Solids Chapter 12.4-12.

7
Metals, well you know what they are, but let us describe some properties

On the macroscopic level metals have

• High electrical conductivity
• High thermal conductivity
• Can be bent (ductile) and beaten into shape (malleable)
• Shiny
• Most are silvery

On the microscopic level metals are composed of

• One kind of ion and a number of weakly bound electrons
• Classically one can view the electrons as moving (more or less) freely in
the metallic lattice
• Quantum mechanically one views the electrons as being delocalized in
the matrix
• This is somewhat similar to the two views of resonance bonding.
 Melting Points
Metal Melting Point The delocalized electrons hold the metallic
Cs 28.4 C lattice together
Ga 29.8
Hg -38.8
The strength of the bonds varies
dramatically as can be seen from the
Ni 2651
melting points of different metals
W 6098

Metals with few (Grp 1) or many

(Grp 12) valence electrons have
low melting points.
In Grp 1 there is only one
electron per metal atom to
participate in bonding.
(Figure from Wikipedia)
 Drude Model
The simplest model of a metal was introduced by Paul Drude in 1900

It is often called the electron sea model, with the metal lattice sitting in a
sea of valence electrons that are free to move. It explains the electrical and
thermal conductivity of metals as well as their shiny appearance
Drude Model
In the Drude model some of the metal atom’s valence electrons move freely
in the metal lattice colliding with metal ions. Resistance to flow because of
the number of collisions is a measure of the conductivity of the metal

The model assumes that the electrons

behave as an ideal gas. This is wrong,
even conceptually, the electrons interact,
but in the end it provides the right answer.

In an oversimplified way, the interaction of

an electron with all the others can be
thought of as a drag. Effectively this can
From the Wikipedia
be represented as an increase in the mass
of the electron slowing it down. The
effective mass is written m *
Since with increasing temperature the kinetic energy of the electrons
increases the number of collisions will also increase. This means that the
conductivity of a metal decreases with increasing temperature.
 Band Model of Metals
Heitler and London were the first to apply the Schrodinger model of atoms to metals.
This extends the molecular orbital picture we built in Gchem 003 for diatomic
molecules with bonding and anti bonding orbitals

If we bring two metal atoms with a single

s electron, say Cu [Ar]3d104s1 together we
will form bonding and anti bonding
orbitals A2

Now if we bring a third Cu atom together

with the two atoms
A1
A2
A3
We can keep on adding atoms
Building Bands

A2
A3
A4 A5 A6 A7 A8

Although it is hard to see (and I am not an artist) as more atoms are added
to the one dimensional lattice we are building the states, both bonding and
antibonding, get closer together
Building Bands

Conduction Band

Valence Band
A2
A3
A4 A5 A6 A7 A8

Until at last they form a continuous band. The part of the band filled with
the bonding electrons is called the valence band. The upper part which has
no valence electrons is called the conduction band. Electrons in the
valence band are localized around metal ions.
Conductors
In metals there is no gap between the conduction and valence bands

At absolute zero all of the electrons are in

the valence band and localized. That
means that at 0 K even metals do not
Conduction Band conduct electricity.

However, as the metal warms up some of

the electrons will have enough energy to
be promoted (moved) into the
Valence Band delocalized conduction band where they
can conduct electricity.
 Insulators

Conduction Band

Band Gap

Valence Band
A2
A3
A4 A5 A6 A7 A8

The details are important. Forming the bands can leave an area between
the valence and conduction bands where there are no orbitals. That is
called a band gap. For electrons to move from the valence to the
conduction band they have to jump the band gap. For an insulator the
band gap is large compared to thermal energy.
 Semiconductors
If the bandgap exists, but is small enough that some electrons in the valence
band are promoted into the conduction band the material is called a
semiconductor. Germanium and silicon are semiconductors, diamond is an
insulator.
 Semiconductors
If a semiconductor is heated it will conduct more easily. The alteration of the
number of conduction electrons is one of the reasons that solid state
electronics fail at high temperatures.

At 298 K, the thermal energy, RT is about 2.5 kJ/mol so the conduction of

pure Si or Ge semiconductors is low because not many electrons will be
promoted into the conduction band.
 Semiconductors
If the temperature increases more electrons will move from the valence to
the conduction band in a semiconductor such as silicon, whereas the
increased number of collisions of an electron with the metal ions in a metallic
conductor will decrease the conductivity.
 Doping Semiconductors
The conductivity of a semiconductor can be manipulated by introducing
impurities that sit interstitually in the metal lattice. These can ether be
donors (n-type) that can donate an electron TO the conduction band

Or acceptors (p-type) that can accept an electron FROM the valence band.
This leaves what is called a hole in the valence band, and conduction occurs
as the hole moves from one metal ion to the next
 Doping Crystals
The color of gemstones is almost always the result of doping a colorless or
clear ionic or covalent crystal with an ionic metal species. For example beryl.
beryllium aluminum silicate,Be3Al2Si6O18, comes in
many forms, the one on the left being aquamarine.
Looking closely at the circled pillar, one can clearly
see the hexagonal nature of the unit cell

VARIETY COLOR CHROMOPHORES

Emerald Chrome-green Cr, V, Fe2+, Fe3+
Aquamarine Light blue to sea green Fe2+, Fe3+
Maxixe beryl` Blue (fades in sunlight) Fe2+, Fe3+ From the Wikipedia
Chrysolite Yellow-green Fe2+, Fe3+
Golden beryl Golden-yellow Fe2+, Fe3+
Heliodor Greenish-yellow Fe2+, Fe3+
Morganite Pink-orange, pale pink Mn2+, Mn3+
Bixbite (Red Emerald) Dark-red Mn2+, Mn3+
Goshenite (Rosterite) Colorless None

http://gemhunter.webs.com/beryl
Substitutional Impurities
As the last slide discussed for
beryl, substitutional
impurities occur when a
different atom or ion is
substituted into the crystal
lattice. In most cases the
substituted ion will be of
approximately the same size
as that of the ion it replaces.
Accommodation of ions of
different charges requires
that in addition to the
substituted ion a hole be
introduced into the lattice to
compensate.
Interstitial Impurities
Interstitial impurities occur
when a smaller atom or ion
becomes trapped into empty
spaces in the crystal lattice.

Steel is an example of this

with smaller carbon atoms
trapped in the iron matrix.

Stainless steel has both

interstitial carbon impurities
and substitutional chromium
and vanadium ions replacing
some of the iron ions.
Metal Alloys

Brass Cu Zn
Bronze Cu Sn
Alnico Al Ni Co
Nichrome Ni Cr
Steel Fe C Various
Stainless Steel Fe Cr C + Various
Solder Pb Sn
 Polymers (aka Plastics)
• Long chain, yuuuuuge organic molecules assembled from smaller
molecules called monomers.

• Polymers consist of many repeating monomer units

• A polymer is analogous to a necklace made from
many small beads
• A chemical reaction forming polymers from
monomers is called polymerization
 Molecular Weight of Polymers
The length of the polymer chain can vary
To an extent it can be controlled
Many properties of the polymer depend on the chain length
These include such things as density, hardness, malleability, etc.
Biopolymers
There are many biologically important
polymers, for example cellulose and
starch. Cellulose forms the cell walls of
plants and is built from beta glucose
monomers.

The monomer unit in starch is alpha

glucose
Nylon
Nylon
Polyethylene/Polyethene

https://youtu.be/U6d_F1jcKzI
Assignment
Working in groups of three

Name 1 other commercial polymer. (Not PET, polystyrene, or nylon)

What is its use?
What monomers is it built out of?

Name 1 other biopolymer. (Not DNA, starch or cellulose)

What is its biological function?