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Lecture 5

Intermolecular Forces

Adopted from various sources including: Lectures from David P. WhiteUniversity of North Carolina,
Wilmington; Presentation slides from Prentice Hall; Presentation Slides to Accompany
Cracolice/Peters Introductory Chemistry: An Active Learning Approach, Second Edition Copyright
2004 Brooks/Cole;& Presentation slides to accompany Silberberg Chemistry 4th edition The
McGraw HillCompanies as well as Zumdahl Chemistry 6th edition Houghton Mifflin

A Molecular Comparison of
Gases, Liquids and Solids
Physical properties of substances understood in terms
of kinetic molecular theory:
Gases are highly compressible, assumes shape and volume of
container:
Gas molecules are far apart and do not interact much with each
other.

Liquids are almost incompressible, assume the shape but not


the volume of container:
Liquids molecules are held closer together than gas molecules,
but not so rigidly that the molecules cannot slide past each other.

Solids are incompressible and have a definite shape and


volume:
Solid molecules are packed closely together. The molecules are
so rigidly packed that they cannot easily slide past each other.

A Molecular Comparison of
Gases, Liquids and Solids

A Molecular Comparison of Gases,


Liquids and Solids
Converting a gas into a liquid or solid requires
the molecules to get closer to each other:
cool or compress.

Converting a solid into a liquid or gas requires


the molecules to move further apart:
heat or reduce pressure.

The forces holding solids and liquids together are


called intermolecular forces.

Intermolecular Forces
The covalent bond holding a molecule together is an
intramolecular force.
The attraction between molecules is an intermolecular
force.
Intermolecular forces are much weaker than
intramolecular forces (e.g. 16 kJ/mol vs. 431 kJ/mol for
HCl).
When a substance melts or boils the intermolecular
forces are broken (not the covalent bonds).
When a substance condenses intermolecular forces are
formed.

Intermolecular Forces in Solutions

Intermolecular Forces

Intermolecular Forces
Ion-Dipole Forces
Interaction between an ion (e.g. Na+) and a dipole
(e.g. water).
Strongest of all intermolecular forces:
Q1Q2
F k
2
d
Since Q1 is a full charge and Q2 is a partial charge, F is
comparatively large.

F increases as Q increases and as d decreases:


the larger the charge and smaller the ion, the larger the
ion-dipole attraction.

Intermolecular Forces

Intermolecular Forces
Dipole-Dipole Forces
Dipole-dipole forces exist between neutral polar
molecules.
Polar molecules need to be close together.
Weaker than ion-dipole forces:
Q1Q2
F k
2
d
Q1 and Q2 are partial charges.

Intermolecular Forces
Dipole-Dipole Forces
There is a mix of attractive and
repulsive dipole-dipole forces as
the molecules tumble.
If two molecules have about the
same mass and size, then dipoledipole forces increase with
increasing polarity.

Intermolecular Forces
London Dispersion Forces
Weakest of all intermolecular forces.
It is possible for two adjacent neutral molecules
to affect each other.
The nucleus of one molecule (or atom) attracts
the electrons of the adjacent molecule (or atom).
For an instant, the electron clouds become
distorted.
In that instant a dipole is formed (called an
instantaneous dipole).

Intermolecular Forces
Ion-Induced Dipole:
An ion induces a dipole moment in an adjacent
molecule or atom.

Interaction between an ion (e.g. Na+) and a


dipole (e.g. water).

Intermolecular Forces
London Dispersion Forces

Intermolecular Forces
London Dispersion Forces
One instantaneous dipole can induce another
instantaneous dipole in an adjacent molecule (or
atom).
The forces between instantaneous dipoles are
called London dispersion forces.
Polarizability is the ease with which an electron
cloud can be deformed.
The larger the molecule (the greater the number
of electrons) the more polarizable.

Intermolecular Forces
Polarizability & Periodic Table
Polarizability increases down a group of atoms or
ions because size increases & larger electron
clouds are more easily distorted
Polarizability decreases from left to right across
a period because the effective nuclear charge
holds the electrons more tightly
Cations are less polarizable than parent atom
because they are smaller, whereas anions are
more polarizable because they are larger

Intermolecular Forces
London Dispersion Forces

Intermolecular Forces
London Dispersion Forces
London dispersion forces increase as molecular weight
increases.
London dispersion forces exist between all molecules.
London dispersion forces depend on the shape of the
molecule.
The greater the surface area available for contact, the
greater the dispersion forces.
London dispersion forces between spherical molecules
are lower than between sausage-like molecules.

Intermolecular Forces

Hydrogen Bonding

Special case of dipole-dipole forces.


By experiments: boiling points of compounds with H-F,
H-O, and H-N bonds are abnormally high.
Intermolecular forces are abnormally strong.
H-bonding requires H bonded to an electronegative
element (most important for compounds of F, O, and
N).
Electrons in the H-X (X = electronegative element) lie much
closer to X than H.
H has only one electron, so in the H-X bond, the + H
presents an almost bare proton to the - X.
Therefore, H-bonds are strong.

Intermolecular Forces
Hydrogen Bonding

Intermolecular Forces
Hydrogen Bonding
Hydrogen bonds are responsible for:
Ice Floating
Solids are usually more closely packed than liquids;
therefore, solids are more dense than liquids.
Ice is ordered with an open structure to optimize Hbonding.
Therefore, ice is less dense than water.
In water the H-O bond length is 1.0 .
The OH hydrogen bond length is 1.8 .
Ice has waters arranged in an open, regular hexagon.
Each + H points towards a lone pair on O.
Ice floats, so it forms an insulating layer on top of lakes,
rivers, etc. Therefore, aquatic life can survive in winter.

Intermolecular Forces
Hydrogen Bonding
Hydrogen bonds are responsible for:
Protein Structure
Protein folding is a consequence of H-bonding.
DNA Transport of Genetic Information

Intermolecular Forces
Comparing Intermolecular Forces

Intermolecular Forces in Solutions


Ion-Dipole (40-600 kJ/mol)
H bond (10-40 kJ/mol)

Strongest

Dipole-Dipole (5-25 kJ/mol)

to

Ion-Induced dipole (3-15 kJ/mol)

Weakest

Dipole-Induced Dipole (2-10


kJ/mol)
Dispersion (0.05-40 kJ/mol)

The Uniqueness of Water


Water has many unusual properties when
compared with properties that periodic trends
would otherwise predict:

Higher boiling point


Higher specific heat capacity
Higher surface tension, capillarity
Higher heat of vaporization
Lower vapor pressure
Higher viscosity
Dissolves many substances
Liquid state at room T & P
Solid form floats on liquid less dense

The electrons forming each bond between


hydrogen and oxygen are drawn strongly toward
the oxygen atom
This results in two very polar bonds
The 104.5 bond angle makes a strong dipole
Water molecules also form hydrogen bonds

Comparison of Ice and Water

Issues: H-bonds and Motion


Ice: 4 H-bonds per water molecule
Water: 2.3 H-bonds per water molecule
Ice: H-bond lifetime - about 10 microsec
Water: H-bond lifetime - about 10 psec
(10 psec = 0.00000000001 sec)
Thats "one times ten to the minus eleven
second"!