Chem 5

Chapter 13

Liquids, Solid, and Intermolecular Forces

Part 1

December 2, 2002
Condensed phases - Solids and Liquids
Chemical Bonds:

• Ionic bond
• Covalent bond
• Metallic bond

Intermolecular Interactions:

• Ion-dipole
• Dipole-dipole
• Dispersion (London) force or instantaneous dipole
• Hydrogen bond
 2s 2s
Two Li atoms

2s 2s 2s
Three Li atoms

Empty delocalized orbitals

Half antibonding responsible for conductivity

Half bonding
Band of 1023 delocalized molecular
Li Li2 Li3 Small spacing orbitals of slightly different energies
Energy Band half filled in lithium 2s band is completely
filled in beryllium but
overlaps with the 2p band.

Be is a conductor.
 Graphite and Conducting Polymers

2p

Electrons in a 2D box
Conductor because
band half-filled
with electrons

Electrons in a 1D box
 Diamond

sp3 hybridization
Conduction and Valence Bands for Diamond
Conduction band

Valence band

Diamond is an insulator due to the large band gap.

 Bands of semiconductors (Si, for example)
formed from equivalent sp3 localized hybrid orbitals
Conduction band

Si-Si bond weaker than C-C bond, smaller

gap between σ and σ* orbitals
Valence band
Semiconductors have small band gaps.
 Band Gaps

Li Be Si Diamond
 Doping in semiconductors
Si doped with P Si doped with Al

Conduction by electrons in the conduction band Conduction by holes in the valence band
Intermolecular Interactions (Van der Waals Forces):
• Ion-dipole
• Dipole-dipole
• Dispersion (London) force
• Hydrogen bond
Van der Waals Forces
• Dipole-Dipole Interaction

- Molecules with dipole moments

Examples: HCl, H2S

• Dispersion (London) Force

- Instantaneous dipoles
Example: He condenses to a liquid at 4K and freezes to a solid under pressure at1K.
Repulsion due to
electron interaction

Attraction due to
Dispersion force
 Dispersion Force

He - He

Ar - Ar

A comparison of the potential energy curves between two Ar atoms and two
He atoms. The larger Ar atoms are more tightly held, although the bond
energy is still 1/400 that of H-H bond.
Hydrogen Bond

A special type of intermolecular attraction between the hydrogen atom in a

polar bond (particularly an H-F, H-O, or H-N bond) and an unshared electron
pair on a nearby small electronegative atom (usually an F, O, or N atom
on another molecule).

.. ..
—N—H : O— H
| |
H
180o H
.. |
: O—H : N—H
| |
H
.. ..
: F—H : F—H
Hydrogen bond energy 15-40kJ/mol .. ..
Comparison of boiling points of some hydrides of the
elements of groups 14, 15, 16, 17

The values for NH3, H2O and HF are unusually high

because of hydrogen bonds.
Hydrogen Bonding in Ice
Movie of Ice and Water Made by Molecular Dynamics Simulation
Molecular dynamics simulation is a powerful computational tool to study
liquids. Real-time trajectories of atoms are obtained by integrating the
equations of motion based on the Newton’s law. These equations describe
motions governed by the potential of interacting molecules in the system.

Ice at 100 K Water 300K

Red, O Silver: H Dashed line: Hydrogen bond
Hydrogen bonds determine the structure of proteins.

Amide planes

The first model

by Linus Pauling
Hydrogen bonds are responsible
for base pairing in DNA.
Watson (left) and Crick proposed the double helix model of DNA in 1953. Their model
was based on data obtained by British chemist Rosalind Franklin. She used the X-ray
diffraction technique to show that the DNA has a helical structure. Without her permission,
her senior colleague Maurice Wilkins shared some of her data with Waston and Crick.
These data together with Waston and Crick’s realization of base pairing by hydrogen
bonding allowed Waston and Crick to deduce the double helix model.

Four years after Franklin’s death, Watson and

Crick shared the Noble Prize with Wilkins for the
discovery of DNA’s structure. Franklin might have
shared in the Prize had she lived.

"It has not escaped our notice that the specific pairing we
have postulated immediately suggests a possible copying
Rosalind Franklin
mechanism for the genetic material." – Waston and Crick
Surface Tension: the energy required to
increase the surface area of a liquid.

There is a tendency for liquids to maintain

a minimum surface area.

Adhesive force between the

water and oil is not enough
to spread water

Water wets a clean glass surface but beads up along a surface coated with oil.

Cohesive Forces:
intermolecular forces between like molecules
Adhesive Forces:
intermolecular forces between unlike molecules
 Anti-fog Coating Film for Bathroom Mirrors

Small water droplets condensed on the glass cause it to appear

foggy. The large adhesive force between the water and the
polymer film helps disperse the droplets, clearing the mirror.
Summary