Ernest Rutherford and the gold foil

experiment
The next ground-breaking experiment in the history of the atom was
performed by Ernest Rutherford, a physicist from New Zealand who spent
most of his career in England and Canada. In his famous gold foil
experiment, Rutherford fired a thin beam of alpha particles at a very thin
sheet of pure gold. Alpha particles are helium nuclei that are given off in
various radioactive decay processes. In this case, Rutherford placed a
sample of radium (a radioactive metal) inside a lead box with a small
pinhole in it. Most of the radiation was absorbed by the lead, but a thin beam
of alpha particles escaped out of the pinhole in the direction of the gold foil.
The gold foil was surrounded by a detector screen that would flash when hit
with an alpha particle.

The apparatus used in Rutherford's gold foil experiment.

In Rutherford's gold foil experiment, a beam of \alphaαalpha particles that was shot at a thin sheet of gold
foil. Most of the \alphaαalpha particles passed straight through the gold foil, but a small number were
deflected slightly, and an even smaller fraction were deflected more than 90^{\circ}90∘90, degree from
their path. Image from Openstax, CC BY 4.0.
 The results of the experiment, however, were striking. While almost all of
the alpha particles passed straight through the gold foil, a
few alpha particles (about 111 in 202020000000000) were deflected more
than 90 degree from their path! Rutherford himself described the results
with the following analogy: "It was quite the most incredible event that has
ever happened to me in my life. It was almost as incredible as if you fired
a shell at a piece of tissue paper and it came back and hit you."

The nuclear model of the atom

Based on his experimental results, Rutherford made the following
conclusions about the structure of the atom:

 The positive charge must be localized over a very tiny volume of the atom,
which also contains most of the atom's mass. This explained how a very
small fraction of the alpha particles were deflected drastically, presumably
due to the rare collision with a gold nucleus.

 Since most of the alpha particles passed straight through the gold foil, the
atom must be made up of mostly empty space!

This led Rutherford to propose the nuclear model, in which an atom consists
of a very small, positively charged nucleus surrounded by the negatively
charged electrons. Based on the number of alpha particles deflected in his
experiment, Rutherford calculated that the nucleus took up a tiny fraction of
the volume of the atom. The nuclear model explained Rutherford's
experimental results, but it also raised further questions. For example, what
were the electrons doing in the atom? How did the electrons keep
themselves from collapsing into the nucleus, since opposite charges attract?
Luckily, science was ready for the challenge! Physicists such as Niels Bohr
continued to design experiments to test the nuclear model of the atom, which
eventually evolved into the modern quantum mechanical model.
Dalton's atomic theory

Part 1: All matter is made of atoms. Dalton hypothesized that the law of
conservation of mass and the law of definite proportions could be explained
using the idea of atoms. He proposed that all matter is made of tiny
indivisible particles called atoms, which he imagined as "solid, massy, hard,
impenetrable, movable particle(s)".

It is important to note that since Dalton did not have the necessary
instruments to see or otherwise experiment on individual atoms, he did not
have any insight into whether they might have any internal structure. We
might visualize Dalton's atom as a piece in a molecular modeling kit, where
different elements are spheres of different sizes and colors. While this is a
handy model for some applications, we now know that atoms are far from
being solid spheres.

Part 2: All atoms of a given element are identical in mass and

properties. Dalton proposed that every single atom of an element, such as
gold, is the same as every other atom of that element. He also noted that the
atoms of one element differ from the atoms of all other elements. Today, we
still know this to be mostly true. A sodium atom is different from a carbon
atom. Elements may share some similar boiling points, melting points, and
electro-negativities, but no two elements have the same exact set of
properties.

Part 3: Compounds are combinations of two or more different types of

atoms.
In the third part of Dalton's atomic theory, he proposed that compounds are
combinations of two or more different types of atoms. An example of such
a compound is table salt. Table salt is a combination of two separate
elements with unique physical and chemical properties. The first, sodium,
is a highly reactive metal. The second, chlorine, is a toxic gas. When they
react, the atoms combine in a 1:1 ratio to form white crystals of NaCl, which
we can sprinkle on our food.

Since atoms are indivisible, they will always combine in simple whole
number ratios. Therefore, it would not make sense to write a formula such
as \text{Na}_{0.5}\text{Cl}_{0.5}Na0.5Cl0.5N, a, start subscript, 0, point, 5,
end subscript, C, l, start subscript, 0, point, 5, end subscriptbecause you can't
have half of an atom!

Part 4: A chemical reaction is a rearrangement of atoms. In the fourth

and final part of Dalton's atomic theory, he suggested that chemical
reactions don't destroy or create atoms. They merely rearranged the atoms.
Using our salt example again, when sodium combines with chlorine to make
salt, both the sodium and chlorine atoms still exist. They simply rearrange
to form a new compound.

What have we learned since Dalton proposed his theory?

The short answer: a lot! For instance, we now know that atoms are not
indivisible—as stated in part one—because they are made up of protons,
neutrons, and electrons. The modern picture of an atom is very different
from Dalton's "solid, massy" particle. In fact, experiments by Ernest
Rutherford, Hans Geiger, and Ernest Marsden showed that atoms are mostly
made up of empty space.

Part two of Dalton's theory had to be modified after mass spectrometry

experiments demonstrated that atoms of the same element can have different
masses because the number of neutrons can vary for different isotopes of
the same element.
J.J. Thomson and the discovery of the electron
In the late 19th century, physicist J.J. Thomson began experimenting
with cathode ray tubes. Cathode ray tubes are sealed glass tubes from which
most of the air has been evacuated. A high voltage is applied across two
electrodes at one end of the tube, which causes a beam of particles to flow
from the cathode (the negatively-charged electrode) to the anode (the
positively-charged electrode). The tubes are called cathode ray tubes
because the particle beam or "cathode ray" originates at the cathode. The
ray can be detected by painting a material known as phosphors onto the far
end of the tube beyond the anode. The phosphors spark, or emit light, when
impacted by the cathode ray.

A diagram of a cathode ray tube.

A diagram of J.J. Thomson's cathode ray tube. The ray originates at the cathode and passes through a slit
in the anode. The cathode ray is deflected away from the negatively-charged electric plate, and towards
the positively-charged electric plate. The amount by which the ray was deflected by a magnetic field
helped Thomson determine the mass-to-charge ratio of the particles. Image from Openstax, CC BY 4.0.

To test the properties of the particles, Thomson placed two oppositely-

charged electric plates around the cathode ray. The cathode ray was
deflected away from the negatively-charged electric plate and towards the
positively-charged plate. This indicated that the cathode ray was composed
of negatively-charged particles.
 Thomson also placed two magnets on either side of the tube, and observed
that this magnetic field also deflected the cathode ray. The results of these
experiments helped Thomson determine the mass-to-charge ratio of the
cathode ray particles, which led to a fascinating discovery- the mass of each
particle was much, much smaller than that of any known atom. Thomson
repeated his experiments using different metals as electrode materials, and
found that the properties of the cathode ray remained constant no matter
what cathode material they originated from. From this evidence, Thomson
made the following conclusions:

 The cathode ray is composed of negatively-charged particles.

 The particles must exist as part of the atom, since the mass of each particle
is only {1}/ {2000} the mass of a hydrogen atom.
 These subatomic particles can be found within atoms of all elements.
1. ALIPHATIC - have no benzene ring in their structure (see 3.) and can
have an open linear carbon chain, or branched carbon chain structure or a
carbon ring structure. If they have a non-benzene ring cyclic structure, they
may be termed alicyclic, but they are still aliphatic (see 2.) examples of
linear and branched aliphatic alkane compounds.

 heptane, or (l
inear alkane)

 2-methylbutane, or (branched
alkane)

2. ALICYCLIC - these molecules have an aliphatic structure but

contain a cyclic or ring structure of at least 3 carbon atoms (can't be less
than 3 and must be carbon!) BUT not a benzene ring e.g.

 Cyclobutane, cyclopentane, cyclohexane

 , and , and , , no
branches here

 Methylcyclohexane, or , a branched example

of an alicyclic alkane.

AROMATIC - These molecules contain a benzene ring based a 'special'

cyclic C6 system, which is an unsaturated ring (BUT not an alkene system)
e.g.

 benzene C6H6, or
  methylbenzene C7H8, C6H5CH3 or or or

 Alkanes are Saturated Hydrocarbons. They consist of the

elements Carbon and Hydrogen, and all the bonds
between the Carbon atoms are single bonds. They have
the general formula CnH2n+2
 Most alkanes you will come across are relatively small molecules in
which all the chemical bonds are covalent bonds.
 All the bonds in alkane molecules are single covalent bonds i.e. C–
C carbon – carbon or single C–H carbon – hydrogen bonds.
 Each carbon atom forms four single bonds and hydrogen atoms form
one single bond.
 These single covalent C-C and C-H bonds are known as sigma
bonds (σ)
 The empirical formula means the simplest possible formula showing
the whole number stoichiometric ratio of the different atoms
(elements) in the compound.
 The molecular formula summarises all the atoms in the molecule
BUT does not show their arrangement at all.
 C3H8 is the of molecular formula for propane and C4H10 that of butane
and 2-methylpropane.
 Note that for propane, the empirical formula is identical to the
molecular formula BUT for 2-methylpropane and butane, they are not
identical. In the case of the latter, the molecular formula is 'twice' the
empirical formula.
 Note also, that the molecular formula, does NOT distinguish the two
structural isomers butane and 2-methylpropane ('methylpropane').

n of
general
1 2 3 4 5 6 7 8 9 10
formula
CnH2n+2
molecular
formula
CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22
of alkane
CnH2n+2
alkane
name methane ethane propane butane pentane hexane heptane octane nonane decane
(straight
 chain
from C4)
empirical
CH4 CH3 C3H8 C2H5 C5H12 C3H7 C7H16 C4H9 C9H20 C5H11
formula
alkyl side
chain
group methyl ethyl propyl butyl pentyl hexyl heptyl octyl nonyl decyl
prefix
name
alkyl
group
CH3 C2H5 C3H7 C4H9 C5H11 C6H13 C7H15 C8H17 C9H19 C10H21
formula
CnH2n+1

 , The structural formula can be written e.g. CH3CH3 (ethane)

CH3CH2CH2CH2CH3 or CH3(CH2)3CH3 pentane

 It shows how groups of atoms are linked or sequenced in a molecule

but it doesn't always show all the bonds.
 propane or , abbreviated and more
detailed styles of alkane structural formulae
 displayed formula gives a '2D' projection-representation of the
molecule and must clearly show how all the atoms are connected

 propane , unfortunately it does give the impression

that the bond angles are 90o, rather than the true angles, many of
which are ~109o based on the tetrahedrally arrangement of four
single bonds around the carbon atoms in alkane molecules.
 Skeletal formula (e.g. of alkanes) are very simplified organic formulae
shown by removing hydrogen atoms from alkyl chains leaving just
lines for the carbon skeleton bonds and associated functional groups
(the latter does not apply to alkanes.
 No lines are shown for C-H bonds, they are assumed.

 methylpropane is showing the main C-C-C chain and a single

carbon branch from the middle carbon.
 butane is showing the 'linear', but actually zig-zag C-C-C-C
chain of 4 with no branching.
  represents 3-methylhexane. A zig-zag line of 5 C-C
bonds (but 6 C atoms) and a dash from the 3rd carbon atom
indicating the C-C bond to the methyl group.
 Alkanes can be long straight chains of Carbon atoms
bonded with each other and Hydrogen, but they can also
come in different shapes. Branching can occur, as can the
formation of cyclic structures. This is called Isomerism.
 If all the carbon atoms of the molecule are in one continuous chain,
it is referred to as unbranched or linear.
o e.g. pentane is linear or
unbranched.
 If another chain of carbon atoms starts out of the main carbon chain,
it is referred to as branching, giving rise to 'branched' alkane, one
with a side-chain.

o e.g. 3-ethylpentane is branched,

because it has an 'ethyl branch' from the 3rd carbon atom in the main
chain.

o Note that you need a minimum of 4 carbon atoms in

the alkane molecule to create a side chain branch as in the case of
methylpropane.

 For example it would be wrong to name the above molecules

triethylmethane or trimethylmethane, and

 would not be named 2-propylpropane or

4-methylpentane, but 2-methylpentane,

 would not be named 2-ethylbutane or 3-

ethylbutane, but 3-methylpentane
 The position of the branch must be specified according to the number of the carbon on the
straight chain to which it is attached. The carbons are always numbered from the carbon at
the end of the chain closest to the functional group. If there is no functional group, the
carbons are numbered from the carbon at the end of the chain closest to the branch.

o The 3- denotes the position of the carbon chain branch i.e. the lowest
number possible for the start of the side-chain.
 The positions of the substituent alkyl groups (side chains or
'branches') are denoted by using the lowest possible number(s)
o e.g. 2, 3 etc. for the associated carbon atoms in the main chain, where
the 1st carbon atom in the chain is considered as C atom 1 and can't
have an alky substituent, since that merely elongates the longest
carbon chain.
o Cyclic Alkanes have the general formula CnH2n and consist
of Carbon atoms bonded in a circular structure. They are
name with the prefix ‘cyclo’, for example cyclohexane

 Isomers are molecules with the same molecular formula but

different in some way in their molecular structure.
 With alkanes you get structural isomerism because you can vary
the arrangement of atoms in the carbon chain.
 Structural chain isomers of alkanes
 No structural isomers exist for methane, ethane or propane.

 C4H10 can be set out as a linear carbon chain to give butane itself.
o
 Or you can make a 3 carbon chain with a 'branch in the
middle to give methylpropane.

o and that's it, two isomers for C4H10.

 For C5H12 you can make 3 isomers:

1. pentane, longest possible linear
or 'unbranched chain'.

2. , 2-methylbutane, longest chain with a

single branch shortening the main chain by 1 carbon.

3. 2,2-dimethylpropane, shortest possible main

chain by double branching and shortening the main chain by 2
carbons.
 C4H10 can be set out as a linear carbon chain to give butane itself.
o
 Or you can make a 3 carbon chain with a 'branch in the
middle to give methylpropane.

o and that's it, two isomers for C4H10.

 For C5H12 you can make 3 isomers:

1. pentane, longest possible linear
or 'unbranched chain'.

2. , 2-methylbutane, longest chain with a

single branch shortening the main chain by 1 carbon.

3. 2,2-dimethylpropane, shortest possible main

chain by double branching and shortening the main chain by 2
carbons.

Some more examples:

1.
(a) or (b) are
abbreviated structural formula
o for pentane (normal or n-pentane), molecular formula (c)
and the skeletal formula is (d)

2. (a) (b) abbreviated

structural formula for methylbutane (isopentane),
 o (prefix 2- isn't strictly needed, but 2-methybutane helps at the
beginning of studying organic nomenclature), the molecular

formula is (c) and the skeletal formula is (d)

3. (a) or (b) are the abbreviated structural

formula for dimethylpropane (neopentane),
o (the prefix 2,2- isn't strictly needed but can help initially),

o molecular formula (c) and the skeletal formula is (d)

4. (a) or (b)

o are abbreviated structural formula for hexane (normal or n-

hexane),
o molecular formula (c) and the skeletal formula is (d)

5. (a) or (b) are

abbreviated structural formula for
o 2-methylpentane (NOTE: prefix numbers definitely needed
from now on),
o molecular formula and the skeletal formula is (d)
6. (a) or (b)

are abbreviated structural formula

o for 3-methylpentane, the molecular formula is (c) and

the skeletal formula is (d)

7. (a) or (b) are abbreviated

structural formula for
o 2,2-dimethylbutane (NOTE: numbers needed here, cross-
check with 7.),
o molecular formula (c) and the skeletal formula is (d)

8. (a) or (b) are

abbreviated structural formula for
o 2,3-dimethylbutane, molecular formula (c) and the

skeletal formula is (d)

9. Cycloalkanes are named according to the rules previously
described, but the name is based on the number of carbon atoms in
the ring itself.
10. The 'smallest' cycloalkanes must have at least 3 carbon atoms in the
ring.
11. The structures are shown as abbreviated structural formulae and
skeletal formulae.
12. They are sometimes referred to as examples
of alicyclic hydrocarbons, that is, aliphatic in nature, but with a ring
i.e. cyclic-aliphatic compounds, as opposed to an aromatic ring
compound based on a benzene ring.
 o cyclopropane, C3H6 , , note C-C-C bond angle
is 60o

because all three carbon atoms are in the same plane, the only
cycloalkane in which all the carbon atoms are in the same
plane. It means the C-C-C bond is highly strained and easily
broken unlike the majority of C-C-C bonds in alkane molecules.

o methylcyclopropane, C4H8 , ,

o 1,1-dimethylcyclopropane, C5H10 , ,

USES of the
fraction

Many are
names of Number The useful fuels -
fractions at of C approxim alkane
the atoms in ate hydrocarbon
THE FRACTIONAL s, but they
different the boiling
DISTILLATION OF are non-
condensati hydrocar range
CRUDE OIL renewable
on bon in oC of
levels (% in molecule the fossil
crude oil) fraction fraction fuels -
specific use
depends on
physical
properties
(see later)

C 1 to 4 methane

Fuel Gas, mainly CH4 (domesti

LPG, propane c heating),
refinery and < 25oC ethane
gas butane another gase
A simplified diagram gases ous fuel, C3–
of a fractionating (1–2%) which can 4 easily
column used in the be liquefied
compress petroleum
fractional distillation of ed or gas, portable
crude oil liquified energy
source e.g.
bottled gas
for heating
and cooking
(butane),
higher
pressure
cylinders
(propane),
feedstock for
other organic
chemicals

easily
vaporised,
Gasoline – highly
petrol flammable,
C 5 to 7 25 to 75oC
easily ignited,
(?%) car fuel –
petrol
molecules

The decrease and

increase trends for the no good as a
hydrocarbon fuel, but
molecules are given valuable raw
on the left of material
fractionating column source of
Naphtha 75 to organic
C 6 to 10
190oC chemicals to
(20–40%) make other
things, cracke
d to make
more petrol
and alkenes

less volatile,
less
flammable
Paraffin,
190 to than petrol,
kerosene C 10 to 16
250oC domestic
central
(10–15%) heating fuel,
(paraffin)
aircraft jet
 fuel
(kerosene)

less volatile
than petrol,
diesel fuel for
some cars
and larger
Diesel oil, vehicle like
gas oil 250 to haulage
C 14 to 20
350oC trucks, trains,
(15–20%) central
heating fuel,
also cracked t
o make more
petrol and
alkenes

not so easily
evaporated,
not as
flammable,
safe to store,
liquid fuel oil
Heavy fuel for power
oil, heating stations and
oil, C >20 to ships, quite
>350oC
lubricating ~30 viscous
oil, (sticky) and
greases can also be
used for
lubricating
oils
(lubricants,
'mineral oils')
and greases.

high Low melting

RESIDUE
boiling solids used
– fuel oil,
liquids or as candle
lubricating C >30,
low wax, clear
oils, waxes maybe up
melting waxes and
to several polishes (can
AND bitu solids,
hundred be dyed)
men that boil
over AND the
350oC biggest
(40–50%) molecules
 make
bitumen
bitumen/asph
compone
alt – low
nts boil
melting solid
over a
used on
500oC -
roads as it
700oC
forms a thick,
range black, tough
and resistant
adhesive
surface on
cooling, used
as a roofing
waterproofing
material (it
sticks rock
chips on roofs
or road
surfaces)

The important physical properties of hydrocarbons like alkanes all depend on the
forces between the molecules - the intermolecular forces (intermolecular bonding). This
is NOT covalent bonding, covalent bonds are the much stronger C-C and C-H bonds
between the atoms in the molecule itself.

As the hydrocarbon molecule gets bigger, the surface to surface contact area increases
allowing more points for the intermolecular bonding attractive forces to happen. Hence the
viscosity, melting points and boiling points increase with molecular mass. The intermolecular
bonds are much weaker than the covalent bonds, so when the hydrocarbon molecules have
enough kinetic energy, it is the intermolecular forces which are overcome on vaporisation
and the molecules stays intact.
1. Viscosity increases as the intermolecular attractive forces between
molecules increases the bigger the molecule in a series of molecules
of similar structure.
o The more strongly the hydrocarbon molecules are attracted to
each other, the less easily they run over each other, so the
liquid itself does not flow as easily - not as fluid.
o Note for advanced level students: Intermolecular forces or
intermolecular bonding, are non–polar weak electrical attractive
forces, often described as Van der Waals forces, and correctly
described as instantaneous dipole – induced dipole forces.
 You need to distinguish this intermolecular attractive force from
the much stronger force of the covalent bonds between the
carbon atoms (C-C) of the chain of the hydrocarbon.
2. Melting point increases as more vibrational kinetic energy is needed
to overcome the increasing intermolecular attractive forces holding
the molecules together to form the crystals.

 Boiling poin:t Alkanes are non–polar molecules where the only

intermolecular force operating is the weakest possible, that is
the instantaneous dipole – induced dipole intermolecular
forces. These are sometimes called London–dispersion
forces and occur between ALL molecules, even single atoms of
the noble gases. Van der Waals forces include all types of
intermolecular forces which are not due to an actual chemical bond
BUT sometimes this name is used just to mean these instantaneous
dipole – induced dipole dispersive forces (sorry but it can be
confusing!). The electro-negativities are: C (2.5) and H (2.1) and
produces a virtually non–polar bond and any very small effects will
tend to cancel out e.g. H–C–H situations and so alkanes are the least
polar organic molecules i.e. as near non–polar molecules you will
get.A transient δ+ in one alkane molecule induces a transient δ–
in a neighbouring alkane molecule, so causing a very weak and
transient electrical attraction.
o Note that these partial charges on the alkane molecule are
shown as a delta + (δ+) or a delta – (δ–) and they are tiny
charges compared to a full single plus charge e.g. on
an Na+ sodium ion or a full single minus charge on
a Cl– chloride ion.
 These electrical attractive forces act between ANY atoms or
molecules and is primarily a function of the number of electrons in the
molecule, though their spatial distribution can be significant.
 The larger the alkane molecule, i.e. the greater the number of
electrons in it, the more polarizable it is and the greater the chance of
a random instantaneous dipole occurring to induce a dipole in a
 neighbouring molecule, so increasing the intermolecular attractive
forces.
o Hence the larger the alkane molecule the higher the boiling
point

3. increases as more particle kinetic energy is needed to overcome the

increasing intermolecular forces between the liquid molecules ie the
intermolecular forces increase between the hydrocarbon molecules
increases as they get bigger (longer carbon chain).
o Trends 2 and 3 are readily appreciated e.g. methane gas
(CH4), liquid petrol (about C5H12 to C7H16) and solid
candle wax (over C21H44).
o The trend in boiling point is the basis for being able to separate
the hydrocarbons into fractions by the use of fractional
distillation.
4. the molecule is less flammable as they become less volatile (less
easily vaporised), again due to increasing intermolecular forces with
increasing size of molecule so for example, petrol (small molecules)
is much more flammable than lubricating oil (much bigger molecules,
much longer carbon chain)

relativ
molecul
abbreviat e flas
ar name melting boiling
ed molec h density
n formula of pointtempera pointtempera
structura ular poin g/cm3
(state at alkane ture oC/K ture oC/K
l formula mass toC
RTP)
Mr
methan
1 CH4 (g) CH4 16.0 –182/91 –164/109 na 0.466(l)
e
2 C2H6 (g) CH3CH3 ethane 30.1 –183/90 –88/185 na 0.572(l)
CH3CH2C propan
3 C3H8 (g) 44.1 –190/83 –42/231 na 0.585(l)
H3 e
CH3CH2C
4 C4H10 (g) butane 58.1 –138/135 0/273 na 0.601(l)
H2CH3
CH3(CH2) pentan
5 C5H12 (l) 72.2 –130/143 36/309 –49 0.626
3CH3 e
CH3(CH2)
6 C6H14 (l) hexane 86.2 –95/178 69/342 –22 0.660
4CH3

CH3(CH2) heptan
7 C7H16 (l) 100.2 –90/183 99/372 –4 0.684
5CH3 e
CH3(CH2)
8 C8H18 (l) octane 114.2 –57/216 126/399 13 0.703
6CH3

CH3(CH2)
9 C9H20 (l) nonane 128.3 –51/222 151/424 31 0.718
7CH3
1 CH3(CH2)
C10H22 (l) decane 142.3 –30/243 174/447 46 0.730
0 8CH3

1 CH3(CH2) undeca
C11H24 (l) 156.3 –25/248 196/469 60 0.740
1 9CH3 ne
1 CH3(CH2) dodeca
C12H26 (l) 170.3 –9/264 216/489 71 0.749
2 10CH3 ne
1 CH3(CH2) trideca
C13H28 (l) 184.4 –5/268 234/507 102 0.756
3 11CH3 ne
1 CH3(CH2) tetrade
C14H30 (l) 198.4 4/279 250/523 99 0.763
4 12CH3 cane
1 CH3(CH2) pentad
C15H32 (l) 212.4 10/283 267/540 132 0.769
5 13CH3 ecane
1 CH3(CH2) hexade
C16H34 (l) 226.4 18/291 281/554 135 0.773
6 14CH3 cane
1 CH3(CH2) heptad
C17H36 (l) 240.5 22/295 302/575 148 0.777
7 15CH3 ecane
1 CH3(CH2) octadec
C18H38 (s) 254.5 28/301 326/599 165 0.777
8 16CH3 ane
1 CH3(CH2) nonade
C19H40 (s) 268.5 31/304 330/603 168 0.786
9 17CH3 cane
2 CH3(CH2) eicosan
C20H42 (s) 282.5 37/310 343/616 na 0.789
0 18CH3 e
relativ
abbreviat e
name melting point boiling point flash
molecula ed molec density
n of temperature o temperature o point
r formula structural ular oC g/cm3
alkane C/K C/K
formula mass
Mr

Reactions of Alkanes
 Alkanes are not very reactive molecules. Most reactions require
some energy input to initiate a reaction e.g. high temperature and
catalyst for cracking, uv light for chlorination or a spark to ignite them
(initiating free radical reactions).
 A combination of two main reasons account for this lack of
reactivity compared to most other homologous groups of
organic molecules.
 Bond Strength:
  The single covalent C-C (bond enthalpy 348 kJ mol-
1
) and C-H (bond enthalpy 412 kJ mol-1) bonds are very
strong so bond fission does not readily happen. The
carbon atom radius is small, giving a short and strong
bond with other small atoms. Therefore the reactions will
tend to have high activation energiesresulting in
slow/no reaction.
 Nature of bonding:
 Carbon and hydrogen have similar electronegativities, so
there is no polar bond giving a slightly positive carbon
(Cδ+) which can be attacked by electron pair donating
nucleophiles. [e.g. see halogenoalkanes(δ+C-Clδ-)
or aldehydes/ketones (δ+C=Oδ-)]
 All the C-C and C-H bonds are single covalent and no
region of particularly high electron densitysusceptible
to attack by electron pair accepting electrophiles. [e.g.
like a double C=C bond see alkeneswhich are highly
reactive despite the fact the C=C double bond has]
 Since Alkanes are Saturated Hydrocarbons, they do not
readily react. However, they can be made to react under
certain conditions, so give useful
products or energy output.
 Alkanes will react with Oxygen if they are given
sufficient Activation Energy. This will result in a
highly Exothermic reaction, producing Carbon
Dioxide and Water, which makes Alkanes very useful
as fuels

 When Alkanes C4-C6 are heated to 150°C with

a Platinum of Aluminium Oxide
Catalyst, Isomerism occurs. The reaction
produces Branched Alkanes, and so is useful in
improving Octane Number.
 Reforming is the process of increasing the amount
of Cycloalkanes and Hydrocarbons containing Benzene
Rings, to improve Octane Number. This is done with
Alkanes in the Naphtha Fraction (C6-C10) at 500°C with
a Platinum or Aluminium Oxide Catalyst. Hydrogenis
recycled through the mixture to reduce ‘coking’.
 Cracking is the process of breaking longer
chained Alkanes down into smaller Alkanes and Alkenes,
sometimes for Polymer manufacture, and sometimes to
improve Octane Number
Combustion of alkanes
Alkanes are often used as fuels (Figure 15.6). We burn them for many reasons:
■■To generate electricity in power stations
■■To heat our homes and cook our food
■■To provide energy needed in industrial processes
■■To provide power for ships, aeroplanes, trains, Lorries, buses, cars and motorbikes.

If an alkane is burnt in plenty of oxygen, it will undergo complete combustion. The carbon will be oxidised
fully to form carbon dioxide and the hydrogen will be oxidised to form water:

Complete combustion
Alkane + oxygen carbon dioxide + water
For example, octane can be found in petrol. Some of it will undergo complete combustion in a car engine:
Octane + oxygen carbon dioxide + water
2C8H18 + 25O2 16CO2 + 18H2O
The equation can also be written as:
C8H18 + 12 _12 O2 8CO2 + 9H2O

Pollution from burning hydrocarbon fuels

When the petrol or diesel is mixed with air inside a car engine, there is a limited supply of oxygen. Under
these conditions, not all the carbon in the hydrocarbon fuel is fully oxidised to carbon dioxide. Some of the
carbon is only partially oxidised to form carbon monoxide gas. This is called incomplete combustion. For
example:
Incomplete combustion
Octane + oxygen carbon monoxide + water
2C8H18 + 17O2 16CO + 18H2O
Or
C8H18 + 8 _12 O2 8CO + 9H2O

Substitution Reaction:
(i) Chain initiation step:-

(ii) Chain Propagation step :-

(iii) Chain Termination step :-

CRACKING

 Cracking is essentially the thermal decomposition of hydrocarbons

such as alkanes into molecules of smaller carbon number, namely
lower alkanes as chemical feedstock for other processes and alkenes
for polymer production.
 Cracking does involve breaking a strong C-C bond in the alkane to
produce smaller molecules.
 Cracking is a type of chemical reaction in which hydrocarbon
molecules, usually saturated hydrocarbons called alkanes, are
broken down into smaller molecules by the application of heat,
pressure and catalysts.
 Cracking is done to provide a greater variety of hydrocarbon
molecules from oil fractions, that perhaps otherwise would be of little
value.
 (a) Steam cracking (thermal cracking) is done at high
temperatures e.g. 900oC and high pressure, with no catalyst.
Naphtha (C6-C10) and kerosene (C10 - C16) are the chemical
feedstocks and the vaporised hydrocarbons are exposed to the high
temperature for just a short time.
 Reaction conditions can be set to maximise alkene production,
remember, alkenes are NOT found in oil but one of the most
important chemical feedstocks for polymer production.
 (b) Catalytic cracking involves passing a fraction like gas oil (C14 -
C20 alkanes) over a zeolite catalyst at 500oC. The reactor pressure is
slightly above normal.
 Catalytic cracking is used to produce hydrocarbons to reduce the
octane number of petrol fuels, e.g. you try to maximise the yield of
lower carbon number alkanes and some aromatic hydrocarbons. You
can minimise the yield of unsaturated alkenes, but some will still be
produced.
 (i) hexane ===> ethene + butane/methylpropane or propene
+ propane
 octane ==> hexane + ethene
 C8H18 C6H14 + C2H4