CARBON

8]VeiZg &+ AND CARBON

COMPOUNDS
Introduction
The element carbon is the basis of life. Organic
chemistry is the branch of chemistry devoted to
understanding the properties and reactions of carbon
compounds. In this chapter, we will examine the
properties of carbon and investigate its unique ability
to bond covalently to itself and to other non-metals.

In this chapter
16.1 Carbon page 294
16.2 Hydrocarbons page 299

Figure 16.1
Oil is an important fossil fuel and a source of many
carbon compounds. The distillation process is a crucial
part of refining crude oil.
 &+#& #!2"/.
Remember
Carbon and its allotropes
Before beginning this section, Carbon is classified as a non-metal. It is the first member of group IV of the
you should be able to: periodic table and is located in period 2 between boron and nitrogen. The
 outline the role of carbon atom has six electrons so its electron configuration is 2, 4. It tends
photosynthesis in
transforming light energy to to form covalent bonds with other atoms by sharing the four electrons
chemical energy and recall the in its valence shell. A unique feature of carbon is its ability to bond
raw materials for this process.
strongly to other carbon atoms. This tendency will be discussed further in
Key content the next section.
By the end of this section, you
should be able to: Carbon exists in three allotropes called diamond, graphite and the
 identify the position of fullerene family.
carbon in the periodic table
and describe its electron
configuration Diamond
 describe the structure of Diamond is a very valuable gemstone, prized for its brilliance and lustre. It
the diamond and graphite
allotropes and account for is the hardest known natural material. For this reason, it is used in diamond
their physical properties in saws and drill bits. Diamond is highly incompressible, and is a better thermal
terms of bonding
 identify that carbon can conductor than any metal. It is transparent to most frequencies of light
form single, double or triple from the far ultraviolet through the visible to the far infrared.
covalent bonds with other The carbon atoms in diamond are arranged tetrahedrally in a strong
carbon atoms
 explain the relationship three-dimensional, covalent network lattice. All four valence electrons are
between carbons combining involved in covalent bonding, so there are no free electrons in the lattice.
power and ability to form
a variety of bonds and the Thus, diamond is a non-conductor of electricity.
existence of a large number of Diamond was created deep underground under conditions of extreme
carbon compounds temperature and pressure, where it was more stable than graphite. Over a
 perform a first-hand
investigation, analyse period of millions of years, sedimentary deposits of carbonaceous materials
information and use slowly crystallised into diamonds.
available evidence to model
the differences in atomic Diamond is resistant to attack from most chemical substances. It burns
arrangement of diamond, in oxygen to form carbon dioxide, although this requires a very high
graphite and fullerenes temperature.
 process and present
information from secondary
sources on the uses of
diamond and graphite, and
relate their uses to their
physical properties
 identify data and choose
resources from secondary
sources, such as molecular
model kits, digital technologies
or computer simulations, to
model the formation of single,
double and triple bonds in
simple carbon compounds.

allotropes: different structural

forms of an element based
on the different spatial
arrangements of the bonds
between the atoms

Figure 16.2 Diamonds are composed of pure carbon. Their properties of brilliance,
durability and hardness are due to their ordered and rigid structure in which each carbon
atom is covalently bonded to four other carbon atoms.

294 ENERGY

fullerenes: a family of carbon
allotropes in which the carbon
atoms are arranged in cage- or
tube-like structures
Figure 16.3
Structures of carbon allotropes
(Note: The carbon atoms shown light
blue in the diamond structure are
inside the unit cell cube.)
Graphite
Graphite is a soft, black solid. The carbon atoms are arranged in layers
held together by weak dispersion forces; quite different from the arrange-
ment in diamond. Within each layer, the carbon atoms are covalently
bonded in interlocking hexagonal rings. These two-dimensional layers
are very strong and rigid. However, the graphite lattice is weak between its
layers, so layers slip when the lattice is subjected to shearing forces. This
slippage plane makes powdered graphite a useful dry lubricant.
Within the hexagonal layers, only three of the four valence electrons
are involved in covalent bonding to other carbon atoms. The remaining
electron from each carbon atom is delocalised, and these electrons form an
electrical conducting band in the lattice. Thus, graphite is a good elec-
trical conductor.
Table 16.1 summarises the physical properties of diamond and graphite.
Graphite has a higher thermal conductivity than diamond along the plane
of hexagonal rings. This is due to the presence of a mobile electron
cloud in the plane. Its thermal conductivity perpendicular to this plane
is quite low.
Table 16.1 Physical properties of diamond and graphite
Allotrope diamond graphite
Melting point (C) <3550 3974 (under pressure)
Density (g/cm3) 3.51 2.26
Specific heat capacity (J/K/g) 0.51 0.71
Electrical conductivity (MS/m) 1017 0.07
Thermal conductivity (J/s/m/K) 1000 1950 (parallel to planes)
5.7 (perpendicular to planes)
Fullerenes
The fullerene family of carbon allotropes was discovered in 1985. Fuller-
enes are ball- or rod-shaped structures (nanotubes) formed by the
bonding of a large number of carbon atoms. The fullerenes are produced
in laboratories in a variety of ways, including laser ablation, chemical
vapour deposition and electric arc discharge.
The structures of carbon allotropes are shown in figure 16.3.
Diamond Fullerenes Graphite
Flat hexagonal rings in layers
C60 (buckyball)
Nanotube
CHAPTER 16 CARBON AND CARBON COMPOUNDS 295
 Clusters of 60 atoms (C60) are the most abundant and named bucky-
balls after the architect R. Buckminster Fuller who had built similar
structures. Other ball- and cage-like molecules from C32 to C84 have been
isolated. Cage-like fullerenes may be used in the future as molecular
lubricants because of the weak intermolecular forces between their ball-
shaped molecules. At the moment, however, other lubricants are much
cheaper to manufacture.

Figure 16.4
Molecules of buckyballs consist of 60 carbon atoms

Another group of fullerenes are called buckytubes or nanotubes,

which consist of molecules with a long tubular shape (several hundred
nanometres long) and an internal cavity with a diameter of about 15 nano-
metres. Nanotubes have high tensile strength. They are stronger than
similar-sized steel wires and have potential for future engineering devel-
opments. These nanotubes can behave as conductors or insulators
depending on their size and shape and the number of twists on the
molecule. Nanotubes can also be single- or multi-walled.
In August 2005, Ken Atkinson of CSIRO and a team at the NanoTech
Institute at the University of Texas announced the production of sheets of
carbon nanotubes that are transparent, flexible, five times stronger than
steel and electrically conductive. When these sheets are welded between two
layers of acrylic glass, the composite material can be used as an electrically
heated window. Due to its conductivity, it could also act as an antenna for
a car radio.

Bonding in carbon compounds

Carbon compounds represent the largest group of compounds in the
world. Most of these compounds are components of the living world, so
the study of carbon compounds is usually called organic chemistry.
Carbon is a tetravalent element. Carbon atoms can link together to form
long stable chains and rings, which can create vast numbers of natural and
synthetic carbon compounds. Apart from hydrogen, oxygen and halogen
atoms are a few of the common elements that bind to these carbon-based
molecules.

296 ENERGY
 Types of bond
single covalent bond: a covalent
bond in which one electron pair Carbon atoms can bond covalently to each other in three different ways:
is shared between neighbouring
atoms single covalent bonds
double covalent bond: a covalent double covalent bonds
bond in which two electron
pairs are shared between triple covalent bonds.
neighbouring atoms
Figure 16.5 shows the Lewis electron dot structures for single, double and
triple covalent bond: a covalent triple covalent bonds between carbon atoms.
bond in which three electron
pairs are shared between
neighbouring atoms
Bonds

Single C C Double C
C Triple C
C

Figure 16.5 H H
Lewis electron dot structures H H
for single, double and triple H C C H C C H C C H
covalent bonds H H H H

When showing the structural formula of an organic molecule, single, double

and triple bonds are represented as follows:
single bond: C C
double bond: C  C
triple bond: C xx C.
Triple covalent bonds between carbon atoms are much stronger than
double or single covalent bonds. Despite the greater strength of double
and triple covalent bonds, they are much more chemically reactive
than single carboncarbon bonds. Thus, compounds containing multiple
bonds undergo chemical reactions more readily that single-bonded carbon
compounds.
The geometrical arrangement of electron pairs around carbon atoms
depends on the type of bonding. Table 16.2 summarises this information.

Table 16.2 Geometry of electron pairs around carbon atoms in compounds

Bond arrangement around the

Carboncarbon bond Bond angles carbon atom

single 10928 tetrahedral

double 120 planar

triple 180 linear

Single bonds Double bonds Triple bonds

Tetrahedral
180
angle = 10928
120
Figure 16.6
Bonding angles around carbon atoms
in single, double and triple covalently
bonded molecules Tetrahedral Planar Linear

CHAPTER 16 CARBON AND CARBON COMPOUNDS 297

 Types of molecule
The presence of single, double and triple covalent bonds in organic
compounds produces a wide variety of molecular structures. These structures
16.1 PRACTICAL include:
ACTIVITIES straight (unbranched) molecular chains
Allotropy branched molecular chains
and bonding ring molecules.
Figure 16.7 shows the structural formulae of some examples of the variety
of organic compounds.

Pentane Methylbutane Cyclohexane

H H H H H H H H
H H
H C H
H H C H
H C C C C C H
H C C H
H H H H H H C C C C H H H
C C
C
H H H H H H
H H
Figure 16.7 Structural formulae of various types of chain and ring carbon compounds

16.1 QUESTIONS C Separate layers in a graphite lattice are

held together by covalent bonds between
carbon atoms.
1. Carbon
D Graphite is less dense than diamond.
A is a member of group V of the periodic
table. 5. Select the correct statement about the
B is a non-conductor of electricity in all its fullerene family.
allotropic forms. A All fullerenes are ball-shaped molecules.
C has an electron configuration of 2, 4. B Fullerenes are excellent electrical
D is a semi-metal. conductors.
C Fullerenes can be produced in electric
2. Allotropes are
arc discharges between carbon
A different structural forms of an element.
electrodes.
B compounds with the same molecular
D Nanotubes are likely to be used in the
formula but different arrangements of
future as lubricants.
atoms.
C found only in the element carbon. 6. Select the true statement about bonding
D radioactive. between carbon atoms in hydrocarbon
molecules.
3. Select the statement that is true of diamond.
A A carboncarbon single bond consists
A The diamond crystal is transparent to
of one electron linking the two carbon
visible light only.
atoms.
B There are no free electrons in the crystal
B Double covalent bonds between carbon
lattice.
atoms consist of two electrons.
C The carbon atoms are arranged in layers
C Triple covalent bonds between carbon
within the lattice.
atoms consist of three electron pairs.
D Diamond is inert and will not combust in
D A double carboncarbon covalent bond
oxygen.
is much weaker than a single carbon
4. Select the correct statement concerning carbon covalent bond.
graphite.
7. Draw a Lewis electron dot structure for
A Graphite is a very hard crystal.
a hydrocarbon ring molecule with the
B Graphite is a very poor electrical
molecular formula C4H8.
conductor.

298 ENERGY
 8. Figure 16.8 shows the Lewis electron-dot 9. Relate each of the following uses of carbon
structure of a hydrocarbon molecule. allotropes to a physical property or structure
Identify the number of single, double of the crystal.
and triple carboncarbon bonds in this (a) Graphite powder is a useful dry
molecule. lubricant.
( (b) Diamonds are used as drill tips.
( ( # ( (c) Graphite blocks are used as electrodes
# in high-temperature electrolytic cells for
( # # #
# the production of aluminium.
( ( ( (
# 10. All allotropes of carbon react with excess
Figure 16.8 Lewis electron dot ( oxygen at high temperatures. Write a
structure of a hydrocarbon molecule balanced equation for this reaction.

&+#'
Remember
Before beginning this section,
you should be able to:
identify that carbon can
form single, double or triple
covalent bonds with other
carbon atoms
explain the relationship
between carbons combining
power and ability to form
a variety of bonds and the
existence of a large number of
carbon compounds.
(9$2/#!2"/.3
Fractional distillation of petroleum
Hydrocarbons are compounds composed of carbon and hydrogen only.
They are commonly found in fossil fuels such as crude oil and natural gas,
which make up the natural product called petroleum. Petroleum formed
gradually over long periods of geological time from the buried remains of
marine organisms that lived about 500 million years ago.
Methane is the simplest hydrocarbon and the major component of natural
gas, although the amount of methane varies considerably. Ethane is usually
the next most abundant component. The hydrocarbons comprising crude
oil include straight chains, branched chains and cyclic molecules, making
it a highly viscous liquid. Petroleum is quite variable in its composition.
Australian crude is lighter than many other crude oils from around the
world. Therefore, Australia imports heavier crude oils (e.g. Arabian Heavy
and Arabian Light) so that it provide the full range of petroleum products,
particularly bitumen and greases. Arabian Heavy is more viscous than
Arabian Light as it has a higher bitumen content.
Bass Strait, Queensland and the North West Shelf off the Western Aus-
tralian coast are major locations for petroleum mining in Australia. The
gaseous components of petroleum (methane, ethane, propane, butane
and traces of pentane, as well as some non-hydrocarbon gases), which
are dissolved in the crude oil, are extracted first. Apart from methane
and some ethane, these gaseous hydrocarbons are liquefied and then
fractionally distilled to obtain separate samples of each. The remainder
is marketed as natural gas. The typical composition of natural gas from
Australian gas wells is 89% methane, 5% ethane, 1% propane, 1% butane,
2% carbon dioxide and 2% air.
The remaining crude oil still contains some dissolved gaseous hydrocar-
bons. The crude oil is separated into fractions using a fractionating column.
This separation is based on differences in boiling point (figure 16.10).
The steps in this process are as follows.
The crude oil is heated to about 370 C at the bottom of a pipe still. This
converts the viscous liquid to vapour and fluid, which then pass into the
base of the fractionating column.
Petroleum vapours and steam move up the column. The vapours cool
and condense on baffles called bubble caps. This condensed liquid is
richer in the least volatile components.

CHAPTER 16 CARBON AND CARBON COMPOUNDS 299


Key content
By the end of this section, you
should be able to:
describe the use of fractional
distillation to separate the
components of petroleum
and identify the uses of each
fraction obtained
identify and use the IUPAC
nomenclature for describing
straight-chained alkanes and
alkenes from C1 to C8
compare and contrast the
properties of alkanes and
alkenes from C1 to C8 and
use the term homologous
series to describe a series
with the same functional
group
explain the relationship
between the melting point,
boiling point and volatility
of the above hydrocarbons,
and their non-polar nature
and intermolecular forces
(dispersion forces)
assess the safety issues
associated with the storage
of alkanes from C1 to
C8 in view of their weak
intermolecular forces
(dispersion forces)
perform a first-hand
investigation and gather
first-hand information using
the process of fractional
distillation to separate the
components of a mixture such
as ethanol and water
plan, identify and gather data
from secondary sources
to model the structure of
alkanes and alkenes from C1
to C8
process and present
information from secondary
sources and use available
evidence to identify safety
issues associated with the
storage of alkanes.
petrochemical feedstock:
petroleum fractions used to
manufacture other products such
as plastics
naphtha: a component of the
gasoline fraction that is used
as a feedstock to manufacture
ethylene for the plastics industry
300 ENERGY
The liquids that form at a
particular boiling point range are
collected in trays. Some liquid
overflows these trays and falls
back to a hotter zone, where it
meets hot ascending vapours that
exchange heat and cause the more
volatile components of the liquid
to vaporise.
This process repeats continuously
so that the most volatile compo-
nents rise higher in the column.
The light (low molecular weight)
components do not condense, so
pass out of the top to be collected
as refinery gas.
The trays eventually collect
liquids in a fairly narrow boiling Figure 16.9 Fractional distillation of
crude oil is carried out in a fractionating
range. The liquids are channelled column or tower.
out and collected.
Liquids from the trays can be mixed to obtain the desired proportions
of each component.
The unvaporised (non-volatile) high molecular weight greases collect
at the base of the column. Vacuum distillation is used to remove the
heavy lubricating oils. Clear waxes are removed from the residue using
solvent extraction. The solid residue that remains after this process is
called asphalt.
Table 16.3 shows the typical fractions obtained from crude oil. The
composition and boiling ranges of these fractions vary somewhat from
one refinery to another.
Table 16.3 Typical crude oil fractions and uses
Boiling Carbon atoms
range (C) per chain Name of fraction Common uses
<30 14 refinery gas natural gas, bottled gas
30125 58 gasoline (petrol car fuel, petrochemical
fraction) feedstock, solvent
90220 713 gasoline (naphtha conversion to petrol and
fraction) alkenes by cracking into
smaller molecules
175275 1116 kerosene home heating, aviation
fuel, conversion to petrol
(cracking)
260340 1518 diesel oil furnace fuel, diesel engines,
conversion to petrol
(cracking)
>350 1640 lubricating and lubrication, clear waxes and
fuel oils, paraffin polishes
waxes
>400 >40 residue asphalt (bitumen road
surfaces)
 Refinery gas

Bubble cap
Gasoline (petrol)
Fractionating column
Trays Gasoline (naphtha)

Kerosene
Crude oil vapours
mix with steam.
Diesel oil/heating oil
Pipe still

Lubricating oil
Vacuum
distillation

Grease/wax
Crude oil Solvent
Steam High molecular
enters extraction
weight greases
collect at base Asphalt
of tower. residue
Heater
Figure 16.10 Fractionating column

The petrol derived from the gasoline fraction is insufficient to meet

Australias needs. Heavier fractions must be broken down (cracked) into
smaller hydrocarbon chains to produce sufficient quantities of petrol to
supply the increasing number of vehicles on our roads.

SAMPLE PROBLEM 16.1 Explain why molecules such as C17H36 are collected lower in the
fractionating tower than molecules such as C7H16.

SOLUTION Hydrocarbons with high molecular weights (such as C17H36) have

much higher boiling points than lower molecular weight hydro-
carbons such as C7H16. The dispersion forces between heavier
molecules are stronger than between lighter molecules. The lighter
molecules move higher in the column before they are cool enough
to condense back into liquids and become trapped in the trays. The
16.2 PRACTICAL heavier vapour molecules condense back to liquids much lower in the
column as they do not require as much cooling to achieve a change
ACTIVITIES
in state.
Fractional distillation

homologous series: a family of

compounds with similar chemical
properties and a gradation of
physical properties with increasing
molar weight or chain length.
A general formula describes all
members of the series.
Alkanes and alkenes
Straight- and branched-chain hydrocarbons can be classified into groups
or homologous series on the basis of the presence or absence of single,
double or triple covalent bonds between carbon atoms. The presence of
a carboncarbon double bond in a hydrocarbon chain gives the molecule

CHAPTER 16 CARBON AND CARBON COMPOUNDS 301

 different physical and chemical properties from hydrocarbons with single
functional group: a group of covalent bonds only. The carboncarbon double bond is, therefore, an
atoms attached to or part of a
hydrocarbon chain that influence example of a functional group.
the physical and chemical Two important families or homologous series of hydrocarbons are the
properties of the molecule
alkanes and alkenes. Alkanes are examples of saturated hydrocarbons;
alkane: a simple, saturated alkenes are examples of unsaturated hydrocarbons. Alkanes are commonly
binary compound of carbon
and hydrogen atoms with single called paraffins (meaning little affinity or unreactive), while alkenes are
bonds between the carbon sometimes called olefins (meaning oil-loving). Alkenes are much more
atoms. The general formula for
all members of this homologous reactive than alkanes.
series is CnH2n+2.
alkene: a simple, unsaturated Alkanes
binary compound of carbon and All molecules in the alkane homologous series have the general formula:
hydrogen atoms with a double
bond between a pair of carbon CnH2n+2, where n = 1, 2, 3 ...
atoms. The general formula for
all members of this homologous
series is CnH2n. In IUPAC nomenclature, the name of each alkane is a combination of
a stem and a common suffix. The suffix used for all alkanes is -ane. The
saturated hydrocarbon:
hydrocarbon with only single names for each stem are shown in table 16.4.
CC bonds and the maximum
number of hydrogen atoms per
carbon Table 16.4 Stems for naming hydrocarbons
unsaturated hydrocarbon: n 1 2 3 4 5 6 7 8
hydrocarbon with double or
triple bonds between carbon Stem meth- eth- prop- but- pent- hex- hept- oct-
atoms and fewer than the
maximum number of hydrogen
atoms per carbon
Thus, an alkane with n = 6 is named hexane.
Figure 16.11 shows the structural formulae and space-filling models of
some straight-chain alkanes.

Propane
H H H
Hydrogen
H C C C H

H H H Carbon

Hexane
H H H H H H

Figure 16.11 H C C C C C C H
Structural formulae and space-filling
models of two straight-chain alkanes H H H H H H

SAMPLE PROBLEM 16.2 Use the IUPAC rules for naming and determining the molecular
formula of alkanes to complete table 16.5.

Table 16.5
n Molecular formula IUPAC name

1 CH4

3 propane

5 pentane

C8H18

302 ENERGY
SOLUTION Use the general formula to calculate the number of hydrogen atoms
in each molecule. Thus, if n = 2, there are two carbon atoms and the
number of hydrogen atoms is 2n + 2 = (2 2) + 2 = 6. So, the molecu-
lar formula is C2H6 and the name is ethane. The complete table is
shown below.
Table 16.6
n Molecular formula IUPAC name
1 CH4 methane

3 C3H8 propane

5 C5H12 pentane

8 C8H18 octane

Alkenes
All molecules in the alkene homologous series have the general formula:
CnH2n, where n = 2, 3, 4 ...
Note that it is not possible to have an alkene with n = 1 as a minimum of
two carbon atoms are required for the double bond.
In IUPAC nomenclature, the suffix used for all alkenes is -ene. Thus, an
alkene with n = 3 is named propene.
IUPAC nomenclature specifies the location of the double bond in the
hydrocarbon chain. The term locant is used to describe the position of a
functional group along the carbon chain. These rules are:
1. Number the longest chain from the end that gives the alkene func-
tional group the lowest locant number possible.
2. The preferred IUPAC method (2005) of naming the alkene is to place
the locant number of the first carbon of the double bond in front of
the -ene suffix (e.g. hept-2-ene).
IUPAC also recognises the systematic method of placing the locant for the
double bond in front of the name of the alkene (e.g. 2-heptene).

H H H H H H
H
C C C C H H C C C C H
H
H H H H H

But-1-ene (1-butene) But-2-ene (2-butene)

H H H H H H H H H H H

H C C C C C C H H C C C C C C H
Figure 16.12 H H H H H H H H H H
Examples of the naming rules for
alkenes Hex-2-ene (2-hexene) Hex-3-ene (3-hexene)

Figure 16.12 provides some examples of these preferred IUPAC naming

rules for straight chain alkenes, showing alternative systematic names.
For alkenes with four or more carbon atoms, the location of the double
bond can vary. For example, an alkene with molecular formula C4H8 can

CHAPTER 16 CARBON AND CARBON COMPOUNDS 303


isomers: compounds with the
same molecular formula but
different structural formulae
have the double bond between the first and second carbon atoms or
between the second and third carbon atoms in the chain. Thus, butene
can exist as but-1-ene (1-butene) or but-2-ene (2-butene). These different
structural forms of the alkene are called isomers. Their physical and
chemical properties are similar but not identical.

SAMPLE PROBLEM 16.3 Determine the number of possible straight-chain isomers of the
alkene with the molecular formula C6H12. Name these isomers using
the IUPAC preferred nomenclature or another IUPAC recognised
systematic nomenclature.

SOLUTION
alkyl group: an alkane molecule
with a missing hydrogen atom.
An alkyl group is always attached
to another molecule and cannot
exist separately (e.g. CH3 is a
methyl group).
The double bond can be located between C1 and C2, C2 and C3, or
C3 and C4. Placing the double bond between C4 and C5 is the same
as placing it between C2 and C3. Thus, there are only three straight-
chain isomers.
CH2==CHCH2CH2CH2CH3
hex-1-ene (1-hexene)
CH3CH==CHCH2CH2CH3
hex-2-ene (2-hexene)
CH3CH2CH==CHCH2CH3
hex-3-ene (3-hexene)
Isomerism also exists when hydrocarbon chains are branched.
Figure 16.13 shows some isomeric examples of alkanes and alkenes
involving hydrocarbon (or alkyl) side chains or functional groups.
The alkyl groups are named after their parent alkane. Thus a CH3
group is called a methyl group. The IUPAC nomenclature rules specify
the position of these alkyl groups using a numbering system to allo-
cate locants (positions) along the carbon chain. The numbering
system requires the alkyl groups to have the lowest locant possible.
Note, however, that the double bond in alkenes maintains its prior-
ity in being assigned the lowest locant. The alkyl groups are named
alphabetically.

H
H H
H H H H C
H H
H H H H H
H C C C C H H C C C H
H C C C C C H H H
H H C H C
H H H H H H H H H
H H

Pentane C5H12 Methylbutane C5H12 Dimethylbutane C5H12

H H H H H H H H H
H H
C C C C C H C C C C H H C C C C H
H H
H H H C H H H C H
H H H H
H H

Pent-1-ene (1-pentene) C5H10 2-methylbut-1-ene 2-methylbut-2-ene

(2-methyl-1-butene) (2-methyl-2-butene)
C5H10 C5H10
Figure 16.13 Examples of isomerism in branched-chain alkanes and alkenes

304 ENERGY
 Properties of alkanes and alkenes
Alkanes and alkenes are non-polar molecules that dissolve readily in non-
polar solvents such as kerosene (a mixture of liquid alkanes), but are
insoluble in polar solvents such as water.

Melting and boiling points

The melting and boiling points of alkanes and alkenes increase with
increasing chain length. This is consistent with the increasing dispersion
forces between molecules as their molecular weight increases. Table 16.7
lists the melting and boiling points of various alkanes and alkenes. The
first four members (C1C4) of the alkanes are gases at 25 C and the next
twelve (C5C16) are volatile liquids. All other alkanes are waxy solids.
Short-chain alkenes generally have slightly lower melting and boiling
points than their corresponding alkanes. This indicates that the double
bond in the short alkene chain reduces the extent of the dispersion forces
between neighbouring chains when compared with short alkane chains of
similar molecular weight.

Table 16.7 Melting and boiling points of alkanes and alkenes

Melting point Boiling point Melting point Boiling point
Alkane (C) (C) Alkene (C) (C)

C3H8 188 42 C3H6 185 48

C5H12 130 36 C5H10 165 30

C6H14 95 69 C6H12 140 64

C7H16 91 98 C7H14 119 94

equilibrium vapour pressure:
the pressure in a closed system
when the rate of vaporisation
of a substance (normally a pure
liquid or a solution) equals the
rate of condensation; also called
vapour pressure
Volatility
Volatile substances readily vaporise at room temperature to produce a high
concentration of vapour above the liquid or solid substance. This high
concentration is measured by a quantity called the equilibrium vapour
pressure. Some alkanes and alkenes vaporise readily at room temperature
while others (such as solid waxes) produce little vapour. Generally, the lower
the molecular weight of the hydrocarbon, the greater its rate of evaportion
and the higher its volatility. This can be understood in terms of the weaker
dispersion forces between hydrocarbon molecules with shorter chains.
The boiling point of a hydrocarbon is a good indicator of its volatility. The
volatility and, therefore, the vapour pressure of a hydrocarbon increase with
increasing temperature, as shown in table 16.8 for octane.

Table 16.8 Vapour pressure of octane as a function of temperature

Temperature (C) 0 20 40 60 80

Vapour pressure (kPa) 0.4 1.3 4.1 10.4 23.3

flash point: the minimum

temperature at which the
vapour pressure of a fuel
(e.g. a hydrocarbon such as
octane) is just high enough to
form a combustible mixture
with air
Flash point and safety issues
The flash point of a liquid hydrocarbon or other volatile liquid is the
minimum temperature at which the vapour pressure of the substance
is just sufficient to form a combustible mixture of the vapour with air.
A combustible fuelair mixture is dangerous as a spark or a flame can
readily ignite it.

CHAPTER 16 CARBON AND CARBON COMPOUNDS 305

 Flash point increases as Flash point varies considerably from one liquid hydrocarbon or fuel to
boiling point increases. another. Generally, the higher the boiling point of a hydrocarbon fuel, the
higher the flash point. Figure 16.14 shows the relationship between flash
50
point and boiling point for hydrocarbon fuels. Hydrocarbon waxes (such
Flash point (C)

as candle wax) have much higher boiling and flash points than liquid
0 hydrocarbons. The intermolecular forces between these molecules are
stronger, so they are less volatile. Consequently, their low vapour pressures
and high flash points make them much safer to store and use. Table 16.9
50
lists the flash points of some common fuels.

100 Table 16.9 Flash points of some common fuels

0 50 100 150 200
Fuel petrol octane kerosene diesel
Boiling point of
hydrocarbon fuel (C) Flash point (C) 43 +14 +48 +65
Figure 16.14
Flash point as a function of the In a petrol engine, a spark is used to ignite the vapourair mixture.
boiling point of hydrocarbon fuels Petrol has a much lower flash point than kerosene, so forms combustible
mixtures more readily than kerosene. This makes petrol more dangerous
to handle than kerosene. Even on very cold days in midwinter, petrol
vapours readily form combustible mixtures with air. For this reason, using
a gas lighter or smoking near a petrol pump is highly dangerous under all
environmental conditions.
Petrol tankers are designed not to rupture in the event of an accident.
Static charges are also prevented from building up by grounding the tanker
with steel chains. In the family car, the fuel tank is located as far away from
the engine as possible. If a combustible vapourair mixture forms in the
tank, it is away from ignition sources in or near the engine.
To avoid the risk of fires and explosions, the following safety precautions
should be taken when handling, transporting or storing hydrocarbons.
Gaseous fuels should be stored in strong, regularly maintained gas
cylinders. The gauge, taps and fittings on LPG and propane gas bottles
should be tested regularly for leaks to prevent fires and explosions.
Liquid hydrocarbon fuels, such as kerosene, should be stored in labelled,
metal containers with narrow openings and close-fitting caps. The storage
cans should be kept in a cool place with good ventilation to avoid the
build-up of any leaking vapours. It is not advisable to store large quantities
of petrol in containers at home as the fuel is highly volatile and dangerous.
Even small quantities should never be stored inside the house.
Figure 16.15 Transfer liquid fuel one container to another (e.g. pouring lawnmower
A lighter or other flame must never
fuel into the tank of the mower) outside in a well-ventilated area to
be lit near a petrol pump as petrol
has a very low flash point. prevent the build-up of combustible vapourair mixtures.
Ensure that all flammable fuels are stored in fully labelled containers
16.3 DATA displaying the appropriate HazChem codes.
ANALYSIS Ensure that a fire extinguisher is close to fuel storage areas and that it
Alkanes and alkenes is checked regularly.
Class 2 Class 3 Class 4

Figure 16.16 FLAMMABLE FLAMMABLE FLAMMABLE SPONTANEOUSLY

GAS LIQUID SOLID COMBUSTIBLE
HazChem labels for
flammable gaseous and 2 3 4 4
liquid substances

306 ENERGY
16.2 QUESTIONS
1. Name the following hydrocarbons.
(a) CH3CH2CH2CH2CH2CH3
(b) CH3CHCHCH2CH2CH2CH2CH3
(c) CH3CH2CH2CH2CH2CH2CHCH2
2. Name the next member of the homologous
series to which each of the following
molecules belongs.
(a) CH3CH2CH3
(b) CH3CH2CH2CHCH2
3. A simple, straight-chain hydrocarbon
has a molar weight of 42.1 g/mol. Draw
a structural formula for a molecule with
this molar weight. Name this molecule
systematically.
4. Hydrocarbons P, Q and R have the physical
properties shown in table 16.10.
Classify each hydrocarbon as a solid, liquid
or gas at 25 C.
5. Read each of the following statements and
identify the petroleum fraction formed after
fractional distillation.
(a) This fraction is used as a furnace fuel
and boils in the range 260340 C.
8. The following statements concern the steps
(b) This fraction is used for polishes and
clear waxes.
(c) This fraction is used as a solvent,
petrochemical feedstock and car fuel.
Table 16.10
Melting point Boiling point
Hydrocarbon (C) (C)
P 5.5 80.1
Q 216 340
R 187.7 42.1
6. A 10 ML sample of natural gas (at 25 C
and 100 kPa) contains 88% by volume of
methane.
(a) Calculate the volume of methane in
the sample at this temperature and
pressure.
(b) Given that 1 mole of any gas occupies
24.79 litres at 25 C and 100 kPa,
calculate the number of moles of
methane in the sample.
(c) Use the information from (b) to
calculate the number of methane
molecules in the sample.
7. Octane is a component of the gasoline
fraction produced by fractional distillation
of crude oil.
(a) Octane is a member of an important
homologous series of hydrocarbons.
Name that series.
(b) Write the molecular formula of octane
and the formula of the next member of
that series.
(c) ii(i) Identify the type of bond or force
that exists between the atoms of the
octane molecule.
i(ii) Identify the type of bond or force
that exists between neighbouring
octane molecules.
(iii) State which of the bonds or forces
named in (i) and (ii) is stronger.
(d) A sample of octane is heated and
converted into a vapour. Identify the
bonds broken during this process.
(e) Hydrocarbons can be classified as
saturated or unsaturated. State the
classification for octane. Justify your
answer.
(f) Identify the safety precautions required
when handling octane.
in fractionating crude oil, but they are out
of order. Arrange the steps in a logical
sequence.
Step A: This process is repeated continuously
so that the most volatile components
rise higher in the column. Refinery gas
passes out of the top of the column.
Step B: Petroleum vapours and steam
move up the column, cooling and
condensing on bubble caps. The
condensed liquid is richer in the
least volatile components.
Step C: Crude oil is heated and vaporised.
The vapour then passes into the base
of the fractionating column.
Step D: Condensed liquids at a particular
boiling point range are collected in
trays. Some of this liquid overflows
and falls back to a hotter zone where
the more volatile components of the
liquid vaporise.
Step E: Non-volatile, high molecular weight
greases collect at the base of the
tower as a residue.
Step F: The trays eventually collect liquids in
a fairly narrow boiling range. These
form the fractions that are collected.
CHAPTER 16 CARBON AND CARBON COMPOUNDS 307
 9. Explain why each of the following safety
precautions is taken when handling or
storing hydrocarbon fuels.
(a) LPG gas bottles should be inspected and
tested regularly.
(b) Motormower fuel should be poured into
the mowers fuel tank in the open.
(c) Large quantities of petrol should never
be stored at home.
10. (a) The boiling points of the members of
the alkane homologous series are shown
in table 16.11. Plot a line graph of the
boiling point versus molar weight and
use the graph to interpolate the boiling
point of pentane.
(b) Explain why boiling point increases with
molar weight.

Table 16.11
Alkane methane ethane propane butane pentane hexane heptane octane

Molar weight (g/mol) 16.0 30.1 44.1 58.1 72.1 86.2 100.2 114.2

Boiling point (C) 162 89 42 0.5 ? 69 98 126

SUMMARY
Carbon can form single, double and triple covalent bonds with
www.jaconline.com.au/chemnsw/chemistry1
other carbon atoms. This allows carbon to produce stable, long-
chain molecules.
Hydrocarbons are binary compounds containing carbon and
CHECKPOINT hydrogen. They can be classified in homologous series, including
REVISION 6 alkanes and alkenes.
Alkanes are saturated hydrocarbons while alkenes are unsaturated.
Unsaturated hydrocarbons do not have the maximum number of
hydrogen atoms per molecule due to the presence of double or
triple carboncarbon bonds.
IUPAC nomenclature is used to name hydrocarbons. The -ane
suffix is used to name alkanes and the -ene suffix is used to name
alkenes.
The volatility of hydrocarbons and their melting and boiling
points can be related to the dispersion forces between the
molecules. The stronger the dispersion forces, the lower the
volatility of the material.
Hydrocarbons are non-polar, flammable substances that must be
stored and handled with care. Hydrocarbon liquids and gases must
be stored in cool places away from ignition sources.
Hydrocarbons are extracted from petroleum by a physical process
called fractional distillation. The hydrocarbons are collected in
fractions based on their boiling point ranges.

308 ENERGY
PRACTICAL ACTIVITIES
16.1 PRACTICAL
ACTIVITIES
ALLOTROPY AND BONDING
Aim
To use models to investigate the allotropes of
carbon and to use model kits to demonstrate
covalent bonding in simple hydrocarbons
Materials
models of diamond and graphite
molecular model kits
Method
Part A: Carbon allotropes
1. For each of the models of diamond and
graphite, draw a section to show the different
geometric arrangement of the carbon atoms.
2. In your drawing of the diamond lattice,
highlight a group of atoms to show that they are
arranged tetrahedrally.
3. In your drawing of the graphite lattice,
highlight a group of atoms to show the
hexagonal fused rings in any one plane.
4. Use the Internet to:
(a) investigate the structure of buckyballs (C60).
(b) identify the arrangement of single and
double covalent bonds in a buckyball
molecule. Print a copy of a suitable graphic
for your workbook.
(c) identify uses of the allotropes of carbon
and relate these uses to their structures and
physical properties.
Part B: Bonding in simple hydrocarbons
1. Use a molecular model kit to make models of
the following simple molecules.
(a) Ethane, C2H6
(b) Ethene, C2H4
(c) Ethyne, C2H2 (Note: This is an alkyne with a
triple bond joining the carbon atoms.)
2. Draw three-dimensional, structural formulae of
your models. Use dotted lines for bonds behind
the plane of the paper and bold lines for bonds
projecting out of the plane of the paper.
3. Identify the model(s):
(a) in which all atoms are arranged linearly
(b) that consists of two intersecting tetrahedra
(c) in which all atoms lie in the same plane.
4. Show, by constructing longer chain
hydrocarbon molecules, that the presence of:
(a) a carboncarbon double bond leads to a
planar region in the molecule and restricted
rotation about the carbon atoms
(b) a carboncarbon triple bond leads to a
linear region in the molecule and restricted
rotation about the carbon atoms.
CHAPTER 16 CARBON AND CARBON COMPOUNDS 309
 PRACTICAL ACTIVITIES
Ethanol is flammable and naked flames should be

16.2 PRACTICAL kept away from it and its vapours.

ACTIVITIES Identify other safety issues relevant to this
experiment by reading the method.
FRACTIONAL DISTILLATION Materials
Quickfit distillation apparatus with 250 mL round-
or flat-bottomed flask
Part A: First-hand investigation fractionating column
Aim 110 C thermometer with teflon sleeve
To separate a mixture of water and ethanol using 2 mL graduated pipettes
fractional distillation
electronic balance
Safety issues electric heating mantle or gauze mat, tripod and
Wear safety glasses throughout this experiment. Bunsen burner
25 mL ethanol/25 mL water mixture (measured
with a 25 mL pipette)
pipette filler
boiling chips
Thermometer
100 mL beaker
11 small beakers
retort stand, bosshead and clamp
ethanol

Distillate collects

Water out Cold water

in 1 2 3 4
to sink
Collect up to 10 mL of each fraction
Fractionating
column Method
Wear your safety glasses.
1. Use a clean beaker to prepare a mixture of
25.0 mL of water and 25.0 mL of pure ethanol
using a 25 mL pipette.
Ethanolwater 2. Weigh a clean, dry beaker. Use a 2.00 mL
mixture graduated pipette to transfer 2.00 mL of the
Boiling chips
waterethanol mixture into the beaker. Reweigh
and determine the mass of the liquid. Calculate
its density (d = m/V ). Return the 2 mL of water
ethanol mixture to the first beaker.
3. Place boiling chips and the 50 mL ethanolwater
mixture in the distillation flask and set up the
Figure 16.17 Fractional apparatus ready for distillation as shown in
distillation apparatus figure 16.17.

310 ENERGY
PRACTICAL ACTIVITIES
4. Put the flask on a gauze mat supported by a
tripod, and heat it slowly with a heating mantle
or Bunsen burner. It is vital to adjust the
heating to ensure gentle boiling and very slow
production of distillate.
5. Use a small, clean beaker (beaker 1) to
collect all the distillate produced while the
thermometer reads between 78 and 80 C (that
is, in the 7880 C boiling range). Allow the
temperature to slowly rise and collect a second
sample of distillate (beaker 2) in the 8185 C
boiling range. Collect subsequent samples of
distillate in the following boiling ranges:
Beaker 3: 8690 C
Beaker 4: 9195 C
Beaker 5: 9698 C
Do not distill all the liquid. Turn off the heat
and allow the vessel to cool.
6. Calculate the density of each fraction by
measuring the mass of 2.00 mL of each fraction.
Use a clean, small beaker for each mass
measurement.
7. Dismantle and store the equipment.
Part B: Second-hand data
A fractional distillation apparatus similar to that
used in part A was used to distill mixtures of
ethanol in water.
The composition of fractions is often expressed as
mole percentage, which is calculated as:
moles of solute
100
total moles in solution
Six mixtures of ethanol in water with different
mole percentages were prepared. In turn, each
one of the ethanolwater mixtures was distilled in
the apparatus. The temperature rose slowly until
distillation commenced, and was constant while
distillate was collected.
Each distillate was analysed using a refractometer.
The mole percentage of ethanol in each distillate
was determined by using a calibration graph. The
results are shown in table 16.13. Process this data
and answer the questions that follow.
Results
Table 16.13 Composition of distillates

Results Distillation
Record your observations in a suitable table. Ethanol in original temperature Ethanol in distillate
mixture (mole %) (C) (mole %)
Questions 90 78.7 90
Answer the following questions in your report on
80 79.0 86
this experiment.
1. Compare the boiling point range of each 60 79.5 78
fraction collected with the boiling points of pure 40 81.0 66
ethanol (78.3 C) and water (100 C).
2. Use your density data to compare the 20 83.0 53
compositions of each fraction collected using 10 86.0 43
table 16.12. Draw a graph of this data and
interpolate your density readings.
Questions
Table 16.12 1. Use millimetre grid paper to plot a graph of the
composition of the distillate on the y-axis and
Ethanol (%v/v) 0 20 40 60 80 100
composition of the original mixture on the
x-axis. Draw a line of best fit.
Density (g/mL) 1.00 0.97 0.93 0.89 0.84 0.79 2. Determine whether the distillate composition is
richer, the same or poorer in ethanol for each
3. Comment on the degree of separation of distillation.
the ethanolwater mixture using fractional 3. Identify the more volatile component of the
distillation. mixture.

CHAPTER 16 CARBON AND CARBON COMPOUNDS 311

 DATA ANALYSIS
4. Fermentation is a common method used by
brewers and winemakers to produce alcohol;
sugar solutions are fermented by yeast to
produce ethanol. The typical concentration of
ethanol in filtered wine is 12%v/v. Convert this
volume % to mole %, given that the density (d)
of ethanol is 0.785 g/mL and that of water is
1.00 g/mL.
5. The techniques used in fractional distillation
do not produce pure (anhydrous) ethanol;
there is usually some water in the ethanol.
Explain, in terms of bonding, why this is so.
Conclusion
Briefly describe the outcome of your investigation.
312 ENERGY
16.3
DATA
ANALYSIS
ALKANES AND ALKENES
Part A: Model construction
1. Use a molecular model kit to construct models
and draw 3-D diagrams of:
(a) propane
(b) butane.
2. Name and construct models of all the straight-
chain isomers of:
(a) C4H8.
(b) C5H10.
Draw structural formulae for each model
constructed.
3. (a) Construct a model of hexane and draw its
structural formula.
(b) Construct branched-chain isomers of
hexane. Identify the maximum number of
isomers of hexane.
Part B: Safe storage of alkanes
Go to:
www.jaconline.com.au/chemnsw/chemistry1
and click on the Methane, Hexane and Gasoline
links for this chapter to find material safety data
sheets (MSDS) with information on storage
of alkanes and petroleum fractions. Use the
information you collect to construct a table
summarising safety issues in the storage of
alkanes.