ALKANES AND

ALKENES
ALKANES
ALKANES

• Alkanes are saturated hydrocarbons

• Has only single C-C bonds
• Because they contain only C¬C and C¬H bonds, most alkanes are relatively unreactive.
• At room temperature, for example, they do not react with acids, bases, or strong oxidizing
agents.
• Their low chemical reactivity, is due primarily to the strength and lack of polarity of C¬C and
C¬H bonds.
• Alkanes are not completely inert, however. One of their most commercially important
reactions is combustion in air, which is the basis of their use as fuels.
ALKANES
fraction uses

Liquefied petroleum gases Camping gas, cooking gas

Petrol Fuel for cars, motorbikes and

COMBUSTION OF ALKANES machines
1. Alkanes as fuels
Kerosine Fuel for aeroplanes, lamps,
• Many of the fractions ovens
produced from crude oil are
Diesel Fuel for lorries, and central
used as fuels. These fractions heating systems
include:
Fuel oil Fuel for ships, power stations

Wax Fuel for candles

 ALKANES
• A fuel is a something that can be changed in a reacting
vessel to produce useful energy.
• Hydrocarbons, and especially alkanes, will react with
oxygen in the air to give carbon dioxide and water. A Reaction Enthalpy change/
reaction with oxygen is known as combustion. As alkanes
are unreactive the reaction needs heat or a spark to get
kJmol-1
going. CH4 + 2O2 → CO2 -890
• These reactions are very exothermic, which means that + 2H2O
heat energy is released. This heat energy can be used for C4H10 + 6½O2 → -2877
direct heating (eg camping gas, central heating, candles). It 4CO2 + 5H2O
can also be converted into mechanical energy (eg cars,
lorries, ships), or even electrical energy (eg power C8H18+ 12½O2 → -5470
stations). 8CO2 + 9H2O
• Typical examples of combustion reactions include:
• The release of heat energy during these combustion
reactions results in their widespread use as fuels.
• Incomplete combustion – with a limited supply of oxygen,
CO is produced instead of CO2.
 ALKANE REACTION WITH HALOGENS
• Chloroalkanes can be made from alkanes in a reaction known as a free radical substitution reaction.

CH4 + Cl2 → CH3Cl + HCl

Mechanism 1: free radical substitution
Free radical substitution reactions proceed in three stages: initiation, propagation and then termination.
• Initiation
Initiation is the production of free radicals by homolytic fission of a covalent bond.
Most bonds do not undergo homolytic fission under normal conditions. Generally, UV light is required.
UV

Cl2 Cl Cl
This process is called photolysis
Chlorine radicals are very reactive
ALKANE REACTION WITH HALOGENS

• Propagation
Propagation is the reaction of a free radical with a molecule to produce another free radical.
The reaction involves two propagation steps:
1. A chlorine radical collides with a methane molecule with sufficient energy to remove a
hydrogen atom forming a methyl radical (•CH3) and a molecule of HCl.
Cl + H CH3 HCl + CH3 .
2. Methyl redicals are also very reactive and eill remove a chlorine atom from a chlorine
molecule, forming a chloromethane molecule and another chlorine radical

CH3 . + Cl Cl CH3Cl + Cl
ALKANE REACTION WITH HALOGENS

• Termination
Termination is the combination of two free radicals to form a single molecule.

Cl + Cl Cl2
• Note that the Cl radicals are recycled during the propagation steps, so the reaction only
requires a very small number of Cl-Cl bonds to undergo fission for the reaction to
proceed.
ALKANE REACTION WITH HALOGENS
• By-products in free radical substitution:
Chloromethane is not generally the only organic product of this reaction. Free radical reactions tend to result in a variety of different products.
i) Different propagation steps
• The propagation steps can continue beyond the formation of methane, and can result in the formation of dichloromethane,
trichloromethane or tetrachloromethane:

Cl + H CH2Cl HCl + CH2Cl .

. CH Cl .
•
2 + Cl Cl CH2Cl2 + Cl
These further propagation steps are likely if excess chlorine is used. If excess methane is used, then chloromethane is likely to be the major
product.
ii) Different termination steps
• It also possible to get other products from alternative termination steps:
• Thus when methane reacts with chlorine, a variety of products are formed including chloromethane, dichloromethane and ethane.
• In order to ensure that chloromethane is the major product, it is important to use excess methane.

.CH .CH
3 + 3 CH3CH3
ALKENES

• Alkenes are unsaturated hydrocarbons that contain at least one C=C bond. The simplest
• alkene is CH2=CH2, called ethene (IUPAC) or ethylene (common name), which plays
important roles as a plant hormone in seed germination and fruit ripening.
• The next member of the series is CH3¬CH=CH2, called propene or propylene.
• Alkenes with four or more carbon atoms have several isomers.
 STRUCTURE AND BONDING IN ALKENES
• Alkenes are hydrocarbons containing a carbon-carbon double bond. The atoms around the carbon-carbon double bond adopt a planar arrangement and the bond
angle is 120o.
• In double bonds, the first bond involves an overlap of atomic orbitals directly in between the nuclei of the two atoms:

• This is known as a σ-bond. All single covalent bonds are σ -bonds.

• The second bond, however, cannot bond in the same place. Instead two p-orbitals overlap above and below the internuclear axis:

• This is known as a 𝜋-bond. All double covalent bonds consist of one 𝜋 -bond and one σ -bond.

• Since these orbitals overlap in two places, it is not possible to rotate a 𝜋 -bond about its axis without breaking the bonds. Resulting in restricted rotation about the
double bond.
• If both carbon atoms on either side of the bond are attached to different groups, then two different structures arise which cannot be interconverted. This is
known as cis-trans isomerism.
• Cis-trans isomerism falls under Stereoisomerism
• Stereoisomers are molecules with the same molecular formula and the same arrangement of covalent bonds but with different arrangements
of the atoms in space.
STEREOISOMERISM- GEOMETRIC ISOMERISM
CH3 CH3
C C
H H

• The diagram shows two molecules: cis-but-2-ene

Br Br Br H

CH3 H
C C C C
C C
H CH3
H H H Br
cis-1,2-dibromoethene trans-1,2-dibromoethene
-trans-but-2-ene
The cis-1,2 dibromoethane has both bromine atoms on the same side
The trans-1,2 dibromoethane has both the bromine atoms on opposite sides.
The arrangements of the two molecules gives them different physical and some chemical properties.
They are two different molecules.
 GEOMETRIC OR NOT H H H Cl

C C C C

Although we've swapped the right-hand groups H Cl H H

around, these are still the same molecule. To get from

one to the other, all you would have to do is to turn Cl H Cl Cl

the whole model over. C C C C

You won't have geometric isomers if there are two H Cl H H

groups the same on one end of the bond - in this

case, the two pink groups on the left-hand end.
Cl H Cl Br

There must be two different groups on the left-hand C C C C

carbon and two different groups on the right-hand
one. H Br H H
 NOMENCLATURE OF ALKENES
IUPAC Rules for Alkene Nomenclature

1. Alkenes gets the suffix (ending) ‘’ene’’

2. The longest chain chosen for the root name must include both carbon atoms of the double bond.
3. The root chain must be numbered from the end nearest a double bond carbon atom. If
the double bond is in the center of the chain, nearest substituent rule is used to determine the
end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double bond is used as the
double bond locator.
5. If more than one double bond is present the compound is named as a diene, triene or equivalent
prefix indicating the number of double bonds, and each double bond is assigned a locator number.
 NOMENCLATURE OF ALKENES
Rule 1 Rule 2
The parent structure is the longest chain containing both
Name Molecular formula carbon atoms of the double bond.
• Ethene C2H4
butane: C4H10( CH3CH2CH2CH3)
• Propene C3H6 butene: C4H8 ( CH2=CHCH2CH3)
• Butene C4H8 But-1-ene
• Pentene C5H10
If the double bond is not terminal (if it is on a carbon
• Hexene C6H12
somewhere in the center of the chain) then the carbons should
• Heptene C7H14 be numbered in such a way as to give the first of the two
• Octene C8H16 double-bonded carbons the lowest possible number, and that
• Nonene C9H18 number should precede the "ene" suffix with a dash, as shown
below.
• Decene C10H20

correct: pent-2-ene ( CH3CH=CHCH2CH3 )

incorrect: pent-3-ene ( CH3CH2CH=CHCH3)
NOMENCLATURE OF ALKENES

Rule 5
• If there is more than one double bond in an alkene, all of the bonds should be numbered
in the name of the molecule - even terminal double bonds. The numbers should go from
lowest to highest, and be separated from one another by a comma. The IUPAC numerical
prefixes are used to indicate the number of double bonds.

• octa-2,4-diene: CH3CH=CHCH=CHCH2CH2CH3
• deca-1,5-diene: CH2=CHCH2CH2CH=CHCH2CH2CH2CH3
 EXAMPLES

Name the following structures

1-pentene or pent-1-ene 2-ethyl-1-hexene or 2-ethylhex-1-ene

4-methylpent-1-ene
Draw a structure for 4-methyl-2-pentene.
EXAMPLES

trans-but-2-ene

cis-3-methylhex-3-ene

trans-3-methylhex-3-ene
 QUESTIONS

Which of the following can have cis/trans isomers? Draw their isomers.
(CH3CH2)CH=CH2, (CH3CH2) 2C=CHCH3, (CH3CH2)CH=CHCH3
Name the following compounds, with cis/trans nomenclature.
ANSWERS

The last compound in the list can be a cis/trans isomer

A trans-4-methyl-2-hexene
B cis-2,5-dibromo-3-hexene
CHEMICAL PROPERTIES OF ALKENES
• The presence of the C=C bond gives alkenes a number of chemical properties that are not seen in
alkanes.

• i) Since the alkene contains 𝜋-bonds, it is possible to break the 𝜋 -bond and form σ-bonds
with other species without forcing any atoms on the molecule to break off. As a result alkenes
(unlike alkanes) are capable of undergoing addition reactions. Molecules which contain 𝜋 -bonds
and which can hence undergo addition are said to be unsaturated. Molecules which do
not contain 𝜋 -bonds and which hence cannot undergo addition are said to be saturated.
• Alkenes are unsaturated and can hence undergo addition.
• Addition is the combination of two or more molecules to form a single molecule.
• Addition reactions are generally faster than substitution reactions since only weak 𝜋 -bonds are broken,
rather than stronger σ -bonds.
CHEMICAL PROPERTIES OF ALKENES

ii) The 𝜋-bond in an alkene is an area of high electron density. It can thus attract electrophiles and
undergo heterolytic fission.
• Alkenes can also undergo homolytic fission

Alkenes can thus react in two ways:

- by free radical addition
- by electrophilic addition

• The ability of alkenes to undergo addition, and their ability to react with electrophiles as well as free radicals,
means that they are much more reactive than alkanes.
ELECTROPHILIC ADDITION REACTIONS OF
ALKENES
• In the presence of electrophiles, the C=C 𝜋-bond tends to undergo electrophilic
addition.

• Possible electrophiles are hydrogen halides (H-Cl, H-Br and H-I) and halogens (Br-Br, Cl-
Cl and I-I).
• Alkenes also undergo an electrophilic addition reaction with H2SO4.
 ELECTROPHILIC ADDITION REACTIONS OF
• ALKENES
with hydrogen halides
Eg CH2=CH2 + H-Br → CH3CH2Br
• The H in the H-X bond has a positive dipole and is attacked by the pair of electrons on the C=C bond, which
undergoes heterolytic fission:

C C
+
C C
+
H
H
-
X -
• Note that the curly arrow indicates the movement of+ a pair
X
of electrons.
• The halide ion then attacks the carbocation to form a haloalkane:

+
C C C C
H X
- H
:X
• This reaction is fairly quick and takes place readily at room temperature.
ELECTROPHILIC ADDITION REACTIONS OF ALKENES
with halogens
Eg CH2=CH2 + Br2 → CH2BrCH2Br
• The Br-Br molecule is non-polar but in the presence of alkenes the electrons move to one side of the molecule and it
acquires a temporary dipole (in other words a dipole is induced by the alkene). The δ+ve Br is then attacked by the alkene:

C C
+
C
+ C C C C
C
+ Br Br
Br Br : Br Br
-
Br + Br
-

• A dibromoalkane is formed. The Br2 should be dissolved in water or an organic solvent, and is decolorised during the
reaction. (orange to colourless).
• The reaction is fairly quick and takes place readily at room temperature.
• If bromine solution is added to an alkene and the mixture shaken, it will thus decolorise and this is a good test for an
alkene.
ELECTROPHILIC ADDITION REACTIONS OF ALKENES
• with H2SO4
eg CH2=CH2 + H2SO4 → CH3CH2HSO4 C C
+
C C C C
Alkenes will undergo an electrophilic addition reaction with cold concentrated +
sulphuric acid:
H
H
.. H O
- O- O
O O S
O S O OH
S O OH
O OH

If the mixture is then warmed and water added, the H2SO4 group will be replaced by an OH group and an alcohol will be formed:
C C O O H O
H H O
H
S + O
C C O H + S
HO O H O O
H

• This is known as a hydrolysis reaction. Hydrolysis means using water to break covalent bonds.
• The overall reaction is thus:
H H C C
C C + O H
O
H
• This is a two step reaction:
• Step 1: cold concentrated H2SO4
• Step 2: warm and add H2O
• It is a useful way of converting alkenes into alcohols in the laboratory.
 UNSYMMETRICAL ALKENES

• Unsymmetrical alkenes are those in which the two carbon atoms in the double bond are not
attached to the same groups.
• Eg propene Eg but-1-ene
H H
H H
C C
H C C
CH3
H CH2CH3
• Eg 2-methylpropene Eg 2-methylbut-1-ene

H CH3 H CH3
C C C C
H CH3 H CH2CH3
UNSYMMETRICAL ALKENES Example ethene Eg but-2-ene
H H
• Alkenes in which both carbon atoms are H CH3
C C C C
attached to the same groups are known as
H H H CH3
symmetrical alkenes.
E.g. propene with hydrogen bromide
• If unsymmetrical alkenes react with
Route 1:
unsymmetrical electrophiles such as H-X or H3C H
H2SO4, there are two possible products C C H CH3 H
H3C
H H +
C C H H C C H
H
• The two products are not formed in equal H
H
Br H
..
quantities. The likelihood of one product being Br Br

formed over the other depends on the Propene → 2-bromopropane

stability of the carbocation intermediate.
Route 2:
H3C H
C C CH3 H CH3 H
H H +
H C C H H C C H
H H Br
H
..
Br
Br
Propene → 1-bromopropane
UNSYMMETRICAL ALKENES
• In route 1, the intermediate is a secondary carbocation, as the carbon holding the positive charged is attached to two
other carbon atoms:
H
H3C +
C C H
H
H

• In route 2, the intermediate is a primary carbocation, as the carbon holding the positive charge is attached to one other
carbon atom:
CH3 H
+
H C C H
H

• Secondary carbocations are more stable than primary carbocations.

• Tertiary carbocations are even more stable than secondary cations.
• Therefore the product of route 1 (2-bromopropane) is a more likely product than the product of route 2 (1-
bromopropane).
• Thus 2-bromopropane will be the major product and 1-bromopropane will be the minor product.
MARKOWNIKOFF'S RULE

• The more stable carbocation will be the one which is more highly substituted.
• The more electronegative part of the electrophile will thus always attach itself to the
more highly substituted carbon atom.
• This is known as Markownikoff's rule: "The more electronegative part of the electrophile
will usually attach itself to the more highly substituted carbon atom".
• The major product of the addition reaction is known as the Markownikoff product.
• The minor product of the addition reaction is known as the anti-Markownikoff product.
MARKOWNIKOFF'S RULE
• Eg but-1-ene + H-Br

CH3CH2 H
C C CH3CH2
H H
H H
CH3CH2 +
C C H H C C H
H
H H
.. Br H
Br Br
secondary carbocation major product

CH3CH2 H CH3CH2
C C H CH3CH2
H
H H +
H C C H H C C H
H H Br
H
..
Br Br
primary carbocation minor product
• The major product is 2-bromobutane.
• The minor product is 1-bromobutane.
MARKOWNIKOFF'S RULE CH3 H
H
CH3 H
C C
CH3 CH3 C C H
C C H
CH3 CH3 +
CH3 CH3
• Eg 2-methylbut-2-ene + H2SO4, then warm and dilute O CH3 OH
H O
S
H O O tertiary carbocation major product

CH3 H CH3 H CH3

C C
CH3 CH3 C C H
C C H
CH3 CH3 +

• The major product is 2-methylbutan-2-ol

H
CH3 OH CH3
H O O
S
H O O
• The minor product is 3-methylbutan-2-ol
secondary carbocation minor product

• Symmetrical alkenes only give one product when electrophiles are added. Unsymmetrical alkenes only give
one product if the electrophile is symmetrical
• (Eg propene Br2).
• Thus two products are only obtained when both the alkene and the electrophile are unsymmetrical. In such
cases the identity of the major and minor products can be predicted by Markownikoff's rule.
OTHER ADDITION REACTIONS OF ALKENES

addition of steam (hydration)

• When alkenes are treated with steam at 300 oC, a pressure of 60 atmospheres and a
phosphoric acid (H3PO4) catalyst, the H2O is added across the double bond and an
alcohol is formed in a reaction known as hydration:
H H
C C + O C C

OH H

Eg CH2=CH2 + H2O → CH3CH2OH

• This is a common industrial method for the production of pure ethanol.
 OTHER ADDITION REACTIONS OF ALKENES
Oxidation of alkenes with cold dilute potassium manganate(VII) solution

• Alkenes react with potassium manganate(VII) solution in the cold.

• If the potassium manganate(VII) solution is acidified with dilute sulphuric acid, the purple solution
becomes colourless.
• If the potassium manganate(VII) solution is made slightly alkaline (adding sodium carbonate solution),
the purple solution first becomes dark green and then produces a dark brown precipitate.
 OTHER ADDITION REACTIONS OF ALKENES
Oxidation of alkenes with cold dilute
potassium manganate(VII) solution

• Manganate(VII) ions are a strong oxidising

agent, and in the first instance oxidise
ethene to ethane-1,2-diol (old name:
ethylene glycol).
Looking at the equation purely from the point
of view of the organic reaction: OH
- 2+
• Under acidic conditions, the manganate(VII) 5 H2C CH2 + 2 H2O + 2MnO 4 + 6 H+ 5 CH2 CH2 + 2 Mn

ions are reduced to manganese(II) ions. HO

• Under alkaline conditions, the OH

manganate(VII) ions are first reduced to - – -
H2C CH2 + 2MnO 4 + 2HO CH2 CH2 + 2 MnO 4
green manganate(VI) ions . . . dark green
HO
solution
 OTHER ADDITION REACTIONS OF ALKENES

Oxidation of alkenes with cold dilute potassium manganate(VII) solution

• eventually you get dark brown solid manganese(IV) oxide (manganese dioxide) formed. The overall equation
for the formation of this from the manganate(VII) ions is:
OH
- –
3H2C CH2 + 2MnO 4 + 4 H2O 3 CH2 CH2 + 2 MnO 2 + 2HO
HO
dark brown
solution

• This last reaction is also the one you would get if the reaction was done under neutral conditions.
 OTHER ADDITION REACTIONS OF ALKENES

Oxidation of alkenes with hot concentrated acidified potassium manganate(VII) solution

If you are using hot concentrated acidified potassium manganate(VII) solution, what you finally end up with
depends on the arrangement of groups around the carbon-carbon double bond.
• The formula below represents a general alkene. In organic chemistry, the symbol R is used to represent
hydrocarbon groups or hydrogen in a formula when you don't want to talk about specific compounds. If
you use the symbol more than once in a formula (as here), the various groups are written as R1, R2,
etc.
OTHER ADDITION REACTIONS OF ALKENES
Oxidation of alkenes with hot concentrated acidified potassium manganate(VII) solution

• The acidified potassium manganate(VII) solution oxidises the alkene by breaking the carbon-carbon
double bond and replacing it with two carbon-oxygen double bonds.
• The products are known as carbonyl compounds because they contain the carbonyl group, C=O.
• Carbonyl compounds can also react with potassium manganate(VII), but how they react depends on what
is attached to the carbon-oxygen double bond.
• So we need to work through all the possible combinations.
 OTHER ADDITION REACTIONS OF ALKENES
Oxidation of alkenes with hot concentrated acidified potassium manganate(VII) solution
• Carbonyl compounds which have two hydrocarbon groups attached to the carbonyl group are called ketones.
Ketones aren't that easy to oxidise, and so there is no further action.
• If the groups attached either side of the original carbon-carbon double bond were the same, then you would end up
with a single ketone. If they were different, then you would end up with a mixture of two.
• For example:

• In this case, you would end up with two identical molecules called propanone. On the other hand, if one of the
methyl groups in the original molecule was replaced by an ethyl group, you would get a mixture of two different
ketones - propanone and butanone.
O

p ro p a n o n e b u ta n o n e

• What would you get if there was a methyl and an ethyl group on both sides of the original carbon-carbon double
bond? Again, you would get a single ketone formed - in this case, butanone.
 OTHER ADDITION REACTIONS OF ALKENES
If a product has one hydrocarbon group and one hydrogen
• For example, suppose the first stage of the reaction was:

• In this case, the first product molecule has a methyl group and a hydrogen attached to the carbonyl group. This
is a different sort of compound known as an aldehyde.
• Aldehydes are readily oxidised to give carboxylic acids, containing the -COOH group. So this time, the reaction
will go on a further step to give ethanoic acid, CH3COOH.

• The acid structure has been turned around slightly to make it look more like the way we normally draw acids,
but the net effect is that an oxyge has been slotted in between the carbon and hydrogen.
• The overall effect of the potassium manganate(VII) on this kind of alkene is therefore:
•
•
• If a product has two hydrogens but no hydrocarbon group
• You might have expected that this would produce methanoic acid, as in the equation:

• But it doesn't! That's because methanoic acid is also easily oxidised by potassium
manganate(VII) solution. In fact, it oxidises it all the way to carbon dioxide and water.
• So the equation in a case like this might be, for example:
QUESTION

The alkene C4H8 has three structural isomers:

Work out the isomers and which of these would give each of the following results if they were
treated with hot concentrated potassium:
• Isomer A gives a ketone (propanone) and carbon dioxide.

• Isomer B gives a carboxylic acid (propanoic acid) and carbon dioxide.

• Isomer C gives a carboxylic acid (ethanoic acid).

ANSWER

• Acids are produced when there is a hydrogen atom attached to at least one of the
carbons in the carbon-carbon double bond.
• Since in C there is only one product, the alkene must be symmetrical around the double
bond. That's but-2-ene.
• If you have got two hydrogens at one end of the bond, this will produce carbon dioxide. A
is 2-methylpropene,
• because the other molecule is a ketone. B must be but-1-ene because it produces carbon
dioxide and an acid.