Hydrocarbons

Objectives
• To study the IUPAC nomenclature,
physical and chemical properties of
saturated, unsaturated and aromatic
hydrocarbons
 Alkanes
• Saturated hydrocarbon: Maximum number
of hydrogens in the structure
• Here, the carbon atom arrangement may
be acyclic (no ring) or alicyclic
• The names of the first ten alkanes should
be known.
• Molecular formula for alkanes is CnH2n+2
 H H
H
C C H
H H H C
H H
H
Methane, CH4 Ethane, C2H6

Physical Properties of Alkanes

At room temperature, 25C:

C1 – C4 - gases
C5 – C17 - liquids
C18 and above - solids
Boiling points

Boiling points increase with increasing numbers of carbon

atoms and increasing molecular weights. This is because larger
molecules have larger surface areas, resulting in increased
intermolecular van der Waals attractions.

For compounds of similar molecular weight, branching lowers

the boiling point. Branching decrease the total surface area of
contact between molecules, thus decrease the strength of van
der Waals forces.
Solubilities and Densities

Alkanes are nonpolar, so they dissolve in nonpolar or weakly

polar organic solvents, for example alkane dissolves in carbon
tetrachloride, CCl4.

Alkanes are insoluble in water because they cannot form

hydrogen bonds with water.

Alkanes are also less dense than water.

Densities of alkanes around 0.7g/mL while density of water =

1.0g/mL), therefore when mixed the mixture separates into two
phases with the alkane on top.
Melting points

-Melting points increase with increasing molecular weights.

Primary source of alkanes is petroleum.

Alkanes are used as energy through combustion eg.

natural gas, gasoline, kerosene, diesel, fuel – all
composed of hydrocarbons. Also alkanes are used as
solvents and lubricants
 Structural formulas
• This is a two dimensional representation that
shows how the various atoms in a molecule are
bonded to each other
• Two types: expanded and condensed structural
formulas
• Expanded (skeletal structural formula): shows all
atoms in a molecule and all bonds connecting
the atoms
• Condensed: uses groupings of atoms. Central
atoms and atoms connected to them are written
as a group
• You must know how to write both.
 Alkane isomerism
• There can be a situation where more than
one structural formula is consistent with
the molecular formula
• This is known as isomerism
• Compounds which are isomers have the
same molecular formula but differ in the
arrangement
• Butane and isobutane
CH3-CH2-CH2-CH3
butane

CH3-CH-CH3

CH3
2-methylpropane (isobutane)
 Conformation of alkanes
• You must be able to distinguish different
conformations of the same molecule,
different compounds that are constitutional
isomers and different compounds that are
not constitutional isomers
• Conformation: 3D arrangement of atoms in
an organic molecule
• Constitutional isomers must have the same
molecular formula
 IUPAC nomenclature of alkanes
• The common alkyl groups are recognized first.
Any alkyl group has the formula:
R = CnH2n+1

Say you are given

How do you name this?

 The rules for naming

-Select the longest continuous chain of carbon

atoms, consider all alkyl groups attached to it.
Here, the longest chain has four carbon atoms.
Thus it is named as butane.
- The methyl group is attached to carbon 2.
- Under IUPAC system, the compound is called 2-
methylbutane
 Name the following

Can you draw the condensed structural formula of 3-ethyl-2,3-

dimethylpentane?
 Name the following
a)

b)
 Cycloalkanes
• A saturated hydrocarbon in which carbon
atoms connected to one another in a cyclic
(ring) arrangement are present
• Formula is CnH2n
• Line angle structures are generally used
for cycloalkane structures
 Nomenclature for cycloalkanes
• Prefix cyclo is used to represent the ring
• One ring substituent, not necessary to
locate by number
• Two ring substituents present, C atoms
numbered with substituent of higher
alphabetical priority and proceed to
direction that gives substituent of lowered
number
Assign IUPAC names for the following
 Isomerism in cycloalkanes
• Constitutional isomers for cycloalkanes
are possible
• For example, isomers with formula C5H10
• Cis-trans isomers: same molecular and
structural formulas but different orientation
of atoms in space due to restricted rotation
about bonds
• Cis: prefix that means “on the same side”
• Trans: prefix that means “across from’.
1. Wurtz Reaction Alkane synthesis
General:

R X + 2 Na + X R R R + 2 NaX

Example:
2CH3CH2CH2Br + 2Na CH3CH2CH2CH2CH2CH3
+ 2NaBr
2. Hydrogenation of Alkene in the presence of metal catalyst.

General:
H H
C C + H2 C C
Ni

metal catalysts: Ni, Pd, or Pt

Example:

CH3CHCHCH3 + H2 CH3CH2CH2CH3
Pt

+ H2
Pd
 Halogenation
• Halogens are group VII elements
• Halogenation reaction: chemical reaction
between a substance and a halogen in which
one or more halogens are incorporated into
molecules of a substance
• Halogen atoms are actually substituted by
hydrogen atoms
• This is a substitution reaction. Conditions for
reaction include initiation by heat or light and
excess alkane to minimize multiple multiple
substitution
• A halogen alkane and hydrogen halide is formed
Nomenclature of halogenated alkanes
• Halogen atoms on a carbon chain are
called fluoro, chloro, bromo and iodo
• If both halogen and alkyl group present,
chain is numbered closer to a substituent
• Alphabetical order is maintained
Combustion
Reaction of alkanes with oxygen produces CO2 and H2O.
Usually occurs in engine or furnace. Large amount of
heat is released.

5O2
CH3CH2CH3 3CO2 + 4H2O
High temp.
C nH(2n+2) + O2 nCO2 + (n+1) H2O
Example:

CH4 + 2 O2 CO2 + 2H2O + 890kJ/mol