A Molecular Comparison of Liquids

and Solids

Copyright 1999, PRENTICE HALL Chapter 11 1

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.
– 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.

Copyright 1999, PRENTICE HALL Chapter 11 2

 The 3 States

Copyright 1999, PRENTICE HALL Chapter 11 3

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.

Copyright 1999, PRENTICE HALL Chapter 11 4

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).
• When a substance condenses intermolecular forces
are formed.
Copyright 1999, PRENTICE HALL Chapter 11 5
Intermolecular Forces

Copyright 1999, PRENTICE HALL Chapter 11 6

 Intermolecular Forces

1. Ion - Dipole
2. Dipole-Dipole Forces
3. Dipole - Induced Dipole
4. Instantaneous Dipole-
Induced Dipole
5. Hydrogen Bonding
Copyright 1999, PRENTICE HALL Chapter 11 7
 Table of Force Energies

Type of Force Energy (kJ/mol)

Ionic Bond 300-600
Covalent 200-400
Hydrogen Bonding 20-40
Ion-Dipole 10-20
Dipole-Dipole 1-5
Instantaneous Dipole/
Induced Dipole 0.05-2
Copyright 1999, PRENTICE HALL Chapter 11 8
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
d2
– 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.
Copyright 1999, PRENTICE HALL Chapter 11 9
Intermolecular Forces

Copyright 1999, PRENTICE HALL Chapter 11 10

 Ion - Dipole Interactions

Copyright 1999, PRENTICE HALL Chapter 11 11

Intermolecular Forces
Dipole-Dipole Forces
• Interaction between an ion (e.g. Na+) and a dipole (e.g.
water).
• Dipole-dipole forces exist between neutral polar
molecules.
• Polar molecules need to be close together.
• Weaker than ion-dipole forces:
Q1Q2
F k
d 2
– Q1 and Q2 are partial charges.

Copyright 1999, PRENTICE HALL Chapter 11 12

 dd
Dipole-Dipole Forces

Copyright 1999, PRENTICE HALL Chapter 11 13

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 dipole-
dipole forces increase with
increasing polarity.

Copyright 1999, PRENTICE HALL Chapter 11 14

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).

Copyright 1999, PRENTICE HALL Chapter 11 15

Intermolecular Forces
London Dispersion Forces

Copyright 1999, PRENTICE HALL Chapter 11 16

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.

Copyright 1999, PRENTICE HALL Chapter 11 17

 London Dispersion Forces

-Temporary Induced Dipole-Dipole interactions

–Very Weak always present in the condensed
phase

Copyright 1999, PRENTICE HALL Chapter 11 18

London
Dispersion
Forces

Copyright 1999, PRENTICE HALL Chapter 11 19

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.

Copyright 1999, PRENTICE HALL Chapter 11 20

Intermolecular Forces
London Dispersion Forces

Copyright 1999, PRENTICE HALL Chapter 11 21

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.
Copyright 1999, PRENTICE HALL Chapter 11 22
 H-Bonding

Occurs when Hydrogen is attached to a

highly electronegative atom.

N-H… N- O-H… N- F-H… N-

N-H… O- O-H… O- F-H… O-
N-H… F- O-H… F- F-H… F-
+ -
Requires Unshared Electron Pairs of Highly
Electronegative Elements
Copyright 1999, PRENTICE HALL Chapter 11 23
Hydrogen
Bonding
in Water
Molecules

Copyright 1999, PRENTICE HALL Chapter 11 24

 Structure of Ice HB-ice
Observe the orientation of the
Hydrogen Bonds

Copyright 1999, PRENTICE HALL Chapter 11 25

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 Å.
• The O…H hydrogen bond length is 1.8 Å.
• 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.

Copyright 1999, PRENTICE HALL Chapter 11 26

 Why Does Ice Float?

D2O(s) H2O(s)

Copyright 1999, PRENTICE HALL Chapter 11 27

 The Boiling Points of the Covalent Hydrides of the
Elements in Groups 4A, 5A, 6A, and 7A

Copyright 1999, PRENTICE HALL Chapter 11 28

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

Copyright 1999, PRENTICE HALL Chapter 11 29

Intermolecular Forces
Comparing Intermolecular Forces

Copyright 1999, PRENTICE HALL Chapter 11 30

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.

Copyright 1999, PRENTICE HALL Chapter 11 31

Some Properties of Liquids
Surface Tension

Copyright 1999, PRENTICE HALL Chapter 11 32

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.

Copyright 1999, PRENTICE HALL Chapter 11 33

Some Properties of Liquids
Surface Tension

Copyright 1999, PRENTICE HALL Chapter 11 34

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.

Copyright 1999, PRENTICE HALL Chapter 11 35