Thermo chemistry of Fuel-Air

Mixtures
 Thermo Chemistry

 Most IC engines obtain their energy from the

combustion of a HC fuel with air, which concert
chemical energy of the fuel to internal energy in the
gases within the engine.
 Deal with the composition and thermodynamic
properties of pre and post combustion gases.
 Thermo chemistry of Fuel-Air
Mixtures
Combustion
 It is an exothermic reaction in a fuel – air
mixture.
 Combustion is defined as the oxidation of a
‘fuel’, with large amounts of released energy. The
oxidizers in most cases air (or more specifically, O2
in air) because of its abundance which effects engine
power, efficiency and emission.
 What is a Flame?

 A combustion reaction
propagating sub sonically through
space, it moves relative to unburned
gas.

 Reaction Zone
 Thermo/Chemical characteristics
 Types of Flame

■ Premixed
■ Diffusion
■ Both can be Laminar or Turbulent
 Premixed

■ Mixed before Combustion

■ Characteristics.
■ Reacts rapidly
■ Constant pressure
■ Propagates as thin
zone
■ Ex: Spark engine
 Diffusion

■ Mixed during Combustion

■ Characteristics.
■ Reaction occurs at Fuel/Air
interface
■ Controlled by the Mixing of
the Reactants
■ Ex: Diesel Engines
 Laminar

■ Premixed
■ Simplest flame type
■ Ex: Bunsen burner
■ Diffusion
■ Ex: Candle
 Turbulent

 Premixed
■ Faster heat release
than laminar
■ Ex: Indirect fuel
injection engines
 Diffusion
■ Ex: Direct fuel engines
injection
 Engine Flames

 Premixed (SI) or diffusion (CI) turbulent

unsteady gas-phase flames.

 Turbulence increases mixing and flame speed.

 Diffusion (motion due to concentration

gradient) of species is slower than connection
(motion due to bulk vel).

 In flame propagation there is strong coupling

between chemical reactions and mass and heat
transport processes.
 Ideal Gas Model

 Usually IC engine working fluids can be

“modeled” as ideal gases ( or mixture of ideal gases)
which follow the ideal gas law:
PV = m RT = n RT
Where, p = pressure
v= volume
m= mass
R= Characteristic gas constant= R/M
T= temp
n= no of moles
R= Universal gas constant
M= Molecular wt.
 Air Composition

On a molar (or volume) basis, dry air composed of:

 Nitrogen (78.1%): Relatively inert and its stable in

nature due to the triple bond NN.

 Oxygen (20.9%) : The reactive component in air.

 Carbon dioxide, Argon, Helium, Neon, hydrogen and

Traces of other gases: 0.9%

 A good approximation of this by molar or volume is: 21%

oxygen, 79% nitrogen

 Thus, in dry air each mole of O2 is accompanied 0.79/0.21

= 3.76 moles of N2.
 Air Composition

 At ordinary combustion temps, N2 is inert, but nonetheless

greatly affects the combustion process because its abundance,
and hence its enthalpy change, plays a large part in
determining the reaction temps.

 This, in turn, affects the combustion chemistry.

 At higher temps, N2 does react, forming species such as

oxides of nitrogen (NOx), which are a significant pollutant.

 Actually air inducted into an IC engine contains some water

vapor . The water vapor in the inlet air, increases the sp heats
(cp & cv) of air. Thus  (cp/cv) is decreased, thus end of
compression temp decreases.
 Fuels
 A ‘fuel’ is any material (mostly HCs) that store energy in
their chemical bonds. Highest energy storage per unit mass or
unit volume (in liquid form)) that can be burned to release
energy. HC fuels of the form CxHy are the most common.

 Many HC fuels are mixtures of many different HCs

although they mainly consist of the following:

 Gasoline ~ Octane: C8H18

 Diesel ~ Dodecane: C12H26
 Methanol = methyl alcohol: CH3OH
 LNG (liquefied natural gas)~ methane: CH4
 LPG (liquefied petroleum gas)~ propane: C3H8
 Combustion Stoichiometry

 Develops relations between the composition of the

reactants (fuel and air) of a combustible mixture and the
composition of the product by using the conservation of mass of
atomic species.

 Stoichiometric air is defined as the theoretical amount of

air required to completely burn a fuel to products with no
dissociation.

 If sufficient oxygen is available, a HC fuel can be

completely oxidized, the carbon is converted to carbon dioxide
(CO2) and the hydrogen is converted to water (H2O).
 Thermo chemistry of Fuel-Air
Mixtures
The stoichiometric or theoretical A/F is defined as the
minimum amount of air that supplies sufficient
oxygen for the complete combustion of all the
carbon, hydrogen and any other elements in the fuel
that may oxidize.
For example, the stoichiometric A/F for the ideal
combustion of octane can be calculated as follows:
On a molar basis:
(A/F)mole= (12.5 moles O2+ 47.0 moles N2)/(1
mole of fuel)
(A/F)mole= 59.5 mole air/mole fuel
 Thermo chemistry of Fuel-Air
Mixtures
On a mass basis:
(A/F)mass= (59.5 mole air/mole fuel)*(28.97
kg/mole air)/(114.2 kg/mole fuel)
(A/F)mass= 15.0 kg air/kg fuel
 Thermo chemistry of Fuel-Air
Mixtures
Ex: The overall chemical equation for the complete
combustion of one mole of propane (C3H8) is:

C3H8+ aO2 = bCO2+ cH2O …………………………….. (1)

We know that elements can not be created or destroyed so, to

find a, b & c , we need to consider element balances:
Carbon balance gives : 3=b  b=3
Hydrogen balance gives : 8 =2c  c=4
Oxygen balance gives : 2a = b + c  a=5

Thus the eqn (1) becomes:

C3H8+ 5O2 = 3CO2+ 4H2O …………………………….. (2)

 Thermo chemistry of Fuel-Air
Mixtures
■ Air contains molecular nitrogen N2, but when the
products are low temps the nitrogen is not significantly
affected by the reaction, it is considered inert. The overall
complete combustion eqn is:
CaHb+(a +b/4)(O2 +3.76N2) = aCO2+ b/2.H2O + 3.76 ( a+ b/2 )N2

The above equation defines the stoichiometric proportions

of fuel and air.

In complete, stoichiometric combustion of hydrocarbons,

the products are water and carbon dioxide. Let y= b/a .
 Thermo chemistry of Fuel-Air
Mixtures
■ In complete, stoichiometric combustion of
hydrocarbons, the products are water and carbon dioxide.
Let y= b/a .

( 1+ y/4) ( 32 + 3.76  28.16)

(A/F)s = (F/A)1s=
12.011 +1.008y

34.56 (4+ y)
=
12.011 +1.008y
 Combustion Stoichiometry

Example: For propane (C3H8) , a= 3 and b = 8

The overall complete combustion eqn is:

CaHb+(a+b/4)(O2 +3.76N2) = aCO2 +b/2. H2O +3.76(a+ b/2)N2

So we can write the above eqn:

C3H8+ (5)(O2 + 3.76 N2)  3CO2+ 4H2O + 3.76 (5) N2

The stoichiometric mass based air/fuel and fuel/air ratio is:

( a+ b/4) MO2 + ( a+ b/4) MN2

(A/F)s = (F/A)1s= ---------------------------------
 Combustion Stoichiometry

Substituting the respective molecular weights and dividing top

and bottom by a = one gets the following expression that only
depends on the ratio of the number of hydrogen atoms to
carbon atoms (b/a)in the fuel.
{1+ (b/a)/4} (32 + 3.76  28)
(A/F)s = (F/A)1s= ----------------------------------
12 + (b/a).1

Note: Above equation only applies to stoichiometric mixture.

For methane (CH4), b/a= 4  (A/F)s = 17.2

For octane (C8H18), b/a = 2.25  (A/F)s= 15.1

■ Now in an actual engine, the amount of air utilized may
be greater than or less than the theoretical air required for
complete combustion of fuel.
■ If excess air is used, then the combustion is said to
occur fuel- lean condition.

■ If less than theoretical amount of is air is used, then the

combustion is said to occur fuel- rich condition.
ma  mas
Percent Excess air = ( ------------ )  100
mas

ma
Percent theoretical air = (---- )  100
mas

  Excess air =  theoretical air  100

 Equivalences ratio ()

The equivalence ratio, , is commonly used to

indicate if a mixture is stoichiometric, fuel lean, or
fuel rich.

Actual fuel air mass ratio

 = -------------------------------------
Stoichiometric fuel air mass ratio

(F/A)a (mf/ma) mas/mfs (A/F)s

= ------ = -------- = ------- = -------
(F/A)s (mfs/mas) ma/mf
 Combustion Stoichiometry

 Fuel-air ratio on mass basis is different from fuel-air

ratio on mole basis.

On mass basis:

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

112 + 4 1
 (F/A)s = mfs /mas = ------------------- = 0.05827
2(32 + 3.7628)
On mole basis:
1 1
 (F/A)s = nfs /nas = ---------- = ----- = 0.1050
(2+7.52) 9.25
 Equivalences ratio ()

Another parameter that is used with reference to

engine is the relative air/ fuel ratio().

The inverse of , the relative air/ fuel ratio 

  =1/ = (A/F)a/(A/F)s

 if   1,  1  Fuel-lean mixture

  1,   1  Fuel- rich mixture

 Fuel Lean Mixture
■ Fuel-air mixtures with more than stoichiometric air,
excess air, can burn.

■ With excess air you get fuel lean combustion, the extra
air appears in the products in unchanged form.
b b
CaHb +  (a + ---)(O2 +3.773N2) = aCO2 + --- H2O + dN2 + e O2
4 2
where for fuel lean mixture have excess air so  > 1

Above reaction equation has two unknowns (d, e) and we have

two atom balance equations (O, N) so can solve for the
unknowns.
 Fuel Rich Mixture

■ Fuel-air mixtures with less than stoichiometric air can

also burn.

■ With less than stoichiometric air you get fuel rich

combustion, there is insufficient oxygen to oxidize all the C and
H in the fuel to CO2and H2O.

■ Get incomplete combustion where carbon monoxide (CO)

and molecular hydrogen (H2) also appear in the products
b
CaHb +  (a + ---)(O2 +3.76N2)= cCO2 +dh2o +eN2 + f CO +gH2
4
where for fuel lean mixture have excess air so  < 1
 Fuel Rich Mixture

Above reaction equation has three unknowns (c, d, e, f,g) and

we only have two atom balance equations (C, H, O, N) so
cannot solve for the unknowns unless additional information
about the products is given.
 Equivalences ratio ():

The equivalence ratio, , is commonly used to indicate if a

mixture is stoichiometric, fuel lean, or fuel rich.
Actual fuel air mass ratio
Equivalences ratio  = ------------------------------------- ---
Stoichiometric fuel air mass ratio

(F/A)a (A/F)s
= ------ = --------
(F/A)s (A/F)a
Stoichiometric : =1
Fuel lean : <1
 Combustion Stoichiometry

Stoichiometric mixture:
b
Ca Hb + (a + ---)(O2 +3.76N2)  Product
4
Off-Stoichiometric mixture:
1 b
Ca Hb + --- (a + --- )(O2 +3.76N2)  Product
 4
Off-Stoichiometric Conditions:
150% Stoichiometric air = 150% theoretical air = 50% excess
air.  = 1.5  mixture is fuel lean
Example: Consider a reaction of octane with 10% excess
air, what is ?
We know the stoichiometric reaction is:
b b b
CaHb+(a+---)(O2 +3.76N2) = aCO2+--- H2O +3.76 ( a+ --- )N2
4 2 4
The stoichiometric reaction for octane is

C8H18 + 12.5 (O2 + 3.76 N2 )  8CO2 +9H2O + 47 N2

10% excess air is:
C8H18 +1.1(12.5)(O2+3.76 N2)  8CO2+9H2O+ aO2+bN2

Oxygen balance gives: 1.1(12.5)(2)=16 + 9 + 2a

a=1.25

Nitrogen balance gives: 1.1(12.5)(3.76)=b

b=51.5
The above eqn become

C8H18 +1.1(12.5)(O2+3.76 N2)  8CO2+9H2O+ 1.25O2+51.5N2

(A/F)s 12.5(32+3.7628)/(8  12 + 1 18)

 = ------ = ----------------------------------------------
(A/F)a 1.1  12.5(32+3.7628)/(8  12 + 1 18)