HYBRIDIZATION

Hybridization is the mixing or blending of atomic orbitals to produce equivalent number of

hybrid orbitals of the same energy in a molecule or ion. The various types of hybrid orbitals are:

1. sp3
2. sp2
3. sp
4. sp2d
5. sp3d
6. sp3d2

Sp3 Hybridization

This involves mixing of one s-orbital and three p-orbitals to form four equivalent sp3 hybrid
orbitals. The shape of sp3 hybrid orbitals is tetrahedral with bond angles of 109° 28'. There is a
coordination number of four in tetrahedral molecules. Examples of molecules/ions with sp3
hybrid orbitals are: CH4, SiCl4, NH3, PF3, H2O, H2S and SF2.

For a methane (CH4) molecule:

The ground state electronic configuration of carbon is; 1s2 2s2 2px1 2py1.

The excited state electronic configuration of carbon is; 1s2 2s1 2px1 2py1 2pz1.

Electron configuration of C in CH4:

The dotted lines indicate electrons

shared by H

sp3 hybridization

The tetrahedral shape of sp3 is shown below.

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Ammonia Molecules: The central atom (nitrogen) in NH3 is sp3 hybridized. Nitrogen has atomic
number 7 and its electronic configuration at the ground state is 1s2 2s2 2p3. In this case, no
electrons are excited to higher energy levels. The 2s and 2p orbitals are hybridized to form
four sp3 orbitals. The 2s orbital has a lone pair (non-bonding) of electrons and this orbital
DOESNOT take part in bonding. The ammonia molecule is therefore formed when the electron
in hydrogen atom (1s1) overlap with sp3 hybrid orbital to form sigma bond.

1s2 2s2 2px1 2py1 2pz1

N in ground state:
1s2 sp3 sp3 sp3 sp3
Hybrid orbitals
of N:

sp3 hybridization
1s2 sp3 sp3-s sp3-s sp3-s
Electronic conf iguration of N in NH3:

However, the shape of ammonia molecule is pyramidal with bond angle of 107° and a
coordination number of 3.

Other molecules/ ions with pyramidal shapes are PF3, PCl3 and H3O+.

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Water Molecule:

The central atom (oxygen) in H2O is sp3 hybridized. Oxygen has atomic number 8 and its
electronic configuration in the ground state is 1s2 2s2 2p4. In this case, no electrons are excited to
higher energy levels. The p-subshell has two unpaired electrons that are used to form two sigma
bonds with hydrogen atoms.

The observed bond angle in a water molecule is 104.5° with a bent tetrahedral shape or V-
shape. V-shaped molecules have coordination number of 2. If the two bonding electrons from
the two p-orbitals were unhybridized, the bond angle would have been 90° and water would have
been a linear and non-polar molecule. The 2s and 2p orbitals hybridized to form four sp3 hybrid
orbitals. The two half filled sp3 hybrid orbitals overlap axially with two 1s1 orbital of hydrogen
to form sigma bonds.

1s2 2s2 2px2 2py1 2pz1

O in ground state:
1s2 sp3 sp3 sp3 sp3
Hybrid orbitals
of O:

sp3 hybridization
1s2 sp3 sp3 sp3-s sp3-s
Electronic conf iguration of O in H2O:

Other examples of molecules with bent tetrahedral shape are H2S, SF2 and SCl2.

Note that: A sp3 hybrid orbital has 25% s-character and 75% p-character.

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 Sp2 Hybridization

This involves mixing of one s-orbital and two p-orbitals to form three equivalent sp2 hybrid
orbitals. Unlike sp3 in which all the atomic orbitals are hybridized, only three atomic orbitals are
hybridized in sp2. The shape of such molecules is trigonal planar with bond angles of 120°.
Their coordination number is 3. Consider boron trifluoride (BF3) molecule.

1s2 2s2 2px1 2py0 2pz0

B in ground state:

1s2 2s1 2px1 2py1 2pz0

B in excited state:

1s2 sp2 sp2 sp2

Hybrid orbitals
of B:

sp2 hybridization
1s2 sp2-p sp2-p sp2-p
Dotted lines indicate
Electronic conf iguration of B in BF3:
electrons contributed
by 3F

Other trigonal planar molecules/ions are BH3, BCl3, CO32-, C2H4, SO3, NO3- and carbonyl carbon
(e.g RCHO, RCOR, RCOOR, RCOOH etc).

In ethene (C2H4), three orbitals are hybridized (2s, 2px and 2py) leaving the 2pz orbital of each
carbon unhybridized. These unhybridized orbitals overlap with each other laterally to form a pi-
(π) bond. Sp2 hybrid orbitals have 33% s-character and 67% p-character.

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Bent/ Angular Planar Shape

Molecules such as GeCl2, GeF2, SO2, O3 and CCl2 have a lone pair electron on the central atom
and two bond pairs that are arranged in distorted trigonal planar geometry also known as bent or
angular. The central atom has sp2 hybrid orbitals but with a bond angle <120°. They also have
coordination number of 2.

Sp Hybridization

This involves mixing of one s-orbital and one p-orbital to form two equivalent sp hybrid orbitals.
In sp hybridization, only two atomic orbitals are hybridized leaving two orbitals unhybridized
(usually 2py and 2pz). The shape of molecules with sp hybrid orbitals is linear with bond angles
of 180°. Liner molecules have coordination number of 2. Typical example is beryllium fluoride
(BeF2) molecule.

1s2 2s2 2px0 2py0 2pz0

Be in ground state:
1s2 2s1 2px1 2py0 2pz0

Be in excited state:

1s2 sp sp
Hybrid orbitals
of Be:

sp hybridization
1s2 sp-p sp-p
Dotted lines indicate
Electronic conf iguration of Be in BeF2:
electrons contributed
by 2F

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Other examples of molecules containing central atoms with sp hybridization are: HC≡CH,
O═C═O, -C≡O+, Cl-Hg-Cl and HC≡N.

Each of the carbon atoms in ethyne (C2H2) has two hybridized (2s and 2px) orbitals and two
unhybridized (2py and 2pz) orbitals. The unhybridized orbitals of one carbon overlap with the
unhybridized orbitals of the other carbon to form two pi-bonds in ethyne. Thus, sp hybrid
orbitals have 50% s-character and 50% p-character.

sp3d Hybridization

This involves mixing of one s-orbital, three p-orbitals and one d-orbital to form five equivalent
sp3d hybrid orbitals. The shape of such molecules is trigonal bipyramidal with bond angles of
120 and 90°. Molecules with trigonal bipyramidal shape have coordination number of 5.
Consider phosphorus pentachloride (PCl5) molecule.

The electronic configuration of P is 1s2 2s2 2p6 3s2 3p3. Hence, the valence shell electronic
configuration of P is 3s2 3p3.

3s2 3px1 3py1 3pz1

P in ground state:
3s1 3px1 3py1 3pz1 3d1

P in excited state:
3s1 3px1 3py1 3pz1 3d1
Hybrid orbitals
of P:

sp3d hybrid orbitals

sp3d-p sp3d-p sp3d-p sp3d-p sp3d-p

Electronic conf iguration of P in PCl5:

Dotted lines indicate

electrons contributed
by 5 Cl

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Other trigonal bipyramidal molecules are PF5, Fe(CO)5 and AsF5.

Molecules such as SF4 have see-saw shape in which one of the five bond pairs in trigonal
bipyramidal is replaced by a lone pair. The lone pair electron is on the equatorial position. They
have coordination number of 4.

In other words, molecules with a total of five electron pairs out of which three are used for
bonding have a T-shaped geometry with bond angles <90° and a coordination number of 3. Such
molecules contain two lone pairs and both are on the equatorial positions. Examples are BrF3,
ClF3 and ICl3.

When there are five electron pairs on the central atom of a molecule/ion in which only two are
used for bonding (coordination number of 2) leaving three as lone pairs, the molecular geometry
of the molecule is linear. The bond angle is 180° because the lone pairs are on the equatorial

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positions. Meanwhile, the hybridization of the central atom remains sp3d. Examples of such
molecules are XeF2 and BrF2-.

sp3d2 Hybridization

This involves mixing of one s-orbital, three p-orbitals and two d-orbitals to form six equivalent
sp3d2 hybrid orbitals. The shape of the molecule is octahedral with bond angles 90°. They have
coordination of 6. Examples are SF6, SCl6 and [Fe(NH3)6]2+. Consider sulphur hexafluoride
(SF6) molecule.

The electronic configuration of S is 1s2 2s2 2p6 3s2 3p4. Hence, the valence shell electronic
configuration of S is 3s2 3p4.

3s2 3px2 3py1 3pz1

S in ground state:

3s2 3px1 3py1 3pz1 3d1

1st excited state of S:

3s1 3px1 3py1 3pz1 3d2

2nd excited state of S:

3s1 3px1 3py1 3pz1 3d2

Hybrid orbitals
of S:

sp3d2 hybrid orbitals

sp3d2-p sp3d2-p sp3d2-p sp3d2-p sp3d2-p sp3d2-p

Electronic conf iguration of S in SF5:

Dotted lines indicate

electrons contributed
by 6 F

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XeF4 has an octahedral geometry and a square planar shape. The hybridization of of Xe in XeF4
is still sp3d2. They have coordination number of 4 and bond angles of 90°.

The electronic configuration of 54Xe is 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6. Thus, the
valence shell electron configuration of Xe is 5s2 4d10 5p6.

5s2 5px2 5py2 5pz2 5d

Xe in ground state:

5s2 5px2 5py1 5pz1 5d2

Xe in excited state:
5s2 5px2 5py1 5pz1 5d2

Hybrid orbitals
of Xe:

sp3d2 hybrid orbitals

sp3d2 sp3d2 sp3d2-p sp3d2-p sp3d2-p sp3d2-p

Electronic conf iguration of Xe in XeF4:

Lone Pairs Four sigma (Xe-F)

bonds

Some transition metal complexes have four bond pairs and with square planar shape. Thus, the
hybridization of the central atom is square planar with bond angles of 90°. This includes, Pd(II),
Pt(II), Ni(II) and Au(II) complexes. Examples are [Pt(NH3)2Cl2], PtCl42- and [Ni(CN)4]2-.