d) Intermolecular forces

Carbon forms single, double and triple bonds with elements other than carbon. The atoms
involved in the bonding are usually oxygen, nitrogen, sulfur and the halogens. These
elements are more electronegative than carbon and thus attract the electrons to
themselves. The bonds are therefore polar covalent bonds. Bonds that contain a
separation of charge possess a dipole moment, a property that contributes to the overall
polarity of the molecule.

The bonds O-H, N-H and F-H are highly polar covalent bonds because the
electronegative atom draws electrons away from the hydrogen atom. In every case the
hydrogen atom has a partial positive charge.
As a result of molecules having these highly polarized bonds, with the hydrogen atom
partly positive in nature, the hydrogen atom is attracted to the basic site in other
molecules, such as the non-bonding electrons on oxygen and nitrogen (non-bonding
electrons are electrons belonging to an element that complete the octet but do not
participate in bonding). This attraction is called hydrogen bonding and is useful for
explaining high boiling points and high melting points of fairly low mass molecules.

Functional groups
In organic chemistry a functional group is a substituent or moiety in a molecule that causes the
molecule’s characteristic chemical reactions. The same functional group will undergo the same
or similar reactions regardless of the rest of the molecule’s composition.
LECTURE 2
ALKANES
Compounds that contain carbon and hydrogen are generally called hydrocarbons. Hydrocarbons
are divided into two broad classes: Aliphatic and aromatic hydrocarbons.
Aliphatic hydrocarbons include three major groups: alkanes, alkenes and alkynes.
Alkanes are hydrocarbons in which all the bonds are single. They have the general formula
CnH2n+2. The simplest member has one carbon, Methane (CH4).
Table 1: Alkanes
Name Molecular formula Structural formula Boiling point, °C
methane CH4 CH4 -160
Ethane C 2 H6 CH3CH3 -89
Propane C 3 H8 CH3CH2CH3 -42

NB: Boiling point in alkanes increases with increase in the number of carbon atoms.
Nomenclature
Nomenclature of organic compounds is of two types: common (trivial) and systematic. The
systematic nomenclature is governed by IUPAC organization. It assigns names to unbranched
alkanes by use of a set of rules. The number of carbon atoms in the chain is specified by a Latin
and Greek prefix preceding the suffix –ane.
IUPAC Rules
1. Pick out the longest continuous carbon chain and assign the parent name. 1 carbon, meth-
; 2 carbons , eth-; 3 carbons, prop-; 4 carbons, but-. Then add the suffix –ane to complete
the parent name.
1 carbon Methane,
2 carbons Ethane
3 carbons Propane
4 carbons Butane
2. Identify the substituent groups attached to the chain. The groups are alkyl groups and
bear the parent name with the suffix –yl, e.g., methyl: CH3-; ethyl: C2H5-.
3. Number the longest continuous chain in the direction that gives the lowest number to the
substituent group at the first point of branching.
4. Write the name of the compound.
Isomerism in alkanes conformational isomers
Isomerism is the ability of compounds of the same formula to exist in different forms
arrangements. Isomers are compounds that have the same formula but different arrangement of
the atoms in space.
Structural isomers have the atoms in each molecule connected in a different order. For example
C2H6O and C4H10.
Conformational isomers results from a sigma bond rotation of C-C. The different
conformations are called conformers, e.g., C2H6 and butane.
a) Ethane, C2H6

In ethane, there are two conformations: eclipsed and staggered. The eclipsed conformation is the
least stable. The staggered is the most stable because the C-H bonds are far away from each other
as possible. The electron in a C-H bond will repel electrons in another C-H bond if the bonds get
too close to each other. This is called torsion strain.
Notice that the staggered conformers are at energy minima whereas the eclipsed conformers are
at energy maxima.
b) Butane, CH3CH2CH2CH3
Butane has three C-C bonds and the molecule can rotate about each of them. The
conformational analysis about C2-C3 bond is as shown below:
Cycloalkanes
Nomenclature
Are alkanes with their carbon atoms arranged in a ring. Because of the ring, a cycloalkane has
two fewer hydrogen than acyclic alkanes of the same number of carbons. They are named by
adding the prefix ‘cyclo’ to the alkane name, that signifies the number number of carbon atoms
in the ring.

cyclic compounds twist and bend in order to attain a structure that minimizes the three different
kinds of strain that can destabilize it, viz:
i. Angle strain: The strain induced in a molecule when the bond angles are different
from the ideal tetrahedral bond angle of 109.5°
ii. Torsional strain: Caused by repulsion between the bonding electrons of one
substituent and the bonding electrons of a nearby substituent
iii. Steric strain: Caused by atoms or groups of atoms approaching each other too
closely
Conformational analysis
Example cyclohexane
The cyclic compound most commonly found in nature, contain six-membered rings because such
rings exist in a conformation that is almost completely free of strain.
Cyclohexane can exist in two conformations, namely chair and boat.
The chair conformation is the most stable because all the bond angles are 111° which are very
close to the ideal tetrahedral bond angle of 109.5°. The cyclohexane interconverts between the
two stable chair conformations because of the rotation about its C-C bonds. This interconversion
is known as ring-flip. When the chair conformer interconverts, bonds that where equatorial
become axial in the new conformer.

The boat conformation is not as stable as the chair conformer because some of the bonds in the
boat are eclipsed, giving it torsional strain.

The boat conformer is further destabilized by the close proximity of the flagpole hydrogens (H at
the ‘stern’ and ‘bow’ of the boat, which causes steric strain.
Conversion of a boat conformer take the cyclohexane through a twist-boat or skew-boat
conformer, which is more stable that the boat conformer because there is less eclipsing and
consequently, less torsion strain and the flagpole hydrogens have moved away from each other.
When the carbon bearing the flagpole hydrogen is in the same plane as the side of the boat, a
very unstable conformer is obtained – the half-chair conformer.
Because the chair conformers are the most stable of the conformers, at any instant more
molecules of cyclohexane are in chair conformation than in any other conformation.

Occurrence and uses of Alkanes

Occurrence
Methane occurs in trace amounts in our atmosphere, ground and oceans and exo-terrestrial
bodies, ethane and propane are found in natural gas. The most important source of alkanes are oil
and natural gas deposits. One of the largest natural deposit of solid alkanes is in an asphalt lake
known as Pitch lake in Trinidad and Tobago
Uses
Alkanes are important raw materials of the chemical industry amd the principal constituents of
gasoline and lubricating oils
 Natural gas mainly contains ethane and methane and is used for heating and cooking
Alkane Uses
C3 - C4 Can be liquefied at fairly low pressures and are used in propane burner, as
propellants in aerosol sprays, butane in cigarette lighters
C5 - C8 Highly volatile liquids used as solvents for non-polar substances. Are used as
fuel in internal combustion engines
C9 - C16 Liquids of higher viscosity – used in diesel and aviation fuel (kerosene)
C17 - C35 Major component of lubricating oil, anti-corrosive agents and paraffin wax for
candles
>C35 Bitumen for road surfacing and waterproofing.

Reactions (Hemolysis of bonds)

Alkanes are unreactive. They react through substitution reactions
1. Oxidation
 Hydrocarbons are oxidized to water and carbon dioxide
2. Substitution
i. Reaction with halogens.
Alkanes react with electronegative atoms through bond hemolysis.
CH4 + Cl2 +Energy CH3Cl + HCl

CH4 + Cl2 +Energy CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl

ii. Halogenation of cycloalkanes

The reaction of cycloalkanes are generally the same as the alkanes with the
exception of the small ones, cyclopropane.
In the presence of UV light cyclopropane will undergo substitution reactions with
chlorine or bromine like non-cyclic alkanes. It also has the ability to react in the
dark. In the absence of light, cyclopropane can undergo addition reactions in
which the ring is broken.

+ Br 2 Br Br