Intermolecular Forces,

Liquids and Solids

CHAPTER 11
CHEM 160

A Molecular Comparison
of 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.

A Molecular Comparison
of Liquids and Solids
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 Liquids and Solids

A Molecular Comparison
of Liquids and Solids

A Molecular Comparison
of 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 forces.
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).

Intermolecular Forces

Intermolecular Forces
Ion-Dipole Forces
Interaction between an ion and a dipole (e.g. water).
Strongest of all 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.
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
dipole-dipole forces increase with increasing polarity.

Intermolecular Forces
Dipole-Dipole Forces

Intermolecular Forces
Dipole-Dipole Forces

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
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.

Intermolecular Forces

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.
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.

Intermolecular Forces
London Dispersion Forces
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
London Dispersion
Forces

Intermolecular Forces
London Dispersion Forces

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.

Intermolecular Forces
Hydrogen Bonding
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.

Hydrogen Bonding

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 H-bonding.
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.

Intermolecular Forces
Hydrogen Bonding

Intermolecular Forces

Some Properties of Liquids

Viscosity
Viscosity is the resistance of a liquid to flow.
A liquid flows by sliding molecules over each other.
The stronger the intermolecular forces, the higher the
viscosity.
Surface Tension
Bulk molecules (those in the liquid) are equally attracted
to their neighbors.

Some Properties of Liquids

Viscosity

Surface Tension

Some Properties of Liquids

Surface Tension
Surface molecules are only attracted inwards towards the
bulk molecules.
Therefore, surface molecules are packed more closely than bulk
molecules.

Surface tension is the amount of energy required to

increase the surface area of a liquid.
Cohesive forces bind molecules to each other.
Adhesive forces bind molecules to a surface.

Some Properties of Liquids

Surface Tension
Meniscus is the shape of the liquid surface.
If adhesive forces are greater than cohesive forces, the liquid
surface is attracted to its container more than the bulk
molecules. Therefore, the meniscus is U-shaped (e.g. water in
glass).
If cohesive forces are greater than adhesive forces, the
meniscus is curved downwards.

Capillary Action: When a narrow glass tube is placed in

water, the meniscus pulls the water up the tube.

Phase Changes
Surface molecules are only attracted inwards towards the
bulk molecules.
Sublimation: solid gas.
Vaporization: liquid gas.
Melting or fusion: solid liquid.
Deposition: gas solid.
Condensation: gas liquid.
Freezing: liquid solid.

Phase Changes

Phase Changes
Energy Changes Accompanying
Phase Changes
Sublimation: Hsub > 0 (endothermic).
Vaporization: Hvap > 0 (endothermic).
Melting or Fusion: Hfus > 0 (endothermic).
Deposition: Hdep < 0 (exothermic).
Condensation: Hcon < 0 (exothermic).
Freezing: Hfre < 0 (exothermic).

Phase Changes
Energy Changes Accompanying
Phase Changes
Generally heat of fusion (enthalpy of fusion) is less than
heat of vaporization:
it takes more energy to completely separate molecules, than
partially separate them.

Phase Changes

Phase Changes
Energy Changes Accompanying
Phase Changes
All phase changes are possible under the right conditions.
The sequence
heat solid melt heat liquid boil heat gas
is endothermic.
The sequence
cool gas condense cool liquid freeze cool solid
is exothermic.

Phase Changes
Heating Curves
Plot of temperature change versus heat added is a heating
curve.
During a phase change, adding heat causes no
temperature change.
These points are used to calculate Hfus and Hvap.

Supercooling: When a liquid is cooled below its melting

point and it still remains a liquid.
Achieved by keeping the temperature low and increasing
kinetic energy to break intermolecular forces.

Phase Changes
Critical Temperature and Pressure
Gases liquefied by increasing pressure at some
temperature.
Critical temperature: the minimum temperature for
liquefaction of a gas using pressure.
Critical pressure: pressure required for liquefaction.

Phase Changes
Critical Temperature and Pressure