4.

0 CHEMICAL BONDING
4.2 Molecular shape and polarity
CHEMISTRY UNIT
KOLEJ MATRIKULASI JOHOR
 VSEPR Theory
Linear
Basic Molecular Trigonal Planar
Shape Tetrahedral
Trigonal bipyramidal
Octahedral
Molecular Shape V-shaped
Molecular Trigonal pyramidal
Shape & T-Shaped
Polarity See-saw
Square pyramidal
Square planar
Bond Angle

Dipole Moment

Molecular & Dipole moment ()

Bond Polarity Resultant Dipole
moment ()
 VSEPR THEORY

 Valence–Shell Electron–Pair Repulsion

Theory

 Each group of valence electrons around

a central atom is located as far away as
possible from the others in order to
minimize repulsion
 The theory is used to predict the
molecular shape from the Lewis structure

EXAMPLE: H

H
C
H C H
H H
H
H

Lewis structure molecular shape

The followings count as one e- group:
H
❶ Bonding pair H C H
- a single bond H
- a double bond
- a triple bond

❷ lone pair

●● ●●
❸ lone e- N● O
 e- groups = 3
●●
 FIVE BASIC SHAPES

❶ Linear ❷ Trigonal planar ❸ Tetrahedral ❹ Trigonal ❺ Octahedral

bipyramidal
 ELECTRON GROUP ARRANGEMENT

 Determined by the number of e- groups

around the central atom
 ELECTRON GROUP ARRANGEMENT
Geometry e- Groups Arrangement

2 linear

3 trigonal planar

4 tetrahedral

Trigonal
5 bipyramidal

6 octahedral
 ELECTRON GROUP REPULSION

 Order:
lone pair – lone pair >

lone pair – bonding pair >

bonding pair – bonding pair

❶ LEWIS STRUCTURE  EXAMPLE: BF3

Lewis structure

●●F●●
● ●
●●F● B
●●
F●
❷ELECTRON GROUP ●●● ●●●
ARRANGEMENT
 Electron group = 3
e- group arrangement = trigonal
planar
●●
●F ●
❸ MOLECULAR ● ●
120o
SHAPE B
●● ●●
●F ●
●●
●
F
●●●
 trigonal planar
bond angle: 120o
 TWO ELECTRON GROUPS
EXAMPLE: BeCl2 (gaseous beryllium chloride)

Lewis structure
180o
●● ●●
●● ●● ● Cl
●●● Be Cl●
●
● Cl
●●● Be Cl●
● ●●
●●

 e- groups arrangement  linear

 Molecular shape  linear
bond angle: 180o
 THREE ELECTRON GROUPS
EXAMPLE: BF3 (boron trifluoride)

Lewis structure ●●
● F●
● ●
●●F●● 120o
● ●
●● B ●●
●
● F● B
●●
F●
●F
● F ●
●●●
●●● ●● ● ●●

 e- groups arrangement  trigonal planar

 repulsion of all bonding pair - bonding pair
electrons are equal.
 Molecular shape  trigonal planar
bond angle: 120o
 EXAMPLE: NOCl (nitrosyl chloride)

Lewis structure 

●●
N
●● ●●● ●● ●●
●O N Cl● ●O Cl●●
● ●●
●
●●
113o

 e- groups arrangement  trigonal planar

 repulsion of lone pair-bonding pair >
bonding pair - bonding pair.
 Molecular shape  V–shaped (bent)
bond angle: < 120o
 FOUR ELECTRON GROUPS
EXAMPLE: CH4 (methane)

Lewis structure

H 109.5o

H C H
H

 e- groups arrangement  tetrahedral

 Molecular shape  tetrahedral
bond angle: 109.5o
 EXAMPLE: NH3 (ammonia)

Lewis structure

●●
H N H

H 107.3o

 e- groups arrangement  tetrahedral

 repulsion of lone pair-bonding pair >
bonding pair - bonding pair
 Molecular shape  trigonal pyramidal
bond angle: < 109.5o(107.3o)
 EXAMPLE: H2O (water)

Lewis structure

●●
H O H
●●
104.5o

 e- groups arrangement  tetrahedral

 repulsion of lone pair-lone pair >
lone pair-bonding pair > bonding pair-bonding pair

 Molecular shape  V–shape (bent)

bond angle: < 109.5o (104.5o)
 TETRAHEDRAL ELECTRON GROUP ARRANGEMENT

●● ●●

tetrahedral trigonal pyramidal V shaped

 

bonding-pair vs. bonding lone-pair vs. bonding lone-pair vs. lone pair
pair repulsion < pair repulsion < repulsion
 FIVE ELECTRON GROUPS
EXAMPLE: PCl5 (phosphorus pentachloride)
Lewis structure
●● 90o
●Cl ●
● ●
●●Cl
● ●●●
120o
●●●
●●●
P Cl 90o
●● ●●
●Cl Cl ●
●●● ●●●

 e- groups arrangement  trigonal

bipyramidal
 Molecular shape  trigonal bipyramidal
bond angle: 120o, 90o
 EXAMPLE: SF4 (sulfur tetrafluoride)

Lewis structure
86.8o
●●F●● ●
● F●●
● ●
●●● ●
S 101.5o
●F● ● ●
●●●● ● F●
●●

 e- groups arrangement  trigonal

bipyramidal
 Molecular shape  see saw
(distorted tetrahedral )
bond angle: < 120o, < 90o
 EXAMPLE: BrF3 (bromine trifluoride)

Lewis structure ●●
● ●
● F● 90o
● ●●
● F● Br F● ●●
● ●●● Br F ●●
●● ●●
●F●
●● ● ● ●
● ● F●
●●

 e- groups arrangement  trigonal

bipyramidal

 Molecular shape  T–shaped

bond angle: 90o
 EXAMPLE: I3– (triiodide ion)

●● –
● ●
Lewis structure ●I ●
–
● ●● I


● I● I I ●
● ●●●
●● ●● ● ● 180o
●I ●
●●

 e- groups arrangement  trigonal

bipyramidal

 Molecular shape  linear

bond angle: 180o
 SIX ELECTRON GROUPS
EXAMPLE: SF6 (sulfur hexafluoride)
Lewis structure
●● 90o
●F●
● ● ●●
● ●
●●F● ● F●
●●
● S
●● ●●●
●F F●
●●● ●●
● F●
●●●●

 e- groups arrangement  octahedral

 Molecular shape  octahedral
bond angle: 90o
 EXAMPLE: IF5 (iodine pentafluoride)

Lewis structure
●● 81.9o
● ●
● F● ●● ● F ● ●
●●
● I
●● ●●
●F F●
●●● ● ● ●●●
●●F●●

 e- groups arrangement  octahedral

 Molecular shape  square pyramidal
bond angle: 90o
 EXAMPLE: XeF4 (xenon tetrafluoride)

Lewis structure
●●
●●F● ●● F●
●● ●●● 90o
● Xe
●● ●● ●●●
●F F●
●●● ●●

 e- groups arrangement  octahedral

 Molecular shape  square planar
bond angle: 90o
SUMMARY
e- X E e- group molecular shape
group arrangement
2 2 0 linear linear

3 3 0 trigonal planar trigonal planar

2 1 trigonal planar V–shaped

4 0 tetrahedral tetrahedral

4 3 1 tetrahedral trigonal pyramidal

2 2 tetrahedral V–shaped

Note : X - number of bonding pair

E - number of lone pair
 e- g. X E e- g. arrangement molecular shape
5 0 trigonal bipyramidal trigonal bipyramidal

4 1 trigonal bipyramidal see saw

5
3 2 trigonal bipyramidal T–shaped

2 3 trigonal bipyramidal linear

6 0 octahedral octahedral

6 5 1 octahedral square pyramidal

4 2 octahedral square planar
Note : X - number of bonding pair
E - number of lone pair
 Example 1 4.2

Draw the molecular shape and predict the

bond angles (relative to the ideal angles) .
What are the electron groups arrangements
and the molecular shapes of:

(a) PF3

(b) ClF2−
 BOND POLARITY
 Atoms with different electronegativities
form polar bonds

 Depicted as a polar arrow:

EXAMPLE:

d+ d– d+ d–
C—Cl C—F

C—Cl C—F
 polar bond  polar bond

C—C Br—Br

 nonpolar bond  nonpolar bond

 Example 2 4.2

(a) Use a polar arrow to indicate the polarity

of each bond: N–H, F–N, I–Cl
(b) Rank the following bonds in order of
increasing polarity: H–N, H–O, H–C
 MOLECULAR POLARITY
 Net imbalanced of charge

 e- rich regions (d–) and e- poor regions (d+)

electron poor electron rich

region region
 DIPOLE MOMENT ()

 Quantitative measure of molecular polarity

=Qxr

Q: charge

r: distance between charges

1 D (Debye) = 3.36 x 10-30 C m

Peter Joseph William Debye (1884-1966). American chemist and physicist.

 RESULTANT DIPOLE MOMENT

 Determined by molecular shape and bond

polarity

•  ≠ 0  polar

•  = 0  nonpolar
EXAMPLE:
●● ●●
●I I●
● ●
●● ●●

Delectronegativity = 0

=0

I2 is a nonpolar molecule
EXAMPLE:

●● ●●
●Cl I●
●
●● ●●
● ≠0

Delectronegativity ≠ 0

≠0

ICl is a polar molecule

EXAMPLE:
●● ●●
O C O
●● ●●

CO2 shape: linear

The C‒O bonds are polar but the two bond dipoles
cancel each other

Resultant dipole moment,  = 0

CO2 is a nonpolar molecule

EXAMPLE:

●● ●●
O C S resultant  ≠ 0
●● ●●

OCS shape: linear

The C‒O and C‒S bond are polar and the two bond
dipoles do not cancel each other

Resultant dipole moment,  ≠ 0

OCS is a polar molecule

EXAMPLE:

●●
●F●
● ●

●● B ●●
●F
● Br● resultant  ≠ 0
●●●
●●

BF2Br shape: trigonal planar

The B‒F and B‒Br bond are polar and the three bond
dipoles do not cancel each other

Resultant dipole moment,  ≠ 0

BF2Br is a polar molecule

 Example 3 4.2

Which of the following molecules have a

dipole moment (polar molecule) ? Explain.
H2O or CCl4
 SUMMARY

 A molecule will be nonpolar if:

• The bonds are nonpolar

EXAMPLE:

●● ●●
● CI
● CI ●
●
●● ●●

a nonpolar molecule
 A molecule will be nonpolar if:
• No lone pair in the central atom and all
the surrounding atoms are the same
(the molecular shape is a basic shape)
EXAMPLE:
●● ●●
●F● ●F●
● ● ● ●

●● B ●● ●● B ●●
●F ●F Br●
● F●● ●
●●●
●● ●● ●●

a nonpolar molecule a polar molecule

 A molecule in which the central atom has
lone pair e- will usually be polar with few
exceptions

EXAMPLE:

O
H H

a polar molecule a polar molecule

EXAMPLE:

●● ●●
● ● ● ●
● F● ●● ●F●
●F
●● ●
● ●● S
Br F● ●●
●● ●
● ●F●
● ● ●F ●
● F● ● ●
●● ●●

a polar molecule a polar molecule

• Exception:
●●
● ●
●X●


A
● ●
●X ●
●●

EXAMPLE:

a non polar
 Example 4 4.2

Predict whether each of the following molecules

is polar and show the direction of bond polarity
and net dipole moment.

(a) Boron trichloride, BCl3

(b) Hydrogen bromide, HBr