ALKANES,

ALKENES,
ALKYNES
NOMENCLATURE, STRUCTURES AND ISOMERISM
Organic Chemistry
The study of carbon compounds.
Over 10 million compounds naturally exist
More than 300 000 are synthesized
 Inorganic vs Organic
◦ oxides of carbon (CO2, CO) Hydrocarbons containing
CxHy
◦ carbonates,bicarbonates
(NaHCO3,CaCO3)

◦ cyanides (NaCN, etc)

◦ any carbon attached to a

metal and no H
Origin of organic compounds
Originally from “organic” meaning life
Not just chemistry of life, chemistry of carbon
Naturally occurring organic compounds are found in plants,
animals, and fossil fuels
All of these rely on the “fixing” of C from CO2
Synthetic organic compounds are derived from fossil fuels or
plant material
The diversity of carbon compounds is based on
the fact carbon atoms Form 4 Bonds
Forms strong covalent and nonpolar bonds with itself
and other elements
Carbon molecules form complex 3-D shapes

Common Molecular Shapes

Tetrahedral

Trigonal planar

Linear

Angular

Trigonal pyramidal
 Simplest Hydrocarbons
Alkanes C C Alkenes C C
H H H H H H H H
H C C C C C H H C C C C C H
H H H H H H H H H H

Alkynes C C Aromatics H
H C H
H H H C C
H C C C C C H C C
H C H
H H H
H
Alkanes = CnH2n+2

Alkenes = CnH2n

Alkynes = CnH2n-2
ALKANES, ALKENES, ALKYNES AND
CYCLOALKANES ARE HYDROCARBONS
(COMPOUNDS CONTAINING ONLY
CARBON AND HYDROGEN).
EACH OF THESE FORM A HOMOLOGOUS
SERIES (A GROUP OF ORGANIC
COMPOUNDS HAVING A COMMON
GENERAL FORMULA/ OR IN WHICH EACH
MEMBER DIFFERS FROM THE NEXT BY A
– CH2
THE HYDROCARBONS MAY BE SATURATED
(CONTAINS ONLY SINGLE BONDS
BETWEEN CARBON-CARBON ATOMS/
CARBON ATOMS BONDED TO THE
MAXIMUM NUMBER OF HYDROGENS)
OR UNSATURATED (CONTAINS AT LEAST
A DOUBLE BOND BETWEEN C-C ATOMS)
Also called paraffins.
A group of saturated hydrocarbons with the
general formula Cn H2n+2 .
They form a homologous series.
Straight chain alkanes have their carbon
atoms bonded together to give a single
chain
Alkanes may also be branched.

ALKANES: NOMENCLATURE
 Hydrocarbon names are based on:
1) type,
2) # of carbons,
3) side chain type and position

1) name will end in -ane, -ene, or -yne

2) the number of carbons is given by a “prefix”
1 meth- 2 eth- 3 prop- 4 but- 5 pent- 6 hex-
7 hept- 8 oct- 9 non- 10 dec-
Actually, all end in a, but a is dropped when next
to a vowel. E.g. a 6 C alkene is hexene
NAMING (GENERAL)
Determine the longest continuous chain
(not always straight) in the molecule. The
base name of the hydrocarbon is the
name of the longest chain.
IUPAC system
Name any chain branching off the longest
chain as an alkyl group (e.g., methyl,
ethyl etc)
The complete name of a branch requires a
number that locates the branch on the
longest chain.
Therefore number the chain in whichever
direction gives the smaller number for all
branches.

IUPAC SYSTEM
6. When two or more branches are identical, use
prefixes (di-, tri-, etc.) (e.g. 2,4-
dimethylhexane). Numbers are separated with
commas. Prefixes are ignored when
determining alphabetical order. (e.g. 2,3,5-
trimethyl-4-propylheptane)
7. When identical groups are on the same
carbon, repeat the number of this carbon in the
name. (e.g. 2,2-dimethylhexane)
Where there are two or more
different alkyl branches, the name
of each branch, with its position
number precedes the name. the
branch names are placed in
alphabetical order.
Both groups are unsaturated hydrocarbons.
Each group is a homologous series.

The main chain is defined as the chain

containing the greatest number of
double/tripple bonds
We number the position of the
double/tripple bond so that it has
the lowest numbers.
ALKENES
alkynes
 Naming side chains
Example: name the following structure
CH2 CH2 CH3

CH3 CH2 C CH2 C CH3

CH3

Step 1 – Identify the correct functional

group
 CH2 CH2 CH3

CH3 CH2 C CH2 C CH3

CH3

Step 2 - find the longest chain

 CH2 CH2 CH3

CH3 CH2 C CH2 C CH3

CH3

Step 3 - add the prefix naming the longest

chain
 CH2 CH2 CH3

CH3 CH2 C CH2 C CH3

CH3

Step 4 - number the longest chain

with the lowest number closest to
the double bond
 CH2 CH2 CH3
1 5 6
CH3 CH2 C CH2 C CH3
2 3 4
CH3

Step 5 - add that number to the

name
 CH2 CH2 CH3
ethyl 1 5 6
CH3 CH2 C CH2 C CH3
2 3 4 methyl
CH3
methyl
Step 6 - Name the side chains
 CH2 CH2 CH3
ethyl 1 5 6
CH3 CH2 C CH2 C CH3
2 3 4 methyl
CH3
methyl
Step 7 - Place the side chains in
alphabetical order & name the
compound
 H 3C CH2 CH2 CH3
H3 C CH2
CH CH CH2 CH3
CH CH3 H3C CH
H2C CH2 CH3
CH3
CH3 CH3 CH3
CH3 CH2 CH CH CH CH2 CH CH3
CH2CH3
1 CH2 CH2 CH2 CH3
CH3 CH2 CH2 CH2

2 CH3 4
CH CH2 CH2 CH3
CH3 CH2 CH CH2 CH3
CH3 H2C

CH
3 CH3 H2C CH2
CH3 CH2 CH CH C CH3 CH2 CH

CH3 CH2 CH3

9 1
0 H3C CH2 CH2 CH3

H3C CH2 CH CH CH2 CH3

CH CH3 H3 C CH
H2C CH2 CH3
CH3

1 CH3 CH3 CH3

1
CH3 CH2 CH CH CH CH2 CH CH3
CH2CH3
 CH3

H3C C CH CH CH3 CH3

H2C CH2
H2C
CH3 CH3
CH CH
CH
H3C H3C

CH2 C C
CH2 CH3
A GOOD TIME TO INTRODUCE ISOMERS
(COMPOUNDS WITH THE SAME
MOLECULAR FORMULA BUT DIFFERENT
STRUCTURAL FORMULAE)
TRY THE FOLLOWING:

ISOMERS
 We study three particular
reaction cases:
Substitution
Addition
Eliminatio
Combustion

Reactions of alkanes & alkenes

Substitution (of H,
commonly by Cl or Br)
Combustion (conversion to
CO2 & H2O)

Reactions of alkanes
Combustion
When alkanes are heated in a plentiful
supply of air, combustion occurs
Alkanes are energetically unstable withrespect to water and carbon
dioxide

They only burn when they are in the

gaseous state

Explain what happens when a candleburns!

 2 C4H10(g) + 13 O2(g) 8 CO2(g) + 10
H2O(g)
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18
H2O(g)
Reactions with chlorine
Alkanes only react with chlorine when a
mixture of the two is exposed to sunlight
or ultraviolet light
The light provides the energy required to
break the very strong bonds
This is an example of a substitution
reaction

SUBSTITUTION
In the presence of light, or at high
temperatures, alkanes react with
halogens to form alkyl halides. Reaction
with chlorine gives an alkyl chloride.

CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)

Cracking happens when alkanes are
heated in the absence of air
The products of the cracking of long-chain
hydrocarbons are shorter chain molecules
Ethane is cracked industrially to produce
ethene

Cracking
Alkanes are non polar so they are
insoluble in water but soluble in each
other.
Low molecular alkanes are gases.
Boiling points increase with increasing
chain length (molecular weight) for the
first few members
Boiling points decrease with increasing
number of branches.(Explain this in terms
of Van der Waals’ forces and surface area.

PHYSICAL PROPERTIES
 Melting and boiling points increase with
increased molecular weight (Methane bp.
-164°C, decane bp. 174°C)
While boiling point decrease with chain
branching (decrease in surface area),
melting
points increase
· Alkanes are less dense than water and
swim on top of water
alkenes: preparation and
reactions
 1. Heat a concentrated solution of
Twopotasium /sodiumalkenes:
ways of making hydroxide in alcohol
(alcoholic KOH) with a haloalkane
(halogenoalkane)

This is dehydrohalogenation (removal of

hydrogen and halogen)
2. Heat concentrated sulphuric acid with
the alcohol- dehydration. THE ACID IS A
DEHYDRATING AGENT

Alkenes: Preparation and

reactions
i) Dehydration of alcohols

conc. H2SO4
R-CH2-CH 2- R-CH=CH2 +
OH H2O
ii) Dehydrohalogenation of haloalkanes
NaOH/ethan
R-CH2-CH2-X ol R-CH=CH2 + HX
reflux

NaOH can be replaced by KOH

Dehydration of alcohols
H+
CH3CH2-CH=CH2 + H2 O
CH3CH2-CH-CH3 1-butene
OH H+
CH3CH=CH-CH3 + H2 O
2-butanol
2-butene
major product

Dehydrohalogenation of haloalkanes

CH3CH-CH-CH2 alcohol CH3CH2CH=CH2

KOH CH3CH=CH-CH3
reflux
H Br H 2-butene
1-butene
2-bromobutane (major product)

LEARNERS MUST KNOW MAJOR PRODUCTS IN ALL CASES AND

REACTION CONDITIONS
REACTIONS OF ALKENES (VIP)
 Catalytic hydrogenation:
- hydrogenation: addition of hydrogen
to a double bond and triple bond to yield
saturated product.
- alkenes will combine with hydrogen in
the present to catalyst to form alkanes.
Pt or Pd
C C H H 25-90oC
C C
H H

- Plantinum (Pt) and palladium (Pd) – Catalysts

- Pt and Pd: temperature 25-90oC
- Nickel can also used as a catalyst, but a higher
temperature of 140oC – 200oC is needed.
Addition of halogens:

i) In inert solvent:
-alkenes react with halogens at room temperature
and in dark.
-the halogens is usually dissolved in an inert solvent
such as dichloromethane (CH2Cl2) and
tetrachloromethane (CCl4).
-Iodine will not react with alkenes because it is less
reactive than chlorine and bromine.
- Fluorine is very reactive.inert
Thesolvent
reaction will produ ce
explosion.
C C X X C C
X X
X X = halogen such as Br2 or Cl2
Inert solvent = CCl4 or CH2Cl2
EXAMPLES:

H H inert solvent (CCl4) H H

HCCH Br Br HCCH
ethene BrBr
1,2-dibromoethane

* the red-brown colour of the bromine solution will fade and the
solution becomes colourless.

Br
CCl4
Br2
Br
cyclohexene 1,2-dibromocyclohexane

CCl4 Cl Cl
CH3CH=CH 2 Cl2 CH3CH CH2
propene 1,2-dichloropropane
Hydrohalogenation
 MARKOVNIKOV’S RULE ( A statement
of the rule is not needed)

There are 2 possible products when hydrogen

halides react with an unsymmetrical alkene.
It is because hydrogen halide molecule can add to
the C=C bond in two different ways.
H H H H
CH3 C C H H-I CH3 C C H
H I
1-iodopropane

H H H. H CH3
CH3 C C H H-I C CH
I. H
2-iodopropane
(major product)
 Markovnikov’s rules (Not for
examination)

- the addition of HX to an
unsymmetrical alkene, the
hydrogen atom attaches itself to the
carbon atom (of the double bond)
with the larger number of hydrogen
atoms.
 Addition reaction with concentrated
sulfuric acid: hydration of alkenes

- the alkene is absorbed slowly when it

passed through concentrated sulfuric
acid in the cold (0-15oC
• Hydration: The addition of H atoms and
–OH groups from water molecules to a
multiple bond.
• Reverse of the dehydration reaction.
• Direct hydration of ethene:
- passing a mixture of ethene and
steam over phosphoric (v) acid (H3PO4)
absorbed on silica pellets at 300oC and a
pressure of 60 atmospheres.
- H3PO4 is a catalyst.

Addition reaction with acidified water

(H3O+): hydration of alkenes
 H3PO4
CH2=CH2 (g) H2O(g) o
CH3CH2OH (g)
300 C, 60 atm
ethene ethanol

H OH
C C H2O C C
alkene alcohol
 The alkenes are highly flammable and
burn readily in air, forming carbon
dioxide and water.
 For example, ethene burns as follows
:
C2H4 + 3O2 → 2CO2 + 2H2O

Oxidation (Combustion of alkenes)

HALOGENOALKANES
Halogenoalkanes are compounds in which one
or more hydrogen atoms in an alkane have
been replaced by halogen atoms (fluorine,
chlorine, bromine or iodine).
Functional group = halogen
◦ Ex. Fluorine = fluoro
Number by which carbon attached to, put
in alphabetical order
Ex.

Bromoethane
Halogenoalkanes fall into different classes
depending on how the halogen atom is
positioned on the chain of carbon atoms.
There are some chemical differences between
the various types.
• Primary

• Secondary

• Tertiary
◦ Primary (1°) – carbon carrying halogen is
attached to only one carbon alkyl group
◦ Secondary (2°)– carbon carrying halogen is
attached to two other alkyl groups
◦ Tertiary (3°) – carbon carrying halogen is
attached to three alkyl groups
Substitution:In a substitution reaction,
one atom or group of atoms, takes the
place of another in a molecule.

Elimination: Halogenoalkanes also undergo

elimination reactions in the presence of
sodium or potassium hydroxide which is
dissolved in ethanol.

Reactions of the halogenoalkanes

When an aqueous solution of NaOH or KOH is
added to haloalkane an alcohol is produced.

propan-2-ol

Example of substitution
Example of elimination
what conditions are needed?
ALCOHOLS (CnH2n+1OH)
Preparation and properties
Select the longest chain which contains
the OH group and number so that the OH
group has the smallest number. See the
examples below

nomenclature
In a primary (1°) alcohol, the carbon
which carries the -OH group is only
attached to one alkyl group.
In a secondary (2°) alcohol, the carbon with the -OH group attached
is joined directly to two alkyl groups, which may be the same or
different.

Classification
directly to three alkyl groups, which
may be any combination of same or
different.
See the examples below
Alcohols are classified as
primary, secondary or Tertiary
H3C CH2 CH2 CH CH3

OH

CH3

H3C CH2 CH2 C OH

CH3

H3C CH2 CH2 CH2 OH

 Alcohols contain an –OH group covalently
bonded to a carbon atom.
We need know:
the esterification reaction
Substitution and
elimination

Reactions of alcohols
 1. By hydration of alkanes
The acid is absorbed in conc sulphuric
acid and then the acid is diluted.

Preparation and reactions

2. Hydrolysis of halogenoalkanes
The halogen of the halogenoalkane is
replaced by an OH group Refer to
Halogenoalkanes
 OH
H2SO4 H2
CH3CHCH3 CH2 CHCH3 CH3CH2CH3
Pt
alcohol alkene alkane

Classic example for learners to

write
 Acid + Alcohol yields Ester + Water
Sulfuric acid is a catalyst.
Each step is reversible.

O CH3 O CH3
H+
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3

+ HOH

esterification =>
 Acid + Alcohol yields Ester + Water
Sulfuric acid is a catalyst.
Each step is reversible.

O CH3 O CH3
H+
CH3 C OH + H O CH2CH2CHCH3 CH3C OCH2CH2CHCH3

+ HOH

=>

Chapter 11 72
 Nomenclature of Aldehydes:
Select the longest carbon chain containing the
carbonyl carbon.
• The -e ending of the parent alkane name is
replaced
by the suffix -al.
• The carbonyl carbon is always numbered “1.” (It is
not necessary to include the number in the name.)
• Name the substituents attached to the chain in the
usual way

Aldehydes and
Ketones (Know the functional
groups)
Nomenclature of Ketones
No reactions. Just naming
SOME FUNCTIONAL GROUPS TO
KNOW