Thermodynamics of Combustion: (With A Few Modifications by R.I.C.)

2M Th Section 6 2007-08
Thermodynamics of Combustion
Introduction to Reactive Systems
Dr. A. Kronenburg
(with a few modifications by R.I.C.)
Problem Description
Example: Simple steam power cycle
reactants Products
furnace composition = ?, T = ?, p = ?

T, p, m
Q = ?
Heat exchanger
W pump Wtur
turbine
pump
condenser
Other Applications
Gas Turbine
combustor
Rolls Royce Industrial Trent (an ‘aeroderivative’ engine)

fuel
air
Combustor in Trent aero-engine

Other Applications
Reciprocating Internal Combustion Engine
fuel
oxidizer
products
Work
Other Applications
Internal Combustion Engine
fuel products
oxidizer
Work
Outline
Combustion in Thermodynamics
non-reacting systems (1M and 2M so far)
→ reacting systems
Consequences:
1. the chemical composition changes
2. species (e.g. CH4, O2, H2O …) are not conserved
3. conservation of mass must be extended to
conservation of elements (e.g. C, H, O …)
...
Outline
Combustion in Thermodynamics
...
4. need to consider latent and sensible enthalpy plus
internal chemical energy
5. conservation of energy must be extended to include
chemical energy and changing chemical composition
Objective:
Find the product composition and state, heat released,
and work done during the combustion process.
Outline
Good News
Fundamentals covered in A-level chemistry
Bad News
Somewhat different approach and
introduction of new nomenclature
Combustion Process
When does a reaction take place?
1. Need fuel and oxidizer, then fuel + oxidiser products

2. Fuel and oxidiser must be
mixed on molecular level
in the “right” proportions
3. Fuel must be brought
above its
ignition temperature
4. An exothermic reaction will proceed

5. An endothermic reaction will stop if not enough energy supplied
Combustion Chemistry
Fuels:
Most practical fuels are terribly complex.
100% TC Aromatics
90% Acenaphthalenes
80% C11+Naphthalenes
70% Naphthalenes
60% Indenes
50% Indanes
40% Alkyl Benzenes
e.g.
30% TC Paraffins
Some 20% DC Paraffins
aviation 10% MC Paraffins
0%
fuels Paraffins
JP-4 JP-7 JET-A DF2
Fuels:
Most fuels are mixtures of hydrocarbons. They can often be
represented adequately by the chemical formula CxHy.
Gasoline (petrol): octane C8H18
Diesel oil: dodecane C12H26
Ethanol: ethanol C2H5OH
Natural gas: methane CH4
Oxidiser (or oxidant):

The most common oxidiser is air since it is free and readily
available. Air consists of oxygen and nitrogen with traces of CO2,
CO, Ar, etc. Trace elements and N2 do not react and can be
considered as a single gas, “atmospheric nitrogen” (AN).
Air:
Composition of air is 21% O2 and 79% AN.
In general, trace elements negligible ⇒ 21% O2 and 79% N2 by
no. of kmol (or by volume, if considering partial volumes)
Therefore (ideal gas law) pN2 / pO2 = 79 / 21 or nN2 : nO2 = 79 : 21
What is this on a mass basis?
Conversion Table (quantities per 100 kmol air)
ni (no. of kmol) Mi (molar mass) mi =Mi• ni Yi =mi /m
O2 21 32 672 0.232
N2 79 28 2212 0.768
total 100 2884 1.000
In Data Book,
mN2 / mO2 = 76.8 / 23.2 Table E5
Products:
Products of complete hydrocarbon combustion are
H2O and CO2 only.
Complete combustion: enough oxygen is provided to
convert all fuel-C atoms into CO2 and all fuel-H atoms
into H2O.
Depending on provision of oxygen, other product
species can occur, e.g. CO, O2 and intermediates/radical
species
Combustion Analysis
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 N2 does not take part in the reaction

(except at T > ~2000K - more about this in 3M).
Combustion Analysis
Excess fuel (fuel rich mixture):

Insufficient O2 supply will result in incomplete
conversion of carbon to CO2.
Some CO (toxic) will form.
Excess air (fuel lean, or weak, mixture):

All fuel is converted to CO2 and H2O.
Excess O2 will leave the system/control volume.
In reality, some excess air is needed due to
imperfect mixing of fuel and air.
Chemical Analysis
Chemical equation :
Combustion of hydrocarbon fuel with oxygen can be represented as:

nF CxHy + nox O2 → nCO2 CO2 + nH2O H2O + nO2 O2 + nCO CO + ...
Combustion of hydrocarbon fuel with air:

nF CxHy + nox (O2+79/21N2) →
nCO2 CO2 + nH2O H2O + nN2 N2 + nO2 O2 + nCO CO + ...
Objective is to know the composition of the products but this will be

a function of the quantity of oxidizer available for burning the fuel.
Chemical Analysis
Chemical equation:
Combustion of hydrocarbon fuel with air:
nF CxHy + nox (O2 + 79/21N2) →
nCO2 CO2 + nH2O H2O + nN2 N2 + nO2 O2 + nCO CO + ...
Normal to write eqn for 1 kmol of fuel, i.e. nF = 1

Combustion Analysis
Specification of Reactants
For a complete analysis of a combustion process,
the following need to be known:
• Fuel composition
• Proportion of fuel to oxidizer
Three common ways of expressing this proportion

1. air/fuel ratio
2. theoretical air
3. excess air
Combustion Analysis
Specification of Reactants (cont.)
Three common ways of expressing proportions of fuel and air

a m
1. air/fuel ratio (AFR) = m F
F m
(sometimes use FAR m a )
2. theoretical air: e.g. 150% theoretical air means

1.5 times that for stoichiometric combustion
3. excess air: e.g. 50% excess air means
the same as 150% theoretical air
Conservation Equations
Conservation of mass - holds, but of limited use
Number of moles is not conserved,
e.g. 2 H2+ O2 → 2 H2O
3 kmol 2 kmol
new
N products N reactants
Number of elements is conserved
∑n l
i =1
i i, j = ∑n l
i =1
i i, j
∑n l
i =1
i i, j = ∑n l
i =1
i i, j
l i , j = number of atoms of element j in species i ,

e.g. for ethanol, C2H5OH
lC2H5OH, C = 2, lC2H5OH, H = 6, lC2H5OH, O = 1, lC2H5OH, N = 0
1 additional equation for each element j, e.g. 4 equations for hydrocarbon

combustion with air. The four elements are C, H, O and N.
The system is determined in the case of complete combustion
(stoichiometric or with excess air).
Additional information may be needed if combustion is incomplete.
Example Calculation
Examples
Calculate the product composition for:
Combustion of Ethane (C2H6) with 20% excess air
1. Solve for stoichiometric combustion: CO2, H2O, N2 only products
2. Chemical equation for stoichiometric combustion

nF C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2
Example Calculation
3. Conservation of elements: ∑n l
i =1
i i, j = ∑n l
i =1
i i, j
C: nCO2 ⋅1 + nH 2O ⋅ 0 + nN 2 , s ⋅ 0 = nF ⋅ 2 + nox , s ⋅ 0 ⇒ nCO2 = 2
H: nCO2 ⋅ 0 + nH 2O ⋅ 2 + nN 2 , s ⋅ 0 = nF ⋅ 6 + nox , s ⋅ 0 ⇒ nH 2O = 3
O: nCO2 ⋅ 2 + nH 2O ⋅1 + nN 2 , s ⋅ 0 = nF ⋅ 0 + nox , s ⋅ 2 ⇒ nox , s = 3.5
N: nN 2 , s ⋅ 2 = nox , s ⋅ 79 21 ⋅ 2 ⇒ nN 2 , s = 13.167
4. 20% excess air: nox = 1.2 ⋅ nox , s = 4.2

⇒ nO2 ,out = 4.2 − 3.5 = 0.2 ⋅ nox , s = 0.7
and nN 2 = 1.2 ⋅ nN 2 , s = 15.8

Example Calculation
∑n l ∑n l
is a formal way of expressing
i i, j = i i, j conservation of elements,
i =1 i =1
suitable if developing software
In practice, for hand calculations in 2M, just do it by inspection.

Set nF = 1 (no need to write the 1)
1 C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2
Carbon balance : 1 x 2 = nCO2 x 1, so nCO2 = 2

Example Calculation
Hydrogen balance : 1 x 6 = nH2O x 2, so nH2O = 3
Oxygen balance : nox,s x 2 = nCO2 x 2 + nH2O x 1

nox,s x 2 = 2 x 2 + 3 x 1 so nox,s = 3.5
Example Calculation
C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2
Nitrogen balance : nox,s x 79/21 x 2 = nN2,s x 2

3.5 x 79/21 x 2 = nN2,s x 2
so nN2,s = 13.167
N.B. Recommended order for doing element balances :

C first, then H, then O, then N
Example Calculation
4. The elements balances above were for

stoichiometric combustion (the subscript s on nox & nN2),
so now account for the 20% excess air
In the reactants,
nox = 1.20 x nox,s = 1.20 x 3.5 = 4.20
In the products,
nO2 = 0.20 x nox,s = 0.20 x 3.5 = 0.70
or nO2 = nox - nox,s = 4.20 - 3.50 = 0.70
nN2 = 1.20 x nN2,s = 1.20 x 13.167 = 15.80

Example Calculation
5. Write balanced chemical eqn for actual reaction (with excess air):
C2H6 + 4.2 (O2 + 79 21N2 ) → 2CO 2 + 3H2O + 0.7O 2 + 15.8N2
Consistency check:
No of C on LHS = No of C on RHS, No of H on LHS = No of H on RHS
No of O on LHS = No of O on RHS, No of N on LHS = No of N on RHS
6. Air to Fuel ratio: AFR ≡ ma/mF MC2H6 from

mF = nF MF = 1 kmol x 30 kg/kmol = 30 kg Data Book
( )
ma = nox MO2 + 79 21MN2 = 4.2 (32 + 79 21 x 28 ) = 576.8 kg
AFR = 576.8 / 30 = 19.22

Summary
You should be able to balance chemical equations, when
1. Fuel composition
2. Proportion of fuel to oxidizer
are known
2M TF Section 6 2007-08
Properties of reactants and products
First Law analysis
Dr A. Kronenburg
Energy
Last Lecture: Chemical Equation
• How to balance the chemical equation for given fuel and air to fuel ratio
C2 H 6 + 4.2 ⋅ (O2 + 79 21 N 2 ) → 2CO2 + 3H 2O + 0.7O2 + 15.8 N 2
This Lecture: Energies in Reactive Systems with Multiple Species
Neglecting kinetic, potential and nuclear energies the molecules of a system

possess energies in the form of
1. Sensible energy (associated with a change of state of species i)
2. Latent heat (associated with phase change of species i)
3. Chemical energy
New
Chemical Energy: internal chemical energy associated with
formation and destruction of chemical bonds
Energy
Energies in Reactive Systems with Multiple Species
Neglecting kinetic, potential and nuclear energies the molecules of a

system possess energies in the form of
1. Sensible energy (associated with a change of state of species i)
2. Latent heat (associated with phase change of species i)
3. Chemical energy
New
Chemical Energy: internal chemical energy associated with

formation and destruction of chemical bonds
Energies
Species energy content
The change in specific energy of a particular species for a flow
process (neglecting nuclear energies) is given by
∆e = ∆ht + ∆ke + ∆pe
∆ht = ∆hs + ∆hc (+ hL ) Perfect gas ∆ht = c p ∆T + ∆hc (+ hL )
Two questions:
1) What is the change in sensible enthalpy of a real (ideal) gas?
2) How can we determine hc?
Sensible Enthalpy
Specific heat
∂h
T2
cp = ⇔ ∆h = ∫ c p (T )dT
∂T p = const T1
cp can be approximated by a polynomial fit

N
c p / R = ∑ anT n
n =0
•Often a fourth order polynomial fit
Polynomial •Different coefficients for each species
coefficients: •Split into two temp. ranges for better fit
•Data & Formulae Book:
1st order fit for simplicity
Sensible Enthalpy
Specific heat
Sensible Enthalpy
Instead of using ∆h = ∫ C p dT or ∆h = ∫ C p dT ,
can look up sensible enthalpies in Data Book Table E7c.
Gases taken as semi-perfect
(ideal but not perfect,
simple linear variation Cp = a + bT),
so sensible enthalpies depend on T only.
Datum state for enthalpies in Table E7c is 25°C. Why?

See later, when finding how to determine chemical enthalpy.
Enthalpy
How to determine “chemical” enthalpy, hc:
½ O O + H H → O Formation of H2O
H H from its elements
Energy required to break 1) single bond H-H = 436 MJ/kmol

2) double bond O=O = 498 MJ/kmol
3) single bond O-H = 463 MJ/kmol
Energy balance for the production of 1 kmol H2O

½ 498 + 436 – 2 x 463 = -241 MJ/kmol
Enthalpy
How to determine “chemical” enthalpy, hc:
½ O O + H H → O Formation of H2O
H H from its elements
So, 1 kmol of H2O has approx. 241 MJ less energy

than its constituent elements
(½ kmol of O2 and 1 kmol of H2),
at the same thermodynamic state
Real Fuel
Imagine trying to do a similar calculation for these!
100% TC Aromatics
90% Acenaphthalenes
80% C11+Naphthalenes
70% Naphthalenes
60% Indenes
50% Indanes
40% Alkyl Benzenes
30% TC Paraffins
20% DC Paraffins
10% MC Paraffins
0% Paraffins
JP-4 JP-7 JET-A DF2
Enthalpy
How to determine “chemical” enthalpy, hc - practical approach:
H2, 25°, 1atm n H 2 = 1 kmol/s

H2O, (diluent), 25°, 1atm
O2, 25°, 1atm nO2 = .5 kmol/s Combustion Cooling
(diluent, 25°, 1atm) n H 2O = 1 kmol/s
(ndil = 50 kmol/s) Q (ndil = 50 kmol/s)
Products must be cooled and Q can be measured.

Q = -241,820 kJ/s.
First Law
SFEE for combustion chamber
0
Q − W = H out − H in
H = ∑ n ht = ∑ m ht with [ht ] = kJ / kg and [ht ] = kJ / kmol
Above equation can be written as
Q = n H 2O h t , H 2O − n H 2 h t , H 2 − nO2 h t ,O2
Q n H 2 nO2
⇔ = h t , H 2O − ht ,H 2 − h t ,O2
n H 2O n H 2O n H 2O
Q n H 2O = -241,820 kJ/kmol of H2O is a measure of the

enthalpy difference between H2O and its elements (H2 and O2)
at the same T and p.
Enthalpy of Formation
Definition:
0
The enthalpy of formation of a substance, h f , is defined as the
heat transfer in a reaction where one kmol of the substance is
formed from its elements, all at their standard states.
The standard state is defined at 25°C and 1 atmosphere. This is
the reference state of a substance. By convention, each element in
the standard state, in a stable form (e.g. N2, not N), is assigned an
enthalpy of zero (or has an enthalpy of formation of zero).
The stable forms of some elements are, e.g. H2(g), O2(g), N2(g),
Hg(l), C(s,graphite).
Table 2 Enthalpies of formation of selected substances at 25°C, 1 atm
Substance Formula h f0 [kJ/kmol]
Carbon C(s) 0
Hydrogen H2(g) 0
Nitrogen N2(g) 0 Look
Oxygen O2(g) 0
up in
Carbon monoxide CO(g) -110,530
Data
Carbon dioxide CO2(g) -393,520
Water vapour H2O(g) -241,820
Book
Water (liquid) H2O(l) -285,830
Table
Methane CH4(g) -74,850 E7b
n-Octane C8H18(g) -208,450
n-Dodecane C12H26(g) -291,010
Ethane C2H6(g) -84,680
Substance Formula h0
[kJ/kmol]
f
Carbon C(s) 0
Hydrogen H2(g) 0
Nitrogen N2(g) 0
Zero
Oxygen O2(g) 0
because
Carbon monoxide CO(g) -110,530
Carbon dioxide CO2(g)
these
-393,520
Water vapour H2O(g) -241,820
substances
Water (liquid) H2O(l) -285,830 are
Methane CH4(g) -74,850 elements
n-Octane C8H18(g) -208,450
n-Dodecane C12H26(g) -291,010
Substance Formula h0
[kJ/kmol]
f Note the
Carbon C(s) 0
minus signs
Hydrogen H2(g) 0
here
Nitrogen N2(g) 0
Oxygen O2(g) 0 Reactions to
Carbon monoxide CO(g) -110,530 form these
Carbon dioxide CO2(g) -393,520 compounds
Water vapour H2O(g) -241,820 from their
Water (liquid) H2O(l) -285,830 elements are
Methane CH4(g) -74,850 exothermic,
n-Octane C8H18(g) -208,450 heat released,
n-Dodecane C12H26(g) -291,010 so –ve Q
Properties
Latent enthalpy (during phase changes) can be allowed for

by having two enthalpy of formation values for a substance,
one for liquid and one for gas/vapour, e.g. hf0H O(l) and hf0H
2 2O(g)
( )
Then, for every species,
we can write ht = hf0 + hat T − hat 25°C
h of formation sensible h
SFEE can be applied to combustion processes without changes to its general

structure Q −W = ∆H . It is seen that the only change is the treatment of the total
enthalpy. Using total enthalpies automatically accounts for the combustion
process.
Fuels containing Hydrogen water can be
present in liquid or
CxHy + (x+0.25 y) O2 → xCO2 +0.5y H2O gaseous phase
Usually, H2O leaves the combustion chamber in the gas phase and
using hf H2O(g) = −241820 kJ/kmol will be correct.
If water vapour condenses to form liquid H2O, e.g. in a condensing

boiler for domestic central heating, latent heat is set free and needs to
be allowed for in the enthalpy of formation :
hf0,H O(l ) ≈ hf0,H O(g ) − MH 2Oh = −241820 kJ/kmol
2 2 fg @25D C
− 18.016kg/kmol ⋅ 2441.7kJ/kg
= -285810 kJ/kmol
(-285830 in Data Book)
Properties
( )
Total Enthalpy of Species
h t (T ) = h + h(T ) − h 25°C ,1atm
o
f molar
ht (T ) = h M + (h(T ) − h25°C ,1atm )

o
f mass
Combustion of Hydrogen
Q
n H 2O
= h t , H 2O −
n H 2
n H 2O
ht ,H 2 −
nO2
n H 2O
0
(
h t ,O2 = h f ,H 2O + hs , H 2O (Tout ) − hs , H 2O (25D C ) )
(h (25 C ) )− ( )
n H 2 0 nO2 0
− + hs , H 2 (Tin ) − hs , H 2 D
h + hs ,O2 (Tin ) − hs ,O2 (25D C ) = h f0, H 2O
n H 2O n
f ,H 2 f ,O2
H 2O
Properties
Why do we need an absolute value of enthalpy?
Non-reacting flow process from state 1 to state 2 involving a mixture
of 3 species A, B and C :
∆H = ∆H A + ∆H B + ∆H C
= H − H + H − H
A, 2 A,1 B,2 B ,1 + H C , 2 − H C ,1
= m A, 2 hA, 2 − m A,1hA,1 + m B , 2 hB , 2 − m B ,1hB ,1 + m C , 2 hC , 2 − m C ,1hC ,1
= m A (hA, 2 − hA,1 ) + m B (hB , 2 − hB ,1 ) + m C (hC , 2 − hC ,1 )
If a reacting system, mass of A, B and C may not be conserved.

Hence, enthalpy change cannot be represented by differences in
specific enthalpies.
Examples
Example
Enthalpy change of reaction CO+½O2→CO2 at 800ºC
∆h@800D C = ∑ nht (800D C) − ∑ nht (800D C)
prod reac 0 0
( ) [ ( )
= h f0,CO2 + hs,CO2 (800D C) − hs,CO2 (25D C − h f0,CO + hs ,CO (800D C) − hs,CO (25D C +
1 0
2
[ (
h f ,O2 + hs ,O2 (800D C) − hs,O2 (25D C) )]]
0 0
⎡
= − 393,520 kJ/kmol + 836 .4 kJ/kg ⋅ 44 kg/kmol - ⎢ − 110 ,530 + 860 .4 kJ/kg ⋅ 28 kg/kmol +

⎢
ht ,CO 2 ( 800 D C ) = −356 , 718 kJ/kmol ⎣ − 86 , 438 .8 kJ/kmol
1 ⎤
⋅ 784 .2 kJ/kg ⋅ 32 kg/kmol ⎥
2 25
⎥
, 094 .4 kJkmol ⎦
= −295 ,374 kJ
Adiabatic Flame Temperature & Enthalpy of Reaction
Dr. A. Kronenburg
(with a few modifications by R.I.C.)
Steady Flow Combustion
Steady Flow Combustion Process
n fuel
Fuel, T, p Products, T, p
Combustion (Cooling)
n products
Air, T, p nair
Q
Given: fuel composition

air/fuel ratio, Tfuel, Tair, Tproducts, velocities if significant
Procedure: (1) write and balance chemical equation
(2) use first law (in molar form)
SFEE, if KE changes negligible:
( ) ( )
Q − W = ∑ n ht − ∑ n ht
all terms in kW
kmol kJ
out in
nh x
s kmol
Divide by fuel molar flow rate nF :
all terms in
⎛ n ⎞ ⎛ n ⎞
Q − W = ∑ ⎜⎜ ht ⎟⎟ − ∑ ⎜⎜ ht ⎟⎟ kJ
out⎝ nF ⎠ in ⎝ nF ⎠ kmol of fuel
These are just the coeff.s in the chemical eqn,

when written with nF = 1 e.g. 2 CO2
Often shorten this to Q – W = HP –HR

products reactants
(here meaning all species,
incl. N2 and
h
excess O2)
For every species in P and R, ht is evaluated as
(
ht = hf0 + hat T − hat 25°C )
Will often drop this superscript all zero for ideal gas
(only consider formation at 25°C) data in Table E7c
Example: gas-fired boiler with stoichiometric combustion
CH4, 25°C products, 200°C
air, 25°C
Q to water
Element
⎛
balances give CH4 + 2⎜ O 2 +
79 ⎞ 79
N2 ⎟ → CO2 + 2H2O + 2 N2
⎝ 21 ⎠ 21
79
HR = ⎡hf CH + 0 ⎤ + 2 [0 + 0] + 2 [0 + 0] = -74850 kJ / kmol fuel
⎣ 4 ⎦ 21
element at 25°C
⎛ 79 ⎞ 79
CH4 + 2⎜ O2 + N2 ⎟ → CO2 + 2H2O + 2 N2
⎝ 21 ⎠ 21
vapour
[ ] [ ]
HP = hf CO2 + hCO2 200°C + 2 hf H2O + hH2O 200°C + 2
79
21
[
0 + hN2 200°C ]
= [-393520 + 7276] + 2 [-241820 + 5964] + (2x79/21) [5110]
= -819509 kJ / kmol fuel
Q = HP – HR = -819509 - (-74850) = -744659 kJ / kmol fuel

or -744.7 MJ / kmol of CH4
-ve because from control vol.
Another SFEE example: gas turbine, assumed adiabatic
control vol. : fuel at Tfuel products

combustor only at T3
air from
compressor at T2 (>> 25°C)
0 = HP at T3 – HR If T3 known, solve for nox & excess air.
If nox known, solve iteratively to find T3.
control vol. :
combustor + turbine
W
0 - W = HP at T4 – HR
If T4 known, solve for W products at T4
Adiabatic Flame Temperature
heat transfer Q to
surroundings
chemical energy
released in an
exothermic reaction increase in energy of
combustion products
In the limit Q → 0 (no useful Q, e.g. to water/steam in a boiler,

and no lost Q to atmosphere)
combustion products will have the maximum energy increase
Tproducts is then known as the adiabatic flame temperature

Adiabatic flame temperature will depend on the amount of

air in the reactants.
For complete combustion, the minimum amount of air is the
theoretical air, where nox = nox,s (stoichiometric).
Then adiabatic flame temperature will have its highest value
for that reaction.
With excess air, there will be a greater mass (O2 and N2) in
the products to absorb the chemical energy released,
so adiabatic flame temperature will be lower.
This is how T3 is controlled in gas turbine combustion,
which is approximately adiabatic.
Computation of the adiabatic flame temperature
0= ∑ n h − ∑ n h
products reactants
or HP = HR
Example:
Find the adiabatic flame temperature of stoichiometric combustion of
methane with air. Inlet fuel flow rate, temperature and pressure are
1 kmol/s, 25°C and 1 atm, respectively.
1. Chemical Equation & Element Balance
⎛ 79 ⎞ 79
CH 4 + 2⎜ O2 + N 2 ⎟ → CO2 + 2 H 2O + 2 N 2
⎝ 21 ⎠ 21
SFEE
79 79
0 = ht ,CO2 (T ) + 2ht ,H2O (T ) + 2 ht ,N2 (T ) − ht ,CH4 (25 C) − 2ht ,O2 (25 C) − 2 ht ,N2 (25D C)
D D
21 21
( ) (
0 = 1 ⋅ h f0,CO2 + hs ,CO2 (T ) − hs ,CO2 (25D C ) + 2 ⋅ h f0, H 2O + hs , H 2O (T ) − hs , H 2O (25D C ) )
+2
79
21
( )
hs , N 2 (T ) − hs , N 2 (25D C ) − h f0,CH 4 T is the only unknown, but the
sensible enthalpies can only
Solve equation be looked up if we know T
79
hs,CO2 (T ) + 2 ⋅ hs,H2O (T ) + 2 hs, N2 (T ) = −h f0,CO2 − 2 ⋅ h f0,H2O + h f0,CH4
21
= 393,520 + 2 ⋅ 241,820 − 74,850 = 802,310kJ/kmol
First guess: TP = 1300°C ⇒ LHS = 477,653 kJ/kmol ≠ RHS

Trial and error: TP = 2126°C
TP = 2126°C is well above the metallurgical limit for a

gas turbine burning natural gas, so up to ~300% excess air
is needed to reduce TP
Acceptable method for finding TP when using Table E7c for

sensible enthalpies :
Evaluate HP for different guessed T until
h(T) from one line of the table gives HP < HR and
h(T) from next line of the table gives HP > HR
Then use linear interpolation to estimate TP
Control of Exit Temperature
How to limit exhaust gas temperature?
SFEE:
∆ 2
∑ ∑
v
Q = n ht − n ht + m , with ht = h f0 + h (T ) − h (T0 )
products reac tan ts
2
Q = const
∑ t f ,CH 4

n h =
reactants

n h 0
= const , with CH 4 as fuel and Treactants = 25 D
C
∑ n h
products
t = ∑ m h
products
t = const
How does excess air affect the product temperature?
m air ↑ ⇒ Tproducts ↓
Closed System
Combustion Process in a Cylinder
p1, T1
Q p2, T2
W Q-W = ?
First Law for Closed Systems
Q −W = ∑ nu − ∑ nu
products reactants
Q −W = ∑ mu − ∑ mu
products reactants
Closed System
Internal Energy of Formation

If the reaction C+O2 → CO2 occurs in a closed cylinder, then
First Law of thermodynamics is
Q = nCO2 u CO2 − nC u C − nO2 u O2
If no work is done, the vessel is cooled and the final pressure is

1atm, then Q is a measure of the internal energy of formation at
standard conditions uf°. The total internal energy is given by
o
u = u + (u T , p − u 25°C ,1atm )
f
Closed System
0 0
Relationship between u and h
f f
Tables usually give enthalpy of formation only,

0
however u f can be recovered using u = h − pv
u = h − Mpv
and for an ideal gas u = h − RT
u = h − RT
In particular: u f0 = h f0 − R T0
u 0f = h 0f − RT0
Enthalpy of Reaction
Standard Enthalpy of Reaction:
Enthalpy of formation does not indicate how much energy is
released as a result of a combustion process.
Standard enthalpy of reaction is the difference between
enthalpies of the products and reactants, both at the datum state
(25°C and 1 atm), when complete combustion occurs
Reactants and products at standard state, hence ht (T0 ) = h f0 + 0
⎛ 0⎞
∆h0 = ⎜⎜ ∑ ni h f − ∑ ni h f ⎟⎟ n fuel
0
⎝ products reactants ⎠
Previous lecture:
- Applied molar-based SFEE to steady-flow combustion
processes, when the chemistry is known
- Defined adiabatic flame temperature
- Quick look at 1st-Law for non-flow combustion
- Defined standard enthalpy of reaction ∆h0
This lecture:
- A bit more on ∆h0 and calorific values
- How to use ∆h0 in mass-based SFEE, especially for
complex fuels where chemical eqn cannot be written
- Quick look at 2nd-Law for combustion
- Greenhouse gas and pollutant emissions from combustion
Enthalpy of Reaction
Standard Enthalpy of Reaction
⎛ 0⎞
∆h0 = ⎜⎜ ∑ ni h f − ∑ ni h f ⎟⎟ n fuel
0
offers an alternative method of taking chemical energy into
account, without using enthalpies of formation
For simple fuels where we can write and balance the chemical
eqn, ∆h0 can be calculated using tabulated hf values
(but no real advantage in doing so)
For complex fuels where the chemical eqn cannot be written

and hf does not exist for the fuel, ∆h0 can be measured
Enthalpy of Formation/Reaction
Enthalpy of Formation: How much energy is set free/consumed
per kmol of respective product. Fully related to product species.
Standard enthalpy of reaction
How much energy will be released if complete combustion of the fuel
occurs.
Example: combustion of graphite (C)
stoichiometric combustion: C+O2 → CO2
enthalpy of formation of products: h0f ,CO =−393,520 kJ/kmol
2
standard enthalpy of reaction: ∆h 0 = h 0f ,CO2 − h 0f ,C − h 0f ,O2 = −393,520 kJ/kmol

fuel rich combustion: C + 0.75 O2 → 0.5 CO2 + 0.5 CO
enthalpy of formation of products: 0.5 ⋅ h 0f ,CO2 + 0.5 ⋅ h 0f ,CO = −252,025 kJ/kmol
standard enthalpy of reaction: ∆h 0 = −393,520 kJ/kmol
Enthalpy of Reaction & Calorific Value
The calorific value of a fuel is

the negative of the standard enthalpy of reaction
e.g. for carbon:
molar CV = - ∆h0 = 393520 kJ/kmol
More common to use mass-based CV =

− ∆h0 393520 kJ/kmol
− ∆h0 = = = 32793 kJ/kg
M 12 kg/kmol
Calorific values for several fuels are listed in Data Book Table E8
Why are there two different values for most fuels?
Calorific (or Heating) Values
Fuels containing Hydrogen water can be
CxHy + (x+0.25 y) O2 → xCO2 +0.5y H2O present in liquid or
gaseous phase
If H2O in products is in liquid phase, we need to use enthalpy
of formation of H2O(l) here
⎛ 0⎞
∆h0 = ⎜⎜ ∑ ni h f − ∑ ni h f ⎟⎟ n fuel
0
Net calorific value (Lower heating value):
NCV or LHV = -∆h0 (all H2O in gas phase)
Gross calorific value (Higher heating value):
GCV or HHV = -∆h0 (all H2O in liquid phase)
Water as Product
Note on product analysis
In some situations, H2O may not be allowed to condense (to minimize
corrosion). Therefore, products should be kept above their dew point.
Example: Methane/air combustion, 200% excess air.

nox = 6, n N 2 = 22.57, n p = 29.57
n H 2O p H 2O
= = 0.0676 Tsat(0.0663 bar) = 38°C
np pt
Tout < 38°C: pH 2O ,( g ) = psat (Tout ) ⇒ nH 2O ,( g ) ⇒ nH 2O ,(l )
Gas phase: use sensible enthalpy difference from table E7c, Data Book
Liquid phase: use tables for sub-cooled water or
subtract hfg from gas phase enthalpy at respective temperature.
Different Reaction Paths
Enthalpy Change of Combustion

2
T
A
1
hs
T0
reactants products
A: Q n F = ∆h = ∑n i [ ( )] ∑ n
n F h f0,i + hi (T ) − hi (T0 ) − i [ (
n F h f0,i + hi (T ) − hi (T0 ) )]

products

reactants

A
Different Reaction Paths
Enthalpy Change of Combustion

2
T
A
1
B hs
D
C
T0
reactants ∆h0 products
Path A = Path (B+C+D)
B+C+D: Q nF = ∆h = ∑n nF (hi (T0 ) − hi (T1 )) + ∆h0 + ∑ ni nF (hi (T2 ) − hi (T0 ) )

i N products

C
reactants

B D
First Law
SFEE using standard enthalpy of reaction

Alternative method to using SFEE with total enthalpies, provided
that fuel calorific value is known and combustion is complete :
Split the reaction, from state 1 (reactants) to state 2 (products),
into three hypothetical sub-processes, A, B & C:
A B C
reactants reactants products products
p1,T1 p0,T0 p0,T0 p2,T2
1 atm, 25°C
First Law
A and C involve pure substances only (no chemical reaction),

so only sensible enthalpy changes.
Combustion takes place in B, reactants and products at the
standard state.
SFEE can be written
Q − W = ∑ n (h0 − h1) + nfuel ∆h0fuel + ∑ n (h2 − h0 )

reactants products
A B C
First Law
Standard enthalpy of reaction or calorific value are usually given

in kJ/kg, as in Data Book Table E8
Hence more useful to write SFEE on a mass basis :
Q − W =
∑m
R
(
h D − hT
25 C reac
+ m )
F ∆h0,F + ∑ m
hT
prod
P
−h D(
25 C
)
A B C
(Gas/vapour species assumed ideal so no need to to say h25°C, 1 atm)

Some Definitions
Net Calorific Value:

NCV = − ∆h0 when product H2O is in gas phase
Gross Calorific Value:

GCV = − ∆h0 when product H2O is in liquid phase
Some Definitions
Combustion efficiency:
Q Q
ηcomb = or ηcomb =
fuel (− ∆h0 )
m fuel NCVfuel
m
for boilers, typically 80-90%
mi
Different definition for a NCVfuel − ∑ NCVi
gas turbine (don’t need to fuel
m
ηcomb,GT ≡
remember): NCVfuel
(no Q, aim is to increase typically 99%
enthalpy of working fluid) any CO & unburned
HC in products
Some Definitions
Power plant thermal efficiency:
W net
ηth =
fuel NCVfuel
m from combustor
Q
Wnet
= = ηcycle ηcomb
Q m fuel NCVfuel
into cycle working fluid
m fuel reciprocal of ηth ,

Specific fuel consumption: sfc =
W net omitting NCVfuel
Real Fuels, Second Law & Emissions of Combustion Processes
Dr. A. Kronenburg
Analysis Based on Mass
Application of 1st Law analysis to real fuels - example
Determine the heat transfer in a boiler for the combustion of 100 kg/s coal*
with 30% excess air, both at 25°C. Products leave the combustion chamber at
500°C. Heat losses are 2% of the net calorific value.
Q losses
coal, 25°C, 1atm
CO2, H2O, N2, O2, 500°C, 1atm
Combustion
Air, 25°C, 1atm

Q = ?
* given its composition, as % by mass of each chemical element

Example Problem
1. We need to know the composition of the coal, e.g. from
Table 5: Fuel composition of different fuels by mass
Content in mass % Wood Peat Coal Oil Natural gas
C 42.5 47.2 79.8 86.8 74.9
H 5.1 4.8 4.8 13.2 25.1
O 37.4 28.0 10.4 0 0
H2O 15 20 5.0 0 0
Total 100.0 100.0 100.0 100.0 100.0
NCV [kJ/kg] 13,500 16,300 30,900 42,720 50,020
GCV [kJ/kg] 15,000 17,850 32,050 45,600 55,500
Want to apply mass-based SFEE:
Q − W = ∑ m h
products
out − ∑ m h
reactant
in
Example Problem
2. Element mass balances
C-balance
All fuel-C is converted to CO2
Chemical equation: C + O2 → CO2 MC = 12 kg/kmol,

Mass balance: 12+ 32 = 44 MO2 = 32 kg/kmol,
Mass balance per kg fuel-C: 1+ 32 12 = 44 12 MCO2 = 44 kg/kmol
Mass flow rate per 100 kg/s fuel: m C = 79.8 kg/s

M CO2
⇒ m CO2 = m C = 292.4 kg/s
MC
M O2
⇒ m O2 ,C = m C = 212.8 kg/s
MC
Example Problem
2. Element mass balances (cont.)
H-balance
All fuel-H is converted to H2O
Chemical equation: 4 H + O2 → 2 H 2 O
MH = 1 kg/kmol,
Mass balance: 4 + 32 = 36 MO2 =32 kg/kmol,
Mass balance per kg fuel-H: 1 + 32 4 = 36 4 MH2O=18 kg/kmol
Mass flow rate per 100 kg m H , F = 4.8 kg/s

fuel: M O2
⇒ m O2 , H = m H , F = 38.2 kg/s
All fuel-H2O is vaporized 4M H
and heated, so add to H2O 2 M H 2O
from burning H2 ⇒ m H 2O = m H , F + m H 2O , F = 48.2 kg/s
4M H
Example Problem
2. Element mass balances (cont.)
O-balance
Stoichiometric oxygen requirements
m O2 , s = m O2 ,C + m O2 , H = 212.8 + 38.2 = 251 kg/s
Mass flow rate of O2 in stoichiometric air:

m O2 ,air , s = m O2 ,C + m O2 , H − m O , F = 251 − 10.4 = 240.6 kg/s
Mass flow rate of O2 in air with 30% excess air: Some O in fuel so
don’t need to
m O2 ,air = 1.3 ⋅ m O2 ,air , s = 1.3 ⋅ 240.6 = 312.8 kg/s supply it all in air
Mass flow rate of N2 76.8

m N 2 = ⋅ m O2 ,air = 1036 kg/s
23.2
Example Problem
3. SFEE
Q − Q losses − W = ∑ m (h 25D C ,1atm

)
− h25D C ,1atm + m coal ∆h0,coal + ∑ m (h 500D C ,1atm
− h25D C ,1atm )
reactants products
Heat losses:
Q losses = 2% ⋅ m coal ⋅ NCV = 0.02 ⋅ 100 ⋅ 30,900 = 61,800 kJ/s
Standard enthalpy of reaction, as tabulated:
∆h0,coal = − NCV = −30,900 kJ/kg

Example Problem
3. SFEE (cont.)
Sensible enthalpy change of reactants (in hypothetical process A)

H reactants = 0 kJ/s (since fuel and air both at 25°C)
Sensible enthalpy change of products (in hypothetical process C)

[ ( ) ( )] [ ( ) ( )]
H products = m CO2 hCO2 500D C,1atm − hCO2 25D C,1atm + m H 2O hH 2O 500D C,1atm − hH 2O 25D C,1atm
+ m O2 [h (500 C,1atm)− h (25 C,1atm)]+ m [h (500 C,1atm)− h (25 C,1atm)]
O2
D
O2
D
N2 N2
D
N2
D
= 746,521kJ/s
Heat transfer to water/steam

Q = Q losses + m coal ∆h0,coal + H prod
= 61,800 + 100 ⋅ (− 30,900) + 746,521 = −2281 MJ/s
Reminder of application of SFEE
Based on molar flows

Q − W =
n h 0
[ (
∑ f + h500D C ,1atm − h25D C ,1atm − )] ∑ n[h + (h f
0
25D C ,1atm
− h25D C ,1atm )]
products reactants
Use Data Book Tables E7b and E7c
Based on mass flows
Q − Q losses − W = ∑ m (h 25D C ,1atm

)
− h25D C ,1atm + m coal ∆h0,coal + ∑ m (h 500D C ,1atm
− h25D C ,1atm )
reactants products
Use Data Book Tables E7a and E8 or data given in question

Irreversibilities of Combustion Processes Optional now - will
be covered in 3M
2nd Law of Thermodynamics reminder
δ Q ⎧= 0, reversible process
Clausius inequality:
∫ ⎨
T ⎩< 0, irreversible process
Reversible process 1→2:

2
δQ
∫
1
T rev
= S 2 − S1
Revision
Second Law of Thermodynamics
p 2
Complete B
cycle:
A 1
v
2 1 2
δQ δQ δQ δQ
∫ ∫ ∫ ∫
Path A irreversible,
= + = + S1 − S 2 < 0
path B reversible: T 1
T irrev 2
T rev 1
T irrev
2
δQ
⇒ ∫
1
T irrev
< S 2 − S1
2
δQ
⇒ S 2 − S1 = ∫
1
T irrev
+ S gen with S gen > 0
Second Law Analysis of Combustion Process
Entropy change due to combustion
∆Ssys
Reactants Combustion Products

Sr Sp
State 1 State 2
Q
Surroundings
∆Ssurr
Second Law of Thermodynamics
2nd Law of Thermodynamics

1. Closed system without reaction
δQ
∫ ∑ ∑
Q
S gen + = m2 s2 − m1s1 , and ∆S surr =
T Tsurr
2. Closed system with chemical reaction

δQ
∫ ∑ ∑
Q
S gen + = mi si − mi si , and ∆S surr =
T products reactants
Tsurr
3. Adiabatic combustion process
S gen = ∑m s − ∑m s ≥ 0
products
i i
reactants
i i
Entropy Change
Entropy change of a reacting system
Problem: the entropy balance involves entropy of reactants and
products, NOT their changes.
Remember how it was done T2 p

s2 − s1 = c p ln − R ln 2
without chemical reaction: T1 p1
(for ideal gas)
Need to specify the absolute value of entropy,

New
i.e. need a common base
Entropy Change
Entropy is Associated with Order
Mixing of two non-reacting species A and B with same properties
pA=1b pB=1b ptot=1b, pA= pB= 0.5b

⎛ p ⎞
n A (s A,2 − s A,1 ) = n A ⎜ c p ln A,2 − R ln A, 2 ⎟
T
Single species:
⎜ TA,1 p A,1 ⎟⎠
⎝
⎛ p ⎞
n B (s B , 2 − s B ,1 ) = n B ⎜ c p ln B ,2 − R ln B ,2 ⎟
T
⎜ TB ,1 p B ,1 ⎟⎠
⎝
Entropy change of system: n A = n B = n, T1 = T2
ptotVtot
S 2 − S1 = −2nR ln 0.5 = 0.69 ⋅
T
Irreversibilities of Combustion
1st Law Reversible Process (neglect KE and PE)

δ qrev − δ wrev = dh
1st Law Irreversible Process
δ qirrev − δ wirrev = dh
2nd Law if inlet and exit states are fixed
δq
ds ≥
T
δ qrev = Tds
δ qirrev ≤ δ qrev
⇒ δ wirrev ≤ δ wrev
Irreversibilities
Measure of irreversibilities
δq
ds = + δ s gen
T
δ qrev = Tds
Tδ s gen = ∆(δ q ) = ∆(δ w)
δ qirrev = Tds − Tδ s gen
δq
∆s = ∫ + sgen
T
δq
Sgen? sgen = −∫ + ∆s
T
sgen = ∆ssurr + ∆s
Example Problem
Combustion of methane with oxygen

Q
CH4, 25°C, 1atm
CO2, H2O, 25°C, 1atm
Combustion
O2, 25°C, 1atm

1) Global reaction CH4 + 2O2→ CO2+2H2O, n CH4 = 1 kmol/s
2) Proportion of H2O in liquid and gaseous phase in products
nH 2O ( g ) psat @ 25D C
= = 0.032
ntotal ptotal
nH 2O ( g ) = 0.032(1 + nH 2O ( g ) ) ⇒ nH 2O ( g ) = 0.033 and nH 2O (l ) = 1.967
Example Problem
Heat Flow from 1st Law
Q − W = nCO2 hCO2 + n H 2O ( g ) hH 2O ( g ) + n H 2O ( l ) hH 2O ( l ) − nCH 4 hCH 4 − nO2 hO2

[ [ ]
= nCO2 h f0,CO2 + hCO2 (T2 ) − hCO2 (T0 ) + n H 2O ( g ) h f0, H 2O ( g ) + hH 2O ( g ) (T2 ) − hH 2O ( g ) (T0 ) ]
[h
+ n H 2O ( l ) +h 0
(T ) − h
f , H 2O ( l ) (T )]
H 2O ( l ) 2 H 2O ( l ) 0
− nCH 4 [h + h (T ) − h (T )]− n [h
0
f ,CH 4 CH 4 1 CH 4 0 O2
0
f ,O2 + hO2 (T1 ) − hO2 (T0 ) ]
= 1 ⋅ (− 393,520) + 0.033 ⋅ (− 241,820) + 1.967 ⋅ (− 285,830) − 1 ⋅ (− 74,850) − 2 ⋅ 0 kJ/s
= -888,878 kJ/s
Absolute Entropy
Relative molar entropy change (single component, perfect gas):

T2 p
s2 − s1 = c p ln − Ru ln 2
T1 p1
Absolute Entropy
Definition (Çengel 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 , p0 ) are given in tables for the
reference pressure p0 = 1atm.
p
Absolute entropy for ideal gas: s (T , p ) = s (T , p0 ) − Ru ln
0
p0
Example Problem
Entropy generation
si0 (298 K , p0 ) -Ru ln
pi
si0from tables
p0
S gen = ∆ S sys + ∆ S surr
= n CO 2 sCO 2 (298 K , (1 / 1.033 ) ) + n H 2O ( g ) s H 2O ( g ) (298 K , ( 0.033 / 1.033 ) ) + n H 2O ( l ) s H 2O ( l ) (298 K ,1)
− n CH 4 sCH 4 (298 K ,1) − n O2 sO2 (298 K ,1) + Q Tsurr
= 1 ⋅ (213.80 − 8.314 ⋅ ln 0.968) + 0.033 ⋅ (188.83 − 8.314 ⋅ ln 0.032 ) + 1.967 ⋅ 69.92
− (1 ⋅ 186.16 + 2 ⋅ 205.04 ) +
888,878
298.15
= 2743.8 kJ/K ⋅ s
Work losses due to irreversibilities
∆W = TS gen = 298.15 ⋅ 2743.8 kJ/s = 818,060 kJ/s

Remember this from Sec. 5 (slide 24)?
Another example for irreversibility I

(which will be better appreciated after Sec. 6, Combustion)
n fuel adiabatic combustor

n prod (best treated on a molar basis) :
n O2, nN2
I = T0 Sgen
n is molar flow rate,
sm is absolute = T0 [ Σ products (n s m)
molar entropy - n fuel sfuel m
(Sec. 6) - n O2 sO2 m - n N2 sN2 m ]
Remember this from Sec. 5 (slide 25)?
400 Example of irreversibility calculation:

Combustion irreversibility I (MJ/kmol CH4)
gas turbine combustor, methane fuel

Net calorific value = 802 MJ/kmol,
300 so I is a substantial fraction of this
200
Combustor inlet conditions: higher T3

100
T 2 = 700K, P 2 = 20 atm
lower I
RIC 2006
0
1000 1200 1400 1600 1800 2000
Combustor exit temperature T 3 (K)
Adiabatic Combustion
CH4, 25°C, 1atm
CO2, H2O, ?? °C, 1atm
Combustion
O2, 25°C, 1atm
Exit temperature from 1st Law

Q − W = nCO2 hCO2 + n H 2O hH 2O − nCH 4 hCH 4 − nO2 hO2
[ ] [
= nCO2 h f0,CO2 + hCO2 (T2 ) − hCO2 (T0 ) + n H 2O ( g ) h f0, H 2O ( g ) + hH 2O ( g ) (T2 ) − hH 2O ( g ) (T0 ) ]
− nCH 4 [h 0
f ,CH 4 ] [
+ hCH 4 (T1 ) − hCH 4 (T0 ) − nO2 h f0,O2 + hO2 (T1 ) − hO2 (T0 ) ]
( ) ( )
0 = 1 ⋅ − 393,520 + hCO2 (T2 ) + 2 ⋅ − 241,820 + hH 2O (T2 ) − 1 ⋅ (− 74,850 ) − 2 ⋅ 0 kJ/s
802 ,310 kJ/s = 1 ⋅ hCO2 (T2 ) + 2 ⋅ hH 2O (T2 )
T2 = 4150 K = 3852 D C
Entropy generation
0
S gen = ∆S sys + ∆Ssurr
= nCO2 sCO2 (4150 K,0.33) + n H 2O s H 2O (4150 K,0.67 )
− nCH 4 sCH 4 (298 K,1) − nO2 sO2 (298 K,1)
= (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
Work losses due to irreversibilities

∆ W = T S gen = 298 .15 ⋅ 385 .7 kJ/s = 114 ,989 kJ/s
2nd Law (or Exergy) Losses
Losses due to combustion process
Products, CO2,,H2O
Reactants, CH4,O2 3852°C,
25°C, “Theoretical”
“Theoretical” Combustion reversible work
reversible work 703,071 kJ/s
818,060 kJ/s
Losses for adiabatic combustion are 114,989 kJ/s, i.e. the reversible work that
can be done by the product gases is reduced by this amount.
Losses due to combustion in the order of 14% do not seem very large,
however, they increase dramatically for methane combustion with air.
→ Tutorial problem
Emissions
Greenhouse Gases and Pollutants
Greenhouse Gases Air Quality Strategy Pollutants
•carbon dioxide, CO2 •particulate matter, PM10
•methane, CH4 •black smoke
•nitrous oxide, N2O •carbon monoxide, CO
•hydrofluorocarbons (HFC) •benzene
•1,3-butadiene
Acidifying Pollutants & Ozone
Precursors Base Cations
•nitrogen oxides, NOx •calcium, Ca
•sulphur dioxide, SO2 •magnesium, Mg
•ammonia, NH3 •sodium, Na
•hydrogen chloride, HCl •potassium, K
•hydrogen fluoride, HF
Heavy Metals
Persistent Organic Pollutants •arsenic, As
•polyaromatic hydrocarbons (PAH) •chromium, Cr
•dioxins and furans (PCDD/F) •copper, Cu
•polychlorinated biphenyls (PCB) •lead, Pb
•pesticides
CO2 Emissions
Major Greenhouse Gas: CO2
Kyoto (1997) treaty committed the UK to reducing its greenhouse gas emissions
to 12.5% below their 1990 level by 2008-2012. National commitment was to
reduce the emissions by 20%.
Now realised that much larger reductions are needed: 60-80% by ~2050
200
180
160
140
CO 2 emissions (Mt)
120
100
80
60
40
20
0
1970 1973 1976 1979 1982 1985 1988 1991 1994 1997 2000 2003 From NAEI report
Public Pow er Domestic Combustion Industrial Combustion
Road Transport Other Fuel Combustion Non-Fuel Combustion
2005
CO2 Emissions
Reasons for CO2 decrease A rise

90
recently! –
more coal
Fuel Input (Million tonnes of oil equivalent)
80
burned
70
because
60 of gas
50 price and
40
supply
problems
30
20
10
0 From NAEI
1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 report 2005
Coal Oil Gas Nuclear Other
Pollutants
Criteria Pollutants: NOx, SOx, soot
European Commision emission standards for large Complex new
combustion plants (1988) regulations in
force from
2008:
emission limit
values (mass
concentration
in flue gas),
dependent on
fuel and
energy input
rate
Table from Electricity Association, 2000
Pollutants
Legislation for Light-Duty Vehicle (cars, small vans) Emissions
Development of emission limits for

petrol engines
The corresponding absolute values for

the year 2000:
Petrol engines: 2,3 g CO/km;
0,2 g HC/km; 0,15 g NOx/km.
Diesel engines: 0,64 g CO/km,
0,56 g HC/km NOx,
0,05 g particulates /km.
VDI Bericht 2000

Pollutants
Reduction in NOx
3.5
3.0
2.5
NO x emissions (Mt)
2.0
1.5
1.0
0.5
0.0
1970 1973 1976 1979 1982 1985 1988 1991 1994 1997 2000 2003
Public Pow er Industry
Domestic and Commercial Road Transport From NAEI
Other Transport and Mobile Other report 2005
Pollutants
Major NOx
Sources
From UK National
Atmospheric
Emissions Inventory
2005
Pollutants
Reduction in SOx
7
5
SO 2 emissions (Mt)
0
1970 1973 1976 1979 1982 1985 1988 1991 1994 1997 2000 2003
From NAEI
Public Pow er Industrial Combustion Domestic/Commercial Road Transport Other
report 2005
Pollutants
Reduction Through New Technologies
Table from
Electricity
Association, 2000
Pollutants
Reduction in PM10 (particulate material of size less than 10 µm)
500
450
400
350
PM 10 emissions (kt)
300
250
200
150
100
50
0
1970 1973 1976 1979 1982 1985 1988 1991 1994 1997 2000 2003 From NAEI
Public Pow er Comm/Resi/Instit Comb Industrial Combustion report 2005
Production Processes Road Transport Other
Engine Design
Challenges
Flue gas treatment, different fuel and compromise on efficiency not always
acceptable ⇒ burner design of increased importance
Ys,YNO T(K)
soot
NO
T
rich AFRst lean lean mixture combustion range AFR

Engine Design
Low NOx Gas Turbine Combustor
Staged combustion, 3 stages:

Burn fuel rich for stability, then quick mixing, fuel-lean to burn UHC,
avoiding highest temperatures, then in third stage dilute with air to reduce
temperature for turbine blades
Summary
After these lectures on combustion you should be able to

1. Write and balance the chemical equation for stoichiometric
and non-stoichiometric combustion
2. Find the absolute enthalpy of each species as a function of
temperature
3. Apply SFEE to combustion processes with known chemistry
4. Apply SFEE to combustion processes of real fuels
5. Discuss major pollution issues due to burning real fuels
6. Optional: 2nd law analysis of combustion processes
(will be covered in 3M Thermodynamics & Energy)

Thermodynamics of Combustion: (With A Few Modifications by R.I.C.)

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Thermodynamics of Combustion: (With A Few Modifications by R.I.C.)

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2M Th Section 6 2007-08

Example: Simple steam power cycle

Rolls Royce Industrial Trent (an ‘aeroderivative’ engine)

Combustor in Trent aero-engine

Reciprocating Internal Combustion Engine

1. Need fuel and oxidizer, then fuel + oxidiser products

4. An exothermic reaction will proceed

Oxidiser (or oxidant):

Stoichiometric combustion occurs when the minimum

The only products will be CO2, H2O and N2 .

The N2 does not take part in the reaction

Excess fuel (fuel rich mixture):

Excess air (fuel lean, or weak, mixture):

Combustion of hydrocarbon fuel with oxygen can be represented as:

Combustion of hydrocarbon fuel with air:

Objective is to know the composition of the products but this will be

Combustion of hydrocarbon fuel with air:

nF CxHy + nox (O2 + 79/21N2) →

nCO2 CO2 + nH2O H2O + nN2 N2 + nO2 O2 + nCO CO + ...

Normal to write eqn for 1 kmol of fuel, i.e. nF = 1

Three common ways of expressing this proportion

Specification of Reactants (cont.)

Three common ways of expressing proportions of fuel and air

2. theoretical air: e.g. 150% theoretical air means

l i , j = number of atoms of element j in species i ,

1 additional equation for each element j, e.g. 4 equations for hydrocarbon

Combustion of Ethane (C2H6) with 20% excess air

1. Solve for stoichiometric combustion: CO2, H2O, N2 only products

2. Chemical equation for stoichiometric combustion

C: nCO2 ⋅1 + nH 2O ⋅ 0 + nN 2 , s ⋅ 0 = nF ⋅ 2 + nox , s ⋅ 0 ⇒ nCO2 = 2

O: nCO2 ⋅ 2 + nH 2O ⋅1 + nN 2 , s ⋅ 0 = nF ⋅ 0 + nox , s ⋅ 2 ⇒ nox , s = 3.5

4. 20% excess air: nox = 1.2 ⋅ nox , s = 4.2

and nN 2 = 1.2 ⋅ nN 2 , s = 15.8

In practice, for hand calculations in 2M, just do it by inspection.

Carbon balance : 1 x 2 = nCO2 x 1, so nCO2 = 2

1 C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2

Hydrogen balance : 1 x 6 = nH2O x 2, so nH2O = 3

1 C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2

Oxygen balance : nox,s x 2 = nCO2 x 2 + nH2O x 1

C2H6 + nox,s (O2+79/21N2) → nCO2 CO2 + nH2O H2O + nN2,s N2

Nitrogen balance : nox,s x 79/21 x 2 = nN2,s x 2

N.B. Recommended order for doing element balances :

4. The elements balances above were for

nN2 = 1.20 x nN2,s = 1.20 x 13.167 = 15.80

6. Air to Fuel ratio: AFR ≡ ma/mF MC2H6 from

AFR = 576.8 / 30 = 19.22

You should be able to balance chemical equations, when

C2 H 6 + 4.2 ⋅ (O2 + 79 21 N 2 ) → 2CO2 + 3H 2O + 0.7O2 + 15.8 N 2

This Lecture: Energies in Reactive Systems with Multiple Species

Neglecting kinetic, potential and nuclear energies the molecules of a system

Energies in Reactive Systems with Multiple Species

Neglecting kinetic, potential and nuclear energies the molecules of a

Chemical Energy: internal chemical energy associated with

cp can be approximated by a polynomial fit

Datum state for enthalpies in Table E7c is 25°C. Why?

Energy required to break 1) single bond H-H = 436 MJ/kmol

Energy balance for the production of 1 kmol H2O

So, 1 kmol of H2O has approx. 241 MJ less energy

H2, 25°, 1atm n H 2 = 1 kmol/s

Products must be cooled and Q can be measured.

Q n H 2O = -241,820 kJ/kmol of H2O is a measure of the

Latent enthalpy (during phase changes) can be allowed for

H2, 25°, 1atm n H 2 = 1 kmol/s

Products must be cooled and Q can be measured.

Q n H 2O = -241,820 kJ/kmol of H2O is a measure of the

Q − W = ∑ n (h0 − h1) + nfuel ∆h0fuel + ∑ n (h2 − h0 )

m fuel reciprocal of ηth ,

Mass flow rate per 100 kg/s fuel: m C = 79.8 kg/s

Mass flow rate per 100 kg m H , F = 4.8 kg/s

Q − Q losses − W = ∑ m (h 25D C ,1atm

Q − Q losses − W = ∑ m (h 25D C ,1atm