Unit-2; Organic Chemistry-1

Reading Capsule:Structure and Bonding in Organic Chemistry

 Reading Capsule
Unit-1 Structure and Bonding in Organic Chemistry
Introduction
Organic Chemistry is the chemistry of compounds which contain the element carbon.

Most of these compounds contain hydrogen and many also contain oxygen, nitrogen or other
elements. There are a few compounds containing carbon, however, which are not normally classified as
organic compounds. Carbon monoxide, carbon dioxide and the metal carbonates are examples.

Although organic substances such as sugars, alcohol and vinegar had been known for thousands of
years, it was not until the eighteen century that organic compounds were first isolated. One of the first
scientists to study organic compounds was the self-taught chemist, Carl Wilhelm Scheele (1742-1786).
He obtained and purified a number of organic acids and other organic compounds from plant and animal
sources. He isolated 2-hydroxypropanoic acid (lactic acid) from milk and showed that this acid was the
cause of turning milk sour.

During the eighteen century chemists believed that organic compounds could only be synthesized by
means of a ‘life force’ in living cells. This was called the vitalistic theory of organic chemistry.
However, in 1828, the German chemist Friedrich Wohler (1800-1882) prepared urea (carbamide) by
heating an aqueous solution of ammonium cyanate :

NH4CNO  CO(NH2)2

This was the first synthesis of an organic compound. It heralded the decline of the vitalistic theory.
The term ‘biochemistry’ is now used for the chemistry of living things and life processes.

All living things contain organic compounds. Furthermore, many of the modern products and
materials upon which we depend are organic.

The unique nature of carbon

Why is that carbon can form such a vast number of naturally occurring and synthetic compounds ?
The answer lies in its unique ability to catenate : to bond with itself and form stable long-chain and
ring structures. Carbon also has the ability to form single, double and triple bonds not only with itself
but also with other elements such as oxygen and nitrogen.

There are three important properties of carbon that enable it to form so many stable carbon
compounds :
1. Catenation
The ability of carbon to form strong bonds to itself means that it can form chains and rings of
varying size. This property is called catenation. The stability of the single, double and triple
carbon-carbon bonds can be seen by comparing the bond enthalpies in table :

Bond C-C C=C C≡C Si-Si Si=Si S-S C-H

Bond enthalpy 346 610 835 226 318 272 413
kJmol-1 (estimated)

Note the strength of the C-C bond compared with that of the Si-Si and S-S bonds. Note too the
high strength of the C-H bond : all but a handful of the vast number of carbon compounds also contain
hydrogen. In the presence of air, carbon compounds are not stable relative to their oxidation products,
carbon dioxide and water. For example, methane :
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -890 kJmol-1
 Although methane is energetically unstable relative to its combustion products, it does not react with
air until heated to quite high temperature. This is because the reaction between methane and oxygen has a
high activation energy which must be supplied before the reaction will proceed. Thus, most carbon
compounds are energetically unstable in the presence of air, but kinetically stable.

2. Carbon can form four covalent bonds

Carbon is also unique in its ability to hybridize. Its four bonding electrons can undergo hybridization
to form :

four single bonds --

one double bond and two single bonds --

one triple bond and one single bond --

3. Carbon has a fully shared octet of electrons in its compounds

Carbon atoms have no lone pairs or empty orbitals in their outer shells, so that they are unable to
form dative bonds. This properties is responsible for the kinetic stability of its compounds.

Bonding and Structure

（1）Orbital hybridisation of carbon

The concept of hybridisation theory involves the following points :

1. Hybridisation is the mixing of pure orbitals to form new hybrid orbitals which are equivalent and have
definite orientations in space.
2. Only orbitals which lie close together in energy can be used in the construction of hybrid orbitals.
3. The number of hybrid orbitals always equals the number of component atomic orbitals.

1. sp3 hybridisation
It is formed by one 2s orbital and three 2p orbitals of a carbon atom to give four equivalent hybrid
sp orbitals pointing towards the vertices of a regular tetrahedron :
3

2. sp2 hybridisation
It is formed by one 2s orbital and two 2p orbitals of a carbon atom to give three equivalent sp2
hybrid orbitals which are pointing towards the vertices of an equilateral triangle :

3. sp hybridisation
 It is formed by one 2s orbital and one 2p orbital of a carbon atom to give two equivalent sp hybrid
orbitals of linear structure :

（2）Structures and shapes of hydrocarbons

1. Saturated hydrocarbons
Hydrocarbons whose molecules contain only single bonds are known as saturated hydrocarbons.
In saturated hydrocarbons the outermost shell electrons of each carbon atoms have hybridised to form
four equivalent sp3 orbitals which are arranged tetrahedrally about the nucleus. This geometry gives
idealized bond angles of 109.5o.

Energy ___ ___ ___ ___

sp3 sp3 sp3 sp3 hybridized state

___ ___ ___ ___

2s 2p 2p 2p excited state
___ ___ ___ ___
2s 2p 2p 2p ground state

When an sp3 carbon atom forms bonds, it does so by overlapping each of its four sp3 orbitals (each
with one electron) with orbitals from other four atoms (each orbital in turn containing one electron).
Therefore it is capable of forming four single bonds. The molecular orbital of a single bond is
symmetrically around the axis passing through the nuclei of two bonded atoms. It is known as a 
bond.

Structures and shapes of saturated hydrocarbons :

Methane CH4
In methane, each sp3 orbital of carbon overlaps with a 1s orbital of hydrogen. Each of the resultant
sp3-1s molecular orbital is symmetrically around the axis passing through the nuclei of the carbon and
hydrogen atoms. The C-H bonds in methane are  bonds.
Structural formula condensed structural formula 3-dimensional structure (shape)
H H
H C H CH4 C H
H H
H

Ethane C2H6
Ethane contains two sp3 carbon atoms. These two carbon atoms form a C-C  bond by the overlap
of one sp3 orbital from each carbon. Each carbon atom has three remaining sp3 orbitals, and each of
these overlap with a 1s orbital of a hydrogen atom to form a C-H  bond.

Structural formula condensed structural formula 3-dimensional structure (shape)

H H
CH3CH3
H C C H

H H

Propane C3H8 and Butane C4H10

Propane and butane are examples of alkanes that are sometimes called unbranched chain alkanes.
Because of the tetrahedral arrangement of the bond pairs around carbon atoms, their chains are zigzagged
in shape.

Structural formula condensed structural formula 3-dimensional structure (shape)

H H H

H C C C H CH3CH2CH3

H H H

H H H H
H C C C C H CH3CH2CH2CH3
H H H H

Cyclohexane C6H12
Cyclohexane is an example of cyclic alkane. If the cyclohexane ring were flat, a serious bond
strain would be resulted and all the hydrogen atoms on the ring would be eclipsed. There are many
shapes that a cyclohexane ring can assume, the most stable one is the ‘chair’ form with minimum bond
strain and all hydrogen atoms staggered.
2. Unsaturated hydrocarbons
Hydrocarbons whose molecules contain double bonds or triple bonds are known as unsaturated
hydrocarbons.

Carbon-carbon double bond : the sp2 hybridization

Formation of the C=C bonds

The atomic orbitals of carbon can also hybridise to give three identical sp2 orbitals arranged
symmetrically in a plane at an angle of 120o to each other, with the remaining electron in a p orbital at
right angles above and below this plane.

Energy ___ ___ ___ ___

sp2 sp2 sp2 2p hybridized state

___ ___ ___ ___

2s 2p 2p 2p excited state
___ ___ ___ ___
2s 2p 2p 2p ground state

Structure and shape of the ethene C2H4 molecule :

In ethene, one of the three sp2 orbitals overlaps with an sp2 orbital of a second carbon atom to form a
 bond. The other sp2 orbitals of the two carbon atoms each overlaps with the 1s orbital of a hydrogen
atom to form four  bonds. The 2p orbitals of the carbon atoms overlap above and below the plane to
form a  bond. A  bond is formed by lateral overlap of the p orbitals and has a plane of symmetry.
A C=C double bond consists of a  bond and a  bond. A  bond is stronger than a  bond as it is
formed between the lines of centres of the bonding atoms and greater orbital overlap is possible.

Shape of the ethene molecule :

Carbon-carbon triple bond : the sp hybridization

Formation of the CC bonds

The hybrid orbitals formed from the 2s and one of the 2p orbitals of carbon atom consists of two
identical collinear sp orbitals with lobes directed in opposite directions on either side of the nucleus.
The two remaining unpaired electrons are in 2p orbitals at right angles to each other.

Energy ___ ___ ___ ___

sp sp 2p 2p hybridized state

___ ___ ___ ___ sp sp

2s 2p 2p 2p excited state
___ ___ ___ ___
2s 2p 2p 2p ground state

Structure and shape of the ethyne C2H2 molecule :

In the ethyne C2H2 molecule, one of the two sp orbitals overlap with an sp orbital of a second carbon
atom to form a  bond, while the two remaining sp orbitals(one on each carbon atom) form  bonds with
hydrogen atoms. The unhybridised 2p orbitals overlap laterally and two  bonds are formed in planes at
right angles above, below and on either side of the linear molecule.
A CC triple bond consists of a  bond and two  bonds. These  bonds draw the carbon atoms
closer together, making the C  C bond both shorter and stronger than the carbon-carbon double and
single bonds.

3. Aromatic hydrocarbons
Organic compounds are divided into two main classes : the aliphatic and the aromatic.
The molecules of both saturated and unsaturated aliphatic compounds are open-chain (acyclic) or
simple rings (cyclic) structures.
The term aromatic refers to a major class of unsaturated cyclic organic compounds which includes
benzene and its derivatives. Benzene is an unsaturated, but highly stable, cyclic molecule containing six
carbon atoms. Aromatic hydrocarbons are hydrocarbons which have benzene ring in their structures.
They are sometimes called arenes.
Structure and shape of the benzene C6H6 molecule :
Benzene C6H6 is a cyclic compound with six carbon atoms joined in a ring. Each carbon atom is
sp2 hybridised, and the ring is planar. Each carbon atom has one hydrogen atom bonded to it and an
unhybridised 2p orbital perpendicular to the plane of the  bonds of the ring. Each of these six 2p
orbitals can contribute one electron for  bonding. This type of p-orbital system leads to complete
delocalisation of all six  electrons giving rise to a highly stable structure of the benzene molecule.

It is known that all carbon-carbon bond length in benzene is the same, 0.140 nm. All six bonds are
longer than C=C double bonds, but shorter than C-C single bonds. From the bond lengths plus a body of
other evidence, chemists have concluded that benzene is a symmetrically molecule with six ring  bonds
(C-C bonds) and six  bonds of C-H bonds. Instead of alternating double and single bonds, the six 
electrons are completely delocalised in a cloud of electronic charge above and below the ring.

 bonds skeleton (C-C : sp2-sp2 ; C-H : sp2-1s)  bonds (6  electrons delocalised)

Benzene is just one example of aromatic compounds that contain aromatic  clouds. If an
unsaturated ring system contains 4n + 2  electrons, complete delocalisation of  electrons and
subsequently stabilised structure is obtained.

Example : Pyridine (C5H5N) and naphthalene (C10H8) are also classified as aromatic compounds :