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3

TOPIC

Thermochemistry of
fuel-air mixtures

Whats covered in this section


Characterization of flames
Fuels
Stoichiometry
First law and combustion
Second law applied to an engine
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

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

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

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

Fuels
Actually blends of many different hydrocarbons
Predominantly hydrogen (~14% by mass) & carbon (~86% by mass)
Diesel fuel can contain some sulfur (~1%)
Alcohol fuels contain some oxygen

Methanol = methane with 1 H replaced by 1 OH

Ethanol = ethane with 1 H replaced by 1 OH

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.

Fuel composition
Gravimetric composition is given by mass fractions of C and H in the fuel.
Used for liquid fuels

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

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

23 4
5
2

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

Composition of air

General stoichiometry
Approximate a fuel with a carbon atoms and b hydrogen atoms

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
AFs

a b 4 31.998 3.773 28.16


12.011a 1.008b

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.

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
C a 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 2 O 3.773 12.5N 2
AFs

12.5 31.998 3.773 28.16


12.011 8 1.008 18

15.12

kg of air
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

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

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

s 32 3.773 28.16
AFa
12.01a 1.008b
AFs

s 32 3.773 28.16
12.01a 1.008b

AFs FAa 1


AFa FAs

Equivalence ratio
Relative ratio

Lean- and rich-burn mixtures


Fuel - lean

Stoichiometric

Fuel-rich

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

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

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

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

Energy of reactants and products


Effect of water in products

U V ,T ,H Oliq U V ,T ,H O vap
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

ni h 0f ,i

Example 3.2
Calculate the enthalpy of the products and reactants, and the
enthalpy increase and internal energy increase of the reaction, 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


0

MJ kmol CH 4

U V H p R nP nR T0 H p 801.3 MJ kmol CH 4
0

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 8.314 103 1 3 298.15 885.4 MJ kmol CH 4


0

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

QHVV U V ,T

Higher heating value differs from lower heating value by latent


heat of vaporization

QHHVp QLHVp

mH2O

h fg H2O

mf

Adiabatic flame temperature


For adiabatic constant-volume process
UP UR 0
U P T0 U R T0 U V ,T

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

Energy of reactants
and products
Find molar enthalpy of N2 at 400 K

hN2 400 K 2973 kJ kmol

R.Stone

Example 3.3 (R. Stone)


In a closed combustion vessel propane (C3H8) and air with
an equivalence ratio of 1.11 initially ant 25C 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.

Example 3.3 (cntd.)


Stoichiometric reaction
C3 H8 5 O 2 3.77N 2 3CO 2 4H 2O 5 3.77N 2

Actual reaction
C3 H8 4.5 O 2 3.77N 2 2CO 2 CO 4H 2O 5 16.93N 2

First law

QR P U P U R

Example 3.3 (cntd.)


Reactants at 298 K: U R U C H 4.5U O 16.93U N
3

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

Example 3.3 (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

Example 3.3 (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

Example 3.3 (cntd.)


To estimate the final pressure, apply the equation of state; use a
basis of 1 kmol of fuel:
pV nRT
Volume of reactants

nR RTR 1 4.5 16.93 R 298


V

p
105

For the products


nP RTP 2 1 4 16.93 R 1800
p

105 6.44 bar


V
1 4.5 16.93 R 298

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

H R TA H P TA
m f QHV

ni h
i , products

0
f ,i

Combustion efficiency

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
In many cases products of combustion can be assumed to
be in chemical equilibrium

Chemically reacting gas mixtures


Chemical reactions may:
be so slow that they have a negligible effect on mixture
composition (mixture composition is frozen)
be so rapid that the mixture state changes and the
composition remains in chemical equilibrium
be one of the rate-controlling process that determine
how the composition of the mixture changes with time

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

Chemical equilibrium
In combustion products of hydrocarbon fuels, the major
species present at low temperatures are N2, H2O, CO2, and
O2 or CO and H2.
At higher temperatures (> about 2200 K), these major
species dissociate and react to form additional species
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.

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

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

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

Condition of chemical equilibrium


Change of Gibbs energy of ideal gas mixture

G p ,T i ni
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

(a )

Mass action law


Substitution in (a) gives

pi
T RT ln p i n 0
0

pi
ln p
0

0
i

T
0
i

RT

G T
0

RT

ln K p

Mass action law


pi
Kp
i p0

Kp is the equilibrium constant

pi are partial pressures of components


p0 is the reference pressure

i are stoichiometric coefficients

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

Equilibrium constant

back to ex.3.4
back to ex.3.5

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

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

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

Example 3.4
The equilibrium relation gives

nP p0

12
2 pP
1

12

Numerical solution for gives

0.0074

27.5

Example 3.4
Composition of products in mole fractions

xCO2

0.893
nP

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

p 5.555nP 5.76 atm

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.

Example 3.5
Solution
The reaction relating these species (often called the water gas
reaction) is
CO 2 H 2 CO H 2O
From table

log10 K p 0.53
Then

K p 3.388

Example 3.5
Combustion reaction
12.5
C8 H18
O2 3.773N 2 aCO 2 bH 2O cCO dH 2 39.30N 2
1.2
Carbon balance gives:

ac 8

Hydrogen balance gives:

2b 2d 18

Oxygen balance gives:

2a b c 20.83

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

Equilibrium equation gives


0

bc p
Kp
ad p0
or
bc
3.388
ad

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

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

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

Simultaneous reactions (N C = 14)


1
O2
2
3
O2
2
1
H2
2

CH 4

C 2H 2

O3

1
N2
2

NO

NO

10

2H 2 O 2

1
1
O 2 H 2 OH
2
2
CO 2 C O 2

5
6

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

HCN

2H 2 O

CO

1
C O2
2

NO 2

1
1
N2 H2
2
2

11
12
13
14

Equation of equilibrium

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

K1 pO pO1 22

K 2 pO3 pO3 22

K 3 pH p1H22

K 4 pH2 2 pO2 pH2 2O

1
1
O 2 H 2 OH
2
2
CO 2 C O 2

K 5 pOH pO1 22 p1H22

K 6 pC pO2 pCO2

K 7 pC p1O22 pCO

CO

1
C O2
2

Equation of equilibrium

K8 pC pH2 2 pCH 4

1
N2 N
2
NO N O

K 9 pN p1N22

10

K10 pN pO pNO

1
NO O 2
2
1
3
NH 3
N2 H2
2
2
NO 2HNO3 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

C 2H 2

NO 2

HCN

1
1
N2 H2
2
2

Conservation of chemical elements


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

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

Effect of pressure on composition


pi
i p
0

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