ALKENES

Introduction
What are alkenes?

Formulae

Alkenes are a family of hydrocarbons (compounds containing carbon and hydrogen only)
containing a carbon-carbon double bond. The first two are:

Ethene Propene
C2H4 C3H6

The general formula :CnH2n

Note: The table is limited to the first two, because after that there are isomers which affect the
names.

Isomerism in the alkenes

Structural isomerism

All the alkenes with 4 or more carbon atoms in them show structural isomerism. This means
that there are two or more different structural formulae that you can draw for each molecular
formula.

For example, with C4H8, it isn't too difficult to come up with these three structural isomers:
There is, however, another isomer. But-2-ene also exhibits geometric isomerism.

Geometric (cis-trans) isomerism

The carbon-carbon double bond doesn't allow any rotation about it. That means that it is possible
to have the CH3 groups on either end of the molecule locked either on one side of the molecule
or opposite each other.

These are called cis-but-2-ene (where the groups are on the same side) or trans-but-2-ene (where
they are on opposite sides).

Physical properties of the alkenes

Boiling Points

The boiling point of each alkene is very similar to that of the alkane with the same number of
carbon atoms. Ethene, propene and the various butenes are gases at room temperature. All the
rest that you are likely to come across are liquids.

In each case, the alkene has a boiling point which is a small number of degrees lower than the
corresponding alkane. The only attractions involved are Van der Waals dispersion forces, and
these depend on the shape of the molecule and the number of electrons it contains. Each alkene
has 2 fewer electrons than the alkane with the same number of carbons.

Solubility

Alkenes are virtually insoluble in water, but dissolve in organic solvents.

Chemical Reactivity
Bonding in the alkenes

We just need to look at ethene, because what is true of C=C in ethene will be equally true of
C=C in more complicated alkenes.
 Ethene is often modelled like this:

The double bond between the carbon atoms is, of course, two pairs of shared electrons. What the
diagram doesn't show is that the two pairs aren't the same as each other.

One of the pairs of electrons is held on the line between the two carbon nuclei but the other is
held in a molecular orbital above and below the plane of the molecule. A molecular orbital is a
region of space within the molecule where there is a high probability of finding a particular pair
of electrons.

The line between the two carbon atoms

represents a normal bond called a sigma
bond.

The other pair of electrons is found

somewhere in the shaded part above and
below the plane of the molecule. This bond is
called a pi bond. The electrons in the pi bond
are free to move around anywhere in this
shaded region and can move freely from one
half to the other.
The pi bond lie exposed above and below the
rest of the molecule, they are relatively open
to attack by other things.

Sigma and Pi Bonds

There are two types of covalent bonds: sigma (σ) and pi (π) bonds. Sigma
bonds occur when s orbitals, p orbitals pointing along the axis to the other
bonding atom, or hybridized orbitals collide and overlap; the region of
maximum electron density is between the two bonded atoms and lies along
the axis between them. Single-order bonds are always σ bonds. Sigma
bonds are like taking the index finger from each hand and pointing them
directly at each other, so one fingertip touches another. Just as you can
rotate your fingers without losing contact, bonded atoms can rotate freely
about a sigma bond.
Pi bonds occur when p orbitals (usually those left over from orbital
hybridization) perpendicular to the axis of bonding overlap; in this case, the
region of highest electron density is "above" or "sideways from" the axis
between bonding atoms. It is important to note that hybridized or s orbitals
never make π bonds. Pi bonds make up the second bond in a double bond
and the second and third in a triple bond. Pi bonds are like pointing two
fingers at the ceiling and moving them sideways until they touch. Unlike
sigma bonds, pi bonds cannot rotate and maintain the bond; you can see
this in our finger model, as turning your fingers out of alignment breaks the
connection. Therefore, double or triple-bonded atoms cannot rotate relative
to each other.

The reactions of alkenes

Like any other hydrocarbons, alkenes burn in air or oxygen, but these reactions are unimportant.
Alkenes are too valuable to waste in this way.
The important reactions all centre around the double bond.

The main reaction of alkenes is addition

Because of the extra electron density in a C=C double bond, alkenes are attacked by species
which ‘like’ electrons. These species are called electrophiles; they possess a positive
or partial positive charge somewhere in their structure.

Examples include... hydrogen halides, concentrated H2SO4

Typically, the pi bond breaks and the electrons from it are used to join the two carbon atoms to
other things. Alkenes undergo electrophilic addition reactions.

For example, using a general molecule X-Y . . .

Electrophilic addition

1. Attack of pi e onto + species.

2. e move onto the - species making it become –vely charged. A carbocation is
formed during that reaction.
 3. The –vely charged species attacks the carbocation.

Addition to Symmetrical alkenes like ethene

1. Addition of Bromine
a. Liquid Bromine

Reagent: Bromine. (Neat liquid or dissolved in tetrachloromethane, CCl4 )

Condition: Room temperature. No catalyst or UV light required!
Equation: C2H4(g) + Br2(l) ——> CH2BrCH2Br(l) 1,2 - dibromoethane

Mechanism:

TEST FOR UNSATURATION

The addition of bromine dissolved in tetrachloromethane (CCl 4) or water (known as

bromine water) is used as a test for unsaturation. If the reddish-brown colour is removed
from the bromine solution, the substance possesses a C=C bond.
Because the bromine adds to the alkene, it no longer exists as molecular bromine and the
typical red-brown colour disappears

b. Aqueous bromine

Reagent: Bromine. (aq)

Condition: Room temperature. No catalyst or UV light required!

Equation: C2H4(g) + Br2(aq) ——> CH2BrCH2OH(l) 2-bromo ethanol

Mechanism:
2. Addition of hydrogen halides

Reagent: Hydrogen bromide... it is electrophilic as the H is slightly positive

Condition:Room temperature.

Equation: C2H4(g) + HBr(g) ———> C2H5Br(l) bromoethane

Mechanism:

3. Addition of hydrogen – Hydrogenation

Reagent: Hydrogen

Condition: 150 0C, Finely divided Nickel catalyst

Equation:

Used in the manufacture of margarine.

4. Addition of steam – Hydration

Reagent: Steam

Condition: 3300C, 60 atm, conc. H3PO4 deposited on celite as catalyst

Equation:
 This reaction is used in the manufacture of ethanol.

Addition to unsymmetrical alkenes

Problem

• addition of HBr to propene gives two isomeric brominated compounds

• HBr is unsymmetrical and can add in two ways

• products are not formed to the same extent

• the problem doesn't arise in ethene because it is symmetrical.

Mechanism: Two possibilities of reaction:

MARKOWNIKOFF’S RULE

In the electrophilic addition to unsymmetrical alkenes the major product is formed via the
more stable carbocation (carbonium ion)

Carbocation Stability

Build up of charge in one place leads to instability. If it can be spread around or neutralised in
some way, stability is increased. Alkyl groups are electron releasing and can “push” electrons
towards the carbocations thus reducing the charge density.
 least stable most stable

methyl < primary (1°) < secondary (2°) < tertiary (3°)

In the addition to propene, path A involves a 2° carbocation, path B a 1° carbocation.

As the 2° ion is more stable, the major product (i.e. 2-bromopropane) is formed this way.

Path A

Path B

The H in the hydrogen halide will add to the carbon which contains most hydrogen atoms

Reaction rates

Variation of rates when you change the halogen

Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen fluoride reacts much more
slowly than the other three, and is normally ignored in talking about these reactions.

When the hydrogen halides react with alkenes, the hydrogen-halogen bond has to be broken. The
bond strength falls as you go from HF to HI, and the hydrogen-fluorine bond is particularly
strong. Because it is difficult to break the bond between the hydrogen and the fluorine, the
addition of HF is bound to be slow.

Variation of rates when you change the alkene

This applies to unsymmetrical alkenes as well as to symmetrical ones. For simplicity the
examples given below are all symmetrical ones- but they don't have to be.

Reaction rates increase as the alkene gets more complicated - in the sense of the number of alkyl
groups (such as methyl groups) attached to the carbon atoms at either end of the double bond.

For example:

There are two ways of looking at the reasons for this - both of which need you to know about the
mechanism for the reactions.

Alkenes react because the electrons in the pi bond attract things with any degree of positive
charge. Anything which increases the electron density around the double bond will help this.

Alkyl groups have a tendency to "push" electrons away from themselves towards the double
bond. The more alkyl groups you have, the more negative the area around the double bonds
becomes.

The more negatively charged that region becomes, the more it will attract molecules like
hydrogen chloride.

The more important reason, though, lies in the stability of the intermediate ion formed during the
reaction. The three examples given above produce these carbocations (carbonium ions) at the
half-way stage of the reaction:
The stability of the intermediate ions governs the activation energy for the reaction. As you go
towards the more complicated alkenes, the activation energy for the reaction falls. That means
that the reactions become faster.

Other reactions of alkenes –Oxidation

Partial Oxidation

With cold dilute potassium manganate(VII)

Alkenes react with potassium manganate(VII) solution in the cold. The colour change depends
on whether the potassium manganate(VII) is used under acidic or alkaline conditions.

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 (often by adding sodium
carbonate solution), the purple solution first becomes dark green and then produces a dark brown
precipitate.

The full equation depends on the conditions.

Under acidic conditions, the manganate(VII) ions are reduced to manganese(II) ions.

Under alkaline conditions, the manganate(VII) ions are first reduced to green manganate(VI)
ions . . .

. . . and then further to dark brown solid manganese(IV) oxide (manganese dioxide).
Complete Oxidation – Bond cleavage
Hot Acidified Potassium Manganate (VII)

Example 1:
Example 2:

Example 3:
Other reactions of alkenes –Polymerisation
Process • during polymerisation, an alkene undergoes an addition reaction with itself

• all the atoms in the original alkenes are used to form the polymer

• long hydrocarbon chains are formed

the equation shows the original monomer and the repeating unit in the polymer

ethene poly(ethene)

MONOMER POLYMER
 ETHENE POLY(ETHENE

PROPENE POLY(PROPEN
E)

CHLOROETHENE
POLY(CHLOROETHENE)
POLYVINYLCHLORIDE

TETRAFLUOROETHE
POLY(TETRAFLUOROETHE
NE)

Many are prepared by a free radical process involving high pressure, high
temperature and a catalyst. A famous type of catalyst is a Ziegler-Natta
catalyst

MAKING ALKENES IN THE LAB

Dehydration of alcohols using aluminium oxide as catalyst

The dehydration of ethanol to give ethene

This is a simple way of making gaseous alkenes like ethene. If ethanol vapour is passed over
heated aluminium oxide powder, the ethanol is essentially cracked to give ethene and water
vapour.
To make a few test tubes of ethene, you can use this apparatus:

It wouldn't be too difficult to imagine scaling this up by boiling some ethanol in a flask and
passing the vapour over aluminium oxide heated in a long tube.

The dehydration of ethanol to give ethene

Ethanol is heated with an excess of concentrated sulphuric acid at a temperature of 170°C. The
gases produced are passed through sodium hydroxide solution to remove the carbon dioxide and
sulphur dioxide produced from side reactions.

The ethene is collected over water.

The concentrated sulphuric acid is a catalyst. Write it over the arrow rather than in the equation.

Cracking of Hydrocarbons

Conditions: Al2O3/SiO2 ; 450 0C- 500 0C ; 70 atm. pressure