Hybridization & Polarity

Sections 9.6, 10.5-10.7

RW Session ID = MSTCHEM1
 Hybridization
• The orbitals in a molecule are not necessarily
the same as the orbitals in an atom.

The standard atomic orbitals can be combined

to form new atomic orbitals called hybrid
orbitals.
– Correspond more closely to the actual distribution of electrons in
chemically bonded atoms
– Different shapes and energies than standard atomic orbitals
– Minimize the energy of the molecule by maximizing the orbital
overlap in a bond
 Hybridization
• The number of standard atomic orbitals added
together always equals the number of
degenerate hybrid orbitals formed.
– 1 s & 1 p – 2 sp orbitals
– 1 s & 2 p – 3 sp2 orbitals
– 1 s & 3 p – 4 sp3 orbitals
– 1 s, 3 p, & 1 d – 5 sp3d orbitals
– 1 s, 3 p, & 2 d – 6 sp3d2 orbitals
 The Five Basic Shapes:
Hybridization
• Linear
– 2 electron groups 180° sp

• Trigonal planar
– 3 electron groups 120° sp2

• Tetrahedral
– 4 electron groups 109.5° sp3

• Trigonal bipyramidal
– 5 electron groups 90°, 120° sp3d

• Octahedral
– 6 electron groups 90° sp3d2
 Bonding
• When orbitals overlap end to end, the resulting bond is
called a sigma(σ) bond.
• When p orbitals overlap side by side the resulting bond is
called a pi(π) bond.

– A single bond is a σ bond

– A double bond consists of one σ bond and one π bond
– A triple bond consists of one σ bond and two π bonds

Hybrid orbitals are formed to accommodate sigma bond

electrons and lone pair electrons
• Pi bond electrons are located in higher energy orbitals that
are not hybridized
 σ π σ
π σ
σ σ σ π
σ σ
SO2 CH2O
BCl3 2σ and 2π bonds 3σ and 1π bond
3σ and 0π bonds

σ π σ π
σ
σ σ π σ
σ σ

C2H4 C2H2
5σ and 1π bonds 3σ and 2π bonds
 Determine the electron geometry, molecular
geometry, and bond angles for each carbon,
nitrogen, and oxygen in the given structure.
Trigonal planar
linear
Linear 180°
Linear
180° Tetrahedral
Tetrahedral
Trigonal pyramidal Bent
< 109.5° < 109.5°
H O
H N C C C C O H
H H
Trigonal planar
Tetrahedral Trigonal planar
Tetrahedral 120°
109.5°
 Determine the hybridization of each
carbon, nitrogen, and oxygen in the given
structure.
sp2

sp

sp3 sp3
H O
H N C C C C O H
H H
sp2
sp3
 Electronegativity
• The ability of an atom to attract electrons to itself
in a chemical bond.
– Results in polar, nonpolar, and ionic bonds
– Inversely related to the atomic size
• The larger the atom, the lower the ability to attract electrons
• The smaller the atom, the greater the ability to attract
electrons

– General trend for electronegativity

• Decreases from top to bottom in a group
• Increases from left to right across a period
– Except for noble gases, which have an electronegativity of zero
 Bond Polarity
The polarity of a bond depends on the
electronegativity difference between the two
bonding elements

• Nonpolar covalent
– Small or no electronegativity difference (0 to <0.4)
• Polar covalent
– Intermediate electronegativity difference (0.4 to 2.0)
• Ionic
– Large electronegativity difference (>2.0)
 Bond polarity
Ionic character (IC) estimation = |χ1-χ2|

IC > 2 → ionic 2 > IC > 0 → polar IC = 0 → nonpolar

ICNaCl ICHCl ICCl2

= χ Na − χ Cl = χ H − χ Cl = χ Cl − χ Cl
> >
= 0.93 − 3.16 = 2.20 − 3.16 = 3.16 − 3.16
= 2.23 = 0.96 = 0.00

Ionic Polar Nonpolar

> 2.0 difference in χ 0.4 - 2.0 difference in χ < 0.4 difference in χ
Polar Bonds & Polar Molecules

Polar bonds
do not imply
a polar molecule

Bond dipoles
may cancel

Therefore:
Molecular polarity is
determined by
bond-dipole
vector addition
 Red arrows indicate bond dipoles
Polar molecules – nonzero net dipole
Blue arrows indicate the net dipole

Non-polar molecule – net dipole is zero

 Linear
Nonpolar if terminal atoms are the same
Polar if terminal atoms are different

Trigonal Planar

Trigonal Planar Bent

Nonpolar if terminal atoms are the same Always polar due to lone pair
Polar if terminal atoms are different
 Tetrahedral

Trigonal Pyramidal
Always polar due to lone pair

Tetrahedral
Nonpolar if terminal atoms are the same
Polar if terminal atoms are different
Bent
Always polar due to lone pairs
 Trigonal Bipyramidal
Trigonal Bipyramidal
Nonpolar if terminal atoms are
the same
Generally polar if terminal
atoms are different

Seesaw
Always polar due
to lone pair

Linear
T-shaped Nonpolar if terminal atoms are the same
Always polar due to lone pairs Polar if terminal atoms are different
 Octahedral

Square Pyramidal
Always polar due
to lone pair

Octahedral
Nonpolar if terminal atoms are
the same Square Planar
Generally polar if terminal Nonpolar if terminal atoms are the same
atoms are different Generally polar if terminal atoms are
different
Is O2 polar or nonpolar?

O O nonpolar

Is ClO- polar or nonpolar?

-
Cl O polar
Is NO2- polar or nonpolar?
-
O N O polar

Is CO32- polar or nonpolar?

2-
O
nonpolar
O C O
Is COCl2 polar or nonpolar?
Cl
polar
Cl C O

Is PF3 polar or nonpolar?

F
polar
F P F
Is PCl5 polar or nonpolar?
Cl
Cl P Cl nonpolar

Cl Cl

Is NH4+ polar or nonpolar?

+
H
H N H nonpolar
H
Is XeF4 polar or nonpolar?
F
F Xe F nonpolar
F