3

TOPIC

Thermochemistry of
fuel-air mixtures

What’s covered in this section
 Characterization of flames
 Fuels
 Stoichiometry
 First law and combustion
 Chemical equilibrium

Characterization of flames
 Combustion of the fuel-air mixture controls engine power, efficiency and
emissions.
 Combustion phenomena are different for spark-ignition engines and diesels

Key combustion phenomena
 Combustion process is a fast exothermic gas-phase reaction.
 Flame is a combustion reaction which can propagate subsonically through the
space
 Reaction zone is usually called the flame front.
 The generation of heat and active species accelerate the chemical reaction; the
supply of fresh reactants, governed by the convection velocity, limits the
reaction. When these processes are in balance, a steady-state flame results

Combustion
phenomena
In spark-ignition engines:
 fuel is mixed with air in the
intake system
 spark initiates the combustion
 flame develops from the “kernel” created by spark discharge and propagates
across the cylinder to combustion chamber walls
 at the walls, the flame is “quenched” or extinguished
 Undesirable combustion phenomenon – ‘knock’

Combustion phenomena
In diesels:
 fuel is injected into the cylinder near the end of compression process
 fuel is self ignited by hot air
 burning then proceeds as fuel and air mix

 Fuel-air mixing plays a controlling role in the diesel combustion process

Flames classification

Composition of reactants as they enter the reaction zone:

premixed flame, diffusion flame

Gas flow regime:

laminar flame, turbulent flame

 Change in flame structure and motion with time:

steady flame, unsteady flame

 Initial phase of reactants:

gas, liquid, solid

Characterization of flames
 The conventional spark-ignition flame is a premixed unsteady turbulent
flame, and the fuel-air mixture through which the flame propagates is in the
gaseous state
 The diesel engine combustion process is unsteady turbulent diffusion flame,
and the fuel is initially in the liquid phase

Ideal gas model
Gas species that make up the working fluid in IC Engines can be treated as ideal
gas, for which

pV  mRT  nRT

Composition of air

44.009

Fuels
 Blends of many different hydrocarbons
 Predominantly hydrogen (~14% by mass) & carbon (~86% by mass)
 Diesel fuel can contain some sulfur (~1%)
 Biodiesel fuel – FAME made from vegetable oil or animal fat
 Alcohol fuels contain some oxygen (methanol, ethanol)
 CNG, LPG
 Appendix D, page 915 in Heywood contains data on many different fuels

Fuel types – Alkyl compounds
 Single bonded open-chain saturated hydrocarbon
molecules
 Methane, ethane, propane, n-octane and isooctane
 “n” – (normal) straight-chain configuration “iso” branched-chain configuration
 Losing 1 H atom (radical) makes it methyl, ethyl,
propyl etc.

Fuel types – Alkyl compounds
 Single bond ring hydrocarbons
 Unsaturated; ring can be broken and
additional hydrogen added
 Cyclopropane, cyclobutane,
cyclopentane, etc.

Fuel types – Alkyl compounds
 Open-chain hydrocarbons containing double
bond;
 Unsaturated
 Ethylene, propylene, butylene, etc.
 Same formula as cycloparaffins, but
different structure

Fuel types – Alkyl compounds
 Open-chain hydrocarbons containing one
carbon-carbon triple bond;
 Unsaturated
 Acetylene, etc.

Fuel types – Aromatics
 Benzene (C6H6) is the building block
 Very stable hydrocarbon
 Toluene (C7H8), xylene (C8H10), etc.

Fuel types – Alcohols
 One H is replaced by hydroxyl radical
 Methane (CH4)  methanol (CH3OH), Ethane
(C2H6)  ethanol (C2H5OH) etc.

Combustion stoichiometry
 Going from reactants (fuel + air) to products
 Depends only on conservation of mass for each atom
 Done on a “per kmole of fuel” basis

Complete combustion
 Enough oxygen to completely oxidize (burn) the fuel
 All carbon oxidizes to CO2 , all hydrogen to H2O
 O2 is used to form H2O first, then the rest is used to form CO
 Any leftover O2 then converts CO into CO2

Fuel composition
 Gravimetric composition is given by mass fractions of C and H in the fuel.
 Atomic composition is given by numbers of atoms of C and H in fuel
molecule: CaHb
 Atomic composition can be determined from gravimetric and vice versa

notes

General stoichiometry. Air/fuel ratio

C3H8   s  O 2  3.77N 2    CO 2   H 2O  3.773 s N 2

notes

General stoichiometry. Air/fuel ratio
b
b


 b
C a H b   a    O 2  3.773N 2   aCO 2  H 2O  3.773 a   N 2
4
2


 4

A Fs

a  b 4   31.998  3.773  28.16 


12.011a  1.008b

or

A Fs 

 a  b 4  4.77 28.97
12a  b

notes

General stoichiometry. Air/fuel ratio

notes

Example
A hydrocarbon fuel of composition 84.1 percent by mass C and 15.9 percent by
mass H has molecular weight of 114.15. Determine the number of moles of air
required for stoichiometric combustion and the number of moles of products
produced per mole of fuel. Calculate (A/F)s, (F/A)s, and the molecular weight of
the reactants and products

notes

Equivalence ratio & relative ratio
b
Ca H b   s  O 2  3.773N 2   aCO 2  H 2O   s   -1 O 2  3.773 s N 2
2

 A F  s  F A a

 A F  a  F A s

1


  Equivalence ratio

  Relative ratio

Fuel - lean
 1
Stoichiometric   1
Fuel-rich
 1

 1
 1
 1

notes

Example – octane with 25% excess air
Octane (C8H18) is burned with 25% excess air. Calculate the AF and the molecular
weights of the reactants and the products.
Compare results with previous example (stoichiometric combustion of octane).
Analyze. Conclude.

notes

Fuel with oxygen
Include fuel oxygen into oxygen balance.

notes

Gas analysis
In IC engines combustion is never complete
Gas analysis is used to determine composition of combustion product
experimentally
Given in mole fractions (per cent, ppm) unless otherwise stated
Differentiate wet and dry gas analysis

notes

Example – dry gas analysis
The measured dry exhaust gas composition of a propane-fueled SI engine is given
below (water was removed before the measurement). Calculate the equivalence
ratio.
CO2 = 10.8%,
O2 = 4.5%,
CO = 0%,
H2 = 0%

notes

Example

notes

Example
A fuel has the following gravimetric composition
hexane (C6H14)
octane (C8H18)
cyclohexane (C6H12)
benzene (C6H6)

40%
30%
25%
5%

If the air/fuel ratio is 17, determine the equivalence ratio

Example
A fuel has a composition by weight of 0.865 carbon, 0.133 hydrogen and 0.002
incombustibles. Find the stoichiometric air/fuel ratio.
When the fuel is burnt with excess air, the dry volumetric exhaust gas analysis is: CO 2
0.121, N2 0.835, O2 0,044. Determine actual air/fuel ratio used and the wet volumetric gas
analysis.

Example
The results of a dry gas analysis of an engine exhaust are as follows: CO 2 10.1%, N2 82.6% .
Calculate gravimetric composition of fuel.

First law and combustion

Energy and enthalpy balances

Combustion at constant V, constant T
Combustion at
constant V,
constant T

QR  P  WR  P  U P  U R

QR  P  U P  U R   U  V ,T 

  U  V ,T  – heat of reaction at constant volume at temperature T 

Combustion at constant p, constant T
WR  P   pdV  p  VP  VR 
P

R

QR  P  p VP  VR  U P  U R

 

QR  P  U P  pVP  U R  pVR  H P  H R  H p ,T 
  H  p ,T  – heat of reaction at constant pressure at temperature T 

Energy of reactants and products
U (or H) of reactants
and products as a
function of temperature

 H  p ,T    U  V ,T   R

n P   nR  T 

notes

Energy of reactants and products
Effect of water in products

 U  V ,T ,H Oliq   U  V ,T ,H O vap
2

2

 mH2Ou fg H2O

Energy of reactants and products

Effect of fuel in reactants

Enthalpy of formation
Enthalpy of products at standard
reference state
H P0 

ni h 0f ,i

products

Enthalpy of reactants at standard
reference state

H R0 

reactants

Back to 3.2

ni h 0f ,i

Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K

solution

notes

Energy of reactants
and products

R.Stone, Introduction to
internal combustion engines

notes

Example
In a closed combustion vessel propane (C3H8) and air with
an equivalence ratio of 1.11 initially ant 25˚C burn to
produce products consisting solely of carbon dioxide
(CO2), carbon monoxide (CO), water (H2O) and
atmospheric nitrogen.
If the heat rejected from the vessel is 820 MJ per kmol of
fuel, find the final temperature.
If the initial pressure is 1 bar, estimate the final pressure.
solution

notes

Heating values
Heating value of a fuel is the magnitude of the heat of reaction at
constant pressure or at constant volume at standard temperature for
the complete combustion of unit mass of fuel
QHV p    H  p ,T

0

QHVV    U  V ,T

0

Higher heating value differs from lower heating value by latent
heat of vaporization

QHHVp  QLHVp

 mH2O

h fg H2O

 mf 

notes

Combustion efficiency
Net chemical energy release due to combustion at constant pressure

 H R  TA   H P  TA   m 

ni h

0
f ,i

i , reactants

Amount of fuel energy supplied is m f QHV
Combustion efficiency

c 

H R  TA   H P  TA 
m f QHV

ni h 
i , products

0
f ,i

Combustion efficiency

Fuel conversion, thermal and
combustion efficiencies

notes

Chemically reacting gas mixtures

Chemical Equilibrium

Chemical equilibrium
 Consider carbon dioxide in a vessel
 At high temperature some of the CO2 molecules dissociate
into CO and O2 molecules
 If the mixture of CO2, CO, and O2 is in equilibrium, then
CO2 molecules are dissociating into CO and O2 at the same
rate as CO and O2 molecules are recombining in the
proportions required to satisfy the equation

1
CO  O 2  CO 2
2
notes

Chemical equilibrium
 Combustion products of hydrocarbon fuels at low
temperatures are: N2, H2O, CO2, and O2 or CO and H2
 At higher temperatures (> about 2200 K), dissociation
occurs. Molar equilibrium composition of the products of
adiabatic combustion of stoichiometric mixture of petrol
is:
N2 ~ 0.7;
H2O, CO2 ~ 0.1;
CO, OH, O2, NO, H2 ~ 0.01;
H, O ~ 0.001; and other species in lesser amounts. notes

Condition of chemical equilibrium

notes

Condition of chemical equilibrium
 By the Second Law for chemical reaction at constant
temperature, constant pressure

H  T S  G  0
 At equilibrium

 G  p ,T

0

notes

Condition of chemical equilibrium
Consider reacting mixture of ideal gases

 a M a  b M b  ...   l M l  m M m  ...
In concise form

 M
i

i

0

i

By convention
i
is negative
for reactants, and positive for products
Let an amount  na of M a react with  nb of M b , etc.,
and produce  nl of M l ,  nm of M m , etc. These amounts
are in proportion

 ni   i n

notes

Condition of chemical equilibrium
Change of Gibbs energy of ideal gas mixture

 G  p ,T   i ni

(a )

i

where  is the chemical potential

 G
i  

 ni
For ideal gas

p ,T , n j  j  i 

pi
i    T   RT ln
p0
0
i

notes

Condition of chemical equilibrium
Substitution in (a) gives

pi
    T   RT ln p   i n  0
0

 pi
 ln  p 
 0

i

0
i




   T   
0
i

RT

G  T 
0

i



RT

 ln K p

notes

Condition of chemical equilibrium
 pi
Kp   
i  p0

i

Kp is the equilibrium constant

pi are partial pressures of components
p0 is the reference pressure

 i are stoichiometric coefficients
notes

Equilibrium constant
 If equilibrium constant is known, partial pressure of
components can be determined
 Equilibrium constant is function of temperature only
 It is tabulated

notes

Equilibrium constant

back to ex.3.4
back to ex.3.5

notes

Example 3.4
A stoichiometric mixture of CO and O2 in a closed vessel,
initially at 1 atm and 300 K, is exploded. Calculate the
composition of the products of combustion at 2500 K and the
gas pressure

notes

Example 3.4
A stoichiometric mixture of CO and O2 in a closed vessel,
initially at 1 atm and 300 K, is exploded. Calculate the
composition of the products of combustion at 2500 K and the
gas pressure
Combustion equation

1
CO  O 2  CO 2
2

From table

notes

Example 3.4
A stoichiometric mixture of CO and O2 in a closed vessel,
initially at 1 atm and 300 K, is exploded. Calculate the
composition of the products of combustion at 2500 K and the
gas pressure
Combustion equation

From table
Then

1
CO  O 2  CO 2
2

log10 K p  1.440

K p  27.54
notes

Example 3.4
If the degree of dissociation in the products is 
(i.e., a fraction of the CO2 formed by complete combustion
is dissociated), the product composition is

CO 2 ,  1    ;

CO,  ;


O2 ,
2

For this mixture, the number of moles of reactants nR is 3/2;
the number of moles of products nP is

nP   1   2 

notes

Example 3.4
The ideal gas law gives

pRV  nR RTR

pPV  nP RTP

Thus

pP
1 2500

 5.556 1 mol
nP p0 1.5 300

notes

Example 3.4
The equilibrium relation gives

 nP p0

12 
   2   pP 
1

12

 27.5

Numerical solution for  gives

  0.0074
notes

Example 3.4
Composition of products in mole fractions

xCO2

1

 0.893
nP


xCO 
 0.071
nP
 2
xO2 
 0.037
nP
Pressure of the product mixture

p  5.555nP  5.76 atm

notes

Example 3.5
In fuel-rich combustion product mixtures, equilibrium between
the species CO2, H2O, CO, and H2 is often assumed to determine
the burned gas composition. For  = 1.2 , for C8H18 –air
combustion products, determine the mole fractions of the product
species at 1700 K.

notes

Example 3.5
Solution:
Combustion reaction:
C8 H18 

12.5
 O2  3.773N 2   aCO2  bH 2O  cCO  dH 2  39.30N 2
1.2

Carbon balance gives:

ac 8

Hydrogen balance gives:

2b  2d  18

Oxygen balance gives:

2a  b  c  20.83
notes

Example 3.5
Water-gas reaction
CO 2  H 2  CO  H 2 O

Equilibrium equation gives
0

bc  p 

  Kp
ad  np0
or
bc
 Kp
ad

notes

Example 3.5
Water gas reaction:
CO 2  H 2  CO  H 2O

From table

notes

Example 3.5
Water gas reaction:
CO 2  H 2  CO  H 2O

From table

Then

and

log10 K p  0.53
K p  3.388
bc
 3.388
ad

notes

Example 3.5
Four equations are solved for c
c 2  19.3c  47.3  0

which gives

c  2.89,

a  5.12,

b  7.72,

d  1.29

The total number of moles of products is

a  b  c  d  39.3  56.3
and the mole fractions of the species in the burned gas mixture are
CO2, 0.0908;

H2O, 0.137;

CO, 0.051;

H2, 0.023;

N2, 0.698
notes

Simultaneous reactions

notes

Simultaneous reactions
 Consider mixture of N reacting gases in equilibrium
 If there are C chemical elements, conservation of elements will
provide C equations which relate the concentrations of N species
 Set of (N – C) chemical reactions, each in equilibrium, which
includes each species at least once will provide additional
equations required to determine concentration of each species in
the mixture
 Complete set of equations is a coupled set of C linear and (N – C)
nonlinear equations
 This set of equations is difficult to solve when (N – C) > 2
notes

Calculation of equilibrium composition for 18
species (N=18)of 4 chemical elements (C=4)

Species to be considered:

O,

O 2 , O3 ,

H,

H 2,

OH,

H 2O, C , CO, CO 2 , CH4 , N,
N2 , NO, NO2, NH3 , HNO3 , HCN
notes

Simultaneous reactions (N – C = 14)
1
O2 ƒ
2
3
O2 ƒ
2
1
H2 ƒ
2

O

 1

CH 4 ƒ

C  2H 2

 8

O3

 2

1
N2 ƒ
2

N

 9

H

 3

NO ƒ

NO

 10 

2H 2  O 2

 4

1
1
O 2  H 2 ƒ OH
2
2
CO 2 ƒ C  O 2

 5
 6

1
NO  O 2
2
1
3
NH 3 ƒ
N2  H2
2
2
NO  2HNO3 ƒ 3NO 2  H 2 O

 7

HCN ƒ

2H 2 O ƒ

CO ƒ

1
C  O2
2

NO 2 ƒ

C

1
1
N2  H2
2
2

 11
 12 
 13
 14 
notes

Equation of equilibrium

1
O2 ƒ O
2
3
O 2 ƒ O3
2
1
H2 ƒ H
2
2H 2 O ƒ 2H 2  O 2

 1

K1  pO pO1 22

 2

K 2  pO3 pO3 22

 3

K 3  pH p1H22

 4

K 4  pH2 2 pO2 pH2 2O

1
1
O 2  H 2 ƒ OH
2
2
CO 2 ƒ C  O 2

 5

K 5  pOH pO1 22 p1H22

 6

K 6  pC pO2 pCO2

 7

K 7  pC p1O22 pCO

CO ƒ

1
C  O2
2

notes

Equation of equilibrium

 8

K8  pC pH2 2 pCH 4

1
N2 ƒ N
2
NO ƒ N  O

 9

K 9  pN p1N22

 10 

K10  pN pO pNO

1
NO  O 2
2
1
3
NH 3 ƒ
N2  H2
2
2
NO  2HNO3 ƒ 3NO 2  H 2 O

 11

K11  pO1 22 pNO pNO2

 12 

K12  p1N22 pH3 22 pNH3

 13

3
2
K13  pNO
pH 2O pHNO
pNO
2
3

 14 

K14  pC p1N22 p1H22 pHCN

CH 4 ƒ

C  2H 2

NO 2 ƒ

HCN ƒ

C

1
1
N2  H2
2
2

notes

Conservation of chemical elements
p 

p 

p 

pC  pCO  pCO2  pCH 4  pHCN
pO  2 pO2  3 pO3  pOH  pH2O  3 pHNO3  pCO  2 pCO2  2 pNO2  pNO
pO  2 pO2  3 pO3  pOH  pH 2O  3 pHNO3  pCO  2 pCO2  2 pNO2  pNO
pNO2  pN  2 pN2  pNO  pNH3  pHNO3  pHCN
pC  pCO  pCO2  pCH4  pHCN
pH  2 pH 2  pOH  2 pH 2O  4 pCH 4  3 pNH3  pHNO3  pHCN

p  pO  pO2  pO3  pH  pH 2  pOH  pH 2O  pC  pCO  pCO2  pCH 4  pN 
pN2  pNO  pNO2  pNH3  pHNO3  pHCN

where:
 p  SC SO

 p  SO S N

  SC S H

notes

Some results

Mole fractions of equilibrium composition of isooctane-air mixtures as a function
of fuel/air ratio at 30 atm and (a) 1750 K, (b) 2250 K, (c) 2750 K
notes

back

notes

back

notes

Back to Ex

back

notes

Back to Ex

back

notes

Effect of pressure on composition
 pi
i  p 
 0

i

i

p   p
  xi   
i
 p0   p0

 i
i

i
x
 i  Kp
i

 If
 i  0 changes in pressure have no effect on the
i
composition.
 If
 i  0 (dissociation reaction), then the mole
i
fractions
of the dissociation products decrease as pressure
increases.
 i  0 (recombination reaction), the converse is true.
 If


i

Propane combustion with the just
right amount of oxygen
Propane  C3H 8
C3 H8  aO 2  bCO2  cH 2 O
Carbon balance:

3  1 b

Hydrogen balance: 8  2  c  c  4
Oxygen balance:

2a  2b  c  a 

C3 H8  5O 2  3CO2  4H 2O

23  4
5
2

Example – dry gas analysis
The measured dry exhaust gas composition of a propane-fueled SI engine is given
below (water was removed before the measurement). Calculate the equivalence
ratio.
CO2 = 10.8%,
O2 = 4.5%,
CO = 0%,
H2 = 0%
Solution
3.6C3H 8  22.5  O 2  3.773N 2   10.8CO 2  14.4H 2O  4.5O 2  84.9N 2

  1.25
  0 .8

Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K
CH 4  2O 2  CO 2  2H 2O

table

Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K
CH 4  2O 2  CO 2  2H 2O

For H2O gas:
H P0  392.52  2  241.83  876.18 MJ kmol CH 4
H R0  74.87 MJ kmol CH 4

 H  P  876.18  74.87  801.31 MJ kmol CH 4
0
0
0
 U  V   H  p  R  nP  nR  T0   H  p  801.3 MJ kmol
0

  U  V  801.3 MJ kmol CH 4

CH 4

0

table

Example 3.2 (cntd.)
For H2O liquid

H P0  393.52  2  285.84   965.20 MJ kmol CH 4

 H  P  965.20  74.87  890.33
0

MJ kmol CH 4

 U  V  890.33  8.314 103  1  3 298.15  885.4 MJ kmol CH 4
0

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Example 3.4 (R. Stone)
In a closed combustion vessel propane (C3H8) and air with
an equivalence ratio of 1.11 initially ant 25˚C burn to
produce products consisting solely of carbon dioxide
(CO2), carbon monoxide (CO), water (H2O) and
atmospheric nitrogen.
If the heat rejected from the vessel is 820 MJ per kmol of
fuel, find the final temperature.
If the initial pressure is 1 bar, estimate the final pressure.
notes

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Example 3.4 (cntd.)
Stoichiometric reaction
C3H 8  5  O2  3.77N 2   3CO 2  4H 2O  5  3.77N 2

Actual reaction

notes

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Example 3.4 (cntd.)
Stoichiometric reaction
C3H 8  5  O2  3.77N 2   3CO 2  4H 2O  5  3.77N 2

Actual reaction
C3H 8  4.5  O 2  3.77N 2   2CO 2  CO  4H 2O  5  16.93N 2

First law

QR  P  U P  U R

notes

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Example 3.4 (cntd.)
Reactants at 298 K: U R  U C H  4.5U O  16.93U N
3

8

2

2

 107.159  4.5   2.479   16.93   2.480 
 160.301 MJ kmol C3H 8
Let TP be 1700 K. Then products at 1700 K
U P  2U CO2  U CO  4U H2O  16.93U N 2

 2   334.239    78.753   4   198.266   16.93   31.265 
 1010.979 MJ kmol C3H8

QR  P  U P  U R  1010.979   160.301  850.678 MJ kmol C3H 8

850  820

therefore T  1700 K

tables

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Example 3.4 (cntd.)
Let TP be 1900. Products at 1900 K
U P  2U CO2  U CO  4U H2O  16.93U N2

 2   323.955    73.233   4   190.01  16.93   36.724 
 859.45 MJ kmol C3H 8

QR  P  U P  U R  859.45   160.301  699.149 MJ kmol C3H 8

699  820

therefore 1700  T  1900 K
tables

notes

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Example 3.4 (cntd.)
Let TP be 1800. Products at 1800 K
U P  2U CO2  U CO  4U H2O  16.93U N2

 2   329.117    76.003   4   194.78   16.93   33.983 
 935.617 MJ kmol C3H 8

QR  P  U P  U R  935.617   160.301  775.316 MJ kmol C3H 8

775  820 so T  1800 K
notes

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Example 3.4 (cntd.)
Volume of reactants (per 1 kmol of fuel)
nR RTR  1  4.5  16.93 R 298
V

pR
105
For the products
nP RTP  2  1  4  16.93 R 1800
pP 

105  6.44 bar
V
 1  4.5  16.93 R 298

notes

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Example 1
Octane (C8H18) is burned with the stoichiometric amount of air.
Calculate the AF and the molecular weights of the reactants and the products, as
well as the dew-point temperature of the products.
a  8 b  18
b
b


 b
Ca H b   a    O 2  3.773N 2   aCO 2  H 2O  3.773 a   N 2
4
2


 4
C8 H18  12.5  O 2  3.773N 2   8CO 2  9H 2O  3.773  12.5N 2
AFs 

12.5  31.998  3.773  28.16 
kg of air
 15.12
12.011  8  1.008  18
kg of fuel

Example – Reactants
nr  1  12.5   1  3.773  60.7 kmole
yC8H18  1 60.7  0.017
yO 2

 12.5 60.7  0.206

yN2

 47.2 60.7  0.777

M r   yi M i  0.017  114   0.206  31.998    0.777  28.16 
r

M r  29.1

kg
kmol

Example – Products
n pr  8  9  47.2  64.2 kmole
yCO2  8 64.2  0.125
yH2O  9 64.2  0.140
yN2  47.2 64.2  0.735
M pr   yi M i   0.125  44.011   0.140  18.016    0.735  28.16 
pr

M pr  28.7

kg
kmole

Example – dewpoint temperature
yH2O  0.140
pv  yH2O  p  0.140 101.33  14.19 kPa
Tdp  Tsat  pv   52.7o C

Example – octane with 25% excess air
Octane (C8H18) is burned with 25% excess air. Calculate the AF and the molecular
weights of the reactants and the products, as well as the dewpoint temperature of
the products.
a 8

b  18

  1.25

b
Ca Hb   s  O 2  3.773N 2   aCO 2  H 2O   s   -1 O 2  3.773 s N 2
2
C8 H18  15.625  O 2  3.773N 2   8CO 2  9H 2 O  3.125O 2  59N 2
AFa 

15.625  31.998  3.773  28.16 
12.01 8  1.008 18

 18.9

kg air
   AFs
kg fuel

Reactants
nr  1  15.625   1  3.773  75.6 kmole
yC8H18  1 75.6  0.013
yO2  15.625 75.6  0.207
yN2  59 75.6  0.780
M r   yi M i  0.013  34.232   0.207  31.998    0.780  28.16 
r

M r  29.0

kg
kmole

kg 
29
.
1

kmol

Products
n pr  8  9  3.125  59  79.1 kmole
yCO2  8 79.1  0.101
yH2O  9 79.1  0.114
yO2  3.125 79.1  0.040
yN2  59 79.1  0.745
M pr   yi M i   0.101 44.011   0.114 18.016 
pr

  0.040  31.998    0.745  28.16 
M pr  28.8

kg
kmole

kg 
28
.
7

kmole

Dewpoint temperature

yH2O  0.114
pv  yH2O  p  0.114 101.33  11.55 kPa
Tdp  Tsat  pv   48o C

 52.7 C 
o

Adiabatic combustion process
For adiabatic constant-volume
process
UP UR  0
U P  T0   U R  T0    U  V ,T

0

Given by initial reactant state (TR , p) we
can determine the final product state (TP , p)
from:

 U P  T   U P  T0    U R  T   U R  T 0     U  V ,T
0

Excess air
b
Ca H b   s  O 2  3.773N 2   aCO 2  H 2O  xO 2  3.773 s N 2
2

s  a 

b
4

2 x  2 s  2a 


b
b 

 2   s   a    2 s    1
2
4 

b
Ca H b   s  O 2  3.773N 2   aCO 2  H 2O   s   -1 O 2  3.773 s N 2
2

Chemically reacting gas mixtures
 Working fluid in engine is a chemically reacting mixture of
gases
 Reaction never goes to completion
 Extent to which reaction proceeds is limited by many
factors
 Actual composition of the products can be determined only
from experiment
notes

Chemically reacting gas mixtures
 Mixture composition may be considered as:
“frozen”
 in chemical equilibrium
 controlled by chemical reaction rate

notes

Example
A fuel has the following composition
pentane (C5H12)
heptane (C7H16)
octane (C8H18)
dodecane (C12H26)
benzene (C6H6)

10% by mass
30% by mass
35% by mass
15% by mass
10% by mass

Calculate gravimetric composition of the fuel and air fuel ratio for equivalence ratio of 1.1

notes