Shapes of molecules and ions

 Our objective is to understand the relationship between 2-

dimensional Lewis structures and 3-dimensional molecular
shapes.
 We will see the intimate relationship between the number of
electrons in a molecule and the overall shape it adopts.
Because armed with this knowledge, we can examine more
closely the nature of covalent bonds.
 The lines used to depict bonds in Lewis structures provide
important clues about the orbitals that molecules use in
bonding. By examining these orbitals, we can gain a greater
understanding of the behavior of molecules.
Shapes of molecules and ions
 Although Lewis structures help us to understand how atoms
are bonded and number and type of covalent bonds present
along with lone pairs on atoms, they do not show one of the
most important aspects of molecules which is their overall
shape.
 For example, the Lewis structure of CCl4 tells us only that
four Cl atoms are bonded to a central C atom:
Shapes of molecules and ions
 The shapes and sizes of polyatomic molecules and ions
are defined by the bond angles and distances between
nuclei of component atoms. Bond angles are more
important.
Shapes of molecules and ions
 The shapes and sizes of polyatomic molecules and ions
are important for us because the shape and size of a
particular substance as well as the strength and polarity
of its bonds largely determine the physical and chemical
properties of that substance
Molecular shapes using VSEPER Theory
 This theory is useful to predict the shape or geometry of
covalent molecules and ions of non-transition elements.
 Focuses on pairs of ens in the valence en shell
 En pairs whether bond pairs or lone pairs repel one
another and assume an orientation in space to minimize
repulsions
 This tendency to minimize repulsion causes bonds from
central atom to assume certain orientations which results
in particular shapes for polyatomic moelcules/ions
 Eg: If there are only two en pairs in the valence shell of an
atom, these en pairs will be at opposite sides of the
nucleus to minimize repulsion

 If three en pairs – trigonal planar with bond angles at

120 o, etc
Possible shapes of ABn molecules
(basic shapes)
 Balloon analogy for en domains

 An optimum geometry exists for each number of

balloons
In the VSEPR model
 We predict the en domain geometry or en pair
geometry and by knowing how many lone pairs are
present, we can then predict the molecular geometry or
shape of a molecule or ion
 If no lone pairs on the central atom,
en geometry = molecular geometry or shape
 When lone pairs or non-bonding pairs of ens are involved
we should ignore them to determine the molecular
geometry or shape
 Molecular geometry is the general shape of a molecule as
determined by the relative position of the atomic nuclei
Bonding en pairs and lone pairs are referred to as electron
domains.
The arrangement of en domains about the central atom of
a molecule or ion electron domain geometry
In contrast, molecular shape or geometry is the
arrangement of only the atoms in a molecule or ion.
Eg: NH3
Four step procedure to predict molecular
shapes by VSEPR model
I. Draw the Lewis structure of the molecule or ion.

II. Count the number of electron pairs around the central atom. Each
nonbonding electron pair, each single bond, each double bond,
and each triple bond is counted as one electron domain. This total
no is referred as VSEPR pairs (pi bonds are not considered because
they do not influence the shape of molecule or ion).

III. Determine the electron-domain geometry or en pair geometry by

arranging these VSEPR pairs about the central atom so that the
repulsions among them are minimized, as shown in Table 1.

IV. Use the arrangement of the bonded atoms (ignore lone pairs) to
determine the molecular geometry or true molecular shape.
(Table 2)
Table 1
Table 2
Table 3
Determine the shape of the following
molecules/ions using VSEPR model
 CO32-
 NO2-
 SF4
 ClF3
 BrF5
 ICl4-
CO32-
 Step 1

 Step II VSEPR pairs = 3 (2 single and 1 double bond)

 Step III
CO32-
 Step 1

 Step II VSEPR pairs = 3 (2 single and 1 double bond)

 Step III VSEPR pairs = 3

en pair geometry = trigonal planar

 Step IV no lone pairs on central atom
en pair geometry = shape
Shape is trigonal planar
NO2-
 Step 1

 Step II VSEPR pairs = 3 (1 single bond, 1 double bond

and one lone pair)
 Step III
NO2-
 Step 1

 Step II VSEPR pairs = 3 (1 single bond, 1 double bond

and one lone pair)
 Step III VSEPR pairs = 3

en pair geometry = trigonal planar

 Step IV one lone pair on central atom
ignore lone pair to get shape
Shape is angular or bent
SF4
SF4
Remember…
 Trigonal bipyramid has two geometrically distinct
positions (axial and equatorial)
 If a molecule/ion has nonbonding pairs (lone pairs), they
will always occupy the equatorial positions here.
(which is why we do not consider the possibility of lone
pair occupying an axial position in Step III).
ClF3
 Step 1

 Step II VSEPR pairs = 5 (3 single bonds and

2 lone pairs)
 Step III VSEPR pairs = 5

en pair geometry = trigonal bipyramidal

 Step IV two lone pairs on central atom

ignore lone pairs to get shape
Shape is T shape
ClF3
 Step 1

 Step II VSEPR pairs = 5 (3 single bonds and

2 lone pairs)
 Step III VSEPR pairs = 5

en pair geometry = trigonal bipyramidal

 Step IV two lone pairs on central atom

ignore lone pairs to get shape
Shape is T shape
IF5 or BrF5
ICl4-
 Step 1

 Step II VSEPR pairs = 6 (4 single bonds and

2 lone pairs)
 Step III VSEPR pairs = 6

en pair geometry = octahedral

 Step IV two lone pairs on central atom

ignore lone pairs to get shape
Shape is square planar
Effect of Nonbonding Electrons and
Multiple Bonds on Bond Angles
We can refine the VSEPR model to explain slight distortions from
ideal geometries. Example: Methane, ammonia and water have a
tetrahedral electron-domain geometry, but their bond angles
differ slightly

Electron domains for nonbonding electron pairs exert greater

repulsive forces on adjacent electron domains and tend to compress
bond angles
Order of repulson between electron pairs
 Lone pair-lone pair repulsion > lone pair-bond pair
repulsion >> bone pair-bond pair repulsion

Example: In general, electron domains for multiple

bonds exert a greater repulsive force on
adjacent electron domains than do
electron domains for single bonds.
Covalent bonding and orbital overlap
 Lewis structures and VSEPR theory are useful in
predicting molecular geometry but they do not provide
detailed information
 They do not tell us what happens to the atomic orbitals
during the process of bond formation
 We resort to two theories based on quantum mechanics
are used to describe the formation of covalent bonds
 Valence Bond Theory (VBT)
 Molecular Orbital Theory (MOT)
 VBT assumes that atomic orbitals do not change during
the formation of a bond but merely overlap to the extent
that the ens get paired as the atoms approach one
another.
 During this process each atom acquires a noble gas
configuration except in hydrogen which acquires the He
gas configuration.
 The case of H2 molecule – explained previously
If we try to use VBT to explain the geometry of BeF 2,
we see that
 Be already has a full 2s orbital cannot form a
sigma bond with a half-filled p orbital of F
Hybridization and promotion
 Hybridization and promotion
 Hybridization accounts for the bond angle of 180° in BeF2
 Promotion provides the two half filled orbitals necessary
for bonding
 Although the promotion of ens into hybrid orbitals
requires energy, input of energy is more than
compensated for by the energy released during bond
formation

Remember, these are not stages that ens and orbitals actually go
through. But treated as independent steps to provide a better
understanding of the transition from isolated atoms to chemical
bonds
Hybridization
 We can think of it as an imaginary mixing process in
which orbitals of an atom rearrange to form new atomic
orbitals called hybrid orbitals
 Atomic orbitals are mathematical functions that come
from the quantum mechanical model for atomic
structure.
 To explain molecular geometries, we often assume that
the atomic orbitals on an atom (usually the central atom)
mix to form new orbitals called hybrid orbitals.
 The shape of any hybrid orbital is different from the
shapes of the original atomic orbitals.
 The process of mixing atomic orbitals is a mathematical
operation called hybridization.
General statements regarding hybridization

 The number of standard atomic orbitals added together

always equals the number of hybrid orbitals formed. The
total number of orbitals is conserved.

 The particular combination of standard atomic orbitals

added together determines the shapes and energies of the
hybrid orbitals formed.

 The particular type of hybridization that occurs is the one

that yields the lowest overall energy for the molecule. Since
actual energy calculations are beyond the scope of this
course, we use electron geometries as determined by
VSEPR theory to predict the type of hybridization.
Question: List 10 salient features of the phenomenon
of hybridization

Eg:
 Valence shell atomic orbitals of the central atom or ion mix
together to form hybrid orbitals
 When a certain number of atomic orbitals are mixed, we get
the same number of hybrid orbitals.
 Each hybrid orbital is equivalent to the others but points in a
different direction.
 Thus, mixing one 2s and one 2p atomic orbital yields two equivalent
sp hybrid orbitals that point in opposite directions.
 Other combinations of atomic orbitals can be hybridized to obtain
different geometries, such as sp2 and sp3.
We will examine the common types of hybridization; notice the
connection between the type of hybridization and some of the
molecular geometries predicted by the VSEPR model: linear, bent,
trigonal planar, and tetrahedral, etc

Type of hybridization can be predicted using the no of VSEPR pairs in a

particular molecule or ion

Let us consider the important types of hybridization: sp, sp2, sp3d, sp3d2,
sp3d3 (which we will look into step by step)