•

RAFFLES INSTITUTION
YEAR 5 H2 CHEMISTRY 2022
Lecture Notes 10: Alkanes

Content

• Alkanes (exemplified by ethane)

(i) free-radical substitution reactions
• Hydrocarbons as fuels

Learning Outcomes

Candidates should be able to:

(a) explain the general unreactivity of alkanes, including towards polar reagents
(b) describe the chemistry of alkanes as exemplified by the following reactions of ethane:
(i) combustion
(ii) free-radical substitution by chlorine and by bromine
(c) describe the mechanism of free-radical substitution with particular reference to the initiation,
propagation and termination reactions

(d) recognise the environmental consequences of:

(i) carbon monoxide, oxides of nitrogen and unburnt hydrocarbons arising from the internal
combustion engine and of their catalytic removal
(ii) gases that contribute to the enhanced greenhouse effect
(e) recognise that petroleum, a chemical feedstock, is a finite resource and the importance of recycling

Lecture Outline
organic compounds
1 Introduction I
2 Isomerism in alkanes
3 Physical properties hydrocarbons halogen derivatives
4 Preparation of alkanes hydroxy compounds
5 Reactions of alkanes carbonyl compounds
6 Free-radical substitution aliphatic aromatic carboxylic acids & derivatives
7 Alkanes as fuels
8 Summary I nitrogen compounds

References saturated unsaturated

.----I.__, .--__._I-.,.-__,
• Chemistry in Context (by I I I
Graham Hill & John Holman) open-chain alicyclic alkenes alkynes arenes
(acyclic or (ring)
• Cambridge International AS non-?clic) \
and A Level Chemistry (by
Peter Cann & Peter Hughes)
alkanes cycloalkanes
• Website: CHn 2n+2 CnH2n
[Link]

-1-
_ 1---Ll_
ln_tr_o_d_
uc_t_:
lo_n_ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _

• The alkanes are the simplest of the homologous series found in organic chemistry.

• Alkanes are hydrocarbons since they contain only carbon and hydrogen. Other hydrocarbons include
alkenes, alkynes and arenes.

• Alkanes are saturated hydrocarbons because they contain only carbon-carbon and carbon-hydrogen
single bonds and do not contain any double or triple bonds. Unsaturated hydrocarbons such as
alkenes and alkynes contain multiple bonds (either double or triple bonds) between carbon atoms.

The first three members of the open-chain alkanes

are methane, ethane and propane.
condensed displayed 3-D ball-and-stick
• The open-chain alkanes form structural formula formula structure model
a homologous series of
saturated hydrocarbons with. H
the general molecular formula,
D-14
H
I I
_........c .... ,,, H
CnH2n+2. Successive members methane H-C-H
I H \ A
differ in composition by one H H..-' 109.5°
CH2 group (methylene group).
H H
• Each C atom in an alkane I I
H-C-C- H
molecule is sp3 hybridised I I
H H
and has a tetrahedral
molecular geometry around it.
The bond angle around each C H H H
I I I
atom (in an open-chain alkane) CH3CH 2CH3 H-C-C-C-H
propane I I I
is approximately 109.5°. H H H

• Cycloalkanes are alkanes

that contain one or more rings The first four members of cycloalkanes are shown below.
of carbon atoms. They are H H
saturated hydrocarbons in H H H \/ H
which the carbon atoms are I I \c,.,...c'-c1-..H
H.-
H- C'-C-H
arranged to form rings. I I H-..cI I
c---H
H-C - C-H I 'c,.,... \
I I H / \ H
• Cycloalkanes with only one H H H H
ring have the same general ,,,.cH2
molecular formula (i.e. CnH2n) CH,, 'cH 2
as the alkenes with only one I - I
C=C bond. C~2 ,,,.cH 2
CH 2
Cyclopropane Cyclobutane Cyclopentane Cyclohexane
Tip:
C3H6 C4H8 C5H10 C6H12
For an unknown compound
with molecular formula CnH2n,
it could likely be a cycloalkane
or an alkene.
0 0

-2-
•
1.1 Nomenclature for Straight-Chain Alkanes

• Straight-chain alkanes have their IUPAC names as shown in the table below.

• Each member has the suffix 'ane'.

Alkane Structural Skeletal formula

IUPAC Names of Straight-Ch ain Alkanes
formula
Number
propane CH3CH2CH3 A Number
of carbon Name of carbon Name
butane CH3CH2CH2CH3 /'./ atoms atoms
1 methane 11 undecane
octane CH3(CH2)sCH3 ethane 12 dodecane
2
3 propane 13 tridecane
4 butane 14 tetradecane
5 pentane 15 pentadecane
6 hexane 16 hexadecane
7 heptane 17 heptadecane
8 octane 18 octadecane
9 nonane 19 nonadecane
10 decane 20 icosane*

• Spelled "eicosane" prior to 1979 version of IUPAC rules

1.2 Nomenclature for Branched-chain Alkanes

• The rules for naming branched-chain alkanes are summarised in the table below.

prefix + parent + suffix

J, ,j, ,j,
What and where are the substituents? What is the longest carbon chain? What is the functional group?
-ane

1. Find the longest continuous chain of carbon atoms, and use the name of this chain as the base
name.

2. Number each carbon atom in the longest chain, beginning with the end nearest a substituent.

3. Name the substituents attached to the longest chain (as alkyl groups). Give the location of each
substituent by the number of the main-chain carbon atom to which it is attached.

• An alkyl group is formed by removing a hydrogen atom from an alkane .

• General formula of an alkyl group: CnH2n+1
• To name an alkyl group, change the -ane ending of the alkane to -yl.

Alkyl group Structure

methyl CHJ- an alkane: CnH2n+2 or R-H
ethyl CHJCH2-
an alkyl group: CnH2n+1 or R-
propyl CH3CH2CHi-
butyl CH3CH2CH2CH2-

4. When two or more substituents are present, list them in alphabetical order. When two or more of
the same alkyl substituents are present, use the prefixes di-, tri-, tetra-, etc. to avoid having to name
the alkyl group repeatedly.

5. Note: Use comma (,) to separate 2 numbers. Use hyphen (-) to separate a number and a word.

Tip: Numbering your carbons is a useful way to draw structures. Practice it!
'

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 -Worked Example 1 -
Give the systematic (IUPAC) name for the following alkanes.

(a)

1.3 Classification of hydrogen and carbon atoms

• Carbon atoms are classified as primary (1°), secondary (2°), tertiary (3°) or quaternary (4°)
depending on the number of carbon atoms to which they are bonded.

two 1° carbons a 3° carbon a 4° carbon

/ I ~IH3 CH 3
I
CH 3 -C~-CH3 CH 3 -
1H-CH3

CH 3
CH 3 -C-CH9-CH-CH 3
I
CH 3
- .
a 2° carbon

propane 2-methylpropane 2,2,4-trimethylpentane

• A 1° C atom is bonded to one other C atom.

• A 2° C atom is bonded to two other C atoms.
• A 3° C atom is bonded to three other C atoms.
• A 4° C atom is bonded to four other C atoms.

• Hydrogen atoms are classified as primary (1°), secondary (2°) or tertiary (3°) depending on the~
of carbon atom to which they are bonded.

H C C

H-C-C
I H-C-C
I H-C-C
I Example:

I I I
t
1° Hatom
H
t H
2° H atom
1 C
3° H atom
1° H
i H .,_3o H
I
CH3CH -C-CH
2 3
A 1° H atom is bonded A 2° H atom is bonded A 3° H atom is bonded
to a C atom that is
bonded to one other C
to a C atom that is
bonded to two other C
to a C atom that is
bonded to three other C
1 tH3
2° H
atom. atoms. atoms.

-4-
__:::2:.......1.j_1s_o_m_e_ri_
sm_ l_
n _A_lk_a_n_es_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

2.1 Constitutional (or structural) isomerism

• Constitutional (or structural) isomerism arises when there exists compounds with the same
molecular formula but different structural formulae.

• From butane onwards, alkanes have constitutional isomers due to the branching of the hydrocarbon
chains.

Example 1 Example 2: Constitutional isomers with molecular formula CsH14

CH3CH2CH2CH3 CH3CH2CH2CH2CH2CH3 CH:3CH:zCl-l;z - CH- CH:3 CH:3CH;z-CH-CH:zCH:3

hexane I I
butane CH3
CH:3
2-methytpentane 3-methylpentane
CH-CH-CH
3 I 3
CH 3 CH3 CH3 c~
I I I
2-methylpropane C~-CH-CH-CH3 c~c~-c-c~
I
2,3-di methyl butane 2,2-dimethylbutane c~

2.2 Stereoisomerism
• Stereoisomerism arises when there exists compounds with the same molecular formula and structural
formula but differ in the way in which their atoms are arranged in space relative to one another.

(a) Enantiomerism

• Some branched-chain alkanes display enantiomerism (or optical isomerism in the old A-level
syllabus). This is because they contain a chiral carbon centre with no plane of symmetry and hence can
exist as a pair of enantiomers, which are non-superimposable mirror images of each other.

Example:
3-methylhexane displays enantiomerism H H
I I
,,.-C ·•q 11 11CH CH CH
CH{' \ 2 2 3 CH3CH2CH2ll'l')c "-cH3
CH2CH3 CH3CH 2

mirror
plane

(b) Cis-trans isomerism

• Some cycloalkanes display cis-trans isomerism. This is because the ring structure restricts the free
rotation of the bonds in the ring.

Example: 1,2-dimethylcyclopentane displays cis-trans isomerism

H~H-Q H,C++H=~
H3C CH 3 CH 3 CH 3 H CH 3 H CH 3
cis-1,2-dimethylcyclopenlane tra11s- I,2-di methylcyclopentane

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_ 3-----ll_P_h....:.y_s_
i c_a_l P
_ ro....:.p_e_rt_ie_s_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ lllll
• Alkanes contain C-C and C-H bonds. As the difference in electronegativity between C and H atoms is
negligible, the C-H bond is essentially non-polar and alkanes are essentially non-polar.

• The intermolecular forces of attraction between alkane molecules are relatively weak instantaneous
dipole-induced dipole interactions.

• Table showing some physical properties of straight-chain alkanes:

Name Formula Melting Boiling Density State Remark

point/ °C point/ °C I g crrr3 at r.t.p.
(20°C)
methane CH• -182 -162 gas gas The C1 to C4 straight-chain
ethane CH3CH3 -183 -89 gas gas alkanes are colourless
gases at room temperature.
propane CH3CH2CH3 -188 -42 gas gas
butane CHJ(CH2)2CH3 -138 -0.5 gas gas
pentane CH3(CH2)3CH3 -130 36 0.626 liquid
hexane CH3(CH2)4CH3 -95 69 0.659 liquid The Cs to C11 alkanes are
heptane colourless liquids of
CH3(CH2)sCH3 -91 98 0.684 liquid
increasing viscosity.
octane CH3(CH2)sCH3 -57 126 0.703 liquid
nonane CH3(CH2)7CH3 -53 151 0.718 liquid The remaining alkanes
decane CH3(CH2)sCH3 -30 174 0.730 liquid containing 18 carbons or
undecane CHJ(CH2)9CH3 196 more are solids at room
-26 0.740 liquid
temperature.
dodecane CH3(CH2)10CH3 -10 216 0.749 liquid
icosane CH3(CH2)1sCH3 37 343 0.789 solid

3.1 Boiling and Melting Points

(a) The boiling and melting points of alkanes increase with increasing number of carbon atoms.

• Explanation: As the number of carbon atoms in alkanes increases, the number of electrons per
alkane molecule increases and the. Sij,L ~1 [Link] of the alkane molecule
increases. As a result, the tJ::'<l, f'v ~ ·Sll.'y\~ '~ -\\,.n.. fil\.\--:,.f' c
J ., , . V \¥\\)NJ,,>,JV> .
leading to increasing strength of instantaneous dipole-induced dipole attractive forces which are
overcome at increasingly higher temperatures.

(b) The boiling and melting points of isomeric alkanes decrease with increasing degree of branching.

Alkane pentane 2-rnethylbutane 2,2-dimethylpropane

CH 3
CH3CH2CH2CH2CH3 CH3 - CH-CH2CH 3 I
I CH 3-C-CH
CH 3 I 3
CH 3

Boilina ooint / °C 36 28 10

• Explanation: With branching , the molecule becomes more spherical (or more compact) and its surface
area available for intermolecular interactions decreases. This reduces the extent of contact between
neighbouring molecules, resulting in weaker instantaneous dipole-induced dipole forces that are
overcome at a lower temperature.

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3.2 Solubility

• Being essentially non-polar, the alkanes are soluble in non-polar solvents such as benzene and are
insoluble in water and other highly polar solvents.

• Some liquid alkanes are used as non-polar solvents (e.g. hexane). These liquid alkanes dissolve
compounds of low polarity and do not dissolve compounds of high polarity (refer to section 5.5 of
Chemical Bonding Part 1 lecture notes)

3.3 Density

• The density of alkanes increases with increasing molecular size of the alkanes but tends to level off
at about 0.8 g cm-a. Thus, all alkanes are less dense than water.

A separatory
funnel with an
upper organic organic layer
layer of alkane (alkane)
and a lower
aqueous layer.

Scan this QR code to see

how to use a separatory I
separating funnel to separate two
immiscible liquids.

4
--'-·
I-
Preparation of Alkanes
------------------
-

4.1 Reduction of alkenes

Ni Pt or Pd
CnH2n + H2 CnH2n+2 CnH2n + H2 CnH2n+2
alkene heat alkane alkene alkane

Reagent and conditions: H2(g), Ni, heat or H2(g), Pt or Pd

• A mixture of the alkene and hydrogen is passed over finely divided platinum, palladium or nickel
catalyst. Nickel is the least active of these catalysts and requires an elevated temperature and
pressure, whereas platinum and palladium function adequately at ordinary temperatures and
pressures.
Ni
• Examples: CH2=CH2+ H2
heat
CH3CH3
ethene ethane

0
cyclohexene
+ H2
Ni
heat 0
cyclohexane

-7-
4.2 Reduction of other unsaturated hydrocarbons

• Alkynes can be reduced to alkanes under suitable conditions.

CH3C=CH + 2H2 _ _ CH3CH2CH3

propyne heat propane

• Benzene can also be reduced to cyclohexane under suitable conditions.

rB1 Ni catalyst
+ 3H2 -n-gh-t-em_p_e_ra_tlre-
ngh presslre
0
- -'I_R_e_a_ct_io_n_s_o_f_A_l_ka_n_e_s_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
_ s

• The effects of various reagents on hexane, a typical alkane, are shown in the table below.
Reagent Effect
NaOH(aq) No effect, whether hot or cold. Two immiscible layers observed.
HC/(aq) No effect, whether hot or cold. Two immiscible layers observed.
Cone. H2S04 No effect, whether hot or cold . Two immiscible layers observed.
Acidified No decolourisation of purple KMn04 even on heating.
KMn04(aq) Two immiscible layers observed.
Air No effect when cold. Bums when heated.
Bromine No effect in the dark. Bromine decolourised in the presence of sunlight.

• From the above table, it can be seen that hexane is rather unreactive. Its behaviour is typical of that
of alkanes which are unaffected by polar reagents such as acids, alkalis, dehydrating agents or
aqueous oxidising agents.

• Alkanes are saturated hydrocarbons and essentially non-polar. They consist of molecules which
have no centres of electrical charge and are unable to attract charged species like W, OH- or
MnQ4-. They contain only non-polar C-C bonds and essentially non-polar C-H bonds.
The general lack of reactivity of alkanes can be attributed to the following reasons:

1. Alkanes are non-polar. 1 \ •

• They do not contain any region of h,,~i, LU~ C,&,\> Aj and thus do not attract
electrophilic reagents. , I
• They also do not contain any a,, J( ~1-l ' -vi-r 5;t',J to attract nucleophilic
reagents.
2. Alkanes have relatively S¾Utj C-C and C-H bonds which do not break under normal
conditions.
• However, alkanes do undergo reactions with non-polar reagents (e.g. Ch and 02) under the right
conditions (e.g. in the presence of ultraviolet light or heat).

-8-
5.1 Combustion

• Alkanes bum readily in air or oxygen when ignited. The reaction is very exothermic, thus making
alkanes an important source of fuel (see Section 7).

• In excess oxygen, alkanes burn with a non-sooty flame. On the other hand, unsaturated hydrocarbons
bum with a sooty flame.

• Complete combustion of alkanes produces C02(Q) and H20(I).

Combustion of a hydrocarbon CxHy + '1:~~ 02(Q) "L C02(g) + H20(I)

3 1 nC02(Q) + (n+1 )H20(I)

Combustion of an alkane CnH2n+2 + " + 02(9)
2

E.g. Combustion of methane CH4(g) + 202(9) C02(g) + 2H20(I)

• Incomplete combustion of alkanes leads to the formation of CO(g) and C (as soot) in addition to
C02(g) and H20(I).
3
Formation of CO CH4(g) + - 02(Q) CO(g) + 2H20(I)
2

Formation of C (as soot) CH4(g) + C(s) + 2H20(I)

5.2 Halogenation (Mechanism: Free Radical Substitution)

• Halogenation of an alkane involves the substitution of one or more hydrogen atoms of the alkane by
halogen atoms.

• Energy input in the form of heat or ultraviolet light is needed to initiate these halogenations. These
reactions may be conducted in either liquid or gaseous phase (but not under aqueous condition as
the water molecules will react with any radical present).

Note: R-H = alkane molecule

ultraviolet light
R-H + X2 R-X + HX X= Cl or Br
or heat
• The focus will be on chlorination and
bromination.

Reagent: C'2 or Br2 • Fluorination is dangerously exothermic.

Condition: ultraviolet light or heat • Iodination does not occur as the overall
reaction is endothermic and is
Mechanism: Free-radical substitution
thermodynamically unfavourable.

-9-
• Examples:
Reaction Observations
• Decolourisation of greenish-yellow C/i.
ultraviolet light • Formation of white HC/ fumes that turn
CH4 + Ch CH3C/ + HC/
damp blue litmus paper red .

• Decolourisation of reddish-brown Br2.

ultraviolet light • Formation of white HBr fumes that turn
CH4 + Br2 CH38r + HBr
damp blue litmus paper red.

• The reaction always produces a mixture of products.

ultraviolet light
chloromethane

• If excess Ch is present, further substitutions can occur.

CH3C/ + Ch ----+ CH2Ch + HC/

dichloromethane

CH2Ch + Ch CHC/J + HC/

trichloromethane (or chloroform)

CHC/3 + Ch ----+ CC/4 + HC/

tetrachloromethane (or carbon tetrachloride)

• For simplicity:

C/2(~ ..U
CH4 - - - - - - - - - + CH3C/ + HC/ CH4 - .....:C:..::'2~(==
/.-'=f(=L)='= =)~
CC/4 + HC/
ultraviolet light major product ultraviolet light major product

-10-
 ls_m_o
_e_c_h_a_n_
_ &____.I_M S_
e-_R_a_d_lc_a_l _
_f_F_r_e_ utl_o_n_ _ _ _ _ _ _ _ _ _ _ _ _ __ _
ub_s_t_it_ _

6.1 Some important tenns

(a) Free radical

• A free radical (or radical) is an atom or group of atoms that has an unpaired electron (which is
represented by •)

.. .. H
I
CH3CH2• H
I
H•
..
:Cl· or Cl• ..
: Br• or Br• CH3• or H-C•
I
or
•
CH 3CH 2
or H3C-C•
I
H H
hydrogen chlorine bromine methyl radical ethyl radical
radical radical radical alkyl radical

• Free radicals are highly reactive and are intermediates in many of the reactions of alkanes. As they
have equal numbers of protons and electrons, they are electrically neutral (unlike cations or anions).
• Stability of alkyl radicals depends on the number of alkyl groups (usually represented by the letter 'R')
attached to the carbon atom with the unpaired electron.
The following shows the relative stability of alkyl radicals:
H R R R

H-C•
I < H-C•
I < H-C•
I < R-C•
I
I
H
stable
I
H
stable
I
R
stable
I
R

Methyl Primary alkyl Secondary alkyl Tertiary alkyl

radical radical radical radical

The carbon with the unpaired electron is electron-deficient. As alkyl groups are electron-donating,
the more alkyl groups attached to the carbon with the unpaired electron, the more stable the
alkyl radical.

(b) Hemolytic fission

• Homolytic fission of a covalent bond occurs when the bond breaks in such a way that each of the
atom involved in forming the bond acquires one of the two bonding electrons, thus forming free
radicals.

• Examples:
··!l .. .. ..
Homolytic fission of the Cl-Cl bond .• U·· -- :Cl·
:Cl··C/: •• + ·Cf:
..
[,)~l ::: Cl•+ Cl·
H H
Hemolytic fission of the C-H bond
ln0 I
H-C-H - H-C• + H•
I I
H H
Note:
A curly arrow with half a head (i.e. 'fish-hook' arrow) represents the movement of one electron.

-11-
6.2 Free-radical Substitution
ultraviolet light
• Reaction: CH. + Ch
• The reaction mechanism for this reaction is termed free-radical substitution.
• It involves a chain reaction consisting of initiation step, propagation steps and termination steps.

Step 1: Initiation
• This step involves_ kl kI
ultraviolet light and will NOT proceed in the dark or atdoom
Cf• + Cf• temperature.
heat
chlorine radicals • II is easier to break the Cl-Cl bond than the
• Chlorine is supplied with energy (from uv light or heat) to split C-H bond or the C-C bond. See Data
Booklet for the relevant bond energy values .
into free radicals via homolytic fission of the Cl-Cl bond.
Step 2: Propagation
• These steps involve both bond breaking
and bond fonnation. The major products
H

(a)
~~00i
H-C-H Cl•
I
H-C• + H-C/
are being formed in these steps.

• Step 2(a) (hydrogen abstraction) - the

I I highly reactive chlorine radical collides with a
H H methane molecule and abstracts one
methyl radical hydrogen atom from it,. forming hydrogen
chloride and a methyl radical.
H H
• Step 2(b) (halogen abstraction) - the
H-60Qfd,
I
H-C-C/ + Cl• methyl radical can react with a chlorine
(b)
molecule, leading to the formation of
I I
H chlorine chloromethane and a chlorine free radical.
H
radical
• The chlorine free radical produced can
Then (a), (b), (a), (b), ... proceed to attack another methane molecule
and hence the steps (a), (b), (a), (b),are
In step 2(a), the reaction that occurs is: CH4 + Cl• •CHJ + HC/ repeated.
Explain why the reaction CH• + Cl• CH3C/ + H• does not occur. Note: sum of all propagation steps gives
overall chemical equation.
The formation of the H-C/ bond is ,.,.,~ t '(o .(,[Link]'l.
than the formation of the C-C/ bond. • As a result, thousands of molecules of
chloromethane are formed by steps 2(a) and
Note: Hydrogen radical H• is r\t,<,-v fw,v..tJ, in free radical 2(b) for every photon of light absorbed in
substitution. step 1.

Step 3: Termination
Cl• + Cl• • This step involves bond formation.

H H • The reaction ends when two free radicals

I H-C-C/
I collide and combine to form a stable product.
H-C• + Cl•
I I • Trace quantities of compounds containing at
least twice the no. of C atoms when
H H
H H compared to the starting alkane can be
H H detected in the mixture of products, e.g.
I I I I ethane being formed from methane.
H-C• + H-C• H-C-C-H
I I I I
H H H H

• Note: A chain reaction is a reaction that involves a series of steps, each of which generates a reactive species
that brings about the next step. Such a reaction essentially consists of
1. a chain-initiating step, in which energy is absorbed and a reactive species generated,
2. one or more chain-propagating steps, each of which consumes a reactive species and generates another,
3. chain-terminating steps, in which reactive species are consumed but not generated.

-12-
 -Work ed Example 2
Propane can undergo reaction to give 2-chloropropane.

(a) Suggest the reagent and condition for this reaction .

... .. ½~ .J.'f~ .. . ·\..clAb#. .G;IW•i~1~ ................................................. .

(b) Write a balanced equation for this reaction .

... ... .. ___-j ... ~-~~(a)P1L.\ .~~-................................... ..

(c) Describe the mechanism for this reaction.

Name of mechanism: Free-radical substitution Name of mechanism: Free-radical substitution

Initiation: Initiation:

If\ n ultraviolet light

c1J__c1 - - - - - - - er + c1·
heat

Propagation: Propagation:

•
(a) + Cl• + HCl
Cl

(b) A+ ch
Then (a), (b), (a), (b), ...

Termination:
Termination:
Cl• Ch
Cl

A
)· + ·< >-<
• Essential oints

Name of mechanism
(free-radical substitution)
Headings for 3 steps.
(initiation, propagation, termination)
Conditions for initiation.
(uv light or heat)
Half arrows from bond to halogen atoms in initiation step.
Label propagation steps (a) and (b).
Then (a), (b), (a), (b) ..... .
.
The termination steps must include a reaction which forms the required product
Placing of • on correct atoms in all steps.

-13-
 -Worked Example 3 -Worked Example 4-
Methane can react with bromine in the Chlorination of propane in the presence of
presence of ultraviolet light to produce CH2Br2. ultraviolet light gives a mixture of two mono-
chlorinated products.
Write an equation to represent this reaction and
describe the mechanism for this reaction. (a) Draw the displayed formulae of these two
products and suggest (with a reason) the
Reaction: expected ratio in which they might be formed.
CH. + 2Br2 ultraviolet light CH2Br2 + 2H8r
Let's start by labelling the different types of H
The above reaction occurs via atoms on propane:
free-radical substitution mechanism,
which consists of the following steps: Ha Hb Ha

Step1: Initiation
I I I
H-C-C-C-H
a I I I a
Ha Hb Ha
{JB ( } ultra--..olet light
r - 9r Br• + Br•

Step 2: Propagation -
H H H
(- ,_, I ,·- CR.r •(H
_ c., - C - C - l9... v{- ( .. ( - ( - w
(a) CH4 + Br• •CH3 + HBr H ' I I - I I I
k H H H 11
(b) •CH3 + Br2 CH38r + Br• Product (A)
(Expected major product) Product (8)
Then (a), (b), (a), (b), .....
To forrh (A), any one of the _ _ L_ Ha in
Propagation steps (a) and (b) give rise to propane can be replaced by the Cl atom.
many molecules of CH38r.

CH38r can undergo further bromination via

propagation steps (c) and (d) to form CH2Br2.
To form (B), any one of the )_ ·
propane can be replaced by the Cl atom.
Hb in
-
Hence, based on probability factor and assuming
(c) CH38r + Br• •CH2Br + HBr that all the H atoms have the same reactivity,
(d) •CH2Br + Br2 CH2Br2 + Br•
molar ratio of (A) to (8) is I r. .

Then (c), (d), (c), (d), ..... (b) When propane is chlorinated, the ratio of the
two products formed in a 1: 1 ratio instead.
Suggest an explanation for the difference
Step 3: Termination between this ratio and the expected ratio from
(a).
Br• + Br• Br2
•CH2Br + Br• CH2Br2 The expected ratio is obtained by assuming that
all H atoms have the same reactivity.
•CH2Br + •CH2Br BrCH2CH2Br
(trace amount) (A) is formed from •CH2CH2CH3 intermediate
•
while (8) is formed from CH3CHCH3 .
•
CH 3CHCH 3 is a 2° radical that is more stable
than •CH2CH2CH3, a 1° radical, due to the
presence of one more electron-donating alkyl
group attached to the electron deficient C atom.
Therefore, it gives rise to a greater proportion of
(8) than expected.

-14-
 s . (a
_ 7_,_I_A_lk_a_n_e_ ls_ _ _ _ _ _ _ _ _ _ _ _ _ _
. :. . _n_d_o_th_e_r_h-=..y_dr_o_c_ar_b_o_ns_;)_a_s_F_u_e_

7.1 Natural Occurrences of Alkanes (for self reading)

• The principal sources of alkanes are natural gas and crude oil (or petroleum).

• Natural gas contains mainly methane with smaller amounts of the other gaseous alkanes such as
ethane, propane and butane.
• Crude oil (or petroleum) is a complex mixture of hydrocarbons consisting of alkanes, cycloalkanes
and aromatic compounds. It contains a wide range of alkanes, from the low molecular weight gases
to the high molecular weight solids.
• The hydrocarbons in crude oil are separated into fractions by fractional distillation in an oil refinery.
The different fractions obtained from crude oil are shown in the table below.

Approximate c·s per Namaof Fraction Approximate Length of Uses

boiling range/ 'C molecule fraction bolling carbon
temperaturefc chain

s=<25 1- 4 LPG (Liquefied

Petroleum Gas)
Refinery
gas
Light
petroleum
20

20-60
C1-C, Fuel: domestic heating,

Cs-Ce
gas cookers
Solvent

Light 60-100 Cs-C1 Solvent

6-12 GASOLINE
~40100 naphtha
Gasoline 30-200 Cs- C12 Fuel for internal
combustion engine (cars
7 - 14 NAPHTHA (petrol)
~100-150
etc.)
Kerosene 175-300 C1i-C1s Fuel for jet engines

KEROSINE
(paraffin)
11 • 15
~150-200 Gas oil 275-400 C1s-C2s Does not vaporise easily.
Used in diesel engines
where ii is injected into
15- 19 GAS OIL compressed air to make
~220050
it ignite. Used in
industrial furnaces, being
20-30 LUBRICATING introduced as a fine mist
~ > ~C OIL to help the oil to bum.
Lubrication Non-volatile C20- C34 Lubricants
30-40 FUEL OIL oil
~ > 4CC
Paraffin Solidifies from C2s- C,o Polished waxes,
wax lubricating oil petroleum jelly
40 - 50 WAA, GREASE
fraction
Bitumen Residue >C30 Road surfacing. roofing.
(asphalt)
>400 > 50 BITUMEN

• In the petroleum industry, some fractions of obtained from the distillation of crude oil can be further
converted to other useful products via cracking , reforming or alkylation.

Process Products
Cracking • Smaller straight-chain/branched-chain alkanes, cyclic hydrocarbons,
alkenes, hydrogen gas.

An example
of cracking:
C12H2a
- C5H10

C7H1e
long-chain alkane
shorter-chain alkanes and alkenes

Reforming • Aromatic hydrocarbons

Alkylation • Hiqhlv branched alkanes

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• Many of the fractions obtained from the distillation of crude oil are used as fuels. These include LPG,
petrol, kerosene, diesel, fuel oil and wax.
• Combustion of alkanes as fuels can give rise to pollution problems (see Section 7.3).

7.2 Pollution Problems

(a) Pollutants from internal combustion engines

• Car exhaust fumes contain carbon monoxide, oxides

of nitrogen and unbumt hydrocarbons as a result of Substance % composition
incomplete combustion. water vapour 9
carbon dioxide 8
• One reason why products of incomplete combustion
are formed although there may be an excess of carbon monoxide 4-6
oxygen is that the reaction time in the combustion oxygen 4
engine is too short. hydrogen 2
hydrocarbons 0.2
• A typical composition of gases in petrol engine oxides of nitrogen 0.3
exhaust fumes is shown in the table on the right. nitrogen (chief component)

(b) Environmental Consequences of CO, NOx and unburnt hydrocarbons

Pollutant Effect How they Methods for reducing pollution

are formed
Carbon Combines with haemoglobin in blood and 1. Careful adjustment of fuel/air
monoxide, renders it ineffective to transport oxygen. Incomplete proportions and design of
co combustion engines.
May affect mental alertness. 10% in air in of fuel. 2. Inclusion of catalytic
confined spaces fatal in 2 minutes. converters in exhaust
assembly to finish the
combustion reaction.
Unburnt A mixture of unburnt hydrocarbons and
hydrocarbons oxides of nitrogen can take part in a Incomplete As for carbon monoxide.
and carbon complex sequence of chemical reactions combustion
particulates that lead to the formation of of fuel:
photochemical smog (in the presence of
sunlight).

Photochemical smog is a yellowish-white

haze containing chemical species, which
irritate the respiratory tract and results in
chest pains and breathing difficulties. It
has a harmful effect on plants.
Oxides of Acidic gases contributing to the formation Combination Inclusion of catalytic converter to
nitrogen, of 'acid rain', which renders farmlands of nitrogen reduce the oxides to nitrogen.
NOx unsuitable for cultivation, causes and oxygen
(i.e. NO and corrosion of architecture and adversely in air at high
N02) affects marine lives (due to the increased temperature
acidity of water). in the internal
combustion
Contributor to photochemical smoq. engines.
(c) Use of Catalytic Converters
• Cars are fitted with reaction catalytic converters in the exhaust system to remove three main pollutants (CO,
NOx and unburnt hydrocarbons) from exhaust gases. These pollutants are converted into CO 2, N2 and water
vapour.
• Refer to lecture notes on Reaction Kinetics for the actions of the different catalysts in the catalytic converter.

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(d) Other pollutants from hydrocarbon fuels
Pollutant Remarks
Carbon • Carbon dioxide is a greenhouse gas. Greenhouse gases in the atmosphere trap a lot of heat that
dioxide, CO2 would otherwise escape to space, thus helping to keep the Earth's surface warm. This natural
greenhouse effect keeps the Earth's surface much warmer than it would be if there was no
atmosphere.

• Since the Industrial Revolution, mankind has been releasing extra quantities of greenhouse gases
into the atmosphere, which trap more heat, enhancing the natural greenhouse effect. This
"enhanced" greenhouse effect is the direct result of human activities. Processes such as the
burning of fossil fuels, industrial operations and forests clearing release carbon dioxide, methane
and nitrous oxide into the atmosphere.

• Man-made emissions of carbon dioxide, more than any other greenhouse gas, have contributed
most to the enhancement of Earth's natural greenhouse effect.

The enhanced greenhouse effect has led to an increase in the earth's temperature, causing global
wanning. The result is the melting of the polar ice caps, which is likely to cause severe flooding
in the future, as well as serious damage to numerous ecosystems.
[Link]/nova/016/[Link]
enhanced greenhouse effect. An increase in the natural process of
the greenhouse effect, brought about by human activities, -...hereby
greenhouse gases such as carbon dioxide, methane,
chlorofluorocarbons and nitrous oxide are being released into the
atmosphere at a far greater rate than would occur through natural
processes and thus their concentrations are increasing . Also called
anthropogenic greenhouse effect or climate change .

global warming. An increase in the average temperature of the Earth's

surface. Global warming is one of the consequences of the enhanced
greenhouse effect and will cause worldwide changes to climate patterns.

greenhouse effect. The trapping and build-up of heat in the lo\.1/er

atmosphere near a planet's surface. Some of the heat flowing back
towards space from the Earth's surface is absorbed by water vapour,
carbon dioxide, methane and other gases in the atmosphere. If the
atmospheric concentration of these gases rises, then theory predicts that
the average temperature of the lo\.1/er atmosphere v,;11 gradually increase.
The greenhouse effect in part explains the temperature differences of
Mars, Venus and Earth.

Sulfur • Most crude oil deposits contain sulfur as an impurity. Oil refineries are increasingly treating the petrol
dioxide, S02 fractions to lower the sulfur content, but some sulfur is still present in most hydrocarbon fuels. When
the fuel is burned, the sulfur also burns, producing sulfur dioxide. Sulfur dioxide can be further oxidised
to sulfur trioxide under suitable conditions.

S(s) + 02(9) SO2(g)

SO2(9) + ½02(9) SQ3(g)

• Both SO2 and SO3 can dissolve in water to form acidic solutions. Hence, when they dissolve in
rainwater, acid rain is produced. This causes various problems, including corrosion of buildings and
statues, killing of plants and trees, and killing of fish through contamination of lakes.

Flue-gas desulfurisation (FGD) is used in power stations to reduce the amount of SO2 reaching the
atmosphere. In this process, the flue gases are passed through a slurry of CaCO3. CaCQ3 (limestone)
is cheap and the CaSO4produced can be sold as gypsum, a component of plaster.
Lead • Lead compounds resulting from leaded petrol are poisonous. Accumulation of lead in the body can lead
compounds to brain damage, especially in young children.

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7.3 Petroleum as a finite resource

(a) Importance of petroleum

• Petroleum (or crude oil} is a natural source of hydrocarbons. It is perhaps the most important
substance consumed in modem society.

o The fuels that are derived from petroleum form a large part of the world's total supply
of energy. Gasoline, kerosene, and diesel oil provide fuel for automobiles, tractors, trucks,
aircraft, and ships. Fuel oil and natural gas are used to heat homes and commercial buildings, as
well as to generate electricity.

o Petroleum also serves as a source of basic raw materials (i.e. chemical feedstocks) for the
chemical industry to produce useful products such as dyes, drugs, plastics, synthetic fibers,
paints, detergents and insecticides.

• Petroleum, like coal, is a fossil fuel. Fossil fuels are formed when marine plants and animals die and
the remains become buried under several thousand feet in the sea beds in the absence of air. Under
the extreme chemically reducing conditions, oxygen and nitrogen are removed from the carbohydrates
and proteins that make up the organisms, and long carbon chains form. This formation of fossil fuels
requires millions of years.

• As a fossil fuel, petroleum is a finite resource. It is present in the Earth in a fixed amount and this
amount is non-renewable and cannot last forever!

• Given our dependence on petroleum, not only for fuel, but also as a chemical feedstock to produce
the many necessities of modern society, it becomes clear that we must not only find alternative
sources of energy but also conserve the remaining limited oil reserves by recycling.

(b) Recycling

• Recycling is the process of converting waste materials into reusable objects. Recycling can ease
major environmental problems. Recycling is an important way of conserving the Earth's natural
resources for future generations. It also helps to cut back the rising amount of waste for disposal.

• Importance of recycling
o Recycling reduces the need for fresh raw materials and so conserves natural resources.

o Recycling reduces the amount of waste materials that go to the landfills and so saves space in
landfills and lowers collection and disposal costs.

o Recycling reduces energy consumption; less energy is required to recycle metals (e.g. A/) than
to produce it from ores.
o Recycling protects the environment.
• It reduces pollution associated with waste such as metal cans, papers and plastics.

• It reduces global warming. This is because with less waste to be disposed by burning, less
fossil fuel is burned at power stations and so less heat-trapping CO2 is released into the
atmosphere.
o Recycling creates green jobs.

-18-
8 IAlkanes - A Summary 1

Main pollutants that are formed when

Alkanes are generally unreacUve. Why?
fossil fuels (e.g. crude oil, natural gas
• Alkanes are non-polar. They do not Be able to and coal) are burnt:
contain any region of high electron elaborate • carbon dioxide (not strictly a
density or electron-deficient sites. and explain. pollutant since it occurs in nature,
• Alkanes contain relatively strong }
but its overproduction can cause
C-H and C-C bonds. problems such as enhanced
greenhouse effect)
• carbon monoxide
Preparation of CH 3CH 3 Reactions of CH 3CH 3 • unburnt hydrocarbons
• nitrogen oxides
CH 2=CH 2 0 2 (in excess) • sulfur dioxide
CO2 + H20
ethene burn

Hi N (or Pt or Pd) Be able to explain/discuss:

heat Br2
(liniting reagent) • catalytic removal of CO, NOx and
CH3CH3 ultraviolet light
CH3CH2Br unburnt hydrocarbons arising from
ethane or heat + HBr the internal combustion engine

Hi Ni (or Pt or Pd) • greenhouse effect and greenhouse

Cl 2 (in excess)
heat '----- ----., CCl3CCl3 gases (e.g. CO2 and CH4)
ultraviolet light
or heat + HCI • enhanced greenhouse effect and
H-C=C- H
global warming
ethyne

Combustion of a hydrocarbon CxHy + (x + r4 ) 02(9) xC02(g) + H20(I)

Combustion of an alkane CnH2n+2 + 3n + 1 02(9) nC02(g) + (n+1)H20(I)

2

Mechanism: Free-radical substitution

Overall reaction:
s~ution of any 12 H. atoms

ultraviolet light CH CH 2CI + HC/

CH3CH3 + C/2 ----- --t 3 UV
k(e
This reaction involves free-radical substitution substlution ot 2 H. atoms

mechanism which consists of the following steps:

~c
Step 1: Initiation Cl
sc,bstilllion or any 2 alOITI$

h 0c
ultraviolet light
Cl- I - - - - - 2 Cl• The11 ltt 3 typt1 of H tlofN. H.. t\ Ind He. Subl~ of
ratio or A;B:C • 8:1: 1

nch 'YP• of H l!Om rt1u k1 In I dlff1r,n1 product.

Step 2: Propagation
(a) CH 3CH 3 + Cl•~ CH3CH2• + HCI Be able to define/explain the following:
(b) CH 3CH 2• + Cl2 CH3CH2CI + Cl• • homolytic bond fission
Then (a), (b), (a), (b), • free radical substitution reaction

Step 3: Termination Be able to explain/discuss:

Cl•+ Cl•~ Ch • petroleum as a finite resource
Cl• + CH 3CH2• CH3CH2C/ • importance of recycling
CH 3CH 2• + CH3CH 2• CH3CH2CH2CH3 (trace quantity)

-19-
 Raffles Institution
Year 5 H2 Chemistry 2022
Tutorial 10: Hydrocarbons -Alkanes

Self-Check Questions

1 (a) Name the following alkanes:

(i) (CH3CH2)3CCH(CH3)CH2CH2CH3

(ii) (CH3)3CCH(CH3)CH(CH2CH3)CH2CH(CH3)CH2CH3

(iii) (iv) (v)

(b) Write the structural formula for the following alkanes:

(i) 2,4,5-trimethylheptane

(ii) 3-ethyl-2,4-dimethylhexane

2 Arrange the following hydrocarbons in order of increasing boiling point and explain your answer:
2-methylhexane, heptane, 3,3-dimethylpentane, hexane and 2-methylpentane

Cyclohexane undergoes reactions (1) and (2) shown below. For each reaction, write a balanced

o
3
equation and name the type of reaction that occurs.
C/
02(9), heat
(1)
C/2(9), UV light
(2) CX Cl

4 Write a balanced equation for the complete combustion of an alkane, CnH2n+2. Hence, sketch a graph
to show how the number of moles of oxygen gas (y-axis) needed for complete combustion varies with
the number of carbon atoms in an alkane (x-axis).
3
5 · 30 cm 3of a gaseous hydrocarbon is completely burnt in 340 cm excess of oxygen and the volume of
residual gases is measured at room temperature and pressure (r.t.p.) . The gases are then shaken
with aqueous sodium hydroxide . Once again, the volume of gas is measured . The results, measured
at r.t.p., are as follow:

Volume of residual gas (before shaking with NaOH) = 250 cm 3

Volume of residual gas (after shaking with NaOH) = 100 cm 3

(a) Using the given data, determine the molecular formula of the hydrocarbon.
(b) Hence, draw and name all the possible isomers of this hydrocarbon.

-1-
6 (2012/1/20]
When heated with chlorine, the hydrocarbon 2,2-dimethylbutane undergo
es free radical
substitution. In a propagation step, the free radical X• is formed by the loss
of one hydrogen
atom.

CH 3
I
CH 3CH 2 -C-C H 3 + Cl• X• + HCl
I
CH 3

How many different forms of X• are theoretically possible?

A 1 B 2 C 3 D 4

7 (2014/1120]
Two structural isomers of molecular formula CeH,, are shown.

P (CH3)2CHCH~H2CH3
Q CH3CH2CH(CH3)CH2CH3

P and Q react with chlorine to form monochloro compounds CeH,JCl.

How many possible structural isomers, each with formula C5H13Cl, could be produce
d by P and
byQ?

isomers formed Isomers formed

byP byQ

A 5 3
B 5 4
C 6 3
D 6 4

-2-
Practice Questions

8 (a) There are 18 constitutional isomers with molecular formula CaH1e and octane is one of them.
Some of these isomers may be distinguished by the number of mono-brominated products they
form upon reaction with bromine in the presence of ultraviolet light.
Draw an isomer with molecular formula CeH1e which reacts with bromine to give
(i) only one mono-brominated product
(ii) three mono-brominated products (ignore stereoisomers).

(b) Octane and bromine dissolved in an inert solvent can react to form 3-bromooctane under
ultraviolet light.
(i) Write a balanced equation for the above reaction.
(ii) Describe what is observed from this reaction.

(iii) Name and describe the mechanism of the above reaction.

(iv) Explain why the reaction requires only a flash of ultraviolet light rather than prolonged
radiation.

(v) Explain why bromine radicals are considered homogeneous catalysts in the propagation
steps.

(vi) How may experimental conditions be adjusted to produce 3-bromooctane and other
monobromooctanes as major products?
(vii) Octane, however, does not react with iodine to form 3-iodooctane or any other substituted
product.

With the aid of suitable bond energy values from the Data Booklet, calculate the enthalpy
change of reaction for the first propagation step of the reaction between octane and iodine
to form 3-iodooctane.
Hence, suggest why it is not possible to make 3-iodooctane by this method.

9 Describe the mechanism for the following reaction.

0 +Br,
UV light
Q-s, + HBr

10 Fis an alkane which contains 83.72% by mass of carbon. When reacted with bromine under ultraviolet
light, F produced only two isomeric mono-brominated compounds G and H. Compound H was chiral.

(a) Suggest the structures of F, G and H, explaining your reasoning.

(b) Suggest, with reasoning, the approximate ratio in which G and Hare formed.

-3-
11 (a) Alkanes are generally considered to be unreactive compounds, showing an inertness to common
reagents such as NaOH, H2S04, and K2Cr2Cn.
Suggest two reasons why these reagents do not attack an alkane such as hexane.

(b) Al~anes react with chlorine in the presence of ultraviolet light. It is found by experiment that, dur!ng
this type of reaction, primary, secondary and tertiary hydrogen atoms are replaced by chlorine
atoms at different rates, as shown in the following table.

reaction relative rate

RCH 3 RCH 2Cl 1
R2CH 2 RiCHCZ 7

R3CH R3CCl 21

Using the above information, and considering the number of hydrogen atoms of each type
(primary, secondary or tertiary) within the molecule, predict the relative ratio of the two possible
products A and B from the chlorination of 2-methylpropane. Explain your answer. [2]

CH 3 CH 3 CH3
I I I
"
CH c-Cl + CH
/"--... / "--... __,.,Cl
H3C CH 3 H3C/ CH 3 H3C CH 2

2-methylpropane A B

(c) Draw the skeletal formulae of four different structural isomers of CsH11C/ that could be obtained
from the chlorination of 2-methylbutane. Indicate any chiral centres in your structures by an
asterisk (*), and hence state the total number of isomers that could be obtained from the
monochlorination of 2-methylbutane. [3]

12 [RI Promo 2017/11/2]

(a) If all the hydrogen atoms were equally reactive, the mono-chlorination of propane should give
a 3:1 ratio of 1-chloropropane to 2-chloropropane. However, an experiment carried out at
25 °C gave 45% 1-chloropropane and 55% 2-chloropropane, via the formation of primary and
secondary free radical intermediates.
(i) Based on the information given above, comment on the relative stability of the primary
and secondary free radical intermediates.

(ii) Given that alkyl groups are electron donating groups, explain your answer to (a)(i).

(iii) Hence, justify why the bond dissociation energy of the (CH3)2CH-H bond is less
endothermic than that of the CH3CH2CHr-H bond.

C-H bond bond dissociation energy / kJ mo1- 1

CH3CH2CHr-H 422.2
(CH3)2CH-H 410.5

(b) Using skeletal formula, describe the mechanism between propane and bromine to form
1,2-dibromopropane.

-4-