Reactions of Alkenes
Black River
High School
Alkenes
Examples 1
4
3
2 3
1 2
4
but-1-ene OR 1-butene trans-but-2-ene OR trans-2-butene
PHYSICAL PROPERTIES OF ALKENES
Boiling point
o trends are similar to those shown in alkanes
o increases as they get more carbon atoms in their formula
o more atoms means greater intermolecular Van der Waals’ forces
o greater intermolecular force means more energy to separate molecules
o greater energy required means higher boiling point
o the lower members are gases at room temperature and pressure
o cyclohexene C6H10 is a liquid
o for isomers, greater branching means lower boiling point
C2H4 (- 104 °C) C3H6 (- 48°C) ....... C6H10 (83°C)
Melting point general increase with molecular mass
the trend is not as regular as that for boiling point.
Solubility alkenes are non-polar so are immiscible (don’t mix with) with water
miscible with most organic solvents.
ELECTROPHILIC ADDITION MECHANISM
The main reaction of alkenes is addition
The -bond in a C=C double bond is electron-rich, thus alkenes are easily 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 (HX)
• concentrated H2SO4
ELECTROPHILIC ADDITION MECHANISM
The electrophile, having some positive character, is attracted to the alkene.
The electrons in the pi bond come out to form a bond to the positive end.
Because hydrogen can only have two electrons in its orbital, its other bond breaks
heterolytically. The H attaches to one of the carbon atoms.
A carbocation is formed. The species that is left now has a lone pair.
It acts as nucleophile and attacks the carbocation using its lone pair to form a covalent
bond. Overall, there is ADDITION
ELECTROPHILIC ADDITION OF BROMINE
Reagent: Bromine. (dissolved in tetrachloromethane, CCl4 or hexane)
Condition: Room temperature.
Equation: C2H4(g) + Br2(l) ——> CH2BrCH2Br(l) 1,2 - dibromoethane
Mechanism
It is surprising that bromine should act as an electrophile as it is non-polar.
The -bond
polarises the
1,2 - dibromoethane
bromine
molecule
ELECTROPHILIC ADDITION OF BROMINE
It is surprising that bromine should act as an electrophile as it is non-polar.
Explanation ... as a bromine molecule approaches an alkene, electrons in the -bond of the
alkene repel the electron pair in the bromine-bromine bond thus inducing a dipole.
NON-POLAR POLAR
THE ELECTRON PAIR IS NOW NEARER ONE
END SO THE BROMINE MOLECULE IS POLAR
AND BECOMES ELECTROPHILIC.
Curved arrows are used to indicate movement of
electrons.
(Fish hook arrow)
ELECTROPHILIC ADDITION OF BROMINE
TEST FOR UNSATURATION
The addition of bromine dissolved in tetrachloromethane (CCl4) 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.
A Place a solution of
bromine in a test tube
Add the hydrocarbon to
B be tested and shake
If the brown colour
C disappears then the A B C
hydrocarbon is an
alkene
Because the bromine adds to the alkene, it no longer exists as molecular bromine and
the typical red-brown colour disappears
Reaction of Alkenes with Hydrogen Halides
Hydrogen halides (HX): HF, HCl, HBr, HI add across C=C double bond forming
haloalkanes
N.B. Hydrogen halides have permanent dipoles
Partial positive charge Partial negative charge
More electronegative element
pulls electron density towards
it, thus polarizing the molecule
ELECTROPHILIC ADDITION OF HYDROGEN BROMIDE
Reagent Hydrogen bromide... is electrophilic as the H is slightly positive
Condition Room temperature.
Equation C2H4(g) + HBr(g) ———> C2H5Br(l) bromoethane
Mechanism
Step 1 As the HBr nears the alkene, one of the carbon-carbon bonds breaks
The pair of electrons attaches to the slightly positive H end of H-Br.
The HBr bond breaks to form a bromide ion (an example of heterolytic fission).
A carbocation (positively charged carbon species) is formed.
Step 2 The bromide ion behaves as a nucleophile and attacks the carbocation.
Overall there has been addition of HBr across the double bond.
ADDITION TO UNSYMMETRICAL ALKENES
Problem • 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 (electrophilic addition)
Two possibilities
2-bromopropane
(major product)
propene
1-bromopropane (little or none forms)
In the addition to propene, path A involves a 2° carbocation, path B a 1° carbocation.
As the 2° ion is more stable, the product is 2-bromopropane.
MARKOVNIKOV’S RULE
A Russian scientist, Markovnikov, investigated the products of the addition of hydrogen halides to
alkenes. He found that, when two products were formed, one was formed in a larger quantity. His
original rule was based only on this reaction. The modern version uses carbocation stability as a
criterion for predicting the products.
“In the electrophilic addition to 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°)
Electrophilic Addition Reactions with Other Hydrogen Halides
Hydrogen fluoride, hydrogen chloride and hydrogen iodide all add on in
exactly the same way as hydrogen bromide.
The only differences lie in the rates of reaction:
Oxidation of Alkenes with Cold Acidified potassium manganate(VII) solution
• The purple solution becomes colourless
ethene
ethane-1,2-diol
Other alkenes react in just the same way.
Oxidation Of Alkenes
With Hot Concentrated Acidified Potassium Manganate(VII) Solution
• the carbon-carbon double bond is broken and replaced 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.
With Hot Concentrated Acidified Potassium Manganate(VII) Solution
Example
propanone
o If there are two alkyl groups at one end of the bond, that part of the molecule will give a ketone.
Note: A single product is formed because either side of the double bond in the alkene
are identical
With Hot Concentrated Acidified Potassium Manganate(VII) Solution
Example
ethanal propanone – a
– an aldehyde ketone
Aldehydes are readily oxidised to give carboxylic acids,
ethanoic acid
o If there is one alkyl group and one hydrogen at one end of the bond, that part of the
molecule will give a carboxylic acid.
With Hot Concentrated Acidified Potassium Manganate(VII) Solution
Example
• You might have expected that this would produce methanal which would oxidise to
methanoic acid. 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.
o If there are two hydrogens at one end of the bond, that part of
the molecule will give carbon dioxide and water.
ELECTROPHILIC ADDITION OF SULPHURIC ACID
Reagent Concentrated sulphuric acid (85%)
Conditions 0°C
Equation C2H4(g) + H2SO4(conc) ——> C2H5OSO2OH(aq)
ethyl hydrogensulphate
Hydrolysis the product can be converted to ethanol by boiling with water.
C2H5OSO2OH(aq) + H2O(l) ——> H2SO4(aq) + C2H5OH(l)
HYDROGENATION
Conditions nickel catalyst - finely divided/150C/500kPa
Equation C2H4(g) + H2(g) ———> C2H6(g) ethane
Ni
ethene ethane
Use margarine manufacture
o Vegetable oils consist mostly of unsaturated hydrocarbon chains.
o They are hardened by reducing the number of double bonds.
o Hydrogenation of fats also produces trans-fats which are harmful to health
o They contribute to heart and circulatory disease.
Hydrogenation of Fats and Oils
Desirable product
Trans fats
Undesirable by-products
