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Chapter 2 Basic Combustion Chemistry

Update: 2016/2/19

(2.1). Combustion Reaction

(2.1.1). Complete reaction of hydrocarbon fuel

The most common fuel that is used for power generation currently is a
chemical compound that contains carbon, hydrogen, and oxygen only,
and is called the hydrocarbon fuel.

The general expression of hydrocarbon fuel is CnHmOy.

Fuel is burned with sufficient amount of air such that all the carbon in the
fuel oxides to carbon dioxide, and all the hydrogen in the fuel oxides to
water. Besides, neither fuel nor oxygen remains.

Composition of air:
N2: 78.08%
O2: 20.95%
Argon: 0.93%
CO2: 0.03%
Others: 0.01%
Water vapor: variable
Average molecular weight: 28.97 kg/kmole

For simplicity, air is considered as a mixture that contains 79% N2 and


21% O2 only. Other components are neglected.

0.21O2 + 0.79N2 = 0.21(O2 + 3.76N2)

It is noted that the average molecular weight of the simplified air is 28.84
kg/kmole. However, the actual value of 28.97 kg/kmole is still used in
the calculation of combustion for accuracy.

The combustion formulas of several fuels with air for industry usage are
as following.

Methane:
CH4 + 2(O2 + 3.76N2) CO2 + 2H2O + 7.52N2

CombustionEngineeringMEDeptNCHU 1
Propane:
C3H8 + 5(O2 + 3.76N2) 3CO2 + 4H2O + 18.8N2

Benzene:
C6H6 + 7.5(O2 + 3.76N2) 6CO2 + 3H2O + 28.2N2

Coal:
C + O2 + 3.76N2 CO2 + 3.76N2

Hydrogen:
H2 + 0.5(O2 + 3.76N2) H2O + 1.88N2

In general, we have

CnHm + (n+m/4)(O2 + 3.76N2) nCO2 + m/2H2O + 3.76(n+m/4)N2

If oxygen is contained in the fuel, the amount of air required to oxide the
fuel is reduced due to the presence of oxygen in the air fuel mixture.

Methanol:
CH3OH + 1.5(O2 + 3.76N2) CO2 + 2H2O + 5.64N2

Ethanol:
C2H5OH + 3(O2 + 3.76N2) 2CO2 + 3H2O + 11.28N2

Dimethyl Ether( DME):


CH3OCH3+ 3(O2 + 3.76N2) 2CO2 + 3H2O + 11.28N2

In general, we have

m y m m y
Cn H m O y ( n )(O2 3.76 N 2 ) CO2 H 2O 3.76( n ) N 2
4 2 2 4 2

(2.1.2). Air fuel ratio

Molar ratio A/Fthe molar ratio of air to fuel


Mass ratio A/Fthe mass ratio of air to fuel

CH4 + 2(O2 + 3.76N2) CO2 + 2H2O + 7.52N2

Molar A/F = 2*4.76/1 = 9.52


Mass A/F = 2*4.76*28.97/16 = 17.24

CombustionEngineeringMEDeptNCHU 2
In general, gasoline and diesel fuels are represented as CH1.85

CH1.85 + 1.4625(O2 + 3.76N2) CO2 + 0.925H2O + 5.499N2

A/F = 1.4625*4.76*28.97/13.85 = 14.56

Stoichiometric combustion:
The air fuel ratio for complete combustion is called stoichiometric air fuel
ratio.

e.g.automotive gasoline engine at cruise condition.

The reaction temperature is high at stoichiometric ratio which would


result in a high concentration of NOx. In most combustion appliance,
stoichiometric combustion is avoided to prevent overheat.

Lean combustion:
If the amount of air is more than that required for complete combustion,
there will be excess air after combustion. This is call lean combustion.

CH4 + 3(O2 + 3.76N2) CO2 + 2H2O + O2 + 11.28N2

In a lean combustion, the air fuel ratio is greater than the stoichiometric
air fuel ratio.

A/F > (A/F)st

e.g.Diesel engine, burner, steam boiler, and gas turbine combustor.

Lean combustion is the normal condition for most combustion appliance.

Rich combustion
If the amount of air is less than that required for complete combustion,
part of the fuel would not be fully oxidized such that either there will be
excess fuel left after combustion or there will be incomplete combustion
products, such as carbon monoxide or unburned hydrocarbon.

CH4 + 1.5(O2 + 3.76N2) CO2H2OO2COHCH2N2

In a rich combustion, the air fuel ratio is less than the stoichiometric air
fuel ratio.

CombustionEngineeringMEDeptNCHU 3
A/F < (A/F)st

e.g.Moped gasoline engine at full load.

In most combustion appliance, rich combustion is avoided because of low


efficiency and high pollution.

Equivalence ratiothe ratio of stoichiometric air fuel ratio to actual air


fuel ratio, usually used in academic research.
A / F st

A/ F
1 lean combustion
1 stoichiometric combustion
1 rich combustion

Fuel air ratiothe reciprocal of air fuel ratio, usually used by Diesel
engine and gas turbine engine people.

Percentage of theoretical airthe ratio of actual air to stoichiometric air,


usually used by boiler and burner people.

100%
% of theoretical air =

Percentage of excess airPercentage of theoretical air 100%, usually


used by boiler and burner people.

% of excess air =
1 100%

Lambda()the reciprocal of equivalence ratio, usually used in


automotive engine control.
>1lean combustion
=1stoichiometric combustion
<1rich combustion
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ExampleThe molar analysis of producer gas is N2 50.9%, CO 27.0%,
H2 14.0%, CO2 4.5%, CH4 3.0%, and O2 0.6%. Determine the
stoichiometric air fuel ratio of producer gas. ((A/F)st = 1.443)

CombustionEngineeringMEDeptNCHU 4
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ExampleMethane is burned with dry air. The molar analysis of the
products on a dry basis is CO2 9.7%CO 0.5%O2 2.95%and N2
86.85%Determine the air fuel ratio, the equivalence ratio, the
percentage of theoretical air, and the percentage of excess air.
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ExampleE50 is a bio fuel which is blended 50% (in volume) of ethanol
with 50% of gasoline. Suppose that the density of gasoline is 750 kg/m3,
and that of ethanol is 800 kg/m3, and gasoline can be expressed as CH1.85,
calculate the stoichiometric air fuel ratio o E50.
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Assignment 2.1
M85 is a bio fuel that was promoted about twenty years ago. It contains
85% (in volume) of methanol and 15% of gasoline. The density of
methanol is 790 g/L, and that of gasoline is 750 g/L. Suppose gasoline
can be expressed as CH1.85, calculate the stoichiometric air fuel ratio of
M85.
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Assignment 2.2
Coal is burned with dry air with the feeding rate of 10 tons/hr. The
molar analysis of the products of combustion on a dry basis is CO2 10%.
Determine the flow rate of air.
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Assignment 2.3
Hydrogen is burned with dry air with the feeding rate of 10 m3/min.
The molar analysis of the products of combustion on a dry basis is O2
10%. Determine the flow rate of air.
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CombustionEngineeringMEDeptNCHU 5
Lambda sensors produces a voltage signal that recognises the amount of
unburned oxygen in the exhaust. An oxygen sensor is essentially a
battery that generates its own voltage. When hot (at least 250.), the
zirconium dioxide element in the sensor's tip produces a voltage that
varies according to the amount of oxygen in the exhaust compared to
the ambient oxygen level in the outside air. The greater the difference,
the higher the sensor's output voltage.
Sensor output ranges from 0.2 Volts (lean) to 0.8 Volts (rich). A
stoichiometric fuel mixture gives an average reading of around 0.45
Volts.

Lambda sensor output and the conversion efficiency of catalytic


converter

CombustionEngineeringMEDeptNCHU 6
(2.2). Energy balance in a reacting system

(2.2.1). Energy equation

In a closed system, the conservation of energy and mass give the


following equations.
m m f ma m p
Q U W m pu p m f u f maua W
e.g.: internal combustion engine.

In an open system,
m f ma m p
Q m f h f m a ha m p h p W
e.g.: gas turbine engine, steam boiler.

m f ma mp

CombustionEngineeringMEDeptNCHU 7
(2.2.2). Enthalpy of formation

For the following exothermic reaction, an amount of heat of 393520 kJ


may be released out if all the reactants and products are kept at 25 and
100 kPa.

C + O2 CO2

Since the process does not produce any output work, the energy equation
of an open system gives the relationship between the enthalpy of products
and that of reactants.

Q m r hr m p hp
Q h h h
C O2 CO2
T
h h h h c p dT
o
f
o
f
T0

Q h f ,C h f ,O2 h f ,CO2
393520 h f ,C h f ,O2 h f ,CO2

The enthalpy of reactants must be lower than that of reactants


because the amount of heat transfer is a negative value. In other words,
the enthalpy of carbon dioxide must be lower than those of carbon and
oxygen although all the reactants and products are kept at 25 and 100
kPa. This is the enthalpy associated with the chemical composition of
species.

We define that all elements at their naturally existing states have a


standard enthalpy of formation of zero.

h of ,C 0
h of ,O2 0

CombustionEngineeringMEDeptNCHU 8
Elements: O, H, S, H, Cu, C
Compound: CO2, H2O, CuO, SO2, CH4

Naturally existing states


Carbon, graphite, diamond
O, O2, O3

Standard condition: 25 and 100 kPa.

The enthalpy of formation of compounds can be obtained by measuring


the heat release in the formation reaction at standard condition.

h f ,CO2 393520kJ / kmole

The enthalpy of formation of CO2 is thus -393520 kJ/kmole. The


negative sign means that the formation reaction is exothermic.

If the formation reaction is endothermic, the enthalpy of formation is of


positive value.

CombustionEngineeringMEDeptNCHU 9
Thermochemical Properties of selected substances at 298 K and 1 atm

Species Phase Chemical Formula Hfo (kJ/mol)


Benzene Liquid C6H6 48.95
Carbon Solid C 0
Carbon(Diamond) Solid C 1.8
Carbon Gas C 716.67
Carbon Dioxide Gas CO2 -393.509
Carbon Monoxide Gas CO -110.525
Ethane Gas C2H6 -83.85
Ethanol Liquid C2H5OH -277.0
Ethanol Gas C2H5OH -235.3
Ethene Gas C2H4 52.3
Ethyne Gas C2H2 226.73
Methane Gas CH4 -74.87
Methanol Liquid CH3OH -238.4
Methanol Gas CH3OH -201.0
Biodiesel Gas C19H34O2 -356.3
Methyl Trichloride Liquid CHCl3 -134.47
Methyl Trichloride Gas CHCl3 -103.18
Propane Liquid C3H8 -104.7
Hydrogen Gas H2 0
Water Liquid H2O -285.830
Water Gas H2O -241.818
Ammonia Aqueous NH3 -80.8
Ammonia Gas NH3 -45.90
Nitrogen Dioxide Gas NO2 33.1
Nitrogen Monoxide Gas NO 90.29
Monoatomic oxygen Gas O 249
Oxygen Gas O2 0
Ozone Gas O3 143

CombustionEngineeringMEDeptNCHU 10
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ExampleStoichiometric mixture of carbon monoxide and oxygen are at
298 K and 100 kPa. Find the heat release of the reaction if the products
are (1). at 298 K, (2). at 1000K.
1
CO O2 CO2
2
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ExampleMethane at 25is mixed with air at 600K in the combustor of
a gas turbine engine. The gas temperature at the inlet of turbine should
be confined to 1200K. Determine the air fuel ratio. (69.53)

25Methane
1200K products

600K air

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ExampleA mixture of liquid methanol and air is fed to the inlet of an
adiabatic fuel reformer to produce hydrogen. The inlet mixture is at 25,
and the outlet gas is at 600K. Determine the air fuel ratio.
(partial oxidation reforming process)
CH3OH + x(O2 + 3.76N2) CO2 + 2H2 + (x-0.5)O2 + 3.76xN2
(Ans: x=3.017, A/F = 13.0)

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ExampleIn an electrolysis reaction, water is decomposed into hydrogen
and oxygen. Calculate the required power if 100 L/min of hydrogen is
produced. (19.23 kW)

CombustionEngineeringMEDeptNCHU 11
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Assignment 2.4
Hydrogen is produced in a steam reformer in which methanol is reacted
with steam as the following equation.
CH3OH + H2O CO2 + 3H2
Determine the heat transfer required to produce one mole of hydrogen if
both the reactants and the products are kept at 25.
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Assignment 2.5
Hydrogen is produced in a partial oxidation reformer in which methanol
is reacted with air as the following equation.
CH3OH +0.5 (O2+3.76N2) CO2 +2H2 +1.88N2
Determine the heat transfer required to produce one mole of hydrogen if
both the reactants and the products are kept at 25.
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Assignment 2.6
Hydrogen is produced in an autothermal reformer in which methanol is
reacted with air and steam to form carbon dioxide and hydrogen as the
following equation.
CH3OH +x(O2+3.76N2) +yH2O Products( CO2 , H2 , N2)
This reaction may occur in an adiabatic way in which neither heat input
nor heat output is required. Determine the yield rate of hydrogen if 1
L/min of methanol is fed into the reformer.
(1). Assume that both the reactants and the products are kept at 25.
(2). The products are at 300K while the reactants are at 25.
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Assignment 2.7
Hydrogen is produced with the electrolysis of liquid water. Determine the
electric current required to produce hydrogen with the rate of 1 L/min at
100 kPa and 25 if the applied voltage is 110 volts. The efficiency of
electrolysis is assumed to be 75%.
H2O 0.5O2 + H2
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CombustionEngineeringMEDeptNCHU 12
(2.2.3). Heating value

Heating value is the heat release of a certain amount of fuel in a


complete combustion at standard condition. It is an important
characteristic of fuel.

Fuel + Oxidants (air) Products

Measurement of heating value: Combustion Calorimeters for solid and


liquid fuels

Combustion Calorimeters for gaseous fuels

Continuous flows of air and fuel are feeding into an adiabatic burner
and the hot exhaust gas is cooled by water coiled around the exhaust pipe.
The flow rate and the temperature difference of water are measured to
calculate the thermal energy released by the combustion products.

fuel

air exhaust

Q HR HP

CombustionEngineeringMEDeptNCHU 13
m y m m y
Cn H m O y ( n )(O2 3.76 N 2 ) CO2 H 2O 3.76( n ) N 2
4 2 2 4 2
m y m y
H R hF ( n )hO2 ( n )3.76hN 2
4 2 4 2
m m y
H P hCO2 hH 2O (n )3.76hN 2
2 4 2
hF h f , F
hO2 hN 2 0
hCO2 h f ,CO2
hH 2O h f , H 2O
m
Q H P H R h f ,CO2 h f , H 2O h f , F
2

Lower heating value (LHV): the heating value of a fuel in which that the
water vapor in the product remains in the form of vapor at 25.
h f , H 2O = -241818 kJ/kmole

Higher heating value (HHV): the heating value of a fuel in which that the
water vapor in the product is condensed to liquid water at 25.
h f , H 2O = -285830 kJ/kmole

HHV is greater than LHV. The difference between LHV and HHV is the
latent heat of water at 25.

The enthalpy of formation of any fuel can be obtained if the heating value
is already known.
m
h f , F h f ,CO2 h f , H 2O Q
2
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ExampleDetermine the lower heating value and the higher heating
value of ethylene.

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ExampleDetermine the lower heating value and the higher heating
value of hydrogen.

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ExampleIf the higher heating value of gasoline is 42000 kJ/kg, and the
H/C ratio is 1.85, determine the equivalent enthalpy of formation of

CombustionEngineeringMEDeptNCHU 14
gasoline.

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ExampleDmethyl ether (DME, CH 3OCH 3 ) is considered to be an
alternative fuel to replace fossil diesel. The lower heating value of DME
is 28900 kJ/kg. Determine the enthalpy of formation of DME.

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Assignment 2.8
DME is produced by catalytic dehydration of methanol with the
following reaction.
2CH 3OH CH 3OCH 3 H 2O
Is this an endothermic reaction or exothermic reaction? Find the heat that
should be added or removed from the reaction if both the reactants and
products are at 25 and 100 kPa.

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Assignment 2.9
Another way to produce is to synthesize DME directly from hydrogen
and carbon monoxide with the following reaction.
3CO 3H 2 CH 3OCH 3 CO2
Is this an endothermic reaction or exothermic reaction? Find the heat that
should be added or removed from the reaction if both the reactants and
products are at 25 and 100 kPa.

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Assignment 2.10
The averaged molecular weight of a jet fuel is 126 kg/kmole. The
hydrogen to carbon ratio is 1.85:1. If the lower heating value of the fuel
is 10280 kcal/kg, calculate the equivalent enthalpy of formation of the jet
fuel.

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Assignment 2.11
A turbojet engine runs on the fuel mentioned above. The temperature
and the pressure of the inlet air are 0 and 90 kPa. Jet fuel is injected
into the combustion chamber at 25. The pressure ratio of the
compressor is 10. The efficiency of compressor is 0.85. Find the air fuel
ratio of the mixture if the temperature at the outlet of combustor is
confined to 1200K. Assume that air is an ideal gas.

CombustionEngineeringMEDeptNCHU 15
CH1.85 X (O2 3.76 N 2 ) CO2 0.925 H 2O ( X 1.4625)O2 3.76 XN 2
h f ,CH1.85 ( X hO2 3.76hN 2 )T2
h f ,CO2 hCO2 0.925( h f , H 2O hH 2O ) ( X 1.4625) hO2 3.76 X hN 2
T3

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A correlation of heating value for a variety of fuels was proposed by


Channiwala and Parikh* and is given as the following.

HHV= 0.3491C+1.1783H+0.1005S0.1034O0.0151N0.0211A

HHV: higher heating value (MJ/kg), 4.745<HHV<55.345


C: carbon mass percentage, 0%<C<92.25%
H: hydrogen mass percentage,0.43%<H<25.15%
S: sulfur mass percentage, 0%<S<94.08%
O: oxygen mass percentage, 0%<O<50%
N: nitrogen mass percentage, 0%<N<5.6%
A: ash mass percentage, 0%<A<71.4%
Reference:
Channiwala S.A. and P.P. Parikh, A unified correlation for estimating
HHV of solid, liquid, and gaseous fuels, Fuel 81 (2002) 1051-1063.

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ExampleThe lower heating value of DME is 28900 kJ/kg. Determine
the LHV of DME with the Channiwala & Parikh correlation.
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CombustionEngineeringMEDeptNCHU 16
(2.2.4). Energy content of air fuel mixture

The amount of heat that can be released in real engines is not


directly related to the heating value of fuel. Fuels with high heating
value are not necessarily to generate more energy as the mixture of fuel
and air is burned inside engine.

The reaction of fuel with stoichiometric amount of air is as


following.

m l m m l
Cn H mOl (n )(O2 3.76 N 2 ) nCO2 H 2O 3.76(n ) N 2
4 2 2 4 2

m l
(n ) 4.76 28.97
( A / F ) st 4 2
12n m 16l

The amount of heat that can be released expressed in terms of much fuel
contained inside cylinder and the heating value of fuel Q f .
ma
QH m f Q f Qf
A/ F
If the fuel is of liquid form like gasoline of methanol, the volume is filled
with air only because liquid fuel would occupy negligible fraction of
volume only.
PV
ma m D
RaTm
P V Qf
QH m D
RaTm A / F

However, if the fuel is of gaseous form like propane or methane, the


volume is filled with the gaseous mixture.
m l
PmVD PmVD ( n 4 2 )4.76
ma xa
RaTm RaTm 1 ( n m l )4.76
4 2

CombustionEngineeringMEDeptNCHU 17
m l
PmVD Q f ( n )4.76
QH 4 2
RaTm A / F 1 ( n m l )4.76
4 2

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Example Fuel is burned with stoichiometric air in an internal
combustion engine. The engine displacement volume is 1 L. The
temperature of mixture is 300K and the pressure is 100 kPa. Find the
energy that can be released in the combustion process.
(1). Hydrogen. (2). Methane. (3). Liquid gasoline. (4). Liquid methanol.

PV nRuT
PV
n = 4.00910-5 kmole
RuT
H 2 0.5(O2 3.76 N 2 ) H 2O 1.88 N 2
Heating value of hydrogen is 241942 kJ/kmole
n -5
nH 2 nxH 2 = 1.18610 kmole
1 0.5 4.76
E nH 2 QH 2 =1.18610-5 kmole241942 kJ/kmole= 2.87 kJ

CH 4 2(O2 3.76 N 2 ) CO2 2 H 2O 7.52 N 2


Heating value of methane is 802340 kJ/kmole
n -5
nCH 4 nxCH 4 = 0.38110 kmole
1 2 4.76
E nCH 4 QCH 4 =0.34810-5 kmole802340 kJ/kmole= 3.06 kJ

CH 1.85 1.4625(O2 3.76 N 2 ) CO2 0.925 H 2O 5.499 N 2


Heating value of gasoline is 44400 kJ/kg
ma na M a = 4.00910-5 kmole28.97 kg/ kmole= 1.16110-3 kg
m f ma /( A / F ) st = 1.16110-3 kg/14.56=7.9710-5 kg
E m f Q f =7.9710-5 kg44400 kJ/kg = 3.54 kJ

CH 3OH 1.5(O2 3.76 N 2 ) CO2 2 H 2O 5.64 N 2


Heating value of methanol is 19930 kJ/kg
m f ma /( A / F ) st = 1.16110-3 kg/6.46=17.96110-5 kg
E m f Q f =17.96110-5 kg19930 kJ/kg = 3.58 kJ

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CombustionEngineeringMEDeptNCHU 18
(2.3). Fuels

(2.3.1). Wood

Wood is composed primarily of cellulose and water. Moisture content


varies as wood is dried.

The chemical formula of cellulose is C6H10O5. The molar analysis of


cellulose theoretically is carbon 44.4%, hydrogen 6.2%, and oxygen
49.4%. However, the actual composition would vary.

The heating value of wood is about 20000 kJ/kg. It is low compared


with other fossil fuel.

Heating values of wood

Type C H O HHV(kJ/kg)
Cedar() 48.8 6.37 44.46 19540
Cypress() 54.98 6.54 38.08 22960
Fir() 52.3 6.3 40.5 21050
Hemlock() 50.4 5.8 41.4 20050
Pine() 59.0 7.19 32.68 26330
Redwood() 53.5 5.9 40.3 21030
Ash() 49.73 6.93 43.04 20750
Beech() 51.64 6.26 41.45 20380
Birch() 49.77 6.49 43.45 20120
Elm() 50.35 6.57 42.34 20490
Hickory() 49.67 6.49 43.11 20170
Maple() 50.64 6.02 41.74 19960
Oak() 48.78 6.09 44.98 19030
Poplar() 51.64 6.26 41.45 20750
SourceE.L. Keating, "Applied Combustion", Marcel Dekker, 1992.

Reference:
K. W. Ragland, D. J. Aerts, & A. J. Baker, Properties of Wood for
Combustion Analysis, Bioresource Technology 37 (1991) 161-168

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Example Determine the equivalent enthalpy of formation of cedar.

CombustionEngineeringMEDeptNCHU 19
C 48.8%, 48.8/12= 4.067
H 6.37%, 6.37/1 = 6.37
O 44.46%, 44.46/16=2.779
4.067+ 6.37/4-2.779/2 =4.27
48.8+6.37+44.46=99.63

C4.067H6.37O2.779 +4.27 (O2+3.76N2)4.067 CO2 +3.185H2O+16.055N2

4.067(-390509) +3.185(-285830)-hf=(-19540)99.63
hf= -3941.5 kJ/kg
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Example Dry cedar log is burned in a fireplace. Determine the amount
of excess air if the burned temperature is 700 K.
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Effect of moisture content

As the wood is burning, part of the heat is used to heat up and


vaporize water content. It is known that the vaporization latent heat of
water is 2400 kJ/kg, if the water content is x (by weight), the heat of
burning would be

Q=20000(1-x)-2400x=(20000-22400x) kJ/kg

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Assignment 2.12
Cedar log is burned in a fireplace, determine the amount of excess air if
the burned temperature is 700 K and the moisture content is 30%.
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Proximate analysis: Wood can be considered to be composed of four


different constituents, the moisture, volatile matter, fixed carbon, and ash.

Ultimate Analysis: Elemental or ultimate analysis encompasses the


quantitative determination of carbon, hydrogen, nitrogen, oxygen, and
sulfur within the wood.

CombustionEngineeringMEDeptNCHU 20
Table 1 Proximate and ultimate analysis of CJ

CJ-Raw CJ-250 CJ-350


Proximate analysis (wt.%, ar)
Moisture 9.33 3.61 0.53
Volatile 78.13 69.02 45.82
matter
Fixed carbon 12.11 26.77 52.61
Ash 0.43 0.6 1.04
HHV (MJ/kg) 18.6 22.7 25.4
Ultimate analysis (wt.%, dry)
C 50.63 58.80 74.26
H 6.06 5.18 3.71
N 0.09 0.09 0.12
S 0.02 0.11 0.07
O 43.22 35.83 21.84

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Example Determine the LHV of CJ-Raw with the Channiwala & Parikh
correlation.
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(2.3.2). Coal

Coal can be categorized as lignite(), sub-bituminous(),


bituminous(), and anthracite().

Proximate analysis: Coal can be considered to be composed of four


different constituents, the moisture, volatile matter, fixed carbon, and ash.

Total moisture is analyzed by loss of mass between an untreated sample


and the sample dried in a minimum free-space oven at 150 C within a
nitrogen atmosphere.

Volatile matter is the components which are liberated at high temperature


in the absence of air. This is usually a mixture of short and long chain
hydrocarbons, aromatic hydrocarbons and some sulfur. The volatile

CombustionEngineeringMEDeptNCHU 21
matter of coal is determined by heating the coal sample to 900C for 7
minutes in a cylindrical silica crucible in a muffle furnace.

Ash content of coal is the non-combustible residue left after coal is burnt.
It represents the bulk mineral matter after carbon, oxygen, sulfur and
water (including from clays) has been driven off during combustion.

The fixed carbon content of the coal is the carbon found in the material
which is left after volatile materials are driven off. This differs from the
ultimate carbon content of the coal because some carbon is lost in
hydrocarbons with the volatiles. Fixed carbon is used as an estimate of
the amount of coke that will be yielded from a sample of coal.

Components and Heating value of coal


water volatile carbon ash HV(kJ/kg)
Anthracite 4.4 4.8 81.8 9.0 30540
Bituminous 3.1 23.4 63.6 9.9 31470
Sub-bituminous 13.9 34.2 41.0 10.9 24030
Lignite 36.8 27.8 30.2 5.2 16190
SourceE.L. Keating, "Applied Combustion", Marcel Dekker, 1992.

Ultimate Analysis: Elemental or ultimate analysis encompasses the


quantitative determination of carbon, hydrogen, nitrogen, oxygen, and
sulfur within the coal.

-----------------------------------------------------------------------------------------
Example An Illinois coal that has the following ultimate analysis:
81.3% C; 5.3% H; 9.8% O; 1.7% N; 1.9% S. Find the stoiciometric air
fuel ratio of the Illinois coal.
-----------------------------------------------------------------------------------------

Heating value

The heating value Q of coal is the heat liberated by its complete


combustion with oxygen. Q is a complex function of the elemental
composition of the coal. Q can be determined experimentally using
calorimeters. Dulong suggests the following approximate formula for Q
when the oxygen content is less than 10%:
Q = 337C + 1442(H - O/8) + 93S

CombustionEngineeringMEDeptNCHU 22
where C is the mass percent of carbon, H is the mass percent of hydrogen,
O is the mass percent of oxygen, and S is the mass percent of sulfur in the
coal. With these constants, Q is given in kilojoules per kilogram.
-----------------------------------------------------------------------------------------
Example An Illinois coal that has the following ultimate analysis:
81.3% C; 5.3% H; 9.8% O; 1.7% N; 1.9% S. Find the heating value of
the Illinois coal.
-----------------------------------------------------------------------------------------

(2.3.3)Hydrocarbon fuels

Gasoline is produced from crude oil via distillation. Typical gasoline


consists of hydrocarbons with between four and 12 carbon atoms per
molecule (commonly referred to as C5-C12).
The typical composition of gasoline hydrocarbons (% volume) is as
follows: 4-8% alkanes; 2-5% alkenes; 25-40% isoalkanes; 3-7%
cycloalkanes; l-4% cycloalkenes; and 20-50% total aromatics (0.5-2.5%
benzene)

PHYSICAL PROPERTIES OF GASOLINE


Boiling point: 20-200C
Relative density (water = 1): 0.70 - 0.80
Flash point: <-21C
Auto-ignition temperature: about 250C
Explosive limits, vol% in air: 1.3-7.1

Alkane()
An alkane is a saturated hydrocarbon. Alkanes consist only of hydrogen
and carbon atoms, all bonds are single bonds, and the carbon atoms are
not joined in cyclic structures but instead form an open chain. They have
the general chemical formula CnH2n+2.

The members of the series (in terms of number of carbon atoms) are
named as follows:
Alkane Formula Boiling Melting Density [gcm3]
point [C] point [C] (at 20 C)
Methane CH4 -162 -182 gas
Ethane C2H6 -89 -183 gas
Propane C3H8 -42 -188 gas

CombustionEngineeringMEDeptNCHU 23
Butane C4H10 0 -138 gas
Pentane C5H12 36 -130 0.626 (liquid)
Hexane C6H14 69 -95 0.659 (liquid)
Heptane C7H16 98 -91 0.684 (liquid)
Octane C8H18 126 -57 0.703 (liquid)
Nonane C9H20 151 -54 0.718 (liquid)
Decane C10H22 174 -30 0.730 (liquid)
Undecane C11H24 196 -26 0.740 (liquid)
Dodecane C12H26 216 -10 0.749 (liquid)
Hexadecane C16H34 287 18 0.773
Icosane C20H42 343 37 solid
Triacontane C30H62 450 66 solid
Tetracontane C40H82 525 82 solid
Pentacontane C50H102 575 91 solid
Hexacontane C60H122 625 100 solid

Alkene()
An alkene is an unsaturated hydrocarbon containing at least one carbon
carbon double bond. They have the general chemical formula CnH2n.

CombustionEngineeringMEDeptNCHU 24
Fuel Property Comparison for Ethanol, Gasoline and No. 2 Diesel

Property Ethanol Gasoline No. 2 Diesel


Chemical Formula C2H5OH C4 to C12 C8 to C25
Molecular Weight 46.07 100105 200
Carbon 52.2 8588 8487
Hydrogen 13.1 1215 3316
Oxygen 34.7 0 0
Specific gravity, 60 F/60 F 0.796 0.720.78 0.810.89
Boiling temperature, F 172 80437 370650
Reid vapor pressure, psi 2.3 815 0.2
Research octane no. 108 90100 --
Motor octane no. 92 8190 --
(R + M)/2 100 8694 N/A
Cetane no.(1) -- 520 4055
Freezing point, F -173.2 -40 -4030a
Centipoise @ 60 F 1.19 0.370.44b 2.64.1
Flash point, closed cup, F 55 -45 165
Autoignition temperature, F 793 495 600
Btu/gal @ 60 F 2,378 900 700
Btu/lb @ 60 F 396 150 100
Btu/lb air for stoichiometric 44 10 8
mixture @ 60 F
Higher (liquid fuel-liquid 12,800 18,80020,400 19,20020000
water) Btu/lb
Lower (liquid fuel-water 11,500 18,00019,000 18,00019,000
vapor) Btu/lb
Higher (liquid fuel-liquid 84,100 124,800 138,700
water) Btu/gal
Lower (liquid fuel-water 76,000b 115,000 128,400
vapor) Btu/gal @ 60 F
Mixture in vapor state, 92.9 95.2 96.9c
Btu/cubic foot @ 68 F
Fuel in liquid state, Btu/lb or 1,280 1,290
air
Specific heat, Btu/lb F 0.57 0.48 0.43
Stoichiometric air/fuel, weight 9 14.7b 14.7
Volume % fuel in vaporized 6.5 2
stoichiometric mixture

(2.3.4). Producer Gas()


Wood gasification is the process of heating wood in an oxygen-
starved environment until volatile pyrolysis gases (carbon monoxide and
hydrogen) are released from the wood. Depending on the final use of the

CombustionEngineeringMEDeptNCHU 25
typically low-energy wood (producer) gas (~5.6 MJ/m), the gases can be
mixed with air or pure oxygen for complete combustion and the heat
produced transferred to a boiler for energy distribution.

Typical components of producer gasN2 50.9%CO 27.0%H2


14.0%CO2 4.5%CH4 3.0%O2 0.6%. Producer gas is toxic because
it contains a high percentage of CO.
-----------------------------------------------------------------------------------------
Example The producer gas is burned with 20% excess air. Find the air
fuel ratio.
-----------------------------------------------------------------------------------------
Assignment 2.13
Find the heating value of producer gas in kJ/m3, and make a comparison
with that of natural gas. Natural gas is composed of 85% CH4, 10% C2H6,
and 5% CO2.
-----------------------------------------------------------------------------------------

(2.3.5). Coke oven gas ()


The coke oven gas is the by-product of the process to convert coal into
coke in the coke oven. The volatile matter in the coal is vaporized and
leaves the coke oven chambers as hot, raw coke oven gas. After leaving
the coke oven chambers, the raw coke oven gas is cooled which results in
a liquid condensate stream and a gas stream. The gas stream can be used
as a fuel in the integrated iron and steel works.

CombustionEngineeringMEDeptNCHU 26
(2.3.6). Comparisons of the heating value of fuels

Lower heating value for some fuels (at 15.4C)


Fuel MJ/kg kJ/mol
Methane 50.009 802.34
Ethane 47.794 1,437.2
Propane 46.357 2,044.2
Butane 45.752 2,659.3
Pentane 45.357 3,272.6
Hexane 44.752 3,856.7
Heptane 44.566 4,465.8
Octane 44.427 5,074.9
Nonane 44.311 5,683.3
Decane 44.240 6,294.5
Undecane 44.194 6,908.0
Dodecane 44.147 7,519.6
Methanol 19.930 638.55
Ethanol 28.865 1,329.8
n-Propanol 30.680 1,843.9
Isopropanol 30.447 1,829.9
n-Butanol 33.075 2,501.6
Isobutanol 32.959 2,442.9
Carbon (graphite) 32.808
Hydrogen 120.971 241.942
Carbon monoxide 10.112 283.24
Ammonia 18.646 317.56
Sulfur (solid) 9.163 293.82
gasoline 44.400
diesel 44.800

CombustionEngineeringMEDeptNCHU 27
(2.4). Adiabatic flame temperature

Adiabatic flame temperature is the temperature of the combustion


products if the combustion process is adiabatic and without doing work.

Q 0 W 0

(2.4.1). Constant pressure adiabatic flame temperature

The combustion process is at a constant pressure. The combustor


in the gas turbine engine, furnace, and boiler are examples of constant
pressure combustion process.

m F hF m a ha m p hp H R H p
T
hF h 0
f ,F hF h 0
f ,F c pF dT
T0
T
hO2 h 0
f ,O2 hO2 c pO2 dT
T0
T
hN 2 h 0
f , N2 hN 2 c pN 2 dT
T0

The enthalpy of products equals to the enthalpy of reactants.


-----------------------------------------------------------------------------------------
Example Hydrogen is mixed with air at an equivalence ratio of 1.0 at
25and 100 kPa. Determine the adiabatic flame temperature.
H 2 0.5(O2 3.76 N 2 ) H 2O 1.88 N 2
-----------------------------------------------------------------------------------------
Example Methane is mixed with air at an equivalence ratio of 0.8 at 25
and 100 kPa. Determine the adiabatic flame temperature.
CH 4 2.5(O2 3.76 N 2 ) CO2 2 H 2O 0.5O2 9.4 N 2
-----------------------------------------------------------------------------------------
Assignment 2.14
Determine the constant pressure adiabatic flame temperature of the
following flames. Assume that the mixture is at 25 before
combustion, and equivalence ratio is 1.0.
(1). Propane flame
C3 H 8 5(O2 3.76 N 2 ) 3CO2 4 H 2O 18.8 N 2
(2). Ethylene flame

CombustionEngineeringMEDeptNCHU 28
C2 H 2 2.5(O2 3.76 N 2 ) 2CO2 H 2O 9.4 N 2
(3). Carbon monoxide flame
CO 0.5(O2 3.76 N 2 ) CO2 1.88 N 2
(4). Coke oven gas: CO 7.0%H2 58.0%CO2 2.5%CH4 25.0%O2
0.5%, and N2 7.0%.
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 29
(2.4.2). Constant volume adiabatic flame temperature

The combustion process is at a constant volume. The internal


engine is an example of constant volume combustion process.

mF u F maua m pu p U R U p
T
u h RT h c p dT RT
0
f
T0

nb RTb
Pb
V
Pb nb Tb

P0 n0 T0
-----------------------------------------------------------------------------------------
Example Hydrogen is mixed with air at an equivalence ratio of 1.0 in a
constant volume chamber at 25and 100 kPa. Determine the adiabatic
flame temperature and the final pressure.
H 2 0.5(O2 3.76 N 2 ) H 2O 1.88 N 2
u H 2 0.5uO2 1.88u N 2 u H 2O 1.88u N 2
hH 2 0.5hO2 3.76hN 2 3.38 RT1 h f , H 2O hH 2O 1.88hN 2 2.88 RTb
Pb 2.88 Tb

100 3.38 298

-----------------------------------------------------------------------------------------
Assignment 2.15
An internal combustion engine runs on the fuel of propane with an
equivalence ratio of 0.9. The temperature and the pressure at the
end of compression stroke are 500 and 2.6 MPa. If a constant
volume combustion process occurs in the cylinder, find the
temperature and the pressure after combustion.
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 30
(2.5). STANJAN

This is a computer program to solve the problems of combustion


chemistry developed by Prof. Reynolds of the Stanford University.

-----------------------------------------------------------------------------------------
Example Methane is burned with stoichiometric air at 25and 100 kPa
in a constant pressure process.
CH 4 2(O2 3.76 N 2 ) CO2 2 H 2O 7.52 N 2
-----------------------------------------------------------------------------------------
Example Methane is burned with 25% excess air at 25and 100 kPa in
a constant volume process.
CH 4 2.5(O2 3.76 N 2 ) CO2 2 H 2O 0.5O2 9.4 N 2
-----------------------------------------------------------------------------------------
Example Methane is burned in a gas turbine engine with an
equivalence ratio of 0.4. The pressure ratio of the engine is 10.0. Find
the specific work of the engine and the thermal efficiency.

CH 4 5(O2 3.76 N 2 ) CO2 2 H 2O 3O2 18.8 N 2


T (K) P (kPa) H (kJ/kg) S (kJ/kg-K)
1 300 100
2 1000
3 1000
4 100

wc h2 h1 = kJ/kg, wt h3 h4 = kJ/kg,
wnet wt wc = kJ/kg, work output per kg of mixture.
A / F = 43.09
mf 1
=0.0227, mass of fuel per kg of mixture.
m 1 A/ F
Q f = 50009 kJ/kg, heating value of methane.
qH m f Q f = 1135.2 kJ/kg, heat of combustion per kg of mixture.
wnet
= , thermal efficiency.
qH
P
2 = 10, pressure ratio.
P1
1
Brayton 1 k 1 = 0.6019, theoretical efficiency of Brayton cycle.

-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 31
Example Methane is burned with stoichiometric air at 25and 100 kPa
in an Otto engine. The compression ratio of the engine is 10.0.

CH 4 2(O2 3.76 N 2 ) CO2 2 H 2O 7.52 N 2

T (K) P (kPa) u (kJ/kg) S (kJ/kg-K) V (m3/kg)


1 300 100
2
3
4

wc u2 u1 , we u3 u4 , wnet we wc
w V
W wnet V Tq 2 , Tq net , engine torque
2
-----------------------------------------------------------------------------------------
Assignment 2.16
A jet engine runs on the fuel of propane with an equivalence ratio of
0.3. The pressure ratio is 9.0. The compressor efficiency is 85%,
and the turbine efficiency is 90%. Find the thrust of the engine.

T (K) P (kPa) H (kJ/kg) S (kJ/kg-K)


1 313 90
2s
2
3
4s
4
5 90

1 2s , isentropic compression, P is specified and s the same as last run


w h h h h
wc h2 h1 , c cs 2 s 1 , h2 h1 2 s 1
wc h2 h1 c
1 2 , compression, P and h are specified

2 3 , constant pressure combustion, P and h are the same as last run


wt h3 h4 , wt wc
h2 h1 h3 h4 , h1 h4
w h h
t t 3 4
wts h3 h4 s

CombustionEngineeringMEDeptNCHU 32
h3 h4
h4 s h3
t
3 4s , isentropic expansion, h and s are specified
Since STANJAN does not have the function of specified h and s, iteration
process is required to find the final pressure.
4 5 , isentropic expansion, P is specified and s the same as last run
V2
h4 h5
2
engine thrust: F mV
m 2( h4 h5 )
-----------------------------------------------------------------------------------------
Assignment 2.17
An internal combustion engine runs on the fuel of propane with an
equivalence ratio of 0.9. The compression process is assumed to be
isentropic and the compression ratio is 9.0. The temperature and
the pressure before the compression stroke are 40 and 90 kPa. If
a constant volume combustion process occurs in the cylinder, find
the IMEP of the engine.

T (K) P (kPa) u (kJ/kg) S (kJ/kg-K) V (m3/kg)


1 313 90
2
3
4

-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 33
(2.6). Applications of combustion calculation

(2.6.1) Determination of A/F


Reaction of gasoline and air inside the internal combustion engine
can be expressed as the following.
n
1
CH n 4 (O 3.76 N ) aCO bCO cCH xO yH zH O wN
2 2 2 n 2 2 2 2

If the concentrations of the components in the engine exhaust are


measured with analyzer, the air fuel ratio can be determined.

There are eight variables to be determined. , a, b, c, x, y, z , w

From conservations of atoms, we have four equations.


C: 1 a b c
O: 2 (1 n ) a 2b 2 x z
4
H: n cn 2 y 2 z
N: 3.76 (1 n ) w
4

We need four more equations to find the values of those unknowns.


These four equations may be in the form of concentration which can be
obtained by direct measurement.

Usually, four components are measured, including carbon monoxide,


carbon dioxide, unburned hydrocarbon, and oxygen.
a
, [CO2 ] b , [ HC ] 1 c , [O2 ] x
[CO ]

abc x yw

Water has been distilled out with a filter ahead of the inlet of
analyzer to avoid the problem of clogging and corrosion.

a [CO ] , b [CO2 ] , c [ HC ] , x [O2 ]


a b c [CO ] [CO2 ] [ HC ] 1
1

[CO ] [CO2 ] [ HC ]
[CO ]
a
[CO ] [CO2 ] [ HC ]

CombustionEngineeringMEDeptNCHU 34
[CO2 ]
b
[CO ] [CO2 ] [ HC ]
[ HC ]
c
[CO ] [CO2 ] [ HC ]
[O2 ]
x
[CO ] [CO2 ] [ HC ]
2 n
z (1 ) ( a 2b 2 x )
4
1 1 2 n
y ( n cn) z ( n cn) (1 ) (a 2b 2 x)
2 2 4
3.76 n
w (1 )
4
1 2 n 3.76 n
a b c x (n cn) (1 ) (a 2b 2 x) (1 )
2 4 4
n n 1.76 n
2a 3b c(1 ) 3 x (1 )
2 2 4
n
1 2[CO ] 3[CO2 ] (1 )[ HC ] 3[O2 ] n 1.76 n
2 (1 )
[CO ] [CO2 ] [ HC ] 2 4
n n
1.76 n 1 2(1 )[CO ] (3 )[CO2 ] [ HC ] 3[O2 ]
(1 ) 2 2
4 [CO ] [CO2 ] [ HC ]

1 1 1 n n
1 3 O2 (2 ) CO (3 ) CO2 HC
1.76(1 n ) CO CO2 HC 2 2
4
( A / F ) st

A/ F
( A / F ) st
A/ F

-----------------------------------------------------------------------------------------
Example Find the air fuel ratio of the following measured data.

CO(%) HC(ppm) CO2(%) O2


2.88 1632 13.18 1.15
-----------------------------------------------------------------------------------------
Assignment 2.18
Find the air fuel ratio of the following measured data.
(1). Four stroke motorcycle

CombustionEngineeringMEDeptNCHU 35
CO(%) HC(ppm) CO2(%) O2
1.02 1408 13.02 2.27
0.61 1232 12.44 2.99
1.40 1028 12.4 2.42
1.06 978 11.5 2.00

(2). Two stroke motorcycle

CO(%) HC(ppm) CO2(%) O2


1.82 3330 8.34 4.91
4.40 5010 5.82 5.52
4.51 6900 3.9 6.84
3.90 5660 5.1 6.56
3.17 4140 3.44 9.18
-----------------------------------------------------------------------------------------

(2.6.2) Oxygen rich combustion

The oxygen concentration in normal air is about 21%. The oxygen rich
combustion is to increase the concentration of oxygen artificially to
enhance combustion. The flame temperature could be raised due to the
less content of dilute gas.

1 n n 1 n X n
CH n (1 )(O2 XN 2 ) CO2 H 2O ( 1)(1 )O2 (1 ) N 2
4 2 4 4

1
y : the molar fraction of oxygen
1 X
1
X 1
y
The amount of oxygen required for oxygen rich combustion:

O2 XN 2 O2 3.76 N 2 zO2 (1 z )O2 3.76 N 2


1
1
1 X y

1 z 3.76 3.76
y
z 3.76 1
1 y

For example, for oxygen rich combustion of methane:

CombustionEngineeringMEDeptNCHU 36
CH 4 2(O2 XN 2 ) CO2 2 H 2O 2 XN 2

For one mole of methane, if oxygen rich air is used as the oxidizer, the
amount of pure oxygen that has to be mixed with normal air is
y
n 2 z 7.52 2
1 y
For example, 40% oxygen rich air is used, 3.013 kmole of pure oxygen is
required for 1 kmole of methane.

-----------------------------------------------------------------------------------------
Example Find the products of methane mixed with oxygen rich air and
the associated adiabatic flame temperature.
(1). y 30%
(2). y 40%
(3). y 80%
-----------------------------------------------------------------------------------------

Heat of combustion is determined by the amount of fuel only. It has


nothing to do with the amount of air.

1 n n 1 n X n
CH n (1 )(O2 XN 2 ) CO2 H 2O ( 1)(1 )O2 (1 ) N 2
4 2 4 4

n
h f , F QHV h f ,CO2 h f , H 2O
2
n
h f , F h f ,CO2 h f , H 2O QHV
2
n n 1 n X n
h f , F h f ,CO2 hCO2 h f , H 2O hH 2O ( 1)(1 ) hO2 (1 ) hN 2
2 2 4 4
n 1 n X n
QHV hCO2 hH 2O ( 1)(1 ) hO2 (1 ) hN 2
2 4 4

If the products are cooled to the room temperature, then the heat of
combustion would be the same no matter how much excess air is.
n
QHV hCO2 hH 2O
2

However, if the load of combustor is at temperature higher than that of


room temperature, energy could be saved for oxygen rich combustion.

CombustionEngineeringMEDeptNCHU 37
Heat of load: QL mc
p (Tb TL )
Heat of waste: Qe mc
p (TL Ta )
QL
Required flow rate: m
c p (Tb TL )
TL Ta
Qe QL
Tb TL

Since both TL and QL are fixed values, the higher the value of Tb is, the
lower the waste heat would be. The advantage of rich oxygen
combustion is that the burned gas temperature could be higher than that
of normal air.

-----------------------------------------------------------------------------------------
Example In a steam boiler, coal is fired with 150% excess air. The flue
gas temperature is 200. Find the saving of fuel if 50% oxygen rich air
is used instead of normal air.
-----------------------------------------------------------------------------------------
Assignment 2.19
In a foundry, molten iron is kept warm with stoichiometric propane flame.
Find the saving of fuel if 40% oxygen rich air is used instead of normal
air. The melting point of iron is 1536.
-----------------------------------------------------------------------------------------
Assignment 2.20
An internal combustion engine runs on the fuel of propane with an
equivalence ratio of 0.9. The compression process is assumed to be
isentropic and the compression ratio is 9.0. The temperature and
the pressure before the compression stroke are 40 and 90 kPa. If
40% oxygen rich air is used instead of normal air, find the IMEP of the
engine.

T (K) P (kPa) u (kJ/kg) S (kJ/kg-K) V (m3/kg)


1 313 90
2
3
4
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 38
In vehicle racing, nitrous oxide (often referred to as just "nitrous") allows
the engine to burn more fuel by providing more oxygen than air alone,
resulting in a more powerful combustion.
1
N 2O N 2 O2
2
The gas itself is not flammable at a low pressure/temperature, but it
delivers more oxygen than atmospheric air by breaking down at elevated
temperatures. Therefore, it is often mixed with another fuel that is easier
to deflagrate.

Nitrous oxide is stored as a compressed liquid; the evaporation and


expansion of liquid nitrous oxide in the intake manifold causes a large
drop in intake charge temperature, resulting in a denser charge, further
allowing more air/fuel mixture to enter the cylinder. Nitrous oxide is
sometimes injected into (or prior to) the intake manifold, whereas other
systems directly inject right before the cylinder (direct port injection) to
increase power.
One of the major problems of using nitrous oxide in a reciprocating
engine is that it can produce enough power to damage or destroy the
engine. Very large power increases are possible, and if the mechanical

CombustionEngineeringMEDeptNCHU 39
structure of the engine is not properly reinforced, the engine may be
severely damaged or destroyed during this kind of operation.

1.85 1.85
CH1.85 (1 )(O2 2 N 2 ) CO2 H 2O 2.925 N 2
4 2

CombustionEngineeringMEDeptNCHU 40
Cost of oxygen production

Production of pure oxygen will consume 60W of electricity power per 1


LPM flow rate, which is equivalent to 80640 kJ/kmole, or 22.4
kWh/kmole.

Max. flow rate 5 LPM


Exit pressure 8.5 psi ( 58.6 kPa )
Oxygen concentration 93% 2%
Power consumption 312 W
Weight 16.8kg

For 1 kmole of methane, 67.5 kWh of electric energy is required to


generate the excess oxygen. The current cost of electric power is about
2 NT$/kWh(2013/10/1, TPC) for off peak rate. As a result, 135 NT$ is
the extra cost to operate in oxygen rich combustion for 1 kmole of
methane.

The current cost of fuel is 19.15 NT$/m3(2013/12/2, CPC), which is


equivalent to 471.5 NT$/kmole.

CombustionEngineeringMEDeptNCHU 41
(2.7). Chemical Equilibrium

(2.7.1). Criteria of Equilibrium

An equilibrium state is the state that a system undergoes no more changes.

In an isolated system, the entropy increases for any spontaneous process.

( dS )isolated 0

An isolated system always proceeds from states of lower entropy to states


of higher entropy until the maximum is reached. At this state, no further
natural process is possible and the system is in a state of equilibrium.

In a closed system, the system exchanges energy with its environment via
heat transfer and work. If an amount of heat Q is transferred from
system to its environment, the entropy change associated with the transfer
of heat is

Q
dS , or TdS Q
T

The inequality holds for irreversible process occurring in the system.


However, according to the first law of thermodynamics, we have

Q dU PdV

Combing the inequality of entropy and the first law results the following
equation.

TdS dU PdV , or dU PdV TdS 0

The inequality implies that ( dS )U ,V 0 , which means that entropy would


increase for all processes in a system in which U and V are kept constant.
As the system reaches the equilibrium state, in which no more changes
would occur, the entropy would be at a maximum value.

Since H U PV , dU dH PdV VdP , the inequality may be


converted to
dH VdP TdS 0

The inequality implies that ( dS ) H , P 0 , which means that the entropy

CombustionEngineeringMEDeptNCHU 42
would reach the maximum value at the equilibrium state for a system in
which H and P are kept constant.

There is another way to interpret the inequality, i.e., ( dH ) S , P 0 . It


means that the enthalpy reaches a minimum value as the system is at the
equilibrium state if S and P are kept constant in the system.

Besides, A U TS , dU dA TdS SdT , the inequality may be also


converted to

dA PdV SdT 0

The inequality implies that ( dA)T ,V 0 , which means that the Helmholtz
function would reach the minimum value at the equilibrium state for a
system in which T and V are kept constant.

And G H TS , dG dH TdS SdT , the inequality may be also


converted to

dG VdP SdT 0

The inequality implies that ( dG )T , P 0 , which means that the Gibbs


function would reach the minimum value at the equilibrium state for a
system in which T and P are kept constant.

When phase equilibrium is reached for a pure substance at constant


pressure and temperature, the Gibbs functions of different phase must be
equal to each other.

-----------------------------------------------------------------------------------------
Example: Calculate the Gibbs function of saturated water and that of
saturated vapor at 100.
g f h f Ts s f = 419.04-373.141.3069 = -68.617
g g hg Ts sg = 2676.1-373.147.3549 = -68.307
The error is caused by the uncertainty of the measured data.
g g g f ( hg Ts sg ) (h f Ts s f ) h fg Ts s fg 0
Note: When two phases are in equilibrium, their Gibbs functions are the
same.
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 43
(2.7.2). Properties of Gibbs Function

For a system in which T and P are kept constant, any spontaneous process
would cause a decrease of the Gibbs function, and the Gibbs function
would reach the minimum value at the equilibrium state. As a result, the
criterion for the equilibrium state of a system in which T and P are kept
constant is that ( dG )T , P 0 .

It is thus of necessity to know how to evaluate the variations of the Gibbs


function of a system in which reactions occur.

Gibbs function of pure substance

The Gibbs function of pure substance is defined as


G H TS

dG VdP SdT

Assume that Gibbs function is a function of temperature and


pressure, we have

G G (T , P )

G G
dG dT dP
T P P T

G G
S V
T P P T

G
Since S 0 , we may conclude that 0 . That is, G
T P
decreases when T is raised at constant pressure.

G
Since V 0 , we may conclude that 0 . That is, G
P T
increases when P is raised at constant temperature.

CombustionEngineeringMEDeptNCHU 44
Temperature dependence of Gibbs function

G H G GH
S
T T P T
G G H

T P T T

G 1 G G 1 H
T T T T T T T
P P

Gibbs-Helmholtz Equation

G H
T T T 2
P

Pressure dependence of Gibbs function

G g
V , v
P T P T

RT
For ideal gas, v
P
g RT

P T P

P
RT P
g
P0
P
dP RT ln
P0
P
g g 0 RT ln
P0

For solid and liquid, v const.


P
g vdP vP
P0

g g 0 v( P P0 )

CombustionEngineeringMEDeptNCHU 45
-----------------------------------------------------------------------------------------
Example: Steam is compressed from a state of 200 and 1.5 bars to
another state of 10 bars adiabatically, calculate the change of the Gibbs
function.

h1=2872.9 kJ/kg, s1=7.6433 kJ/kg-K


s2=s1=7.6433 kJ/kg-K
h2=3390.2, T2=459
g2-g1 = h2-T2s2 (h1-T1s1) = (3390.2 2872.9) (7327.6433 -
4737.6433) = -1462.3 kJ/kg
-----------------------------------------------------------------------------------------
Assignment 2.21
Air is compressed from a state of 200 and 1.5 bars to another state of
10 bars adiabatically, calculate the change of the Gibbs function
assuming that air is an ideal gas.
-----------------------------------------------------------------------------------------

Gibbs function of mixture

If a system is composed n different species with the mole numbers ni


respectively.

G G (T , P, n1 , n2 , , nr )

G G G
dG
T P ,n
dT
P T ,n
dP n dni
i T , P ,n j
G
Define i chemical potential of component i

i T , P ,n j
n
dG SdT VdP i dni

By use of the relationship of exact differential

i
k the effect of the mole number of component j

k T , P ,n j i T , P ,n j
n n
on the Gibbs function of the component i.

CombustionEngineeringMEDeptNCHU 46
Why does the mole number of component j affect the Gibbs function of
the component i ?

For a system in which T and P are kept constant, the variations of Gibbs
function in terms of the variations in the mole fractions of each
component is

dG i dni , dg i dxi

Eulers Theorem
f f ( z1 , z2 , , zr )
f is homogeneous of degree m if
f ( z1 , z2 , , zr ) m f ( z1 , z2 , , zr )
f
then mf ( z1 , z2 , , zr ) zi
zi z j

H H (T , P, n1 , n2 , , nr )

H TS i ni

G H TS i ni

When ni 1 , G g

g i xi gi xi , where g i is the molar Gibbs function of the


component of the mixture. However, the molar Gibbs function of each
component can be expressed as the following.
P
g i g i0 RT ln i
P0
As a result, the Gibbs function of a mixture is determined by the molar
fraction as well as the Gibbs function at the reference state of each
component.
P
g g i0 RT ln i xi
P0

CombustionEngineeringMEDeptNCHU 47
Gibbs function of formation

The Gibbs function of each component at the reference state will not
be the same.

g h Ts

Consider the reaction of carbon and oxygen to form carbon dioxide.

C O2 CO2

g C hC TsC

g O2 hO2 TsO2

g CO2 hCO2 TsCO2

At 25 and 1 atm pressure

g CO2 g C g O2 ( hCO2 TsCO2 ) ( hC TsC ) ( hO2 TsO2 )


( hCO2 hC hO2 ) T ( sCO2 sC sO2 )
( h f ,CO2 h f ,C h f ,O2 ) T ( sCO
0
2
sC0 sO0 2 )
( h f ,CO2 T0 sCO
0
2
) (h f ,C T0 sC0 ) ( h f ,O2 T0 sO0 2 )
g CO
0
2
g C0 g O0 2

h f ,CO2 -393520 kJ/kmole, sCO


0
2
213.69 kJ/kmole-K, g CO
0
2
=-457199.62
kJ/kmole

h f ,C 0, sC0 5.74 kJ/kmple-K, g C0 =-1710.52 kJ/kmole

h f ,O2 0, sO0 2 205.03 kJ/kmole-K, g O0 2 =-61098.94 kJ/kmole

g CO2 g C g O2 -393520 - 298.14(213.69-5.74-205.03)


= -394390 kJ/kmole

The Gibbs functions can be defined as


g f ,CO2 -394390 kJ/kmole
g f ,C 0 g f ,O2 0

CombustionEngineeringMEDeptNCHU 48
Gibbs function of formation is the change of Gibbs function when a
compound is formed from its elements.

The standard Gibbs function of formation is Gibbs function of any


compound at 25 and 1 atm pressure.

The Gibbs function of formation for element at natural state is defined to


be zero.

It is noted that the Gibbs function of formation does not equal to the
enthalpy of formation minus the product of temperature and entropy.

g f ,CO2 h f ,CO2 T0 sCO2

g f ,C h f ,C T0 sC

The Gibbs function of formation is the Gibbs function of one compound


relative to the Gibbs function of another compound.

Since a compound is formed from elements, it is important to know the


relative relationships among the compound and its forming elements.

However, an element can not be formed from another element, it is


meaningless to discuss the relative Gibbs function between two distinct
elements. As a result, the Gibbs functions of formation for all elements
at natural state can be set to zero.

-----------------------------------------------------------------------------------------
Example: Calculate the Gibbs function of formation H2O at 298K and 1
bar.
g H 2O g H 2 0.5 g O2 ( hH 2O TsH 2O ) ( hH 2 TsH 2 ) 0.5( hO2 TsO2 )

g 0f , H 2O -241820- 298(188.72-0.5205.03-130.57) = -228599 kJ/kmole


-----------------------------------------------------------------------------------------

The Gibbs function of formation of a compound at states other than 25


and 1 atm pressure can be obtained from its standard Gibbs function of
formation and the deviations of pressure and temperature.

CombustionEngineeringMEDeptNCHU 49
g 0f g 0f ,0 ( h h0 ) (Ts T0 s0 )

-----------------------------------------------------------------------------------------
Example: Calculate the Gibbs function of formation H2O at 1000K and
1 bar.

g f , H 2O -228599 + (25978 11354 20686) - 1000(232.597-


243.4710.5-166.114) + 298(188.72-0.5205.03-130.57) = -192630
kJ/kmole
-----------------------------------------------------------------------------------------

The Gibbs function of formation at elevated temperature for the can be


found in Table A.1 ~ A.12 in the text book.

-----------------------------------------------------------------------------------------
Assignment 2.22
Calculate the Gibbs function of formation of the following component
and find out its value in Table A.1 ~ A.12 in the text book.
(1). H2O at 1000K and 1 bar.
(2). H2 at 1000K and 1 bar.
-----------------------------------------------------------------------------------------
Example: Methane is burned with stiochiometric amount of air.
Assume the reaction is complete, and the products are at 1000 K and 1
bar. Calculate the Gibbs function of the products.

CH4 + 2 (O2 + 3.76 N2 ) CO2 + 2 H2O + 7.52 N2

The molar fraction of each component is


CO2 9.5%, H2O 19%, N2 71.5%
0
g CO2
-395939 kJ/kmole
PCO2
g CO2 g CO
0
2
RT ln = -395939 + 8.3141000 ln(0.095) = -415509
P0
g H0 2O -192652 kJ/kmole
PH 2O
g H 2O g H0 2O RT ln = -192652 + 8.3141000 ln(0.19) = -206459
P0
g N0 2 0 kJ/kmole

CombustionEngineeringMEDeptNCHU 50
PN 2
g N 2 g N0 2 RT ln = 0 + 8.3141000 ln(0.715) = -2789
P0
1
g i xi ( g CO2 2 g H 2O 7.52 g N 2 ) -80741 kJ/kmole
10.52
-----------------------------------------------------------------------------------------
Assignment 2.23
Methane is burned with stiochiometric amount of air, and the products are
at 1000 K and 1 bar. Assume the reaction is not complete, as shown
below.
CH4 + 2(O2 + 3.76 N2 ) (1-X)CO2 + XCOX/2 O2 + 2 H2O + 7.52 N2
Calculate the Gibbs function of the products for different values of X, and
plot the results of calculations in terms of X values.
X=0.05, 0.01, 0.001, 0.0001, 0
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 51
(2.8). Equilibrium constant

Assuming that a chemical reaction takes place in that A and B reacts to


become C and D with the associated mole numbers as following.

A A B B CC D D

As the equilibrium is reached, the Gibbs function should be at a minimum


value, and the criterion of equilibrium is

AdA B dB C dC D dD 0

However, the reaction equation shows that consumption of A moles of


A would accompany consumption of B moles of B, as well as
appearance of C moles of C and D moles of D. As a result, the
rates of change of each component in the reaction can be represented as

dA A d dB B d dC C d dD D d

The equilibrium criterion can thus be represented as

A Ad B B d C C d D D d 0

A A B B C C D D 0

g A A g B B g C C g D D 0

Since the Gibbs function of each component is related to its Gibbs


function of formation and partial pressure,

P
g A g 0A (T ) RuT ln A
P0

P P
g A0 RuT ln A A g B0 RuT ln B B
P0 P0
P P
g C0 RuT ln C C g D0 RuT ln D D 0
P0 P0

CombustionEngineeringMEDeptNCHU 52
C D
PC PD

C gC D g D A g A B g B RuT ln 0 A 0 B
0 0 0 0 P P
PA PB

P0 P0

Let G C g C0 D g D0 A g 0A B g B0 , and note that the partial pressure


can be decomposed as product of molar fraction and absolute pressure
ratio.
PA PA P P
xA
P0 P P0 P0

The equilibrium criterion becomes as


C D A B
xC C xD D P

G
ln
x A A xB B P0

RuT

We may have the final form of the equilibrium criterion as


C D A B
xC xD
C D
P G
exp Kp
x A xB

P0 RuT
A B

Where K p is denoted as the equilibrium constant.


-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
1
CO2 CO + O2
2
1
G1 g O0 2 gCO 0
g CO
0
= -285948 (-396410) = 110462 kJ/kmole
2 2

G -3
K p1 exp 1.30310
RuT
-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
1
H 2 O2 H 2O
2

CombustionEngineeringMEDeptNCHU 53
1 0
G2 g H0 2O g O2 g H0 2 -135643 (0) = -135643 kJ/kmole
2
G
K p2 exp 3489.47
u
R T
-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
1 1
G g H0 2O g CO
0
g CO
0
g H0 2 ( g O0 2 g CO
0
g CO
0
) ( g H0 2O g O0 2 g H0 2 )
2
2 2
2
G G1 G1
G1 G2 G1 G2
G
K p exp e
RuT
e RuT
e RuT
K p1 K p 2
RuT
K p 4.547
-----------------------------------------------------------------------------------------
Assignment 2.24
Calculate the equilibrium constant of the reaction at temperature of 2000
K and pressure of 10 bars.
N 2 O2 2 NO
-----------------------------------------------------------------------------------------

If an equilibrium equation can be composed with two other equilibrium


equations, then the equilibrium constant of this equation can be expressed
as the product of the equilibrium constants of the other equations.
-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2O CO H 2 CO2
-----------------------------------------------------------------------------------------

If a reaction is the reverse of other reaction, then the equilibrium constant


of this equation is the reciprocal of the equilibrium constant of the other
equation.

-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 54
If a reaction is expressed as N multiple of another reaction, the
equilibrium constant of this equation is the Nth order of that of the other
equation.

-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
2CO2 2CO +O2
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 55
Equilibrium constants of come commonly used reactions

T B
log K p A ln( ) C DT ET 2
1000 T
1
1: H2 H
2
1
2: O2 O
2
1 1
3: H 2 O2 OH
2 2
1 1
4: N 2 O2 NO
2 2
1
5: H 2 O2 H 2O
2
1
6: CO O2 CO2
2

A B C D E
1 0.432168e+00 -0.112464e+05 0.267269e+01 -0.745744e-04 0.242484e-08

2 0.310805e+00 -0.129540e+05 0.321779e+01 -0.738336e-04 0.344645e-08

3 -0.141784e+00 -0.213308e+04 0.853461e+00 0.355015e-04 -0.310227e-08

4 0.150879e-01 -0.470959e+04 0.646096e+00 0.272805e-05 -0.154444e-08

5 -0.752364e+00 0.124210e+05 -0.260286e+01 0.259556e-03 -0.162687e-07

6 -0.415302e-02 0.148627e+05 -0.475746e+01 0.124699e-03 -0.900227e-08

-----------------------------------------------------------------------------------------
Example: Calculate the equilibrium constant of the reaction at
temperature of 2000 K and pressure of 10 bars.
H 2 CO2 H 2O CO
-----------------------------------------------------------------------------------------
Assignment 2.25
Calculate the equilibrium constant of the following reaction at
temperature in the range of 1000~3000K.
H 2 CO2 H 2O CO
-----------------------------------------------------------------------------------------

CombustionEngineeringMEDeptNCHU 56
(2.9). Equilibrium calculations

(2.9.1). Procedures of equilibrium calculation

For any reaction in consideration, the procedure to calculate the


equilibrium state should include the following steps.

(1). Conservation of each kind of atom that participates the reaction


before and after reaction. If there are n kinds of atoms present in the
reaction, there would be n conservation equations.

(2). Criteria of equilibrium. If m reactions are in equilibrium, there


would be m equilibrium equations.

The molar fraction and concentration.

PV nRuT

ni P P P P
[Ci ] i i xi
V RuT P RuT RuT

-----------------------------------------------------------------------------------------
Example: Carbon monoxide reacts with excess oxygen at temperature of
2000 K and pressure of 10 bars. Calculate the CO remaining in the
exhaust.
CO +O2 aCO2 bCO cO2
Balance in C atoms: a b 1 , b 1 a
a
Balance in O atoms: 2a b 2c 3 , c 1
2
a a
a b c 11 2
2 2
1
CO2 CO + O2
2
a a 2a
xCO2
abc 2 a 4a
2
b 1 a 2 2a
xCO
abc 2 a 4a
2

CombustionEngineeringMEDeptNCHU 57
a
1
xO2
c
2 2a
abc 2 a 4a
2
2 2a
PCO P
4a
2a
PCO2 P
4a
2a
PO2 P
4a
0.5
(2 2a )(2 a )0.5 P
K P =1.30310-3
2a (4 a ) 0.5 P0
1 a 2 a
= 4.1210-4
a 4a
a= 0.9994
CO +O2 0.9994CO2 0.0006CO 0.5003O2
-----------------------------------------------------------------------------------------
Example: Hydrogen is produced from steam and carbon monoxide in a
water shift reaction. It is known that steam and carbon monoxide are
mixed with the mole ratio of 1:1 at 800 K and 1 atm, calculate the mole
fraction of hydrogen at the outlet.

H 2O CO H 2 CO2
1 1 0 0
1-y 1-y y y
1111
xCO2 xH 2 P y y
K p =4.2435
xCO xH 2O P0 (1 y )(1 y )

y=0.319

xH 2 16%

(2.9.2). Equilibrium of hydrocarbon fuel burning

1 m
Cn H m ( n )(O2 3.76 N 2 )
4
CO2 , CO, H 2O, H 2 , O2 , N 2 , OH , O, H , N , NO,.........

CombustionEngineeringMEDeptNCHU 58
For a lean combustion, CO2, H2O, and O2 are abundant in the products of
reaction, dissociation reactions do not affect the concentrations of these
components. As a result, it is reasonable to obtain the concentrations of
CO2, H2O, and O2 directly from atom balance.
-----------------------------------------------------------------------------------------
Example: A gas turbine engine runs on natural gas with an equivalence
ratio of 0.3. The inlet air is at 25 and 101.3 kPa. Fuel is injected into
the combustion chamber at 25. The pressure ratio of the compressor
is 10. The efficiency of compressor is 0.85. Assume that NO is in
equilibrium. Find the molar fraction of NO and CO at the exit of
combustor. Assume that air is an ideal gas.
1 1
N 2 O2 NO
2 2
1
CO2 CO + O2
2
-----------------------------------------------------------------------------------------

However, for rich and stoichiometric mixtures, O2 and H2 are rare in the
products of reaction, dissociation reactions play an important role to
determine the concentrations of these components.

-----------------------------------------------------------------------------------------
Example: Methane is burned with stiochiometric amount of air.
Assume the products are at 2000 K and 10 bar. Calculate the mole
fraction of each component assuming that the products contain CO, CO2,
H2O, H2, O2, and N2 only.

CH 4 2(O2 3.76 N 2 ) aCO2 bCO cH 2O dH 2 eO2 fN 2

Carbon balance: a + b = 1
Hydrogen balance: 2c + 2d = 4
Oxygen balance: 2a + b + c + 2e =4
Nitrogen balance: f = 7.52

There are six unknowns in the reaction equation. However, there are
only four balance equations. We need two more equations. These two
equations should be derived from the equilibrium between components.
We propose the following equations.

1
CO2 CO O2
2
CombustionEngineeringMEDeptNCHU 59
1
H 2O H 2 O2
2
0.5 0.5 0.5
xCO xO2 P b e P
K p1
xCO2 P0 a P0
0.5 0.5
xH 2 xO0.52 P d eP
K p2
xH 2O P0 c P0

a + 1 + c + 2e =4, e = 1.5 0.5(a+c)

a b c d e f 1 2 e 7.52 10.52 e 12.02 0.5( a c)


0.5
(1 a ) 1.5 0.5( a c) P
K p1 0
a 12.02 0.5(a c) P
0.5
(2 c) 1.5 0.5( a c) P
K p2 0
c 12.02 0.5( a c) P

This is a set of nonlinear simultaneous equations that has to be solved


numerically.
-----------------------------------------------------------------------------------------
Assignment 2.26
Propane is burned with insufficient air with an equivalence ratio of
1.1. If the temperature is 2000 K and the pressure is 10 bar, calculate
the equilibrium constants and find the equilibrium concentrations of
the products. Assume the combustion products contain CO, H2,
H2O, CO2, and N2 only.
-----------------------------------------------------------------------------------------
Example: Methane is burned with stiochiometric amount of air.
Assume the products are at 1000 K and 10 bar. Calculate the mole
fraction of each component assuming that the products contain CO, CO2,
H2O, H2, O2, H, O, OH, NO, N, and N2.

CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO

Carbon balance: a + b = 1
Hydrogen balance: 2c + 2d +g + I = 4
Oxygen balance: 2a + b + c + 2e + g + h + k =4
Nitrogen balance: 2f + j + k = 15.04

CombustionEngineeringMEDeptNCHU 60
There are eleven unknowns in the reaction equation. However, there are
only four balance equations. We need seven more equations. These
seven equations should be derived from the equilibrium between
components.
We propose the following equations.

1
CO2 CO O2
2
1
H 2O H 2 O2
2
O2 2O
H 2 2H
N2 2N
H 2 O2 2OH
N 2 O2 2 NO

0.5 0.5
xCO xO0.52 P b e P
K p1
xCO2 P0 a P0
0.5 0.5
xH 2 xO0.52 P d eP
K p2
xH 2O P0 c P0
xO2 P h 2 P
K p3
xO2 P0 e P0
xH2 P i2 P
K p4
xH 2 P0 d P0
xN2 P j2 P
K p5
xN 2 P0 f P0
2
xOH g2
K p6
xO2 xH 2 de
2
xNO k2
K p7
xO2 xN 2 fe

abcd e f g hi jk

This is a set of nonlinear simultaneous equations that has to be solved


numerically.

CombustionEngineeringMEDeptNCHU 61
-----------------------------------------------------------------------------------------
Example: Methane is burned with stiochiometric amount of air
adiabatically in a constant pressure combustor. Assume the reactants
are at 298 K and 10 bar. Calculate the mole fraction of each component
assuming that the products contain CO, CO2, H2O, H2, O2, H, O, OH, NO,
N, and N2.

CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO

There are twelve unknowns in the reaction equation. Besides the mole
fractions that are not known, the temperature is also unknown. We need
eight more equations. These seven equations should be derived from the
equilibrium between components. The last equation is derived from the
conservation of energy before and after combustion.

HR=HP

hCH 4 2(hO2 3.76hN 2 ) a hCO2 b hCO c hH 2O d hH 2 e hO2


f hN 2 g hOH h hO i hH j hN k hNO

The mole fractions to be determined are functions of temperature.


However, temperature should be solvable only when all the mole
fractions are already known. As a result, temperature should be guessed
before calculations proceed. The energy equation is used to check if the
guessed temperature is correct or not.

-----------------------------------------------------------------------------------------
Example: Methane is burned with stiochiometric amount of air in a
constant volume combustor. Assume the reactants are at 298 K and 1 bar.
Calculate the mole fraction of each component assuming that the products
contain CO, CO2, H2O, H2, O2, H, O, OH, NO, N, and N2.

CH 4 2(O2 3.76 N 2 )
aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO

There are thirteen unknowns in the reaction equation. Besides the mole
fractions that are not known, the temperature and the pressure are also
unknown. We need nine more equations. These seven equations
should be derived from the equilibrium between components. One
equation is derived from the conservation of energy before and after

CombustionEngineeringMEDeptNCHU 62
combustion, and the other equation is derived form the state equation of
ideal gas.

UR=UP
uCH 4 2(uO2 3.76u N 2 ) a uCO2 b uCO c u H 2O d u H 2 e uO2
f u N 2 g uOH h uO i u H j u N k u NO
ni RT
P
V
The mole fractions to be determined are functions of temperature and
pressure. However, temperature should be solvable only when all the
mole fractions are already known. As a result, temperature and pressure
should be guessed before calculations proceed. The energy equation is
used to check if the guessed temperature is correct or not, and the ideal
gas equation is used to check if the pressure is correct or not.
-----------------------------------------------------------------------------------------

(2.9.3). STANJAN

The equilibrium calculation can be carried out with the STANJAN


program.

-----------------------------------------------------------------------------------------
Example: Methane is burned with air at 2000K and 10 bar. If the
combustion products contain CO, CO2, O2, H2, H2O, HO, H, O, NO,
N, and N2, find the equilibrium concentrations of products at
equilibrium ratio of 1.0.
-----------------------------------------------------------------------------------------
Example: Mixtures of methane and air at 300K and 100 kPa are
burned in a constant pressure process. If the combustion products
contain CO, CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the
equilibrium concentrations of products at equilibrium ratio of 1.0.
-----------------------------------------------------------------------------------------
Example: Mixtures of methane and air at 300K and 100 kPa are
burned in a constant volume process. If the combustion products
contain CO, CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the
equilibrium concentrations of products at equilibrium ratio of 1.0.
-----------------------------------------------------------------------------------------
Example: An Otto engine runs with stoichiometric methane mixture.
The volume of the cylinder is 1L, and the compression ratio is 10. The
initial temperature and pressure inside cylinder are 300 K and 1 atm

CombustionEngineeringMEDeptNCHU 63
respectively. Calculate the work output, assuming that the products
contain CO, CO2, H2O, H2, O2, H, O, OH, NO, N, and N2.
-----------------------------------------------------------------------------------------

Comparison of adiabatic flame temperature with difference assumptions


in the final species of equilibrium:

ANo dissociation
2 2 2
CH 4 (O2 3.76 N 2 ) CO2 2 H 2O ( 2)O2 3.76 N 2 , 1

2 2
CH 4 (O2 3.76 N 2 ) aCO2 bCO 2 H 2O 3.76 N 2 , 1

BWeak dissociation
2
CH 4 (O2 3.76 N 2 ) aCO2 bCO cH 2O dH 2 eO2 fN 2

CStrong dissociation
2
CH 4 (O2 3.76 N 2 )

aCO2 bCO cH 2O dH 2 eO2 fN 2 gOH hO iH jN kNO

A B C
0.8
0.9
1.0
1.1
1.2

-----------------------------------------------------------------------------------------
Assignment 2.27
Propane is burned with air at 2000K and 10 bar. If the combustion
products contain CO, CO2, O2, H2, H2O, HO, H, O, NO, N, and N2,
find the equilibrium concentrations of products at equilibrium ratios
from 0.7 to 1.3 with an increment of 0.1. The calculations may be
conducted with STANJAN. Plot the results of calculations.
-----------------------------------------------------------------------------------------
Assignment 2.28

CombustionEngineeringMEDeptNCHU 64
Mixtures of propane and air at 300K and 100 kPa are burned in a
constant pressure process. If the combustion products contain CO,
CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the adiabatic
flame temperature and the equilibrium concentrations of products at
equilibrium ratios from 0.7 to 1.3 with an increment of 0.1. The
calculations may be conducted with STANJAN. Plot the results of
calculations.
-----------------------------------------------------------------------------------------
Assignment 2.29
Mixtures of propane and air at 300K and 100 kPa are burned in a
constant volume process. If the combustion products contain CO,
CO2, O2, H2, H2O, HO, H, O, NO, N, and N2, find the adiabatic
flame temperature, the final pressure, and the equilibrium
concentrations of products at equilibrium ratios from 0.7 to 1.3 with
an increment of 0.1. The calculations may be conducted with
STANJAN. Plot the results of calculations.
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Assignment 2.30
A gas turbine engine runs with mixtures of propane and air. The
equivalence ratio is 0.4. The inlet air is at 300 K and 1 bar. The pressure
ratio is 10.0. Fuel is injected into the combustion chamber at 300 K and
10 bars. Calculate the work output. Assume that the products contain CO,
CO2, H2O, H2, O2, H, O, OH, NO, N, and N2.
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Assignment 2.31
An Otto engine runs with stoichiometric mixtures of propane and air.
The inlet condition is 300K and 100 kPa. The compression ratio is
11. If the combustion products contain CO, CO2, O2, H2, H2O, HO,
H, O, NO, N, and N2, find the equilibrium concentrations of
products during the expansion stroke. The calculations may be
conducted with STANJAN. Plot the results of calculations.
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CombustionEngineeringMEDeptNCHU 65
(2.10). Applications of equilibrium calculations

(2.10.1) Determination of A/F


Reaction of gasoline and air inside the internal combustion engine
can be expressed as the following.
n
1
CH n 4 (O 3.76 N ) aCO bCO cCH xO yH zH O wN
2 2 2 n 2 2 2 2

If only the concentrations of CO, CO2, and unburned hydrocarbons in the


engine exhaust are measured, just like the normal operation of emission
check in the motorcycle smoke test stand, the air fuel ratio can not be
determined because of insufficient conditions.

There are eight variables to be determined. , a, b, c, x, y, z , w

From conservations of atoms, we have four equations.


C: 1 a b c
O: 2 (1 n ) a 2b 2 x z
4
H: n cn 2 y 2 z
N: 3.76 (1 n ) w
4

We need four more equations to find the values of those unknowns.


Three of them may be in the form of concentration which can be obtained
by direct measurement.

a
, [CO2 ] b , [ HC ] 1 c
[CO ]

abc x yw

We need one more condition to solve these variables. Usually, it is


assumed that CO, CO2, H2, and H2O are in equilibrium in the exhaust.

H 2 CO2 H 2O CO
[ H 2 ][CO2 ]
K
[ H 2O ][CO ]

CombustionEngineeringMEDeptNCHU 66
1 1 1

n CO CO2 HC
4.76(1 )
4
n 1 n 3 kn CO CO CO2
1 ( ) CO CO2 HC
4 2 4 4 CO2 k CO
1 n 1 1 n [CO ] [CO2 ]
x (1 ) ([CO ] 2[CO2 ] )
4 2 [CO ] [CO2 ] [ HC ] 2 [CO ] K 1
[CO2 ]
x
[O2 ]

( A / F ) st
A/ F

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Example The measured emission data of a motorcycle at idling are
shown as the following.

CO(%) HC(ppm) CO2(%) O2


2.88 1632 13.18 1.15
Find the air fuel ratio with and without the oxygen concentration.
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Assignment 2.32
Derive the equation for the determination of air fuel ratio from measured
exhaust data and find the expression of the molar fraction of oxygen.
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Assignment 2.33
Find the air fuel ratio of the following measured data without the oxygen
concentration, and then compare the oxygen concentration obtained with
the measured one.

(1). Four stroke motorcycle


CO(%) HC(ppm) CO2(%) O2
1.02 1408 13.02 2.27
0.61 1232 12.44 2.99
1.40 1028 12.4 2.42
1.06 978 11.5 2.00

(2). Two stroke motorcycle


CO(%) HC(ppm) CO2(%) O2

CombustionEngineeringMEDeptNCHU 67
1.82 3330 8.34 4.91
4.40 5010 5.82 5.52
4.51 6900 3.9 6.84
3.90 5660 5.1 6.56
3.17 4140 3.44 9.18
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CombustionEngineeringMEDeptNCHU 68