RVCC Fall 2008

CHEM 103 General Chemistry I

Chapter 9:

Molecular
Structures
Chemistry: The Molecular Science, 3rd Ed.
by Moore, Stanitski, and Jurs

Molecular Structure
Molecular geometry is the
general shape of a molecule or
the arrangement of atoms in
three dimensional space.
Physical and chemical properties
depend on the geometry of a
molecule.
2

Molecular Structures

3-D Model

3-D Drawing

Does it matter?
The Thalidomide Story

The chemical structure of thalidomide.

models enantiomers (mirror image)

The Same and Not the Same, by Roald Hoffmann
1995, Columbia University Press
4

Does it matter?
Fatty Acids

trans fatty acid

cis fatty acid

VSEPR Model
The Valence Shell Electron Pair Repulsion
model predicts the shapes of molecules and
ions by assuming that the valence shell
electron pairs are arranged as far from one
another as possible to minimize the repulsion
between them.

VSEPR Model
H
N

Electron Pair Geometry

is determined by the number
and arrangement of all
electron pairs (bonding and
lone) around the central atom.
Molecular geometry
is determined by the
arrangement of atoms (or
bonding electron pairs only)
around the central atom.

In molecules with no lone pairs,

Electron Pair Geometry = Molecular Geometry

7

Fig. 9-4, p.383

AX3E0

AXE shorthand notation:

A - central atom
X - terminal atoms
E - lone pair electrons

Predicting Molecular
Geometry: VSEPR

Only five basic shapes.

When a lone pair replaces an atom, the
molecular geometry changes as well as the
#angles.
e- pairs 2
3
4
5
6

Fig. 9-4, p.383

Predicting Molecular
Geometry: VSEPR
1. Draw the Lewis structure.
2. Determine how many electron pairs (bonded and non-bonded) are
around the central atom. **Treat a multiple bond like a single
bond when determining a shape.
3. Write the AXE shorthand notation.
4. Determine the electron pair geometry (**one of the five basic
shapes).
5. If the molecule has lone pairs around the central atom, then
determine the molecular geometry. (This is a subset of the
electron geometry.)
10

Linear (Electron Geometry)

Two e- pairs about central atom

lone
pairs

1-3

Molecular
Geometry
linear

..

bond
pairs

linear

The molecular geometry here is the same as the electronic

geometry even though there is a lone pair. Two points
11
make a line.

Predicting Molecular
Geometry
Example 1: BeCl2
1. Draw the Lewis structure

Cl

Be

AX2E0

Cl

2. Two electron pairs around the

central atom.
Two bonded and Zero lone pairs.
electron pair geometry = molecular geometry
Geometry is Linear. Bond angle is 180o.
12

Trigonal Planar (Electron Geometry)

Three e- pairs about central atom
bond
pairs

Molecular
Geometry
triangular planar

angular (bent)

Model

..

..

..

lone
pairs

linear

13

Predicting Molecular
Geometry
Example 2: BF3

..
:F:

..
:F
..

AX3E0

..
F:
..

Three electron pairs around the

central atom.
Three bonded and Zero lone pairs.

triangular planar
(or trigonal planar)
14

Predicting Molecular
Geometry
Example 3:SO2
AX3E0
O

AX2E1

Three electron pairs around the

central atom.
Two bonded and One lone pairs.

S
electron geometry = triangular planar.

molecular geometry = bent or angular.

O
15

Tetrahedral (Electron Geometry)

Four e- pairs about central atom
bond
pairs

lone
pairs

Model

tetrahedral

..
triangular

pyramidal

..

angular
(bent)

..

16

Predicting Molecular
Geometry
Example 4:CH4
AX4E0

H
H

C
H

Four electron pairs around the

central atom. Zero lone
pairs.

tetrahedral

electron pair geometry = molecular geometry

17

Predicting Molecular
Geometry
Example 5:NH3
H

AX4E0

AX3E1

H
Four electron pairs around the
central atom.
Three bonded and One lone pair.
electron geometry = tetrahedral.

molecular geometry = triangular pyramidal

H
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Geometry
Example 6:H2O
AX4E0 AX2E2
H

Four electron pairs around the

central atom.
Two bonded and Two lone pairs.
electron geometry = tetrahedral

molecular geometry = angular or bent

O
H

H
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Predicting Molecular
Geometry
Tetrahedral - bond angles

Order of increasing repulsion:

bonding pair-bonding pair

<

bonding pair-lone pair

<

lone pair-lone pair

20

Trigonal Bipyramidal (Electron

Geometry)
Five e- pairs about central atom

..

..

..

90

120

Triangular bipyramidal

Seesaw

The atoms are non-equivalent.

Green atoms are axial;
blue atoms are equatorial.

T-shaped

Linear

**Put lone pairs

in the equatorial
positions.
21

Predicting Molecular
Geometry
Example 7: PF5

: :

:F

F:
F:

:F:

: : : :

:F:

AX5E0

Five electron pairs around the

central atom.
electron and molecular geometry=
Zero lone pairs.

trigonal bipyramidal

22

Predicting Molecular
Geometry
Example 8: SF4

: :: :

:F

AX4E1

:F
S:
:F
:F :

AX5E0

Five electron pairs around the

central atom.
Four bonded and One lone pair.
electron geometry = trigonal bipyramidal

molecular geometry = seesaw

23

Predicting Molecular
Geometry
Example 9: BrF3

:F :

AX5E0

AX3E2

: :

Br F:

:F :
Five electron pairs around the
central atom.
Three bonded and Two lone pairs.
electron geometry = trigonal bipyramidal

molecular geometry = T-shaped

24

Predicting Molecular
Geometry
Example 10: XeF2

AX5E0

:F :

AX2E3

:
Xe
:
:
:F :
Five electron pairs around the
central atom.
Two bonded and Three lone pairs.
electron geometry = trigonal bipyramidal

molecular geometry = linear

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Octahedral (Electron Geometry)

Six e- pairs about central atom

90

Octahedral

..

Square pyramid

Square planar

Equivalent atoms

26

Predicting Molecular
Geometry
Example 11: SF6

: :

: :

F:
F:

:F:

:F

:
:F

:F:

AX6E0

Six electron pairs around the central atom.

Six bonded and Zero lone pairs.
electron geometry = octahedral

molecular geometry = octahedral

27

Predicting Molecular
Geometry
Example 12: IF5

AX6E0

:F :
I

F:

: :: :

: :: :
:

:F
:F

AX5E1

F:

Six electron pairs around the

central atom.
Five bonded and Two lone pairs.
electron geometry = octahedral

molecular geometry = square pyramidal

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Predicting Molecular
Geometry
: :: :

:
:

F
F
Xe
F
F

AX6E0

AX5E1

:
:

: :: :
: :

Example 13:
XeF4

Six electron pairs around the

central atom.
Four bonded and Two lone pairs.
electron geometry = octahedral

molecular geometry = square planar

29

Predicting Molecular
Geometry

30

Fig. 9-5, p.391

Predicting Molecular
Geometry

Fig. 9-6, p.393

31

Practice
ICl
ICl3

CO2

SO2

ICl5

ClO2-

GeF4

SeF4

XeF4

32

Bond Angles
CHO

Give the
approximate values
for the indicated
bond angles.

COH

OCN
HNH

33

Molecular Geometry
Dipole Moment and Polarity
Electronegativity (EN) values are used to predict the
polarity of covalent bonds. The greater EN, the more
polar will be the bond. A polar bond has a dipole or
slight separation of charge (from the unequal sharing of
bond electrons). [Chapter 8]
The polarity of a molecule depends on the sum of all the
bond dipoles (vectors). If there is a net dipole for the
molecule, than the molecule is polar. A molecule that
has polar bonds may or may not be polar.
The dipole moment () is a measure of the degree of
charge separation or the polarity.
34

Molecular Geometry
Dipole Moment and
Polarity

nonpolar, bp=-79C

dipole moment, = 0 D

polar, bp=100C

. ..
.O
H
H

Net
dipole

dipole moment, = 1.85 D

35

Molecular Geometry
Dipole Moment and
Polarity
In general, a molecule is polar if:

it isnt a basic VSEPR shape (symmetrical)

Ex: H2O, bent (polar)

or if the terminal atoms/groups in a

basic VSEPR shape differ.
Ex: CH2Cl2, tetrahedral (polar)

36

Dipole Moment and Molecular

Geometry
Molecules that exhibit any asymmetry in the
distribution of electrons would have a nonzero
net dipole moment. These molecules are
considered polar.

Non polar
VSEPR shape
identical atoms

Polar
VSEPR shape
atoms differ
37

Dipole Moment and

Molecular Geometry

38

Molecular Geometry
Dipole Moment and
Polarity

+
Non polar
VSEPR shape
identical atoms

PF4Cl

PF5

PF3Cl2

Non polar
Atoms differ. BUT
can be divided into
nonpolar VSEPR
shapes:
linear + triangular
planar

Polar
VSEPR
shape
atoms differ

PF3Cl2

Polar
Atoms differ.
Doesnt divide into
nonpolar VSEPR
shapes
39

UNIT 2

Chapter 4: Chemical Bonding and Properties of

Matter

Molecular Shapes and Polarities

TO PREVIOUS
SLIDE

Section
4.2

Dipole Moment and

Molecular Geometry
F
: Cl
:

ClF3

F
T-shaped
No symmetry polar

F
F
XeF4

F
F
S:
F
F

Xe

F
F

Square Planar
Symmetric non polar

F
:Xe:

SF4
SeeSaw
No symmetry polar

XeF2
Linear
Symmetric non polar
41

Molecular Geometry
Dipole Moment and
Polarity
CO, PCl3, BCl3, GeH4, CF4

Which compound is the most polar?

Which compounds on the list are nonpolar?

42

Types of Intermolecular
Forces
+

Intermolecular Interactions

London Forces
(0.05 40 kJ/mol)

Dipole-Dipole Forces
(5 25 kJ/mol)

Hydrogen Bonding
(10 40 kJ/mol)

(Intramolecular Covalent Bond

150 1000 kJ/mol)
43

Types of Intermolecular
Forces
London Forces
(dispersion forces)

When electrons are momentarily

unevenly distributed in the
molecule, polarization occurs.

Induced Dipole

All molecules, EVEN nonpolar ones experience London Forces!

(Nonpolar molecules do not experience any other intermolecular
44
interaction)

Types of Intermolecular
Forces
To boil (l g), molecules must
have enough energy to
overcome their intermolecular
forces.

The higher the intermolecular

force the higher the boiling
point!

Dispersion Forces increase with increased number of electrons.

45

increased
polarizability

Types of Intermolecular
Forces
A polar molecule is a
Permanent Dipole that
creates .

Dipole-Dipole forces
46

Types of Intermolecular
Forces
The more polar the molecule
(at a given size)

the higher the boiling

point!

47

Types of Intermolecular
Forces
Hydrogen bond
is established by the attraction between
hydrogen and an electron pair on a small, very
electronegative atom.
+

XH

---

X = N, O, F

:Z

Z = N, O, F

This bond is responsible of determining the three

dimensional structure of large proteins molecules

48

Types of Intermolecular
Forces
Water:
One molecule can participate in four
H bonds with other molecules.
Because of the hydrogen bond, water
has a boiling point 200 C higher than
if the bond were not present.

49

Practice

Explain the following boiling points,

Which of the following will form H-bonds:

HF (20C), HCl (-80C), HBr (-60C), HI (-25C)

CH2Br2, CH3OCH2CH3, CH3CH2OH, H2NCH2COOH

What types of forces must be overcome in

these changes?

The sublimation of solid C10H8

The decomposition of water into H2 and O2

The evaporation of PCl3

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