II.

Combustion of Alkane
To move an airplane or a model
rocket through the air, we must use
a propulsion system to
generate thrust. Different types of aircraft use
different types of propulsion devices, but all
aircraft rely on some type of engine to
generate power. Rocket engines, internal
combustion, or piston engines, and jet
engines all depend on the burning of fuel to
produce power. Burning a fuel is
called combustion.

Combustion or burning is the sequence of exothermic chemical reactions between a fuel and
an oxidant accompanied by the production of heat and conversion of chemical species. The
release of heat can produce light in the form of either glowing or a flame.

A. Complete Combustion
The reactant burns in oxygen, producing a limited number of products. When a
hydrocarbon burns in oxygen, the reaction will primarily yield carbon dioxide and water. When
elements are burned, the products are primarily the most common oxides. Carbon will
yield carbon dioxide, sulfur will yield sulfur dioxide, and iron will yield iron (III) oxide. Nitrogen is
not considered to be a combustible substance when oxygen is the oxidant, but small amounts
of various nitrogen oxides (commonly designated NOx species) form when air is the oxidant.
Combustion is not necessarily favorable to the maximum degree of oxidation, and it can be
temperature-dependent. For example, sulfur trioxide is not produced quantitatively by the
combustion of sulfur. NOx species appear in significant amounts above about 2,800 F
(1,540 C), and more is produced at higher temperatures. The amount of NOx is also a function
of oxygen excess.

Stoichiometric combustion of a hydrocarbon in oxygen

Generally, the chemical equation for stoichiometric combustion of a hydrocarbon in oxygen is:

where z = x + y.
For example, the stoichiometric burning of propane in oxygen is:

The simple word equation for the stoichiometric combustion of a hydrocarbon in oxygen is:

Stoichiometric combustion of a hydrocarbon in air

If the stoichiometric combustion takes place using air as the oxygen source,
the nitrogen present in the air can be added to the equation (although it does not react) to
show the composition of the resultant flue gas:

where z = x + y.
For example, the stoichiometric combustion of propane in air is:

The simple word equation for the stoichiometric combustion of a hydrocarbon in air is:

The combustion of methane, a hydrocarbon. Because the products are carbon dioxide and
water, this is a complete combustion reaction.

B. Incomplete Combustion
When there is not enough oxygen to allow the fuel to react completely to produce carbon
dioxide and water, incomplete combustion occues. It also happens when the combustion is
quenched by a heat sink, such as a solid surface or flame trap.
For most fuels, such as diesel oil, coal or wood, pyrolysis occurs before combustion. In
incomplete combustion, products of pyrolysis remain unburnt and contaminate the smoke with
noxious particulate matter and gases. Partially oxidized compounds are also a concern; partial
oxidation of ethanol can produce harmful acetaldehyde, and carbon can produce toxic carbon
monoxide.
The incomplete (partial) combustion of a hydrocarbon with oxygen produces a gas mixture
containing mainly CO2, CO, H2O, and H2. Such gas mixtures are commonly prepared for use as
protective atmospheres for the heat-treatment of metals and for gas carburizing. The general
reaction equation for incomplete combustion of one mole of a hydrocarbon in oxygen is:
The simple word equation for the incomplete combustion of a hydrocarbon in oxygen is:

For stoichiometric (complete) combustion, z = x + y. When z falls below roughly 50% of the
stoichiometric value, CH4 can become an important combustion product; when z falls below
roughly 35% of the stoichiometric value, elemental carbon may become stable.
The products of incomplete combustion can be calculated with the aid of a material balance,
together with the assumption that the combustion products reach equilibrium. For example, in
the combustion of one mole of propane (C3H8) with four moles of O2, seven moles of
combustion gas are formed, and z is 80% of the stoichiometric value. The three elemental
balance equations are:

These three equations are insufficient in themselves to calculate the combustion gas
composition. However, at the equilibrium position, the water gas shift reaction gives another
equation:

For example, at 1,200 K the value of Keq is 0.728. Solving, the combustion gas consists of
42.4% H2O, 29.0% CO2, 14.7%H2, and 13.9% CO. Carbon becomes a stable phase

at 1,200 K and 1 atm pressure when z is less than 30% of the stoichiometric value, at which
point the combustion products contain more than 98% H2 and CO and about 0.5% CH4.

Most vehicle fuels (gasoline, diesel, natural gas, ethanol, etc.) are mixtures of hydrocarbons,
compounds that contain hydrogen and carbon atoms. In a perfect engine, oxygen in the air
would convert all of the hydrogen in fuel to water and all of the carbon in the fuel to carbon
dioxide (carbon mixed with oxygen).

C. Alkane Heats of Combustion

The combustion of carbon compounds, especially hydrocarbons, has been the most important
source of heat energy for human civilizations throughout recorded history. The practical
importance of this reaction cannot be denied, but the massive and uncontrolled chemical
changes that take place in combustion make it difficult to deduce mechanistic paths. Using the
combustion of propane as an example, we see from the following equation that every covalent
bond in the reactants has been broken and an entirely new set of covalent bonds have formed
in the products. No other common reaction involves such a profound and pervasive change,
and the mechanism of combustion is so complex that chemists are just beginning to explore
and understand some of its elementary features.
CH3CH2CH3+5O23CO2+4H2O+heat
Two points concerning this reaction are important:
1. Since all the covalent bonds in the reactant molecules are broken, the quantity of heat evolved
in this reaction is related to the strength of these bonds (and, of course, the strength of the

bonds formed in the products). Precise heats of combustion measurements can provide useful
information about the structure of molecules.
2. The stoichiometry of the reactants is important. If insufficient oxygen is supplied some of the
products will consist of the less oxidized carbon monoxide CO gas.
CH3CH2CH3+4O2CO2+2CO+4H2O+heat

Heat of Combustion
From the previous discussion, we might expect isomers to have identical heats of combustion.
However, a few simple measurements will disabuse this belief. Thus, the heat of combustion of
pentane is 782 kcal/mole, but that of its 2,2-dimethylpropane (neopentane) isomer is 777
kcal/mole. Differences such as this reflect subtle structural variations, including the
greater bond energy of 1-CH versus 2-CH bonds and steric crowding of neighboring groups.
In small-ring cyclic compounds ring strain can be a major contributor to thermodynamic
stability and chemical reactivity. The following table lists heat of combustion data for some
simple cycloalkanes and compares these with the increase per CH2 unit for long chain alkanes.
Cycloalkane
(CH2)n

CH2 Units
H25
H25
Ring Strain
n
kcal/mole per CH2 Unit kcal/mole

Cyclopropane

n=3

468.7

156.2

27.6

Cyclobutane

n=4

614.3

153.6

26.4

Cyclopentane

n=5

741.5

148.3

6.5

Cyclohexane

n=6

882.1

147.0

0.0

Cycloheptane

n=7

1035.4

147.9

6.3

Cyclooctane

n=8

1186.0

148.2

9.6

Cyclononane

n=9

1335.0

148.3

11.7

Cyclodecane

n = 10

1481

148.1

11.0

m = large

147.0

0.0

CH3(CH2)mCH3

The chief source of ring strain in smaller rings is angle strain and eclipsing strain. As noted
elsewhere, cyclopropane and cyclobutane have large contributions of both strains, with angle
strain being especially severe. Changes in chemical reactivity as a consequence of angle strain
are dramatic in the case of cyclopropane, and are also evident for cyclobutane. Some examples
are shown in the following diagram. The cyclopropane reactions are additions, many of which
are initiated by electrophilic attack. The pyrolytic conversion of -pinene to myrcene probably
takes place by an initial rupture of the 1:6 bond, giving an allylic 3-diradical, followed
immediately by breaking of the 5:7 bond.

D. Global Warming
What is Global Warming?
Carbon dioxide and other global warming pollutants are collecting in the atmosphere like a
thickening blanket, trapping the suns heat and causing the planet to warm up.
Although local temperatures fluctuate naturally, over the past 50 years the average global
temperature has increased at the fastest rate in the recorded history. Scientists say that unless
we curb the emissions that cause climate change, average U.S. temperatures could be 3 to 9
degrees higher by the end of the century. The main cause of this phenomenon is the burning of
fossil fuels, all of which contain alkanes and alkenes, a method of acquiring energy which has
intensified in recent decades.
This is the global warming effect.

The impact of burning alkanes on acid rain

Hydrocarbon fields originally came from living matter and a seminal component of living of
matter are amino acids. All of the elements present in amino acids must also be present in the
hydrocarbon mixtures found in crude. One of these elements is sulfur. When the fuels are burnt
sulfur dioxide is produced, a poisonous gas responsible for acid rain.

Incomplete combustion
These usually use hydrocarbon as fuels. Petrol engines burn isomers of octane, C8H18, with
many additives designed to increase flow efficiency, burning, engine lubrication, etc.
Invariably, the sparks that ignite the petrol air mixtures also causes a reaction between nitrogen
and oxygen in the air producing oxides of nitrogen, NOx, which are a pollutant health hazard as
well as unburnt hydrocarbons and carbon monoxide gas, both of which are health hazards.

Acid Rain
Acidic gases such as sulfur dioxide are produced when fossil fuel like coal, oil, and gas burn.
Sulfur dioxide dissolve in the clouds and causes acid rain. This damages buildings, trees, and
harms life in rivers and lakes. It also causes chemical weathering of rocks to happen much faster
than normal.