Hybridization

Lecture # 01(Part 2)
sp3 Hybrid Orbitals and the
Structure of Methane
• The bonding in the H2 molecule is fairly straightforward,
but the situation is more complicated in organic
molecules with tetravalent carbon atoms.
• Take methane, CH4, for instance. Carbon has four
valence electrons (2s2 2p2) and forms four bonds.
• Because carbon uses two kinds of orbitals for
bonding, 2s and 2p, we might expect methane to have
two kinds of C H bonds.
• In fact, though, all four C H bonds in methane are
identical and are spatially oriented toward the corners of
a regular tetrahedron. How can we explain this?
• The concept of hybridization explains how carbon forms
four equivalent tetrahedral bonds
• Linus Pauling in 1931 proposed that an s orbital and
three p orbitals can combine, or hybridize, to form four
equivalent atomic orbitals with tetrahedral orientation.
 Bonding in Methane(CH4)

Carbon has two core

electrons, plus four valence
electrons.

In this description, carbon

should form only two In CH2, carbon would not
bonds because it has only have an octet of electrons.
two unpaired valence
electrons, and CH2 should
be a stable molecule.
 • There is a second possibility. Promotion of an electron
from a 2s to a vacant 2p orbital would form four
unpaired electrons for bonding.

This description is still not adequate. Carbon would form two different types of bonds: three with 2p
orbitals and one with a 2s orbital. But experimental evidence points to carbon forming four identical
bonds in methane.
• Hybridization of one 2s orbital and three 2p orbitals for carbon forms four hybrid
orbitals, each with one electron.
• These new hybrid orbitals are intermediate in energy between the 2s and 2p orbitals.
Mixing a spherical 2s orbital and three dumbbell shaped 2p
orbitals together produces four orbitals having one large
lobe and one small lobe, oriented toward the corners of a
tetrahedron.

The four hybrid

orbitals form four
equivalent bonds.
Other Hybridization Patterns—sp2 and sp Hybrid
Orbitals
• Three common modes of hybridization are seen in organic molecules.
 To determine the hybridization of an atom in a
molecule, we count groups around the atom, just as
we did in determining geometry.
Determination The number of groups (atoms and nonbonded
electron pairs) corresponds to the number of atomic
of hybridization orbitals that must be hybridized to form the hybrid
orbitals.
Problem
• What orbitals are used to form each bond in methanol, CH3OH?

• What orbitals are used to form each bond in the following molecule?
(CH3)3B
 Sp2 and Sp Hybridization
Forming three
sp2 hybrid
orbitals

Forming two sp
hybrid orbitals
BF3
In BF3, the B atom is sp2 hybridized because it
is surrounded by three groups (three F atoms).
Each B – F bond is formed by overlap of an sp2
hybrid orbital from B and a 2p orbital from F.
The sp2 hybrid orbitals all lie in a plane, and
are oriented 120° apart. The B atom also has a
vacant unhybridized 2p orbital. This orbital is
located above and below the plane of the BF3
molecule.

BeH2
In BeH2, the Be atom is sp hybridized
because it is surrounded by two groups (two
H atoms). Each Be – H bond is formed by
overlap of an sp hybrid orbital from Be and a
1s orbital from H. The sp hybrid orbitals are
oriented 180° away from each other.
Examples: Ethane—CH3CH3
• According to the Lewis structure for ethane, CH3CH3, each carbon atom is
singly bonded to four other atoms. As a result:
Ethylene—C2H4
• Based on the Lewis structure of ethylene, CH2––CH2, each carbon
atom is singly bonded to two H atoms and doubly bonded to the
other C atom, so each C is surrounded by three groups. As a result:
One of the C – C bonds results from the
end-on overlap of an sp2 hybrid orbital
on each carbon atom. Each of these
bonds is a σ bond.

The second C – C bond results from the

side-by-side overlap of the 2p orbitals on
each carbon. Side-by-side overlap creates
an area of electron density above and
below the plane containing the sp2 hybrid
orbitals (that is, the plane containing the
six atoms in the σ bonding system).

Thus, a carbon–carbon double bond has two components:

The σ and π bonds in ethylene

Acetylene—C2H2
• Based on the Lewis structure of acetylene, HC ––CH, each carbon atom is singly
bonded to one hydrogen atom and triply bonded to the other carbon atom, so
each carbon atom is surrounded by two groups. As a result:
Each carbon atom also has two unhybridized 2p orbitals that are perpendicular to each other and to the sp hybrid
orbitals. Side-by-side overlap between the two 2p orbitals on one carbon with the two 2p orbitals on the other
carbon creates the second and third bonds of the C – C triple bond.
The electron density from one of these two bonds is above and below the axis joining the two nuclei, and the
electron density from the second of these two bonds is in front of and behind the axis, so both of these bonds
are π bonds.

Thus, a carbon–carbon triple bond has three components:

Summary
References
1. Zuzana Országhová, Textbook of Medical Chemistry, 2018.
2. J. McMurry, Fundamental of Organic Chemistry, 7th edition.
3. J.G. Smith, Organic Chemistry, 3rd edition, 2010, McGraw Hill.