General Chemistry

Course # 111, two credits

Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Textbook: Principles of Modern Chemistry

by David W. Oxtoby, H. Pat Gillis, and Alan Campion (6 edition; 2007)

Dr. Rabih O. Al-Kaysi

Ext: 47247
Email: kaysir@ksau-hs.edu.sa
 Lecture 11
Intermolecular Forces

A Molecular Comparison of
Liquids and Solids
• Physical properties of substances understood in terms of
kinetic molecular theory:
• 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.
Comparison of Liquids
and Solids Cont.
 Intermolecular Forces
•These are the forces holding solids and liquids
together are called intermolecular forces.


What are Intermolecular

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).
• However, when a substance condenses, intermolecular
forces are formed.
 Vaporizing HCL
intermolecular forces
are broken Vapor phase

Formation
intermolecular forces

Heating Liquid Solutions

Liquid phase


Inter- vs. Intramolecular Forces

The covalent bond holding a molecule together

is an intramolecular force.


Properties Reflecting
Molecular Force Strengths
• Boiling and melting points reflect the strengths of
intermolecular forces.
• High boiling points indicate strong attractive forces
between molecules.
- For example, HCl boils at -85oC at room temperature due
to its weak attractive forces.
• Melting points increase with increasing attractive forces
(i.e., molecules become harder to separate).
 

Types of Molecular Forces

• There are four types of molecular forces:
• Ion-dipole Forces
• Dipole-dipole Forces
• London Dispersion Forces
• Hydrogen Bonding Forces
• The lateral three forces are general called van der
Waals forces (developed by Johannes van der Waals)
and exist between neutral molecules
• The ion-dipole forces exist between ions and polar
molecules.
Water (H2O)
Molecular Polarity


Ion-dipole Forces
• Interaction between an ion and a dipole.
• Dipole is a polar molecule (e.g. water).
• Strongest of all intermolecular forces.


Dipole-dipole Forces
• Dipole-dipole forces exist between neutral polar
molecules.
• Only effective when polar molecules are close together.
• These forces are weaker than ion-dipole forces.
• There is a mix of attractive and repulsive dipole-dipole
forces as the molecules tumble (free flow in liquids)
• If two molecules have about the same mass and size, then
dipole-dipole forces increase with increasing polarity.
Dipole-dipole Forces
Schematic


London Dispersion Forces

• Weakest of all intermolecular forces.
• Primary property that cause nonpolar substances to
condense to liquids and to freeze into solids at low
temperatures.
• Form when electrons occupy positions around the
nucleus in two adjacent atoms causing a temporary
dipole.
• The nucleus of one molecule (or atom) attracts the
electrons of the adjacent molecule (or atom).

Formation of London Dispersion
Forces
• 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).

Properties Effecting London
Dispersion Forces
• Dispersion forces are present in all molecules whether
polar or nonpolar
• The larger the molecule (the greater the number of
electrons) the more polarizable.
• London dispersion forces increase as molecular weight
increases.
• London dispersion forces depend on the shape of the
molecule.
• Example: neopentane (gas at 25oC), n-pentane
(liquid at 25oC)
 Trends in London Dispersion
Forces

Notice that as the molecular weight increases the

boiling points of the halogen increases, indicating
greater London dispersion forces between atoms.


Hydrogen Bonding
• By experiments: boiling points of compounds with H-
F, H-O, and H-N bonds are abnormally high.
• In the case of NH3, H2O, and HF, additional
intermolecular forces must be present which increases
the amount of heat energy needed to separate the
atoms.
• These additional intermolecular forces are called
hydrogen bonds.


The Origin of Hydrogen Bonding

• Notice that the hydrogen is attached to the

most electronegative elements. Thus, causing
the hydrogen to acquire a significant amount
of positive charge.
Hydrogen Bonding Schematic
 Hydrogen Bonding in H2O
• Hydrogen bonds are responsible for:
• Ice Floating
– 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 Å.
– The O…H hydrogen bond length is 1.8 Å.
– Each δ + H points towards a lone pair on O.


Comparing Intermolecular Forces

• Dispersion forces are found in all substances.
• Their strength depends on molecular shapes and weights.
• Dipole-dipole forces add to the effect of dispersion forces.
• They are found only in polar substances.
• H-bonding is a special case of dipole-dipole interactions.
• Strongest of the intermolecular forces involving neutral species.
• Most important for hydride compounds (NH3, H2O, etc.).
• Ion-dipole forces are interactions between ionic and polar
molecules.
• Ion-dipole are stronger than H-bonds.
• Covalent bonds are stronger than any of these reactions.

Intermolecular Forces
Chart