ICE: Generalities about combustion

Internal combustion engines: generalities about combustion

1. Introduction

2. Different types of combustion

2.1. Chemical equation of combutsion

2.2. Parameters of a reactive mixture

3. Combustion equations

3.1. Main stoichiometric combustion equations

3.2. Heat of combustion and heat of formation

3.3. Calorific (pouvoir calorifique), combustive (comburivore) values, smoke density rating (pouvoir
fumigène)

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Internal combustion engines:
generalities about combustion
1. Introduction
Combustion is a chemical reaction between a fuel and pure
oxygen, diluted oxygen (air) or chemical species which contain
big amount of oxygen.
This reaction is globally and generally strongly exothermic,
autonomous, that can be roughly accelerated and emit
radiations.
Combustion velocity can vary a lot as a function of parameters
involved in such a mechanism.

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ICE: generalities about combustion - Introduction
From a chemical point of view, combustion can be assimilated
to a reduction: reducer agents are called combustibles or fuels;
oxidizing agents are simply called oxidizers (air).

Fuels contain carbon and hydrogen.

Examples of fuels:
- gases: natural gas, methane, hydrogen…
- liquids: oil, gasoline…
- solids: wood, coal, plastics…

Oxidizers are very generally gaseous.

Examples of oxidizers: air, oxygen…

Examples of industrial applications of combustion:

- Internal combustion engines (gasoline, diesel),
- Gas turbines,
- Turbojets,
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- Industrial boilers…
ICE: generalities about combustion - Introduction
Generally, a unit of fuel is taken into account:
- unit of mass for liquids and solids,
- unit of volume for gases.
Amount are expressed:
- in %,
- in content/fraction (varies from 0 to 1):
 for liquids and solids, in % or in mass fractions,
 for gases, in % or in volume fractions.
Generally, the amount of a component is marked as the
lowercase letter of its chemical formula.
Particular case: the amount of water is marked as w.

Example: H2 + 0,5 O2 H20: h2= 1/(1+0,5) = 67 %

02: o2 = 0,5/(1+0,5) = 33 %
Reminder: For a 4 stroke engine, which rotational velocity is
3000 tr/min, calculate the maximal time corresponding to the
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air/fuel mixture combustion phase.
ICE: generalities about combustion–types of
combustions
2. Different types of combustion (see TD)
1- complete or incomplete combustions:
a) complete (total): there is no more fuel in the products
b) incomplete: some fuel remains (« unburnt ») in the products
2- stoichiometric combustions:
a) complete
b) performed with necessary and sufficient amount of oxidizer
So, there is neither fuel nor oxidiser remaining in the products.
3- combustions with excess of air:
a) more oxidizer than the necessary and sufficient minimum amount

b) combustion can consequently be:

 oxidising: if the reaction is complete
 « half-oxidising » reaction: if the reaction is incomplete
4- combustions with default of air:
a) less oxidizer than the necessary and sufficient minimum amount
b) combustion is consequently incomplete: reductive (no more air)
or « half-reductive » reaction (air remaining). 7
ICE: generalities about combustion–types of
combustions
2.1. Chemical equation of combustion:

If the combustion is stoichiometric:

CxHy + (x+y/4) (O2 + 3,76 N2)  x CO2 + y/2 H20 + (x + y/4)3,76
N2

Volume composition of dry air: 21% O2 and 79% N2.

« Expression » for a mole of air: O2 + (79/21) N2: O2 + 3,76 N2.
Molar mass for O: 16 g.mol-1.
Molar mass for N: 14 g.mol-1.

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ICE: generalities about combustion–types of
combustions
2.2. Parameters of a reactive mixture:

- Dilution:

Only for mixes containing air.

Hydrocarbon CnHm: Dstoechio# 15
Turbojet : D# 40-60

- Mixing ratio:

Mainly used in propulsion.

For Vulcain engine (H2-O2): ϕ # 6

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ICE: generalities about combustion–types of
combustions
- Fuel-air equivalence ratio:

Poor mixture : r < 1

Rich mixture : r > 1
Stoichiometric mixture: r = 1

- Air-fuel equivalence ratio:

For engines and turbojets aircrafts:

poor mixtures (r= 0,10 to 0,80), very heterogeneous
environment.

For ICE:
rich mixtures, stoichiometric or poor.

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ICE: generalities about combustion–types of
combustions
For a poor mixture, (complete) combustion equation becomes:
rCxHy + (x+y/4) (O2 + 3,76 N2) 
x.r CO2 + y.r/2 H20 + (x + y/4) (1-r)O2 + (x + y/4) 3,76 N2

And for a real and general case (incomplete), one has:

rCxHy + (x+y/4) (O2 + 3,76 N2) 
a CO2 + b CO + c CxHy + d H2 + e O2 + f H20 + g N2 + h
NO

Exercises:
Exercise 1: Write the combustion equation of n-heptane (C7H16).
r is taken equal to r = 1.
Exercise 2: Calculate the volume of air needed to
stoichiometrically burn 1 mol of propane gas in the air
(298 K; 0,98 bar). 11
ICE: generalities about combustion–combustion
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3. Combustion equations
3.1. Main stoichiometric combustion equations
Some examples of stoichiometric reactions:

H2 + 0,5 O2  H2O
C + O2  CO2
S + O2  SO2
CH4 + 2 O2  CO2 + 2 H2O
C2H2 + 2,5 O2  2 CO2 + H2O
C4H10 + 6,5 O2  4 CO2 + 2 H2O

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ICE: generalities about combustion–combustion
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3.2. Heat of combustion and heat of formation
3.2.1. Definition of the heat of combustion
Heat of combustion (or reaction) is the amount of heat
transferred between reactive species and the outdoor
environment during the combustion reaction when products are
at the same temperature than the reactive species.
Reference temperature θ0 is usually set at 0°C or 25 °C.
Two cases can occur:
• combustion at a given pressure (more common): heat of
combustion corresponds to the enthalpy variation of the
system.
• combustion at a given volume: heat of combustion
corresponds to the internal energy variation of the system.

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ICE: generalities about combustion–combustion
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The following table indicates heats of combustion for some
compounds (θ0 = 298 K):

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ICE: generalities about combustion–combustion
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3.2.2. Definition de the heat of formation
Heat of formation corresponds to the amount of heat
transferred during the formation of a pure component from its
constitutives when products are at the same temperature than
the reactive species.
Although it is generally defined at constant pressure, it can also
be calculated at constant volume.
3.2.3. Standard parameters
Standard pressure = 1 bar.
Standard state of reference for an element: the one for which
this element is in its more stable state at standard pressure (1
bar).
Standard enthalpy of formation ∆Hf0: heat of formation
corresponding to the synthesis of a mole performed at standard
pressure.
Standard enthalpies of pure compounds are conventionally
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null.
ICE: generalities about combustion–combustion
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The following table gives standard heats of formation (θ0 = 298
K):

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3.2.4. Calculation of the heat of combustion (or reaction)
The following relation relies heat of combustion and heat of
formation (Hess law):
Heat of combustion = Σ heats of formation of products –
Σ heats of formation of reactive species

If the following reaction is considered:

Reactive species (j)  Products (i):

The standard heat of reaction (P0 = 1 bar, T0 = 298 K) is:

So, the heat of reaction at T≠ T0 is:

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ICE: generalities about combustion–combustion
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Exercises:
1) Write the stoichiometric equation of combustion of CH4 in
Air.
2) Give the value of heat combustion of the standard reaction.
One gives:
= -94,5 kcal/mol;
= -68,29 kcal/mol;
= -17,89 kcal/mol.

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ICE: generalities about combustion–combustion
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Examples of reactions of combustion at constant pressure with
corresponding standard enthalpies of combustion:

H2 (gaz) + 0,5 O2 (gaz)  H20 (liq.) ∆Hr0= - 285,83 kJ/mol

H2 (g) + 0,5 O2 (g)  H20 (gaz) ∆Hr0 = - 241,83 kJ/mol
C (graphite) + O2 (g) CO2 (gaz) ∆Hr0 = - 393,51 kJ/mol
S (solide) + O2 (g)  SO2 ∆Hr0 = - 296,81 kJ/mol

CH4 (g) + 2 O2 (g)  CO2 (g) + 2 H2O (g) ∆Hr0 = - 802,4 kJ/mol
C2H4 (g) + 3 O2 (g)  2 CO2 (g) + 2 H2O (g) ∆Hr0 = - 1323 kJ/mol
C2H2 (g) + 2,5 O2 (g)  2 CO2 (g) + H2O (g) ∆Hr0 = - 1257 kJ/mol
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (g) ∆Hr0 = - 2044 kJ/mol
C3H8 (l) + 5 O2 (g)  3 CO2 (g) + 4 H2O (g) ∆Hr0 = - 2030 kJ/mol

They are exothermic reactions. 19

ICE: generalities about combustion–combustion
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3.3. Calorific (pouvoir calorifique), combustive
(pouvoir comburivore) values and smoke density
rating (pouvoir fumigène):
3.3.1. Calorific value
It is the absolute value of the amount of heat corresponding to
the complete combustion of a unit of fuel.
Reactive species are taken at 298 K and 1 atm.
Products are also assumed to be at 298 K.

Unit: kJ/kg of fuel (solid or liquid),

kJ/m3 of fuel for gases.

There is no fundamental difference between calorific power and

heat of combustion, except the sign convention.
Indeed, for an exothermic reaction:
- calorific power is > 0
- heat of combustion is < 0 20
ICE: generalities about combustion–combustion
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Superior (P or SCP) and Inferior (I or ICP) calorific powers:
For a superior calorific power (P) calculation, water in the fuel
or created during combustion is at condensated state in the
products .
So P takes into account the heat of condensation of water.

For a inferior calorific power (I) calculation, water in the fuel or

created during combustion is at gaseous state in the products .
So I does not take into account the heat of condensation of
water.

One can usually distinguish superior and inferior calorific

powers at constant volume Pv and Iv and superior and inferior
calorific powers at constant pressure Pp and Ip.

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ICE: generalities about combustion–combustion
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Relation between superior (P) and inferior (I) calorific powers:
At constant pressure, one has the following equation:
Pp – Ip = Qcond
where Qcond= mliquidxL with L, the latent heat.
Pp – Ip = mliquidxL
So where mliquid is the mass of liquid
per unit of mass of fuel
Calculation of calorific power:
Gaseous fuel:
Not really difficult, calculation similar to the one of heats of
reaction or combustion.
Be careful to units!
Solid fuel:
Difficult: components are not mixtures but combinations.
Liquid fuel:
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Difficult. The calculation is often limited to only one
ICE: generalities about combustion–combustion
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Relation between superior (P), inferior (I) calorific powers and
heat of combustion:

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ICE: generalities about combustion–combustion
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Examples of inferior calorific powers of some fuels:

Fuel Massic I ρ Volumic I

(kJ.kg-1 à 25 °C) (kg.dm-3 à 25 °C) (kJ.dm-3 à 25 °C)
GPL 46000 0,550 25300
Essence 43325 0,735 31845
ordinaire
Supercarburant 42900 0,755 32390
Carburéacteur 42850 0,795 34065
Gazole 426000 0,840 35785

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ICE: generalities about combustion–combustion
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Exercise 1:
SCP (or P) of kerosene is equal to 46890 kJ.kg-1.
The composition of kerosene is assumed to be, in mass:
86% of carbon and 14% of hydrogen.
The condensation of a mole of water corresponds to a heat
equal to 41,1 kJ/kgkerosene.
1) Give the chemical formula of kerosene (one considers 1kg)
2) Write the stoichiometric equation of the combustion of
kerosene in O2.
3) Calculate the ICP (or I) for kerosene.

Exercise 2:
Calculate the ICP and SCP of propane knowing that:
∆Hf0(C3H8)= -104 kJ.mol-1, ∆Hf0(CO2)= -393 kJ.mol-1,
∆Hf0(H20)g= -241 kJ.mol-1, ∆Hf0(H2O)l= -285 kJ.mol-1.

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ICE: generalities about combustion–combustion
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3.3.2. Combustive power

It corresponds to the volume of air necessary and strictly

sufficient to perform the neutral combustion of a unit of fuel
mass (or volume).
Notation: Vao
Unit: Nm3 d’air/kg of fuel (solid or liquid),
Nm3 d’air/Nm3 of gaseous fuel

Remarque: Nm3 is a unit called « normo mètre cube ». It

corresponds to the volume of a cubic meter for a gas in normal
temperature and pressure conditions (0 or 15 °C et 1 atm).

Calculations are simple:

1) The volume VM of a mole of an ideal gas is 22, 4 l. VM= 22,4
l/mol
2) To have 1 m3 of O2, 4, 762 m3 of air is needed
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(« 1 mole of air = 02 + 3, 762 N2 »)
ICE: generalities about combustion–combustion
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Example of calculations:
1- Solid and liquid fuels:
A solid or liquid fuel can contain oxygen O.
The number of moles of 02 needed for its combustion is
consequently the sum of the number of moles of 02 needed to
the oxidation of every component of this fuel minus the number
of moles of 02 already present in the latter (as they have not
been brought).
Exercise:
Let’s consider the combustion of 1 kg of a given fuel:
CH4 + S + 02 + 2 (02 + 3,76 N2)  1 C02 + 2 H20+ SO2 + 02
c, h, s et o are, respectively, the mass fractions for C, H, S et O
in the fuel.
1) For every element C, H et S, give the number of mol per kg
of fuel of 02 needed for combustion.
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ICE: generalities
Example about combustion–combustion
of calculations:
equations
2- Gaseous fuels:
The procedure is the same than the one for liquid and solid
fuels.
However, the calculation is more simple, fractions of quantities
being already given in m3 (gas)/m3(fuel).

Example:
We consider a fuel mixture composed by CmHp, C0, and 02.
Calculate the combustive power of the reaction.

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ICE: generalities about combustion–combustion
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Example:
Neutral combustion of 1 mol of Butane:
C4H10 + 6,5 (02+ 3,762 N2) 4 C02+5 H20 + 24,45 N2
Va0 ? (see previous slide):

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ICE: generalities about combustion–combustion
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3.3.3. Smoke density rating
It corresponds to the volume of products (or smokes) resulting
from the neutral combustion of a unit of fuel (mass or volume).
Notation: Vf’o or Vfo
Unit: Nm3 of products/kg of fuel (solid or liquid),
Nm3 of products/Nm3 of gaseous fuel

We have:
- Wet smoke density rating Vf’o :
Water produced by the combustion is at vapour state.
It is the real quantity of gaseous products.
- Dry smoke density rating Vfo :
Water produced by the combustion is at liquid state.
Gaseous products that are taken into account are only CO2, N2,
(SO2).
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ICE: generalities about combustion–combustion
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Example:

Neutral combustion of 1 mol of gaseous methane:

CH4 + 2 (02 + 3,762 N2) C02+ 2 H20 (l)+ 7,52 N2
Wet smoke density rating:
1) Vf’o?

Dry smoke density rating:

2) Vfo?

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