Content of Lecture

1. Phenomenology of Combustion
2. Thermodynamic Fundamentals
3. Chemical Reaction Kinetics
4. Ignition and Ignition Limits
5. Laminar Flame Theory
6. Turbulent Combustion
7. Pollutants of Combustion
8. Combustion of Liquid and Solid Fuels
9. Numerical Simulation
10. Measurement Techniques of Combustion Processes
11. Applied Aspects of Turbulent Combustion
12. Technical Burner Systems
13. Internal Combustion Engines

2/1

Content
Content

2. Thermodynamic Fundamentals
• Concentrations
• Balances

2.1 Mass Balance

• Reaction equation
• Air/Fuel Ratio

2.2 Thermodynamical Quantities

• Heat release
• Lower and Higher Heating Value
• Flue gas composition
• Adiabatic flame temperature
• Efficiency
• Efficient Combustion

2/2

1
 Thermodynamic Fundamentals

2.0.1. Concentrations
Definitions
Mass m, mi [kg] (Component i)
m
Mass fraction Yi  i [-] (also  i , wi )
m
Number of moles ni [mol] 1 mol = 6.023 • 1023 Atoms, Molecules
n
Mole fraction Xi  i [-] (also  i , xi )
n
m
Molecular weight Mi  i [kg/mol] (e.g. MH = 1 g / mol, MO2 = 32 g / mol)
ni
Mean molecular weight M   X i  M i [kg/mol]
i

Mi
Yi  X i  (2.1)
M
m
Mass density (density)  [kg/m³]
V
n
Molar density ci  i [mol/m³] also "Concentration", "[H2O]"
V 2/3

Thermodynamic Fundamentals

Concentrations
Definitions
Ideal gas law: (Real gas law for high pressure, low temperature)
p V  n Rm T (2.2) p [Pa=N/m²]
1 bar = 105 Pa = 1000 hPa
Rm T
Partial pressure pi  ni Rm = 8.314 J/(mol K)
V
pi
ci  (2.3)
RmT ci M i
Yi 
R T 
X i  ci   m  (2.4)
 p 
For gases
Mole fraction Xi ~ Volume fraction
 Common for:
Vol-% = Mol-% Xi [%] • Atmosp. Gas flames, Chemistry, Lab
Mass-% Yi [%] • Liquid and solid fuels,
Gas turbine, Process with change of pressure
Combustion calculations: often related to amount of fuel:
Yi Xi
Mass ratio i  Molar ratio yi 
YB XB 2/4

2
 Thermodynamic Fundamentals

2.0.2. Balances
Procedure
• Definition of system boundary
• Balance of temporal change of quantity F due to
• Inflow / Outflow (Flow rates F )
• Production / Consumption (Sink- / Source term S )

System volume
V = A •Dz Balance of:
• Total mass
Inflow S Outflow • Mass of Species or Atoms
F1•A (Source/Sink) F2•A • Energy
Area A • Momentum
Dz

2/5

Mass Balance

2.1.1. Reaction equations

Material conversion in combustion is described by reaction equations
--> Regrouping of chemical atoms --> Atoms are conserved (Mass conservation)
Example for reaction equation:
H2 + 1/2 O2 --> H2O stoichiometric combustion
2 H2 + 1/2 O2 --> H2O + H2 rich (fuel rich) = more fuel than needed
H2 + 1 O2 --> H2O + 1/2 O2 lean (fuel lean) = more air than needed

nN 2
Air: 21 % O2  3,76
nO 2
79 % N2 (including inert gases) (2.5)
nL  4,76  nO 2

Example:
H2 + 1/2 (O2 + 3,76 N2) --> H2O + 1/2 • 3,76 N2

nL = 1/2 4,76 mol Air = 2,38 mol

nB = 1 mol 2/6

3
 Mass Balance

2.1.2. Air / Fuel Ratio

Molar Air Ratio nL
' Molare Luftmenge' L : (2.6)
nB
Minimum Air n
' Mindest - Luftmenge' Lmin : L,min for stoich. Combustion (2.7)
nB
Note: The term 'Mindest'-Luftmenge (minimum air) comes from the fact, that technical
burner generally operate with excess air nL >nL,min

nL L
' Relative air/fuel ratio'  :  (2.8)
nL,min Lmin

(also called 'air ratio', common in germany: 'Luftzahl' or 'Luftverhältnis', measure for
excess air)
International:
1
' Equivalenc e Ratio' F (2.9)

(also 'Stoichiometric ratio', 'Stoichiometry')
2/7

Mass Balance

Air / Fuel Ratio

Stoich. Combustion: F=1 =1
Rich Combustion: F>1 <1
Lean Combustion: F<1 >1

nB 1
' Brennstoffanteil' X B,(st) :  (2.10)
Fuel mole fraction nB  nL,(min) 1  L(min)

Also 'specific' = mass related quantities common (liquid or solid fuels).

(Sometimes dimension of air is given in norm cubic meters (standard cubic meters at 0°C)
and dimension of fuel is given in kg. In praxis watch for the given dimensions!).

mL m mL l mB 1
l : , l min  L,min ,    , YB,(st)   (2.11)
mB mB mL,min l min mB  mL,(min) 1  l (min)

2/8

4
 Mass Balance

General Reaction Equation

General form of global reaction equation for hydrocarbon combustion (for   1)

C xHy    a O2  3,76 N2   x CO2 

y
H2O  (  1) a O2  3,76  a N2 (2.12a)
2
y 1
ax ;  (2.12b)
4 F

for the amount of air L = nL / nB follows:

Lmin  4,76 a
L    4,76 a (2.13)

2/9

Mass Balance

Table: Stoichiometric Air and Fuel Fraction

Fuel Stoichiometric Air ("Minimum Air") Stoichiometric fuel fraction

Brennstoff Mindestluftmenge Stöch. Brennstoffanteil
a Lmin [m3N/m3N] lmin [m3N/kg] lmin [kg/kg] XB,st [Vol%] YB,st [Massen%]
H2 0,5 2,38 26,44 34,06 29,59 2,85
CH4 2 9,52 13,29 17,12 9,51 5,52
C2H4 3 14,28 11,40 14,69 6,54 6,38
C3H8 5 23,80 12,09 15,57 4,03 6,03
C7H16 11 52,36 11,70 15,07 1,87 6,22
C8H18 12,5 59,50 11,67 15,03 1,65 6,24
Benzin 11,5
Diesel 11,2
Steinkohle ca. 8

2/10

5
 Thermodynamic Quantities

Energetic and exergetic balances

What can be determined with energetic and exergetic balances ?

2.2.1 Heat release
2.2.2 Heating values (LHV, HHV)
2.2.3 Equilibrium composition of flue gas
2.2.4 Adiabatic flame temperature
2.2.5 Efficiencies
2.2.6 Efficient combustion design

What else is necessary ?

Reaction rates
Reaction paths
Molecular and turbulent transport
Models to couple chemistry and turbulent flow

2/11

Thermodynamic Quantities

2.2.1. Heat Release

Energy balance:
1. Law of Thermodynamics (Ekin, Epot is neglected in the following):

Change of internal energy = In-/Outflow of heat + In-/outflow of work

U2 - U1 = Q12 + W12 or H2 - H1 = Q12 + Wt,12 (2.14)

Depending on the system boundaries:

Internal energy U or Enthalpy H

("closed system") ("open system")

In combustion calculations enthalpy is used frequently, since combustion often takes place in
thermodynamically "open" systems for given pressure. (H = U + p V)

2/12

6
 Thermodynamic Quantities

Heat Release
for each component i molar enthalpy is described by:
T
(2.15)
hi (T , p)  h f q ,i (q ) 
25C
c p ,i (T )  dT

The first term is the 'Standard formation enthalpy', to be measured at the formation of this
component in a formation reaction at 'standard conditions' (q = 25°C, 1 bar). Can be obtained
from tables.

The second term describes the temperature dependency. Often average values of specific
heat are used from tables.

(2.16)
(T )  dT  c p  t 1  t 2  t1 
t2

c
t2
p
t1

2/13

Thermodynamic Quantities

Heat Release
Molecule hfq
Table: Standard Formation
Enthalpies At 25°C, 1bar [ kJ / mol ]
O2 0
N2 0
H2 0
H2O (g) - 241,8
H2O (liq.) - 285,8
CO -110,5
CO2 - 393,5
CH4 - 74,8
C2H2 (g) 226,7
C2H4 (g) 52,3
C2H6 (g) - 84,7
C3H8 (g) - 103,9
C4H10 (g) - 124,7
C6H6 (liq) 49,0
C7H16 (liq) - 224,4
C8H18 (liq) - 250,0

2/14

7
 Thermodynamic Quantities

Heat Release
Reactor with stationary combustion

Products P
Reactants R Reaction chamber

State 1 Q 12 State 2

From energy balance Eq. (2.14) follows for the heat release per unit time
(2.17)
Q  H  H
12 2 1

(Note, heat flow is defined with negative sign, since leaving the system "reaction chamber".)

For mixtures of ideal gases enthalpy is the sum of the single component enthalpies:


H  n h (T , p ), H  n h (T , p )
1
R
R R 2 P
P P
(2.18)

With eq. (2.15), (2.16) and (2.17) the heat release can be calculated.

2/15

Thermodynamic Quantities

Heat Release
Together the sequence of summation can be changed to:

  
TP TR

Q 12  H 2 - H 1    n P  h f q ,P   n R  h f q ,R     n P  c p,P (T )dT   n R  c p,R (T )dT  (2.19)
 P 
  P 
R 25C R 25C 

The first term of r.h.s. describes the chemical change of enthalpy at standard conditions (25°C),
the second term describes the temperature dependency of initial and final components.

Example 1: Calculate the heat release, if reactants and products have 25°C (tR = tP = 25°C) ?
Now only the first term of eq. (2.19) must be calculated. It follows with tabulated standard
formation enthalpies (next page)
Example: H2 + 1/2 O2 --> H2O (gaseous)
The standard formation enthalpies of stable species H2 and O2 are zero, thus follows per mole
of fuel : Q12 = -241,8 kJ/mol.
For a fuel flow of 1 mol/s follows the heat release rate is 241,8 kW.

2/16

8
 Thermodynamic Quantities

Heat Release
Example 2: Calculate the heat release, if the temperature of the products is tP =
2200°C (tR = 25°C) ?

Here some of the released chemical energy will remain as sensible energy in the
hot products, thus the heat release is lower.

Calculation of the second term of eq. (2.19) (for example with cp from table in
"Baehr, Thermodynamik", Appendix) gives Q12 = (-242 + 97) kJ/mol fuel = -145
kJ/mol fuel.

For a fuel flow of 1 mol/s the heat release rate is 145 kJ/s = 145 kW.

2/17

Thermodynamic Quantities

2.2.2. Heating Value

Note: for technical furnaces as much heat as possible should be utilized,
therefore the temperature of the exhaust should be as low as possible just above
the dew point (condensation of H2O).

Hence, in typical technical combustion systems the temperature dependent

second term in eq. (2.21) is relatively low. Often it can be neglected compared to
the first term.

The first term is a pure property of the fuel, being independent of the form of the
oxidant, either stoichiometric air, excess air ( > 1) or pure O2 ) (Reason: the
standard formation enthalpy of N2 is zero).

This simplifies the calculation of heat release significantly, and thus only fuel data
is enough

Introduction of HEATING VALUE of a fuel:

2/18

9
 Thermodynamic Quantities

Heating Value

Heating value (molar)

Hu  Q 12 / n B
(2.20)
Heating value (mass)
Hu  Q 12 / m
B

The heating value is the released heat of combustion per unit mol or
mass of fuel, if reactants and products are at standard temperatures
(25°C).

(Note: No different symbol for molar and mass based heating value is used.
Differentiate by the given dimension.)
The heat release per mol fuel is then:

 Q12  n TR
n P
TP

q12B   Hu    R c (T )dT   c (T )dT 
n B  R n p,R
n B
p,P  (2.21)
 B 25 C P 25 C 
2/19

Thermodynamic Quantities

Heating Value
H2O in the products can be gas or liquid (after condensation). Then
additional heat is released from condensation enthalpy. Therefore we
differentiate:
'Higher Heating Value' Ho if H2O liquid
Ho > Hu
'Lower Heating Value' Hu if H2O gaseous

Other names are:

'Higher Heating Value' HHV, 'higher calorific value', 'gross calorific value',
german 'Brennwert', or 'oberer Heizwert' Ho

'Lower Heating Value' LHV, 'lower calorific value', 'net calorific value',
german 'Heizwert', or 'unterer Heizwert' Hu ,

2/20

10
 Thermodynamic Quantities

Heating Value

Table: Heizwert and Brennwerte (Examples)

Fuel mol. mol. spez. spez.
Heizwert Brennwert Heizwert Brennwert
Hu Ho Hu Ho
[kJ/mol] [kJ/mol] [MJ/kg] [MJ/kg]
H2 241,8 285,8 119,9 141,8
CH4 802,3 890,3 50,0 55,5
C3H8 2044 2220 46,4 50,3
C8H18, fl. 5074 5471 44,4 47,9
Coal ca. 30 ca. 31
Heizöl EL 42,9 45,8
Waste ca. 15

Memorize: Typical Fuels (CxHy) release around 45 MJ/kg

2/21

Thermodynamic Quantities

Heating Value
Calorific value method
Brennwert-Technology
with 108 % efficiency !
Brennwert-Kessel (boiler)
Is that possible ???

• Brennwert > Heizwert

• Traditional: Exhaust temperature > dew point (typ. 70°C), to avoid condensation
in chimney (from corrosion, especially from sulfuric acid). -> Heizwert.
• Today: 'Brennwert-Kessel' with exhaust temperature < dew point -> Brennwert.
(only for fuels without sulfur -> natural gas)
• Historically (in Germany) the 'Efficiency of the boiler' ('Kesselwirkungsgrad')
hk is based on the Heizwert Hu (hk typ. 0,86 - 0,95).
• --> Thus for Brennwert-Kessel hk can be > 1 !!!

2/22

11
 Thermodynamic Quantities

2.2.3. Equilibrium-Composition of Flue Gas

• For most combustion reactions the 1,0E+00

thermodynamic equilibrium is far on CO2

the product side. 1,0E-01

1,0E-02

Molenbruch Xi
• At high temperatures a significant 1,0E-03
CO
NO
amount of intermediate products can 1,0E-04
exist in the thermodynamic
equilibrium (CO, OH, ... ). 1,0E-05

1,0E-06

• Calculation of the equilibrium 1,0E-07

concentration is possible from the 1200 1800 2400

minimum of Gibbs free enthalpy. T [K]

Methan/Air, =1, 1 bar
(Result of the 2. law of
thermodynamics. Details see
textbooks).
2/23

Thermodynamic Quantities

2.2.4. Adiabatic Flame Temperature

Adiabatic flame temperature := theoretically achievable maximum
combustion temperature

• Adiabatic flame temperature: Reaction without heat leaving or entering the

reactor ('adiabatic'), i.e. qB12 = 0 in eq. (2.21).
• For calculation, solve eq. (2.21) for Tad = TP .

• The flame temperature is an important quantity for processes in flames

(--> Reaction kinetics, pollutant formation, material stress).

• In real flames the maximum flame temperature is below the adiabatic flame
temperature, since heat is lost by radiation or due to soot formation.

• Note: Tad depends on the thermodynamic equilibrium composition of the

products. Since this depends by itself on the temperature Tad both has to be
calculated iteratively for detailed calculations.

2/24

12
 Thermodynamic Quantities

Adiabatic Flame temperature

Adiabatic flame temperature depends on air/fuel ratio

Tad Tad (for =1, to=25°C, 1 bar):

H2-Air 2380 K
H2-O2 3083 K
CH4-Air 2226 K
C2H2-Air 2539 K
C2H2-O2 3069 K
C3H8-Air 2267 K
1 2
C8H18-Air 2275 K
Air/Fuel Ratio 

• Tad increases for preheated air, or for O2 instead of air.

• Tad decreases, if cooled exhaust gas is mixed with reactants
(Exhaust gas recirculation EGR).
2/25

Thermodynamic Quantities

2.2.5. Efficiencies
Firing Efficiency (Feuerungstechnischer Wirkungsgrad)
Defined, if use of heat is the primary aim:
B
q12 Available heat (2.22)
hF  
Hu Lower Heating Value

being traditionally based on Lower Heating Value (in Germany). Also for
Brennwert-Technology, then hF can be larger than 100%).

Exhaust Loss (Abgasverlust)

The exhaust loss (Abgasverlust) q A (in %) is the part of the combustion energy
leaving the furnace with the heated exhaust. It can be related to the firing
efficiency (feuerungstechnischer Wirkungsgrad) assuming no further heat loss:

hF  100%  q A (2.23)

In germany the maximum exhaust loss is reglemented e.g. for heating boilers.
2/26

13
 Thermodynamic Quantities

Efficiencies
Note on thermal efficiency
if technical work is desired output.

• Maximum efficiency of a heat engine (Wärme-

Kraft Maschine) is described by the Carnot cycle:
P Tin  Tout T1
hC    (2.25)
Q in Tin Combustion

Tin = TComb.
Thermal efficiency increases, if the
combustion temperature TComb increases. WKM P

• This was one of the most important guiding rules Tout

in the past for burner development !
• Today NOx formation is of importance: Then
reduction of combustion temperature is needed !
2/27

Thermodynamic Quantities

Efficiencies
Exergetic Efficiency
Independent of the exhaust losses combustion processes are related with
significant irreversibility's which can be analyzed with the concept of
Exergetic Efficiency (Exergy: part of energy which can be transformed fully into
usable energy).

The energy of the fuel is nearly fully usable*--> EB (= exergy of fuel).

With the loss of exergy EV follows the exergetic efficiency

E B  EV E
hE   1- V (2.26)
EB EB
(hE can be 1; other than hC !)

Minimization of exergy losses determines the best achievable efficiency of

combustion control.

* Baehr Thermodynamik or Leipertz Engineering Thermodynamics

2/28

14
 Thermodynamic Quantities

2.2.6. Efficient Combustion

Efficient Combustion can be reached, if exergy losses are as small as possible.
Exergy losses can be deduced from the balance of entropy (Entropy production).
 B , TB
m Mass balance:
 V , Tad
m
Adiabatic m V m
 L , TL
m Process  m V  1  L,min  1    lmin

m B m B

Loss of exergy (based on fuel mass, calculated from increase of entropy):

eV  Tu Dsirr  Tu sab  s zu 
eV  Tu m  sL (TL , pL )
 v  sv (Tad , pV )  sB (TB , pB )    l min (2.27)

--> Process is more efficient, if air is preheated and if air/fuel ratio is near one ( = 1).

Example: Exergy loss of combustion of 1 kmol CO with air at  = 1 (tB=tL=25°C; tU =25°C,

pu=1bar) ?
With tabulated data ... follows:
m V  sV  838,4 kJ/(kmol B)K; sB  197,4 kJ/(kmol B)K;   lmin
 sL  473 kJ/(kmol B)K
--> ev = 50 MJ/kmol B
(molar Exergy of CO is 275,2 MJ/kmol ---> Exergy loss about 18,2% !)
2/29

Summary

What can be determined with energetic and exergetic balances ?

2.2.1 Heat release
2.2.2 Heating values (LHV, HHV)
2.2.3 Equilibrium composition of flue gas
2.2.4 Adiabatic flame temperature
2.2.5 Efficiencies
2.2.6 Efficient combustion design

What else is necessary ?

Reaction rates
Reaction paths
Molecular and turbulent transport
Models to couple chemistry and turbulent flow

2/30

15