LEARNING PACKET 6 | Chemistry for Engineers 1

UNIT 6

Fuels as Source of Energy

6.0 Intended Learning Outcomes

At the end of the unit, you are expected to manifest the following:

a. Differentiate the types of fuels according to occurrence and state of aggregation; and
provide example of each classification.
b. Describe and discuss the refining of crude oil.
c. Appreciate the importance of fuels to society by joining organizations that promotes
the Clean Air Act.

6.1 Introduction

In this present age of population growth and rapid industrial development, the energy
requirement is increasing day-by-day. Energy is the essence of our very existence as individuals
and as a society. Along this line, four major energy-related services have been identified: 1)
electrical services (consumption of electricity by final consumers); 2) mobility (non-electricity
fuels consumed in all forms of transport); 3) stationary services (fuels used for heating in
building and industrial processes); and 4) fuels used in power generation. So, the focus of this
unit is energy generation by burning combustible materials in solid, liquid and gaseous states.

Basically, this unit is an extension of chemical reactions or changes but it will now include the
other side of chemistry which is changes of matter that involve energy changes particularly
exothermic reactions.

6.2 Unique Characteristics of Carbon Atom

Recall from Unit 1 that the ground state electron configuration of carbon atom with
atomic number of six (Z = 6) as shown below.

Since carbon is a non-metal, it will form a covalent bond with another non-metal atom like
hydrogen. However, there are only two unpaired electron in carbon atom. The possible molecule
has the formula of CH2. Unfortunately, there is no such molecule or compound with such
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chemical formula. The lowest carbon atom to hydrogen atom found in nature is 1C atom:4H
atoms or equivalent to CH4.

The explanation is that when carbon atom forms a molecule or reacts with other non-
metals, it is in the excited state as depicted below.

Carbon atom will always form four (4) bonds where it could be four (4) single bonds; two (2)
double bonds; or a combination of one (1) single bond and one (1) triple bond. This means
carbon atom has a valency of four (4) or tetravalent.

Another uniqueness of the carbon atom is it can form covalent bond with itself or with
atoms like H, N, or O.

Because of this unique characteristic of carbon atom, it can form four (4) strong covalent bonds
with other carbon atoms or in combination with other atoms.

Carbon atoms can link with each other to form linear, branched or cyclic backbone for a
wide variety of organic compounds.

Moreover, carbon atoms may participate in single, double and triple bonds.

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The ability of carbon to form single as well as multiple bonds, not only with another
carbon atom, but with atoms like nitrogen and oxygen, results in greater diversity of molecular
frameworks which constitute the skeletons of small and simple molecules or big or complex
molecules found in living organisms and non-living materials.

Assessment Question 6.1: What are missing in the following Lewis structures? Make the
necessary corrections.

6.3.1 Alkanes and Cycloalkanes

Compounds that consist solely of carbon and hydrogen are called “hydrocarbons”.
Hydrocarbons may be regarded as the parent compounds of organic chemistry from which all
other compounds were derived. If the carbon atoms in a hydrocarbon are joined by single bonds,
it is called saturated hydrocarbons. Saturated hydrocarbons having open-chain structures are
called “alkanes” while those having cyclic structures are called “cycloalkanes”.

The Lewis structure shown above is also called a “structural formula”. The structural
formula can be simplified using a “condensed formula” wherein the bonding between carbon
atoms is given emphasis, or the bonds are not shown (not possible for cycloalkanes), but the four
bonds around each carbon atom must be maintained.

Still we can further simplify the condensed formulas into molecular formulas – C6H14 and
C4H8. Molecular formulas have little significance because of the possibility of isomers
(compounds that have the same molecular formula but different structural formula).

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Depending on the situation, it is more meaningful to use structural formulas (to differentiate the
identity of molecules) which clearly indicate bonding patterns (how atoms are connected to one
another) in a molecule.

The molecular formula of alkanes follows the following formula: C2H2n+2, where ‘n’ refers
to the number of carbon atoms.

When the ends of a straight chain hydrocarbon are joined together, two hydrogen atoms are lost
so that the general molecular formula becomes CnH2n for cycloalkanes.

The International Union of Pure and Applied Chemistry (IUPAC) came up with a
systematic way of naming organic compounds known as the IUPAC System of Nomenclature.
Systematic names of organic compounds consist of three main parts:

The stem indicates the number of carbon atoms in the ‘backbone’ or parent chain of the molecule.
For alkanes, the suffix is “ane”. Attached to the longest continuous carbon chain or ‘backbone’
are the side-chains or substituents. Alkyl groups are derived from alkane through the removal
of one hydrogen atom.

Step 1: Locate the parent chain.

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a) Find the longest continuous chain present in the molecule and use the name of that
chain as the parent name.
b) If there are two different chains of equal length, choose the one with the larger number
of branched points as the parent chain.

The longest chain is nine (9) carbon atoms with four (4) substituents (blue colored carbons
atoms).

Step 2: Number the carbon atoms in the parent chain so that the substituents are given the lowest
position numbers.

We can reverse the numbering as depicted below.

We add the carbon number to which the substituents are attached to. In the first case, it is: 5 + 6
+ 7 + 7 = 25. In the second case, it is: 5 + 4 + 3 + 3 = 15. Fifteen (15) is lower than twenty five
(25), so the appropriate numbering is the second case.

Step 3: Identify the substituents and the position of the carbon atoms to which they are attached.

There is one (1) “propyl” group and three (3) “methyl” groups.
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Step 4: Write the name as a simple word, using hypens to separate the different prefixes and
using commas to separate numbers.
a) If there are different kinds of alkyl groups present, arrange them in alphabetical order.
b) If the same alkyl group occurs more than once as a substituent, indicate by prefixes di-
, tri-, tri-, tetra-, etc. However, do not use the prefixes for alphabetizing purposes.

There are three (3) methyl groups, so we can use the Greek prefix “tri” and still use the “carbon
locators”. Therefore, the name of the molecule (or compound) is

Assessment Task 6.1: Provide IUPAC names to the following compounds.

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Cycloalkanes are almost always written as skeletal structures. Skeletal structures show
the carbon–carbon bonds as lines, but do not show the carbons or the hydrogens bonded to
carbons. Each vertex in a skeletal structure represents a carbon, and each carbon is understood
to be bonded to the appropriate number of hydrogens to give the carbon four bonds.

Skeletal structures is also applicable to “acyclic” molecules. Acyclic means linear or branched
alkane. However, the end of the chain is also carbon with three (3) hydrogen atoms.

The rules for naming cycloalkanes resemble the rules for naming acyclic alkanes:

1. In a cycloalkane with an attached alkyl substituent, the ring is the parent hydrocarbon unless
the substituent has more carbons than the ring. In that case, the substituent is the parent
hydrocarbon and the ring is named as a substituent. There is no need to number the position of a
single substituent on a ring.

2. If the ring has two different substituents, they are listed in alphabetical order and the number-
1 position is given to the substituent listed first.

3. If there are more than two substituents on the ring, they are listed in alphabetical order, and
the substituent given the number-1 position is the one that results in a second substituent
getting as low as possible. If the two substituents have the same low numbers, the ring is
numbered – either clockwise or counterclockwise – in the direction that gives the third
substituent the lowest possible number.

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Assessment Task 6.2: How many hydrogen atoms are attached to each carbon atom in
cholesterol?

Among organic compounds of similar molecular masses, alkane would have the lowest
boiling points because only the weak dispersion forces are present in the non-polar alkanes. At
room temperature and one atmosphere pressure, the first four members of the unbranched
alkanes are gases (methane, ethane, propane, and butane); the C5 – C17 unbranched alkanes are
liquids; and unbranched alkanes with 18 atoms or more are solids.

Name Molecular formula Boiling point, oC (1 atm)

Methane CH4 -162
Ethane C2H6 -88
Propane C3H8 -42
Butane C4H10 0
Pentane C5H12 36
Hexane C6H14 69
Heptane C7H16 98
Octane C8H18 126
Nonane C9H20 151
Decane C10H22 174

For linear alkanes, the smaller the molecules, the lower their molecular masses, and the
lower their boiling points – methane with molecular mass of 10 amu has a lower boiling point
of -162oC compared to ethane with a molecular mass of 18 amu has boiling point of -88oC. An

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increase in boiling point is observed as the molecular mass (molecular size) of the alkane
increases as you will notice in the table above.

Larger molecules would have greater surface contact between molecules and, thus,
would have greater dispersion forces that smaller molecules. This increase in intermolecular
forces would require more energy (a higher temperature) for the separation of molecules from
one another and for boiling to take place.

Branching effectively decreases surface contact between molecules and as such, the
dispersion forces present in branched isomers are less than that in the normal isomer. Being non-
polar molecules, alkanes and cycloalkanes do not dissolve in polar solvents like water but they
dissolve in non-polar solvents like ether and chloroform. The liquid alkanes are themselves
considered as non-polar solvents. The alkanes and cycloalkanes are the least dense of all groups
of organic compounds. All alkanes and cycloalkanes have densities considerably less than 1.00
g/mL, the density of water at 4oC. Alkanes are also referred to as paraffins or aliphatics.

For carbon atoms greater than 10 that are linear:

6.3.2 Alkenes, Alkynes, and Arenes

Hydrocarbons that contain double and triple bonds are called unsaturated hydrocarbons.
There are three classes of unsaturated hydrocarbons: alkenes, alkynes, and arenes. Alkenes
contain one or more carbon–carbon double bonds. Ethene (or ethylene) is the simplest alkene
with one double bond. Alkenes are also called olefins.

Unfortunately, ethene or ethylene with only one single bond is only present in limited
amount in nature. What is unusual about ethylene is that it occurs only in trace amounts in
nature. When a fruit starts to ripen, ethylene is being produced. Yet, it has an enormous
commercial importance in our modern, industrialized society. So, collecting ethylene from
ripening fruits is quite impractical.

Another source of ethylene in limited amount is in natural gas but not enough to meet
the demands of chemical industries to make plastics bags and bottles, textiles, as an ingredient
in making tires, cosmetics, pharmaceuticals, etc. The enormous amounts ethylene required to

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meet the needs of chemical industries are derived from cracking (thermal or catalytic) of natural
gas and other high molecular mass hydrocarbons from crude oil.

Europe, Japan, and other areas of the world with limited supplies of natural gas depend
almost entirely on thermal cracking of petroleum for their ethylene. The crucial point to
recognize is that ethylene and all of the commercial and industrial products made from it are
derived from either natural gas or petroleum - both non-renewable natural resources!

Ethyne (or acetylene) is the simplest alkyne with one triple bond.

Acetylene is used for welding and cutting. The welding process that uses acetylene is known as
oxy-fuel cutting or gas cutting. This method is used to cut or weld materials that require
temperatures as high as 3,500°C (6,330 °F). Among all other gases, acetylene is capable of
producing the hottest flame.

Arenes are the third class of unsaturated hydrocarbons that contain the benzene ring.
They are also called “aromatic” compounds.

Benzene ranks in the top 20 chemicals for production volume. Some industries use
benzene to make other chemicals that are used to make plastics, resins, and nylon and synthetic
fibers. Benzene is also used to make some types of lubricants, rubbers, dyes, detergents, drugs,
and pesticides.

6.3 Fuel

The word “fuel” is a complicated term to define since it can be viewed in different
perspectives as depicted in the fire triangle below.

For a “fire” to be produced (meaning, fire is a product of

chemical reaction), there should be “fuel”, “oxygen”, and
“heat”. The reactants are “fuel” and “oxygen” and the
products are “fire” and “more heat”. For the chemical reaction
to start (production of fire), the presence of “heat” is needed.
The initial heat used to start the chemical reaction will produce
more “heat”.

Now, let me employ an analogy. You are a business man with plenty of money (fuel).
There are plenty of customers (oxygen). For you to gain more money (fire), you have to invest
some of your money (heat) to start the business. Kon may ada ka kuarta (fuel), may mga

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customers ka (oxygen), kon dire ka mag puhunan (heat), so waray ka ganansya (fire or more
heat).

Before you proceed your reading, try to digest first the “fire triangle” and the “analogy”
I employed.

So, a fuel is any carbon containing substance which has stored energy and during
combustion the stored energy is released. The heat energy released is used for industry and
domestic purposes.

Combustion is the reaction between a fuel and an oxidizer, which gives out more heat
energy and is an exothermic reaction as illustrated in the equation below. Usually, the oxidizer
is oxygen as shown in the fire triangle.

When not enough oxygen is supplied during combustion, then the reaction is termed
“incomplete combustion” where the main product is carbon monoxide (CO). When sufficient
oxygen gas is supplied during combustion, then the reaction is called “complete combustion”
and the main product is carbon dioxide (CO2).

Assessment Question 6.2: Combustion is a redox reaction. a) Which is the oxidant? b) Which
is the reductant? c) Which atom is reduced? d) Which atom is oxidized?

Assessment Question 6.3: Explain the statement “Every combustion is an oxidation reaction
but not all oxidation reactions are combustion.”

Example of fuels are wood, charcoal, coal, gasoline, diesel, oil, etc. Some of these fuels
are used for cooking and in lighting like kerosene lamps. Fuels are also used to run vehicles and
cargo vessels. Usually, fuel is burned to produce steam in a “boiler”. The steam produced
enters a steam engine where the crank shafts inside will cause another shaft to rotate. The
rotating shaft can be connected to the propeller of a ship or to the wheel of a train. You need to
watch this video to understand the basic principle behind a steam engine – “Steam_Engine”.

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For industrial application, fuels are used to heat water inside large boilers to produce
steam in large quantities. The heat energy coming from the boiling water is converted to kinetic
energy of the steam produced. The steam then goes to the turbine that turns a generator to
generate a constant supply of electricity. The electricity produced can light a city or a big
shopping mall or make other equipment work. Watch these videos –“Production of
Electricity_1”, “Production of Electricity_2”, and “Production of Electricity_3”.

Relative to the first video, para may continuous supply of electricity, sige dapat pag
pinabirik han wheel. Kon hi ikaw an magpipinabirik han wheel, mailob ka? So, ano man an
solusyon? This is answered by the second video and the third video. Without fuel, steam, and
generator; there will be no continuous electricity to light a city or a mall.

Assessment Question 6.4: Both battery and generator produces electricity. What is the
difference between the two, except their spelling?

6.3.1 Classification of Fuels

Fuels are classified based on two factors: 1) occurrence (and preparation) and 2) state of
aggregation. On the basis of occurrence, fuels are further divided into two types:

1. Natural or primary fuels - these fuels are found in nature such as wood, peat, coal,
petroleum, natural gas, etc.
2. Artificial or secondary fuels - these fuels prepared artificially from the primary fuels.
Examples are charcoal, coke, kerosene, diesel, petrol, coal gas, oil gas, producer gas,
blast furnace gas, etc.

The second classification based upon their state of aggregation like a) solid fuels, b) liquid
fuels, and c) gaseous fuels.

Type Aggregation Natural or primary fuel Artificial or secondary fuel

Solid wood, peat, lignite, dung, charcoal, coke
bituminous coal, and
anthracite coal
Liquid crude oil gasoline, petrol, diesel and
other fractions of petroleum
Gaseous natural gas coal gas, oil gas, biogas, etc.

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6.3.2 Characteristics of a Good Fuel

The following are the characteristics for a good fuel which are self-explanatory:

1. The fuel should be easily available.

2. The combustion should not be explosive.
3. The combustion speed should be moderate.
4. It should not burn spontaneously to avoid fire hazards.
5. It should be cheap, easily transportable and has high calorific value.
6. Its handling should be easy and should not give poisonous gases after combustion.
7. It should be dry and should have less moisture content. Dry fuel increases its calorific
value.
8. It must have moderate ignition temperature and should leave less ash after
combustion.

6.3.3 Characteristic Properties of Solid, Liquid, and Gaseous Fuels

Characteristic Property Solid fuels Liquid fuels Gaseous fuels

Example Coal Crude oil Coal gas
Cost cheap costlier costly
Storage easy to store closed container should Storage space
be used for storing required is huge and
Risk towards fire less more Very high, since this
hazards fuel is highly
flammable
Combustion rate slow process fast process very rapid and
efficient
Combustion control cannot be cannot be controlled or controlled by
controlled stopped when necessary regulating air supply
Handling cost high since low, since the fuel can be low, similar to liquid
labor is transported through fuels, it can be
required in pipes transported through
their storage pipes
and transport
Ash ash is no problem with ash no problem with ash
produced and
its disposal
also possess
problems
Smoke produce clean, but liquids smoke is not
smoke associated with high produced
invariably carbon and aromatic fuels
produce smoke
Calorific value least high highest
Heat efficiency least high highest

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6.4 Solid Fuels

The main solid fuels are wood, charcoal, peat, lignite, and coal. The following are the
characteristics of the four solid fuels:

Fuel % carbon by Calorific value Application

weight (kcal/kg)
Wood 50 4,000 – 4,500 Domestic fuel
Peat 50 -60 4,125 – 5,400 Used if deficiency of high rank coal is
prevailing
Lignite 60 - 70 6,500 – 7,100 For steam generation in thermal
power plants
Bituminous 80 - 90 8,00 – 8,500 Used in making coal gas and
metallurgical coke
Anthracite 90 - 98 8,650 – 8,700 Used in households and for steam
raising

6.4.1 Wood

Wood burns readily. Wood must have been one of the first, if not the first, fuels used by
our pre-human ancestors, dating many millennia back into prehistoric times. Our ancestor
Homo erectus was using fire at sites in Africa about 1.5 million years ago. Wood was the first
major fuel to be exploited by humans, and was the dominant fuel world-wide well into the
nineteenth century, when it was displaced by coal in Europe and the United States.

Wood remains an important fuel in many parts of the developing world, particularly for
domestic use. Half the world’s population uses various biofuels, including wood, for cooking
and other household uses. Material considered by the forest product industry to be waste, such
as bark or pieces of wood too small to be cut in usable lumber, makes useful fuel. Forest litter –
the debris of dead branches and felled trees found in forests – constitutes another source of wood
fuel.

In several respects, wood is an ideal fuel for pre-industrial or developing societies. It

occurs naturally on the Earth’s surface, so that technology is not needed to mine or extract it
from inside the Earth. Wood, at least in the past, was widely and abundantly available in many
parts of the world. Wood can be burned in simple appliances with minimal knowledge of
combustion principles; almost everyone with experience in overnight camping or outdoor
cooking can attest that, given enough matches and enough patience, practically anybody can get
a wood fire going.

One problem of wood as source of fuel is that wood fires produce significant air pollution
in the open or in relatively simple domestic appliances. Volatile compounds escape as the wood
is heated to its ignition point. Many of these contribute to the characteristic “smoky” odor
noticeable in the clothes or hair of anyone spending time near a wood fire. Some of the volatiles
could also have adverse health effects. Incomplete combustion can produce carbon monoxide,
which is potentially deadly. Smoke also contains fine particles such as ash and soot which are
hazardous to human health.

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In one sense, wood is a renewable energy source, because a new tree can be grown to
replace every one that was harvested. Unlike corn, sugar cane, and crops grown for oils, the next
generation tree, replacing one that had been harvested, does not grow to maturity in a year.
Abundant evidence, both from history and from current experience, shows that large-scale
cutting of trees for domestic or industrial fuel leads to destruction of forested areas. Such
deforestation brings with it a host of other environmental problems. A sustainable strategy for
assuring a renewable supply of wood relies on cutting in rotation from woodlots specifically
grown and managed for the periodic harvesting of wood, a practice known as coppicing.

Assessment Question 6.5: Enumerate at least two uses of wood as fuel aside from cooking
purposes.

6.4.2 Charcoal

I am sure you have experienced since childhood in which a fire did not consume the wood
completely, but left behind a black, brittle residue, which can be re-ignited again, is itself a good
fuel. We call this solid fuel as charcoal. The charcoal is a result of insufficient oxygen (air) to
consume the wood completely. From this understanding came the recognition of the possibility
of making charcoal deliberately by heating wood in the absence of air, or burning wood under
severely air-limited conditions.

Production of charcoal involves pyrolysis - decomposition of compounds through

application of heat. Because pyrolysis converts wood to a highly carbonaceous material, the
process is also known as carbonization. Since volatile compounds are driven off, but the residual
non-volatile material is obviously quite altered, yet another name for the same process is
destructive distillation.

Charcoal yield depends on the wood used as feedstock, its moisture content, and on
specific process conditions, but in best cases could be in the range of 30 to 40%. Production of
charcoal relies on burning a portion of the available wood to provide the heat necessary to
carbonize the remainder. Therefore the process is inherently wasteful, and probably in pre-
industrial societies was exceptionally so.

In its simplest form, charcoal production involved creating a heap of wood, on the ground
or in a pit, igniting the wood, and allowing the heat to carbonize the unburned wood. The yield
of charcoal was likely to be no better than about 25% of the initial charge of wood, possibly as
bad as 10%. When wood is carbonized with some care, as in permanently constructed brick kilns
(pogon), charcoal yield increases to about 40%.

In addition to direct use as a fuel, charcoal has been used since ancient times as a reducing
agent in metallurgy. The first application was in production of copper, for use in bronze alloys,
and then production of iron. Charcoal has several virtues in this application, containing virtually
no impurities – such as phosphorus or sulfur – that would contaminate the metal. Unfortunately,
the metallurgical application of charcoal will consume large quantities of wood resulting
deforestation.
Charcoal is an excellent fuel. The sulfur content of charcoal is zero; sulfur oxide emissions
are not a problem. Charcoal burns with a clean, smokeless flame. These factors make charcoal
much preferable to wood for domestic use, as well as for industrial uses, such as firing ceramics,

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where it is important that the product not be contaminated by products of the fuel combustion.
Brick kilns and lime kilns have also been fired with charcoal. A charcoal fire can, however,
produce significant amounts of carbon monoxide if care is not taken to supply adequate amounts
of air.

6.4.3 Coal

Before I start discussing this topic, kindly watch the following videos: “Fossel_fuel_1”,
“Fossil_fuel_2”, and “Fossil_fuel_3”.

Fossils are naturally preserved remains, or traces of remains, of ancient

organisms. Fossils are not the remains of the organism itself! They are rocks. A fossil can
preserve an entire organism or just part of one. Bones, shells, feathers, and leaves can all
become fossils. Examples include bones, shells, exoskeletons, stone imprints of animals or
microbes, objects preserved in amber, hair, petrified wood, oil, coal, and DNA remnants.
Specimens are usually considered to be fossils if they are over 10,000 years old.

If the remains has the ability to burn when ignited and produce heat, then the fossil is
considered a “fossil fuel.” So, a fossil fuel is a general term for buried combustible geologic
deposits of organic materials (living things) that were formed by exposure to heat and pressure
in the earth's crust over millions of years ago under anaerobic (absence of oxygen gas) condition.
There are three types of fossil fuels – coal, crude oil (or petroleum oil), and natural gas.

You may have seen coal or heard about it. It is as hard as stone and is black in color. Coal
is one of the fuels used to cook food. Earlier, it was used in railway engines to produce steam to
run the engine. It is also used in thermal power plants to produce electricity. Coal is also used
as a fuel in various industries.

About 300 million years ago the earth had dense forests in low lying wetland or swampy
areas. Due to natural processes, like flooding, these forests got buried under the soil. As more
soil deposited over them, they were compressed. The temperature also rose as they sank deeper
and deeper. Under high pressure and high temperature, dead plants got slowly converted to
coal in the absence of air. As coal contains mainly carbon, the slow process of conversion of dead
vegetation into coal is called carbonization. Formation of coal and coal mine are shown below.

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The process of conversion of wood into coal can be represented as:

Along this line, coal is divided into four (4) ranks according to the amount of volatile matter,
fixed carbon, inherent moisture that it contains, and the amount of ash produced when burned.
Typically, coal rank increases as the amount of fixed carbon increases; and the amount of volatile
matter, moisture, ash produced decreases.

1. Peat – it is a deposit resembling soil.

2. Lignite coal or brown coal – it is a soft, brown colored, lowest rank coal. When used as
fuel, it emits more pollution that other types of coal.
3. Bituminous coal – it is a pitch black to dark grey coal .
4. Anthracite coal – it is the highest class of coal. It is dense, hard rock with jet-black color
and metallic luster.

Peat Lignite coal

Bituminous coal Anthracite coal

6.4.4 Coke

In the coke-making process, coal or crude oil is fed (usually after processing operations
to control the size and quality of the feed) into a series of ovens, which are sealed and heated at
high temperatures in the absence of oxygen, typically in cycles lasting 14 to 36 hours. The
process is called destructive distillation. Volatile compounds that are driven off the coal are
collected and processed to recover combustible gases and other by-products.

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The solid carbon remaining in the oven is “coke”. It is taken to a quench tower, where it
is cooled with a water spray or by circulating an inert gas like nitrogen, a process known as dry
quenching.

Coke is a grey, hard, and porous fuel with a high carbon content and few impurities. It
is an important industrial product, used mainly in iron ore smelting, but also as a fuel in stoves
and forges when air pollution is a concern.

On the other hand, the collected volatile matter is made up of coke-oven gas, coal tar,
benzene, ammonia, and hydrogen sulfide. Coal tar is used as a raw material for the production
of naphthalene and other aromatic compounds. Ammonia and hydrogen sulfide are converted
into fertilizers. Benzene is converted to other useful chemicals. Coke-oven gas can be refined to
obtain useful hydrocarbons.

How coke and how it is used iron ore smelting can be observed through these videos –
“Coke_1”, “Coke_2”, and “Steel_1”.

6.5 Analysis of Coal

To determine that quality of coal that serves as basis for its ranking, it has to undergo
chemical analysis – proximate analysis and ultimate analysis.

6.5.1 Proximate analysis

In this analysis, the amount of moisture, volatile matter, fixed carbon are determined; and
the amount ash produced when the fuel is burned.

1. Moisture content

Moisture is liquid water. When present in coal, it will take some of the heat energy during
burning of the fuel to convert it into water vapor. Therefore, moisture lowers the effective
calorific value of coal. Hence, the lesser the moisture content, the better the quality of coal as a
fuel.

Procedure:

About one (1) gram of the finely powdered air-dried coal sample is weighed into a porcelain
crucible and the crucible is placed inside an electric hot air oven maintained at 105 oC to 110oC

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for an hour. After 1 hr, the crucible is covered and placed in a dessicator to cool. The mass of
the crucible is measured using an electronic balance until a constant mass is obtained.

2. Volatile matter

A high volatile matter content means that a high proportion of fuel will distil over as gas
or vapor. A large proportion of which escapes un-burnt. So, higher volatile content in coal is
undesirable. A high volatile matter containing coal burns with a long flame, high smoke and has
low calorific value. Hence, lesser the volatile matter, better the rank of the coal.

Procedure:

The air-dried sample inside the covered porcelain crucible is transferred to an electric furnace or
muffle furnace, maintained at 925oC for seven (7) minutes of heating. After which, the crucible
is taken out of the furnace and allowed to cool in air, then inside the dessicator and weighed
again several times until a constant mass is obtained. The decrease in mass is reported as volatile
matter on percentage basis.

3. Ash

Ash is a useless, non-combustible matter, which reduces the calorific value of coal.
Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering the
temperature. Also, it often causes trouble during firing by forming clinkers, which block the
interspaces of the grate, on which coal is being burnt. This in-turn causes obstruction to air
supply; thereby the burning of coal becomes irregular. Hence, the lower the ash content, better
the quality of coal. The presence of ash also increases transporting, handling and storage costs.
It also involves additional cost in ash disposal. The presence of ash also causes early wear of
furnace walls, burning of apparatus and feeding mechanism.

Procedure:

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The cover of the crucible is remove. Then the uncovered crucible is heated in a muffle furnace at
750oC for one half (1/2) hour. The crucible is then taken out from the furnace, cooled first in air,
then placed inside the dessicator to cool further and weighed. Heating, cooling and weighing
are repeated several times until a constant mass is obtained. The amount of residue is reported
as ash on percentage basis.

4. Fixed Carbon

Higher the percentage of fixed carbon, greater is coal’s calorific value and the better the
quality of the coal. The greater the percentage of fixed carbon, the smaller is the percentage of
volatile matter, the better quality of coal. This also represents the quantity of carbon that can be
burned by a primary current of air drawn through the hot bed of a fuel. Hence, high percentage
of fixed carbon is desirable. The percentage of fixed carbon helps in designing the furnace and
the shape of the fire-box, because it is the fixed carbon that burns in the solid state.

6.5.2 Ultimate analysis

This is the elemental analysis and often called as qualitative analysis of coal. This analysis
involves the determination of carbon and hydrogen, nitrogen, sulphur and oxygen.

1. Carbon and Hydrogen

The greater the percentage of carbon and hydrogen, the better is the coal in quality and
calorific value. However, hydrogen is mostly associated with the volatile mater and hence, it
affects the use to which the coal is put.

Procedure:

About 1 to 2 gram of accurately weighed coal sample is burned in a current of oxygen in a

combustion apparatus in the presence of copper oxide (CuO) as shown below.

C, H + CuO + O2 → Cu + CO2 + H2O

Carbon and hydrogen of the coal are converted into CO2 and H2O, respectively. The gaseous
products of combustion are absorbed respectively in Mg(ClO4)2 and NaOH tubes of known

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weights. The tubes are then weighed in order to determine the amounts of water and carbon
dioxide produced from combustion of the weighed coal sample. From these measurements, the
masses and percentages of carbon and hydrogen in the sample can be calculated as follows:

2. Nitrogen

Nitrogen has no calorific value and hence, its presence in coal is undesirable. Thus, a good
quality coal should have very little nitrogen content.

Procedure:

About 1 gram of accurately weighed powdered coal is heated with concentrated H 2SO4 along
with K2SO4 (as catalyst) in a long-necked Kjeldahl’s flask. After the solution becomes clear, it is
treated with excess KOH and the liberated ammonia is distilled over and absorbed in a known
volume of standard acid solution. The unused acid is then determined by back titration with
standard NaOH solution. Form the volume of acid used by ammonia liberated, the percentage
of nitrogen in coal is calculated as follows:

3. Sulfur

Sulfur, although contributes to the heating value of coal, yet on combustion produces
acids like SO2 and SO3, which have harmful effects of corroding the equipment and also cause
atmospheric pollution. Sulphur is, usually, present to the extent of 0.5 to 0.3% and derived from
ores like iron, pyrites, gypsum, etc., mines along with the coal. Presence of sulphur is highly
undesirable in coal to be used for making coke for iron industry since it is transferred to the iron
metal and badly affects the quality and properties of steel. Moreover, oxides of sulphur pollute
the atmosphere and leads to corrosion.

Procedure:

Sulfur is determined from the washings obtained from the known mass of coal used in bomb
calorimeter for determination of a calorific value. During this determination, sulfur is converted
to sulfate (SO42-). The washings are treated with barium chloride (BaCl2) solution, when barium
sulfate is precipitated. The precipitate is filtered, washed and heated to constant mass.

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4. Ash

Ash is a useless, non-combustible matter, which reduces the calorific value of coal.
Moreover, ash causes the hindrance to the flow of air and heat, thereby lowering the
temperature. Hence, lower the ash content, better the quality of coal. The presence of ash also
increases transporting, handling and storage costs. It also involves additional cost in ash
disposal. The presence of ash also causes early wear of furnace walls, burning of apparatus and
feeding mechanism.

Procedure:

The residual coal taken in the crucible and then heated without cover in a muffle furnace at
750oC for one–half hour. The crucible is then taken out, cooled first in air, then in a dessicator
and weighed. Heating, cooling and weighing are repeated until constant mass is obtained. The
residue is reported as ash on percentage basis.

5. Oxygen

Oxygen content decreases the calorific value of coal. High oxygen-content coals are
characterized by high inherent moisture, low calorific value, and low coking power. Moreover,
oxygen is a combined form with hydrogen in coal and thus, hydrogen available for combustion
is lesser than actual one. An increase in 1% oxygen content decreases the calorific value by about
1.7% and hence, oxygen is undesirable. Thus, a good quality coal should have low percentage of
oxygen.

Procedure:

Oxygen is determined indirectly by subtracting the combined percentages of carbon, hydrogen,

nitrogen, sulfur, and ash from 100%.

Percent of O = 100% - % of (C + H + S + N + ash)

6.6 Crude Oil

The word petroleum derives from the Latin words petra, meaning rock, and oleum, denoting
oil, when combined literally means rock-oil. It means oil from rocks. Petroleum was formed from
marine organisms living (plants, animals, algae, etc.) in the sea. As these organisms died, their
bodies settled at the bottom of the sea and got covered with layers of sand and clay. Over
millions of years, high temperature and high pressure and in the absence of air, transformed the
dead organisms into petroleum and natural gas as illustrated below.

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Offshore, crude oil is extracted by drilling using an equipment called an oil rig or drilling
rig. On land, crude oil is extracted or drilled from an oil platform.

Oil rig Oil flatform

Petroleum just as it is being pumped from an oil well (oil source) is known as “crude oil”.
It is also called crude oil because it is not a pure substance but a mixture of different
hydrocarbons – compounds of carbon and hydrogen. The combustion reaction is:

Other elements such as nitrogen (about 0.5%), sulfur (0.5%), oxygen (1%), and metals such
as iron, nickel, and copper (less than 0.1%) can also be mixed in with the hydrocarbons in small
amounts.

Crude oil is usually black or dark brown, but can also be yellowish, reddish, tan, or even
greenish. Variations in color indicate the distinct chemical compositions of different supplies of
crude oil. Petroleum that has few metals or sulfur, for instance, tends to be lighter (sometimes
nearly clear).

6.6.1 Petroleum Refining

Crude oil obtained from the mine contains a lot of soluble and insoluble impurities which
must be removed. The purification of crude oil is done by fractional distillation. Further
treatment of the products is done by refining. Refining can be defined as the process by which
crude oil is made free of impurities, division of petroleum into different fractions of
hydrocarbons that have different boiling points, and further treatment to impart specific

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properties in making useful products or chemicals used in making plastics, asphalt, candles,
ointments, anesthetics, etc.

The following are the preliminary stages in the refining of crude oil:

1. Removal of solid impurities

The crude oil is a mixture of solid, liquid and gaseous substances. The crude oil is allowed
to stand undisturbed for some time so that the heavy solid particles settle down and gases
evaporate. The supernant liquid is then centrifuged to remove the solids.

2. Removal of water (Cottrell’s process)

The crude oil obtained from the earth’s crust is in the form of stable emulsion of oil and
brine. This mixture when passed between two highly charged electrodes will destroy the
emulsion films and the colloidal water droplets coalesce into bigger drops and get separated out
from the oil.

3. Removal of harmful impurities

In order to remove sulfur compounds in the crude oil, it is treated with copper oxide. The
sulfur compounds are converted to insoluble copper sulfide (CuS), which can be removed by
filtration. Substances like NaCl and MgCl2 if present will corrode the refining equipment and
result in scale formation. These compounds are removed by techniques like electrical desalting
and dehydration.

The final stage in the refining of crude oil involves fractional distillation. Kindly watch
the early part of this video – “Petroleum_Refining”.

6.6.2 Fractional Distillation

In an oil refinery, the different hydrocarbon components of crude oil are separated by
“fractional distillation”. The theory behind fractional distillation is that different hydrocarbons
(fractions) of crude oil are separated based on differences in boiling points in a fractionating
column or distillation tower.

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A fractionating column or distillation tower is a cylindrical structure divided into several

sections or compartments separated by “plates” or “trays”. The compartments are maintained
at different temperature ranges like 450oC – 400oC, 400oC – 350oC, 350oC – 300oC, etc.

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The plate or tray is perforated (holes) like a chimney with bubble caps that allow passage
of the vaporized hydrocarbon from a lower tray to the next upper tray. The bubble caps partially
cool the vapor entering the next upper tray. When the temperature of the vapor is lower than
the temperature of the bubble cup, then the vapor condenses as liquid in the particular tray, as
depicted in the figure above.

Since the compartments are at different temperature ranges, the hydrocarbon products
condense at different compartments within the column, so that the lighter components separate
out at the top of the column (they have lower boiling points than heavier ones) and the heavier
ones fall towards the bottom. Watch this old video to understand fractional distillation -
“Shell_Fractionation”.

In the video, the different hydrocarbons are likened to a deck of cards. At the end of the
fractional distillation process, different fractions of hydrocarbons are produced as depicted
below.

By the way different writers will identify different hydrocarbons products to the different
compartments of the fractionating column. For example, in the figure above, “naphtha” is lower
than “gasoline” but in the second figure below, “gasoline” is a lower fraction than “naphtha”.

Even the design of the fractionating columns differ. But, do not bother, what is important
is you understand the principle behind fractional distillation.

Let me check your understanding.

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Assessment Question 6.6: Crude oil is a

mixture of hydrocarbons. Crude oil can
be separated into fractions (shown at
right). Complete the following
sentences.
a) The process used to separate crude oil into
fractions is called ____________________.
b) Why do the fractions separate at different
temperatures?
------------------------------------------------------------
------------------------------------------------------------

The following are the primary products after refining crude oil:
1. Gasoline – automobile, light truck, small engine fuel
2. Diesel – automobile, heavy trucks, trains, heavy equipment
3. Jet fuel – commercial and military aircraft

The secondary products are:

o Liquefied Petroleum Gas (LPG) – chemical feed, heating, commercial applications
o Kerosene – home heating, charcoal fluid
o Fuel oil – home heating, ships, boilers, furnaces
o Asphalt – roads, roofing materials, sealants
o Carbon black oil – carbon black manufacture, carbon composites, tires
o Lubricating oil – engine and machinery lubrication
o Waxes – candles, industrial sealants
o Petroleum coke – coal fired boilers, metals manufacture
o Sulfur – chemical and fertilizer manufacture
o NaHS (sodium hydrosulfite) – paper, copper mining, leather industries

6.6.3 Cracking

Refining of crude oil does not stop at separating the different hydrocarbon contents of
crude oil. Cracking is the process of transforming larger hydrocarbon molecules (meaning,
higher carbon contents) into smaller and lighter hydrocarbon molecules. Example, from a high
molecular mass alkane producing a smaller molecular alkane and alkene.

The main purpose of cracking is to obtain more of the smaller and lighter hydrocarbons because
they are more useful for commercial or consumer use than larger and heavier hydrocarbons like
gasoline, etc. For example, smaller and lighter molecules can be converted into polymers which
will serve as starting material for the production of plastics. Watch this video to learn more
about cracking – “Fractional_Distillation_Cracking” and “Hydrocarbon_Cracking”.

Cracking is mainly of two types: a) thermal cracking, and b) catalytic cracking which are
clearly explained in the videos.

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6.7 Liquid Fuels

Liquid fuels are the most important commercial and domestic fuels used these days. Most
of these fuels are obtained by fractional distillation from naturally occurring petroleum or crude
oil.

6.7.1 Gasoline

As you can see form the figures above, the fraction that contains hydrocarbons containing
5 to 10 carbon atoms is termed “gasoline”. Gasoline from crude oil refining is a complex mixture
of at least 100 different compounds, mostly hydrocarbons. Most of these are branched-chain
alkanes, and some are aromatic compounds. Gasoline serves as fuel for cars and other vehicles.

When used as a fuel, a number of things happen to the gasoline in the internal combustion
engine:

1. Gasoline is vaporized.
2. The vapor is mixed with air.
3. The gasoline vapor-air mixture is compressed.
4. The mixture is ignited by a spark from the spark plug and burned.
5. The gases produced by the combustion reaction expand.
6. Expansion causes the piston to move, i.e. kinetic energy is produced.

Kindly watch these videos before you continue reading - “Knocking_1” and
“Knocking_2”.

In short, in a traditional automobile engine, the air and gasoline vapor mixture is
compressed by a piston, and then ignited by a spark plug. Then the flame spreads rapidly and
smoothly through the gaseous mixture; where the expanding gas drives the piston down the
cylinder and imparting force along the driveshaft of the engine clockwise in Figure A to Figure
B.

However, if the gasoline vapor and air mixture ignite without the use of the spark plug
(pre-mature ignition), the piston receives a single hard slam with “pinging” sound as illustrated
from Figure C to Figure D. This situation is called “knocking” which results to reduction in the
efficiency with which energy produced by the combustion is converted to work and cause
damage to the engine.

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A common way of expressing the knocking characteristics of a combustion engine fuel is

by “octane number” introduced by Edger in 1972 based on “compression ratio” which is defined
as the ratio of the gaseous volume in the cylinder at the end of the suction-stroke (Figure E) to
the volume at the end of compression (Figure F).

It was found out that the tendency of fuel constituents to “knock” decreases in the
following order:

straight chain paraffins > branched chain paraffins > olefins > cycloparaffins > aromatics

Since n-heptane (n read as “normal”) was found to knock very badly, its antiknock value
has been arbitrarily given zero (0) octane number. On the other hand, highly branched octane
(2,2,4–trimethylpentane or simply called iso-octane) gives very little knocking, so its antiknock
value has been given as 100.

The octane number is equal to the percent by volume of 2,2,4-trimethyl pentane present
in a 2,2,4-trimethyl pentane and n-heptane mixture. Thus, an octane number of 80 indicates that
the gasoline is equivalent to the performance characteristics in a fuel engine fed with 80 %vol
2,2,4-trimethyl pentane and 20%vol of n-heptane.

How is this done? By comparing the compression ratio of an engine fed with different
2,2,4-trimethlypentane and n-heptane mixtures. Let us say, the compression ratio of 80:20 by
volume ratio between 2,2,4-trimethylpentane and n-heptane mixture is A, the a gasoline is used
to run an engine and the compression obtained is B, then the octane number of the gasoline is
NOT “80”.

But if the calculated compression ratio obtained is A, then the gasoline has an octane rating of
80.

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Octane number depends of on the design of the internal combustion engine of a vehicle.
If the manual of the car you bought says you have to use gasoline with an octane number of 90,
then you have to use a gasoline with an octane number of 90 or above.

Assessment Question 6.7: A gasoline has an Octane number of 90. Does it mean that the
gasoline is made up of 90% of 2,2,4-trimethylpentane and 10% n-heptane by volume?
Explain.

Assessment Question 6.8: What is the relationship between octane number and pre-mature
ignition? Explain.

Gasoline from crude oil refining with low octane number is not a good quality for engine
fuel. It often knocks (produces huge noise due to improper combustion). As a result of knocking,
the gasoline is wasted because the energy produced is not used in a proper way.

The octane number of poor gasoline from crude oil refining can be raised by the addition
of extremely poisonous materials as tetraethyl lead (C2H5)4Pb and diethyl telluride (C2H5)2Te
called “antiknock” agents.

When (CH3CH2)4Pb burns, it produces not only carbon dioxide and water, but also lead:
(CH3CH2)4Pb + 13 O2 → 8 CO2 + 10 H2O + Pb
This lead can oxidize further to give species such as lead(II) oxide:
2 Pb + O2 → 2 PbO
Pb and PbO would quickly over-accumulate and destroy an engine. For this reason, the
lead scavengers 1,2-dibromoethane and 1,2-dichloroethane are used in conjunction with
tetraethyl lead—these agents form volatile lead(II) bromide and lead(II) chloride, respectively,
which are flushed from the engine and into the air.

In most industrialized countries, a phase out of tetraethyl lead from road vehicle fuels
was completed by the early 2000s because of concerns over air and soil lead levels and
the accumulative neurotoxicity of lead.

Assessment Task 6.3: Visit a gasoline station and ask how gasoline is categorized in terms of
octane numbers.

6.7.2 Diesel

The fraction of the crude oil that contains C14 to C20 hydrocarbons that condenses at 270oC
is called diesel oil or diesel, which is used as fuel of automobiles and light trucks. Engines that
run using diesel fuel belong to the category of internal combustion engines known as
“compression ignition” (CI) engines.

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The name derives from the fact that CI engines depend on compression of the air-fuel
mixture to ignite the mixture. In a sense, we require a CI to knock, whereas knocking is very
undesirable in an “spark ignition” (SI) engine or gasoline engines. We have seen that knocking
tendency increases with increasing compression ratio of an engine. Since ignition on
compression is desired in a diesel engine, the compression ratios are much higher than typical
SI engines. The heat needed to ignite the fuel-air mixture is obtained from the heat of
compression of the mixture. An analogy is the experience of having the metal casing of a
manually operated air pump become palpably hot while, for example, inflating a bicycle tire.

Just like gasoline, the quality of a diesel fuel is measured in terms of “cetane number”.
Cetane number is defined as the percentage of hexadecane (n-cetane) present in a mixture of
hexadecane and 2-methylnaphthalene, which has the same ignition characteristic of diesel fuel
in test. Generally, diesel fuels with cetane numbers of 70-80 are used.

Cetane (n-cetane) or hexadecane [CH3-(CH2)14-CH3] is a saturated hydrocarbon, its cetane

number is arbitrarily fixed as 100. A methylnaphthalene is an aromatic hydrocarbon, its cetane
number is arbitrarily fixed at zero (0).

6.8 Gaseous Fuels

The gaseous fuels are most preferred because of their ease of storage, transport, handling
and ignition. These are classified into two types.

a) Primary fuels – example: natural gas

b) Secondary fuels – examples: coke-oven gas, producer gas, water gas.

6.8.1 Natural Gas

Natural gas is defined as a mixture of hydrocarbons with varying quantities of non-

hydrocarbons that exists either in the gas phase or in solution with crude oil in natural
underground reservoirs. The principal hydrocarbon component of natural gas is methane.
Often, however, the gas also contains the other light alkanes and a variety of inorganic
compounds, including carbon dioxide, nitrogen gas, and helium. A typical composition of
natural gas in percent by volume is given below.

Component % by volume
CH4 83.0
C2H6 7.2
C3H8 2.3
C4H10 1.0
C5H12 and larger 0.3
N2 5.8

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CO2 0.2
He 0.2

In terms of the hydrocarbon components, we may encounter two types of natural gas: one
in which methane is the only hydrocarbon component; and the other one contains methane and
other small alkanes and alkenes.

Among the first few members of the alkanes, there are very significant differences in the
boiling points of the compounds as the size of the molecules increases as shown below.

These differences in volatility make it easy to condense the gases heavier than methane – ethane,
propane, butane, and pentane. When natural gas contains less than 0.013 L/m3 of the
condensable gases, natural gas is termed “dry gas”. When natural gas contains greater than
0.040 L/m3 of the condensable gases, it called “wet gas”

Condensing liquid from a wet gas and subjecting the condensate to fractional distillation
(which must be performed at elevated pressure, to keep some of the components in the liquid
phase) makes it possible to produce ethane pure fractions. Ethane is valued as a starting material
for the production of ethylene, which is a feedstock of enormous importance for the
petrochemical industry.

Assessment Question 6.9: In terms of leakage of storage containers, which is more dangerous
- natural gas, oil leak, or coal spill? Explain.

6.8.2 Liquefied Petroleum Gas (LPG)

Another pure hydrocarbon that is obtained from a wet gas is propane. Propane, which
boils at -42°C at atmospheric pressure, is liquefied fairly easily and is the principal component
of the useful fuel liquefied petroleum gas, which is almost universally known by its acronym, LPG.
The hydrocarbons having three to eight carbon atoms condensed from natural gas compose a
material known as natural gasoline.

Liquefied petroleum gas is also a by-product in refineries during fractional distillation of

crude oil. Nowadays LPG has been a common fuel for domestic work and also in most of the
industries. The main components of LPG are propane, n-butane, iso-butane, and butylenes. The
hydrocarbons are in gaseous state at room temperature and 1 atmospheric pressure but can be
liquefied under higher pressure.

Assessment Question 6.10: Naturally, LPG is an odorless gas and odorants such as thiols or
sulfides are added, the prominent smell that you experience when there is a leakage.
What do you think is purpose of adding odorants to LPGs? Explain.

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6.8.3 Compressed Natural Gas (CNG)

Natural gas contains mainly CH4. When natural gas is compressed at high pressure
(1000atm) or cooled to -160oC, it is converted to CNG. It is stored in cylinder made of steel. It is
now replacing gasoline as it releases less pollutant during its combustion. In some of the metro
cities, CNG vehicles are now used to reduce pollution.

6.8.4 Biogas and Landfill Gas

Biogas is the gas produced by anaerobic biological process (popularly called anaerobic
digestion) of organic materials and is composed mainly of methane, carbon dioxide, and water
vapor, along with small amounts of hydrogen sulfide, nitrogen, and hydrogen. The gas formed
from the treatment of sewage and industry waste water is also called biogas.

Biogas production takes place mainly in two stages – acidogenesis and methanogenesis.
Acidogenesis involves breaking down of complex organic molecules into simple organic acids
by microbes called acidogenic bacteria. These acids are later converted in the methanogenesis
step into methane and carbon dioxide by the methanogenic bacteria. In the acidogenesis stage,
hydrogen gas is also evolved; however, hydrogen is not seen in significant amounts in the final
biogas because it is used up by the methanogenic bacteria in making methane. The digestible
organic material is called the substrate. Watch these videos to learn more about biogas
production – “Biogas_1” and “Biogas_2”.

Another source of methane is landfill gas. Similarly to anaerobic digestion in the biogas
plant, the organic matter in the garbage dumped into landfills also biodegrades and methane is
evolved. Although this gas contains methane, the percentages are appreciably lower than those
in natural gas and biogas and are in the range 30–50%, the remainder mainly being carbon
dioxide. Landfill gas also contains varying amounts of nitrogen, oxygen, sulfur, and so on.
Mercury is also known to be present in landfill gas and sometimes the radioactive contaminant
tritium has also been reported. Many toxic chemicals such as benzene, toluene, chloroform, vinyl
chloride, and carbon tetrachloride have also been reported.

Landfill gas is obtained by carefully installing gas collection systems which include a
series of wells and a flare system installed in the landfills during construction. The gas thus
formed is diverted to a central point where it is processed and treated in accordance with its
ultimate usage – to be flared off or used to fuel a generator.

6.8.5 Producer Gas, Synthesis Gas and, Blue Gas

Producer gas (mainly CO and N2 in high concentration) is a product of partial combustion

of biomass, coal or coke with air or a mixture of air and steam. (Air is a mixture of 79% oxygen
and 21% nitrogen.) This process is called “gasification”. The reactor wherein this process occurs
is called a gasifier. The reaction is,

C + O2 + N2 → CO2 + N2 + heat

Urban waste and natural gas are also used as starting materials. Carbon monoxide and
hydrogen are the two principle combustible components of producer gas. Carbon dioxide and
nitrogen are also present in relatively large quantities and consequently the resultant gas is of
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low calorific value. The typical producer gas composition in volume is N2 = 55%, CO = 29%,
CO2 = 5.5% and H2 = 10.5%.

When the producer gas consists of varying amounts of hydrogen and carbon monoxide,
and used as intermediate for producing synthetic natural gas, methanol, or synthetic petroleum,
then the gas is called “synthesis gas”. Normally, synthesis gas has a higher calorific value than
producer gas because of the absence of nitrogen. Oxygen instead of air is generally used as
oxidant in such cases.

When superheated steam is used for the gasification reaction involving mainly the water
gas reaction shown below, then water gas is generated.

C + H2O → CO + H2

Owing to the high carbon monoxide content, this gas gives a blue flame and is therefore
called “blue water gas” or “blue gas”.

6.8.6 Hydrogen (H2)

Hydrogen is today considered to be an attractive source for replacement of conventional

fossil fuels. Since hydrogen is a fuel which generates no pollutants upon combustion, it is
considered to be a clean energy source. Hydrogen can be used as a fuel directly in internal
combustion engines, and can be used to power a vehicle via fuel cells. Hydrogen for fuel cells
can be generated either on-board through catalytic steam reforming of hydrogen or by storing it
as hydrates or in carbon nanotubes as an intermediate step.

Natural gas and naphtha have been the main source of commercial hydrogen.
Gasification of coal and electrolysis of water are other industrial methods used for hydrogen
production. Recently, alternative resources such as biomass are being exploited for production
of biomass. For hydrogen production from biomass, various routes are being explored which
include biomass gasification coupled with the water gas shift reaction; fast pyrolysis followed
by reforming of the resultant oil is also being investigated.

Microbial conversion of biomass is being studied extensively and is fast gaining

popularity. Various hydrogen-producing microorganisms have been used to produce hydrogen
selectively upon breaking up of biomass carbohydrates at various stages.

Molecular hydrogen can also be recovered as a product or co-product of the anaerobic

fermentation of biomass. It is reported that photosynthetic algae are capable of generating
molecular hydrogen by bio-photolysis. However, the microbial generation of hydrogen is still
far from achieving commercial success

6.8.7 Blast Furnace Gas

A furnace is like an oven but much a “pogon” in vernacular. An ordinary oven is usually
made up of a metal casing but a furnace like a pogon is made up of bricks or ceramics to contain
the heat inside it. The main function of a furnace to heat a material at very high temperature
like the one shown below.

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In the smelting (purification) of iron ore, a blast furnace is used. Kindly watch these
videos – “Blast_furnace_1” and “Blast_furnace_2”. The combustion gases formed is called “blast
furnace gas” which contains carbon monoxide (CO).

The typical blast furnace gas composition in volume is N2 = 55.19%, CO = 20.78%, CO2 =
21.27% and H2 = 2.76%. The blast furnace gas can still serve as a source of fuel because of the
presence of carbon dioxide and hydrogen gas which can undergo combustion or oxidation.

CO + ½ O2 → CO2 + heat
2H2 + O2 → 2H2O + heat

6.8.8 Coke-Oven Gas

Coke-oven gases are by-products of the coal carbonization process to produce coke. Coke
is one of the major ingredients in the production of iron as discussed previously. The
classic composition of coke gas is: hydrogen (H2 - 51%), methane (CH4 - 34%), carbon monoxide
(CO - 10%), ethylene (C2H4 - 5%). The composition may also include benzene (C6H6), ammonia

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(NH3), hydrogen sulfide (H2S) and other components. The presence of methane and ethane
make coke-oven gas another source of fuel.

2CH4 + 4O2 → 2CO2 + 4H2O + heat

2C2H4 + 6O2 → 4CO2 + 4H2O + heat

6.9 Calorific value

There are different units for measuring the quantity of heat – calorie, kilocalorie, and
British thermal unit (Btu).

1. Calorie - it is the amount of heat required to increase the temperature of 1 gram of water
by one centigrade degree.
2. Kilocalorie - this is the unit of heat in metric system, and is defined as the quantity of
heat required to raise the temperature of one kilogram of water by one centigrade
degree.
3. British thermal unit (Btu) - this is the unit of heat in English system, it is defined as “the
quantity of heat required to increase the temperature of one pound of water
through of one Fahrenheit degree”.

1 kcal = 1000 cal and 1 kcal = 3.968 Btu and 1 Btu = 252 cal

Assessment Question 6.11: What is the difference between 10oC and 10Co? Definitely, the
placement of the degree (o) sign and the symbol “C” for centigrade. Explain the
difference.

The prime property of a fuel is its capacity to supply heat. Normally, when a combustible
substance burns, the total heat produced depends upon the quantity of fuel burned, its nature,
air supplied for combustion, and certain other conditions governing the combustion. Further,
the heat produced is different for different fuels and is termed as its “calorific value”.

Calorific value of a fuel may be defined as “the total quantity of heat liberated, when a
unit mass (or volume) of a fuel is burned completely in air or oxygen”. The unit of calorific value
is usually expressed as calorie/grams, or kilocalorie/kilogram, or British thermal unit/pound.

It is also possible that the calorific values might be expressed per unit of gas volume or of liquid
volume.

Dire ko karuyag maghimo hin kalugaringon nga definition kay dire ako author this
chemistry nga libro. My role as a teacher is to unlock definitions cited in books to help you
understand the concept. OK? Ganito yun.

Combustion of carbon occurs at very very high temperature, say 500 oC. Carbon dioxide
will be in the gaseous form. (Let me use an analogy – heat represented by small green circles.)

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Pahagkuton man hi carbon dioxide (CO2) ngada ha room temperature (25oC), hi carbon dioxide,
“gas” la gihapon. So, maski kumain hi CO2 dire niya dara-dara an “heat” nga iya gin-release.
So, nagagamit an iya heat nga gin release para pagpaso hin iba nga butang.

It is different in the case of water. Combustion of hydrogen occurs also at very very high
temperature, say 500oC. Water will be in the gaseous form. So, after combustion, dara-dara ni
water an “heat” energy. Dire nagagamit pagpaso han iba nga butang.

Water at 25oC (room temperature is liquid). To change liquid water at 25 oC will require
heat energy to convert it into a gaseous form, say 500oC. This heat energy is called “latent heat
of vaporization” of water.

Saka la magagamit an heat ni hydrogen nga na produce after combustion, when water condenses
into a “liquid” – “latent heat of condensation” of water.

There are several types of calorific values.

1. Gross Calorific Value (GCV) or Higher Heating Value (HHV) - is the amount of heat
liberated when a unit quantity (mass or volume) fuel is completely burned and the products of
combustion (CO2 and H2O) are cooled to room temperature (around 25oC). This heat includes the
latent heat of condensation of water. Because when a fuel containing hydrogen is burned, the
hydrogen present is converted to steam. As the products of combustion are cooled to room
temperature, the steam gets condensed into water and the latent heat is evolved. Thus the latent
heat of condensation of steam, so liberated, is included in the gross calorific value.

Gross calorific value = heat liberated when carbon is changed to CO2 + latent heat of
condensation of water.

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2. Net calorific value (NCV) or lower calorific value (LCV) - is defined as “the net heat
produced, when unit mass or unit volume of the fuel is burnt completely and the combustion
products are allowed to escape”. Meaning, the combustion gases are not cooled down to room
temperature (25oC).

Net calorific value = heat liberated carbon is changed to CO2 + heat of vaporization of
water (H2Osteam)

Net calorific value is the gross calorific value excluding the latent heat of condensation of
water (the weight of water formed is nine times the weight of hydrogen in the fuel). Therefore,

Net calorific value = Gross calorific value – latent heat of vaporization of water
= Gross calorific value – (mass of hydrogen per mass of fuel burned x
9 x latent heat of vaporization of water)

The latent heat of vaporization of water is 857 kcal/g. Usually, hydrogen is expressed in terms
of percentage. So,

Net calorific value = Gross calorific value – 52.83 x %H2

The gross and net calorific values of coal can be measured using a bomb calorimeter discussed
in Learning Packet 5.

6. 10 Alternative Energy Resources

All of the Earth’s organisms, air, water, and soil, as well as materials such as oil, coal, and
ore that are removed or extracted from the ground, surface or atmosphere are called natural
resources. Natural resources can be divided into two broad categories – renewable resources
and non-renewable resources.

6.10.1 Non-renewable Energy Resources

Hydrocarbon-based fuels are also known as fossil fuels because they are derived from the
centuries-old remains of decayed plants and animals that were captured in geological deposits.

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These fuels include coal, oil, and natural gas. They are considered nonrenewable energy sources
because they take millions of years to form and cannot be easily replenished after their use
during the time of a human life span.

As fossil fuels became the dominant source of energy, less and less attention was paid to
the energy sources of the past: wood, the sun, water, and wind. Developed countries came to
rely on fossil fuels for electricity production, for commercial and industrial processes, and
eventually for fuel in the transportation sector.

Remember that using more fossil fuels accelerates the global warming trend due to more
greenhouse emissions and pollution - carbon dioxide, methane and nitrous oxide.

6.10.2 Renewable Energy Resources

These are energy resources that cycles or can be replaced within a human life span. They
are also energy resources that harness energy from an inexhaustible source. Such sources
include the sun, wind, falling water, waves, tides, biomass, or heat generated beneath the surface
of the Earth. Most renewable energy sources, except geothermal, are derived from the sun.

Solar energy comes directly from the thermal energy given off by the sun. Sources like
wind, hydropower (hydro), waves, and tides are the result of solar energy. Wind is created from
the differential heating of the Earth’s surface by the sun, wind creates waves, and tides are the
result of the gravitational pull of the moon and the sun on the Earth. Biomass is actually chemical
energy stored in plants that was converted from solar energy through the process of
photosynthesis.

Renewable energy resources include solar, wind, hydro, geo-thermal, biomass, and
ocean, which includes tidal and wave power as depicted in the figures below.

Solar energy Wind energy

Assessment Question 6.12: Cite another advantage of renewable energy resources from non-
renewable energy sources.

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Hydropower Nuclear energy

On the other hand, alternative energy resources include those that are not derived from
fossil fuels but that are also considered nonrenewable. Nuclear power and energy stored in
hydrogen are the main alternative energy resources.

One major effect of consuming fossil fuels is global warming. Almost every resource
needs to be removed from the Earth and processed in some way before it can be used. What
ultimately determines the availability of energy resources are the costs involved in
removing/extracting it from the Earth and the costs involved in processing/refining them into
products. The solution to global warming must be based on diverse clean, renewable and
environmentally sound sources of energy.

Assessment Task 6.3: Write a 50 words essay to the following prompt, “As the world’s
scientists and engineers work to develop renewable energy sources, the world
continues to use unprecedented amounts of non-renewable fossil fuels to power homes
and businesses. Why do you think it is important for society to move away from using
fossil fuels?

6.11 Assignment

1. The table below shows five hydrocarbons.

Compound State at room Boiling point in oC

temperature (25oC)
Ethane, C2H6 gas -88
Butane, C4H10 gas 0
Hexane, C6H14 liquid 69
Pentadecane, C15H32 liquid 270
Heptadecane, C17H36 solid 302

Tick () two correct statements about the above hydrocarbons.

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Statement Tick ()

Ethane has the smallest molecules.
Hexane and pentadecane are liquid at 100oC.
Heptadecane has the highest boiling point.
Butane boils at 100oC.

2. Write the number 2, 3, 4, or 5, next to each stage so that the description of fractional distillation
is in the correct order. Numbers 1 and 6 have been done for you.

Number Stage
1 The crude oil is heated to 350oC or higher
When a fraction in the vapor cools to its boiling point, the
fraction condenses.
Any liquids flow down to the bottom of the column and
the hot vapors rise up the column.
6 The condensed fraction is separated and flows out through
a pipe.
When the hot vapors rise up the column, the vapors cool.
Most of the compounds in the crude oil evaporate.

3. Crude oil is a mixture of hydrocarbons. The diagram at right shows a method of separating
crude oil.

A. Complete the following sentences.

1. This method of separation is called ______________.

2. A hydrocarbon is a compound that contains
_________ and __________ only.

B. Give the letter from the diagram that represents the

least flammable fraction. ______

C. Give the letter from the diagram that represents the

most viscous (“masaputok”) fraction. ______

4. What natural element helps gasoline to burn better?

5. What is the difference between octane number and cetane number in terms of fuel
combustion?

6. “Engine knocking” occurs when a car or vehicle rated to run at minimum 95 octane number
fuel is accidentally loaded with 91 octane number fuel. True or false? Explain.

6.12 References

Brown, W., Iverson, B., Anslyn, E., & Foote, C. (2018). Organic Chemistry. 8 th Edition. United
States: Cengage Learning.

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Schobert, H. (2013). Chemistry of Fossil Fuels and Biofuels. New York: Cambridge University
Press.
Smith, Z. and Taylor, K. (2008). Renewable and Alternative Energy Resources. USA: ABC-CLIO,
Inc.
Wiehe, I. (2008). Process Chemistry of Petroleum Macromolecules. New Jersey: CRC Press

6.13 Acknowledgement

All figures, diagrams, tables and other information contained in this module were taken
from the references enumerated above.

E.A. Malindog Jr.