Week 2

PETROLEUM CHEMISTRY

Petroleum or crude oil is a complex mixture of naturally occurring hydrocarbons representing

several classes of compounds, most of which include alkanes (parafins), cycloalkanes
(naphthenes) and aromatics found beneath the earth surface. Compounds containing oxygen,
nitrogen and sulphur as well as some trace metals have also been reported in petroleum. The
word “petroleum” was derived from the Greek words “petra” and “oleum” meaning “rock” and
“oil” respectively. It is formed by anaerobic decomposition of dead plants and animals that were
buried and exposed to immense pressure and temperature several millions of years ago. Crude
oil, whether heavy, medium or light is a major source of energy for electricity generation and
fuels. The aliphatic hydrocarbons in crude oil may contain between C 1 to C40. Crude oil and its
fraction possess some physico-chemical characteristics that distinguish a fraction from others
these properties are;
1. Viscosity: Viscosity is a measure of the flow properties of the refinery stream. It is
measure using viscometer out at 100 and 210 °F.
2. Flash and Fire Points: The flash point is the temperature above which the product
flashes forming a mixture capable of inducing ignition with air. The fire point is the
temperature well above the flash point where the product could catch fire.
3. Pour and Cloud Points: The cloud point is the temperature at which the first cloudy
appearance of the petroleum product occurs when it is cooled. Upon further cooling, the
product will ceases to flow at a temperature. This temperature is termed pour point.
4. Surface tension: This is a net force that acts inward at the surface of a liquid and tend
minimize the number of molecules at the surface and the surface area of the liquid.
5. Colour and Fluorescence: Crude oils vary in colour from light, yellow, green, red, brow
to black. The darker and brownish colours are caused by the asphaltic resinous material
in the oil
6. Optical Property. Most crude oil types and their products rotate the plane polarized light
and the rotation most of the time is to the right.
7. Refractive Index: This is the inverse ratio of the speed of light in a vacuum. TI refractive
index of crude oils vary in respect to source and geographical locations
Refining of Crude Oil
Refining is the process of converting crude oil into other useful products or fractions either by
fractional or vacuum distillation. Each refining process begins with the separation of crude oil
into different fractions by distillation. The fractions are further treated to convert them into
mixture of other products by various conversion processes. These mixtures of new compound are
then separated by fractional distillation and solvent extraction while impurities are removed by
desalting, dehydration, sulphur removal, hydrotreating etc

Distillation process

The crude oil is heated to 350oC or above using heat exchangers and is converted to vapours.
These vapours are charged to the distillation tower and they travel from bottom to top. The
whole process is typically conducted in a vertical tower or column ranging from 0.5 to 6.0 meters
in diameter and 6-60 meters in height. The tower has a temperature gradient, which means it is
hot at the bottom and cooler at the top. It contains a series of trays installed to collect fractions
that are finally removed via outlets. Because different fractions have different boiling points,
they condense at different heights at different levels of the column. The large molecules with
higher molecular weight stay in the bottom while smaller molecules with low molecular weight
travel upward and condense at their respective collection tray. The solid waxy residue is
removed from the bottom while molecules with very low molecular weight stay as gases and are
collected from the top. They are called petroleum gas.

Different Fractions obtained by distillation

The two major groups of a class of organic compounds obtained from distillation are
hydrocarbons and hetero-atomic compounds. Among hydrocarbons, the fraction distillation gives
paraffins, Naptha, unsaturated aliphatic, and aromatic compounds.

Paraffins
Paraffins are saturated hydrocarbons where a carbon atom is attached to four other separate
atoms. The general formula for such a class of compounds can be described as (CnH2n+2) where
n is the number of carbon atoms in the compound. They are also called alkanes. They are the
major fraction obtained from crude oil (30-60%). They may range from simple molecules such
as methane, ethane, propane, and butane to longer carbon chain molecules such as
Hentriacontane (C31H64). These molecules are stable and due to saturation are less reactive
among other hydrocarbons. Paraffins could be straight-chain (n-paraffins) or branched-chain
molecules (iso-paraffins).

(A)

(B)

Figure 1: (A) n-paraffin, (B) Isooctane (2,2,4-Trimethylpentane).

n-paraffins have poor anti-knocking properties compared to their branched-chain analogues (iso-
paraffins). Branched-chain fractions perform better in the internal combustion engines and hence
are more in demand. This drives a series of chemical modifications to convert n-paraffins to iso-
paraffins by catalytic reforming, alkylation, polymerization, or isomerization.

Gasoline or petrol also belongs to this class and is the major light vehicle fuel. It is branched-
chain octane mixed with anti-knocking agents and octane enhancers. Kerosene and famous diesel
oil are all predominantly paraffins.

Alkenes

Alkenes or olefins are actually not present in crude oil. They are made during petroleum
processing via cracking. Their general formula is CnH2n. They are reactive molecules as they
have a double bond in their chemical structure. They easily undergo oxidation and hence
improve the anti-knocking quality of finished fuel. Due to their reactivity, they are utilized to
synthesize various other organic compounds used in various other chemical industries. Such
chemicals are generally called petrochemicals.

Napthalene series

They are saturated cyclic organic compounds also known as cyclic alkanes. Their general
formula is the same as alkenes, CnH2n. They are the second most abundant fraction (30-50%) of
crude oil. The dehydrogenation of these compounds gives a series of benzene compounds which
are important precursors for other organic compounds. They are also good to stock for lube oil.

Figure 2: Naphthalene molecule.

Aromatic Compounds or Benzenes

They make only a small portion of crude oil. They have a high anti-knocking value and hence are
highly desirable for gasoline mixture. Their general formula is CnH2n-6. Simple aromatic
compounds such as benzene, toluene, and xylene are a good sources of carbon for further organic
synthesis f petrochemicals.

Benzene toluene and xylene.

Hetero-Atomic Compounds

The most common hetero-atomic class in crude oil is sulfur-containing compounds. They are
present in crude oil as mercaptans, mono- and disulfides with the general formula R-SH, R-S-R1,
R-S-S-R1, where R and R1 are the alkyl radicals. Cyclic sulfur compounds e.g. thiophenes and
benzothiophene are also obtained from crude oil. Sulfur present in petroleum fuel products may
form various oxides of sulfur (SOx) during combustion, which are strong environmental
pollutants.

Nitrogen-containing compounds are also present in small amounts in crude oil. They are
responsible for the colour. Nitrogen in petroleum fuels causes the generation of oxides of
nitrogen (NOx), which are also strong pollutants in the atmosphere. Nitrogen can be removed
from petroleum products by catalytic hydrogenation.

Crude oil may also contain metallic compounds of vanadium, nickel, lead, arsenic, etc.
Vanadium and nickel are found in the form of organometallic compounds mostly in the heavier
fractions of crude oil. Petroleum fuels containing these metallic compounds may damage the
burners, lines, and walls of the combustion chambers and hence must be removed.Small amounts
of oxygen-containing organic compounds are also obtained from crude oil. They are phenols,
cresols, organic acids, etc.

The table below shows the various fractions of petroleum and their uses.
Table 1.1. Petroleum products and their use

S/N Fraction No. of Boiling Uses

Carbon Point
Atoms Range (0C)

1 Liquefied Petroleum Gas C1-C4 Below 30 Domestic fuel, fuel for engines,
soldering, brazing and raw materials
for Chemicals

2 Gasoline (petrol) C5-C9 30-150 Motor fuel

3 Naphtha C5-C11 30-180 Fertilizer feedstock, thinner for paints,

vanishes & lacquers

4 Kerosene C8-C16 150-230 Domestic fuel, aviation fuel &

manufacturer of pesticides

5 Diesel C13-C18 200-300 Fuel for trucks and lorries, raw material
for gasoline through cracking

6 Lubrication oil C16-C25 250-360 Lubricants

7 Heavy oil C18-C28 250-380 Drug production

8 Petroleum jelly/ paraffin wax ˃ 30 ˃ 350 Candle, waxes

9 Bitumen ˃ 30 ˃ 350 Tarring of roads, roofing material

Various Conversion Processes in Crude Oil Refining

1. Cracking
Cracking is the process by which heavy organic molecules such as kerosene and straight —
chain hydrocarbons are converted to simpler organic molecules by the breaking of carbon —
carbon bonds in the precursor. The two important types of cracking are; thermal cracking also
known as Pyrolysis and catalytic cracking. Examples are:
C6H12 + H2
C6H14 C4H8 + C2H6
n-hexane
C3H6 + C2H4 + CH4
C6H12 + C2H4
C8H18
n-octane C4H10 + C2H4 + CH4 + C

2. Reforming
Reforming is the process of converting low octane, heavy, straight — run gasolines and napthas
to high octane hydrocarbons called reformates, It can also be carried out using catalyst (catalytic
reforming).
3. Alkylation
Alkylation is a reaction involving isobutene with a light olefin such as propene or butene to
produce alkylate, high octane rating petroleum, in the presence of acid (H2SO4, or HF) catalyst.

CH3 CH3 CH3 CH3

H
CH3- C= CH2 + CH3- CH- CH3 CH3- C - CH2 –CH – CH3
Isobutene isobutane CH3 isooctane
4. Catalytic Polymerization
Catalytic polymerization in petroleum refinery is used to convert light olefins such as, propene
and butene, into a high octane number motor gasoline component (polymer gasoline) in the
presence of an acid catalyst.
CH3
CH3- C= CH2 H+ CH3 – CH2 – CH2 – C = CH2
propylene CH3 2-methylpent-1-ene
5. Petroleum Coking
Coking is a thermal process of converting reduced crude, straight-run residues, cracked residues
or heavy oil and tar-sand bitumen into lower-boiling products, such as gases, naphtha, fuel oil
and coke. The coke obtained may be used as fuel, but processing and marketing for special uses
such as electrode manufacture, production of chemicals and metallurgical coke.
C8H18 C4H10 + C2H4 + 2C + 2H2
Octane butane ethene Carbon Hydrogen
6. Isomerization
Isomerization in petroleum refining is the process of converting straight chain hydrocarbons int,
branched chains so as to obtain high octane rating petroleum products.
AlCl3/300 0C
CH3CH2CH2CH2CH2CH3 CH3-CH(CH3)–(CH2)2–CH3 + CH3CH2CH(CH3)CH2CH3
n-hexane 2-methylpentane 3-methylpentane

7. Aromatization

The conversion of straight chain hydrocarbons in petroleum refining to aromatic hydrocarbons when
heated to 500 °C at about 15 atmosphere pressure using chromium (VI) oxide (CrO3)), molybdenum (III)
oxide (Mo203) of vanadium (V) oxide (V2O5) catalyst is known as aromatization.

8. Octane Rating of Petrol

Octane rating is the measure of the ability of a fuel resists “knocking” or “pinging” during combustion,
caused by the air/fuel mixture detonating prematurely in the engine. Higher octane fuels are often
required for engines that use a higher compression ratio and/ or use supercharging or turbocharging to
force more air into the engine. A lower performance engine will no generally perform better with high
octane fuel, since the compression ratio is fixed by the engine design.

The octane number of a fuel is measured in a test engine, and is define by comparison with the mixture of
iso-octane and normal heptane, which would have the same anti-knocking capacity a the fuel under test:
the percentage by volume, of iso-octane in the mixture is the octane-number of the fuel. For instance,
gasoline with the same knocking characteristics as a mixture of 90° iso-octane and 10% heptane would
have an octane rating of 90. This is because some fuels are more knock-resistant than iso-octane, the
definition has been extended to allow for octane numbers higher than 100.

The octane rating of a spark ignition engine fuel is the detonation resistance (anti-knock rating) compared
to a mixture of iso-octane (2,2,4-trimethylheptane, an isomer of octane) and n-heptane. By definition, iso-
octane is assigned an octane rating of 100 and heptane is assigned an octane rating of zero. An 87-octane
gasoline, for example, possesses the same anti-knock rating of a mixture of 87% (by volume) iso-octane
and 13% (by volume) n-heptane. This does not mean, however, that the gasoline actually contains these
hydrocarbons in these proportions. It simply means that it has the same detonation resistance as the
described mixture. Octane rating does not relate to the energy content of the fuel. It is only a measure of
the fuel’s tendency to burn rather than explode.

Types of Additives to Gasolines

The use of additives in gasoline has become imperative for the following reasons:

1. To enhance the properties of gasoline to meet the specification requirements; and

2. To introduce new properties which are not in the gasolines obtained by refining of crude oils.

Gasoline additives carry out these two functions in an economical ways. These gasoline additives and
their functions are listed below.
 1. Anti-knock Compounds

These compounds are required to increase the octane number of gasolines used in sparked ignition
engines. Although several types of compounds are known to improve octane number, only lead alkyls
gained commercial status. Some of the anti-knock compounds are tetraethyl lead, tetramethyl lead, iron
carbonyls, methyl cyclopentadienyl manganese tricarbonyl.

2. Antioxidants

The oxidative degradation of gasoline is believed to proceed via a free radical chain reaction, which
involves peroxide radicals. Antioxidants such as alkyl phenols or phenylene diamines, inhibit this chain
reaction by reacting with peroxide radical and thereby minimizing gum formation and improve storage
stability.

3. Metal Deactivators

Some of the trace amounts of metals that may find their ways into the gasoline have been found to have a
pronounced deleterious effect on the storage quality of gasoline. Certain metals such as copper can
catalyze the oxidation reactions, and metal deactivator inhibitors are used to prevent this action. The most
common of these are the ethylene diamine and propylene diamine derivatives of disalicylidene.

4. Anti-icing Compounds

Ice formation in the carburetors can upset air/ fuel ratio and increase fuel consumption. Under conditions
of high humidity and relatively low ambient temperature, moisture from the inlet air can freeze within the
carburetor. This results in rough engine running and even stalling particular ly during engine warm up.
Examples of anti-icing agents are isopropanol, ethylene glycol and methyl ethyl ether.

9. Isomerism

In organic chemistry, isomers are molecules with the same molecular formula (i.e. the same
number of atoms of each element), but different structural or spatial arrangements of the atoms
within the molecule. Isomerism is the phenomenon whereby two or more compounds possess
the same molecular formula but have different structural formulae.

1.8.1 Types of Isomerism

There are two main types of isomerism: This graphic looks at the 5 main types of isomerism in
organic molecules, with a more detailed explanation of each given below, as well as the
reason why isomerism is important in our day-to-day lives.
1.8.2 STRUCTURAL ISOMERISM

In structural isomerism the atoms are linked in different ways.

Types of Structural Isomerism

Chain Isomers

Chain isomers are molecules with the same molecular formula, but different arrangements of the
carbon atoms in the ‘skeleton’. For example, pentane has three possible chain isomer as shown
below;
Positional Isomers

These are molecules have substituents in different positions on the same carbon skeleton. For
example, the positional isomers are seen in pentanol as follows;

Functional Isomers

This isomerism occurs between compounds in different homologous series. As an example,

ethanol and dimethylether are common example of functional isomers.

Metamerism: Metamers are the isomers having the same molecular formula but different alkyl
groups on two sides of functional groups. This phenomenon of isomerism is called Metamerism.
The structural formula of diethyl ether and methyl propyl ether are CH3CH2 –O-CH2CH3 and
CH3-O-CH2CH2CH3 respectively. Both have the same molecular formula of C4H10O. Both
diethyl ether and methyl propyl ether have ether functional groups. The general formula of ethers
is R−O−R.
1.8.3 STEREOISOMERISM

There are two main types of stereoisomerism – conformational stereoisomerism and

configurationally stereoisomerism. These, as the difference in name suggests, aren’t to do with
any large scale rearrangements of the structure of molecules; instead, they involve different
arrangements of parts of the molecule in space. They’re a little more complicated to think about
than the structural isomers, so let’s have a look at each of them in turn.

1.8.4 Types of Stereoisomerism

Stereoisomerism can be divided into two;

I. Conformational stereoisomerism
II. Configurationally stereoisomerism

1.8.5 Conformational stereoisomerism

This is a phenomenon whereby two or more organic molecules interconvert into one another
just by rotation about carbon-carbon single bonds. Organic molecules that interconvert to
one another when they rotate about their carbon-carbon single bonds are called
Conformational isomers or Conformers. The process by which carbon-carbon single
bonds in organic molecules are twisted or rotated to obtain different structures of roamers is
called Conformation. The study of kinetic and thermodynamic properties of various
conformation of a compound is known as Conformational Analysis.

1.8.5.1 Carbon - Carbon Single Bond Rotation

Methane has just one three-dimensional structure, but this is not the case for ethane. This is
because the two CH3 groups of ethane (H3C-CH3 ) are sp3 hybridized, joined by a sigma
bond formed by sp3 - sp3 hybrid orbital Overlap and rotate with respect to each other about
C-C bond. Several structures of ethane can be obtained when one methyl group is twisted in
relation to the other.
1.8.5.2 Staggered and Eclipse Conformations
The staggered and eclipse conformations of alkanes are the two extremes of the molecules.
In the staggered conformation, the C-H bonds on one carbon are as far away from those on
the other carbon as possible. In contrast, they are as close to each other as possible in the
eclipse conformation. Thus, the staggered conformation is more stable (less energy) than
the eclipse conformation (more energy). In other to keep the electron pairs in its bonds as far
apart as possible, the alkanes (e.g ethane) molecules preferentially exists in a staggered
conformation. The Newman projection, a perspective and Sawhorse projection formula
gives the graphic representation of such a view.

1. The Newman projections

2. The perspective formula

 3. The Sawhorse Projection formula

Conformers will be of different energy due to strain. There are three sources of strain
conformers.

i. Torsional Strain: This type of strain is due to the interactions as group change
relative position with a change in torsional bond angle. For instance, the extra
energy of the eclipsed conformation is due to torsional strain. Hence, torsional
strain is only present in eclipse while both eclipse and staggered may have steric
strain.
ii. Van der Waal’s Strain: This strain occurs when groups are place in positions
closer than the sum of their van der Waals radii. For instance, in the rotation of
butane. total eclipsed conformation (which has largest groups eclipsing each
other) is higher in energy than other eclipsed conformations due to van der Waals
strain. This energy difference thereby affects the amount of each conformer
present.
 iii. Angle Strain: this occurs due to molecules that are forced to have bond angle far
from the ideal 109.50 for sp3 – hybridized carbon.

1.8.6 Configurational Isomerism

This is a phenomenon that explains the stability of organic molecules of stereoisomers that do
not interconvert under normal conditions. They are divided into two;

1. Geometrical isomerism and

2. Optical isomerism

1.8.6.1 Geometric Isomers

Geometric isomerism is actually a term that is ‘strongly discouraged’ by IUPAC (the

International Union of Pure & Applied Chemistry), who prefer ‘cis-trans’, or ‘E-Z’ in the
specific case of alkenes. However, ‘geometric isomerism’ is still consistently used in many A
Level courses to refer to both, so for that reason I’ve used that name here.

This type of isomerism most frequently involves carbon- carbon double bonds (shown by two
lines joining each carbon instead of one). Rotation of these bonds is restricted, compared to
single bonds, which can rotate freely. This means that, if there are two different atoms, or groups
of atoms, attached to each carbon of the carbon -carbon double bond, they can be arranged in
different ways to give different molecules. These atoms or groups can be given ‘priorities’, with
atoms with higher atomic numbers given higher priorities. If the highest priority groups for each
carbon are on the same side of the molecule, that molecule is denoted as the ‘cis’ or ‘Z’ isomer.
If they’re on opposite sites, it’s denoted as the ‘trans’ or ‘E’ isomer.
The two different nomenclatures are a little confusing – cis/trans is now less commonly used,
with E/Z instead being favoured. E stands for ‘entgegen’ (‘opposite’ in german) whilst Z stands
for ‘zusammen’ (‘together’ in german). The letter is simply added in brackets at the start of the
molecule’s name in order to indicate which isomer it is.

Examples of cis and trans geometric isomers are as follows

a.

b.

Cis-1-bromo-2-chloroethene trans-1-bromo-2-
chloroethene

or (E) -1-bromo-2-chloroethene or (Z) -1-bromo-2-

chloroethene

c.
 d.

1.8.6.2 Optical Isomers

Optical isomers are so named due to their effect on plane-polarized light, and come in
pairs. They usually contain a chiral centre – this is a carbon atom, with four different atoms (or
groups of atoms) attached to it. These atoms or groups can be arranged differently around the
central carbon, in such a way that the molecule can’t be rotated to make the two arrangements
align. Since one arrangement can’t line up to look exactly like the other, we refer to them as
‘non-superimposable mirror images’ – one of the isomers is the mirror image of the other. Think
of it like your hands – you can’t exactly superimpose one hand on top of the other, because your
thumbs will stick out in opposite directions.

These can be allocated an identifying letter, in much the same way as with geometric isomerism.
The groups around the carbon are given priorities, then the lowest priority group is oriented
pointing away. Looking at the remaining groups, if they decrease in priority going in an anti-
clockwise direction, it’s the S isomer (from the Latin ‘sinister’, meaning ‘left’). If they decrease
in priority going in a clockwise direction, it’s the R isomer (from the Latin ‘rectus’, meaning
‘right’). Again, this letter is simply added in front of the isomer’s name in order to indicate
which one it is.
There are other ways in which optical isomerism can be exhibited, but this is the simplest.

For example,

2-hydroxypropanoic acid (lactic acid) contains a single chiral centre and exhibits these properties

(S) 2Hydroxypropanoic acid (R) 2Hydroxypropanoic acid

(S- Lactic acid) (R— Lactic acid)