liquid n-Dodecane Benzene Methanol vapour Methanol liquid Ethanol vapour Ethanol liquid Oxygen Hydrogen Nitrogen Hydroxyl Formula C(s) H2(g) N2(g) O2(g) CO(g) CO2(g) H2O(g) H2O(l) H2O2(g) NH3(g) CH4(g) C2H2(g) C2H4(g) C2H6(g) C3H6(g) C3H8(g) C4H10(g) C8H18(g) C8H18(l) C12H26(g) C6H6(g) CH3OH(g) CH3OH(l) C2H5OH(g) C2H5OH(l) O(g) H(g) N(g) OH(g) 7
h f0 [kJ/kmol]

0 0 0 0 -110,530 -393,520 -241,820 -285,830 -136,310 -46,190 -74,850 +226,730 +52,280 -84,680 +20,410 -103,850 -126,150 -208,450 -249,950 -291,010 +82,930 -200,670 -238,660 -235,310 -277,690 +249,190 +218,000 +472,650 +39,460

2M TF Thermodynamics Sec. 5 2001-02

Table 3 above gives enthalpies of formation at standard state. However, inlet and outlet conditions of a combustion chamber may not be at standard state but at an arbitrary temperature T. T 1 B C T0
h f0

2 hs

Reactants

Products

Fig 4: Two different temperature-reaction paths Initial and end states are state 1 and 2, respectively. The process path is of no importance since enthalpies (temperatures) and molar (mass) concentrations are properties. Hence, path A is equivalent to path (B+C) and the difference in enthalpies between state 1 and 2 can be expressed as function of enthalpy of formation at standard state and sensible enthalpies, viz,
h (T ) =
elements

144424443
B

h ( + h T ) h (T ) n (h (T ) h (T )) + [14T4)44(42444]443
i 0 0 f 0 0 compound C

Eq. (6)

The first term accounts for changes in sensible enthalpies of all reactants when cooled from T to T0. The second term accounts for change in chemical energy at T0 and change in sensible enthalpy when the product is heated to temperature T. Note: It can also be seen from First Law analysis (equation (4)) that enthalpies (and internal energies) of reactants and products are not identical although they are at identical thermodynamic states (equal T and p). Obviously, two properties are not sufficient to fully describe the state of the mixture, but the exact composition must also be known. 5.5.2 Examples:

Examples for absolute enthalpy of CO2 at 800 K and enthalpy change of the reaction C+O2 CO2 with reactants and products at 800 K are given in the lecture. Answer: hCO 2 (800 K ) = 356,718 kJ/kmol, h (800 K ) = 380,195 kJ/kmol

2M TF Thermodynamics Sec. 5 2001-02

5.6

STEADY FLOW COMBUSTION PROCESS

& Fuel, T, p, n fuel

Combustion (cooling)

& Products,T, p, n products

& oxidizer, T, p, nox

& Q Fig. 5: Steady flow process In most cases, the fuel composition, air/fuel ratio, inlet and outlet temperatures and pressures are given. To obtain the heat flow rate the following steps should be carried out: 1. find the appropriate chemical equation, 2. write element balances for all elements, 3. apply first law and 4. apply continuity of mass whenever necessary Hint: First law analysis may be simpler on a molar basis. 5.6.1 Example Problem:

Methane and air enter the combustion chamber in separate streams at 25C and 1 atm. The flow rate of CH4 is 1 kmol/s. The heat flow from the walls of the combustor is measured to be 20 MJ/s. Calculate the amount of excess air needed to keep the product temperature down to 1100 K. This example is calculated in the lecture. Answer: 131% 5.6.2 Adiabatic Flame Temperature

The combustion process is said to be adiabatic when the combustion chamber is isolated such that no heat is lost to the surroundings. All the chemical energy released during the combustion process is used to raise the temperature of the gases. In the absence of any work done by the system, the adiabatic flame temperature is the maximum temperature that can be achieved and it is a characteristic quantity for a certain fuel/oxidiser mixture. The adiabatic temperature is of high significance in the design of combustion chambers since it gives a first estimate of the temperatures that can be expected. Metallurgical constraints may limit the maximum allowable temperature and adiabatic flame temperatures can be taken as a measure of the degree to which additional excess air needs to be supplied to reduce the maximum temperature to acceptable levels. The first law (eq. 3) for a steady adiabatic flow process reduces to
0=
products

& & n h nh
reac tants

Eq. (7)

Example: Find the adiabatic flame temperature of stoichiometric combustion of methane with air. Inlet fuel flow rate, temperature and pressure are 1 kmol/s, 25C and 1 atm, respectively. This is example is given in the lecture. Answer: T=2126 K 9

2M TF Thermodynamics Sec. 5 2001-02

5.7

COMBUSTION PROCESS IN A CLOSED SYSTEM

p1, T1

Q W Q-W = ?

p2, T2

Fig. 6: Combustion process in a cylinder

Combustion in closed systems can be treated similarly to combustion in flow processes. First Law analysis for non-reacting and reacting processes do not differ if the correct internal energies are taken. The total internal energy can be defined as
u = u f + ( u T , p u 25C,1atm )
o

Eq. (8)

Overbar denotes molar quantities and again, molar based and mass based quantities are related by u (T ) = Mu (T ) . The internal energy of formation at standard conditions, u f0 , can be obtained from the experiment shown in Fig. 6. If no work is done, if the vessel is cooled to T0=25C and the final pressure is 1atm, then Q is a measure of u f0 . The first law for closed reacting systems can then be written as
Q W = Q W =
products

products

nu nu mu mu
reactants reactants

Eq. (9) Eq. (10)

In general, only enthalpy of formation is given in tables. However, internal energy of formation can be recovered from enthalpy of formation using u = h pv u = h Mpv and for ideal gases these relationships yield

u = h RT u = h RT
In particular

u f0 = h f0 R T0 u 0 = h f0 RT 0 f

10

2M TF Thermodynamics Sec. 5 2001-02

5.8

ENTHALPY OF REACTION & CALORIFIC VALUES

Enthalpy of formation refers to a particular species i and is needed in order to refer properties to the same datum state when chemical reactions occur. In other words, enthalpy of formation enables us to assign absolute enthalpy values to each substance at each temperature. However, if species i is a fuel, h f0 does not indicate how good a fuel is, i.e. how much energy is released as a result of combustion. For that purpose we define the 5.8.1 Standard Enthalpy of Reaction:

The standard enthalpy of reaction, h 0 , is the difference in enthalpy of the products and reactants at the standard state of 25C and 1 atm when complete combustion occurs in a flow process. The standard enthalpy of reaction per kmol fuel is then
& & & h 0 = nh n h n fuel reac tan ts products

Since h 0 is evaluated at standard state all enthalpies equal h t (T0 ) = h f0 + 0 for both products and reactants and h 0 can be simplified as
& f & f & h 0 = nh 0 nh 0 n fuel reac tan ts products

Eq. (11)

The enthalpy of reaction can easily be calculated for a particular fuel if the chemical composition is known. For complex fuels, however, it is easier to find h 0 experimentally. Note: Values for standard enthalpy of reaction are often given per kg rather than per kmol. 5.8.2 Fuels Containing H

If complete combustion occurs all hydrogen content in the fuel will be converted to H2O. In most cases temperatures are high enough that all H O leaves the combustor as water vapour. If the 2 water condenses latent heat is set free and h 0 will increase. It then follows from equation (11) that enthalpy of formation of liquid water needs to be smaller than enthalpy of formation of water vapour. The difference equals the heat that is released during condensation. In general we can deduce the relationship between enthalpies of formation of the same species in liquid and gaseous phase as Eq. (12) h 0 h0 h
f,l f,g fg,25 C

Note that this is not an exact equality. The liquid product water is subcooled (pressure generally about 1 atm) and its enthalpy is below h f,25o C which assumes a saturation pressure of 0.032 bar. Therefore, equation (12) underpredicts the difference between h f,l and h f,g Some enthalpies of formation for species in liquid and gas phase are listed in Table 3 of these notes. Example: H2O
h f0, g h f0,l + M H 2 O h fg ,25C

-241820 kJ/kmol -285830 kJ/kmol +18 kg/kmol2441.5 kJ/kg = -241883 kJ/kmol The error introduced is 0.02%. 11

2M TF Thermodynamics Sec. 5 2001-02

Note: Often, water should not be allowed to condense since liquid water may cause corrosion or the impact of water droplets may cause damage to the casing if velocities are high. Therefore, all products should be kept in the gas phase, i.e. above dew point. The partial pressure can be obtained from the product analysis. For example, methane/air combustion with 200% excess air yields nH2O=2 and nproducts =29.571. Therefore n H 2O p = H 2O = 0.0676 n products ptotal and Tsat(0.0676 bar)=36C. The products should be kept above 36C. Traditionally, engineers dislike negative numbers ( h 0 is negative for exothermic reactions). Therefore, two new quantities are commonly in use. 5.8.3 Net Calorific Value

The Net Calorific Value (NCV) (or lower heating value, LHV, in the U.S.) is the negative of h 0 when the product H2O is vapour (used mainly in the UK and Europe) 5.8.4 Gross Calorific Value

The Gross Calorific Value (GCV) (or higher heating value, HHV, in the U.S.) is the negative of h 0 when the product H2O is liquid (used mainly in the U.S.)

5.9

SFEE USING STANDARD ENTHALPY OF REACTION

This is an alternative method to using equation (3) provided that the standard enthalpy of reaction of the fuel is known and the combustion is complete. The reaction can be split into three subprocesses, see Fig. 7. A Reactants p1, T1 Reactants p0, T0 B Products p0, T0 C Products p2, T2

Fig. 7: Combustion process in three stages First the reactants are cooled to standard temperature (A). The combustion takes place in B under standard conditions and in C, the products are heated to the exit temperature. Processes A and C involve pure substances only, i.e. enthalpy changes are differences in sensible enthalpy. Enthalpy changes in B correspond to h 0 provided the combustion is complete. Then the SFEE can be written as
& & Q W =
reac tan ts

& n (h

& h1 ) +n fuel h0 fuel +

products

& n (h

h0 )

Eq. (13)

Note: Compare this process with Fig. 4.

12

2M TF Thermodynamics Sec. 5 2001-02

5.10

COMBUSTION EFFICIENCY

The combustion efficiency compares the heat released in a combustion process with the heat that is potentially available from complete combustion with products and reactants all at 25C, 1 atm. The efficiency is defined as
comb & Q & m fuel ( h0 )

Eq. (14)

h0 may be based on liquid or vapour H2O, i.e. h0 is either NCV or GCV. In 2M you should always assume that h0 is based on NCV, however, it should usually be stated if NCV or GCV was used to compute the efficiency. The thermal efficiency of a power plant has been defined as the cycle efficiency

& Wnet & Qin

& The use of the heat transfer to the working fluid, Q , did not take into account of any loss of & & energy during the combustion process which is necessary to provide Q . To compare Wnet with the energy which is potentially available from complete combustion of a fuel, we define the thermal efficiency of the plant as Eq. (15) & Wnet th & m fuel NCV fuel The NCV is usually taken here since water vapour is not normally allowed to condense. As an alternative to thermal efficiency it is common to use the specific fuel consumption, sfc, which is & m Eq. (16) specific fuel consumptio n = & fuel Wnet 5.11 REAL FUELS

Application of the first law of thermodynamics to combustion of real fuels is best demonstrated by an example. 5.11.1 Problem Description Determine the heat transfer from a combustion chamber for a combustion process of 100kg/s coal with 30% excess air. Heat losses are 2% of the net calorific value and products leave the combustion chamber at 500 C. & Q
losses

Coal, 25C, 1atm

Combustion

CO2, H2O, N2, O2, 500C, 1atm

Air, 25C, 1atm

& Qout
Fig. 7: Steady state coal combustion with excess air.

13

2M TF Thermodynamics Sec. 5 2001-02

As outlined in Section 5.6 the following steps are necessary for a complete analysis of the present problem. 1. find the appropriate chemical equation 2. write the element balance for all elements 3. apply first law First, we need to know the fuel composition. Table 5 lists the composition of different fuels by mass of carbon, hydrogen, oxygen and water. Table 5: Typical fuel composition of different fuels by mass, H2O is in the form of moisture
Content in mass % C H O H 2O Total NCV [kJ/kg] GCV [kJ/kg] Wood 42.5 5.1 37.4 15 100.0 13,500 15,000 Peat 47.2 4.8 28.0 20 100.0 16,300 17,850 Coal 79.8 4.8 10.4 5.0 100.0 30,900 32,050 Oil 86.8 13.2 0 0 100.0 42,720 45,600 Natural gas 74.9 25.1 0 0 100.0 50,020 55,500

Note: Fuel composition and NCV are given on a mass basis and none of the ni,f nor nox is known. This is a typical example where mass based quantities should be used throughout. Conversion into molar-based units is not necessary and the following approach will facilitate the analysis. However, conversion can be quickly done by division/multiplication with the molar mass of species i. Due to the excess air in the inlet stream it can be assumed that combustion is complete and all C is converted into CO2 and all H is converted into H2O. 1. The chemical equation can be written as nC,f C + nH.f H + nO,f O + nH2O,f H2O +nox (O2+79/21 N2) nCO2,out CO2 + nH2O,out H2O + nO2,out O2 + nN2,out N2 2. Element balance on a mass basis C: Conversion of C in fuel to CO2: Mass balance for 1 kmol of CO2: Mass balance for 1 kg of C atoms: H: Conversion of H in fuel to H2O: Mass balance for 1 kmol of H2O: Mass balance for 1 kg of H atoms: 2H 2 1 + + + 0.5 O2 16 16/2 = = H2O 18 18/2 (B) C 12 1 + + + O2 32 = CO2 44 44/12 (A)

32/12 =

14

2M TF Thermodynamics Sec. 5 2001-02

During every single chemical reaction, total mass must be conserved. Hence, the mass balance for 32 & & & & carbon [see (A)] results in mO 2,C = mCO2 mC = mC , f . From the mass balance for hydrogen 12 16 & & & & [see (B)] we get mO 2, H = mH 2O m H = mH , f . The second subscripts C and H denote that this 2 oxygen mass flow is needed for conversion of C to CO2 and H to H2O, respectively. O:

& & & Mass flow rate of O2 for stoichiometric combustion: mO 2,in = mO 2,C + mO 2, H
Mass flow rate of O2 in air for stoich. combustion: Mass flow rate of O2 in air with 30% excess air: N:

& & & & mO 2,ox = mO 2,C + mO 2,H mO, f

& & & & mO 2 ,ox = 1.3 (mO 2 ,C + mO 2, H mO , f )

& & & Mass flux of N2 for stoichiometric combustion: m N 2 ,in = m N 2 ,out = 76.8 / 23.2 mO 2 ,ox
& & & Mass flux of N2 for combustion with excess air: m N 2 ,in = m N 2,out = 76.8 / 23.2 m O 2,ox using & corresponding value for mO 2,ox from O-balance.

The fuel water is assumed not to take part in the reaction. The liquid water will evaporate and form water vapour. From above element mass balances all mass flows in and out of the combustion chamber can be & & & & calculated. The fuel mass flow rates m C,f , m H,f , m O,f and m H,f are known quantities and

& & & & & m CO2,out , m H2O,out , m O,out , m N2 and m O,ox can be found from
44 & m = 292.6 kg/s 12 C , f 18 & & & m H 2O ,out = m H , f + m H 2O , f = 48.2 kg/s 2 16 32 & & & & mO , out = 0.3 m C, f + m H , f m O , f = 72.2 kg/s 12 2 & mCO 2 ,out = 16 32 & & & & mO , ox = 1 .3 m C , f + m H , f mO , f = 313. 0 kg/s 2 12 76.8 & & mN 2 = m O ,ox = 1036.2 kg/s 23.2

3. SFEE We can either apply equation (3)

& & Q W =

products

& m [h + (h (T
0 f

out

) h25 o C , 1 atm

& )] m [h + (h (T
0 f reac tan t

in

) h 25 o C ,1 atm

)]

or equation (13)

& & Q W =

reac tan ts

& m (h

& h (Tin )) +m fuel h0 fuel +

products

& m (h (T

out

) h0 )

The latter may be more suitable for the current problem since h0 is known. Equation (13) can then be written as 15

2M TF Thermodynamics Sec. 5 2001-02

& & & Qout Qlosses W =

reactants

& m(h

25o C ,1atm

& h25o C,1atm + mcoalh0,coal +

products

& m(h

500o C ,1atm

h25o C,1atm

& & & & where Q is split into Qout and Qlosses and W equals zero. The standard enthalpy of reaction is
h 0 = NCV = 30,900 kJ/kg
and the heat losses are & & Qlosses = 2% m fuel NCV = 61,800 kJ/s The change of sensible enthalpy of the reactants (first RHS term) is zero and the change in sensible enthalpy of the products is
& H s, prod = 292 .6 480 .7 + 48 .2 943 .6 + 72.2 465 .0 + 1036 .2 508 .6 kJ/s = 746,719 kJ

Finally, the heat transfer from the combustion chamber can be calculated as & Q = 61,800 + 100 (30,900) + 746719 kJ/s = 2281 MJ/s 5.12 SECOND LAW ANALYSIS OF COMBUSTION PROCESSES 5.12.1 Second Law for Steady Flow Processes The second law of thermodynamics for reversible non-reacting steady flow processes can be expressed as
& Q T & & & = m e se m i si , and S surr =
rev

& Q Tsurr

Eq. (17)

where e denotes the exit state, i denotes the inlet state and surr refers to the surroundings. If the process is irreversible then the equality needs to be replaced by the inequality
& Q & & T m e s e m i s i & Q & & + = m e se m i si T

Eq. (18) Eq. (19)

& S gen

& The positive entropy generation term, S gen , has been introduced. This term quantifies the irreversibilities of the process1. Equations (17-19) are essentially identical to equation (7-3) in the 1M Thermodynamics lecture notes. Similar to equation (19), the second law can be written for a steady combustion process as
1

Example 1: Consider a process in an adiabatic and reversible turbine. No heat is exchanged over the boundaries and the RHS of equation (18) is zero (adiabatic and reversible = isentropic). Consider now a process in an adiabatic turbine with irreversibilities due to friction. No heat is exchange but s e>si. This change in entropy equals the entropy generation.

16

2M TF Thermodynamics Sec. 5 2001-02

& Q & = S gen + T

products

& m

sp

reac tan ts

& m s

r r

Eq. (20)

Remember that in 1M Thermodynamics only entropy changes have been calculated, e.g. for ideal & & gases S = m (c p ln T2 T1 R ln p2 p1 ) . However, in the presence of combustion entropy changes & & cannot be expressed in the form of S = ms since species are not conserved. Absolute entropy needs to be introduced to solve equation (20). This is similar to the definition of absolute enthalpy that was needed to solve equation (3) (see Section 5.5 Definition of Standard State). 5.12.2 Absolute Entropy For the definition of absolute entropy a common base is needed. You may remember that entropy can be associated with order. Lower entropy is associated with a higher degree of order2. Therefore, the common base is at T = 0K. At absolute zero, the oscillations of the molecules vanish and the molecules reach a state of maximum order. Definition (engel and Boles): The entropy of a pure crystalline substance at absolute zero temperature is zero. The entropy with respect to the common base at T = 0K is called absolute entropy. Absolute entropy values s 0 (T , p 0 ) are given in Table 6 for the reference pressure p = 1atm. The absolute entropy for ideal gases at arbitrary T and p can be obtained from

s (T , p ) = s 0 (T , p0 ) Ru ln

p p0

Eq. (21)

Table 6: Absolute entropy for selected substances at p=1atm in kJ/kmol K Temperature C(s) 0K 220K 298K 5.74 300K 400K 500K 600K 700K 800K 900K 1000K 1100K 1200K 1500K 2000K 2500K H2(g) 0 107.15 130.68 130.75 139.11 145.63 150.97 155.49 159.44 162.94 166.11 169.00 171.68 178.72 188.30 196.13 N2(g) 0 182.64 191.61 191.68 200.07 206.63 212.07 216.76 220.91 224.65 228.06 231.20 234.12 241.77 251.97 260.07 O2(g) 0 196.17 205.04 205.21 213.76 220.59 226.35 231.36 235.81 239.82 243.47 246.82 249.91 257.97 268.66 277.21 CO(g) CO2(g) H2O(g) CH4(g) 0 0 0 188.68 202.97 178.57 197.65 213.80 188.83 186.16 197.72 213.92 188.93 206.13 225.23 198.67 212.72 234.81 206.41 218.20 243.20 212.92 222.95 250.66 218.61 227.16 257.41 223.69 230.96 263.56 228.32 234.42 269.22 232.60 237.61 274.44 236.58 240.66 279.31 240.33 248.31 292.11 250.45 258.60 309.21 264.57 266.76 322.81 276.28

Consider adiabatic mixing of two substances with identical physical properties in a closed container of volume, V. At time t=t1, both substances are separated by a membrane and occupy exactly half the volume. The membrane is removed and at time t=t2, both substances are perfectly mixed. Initial pressures and final total pressure are 1 bar. Entropy changes can be obtained from S sys = S A + S B = 2 c p ln T2 T1 R ln p2,i p1 . From the ideal gas

law we obtain T2=T1 since piVi and mi are constant. Hence, S sys = 2 R ln 0.5 > 0 which is consistent with the concept that mixing of two substances increases disorder.

17

2M TF Thermodynamics Sec. 5 2001-02

5.12.3 IrreversibilitiesThe first law for a fully reversible flow process is q rev w rev = dh
2 2

Eq. (22)

where d denotes the exact differential of a property and is the differential in a path function ( dh = h2 h1 but
1

w w
1

w1 since work is not a property and it does not have a specific

value at a specific state). Similarly, the first law for an irreversible process is qirrev wirrev = dh From the second law we get
ds = q T
rev

Eq. (23)

q T

Eq. (24)

and qrev = Tds

& Dividing eq. (19) by m gives for single inlet and single exit

Eq. (25)

Ts gen + qirrev = Tds

Eq. (26)

If inlet and exit states are fixed (Tds = const) then qirrev < qrev and therefore it follows from the first law (equations 22-23) that wirrev < wrev Eq. (27)

We need to introduce now a measure for the irreversibilities. The difference between the work done by the reversible and the irreversible process, w = (wrev-wirrev), quantifies the work that is lost due to irreversibilities. Subtracting eq. (23) from (22) we get w=q and q can be obtained from the difference of eqs. (25) and (26). Eq. (28)

w = q = Ts gen

Eq. (29)

Obviously, the entropy generation term quantifies the losses due to irreversibilities. Sgen can be obtained from equation (19). What does it mean for a combustion process? Effects of irreversibilities due to combustion can be best illustrated with an example:

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2M TF Thermodynamics Sec. 5 2001-02

5.12.4 Irreversibilities due to combustion of methane with oxygen Surroundings & S Q surr CH4, 25C, 1atm O2, 25C, 1atm
Combustion

CO2, H2O, 25C, 1atm Ssys

Fig 8: Entropy changes in steady state combustion process The global reaction mechanism is CH4 + 2O2 CO2 + 2H2O and the molar flow rate is & n CH4 = 1 kmol/s First, we need to know how much water condenses.
n H 2O ( g ) n tot = p sat @ 25o C p tot = 0.032 n H 2O ( g ) = 0.032 (1 + n H 2O ( g ) ) n H 2O ( g ) = 0.033 n H 2 O ( l ) = 1.967

From a first law analysis we get the heat flow across the system boundaries.
& & & & & & & Q W = n CO 2 h CO 2 + n H 2O ( g ) h H 2 O ( g ) + n H 2 O ( g ) h H 2 O ( l ) n CH 4 h CH 4 n O 2 h O 2 & & = n CO 2 h f0 ,CO 2 + h CO 2 (T 2 ) h CO 2 (T 0 ) + n H 2O ( g ) h f0,H 2 O ( g ) + h H 2 O ( g ) (T 2 ) h H 2 O ( g ) ( T 0 ) & + n H 2O ( l ) h & & n CH 4 h f0 ,CH 4 + h CH 4 (T 1 ) h CH 4 ( T 0 ) n O 2 h f0,O 2 + h O 2 ( T1 ) h O 2 (T 0 )

& Q = 1 ( 393 , 520 ) + 0 . 033 ( 241 ,820 ) + 1 . 967 ( 285 ,830 ) 1 ( 74 ,850 ) 2 0 kJ/s = -888 ,878 kJ/s
0 Using equation (19) and s H 2O ( l ) = 69.92 kJ/kmol K

0 f , H 2O ( l )

+ h H 2 O ( l ) (T 2 ) h H 2 O ( l ) (T 0 )

& Q & & S gen = S sys T & + S & = S sys surr

& & & = n CO2 s CO2 (298K , (1 / 1 .033)b ) + n H 2O ( g ) s H 2O ( g ) (298K , (0 .033 / 1.033)b ) + n H 2O ( l ) s H 2 O ( l ) (298K ,1b ) & & & n CH 4 s CH 4 (298K ,1b ) n O 2 s O2 (298K ,1b ) + Q T surr

= (1 (213.80 8. 314 ln 0 .968) + 0.033 (188.83 8.314 ln 0. 032) + 1 .967 69.92) kJ/K s 888,878 (1 186.16 + 2 205.04) + kJ/K s 298.15 = 2743.8 kJ/K s

Here we have made use of the fact that the heat flow across the system boundaries is equivalent to & & the heat absorbed by the surroundings. Therefore Q T = Ssurr . Since no work is done during

this process and the process is irreversible the work losses due to irreversilibilities amount to
& & W = T S gen = 298.15 2743.8 kJ/s = 818,060 kJ/s

This also means that the process could have provided 818,060 kJ/s work output if it was fully reversible.

19

2M TF Thermodynamics Sec. 5 2001-02

We will now consider an adiabatic process with identical inlet conditions as pictured in Fig. 9. Ssurr=0 CH4, 25C, 1atm O2, 25C, 1atm
Combustion

CO2, H2O, ?? C, 1atm

Fig 9: Entropy changes in adiabatic steady state combustion process The exit temperature can be obtained from first law analysis:
& & & & & & Q W = nCO2 hCO2 + n H 2O( g ) hH 2O ( g ) n CH4 hCH4 nO2 hO2 & & = nCO2 h f0,CO2 + hCO2 (T2 ) hCO2 (T0 ) + n H 2O ( g ) h f0,H2 O( g ) + h H2 O( g ) (T2 ) h H2 O( g ) (T0 ) 0 = 1 393,520 + hCO2 (T2 ) + 2 241,820 + h H2 O (T2 ) 1 ( 74,850) 2 0 kJ/s 802,310 kJ/s = hCO2 (T2 ) + 2 hH 2O (T2 ) T2 = 4150 K = 3852o C & nCH 4

[ [h

0 f , CH4

& + hCH4 (T1 ) hCH4 (T0 ) n O2 h

0 f ,O 2

+ hO2 (T1 ) hO2 (T0 )

This temperature T2 has been obtained by trial and error. The entropy generation for the adiabatic flow process can be obtained from the second law (eq. 19) as
& Q & & S gen = S sys T & & = n CO2 s CO2 (4150 K,0.33b ) + n H2O s H 2O (4150 K,0.67 b)

= (1 [354 .4 8.314 ln 0.33] + 2 [305.9 8.314 ln 0.67 ] 1 186.2 2 205.1) kJ/K s = 385.7 kJ/K s

& & n CH 4 s CH 4 (298 K,1b ) n O2 sO2 (298 K,1b ) + 0

Then, the work losses due to irreversibilities are

& & W = TS gen = 298.15 385.7 kJ/s = 114,989 kJ/s

These are the losses that can be associated with the combustion process itself. Combustion irreversibilities are visualised in Fig. 10. If a fully reversible process existed that converted the reactants to products at 25C then 818,060 kJ/s work could be gained. However, irreversibilities of the combustion process amount to 114,989 kJ/s and the amount of work that is available from the hot product gases is 818,060-114,989 kJ/s = 703,071 kJ/s. Now it becomes clear why the second law analysis is needed to quantify losses of a combustion process. Using the first law of thermodynamics we have no means of quantifying the loss of potential reversible work due to combustion.

20

2M TF Thermodynamics Sec. 5 2001-02

Reactants, CH4,O2 25C, 1atm Theoretical reversible work

Combustion

Products, CO2,,H2O 3852C, 1atm Theoretical reversible work

888,878 kJ/s

703,071 kJ/s

Fig 10: Theoretical available work from reactants and combustion products Note: Combustion of methane with pure oxygen has been chosen as example problem due to its simplicity. However, the resulting high exit temperatures result in dissociation of the combustion products and the assumption of CO2 and H2O as the only product gases introduces significant errors. In addition, losses in the order of 14% do not seem very large. The tutorial problem of methane/air combustion is much more realistic and shows a dramatic increase in losses due to irreversibilities of combustion.

21