Seps - Oil and Carbon Chemistry p.

Section 3 - Oil and Carbon Chemistry

Fractional Distillation of Crude Oil
*
Crude oil is mainly a mixture of hydrocarbons, with impurities such as dissolved
sulphur. It forms a valuable resource, both as the origin of many types of fuel, and as the
starting point for petrochemicals (plastics, detergents, solvents etc). However, it must first be
separated into mixtures with a much narrower boiling range.
*
In the laboratory, fractional distillation is used to separate liquids with different boiling
points, by heating the mixture in a flask, separating on a column packed with glass beads, and
collecting the different samples as they emerge from the top at different temperatures.
*
In industry, crude oil is separated by a continuous process, taking off the samples at
different levels from the column. The dissolved gases come out of the top, and the boiling
points rise as one goes down the column. Note that the process does not produce single
substances, but less complex mixtures than in crude oil. A simplified diagram is shown below:

HEAT

increasing temperature

crude oil in

FRACTIONATING COLUMN

Refinery gases (used for bottled

gases such as Gaz, propane, butane)
Gasoline: fuel for cars (petrol)

Kerosene: fuel for jet planes

Diesel: for lorries and larger cars

Fuel oil: for heating homes and
factories
Bitumen: for making roads and tar.

The Crude oil is initially heated and evaporated.

The small molecules have a low boiling point and rise to the top of the tower.
As the tower is descended the molecules get longer and have a higher boiling point
and so condense at higher temperatures.

Seps - Oil and Carbon Chemistry p.2

Carbon compounds
*
Carbon can form strong carbon-carbon bonds and so produces a wide range of
compounds, including chain and ring compounds. Carbon always forms four bonds and
hydrogen forms one bond. For example:
H H
HCCH
H H H H H
HCCH

HCCCCCH
H H H H H
Pentane

H H
cyclobutane

*
The simplest carbon compounds are the hydrocarbons (defined as compounds which
contain carbon and hydrogen only).
*
The molecular formula of a compound shows how many of each type of atom there
are in a molecule. For pentane (above) this is C5H12.
*
The displayed formula of a compound shows all the bonds between the atoms in a
molecule (as shown for pentane and cyclobutane above).
Remember that real molecules are three dimensional, so the angles are not 90o.

ALKANES
*
Most of the hydrocarbons present in crude oil are alkanes.
*
The alkanes are said to form a homologous series, that is a series of organic
compounds with the same general formula. Each member (after the first) differs from the one
before by addition of a CH2 group.
*
General formula CnH2n+2.
*
The physical properties of a homologous series usually show a regular trend. For
example, their boiling points increase steadily along the series; this is because, as the
molecules get larger, the attractions between molecules increase. Chemical properties are
usually similar for all members.
*
N.B. Physical state: a substance is normally a solid at all temperatures below its
melting point, a liquid at temperatures between its melting point and its boiling point, and a
gas above its boiling point (at atmospheric pressure). e.g. pentane melts at 130 oC and boils at
36oC. At 140oC it will be a solid, at 20oC it will be a liquid, and at 40oC it will be a gas.
*
The alkanes may be defined as hydrocarbons of general formula CnH2n+2. You should
learn the names and structures of the first five members:
H
H H
H H H H
H H H
HCH
HCCH
HCCCCH
HCCCH
H
H H
H H H
H4H10H H H
methane CH4
ethane C2H6
propane C3H8
butane C
Pentane, C5H12, is shown at the top of this page.

Seps - Oil and Carbon Chemistry p.3

Isomers
Alkanes with four or more C atoms can show isomerism.
Isomerism: when two or more different compounds have the same molecular formula, they
are called isomers. For example there are two compounds of formula C4H10:
H H H
HCCCH
H H H H
HCCCCH
H
H
H C H
H H H H
H
butane
methylpropane
The one on the right is a branched-chain compound (i.e. the carbon atoms are not all in a
row). For C5H12 there are three isomers, two of which are branched:
CH3
CH3
CH3CH2CH2CH2CH3
HCCCCH

CH3CH2CCH3
H

pentane

CH3CCH3
CH3

methylbutane

dimethylbutane

Shapes of Alkanes
*

Alkanes consist of carbon atoms with four covalent bonds.

Each carbon atom therefore adopts a tetrahedral shape with a bond angle of 109.5 o.
Methane

Ethane

Propane
H

109.5O
C
H

H
H

109.5

109.5O

C
H

109.5O
H

H
C

C
H

109.5O
H

109.5O

Seps - Oil and Carbon Chemistry p.4

Uses of Alkanes
*
Alkanes are widely used as fuels. When they burn in air they form waste gas (carbon
dioxide and water vapour), and the reaction gives out heat to the surroundings (an
exothermic change). Examples:
CH4 + 2 O2
CO2 + 2H2O (combustion of natural gas)
C5H12 + 8 O2
5CO2 + 6H2O
C8H18 + 12O2
8CO2 + 9H2O (or this can be doubled)
*
In a restricted supply of air, carbon monoxide is formed: this is highly toxic (and
particularly dangerous since it has no colour or smell). Carbon monoxide is poisonous because
it reduces the capacity of blood to carry oxygen
*
During the combustion of fuels such as petrol and diesel, sulphur dioxide and nitrogen
oxides may also be formed. These gases are pollutants which contribute to acid rain.
Apart from combustion, alkanes are relatively unreactive: they dont react with acids or
alkalis, bromine (except in sunlight), or most other laboratory reagents.
However, they can react with chlorine and bromine in the presence of sunlight, and be split up
by strong heating:Reaction of alkanes and bromine in sunlight.
Alkanes react with chlorine and bromine in the presence of sunlight, as shown below.
CH4 + Cl2
CH3Cl + HCl
C2H6 + Br2
C2H5Br + HBr
Splitting alkanes up by strong heating.
*
Cracking: this is an example of a thermal decomposition (a reaction in which a
substance is heated until it breaks down into other substances). Thermal decomposition
reactions take in heat from the surroundings (endothermic). When an alkane is cracked, by
passing its hot vapour over a catalyst, it splits into a shorter-chain alkane and an alkene:
cracking: long-chain alkane
shorter-chain alkane + alkene
e.g.
C10H22

C8H18
+ C2H4 (high temp, catalyst)
or
C3H8

C3H6
+ H2
(i.e. alkene+hydrogen)
Importance of Catalytic Caracking
*
Cracking is important because: (a) it produces valuable alkenes, which are the starting
point for petrochemicals; (b) it also gives shorter alkanes, so can convert longer-chain alkanes
into those suitable for making gasoline (petrol), normally with 610 carbon atoms.
*
We can illustrate this using displayed formulae, for cracking pentane, the fifth alkane:
H H H H H
HCCCCCH
H H H H H
pentane

H H H
HCCCH
H H H
propane

H
+

C
H
+

C
H
ethene

In some cases it is possible to obtain an alkene and hydrogen gas, as mentioned before:
C2H6 C2H4 + H2
Hydrogen gas obtained like this is used as a fuel in the oil refinery to drive other processes
(e.g. to heat up vapour for cracking).

Seps - Oil and Carbon Chemistry p.5

ALKENES
*
These are also hydrocarbons, and have they form another homologous series of
general formula CnH2n. The first two members are: ethene, C2H4 and propene, C3H6.
*
Whereas the alkanes only contain single CC bonds, the alkenes each have a C=C
H
double covalent bond:
H
H
C
H
H
H
C C
C C
H
H
H
H
ethene
propene

Shapes of Alkenes
*
Around the double bond the carbon atoms adopt a trigonal planar shape so the the
bonds are directed to the corners of an equilateral triangle with a bond angle of 120o.
Ethene

Propene

120O
C
H

H
C

120O

120O

120O
H

Reactions of alkenes
*
The presence of double bonds means that alkenes are more reactive, since they can
undergo addition reactions.
*
In an addition reaction a molecule adds to the C=C bond to give a single product with a
CC bond. Molecules with double bonds that can undergo addition reactions are said to be
unsaturated, while compounds (such as alkanes) which only have single bonds are called
saturated.
(i)
With bromine
When a small amount of alkene is shaken with bromine water in a test tube, the orange colour
of the bromine disappears. This reaction is used as a test for unsaturated compounds, as
saturated compounds do not decolorise bromine water (orange colour remains).
H

H
C
H

C
H

+ BrBr

H H
HCCH
Br Br

Seps - Oil and Carbon Chemistry p.6

(ii) Addition polymerisation

This is the process in which a large number of small molecules link together to form a large
molecule. Ethene molecules can be made to join together to form the polymer called
poly(ethene) or polythene which is used in plastic bags, etc. High temperature and pressure
are needed for the reaction to occur.
H
H
H
H
H H
H H H H
+
or
CC
C C
C C
CCCC
n
H
H
H
H
H H
H H H H
ethene
+
ethene

poly(ethene)
shows repeat unit

In this reaction the double bond is opened up, to form a link either side to another molecule:
note that double bonds are not present in the long chain polymer.
When propene polymerises it forms poly(propene) note how this differs from
poly(ethene),since it has one CH3 attached to alternate C atoms in the chain:
CH3
CH3
CH
CH3
H
H
CH3 H
H 3 H
CCCC
C C
C C
+
or
CCn
H
H
H
H
H H H H
propene +
propene
poly(propene)
H H

*
In general any ethene molecule which has an H atom replaced with an
polymerise in a similar way. For example if X is Cl, the polymer is called
poly(chloroethene) [or commonly PVC, for polyvinylchloride]:
X
C
H

H
C

monomer

X
C

H
+

X H X H
CCCC or

C
H

monomer

H H H H
polymer

Xgroup will

X H
CC

H H
from n monomers

Study the repeat unit on the right, and see how to work out the monomer molecule on the left
by putting in the double bond between the C atoms in place of the trailing bonds on left and
right. Apart from some termination group at either end, the whole chain is built up from
joining these repeat units together.
The properties of the polymer depend on the group X. Polymers with a different X (e.g. H or
CH3 or Cl) will have different physical properties (e.g. softening temperature, flexibility,
toughness etc), and so will have different uses.
You need to know common uses for these three polymers:
poly(ethene) for plastic bags and plastic bottles (since it forms a flexible film and is
transparent)
poly(propene) for plastic crates and ropes (since it is stronger and less flexible than
poly(ethene), and the fibres in ropes are flexible)
poly(chloroethene), or PVC, for drain pipes and for insulation on electric cables
(since it is strong but flexible, and doesnt conduct electricity).
Note Most addition polymers are not biodegradable (not broken down by bacteria in the
environment), and so last for very long periods in landfill sites.
When burnt some give toxic fumes, so safe disposal, especially of packaging, is difficult.

Seps - Oil and Carbon Chemistry p.7

Ethanol
Ethanol, C2H5OH is the second member of the alcohol homologous series.

Industrial formation of ethanol.

*
Ethanol can be made from ethane and steam.
*
High temperature (450oC), a catalyst (H3PO4) and high pressure (60 atm) are needed.
The ethene combines with steam to produce ethanol, which is used as a solvent:
H

H
C

H
ethene

+ HOH

H
+

steam

H H
HCCH
H OH
ethanol

Making ethanol using fermentation.

*
Another way of producing ethanol is from fruit juices: fermentation is the process by
which yeast, in the absence of oxygen, produces ethanol and carbon dioxide from glucose.
*
A sugar solution (such as grape juice) is mixed with yeast and warmed slightly (2025oC). An airlock is used to keep air out. The yeast undergoes anaerobic respiration, and
releases enzymes, including zymase, which catalyse the breakdown. You need to know the
word equation:
glucose
ethanol
+ carbon dioxide
C6H12O6
2C2H5OH + 2CO2
This is the basic process by which wine and beer are made.
Advantages of fermentation:

cheap and renewable resource like sugar cane

Disadvantages of fermentation:

slow reaction made by an inefficient batch process, poor

quality product eg low aqueous concentration <14%.

Advantages of ethene route:

fast and efficient continuous process,

relatively pure product

Disadvantages of ethene route:

non-renewable finite resource

Reactions of Ethanol
Ethanol can be dehydrated (i.e. have water removed chemically from the molecule) to ethane
by passing the vapour over hot aluminium oxide. This is the reverse of its formation from
steam, above:
H H
H
H
HCCH

+ H2 O
C C
H

OH

Seps - Oil and Carbon Chemistry p.8

Condensation Polymerisation
* Carboxylic acids can be used as monomers to make a second type of polymer called
condensation polymers.
* Condensation polymers are polymers formed from condensation reactions between
monomers. A small molecule (often water but sometimes HCl) is produced as well as the
polymer.
*

Many natural polymers are condensation polymers, e.g. silk, starch and DNA.

Polyesters

* Polysters are formed between monomers containing two carboxylic acid groups and two
alcohol groups.
e.g. Terylene
n

HO

OH

HO

CH2

CH2

OH

ethane-1,2-diol

benzene-1,4-dicarboxylic acid

strong acid or
specific enzyme

CO

terylene

O O CH2

CH2 HO

2n H2O

Polyamides - Nylon

* Nylon is a condensation polymer formed between monomers containing two amine and
two carboxylic acid groups.
O

O
n

HO

(CH2) 4

OH

hexanedioic acid

H2N

(CH2) 6

NH2

hexane-1,6-diamine

strong acid or
specific enzyme

O
(CH2) 4

(CH2)4

NH

(CH2) 6

Cnylon-6,6
N (CH2)6
H

NH

N
H

2n H2O

+ HCl