Chapter 4

Chapter 4
Thermochemistry and Fuels

Thermochemistry and fuels (cont.)
Objectives of this chapter:
● Review combustion reaction
● Analyze engine exhaust analysis
● Identify different fuels and their properties

● Most IC engines obtain their energy from the

combustion of hydrocarbon fuel with air.
● The hydrocarbon fuel contains mainly of

hydrogen and carbon.
● The maximum amount of energy released

from fuel combustion occurs at
stoichiometric reaction.
● At stoichiometric reaction (complete

combustion) of hydrocarbon fuel with air is
converted into CO2 and H2O as combustion
products.
● For complete combustion of propane:

C3H8 + aO2 = bCO2 + cH2O
● A carbon balance between the reactants and

products gives b = 3 moles.
● A hydrogen balance gives c = 4 moles.
● An oxygen balance gives a = 5 moles.

C3H8 + 5O2 = 3CO2 + 4H2O
● Air contains nitrogen but when the products
are at low temperatures the nitrogen is not
affected by the reaction.
● Ex1:
The stoichiometric combustion of diesel fuel is:
C12H21+a(O2+3.76N2) → bCO2+cH2O+dN2
- Carbon balance gives:
12 = b
- Hyrogen balance gives:
21 = 2C
C = 10.5
- Oxygen balance gives:

2a = 2b + C
a = [2(12) + 10.5 ] / 2 = 17.25
- Nitrogen balance gives:
3.76*2*a = 2d
d = 64.86
The balanced combustion equation becomes:
→
C12H21+17.25(O2+3.76N2) 12CO2+10.5H2O+64.86 N2
● The overall complete combustion equation

based on molecular weight is:
C H +(a+b/4)(O +3.76N )→ aCO +b/2H O+3.76(a+b/4)N
a b 2 2 2 2 2
● The stoichiometric air fuel ratio is:
(A/F)st = [(a+b/4)(32+3.76*28.16)]/[(12a+b)]
OR
(A/F)st = [137.88(a+b/4)]/[(12a+b)]
● What is the balance equation for the reaction of isooctane (C8H18)
with air? What is the (A/F)st?
Engine exhaust analysis
● New cars are equipped with sensors such as the oxygen sensors to
determine the oxygen contents leaving the engine with the exhaust
gases.
● There sensors is used to monitor the combustion efficiency of the
engine and as a result, the computer alter the quantity of fuel
injected, its timing and spark timing.
● Monitoring oxygen contents in the exhaust gases can be done by
taking a sample of the exhaust gases and running it through
external analyzer.
● Exhaust analyzers are usually operate on a dry basis (removing all
condensed water before analyzing).
Ex2:
Methane (CH4) is burned with dry air. The volumetric analysis of the
products on a dry basis is:
CO2: 10 %; O2: 2.37 %; CO: 0.53 % and N2: 87.1 %
Determine (a) the air–fuel ratio, (b) combustion equation
Solution:
From the analysis of the products, the following equation can be
written keeping in mind that this analysis is on a dry basis.
Considering 100 kmol of dry products for convenience, the
combustion equation can be written as:
aCH4 + bO2 + cN2 10CO2 + 0.53CO + 2.37O2 + dH2O + 87.1N2
FOLLOW THE SAME STEPS AS IN EX 1

Fuels
● Fuels are the natural source of energy that contains high
amount of energy which can be released through the
combustion process.
● Lubricating oils importance will appear whenever the
production of energy starts.
● Engines will never operate without lubricating oil which
is essential to reduce friction effects as well as it cools
the moving parts of energy.
● Fuels can be classified into liquid and gaseous fuels.
LIQUID FUELS
1. Petroleum fuels
The most common liquid fuels used for internal
combustion engines are gasoline, diesel, kerosene, gas
oil, fuel oil, etc.)
2. Non-petroleum fuels
Alcohols are the non petroleum fuels which are obtained
from vegetable substances that are rich by hydrocarbons
such as:
○ Methanol (CH3OH)
○ Ethanol (C2H5OH)
1. Petroleum fuels
Petroleum liquid fuels are obtained by means of physical
and chemical processes.
1. Distillation process: a physical process in crude oil is

heated in a distillation tower and allowed to
condense and separate into different compounds.
2. Cracking process: a chemical process in which the
heavy compounds are broken into lighter compounds
by means of catalysts. It is performed under higher
temperature and pressure.
Atmospheric tower
Properties of the most important liquid fuels
1. Gasoline
a. Has a distillation range of 25-2200C and average
composition of C8H18.
b. It has a specific gravity range of 0.72-0.78 and a lower
calorific value of 44000kJ/kg.
2. Kerosene
composition of C10H22.
b. It has a specific gravity is about 0.81 and a lower
heating value of 43100 kJ/kg.
3. Diesel
composition of C15H32 .
b. It has a specific gravity range of 0.84-0.88 and a lower
heating value of 42500kJ/kg.
2. Non-petroleum liquid fuels
● Alcohol is the chief fuel obtained from vegetable origin
and can be produced from potatoes, rice and sugar-beet.
● Basic groups of alcohol are methyl alcohol CH3OH
(methanol) and ethyl alcohol C2H5OH (ethanol).
● Their specific value is 0.8.
● Their average calorific value is 26200kJ/kg.
● They are cheaper than gasoline.
● They cause negative effect on the engine due to their
high hydrogen content which produces a lot of water
vapor in the exhaust causing rust in the exhaust pipe.
● Methanol can easily damage the rubber fitting in the fuel
system.
● Most countries use alcohol-gasoline blend fuel which
has a ratio of 10-15% ethanol and 85-90% gasoline.
● They have higher octane number (104-106) but causes
icing in the intake manifold due to their high evaporation
rates.
Benzol
● Is produced from the distillation of coal tar.
● Its chemical formula is C6H6 and has a specific gravity of
0.88 and an average calorific value of 39770kJ/kg.
● It has high anti-knock properties and is used as an
additive to the petrol fuels to raise their octane number.
● It is mainly used for racing cars due to its high
performance in engines.
● In some countries, it can be produced in commercial
scale and can be blended with gasoline to get better
performance.
● It burns with smoky flame resulting in high air pollution.
GASEOUS FUELS
● The main gaseous fuels used for ICE are compressed natural
gas (CNG) and liquefied petroleum gas (LPG).
● In some applications, propane and butane mixture are used as
fuel such as in some types of forklifts.
● Gaseous fuels are used either for the higher cost of
liquid fuels or to reduce air pollution.
● LPG and CNG are used as fuels in automotive engines
through a conversion kit.
CNG
● CNG contains mainly 80-95% of methane (CH4) and 3-13% of
ethane (C2H6).
● The composition differs from one well to another or from the
same well from one time to another.
CNG advantages:
● CNG is collected at high pressure of 220 bar and stored in
high-pressure tanks.
● Its low cost and does not require any complicated purification
or chemical processing.
● it produces cleaner combustion products than liquid fuels.
LPG
● LPG is liberated during the refining process of crude oil.
● It contains mainly 80% of propane (C3H8) and 20% of
butane (C4H10) and the main constituents and traces of
other hydrocarbon gases.
● it is mainly used for home gas cookers, camping fuel
bottles, gas lighters as well as for automotive
applications.
LPG advantages:
● The main advantage of LPG over CNG is that it can be
liquefied at relatively low pressure (2.5 bar at room
temperature).
● It can be stored at minimal space.
● LPG costs more than CNG, however, it gives better
performance in engines.
Advantages of gaseous fuels:
1. Produce clean exhaust emissions.
2. Have higher octane number than gasoline without its
additives.
3. Gives better engine performance, smoother engine
running and lower noise even for diesel engines.
4. Lower running cost due to the almost fixed pricing of
CNG and LPG.
5. Suitable for all applications and engines.
Disadvantages of gaseous fuels:
1. Conversion kit is costly ($1500 - $2000).
2. Conversion should only be performed by qualified personnel
and needs high safety precautions.
3. Needs special costly refill gas stations (CNG requires
underground network to connect the gas stations to the main
supply stations).
4. Longer refill time than liquid fuels.
5. Shorter vehicle range (lower specific volume).
6. Requires thick tanks to withstand the high pressure of the
fuel. (Heavier tanks).
Conclusion:
Gaseous fuels are suitable for crowded countries where gas
network is available and exhaust emissions are concern issues.
END OF CHAPTER 4

Chapter 4 - Thermochemistry and Fuels

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Thermochemistry and Fuels

Objectives of this chapter:

● Review combustion reaction

● Analyze engine exhaust analysis

● Identify different fuels and their properties

● Most IC engines obtain their energy from the

● The hydrocarbon fuel contains mainly of

● The maximum amount of energy released

● At stoichiometric reaction (complete

● For complete combustion of propane:

● A carbon balance between the reactants and

● A hydrogen balance gives c = 4 moles.

● An oxygen balance gives a = 5 moles.

- Oxygen balance gives:

● The overall complete combustion equation

aCH4 + bO2 + cN2 10CO2 + 0.53CO + 2.37O2 + dH2O + 87.1N2

FOLLOW THE SAME STEPS AS IN EX 1

1. Distillation process: a physical process in crude oil is

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