STRUCTURE AND FORMULAE

At the end of this lesson you should be able to:

● Explain the occurrence of carbon compounds with straight chains, branched chains and the rings with respect
to catenation, tetravalency, hybridization and resonance.
● Explain the term homologous series.
● Distinguish between empirical, molecular and structural formula and determine the formulae from
experimental data.
● Write structural formulae and name the organic compounds using IUPAC rules
● Define with examples isomerism – structural and stereoisomerism
● Determine possible isomers from given molecular formulae.

Carbon
Organic Chemistry is the study of Carbon. Carbon forms more compounds than any other element in the periodic table
and this is attributed to the following conditions:

● Carbon forms relatively strong bonds with the elements H, N, O S and the halogens.
● It forms stable bonds with other carbon atoms using either single, double or triple bonds.
● It is able to catenate i.e. it has the ability to form rings or chains of carbon atoms.

Carbon is in group4 and forms 4 bonds, the other elements are able to expand their octet by making use of the vacant
‘d’ orbitals in the outer shell. These unique features result in the formation of a wide range of organic compounds. The
immense quality of organic compounds which exist makes an individual study of formidable task. However since many of
these organic compounds are found to contain the same functional group, we then refer to their similar chemical
properties.

A functional group is an atom or group of atoms which determine the chemical reactions undergone by the particular
compound. Compounds which possess the same functional group are said to belong to the same homologous series..

The members of a homologous series have the following characteristics:

1. They can be represented by the same general formula
2. They have similar chemical properties
3. They show a gradual change in physical properties i.e. their physical properties are directly related to their
molecular size for each member differs from a successive one by a constant amount of CH2.

e.g. Homologous Series Functional group

Alkenes
Alcohols
Carboxylic acids

TYPES OF FORMULAE
Empirical formulae - This shows the simplest whole number ratio of atoms of each element present in one molecule of
the compound.
Molecular formulae – This shows the actual no. of atoms of each element present in one molecule of the compound. It
tells us nothing about bond arrangements or types.
Structural formulae – This shows the order in which atoms are joined together in a molecule. There is also the
Shortened Structural formulae which shows the sequence and arrangement of atoms in an organic molecule. Carbon
and hydrogen are omitted but the other groups may be included.
e.g. Hexane

THE CONCEPT OF HYBIDISATION

The electronic structure of carbon is not consistent with a number of properties of the compounds which it forms.
Example 6C with two singly filled ‘p’ orbitals in its valency shell. One would expect a covalency of
four in all its compounds. A possible solution is to promote one of the 2s electrons into the vacant 2p orbital, so giving 4
unpaired electrons in its valency shell. It is expected that two different kinds of bonds are formed, using one ‘s’ orbital
and three ‘p’ orbital; but actually the electron density distributes itself evenly through four bonding orbitals, which are
called sp3 hybrid orbitals.
ground state

Promotion

excited state

‘s’ + 3 x ‘p’

sp3 hybrid orbitals

e.g. methane

Although the problem of its covalency was solved, it could not be accurate for the formation of multiple bonds in alkenes
and alkanes as well as the range of shapes and bond angles in different carbon compounds e.g. methane is tetrahedral
with a bond angle of 109.5o; ethane is planar with a bond angle 120o; benzene is hexagonal planar with a bond angle of
120o.

ground state
 Promotion

excited state

‘s’ + 2 x ‘p’

sp2 hybrid orbitals unhybridized orbitals

The sp2 hybrid orbitals are coplanar with angle of 120o between them. The C-C bond formed when the sp2 orbitals of
neighboring carbon atoms overlap is called a σ (sigma) bond. In σ bonds e.g. any single bond, overlap of atomic orbitals
occurs along the line joining the two bonded atoms. There is an unhybridised ‘p’ orbital on adjacent carbon atoms are
close enough to overlap. The overlap occurs at the sides of the orbitals (above and below the plane) and are called π
bonds. π bonds are not as strong as σ bonds since there is less overlapping of orbitals.

ISOMERISM
Two molecules having the same molecular formula, but different structural formula are called isomers. The difference in
the arrangement of the atoms may arise in two different ways and so give rise to two broad categories of isomerism:
1. If the atoms are bonded together in a different order in each isomer, they are called structural isomers.
2. If the atoms are bonded together in the same order but are arranged differently in space, they are called
stereoisomers

Structural Isomerism
There are four major types of structural isomerism. These are:
1. Chain isomerism
2. Positional isomerism
3. Functional group isomerism

Chain Isomerism
These are molecules which differ in the no. of C-atoms present in the principle carbon chain. The principle carbon chain
is the longest carbon chain which bears the functional group. Here the physical properties are different but the chemical
properties are the same
e.g. CH3CH2CH2CH3 and CH3CH(CH3)CH3

Positional Isomerism
In these molecules the same functional group occupies different positions. The physical properties are different and the
chemical properties are the same
e.g. (C3H7OH) propanol and propan-2-ol

Functional Group Isomerism

These molecules have the same molecular formula but different functional group. Both the physical and chemical
properties are different.
e.g. but-2-ene and cyclobutane

Stereoisomerism
There are two types of stereoisomerism: 1. Geometric
2. Optical

Geometric Isomerism
These occur in pairs. The members of the pairs differ in terms of their 3D arrangement, but are not mirror images of each
other. What characterizes the group of the isomers is that their existence is due to an element of rigidity within their
structures i.e. the presence of a double bond or saturated ring.

Geometric Isomers in Alkenes

Due to the rigidity of the double bond, the atoms or groups that are bonded to the C=C are relatively fixed in space. It is
therefore possible for these groups to occupy different position in space and so give rise to a pair of geometric isomers.
Not all alkenes display geometric isomerism, if two identical atoms or groups are bonded to the same carbon atom of the
C=C then the molecule shows no isomerism. In general, for an alkene of type geometric isomerism is
possible provided a≠b or c≠d.
If the alkene contains at least one identical pair of atoms or groups on the separate carbon atoms, then the prefixes ‘cis’
and ‘trans’ are used to distinguish the isomers. The members of the pair that has the identical atom or groups on the
same side of the molecule is called the ‘cis’ isomer. The other member of the pair in which the atoms or groups is on the
opposite side is called the ‘trans’ isomer.

Below these two are geometric isomers, but not ‘cis’ or ‘trans’ isomers.

Geometric Isomers in Ring Compounds

Saturated ring such as cyclohexane ring are generally flat and rigid ring of C-atoms with groups or atoms pointing above
and below the plane of the ring. It the right groups are present on adjacent C-atoms, example an identical pair of atoms
or groups then the ‘cis’ and ‘trans’ isomers can exist. Consider 1,2-dibromocyclohexane.

Optical Isomerism
This is found only in asymmetric C-atoms i.e. C-atoms which contains four different groups. These asymmetric C-atom are
referred to as chiral centres.
The most common forms occur when a C-atom is attached to four different groups.

These compounds exist in two forms called Enantiomers (optical isomers), which are non-superimposable mirror images
of each other. Enantiomers have identical chemical properties as well as physical properties except that they rotate plane
polarized light in different directions. One isomer rotates plane polarized light in a clockwise (to the right) and is said to
be dextrorotatory. This is distinguished by placing ‘d’ or ‘+’ before its chemical name. The other member of the pair
rotates plane polarized light in an anticlockwise manner and is said to be laevorotatory. This isomer is distinguished by
placing ‘l’ or ‘-‘ before the chemical name.

When prepared in the lab optically active compounds show no optical activity when plane polarized light is incident upon
it. The reason for this is that the prepared sample contains an equimolar mixture of ‘+’ or ‘-‘ isomers. Both isomers rotate
plane polarized light to the same extent but in the opposite directions. Consequently, their effects cancel out each other,
the sample is therefore optically inactive. Such equimolar mixture of optical isomers is called a racemix mixture.