SHAPES

OF
MOLECULES
Chemistry @ MBCC
Pre-University Sciences
Science 1
Recall that:
Covalent bonds are formed from the overlap of two atomic
orbitals

Each pair of covalent bond contains a pair of electrons

Two types of covalent bonds are formed:

1. Sigma (σ) bonds
2. Pi bonds (π) bonds
Electron Pairs
In molecules there are 2 types
of electron pairs
1. Bonding Pairs
2. Non-bonding or lone pairs
The bonding pair may be
represented by a line
What is the shape of the molecule?
We will use the geometric arrangement of atoms around a
central atom in a covalent compound (or charged ion) to
determine the shape of the molecule

Pi - bonds have a very limited impact on shape

Sigma - bonds have a much more important effect on shapes

 Valence Shell Electron Pair Repulsion (VSEPR) Theory
VSEPR theory is a model that helps us to understand the known 3-D
structure (geometry) of molecules

The VSEPR theory proposes that the shape of the molecule is

determined solely by the repulsions between electron pairs present in the
valence shell of the central atom

The number of electron pairs around the central atom can be determined
by writing the Lewis structure for the molecule
The VSEPR Model
May be used to predict the shapes and bond
angles of molecules and molecular ions

Pairs of electrons that surround the central

atom of a molecule or ion are arranged as far
apart as possible to minimize electron-
electron repulsion

Applicable only to covalent compounds

o Ionic bonds are non-directional while covalent
bonds have a preferred direction in space
VSEPR Theory and Repulsion
Electrostatic force of repulsion between electron pairs

Repulsion occurs to attain most comfortable arrangement

Three types of repulsion to consider:

1. Bonding pair - Bonding pair repulsion
2. Lone pair - Lone pair repulsion
3. Bonding pair –Lone pair repulsion
Strength of Repulsion
Depends on proximity of electron pairs to central atom

Bonding pair
- located between two nuclei

Lone pairs
- closer to central atom
- they are delocalized
- have no other nucleus to attract them

Lone pairs push bond pairs closer

- As bonds are pushed closer together the bond angle decreases

LP-LP REPULSIONS > LP-BP REPULSIONS > BP-BP REPULSIONS

Strength of Repulsion
“The shape adopted by a simple molecule or ion
is that which keeps repulsive forces to a
minimum”
Bonds are closer
together so repulsive All bonds are
forces are greater equally spaced
out as far apart
as possible
Al Al
Note – you must
think of spacing
in 3D not just 2D
Bonds are further
apart so repulsive
forces are less
Molecular Geometries
TWO regions of electron
density

THREE regions of electron

density

FOUR regions of electron

density
FIVE regions of electron density

SIX regions of electron density

Molecular Geometries (Cont’d)
SEVEN regions of electron
density
Using VSEPR theory to predict the shape of the molecule
1. Decide which is the central atom in a molecule.
- In cases of ambiguity, pick the least electronegative atom (aside from hydrogen)
as this atom will be better able to share its electrons with the other atoms in the
molecule

2. Count up the valence electrons on the central atom.

3. Count up the electrons used by the outer atoms to make bonds with
the central atom
Using VSEPR theory to predict the shape of the molecule
4. The sum of steps (2) + (3) divided by two gives the Valence Shell
Electron Pair (VSEP) count

The VSEP count gives the number of electron pairs around the central
atom

5. Assign one electron pair for each bond (or two pairs for each double
bond). Any unassigned electron pairs are lone pairs and are placed on
the CENTRAL atom.
The VSEP Count
The predicted geometry of the
molecule is based on the number
of VSEP count

VSEP Count gives the

1. Central Atom is Oxygen
arrangement of electron pairs 2. Number of valence electrons = 6 e-
around the central atom (both 3. Number of electrons used by peripheral atoms to
lone pair and bonded pair) bond to central atom = 2 (1) = 2 e-

VSEP count = (6 e-) + (2 e-) /2 = 4 e- pairs

Eg. Calculate the VSEP count
for the water molecule The O central atom has 4 e- pairs around it
2 bonding pairs and 2 non-bonding (or lone) pairs
Predicting the Shapes of Molecules
BeCl2
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Beryllium
2. Number of valence electrons = 2 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 2 (1) = 2 e-
4. VSEP count = (2 e-) + (2 e-) /2 = 2 e- pairs

The Be central atom has 2 e- pairs around it

2 bonded pairs and NO non-bonded or lone pairs
Predicting the Shapes of Molecules
BeCl2 In general molecules ,
What is the shape of the AX2, with 2 bonding pairs
molecule? Bond angle?
and no lone pairs are
Linear.

Bond Angle = 1800

Linear Shape
Linear Molecules (AX2)
 When applying the VSEPR model, we count a double or triple
bond as a single electron domain
 Double and triple bonds are linear, and behave very much like
a single bond when it comes to repulsions
Predicting the Shapes of Molecules
BF3
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Boron
2. Number of valence electrons = 3 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 3 (1) = 3 e-
4. VSEP count = (3 e-) + (3 e-) /2 = 3 e- pairs

The B central atom has 3 e- pairs around it

3 bonding pairs and NO non-bonding or lone pairs
Predicting the Shapes of Molecules
BF3
What is the shape of the In general
molecule? Bond angle?
molecules , AX3,
with 3 bonding
pairs and no
lone pairs are
Trigonal Planar
Bond Angle = 1200
Trigonal Planar
Trigonal Planar (AX3)
Examples include BH3, SO3, CO32- and C2H4

http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Molecular_Geometry/Trigonal_Planar_______Molecular_Geometry
Predicting the Shapes of Molecules
CH4
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Carbon
2. Number of valence electrons = 4 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 4 (1) = 4 e-
4. VSEP count = (4 e-) + (4 e-) /2 = 4 e- pairs

The C central atom has 4 e- pairs around it

4 bonding pairs and NO non-bonding or lone pairs
Predicting the Shapes of Molecules
CH4 In general molecules , AX4,
What is the shape of the with 4 bonding pairs and no
molecule? Bond angle? lone pairs are Tetrahedral

Bond Angle = 109.50

Tetrahedral
Homework
Q. Show that the following molecules have a tetrahedral
structure?
a) CCl4
b) CH4
c) SiCl4
Predicting the Shapes of Molecules
NH3
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Nitrogen
2. Number of valence electrons = 5 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 3 (1) = 3 e-
4. VSEP count = (5 e-) + (3 e-) /2 = 4 e- pairs

The N central atom has 4 e- pairs around it

3 bonding pairs and 1 non-bonding or lone pair
Predicting the Shapes of Molecules
NH3 In general molecules , AX3E,
What is the shape of the with 3 bonding pairs and 1
molecule? lone pair are Trigonal
Pyramidal

Bond Angle = 1070

Trigonal Pyramidal
More Homework…
Q. Show that the PH3 molecule has a trigonal
pyramidal structure?
Predicting the Shapes of Molecules
H2O
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Oxygen
2. Number of valence electrons = 6 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 2 (1) = 2 e-
4. VSEP count = (6 e-) + (2 e-) /2 = 4 e- pairs

The O central atom has 4 e- pairs around it

2 bonding pairs and 2 non-bonding or lone pairs
Predicting the Shapes of Molecules
H2O
What is the shape of the molecule?
Bond angle?
In general molecules , AX2E2, with
2 bonding pairs and 2 lone pairs
are Bent or V-shaped

Bond Angle = 104.50

Bent (or V-shaped)
Homework
Q. Show that the following molecules have a bent
structure?
a)H2S
b)SO2
c) H2O
Predicting the Shapes of Molecules
PCl5
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Phosphorus
2. Number of valence electrons = 5 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 5 (1) = 5 e-
4. VSEP count = (5 e-) + (5 e-) /2 = 5 e- pairs

The P central atom has 5 e- pairs around it

5 bonding pairs and NO non-bonding or lone pairs
Predicting the Shapes of Molecules
PCl5 In general molecules , AX5, with 5
What is the shape of the molecule? Bond
angle?
bonding pairs and 0 lone pairs are
Trigonal Bipyramidal

Bond Angle = 900 and 1200

Trigonal Bipyramidal
Predicting the Shapes of Molecules
SF6
What is the VSEP count? How many bonding pairs and
lone pairs?
1. Central Atom is Sulphur
2. Number of valence electrons = 6 e-
3. Number of electrons used by peripheral atoms to bond to
central atom = 6 (1) = 6 e-
4. VSEP count = (6 e-) + (6 e-) /2 = 6 e- pairs

•The S central atom has 6 e- pairs around it

•6 bonding pairs and NO non-bonding or lone pairs
Predicting the Shapes of Molecules
SF6 In general molecules , AX6, with
What is the shape of the molecule? 6 bonding pairs and 0 lone pairs
Bond angle? are Octahedral

The F-S-F Bond Angles are all 900

Octahedral
Predicting the shapes of ions
The number of electrons depends on the charge on the ion
If the ion is positive you remove as many electrons as there are positive
charges
If the ion is negative you add as many electrons as there are negative
charges

e.g. for PF6- add one electron to the outer shell of P, while for PCl4+ remove one
electron from the outer shell of P
Homework
Q. Give the shapes of the following polyatomic ions. In each case state
the bond angle present.
a) NH4+
b) SO42-
c) PO43-
d) NH2-
e) CH3-
f) CH3+
g) SO32-
 SHAPES AND BOND
ANGLES OF SIMPLE
ORGANIC COMPOUNDS
Organic Compounds
Organic compounds belong to a large class of chemical compounds
whose molecules contain carbon (except CO2 and carbonates)

The simple picture of overlap of half-filled atomic orbitals cannot be used

to explain the geometry of all molecules especially organic molecules

We use a concept known as hybridization to explain bonding in carbon

compounds
Electronic Configuration of Carbon in the Ground State

http://www.chemistryland.com/CHM151S/09-CovalentBonds/Covalent.html
Methane (CH4)
Each carbon in methane forms four single bonds equal in length
and energy
− Carbon atom must possess four orbitals with one electron each
− Carbon in the ground state has only two singly filled orbitals
− To form 4 bonds, 4 singly filled orbitals are needed

How will this be achieved?

Promotion of an electron from the 2s orbital to the 2p orbital (excitation)

Mixing the 2s and 2p orbitals (hybridization)

Excitation of Carbon

One of the 2s electrons is

spontaneously promoted to
the empty 2p orbital
sp3 Hybridisation in Methane
 ONE “s” orbital and THREE “p” orbitals mix to form
FOUR hybrid orbitals (sp3) with four single electrons
 number of orbitals is conserved during hybridization

 Four identical sp3 orbitals formed

 All the same shape, size and energy
http://ibchem.com/IB/ibnotes/full/bon_htm/14.2.htm
sp3 Hybridisation in Methane

http://www.chemistryland.com/CHM151S/09-CovalentBonds/Carbonsp3tetrahedron.jpg
sp Hybrid Orbitals
3
Each hybrid orbital contains
25% s character and 75 % p
character

The FOUR sp3 hybrid orbitals

each contains one electron

Hybrid orbitals arrange

themselves in a three
dimensional space to get as far
apart as possible (to minimize
repulsion)

Arrangement gives rise to a

tetrahedral structure bond
angle of 109.5
Sp3 Hybridization (Methane)

Overlapping of sp3 orbitals on carbon

with s orbital of hydrogen gives rise to a
sigma bond
 Sp3 Hybridization (Ethane)
 sp3 orbitals of
carbon overlap
with s orbital of
hydrogen to
give a sigma
bond

 sp3 orbitals on
both carbons
overlap to give
a sigma bond
Sp Hybridization
2
Sp Hybridization
2
Sp hybridization
2
Found in compounds such as alkenes (eg.
ethene)

Each carbon needs to bond to THREE

atoms (two hydrogens and one carbon)

Electron promotion still occurs in carbon

followed by mixing of the 2s and 2p
orbitals (hybridization)

However, only two of the p orbitals are

mixed with the s orbital to form three sp2
hybrid orbitals

The unused p orbital remains pure

(unhybridized)
sp2 Hybridization (C2H4)
Two sp2 orbitals will overlap with
hydrogen 1s orbital; the third
sp2orbital will overlap with a
similar sp2 orbital on the other
carbon atom

Each carbon has a pure, unused p

orbital containing an electron

The unused p orbitals are

perpendicular to the plane of the sp2
orbitals; projects above and below
the plane

Close proximity of p orbitals causes

sideways overlap forming a pi bond
- Pi bonds are weaker than sigma bonds
Bonding in Ethyne (C2H2)

Ethyne contains a triple bond

In each carbon of the triple bond there are two sp hybrid
orbitals and two unused p orbital
Each carbon in the triple bond is sp hybridised
The two unused p orbitals overlap above and below the
plane to form two pi (π) bonds
What is the shape of the ethyne molecule?
 The triple bond consists of one sigma bond and
two pi bonds

 The geometry around each carbon is linear with a

bond angle of 180o http://pages.towson.edu/ladon/carbon.html
What is the bond angle around
a)sp3 hybridized carbon?
b)sp2 hybridized carbon?
c)sp hybrid carbon?
Benzene
Six carbon atoms in a ring

Hexagonal in shape - at each

apex there is a carbon bonded
to a hydrogen

Each carbon is bonded to three

other atoms; a hydrogen and
two other carbon atoms

Each carbon uses sp2 hybrid

orbitals

Each carbon contains a pure p

orbital perpendicular to the
plane of the ring http://www.chemistryland.com/CHM151S/09-CovalentBonds/Benzenesp2.jpg
Benzene
Each unhybridized p orbital overlaps with two
other p orbitals, one on each of the two
neighbouring carbon atoms

A large circular pi-type bond is formed above

and below the plane

Electrons are delocalized in the benzene ring

Benzene
Overlapping of p orbitals
Representations of Benzene
 Summary:
Fundamental Shapes – no lone pairs

All the bond pair-bond pair repulsions are C

equal.
A covalent bond will repel
another covalent bond

BOND ELECTRON BOND

PAIRS GEOMETRY ANGLE(S) EXAMPLE

2 LINEAR 180º BeCl

2

3 TRIGONAL PLANAR 120º AlCl

3

4 TETRAHEDRAL 109.5º CH4

5 TRIGONAL BIPYRAMIDAL 90º & 120º PCl5

6 OCTAHEDRAL 90º SF
6
 Summary:
Effect of Lone Pairs on Molecular Shape
If a molecule, or ion, has lone pairs on the central atom, the shapes are slightly
distorted away from the regular shapes. This is because of the extra repulsion
caused by the lone pairs.

BOND PAIR - BOND PAIR < LONE PAIR - BOND PAIR < LONE PAIR - LONE PAIR

O O O

As a result of the extra repulsion, bond angles tend to

be slightly less as the bonds are squeezed together.
 Test Questions
For each of the following ions/molecules, state the number of bond pairs
state the number of lone pairs
state the bond angle(s)
state, or draw, the shape

BF3

SiCl4

PCl +
4

PCl6-

SiCl62-

HS
2
 Test Questions
For each of the following ions/molecules, state the number of bond pairs
state the number of lone pairs
state the bond angle(s)
state, or draw, the shape

BF3 3 bp 0 lp 120º trigonal planar boron pairs up all 3 electrons in

its outer shell

SiCl4 4 bp 0 lp 109.5º tetrahedral silicon pairs up all 4 electrons in

its outer shell

PCl +
4 bp 0 lp 109.5º tetrahedral as ion is +, remove an electron
4
in the outer shell then pair up

PCl6- 6 bp 0 lp 90º octahedral as the ion is - , add one electron to

the 5 in the outer shell then pair up

SiCl62- 6 bp 0 lp 90º octahedral as the ion is 2-, add two electrons

to the outer shell then pair up

HS 2 bp 2 lp 92º bent planar sulphur pairs up 2 of its 6

2
electrons in its outer shell -
2 lone pairs are left
More Test Questions…
The following triatomic compounds are planar.
However, their shape may be linear or bent. Determine
whether the following atoms are linear or bent.
a. HCN
b. O3
c. SO2
d. CO2
e. H2S
f. N2O

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Questions/General/shapes.htm
More Test Questions…
The shape assumed by the atoms of the following
compounds may be trigonal-planar, square-
planar, pyramidal or tetrahedral. Choose one of these
shapes for the following compounds.
a. BF3
b. CH2Br2
c. SO3
d. Cl3N
e. SiCl4

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Questions/General/shapes.htm