Unit 04: BONDING

IB Topics 4 & 14
Text: Ch 8 (all except sections 4,5 & 8)
Ch 9.1 & 9.5
Ch 10.1-10.7
My Name is Bond.
Chemical Bond
PART 4:
Intermolecular Forces
Intermolecular Forces
Dipole-Dipole
Hydrogen Bonding
(special case of dipole-dipole)
London Dispersion Forces
Ionic
Intermolecular Forces
The forces that act between different
molecules are called intermolecular forces.

These are the forces that make solids and

liquids.
Intermolecular Forces

The intermolecular forces (forces

between molecules) are weaker
than intramolecular forces (the
chemical bonds within an individual
molecule). This distinction is of
course why molecules exist.
Solids
In solids the intermolecular attractive
forces are strong enough not only to hold
molecules close together but to virtually
lock them in place.
Solids, like liquids, are not very
compressible because the molecules have
little free space between them. Often the
molecules take up positions in a highly
regular pattern. Solids that possess
highly ordered structures are said to be
crystalline.
Liquids
In liquids the intermolecular attractive
forces are strong enough to hold
molecules close together. Thus liquids are
much denser & far less compressible than
gases.
The attractive forces in liquids are not
strong enough, however, to keep the
molecules from moving past one another.
Thus liquids can be poured, and assume
the shapes of their container.
Intermolecular Forces
Many properties of materials, including
their boiling and melting points, reflect the
strength of the intermolecular forces.
Intermolecular Forces
A liquid boils when bubbles of its vapor
form within the liquid. The molecules
of a liquid must overcome their
attractive forces in order to separate
and form a vapor.
The stronger the attractive forces, the
higher the temperature at which the liquid
boils.
Similarly, the melting points of solids
increase with an increase in the
strength of the intermolecular forces.
Kinds of Solids
Ionic solids
Covalent-network solids
Metallic solids
Molecular solids
Dipole-dipole

Hydrogen bonded
London dispersion force These forces can also
hold molecules together
to form liquids.
Kinds of Solids
Ionic high melting points

sodium chloride
Kinds of Solids
Covalent-network
Kinds of Solids
Metallic delocalized electrons

silver
Kinds of Solids
Molecular solids - solids and liquids
held together primarily by one or
more of the following forces
1. Dipole Dipole Forces (Interactions)
2. Hydrogen Bonding
3. London Dispersion Forces

Colletively these forces are

called van der Waals Forces
Warning! There's a bit of a problem here with
modern A'level text books. Some texts talk as if
dipole-dipole interactions are quite distinct from van
der Waals forces. Such a text will talk about van der
Waals forces (meaning dispersion forces) and,
separately, dipole-dipole interactions.

All intermolecular attractions are known collectively

as van der Waals forces. The various different types
were first explained by different people at different
times. Dispersion forces, for example, were
described by London in 1930; dipole-dipole
interactions by Keesom in 1912.

This oddity in the texts doesn't matter in the least as

far as understanding is concerned - but you
obviously must know what your particular examiners
mean by the terms they use in the questions.
Intermolecular Forces
Molecular
Dipole-dipole forces - the electrical
attractive forces that exist between polar
molecules.
Dipole-Dipole Interactions
The attractive forces are stronger than the
repulsive forces, so there is an overall
attraction between the molecules.

Attractive
Forces
++++ ----
++++
----

Repulsive Forces
Hydrogen Bonding
Special case of dipole-dipole interactions
Seen among molecules where H is bonded to a
highly electronegative atom, such as N, O or F.
Example: water

H O

H
Hydrogen Bonding
Special case of dipole-dipole interactions
Seen among molecules where H is bonded to a
highly electronegative atom, such as N, O or F.
Example: water
-

+ H O -
Water is a very
polar molecule due
to its geometry and
H very polar bonds
+
Water
Draw THIS diagram:
Hydrogen Bonding
Remember: H- bonding
only exists between
hydrogen and nitrogen,
oxygen or fluorine

HN
HO
H-F
Water
Water
Water
This causes lakes to freeze at the top first.
This is very nice for fish.
and ice skaters!
Water
May the Force be with you, Luke.

Understanding the ways of the intermolecular

forces allows us to understand why substances
are the way they are.
When approaching IB Chemistry

Do or do
not.
There is
no try.
 Why is methane a gas
at room
temperatures, yet
methanol is a liquid?

H-bonding the
answer is.
H-bonding
Why is methane a gas at room temperatures, yet
methanol is a liquid?

H H
..
H C H H C O

..
H H H

Methane Methanol
H-bonding
Why is methane a gas at room temperatures, yet
methanol is a liquid?
O
H H
.. H
H C H H C O

..
H H H
Methane Methanol

Methanol has H-bonding; methane only has weak

dispersion forces
H-bonding in Methanol
 Consider the boiling points of
several hydrides..

100
Normal
Boiling Point
(oC)
SnH4
0

-100

0 50 100 150
Molecular Mass
 100
Normal
Boiling Point
(oC)
SnH4
0
GeH4

-100

0 50 100 150
Molecular Mass
 100
Normal
Boiling Point
(oC)
SnH4
0
GeH4

SiH4

-100

0 50 100 150
Molecular Mass
 100
Normal
Boiling Point
(oC)
SnH4
0
GeH4

SiH4

-100
CH4
0 50 100 150
Molecular Mass
 100
Normal H2Te
Boiling Point
(oC)
SnH4
0
GeH4

SiH4

-100
CH4
0 50 100 150
Molecular Mass
 100
Normal H2Te
Boiling Point
(oC) H2Se
SnH4
0
GeH4

SiH4

-100
CH4
0 50 100 150
Molecular Mass
 100
Normal H2Te
Boiling Point
(oC) H2Se
SnH4
0
H2S GeH4

SiH4

-100
CH4
0 50 100 150
Molecular Mass
 H2O
100
Normal H2Te
Boiling Point
(oC) H2Se
SnH4
0
H2S GeH4

SiH4

-100
CH4
0 50 100 150
Molecular Mass
London dispersion forces

X
London City Fritz London
(1900-1954)
Dispersion forces
Attractions are electrical in nature. In a
symmetrical molecule like hydrogen,
however there doesnt seem to be any
electrical distortion to produce positive or
negative parts.

But this is only true when

averaged over time.
Dispersion forces
Example: consider a small symmetrical
molecule, such as H2 or Br2.

The even shading shows that on average

there is no electrical distortion.
Dispersion forces
However, the electrons are mobile. At any
one instant they might find themselves
towards one end of the molecule, making
that end (-) and the other end (+). This
is called an instantaneous dipole.

+ -
Dispersion forces
An instant later the electrons may well
have moved to the other end, reversing
the polarity of the molecule.

- +
Dispersion forces
This constant sloshing around of the
electrons in the molecule causes rapidly
fluctuating dipoles even in the most
symmetrical molecules.
Dispersion forces
This sloshing even happens in
monatomic atoms --- noble gases, like
helium which consist of a single atom.
If both the helium electrons happen to be
on one side of the atom at the same time,
the nucleus is no longer properly covered
by electrons for that instant.
Dispersion forces
Imagine a molecule which has a temporary
polarity being approached by one which
happens to be entirely non-polar just at that
moment.

- +

Non-polar
(This is actually pretty unlikely, but it makes the
diagrams easier to draw. In reality, one of the
molecules is likely to have a greater polarity than the
other at that time, and so will be the dominant one.)
Dispersion forces
As the molecule approaches, its electrons
will tend to be attracted by the slightly
positive end of the other molecule.

- + - +
induced dipole

This sets up an induced dipole in the molecule,

and it to becomes polar (at least for the
moment).
Dispersion forces
An instant later the electrons in the left-hand
molecule may well have moved to the other end.
In doing so, they will repel the electrons in the
right hand one.

+ - - +
Dispersion forces
The polarity of both molecules reverses, but you
still have attraction. As long as the molecules stay
close to each other the polarities will continue to
fluctuate in synchronization so that the attraction
is always maintained.

+ - + -
Dispersion forces

(London) Dispersion Forces

Two Nonpolar Molecules
Dispersion forces

There is no reason why this has to be restricted

to two molecules. As long as the molecules are
close together this synchronized movement of
the electrons can occur over huge numbers of
molecules.
Dispersion forces

An instant later, of course, you would have to

draw a quite different arrangement of the
distribution of the electrons as they shifted
aboutbut always in synchronization.
Dispersion forces
Its important to understand that
dispersion forces act between all
molecules.
They are usually only important when they
are the only force acting.
Dispersion forces
POLARIZABILITY: The ease with which the
charge distribution in a molecule can distorted by
an external electric field is called its polarizability.

You can think of the polarizability of a molecule

as a measure of the squishiness of its electron
cloud; the great greater the polarizability of a
molecule, the more easily its electron cloud can
be distorted to give a momentary dipole, which
leads to stronger London dispersion forces.
Dispersion forces
In general, larger molecules tend to have
greater polarizabilities because they have
a greater number of electrons and their
electrons are farther from the nuclei.
Dispersion forces tend to increase in
strength with increasing molecular
weight.
Dispersion forces and molar mass

Gas

Gas
Liquid
Solid
Solid
Dispersion forces
The shapes of molecules can also play a
role in the magnitudes of dispersion
forces.
Typically, the greater the surface area of
the molecule, the greater the dispersion
forces.
Dispersion forces
Example: Which will have the higher BP,
pentane (C5H12) or 2,2-dimethylpropane (C5H12)?

BP = 309.4K BP = 282.7K
Rules of Thumb
When the molecules have comparable
molecular weights and shapes, dispersion
forces are approximately equal.
In this case, differences in the magnitudes
of the attractive forces are due to
differences in the strengths of dipole-
dipole attractions, with the most polar
molecules having the strongest
attractions.
Challenge: benzene v. toluene v. phenol
H
H-C-H O-H

Benzene Toluene Phenol

Melting Point (oC) 5 -95 43
Boiling Point (oC) 80 111 182
Example: benzene v. toluene v. phenol
The properties of molecular solids depend not
only on the strength of the forces that operate
between molecules but also on the abilities on
the molecules to pack efficiently in three
dimensions

H
H-C-H O-H

Benzene Toluene Phenol

Example: benzene v. toluene v. phenol
Benzene is a highly symmetrical planar molecule. It
has a higher melting point than toluene. The lower
symmetry of toluene molecules prevents them from
packing as efficiently as benzene molecules. As a
result, the intermolecular forces that depend on close
contact are not as effective, and the melting point is
lower.
H
H-C-H O-H

Benzene Toluene Phenol

Example: benzene v. toluene v. phenol
In contrast, the boiling point of toluene is higher
than that of benzene, indicating that the
intermolecular attractive forces are larger in
liquid toluene than in liquid benzene. (greater
molecular weight greater dispersion forces)

H
H-C-H O-H

Benzene Toluene Phenol

Example: benzene v. toluene v. phenol
For phenol, both the melting and boiling
points are higher than those of benzene
because of the hydrogen bonding ability of
the OH group in phenol.

H
H-C-H O-H

Benzene Toluene Phenol

Relative strengths of forces:

Covalent Hydrogen Dipole-dipole London

bonds > bonding > interactions > forces

less than 1
400 kcal > 12-16 kcal > 2-0.5 kcal >
kcal