MOLECULAR GEOMETRY

CHM12

MOLECULAR GEOMETRY
refers to the three dimensional arrangement of atoms in a molecule.
can be reliably predicted by the valence-shell electron-pair repulsion
(VSEPR) model.
VSEPR
it accounts for the geometric arrangements of electron pairs around a
central atom in terms of the electrostatic repulsion between electron pairs.
this model is based on the assumption that chemical bonds and lone pairs
tend to remain as far apart as possible to minimize repulsion.
Rules Governing the Use of VSEPR
1. As far as electron pair repulsion is concerned, double bonds and triple bonds
can be treated like single bonds. (In reality, multiple bonds are larger than
a single bond; that is, because there are two or three bonds between two
atoms, the electron density occupies more space).
2. If a molecule has two or more resonance structures, we can apply the VSEPR
model to any one of them. Formal charges are usually not shown.
MOLECULES IN WHICH THE CENTRAL ATOM HAS NO LONE PAIRS:
Species
Type

Predicted
Bond Angles

Example

AX2

Orientation
of Electron
Pairs
Linear

180o

BeCl2

AX3

Trigonal Planar

120o

BF3

AX4

Tetrahedral

109.5o

CH4

AX5

Trigonal
Bipyramid

90o
1200
180o

PF5

Image

MOLECULAR GEOMETRY
CHM12

AX6

Octahedral

90o
180o

SF6

AX7

Pentagonal
Bipyramidal

72o
90o

IF7

MOLECULES IN WHICH THE CENTRAL ATOM HAS ONE OR MORE LONE

PAIRS
Species
Type

Orientation
of Electron
Pairs
Bent or
Angular

Predicted
Bond Angles

Example

<120o (119o)

SO2

AX3E

Trigonal
Pyramidal

109.5o

NH3

AX4E

Sawhorse or
See-saw

90o
120o

SF4

AX5E

Square
Pyramidal

90o

BrF5

AX2E2

Bent or
Angular

<109.5o
(104.5o)

H2O

AX2E

Image

MOLECULAR GEOMETRY
CHM12

AX3E2

T-shape

90o
180o

ClF3

AX4E2

Square Planar

90o

XeF4

AX2E3

Linear

180o

XeF2

VSEPR GEOMETRIES:

MOLECULAR GEOMETRY
CHM12

Geometry of molecules with more than one central atom:

MOLECULAR GEOMETRY
CHM12

Methanol
the two central atoms in methanol are C and O
the three CH and the CO bonding pairs are tetrahedrally arranged
about the C atom.
the HCH and OCH bond angles are approximately 109o.
the HOC portion of the molecules is bent, and the angle is
approximately 105o

Example:
Use the VSEPR model to predict the geometry of the following molecules and ions:
1. AsH3
2. OF2
3. AlCl414. I35. C2H4
POLARITY
Polarity of Bond:
All bonds are polar unless the two atoms joined are identical.
The extent of polarity depends upon the difference in electronegativity.
Ex. H-H
E.N. = 0
non polar
H-C
E.N. = 0.3
slightly polar
H-F
E.N. = 1.8
strongly polar
Polarity of Molecules:
Diatomic Molecules:
polar if atoms differ
Polyatomic Molecules:
Polar result of an unsymmetrical distribution of electrons,
molecules contains positive and negative poles and is therefore dipole.
Ex. H2O and HCl
Non-Polar - symmetrical distribution of electrons lead to bond or
molecule with no positive or negative poles
Ex. CCl4 and BF3
Determine whether each of the following is polar or non-polar.
1. CO2
2. BF3

MOLECULAR GEOMETRY
CHM12

3.
4.
5.
6.

XeF2
HF
SO2
CH2Cl2

VALENCE BOND THEORY

assumes that the electron in a molecule occupy atomic orbitals of the
individual atoms.
it enables us to retain a picture of individual atoms taking part in the bond
formation.
HYBRIDIZATION:
the mixing or blending the atomic orbitals within an atom to form a new
hybrid orbitals
sp Hybridization
BeF2

1s22s22p5

Be

1s22s2

MOLECULAR GEOMETRY
CHM12

The orbital diagram of this hybridization would be represented as:

sp2 and sp3 Hybridization

BF3

MOLECULAR GEOMETRY
CHM12

Boron

CH4
Carbon

MOLECULAR GEOMETRY
CHM12

H2O
O

Hybridization Involving d Orbitals:

MOLECULAR GEOMETRY
CHM12

atoms in the third period or higher can utilize d orbitals to form hybrid
orbitals
PF5
P

HYBRID ORBITALS
Number of
Electron Pairs

Atomic Orbitals

Hybrid
Orbitals

Examples

2
3

s, p
s, two p

sp
sp2

BeF2, CO2
BeF2, SO3

4
5
6

s, three p
s, three p,d
s, three p, two d

sp3
sp3d
sp3d2

CH4, NH3, H2O

PCl5, SF4, ClF3
SF6, ClF5, XeF4

SHAPE OF HYBRID ORBITALS

Hybrid Orbitals
Orientation

Shape

10

MOLECULAR GEOMETRY
CHM12

Linear
sp
sp2

Trigonal Planar

sp3

Tetrahedral

sp3d

Trigonal Bipyramidal

sp3d2

Octahedral

Examples:
1. What is the hybridization state of Si in:
a. SiH4
b. H3Si-SiH3
2. Specify which hybrid orbitals are used by carbon atoms in these species:
a. CO
b. CO2
c. CN1-

11

MOLECULAR GEOMETRY
CHM12

Hybridization in Molecules Containing Double and Triple Bonds:

Sigma Bonds () covalent bonds formed by orbitals overlapping end-to-end,
with the electron density concentrated between the nuclei of the bonding atoms.

Pi Bonds () covalent bonds formed by sideways overlapping orbitals with

electron density concentrated above and below the plane of the nuclei of the
bonding atoms.

12

MOLECULAR GEOMETRY
CHM12

Single Bond 1 sigma bond

Double Bond 1 sigma bond and 1 pi bond
Triple Bond 1 sigma bond and 2 pi bonds
Example:
Give the number of sigma and pi bonds in:
1. HNO3
2. NH3
3. SO2
4. CH3CH=CHCCH

13